WasteEng2018 Proceedings

PROCEEDINGS
7th International Conference

on Engineering for Waste
and Biomass Valorisation
July 2-5, 2018

Prague, Czech Republic
www.wasteeng2018.org
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The 7th International Conference on Engineering
for Waste and Biomass Valorisation
(WasteEng2018)
PROCEEDINGS
Edited by
A. Nzihou and P. Stehlik
July 2-5, 2018
Prague (Czech Republic)
Organised by

ISBN: 979-10-91526-07-4
Published by:
IMT Mines Albi
Campus Jarlard
Route de Teillet
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France
2018
This work is licensed under the Creative Commons

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2
WasteEng2018 COMMITTEES
Conference Chairs
Professor Ange Nzihou
Mines Albi
Professor Petr Stehlik
Czech Society of Chemical Engineering
Organising Committee Members

Dr. Francisco Javier Escudero Sanz (Mines Albi)
Dr. Elsa Weiss-Hortala (Mines Albi)
Zuzana Boháčová (CSCHI, Czech republic)
Radek Halfar (CSCHI, Czech republic)
Scientific Committee
Adschiri, T., Japan Gomez Barea, A., Spain Oyekola, O., South Africa
Andrés Payán, A., Spain Grigiante, M., Italy Paul, E., France
Arena, U., Italy He, P., China Pavlas, M., Czech Republic
Baratieri, M., Italy Ikhu-Omoregbe, D., S. Africa Pontikes, Y., Belgium
Bello Bugallo, P., Spain Kano, J., Japan Py, X., France
Billen, P., Belgium Krzystek, L., Poland Ramli, A.B., Malaysia
Boulif, R., Morocco Kulczycka, J., Poland Ribeiro, T., France
Carrère, H., France Kumar, N., Finland Saake, B., Germany
Castaldi, M., USA Kwapinski, W., Ireland, San Miguel, G., Spain
Castro, F., Portugal Lavoie, J.-M., Canada Sanchez Hervas, J.M., Spain
Chang, Z., China Le Coq, L., France Sharrock, P., France
Chi, Y., China Lee, C.T., Malaysia Sierra Vargas, F.E., Colombia
Chojnacka, K., Poland Lee, J.W., Korea Skiadas, I., Denmark
Coronella, C., USA Legrand, J., France Stehlik, P., Czech Republic
Da Silva Perez, D., France Lemont, F., France Trémier, A., France
Dupont, C., France Lin, C.S.K., Hong Kong Valix, M., Australia
Evangelista, L., Norway Liu, J., China Van Deventer, J., Australia
Filippov, L., France Loizidou, M., Greece Vandecasteele, C., Belgium
Fiori, L., Italy Lyberatos, G., Greece Vasudevan, P.T., USA
Flamant, G., France Marias, F., France Wang, F., China
Fröhling, M., Germany Nzihou, A., France Watanabe, M., Japan
Gavala, H., Denmark Oakley, S., USA White, C., USA
Germeau, A., Belgium Onwona-Agyeman, B., Ghana Zhao, Y., Ireland

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Proceedings Index
Monday - July 2, 2018
Invited Lecture: M. Milukas, European Commission
509 Circular Economy: a collaborative approach to waste management 34
ARNOLDAS MILUKAS
PL1 - Plenary Lecture: Prof Arena, Italy
503 Co-gasification as a possible alternative for an efficient Waste-to-Energy conversion 35
UMBERTO ARENA
C1 - Biogas & bioethanol from industrial wastewaters
89 Simulation of biogas production from slaughterhouse wastewater in continuously 37
operated anaerobic digesters
APOSTOLOS SPYRIDONIDIS , KATERINA STAMATELATOU
122 Anaerobic codigestion of tannery and slaughterhouse sludge 39
ASHTON MPOFU, PAMELA WELZ, OLUWASEUN OYEKOLA
248 Sustainability analysis of biorefining schemes for revalorization of tequila industry 41
residues and wastes
ARTURO SANCHEZ, SEBASTIAN SANCHEZ, PALOMA DUEÑAS
58 Potential for treating dairy industry wastewater cogenerating biogas 42
DANIEL IKHU-OMOREGBE, MERCY MANYUCHI
D1 - Char applications for gas cleaning
130 Comparison of wood chars from gasification and pyrolysis for adsorption and 49
conversion of tar model compounds
GIULIA RAVENNI, OMID-HENRIK ELHAMI, YORK NEUBAUER, JESPER AHRENFELDT,
ULRIK BIRK HENRIKSEN
308 Valorization of millet and buckwheat husks chars in a fixed bed as low-cost sorbents 58
in H2S removal from biogas
JENNY PEÑA, AUDREY VILLOT, CLAIRE GERENTE
187 Utilization of residual carbon and mineral content from gasification char to reform 59
tars from syngas
JEAN-MICHEL LAVOIE
500 Hot syngas cleaning by means of activated chars or activated carbons available on the 60
market
FRANCESCO PARRILLO, UMBERTO ARENA, DIEGO FUENTES CANO, GIOVANNA
RUOPPOLO
J1 - Waste & wastewater treatment assessment
152 Proposal of a GIS method for designing a spatially optimized micro-ad network in 67
urban and peri-urban areas
PIERRE THIRIET, THIERRY BIOTEAU, ANNE TREMIER
5
391 Environmental and socio-economic impact assessment of the production of perennial 68
crops when irrigated with treated wastewaters
JORGE COSTA, BRUNO BARBOSA, ANA LUISA FERNANDO
327 The 3T method as an assessment tool for comparing different waste management 76
strategies
STERGIOS VAKALIS, KONSTANTINOS MOUSTAKAS, MARIA LOIZIDOU
135 Comparative assessment of global warming and water footprint impacts of 77
polybutylene succinate (PBS) from cassava and sugarcane
UNCHALEE SUWANMANEE
G1 - Recycled cementitious materials
497 Low-grade concrete made of 100% recycled materials – feasibility study 87
POLYKA BUN, RACHIDA IDIR, KIMNGUN BUN, MARTIN CYR
67 Recycling concrete aggregates in new concrete - investigations of quality and origin of 97
the concrete waste
LOUISE GREEN PEDERSEN, KRISTIAN NYVANG JENSEN, MADS EMIL HERLOEV,
GUNVOR MARIE KIRKELUND, LISBETH M. OTTOSEN
303 Recycling 100% of waste concrete 98
FRANK ZEMAN
434 Valorization of rice husk ash (RHA) as silica precursor for the obtainment of heavy clay 99
bricks and deflocculating additives
FERNANDA ANDREOLA, LUISA BARBIERI, ISABELLA LANCELLOTTI
KN01 - Keynote Lecture
413 Global urban food waste management report from WBA and C40 cities climate 101
leadership group How food waste management is needed to meet the climate change
and sustainable development goals
DAVID NEWMAN
191 Progress in the development of torrefaction for solid biomass applications in industry 102
WEI-HSIN CHEN
240 Reuse of alum sludge in water and environmental engineering: R&D of 10 years’ 103
experience
YAQIAN ZHAO
C2 - Biogas & digestate quality & treatment
156 Kinetics of biological mineralisation of nitrogen during anaerobic digestion 105
HENRY FISGATIVA, CYRIL MARCILHAC, CAROLINE JAUDOIN, FABRICE BELINE
448 Management of waste to energy plants: quantifying total silicon in biogas 106
HÉLÈNE METIVIER-PIGNON, VINCENT CHATAIN, MARTA GALERA-MARTINEZ, ETIENNE
BASSET, RÉMY BAYARD
31 Development and validation of a novel simplified Nordmann titration method for 107
monitoring volatile fatty acids in anaerobic digestion processes treating organic waste
SHUBIAO WU, HAO SUN
319 How to accurately estimate ammonium content in the digestates: a lab-scale study 108
YOUNES BAREHA, ANNE TREMIER, ROMAIN GIRAULT
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D2 - Thermal conversion fundamentals
245 Analysis and interpretation of intraparticle sampling data: assessment of the 110
exothermicity effect during biomass pyrolysis
FRANCESCO PATUZZI, SIMONA CIUTA, MARCO BARATIERI, MARCO CASTALDI
217 Kinetic analysis of tropical lignocellulosic biomass steam gasification 111
LINA MARIA ROMERO MILLAN, FABIO EMIRO SIERRA VARGAS, ANGE NZIHOU
174 Combustion behavior of animal manure-based hydrochar 112
KYOUNG RO, JUDY LIBRA, ANDRES ALVAREZ-MURILLO, NICOLE BERGE
467 Investigation into the oxygen- and carbon-containing functional groups 113
transformation during sewage sludge pyrolysis by combining various experiments
YANJUN HU, YANJUN LU, WENJING YU
J2 - Environmental assessment of e-waste & marine equipment
65 Quantifying temporal effects of various GHG abatement strategies for conventional 114
and district heating
SAURAJYOTI KAR, PIETER BILLEN, BETH KATZ, SHENG YANG, TIMOTHY A. VOLK,
SABRINA SPATARI
229 Environmental assessment of bioleaching of copper from electronic waste, life cycle 115
assessment approach
MARJORIE VALIX
159 Life Cycle Assessment of e-waste management in a public university in Brazil 116
BRUNA COSTA, LAÍS PEIXOTO ROSADO, TIAGO BARRETO ROCHA, CARMENLUCIA
PENTEADO
70 Sustainable production and use of marine equipment: a circular economy prospective 126
GABRIELLE ZAPELLONI, ADRIANA GARCÍA RELLÁN, PASTORA BELLO BUGALLO
H1 - High temperature energy storage

312 Peak-load high-temperature carbonate storage 138
CHRISTOPH LANGE, DOMINIK MÜLLER, JÜRGEN KARL
301 Experimental and numerical investigations of thermocline ceramic bed for thermal 139
storage system at high temperature
ABDOUL RAZAC SANE, DOAN PHAM MINH, PATRICK SHARROCK, ANGE NZIHOU
134 Air/ceramic packed bed thermocline storage system at pilot scale - influence of 140
operating conditions on system behaviour
NICOLAS LOPEZ-FERBER, VINCENT GOETZ, QUENTIN FALCOZ, ANGE NZIHOU, DOAN
PHAM MINH, ANTOINE MEFFRE, JEAN-FRANÇOIS HOFFMANN
OF5-1 - Anaerobic digestion
147 Performance of coupling an aerobic pre-treatment and solid-state anaerobic 141
digestion of food waste
HENRY FISGATIVA, ANNE TREMIER, PATRICK DABERT
419 Optimization of biogas production in a cassava processing unit in Benin by anaerobic 142
digestion of waste generated for the development of sustainable energy
YVES ANDRES, LAMINE SAÏD BABA-MOUSSA , SYLVESTRE AHOU
258 Relationship between commercial enzymes and natural extracellular enzymes for 144
improved biogas production
JANA JANTOVA-PATEL, ANNA CERMÁKOVÁ, RAFFAELLA VILLA, YADIRA BAJÓN
FERNÁNDEZ
267 Anaerobic digestion of vinasse and CFD modelling approach 145
HÉLÈNE CAILLET, ALAIN BASTIDE, GRAZIELLA TOSTAIN, LAËTITIA ADELARD
7
487 Recovery of humic-like substances from urban digestates 158
FELIPE GUILAYN, PAULO T. CARRENHO, JULIE JIMENEZ, MAXIME ROUEZ, MARION
CREST, DOMINIQUE PATUREAU
OF5-2 - Hydrothermal process & hydrochar
72 Effect of water-soluble additives on the denitrification and viscosity-breaking of oil 159
products obtained from hydrothermal liquefaction of kitchen waste
DI SHU, YONG CHI
455 Characteristics of biochar and hydrochar obtained from thermal treatment of manure 160
waste
ELIANA CÁRDENAS AGUIAR, GABRIEL GASCO, ANA MENDEZ
396 Biofuel upgrading: ash reduction and energy density enhancement of Opuntia-ficus 161
indica cladodes via hydrothermal pretreatments using metal ions chemical
sequestration
MAURIZIO VOLPE, MICHELA LUCIAN, ELSA WEISS-HORTALA, LUCA FIORI
254 Hydrothermal carbonization of lignin and hydrochar activation 162
EDOARDO MILIOTTI, LORENZO BETTUCCI, STEFANO DELL'ORCO, ANDREA MARIA
RIZZO, DAVID CASINI, DAVID CHIARAMONTI
OF4-1 - Construction materials from wastes
14 Polyurethane foams produced from pyrolysis oil – their production and potential 163
application as building insulation
TIM SCHULZKE, STEFAN CONRAD, ANASTASIIA IAKOVLEVA, SERGEY ZABELKIN,
ANDREY GRACHEV
97 Utilization of Class-C fly ash for geopolymer precursor 164
DIAN ADISTY, SOTYA ASTUTININGSIH
132 Innovative ceramic thermal storage material elaborated from municipal incinerator 172
bottom ashes
NICOLAS LOPEZ-FERBER, DOAN PHAM MINH, ANGE NZIHOU, VINCENT GOETZ,
QUENTIN FALCOZ, NICOLAS TESSIER-DOYEN, JEAN-FRANÇOIS HOFFMANN, ANTOINE
MEFFRE
305 Ashes from biomass combustion: recycling as mortars raw material in a sustainability 173
perspective
REGINA CÉLIA ESPINOSA MODOLO, GUILHERME ASCENSÃO, LUCIANO SENFF, LUÍS
ANTÓNIO DA CRUZ TARELHO, VICTOR MIGUEL FERREIRA, JOÃO ANTÓNIO
LABRINCHA, CARLOS ALBERTO MORAES, ANTÓNIO SILVA
522 Potential application of microalgae culture to wastewater treatment 180
JACK LEGRAND
226 Commercial adoption of low CO2 cement: what is missing? 181
JANNIE VAN DEVENTER
538 Foodwaste from an environmental problem to a valuable resource 182
MARIA LOIZIDOU
86 Role of the Circular Economy in the saving of resources 183
CHANTAL BLOCK, CARLO VANDECASTEELE
8
C3 - Pretreatment & anaerobic digestion
449 Improving continuous anaerobic mono-digestion of manure by an optimized 184
ammonia pretreatment
ANNA LYMPERATOU, HARIKLIA GAVALA, NIELS RASMUSSEN, IOANNIS SKIADAS
223 Enhancement of methane potential and conversion kinetics of the anaerobic 185
digestion of agave bagasse by ozone delignification
VASTI KRISTEL AREVALO-PEREZ, OCTAVIO GARCIA-DEPRAECT, ELIZABETH LEÓN-
BECERRIL
173 In storage anaerobic digestion of pig manure using a floating cover, from the lab to 193
the farm
PATRICK DABERT, THOMAS LENDORMI, FABRICE BELINE, AURORE TOUDIC, KRISTELL
LAVENAN
418 Dry fractionation of olive pomace for biogas production: milling, sieving and 195
electrostatic separation
DOHA E. ALAMI, HÉLÈNE CARRERE, AHMED LEBRIHI, DRISS DHIBA, ABDELLATIF
BARAKAT
D3 - Gasification & pyrolysis I: experimental performance
288 Experimental investigations of CO2 feed in a downdraft biomass gasifier 196
DANIELE ANTOLINI, SNEHESH SHIVANANDA AIL, FRANCESCO PATUZZI, MAURIZIO
GRIGIANTE, MARCO BARATIERI
294 Pilot scale pyrolysis of sludge from milk processing factories 197
MARZENA KWAPINSKA, ALEN HORVAT, J.J. LEAHY
272 Fluidized-bed gasification of various solid refused fuels: influence of the operating 206
conditions
MAXIME HERVY, DAMIEN REMY, GUILLAIN MAUVIEL
302 Plasma-assisted biomass gasification in an atmospheric drop tube reactor 207
YIN PANG
D4 - Residues characterization
398 Characteristics of particulate matter from municipal solid waste pyrolysis, gasification 217
and incineration
JUN DONG, ANGE NZIHOU, YONG CHI, YUANJUN TANG, ELSA WEISS-HORTALA,
MINGJIANG NI
362 Carbonized rice husk characterization for soil substrate application 218
GENYR KAPPLER, DEBORA MACHADO SOUZA, SUELLEN BRASIL SCHRÖPFER, REGINA
CÉLIA ESPINOSA MODOLO, CARLOS ALBERTO MORAES, PAULO ROBERTO WANDER,
LUÍS ANTÓNIO DA CRUZ TARELHO
80 Co-combustion of bituminous coal and pickling sludge in a high-temperature tubular 229
furnace system: the effect of bituminous coal kaoline and water content on the
distributions of Cr, Ni, Sb, Mn, Cu, As and Pb
SHAORUI ZHANG, XUGUANG JIANG, GUOJUN LV, XIANG NI, YUQI JIN, JIANHUA YAN
338 Characterization of industrial wastes in relation with incineration fumes and residue 240
composition
LAURENCE LE COQ, AURÉLIE JOUBERT, RACHID BOUDHAN, CHRISTOPHE
DUTOUQUET, DANIELLE VENDITTI, SYLVAIN DURECU, EMMANUEL FIANI, OLIVIER LE
BIHAN
9
G2 - From waste to construction material
335 Microstructural tailoring of BOF steel slag for construction applications: amorphous 241
content and its impact on reactivity and mechanical strength after alkali activation
PAVEL LEONARDO LOPEZ GONZALEZ, YIANNIS PONTIKES
98 Firing of zinc phosphate sludge – kaolin mixture for waste containment 242
SOTYA ASTUTININGSIH, JACKSON MULIAWAN
44 From waste to a green construction material: fire-resistant cellulose panels for 243
ceilings
PAALO MORENO, NICOLE VILLAMIZAR, JEFFERSON PEREZ, ANGELICA BAYONA,
NICOLAS MORENO, JESUS ROMAN, NILO SERGIO MEDEIROS CARDOZO
331 Vitrified asbestos waste used as filler material in a thermocline storage tank 244
MUHAMMAD ASAAD KEILANY, MATHIEU MILHE, JEAN JACQUES BEZIAN, THOMAS
FASQUELLE, QUENTIN FALCOZ, GILLES FLAMANT
C4 - Biohydrogen & syngas
170 Potato peels as feedstock for bioethanol production: a comparison of chemical, 254
thermal and enzymatic pretreatment
IMEN BEN ATITALLAH , GEORGIA ANTONOPOULOU , IOANNA NTAIKOU, MARIA
ALEXANDROPOULOU, M NASRI, TAHAR MECHICHI, GERASIMOS LYBERATOS
212 Biomethanation of syngas by mixed microbial consortia in a trickle bed reactor 264
KONSTANTINOS ASIMAKOPOULOS, HARIKLIA GAVALA, IOANNIS SKIADAS
332 Valorization of beer production wastes: biohydrogen production by dark 265
fermentation
MARIE RENAUDIE, CHRISTINE DUMAS, BARBARA ERNST
314 Optimization of rice husk particle size on bio-hydrogen gas production using co- 266
culture
G. GIZEM TAYLAN, SERPIL OZMIHCI
D5 - Gasification & pyrolysis II: experimental performance
285 Experimental investigations on an open top downdraft gasifier coupled with a dual 267
fuel compression ignition engine micro-cogeneration system
CARLO CALIGIURI, DANIELE ANTOLINI, FRANCESCO PATUZZI, MASSIMILIANO RENZI,
MARCO BARATIERI
46 Experimental study of solid recovered fuel fluidised bed gasification 268
SYLVIE VALIN, SERGE RAVEL, PHILIPPE PONS DE VINCENT, SÉBASTIEN THIERY, HÉLÈNE
MILLER
209 Performance tests of 8 ton/day gasification process to generate electricity from fluff 269
type solid refuse fuel
YONG-CHIL SEO, SE-WON PARK, JONG-HYEOG OH, JAE-HOI GU, YEONG-SU PARK
108 Combustion study of a massive polyethylene hanged in an oven 270
QUENTIN BALME, FLORENT LEMONT, PATRICE CHARVIN, FREDERIC MARIAS
I1 - Waste reduction & valorisation
521 Ball milling as a tool for waste treatment 271
BALÁ_ MATEJ
516 Biodegradable films physical properties change with respect to degradation exposure 272
to various media
SULTAN AL-SALEM, AFAF AL-NASSER, MAJED AL-WADI, HANAN SULTAN, AL-
FOUDAREE MOHAMMAD, HAJAR KARAM, AYYAD AL-DHAFEERI
10
175 Biochar as an adsorbent for odor removal 283
KYOUNG RO, OKWHA HWANG, SANG RYONG LEE, DEUG WOO HAN, SUNGBACK CHO,
MINDY SPIEHS, BRYAN WOODBURY
K1 - Waste valorisation & emissions mitigation
265 Selection of recovery paths for industrial wastes: a multicriteria analysis approach 284
MICKAEL BURONFOSSE, YOUCEF BOUZIDI, NICOLAS ANTHEAUME, SOKHA LEANG,
FRANÇOIS THERY
364 Competitiveness of waste processing centers and generation of new companies and 285
businesses in developing countries and emerging economies vulnerable to water
shortages: a Brazilian perspective
SERGIO AUGUSTO LUCKE, ANTONIO CARLOS ZUFFO
367 Practical feasibility aspects of waste processing centers with power generation in 286
developing countries and emerging economies: the Brazilian perspective
SERGIO AUGUSTO LUCKE, ANTONIO CARLOS ZUFFO
439 A Model Framework for Evaluating Socio-economy Changes on Non-Point Source 296
Pollution
HAN XIA, JINGJING XIA, WANSHUN ZHANG, HONG PENG
Tuesday - July 3, 2018

PL2 - Plenary Lecture: Prof Angelidaki, Denmark
8 Bioconversion of organic matter to useful chemicals and fuels in a circular 297
bioeconomy approach
IRINI ANGELIDAKI
E1 - Biowaste to chemicals
100 Aldol condensation of biomass-derived valeraldehyde and cyclopentanone over oxide 298
catalysts for production of fine chemicals and fuels
PÄIVI MÄKI-ARVELA, NATALIYA SHCHERBAN, NARENDRA KUMAR, ATTE AHO, KARI
ERÄNEN, KONSTANTIN VOLCHO, DMITRY YU. MURZIN
199 Valorization of digestate through solid state fermentation to produce biopesticides 299
with Bacillus thuringiensis
PAULA RODRÍGUEZ , ANTONI SÁNCHEZ, XAVIER FONT, ADRIANA ARTOLA
219 Food waste pigments for natural hair dyes: ultrasound-enhanced enzymatic 307
extraction and hair dye application
MADELEINE BUSSEMAKER, JUDY LEE
B1 - Thermal treatments
210 An improved model-free kinetic approach to study the thermal degradation of solids 308
MAURIZIO GRIGIANTE, MARCO BRIGHENTI, MATILDE MALDINA, DANIELE ANTOLINI
360 Distribution of ash forming elements during pyrolysis of waste water treatment 309
sludge from milk processing factories
MARZENA KWAPINSKA, J.J. LEAHY
431 Production of fiberboard from thermally treated furniture wood waste 320
PIERRE GIRODS, BAPTISTE COLIN, YVES JANNOT, YANN ROGAUME
C5 - Potential & economics of biogas production
62 Technical-economical feasibility study on biogas treatment using municipal solid 321
waste incineration bottom ash
MARTA FONTSERE OBIS, PATRICK GERMAIN, HASSEN BENBELKACEM
11
506 Biogas biorefinery: techno-economic analysis 322
ANDREY KUTSAY, LUKAS KRATKY, TOMAS JIROUT
101 Simulation of integrated sludge anaerobic digestion and CHP 323
YANGQING HU, PATRICIA ARLABOSSE, FEI WANG, MARTIAL SAUCEAU, YONG CHI
F1 - Construction from waste
530 Vitrification of fly ash from municipal solid waste incinerator based on CaO-Al2O3- 324
SiO2 ternary system by DC arc plasma
WENCHAO MA, DONGMEI CHEN, XIAO HE, GUANYI CHEN
110 Fungal resistance of cellulose panels for ceilings 325
PAALO MORENO, ANDREA BERMUDEZ, AMPARO GUALDRON, NILO SERGIO
MEDEIROS CARDOZO
462 Hygrothermal performance of a new bio-based concrete wall 326
NAWAL CHENNOUF, BOUJDMAA AGOUDJIL, ABDERRAHIM BOUDENNE , KARIM
BENZERTI , FETHI BOURAS
E2 - Biowaste to hydrogen & biofuels
269 Mixed culture biotechnology for biofuels production in syngas fermentation 328
processes
ANTONIO GRIMALT-ALEMANY, IOANNIS V. SKIADAS, HARIKLIA N. GAVALA
271 Acidogenic fermentation of household solid waste: bacterial enrichment at controlled 329
pH
LAURA DIGAN, SIMON DUBOS, EVRARD MENGELLE, ETIENNE PAUL, CLEMENCE
PAGES, ERIC TRABLY, HÉLÈNE ROUX DE BALMANN, CLAIRE DUMAS
92 Hydrogen production from sewage sludge without methane fermentation 331
JUNYA KANO, SHUJI NOBORIYA
F2 - Pyrolysis & copyrolysis
306 Using the chemical structure of biomass to inform pyrolysis modelling: formulation of 332
pseudo-components of hemicellulose and lignin
KARLA DUSSAN, STEPHEN DOOLEY, RORY MONAGHAN
476 Characteristics of pyrolysis oil as renewable source of chemical materials and 333
alternative fuel from the sewage sludge treatment
JAKUB RACEK, TOMAS CHORAZY, JOSEF CASLAVSKY, VERONIKA ZVAKOVA, PETR
HLAVINEK
511 Products properties and interaction mechanism of co-pyrolysis of waste biomass and 343
plastics
PENG LU, QUNXING HUANG, YONG CHI, A.C.(THANOS) BOURTSALAS, FEI WANG, KAI
SUN
E3 - Bioconversion for added value chemicals
368 Scaling up of a disruptive process for hemicellulose conversion to value added 344
products
BRUNA REGO DE VASCONCELOS, JUSTINE BROSSE, XAVIER DURET, JEAN-MICHEL
LAVOIE
472 Novel bacterial strains for the direct upgrade of hemicellulose derived 345
oligosaccharides
IVONE TORRADO, PEDRO MARTINS, PATRÍCIA MONIZ, MARIA TERESA SANTOS,
FLORBELA CARVALHEIRO, MARIA DA CONCEIÇÃO FERNANDES, HELENA PEREIRA, LUÍS
C. DUARTE
12
517 The potential bioconversion of tropical agricultural wastes producing value added 346
chemicals (vanillin) using lignocellulose degrading fungus
IRNIA NURIKA
H2 - Material characteristics & use
399 Study of materials in corrosive environments using fuels with high chlorine content in 347
oxy-fuel atmosphere
ALBERTO BAHILLO
74 Sustainable production and use of buildings: a circular economy prospective 348
MARÍA DEL CARMEN TABOADA GÓMEZ, F. CULOTTE, PASTORA BELLO BUGALLO
316 Application of modified bentonite as foam stabilizer in enhanced oil recovery 358
ZHIDONG CHANG
E4 - Bioconversion & added value chemicals
126 Sophorolipid production from food waste hydrolysate using a native Starmerella 359
bombicola
HUAIMIN WANG, CAROL SZE KI LIN, GUNEET KAUR, KRISTIADI UISAN
189 Valorisation of corn fibre: optimisation of an integrated process for the production of 360
bio-vanillin
RITA VALÉRIO
341 Recovery of volatile fatty acids from waste-derived fermentation broth using 361
nanofiltration
YIN ZHU, SYLVAIN GALIER, CLAIRE DUMAS, HÉLÈNE ROUX-DE BALMANN
504 Valorisation of copper slag for the photocatalytic degradation of organic pollutants in 362
water
CLAUDIA MONTOYA-BAUTISTA, REYNA GARCIA-ESTRADA, EDWIN IVAN AVELLA-
FERNANDEZ, ROSA MARÍA RAMIREZ-ZAMORA, RAFAEL SCHOUWENAARS
F3 - Pyrolysis
186 Hydrodeoxygenation of biomass pyrolysis oil using hydrogen donor solvent and Co- 369
Mo catalysts
JULIUS GANE, MOHAMAD ANAS NAHIL, PAUL WILLIAMS
185 Primary pyrolysis reactions of lignin 370
HARUO KAWAMOTO
155 Pyrolysis of low-grade plastic-rich wastes to produce liquid fuels and chemicals 371
STUART WAGLAND
E5 - CO2 valorisation & catalysis
275 CO2 adsorption on chemically activated chars from commercial biomass gasifiers 372
ELEONORA CORDIOLI, VITTORIA BENEDETTI, FRANCESCO PATUZZI, MARCO BARATIERI
318 Eggshell as a potential CO2 sorbent in chemical looping gasification of biomass: 373
calcination, carbonation and characterization studies
ANIMESH DUTTA
125 Novel catalytic materials synthesis from industrial slags for application in catalytic fast 374
pyrolysis of pine sawdust
EKATERINA KHOLKINA, NARENDRA KUMAR, CHRISTIAN LINDFORS, TAINA OHRA-AHO,
JUHA LEHTONEN, DMITRY MURZIN
214 Hydroxyapatite and Magnesium-doped hydroxyapatite as new supports for dry 375
reforming of methane
THANH SON PHAN, DOAN PHAM MINH, DIDIER GROUSET, ANGE NZIHOU
13
A1 - Ash & biochar valorisation strategies
299 Material characterization of bottom ash fine fraction 376
MICHAL SYC
347 Leaching and recovery of trace elements from bottom ash – preliminary study 377
MARIA LUPSEA-TOADER, LENKA SVECOVA, DENISE BLANC, CHRISTINE DE BRAUER
473 Biochar – recovery material from microwave pyrolysis of sewage sludge 379
JAKUB RACEK, JAN SEVCIK, TOMAS CHORAZY, JIRI KUCERIK, PETR HLAVINEK
508 Solid issued from tyre pyrolysis: a valuable recycled product 389
C.GISELE JUNG, JEAN-PAUL BOUYSSET
Mobile and Flexible Biomass Processing - H2020 Mobile Flip 1
151 Utilisation of forest and agricultural biomass in pellet making – How flexible is the 391
process to unconventional feedstock?
DAVID A. AGAR, MAGNUS RUDOLFSSON, GUNNAR KALÉN, MATTHIEU CAMPARGUE,
SYLVIA H. LARSSON
166 Multivariate predictive modeling for flexible process control in lignocellulosic biomass 392
pelletizing
SYLVIA H. LARSSON, MAGNUS RUDOLFSSON, DENILSON DA SILVA PEREZ, MATTHIEU
CAMPARGUE, DAVID A. AGAR
242 Woody and agricultural biomass torrefaction: a new approach to model solid 393
conversion and volatiles formation based on biomass extracted components
MARIA GONZALEZ MARTINEZ, CAPUCINE DUPONT, SÉBASTIEN THIERY, DENILSON DA
SILVA PEREZ, XUAN-MI MEYER, CHRISTOPHE GOURDON
389 How to convert the European underexploited biomass side streams into marketable 394
products: an extensive study of suitability feedstock/process/product up to pilot scale
CAPUCINE DUPONT
A2 - Biorefinery, phytochemical extraction

470 Extraction of humic substances from residual mixed municipal solid waste 395
DANIELA ZINGARETTI, ALESSIO LIETO, FRANCESCO LOMBARDI, MIRKO DI CIOCCO
454 The effect of biochar and hydrochar in the metal phytoextraction from mining soils 397
ELIANA CÁRDENAS AGUIAR, GABRIEL GASCO, JORGE PAZ-FERREIRO, ANA MENDEZ
184 Towards a real marine biorefinery for the efficient management of the biomass 398
associated to the EC landing obligation
LUIS T. ANTELO, AMAYA FRANCO-URIA, JOSÉ ANTONIO VÁZQUEZ, RICARDO PÉREZ-
MARTÍN
F4 - Biomass combustion & gasification
357 Energy conversion of gasification residual char: combustion and cofiring scenarios in 399
Northern Italy
STEFANO PIAZZI, XIAOLEI ZHANG, FRANCESCO PATUZZI, MARCO BARATIERI
423 Combustion and emissions characteristics of palm acid oil-diesel mixed fuel and 400
improvement on its low temperature fluidity
HIROFUMI NOGE, WIRA JAZAIR YAHYA
397 A non-waste, solid recovered fuel from municipal solid waste for co-firing with coal 410
JENNY JONES, BIJAL GUDKA, PETER METCALF, MARK GRONNOW, PETER HURST,
JEREMY RIX, STEVEN BUTLER
232 From biomass and residues to fuels 416
SANDER GROOTJES, BEREND VREUGDENHIL, ROBIN ZWART
14
A3 - Separation & recovery strategy for municipal solid waste
10 Challenges of food waste avoidance and collection on the example of the city of 417
Hamburg
INA KÖRNER, JESSICA SCHERMULY, STEFFEN WALK
15 The potential for recovery of residual municipal solid waste: sustainability of urban 418
mining strategies
ALESSANDRA CESARO, VINCENZO BELGIORNO
358 Municipal solid waste fractions and their source separation – forecasting for large 419
geographical area and its sub-regions
MARTIN PAVLAS, RADOVAN _OMPLÁK, VERONIKA SMEJKALOVA, PETR STEHLÍK
117 Composition of mixed solid waste using deep neural networks 420
CARLOS VRANCKEN, PHIL LONGHURST, STUART WAGLAND
409 Performance of pyrolysis and HTC liquids in plant protection 421
MARLEENA HAGNER, ISA LINDQVIST, KLAUS NIEMELÄ, HANNE WIKBERG, ANSSI KÄLLI,
KIMMO RASA, KARI TIILIKKALA
437 Activated carbons from various biomass residues via hydrothermal carbonization and 422
activation
HANNE WIKBERG, VIRPI SIIPOLA, TARJA TAMMINEN
442 Micron-scale pore structure of biochars derived from pyrolysis and hydrothermal 423
carbonization processes
JARI HYVALUOMA, JAAKKO HEIKKINEN, SAMPO KULJU, MARKUS HANNULA, HANNE
WIKBERG, ANSSI KÄLLI, KIMMO RASA
445 Pelletizing optimization versus biomass properties – determination of optimal 424
moisture content and compression rate
SIMON LAVERGNE, MAXIME ROJAS, MATTHIEU CAMPARGUE, SYLVIA H. LARSSON,
THIERRY MELKIOR, MURIEL MARCHAND, CAPUCINE DUPONT
J3 - Assesment approaches and waste management
5 Comparative environmental assessment of vine shoots valorisation strategies into 426
high added compounds
BEATRIZ GULLÓN, PATRICIA GULLÓN, JALEL LABIDI, SARA GONZALEZ-GARCIA
356 A life cycle perspective for optimal design of a closed-loop supply chain: the case 427
study of lead acid batteries
MAGNO GONZALEZ RODRIGUEZ, CATHERINE AZZARO-PANTEL, ALBERTO AGUILAR
LASSERRE
218 Are biomass, carbon dioxide and electrical power the main renewable feedstock of a 428
sustainable carbon economy?
THOMAS MARZI
539 Overview and perspective of MSW management based on source separation in China 429
JIANGUO LIU
OF4-2 - Metal recovery
9 Concentration of heavy metals in fly ash from empty fruit bunches combustion by 430
particle size
CHRISTOF LANZERSTORFER
55 Thermochemical eradication of heavy metals from sewage sludge incineration fly ash 435
ALTAF HUSSIAN KANHAR, FEI WANG
15
422 Production of Mg- and Fe- containing compounds during the valorisation of diamond 436
mine slimes via thermochemical treatment
BARBARA CASTLEMAN, FREDERIC DOUCET, ELIZABET VAN DER MERWE
458 Recovery of iron from platinum group metal (PGM) tailings and synthesis of iron- 437
based nanomaterials
SAMEERA MOHAMED, FREDERIC DOUCET, ELIZABET VAN DER MERWE
OF4-3 - Gasification & syngas upgrading
88 Microwave Induced Plasma Gasification as a waste management strategy for 438
Kathmandu: a case study
RAUNAK SHRESTHA, PHILIP PANICKER
169 Municipal solid waste gasification technologies for electrical energy generation 449
ANA CAROLINA MEDINA, REYNALDO PALACIOS, SILVIA NEBRA
26 A study on syngas analysis of high iron content industrial sludge by fluidized 459
gasification process
YEN-TING KUO
276 Co-gasification of agricultural residues 461
MAMY HARIMISA RADANIELINA, AUGUSTINA EPHRAIM, DOAN PHAM MINH, ANGE
NZIHOU, JEAN PHILIPPE PRAENE, DOMINIQUE MORAU, MINOSON SENDRAHASINA
RAKOTOMALALA, HERY TIANA RAKOTONDRAMIARANA
OF4-4 - Ecosystems & urban mining
33 Evolution of environment performance of integrated municipal solid waste 462
management system in Hangzhou, China
ZHAOZHI ZHOU, YUANJUN TANG, YONG CHI, MINGJIANG NI
343 Understanding fat, oil and grease management in food service establishments to help 464
preventing sewers’ blockages
ANNA CERMAKOVA, PAUL JEFFREY, BRUCE JEFFERSON, RAFFAELLA VILLA
478 Evaluation of Cynara cardunculus flowers ecotypes (Alentejo, Portugal) for 465
cheesemaking
ANTÓNIO MARTINS, SANDRA GOMES, NUNO ALVARENGA, CRISTINA PINHEIRO,
FÁTIMA DUARTE
435 The impact of land use/land cover change on ecosystem services in the Three Gorges 466
Reservoir
JINGJING XIA, HAN XIA, HONG PENG, WANSHUN ZHANG
OF4-5 - Residual energy valorisation & emissions mitigation
35 Adsorption of heavy metals by microwave-assisted hydrothermal modified MSWI fly 467
ash
QILI QIU, XUGUANG JIANG, SHENGYONG LU, MINGJIANG NI, YONG CHI, JIANHUA YAN
81 Treatment of industrial wood dyeing effluents by adsorption on pinus pinaster bark 475
JORGE GONZÁLEZ-RODRÍGUEZ, LETICIA VÁZQUEZ-BENGOCHEA, ANTONIO MAGÁN,
M. SONIA FREIRE, JULIA GONZÁLEZ-ÁLVAREZ
131 Modeling of a small scale adiabatic compressed air energy storage (SS-A-CAES) 476
MYLÈNE MARIN GALLEGO, NATALIA MONTOYA AREVALO, MOHAND TAZEROUT
76 Valorisation of residual energy in comfort buildings: the relevance of solar inputs and 477
thermal inertia
ANDRÉS VILABOA DÍAZ, ALEXANDRA DEL CASTILLO LLAMOSA, PASTORA BELLO
BUGALLO
16
OF4-6 - Mobile Flip
246 Evaluation of nozzle system for late moisture and heat addition in pellet production 488
MAGNUS RUDOLFSSON, TORBJÖRN A LESTANDER, DAVID A. AGAR, SYLVIA H.
LARSSON
298 Comparing supply-chain relevant qualities of pellets made from non-treated and 489
torrefied lignocellulosic biomass
DAVID A. AGAR, MAGNUS RUDOLFSSON, THIERRY MELKIOR, MARC PEREZ, CAPUCINE
DUPONT, MATTHIEU CAMPARGUE, SYLVIA H. LARSSON
453 Wet oxidation as a treatment for effluent from mobile hydrothermal carbonization 490
(HTC) process
KRISTIAN MELIN, JONNA ALMQVIST, KIMMO RASA, HANNE WIKBERG
480 Use of torrefied wood in the production of particleboards 491
ELECTRA PAPADOPOULOU, CAPUCINE DUPONT
270 Blending biomass: dilution or chemical reaction in combustion process 492
FRANCOISE DEFOORT, MATTHIEU CAMPARGUE, GILLES RATEL, MURIEL MARCHAND,
CAPUCINE DUPONT
C6 - Anaerobic codigestion
109 Feasibility study of small anaerobic-co-digestion at urban district level 493
JEAN-ROMAIN BAUTISTA ANGELI, AUDREY VILLOT, ABDELKADER LAKEL, THOMAS LE
FLOC'H, YVES ANDRES
145 Evaluation of co-digestion of winery solid waste with cassava biomass for optimal 494
biogas production
UNATHI MKRUQULWA, VINCENT OKUDOH, OLUWASEUN OYEKOLA
496 Optimising biogas production through co-digestion of sewage sludge with food waste 495
and fog
OLUMIDE WESLEY AWE, LIU RANBI, YAQIAN ZHAO
351 Production of lactic acid in batch and fed-batch mode by Lactococcus lactis LCL using 497
date waste
FATMA ZOHRA RAS EL GHERAB, KASSEM ALSAYED MAHMOUD, OMAR HASSAINE,
HALIMA ZADI-KARAM, NOUR-EDDINE KARAM, SERGE HILIGSMANN
359 Production of lactic acid from waste potato industry 498
KASSEM ALSAYED MAHMOUD, MOUNA AOUN, EMNA MEJRI, FATMA ZOHRA RAS EL
GHERAB, SERGE HILIGSMANN
D6 - Waste-to-Energy global and regional perspective
40 Thermochemical energy recovery of municipal solid waste scenario in the state of São 499
Paulo, Brazil
FRANCISCO DALMO, NATHALIA SIMAO, HELENO QUEVEDO, ANA CAROLINA MEDINA,
SILVIA NEBRA, GILBERTO MARTINS, REYNALDO PALACIOS, PAULO SANTANA
87 The role of Waste-to-energy in the circular economy 509
CARLO VANDECASTEELE, JO VAN CANEGHEM, CHANTAL BLOCK
283 Poly-generation in biomass gasification in South-Tyrol: The NEXT Generation project 510
DANIELE BASSO, FRANCESCO PATUZZI, DANIELE ANTOLINI, SNEHESH AIL, ELEONORA
CORDIOLI, VITTORIA BENEDETTI, ANDREA MARIA RIZZO, DAVID CHIARAMONTI,
MARCO BARATIERI
532 Developing waste management systems that recover materials and energy in the 511
developing world
ATHANASIOS BOURTSALAS, NICKOLAS THEMELIS
17
202 Screening the potential of waste-to-energy plants using sewage sludge in Andalusia 512
(Spain)
PEDRO HARO, ALESSANDRO SINGLITICO, KARLA DUSSAN, RORY MONAGHAN,
ALBERTO GOMEZ-BAREA
F5 - Fertilizers & biobased
491 Micronutrient fertilizers and feed additives from alfalfa and goldenrod: towards the 513
implementation of circular economy
KATARZYNA CHOJNACKA, GRZEGORZ IZYDORCZYK
293 Optimization of wood gasification chain in South Tyrol to produce bio-energy and 514
other high-value green products to enhance soil fertility and mitigate climate change:
the wood-up project
DANIELE BASSO, FRANCESCO PATUZZI, TANJA MIMMO, GIUSTINO TONON, MARCO
BARATIERI
405 Utilization of waste versus commercial Mg sources to struvite-based fertilizer 515
production from source-separated human urine
JORGE SANTOS, TAMARA LLANO, EVA CIFRIAN, ANA ANDRES
385 Evaluation of in-vessel and pilot scale composting as an alternative for food waste 516
valorization
IOANNIS MICHALOPOULOS, GEORGE MARIOS LYTRAS, SOFIA MICHALAKIDI, SOFIA
ZGOURI, KONSTANTINA PAPADOPOULOU, GERASIMOS LYBERATOS
394 Effect of pH on the anaerobic fermentation of fruit/vegetables and disposable 517
nappies hydrolysate for bio-hydrogen production
KONSTANTINA TSIGKOU, PANAGIOTA TSAFRAKIDOU, SOPHIA ATHANASOPOULOU,
CONSTANTINA ZAFIRI, MICHAEL KORNAROS
A4 - Metal recovery using biological, chemical, hydrothermal leaching
403 Molybdenum extraction from spent catalyst using E. Coli: pre-treatment and 518
bioleaching studies
SUBHABRATA DAS, QING WEN WOON , YEN PENG TING
404 Optimization of gold biorecovery and biomineralization of gold bioleachate from 519
electronic waste
SUBHABRATA DAS, GAYATHRI NATARAJAN, YEN-PENG TING
378 Hydrothermal leaching of cathode material of lithium ion battery 520
DAIKI AZUMA, MASARU WATANABE, RICHARD SMITH
215 Selective hydrometallurgical recovery of Zn and Pb from jarosite residue 521
LIESBETH HORCKMANS, FRANTISEK KUKURUGYA, JEROEN SPOOREN, WILLEM
VEREYCKEN
279 Lithium recovery from simulated pyro-slag of lithium battery by chlorinated roasting 522
ZHIDONG CHANG, WENJUN LI, XINXUE LI
430 Sustainability assessment - case slow pyrolysis 523
HELENA WESSMAN-JÄÄSKELÄINEN, KRISTIAN MELIN, MATIAS ALAROTU
469 Economic feasibility and business plans for small-scale field operating biorefinery 524
units
EMILIA MARKSTRÖM, ANDERS BYSTEDT, FINN ENGLUND, HANS HOLMBERG, KRISTIAN
MELIN, GEERT HAARLEMMER
18
481 Torrefaction of agricultural and forestry feedstocks in a pilot scale facility: comparison 525
of mass and energy balances
MURIEL MARCHAND, THIERRY MELKIOR, MARC PEREZ, SEBASTIEN THIERY, PHILIPPE
PONSDEVINCENT, ANDRE CHATROUX
484 Development of the mobile demonstration unit for biomass torrefaction from pre- 526
industrial scale tests
MURIEL MARCHAND, MAITE HURON, PHILIPPE SAJET, OLIVIER LEPEZ, THIERRY
MELKIOR, MARC PEREZ, SÉBASTIEN THIERY, PHILIPPE PONSDEVINCENT, ANDRE
CHATROUX, MARIA GONZALEZ-MARTINEZ, CAPUCINE DUPONT, MURIEL MARCHAND
485 Evaluation and demonstration of slow pyrolysis technology in conversion of various 527
biomasses in mobile application
ANSSI KÄLLI
525 Strategic development of efficient Ni-based catalysts for biomass tar reforming 528
SIIBUDJING KAWI
315 Bioproducts from biowaste: a circular economy concept 529
ANIMESH DUTTA
177 Catalytic hydrodeoxygenation of biodiesel to green diesel 531
P.T. VASUDEVAN, YE DENG
490 Hormones of the holobiont: Microbe-to-plant signals as a way to increase biomass 532
production under climate change conditions
DONALD SMITH
Wednesday - July 4, 2018

PL3 - Plenary Lecture: Prof Savage, USA
292 Hydrothermal conversion of biomass to fuels and chemicals 533
PHILLIP SAVAGE, JAMES SHEEHAN, JIMENG JIANG, AKHILA GOLLAKOTA, DAVID
HIETALA
B2 - Extraction of added value materials from biomass
471 Fractionation of ethanolic ultrasound extracts from Cynara cardunculus by membrane 534
separation processes
TERESA BRAS, ANA PAULINO, LUISA NEVES, FÁTIMA DUARTE, JOÃO PAULO CRESPO
222 Factors affecting the sugars release in ozonolysis pretreatment of sugarcane bagasse 535
ELIZABETH LEÓN-BECERRIL, DARYL RAFAEL OSUNA-LAVEAGA
20 Grapefruit waste valorisation: toward a cost-effective and low-energy process chain 543
for high-added-value compounds recovery from peels
ÉMILIE GUÉ, CLAUDINE BELON, ADRIEN SERVENT, MORGANE CHAPRON, EMILIE RUIZ,
MICHÈLE DELALONDE, CHRISTELLE WISNIEWSKI
407 Effects of aeration on matrix temperature by infrared thermal imager and 545
computational fluid dynamics during sludge bio-drying
DAWEI YU, YUANSONG WEI, YAWEI WANG, MENGMENG LIU
19
F6 - Gasification
350 Assessment of the behaviour of a commercial gasification plant during load 550
modulation and feedstock moisture variation: preliminary results of the “Flexi-Fuel-
Gas-Control” project
DANIELE ANTOLINI, CLEMENS HOLLENSTEIN, STEFAN MARTINI, FRANCESCO PATUZZI,
CHRISTOPHER ZEMANN, WOLFGANG FELSBERGER, MARCO BARATIERI, MARKUS
GOELLES
205 Analytical characterization of olive oil solid residues for their potential use as a 560
gasification fuel
GAËLLE DUCOM, MATHIEU GAUTIER, MATTEO PIETRACCINI, RÉMY GOURDON
11 Power-to-Gas: dynamic modeling of a catalytic methanation reactor 566
AXEL FACHE, FRÉDÉRIC MARIAS, VINCENT GUERRE, STÉPHANE PALMADE
280 Valorization of char from biomass gasification as catalyst support in dry reforming of 567
methane: preliminary investigations
VITTORIA BENEDETTI , SNEHESH SHIVANANDA AIL, FRANCESCO PATUZZI, MARCO
BARATIERI
F7 - Biochar & thermal conversions
114 Using wheat straw-derived biochar for cracking and reforming of pyrolysis vapor 568
model compounds
CHRISTIAN DI STASI, BELEN GONZALEZ, JOAN MANYA
512 Aromatic enriched oil production from mixed plastics using different zinc-activated 569
biochar catalysts
KAI SUN, CHEN SUN, QUNXING HUANG, YONG CHI, JIANHUA YAN
309 Modeling the reaction kinetics of agro-waste during hydrothermal carbonization 570
MICHELA LUCIAN, GIOVANNI PIRO, MAURIZIO VOLPE, LUCA FIORI
523 From RDF to chemicals: an effective example of circular economy 571
ANNARITA SALLADINI
B3 - Toxicity remediation
157 Overview of drying of faecal sludge from on-site sanitation 573
SANTIAGO SEPTIEN STRINGEL, SAMUEL TENAW, DANICA NAIDOO, TOSIN ONABANJO,
ATHANASIOS KOLIOS, IAN MABBETT, CHRISTOPHER A. BUCKLEY
171 Bioremediation of bovine wastewater using a pretreatment and microalgae 574
CATARINA VIEGAS, MARGARIDA GONÇALVES, VASCO JORGE, BENILDE MENDES
402 A dynamic intensified process and mechanism of wastewater pretreatment for 580
internal micro-electrolysis
GANG QIN, YA PING YE, ZHAOCHANG ZHANG
OF4-7 - Biorefinery
129 Bioconversion of cellulosic materials into succinic acid using Yarrowia lipolytica PSA 581
02004
KHAI LUN ONG, CHUN YIN YAP, CHONG LI, XIAOTONG LI, CAROL SZE KI LIN
141 Municipal solid waste as a sustainable bioresource to produce culture media 582
JON KEPA IZAGUIRRE CAMPOVERDE, IRATXE URRETA, SONIA SUAREZ, SONIA
CASTANÓN
355 The effect of initial pH on the bacterial community during dark fermentation of 583
kitchen wastes
RADOSLAW SLEZAK, JUSTYNA GRZELAK, LILIANA KRZYSTEK, STANISLAW LEDAKOWICZ
20
128 Assessing the environmental profile of nuts shells valorisation into valuable products 584
BEATRIZ GULLÓN, PATRICIA GULLÓN, JALEL LABIDI, GUMERSINDO FEIJOO, MARIA
TERESA MOREIRA, SARA GONZALEZ-GARCIA
OF4-8 - Processes & emissions mitigation (I)
96 Bromine recovery from combustion gases of bromine-containing plastics 586
SEBASTIAN HIPPMANN, TIMM WOLFF, UTE _INGLIAR, MARTIN BERTAU
257 The environmental characteristics of using refused derived fuels in production of 587
ceramic materials: CO2 emissions and distribution of chlorine
RABABE SANI, DOAN PHAM MINH, THIERRY CUTARD, ANGE NZIHOU
188 Calcium phosphates as a new support material for catalysis in Fischer-Tropsch 588
synthesis
RAJESH MUNIRATHINAM, DOAN PHAM MINH, ANGE NZIHOU
510 Py-GC-MS study of tar formation characteristics from main MSW components 589
YIJING TANG, QUNXING HUANG, KAI SUN, YONG CHI, JIANHUA YAN
OF4-9 - Processes & emissions mitigation (II)
296 Statistical analysis of the significant parameters affecting nitrous oxide emission 590
during management of organic solid wastes
RIM AFFES, ROMAIN GIRAULT, ANNE TREMIER
333 NanoWet project: characterization of nanoparticle emission from high temperature 591
incineration of nano-/halogen-/sulfur-containing wastes and performances of wet-
scrubber units
AURÉLIE JOUBERT, RACHID BOUDHAN, CHRISTOPHE DUTOUQUET, DANIELLE
VENDITTI, SYLVAIN DURECU, EMMANUEL FIANI, OLIVIER LE BIHAN, LAURENCE LE COQ
69 Purification of biodiesel by the use of a stacked bed of sawdust and ion exchange 592
resin
MOHAMED EL AMINE KADI, KHALED LOUBAR, SARY AWAD, MOHAND TAZEROUT
438 Reuse of aluminum-based water treatment sludge as coagulant for animal farm 593
wastewater treatment
CHUN KANG, YAQIAN ZHAO, CHENG TANG
OF5-3 - Pretreatments & thermal process
220 Enhancing oil palm yield using Thermally Assisted Mechanical Dewatering (TAMD) 594
PATRICIA ARLABOSSE, SUZANA YUSUP, HASMIERA HASHIM
256 Obtaining and characterization of pellets based on walnut shells and waste paper and 595
paperboard
YAM PEREZ, AIXA GONZALEZ RUIZ, ALVARO-HIDALGO ROJAS
113 Solid-liquid phase equilibria and thermodynamic properties of mixtures of 20 alpha- 596
amino acids in a model system of industrial residues
NATHAN BOWDEN, JOHAN SANDERS, MARIEKE BRUINS
274 Feasibility of anaerobic digestion of tar-laden condensate from small scale biomass 597
gasification plants
DAVID CASINI, ANDREA MARIA RIZZO, GIULIA LOTTI, SILVIA PENNAZZI, DANIELE
BASSO, FRANCESCO PATUZZI, MARCO BARATIERI, DAVID CHIARAMONTI
B4 - Biological treatments & separation
59 Nitrogen removal and characteristics of anaerobic ammonia oxidation bacteria in 598
NUA–DAS ecofilters
LONG MIAN WANG, MENG YUE ZHOU
21
7 Improved dewatering of deinking sludge by enzymatic pretreatment 599
BODO SAAKE, RON JANZON, FRIEDRICH STEFFEN
79 A novel process “advanced thermal treatment + HSAD” to treat swine manure: 600
kinetics and microbial community analysis
YUYING HU, JING WU, ZHONGHUA LI, HUAIZHI LI, JIANE ZUO, KAIJUN WANG
488 Mass balance and performance of common digestate mechanical separation 601
equipment and fertilizing-value typology of liquid and solid fractions
FELIPE GUILAYN, JULIE JIMENEZ, MAXIME ROUEZ, MARION CREST, DOMINIQUE
PATUREAU
F8 - Thermal degradation
307 Breaking the chain: the role of degree of polymerisation on the thermal 602
decomposition of xylan
KARLA DUSSAN, JAMAL TOUITOU, RORY MONAGHAN, STEPHEN DOOLEY
48 Fuels from reliable bio-based refinery intermediates – BioMates 603
TIM SCHULZKE, STEFAN CONRAD, DAVID KUBICKA, STELLA BEZERGIANNI, ULRICH
PFISTERER, NILS RETTENMAIER, ROCIO DIAZ-CHAVEZ, MARTIJN MULDER, MICHAEL
MARTIN
161 Carbonaceous materials from lignocellulosic biomass under hydrothermal conditions 604
DOMINIK WUEST, DENNIS JUNG, MICHELA LUCIAN, ANDREA KRUSE, LUCA FIORI
150 Characterization of odorous gas emissions during composting active phase of eight 605
solid wastes and four digestates
CARLOS ANDRES RINCON MEJIA, AMAURY DE GUARDIA, ANNABELLE COUVERT,
SOPHIE LE ROUX, ISABELLE SOUTREL, MYLÉNE DAUMOIN
F9 - Catalysts
104 Catalytic degradation of polyethylene and polypropylene wastes over USY zeolite into 607
gasoline and diesel-like fuels
CHANTAL KASSARGY, SARY AWAD, KHALIL KAHINE, MOHAND TAZEROUT
259 Imogolite from cement kiln dust as catalyst in bio-oil upgrading 608
AIXA GONZALEZ RUIZ, ADAN MONTECINOS, MIGUEL-ANGEL PLACENCIA, NICOLAS
ARANCIBIA-MIRANDA
237 In-situ hydrotreatment of spent coffee grounds using a nickel molybdenum gamma 609
alumina catalyst
ROELF VENTER, SANETTE MARX
447 Effect of pore structures on catalytic fast pyrolysis of Sacha inchi residues using 610
microporous and mesoporous zeolites
DUANGDUEN ATONG, VIBOON SRICHAROENCHAIKUL, SUPAWAN VICHAPHUND
K2 - Biomass valorisation
111 Biorefinery concepts within the agri-food supply chain: a road to success 611
MARIEKE BRUINS
160 Profitability of food waste biorefinery concept in Europe 612
JORGE CRISTOBAL, CARLA CALDEIRA, SARA CORRADO, SERENELLA SALA
142 Valorisation of waste wood for energy 613
BIJAL GUDKA, JENNY JONES, ALAN WILLIAMS, AMANDA LEA-LANGTON, EDWARD
MITCHELL, JULIUS GANE, GEORGE STAMMERS, RICHARD KIRKMAN, FOWLER PAUL
22
384 Waste-to-biofuels: valorization of food residue biomass (FORBI) for hydrogen and 618
methane production
GEORGE MARIOS LYTRAS, IOANNIS MICHALOPOULOS, DIMITRIOS MATHIOUDAKIS,
THEODORA DIMITRIOU, IOANNIS ZACHAROPOULOS, CHRISTOS LYTRAS,
KONSTANTINA PAPADOPOULOU, GERASIMOS LYBERATOS
28 Valorisation of cellulose, hemicellulose, and lignin using supported metal catalysts 629
ARITOMO YAMAGUCHI, NAOKI MIMURA, MASAYUKI SHIRAI, OSAMU SATO
295 Hydrothermal liquefaction for valorising wet bio-waste – tunable kinetics enables 630
optimum bio-product mix
RAMESH BHUJADE, AJIT SAPRE
392 Solid anaerobic digestion: current trends and scientific hurdles 631
LAURA ANDRE, ANDRÉ PAUSS, THIERRY RIBEIRO
C7 - Bioethanol & composting
260 Conversion of aqueous ethanol and ABE mixtures to the bio-gasoline blending stock 632
with Zn(Cd)-Zr based catalysts
MIRON LANDAU, TOMMY T.HOS, BEN PORGADOR, ROXANA VIDRUK NEHEMYA, MOTI
HERSKOWITZ
282 Monitoring of carbon and nitrogen biodegradation and gas emissions during storage 633
and composting of digestates to develop models
ANNE TREMIER, RIM AFFES, ROMAIN GIRAULT
153 Exploitation of Tunisian date palm sap as a promising carbon source for bioethanol 634
production by a newly isolated yeast strain
IMEN BEN ATITALLAH, IOANNA NTAIKOU, GEORGIA ANTONOPOULOU, MARIA
ALEXANDROPOULOU, GERASIMOS LYBERATOS, MONCEF NASRI, TAHAR MECHICHI
68 Valorisation of edible oil wastewater sludge: Bioethanol & biodiesel production 644
WIGHENS ILUNGA NGOIE, PAMELA WELZ, OLUWASEUN OYEKOLA, DANIEL IKHU-
OMOREGBE
D7 - Co-products & contaminants evaluation
51 On the measurement of main inorganic contaminants (HCl, H2S and NH3) in waste- 645
derived syngas
VANESSA FERREIRA DE ALMEIDA, JAVIER ARROYO CAIRE, MONTSERRAT SUARÉZ
ALMEIDA, ISRAEL PARDO ARIAS, SUSANNA NILSSON, PEDRO HARO, ALBERTO GÓMEZ
BAREA
206 Pyro-gasification of biomass, biowastes and industrial co-products: a review on the 646
purification and utilization of syngas with demonstrations at industrial scale
DOAN PHAM MINH, ANGE NZIHOU
228 Toxic anions removal using layered double hydroxides synthesized from serpentine 647
ore tailings and steel slag
MARJORIE VALIX
99 Valorisation and effectiveness of using two waterworks residues for gas purification 648
BAIMING REN, YAQIAN ZHAO, NATHALIE LYCZKO, ANGE NZIHOU
23
I2 - Fly ash, biochar & carbon black
416 Steam-thermolysis of used tires: influence of the process operating conditions on the 649
recovered carbon black bulk and surface properties
LUDOVIC MOULIN, ELSA WEISS-HORTALA, YANNICK SOUDAIS, SERGE DA SILVA, RADU
BARNA
393 Production of fuel briquettes for improved cooking systems: thermo-physical 650
characterization, combustion, emissions and energy efficiency of biomass co-products
from Casamance regions
MAMADOU SEYDOU BA, JUN DONG, LAT-GRAND NDIAYE, ELSA WEISS, ISSAKHA
YOUM, ANGE NZIHOU
84 Mechanochemical treatment of fly ash 651
YAQI PENG, MINGHUI TANG, SHENGYONG LU
95 PCB reduction/reformation in milled model fly ash 652
ISHRAT MUBEEN, ALFONS BUEKENS, SHENGYONG LU, JIANHUA YAN
J4 - Bioeconomy & biorefinery
158 Unveiling the contribution of bioeconomy to circular economy through Life Cycle 653
Thinking
SARA CORRADO, CARLA CALDEIRA, SERENELLA SALA
236 Combining process simulation and life cycle assessment for the eco-design of 654
biorefinery processes
RÉMI JULIO, CAROLINE SABLAYROLLES, CLAIRE VIALLE, JOEL ALBET
133 Embedding the production of HMF into the biorefinery route 655
MARIA TERESA MOREIRA
336 Sustainability analysis of biorefineries for high value bioproducts and biofuels 656
production
GABRIELA MAGANA, LORENA AMAYA, ARTURO SANCHEZ
Thursday - July 5, 2018

PL4 - Plenary Lecture: Prof Tao, China
195 Health and climate co-benefits of the rural residential energy transition in China 657
SHU TAO, MU YE RU, WEI DU, XI ZHU, QI RUI ZHONG, BEN GANG LI, GUOFENG SHEN
J5 - Valorisation of organic waste
50 Minimization of the resource consumption and carbon footprint of a circular organic 658
waste valorization system
SELENE COBO, ANTONIO DOMINIGUEZ-RAMOS, ANGEL IRABIEN
12 Homogenous hydrothermal synthesis of calcium phosphate with calcium carbonate 659
and corbicula shells
HIROAKI ONODA, SHIN YAMAZAKI
241 Hydrothermal oxidation of fermentation sludge for use in a bioregenerative life 660
support system
DONGDONG ZHANG, FREDERIK RONSSE, AMANDA LUTHER, PETER CLAUWAERT,
DIEGO LÓPEZ BARREIRO , WOLTER PRINS, WIM BRILMAN
395 Potential of wood waste in Portugal – a bio-based ecosystem model 662
JORGE COSTA, ANA LUISA FERNANDO
211 Optimisation of a dissolving pulp bleaching sequence towards its valorisation 669
CARLOS ARCE, TAMARA LLANO, GEMA RUIZ, NAVEEN CHENNA, ALBERTO COZ
24
D8 - Catalytic & additive performances
17 Catalytic hydrodeoxygenation of napier grass pyrolytic oil via in-situ hydrogen 670
generation
ISAH MOHAMMED, YOUSIF ABAKR, FEROZ KAZI, ROBERT MOKAYA
311 Thermo-catalytical optimization of forestry waste pyrolysis vapours 680
JON SOLAR IRAZABAL, BLANCA CABALLERO IGLESIAS, ISABEL DE MARCO, JAVIER
ALONSO, ALEXANDER LOPEZ-URIONABARRENEC, NAIA GAZTELU
412 Effects of CaO additive on municipal solid waste pyrolysis 681
YUANJUN TANG, YONG CHI, JUN DONG, ANGE NZIHOU, ELSA WEISS-HORTALA,
MINGJIANG NI
230 Effect of potassium on the thermal degradation of biomass evaluated using 682
thermogravimetric analysis
MICHAL SAFAR, DAVID LANGAUER, HELENA RACLAVSKA, MATHIEU PÉTRISSANS, WEI-
HSIN CHEN, ANÉLIE PÉTRISSANS, BO-JHIH LIN
196 Synthesis and characterization of ZrO2-Bi2O3 catalysts for conversion of N. oculata 683
microalgae lipid to biodiesel
NURUL JANNAH ABD RAHMAN, ANITA RAMLI, KHAIRULAZHAR JUMBRI, YOSHIMITSU
UEMURA
D9 - Treatment & conversion of diverse residues
22 The ELIPSE process: an underwater plasma technology for hazardous organic liquid 684
treatment
FLORENT LEMONT, MICKAEL MARCHAND, RODOLPHE MAGNIN, MAJDI MABROUK
38 Techno-economic assessment for implementing gasification technologies to process 685
MSW refuse in Spain
MONTSERRAT SUÁREZ ALMEIDA, VANESSA FERREIRA DE ALMEIDA, JAVIER ARROYO
CAIRE, PEDRO GARCÍA HARO, ALBERTO GÓMEZ BAREA
64 Thermo-catalytic reforming of digestate 686
MARKUS HEBERLEIN, FABIAN STENZEL, ANDREAS HORNUNG
252 Combined production of hydrogen and electricity from hospital solid waste: 687
technology
JOSE RAMOS, ALBERTO INGA, SEBASTIEN QUESNEL, EMILIO GONZALES, YLEN
CARHUARICRA, WILMAR HUACCACHI
361 Preparation and air gasification of bio thermo stabilized municipal solid waste 688
VIRGINIA PÉREZ, RAQUEL RAMOS, RAQUEL BADOS, LUIS ESTEBAN, RUTH BARRO,
ISABEL ORTIZ, YARIMA TORREIRO, JOSE MARÍA SÁNCHEZ
A5 - Construction materials from waste
249 Sulfoaluminous concrete: an advanced way of wastes reduction and reuse 689
JIHENE NOUAIRI, WALID HAJJAJI, JOAO LABRINCHA, FERNANDO ROCHA, MOUNIR
MEDHIOUB
424 Inorganic polymers for out of the box applications using biomass fly ash waste 690
RUI NOVAIS, PAULA SEABRA, JOÃO LABRINCHA
400 Development of a binder matrix based on ground granulated blast-furnace slag and 691
fly ash as a replacement of cement in mortars
SAHAR SEIFI, DANIEL LEVACHER, MOHAMED BOUTOUIL, NASSIM SEBAIBI
369 Obtention of aluminum zinc alloys from recycled alkaline batteries: effect of fluxing 692
additives on melt treatment
PEDRO DELVASTO, JHON CABALLERO-JAIMES
25
526 Assessment of materials and recycling in ancient times: models of human behaviour 693
AGNE CIVILYTE
A6 - Anaerobic digestion & biorefinery
165 Variation of food waste characteristics during aerobic storage: consequences for solid- 694
state anaerobic digestion process
AXELLE DEGUEURCE, PASCAL PEU, ANNE TREMIER
428 Biochar assisted thermophilic co-digestion of food waste and waste activated sludge 696
under high organic loading
QIAN LI, LUXIN ZHANG
323 Development and characterization of adsorbents for new anaerobic digestion bio- 698
refinery concepts
MANUEL GARCIA-PEREZ
E6 - Biowaste to valuable chemicals
253 Hydrolyzed organic residues as sources of secondary raw materials 699
DANIEL PLEISSNER, JAN PEINEMANN
334 Valorisation of molasses for the production of biolubricants via fermentation using 700
oleaginous yeasts
AIKATERINI PAPADAKI, EFTHYMIA BOVIATSI, MARIA KYRIAKOU, GEORGIOS-IOANNIS
NYCHAS, JOSÉ ANDRÉ DA SILVA, DENISE FREIRE, APOSTOLIS KOUTINAS
337 Valorisation of municipal solid waste for succinic acid production by Basfia 701
succiniciproducens
ELENI STYLIANOU, CHRYSANTHI PATERAKI, DIMITRIOS LADAKIS, ANESTIS VLYSIDIS,
APOSTOLIS KOUTINAS
H3 - Biofuels energy storage
60 Methanol synthesis through CO2 hydrogenation over Cu/ZnO/Al2O3 catalysts under 702
fluctuating conditions
MICHAEL KRAFT, ALEXANDER ZURBEL, QUIRINA ROODE-GUTZMER, MARTIN BERTAU
415 Characterization of bio-oil produced by HTL of binary mixture of phenylalanine and 703
glucose
AISHA MATAYEVA, FRANCESCO BASILE, FABRIZIO CAVANI, DANIELE BIANCHI,
STEFANO CHIABERGE
425 3DOM ceria ecoceramics from sustainable cork templates for solar thermochemical 704
CO2 splitting
ROBERT PULLAR, RUI NOVAIS, ANA CAETANO, FERNANDO OLIVEIRA, ALEXANDRA
BARREIROS, STEPHANE ABANADES
I3 - Gas emission & remediation from incineration and combustion
54 Impact of municipal solid waste incinerators on heavy metals in the surrounding soils 705
by multivariate analysis and Pb isotope analysis
HUA ZHANG, YANG LI, LIMING SHAO, PINJING HE
444 Mercury emissions control in hazardous waste incineration plants 706
XAVIER CHAUCHERIE, MICHAEL BACQUET, THIERRY GOSSET, BERNHARD VOSTEEN
499 Reducing chlorine content in pyrolysis gas from RDF 707
MAÏTÉ HURON, PHILIPPE SAJET, OLIVIER LEPEZ
388 Characterization of nanomaterials from bio-wastes 708
SABU THOMAS, NANDAKUMAR KALARIKKAL
26
513 Systematic and integrated approach in hazardous medical waste treatment 709
VÍTEZSLAV MÁ_A, MICHAL TOU_, EVA KONECNÁ, PETR STEHLÍK
Posters
The influence of plant cultivation methods on biogas production: energy efficiency
LILIANA KRZYSTEK , KAROL WAJSZCZUK, ANNA PAZERA, MARIUSZ MATYKA,
13 STANISLAW LEDAKOWICZ, RADOSLAW SLEZAK 710
Use of natural bentonite clay for fluoride removal from synthetic aqueous solution
16 JIHANE ASSAOUI, ABDELMOULA KHERIBECH 721
Experimental studies on solidification of heavy metals in municipal sewage sludge by
alkaline thermal hydrolysis
18 JUNYING ZHANG, YING ZHOU, YONGCHUN ZHAO 722
Utilization of sandy tailings from iron ore beneficiation in cement mortars
23 ANTONIO PERES, MARIA AGUIAR, KELLY FERREIRA 723
Novel inorganic polymer spheres for methylene blue extraction from wastewaters
RUI NOVAIS, JOÃO CARVALHEIRAS, DAVID TOBALDI, PAULA SEABRA, JOÃO
25 LABRINCHA 728
Analysis of the state of combustion in SRF co-firing in 2MW CFB
27 JUSOO HYUN, YUNTAE HWANG, JEONGMIN KIM 729
Study on purification efficiency of tail water in baffled vertical-flow constructed
wetlands using broken bricks as substrate
30 XINBAO SHANG, GUOZHEN ZHANG, FUPING WU, HONGWEI ZHANG 735
Comparison of filtration performance with rounded filter bags and pleated filter bags
in pilot scale test unit using simulated flue gas of waste incinerator for application of
waste to energy industries
KWANG-DEUK KIM, KANG-SAN LEE, SEONG-MIN JEON, NAIM HASOLLI, JAE-RANG LEE,
32 YOUNG-OK PARK 737
Bimetallic gold-copper catalysts for glycerol conversion to lactic acid
42 DIANA HERNANDEZ, DIANA PATRICIA LOPEZ, RUBEN PALACIO 738
RECOMBINANT EXPRESSION OF A XYLANASE VI (GH30) FROM TRICHODERMA REESEI
WITH POTENTIAL APPLICATION IN THE XYLAN EXTRACTION FROM SUGARCANE
BAGASSE
43 BARBARA FERREIRA, ADRIANE MILAGRES 739
HCl removal characteristics of calcium hydroxide at the real scale dry-type sorbent
reaction accelerator in the municipal waste incineration plant
YOUNG OK PARK, KWANG-DEUK KIM, SEONG-MIN JEON, NAIM HASOLLI, KANG-SAN
45 LEE, JAE-RANG LEE, JIN-DO CHUNG 740
Heavy metals partitioning during thermal devolatilization of solid wastes in a fluidized
bed reactor
VANESSA FERREIRA DE ALMEIDA, ALICIA RONDA GALVEZ, JAVIER ARROYO CAIRE,
MONTSERRAT SUARÉZ ALMEIDA, ISRAEL PARDO ARIAS, DIEGO FUENTES, PEDRO
52 HARO, ALBERTO GÓMEZ BAREA 741
Material, energy and exergy flow analysis to reduce the energy consumption in an
optimized ceramic plant
TIMOTHÉ GRONIER, MARÍA DEL CARMEN TABOADA GÓMEZ, PASTORA BELLO
71 BUGALLO 742
27
Assessment of the physico-chemical properties of residues and emissions generated
by biomasses combustion under N2/O2 and CO2/O2 atmospheres in a Drop Tube
Furnace (DTF)
73 GLAUBER CRUZ, PAULA MANOEL CRNKOVIC 755
Towards sustainable re-construction systems: from ruins to eco-efficient buildings
75 ALEXANDRA DEL CASTILLO LLAMOSA, PASTORA BELLO BUGALLO 773
Onsite sorting and pyrolysis of coffee residues for biochar production – a case study
STERGIOS VAKALIS, VITTORIA BENEDETTI, ELEONORA CORDIOLI, FRANCESCO
77 PATUZZI, MARCO BARATIERI 783
Energetic potential of pulp and paper industry solid wastes for thermochemical
conversion processes
BRENER FELIPE MELO LIMA GOMES, CINTIA MARIA DE MEDEIROS, POLLYANA
78 CAETANO RIBEIRO FERNANDES, SILVIA LAYARA FLORIANI ANDERSEN 784
Study on the release law and influencing factors of phosphorus in excess sludge under
thermal hydrolysis
83 XU ZHIQIANG , LI YAO, YAO CHENZHEN 793
Lignocellulosic by-products from Brazilian sugarcane agroindustry for biotechnological

production of xylitol: study of oxygen supply and supplementation with sucrose
ANDRÉS HERNÁNDEZ-PEREZ, FERNANDA SIMÕES MOSIMANN, MARIA DAS GRAÇAS
91 DE ALMEIDA FELIPE 803
Nanofiber preparation for adsorption of low level CO2 through electrospinning
DONG WON JEONG, JONG MIN OH, SANG BUM KIM, YOUNG GOO PARK, ADEDEJI
103 ADELODUN, YOUNG MIN JO 804
Process gas purification by centrifugal cooling device
SANG BUM KIM, JU HOE KIM, JONG MIN OH, YOUNG GOO PARK, ANDY KIM, YOUNG
105 MIN JO 805
Ethanol production from high solids loading of rice straw by simultaneous
saccharification and fermentation using a non-conventional reactor
107 RAFAEL CASTRO, SOLANGE MUSSATTO, INES ROBERTO 806
The use of cassava harvest residues (manihot esculenta crantz) in thermal conversion
processes for bioenergy purposes: a literature review
ALYSON DA LUZ PEREIRA RODRIGUES, MARIA MARIA, GLAUBER GLAUBER CRUZ,
115 WOLIA WOLIA GOMES 807
Energy valorisation of grasses by dry process
119 JEAN-FRANCOIS LARGEAU, MOHAND TAZEROUT 823
Assessment of thermal properties of dried fish waste
121 BUSISIWE GCOBO, DANIEL IKHU-OMEREGBE 824
Evaluation of antioxidant action of peels of Annona Muricata L. to application on
biodiesel
PALOMA DETLINGER, GULHERME A.R.MAIA, LARISSA A.C.MATOS, MAURICIO
123 A.MOLINARES, PAULO R.P.RODRIGUES, EVERSON P.BANCZEK 833
Assessment of alkaline pretreatment for lignin extraction from peanut shells
BEATRIZ GULLON, GEMMA EIBES, JALEL LABIDI, MARIA TERESA MOREIRA, GONZALEZ-
139 GARCIA SARA, PATRICIA GULLON 834
Characterization of biomass by means of elutriation and sedimentation
154 DEYBER ALEXANDER RAMIREZ-QUINTERO, WALDIR ANTONIO BIZZO 835
28
Holistic approach for the management of domestic waste waters via constructed
wetlands and exploitation of biomass and effluents for nutrients, water and energy
recovery
IOANNA NTAIKOU, GEORGIA ANTONOPOULOU, STEFANOS DAILIANIS, VASILIS
DRAKOPOULOS, FATOS HARIZAJ, PERPARIM LAZE, JULIAN SHEHU, IOANNIS VYRIDES,
163 GERASIMOS LYBERATOS 845
Transformation mechanism of nitrogen in a biochar ‘preparation-application’ system
192 ZHONGXIN TAN 846
Effect of CaO loading on transesterification of Jatropha oil to biodiesel in the presence
of SAPO-34 supported catalysts
197 BASHIR ABUBAKAR ABDULKADIR, ANITA RAMLI, JUN WEI LIM, YOSHIMITSU UEMURA 847
Strategy for the design of waste to energy processes based on physicochemical
characterisation
ISABEL ORTIZ, JOSÉ MARÍA SANCHÉZ-HERVÁS, YARIMA TORREIRO, MARTA MAROÑO,
198 VIRGINIA PÉREZ, RAQUEL RAMOS, MIGUEL FERNANDEZ, RUTH PIÑEIRO 848
A new and accurate method to measure surface temperature and size of solid
particles during fuel conversion in fluidized beds
JESUS SALINERO, DIEGO FUENTES, ANA BERDUGO, PEDRO HARO, ALBERTO GOMEZ-
201 BAREA 849
Food waste: analysis and proposal of a quantification methodology
204 MARIA BAQUERO, ANA ANDRES, EVA CIFRIAN 850
A comparison of alum sludge with Irish peat for aqueous glyphosate removal with
special focus to maximize their value in practical use
207 YAE WANG 851
Impact of tropical lignocellulosic biomass composition in steam gasification char
properties
216 LINA MARIA ROMERO MILLAN, FABIO EMIRO SIERRA VARGAS, ANGE NZIHOU 853
Assessment of the energy production potential from phytoremediation derived
biomass
221 ANA MARQUES, PAULA CASTRO, NÍDIA CAETANO 854
Graphene sponges for oil removal
224 GEORGE KYZAS, ATHANASIOS MITROPOULOS 855
Waste agricultural sugar cane biomass for the recovery of Gold (I) thiourea complexes
227 MARJORIE VALIX 857
An experimental study on emulsification of liquefaction bio-oil, diesel and alcohols
231 DAVID LÄNGAUER, MICHAL SAFAR 858
Steam-thermolysis of thermoplastic and thermal resistant carbon fiber composites.
Formulation of new composites with recovered carbon fibers
235 PAULINE FONTAINE, ELSA WEISS, YANNICK SOUDAIS, RADU BARNA 859
Modeling and design of an industrial reactor for tar thermal cracking and syngas
upgrading
238 FREDERIC MARIAS, JEAN PAUL ROBERT-ARNOUIL 860
Hydrothermal carbonisation of poultry litter: effects of initial pH on yields and
chemical properties of hydrochar
239 BASHIR GHANIM 861
29
Combined production of hydrogen and electricity from hospital solid waste:
application
JOSE RAMOS, ALBERTO INGA, SEBASTIEN QUESNEL, EMILIO GONZALES, MIGUEL
251 RIVERA 862
Sustainability of the valorisation of discarded cartilaginous biomass
XELA GARCÍA-SANTIAGO, AMAYA FRANCO-URÍA, LUIS ANTELO, JOSÉ A. VÁZQUEZ,
255 GUMERSINDO FEIJOO 863
Treatment of osmium wastewater for recovery of osmium tetroxide
268 TEPPEI NUNOURA, HARUNA HIRAI, RETSU MIYOSHI, OSAMU SAWAI 864
Process scale-up for a complete valorization of winemaking waste using supercritical
CO2
273 KURABACHEW DUBA, LUCA FIORI 865
Thermal degradation and tar removal tests with char from commercial gasification
systems
277 ELEONORA CORDIOLI, FRANCESCO PATUZZI, MARCO BARATIERI 866
Load modulation capability of an open top gasifier by varying the second stage air
flow rate
DANIELE ANTOLINI, SNEHESH SHIVANANDA AIL, CARLO CALIGIURI, FRANCESCO
284 PATUZZI, MASSIMILIANO RENZI, MARCO BARATIERI 867
Experiments and molecular dynamics simulations on the interaction of
trioctylaminesulfuric acidwater system
297 ZHIDONG CHANG 868
Influence of thermal treatment on the mineralogy and the leaching behaviour of
heavy metals in Bottom Ash
OLA HAMMOUD, MARIA LUPSEA-TOADER, DENISE BLANC, CHRISTINE DE BRAUER,
310 FAOUZI EL HASSOUNI 869
Waste transportation cost in advanced network flow models
317 JIRI GREGOR, FRANTISEK JANOSTAK, MARTIN PAVLAS, RADOVAN SOMPLAK 870
Research on the extraction behavior of oil sands and ground crude oils by aqueous
two-phase extraction
320 ZHIDONG CHANG 871
Characterization of solid products from thermochemical conversion of municipal and
textile wastes
325 MANUEL GARCIA-PEREZ 872
Hydration of lignocellulosic biomass. Non-linear modeling with modified Langmuir
isotherms
348 ARTURO SANCHEZ, PABLOS HERNANDEZ-SANCHEZ, RAMON PUENTE 873
Characterization and degradation of agricultural residues of Sinaloa Mexico for
bioethanol production
LAURA IVONNE BELTRAN ARREDONDO, IGNACIO CONTRERAS ANDRADE, MARIA
363 GUADALUPE AGUILAR USCANGA, CLAUDIA CASTRO MARTÍNEZ 874
Geographic information system as an auxiliary tool of data collection for the life cycle
inventory phase
MAGALI RIGON, CARLOS ALBERTO MENDES MORAES, MAURICIO MANCIO, REGINA
374 CÉLIA ESPINOSA MODOLO 880
Cellulase production using agricultural residues of Sinaloa, Mexico
CLAUDIA CASTRO-MARTINEZ, LELIE CASTRO-OCHOA, SANDY HERNÁNDEZ-LEYVA,
377 LAURA BELTRÁN-ARREDONDO, MARIA GUADALUPE AGUILAR-USCANGA 887
30
Preparation of soluble peptide from defatted soybean in the presence of base
additives in hydrothermal condition and evaluation of its function
379 MASARU WATANABE, MASAYOSHI WAGATSUMA, RICHARD SMITH 895
Effect of temperature, time and ZnCl2 addition on formation of oxygenated functional
groups on the surface of flexible carbon of Pseudotsuga menziesii prepared by
hydrothermal carbonization
380 TAIGA WATANABE, MASARU WATANABE, RICHARD SMITH 896
Experimental determination of self-heating and self-ignition risks of industrial
hazardous wastes
KALLIOPI PAPANIKOLA, KONSTANTINA PAPADOPOULOU, VASILIKI RONTOGIANNI,
386 APOSTOLOS KORKOLIS, GERASIMOS LYBERATOS 897
Production of an adsorbent from food residue biomass (FORBI): evaluation of its
physical, chemical and adsorption properties
KONSTANTINA PAPADOPOULOU, XARALAMPOS PAVLOPOULOS, PANTELITSA
387 GEORGIOU, ANTONIOS PEPPAS, LOUKAS ZOUMPOULAKIS, GERASIMOS LYBERATOS 898
Extraction of contaminants from HDPE wastes: is a rinse sufficient?
401 ESTÉBAN HÉLIAS, FRANCISCO JAVIER ESCUDERO-SANZ, DIDIER GROUSET 899
Review on biomethanation of syngas to biogas
411 WENNAN ZHANG 907
In-rubber performance of the recovered carbon black reinforcing filler obtained from
the steam-thermolysis of used tires
LUDOVIC MOULIN, ELSA WEISS-HORTALA, YANNICK SOUDAIS, SERGE DA SILVA, RADU
417 BARNA 908
Activated pyrolysed cork residues for methylene blue removal from wastewaters
427 RUI NOVAIS, ANA CAETANO, ROBERT PULLAR 909
Methane decomposition to hydrogen and carbon black using solar energy
429 HAKJOO KIM 910
The role of secondary tar reactions on the product yields and gas composition during
solar-driven fast pyrolysis of biomass pellets
436 JOSE SORIA, RUI LI, DANIEL GAUTHIER, GILLES FLAMANT, GERMAN MAZZA 911
A textile-based biorefining strategy for polyester recycling from blended fabrics via
biological method
XIAOTONG LI, KAI-JEN HSIAO, ZHI-FENG JUE, YUNZI HU, CAROL SZE KI LIN, CHENYU
440 DU, SHAO-YUAN LEU, HOUDE JING, SHI-KUANG HWANG 920
Activity of fly ash-derived ZSM-5 and zeolite X on fast pyrolysis of Millettia (pongamia)
pinnata waste
446 DUANGDUEN ATONG, VIBOON SRICHAROENCHAIKUL, KANIT SOONGPRASIT 921
ZrO2-supported transition metals in supercritical water conversion of pulping waste
for fuel gas generation
450 VIBOON SRICHAROENCHAIKUL, YOTWADEE HAWANGCHU 922
High efficient superparamagnetic solid extraction for heavy metal ions removal
452 LIANGRONG YANG, JIEMIAO YU, HUIFANG XING, HUIZHOU LIU 923
Numerical study of heat and moisture properties of wall based on waste date palm
fibers concrete
TAREK ALIOUA, BOUDJEMAA AGOUDJIL, NAWAL CHENNOUF, ABDERRAHIM
461 BOUDENNE, KARIM BENZARTI 924
31
Influence of promoter MgO on Ni/Al2O3 catalysts for the steam reforming of volatiles
derived from biomass pyrolysis
LAURA SANTAMARIA, GARTZEN LOPEZ, MAIDER AMUTIO, JON ALVAREZ, MARIA
463 CORTAZAR, ENARA FERNANDEZ, MARTIN OLAZAR 925
Pyrolysis-catalytic steam reforming of plastics and mixed plastic in a two stage
reaction system
ITSASO BARBARIAS, GARTZEN LOPEZ, MAIDER AMUTIO, MAITE ARTETXE, JON
464 ALVAREZ, AITOR ARREGI, ENARA FERNANDEZ, MARTIN OLAZAR 926
Catalytic steam reforming of plastic pyrolysis model compounds
ITSASO BARBARIAS, GARTZEN LOPEZ, MAITE ARTETXE, AITOR ARREGI, LAURA
465 SANTAMARIA, MARIA CORTAZAR, MARTIN OLAZAR 927
Investigation on the evolution of polycyclic aromatic hydrocarbon (PAHs) in bio-oil
during wastewater sewage sludge catalytic pyrolysis
468 WENJING YU, YANJUN HU 928
Cynara cardunculus experimental field installation a source of natural variability
477 ANA PAULINO, TERESA BRAS, LILIANA MARUM, ANABELA BELO, FÁTIMA DUARTE 929
Use of agro wastes and forestry materials in the production of particleboards
479 ELECTRA PAPADOPOULOU, SYLVIA LARSSON 930
Life cycle assessment of waste biomass treatment in mobile context
483 MATIAS ALAROTU, HANNE WIKBERG, VESA ARPIAINEN 931
Composition of municipal solid waste in Athens - Greece
492 DEMETRIS FRANCIS LEKKAS, TASOS ARVANITIS, YANNIS RAZIS 932
Evaluation of the effectiveness of the IPPC legal framework by life cycle thinking
tools: the case of slaughterhouses in Galicia
FRANCISCA GONZÁLEZ DURÁN, ADRIANA GARCÍA RELLÁN, EDELINA ROSA TÓRRES
507 LÓPEZ, PASTORA BELLO BUGALLO 934
Straw xanthate as a heavy metal sorbent in biogas slurry - synthesis, characterization
and application
519 JUNHAO CHEN, YING SUN 944
Assessing the potential of digestate from biowaste for cellulase and xylanase
production
LAURA MEJIAS TORRENT, ALEJANDRA CERDA, RAQUEL BARRENA, TERESA GEA,
528 ANTONI SÁNCHEZ 945
Screening of support materials for the production of sophorolipids through solid state
fermentation
529 ALEJANDRA RODRIGUEZ GUTIERREZ, TERESA GEA LEIVA, XAVIER FONT SEGURA 946
Biomass hydrolysis by a carbon-based solid catalyst
531 WEI-CHUN HUNG, CHIUNG-FANG LIU, HOU-PENG WAN 947
Conversion of shrub biowaste through torrefaction mobile units for reducing fire risk
in the southern Europe
MARIA GONZALEZ MARTINEZ, CAPUCINE DUPONT, LUIS MIGUEZ RODRIGUEZ,
SÉBASTIEN THIERY, MAGUELONE GRATEAU, DENILSON DA SILVA PEREZ, XUAN-MI
534 MEYER, CHRISTOPHE GOURDON 948
Modelling of bioelectrochemical reactors to design scaled-up systems
REMY LACROIX, EMMA ROUBAUD, ALAIN BERGEL, REGINE BASSEGUY, BENJAMIN
535 ERABLE, SERGE DA SILVA 949
32
Proceedings - WasteEng2018 Conference - Prague - July 2-5, 2018
Regeneration performances of activated coke and carbon consumption in different

regeneration atmospheres
536 MENG YE, YURAN LI, FENG QI, SONG DING, TINGYU ZHU, GUANYI CHEN 950
Eco Sustainable Rail: production of sustainable railway sleepers from mixed plastics
waste
BRUNO SILVA, JOÃO PEDRO NUNES, MARIA CONCEIÇÃO PAIVA, JORDANA
GONÇALVES, ANDREIA VILELA, ÂNGELO MARQUES, SANDRA CASTRO, RUI
537 RODRIGUES, JOÃO AMARO, SOFIA SANTOS, PEDRO GAIATO 962
33
CIRCULAR ECONOMY: A COLLABORATIVE APPROACH TO WASTE MANAGEMENT
A. MILUKAS1
1 European Commission, EASME, Brussels, Belgium.
Abstract
Circular Economy is one of the priorities of the European Commission Work Programme. The 2015
Circular Economy Package launched a series of actions that are addressing the different the phases
needed to close the loop in a circular economy, from production to consumption, repair and
manufacturing, waste management and secondary raw materials that are fed back into the
economy. In order to effectively address all these phases, and improve waste management,
collaboration among key stakeholders should be considered, including engaging with citizens.
Innovation is a cross-cutting element that is essential to boost the transition from a linear to a
circular economy. A systemic approach built on LCA should be adopted to support decision making
that is environmentally, economically and socially sound. EU funding programmes, e.g. Horizon 2020
and Life, are supporting projects in the field of Circular Economy in order to demonstrate on the
ground the feasibility of new technologies, services and business models.
34
CO-GASIFICATION AS A POSSIBLE ALTERNATIVE FOR AN EFFICIENT

WASTE-TO-ENERGY CONVERSION
U. ARENA1
1 Department of Environmental, Biological and Pharmaceutical Sciences and Technologies, University
of Campania “Luigi Vanvitelli”, Caserta, Italy.
Abstract
The contribution aims at defining the status of thermochemical co-conversion processes of waste
and biomass, with a particular focus on the co-gasification in medium or large-scale facilities.
It is known that the several potential benefits of gasification mainly relate to the possibility of
combining the process operating conditions with the features of the specific reactor (such as the
ways of contact between fuel and gasifying agent, operating temperature, residence times of gas and
solids) in order to obtain a syngas suitable for different applications. Co-gasification of mixtures of
different fuels can be an interesting alternative to enhance the quality and yield of products and to
prevent or attenuate operating and environmental problems of the individual gasification of different
types of waste and biomass. In particular, the utilization of biomass by co-gasification with wastes
implies reductions in fossil carbon dioxide, chlorine and sulphur emissions due to the renewable
character of biomass and its low contamination content. Moreover, the relatively low specific energy
content of biomass makes its use economically effective only if transportation costs are low. If not
enough biomass is available in the areas surrounding the plant, co-gasification of a mixture of high-
heating value waste and biomass could provide an opportunity to build larger plants, so making
advantageous the idea of gasifying mixtures. Co-gasification gives also the chance of co-converting
different types of wastes, offering the possibility to treat materials with increasing difficulties to find
adequate sites for their disposal (such as reclamation waste or sewage sludge) and at the same time
to obtain resource recovery and minimization of the amount of end-waste to be sent to final disposal
[1, 2].
A well designed and performed co-gasification takes advantage of the possible synergy between the
intermediates and final products to maximize the process performance, by reducing carbon losses in
particulate and tar fractions, and increasing the energy content of syngas. A review of the possible
mechanisms that promote these synergic effects will be also proposed.
Among the possible gasification technologies (fixed bed, fluidized bed, entrained bed, vertical shaft,
moving grate, rotary kiln, plasma), the fluidized bed reactors appear to have some special advantages
for co-gasification of waste and biomass. The rapid and good mixing of solids leads to almost uniform
isothermal conditions throughout the reactor, so allowing a reliable process control and a great fuel
flexibility, which provide a reliable co-feeding, permit a broader particle size range and achieve higher
process efficiencies [3]. Therefore, a special attention will be given to experiences of co-gasification
carried out in different types of fluidized bed reactors [4, 5].
References
[1] Arena, U.: Process and technological aspects of municipal solid waste gasification. A review, Waste Management,
32: pp. 625-639 (2012)
[2] Ramos, A., Monteiro, E., Silva, V., Rouboa, A.: Co-gasification and recent developments on waste-to-energy
conversion: A review, Renew Sust Ener Rev. 81: pp. 380-398 (2018)
35
[3] Arena, U.: Fluidized bed gasification, chap. 17 in Fluidized-bed technologies for near-zero emission combustion and
gasification, F. Scala (Ed.). Woodhead Publishing, p. 765-812. ISBN 978-0-85709-541-1, DOI:
10.1533/9780857098801.3.765 (2013)
[4] Mastellone, M.L., Arena, U., Zaccariello, L.: Co-Gasification of Coal, Plastic Waste and Wood in a Bubbling Fluidized
Bed Reactor, Fuel, 89: pp.2991-3000 (2010)
[5] Aigner I., Pfeifer C., Hofbauer, H.: Co-gasification of coal and wood in a dual fluidized bed gasifier, Fuel, 90: pp. 2404–
2412 (2011)
36
SIMULATION OF BIOGAS PRODUCTION FROM SLAUGHTERHOUSE WASTEWATER IN

CONTINUOUSLY OPERATED ANAEROBIC DIGESTERS
A. SPYRIDONIDIS1, K. STAMATELATOU1
1 Democritus University of Thrace, Department of Environmental Engineering, Vas. Sofias 12, 67132
Xanthi, Greece
Abstract
Slaughterhouse wastes consist mainly of lipids and proteins which result in a high biogas production
during anaerobic digestion. According to the European legislation, the rendering process (140 oC, 4-
5bar for 20 min) of category 2 slaughterhouse wastes is obligatory prior to their usage as substrate
for the digestion process. The rendering product, even after the removal of fats, contains a
considerable amount of lipids and proteins making it a promising biogas feedstock.
The objective of this work was to simulate the anaerobic digestion of the rendering product using
the anaerobic digestion model (ADM1) [1]. For this purpose, two mesophilic (38-39οC) anaerobic
continuous stirred tank reactors (CSTR) of 2.6 L working volume were studied in parallel; sludge
recirculation after settling was applied to one of them (CSTR_rec) resulting in higher solids’
concentration. Both reactors were operated under a hydraulic retention time of 21.5±2.14 d, while
the organic load was increased stepwise (50 – 149.6 gCOD.L-1).
Kinetic experiments were performed at the CSTR under an organic loading rate (OLR) of 2.32
gCOD/L/d and organic load of 50 g COD/L. The experiments allowed to estimate the kinetic
parameters of volatile fatty acids’ degradation (e.g. butyrate, propionic and acetic acid). The
adjusted model was used to predict the dynamic behavior of the CSTR as well as CSTR_rec under
increasing OLRs successfully, confirming that the anaerobic digestion system was stable even at a
high organic loading rate (6.96 gCOD/L/d) (Fig. 1).
Figure 1: Biogas production rate under an organic load of 50 g/L (phase I), 75 g/L (phase II) and 86.4 to 149.6 g/L (Phase III) in CSTR
References
[1] Batstone D.J., Keller J., Angelidaki I., Kalyuzhnyi S.V., Pavlostathis S.G., Rozzi A., Sanders W., Siegrist H., Vavilin V.A.:
The IWA anaerobic digestion model no 1 (ADM1). Water Science and Technology, 45(10), 65-73 (2002).
37
Acknowledgements
We acknowledge support of this work by the project “INVALOR” (MIS 50002495) which is
implemented under the Action “Reinforcement of the Research and Innovation Infrastructure”,
funded by the Operational Programme "Competitiveness, Entrepreneurship and Innovation" (NSRF
2014-2020) and co-financed by Greece and the European Union (European Regional Development
Fund).
38
ANAEROBIC CODIGESTION OF TANNERY AND SLAUGHTERHOUSE SLUDGE
A.B. MPOFU1, P.J. WELZ1, O.O. OYEKOLA1

1 Cape Peninsula University of Technology, Cape Town, South Africa.
Abstract
The innovative incorporation of slaughterhouses and tanneries nowadays as a way of vertically

integrating the value chain [1] has complicated waste management. Tanneries discharge large
quantities of hazardous sludge with low carbon to nitrogen (C/N) ratios prone to inhibition by
ammonia and volatile fatty acids (VFAs) during anaerobic treatment [2]. An attractive novel
alternative of co-digesting tannery sludge with lipid rich slaughterhouse sludge was envisaged and its
feasibility investigated using batch mesophilic biomethane potential (BMP) tests [3]. The tests were
carried out at different influent substrate ratios (ISR) of 1-4 and co-substrate volumetric fractions (0-
100%). The two factors were optimised following the response surface methodology using the design
expert 10 Software. The sludge samples from the wastewater treatment works of an integrated
exotic skins facility in South Africa were characterised for solids, nutrient and metal content using
gravimetric and spectrophotometric techniques. Biogas content was quantified using a portable
biogas analyser. Optimal results were obtained at 50% co-substrate composition and ISR of 4 with an
average 50% CH4 as shown in Table 1, showing the synergistic effect of co-digestion without any signs
of inhibition. The BMP was affected and positively correlated with ISR and reactor contents with
ISR≤2.5 were inhibited by VFA accumulation whereas biodegradability was negatively correlated
with tannery composition.
Table 1: BMP and Biodegradability results
Composition Biogas yield %VS %TS %COD

Run ISR BMP mLCH4/gVS
% mL/gVS Reduction Reduction Reduction
1 50 2.5 214 77.2 57.5 51.5 40.2
2 25 2 73.8 24.3 63.9 54.9 47.2
3 75 3 234 108 60.1 48.3 36.3
4 50 2.5 135 55.5 54.2 47 34.5
5 0 2.5 175 68.2 70.8 64.6 49.6
6 50 1 0 0 58.7 46.1 29.7
7 75 2 0 0 51.6 14.7 15.1
8 100 2.5 0 0 1.9 1.5 15.4
9 50 2.5 134 48.3 53 32.1 45.1
10 50 4 431 215 44.2 27.7 47.6
11 25 3 160 60.9 86.8 81 50.5
12 50 2.5 112 42.7 63.7 57.7 50.2
13 50 2.5 0 0 78.4 56.2 27
References
[1] J. Buljan and I. Král, “The framework for sustainable leather manufacture,” Vienna, 2015.
[2] P. Shanmugam and N. J. Horan, “Optimising the biogas production from leather fleshing waste by co-digestion with
MSW,” Bioresour. Technol., vol. 100, no. 18, pp. 4117–4120, 2009.
[3] I. Angelidaki, M. Alves, D. Bolzonella, L. Borzacconi, J. L. Campos, A. J. Guwy, S. Kalyuzhnyi, P. Jenicek, and J. B. Van
Lier, “Defining the biomethane potential (BMP) of solid organic wastes and energy crops: A proposed protocol for
batch assays,” Water Sci. Technol., vol. 59, no. 5, pp. 927–934, 2009.
39
Please provide a structured one page abstract describing:
 the purpose
 the main materials and methods used
 the main results obtained
 the main conclusions of the work
Figures, Tables and equations can be included.

Figure 1: use WasteEng Label style
The title should be written in bold capital letters (Calibri 14), the author list should also be in capitals
(Calibri 12). Main text is Calibri 12 in single space. Margins are 2.5cm (bottom and top), and 1.8cm
(left and right).
Abstract submission should be done through the website (www.wasteeng2018.org) before October
3, 2017.
References
[4] Hamburger, C.: Quasimonotonicity, regularity and duality for nonlinear systems of partial differential equations.
Ann. Mat. Pura. Appl. 169, 321–354 (1995)
[5] Geddes, K.O., Czapor, S.R., Labahn, G.: Algorithms for Computer Algebra. Kluwer, Boston (1992)
[6] Broy, M.: Software engineering — from auxiliary to key technologies. In: Broy, M., Denert, E. (eds.) Software
Pioneers, pp. 10–13. Springer, Heidelberg (2002)
40
SUSTAINABILITY ANALYSIS OF BIOREFINING SCHEMES FOR REVALORIZATION OF

TEQUILA INDUSTRY RESIDUES AND WASTES
A. SANCHEZ1, S. SANCHEZ1, P. DUEÑAS1

1 Centro de Investigación y Estudios Avanzados (CINVESTAV), Zapopan, Mexico .
2 Affiliation, City, Country.
Abstract
Purpose
The tequila industry plays a very important role in Western Mexico (over 70 thousand jobs and 1.2
billion of US Dollars in exports [1]). However, residues (agave bagasse) and highly pollutant wastes
(vinasses) are produced in considerable amounts, both of which, if not properly treated, represent a
serious environmental issue in the region. Bagasse is commonly used as compost and as a solid fuel
[2], while vinasses are treated via anaerobic digestion and in some cases employed for biogas
production [3]. The purpose of this work is to propose an alternative for the revalorization of these
residues and wastes, using them as feedstock in an integrated multi-feedstock biorefinery (MFB),
which co-produces 2G bioethanol and electricity. The paper provides an environmental and economic
sustainability analysis of the proposed MFB against process schemes for handling the vinasses and
bagasse separately.
Main materials and methods
Economic and sustainability analyses were carried out in order to compare MFB against a single-
feedstock biorefinery (SFB) using bagasse for producing 2G bioethanol and a vinasses treatment plant
(VTP). The proposed sustainability analysis method considers six environmental indicators in three
categories and six economic sustainability indicators in two categories. The capacities were fixed at
500 ton/day for bagasse and 391 ton/day for vinasses, representing approximately 40% of residues
and 5% of wastes available in the region [1].
Main results obtained
The paper will elaborate on the conceptual design of the proposed biorefineries. A detailed discussion
of the impact of each one of the sustainability indicators will be presented. As a summary, SFB presents
the lowest capital investment because it requires smaller equipment than MFB, but because of a credit
charged to the tequila industries for the treatment of their vinasses (which is equivalent to vinasses
treatment costs in VTP), MFB has the smallest TPC (1.01 to 1.26 US Dollars per liter of ethanol). MFB
exhibits better sustainability mainly to a larger electricity production and lower 2G bioethanol TPC.
Main conclusions of the work
Revalorization of the tequila industry residues and wastes in an integrated biorefinery contributes to
the solution of a serious pollution problem in Western Mexico, reducing also the TPC of 2G bioethanol,
which is imperative in order to reach competitive market prices in the medium term.
References
[1] Cámara Nacional de la Industria Tequilera (2016). Basic information of the Tequila industry 2016.
http://www.tequileros.org/stuff/file_estadistica/1452616307.pdf (In Spanish)
[2] Crespo, M., (2011), Proceso de compostaje de bagazo de agave tequilero a gran escala y uso de la composta para el
cultivo del agave tequilana en contenedor. Universidad de Guadalajara, Guadalajara, México (in Spanish).
[3] Fuess, L., Araújo, M., Loureiro, M., & Zaiat, M. (2017). Designing full-scale biodigestion plants for the treatment of
vinasse in sugarcane biorefineries: How phase separation and alkalinization impact biogas and electricity production
costs. Chemical Engineering Research and Desing 119, 209-220.
41
POTENTIAL FOR TREATING DAIRY INDUSTRY WASTEWATER COGENERATING BIOGAS
M. M. MANYUCHI1,2, R. JAMAKAMGA2, D.I.O. IKHU-OMOREGBE1, O.O. OYEKOLA1,2

1
Chemical Engineering Department, Cape Peninsula University of Technology, South Africa
2
Department of Chemical and Process Systems Engineering, Harare Institute of Technology,
Zimbabwe
Keywords: Hycura, bio-catalysis, biogas, integrated waste water management.
Abstract
Huge amounts of wastewater are being deposited in water bodies from industries, yet these can be
recycled to curb the water challenges while producing a renewable source of energy (biogas) as an
initiative towards a green economy. In this study, dairy wastewater was used as a case study
employing the membrane bioreactor and nanofiltration for wastewater treatment, while harnessing
biogas in a fluidized bed biodigester augmented with Hycura. There was 98.7% removal of TSS,
93.9% COD reduction, 95% BOD5 reduction as well 90% color removal after membrane bioreactor
treatment of the wastewater sample. A 99% removal of COD, 97% removal of BOD5, 99.9% removal
for total solids, 99.9% removal of nutrients was also achieved with a 75% recovery of water. A 78%
yield of biogas was realized from the biodigester at an optimum temperature of 37 oC. Integrated
wastewater treatment supports water sustainability while creating clean, renewable and sustainable
energy.
42
1. INTRODUCTION
There is an immediate need for a suitable technology for recycling a reasonable quantity of the dairy
wastewater (Balannec et al., 2002). Conventional water treatment technologies present multiple
stages of water treatment which uses a lot of chemicals as well as space. Recent studies revealed
that membrane separations may help in solving problem of attaining a quality of water that can be
recycled back to the process without chemicals and incorporating fewer steps (Koyuncu et al., 2000).
Membrane filtration is a pressure driven process in which membrane acts as selective barriers to
restrict the passage of pollutants such as organics, nutrients, microorganisms, inorganic metal ions
and other oxygen depleting pollutants, and allows relatively clear water to pass through (Kulkarni,
2014). Membrane filtration potentially offers the advantages of highly selective separation,
separation without any chemical additives, ambient temperature operation, usually no phase
changes, continuous and automatic operation, economical operational so in small units, modular
construction and simple integration in existing production processes, as well as relatively low
capital and running costs (Andrade et al., 2014). The works that have been dedicated to the
treatment of the process waters (flushing waters and first rinse waters) show that nanofiltration for
making wastewater reusable. Integrating two processes such as biological treatment and an
advanced membrane filtration, may yield a better filtration quality thus combination of a membrane
bioreactor and nanofiltration as tertiary treatment (Andrade et al., 2014).
Anaerobic digestion is a proven technology for wastewater sludge which allows generation of
renewable energy from the same process (Mes et al., 2003). The sludge contains the particles
removed from the wastewater, which are rich in nutrients and organic matter (Bachmann, 2015).
The sludge is pumped into an anaerobic biodigester where the digestion takes place. Conventional
digesters have a retention time of 30-60 days. Microorganisms break down part the organic matter
that is contained in the sludge and produce biogas, which is composed of methane, carbon dioxide
and trace gases. It usually contains hydrogen sulphide (H2S) and other trace components which need
to be removed in order to obtain a good combustible gas.
Catalyst immobilization is an attractive method which helps maintain high catalyst concentration in
the digestion while also improving the process (Nisha et al., 2012). The bio-catalyst to be
immobilized, Actizyme is bio-catalytic in nature and has been reported to enhance biogas production
(Manyuchi et al., 2015). Hycura contains multiple enzymes including protease, amylase, catalase and
gelatine etc. One of the novel properties of this biocatalyst is that it produces H 2S free biogas. It also
reduces odour. Hycura can work in both aerobic and anaerobic conditions but in this work, it will be
used in anaerobic conditions (Manyuchi et al., 2015). The aim of the present work is to develop a
process of recycling dairy wastewater while harnessing renewable energy (biogas) in a system bio
augmented with Hycura.
2. EXPERIMENTAL
2.1 Materials
Dairy wastewater was obtained from a local farm. Hycura was obtained from Hycura, Australia.
2.2 Methods
2.2.1 Wastewater physicochemical properties
The wastewater was characterized for pH, color, turbidity, total nitrogen, biological oxygen demand
(BOD5), chemical oxygen demand (COD), total suspended solids (TSS) using the APHA (2005)
standard methodology.
43
2.2.2 Methodology for microfiltration

A sample of 100 mL wastewater was filtered by a microfiltration membrane of average pore size of
0.5 micron. The permeate was collected into a beaker. The retention time was 8 hours.
2.2.3 Methodology for nanofiltration

A self-made nanofiltration membrane was used. Distilled water was first used to measure the water
permeability of the membrane the effluent form the membrane bioreactor was nanofiltered at
different pressures. The rejection of the nano-membrane was noted and the permeate
characterized. A permeate flux of 20 L/m2h was used in cross flow mode.
2.2.4 Biogas production

A cylindrical 5 litre vessel filled with pall rings was filled with waste water. A tight sealing stopper
with two holes drilled in it is put on the flask as to exclude air totally. Hycura was applied in powder
and was made to stand for a week at a loading of 50 g/m 3. Application ratios were varied and the
experiment was done 5 times. The system was allowed to run uninterruptedly until a steady state is
reached, this being established by a constant rate of gas generation. The volume of the biogas
produced can be assessed by measuring the volume of the balloon. The volume of the balloon was
be estimated directly by calculation using the diameter of the balloon. These experiments were done
at 30-45 0C for a period of 30 days.
3. RESULTS AND DISCUSSION

3.1 Wastewater treatment
There was 98.7% removal of TSS, 93.9% COD reduction, 95% BOD 5 reduction as well 90% color
removal after membrane bioreactor treatment of the dairy wastewater sample (orange scale). The
wastewater was then sent for nanofiltration (grey scale) whereby a 99% removal of COD, 97%
removal of BOD5, 99.9% removal for total solids, 99.9% removal of nutrients. The results are
represented graphically in Figure 1.
Total nitrogen
BOD
Turbidity (NTU)
COD
Oil and grease
Total suspended solids
Conductivity (µS/cm)
pH
0 200 400 600 800 1000 1200 1400 1600

(mg/L)
Série3 Série2 Série1
Figure 1: Water characterization results during the membrane bioreactor treatment and nanofiltration
44
3.2 Biogas generation

The amount of biogas generated from dairy wastewater was optimal at 37 ◦C as this is the
recommended optimal temperature for Hycura activity (Cail et al., 1986). This is diagrammatically
represented in Figure 2.
2,5
1,5
0,5
0
30 35 40 45
Temperature (° C)
Figure 2: Biogas production temperature profile from the dairy effluent
The biogas generated from the dairy effluent bio augmented with Hycura had a 78-80% composition
of bio methane, 20-25% carbon dioxide and 2-8% of traces including nitrogen and water vapour
(Figure 3). Bio augmentation of waste water effluent with for biogas production enhances the bio
methane yield increasing the calorific value (Manyuchi et al., 2015).
80
70
60
% Composition
50
40
30
20
10
0
Methane Carbon dioxide Nitrogen Vapour Trace elements
Figure 3: Composition of biogas from dairy waste water
4. DESCRIPTION OF THE PROPOSED PROCESS

The process does not involve any use of chemicals. It involves screening and grit separation before
equalization. The wastewater then goes through membrane separation by use of a microfiltration
membrane submerged in an aerobic bioreactor. The permeate proceeds to nanofiltration for tertiary
treatment while the sludge goes to the anaerobic fixed film biodigester for biogas production. This
45
particular process involves a dryer where the sludge form the biodigester is dried into biosolids
which are nutrient rich. The process is not very energy intensive. Only the biodigester and the dryer
require energy and can be potentially used as bio-fertilizer. The biogas can be used to cater for the
energy required by this treatment process. The stages are explained in detail below and the process
flow diagram given in Figure 4.
4.1 Pre-treatment
This is the stage where the large solids in the wastewater are removed by screens. These screens
consist of metal bars placed across the influent channels.
4.2 Flow equalization

Flow equalization is the process used to minimize the variability of water and wastewater flow rates
and composition i.e. to mitigate changes in flow rate. It provides storage to hold water when it is
arriving too rapidly, and to supply additional water when it is arriving less rapidly than desired. In
treating wastewater, the rate at which the waste arrives at the treatment process might vary
dramatically, so it is convenient to equalize the flow before feeding it to the various treatment steps.
There will be a flow equalisation tank with a level controller.
4.3 Membrane bioreactor system

The membrane bioreactor system (MBR) comprises of hollow fiber microfiltration membranes. The
tank is filled with feed water to above the tops of hollow fiber sub-modules. The inside of the
microfiltration membranes are then placed under the suction head of the filtrate pump. Filtration
takes place from the outer surface of the fibers to the hollow inner core. Feed liquid passes through
the porous wall of the fibers while the suspended matter remains on the feed side. This filtration
process removes solids larger than approximately 0.5 µm. An air compressor will be used to inject an
adequate air supply into the tank. The aerobic system includes air blowers which will be installed
adjacent to the system. The required process air will be introduced at the bottom through air scour
distribution header pipes. After passing through the upstream flow, the mixed liquor will be
transferred by overflow to a suitable buffer flow tank and then pressurized to an operating pressure
in accordance with the membrane’s design. As deposits build upon the fibers, filtration flow
resistance increases, resulting in a drop in filtration flow rate. To reduce the flow resistance caused
by the fouling and to restore the filtration flow rate, the membrane is backwashed. During the
backwash, filtration is stopped and air is applied from the outside of the fibers. A small amount of
filtrate is pushed through the fibers from inside to out to further remove deposits from the outer
surface of the fibers. The MBR is operated automatically while the filtration and backwash
operations are to occur successively. The backwash flow rate can be made to be controlled by a
bypass line and the backwash pressure, by a needle valve. There will be a vacuum pump for the
microfiltration, a diaphragm pump for backwash, solenoid valves, level sensors, control valves, flow
indicators (for permeate, backwash and air), a pressure indicator for the permeate and the backwash
and a skid with an electrical panel.
4.4 Nano filtration

An MBR can have high removal efficiencies for COD, BOD 5, colour and nutrients according to the
experimental work done and shown by a microfiltration. However, the concentration of dissolved
solids in the permeate still prevent reuse of the water hence the introduction of nanofiltration to be
able to apply it to cooling, steam generation, or washing of external areas and trucks. A spiral wound
nanofilter of pore size 1nm will be used for this process.
46
4.5 Fixed film bio digester

The type of digester employed to generate and capture methane is dependent on the solids content
of the effluent stream. Sludge removal pipes will be installed across the base of the digester to
enable sludge to be pumped out on a regular basis. By using anaerobic technology for wastewater
cleaning, biogas can be generated.
4.6 Dryer
A rotary dryer will be employed to dry the sludge form the biodigester.
E-23
E-20
E-13
E-16
E-15
E-17
E-14
E-21
E-22 E-19 Equipment List

Displayed Text Description
E-12Permeate and backwash tank for micro membranes
E-13 Microfiltration membranes
E-14 Nanofiltration membranes
Backwash lines E-15 Air diffuser
Air
Raw wastewater E-16 Equalisation tank
Permeate from membrane bioreactor and backwash line E-17 Storage tank of regenerated water
Permeate from nanofilter E-19 Rotary drier
Biogas E-20 Bar screen
Raw sludge
Retentate E-22 Biodigester
Digestate E-21 Gas cylinder
Nutrient rich bio-solids E-23 Permeate and backwash tank for nanomembranes
Figure 4: Process flow diagram
5. CONCLUSION
1. Integrated wastewater treatment has potential to harness biogas as well water for reuse in
the system.
2. A significant reduction of the dairy wastewater pollutants was noted a more than 90%
decrease whilst the bio methane yield was high with more than 78% bio methane
composition.
REFERENCES CITED
Andrade L. H, Mendes F. D. S, Espindola J. C and Armal, M. (2015). ‘Reuse of Dairy Wastewater Treated by Membrane
Bioreactor and Nanofiltration: Technical and Economic Feasibility’. Brazilian Journal of Chemical Engineering, 32 (3),
735-747.
APHA Standard Methods for the Examination of Water and Wastewater, 21st Edition, America Public Health Association,
American Water Works, Association, Water Environment Federation, Washington, DC, USA. 2005.
Bachmann, N. Sustainable Biogas Production in Municipal Treatment Plants. IEA Bioenergy. 2015, 1-20.
Balannec. B, Gesan-Guiziou, G., Chaufer, B. M., Rabiller-Baudry and Daufin, G. (2002). ‘Treatment of Dairy Process Waters
by Membrane Operations for Water Reuse and Milk Constituents Concentration’. Desalination, 147, 89–94.
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Cail, R. G., Barford, J. P., and Linchacz, R. (1986). ‘Anaerobic Digestion of Wool Scouring Wastewater in Digester Operated
Semi-Continuously for Biomass Retention’. Agricultural Wastes, 18, 27-38.
Koyuncu, I, Turan. M, Topacik, D and Ates, A. (2000). ‘Application of Low Pressure Nanofiltration Membranes for the
Recovery and Reuse of Dairy Industry Effluents’. Water Science and Technology, 41 (1), 213–221.
Kulkarni, S. J. and Goswami, A. K. (2014). ‘Applications and Advancements in Treatment of Waste Water by Membrane
Technology’. International Journal of Engineering Sciences and Research Technology, 3 (9), 446-450.
Manyuchi, M. M., Ikhu-Omoregbe, D. I. O. and Oyekola, O. O. (2015). ‘Hycura Biochemical Properties: Potential for Use in
Anaerobic Sewage Treatment Co-generating Biogas’. Asian Journal of Science and Technology, 6 (3), 1152-1154.
Nisha. S, Arun Karthick, S and Gobi N. A. (2012). ‘Review on Methods, Application and Properties of Immobilized
Enzyme’. Chemistry Science Review Letters, 1 (3), 148-155.
Mes, T. Z. D., Stams, A. J. M., Reith J. H. and Zeeman, G. (2003). ‘Methane Production by Anaerobic Digestion of
Wastewater and Solid Wastes’, 58-102.
48
COMPARISON OF WOOD CHARS FROM GASIFICATION AND PYROLYSIS FOR

ADSORPTION AND CONVERSION OF TAR MODEL COMPOUNDS
G. RAVENNI1, O.H. ELHAMI2, Y. NEUBAUER2, J. AHRENFELDT1, U.B. HENRIKSEN1
1
Danmarks Tekniske Universitet, Department of Chemical and Biochemical Engineering,
Frederiksborgvej 399, 2300 Roskilde, Denmark
2
Technische Universität Berlin, Institute of Energy Engineering, EVUR,
Fasanenstrasse 89, 10623 Berlin, Germany
Keywords: char, activated carbon, gas cleaning, tar removal, tar model compounds
Abstract
The carbonaceous products of gasification or pyrolysis (chars) and active carbons (ACs) have been
found suitable for adsorbing tar compounds and active as catalysts for tar conversion [1–4];
therefore they can be beneficial for the treatment of biomass producer gas. The aim of this work is
to investigate the nature of the interaction between aromatic compounds (toluene and
naphthalene) and chars with different surface structure. A dedicated setup was used to test a
gasification-derived char, a commercial activated carbon, and a pyrolysis char (non-activated). A flow
of N2, mixed with vapors of toluene and naphthalene, was passed in a reactor housing a char bed
and heated up to the desired temperature (250, 800˚C). The concentration of aromatics and the
composition of the exit gas were continuously monitored. At 250˚C, a breakthrough behavior was
observed, suggesting that physical adsorption was taking place. At 800˚C, H2 and CH4 were detected
in the exit gas, indicating ongoing cracking reactions. Under these conditions, all chars showed signs
of deactivation, but the pore structure of gasification char was beneficial in preserving the activity of
this material. Characterization of spent chars showed carbon build-up on the surface of both
gasification char and AC. In all tests, non-activated pyrolysis char was the least effective in reducing
the concentration of aromatics, and no carbon deposited on its surface during the tests. Both
gasification char and commercial AC appeared to be promising materials to be used as substrate for
producer gas treatment and upgrading.
49
1- INTRODUCTION
Tar is a problematic contaminant found in biomass producer gas, because it can be very abundant
and can easily condense and damage components. Tar is a mixture of organic compounds which very
often have aromatic structures. The carbonaceous products of gasification or pyrolysis (chars) and
active carbons (ACs) have been found effective in adsorbing tar compounds [1,2] and active as a
catalyst for tar conversion [3–5]. Therefore they may be applied to gas treatment: particularly, the
use of residual char from gasification would represent a favorable solution for downstream tar
removal in biomass producer gas. Char is continuously produced in gasification plants. Spent char
can be recycled within the system or find alternative end-life applications: for example, it could be a
precursor for carbon materials or used as biochar for soil amendment, if the relevant thresholds for
noxious contaminants (e. g. heavy metals, polycyclic aromatic hydrocarbons, dioxins) are verified.
Moreover, residual char is currently considered as waste, therefore its repurposing would represent
an economic and environmental benefit [6]. The irreversibility of the interaction between aromatics
and char surface is known to be influenced by temperature [7], but further research is needed in
order to define the necessary char characteristics and the reaction conditions that can guarantee an
efficient removal of tar by either physical adsorption or conversion (cracking). The aim of this work
is to compare the performances of different chars in removing a mixture of toluene and naphthalene
from a N2 flow at different temperature (250 and 800˚C) and to identify the processes involved in the
interaction between aromatic molecules and the surface of chars. Three materials were tested: a
commercial activated carbon, a residual char from TwoStage gasification [8] of spruce wood chips
and char obtained by pyrolysis of beech wood chips. These materials were compared to study the
response of different carbonaceous surfaces to contacting aromatic compounds at different
temperature levels.
2- MATERIALS AND METHODS

A laboratory setup was assembled at TU Berlin (Institute for Energy Engineering) to test the effects
of three char beds on tar model compounds at different temperatures. A N2 flow (4.7 l/min) was
mixed with vapors of a toluene-naphthalene solution that was dosed with a syringe pump (Cetoni,
Germany). Toluene and naphthalene were chosen as model representatives of different tar classes.
The flow was passed in a heated stainless steel reactor of 500 mm in length with an internal
diameter of 36 mm. Before each test, the reactor was filled with a 50 mm layer of alumina (Al2O3)
beads (Sasol, Germany), used as a support for the tested bed materials. In all tests, the bed of char
was 100 mm tall whereas the weight varied from 8 to 22 g, depending on the bulk density of chars.
All chars were dried prior to the experiments. Concentrations of aromatics were monitored with a
gas chromatograph equipped with flame ionization detector (GC-FID) (SRI Instruments, USA). The
permanent gas composition (H2, CO, CO2, N2, O2, CH4 and light hydrocarbons) was measured with a
gas chromatograph with a thermal conductivity detector (microGC) (Inficon, Switzerland). Both
instruments automatically sampled the gas flow in 3 and 5 minutes time intervals, respectively. The
setup is schematized in Figure 1.
50
Figure 1: Experimental setup diagram
The concentrations of aromatics in the gas flow fed to the reactor were maintained at a constant
value (C0) during the experiments: 18280 ± 5% mg/Nm3 for toluene and 1850 ± 5% mg/Nm3 for
naphthalene. Prior to each test, the toluene and naphthalene concentrations were measured in
bypass mode until stable. Afterwards, the experiment was started by deviating the gas flow through
the reactor. The evolution of the instantaneous concentrations (C) of toluene and naphthalene was
monitored alongside the gas composition, to detect possible decomposition products. All lines were
heated to 200˚C to avoid any condensation prior to the GC measurements.
The effect of the char beds was evaluated at 250 and 800 ˚C, and blank experiments were run to
quantify the effect of pure thermal decomposition and the effect of the alumina beads that were
used as a support for the char beds. Three different chars were tested with the setup. Residual
gasification char (Viking char) was collected at the TwoStage demonstration plant at DTU (known as
the Viking gasifier) [8]. The commercial active carbon (W48) was a wood-derived, steam-activated AC
and was kindly provided by Silcarbon Aktivkohle GmbH (Germany). The non-activated char (900NN)
was produced at TU Berlin by pyrolysis of beech chips at 400˚C, followed by heat treatment at 900˚C
under N2 atmosphere to guarantee its thermal stability during high temperature experiments.
After the tests, spent chars were collected and weighed. The elemental composition (CHNS) of the
fresh and spent materials was measured (VarioEL III, Elementar Analysensystem GmbH, Germany). In
addition, the specific surface area was quantified by Brunauer-Emmett-Teller (BET) analysis through
N2 adsorption at 77K (Nova 2200, Quantachrome Instruments, USA).
3- RESULTS AND DISCUSSION

The characterization of chars by BET analysis prior to the experiments showed that the three
materials had different surface properties. The residual gasification char (Viking) had the highest
surface area and pore volume, while the pyrolysis char (900NN) showed a very limited surface area
and pore volume. Table I compares the surface properties and elemental composition of the tested
chars.
Char BET surface area DFT pore volume Density C H N S

(m2/g) (cm3/g) (Kg/m3) (wt%) (wt%) (wt%) (wt%)
Viking 1235 0.78 88 87.6 0.63 0.10 0.04
W48 AC 553 0.24 221 88.9 0.19 0.33 0.09
900NN 35 0.02 198 93.1 0.26 0.92 0.37
Table I: Surface characteristics of the tested materials
51
The isotherms obtained by N2 adsorption at 77K were compared with the ones described in the
IUPAC Technical Report [9]. The shape of the isotherms (Figure 2) indicated that the Viking char is a
micro-mesoporous carbon, also containing macropores (> 50nm in diameter). On the other hand, the
other two chars appeared to have mainly narrow micropores (< ≈ 1nm).
Figure 2: Isotherms obtained by nitrogen adsorption at 77K for the tested chars
Overall, during the experiments with the described setup, Viking char and the W48 AC gave similar
or comparable results, whereas the 900NN pyrolysis char showed a markedly different behaviour.
Figure 3 shows the evolution of the normalized concentration of naphthalene (C/C0) at the outlet of
the reactor, obtained by experiments at 250˚C.
Figure 3: Naphthalene breakthrough curves obtained at 250˚C
Under these conditions, a preliminary test was performed by filling the reactor with alumina (130 g),
to obtain the same bed height used in the char tests: the effect on the outlet concentration of
naphthalene ceased after about 10 minutes from the start of the experiment.
During the tests at 250˚C, all three chars caused the naphthalene concentration to drop quickly when
the gas flow was allowed through the reactor, and then to gradually increase again back to the
52
original value (C0). The typical shape of adsorption breakthrough curves could be identified,
suggesting that the only way of interaction between the aromatics and the surface of char at this
temperature was physical adsorption (physisorption). This was confirmed by the fact that only N2 gas
was detected by the microGC instrument at the outlet of the system.
The longest time to naphthalene breakthrough was measured during the experiment with W48 AC,
but the effect was also due to the high density of this material. Indeed, the naphthalene adsorption
capacity resulted to be comparable for W48 and Viking char: 60.5 mg/gchar and 61.2 mg/gchar
respectively. In contrast, the adsorption capacity resulted dramatically lower for the 900NN pyrolysis
char: 4.1 mg/gchar .
The high concentration of toluene caused the breakthrough to be almost instantaneous for all the
materials; therefore it was not possible to calculate the adsorption capacity. Nevertheless, the
relative differences between the chars were also confirmed in relation to toluene, with W48 AC
showing the longest breakthrough time, followed by Viking char and 900NN.
When experiments were performed at higher temperature (800˚C), the concentration of

naphthalene in the exit gas evolved differently and the typical breakthrough shape was not
distinguishable anymore. The evolution of the relative concentrations is showed in Figure 4 for the
three chars, together with the results obtained with the reactor filled exclusively with 30g Al2O3
(blank test). This amount of alumina was used in all tests as a support for the char beds.
Figure 4: Naphthalene breakthrough curves obtained at 800˚C
It is evident that the effect of the 900NN char bed was negligible if compared with the blank test
results. On the other hand, both Viking char and W48 AC assisted cracking reactions of naphthalene
for an extended time. Under these conditions, H2 and CH4 were detected in the exit gas; both are
identified as pyrolysis products of aromatic molecules, together with solid carbon (soot) and
benzene [10]. Benzene was not detectable with the method used for the GC-FID. Both materials
53
showed a decreased effect over time, as a consequence of surface deactivation. This was probably
due to deposition of solid carbon over the porous surfaces of char: the phenomenon has been
previously observed in similar experiments [5].
Figure 5: Toluene breakthrough curves obtained at 800˚C
A similar trend was observed for toluene (Figure 5) at 800˚C.
The gas composition at the outlet of the system measured by microGC confirmed that cracking
reactions took place during the tests. H2 was produced in the largest amount by Viking char and
W48. The amount of H2 generated by 900NN pyrolysis char was only slightly higher than the blank
test with alumina. Figure 6 shows the evolution of H2 in the exit gas.
54
Figure 6: Concentration of H2 detected in the exit gas during tests at 800˚C with three chars
The H2 production was declining during all tests, confirming that the materials were undergoing
deactivation. The shape of the H2 curve relative to W48 AC shows a steep decline, while Viking char
maintained a higher activity for a longer time. Such difference is likely to be due to the different pore
size distribution of the two chars: according to the isotherms in Figure 2, W48 is rich in micropores,
while Viking char also contains meso-and macropores. Micropores are easily blocked by carbon
deposition, therefore the lack of larger pores led to a faster deactivation. The evolution of H2 in the
exit gas produced by the 900NN pyrolysis char followed closely the blank test results. The surface of
this char appeared to have a negligible activity in comparison with the other tested materials.
Other than H2, only CH4 was detected in the exit gas, and only in small amounts. The CH 4 production
from Viking and W48 curves peaked at 0.15 Vol% and 0.10 Vol% respectively, to then decline with a
similar patter as for H2. During 900NN char and alumina tests, hardly any CH4 was detected at the
outlet.
During the tests, the three chars were exposed for the same amount of time to the N2 flow enriched
with model compounds. After the tests, the spent chars were collected, weighed and analysed in
terms of elemental composition and surface properties. Some of the results are collected in Table II.
The weight of Viking char used as bed material increased from 9 to 14.6 g after the test. The gain was
smaller for W48, which increased from 22.4 to 24.2 g, and it was even negative for 900NN char,
which had an initial weight of 20.5 g and a final one of 19.8 g. For the three materials, the weight
change corresponded quantitatively with the carbon content variation.
55
Char BET surface area DFT pore volume C H N S

(m2/g) (cm3/g) (wt%) (wt%) (wt%) (wt%)
Viking 55 0.04 93.9 0.14 0.28 0.14
W48 AC 389 0.17 94.2 0.11 0.38 0.10
900NN 267 0.12 94.2 0.21 0.62 0.08
Table II: Analysis on spent chars from experiments at 800˚C
Viking char gained the most weight during the tests, and also its carbon content increased
significantly. The same effect, less marked, was observed for W48. Again, 900N behaved differently,
by losing some weight and some of its carbon content. Also its surface area increased significantly, in
contrast with the other two chars. Results suggest that the naphthalene and toluene decomposed on
the surface of Viking char and W48 active carbon following the mechanism described by [5] and
confirmed by [3]. The carbon deposition appears to take place primarily on micropores, but also on
larger pores, once the smaller ones are blocked and deactivated. Indeed, deposited carbon was
particularly abundant on Viking char, which lost also most of the surface area during the experiment.
4- CONCLUSIONS
The experiments performed with the described setup on the three chars showed clearly the different
ways of interaction between char and the tar model compounds at the two different temperatures
(250 and 800˚C). Physical adsorption took place at 250˚C on all three tested materials: breakthrough
curves could be identified in the evolution of the relative concentration at the outlet, while no gas
was detected other than N2. Pyrolysis char (900NN) showed a very low adsorption capacity. On the
other hand, residual gasification char (Viking char) and the commercial AC (W48) showed much
higher adsorption capacities and the two exhibited comparable performances.
At higher temperature (800˚C), the production of H2 (and to some extent of CH4) was clearly
detectable in the exit gas. The evolution of the gaseous products showed that cracking of aromatics
took place preferentially on the surface of Viking char and W48, while the surface of 900NN char was
not significantly active. Both gasification char and AC showed signs of deactivation, but with different
trends. Viking char suffered a slower deactivation, probably due to its pore structure with
micropores as well as meso- and macropores. W48, solely rich in micropores, showed a steep
deactivation. However, under real conditions, deactivation could be delayed through addition of a
reforming agent to assist the reactions of deposited carbon. The characterization of spent chars
revealed that Viking char and W48 gained weight and their carbon content increased. An opposite
trend was observed for the 900NN char.
At 800˚C or higher temperatures, chars can assist cracking reactions of aromatics with H2 production.
However, the surface characteristics (specific surface area, pore volume and pore structure) are of
importance in determining the performance of the carbonaceous materials: in these experiments,
the surface of non-activated char did not perform nearly as well as the two chars with large BET area
and developed porosity. In addition the pore size distribution appeared to influence the deactivation
rate.
56
All in all, the results suggest that some chars could perform well if applied for gas cleaning and
upgrading; in particular the residual gasification char tested in this work seems especially promising
for this application. Finally, it is interesting to point out that the increased carbon content on the
spent materials could hint to possible end-life applications with potential carbon sequestration
benefits. Carbon-enriched chars could have interesting properties as soil enhancers (biochars) or as
precursors for carbon based materials. Indeed, deposited carbon could have some degree of
crystalline order [11]. Further experimental work in real conditions is needed to verify the effectivity
of chars as materials for gas treatment and to optimize the reaction conditions to obtain an efficient
and durable effect on the producer gas quality. In addition, further structural and chemical
characterization should be carried out on spent chars to evaluate their suitability and safety for
various end-life applications.
REFERENCES
[1] Mastral AM, García T, Callén MS, Navarro M V., Galbán J. Removal of naphthalene, phenanthrene, and pyrene by
sorbents from hot gas. Environ Sci Technol 2001;35:2395–400. doi:10.1021/es000152u.
[2] Mastral A, García T, Murrillo R, Callén MS, Lopez JM, Navarro M V, et al. Study of the Adsorption of Polyaromatic
Hydrocarbon Binary Mixtures on Carbon Materials by Gas-Phase Fluorescence Detection. Energy & Fuels
2003:669–76.
[3] Fuentes-Cano D, Gómez-Barea A, Nilsson S, Ollero P. Decomposition kinetics of model tar compounds over chars
with different internal structure to model hot tar removal in biomass gasification. Chem Eng J 2013;228:1223–33.
doi:10.1016/j.cej.2013.03.130.
[4] Klinghoffer N, Castaldi MJ, Nzihou A. Catalyst Properties and Catalytic Performance of Char from Biomass
Gasification. I&Ec 2012:13113–22. doi:10.1021/ie3014082.
[5] Hosokai S, Kumabe K, Ohshita M, Norinaga K, Li C, Hayashi J-I. Mechanism of decomposition of aromatics over
charcoal and necessary condition for maintaining its activity. Fuel 2008;87:2914–22.
doi:10.1016/j.fuel.2008.04.019.
[6] Benedetti V, Patuzzi F, Baratieri M. Characterization of char from biomass gasification and its similarities with
activated carbon in adsorption applications. Appl Energy 2017:1–8. doi:10.1016/j.apenergy.2017.08.076.
[7] Egsgaard H, Ahrenfeldt J, Ambus P, Schaumburg K, Henriksen UB. Gas cleaning with hot char beds studied by
stable isotopes. J Anal Appl Pyrolysis 2014;107:174–82. doi:10.1016/j.jaap.2014.02.019.
[8] Ahrenfeldt J, Henriksen U, Jensen TK, Gøbel B, Wiese L, Kather A, et al. Validation of a continuous combined heat
and power (CHP) operation of a two-stage biomass gasifier. Energy and Fuels 2006;20:2672–80.
doi:10.1021/ef0503616.
[9] Thommes M, Kaneko K, Neimark A V, Olivier JP, Rodriguez-reinoso F, Rouquerol J, et al. Physisorption of gases ,
with special reference to the evaluation of surface area and pore size distribution ( IUPAC Technical Report ).
Pure Appl Chem 2015. doi:10.1515/pac-2014-1117.
[10] Moldoveanu SC. Techniques and Instrumentation in Analytical Chemistry - Pyrolysis of Organic Molecules. vol.
28. Elsevier Science Ltd; 2009.
[11] Brown HR, Hesp WR, Taylor GH. Carbons obtained by thermal and catalytic cracking of coal tars. Carbon N Y
1966;4:193–9.
ACKNOWLEDGMENTS
The authors thank Innovationsfonden (Denmark) for the financial support received as part of the project “SYNFUEL -
Sustainable synthetic fuels from biomass gasification and electrolysis” (4106-00006B), as well as the German Federal
Ministry of Education and Research for the funding to the junior research group “NWG-TCKON” (FKZ: 03SF0442).
The authors would also like to thank Susanne Hoffmann (Technical University of Berlin, Institute for Energy Engineering)
for the help with char analysis.
57
VALORIZATION OF MILLET AND BUCKWHEAT HUSKS CHARS IN A FIXED BED AS LOW-

COST SORBENTS IN H2S REMOVAL FROM BIOGAS
J.PEÑA1,2, A. VILLOT 1, C.GERENTE 1

1 IMT Atlantique, GEPEA UMR CNRS 6144, Nantes, France.
2 ADEME, Angers, France.
Abstract
Biomass pyrolysis is nowadays a solution for the decentralized energy production economically
interesting if all the by-products can be valorized. In addition to pyrolysis gas and condensables,
chars are produced and innovative routes for their recycling have to be investigated depending on
their composition. Thus, the aim of this work is to study the properties of pyrolysis chars as well as
their activation and their performance in biogas treatment. More specifically these chars and
activated chars are implemented in a fixed bed for the removal of H2S, one of the main pollutants
from biogas whose concentration can vary from 100 and 4 000 ppm [1]. From this perspective,
buckwheat husk (BH) and millet husk (MH) were tested as precursors for preparing raw and
activated chars by means of activation with steam and CO2. Produced materials were characterized
in terms of chemical composition and textural properties. Results showed that raw and activated
chars differ in terms of carbon, ash content and inorganic composition (Table 1). Materials obtained
from BH have high percentage of C (above 72.3 wt.%) and ash content starting from 5.7 up to 10.4
wt.%. Their inorganic content is mainly composed by K (from 0.9 to 3.7 wt.%) and Ca (from 0.5 to 5.8
wt.%). On the contrary, MH gave materials with lower C content (56.9 and 53.7 wt.%) and higher ash
content (29.6 and 35.5 wt.%). In addition, MH-Char and MH-CO2 have strong presence of Si (21.0 and
29.1 wt.% respectively) and some P (0.9 and 1.9 wt.%). CO2 activation strengthened K content while
steam activation increased percentage of Ca in BH-Char. Both activation techniques granted the
basic surface to the chars (pHpzc = 9.7, 10.7 and 10.8). Regarding textural properties, steam activation
(BH-H2O) developed high porosity at level of micro- (71 %) and mesopores (29 %) whereas CO2
activation (MH-CO2 and BH-CO2) created a moderate porosity mostly at micropore scale (92 and 96
%). The chars performance is currently being tested in biogas treatment for the removal of H2S at
200 ppm at room temperature. Experiments were started with a simple biogas matrix composed by
N2 and H2S. In order to investigate competing reactions a complex matrix will be tested adding CH4
and CO2. It is expected that mineral content, basic surface and porosity of chars will promote their
efficiency in biogas purification.
Table 1 : Chemical and textural characterization of raw and activated chars.
VMicro VMeso Surface BET
Sample C (%) Ash (%) K (wt.%) Ca (wt.%) P (wt.%) Si (%) pHpzc 3 3 2
(cm /g) (cm /g) (m /g)
MH-Char 56.9 ± 0.3 29.6 ± 0.2 4.5 ± 0.6 0.2 ± 0.0 0.9 ± 0.2 21.0 ± 0.9 5.3 - - -
BH-Char 78.4 ± 1.0 5.7 ± 0.1 0.9 ± 0.0 0.5 ± 0.0 0.3 ± 0.0 0.0 ± 0.0 5.7 - - -
MH-CO2 53.7 ± 0.7 35.5 ± 0.7 6.5 ± 0.3 0.3 ± 0.0 1.9 ± 0.3 29.1 ± 0.5 9.7 0.147 ± 0.002 0.013 ± 0.000 329 ± 6
BH-CO2 83.3 ± 0.3 7.9 ± 0.1 2.8 ± 0.1 1.9 ± 0.1 0.7 ± 0.0 0.0 ± 0.0 10.7 0.261 ± 0.004 0.012 ± 0.010 578 ± 4
BH-H2O 72.3 ± 1.9 10.4 ± 0.2 3.7 ± 0.2 5.8 ± 0.1 0.4 ± 0.1 0.0 ± 0.0 10.8 0.419 ± 0.010 0.175 ± 0.083 997 ± 81
MH: Millet Husk; BH: Buckwheat Husk; Char: char from pyrolysis; CO2: CO2 activated char; H2O: Steam activated char.
Micropores: Pore diameter < 2 nm; Mesopores: 2 nm < Pore diameter < 50 nm.
References
[1] Q. Sun, H. Li, J. Yan, L. Liu, Z. Yu, X. Yu, Selection of appropriate biogas upgrading technology-a review of biogas
cleaning, upgrading and utilisation, Renew. Sustain. Energy Rev. 51 (2015) 521–532.
58
UTILIZATION OF RESIDUAL CARBON AND MINERAL CONTENT FROM GASIFICATION

CHAR TO REFORM TARS FROM SYNGAS
G. PALLA ASSIMA1, J.-M. LAVOIE1

1 Industrial Research Chair on Cellulosic Ethanol and Biocommodities (CRIEC-B)
Centre de Mises à l’Échelle (CME), Université de Sherbrooke
3000 boul de l’Université, Sherbrooke, Québec, J1K0A5
Abstract
Thermochemical processes are known to generate carbon-based side products, mostly char and tars,
that are often associated with significant operational problems in gasification technologies. In many
cases, the latter are linked to different clogging problems among the piping system and in order to
solve such problems, different gas treatments have to be considered. High temperature reforming
right after the gasifier can also be an option although it comes itself with a certain number of
downsides.
Volatile tars in the syngas undoubtedly represents a problem at two levels (both for technical
aspects and for the obvious loss of carbon) but char and its mineral content may represent an
opportunity because of its solid form combined with potential catalytic activity. In order to
investigate this potential, this work was dedicated on using biochar produced from RDF gasification
as a fixed bed for primary syngas reforming. The steam and carbon dioxide-rich primary syngas
produced in situ in an updraft gasifier was reformed on a char pellet packed reformer that was
operated at temperatures close to 900oC. Utilization of an updraft gasifier to process RDF pellets was
far from being optimal since it produced large amounts of tars as compared to a fully optimized
industrial unit. Nevertheless, this approach was considered as a “worst case scenario” to validate
that char pellets could be used as a reforming catalyst right after a gasifier. Results showed a 95%
conversion of carbon after the reaction (both from the tars and the char) as well as an hydrogen-rich
syngas (H2/CO = 1.4) and a reduced amount of CO2 resulting from the reverse-Boudouard reaction.
The results suggested that char owing to its mineral content could be used as a cheap and disposable
catalyst to reform tars into permanent gases directly in the primary syngas, hence reducing the
necessity for more expensive gas cleaning processes.
59
COMPARISON BEHAVIOUR OF COMMERCIAL ACTIVATED CARBON AND COAL-

DERIVERED CHARS IN HOT SYNGAS CLEANING
F. PARRILLO1, D. FUENTES CANO2, G. RUOPPOLO3, U. ARENA1

1Department of Environmental, Biological and Pharmaceutical Sciences and Technologies, University
of Campania “Luigi Vanvitelli”, via A. Vivaldi 43, 81100 Caserta, Italy.

2Bioenergy Group, Chemical and Environmental Engineering Department, University of Seville,
Camino de los Descubrimientos s/n, 41092 Seville, Spain

3Combustion Research Institute, National Research Council-CNR, P.le Tecchio 80, 80125 Naples, Italy.
Keywords: Gasification, Activated char, Activated carbon, Tar removal
Abstract
This study aims at analysing and comparing the performances provided by two coal-derived chars and
a commercial activated carbon as catalysts for tar conversion. The chars have been specifically
produced in our facilities by steam activation of Colombian coal’s granulates, carried out at 900°C for
50 and 100 minutes. The activated carbon, named Norit RB4W, has been selected among those
available on the market for utilization at temperatures above 700°C.
Naphthalene has been used as tar model compound during the experimental tests. The influence of
temperature (in the range 750-900°C) on the initial naphthalene conversion and the evolution of the
naphthalene conversion with time at 750°C have been investigated. The internal structure (pore size
distribution and total surface area) of the tested chars have been measured before and after the tests.
Preliminary results show that increasing the reactor temperature, especially above 800°C, the char
activity towards naphthalene conversion is strongly enhanced. The results show the importance of the
internal structure over the activity of the catalysts. In particular, the reduction of activity is associated
to a decrease of the total specific pore surface.
60
1- INTRODUCTION
The gasification of a solid fuel (biomass, waste, coal) produces a syngas consisting of some major
compounds (CO, CO2, H2, H2O, and CH4). This fuel gas can be burned to produce electricity or further
processed to produce chemicals and liquid or gaseous fuels. The syngas generally contains a not
negligible amount of tars, a mixture of heavy hydrocarbons condensing at temperatures below 400°C,
which can strongly limit the number of possible final applications [1]. One of the most promising
options for tar removal is its adsorption on the surface of activated carbons or chars [2-8]. These
materials appear attractive for their low cost and the extraordinary physical adsorption capability,
which can be coupled with a catalytic action for the tar cracking reactions, at temperatures generally
above 700°C.
Several studies in the last years investigated the potential huge importance of this catalytic activity,
focusing in particular on the type and role of key parameters. Some authors report that tar conversion
depends on the amount and nature of the char surface available for tar cracking reaction [9]. Other
researchers attribute the high activity to the presence of oxygenated surface groups and alkali and
alkaline earth metallic (AAEM) species over the char surface [8-10].
The physico-chemical properties of activated chars mainly depend on the composition of the parent
material, activating agent and activation process temperature [11]. Steam activation produces chars
with higher mesopore volume while CO2 activation produces higher micropore volume [10-12]. It has
been also reported that the activity changes during the tar conversion [5, 9] due to the evolution of
the pore size distribution and the concentration of active groups on the surface, as consequence of a
balance between the rate of carbon conversion and that of soot deposition.
This study investigates the decomposition of naphthalene (utilised as a model tar compound) over two
coal-derived chars and one commercial activated carbon, with a special attention to the evolution of
the pore size distribution and the surface composition during the conversion of naphthalene.
2.1 Characterisation of the adsorbent materials

A commercial activated carbon (Norit RB4W) and two coal-derived chars prepared in our facilities
(Char 50 and Char 100) have been used. The Norit RB4W has been produced starting from a Chinese
coal and by using a steam-activation. The chars have been prepared by devolatilising Colombian coal
granulates at 900°C in a bubbling fluidized bed, and a successive steam activation at 900°C for 50 and
100 min, in order to obtain materials with different porosity. The obtained chars have been finally
cooled down to room temperature by a nitrogen gas stream. The adsorbents have the characteristics
reported in Table 1.
61
Table 1. Proximate and ultimate analyses of Norit RB4W, Char 50 and Char 100
Norit RB4W Char 50 Char 100

Proximate Analysis (d.b.)
Volatile matter 6.34 3.92 4.33
Fixed Carbon 84.55 90.73 89.74
Ash 9.11 5.35 5.93
Ultimate Analysis (as received)
Carbon 85.89 91.41 91.22
Hydrogen 0.21 0.40 0.48
Nitrogen 0.57 2.11 1.89
Oxygen 4.22 0.73 0.48
Ash 9.11 5.35 5.93
Porosimetric Analysis
Specific Surface Area, m2/g 958 248 388
Micropore Area, m2/g 866 116 329
Mesopore Area, m2/g 92 132 59
Scanning electron microscopy (SEM) analyses of raw and activated chars have been performed by
means of a FEI Inspect™ S50 Scanning Electron Microscope. The obtained SEM images at different
magnification scales are reported in Figure 1. The images at the figure top are those of the char
surfaces at a magnification between 70x and 130x. Norit RB4W appears to have a compact structure
while the activated chars show an increasing amount of macro-channels on their surface. The images
at the bottom of the figure indicate the modifications in the internal structure at a magnification
between 24000x and 25000x. The "apparent" smooth surface of commercial activated carbon is in
contrast with the numerous small grains of the activated chars prepared in our facilities. Anyway, also
on the apparent smooth surface of RB4W it is possible to detect a large number of mesopores, which
is in the range 2-50 nm. Finally, it is also possible to individuate a rather diffused crystalline phase on
the surface of the Norit RB4W and Char 100. This can be explained with the presence on the surface
of significant amount of minerals with potential catalytic effects [13].
Figure 1. SEM images of Norit RB4W, Char 50 and Char 100
62
2.2 Experimental apparatus and procedure

Naphthalene conversion tests have been carried out in the experimental apparatus reported in Figure
2, having four different sections: feeding system, reactor, sampling/cleaning device and gas analyser.
Further details can be found elsewhere [13].
Figure 2. Photo and scheme of the experimental apparatus used for the naphthalene conversion
tests
The gas at the exit of the cleaning section is analysed by means of a micro-GC with a TCD for the online
determination of short chain hydrocarbons (from acetylene to benzene) and molecular hydrogen. The
off-line determination of the naphthalene concentration in the isopropanol sample has been
performed by using a gas chromatography coupled with mass analysis.
Two kinds of tests have been carried out. In the first set of experiences, the initial conversion of
naphthalene is measured. A known amount of solid naphthalene is deposited within two glass
impingers (about 20 g each) immersed in oil at 65°C. The reactor, with the char bed inside, is heated
at 750°C, 800°C or 900°C in pure nitrogen stream. When system reaches the steady state, the nitrogen
flow is driven through the naphthalene saturator to the reactor (naphthalene concentration 22.5
mg/Nl). After five minutes of stabilization, naphthalene is sampled for two minutes. Then, the reactor
is purged, and cooled down with pure nitrogen. A residence time of 0.15 s in a catalyst bed of 3 cm
height is used for all the tests.
In the second kind of experiences, the evolution with time of the naphthalene conversion and the
internal structure of the char 100 and Norit RB4W have been studied. To achieve this, the same
conditions of the first set of tests are used, but the test duration varied between 5 and 310 minutes.
Various gas samples are taken during the tests to measure the naphthalene concentration in the exit
gas at different times.
63
Figure 3 presents the naphthalene conversion as measured after five minutes of test (i.e. initial
conversion), of the three different materials at different temperature for a gas residence time of 0.15
s.
100%
80%
Conversion, %
60%
40%
20%
0%
750°C 800°C 900°C
Char 50 Char 100 Norit RB4W
Figure 3. Naphthalene conversion obtained with Norit and Char-100 at 750°C, 800 °C and 900 °C for
a gas residence time of 0.15 s.
The results show that in the range 750°C-800°C the temperature does not have a significant influence
on the naphthalene conversion. A further increase of temperature improves the naphthalene
conversion up to 100%, in agreement with results obtained in a previous study [13]. The initial activity
of the Char 50 and Char 100 is slight lower than that obtained for the commercial activated carbon
whatever the reaction temperature adopted.
Figure 4 reports the evolution of the naphthalene conversion and hydrogen concentration for Norit
RB4W and Char 100 obtained at 750 °C for a gas residence time of 0.15 s.
100% 0.4
80% 0.3
Conversion, %
60%
[H2], %
0.2
40%
0.1
20%
0
0%
0 50 100 150 200 250 300 350
0 50 100 150 200 250 300 350
Time, min
Time, min
Char 100 Norit RB4W Char 100 Norit RB4W
Figure 4. Evolution of the naphthalene conversion and hydrogen production for Norit and Char 100
at 750 °C, at a gas residence time of 0.15 s.
The conversion efficiency of the commercial activated carbon is higher than that of char whatever is
the adopted length of the reaction. Moreover, a longer deactivation time is observed for the
commercial sample. According to a high naphthalene conversion, a higher amount of hydrogen is
produced using the Norit RB4W.
64
The porosimetric analysis of the utilized adsorbents compared to the fresh material are reported in
Table 2.
Table 2. Naphthalene conversion obtained on Norit and Char-100 at 750°C, 800 °C and 900 °C for a
gas residence time of 0.15 s.
Sample Time, Specific Micropore Mesopore

min Surface Area, m2/g Area, m2/g
Area,
m2/g
0 958 866 92
Norit 5 993 586 407
RB4W
307 74.8 33.6 41.2
0 248 116 132
Char 50
5 139.6 108.5 31.1
0 388 329 59
Char 100 5 357 284 73
231 16 2.6 13.4
It is possible to observe that the amount of mesopores initially present in the Norit RB4W is enhanced
in the first five minute, as confirmed by repeated tests under the same experimental conditions. A
possible explanation could be a release of residual volatile matter in the commercial activated carbon,
which is promoted in the first minutes of the test. This increase of porosity could also explain the
higher hydrogen concentrations that Norit RB4W shows in the first 30 minutes. Finally, for all the
catalysts, a progressive reduction of the specific surface area occurs up to the complete deactivation
of the sample. This can be explained by the soot deposition originated by tar cracking. Further studies
are required to assess the role of the presence of oxygenated surface groups and alkali and alkaline
earth metallic (AAEM) species since the deactivation occurs for different value of the final surface area
for the two samples.
4- CONCLUSIONS
The decomposition of naphthalene (model tar compound) under the same experimental conditions
over a chars produced in laboratory (char 50 and char 100) from coal and a commercial activated
carbon (Norit RB4W) has been investigated. The adsorbents have been characterized by ultimate,
proximate, porosimetric and SEM analyses.
The increasing of temperature, especially for values higher than 800°C, influences the activity. The
Norit RB4W shows better performances when compared to those of Char 50 and Char 100, in terms
of both higher initial conversion and slower deactivation. The activity decreases for both samples is
associated to the reduction of the amount of mesopores, even though further studies are necessary
to clarify the role of oxygenated surface groups and alkali and alkaline earth metallic (AAEM) species.
65
REFERENCES
[1] Li, C., Suzuki, K.: Tar property, analysis, reforming mechanism and model for biomass gasification,
An overview. Reew. Sust. Ener. Rev. 13, 594–604 (2009).
[2] Abu el-Rub Z., Bramer E.A., Brem G.: Experimental comparison of biomass chars with other
catalysts for tar reduction. Fuel 87, 2243-2252 (2008).
[3] Hosokai S., Norinaga K., Kimura T., Nakano M., Li C.Z., Hayashi J.I.: Reforming of volatiles from the
biomass pyrolysis over charcoal in a sequence of coke deposition and steam gasification of coke. Energ.
Fuel. 25, 5387-5393 (2011).
[4] Fuentes-Cano D., Gómez-Barea A., Nilsson S., Ollero P. Decomposition kinetics of model tar
compounds over chars with different internal structure to model hot tar removal in biomass
gasification. Chem. Eng. J. 228, 223-1233 (2013).
[5] Di Gregorio F., Parrillo F., Cammarota F., Salzano E. and Arena U. Removal of naphthalene by
activated carbons from hot gas. Chem. Eng. J. 291, 244-253 (2016).
[6] Nestler F., Burhenne L., Amtenbrink M.J., Aicher T. Catalytic decomposition of biomass tars: The
impact of wood char surface characteristics on the catalytic performance for naphthalene removal.
Fuel Process. Technol. 145, 31-41 (2016).
[7] Morgalla M., Lin L., Strand M. Decomposition of benzene using char aerosol particles dispersed in
a high-temperature filter. Energ. 118, 1345-1352 (2017).
[8] Feng D., Zhao Y., Zhang Y., Sun S., Meng S., Guo Y., Huang Y. Effects of K and Ca on reforming of
model tar compounds with pyrolysis biochars under H2O or CO2. Chem. Eng. J. 306, 422-432 (2016).
[9] Moliner R., Suelves I., Lazaro M., Moreno O. Thermocatalytic decomposition of methane over
activated carbons: influence of textural properties and surface chemistry. Int. J. Hydrogen. Energ. 30,
293-300 (2005).
[10] Wang Y., Chen X., Yang S., He X., Chen Z., Zhang S. Effect of steam concentration on char reactivity
and structure in the presence/absence of oxygen using Shengli brown coal. Fuel Process. Technol. 135,
174-179 (2015).
[11] Guizani C., Jeguirim M., Gadiou R., Escudero Sanz F.J. Salvador S. Biomass char gasification by H2O,
CO2 and their mixture: Evolution of chemical, textural and structural properties of the chars. Energ.
112, 133- 145 (2016).
[12] Rodríguez-Reinoso F., Molina-Sabio M., González M.T. The use of steam and carbon dioxide as
activating agents in the preparation of activated carbons. Carbon 33, 15-23 (1995).
[13] Cano D.F., Parrillo F., Ruoppolo G., Gomez Barea A., Arena U. The influence of the char internal
structure and composition during heterogeneous naphthalene conversion. Fuel Process. Technol. 172,
125-132 (2018).
66
PROPOSAL OF A GIS METHOD FOR DESIGNING A SPATIALLY OPTIMIZED MICRO-AD

NETWORK IN URBAN AND PERI-URBAN AREAS
P. THIRIET, T. BIOTEAU, A. TREMIER1

1 Irstea Rennes, France.
Abstract
The growing attractiveness of cities in Europe leads to an increasing dependence of urban centers on
food importations and waste exportations. The DECISIVE project (www.decisive2020.eu) founded by
European H2020 program (grant agreement N°689229) aims at developing, testing and promoting
tools to a shift from a linear and centralized paradigm of waste treatment to a local waste
management system producing valuable products for urban farming and thus closing the organic
loop. Moving to a decentralized system and to a closer valorisation loop requires an increase of
treatment units located near sources of biowaste and close to outlets for the energy (electricity and
heat) and the digestate. The spatial organization is thus a key element to ensure an effective
operation of the whole system.
A method, based on GIS tools, has been developed to tackle two main challenges: to get very
detailed information for large areas such as municipality communities and to find the optimal size
and location for a micro-AD network. The approach is organized in 2 steps: 1) a large-scale spatial
inventory of waste sources, products outlets and potential site locations and 2) an in-depth
optimization of location for the micro-AD network.
In the first step, the inventory focused on the 3 biowaste sources targeted by the project: household,
garden, and catering waste. Some methods are already proposed to estimate such quantities but
adapted to a larger scale of analysis. So, we refined methods to fit our specific scale. For example,
the lawn cutting quantities are derived from an object-based image analysis method, apply on aerial
images completed with Lidar data (giving height) to improve the distinction between grass and trees.
A multi-criteria evaluation is also used to select all potential sites for micro AD that comply with
environmental and urban planning rules and proximity criteria.
In the second step, the optimal set of micro-AD units was located among the previous selected sites
using an innovative method based on two main approaches: a network analysis and a linear
programming optimization. First, an objective function has been built as a linear combination of the
network distances between waste sources to AD units and digestate outlets, which will be minimized
during the process. This new method ensures to select the system that minimizes simultaneously the
overall distances. Second, a set of constraints have been defined to characterize the suitability
criteria related to the whole waste management chain. For the first analysis, the criteria include in
particular the total quantity of waste to retrieve, a realistic limit of distances between AD and
sources, a range of size for the AD and a maximal quantity of digestate spreadable in outlets. The
model has been developed with R and solved with Gurobi Optimizer.
The optimization step is currently tested on the study case of Grand Lyon (France) and the
preliminary results already demonstrate the strength of the method. The tool is modular and
adaptable to new criteria and thus allows testing easily different scenarios. Therefore, the
optimization of the network can be refined according to new technical input in close cooperation
with project partners specialized in process engineering.
67
ENVIRONMENTAL AND SOCIO-ECONOMIC IMPACT ASSESSMENT OF THE

PRODUCTION OF PERENNIAL CROPS WHEN IRRIGATED WITH TREATED
WASTEWATERS
J. COSTA1,2, B. BARBOSA1,3, A. L. FERNANDO1,*

1 MeTriCs, FCT-Universidade NOVA de Lisboa, Caparica, Portugal.
2 Instituto Superior de Educação e Ciências, Lisboa, Portugal.
3 Universidade de São Paulo, São Paulo, Brazil.
Keywords: Wastewater irrigation, perennial grasses, environmental sustainability, socio-economic

sustainability.
Abstract
The production of energy crops has been presented as a promising alternative to partially replace
fossil fuels. Perennial crops are promising because of their high productivity, resistance to low water
regimes, and pests. Yet, the need to irrigate biomass during cultivation can cause the depletion of
water resources, an environmental constraint in the Mediterranean region, due to water scarcity. In
this context, the aim of this work was to evaluate the environmental and socio-economic impact of
the production of perennial crops, when irrigated with wastewaters, in order to integrate them into
a sustainable agriculture development. Studies conducted at FCT-Universidade Nova de Lisboa
indicate that perennials show potential to simultaneously deliver high yields, restore soil properties
and promote water quality improvement under wastewater irrigation. To determinate the
environmental and socio-economic sustainability, different categories were studied: energy savings,
reduction of greenhouse gases, carbon sequestration, emissions to soil, air and water, impact on
water and mineral resources, costs savings, employment potential creation and
consumers/producers acceptance. Overall results suggest that reuse of wastewater on the
production of perennial crops have an advantage over traditional irrigation, namely regarding use of
water and mineral resources and costs savings. No effects were observed in terms of energy savings,
reduction of greenhouse gases, or carbon sequestration. But the reuse of wastewater still involves
much controversy, and not always have social acceptance. In the study, several technical and
economic barriers were also addressed, namely those related with the quantity and quality of
biomass produced.
68
1- INTRODUCTION
The irrigation of energy crops with treated wastewaters in water-scarce regions is not new. This
approach was developed as an additional stage to remove the wastewater nutrient loads prior to its
disposal in the environment and also to save water resources in regions with low water availability.
Because agriculture is a major consumer of water worldwide [1] the same technique is also used to
irrigate drought tolerant crops that are very efficient in the removal of the constituents present in
treated wastewaters. This can promote the creation of crop rotation systems more resilient, adding
economic value and social benefits to water-scarce regions like the Mediterranean. The production
of drought tolerance crops must be studied and evaluated in terms of environmental, economic and
social impacts, in order to integrate them into a sustainable agriculture development. The reuse of
treated wastewaters in their irrigation could be a strategy to minimize freshwater abstraction, field
fertilization and also energy consumption in the treatment of these types of water. However, treated
wastewater reuse for crops irrigation (even when used to irrigate non-food crops), are involved in
much controversy and not always have social acceptance. Nevertheless, considering the high
consumption of energy for treating wastewater [1], and also the quantity of treated wastewater
daily available, and its high nutrient loads, research focus on more sustainable and cheapest
methods of depuration of those waters is mandatory, especially in water-scarce regions.
Furthermore, this source of water could constitute an economic valuable resource for these regions
and not necessarily a negative externality.
From all the crops identified as suitable for combining high biomass production with wastewater
treatment, Arundo donax and Miscanthus spp. are highlighted by several authors as two of the most
promising cultures because they are both perennial and well adapted to water-scarce regions,
presenting higher soil coverage and high resistant to diseases [2]. Considering Arundo donax and
Miscanthus x giganteus ability for wastewater phytoremediation and nutrients removal, the aim of
this work was to evaluate the environmental and socio-economic impact of its production when
irrigated with wastewaters, in order to integrate them into a sustainable agriculture development in
the Mediterranean region.

In this study, it was assumed that only stems were used as solid fuel. Leaves must be left in the field
as they produce large amounts of ash, contributing to field fertilization and carbon sequestration.
To estimate the environmental and socio-economic impact on the production of Arundo donax and
Miscanthus x giganteus irrigated with wastewaters, results obtained in the work of Costa et al. [3]
and Lino et al. [4] were the basis for the assessment. In this work, both crops, in pots, were irrigated
with three water regimes: 950 mm, 475 mm and 238 mm of treated wastewater. Controls were
irrigated with tap water and the same water regimes were used.
For the environmental impact assessment, the study focused on several categories, according to the
methodology developed and applied by Biewinga and van der Bijl [5], and Fernando et al. [6]. Energy
savings were calculated by subtracting the energy input to the potential energy produced by the
combustion of the biomass stems being produced. Energy balance results obtained from the work of
Cherubini et al. [7] were used to estimate energy savings. Carbon sequestration (Mg C/ha) was
calculated assuming a carbon content of 48.7% for the whole plant [8] and the productivities in pilot
fields in Italy [9]. Reduction of greenhouse gases emissions was estimated based on the work of
Cherubini et al. [7]. Economic analysis was based in the work of Soldatos et al. [10]. Irrigation costs
were assumed to be the same in the control and in wastewater irrigation.
69

3.1- Crop productivity
Perennial crops yields were determined based on the results of Costa et al. [3] and Lino et al. [4].
Comparisons were made with 950 mm control. Results are presented in Figure 1.
Figure 1: Yield of perennial grasses irrigated with wastewaters compared with the control (%).
According to the results in Figure 1, it is possible to observe that, for the crops in study, there are no
statistical significant differences in yields between wastewater irrigation (WW) and tap water
irrigation (Control) but yields are directly proportional to different water regimes, i.e., the lower the
water provided the lower the yields.
3.2- Energy balance

The energy balance (GJ/ha) estimated for perennial crops irrigated with treated wastewaters is
presented in Figure 2. Calculations were made assuming the combustion of stems to produce heat
and the use of stems to produce electricity by cogeneration. According to these scenarios, it was
estimated that crops obtained through wastewater irrigation can save the same amount of energy
produced by crops irrigated with fresh water. Reduced energy savings are obtained when yields
obtained are lower due to lower irrigation regimes provided, but still the overall energy balance is
positive, indicating that fossil energy can be saved.
3.3- Carbon sequestration

Estimated carbon sequestration (Mg C/ha) is presented in Figure 3. For the estimation of this
parameter it was only considered the carbon sequestered by the leaves. This fraction will remain in
the soil, increasing organic matter content and improving its quality. The carbon sequestrated by the
rhizomes and roots was not considered, meaning that the results presented are underestimated.
70
Figure 2: Estimated energy balance (GJ/ha) for perennials production and use.
12
10
8
Carbon
sequestration Control
6
(Mg (C)/
/(ha.year)) WW
4
0
950mm 475mm 238mm
Figure 3: Carbon sequestration (Mg C/(ha.year)) by leaves of perennial grasses and by water regime.
Carbon sequestration in leaves, roots and rhizomes may also improve soil structure and soil aeration,
factors that contribute to reduce soil erosion and to control desertification. Carbon sequestered by
the stems was not considered because it will be released by combustion for energy production.
Carbon sequestration results from Figure 3 are coincident with crops yields presented in Figure 1,
which means the higher the yield, more carbon can be sequestered and stored in the soil. No
significant differences were observed between fields irrigated with wastewaters and fresh waters,
and the lower the amount of water provided the lower the yields and the carbon sequestered.
3.4- Emissions to soil, air and water

Reduction of greenhouse gases emissions (GHG) due to both crops production and use is presented
in Figure 4. According to the estimated results, the use of stems as solid fuel is relevant to reduce
GHG emissions as the released of CO2 emissions is counterbalanced by the CO2 sequestered by
71
biomass in the photosynthetic process. Higher water regimes (and consequently higher yields)
represent higher CO2 savings. No differences were observed due to irrigation with wastewaters.
Figure 4: Estimated reduction of greenhouse gases emissions (Mg CO 2eq saved/ha per year) due to perennial grasses production and
use.
Nitrogen applied to the soil can contribute to several environmental problems, which includes
contribution to acidification, due to the volatilization of ammonia (NH3) and N oxides (NOx),
contribution to greenhouse effect and ozone depletion, due to denitrification to nitrous oxide (N 2O)
and ground and surface waters eutrophication, due to ammonium (NH 4+) and nitrate (NO3-) leaching
and runoff [6]. Excess of nitrate in drinking water can also be a threat to human health. NO x are also
emitted during the combustion of the stems [5] (Figure 5).
Figure 5: Estimated emissions to air, soil and water derived from N fertilizer and water/wastewater application and from biomass
combustion.
72
Compared to control, wastewater irrigation presents higher N emissions due to higher N application
(derived from a wastewater rich in ammonium and nitrate ions). The combustion of solid fuel also
presents higher N emissions. This is because higher nitrogen is accumulated in the biomass due to
the N richness of the wastewaters. These facts represent an environmental constraint for the
irrigation of perennial crop fields with treated wastewaters. Yet, using wastewater in crops irrigation
can decrease the amount of N-based nutrients artificially added to the soil, and it contributes to the
pollutant load reduction once the soil-biomass system represents a depuration system. The highest
share of N emissions are due to the NH4 and NO3 leaching and runoff from N application. N2O
emissions due to N application are not significant and represent the lowest share in N emissions.
Lowering the amount of water used in the irrigation also reduces the nitrogen emissions pollutant
load to air, soil and water.
3.5- Other environmental considerations

Irrigation with wastewaters enables the recycle of nutrients (N, P and K) from this water source,
minimize fertilizers applications in soils, reduces the amount of energy and money spent in their
extraction from mineral ore reserves and represent also a way to economize freshwater for more
noble uses.
According to Costa et al. [3] and Lino et al. [4], 950 mm of freshwater resources can be saved if
wastewaters are used in irrigation, contributing to recycling wastewater and its load. This practice is
important also for combating the imbalance between the amount of water that falls by precipitation
and losses by evapotranspiration (especially in water-scarce regions). It is also possible to save
mineral resources, namely 230 kg P2O5/ha and 170 kg K2O/ha [3], if no PK fertilization is added. Use
of wastewater minimizes the energy utilized in the extraction, production and transportation of
mineral ores as well as the depletion of those mineral resources.
3.6- Economic and social considerations

Profits per ha per year of perennial grasses production and use are presented in Figure 6. Irrigation
with wastewaters is more valuable than control in all water regimes if no NPK fertilizers are added in
fields irrigated with wastewaters. In fact, wastewater irrigation at 950 mm and at 450 mm is much
more interesting than freshwater irrigation because it provides a higher and positive income.
Concerning the use of only 238mm of water, the lower yields obtained do not allow to provide a
positive income. Moreover, the use of wastewaters in the irrigation of energy crops may represent a
viable environmental and economic opportunity as a tertiary treatment.
Energy crops Irrigation with wastewaters can also provide many social benefits to human
communities. The reuse of wastewater for agriculture irrigation is still involved in much controversy,
and not always have social acceptance, but simultaneously this approach involves new
opportunities. Use of wastewaters in the irrigation of non-food crops, contributes to recycling of
these liquid wastes, returning them back to environmental systems in a non-harmful way, and thus
reducing human and environment exposure to pollutants. Also, the production of biomass for energy
or for other applications, when irrigated with wastewaters, reduces the emissions of several
pollutants and thus the human exposure to their effects on health and also the environment
exposure.
73
Figure 6: Perennial grasses production and use profit (€/ha, per year) under different types of irrigation. without NPK*: control receives
NPK but trials irrigated with wastewaters do not receive NPK.
Energy crops production and use presents also a positive gain in terms of employment in small and
medium-size enterprises and on rural areas. The positive influence on employment is also due to the
contribution towards avoiding a rural exodus and to the contribution towards a more balanced rural
development. Labour requirements per hectare for the production, in the farm, of giant reed is
similar to the one showed for Miscanthus (9 hours per hectare per year) [5]. Irrigation with
wastewaters doesn’t represent an increase in agricultural activities but may increase indirect
employment, mainly in transport or in the conversion sector when productivities higher than control
can be obtained. But, labour requirements for conversion do not vary much, and so, no additional
employment is expected with the yield increment.
4- CONCLUSIONS
Irrigation of perennial grasses with wastewaters could be a relevant tool to reduce water and
mineral resources consumption and the associated environmental burdens arising from the
combustion of fossil fuels. At the same time, it could constitute an opportunity to develop rural
areas. This approach may display other environmental benefits, e.g. fossil energy savings, carbon
sequestration, and it represent a viable economic opportunity and provide social benefits in
Mediterranean regions. Combining wastewater irrigation with biomass production may also
contribute to improve the effluents quality, with environmental, economic and social benefits.
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[4] Lino, J., Fernando, A.L., Barbosa, B., Boléo, S., Costa, J., Duarte, M.P., Mendes, B.: Phytoremediation of Cd and Ni
Contaminated Wastewaters by Miscanthus. In: Hoffmann C, Baxter D, Maniatis K, Grassi A, Helm P (eds.),
Proceedings of the 22th European Biomass Conference and Exhibition, Setting the course for a Biobased Economy,
23 - 26 June 2014, Hamburg, Germany, ETA-Renewable Energies, pp 303 – 307 (2014).
[5] Biewinga, E., van der Bijl, G.: Sustainability of energy crops in Europe. A methodology developed and applied, Centre
for Agriculture and Environment, Utrecht, February, CLM 234 (1996).
[6] Fernando, A.L., Duarte, M.P., Almeida, J., Boléo, S., Mendes, B.: Environmental impact assessment of energy crops
cultivation in Europe, Biofuels, Bioproducts and Biorefining, 4, 594-604 (2010).
[7] Cherubini, F., Bird, N.D., Cowie, A., Jungmeier, G., Schlamadinger, B., Woess-Gallasch, S.: Energy - and greenhouse
gas - based LCA of biofuel and bioenergy systems: Key issues, ranges and recommendations. Resources,
Conservation and Recycling, 53, 434-447 (2009).
[8] Vassilev, S.V., Baxter, D., Andersen, L.K., Vassileva, C.G.: An overview of the chemical composition of biomass. Fuel,
89, 913-933 (2010).
[9] Mantineo, M., D’Agosta, G.M., Copani, V., Patanè, C., Cosentino, S.L.: Biomass yield and energy balance of three
perennial crops for energy use in the semi-arid Mediterranean environment. Field Crops Research, 114, 204–213
(2009).
[10] Soldatos, P., Lychnaras, V., Asimakis, D.: Cost Analysis & Economic Evaluation of Future Crops in Europe. 4F – Future
Crops for Food, Feed, Fibre & Fuel. FP7-KBBE-2007-1. Agricultural University of Athens, Laboratory of Agribusiness
Management. Athens (2009).
ACKNOWLEDGEMENTS
This work was supported by the European Union (MAGIC - Marginal lands for Growing Industrial
Crops: Turning a burden into an opportunity, Project Number: 727698-2, H2020-RUR-2016-2 and
PANACEA - A thematic network to design the penetration PAth of Non-food Agricultural Crops into
European Agriculture, Project Number: 773501, H2020-RUR-2017-1)
75
THE 3T METHOD AS AN ASSESSMENT TOOL FOR COMPARING DIFFERENT WASTE

MANAGEMENT STRATEGIES
S. VAKALIS 1, 2, K. MOUSTAKAS 2, M. LOIZIDOU 2

1 Free University of Bolzano, Faculty of Science and Technology, Piazza Università 5 – 39100 Bolzano,
Italy.
2 National Technical University of Athens, School of Chemical Engineering, Unit of Environmental
Science & Technology, 9 Iroon Polytechniou Str., GR-15780 Athens, Greece.
Abstract
Historically, all the “Waste Framework Directives” that have been issued by the European Commission,
separate the waste management strategies into Recovery Operations and Disposal Operations. The
Directive 2008/98/EU of the European parliament and of the council of 19 November 2008 on waste
and repealing certain Directives, defines the Recovery Operations on ANNEX I and the Disposal
Operations on ANEX II [1]. Waste-to-energy technologies have the inherent problem that they do not
belong entirely on the one category or the other. On one hand, waste is used principally as a fuel for
energy generation and thus they belong to category 1 of the Recovery Operations, i.e. R 1. On the
other hand, the residues of the treatment are landfilled on land and thus they belong to category 10
of the Disposal Operations, i.e. D 10. Therefore, there is not a clear framework for comparing waste-
to-energy technologies on an integrated basis. In order to address this issue Vakalis et al. [2]
introduced the 3T method which combines in a radar graph the following efficiencies: CHP, physical
exergy, chemical exergy of the products and chemical exergy of the metals. The overall efficiency can
be assessed by calculating the area of the developed trapezoid and this generalized solution is defined
as “Trapezoidal Thermodynamic Technique” or with the abbreviation “3T”. Thus, different waste-to-
energy technologies, like combustion or gasification, can now be directly compared.
What became evident from the application of this method is that except from the specialized case of
waste-to-energy facilities, the 3T method can be used to compare all the recovery waste management
strategies including complex facilities like biorefineries. The present study aims to assess the feasibility
of evaluating and comparing different waste management scenarios by means of the 3T method. The
scope of the study is to create a single efficiency assessment methodology that will reliably compare
waste management strategies that otherwise can’t be compared directly with each other, e.g.
landfilling and combustion.
References
[1] European Commission. (2008). Directive 2008/98/EC of the European Parliament and of the Council of 19 November
2008 on waste and repealing certain Directives. Brussels, Belgium.
[2] S. Vakalis, K. Moustakas, M. Loizidou. Assessing the 3T method as a replacement to R1 formula for measuring the
efficiency of waste-to-energy plants. 5th International Conference on Sustainable Solid Waste Management, 21st –24h
June 2017, Athens.
76
COMPARATIVE ASSESSMENT OF GLOBAL WARMING AND WATER FOOTPRINT

IMPACTS OF POLYBUTYLENE SUCCINATE (PBS) FROM CASSAVA AND SUGARCANE
P. PHAIROH1, M. CHARUMRAM1, T. LEEJARKPAI2, U. SUWANMANEE1,*

1 Department of Chemical Engineering, Faculty of Engineering, Srinakharinwirot University,
Nakornnayok 26120, Thailand

2 National Metal and Materials Technology Center, National Science and Technology Development
Agency, Pathumthani 12120, Thailand.
Corresponding author*, e-mail: unchalee@g.swu.ac.th
Keywords: polybutylene succinate, cassava, sugarcane, global warming impact, water footprint
impact.
Abstract
The aim of this research work is to assess water footprint (WF), water deprivation potential (WDP)
and global warming potential (GWP) impacts of two types of bio-based plastics, namely polybutylene
succinate from sugarcane (sugarcane-based PBS) and cassava (cassava-based PBS). LCA is an
important tool to identify the potential environmental load during the product life cycle and is
performed according to the ISO 14040: 2006. The evaluations in the first studies are based on based
on the water footprint network (WFN) and international standards ISO 14046 (2014) which are
essential to assess water footprint (WF) and water deprivation potential of PBS pellet production
chains. The functional unit of studied materials was set as 1 kg of PBS pellet. This study has shown
significant results that WF, WDP and GWP impacts of sugarcane-based PBS are lower than those
impacts of cassava-based PBS in all respects. The WF and WDP impacts of sugarcane-based PBS are
11.42 m3 H2O and 0.117 m3 H2O equivalent which exhibit 3.78 m3 H2O and 0.113 m3 H2O equivalent
lower than cassava-based PBS, respectively. Meanwhile, GWP impact of sugarcane-based PBS is 3.81
kg CO2 equivalent which is 0.579 kg CO2 equivalent lower than cassava-based PBS. The main
contributions of sugarcane-based PBS to dramatic effect of WF and WDP occurred during the stages
of molasses transportation and sugarcane plantation. The high GWP impact during the productions
of molasses and cassava starch contributes 84.15% and 78.62% to the total impact of sugarcane and
cassava-based PBS productions, respectively. This assessment can also be used in product
development and strategy plans for the plastics industry by evaluating the environmental impacts of
a product throughout its cradle-to-production gate life cycle.
77
1- INTRODUCTION
Currently, freshwater scarcity is recognized as a major environmental concern. Water covers about
70% of the Earth’s surface. Only 0.3% of water is found in rivers and streams, while almost 70% of
freshwater withdrawals are used for irrigation system [1, 2]. UNESCO estimates the world could
encounter a 40% global water deficit by 2030. Because global freshwater demand is estimated to
increase moderately by 55% due to high growing demands from manufacturing, thermal electricity,
and domestic use [2]. A total of 70% of existing global freshwater is withdrawn in agriculture
(irrigation, livestock watering and cleaning, aquaculture), 12% for municipal, and 19% for industrial
[3]. The global water footprint (WF) of agriculture is 8,360 km3 yrоϭ [4]. The use of fertilizers can lead
to pollutions to waterways (river and lake) and ground water. In Thailand, agricultural activities were
accounted for 65% of total amount of water requirement because of the high production of
agricultural commodities [5]. Between 2017 and 2022, the global bioplastics production is predicted
to grow by 1.74% per year reaching between 2.05 million t and 2.44 million t in 2022. This represents
a 19.02% increase compared to production in 2017 [6]. In the same year, a distance second behind
bio-based PET was bio-based PE, which was followed by starch-blends, polylactic acid (PLA),
poly(butylene adipate-co-terephthalate) (PBAT), polybutylene succinate (PBS) and
polyhydroxyalkanoates (PHA). PBS is promising biolastics because of its bio-based and
biodegradability properties and produced from 1,4-butanediol (1,4-BDO) and succinic acid. It was
estimated to grow and yield profit because of the availability and lower cost of bio-based succinic
acid. Three main raw materials — corn, cassava, and sugar — are now being used for bio-plastics
production chains. Many studies employed the WF and carbon footprint (CF) concepts to assess the
water use and greenhouse gas (GHG) emissions from bio-based (crops) productions. For example, in
a study by charoennet et al. (2018) on the WF impact and global warming potential (GWP) impact,
three types of bio-based boxes, i.e., polylactic acid (PLA) from sugarcane, PLA from sugarcane-starch
blends and polybutylene succinate (PBS) from sugarcane and corn, and petroleum-based of
polystyrene (PS), were considered. Their results indicated that PBS shows the lowest WF at 0.38 m3
H2O of all bio-based boxes and presents the second lowest WF impact at 0.008 m3 H2O equivalent
and the lowest GWP impact at -0.06 kg CO2 equivalent [7]. Leejarkpai et al. (2016) evaluated and
benchmarked the GWP impact and energy used of bio-based (PLA) against petroleum-based of PS
and PET for single used boxes. The results show that PS in landfill revealed the lowest GWP impact at
0.152 kg CO2 equivalent. Whereas, PLA in compost scenario exhibited the second lowest GWP
impacts at 0.0514 kg CO2 equivalent [8]. Therefore, the aim of this study is to assess the life-cycle
water consumption and GWP impact of sugarcane and cassava -based PBS pellet productions. In this
present work, 1 - year data has been considered to cover the economic life span of sugarcane and
cassava for evaluation WF and water deprivation values of PBS.
2. MATERIALS AND METHODS

Life Cycle Assessment (LCA) methodology used in this present work is according to the ISO 14040
(2006) [9] and 14046 (2006) [10] and 14067 (2013) [11] standards. Environmrntal impacts in the first
study is evaluated based on the water footprint network (WFN) and international standards ISO
14046 (2014) for assessing water footprint (WF) and water deprivation potential (WDP) of PBS pellet
production chains. The reference crop ETo represented the Penman-Monteith evaporation and is
estimated on the basis of the monthly climatic ĚĂƚĂŽĨϯϬǇĞĂƌƐ;ϭϵϴϲоϮϬϭϱͿ͘The consomptive water
only refers to direct water use. The WF over the complete production and supply chain (WFproc) can
be calculated by,
78
WFproc = Water Consomption (WC) + Water Pollution (WP) (1)
WC = WFdirect,green + WFdirect,blue +WFindirect,green + WFindirect,blue (2)
WP = WFdirect,grey + WFdirect,grey (3)
In the the second study, the carbon footprint (CF) is evaluated according to the life cycle assessment
concept and ISO/TS 14067: 2013 (ISO, 2013) and IPCC (2007) [12].
1.1. Goal and scope definition

The goal of this study is to assess the WF, water deprivation potential, GWP impacts of PBS produced
from sugarcane and cassava in Thailand. The scope of the study for the production of 1 kg PBS
includes plantation, processing, transportation, and PBS conversion (see Figure 1).
Figure 1: Sugarcane and cassava-based PBS production chains.
1.2. Life cycle inventory analysis

The data of cassava plantation stage were collected as primary data at the actual plantation,
covering 18 ha of arable land in Kanchanaburi province, Thailand. Information of cassava-based
starch production was available from primary data in Nakornratchasima province. The production of
cassava starch-based sugar is separated into two main stages: the processing of starch into slurry by
gelatinization and liquefaction and conversion of starch into glucose by sacchrification. The average
transport distance from cassava transportation of plantation to the plants of cassava starch
production in Kanchanaburi province is 109 km. The average delivery distance of starch from
Kanchanaburi province to PBS production is 238 km. The LCI data of sugarcane-based PBS production
79
were supplemented by charoennet et al. (2018) [7]. The secondary data used in this study were
available from literature, Ecoinvent database and Thai national database.

3.1 WF of corps (sugarcane and cassava)
The comparative results from different show that WF of sugarcane is estimated to be 0.34 m3 per kg,
which is 57% lower than WF of cassava (see Table 1 and 2). The WF per kg sugarcane is lower
because the sugarcane yield in this work (11,050 kg per rai) is higher than cassava yield (3,290 kg per
rai). The results showed that water requirements of sugarcane and cassava roots are evaluated as
2,332.5 mm and 1,591.65 mm per a growing period. The WF of sugarcane is 0.34m3 per kg, with
green water contribution of 27.3% and a blue water contribution of 72.7%. The WF of cassava is 0.79
m3 per kg, with green water contribution of 47.9%, a blue water contribution of 50.7% and a grey
contribution of 1.4%. Geographic Information System was used to specify the location where fresh
water consumption occurs. The irrigation water requirement (direct blue water) was accounted in
this study because there are irrigating water systems available in sugarcane and cassava plantation
areas in Kanchanaburi province. The effective rainfall value obtained from this study represented
that sugarcane and cassava can grow with irrigation supply. Therefore, the value obtained is
different from Pongpinyopap and Mungcharoen (2014) [13] because their results reported that the
green WF is found to be 99% of total water use for cassava.
Crop water requirement (CWR) of sugarcane root WF of sugarcane

- Effective rainfall 2,332.45 mm - Direct green WF 0.09284 m3 per kg
- Irrigation water requirement 0 mm - Direct blue WF 0.24488 m3 per kg
- Yield 11,050 kg per rai - Direct grey WF 5.00u10-6 m3 per kg
- Indirect green WF 0 m3 per kg
- Indirect blue WF 0.006065 m3 per kg
- Indirect grey WF 0 m3 per kg
Table 1: Crop water, irrigated water requirements, and WF for sugarcane using Geographic Information System (GIS) in Thailand.
Crop water requirement (CWR) of cassava root WF of cassava

- Effective rainfall 1,591.65 mm - Direct green WF 0.37847 m3 per kg
- Irrigation water requirement 0 mm - Direct blue WF 0.39371 m3 per kg
- Yield 3,290 kg per rai - Direct grey WF 0.01126 m3 per kg
- Indirect green WF 0 m3 per kg
- Indirect blue WF 6.72u10-6 m3 per kg
- Indirect grey WF 0 m3 per kg
Table 2: Crop water, irrigated water requirements, and WF for cassava using Geographic Information System (GIS) in Thailand.
80
3.2 WF of sugarcane-based and cassava-based PBS

Figure 2 presents the comparisons between WF of sugarcane-based and that of cassava-based PBS.
The WF of a sugarcane-based PBS is 11.42 m3 H2O, which is 3.78 m3 H2O lower than that of cassava-
based PBS. The water supply in the sugarcane-based PBS production chain is 11.42 m3 H2O per 1 kg
PBS, with the green, blue, and grey water contribution of 3.21, 83.15, and 13.64%, respectively. The
blue WF of sugarcane-based PBS is 9.49 m3 H2O per kg, which present indirect and direct blue water
contributions of 83.6% and 16.4%, respectively. From the results, the most important contributions
from sugarcane-based PBS are the sugarcane plantation and molasse transportation, representing
30.56% and 50.71% of the total WF, respectively (see Figure 3). Similarly, the WF of cassava-based
PBS is 15.29 m3 H2O per 1 kg PBS, with a green water contribution of 18.65%, a blue water
contribution of 81.27%, and a grey water contribution of 0.07%. The blue WF of cassava-based PBS is
12.43 m3 H2O per kg, which displays indirect blue water contribution of 83.6% and direct blue water
contribution of 16.4%. The WF of cassava-based PBS mainly came from cassava plantation (38.46%)
and cassava transportation (26.85%) (see Figure 4).
Figure 2: WF of sugarcane and cassava-based PBS.
81
3
Figure 3: WF of sugarcane-based PBS (m H2O per kg PBS).
3
Figure 4: WF of cassava-based PBS (m H2O per kg PBS).
3.3 Water deprivation potential sugarcane-based and cassava-based PBS

The comparisons of water deprivation potential between sugarcane-based and cassava-based PBS
are revealed in Figure 5. The WSI values of water consumption for each place are summarized in
82
Table 2. The water deprivation of a sugarcane-based PBS is 0.117 m3 H2O equivalent, which is 49.1%
lower than the value of cassava-based PBS. The main contributions of sugarcane-based PBS at
molasses transportation and sugarcane plantation stages result in a dramatic effect on water
deprivation potential at 74% and 12% of total impact, respectively (see Figure 6). The transportation
of molasses in high quantity (2.59 kg) and in long distance (335 km) between molasses and PBS pellet
plants caused an increasing level of environmental impact during the sugarcane-based PBS
transportation stage. From the results, succinic acid production, cassava transportation, and cassava
plantation stages are the main contributions to the total impact of cassava-based PBS production,
representing 27.7%, 26% and 22%, respectively. Note that the ratios of direct blue WF and indirect
blue WF impacts are 4.8о6.1% and 93о95% for two types of PBS study. The main contribution of
indirect blue WF impacts in sugarcane-based PBS is from molasses transportation stage. The high
amonts of chemical used during cassava plantation and succinic acid productions, and the high
quantity of energy used in long distances between cassava root to PBS pellet plants stages are the
cause of the total impacts, accounting for 76.9% of the total indirect blue WF.
Productions/Activities Energy and chemicals used Region/Related WSI

watershed
Sugarcane and - Mae Klong 0.018a
cassava plantations Diesel East-Coast Gulf 0.015a
Fertilizers and pesticide China 0.478b
Starch production Sulphur, water, and heavy oil East-Coast Gulf 0.015a
Electricity Pasak 0.050a
Sugar production Water and steam East-Coast Gulf 0.015a
Electricity Bangpakong 0.026a
Ca(OH)2 Pasak 0.050a
Bio-ethanol Electricity Bangpakong 0.026a
Water and steam East-Coast Gulf 0.015a
NH4SO3 China 0.478b
PBS pellet production Natural gas, NaCl, water, and CO2 East-Coast Gulf 0.015a
Electricity Bangpakong 0.026a
Transportation Diesel East-Coast Gulf 0.015a
Table 2: Water Stress Index values used in LCA studies.

a b
Gheewala et al. (2014) [14] and Pfister et al. (2009) [15]
3.4 Global warming potential (GWP) impact of sugarcane-based and cassava-based PBS
The GWP impact of sugarcane and cassava-based PBS is shown in Figure 8. The total GWP impact of
sugarcane-based PBS is 3.81 kg CO2 equivalent, which is 0.579 kg CO2 equivalent lower than the
cassava-based PBS as as the high GHG emissions during the productions of molasses and cassava
starch contribute 84.15% and 78.62% to the total impact of sugarcane-based and cassava-based PBS,
respectively. The primary source of the total impact during molasses production is from the usage of
steam and electricity, which caused 90% and 7.7% of the total impact, respectively. Bio-based PBS
also leads to environmental benefit by decreasing the GWP impact by 0.37-1.3% because of the CO2
83
absorption from the photosynthesis reaction during plantation stages of sugarcane (3.95 kg) and
cassava (7.54 kg).
3
Figure 5: Water deprivation potential of sugarcane and cassava-based PBS (m H2O eq. per kg PBS).
3
Figure 6: Water deprivation potential of sugarcane-based PBS (m H2O eq. per kg PBS).
84
3
Figure 7: Water deprivation potential of cassava-based PBS (m H2O eq. per kg PBS).
Figure 8: GWP impact of sugarcane and cassava-based PBS (kg CO2 eq. per kg PBS).
85
4. CONCLUSIONS
The comparative data suggested that WF and GWP impact scores of sugarcane-based PBS are overall
49.1% and 13.2% lower than the scores of cassava-based PBS because of a high process yield of
sugarcane and intermediate products in the PBS production chains. From the results, molasses
transportation and sugarcane plantation stages lead to the most significant impacts on the total WF
and WF impact of sugarcane-based PBS production. The main contributions from molasses and
cassava starch productions stages result in GWP impact for sugarcane and cassava-based PBS,
respectively.
ACKNOWLEDGEMENT
This work has been supported by the Thai Research Fund (MRG6180218), Faculty of Engineering,
Srinakharinwirot University.
REFERENCES
[1] USGS.: Available: http://water.usgs.gov/edu/watercycle.html. (2016)
[2] UN Water.: The united national world water development report 2016. Available: http://unesdoc.unesco.org. (2016)
[3] FAO.: Water use. Available: http://www.fao.org/nr/water/aquastat/water_use/index.stm (2016)
[4] Hoekstra, A., Mekonnen, M.: The water footprint of humanity. Proc. Natl. Acad. Sci. USA1093232–7. (2012)
[5] RID, Royal Irrigation Department. : Annual Report 2014. Ministry of Agriculture and Cooperative. Available:
http://www.rid.go.th/ (2015)
[6] European Bioplastic.: Bioplastics market data 2017.
Available: http://docs.european-bioplastics.org/publications/market_data/2017/. (2017)
[7] Leejarkpai, T., Mungcharoen, T., Suwanmanee, U.: Comparative assessment of global warming impact and eco-
efficiency of PS (polystyrene), PET (polyethylene terphthalate) and PLA (polylactic acid) box. J. Clean. Prod. 125,
95107. (2016)
[8] Cheroennet, N., Pongpinyopap, S., Leejarkpai, T., Suwanmanee, U.: A trade-off between carbon and water impacts in
bio-based box production chains in Thailand: A case study of PS, PLAS, PLAS/starch and PBS. J. Clean. Prod. 167,
9871001. (2017)
[9] ISO 14040.: Environmental management о >ŝĨĞĐǇĐůĞĂƐƐĞƐƐŵĞŶƚоWƌŝŶĐŝƉůĞƐĂŶĚĨƌĂŵĞǁŽƌŬ͕/ŶƚĞƌŶĂƚŝŽŶĂů
Organization for Standardization. Geneva, Switzerland. (2006)
[10] ISO 14046.: Environmental management water footprint principles, requirements and guidelines. (2014)
[11] ISO 14067.: Greenhouse gasCarbon footprint of productsRequirements and guidelines for quantification and
communication. International Organization for Standardization. (2013)
[12] IPCC.: Fourth assessment report: climate change 2007 (AR4). Geneva, Switzerland. (2007)
[13] Pongpinyopap, S., Mungcharoen, T. : Comparative study of green water footprint estimation method for Thailand : a
case study of cassava-based ethanol. Environ. Nat. Resour. J. 75, 4152. (2014)
[14] Gheewala, S.H., Silalertruksa, T., Nilsalab, P., Mungkung, R., Perret, S.R., Chaiyawannakarn, N. : Water footprint and
impact of water consumption for food, feed, fuel crops production in Thailand. Water. 6, 16981718 (2014)
[15] Pfister, S., Koehler, A., Hellweg, S.: Assessing the environmental impacts of freshwater consumption in LCA.
Environ. Sci. Technol. 43(11), 40984104. (2009)
86
CONCRETE MADE OF 100% RECYCLED MATERIALS - FEASIBILITY STUDY
P. BUN1,3, R. IDIR2, K. BUN1 , M. CYR3

1 Institute of Technology of Cambodia, Phnom Penh, Cambodia.
2 Cerema Ile-de-France, Paris, France.
3 LMDC-INSA/UPS-Université de Toulouse, Toulouse, France.
Keywords: low-grade concrete, granulated blast-furnace slag (GGBS), recycled concrete aggregates,
waste glass, dredge sediments, lime residue, used cooking oil, waste water.
Abstract
The main purpose of this paper is to study the feasibility of producing concrete made of 100%
recycled materials, by using granulated blast-furnace slag (GGBS) activated by waste water coming
from concrete production and with lime residue coming from waste of slaked lime factory as binder
instead of conventional Portland cement binder. Conventional aggregates were replaced by different
percentage of recycled concrete aggregates, recycled bottles glass aggregates and sediments. Used
cooking oil was incorporated as an admixture to improve fresh properties of the concretes. Four
formulations of concrete were tested in order to evaluate their fresh and hardened states
properties. The results showed that it is feasible to formulate concretes containing only recycled
materials. The dry concretes obtained could reach compressive strength up to 37 MPa at 9.5
months. However, before any generalization of the results, the variability of the wastes used should
be taken into account.
87
1- INTRODUCTION
Construction materials and especially concrete have for several years incorporated wastes and/or
by-products as minor or major constituents. Examples are numerous in the literature and concern all
concrete components: natural aggregates could be partially replaced by plastic, rubber, bricks,
recycled bottle glass, recycled concrete aggregates, etc. [e.g. 1, 2, 3]. Ordinary Portland cement
(OPC) can be partly made with by-products by replacing either calcite or clay in the raw mix [e.g. 4,
5]. Fractions of OPC can also be replaced in the concrete by supplementary cementing materials (e.g.
fly ash, ground granulated blast furnace slag, etc.), or by other fine materials coming from industry,
agriculture or municipal wastes. Recycled water (or even sea water) could sometimes be used to
replace tap water [e.g. 6]. Waste materials had also been used as chemical admixtures to improve
the fresh state of the concrete [e.g. 7, 8].
Most of the papers report the partial replacement of conventional constituents, but the use of
wastes or by-products as sole materials to formulate a concrete mix is almost never seen in the
literature. This could be due to the difficulty of managing the problems related to the use of a by-
product. For instance, recycled concrete aggregates are known to absorb high quantity of water, so a
total replacement is usually not permitted for normal concrete. However, the production of a
concrete made of 100% recycled materials could be a challenge, at least in terms of a feasibility
concept.
The objective of this work is thus to show the concept on the feasibility of producing concretes made
of 100% recycled materials, by using different wastes and by-products. Each constituent was chosen
and studied separately, then they were mixed to cast concretes that were evaluated at fresh and
hardened states.

The binder was based on ground granulated blast-furnace slag (GGBS), a by-product from steel
production (specific gravity of 2.9). GGBS was composed mainly of CaO, SiO2 and Al2O3 (Table 1),
mixed in a vitreous phase (Figure 1). Its Blaine specific surface was 400 m2/g. As GGBS had only
latent hydraulic properties, it was activated by waste wash water coming from concrete production
(used to replace tap water) and with lime (Ca(OH)2), a residue coming from waste of slaked lime
factory. The work on the binder showed that the pH of waste wash water was not high enough to
activate the GGBS, and that the use of 5% (in mass) of lime residue was necessary to reach an
acceptable setting time and development of strength.
Table 1: Composition of oxides in GGBS.
Material Oxides (% of mass)

SiO2 Al2O3 Fe2O3 CaO SO3 K2O Na2O
GGBS
36.85 11.44 0.10 41.35 1.93 0.44 0.34
88
Figure 1: X-Ray diffraction diagram of GGBS.
Natural aggregates were replaced by recycled materials. Table 2 shows the physical characteristics of
those aggregates and Figure 2 illustrates the results of sieve analysis.
- Recycled concrete aggregates (fine: FC and coarse: CC) came from Gonesse (France) and were
intensively used in the National Project RECYBETON (http://www.pnrecybeton.fr/). They
were classified as Rcu98 according to standard NF EN 933-11 [9] and were composed of old
cement paste and old aggregates made of limestone with a small fraction of silica (quartz and
flint).
- Recycled waste bottle glass (fine: FG and coarse CG), coming from soda-lime silica bottle glass
of mixed colors type.
- Dredged sediment (Se) coming from harbors in the north of France. It was mainly composed
of quartz and calcite, with traces of clays (Methylene blue test – EN 933-9: 1.2), hematite,
gypsum, feldspars and halite. The total organic carbon was evaluated at 5%.
Non-conventional admixture from used cooking sunflower oil (UCO) was incorporated in the mixture
to improve the fresh state of the concrete.
Table 2: Physical characteristic of aggregates.

Note: FC: recycled fine concrete aggregates; CC: recycled coarse concrete aggregates; FG: recycled fine glass aggregates; CG: recycled
coarse glass aggregates; Se: dredged sediment
Specific gravity Humidity Water absorption coef.

Materials
(g/cm3) (%) (%)
FC(0/4) 2.18 1.6 9.2
CC(4/10) 2.29 1.1 5.2
FG(0/4) 2.50 - -
CG(4/10) 2.50 - -
Se - 17.4 47
Based on the characteristics of the constituents of concrete mentioned above, four concrete
mixtures with a water-binder ratio of 0.4 were studied (Figure 3) for optimizing the rheological
characteristic and mechanical strength of 100% recycled concrete. Three types of recycled
aggregates were used in this experimental program: recycled concrete aggregates, sediment and
recycled bottles glasses aggregates. By keeping the same type and the same quantity of binder,
investigation the influence on compressive strength and rheological characteristics of 100% recycled
concrete was proceeded by replacing different percentage of each type of recycled aggregates.
Moreover, cooking oil was used to evaluate its effect on the slump value and compressive strength.
89
100
90
80 Se
70
FC
Passing (%) 60
50
FG
40
30 CG
20 CC
10
0
0.01 0.1 1 10 100
Particle diameter (mm)
Figure 2: Sieve analysis curves of recycled aggregates.
F1 F2 F3 F4
140 350 kg/m3

140 350 kg/m3
140 350 kg/m3
140 350 kg/m3

95% GGBS 95% GGBS 95% GGBS 95% GGBS
Binder 5% lime 5% lime 5% lime 5% lime
Water Recycled Recycled Recycled Recycled

F1 F3 – Decrease of the water demand
F1 F2 - Improve grading of aggregates
Recycled sand
350 kg/m3
F1 F4 – Increase workability

from old
Recycled sand
595 kg/m3
concrete
700 kg/m3
700 kg/m3
Recycled sand Recycled sand
Fine from old
from old concrete from old
aggregate concrete concrete
350 kg/m3
Sediments
105
Waste glass
Recycled
Recycled Recycled Recycled
1100 kg/m3
1100 kg/m3
1100 kg/m3
935 kg/m3
aggregates
Coarse aggregates aggregates from old aggregates
aggregate from old from old from old
concrete
concrete concrete concrete
165
Waste glass
Admixture - - - Used oil 14
Figure 3: Mix design for 100% recycled concrete.
The first concrete (F1) used as the reference formulation, contained the binder and recycled
aggregates as coarse and fine aggregates. Trials to improve the fresh state properties led to the
following concretes (Figure 3):
- Recycled aggregates were partially replaced in two concretes to produce F2 (50% of sediment
in fine aggregates) and F3 (15% in mass of bottle glass waste in fine and coarse aggregate) to
improve grading of aggregates and to decrease water demand, respectively. The grading
curves of the concretes F1, F2 and F3 are given in Figure 4. The optimal grading curve was
obtained by applying the principle of Dreux [10]. According to this figure, aggregate grading
90
in F1 and F3 included low percentage of fines particles compared to the optimal curve, while
aggregate grading in F2 fitted better the optimal curve.
- Formulation F4 with 4% of used vegetal cooking oil was used in concrete F1 to increase its
workability.
Slump test (NF EN 206 [11]) was used to evaluate the workability and 12 cubic concrete samples
(10x10x10cm) were casted for each concrete formulation to estimate the compressive strength at 7,
14, 28 and 287 days. After casting, all samples were covered and kept in the conditioned room
(20°C±1°C, RH=50%). After 24h, they were demolded, wrapped in plastic sheet and kept in a
conditioned room (20°C±1°C, RH=50%) until compression testing date.
100
90
80
Optimal grading curve
70 F1
Passing (%)
60 F2
50 F3
40
30
20
10
0
0.01 0.1 1 10 100
Particle diameter (mm)
Figure 4: Grading of aggregates of F1, F2 and F3 concrete formulation compared to an optimal curve (Dreux).

3.1 Binder
One of the main difficulties of producing a concrete from 100% recycled wastes and by products is to
find a binder to replace ordinary Portland cement, binder that can develop strength in a relatively
short period of time. Among the different wastes and by products that can fulfill the requirements,
granulated blast-furnace slag (GGBS) is probably the easiest to be used, as it is already well known
for several years as a latent hydraulic binder. However, GGBS needs to be activated, otherwise it will
take several days or weeks to set and harden.
Thus the first attempt to formulate the hydraulic binder based on GGBS was to mix it with waste
washed water of concrete mixer. However, the pH value of this water (8.05) was too low to activate
alone the GGBS. Consequently, lime (in the form of Ca(OH)2) was used to increase the pH of the pore
solution. This slaked lime can possibly come from waste of slaked lime production factory.
Several experiments were done to test the setting behavior of the binder with the liquid-solid ratio
of 0.4. The results of pH measurement of the mixtures with increasing lime content are given in
Figure 5. It can be seen that the use of 2% of Ca(OH)2 led to a low pH and thus was not enough to
activate the GGBS. By increasing its percentage up to 4%, the pH increased to values over 12 and
91
GGBS was activated to get a setting only after 48h. Nevertheless, it was possible to decrease the
setting time by using 5% of Ca(OH)2.
14
Setting in 12.67
pH of the mixture GGBS-lime

13 less than 48h
12
12.05
11
10 No setting
9 after 48h
8
8.36
8.05
7
0 1 2 3 4 5
Lime content (%)

Figure 5: pH of the mixtures of GGBS and lime.
3.2 Concretes
Table 3 summarizes the results in fresh (slump) and hardened states (compressive strength at 7, 14,
28 and 287 days) of the 4 concrete formulations described on Figure 3. It can be seen that:
- The slump of all four concretes remained low, meaning that the workability obtained would
not allow them to be cast easily, except for applications such as Roller-Compacted Concrete
and concretes cast by vibro-compaction (pavement, blocks, etc.).
- It seemed possible to achieve strength at 7 days of more than 7 MPa, with a quite fair
evolution over time, especially for F1 and F3. The reference concrete (F1) reached 37 MPa at
287 days, due to the reaction of GGBS. Concretes F2 and F4 did not developed high strength
at long term, probably due to the presence of organic matter in the sediment (F2) and in oil
(F4). Organic matter is known to limit the reactivity of hydraulic binders.
Table 3: Slump and compressive strength of 100% recycled concrete.
Compressive strength fc (MPa)

Formulation Slump (cm)
7d 14d 28d 287d
F1 – reference 1.7 7.6 10.3 12.8 37.0
F2 – sediments 0.3 2.2 4.8 9.1 8.0
F3 – waste glass 4.5 7.6 9.3 12.7 26.6
F4 – used oil 3.8 6.1 7.5 9.4 13.8
Figure 6 shows the relative values of compressive strength versus the relative slump of the
concretes, by taking concrete F1 as the reference. From this figure, by considering each effect
separately, it can be observed that:
- The replacement of fine recycled concrete aggregates by sediment (F1F2) decreased the
slump value (-82%) and also the compressive strength (-78% at 287 days), even if the grading
of the concrete seemed to be optimized (Figure 4). The reduction of the slump was due to
92
the high water absorption and maybe to the presence of fine clay particles in the sediment.
Consequently, it could lead to a decrease in the strength due to an incorrect concrete
placement (compatible with the small evolution of strength between 7 and 287 days). Clay is
also known to reduce the reactivity of hydraulic binders. Moreover, it is not excluded that the
5% of organic matter present in the sediment could alter the reactivity of GGBS.
- The replacement of 15% of recycled aggregates (fine and coarse) by recycled glass (F1F3)
improved the slump value. This was probably due to the absence of water absorption of the
glass particles (Table 2). It is interesting to note that the replacement of only 15% of
aggregates was sufficient to multiply the slump value by 2.6. However, long term
compressive strength decreased, which was not the case at short term (7 days). This may be
the effect of the loss of adherence between aggregates and binder, which can happen when
glass aggregates are attacked by an alkaline solution [12].
- Addition of used cooking oil to F1 (F1F4) improved the slump (by more than a factor 2), but
also led to the reduction of the compressive strength (as for F3). This lost was much more
significant with time, as shown by the decrease of the relative strength between 7 and 287
days. This can be probably due to a harmful effect of used cooking oil on the hydration
mechanism of binder. As shown in Figure 7 which presents the results of the speed of sound
through the material during its setting and hardening (proportional to the elastic modulus
and so to the compressive strength), the oil had a retarding effect in the first 7 days of the
measurement. It is noteworthy that the decrease of the sound velocity (19%) was in the same
order of magnitude than the decrease of compressive strength between F1 (without UCO)
and F4 (with 4% UCO), i.e. 20% according to Table 3 (7.6 and 6.1 MPa for F1 and F4,
respectively). It is probable that this effect could have continued over time and would explain
the weak strength of F4 compared to F1 (Figure 8).
F1 (100% aggregates from recycled concrete)

Relative compressive strength
1.0
0.9
0.8
0.7
F3
0.6
0.5
0.4
0.3
F4
0.2
7d
0.1 F2
287d
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
Relative slump
Figure 6: Relative compressive strength (7d and 287d) vs. relative slump of concretes F2, F3 and F4, by taking F1 as the reference.
93
2 500 No admixture
-19%
Velocity (m/s)
2 000
1 500
4% UCO
1 000
95% GGBS + 5% lime

500
Water/binder = 0,4
0
0 1 2 3 4 5 6 7
Time (days)
Figure 7: Ultrasound test result of binder GGBS paste setting process from 0d to 7d with and without used cooking oil.
6
F1
Relative compressive stregnth
5 F2
F3
4
F4
3
0
1 10 100 1000
Time (days)
Figure 8: Relative compressive strength (7d, 14d, 28d and 287d) vs. time by taking compressive strength at 7d as the reference.
94
3.3 Discussion
A few practical implications could be deduced from the precedent results:
Binder
The binder composed of GGBS with water recycled from concrete washing presented a kinetics of
reaction too low to be used in concrete. A source of alkalinity must be added to activate the GGBS.
Waste water did not seem to deteriorate the properties of the concretes and remained interesting
to be used in replacement of tap water, mainly for environmental issues.
Concrete F1
Concrete F1 had very good performances at long term, but its slump was too low to be cast as a
flowing concrete. This kind of dry concrete could however by used in vibro-compaction applications
(e.g. masonry units) or as Roller-Compacted Concrete.
Concrete F2
Concrete F2, due to its low performances (slump and strength) related to the water absorption
characteristic and the possible organic matter content of the sediment, can be considered as a low-
grade concrete. It could potentially be used in the field of lean concrete, bicycle runway path,
pavement which support low stress, etc.
Concretes F3 and F4
Concretes F3 and F4 had slightly higher slump characteristics than F1, but they remained quite dry as
the maximum slump was around 45 mm. However, the long-term strengths were significantly
degraded by the use of waste glass aggregates and used cooking oil (initially used to improve the
workability).
So the choice of using these materials might be questionable, as the workability was marginally
improved while the strength was significantly decreased. If one of the two solutions was to be used
(waste glass aggregates or used cooking oil), waste glass could be the less damaging option since
both slump and strength were higher than for used oil. However, the impact of glass aggregates on
the durability of concrete against alkali-silica reaction still needs to be assessed.
4- CONCLUSION
The results presented in this paper seem to show that it is feasible to formulate concretes containing
only recycled materials and obtain fair good properties. The binder composed of GGBS and slake
lime could lead to quite high performance at long term, especially when used with recycled concrete
aggregates. Attempts to improve the workability by the use of admixture (e.g. used oil) or aggregates
with less absorption (e.g. waste glass) led to a limited action and still need to be developed, in order
to limit the loss of strength. However, before any generalization of the results, the variability of the
wastes used should be taken into account.
95
REFERENCES
[1] Debieb, F., Kenai, S.: The use of coarse and fine crushed bricks as aggregate in concrete, Construction and Building
Materials, 22, 886-893 (2008)
[2] Ismail, Z.Z, AL-Hashmi, E.A.: Recycled of waste glass as a partial replacement for fine aggregate in concrete, Waste
Management, 29, 655-659 (2009)
[3] Martin-Morales, M., Zamorano, M., Ruiz-Moyano, A., Velverde-Espinosa, I.: Characterization of recycled aggregates
construction and demolition waste for concrete production following the Spanish Structural Concrete Code EHE-08,
Construction and Building Materials, 25, 742-748 (2011)
[4] Kacimi, L., Cyr, M., Clastres, P.: Synthesis of α'L-C2S cement from fly-ash using the hydrothermal method at low
temperature and atmospheric pressure, Journal of Hazardous Materials, 181, 593-601 (2010)
[5] Miyazaki, H., Yoshikawa, M., Atarashi, D., Tanaka, H., Ota, T.: Synthesis of recycled cements using hydrothermally
treated waste soda lime glass, Journal of the Ceramic Society of Japan, 125, 55-56 (2017)
[6] Ekolu, S.O., Daweerangen, A.: Evaluation of recycled water recovered from a ready-mix concrete plant for reuse in
concrete, Journal of the South African Institute of civil engineering, 52, 77-82 (2010)
[7] Hamad, B.S., Rteil, A.A, El-Fadel, M.: Effect of used engine oil on properties of fresh and hardened concrete,
Construction Building Materials, 17, 311–318 (2003)
[8] Beddu,S., Talib, S.H.A., Kamal, N.L.M. , Zakaria, C.M., Yap, A.B.M.: The performance of concrete containing used
cooking oil, Proc. of the Third Intl. Conf. on Advances in Civil and Structural Engineering – CSE (2015)
[9] EN 933-11, Tests for geometrical properties of aggregates – Part 11: Classification test for the constituents of coarse
recycled aggregate, European Standard (2009).
[10] Dreux, G., Festa J. : Nouveau guide du béton et de ses constituants, 8th Edition, Eyrolles (1995)
[11] AFNOR, Béton - Spécification, performance, production et conformité - Complément national à la norme NF EN 206
(2014)
[12] Idir, R., Mechanisms of action of glass powders and glass aggregates on alkali-silica and pozzolanic reactions, Thesis,
INSA Toulouse (2009)
96
RECYCLING CONCRETE AGGREGATES IN NEW CONCRETE: INVESTIGATIONS OF

QUALITY AND ORIGIN OF THE CONCRETE WASTE
L.G. PEDERSEN1, K.N. JENSEN1, M.E. HERLØV1, G.M. KIRKELUND1, L.M. OTTOSEN1
1 Department of Civil Engineering, Technical University of Denmark, 2800 Kgs. Lyngby, Denmark.
Abstract
This study investigates recycled concrete aggregates (RCA), RCA has gained interest the last years [1].
The RCA investigated is in the fractions 4-8 and 8-16 mm of unknown sources, as partial replacement
of natural aggregates (NA) in new concrete. The mix designs of the new concrete has been
investigated without admixtures or increasing the amount of cement.
The RCA was obtained from concrete waste from four different construction sites in the area around
Copenhagen. Three of the construction sites had RCA of unknown sources and the fourth RCA was
from Copenhagen airport, which was concrete from a known source with a compressive strength of
45 MPa without contamination from the demolition. The unknown sources of the RCA gave a picture
of the average concrete waste around Copenhagen, the quality and level of sorting at the
demolition.
A total of 83 concrete mixtures were produced throughout this study, this includes 24 different mix
designs and types of concrete curing for 28 days and 59 mix designs curing for 7 days. The amount of
cement in the different mix designs was kept equivalent to the references in order to not increase
the CO2 emission due to the amount of cement. The constant amount of cement meant that the
workability of the new concrete was very dry. This problem was met by investigating different
processing procedures of the RCA together with the results from the characterization of the RCA.
Characteristics of the RCA showed that the aggregates had a lower density than NA and a higher
water absorption due to the attached mortar. The RCA’s high water absorption was encountered by
saturating the aggregates, which ensured the amount of free water for the water/cement-ratio (w/c)
and thereby also the workability of the concrete.
The proposed mix design methodology demonstrates that the deviation of the compressive strength
and the workability of RAC could be met by RCA being saturated by pre-soaking, with the
compressive strength at 25.48 - 37.01 MPa depending on the percentages of RCA in relation to the
references at 30 MPa for 0.6 w/c-ratio.
The compressive strength and characterization of the RCA of unknown sources show that the
maximum requirement according to DS/EN 206 can be used and even exceeded, especially when
applying concrete of a known source. Thus, there is a potential for using RCA in new concrete, even
without knowing which sources the RCA came from.
Reference
[1] Safiuddin et al., (2013). Use of Recycled Concrete Aggregate in Concrete: A Review. Journal of Civil Engineering and
Management, pp 796-810
97
RECYCLING 100% OF WASTE CONCRETE
D. GARCIA1, F. ZEMAN2
1 Ecoles Supérieures des Mines, St. Etienne, France
2 Royal Military College of Canada, Kingston, Canada
Abstract
The purpose of this study was to recycle 100% of waste concrete into usable products. Current
industrial practice is to use waste concrete as earthfill or grind it into large aggregates (2” dia) and
use as road base. The fine content produced during the size reduction has been shown to
preferentially contain the old cement and is termed waste cement. This small fraction has been used
as a source material for recovery of calcium and subsequent carbonation as a more of mineral
sequestration. This fraction accounts for less than half of the cement calcium and leaves the
remaining fines as a waste product as they are too small to be used in new concrete. By converting
100% of the waste concrete to usable sand fraction and recovering 100% of the calcium, a zero
waste process results where waste concrete is converted to sand, precipitated calcium carbonate
(PCC) and iron/aluminum residues suitable for return to the cement plant.
Previous work showed that 100% of the Ca can be recovered and converted from particles of less
than 0.5 mm diameter. This work is a continuation of previous efforts with a focus on larger particles
sizes (0.5mm<d50<5mm) that are more readily amenable to fresh concrete. In addition, work focused
on the fate of the silicon (Si). Previous researchers have shown that excessive Si leached from the
waste cement can result in silica gels, which significantly hinder filtration and solid recovery. This
work targets the silica gel and quantifies how much gel is produced from each size fraction analyzed
and the moisture content, fraction solids retained. This is being done in a step wise fashion from pH8
(partial precipitation of Fe/Al) up to pH11 (complete precipitation of all impurities).
Work is ongoing with completion expected prior to July 2018. To date conclusions are that Si gel
formation increases with particle size and purification pH. This places a premium on removing the Si
colloids from solution prior to purification. Separation of Si colloids prior to purification will produce
another commodity, silica gel. This will increase the complexity of the process but also increase the
revenue generated by the process.
98
VALORIZATION OF RICE HUSK ASH (RHA) AS SILICA PRECURSOR FOR THE

OBTAINMENT OF HEAVY CLAY BRICKS AND DEFLOCCULATING ADDITIVES
F. ANDREOLA1, L. BARBIERI1, I. LANCELLOTTI1

1 Department of Engineering “Enzo Ferrari”, University of Modena and Reggio Emilia, Via P.Vivarelli
10, 41125 Modena, Italy.
Abstract
RHA is an ash product during combustion of the rice husk in the parboiled process or in industrial
kilns. It contains around 90% of amorphous silica and unburned carbon (~10%.). Generally,
amorphous ash is formed during combustion (550-800°C) only at higher temperatures a crystalline
ash is developed. The presence of silica is well known and a large number of scientific literature
highlighted different industrial uses: as insulator in the steel industry in the production of high
quality flat steel, as pozzolanic material in the cement industry, in the manufacture of low cost
building blocks, and in the production of high quality cement. In the ceramic sector, scientific studies
reported its use in substitution of quartz in Whiteware [1] and as silica source in the synthesis of
glass ceramics. This study proposes two different ways for the RHA valorisation in the ceramic field,
in particular as alternative raw material in the production of heavy clay and as silica precursor to
obtain sodium silicates solutions used as deflocculating additives.
For the brick study different mixtures containing 5-20wt% of RHA in substitution of clays were
obtained by mixing the paste with suitable water content (20-25%). Laboratory brick samples were
obtained by extrusion (P=10bar), dried for 24hs at 110°C and then fired in an industrial camera kiln
with a thermal cycle (24 hrs total time, Tmax=960°C and 6 hrs soaking time). Linear shrinkage (LS%)
and naphtha absorption were measured on dried specimens and linear shrinkage, (24-hour
immersion) water absorption, weight loss and flexural strength were determined on fired materials
in comparison to the standard one. The substitution of RHA to clayed raw materials modify the
behavior of the bodies in the drying and firing phase. The results highlighted that samples prepared
up to 5 wt% of RHA are in according to the recommended values for roof. Bricks containing higher
amounts of RHA could be used in building manufacturing (light weighted faced load bearing walls)
where moderate strengths and penetration protection (porosity/permeability) are required.
Sodium silicate solutions were chemical synthesized treating RHA in environmental friendly
conditions (T <100°C and P=1 atm), compared to processes currently used in industry. with sodium
hydroxide solutions. During the study the operative conditions (particle size of RHA, time of contact
and sodium hydroxide concentration) were optimized. The Silica (SiO2%) extracted from the RHA was
determined by a titration method using HCl 1M following ISO 2124-1972 rule. Raman spectroscopy
was used to check the chemical nature of the solutions obtained by comparison with commercial
sodium silicates. In order to check the deflocculating efficiency of the synthesized, silicate,
rheological measures (flow curves, viscosity curves) were performed on clay suspensions added with
equal concentration (0.5 wt%) of commercial sodium silicate (deflocculating agents) and the
solutions obtained.
The tests conducted showed that the RHA is very reactive in contact with NaOH, it was verified that
1.5 and 2M [NaOH] and 3 contact hours are the best conditions to achieve molar ratio around 2-3,
typical of commercial silicate used in the ceramic industry as deflocculants. The production of
sodium silicate from the waste agri-food leads to a saving of natural raw materials (quartz,
carbonates, ..) and are avoided greenhouse gas emissions
99
References
[1] Prasad C.S, Maiti K.N., Venugopal R., Effect of rice husk ash in whiteware compositions, Ceramics Int. 27, 629-35
(2001).
100
GLOBAL URBAN FOOD WASTE MANAGEMENT REPORT FROM WBA AND C40 CITIES
CLIMATE LEADERSHIP GROUP
HOW FOOD WASTE MANAGEMENT IS NEEDED TO MEET THE CLIMATE CHANGE AND
SUSTAINABLE DEVELOPMENT GOALS
D. NEWMAN1
1 World Biogas Association, and Bio-based and Biodegradable Industries Association, UK.
Abstract
WBA with C40 and with help from the USA EPA, presents its global report for cities on how to
measure, prevent, collect and treat food waste produced within urban areas. The report shows that
food waste is a major urban challenge, both in terms of human health and the wider environment;
but it also shows how the correct management can lead to enormous benefits in terms of energy,
soil quality, air quality and recycling of other wastes.
The report brings together experiences from cities around the world, showing how they are tackling
the food waste challenge and suggests policies and actions from policy makers to move forward. The
report is particularly directed towards large urban conurbations, in which, by 2050, more than 70%
of the world's population will be living. Cities have a unique role to play therefore in meeting the
environmental goals the international community has agreed upon and can influence and implement
policies to meet these.
101
PROGRESS IN THE DEVELOPMENT OF TORREFACTION FOR SOLID BIOMASS

APPLICATIONS IN INDUSTRY
WEI-HSIN CHEN1
1
Department of Aeronautics and Astronautics, National Cheng Kung University
Tainan 701, Taiwan
Abstract
Development of renewable energy is considered as an effective countermeasure to abate

anthropogenic CO2 emissions and mitigate global warming. Among reviewable energies, bioenergy
accounts for the largest share and has been extensively applied in heat and power generation as well
as residential and transport sectors. Biomass can also be utilized as a solid fuel and burned directly
for heat and power generation. However, biomass possesses a number of disadvantages such as
hygroscopic and biodegradable nature, high moisture content, low calorific value, poor grindability,
large volume or low bulk density, and low homogeneity. These drawbacks result in a low conversion
efficiency as well as difficulty in the collection, grinding, storage and transportation of biomass.
Torrefaction is a promising technology to upgrade biomass for solid fuel production [1, 2]. After
undergoing torrefaction, the aforementioned properties of biomass are improved to a great extent
and close to those of coal. As a consequence, torrefied biomass can be used as an alternative to coal
consumed in industry. This talk addresses recent development of biomass torrefaction, especially in
the impact of this thermal pretreatment on the property variation of biomass. The applications of
torrefaction in industry such as combustion, gasification, ironmaking, pyrolysis, and liquefaction are
also underlined.
References
[1] Chen, W,H,, Peng, J.H., Bi, X.T.: A state-of-the-art review of biomass torrefaction, densification and applications.
Renewable and Sustainable Energy Reviews. 44, 847-866 (2015).
[2] Kumar, G., Shobana, S., Chen, W.H., Bach, Q.V., Kim, S.H., Atabani, A.E., Chang, J.S.: A review of thermochemical
conversion of microalgal biomass for biofuels: Chemistry and processes. Green Chemistry. 19, 44-67 (2017).
102
REUSE OF ALUM SLUDGE IN WATER AND ENVIRONMENTAL ENGINEERING: R&D OF

10 YEARS’ EXPERIENCE
Y. ZHAO1,2
1 UCD Dooge Centre for Water Resources Research, School of Civil Engineering, University College
Dublin, Belfield, Dublin 4, Ireland.

2 Institute of Water Resources and Hydro-electric Engineering, Xi’an University of Technology, Xi’an
710048, Shaanxi, P.R. China.
Abstract
Alum sludge refers to inevitable suspended and dissolved solids during water purification process
when producing tap water where aluminum sulphate was used as coagulant worldwide. Alum sludge
is dewatered and the resultant cakes are treated as a “waste” for landfill as their major final disposal
although 11 ways of reuse/recycle have been identified [1,2]. As slum sludge is the residual of
potable water treatment process, it is not harmful, without toxic elements and heavy metals in most
cases. Thus, alum sludge has high potential of reuse as raw materials in civil and environmental
engineering. However, little was progressed on it except for the recent years. Research and
development (R&D) with special interest and focus of alum sludge reuse was conducted in our group
in the last 10 years and this paper reports the main work and its novel application profile.
Alum sludge is used as low-cost adsorbent for P, pesticide, As immobilization and unpleasant gas
purification: Extensive studies were conducted to explore the ability and capacity of alum sludge as
adsorbent for P, pesticide, arsenic adsorption/immobilization [3,4]. In addition, alum sludge was
recently investigated as raw material for purification of unpleasant odours from wastewater
treatment plants. Trials have demonstrated its effectiveness and promising future for nauseous
odorous control.
Alum sludge is used as substrate in wide range of constructed treatment wetland systems: Great
efforts have been made to develop the new generation of constructed treatment wetland by
employing alum sludge cakes as main substrate, turning alum sludge as a “waste” for wastewater
treatment. An alum sludge-based treatment wetland system has been well developed with novel
operation strategy of tidal flow, allowing it to treat high strength wastewater [5]. In addition, alum
sludge-based wetland system has been embedded into the traditional main wastewater treatment
process (activated sludge process) to establish a so-called “Green-Bio-sorption Reactor” (GBR) [6].
Alum sludge-based wetland system has been integrated with microbial fuel cell to achieve the dual
goals of wastewater treatment and bioelectricity generation [7]. Most recently, floating wetland has
been well studied to further use the alum sludge as media to enhance the wastewater treatment
efficiency.
Alum sludge is used as a partial replacement for clay in clay brick manufacturing: The lab-scale trial
was found that bricks containing up to 20% sludge, fired at 1200°C, have greater compression-
strength properties than 100% clay bricks. Although there were negative effects associated with the
incorporation of alum sludge, it was found that some of the bricks under the recipe in the study met
the standards as set out by Eurocode 6 – ‘Design of Masonry Structures’, demonstrating promising
potential and prospects of Irish dewatered alum sludge cakes in brick making [8].
103
Liquid alum sludge is used as coagulant for wastewater treatment and as conditioner for
wastewater sludge co-conditioning and dewatering: It has been studied and demonstrated that
alum sludge in liquid form can also be reused as coagulant in wastewater industry due to its
abundant content of Al3+ [9,10]. Overall, it is believed that the R&D of alum sludge is useful and will
help to develop the national strategy of the entire waterworks sludge management, allowing
transforming alum sludge from a “waste” into value added products, contributed to sustainable
development.
Acknowledgements
The following people are acknowledged as group members to work on different kinds of projects
towards the R&D of alum sludge reuse. Dr Yongzhe Yang, Dr Akintunde Babatunde, Dr Lordwin
Kumar, Dr Maha Tony, Dr Xiaohong Zhao, Dr Yuansheng Hu, Dr Liam Doherty, Mr Ranbin Liu, Mr Lei
Xu, Mr Baimin Ren, Ms Cheng Shen, Mr Cheng Tang, Mr Wesley Awe and Ms Chun Kang.
References
[1] Zhao, Y.Q., Babatunde, A.O. Constructive approaches toward water treatment works sludge management: an
international review of beneficial reuses. Critical Review in Environmental Science and Technology, 37, 129–164,
(2007)
[2] Elangovan, C., Subramanian, K. Reuse of alum sludge in clay brick manufacturing. Water Science & Technology:
Water Supply 11(3), 333–341, (2011)
[3] Zhao, Y.Q., Razali, M., Babatunde, A.O., Yang, Y., Bruen, M. Reuse of Aluminium-based water treatment sludge to
immobilize a wide range of phosphorus contamination: Equilibrium study with different isotherm models,
Separation Science and Technology, 42(12), 2705-2721, (2007)
[4] Zhao X.H., Luo H.L., Tao T., Zhao Y.Q. Immobilization of arsenic in aqueous solution by waterworks alum sludge:
prospects in China, International Journal of Environmental Studies, 72(6), 989-1001, (2015)
[5] Zhao, Y.Q., Babatunde, A,O., Hu, Y.S., Kumar, J.L.G., Zhao, X.H. Pilot field-scale demonstration of a novel alum sludge-
based constructed wetland system for enhanced wastewater treatment, Process Biochemistry, 46(1), 278-283,
(2011)
[6] Liu Ranbin; Zhao Yaqian; Zhao Jinhui; Xu Lei; Sibille Caroline. A Fancy Eco-compatible Wastewater Treatment System:
Green Bio-sorption Reactor, Bioresource Technology, 234, 224-232, (2017)
[7] Xu Lei., Zhao Yaqian., Wang Tongyue., Liu Ranbin., Gao Fei. Energy capture and nutrients removal enhancement
through a stacked constructed wetland incorporated with microbial fuel cell, Water Science and Technology, 76(1),
28-34, (2017)
[8] Zhao Yaqian; Ren Baiming; O’Brien Andrew; O’Toole Simon. Using alum sludge for clay brick: an Irish investigation,
International Journal of Environmental Studies, 73(5), 719-730, (2016)
[9] Yang, Y., Zhao, Y.Q., Babatunde, A.O., Kearney, P. Two strategies for phosphorus removal from reject water of
municipal wastewater treatment plant using alum sludge. Water Science and Technology, 60(12), 3181-3188, (2009)
[10] Kang Chun. Reuse of aluminum-based water treatment sludge as coagulant for animal farm wastewater treatment,
MEngSc thesis, University College Dublin, 2017.
104
KINETICS OF BIOLOGICAL MINERALISATION OF NITROGEN DURING ANAEROBIC

DIGESTION
H. FISGATIVA1, C. MARCILHAC1, C. JAUDOIN1, F. BELINE1

1 Irstea, 17 avenue de Cucillé, CS 64427, 35044 Rennes cedex, France
Abstract
Nutrient valorisation of digestate is a key point for anaerobic digestion (AD). In fact, price of mineral
fertilisers is steadily increasing due to their scarcity. However, huge quantities of mineral fertilisers
are still spread on crops while these mineral fertilisers could be substituted by fertilisers from
organic sources, as digestate [1]. AD lead to transformations of initial nitrogen modifying the forms
of nitrogen in digestate. These transformations and their kinetics are not enough well-known and
then management of nutrients for crop fertilisation using digestate may be difficult. Consequently,
the kinetics of nitrogen transformations of different substrates and links with methane production
were investigates.
The kinetics of mineralisation and kinetics of methane production were studied on 13 substrates
from agro-industrial, agricultural or urban sources. In parallel, AD trials were performed in batch
reactors composed of 2 L glass bottle with 1 L working volume for study of mineralisation and in 1.5
L glass bottle with 1 L working volume for study of methane production, the latter as developed by
Girault et al. (2012) [2]. After inoculation and substrate addition, all reactors were flushed with a gas
mixture of N2 and CO2 (70/30) to ensure anaerobic conditions and maintained at 37°C. As initial
content of nitrogen in inoculum may prevent the observation of the substrate mineralisation, the
inoculum was previously washed. Experiments were performed during 17 days. Gas and the
digestate were sampled at a frequency of three times a day at the beginning of the experiments up
to once a day at the end.
Results show that kinetics of nitrogen mineralisation depends principally of initial substrate and that
mineralisation is not directly linked to methane production kinetics. Nitrogen was transformed
quickly before stabilisation (from 2 to 8 days depending on substrate). Experiments allow identifying
3 types of behaviour of transformation of nitrogen although the AD: (a) rapid mineralisation
(transformation of organic nitrogen into inorganic nitrogen) in substrates as blood, sludge or food
waste, (b) immobilisation of nitrogen (transformation of inorganic nitrogen into organic nitrogen in
biomass) in substrates as fruits, straw or grasses, and (c) limited protein hydrolysis (not modification
of initial nitrogen content or neutralisation of mineralisation and immobilisation phenomena) in
substrates as slurry or manure.
Then, results allow to conclude that experiments preformed in this study demonstrate that kinetics
of mineralisation of nitrogen can be clearly assessed. These results can be used to predict the
mineralisation rate of studied substrates. Further studies may allow to propose a modelling tool
predicting the rate of mineralization of the nitrogen during AD and consequently the digestate
composition according to the cocktails of substrates.
References
[1] Alburquerque, J.A., et al., Assessment of the fertiliser potential of digestates from farm and agroindustrial residues.
Biomass and Bioenergy, 2012. 40: p. 181-189.
[2] Girault, R., et al., A waste characterisation procedure for ADM1 implementation based on degradation kinetics.
Water Research, 2012. 46(13): p. 4099-4110.
105
MANAGEMENT OF WASTE TO ENERGY PLANTS:

QUANTIFYING TOTAL SILICON IN BIOGAS
H. MÉTIVIER-PIGNON1, V. CHATAIN1, M.GALERA-MARTINEZ1, E. BASSET2, R. BAYARD1,3

1 Université de Lyon – INSA Lyon / Laboratoire DEEP – EA 7429, Villeurbanne, France.
2 ENGIE, Research and Technologies Division, CRIGEN, Saint-Denis-La-Plaine, France.
3 REseau Coopératif de Recherche sur les Déchets et l’environnement (RECORD), Villeurbanne, France.
Abstract
Anaerobic digestion is intended to produce almost 20 MTep in Europe by 2020, hence giving credibility to
biogas in the energy mix. Nevertheless, biogas often contains Volatile Organic Silicon Compounds (VOSiCs)
and it is an issue even at low concentrations since silicates deposits are formed during biogas combustion
which damage conversion systems. The quantification of total silicon (Sitot) in biogas is thus a key point to
assess risks or monitor treatment processes. Unfortunately there is so far no standard method for the
sampling and the analysis of Sitot. Hence, the objective of the study is to assess several methods including
both conventional technologies and innovative ones through laboratory tests and onsite measurements.
Online analysers based on FTIR spectroscopy or GC-IMS (Ion Mobility Spectrometry) were compared to
more conventional techniques that are GC-FID or GC-MS and ICP-OES. Several sampling methods can be
used: Tedlar bags, adsorbent tubes, or direct sampling, impingers in the case of ICP-OES. The production
of analytical standards remains difficult for VOSiCs. Two methods were implemented: the production
of gas from VOSiCs in liquid form and the dilution of multicomponent gas standards (cylinders). Based
on these standards, analytical techniques were assessed in the laboratory in terms of linearity, accuracy
and precision. Finally, onsite measurements were conducted on two gas: a biomethane produced on a
wastewater treatment plant and a landfill biogas used to produce electricity.
This study shows that onsite measurements are essential for the assessment of analytical techniques:
biogas are complex gas (hundreds of trace compounds) so that using standards gas, even with so called
biogas or biomethane matrix, is not sufficient to ensure the reliability of measurements. For example,
FTIR analyser gave quite satisfactory results during laboratory experiments but inconsistent ones
onsite. As regards VOSiCs’ standards, cylinders of multicomponent gas mixtures seem to be the most
suitable but require strict conditions of use due to physicochemical properties of these compounds
and are rather expensive. As far as sampling is concerned, results show that Tedlar bag are unsuitable
since no satisfactory repeatability was obtained, despite a passivation step. GC-IMS is a promising
technique for the determination of low VOSiC concentrations which corresponds to biomethane or
treated biogas. At last, GC-MS (with preconcentration on adsorbent tubes) and ICP-OES (sampling with
impingers) seem to be the most mature technologies, but require further work for a complete
validation (standards, sampling, measurement) with respect to the specific application considered:
determining the Sitot content of a biogas or biomethane.
In conclusion, the comparison of several techniques for the determination of Sitot content of real biogas
and biomethane show good agreement when considering order of magnitude, but without converging
to a “real” precise value. There is a need for standard procedures to be used to determine the
compliance with a threshold value (0.3 to 1 mgSi.m-3 recommended for the quality of biomethane1).
References
[1] European standard EN 16723 Natural gas and biomethane for use in transport and biomethane for injection in the
natural gas network
106
DEVELOPMENT AND VALIDATION OF A NOVEL SIMPLIFIED NORDMANN TITRATION

METHOD FOR MONITORING VOLATILE FATTY ACIDS IN ANAEROBIC DIGESTION
PROCESSES TREATING ORGANIC WASTE
SHUBIAO WU1,2, HAO SUN1

1 College of Engineering, China Agricultural University, Key Laboratory for Clean Renewable Energy
Utilization Technology, Ministry of Agriculture, Beijing, China.

2 Aarhus Institute of Advanced Studies, Aarhus University, Høegh-Guldbergs Gade 6B, DK-8000
Aarhus C, Denmark.
Abstract
Anaerobic digestion (AD) is a complex series of biological processes, and has attracted
worldwide attention owing to its ability to treat various types of organic wastes in a robust and
efficient manner, while simultaneously producing bio-energy in the form of methane. Although AD
technology has been investigated for several decades, poor performance and fermentation failure
are still frequently reported, mainly due to insufficient operational management and lack of process
monitoring and control. A few modern industrial bio-digesters can be continuously monitored
online, but the limited measurable parameters, including pH, temperature, production, and
composition of resultant gas, which, in most cases are insufficient to trigger the warning alarm fast
enough to prevent system failure. Therefore, in order to improve the AD efficiency and stability, and
achieve successful operation of anaerobic treatment facilities, reasonably accurate and rapid
monitoring techniques are essential. This study undertakes the development and validation of a
simplified Nordmann titration method for VFA measurement. The relationship between the different
VFAs measured by gas chromatography (GC) and the traditional Nordmann method was then
correlated with the content of total solids in the titrated samples. The proposed method will be
validated using a long-term lab-scale anaerobic digestion experiment.
The results indicated that the influence of ion
interfering subsystems on the accuracy of VFA
measurements by Nordmann method can be
neglected. The content of total solids in titrated
samples was found to be the main contributing factor.
A high linear correlation was established between the
different total solids contents and difference in VFA
measurements afforded by the traditional Nordmann
equation and the GC method by involving several tests
of the digested effluents from various biogas plants. A
simplified method was developed and finally validated
using a semi-continuous experiment of chicken manure
anaerobic digestion with various organic loadings. The
good fitting of the results obtained by this method
compared with GC results strongly supported the
potential application to VFA monitoring in the AD
process.
The influence from pH, temperature on this simplified method and its full scale validation are
considered to be interesting for further investigation.
107
HOW TO ACCURATELY ESTIMATE AMMONIUM CONTENT IN THE DIGESTATES : A

LAB-SCALE STUDY
Y. BAREHA1, A. TREMIER1, R. GIRAULT1

1 IRSTEA UR OPAALE, Rennes, France..
Abstract
Prediction of the ammonium content of digestates is a great challenge to optimize :

(i) design and management of the anaerobic process in order to prevent inhibition due to
ammonia into the digester;
(ii) design and management of digestate post-processings such as ammonia stripping or
struvite precipitation.
(iii) agricultural recovery of digestates. Indeed, ammonia is the most available form of
nitrogen for crops.
During anaerobic digestion design and management, ammonium content in the digestate is often
estimated from BioMethanogenic Potential (BMP) value of substrates by considering the same
biodegradability for organic carbon and nitrogen. But, due to the complexity of biodegradability
control factors, this kind of hypothesis is not always verified and estimation methods have to be
improved. Hence, the objective of this study was to evaluate which factors have to be taken into
account to accurately estimate ammonium content in the digestates.
To this purpose, 3 estimation methods were developed and evaluated in term of accuracy:
(i) Method 1 :estimation from total carbon biodegradability calculate from BMP values of
substrates
(ii) Method 2: estimation by a developed statistic model (PLS) using the characterisation of
organic nitrogen bioaccessibility thanks to organic matter fractionation method
developed by Jimenez et al. (2015)
(iii) Method 3: estimation from a biodynamic model specifically adapted from ADM1
(Batstone et al., 2002)
To evaluate the accuracy of each method, organic nitrogen biodegradability was quantified on a
panel of substrates in batch and CSTR experiments.
Results highlight that method 1 allows a suitable estimation of the maximal ammonium content in
the digestate only for non-previously mineralized substrates ( < 30%). For other substrates
(stored foodwaste, livestock manures, etc), significant deviation is observed between organic carbon
and nitrogen biodegradability. For method 2, statistic model development and its evaluation shown
that bioaccessibility indicators can allow a very accurate prediction of organic nitrogen
biodegradability and, as a consequence, of the maximum ammonium content in the digestate.
However, this kind of indicators doesn’t enable degradation kinetics to be taken into account. After
model calibration, method 3 allows an accurate prediction of the ammonium content in the
digestate taken into account the impact of the hydraulic retention time (HRT) of the digester. In
addition, results highlight that, depending on the substrates, the effect of digester HRT has to be
considered or not for an accurate prediction.
Results provide guidelines to select an accurate method for the estimation of ammonium content in
the digestate during anaerobic digestion plant design and management, taken into account required
accuracy and substrate characteristics.
108
References
[1] Batstone D.J., Keller J., Angelidaki I., Kaluzhnyi S.V., Pavlostatis S.G. Rozzi A., Sanders W.T.M., Siegrist H., Vavilin.
2002. Anaerobic Digestion Model No.1, Scientific and Technical Report No.13, IWA Publishing, ISBN: 1 900222 78 7
[2] Jimenez, J., Aemig, Q., Doussiet, N., Steyer, J.-P., Houot, S., Patureau, D., 2015. A new organic matter fractionation
methodology for organic wastes: Bioaccessibility and complexity characterization for treatment optimization.
Bioresour. Technol. 194, 344–353.
109
ANALYSIS AND INTERPRETATION OF INTRAPARTICLE SAMPLING DATA:

ASSESSMENT OF THE EXOTHERMICITY EFFECT DURING BIOMASS PYROLYSIS
F. PATUZZI1, S. CIUTA2, M. BARATIERI1, M.J. CASTALDI2

1 Free University of Bozen-Bolzano, Bolzano, Italy.
2 The City College of New York, New York, USA.
Abstract
Thermal treatment processes have the highest conversion efficiencies when comparing the various
treatment options for biomass into fuels, energy or valuable chemicals. Therefore, for the optimal
design of thermal treatment reactors, the knowledge of mechanisms and transformations occurring
during the thermochemical conversion processes are fundamental. An understanding of the pyrolytic
reactions is imperative because it represents a current practical process and the early stage to other
biomass thermochemical processes such as gasification or combustion [1]. Therefore understanding
pyrolysis kinetics is imperative for the assessment and feasibility for design and scaling of industrial
biomass conversion applications [2].
Recently our group has investigated the pyrolysis of biomass using a gas sampling technique to
determine the enthalpy change as a function of sample temperature. Previously we have reported
on the gaseous concentration profile as a function of temperature leading to a phenomenological
understanding of the overall reaction sequence occurring within the biomass particle [3,4]. The
experimental tests in this work have been performed on birch wooden spheres. The conclusions
attained could be applied to other geometries taking into account the corresponding coordinates
and boundary conditions [1]. One of the morphological properties of the feedstock which influences
its thermal decomposition is the size of the sample, therefore different sizes of biomass particles
were tested during the experiments. For a preliminary insight on material decomposition, thermal
analysis measurements have been performed, which gave only about the aggregate behavior of the
biomass. Intra-particle gas sampling tests were performed afterwards for explaining possible
reaction sequences happening during pyrolysis.
The present work reports the most recent results obtained with an improved intraparticle sampling
technique. One specific improvement is the exact quantification of the different gas flow rates
during the reaction process. The injection of 0.25 ml/min of Krypton allowed the calculation of the
exact amount of moles of each gas species (CO2, CO, CH4, H2, C2H4, C2H6) extracted and analyzed at
each sampling time. Moreover, supporting the intraparticle gas sampling results with
thermogravimetric tests and the macroscopic assessment of the main pyrolysis products, it was
possible to confirm the exothermic character of the reactions occurring at the center of the particle
between 350 °C and 460 °C temperature range and to quantify the amount of energy released by
the process itself.
References
[1] Bilbao, R., Millera, A., Murillo, M.B.: Temperature Profiles and Weight Loss in the Thermal Decomposition of Large
Spherical Wood Particles. Ind. Eng. Chem. Res. 1811–1817 (1993)
[2] White, J.E., Catallo, W.J., Legendre, B.L.: Biomass pyrolysis kinetics: A comparative critical review with relevant
agricultural residue case studies. J. Anal. Appl. Pyrolysis. 91, 1–33 (2011)
[3] Ciuta, S., Patuzzi, F., Baratieri, M., Castaldi, M.J.: Biomass energy behavior study during pyrolysis process by
intraparticle gas sampling. J. Anal. Appl. Pyrolysis. 108, 316–322 (2014)
[4] Patuzzi, F., Ciuta, S., Castaldi, M.J., Baratieri, M.: Intraparticle gas sampling during wood particle pyrolysis:
methodology assessment by means of thermofluidynamic modeling. J. Anal. Appl. Pyrolysis. 113, 638–645 (2015)
110
KINETIC ANALYSIS OF TROPICAL LIGNOCELLULOSIC BIOMASS STEAM GASIFICATION
L. M. ROMERO MILLAN1,2, F. E. SIERRA VARGAS1, A. NZIHOU2

1 Facultad de Ingeniería, Universidad Nacional de Colombia-Sede Bogotá, Bogotá, Colombia.
2 Université de Toulouse, Mines Albi, CNRS, Centre RAPSODEE, Albi, France.
Abstract
Purpose: The aim of this work is to better understand the influence of lignocellulosic biomass
characteristics and composition in their steam gasification behavior and kinetics. A new modeling
approach is proposed to predict the steam gasification behavior of tropical lignocellulosic biomasses
and biomass blends from their inorganic composition.
Materials and methods: Three agricultural residues with different macromolecular and inorganic
composition, and H/C and O/C ratios near 1.5 and 0.8 were chosen: coconut shells (CS), oil palm
shells (OPS) and bamboo guadua (BG). The raw biomasses and their blends were gasified using a
thermogravimetric analyzer. Isothermal steam gasification experiments were carried out with
gasification temperatures ranging from 750°C to 900°C, and steam partial pressure from 0 to 0.1 bar.
The gasification kinetic parameters were calculated using a model-free isoconversional method.
Decomposition model identification was performed using master plots approach.
Results: Gasification experiments highlighted the impact of inorganic elements in the biomass
gasification behavior; In particular, the catalytic effect of potassium (K) and the inhibiting effect of
silicon (Si) and phosphorous (P) in the gasification reactions [1,2]. The reaction mechanism of
biomasses and blends steam gasification was well described by an order based model. Notably, a
linear relationship was found between the inorganic ratio K/Si+P and the reaction mechanism order.
For all the analyzed samples, a good agreement was found between the experimental and the
calculated data, with model fitting errors below 13%.
Conclusion: The inorganic composition of raw biomasses has an important impact on their steam
gasification behavior. The proposed modeling approach showed to be suitable for the description
and prediction of the steam gasification behavior of lignocellulosic biomasses and biomass blends
from the knowledge of the inorganic composition of the raw materials.
References
[1] Dupont C, Jacob S, Marrakchy KO, et al (2016) How inorganic elements of biomass influence char steam gasification
kinetics. Energy 109:430–435. doi: 10.1016/j.energy.2016.04.094
[2] Nzihou A, Stanmore B, Sharrock P (2013) A review of catalysts for the gasification of biomass char, with some
reference to coal. Energy 58:305–317. doi: 10.1016/j.energy.2013.05.057
111
COMBUSTION BEHAVIOR OF ANIMAL MANURE-BASED HYDROCHAR
KYOUNG S RO1, JUDY A LIBRA2, ANDRÉS ALVAREZ-MURILLO 3, NICOLE D. BERGE4

1 USDA-ARS Coastal Plains Soil, Water & Plant Research Center, Florence, SC, USA.
2 Leibniz Institute for Agricultural Eng. and Bioeconomy, Postadm-Bornim, Germany.
3 University of Extremadura, Applied Physics Dept, Badajoz, Spain.
4 University of South Carolina, Civil & Envrion. Dept., Columbia, SC, USA.
Abstract
Combustion behavior of animal manure-based hydrochar was investigated using thermogravimetric

analysis. Swine manure and chicken litter were carbonized at 200 and 250 oC for 4 or 20 hrs. The
thermogravimetric analysis showed that the hydrochars underwent two combustion stages - active
and char combustion, while only one stage was seen for the four local coals. The activation energies
calculated for the hydrochars in the first stage were similar to those of the four coals. All hydrochars
required higher activation energies in the second stage. Ignition, peak, and burnout temperatures of
the animal hydrochar samples were mostly lower than that of the coal samples. The substantial
differences in characteristic combustion temperatures and the kinetic parameters between
hydrochar and actual coal samples suggest that the fossil coals used by existing coal power plants
should not be replaced entirely with hydrochar, but preferably as a blend. More detailed results will
be presented at the conference.
112
INVESTIGATION INTO THE OXYGEN- AND CARBON-CONTAINING FUNCTIONAL

GROUPS TRANSFORMATION DURING SEWAGE SLUDGE PYROLYSIS BY COMBINING
VARIOUS EXPERIMENTS
Yanjun Hu 1, Yanjun Lu 1, Wenjing Yu 1, Yanan Wu 1

1
Institute of Thermal and Power Engineering, Zhejiang University of Technology, HangZhou, China
2
.
Abstract
Pyrolysis is an emerging technology for the disposal of huge amounts of sewage sludge [1]. However,
Pyrolysis artwork of sludge is still at an unmatured stage in many countries, and is absent of
industrial application because of some issues, such as unstable chemical properties of the pyrolysis
products and a low thermal-chemical conversation efficiency. Investigation into the thermochemical
decomposition mechanism of organic compounds in sludge will be helpful to better understand the
mechanism of sludge pyrolysis and improve pyrolysis products quality.
In this study, the effects of heat treatment conditions on the organic structural transformation
of gas and solid products from sewage sludge pyrolysis were studied using Fourier transform infrared
spectroscopy (FTIR) and PY-GC-MS techniques. Sewage sludge was sampled after mechanical
dewatering using a filter press and without using any additives in Linàn Urban wastewater plant,
Hangzhou, China. The development of microstructure evolution of volatile matter in sludge with
temperature rising from 350 to 850 ℃ was in detailed investigated through the observation and
measurement of the evolved carbon- and oxygen-containing functional groups.
Heating rate of pyrolysis can significantly change the species of liquid organic compounds
produced, but cannot change the gaseous species produced under the same conditions. The FT-IR
spectra of the biochar show that pyrolysis temperature highly influenced the thermal transformation
behaviour of major functional groups of sludge, such as -OH, -CH3, -CH2, C=C, and C=O. An evident
decrease in –OH, -CH3, -CH2 and C=O functionalities with the increasing pyrolysis temperature,
corresponding to a decrease in the acidity of the char. FTIR analysis further verified the
enhancement of the second crack at a higher temperature. For sludge pyrolysis at lower than 550℃
by GC-MS analysis, fatty hydrocarbon structures were evidently cracked, but aromatic structures
were little influenced. Hydrogen-enriched degree of biochar was changed irregularly due to the
integrative influence of cracking, aromatization and condensation reactions. The aromatization and
condensation degrees of sludge after 650℃are higher than that of lower temperature pyrolysis, and
the degree of fat chain length of biochar was also increased, but branched degree was little changed.
References
[1] Y. Kim, W. Parker, A technical and economic evaluation of the pyrolysis of sewage sludge for the production of bio-oi,
Bioresource Technology, 99, 1409–1416 (2008) l
113
QUANTIFYING TEMPORAL EFFECTS OF VARIOUS GHG ABATEMENT STRATEGIES FOR

CONVENTIONAL AND DISTRICT HEATING
S. KAR1, P. BILLEN1,2,*, B. KATZ1, S. YANG3, T.A. VOLK3, S. SPATARI1

1 Drexel University, Philadelphia, PA, USA.
2 University of Antwerp, Antwerp, Belgium.
3
State University of New York, Syracuse, NY, USA.
Abstract
In this work, we quantified the distinct effect on climate change of using various types of biomass
(i.e. forest residues versus willow) and fossil fuels (i.e. natural gas and household heating oil), for two
different heating types; conventional home heating (CH) and district heating (DH). Whereas standard
life cycle assessment (LCA) does not discriminate future from contemporary emissions, such
discrimination is crucial to quantify why purposely grown short-rotation biomass may have a lower
impact than wood residues. The difference mainly originates from the very slow decay of wood,
strongly delaying GHG emissions. The tradeoff between CH and DH involves an immediate GHG peak
from DH network installation versus lower operational emissions due to higher energy efficiency.
Therefore, we performed a comparative temporal life cycle analysis of GHG emissions from both CH
and DH systems with various fuels, focused on the Northeastern United States (New York and New
England) as a case study, with two sets of 10 counties (one with and one without pre-existing natural
gas pipeline connection) selected as a result of a prior carbon abatement cost study [1]. In doing so,
the life cycle emissions are disaggregated to annual values to study temporal effects. The
comparative study on the temporal effects of GHG emissions for residential heating considers five
different scenarios: (1) DH by biomass, (2) DH by natural gas, (3) CH by biomass, (4) CH by natural gas
and (5) CH by household heating oil. The latter, current day common practice, serves as a
benchmark.
Our study reveals that purposely grown biomass, in this case willow, often have a lower effect on
climate change (quantified as radiative forcing as a function of time) over the life cycle of DH and CH
systems. This is partially because of the carbon sequestration via belowground roots build-up.
However, more importantly, avoiding the use of forest residues (wood) leaves them to decay very
slowly in the forest, or elsewhere, which serves as effective carbon storage for numerous years. This
decreases the impact of other investigated scenarios significantly. DH systems typically outperform
CH in the medium run, given the higher efficiencies achievable, despite the material and energy cost
of construction/reconversion.
References
[1] L. Björnebo, S. Spatari, P. L. Gurian. Life cycle assessment and cost-effectiveness feasibility study of district heating in
the Northeastern United States, 2017. (submitted)
114
ENVIRONMENTAL ASSESSMENT OF BIOLEACHING OF COPPER FROM ELECTRONIC

WASTE, LIFE CYCLE ASSESSMENT APPROACH
J. LONGSTAFF, D. WHITE, AND M.VALIX

The University of Sydney, Sydney, NSW 2006, Australia
Abstract
Life cycle assessment (LCA) methodology was used in the comparative environmental study of
copper production via the bioleaching of e-waste, flash smelting from ore and flash smelting of ore
and e-waste. The environmental merits of the three treatment techniques were compared by taking
into account the raw materials and energy consumption, air and water emission and waste
production using SimaPro. This study established that the bioleaching technology is the least energy
consuming technique and contribute least to global warming. The impact of the bioleaching process
to the acidification effect and water usage was also significantly lower. However, it was shown that
bioleaching of the metallic components only, results in higher eco-toxicity impact attributed to the
generation of tertiary non-metallic wastes (plastics, glass). This highlights the importance of
addressing the recycling of the wastes as a whole with focus on zero waste generation.
Figure 1: Environmental impacts from LCA models for the production of 1kg refined copper, (a) global warming impact,
(b), acidification impact, (c) eco-toxicity impact, and (d) water usage.
115
LIFE CYCLE ASSESSMENT OF E-WASTE MANAGEMENT IN A PUBLIC UNIVERSITY IN

BRAZIL
B. COSTA1, L.P. ROSADO1, T.B. ROCHA1 and C.S.G. PENTEADO1

1
School of Technology, University of Campinas, Limeira, Brazil.
Keywords: e-waste, WEEE, life cycle assessment
Abstract
The aim of this study is to evaluate the environmental impacts of the waste electrical and electronic
equipment (WEEE) management system adopted in the University of Campinas, Brazil, by means of a
life cycle assessment. The total WEEE generated in 2015 and 2016 were grouped into five classes:
computers (3475 units), laptops (365 units), printers (1090 units), multifunction printers (143) and
miscellaneous (1989 units). The system boundaries include: WEEE transport from University to a
dismantling company; dismantling process; materials transport to recycling companies; recycling
processes, and avoided burdens. Energy and materials consumption from the recycling processes,
avoided products and the environmental burdens related to refuse landfilling were obtained from
the Ecoinvent v3.01. LCA modelling has been performed using the SimaPro software. The study
utilised CML baseline and USEtox life cycle impact assessment methodologies, according to the
impact categories: “Abiotic Depletion”, “Abiotic Depletion (fossil fuels)”, “Global Warming”, “Ozone
Layer Depletion”, “Photochemical Oxidation”, “Acidification”, “Eutrophication”, “Terrestrial
Ecotoxicity”, “Human Toxicity (cancer and non-cancer)”. The recycling of computers and
miscellaneous is the main contributor for the avoided impacts. The electricity consumption in the
dismantling process presents significant impacts for “Human Toxicity (cancer and non-cancer)”. The
impacts of WEEE transport to the dismantling company are negligible compared to the other
processes; the transport of materials and components to recycling presents significant impacts for
“Ozone Layer Depletion”, due to the crude oil extraction. The WEEE management system has
environmental benefits for all impact categories, except for “Human Toxicity (non-cancer)”.
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1- INTRODUCTION
Waste electrical and electronic equipment (WEEE), also known as e-waste, stands out for the volume
generated and the presence of heavy metals and other hazardous substances in its composition [1].
According to the United Nations University (UNU), approximately 42 million tons of WEEE are
generated annually around the world [2], and in Brazil, it is estimated an annual generation of 1.3
million tons [3].
Universities have a significant contribution to the generation of WEEE, since information and
communication equipment such as desktop and laptop computers, printers and photocopy machines
are widely used and frequently replaced [4], and then, the higher education institutions are expected
to internalize policies and programs to properly manage such wastes.
In Brazil, the National Solid Waste Policy has encouraged the reverse logistics as an alternative to
WEEE management, in order to reduce the environmental impacts caused by the incorrect disposal,
and to recover and recycle the materials from the equipment [5]. On the other hand, the reverse
logistics demands transportations, dismantling and recycling operations that consume material and
energy resources, and may also cause environmental impacts. Therefore, it is necessary to assess
whether the benefits of reverse logistics outweigh the impacts of the activity itself.
Life Cycle Assessment (LCA) has been consolidated as an important tool to quantify the potential
environmental impacts of products or systems, from the raw material extraction, through
manufacturing, use and final destination or disposal. Several authors have used LCA to evaluate the
waste management strategies [6, 7, 8].
One of the earliest studies that used LCA to assess the WEEE management, performed by HISCHIER
et. al. (2005) [9] introduced the question: “Does WEEE recycling make sense from an environmental
perspective?”. The results obtained by the authors have shown that WEEE reverse logistics in Swiss
had a massive environmental advantage compared to incineration [9]. In another LCA study,
HUISMAN et al. (2008) [10] have found that the reverse logistics in the European Union has
contributed to an environmental impact reduction by avoiding the emission of approximately 36
million tons of CO2 and 34 million tons of chlorofluorocarbons (CFCs), due to the WEEE recycling.
Although a study conducted by Barba-Gutiérrez et al. (2008) [11] has indicated that the distance of
WEEE collection may jeopardize the benefits of reverse logistics, most studies indicate that the
benefits outweigh the impacts caused by the reverse logistics itself. The main benefits are associated
with the metals and plastics recovery. However, Biganzoli et al. (2015) [12] warn about the adverse
effects related to the toxicity and ecotoxicity impact categories, due to the emissions from steel
recycling.
It is important to emphasize that the results of a LCA study are influenced by the scope and several
assumptions throughout the study. Thus, the geographic and technological scenario can be decisive
for the LCAs results, because the system expansion and substitution points should represent the
local technology and market reality of recycled materials, mainly for the definition of the virgin
materials that are avoided by the recovered ones.
The aim of this study is to assess the potential impacts and environmental benefits of the WEEE
management in the University of Campinas (São Paulo, Brazil), which is considered one of the most
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important universities of Latin America, with 1,910 faculties and 36,598 undergraduate and graduate
students in 2016.

The study consisted of two major phases: (i) gathering data on WEEE generation, characterization
and management in the University; and (ii) conducting a life cycle assessment study on the WEEE
management.
2.1 WEEE management

The WEEE generated in the University of Campinas are composed of broken-down electrical and
electronic equipment, from the Center for Equipment Maintenance1 (CEMEQ), and end-of-use
equipment replaced by new ones. The total amount of WEEE generated are registered, grouped in
lots and stored in a shed of DGA (General Administration Department), from where they are
auctioned to dismantling companies at the end of a year.
Data about the WEEE auctioned in 2015 and 2016 were obtained, and then, the equipment were
classified according to the Brazilian Agency for Industrial Development (ABDI), in four lines: brown
(television, monitor, DVD/VHS, audio devices, camera, etc.); green (laptop, desktop PC, printer,
phone, tablet, etc.); white (refrigerator, stove, washing machine, air conditioner, etc.) and, blue
(blender, electric oven, drill, coffee machine etc.). Figure 1 shows the total WEEE generated in 2015
and 2016 (units), and the respective quantities (average mass) of each line; as expected, the green
line was the most representative in both years, and is the focus of this study. According to the
composition data available in the literature (Table 1), the WEEE were grouped into: desktop PC,
laptop, printer, printer with scanner and other (fax machines, telephones, multimedia projector,
router, keyboard, mouse, and other). For the equipment classified as “other”, it was used data from
a characterization of different types of WEEE. The average mass of each equipment was determined
based on the literature, and the total amount of each group are shown in Figure 1.
Figure 1: WEEE generation in the University of Campinas in 2015 and 2016.
1
The equipment that present any failure or damage is sent to CEMEQ where, if possible, it is repaired and sent back to
the original institute or laboratory, or, it becomes available to other users within the University. If the equipment cannot
be repaired, it is considered as WEEE.
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Composition (%)
Materials
Desktop PC[13] Laptop[13] Printer[14] Printer/Scanner[14] Other[15]
Iron and steel 67 12 21 12 11
Mixed plastics 7 31 71 64 56
Printed Circuit Board (PCB) 15 8 - - 21
Wires and cables 5 11 - - 10
Glass - 18 - 16 1
Aluminum 6 20 - - -
Other - - 8 8 1
Table 1: Data about the WEEE composition used in this study.
2.2 Life cycle assessment

The attributional LCA study was developed according to the requirements of ISO 14.040 and ISO
14.044 standards [16, 17], by means of its four major stages: goal and scope definition; life cycle
inventory (LCI); life cycle impact assessment (LCIA) and interpretation.
Goal and scope definition

The goal of this study was to assess the potential impacts and environmental benefits of the WEEE
management in the University of Campinas. The functional unit was defined as the management of
the total amount of WEEE classified as green line (desktop PC, laptop, printer, printer/scanner and
other) generated in 2015 and 2016, as shown in Figure 1.
The LCA study considered the WEEE transport from the University to a dismantling company; WEEE
dismantling to its different materials and components; materials transport to recycling companies;
recycling processes and, avoided burdens due to the materials recovering. Figure 2 shows the system
boundaries, with the indication of the background and foreground systems [18]. Most of the direct,
indirect and avoided burdens for the LCI elaboration were obtained from the literature and from
Ecoinvent v3.01 [19] database, updated with Brazilian data where possible. The allocation problem
in the LCA model was avoided by using the system expansion method.
The LCA study was performed using the SimaPro software and utilized the CML baseline and USEtox
LCIA methodologies. The impact categories selected from CML baseline methodology were “Abiotic
Depletion” (AD), “Abiotic Depletion (fossil fuels)” (AD-f), “Global Warming” (GWP), “Ozone Layer
Depletion” (ODP), “Photochemical Oxidation” (PO), “Acidification” (AC) and “Eutrophication” (EU).
The impact categories selected from USEtox methodology (consensus only) were “Human Toxicity
(cancer)” (HT-c), “Human Toxicity (non-cancer)” (HT-nc) and “Ecotoxicity” (EC).
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*PCB sorted in the dismantling company are transported to other company (100 km), which clusters PCBs in a larger
batch and send it to another country by ship (12,000 km).
Figure 2: System boundaries for the WEEE management system considered in this study, with the indication of
the foreground and background systems.
Life cycle inventory

The WEEE transport from the University to the dismantling company (primary transport) is done by
truck with capacity of 3.5-7.5 ton (Euro 4); the distance was based on primary data. According to
technical visits carried out in Brazilian dismantling companies in 2016, it was estimated an energy
consumption of 0.2 kWh per kg of WEEE dismantled. Direct and indirect environmental burdens
related to the transport, recycling processes, landfilling and avoided products were obtained from
the Ecoinvent v3.01 and updated with data from the Brazilian electricity mix.
Transport distances of the materials sorted from the dismantling company to the recycling industries
were estimated based on the current scenario, considering the use of a truck with capacity of 16-32
ton (Euro 4). Table 2 lists the recycling processes used in this study, selected from Ecoinvent v3.01
database.
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Recycling Ecoinvent
Avoided products Source*
process module used
Wires and Disposal, treatment of Copper gold-silver-zinc-lead-copper mine operation
[19]
cables cables and refining
Steel production, electric, [20] and
Iron and steel Primary (60%) and secondary (40%) steel
low-alloyed [21]
Aluminum (waste
Aluminum treatment), recycling of Aluminum, primary (ingot) [19]
aluminum
Lead (gold-silver-zinc-lead-copper mine operation
and refining)
Nickel, 99.5% (nickel mine operation, sulfidic ore)
Copper (gold-silver-zinc-lead-copper mine
operation and refining)
Electronics scrap,
Palladium (platinum group metal mine operation,
PCB treatment of, metals [22]
ore with high content)
recovery in copper smelter
Silver (gold-silver-zinc-lead-copper mine operation
and refining)
Gold (gold-silver-zinc-lead-copper mine operation
and refining)
Aluminum, primary (ingot)
Acrylonitrile-butadiene-styrene (ABS) [13];
Electricity, diesel and
Polycarbonate (PC) [14];
Plastics water consumption based
Polystyrene, high impact (HIPS) [15] and
on primary data
Polypropylene (PP) [23]
Disposal, treatment of CRT
Glass Frit, for ceramic tile [24]
glass
*
Note: Source used to determine the substitute materials.
Table 2: Recycling processes used in this study, selected from Ecoinvent v3.01 (2014) database, and the
avoided products considered.
Table 3 presents the total amount of materials obtained from WEEE dismantling and Table 4 shows
the avoided products. It is important to note that the functional units named as “2015” and “2016”
refer to the total amount of WEEE (green line) generated in these years (13.71t and 51.58t,
respectively).
Total amount (kg) related to the functional unit

Materials sorted
2015 2016
Iron and steel 6,242 29,205
Mixed plastics 3,885 9,698
PCB 2,005 6,780
Wires and cables 793 2,417
Glass 85 260
Aluminum 525 2,623
Other (refuse) 174 595
Table 3: Materials obtained from the WEEE dismantling.
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Total amount (kg) related to the functional unit

Avoided products
2015 2016
Copper 955 3,060
Primary steel 3,322 15,541
Secondary steel 2,260 10,572
Aluminum 709 3,241
Precious metals
Lead 12 41
Nickel 67 224
Palladium 1 2
Silver 12 41
Gold 0.4 1
Plastics
ABS 1,184 2,221
PC 515 1,024
HIPS 1,870 5,263
PP 544 803
Frit 72 221
Table 4: Avoided products related to the WEEE management.

Figures 3 and 4 show the characterized results of the WEEE management in 2015 and 2016. In both
years, the impacts of primary and secondary transport are insignificant compared to the other
processes considered in the study. The secondary transport, due to the larger distances and diesel
consumption, contributes to “Ozone Layer Depletion” category.
The dismantling process contributes to “Human Toxicity (cancer and non-cancer)”, due to the
electricity consumption. That impact is explained by the use of biomass energy from sugar cane
bagasse in the Brazilian energy mix (approximately 2%), which, in turn, carries a portion of the
impacts caused by the use of pesticides in sugar cane production.
100% Other EEE recycling
80%
Printer/Scanner recycling
60%
40% Printer recycling

Process contribution
20%
Laptop recycling
0%
Desktop PC recycling
-20%
-40% Transport from dismantling to

recycling chain (secondary)
-60%
Dismantling process
-80%
-100% Transport from DGA to dismantling

AD AD-f GWP ODP PO AC EU HT-c HT-nc EC (primary)
Figure 3: Environmental impact contribution of the WEEE management in 2015.
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In 2015 the recycling of desktop PCs and other EEE has presented the major contribution to the
avoided impacts; in 2016, computer discarding has increased, and consequently, its recycling
presented a remarkable contribution for the majority of avoided impacts. The recycling of these
equipment presents a higher contribution compared to printers and laptops, because they contain a
greater amount of printed circuit boards (PCB) in their composition. Despite representing 15% and
21% of the composition of desktops and other EEE respectively, the recovery of precious metals
from the PCB is the main contributor for the avoided impacts.
100%
Other EEE recycling
80%
Printer/Scanner recycling
60%
40% Printer recycling

20%
Laptop recycling
0%
-20% Desktop PC recycling
-40%
Transport from dismantling to
recycling chain (secondary)
-60%
Dismantling process
-80%
-100% Transport from DGA to

AD AD-f GWP ODP PO AC EU HT-c HT-nc EC dismantling (primary)
Figure 4: Environmental impact contribution of the WEEE management in 2016.
Figure 5 presents the impacts resulting from the recycling of 1 ton of each material obtained from
WEEE dismantling. The copper recovering from cables recycling presents avoided impacts for all
impact categories, especially “Abiotic Depletion”, “Ecotoxicity”, “Human Toxicity (cancer)” and
“Eutrophication”. For “Ecotoxicity” and “Eutrophication” are due to avoided air emissions from
blasting process during the primary copper mining, while for “Human Toxicity (cancer)” is related to
electricity energy saving. The ferrous metals recycling presents impacts for “Human Toxicity (non-
cancer)” and “Ecotoxicity”, due to the electricity consumption in the recycling process; the avoided
impacts are insignificant, compared to the other recycling processes.
The PCB recycling presents avoided impacts for all categories, except “Human Toxicity (cancer)”,
which is mainly influenced by the emission of TCDD (2,3,7,8-tetrachlorodibenzo-p-dioxin) from the
pyrometallurgical process. The avoided impacts related to the “Abiotic Depletion” are due to the
metals recovery (silver, copper, gold and palladium), while the avoided impacts related to
“Photochemical Oxidation” and “Acidification” are due to the avoided emissions of sulphur dioxide
from the palladium mining.
The plastics recycling contributes mainly for the avoided impacts related to the category “Abiotic
Depletion (fossil fuels)”, due to the avoided production of crude oil and natural gas used in plastic
resin manufacturing. The production of recycled HIPS (high impact polystyrene) contributes to the
avoided impacts related to “Global Warming” due to the avoided emissions of CO2 from virgin HIPS
manufacturing; to “Photochemical Oxidation” and “Acidification” due to the avoided emissions of
SO2, and to “Human Toxicity (cancer)” due to the avoided emissions of styrene. The recycling of
polycarbonate contributes in a smaller scale to the avoided impacts of the category “Ecotoxicity”,
due to the avoided emissions of phenol. On the other hand, the plastics recycling presents impacts
123
related to “Human Toxicity (non-cancer)” due to the electricity consumption from the Brazilian
energy mix.
The glass recycling contributes mainly to the avoided impacts of “Ozone Depletion” and “Human
Toxicity (non-cancer)” due to the avoided emissions of CFC-10 from the sodium hydroxide
manufacturing, which is used in primary glass production.
The aluminum recycling contributes to the avoided impacts for most categories; specifically for the
category “Abiotic Depletion (fossil fuels)”, the contribution is related to the avoided coal mining,
while for “Global Warming” it is related to the avoided emissions of CO2, and for “Ozone Layer
Depletion” it is again related to the avoided emission of CFC-10, from the sodium hydroxide
manufacturing, which is now used in primary aluminum production.
60%
Aluminum recycling
40%
Glass recycling
20%
Recycling of plastics from printers/scanner
0%
Recycling of plastics from printers
-20%
Recycling of plastics from desktop PC, laptop

-40% and other
Electronics boards recycling

-60%
-80% Steel recycling
-100% Cable recycling

AD AD-f GWP ODP PO AC EU HT-c HT-nc EC
Figure 5: Environmental impact contribution of the recycling of 1 ton of each material obtained from WEEE
dismantling process.
4- CONCLUSIONS
This study assessed the potential impacts and environmental benefits of the WEEE management in
the University of Campinas, Brazil, by means of LCA, based on data from 2015 and 2016. In both
years, the impacts of the WEEE transport from the University to the dismantling company are
insignificant, if compared to the other processes; the transport of materials and components to the
recycling companies presents significant impacts for the “Ozone Layer Depletion” category, due to
the crude oil extraction. The dismantling process contributes to “Human Toxicity (cancer and non-
cancer)”. The recycling of desktop PCs and other EEE has presented the major contribution to the
avoided impacts. By analysing the impacts of the recycling materials obtained from WEEE
dismantling, it was found that it results in environmental benefits for all categories except for
“Human Toxicity Cancer” (due to the recycling of electronic boards), “Human Toxicity Non-Cancer”
(due to the recycling of plastics and steel) and “Ecotoxicity” (due to the recycling of steel).
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125
SUSTAINABLE PRODUCTION OF FIBRE-REINFORCED POLYMERS MARINE

EQUIPMENT: A CIRCULAR ECONOMY PROSPECTIVE
G. ZAPELLONI, A. GARCÍA RELLÁN, P.M. BELLO BUGALLO

Department of Chemical Engineering, University of Santiago de Compostela, Av. Lope Gómez de
Marzoa, s/n, E-15782 Santiago de Compostela, Spain
Keywords: surfboard, circular economy, Life Cycle Thinking, Material and Energy Flow Analysis,
Improvable Flows
Abstract
The current challenge of the world of manufacture is the conversion towards cleaner and ecological
productive trials. For this, a radical revolution nowadays is possible thanks to policies to fight against
the environmental crisis and the technological progress, like the Circular Economy (CE), a concept
included in the newest environmental policies that World’s countries are adopting.
This work aims to analyse the Fibre-Reinforced Polymers marine equipment activities from the CE
prospective to identify sustainable solutions for the of manufacturing process stage. A surf-boards
job-shop has been selected as case study. Hot spots or Improvable Flows (IF) are identified by
examination of the Material and Energy Flow Analysis results showed by Sankey diagrams. Once
highlighted the entire IF, to minimize the bigger ones, a Best Available Techniques Analysis (BAT) is
done. For that, an inventory of the techniques candidates to be BAT for the sector is completed,
selecting the most adequate to correct the IF in the case study. A “more sustainable” scenario for the
job shop is then defined. Finally Impact Analysis is done to evaluate and compare the effects on
humans and ecosystems of both scenarios.
Ten Improvable Flows have been identified for the process; consequently fifteen candidates to be
BAT have been proposed aiming to act upon these flows. This combination has confirmed to be a
very good option for process evaluation considering sustainability criteria. The use of USETOX
software has permitted to compare the base case scenario with the improved one in the basis of
toxicity impact showing a reduction of the impacts after application of the BAT selected.
126
1- INTRODUCTION
The concept of Circular Economy (CE), which pretends to turn from the linear economic model of
production “take, make, disposal” to the closed loop (in where the raw technical materials may be
recycled and reused and the biological materials may turn back to the soil) is one of the most recent
production philosophies [1]. A shift to CE requires eco-innovations to close the loop of the products
lifecycle, to get valuable products to others from waste and to solve the needs of environmental
resilience despite the tendency towards economic growth [2].
Leisure activities at sea are anthropogenic activities that have a potential impact on the marine
environment, not only at the use stage (such as microplastics) and at the end-use stage (such as
“ocean plastic wastes”), but also because of the impacts on the entire life cycle of the product, being
manufacturing the more relevant stage in terms of impacts. Ships, boats, canoes and surfboards are
generally made of polymers. Fibre-Reinforced Polymer (FRP) is the prevalent material used for this
marine equipment. Volatile Organic Compounds (VOCs) are emitted during the fiberglass marine
equipment production, mainly styrene, classified as possible human carcinogen.
There are many examples of companies implementing CE strategies on specific products in various
sectors [3]. The European Commission has integrated circular economy aspects into the Best
Available Techniques Reference Documents (BREFs) which EU Member States must reflect when
issuing permits for industrial installations [4]. These documents reference the Best Available
Techniques (BAT) for each sector and they are defined by the IPPC directive (Integrated Pollution
Prevention and Control [5]). BAT are considered technologies and organizational measures that are
most effective in achieving a high level of protection of the environment as a whole, and it can be
implemented under economically and technically viable conditions [6]. The analysis of BAT in the
industry is a tool applicable together with Life Cycle Thinking focus with the aim to optimize the
sustainable behavior in the industry [7, 8].
Other tools are used to analyze the sustainable behavior of systems, as MEFA (Material and Energy
Analysis), a tool derived from industrial metabolism; this tool explores the material and energy flows
and stocks in a system [9]. The data and results of MEFA can be used in LCIA (Life Cycle Impact
Assessment) that is used for quantifying potential environmental impacts of products, processes, or
services [10], but also to identify improvable flows inside the system to improve its sustainability.
The goal of this work is to develop, to apply and to validate a methodology focused in the Circular
Economy to build a more sustainable model for the Fibre-Reinforced Polymers (FRP) marine
equipment. The study is mainly applied to the manufacturing process, and the selected plant is a
surfboards job-shop. To achieve this objective three tools are used: Material and Energy Flow
Analysis (MEFA), Best Available Techniques (BAT) analysis, and toxicological Impact Assessment (IA)
on human beings and ecosystems. A methodology to identify sustainable industrial systems
previously proposed is adapted to be applied in this case. It includes a Material and Energy Flow
analysis (MEFA) of the production process that is developed using the STAN software. Furthermore,
hot spots or Improvable Flows (IF) are identified by examination of the Material and Energy Flow
Analysis results showed by Sankey diagrams. Once highlighted the entire Improvable Flows, to
minimize the bigger ones, a Best Available Techniques Analysis is done. For that, an inventory of the
techniques candidates to be Best Available Techniques for the sector is completed. The most
127
adequate Best Available Techniques candidates to correct the Improvable Flows in the case study are
selected to build new “more sustainable” scenarios for the job shop. To compare the real scenario
(base case) and the hypothetic (proposed case), Life Cycle Thinking Tools are used: Impact Analysis is
done to evaluate and compare the effects on humans and ecosystems of both scenarios, real
scenario (base case) and the hypothetic (built case). As suggested by the Life Cycle Initiative [11] the
impacts on the human health and on the environment are calculated using the USETOX software,
specific software for the ecotoxicological impacts. Finally, an outline related to the substitution of
the raw material during the production process by more ecological ones is presented and included in
the more sustainable scenario. This more sustainable scenario will also be analysed with USETOX
software including these changes in raw materials.
The intention is to search an improved process configuration and compare it with the conventional
one, to show how the combination of the previous tools turns out to be a good criteria of
sustainability evaluation. In this work the emphasis will be for the production phase rather than for
the use of the marine equipment product.

A new combination of tools defined in the framework of life cycle thinking is proposed as a
methodology based in previously works [12, 13, and 14]. This methodology combines, MEFA, BAT
analysis and Impact assessment on human beings and ecosystems, following the steps:
1. Case study selection and description. This step includes the research of the Fibre Reinforced
Plastic (FRP) equipment production plant in Spain and in Portugal. Some of the main factories
in both countries have been selected and contacted. The result of this point was the
identification of the industrial plant to be considered as the case study.
2. Qualitative analysis of the selected industrial system. Identification of the system limits,
definition and description of its stages, and analysis of inputs, outputs and internal flows.
These analyses are based on technical visits to the plant and on bibliographic reviews.
3. Quantitative analysis of the productive process. Data acquired during the visit of the plant are
reported and explained. This step will be completed by a Material and Energy Flow Analysis
of the system (MEFA). The steps are:
a. Data acquisition: identification of the data needed to fill the model. Data may be
acquired by direct measurements at the industrial plant, best estimates, interviews,
databases of environmental protection agencies and articles from scientific journals.
b. Model and scenario building. The network of the process is built, the model is run and
MEFA results are obtained. This point includes the following steps:
i. Software selection.
ii. System modelling using the selected software: scenario building creating
networks and subnets. The model is fed with the data collected.
iii. Model running and results of MEFA: when the model is completely
implemented in the software, it is ran in order to obtain the results of the
MEFA.
4. Selection of improvable flows. The results obtained from the MEFA are analysed to identify
the IF. Sankey diagrams of the flows facilitate this task.
5. Best Available Techniques (BAT) Analysis.
128
a. Recompilation and inventory of the techniques candidate to be BAT in the selected

system. The candidate techniques are inventoried according to the methods proposed
in previous works.
b. Proposal of alternatives to the process. Candidate techniques to be BAT are selected
for each IF identified.
6. Human and ecological impact assessment. Selection and use of the USEtox model tool. The
characterization factors of each pollutant are combined to calculate the impact of the job-
shop on the human end ecosystems health.
a. Impact score of base case scenario.
b. Impact score of improved scenario.
c. Results and comparison between the base case scenario and the improved scenario.

3.1. CASE STUDY SELECTION
The surfboards job shop is and industry similar to the shipyard one. Part of the production processes
and the used raw material are the same or very similar using Fiber Reinforced Polymer (FRP).
Before choosing the plant to be analyzed, different producers in Portugal and in Spain have been
contacted; the choice has considered the geographical situation of the plants (factors that influence
the accessibility to the it) and the availability of the data/information required for the work. Finally,
the selection is reverted on a smaller surfboards factory in Galicia, STINKY TOFU. The plant is a
atomized one fact that makes it interesting to jointly evaluate the potential for improvement in
sustainability in this type of plants often forgotten by the administration due to its size.
Figure 1. Qualitative flowchart of the surfboards production process
129
The installation, situated in Ribeira (Galicia, Spain), is a job-shop with only one employer which is
helped by another one during the period with more intense work (that generally is taken place in the
summer). The employer declared he works 7 hours per day and 6 days per week. In 2016 he
produced 140 surfboards. His boards are manufactured following the typical operational steps
carried out in most of the plants all over the world for the same purpose, for which the case study is
taken as example between all the similar realities.
3.2. QUALITATIVE ANALYSIS OF THE SELECTED INDUSTRIAL SECTOR

As it can be seen in Figure 1, the production of surf board requires a series of activities that can be
classified in five main stages. Each stage is explained below in accordance with Figure 1.
3.2.1. EXTERNAL OPERATIONS
There are some operations that are held outside the workshop. It is the case of the foam, cloth, resin
and others material purchase.
3.2.2. PRELIMINARY OPERATIONS

This stage is composed by several operations necessary for the following workmanship.
- Material reception and storage. Part of the materials required came from national or
international companies which send the goods directly to the plant.
- Resin preparation. This operation is needed before starting the glassing and it is carried out in the
glassing room
- Programming of the PC software connected with the “cutting machining”. This is not always a
necessary operation because the pre-shaping with the cutting machine is only sometimes used.
- Templates preparation. The employer needs a wood foil for cutting to transform it into a new
template Surfboard lines design.
- Surfboard lines design. Surfboard lines design is the last operation before starting the pre-shaping,
in the case of 100% handmade surfboards, or the shaping, in the case of automatic pre-shaped
boards.
3.2.3. PROCESSING
The “Processing” stage is the main surfboard manufacturing step
- Pre-shaping. This operation consists on producing an almost definitive form from starting foam
blank.
- Shaping. It consists on a use of a series of tools that permit to achieve the desired final shape.
The use of measuring tools is necessary, sure form, sandpapers, and planer.
- Fins attachment system holing. A template is supported on the exact point where it needs to be
holed and with an electric router the foam is cut and taken off.
- Glassing. The operation consists on unrolling one layer of fiber on the bottom surface and on
impregnating it with the resin with the help of a spatula, and then when it dries, he turns the
board and unrolls two layers of fiber on the top surface, and again the resin is sprinkled
- Curing. At this point, the operator can’t make anything upon the current board, so he can work
on other board operations, or auxiliary operations that suppose no use of the board.
- Leash plugs cap installation. Once the resin is dried it is time to hole the back part of the board to
integrate the plug cap.
- Sanding. It is the operation in which the electric sander is used to make the board surface
smooth and homogenous
130
- Polishing. This operation is not always carried out, it is needed when you want the surface’s
board to shine
3.2.4. FINAL OPERATIONS

These operations are carried out additionally as complementary, but that are not functional to the
production of the surfboards.
- Painting. When required by the client, the employer utilizes acrylic paints. To fix the paint a lake
is used.
- Packaging. Some surfboards are packaged and shipped.
3.2.5. AUXILIARY OPERATIONS

The auxiliary operations consist mainly on water and electric supply, the first for cleaning especially
after glassing
- Air pressure washing. During the shaping, to wipe out the dust from the foam form is important,
with an electrical air compressor.
- Water pressure washing. A flow of compressed water is used to clean the board from the resin
dust after the sanding.
- Tool cleaning. The main important tools to be cleaned are those that were in contact with the
resin.
- Tap water supply. This stage includes all the operations which use tap water, like water pressure
washing, but also hand washing, use of toilet and others.
- Room cleaning. Due to the big quantity of dust and others particles and drop of resin and paint,
the whole plant needs to be cleaned periodically
- Dehumidifier. It is required in the glassing room to maintain a low humidity level. Electricity
supply is necessary.
- Electric fire. To keep a specific temperature in the glassing room is also required, for this an
electric/liquid fuel heater is utilized.
3.3. QUANTITATIVE ANALYSIS OF THE SELECTED INDUSTRIAL SECTOR

3.3.1 DATA ACQUISITION
Data acquisition is acquired directly at the workshop, by visits or by interviews. This data
corresponds to the production of surfboards in 2016. Not every data is being of easy acquisition, so
part of them which was necessary for the material and energy flows networks modelling was
calculated later indirectly. Whereas a remaining small part of the materials are not considered
because of the lack of data, and the associated environmental aspects have been not identified as
potential in the qualitative analysis.
3.3.2. MODEL AND SCENARIO BUILDING

This activity is very variable during the year and it depends firstly on the client demand, but other
factors can change the production intensity. For this reason, and according to the objective of this
work, the developed model is a steady state model. MEFA is an adequate focus to identify the
improvable flows.
In order to build the model of the conventional scenario, three different types of software are
considered and evaluated: ASPEN HYSIS (a process simulator), Umberto (specific and commercial
131
MEFA software) and STAN (non-commercial and specific MEFA software). Aspen HYSIS and Umberto,
even if they are stated softwares, they are more suitable to develop the quantitative analysis for
other types of systems. On the other hand, STAN is a free software that permits to perform material
and energy flow analysis for simpler systems, thanks to a simple and clear graphical interface, and it
is of easy use.
To build the model in STAN flows and stocks network is implemented. In STAN this is made with
predefined components named: “processes”, which are the stocks, “flows”, “system boundary” and
auxiliary text field. The processes are represented by polygonal boxes, the flows by arrows and the
system boundary by closed dotted lines. In this model the external operations to the job-shop have
not been examined, whereas all the workshop internal operations, even if those are not directly
connected with the manufacturing work because they are carried out occasionally (like for example
the “room cleaning”), have been considered by means of their input and output (see Figure 1).
The results for the material flows are shown in Figure 2, representing the Glassing process sub-
system and in Figure 3 representing the entire diagram of the production model.
Figure 2: Material Sankey diagram obtained for the Glassing process. Expressed in kg/yr
132
Figure 3: Material Sankey diagram obtained for the whole process. Expressed in kg/yr
3.5. SELECTION OF IMPROVABLE FLOWS

According to with the results of MEFA, ten Improvable Flows have been identified (Table 1). Keeping
in mind the previous IF, the following point will be shown all candidates BAT that could improve
these flows, but also other aspects of the production process.
OPERATION IMPROVABLE FLOW

INPUT OUTPUT ENERGY
SHAPING PU consumption PU dust and scraps Electricity
consumption
RESIN PREPARATION Ruined resin (barrels)
GLASSING Acetone VOCs Energy( termal and

Consumption electricity)
consumption
SANDING Water
PAINTING Spray paint cans

Electricity
WASTE consumption
Table 1: Potential IF identified after evaluating the results of MEFA.
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3.6. BEST AVAILABLE TECHNIQUES (BAT) ANALYSIS

The methodology used for the BAT analysis follows that of other works [15] and the inventory of all
the possible Best Available Technique (candidates) is done after consulting different documents [16,
17, 18, 19, 20, 21 and 22]. An inventory of almost 70 candidate BAT has been implemented. 15 BATs
have been selected to be implemented in the case study. Table 2 the selected BATs are presented
with their relative benefit’s values. The benefits are not quantifiable for all the selected techniques.
Stage BAT Benefits
Ensure the isolation of the different work Reduce till 90% fugitive VOCs emissions
General spaces the more efficient possible, to from the glassing/curing room
avoid high air exchange.
Computerized inventory control No data found

Solid waste segregation No data found
Glassing Store and reuse cleaning solvents 80 - 90 % of cleaning and purge solvent
can be recovered for re-use [18]
Cover containers and vats Till -80% VOC (acetone) emission [18]
Conserve the resin between 18 to 25 It allows the resin exploitation till 100%
grades Celsius. [22]
Resin Use smaller barrels of resin It allows the resin exploitation till 100%
preparation
Add a nitro diluent It allows the resin exploitation till 100%
[22]
Glassing/ Air extraction from coating and Ensure 100% waste air treatment
curing/ drying(curing) processes
painting
UV oxidation VOCs removal efficiency 95% [18]
Shaping/ Air extraction from shaping and painting Ensure 100% waste air treatment
sanding room processes
/Painting
Cyclones or fabric filter Particulate removal <70% to 99% [18, 23]

Painting Water-based paints VOC reduction < 80% to 90%. [18]
Table 2: Selected BATs for the case study.
3.7. HUMAN AND ECOLOGICAL IMPACT ASSESSMENT
In this point is estimated how much the selected surfboard production job-shop affects the human
health and the environment in the current configuration and then with the improvable one, and thus
compare the results to decree the more sustainable. The tool used for the Impact Assessment (IA) is
USEtox® model. The USEtox model is currently constructed to provide characterization factors (CFs)
for human health and freshwater ecological damages for pollutants emissions to indoor air, urban
air, rural air, freshwater and agricultural soil. Combined with emitted mass, the CFs thus serve
134
derivation of an Impact Score (IS) for all compounds for each product or product system in a
comparative LCA-setting, which concerns our goal, in fact the final impact scores are used as input
for selecting the preferred product system (scenario). Human health damages include carcinogenic
impacts, non-carcinogenic impacts, and total impacts (carcinogenic and non-carcinogenic). Ecological
damages addressed in USEtox are freshwater ecotoxicity for a range of aquatic species [24].
In order to compare the two configurations of production, the chosen functional unit is: “production
of 140 surfboards” because this is the production considered in the previous points of this work
(year 2016). The referred board size is the same chosen for the quantitative analysis.
The results of the IS obtained are here debated and compared to evidence the variation on the
human and ecotoxicological impacts (Figure 5 and Figure 6), due to change on the base process
configuration (base case scenario) after the adoption of the BATs. The new trial configuration
appears as “Improved Scenario”.
Regarding the endpoint human toxicity, the gap between the impacts of the relative scenarios is
more accentuated that the midpoint, and the reason is the major availability of the pollutants CFs
data that make the results more reliable. Anyway, the IS values remain in the same order of
magnitude. Ecotoxicity (only for fresh water) shows a clear difference between the IS values of the
two scenarios. At the midpoint level the improved scenario is more than 25 CTUe down of the
conventional scenario, whereas at the endpoint level the difference is about of 20 CTUe.
Comparing Figure 7 and Figure 8 is observed that the ecosystem is more affected by this activity,
demonstrating a higher vulnerability to the pollutant generated from the job-shop analysed. In both
cases, the impacts are reduced by the improved scenario. In conclusion, also keeping in mind the
existence of a grade of uncertain of the results, it is can state that the application of the BATs have
permitted to reduce the amount of material and his relative emissions, so the relief of the impact is
unavoidable.
120
Human Toxicity Ecotoxicity
100
1,00E-01
80
8,00E-02 base case
base case 60 scenario
6,00E-02
scenario improved
4,00E-02 40 scenario
improved
scenario 20
2,00E-02
0,00E+00 0
1 2 1 2
Figure 5: Impact Scores of Human Toxicity. 1- Midpoint human Figure 6: Impact Score of Ecotoxicity. 1- Midpoint ecotoxicity; 2-
toxicity; 2- Endpoint human toxicity Endpoint ecotoxicity.
4. CONCLUSIONS
This paper presents a methodology intended to use sustainable indicators and the LCT focus into a
job-shop production process. The method combines three tools: the MEFA, to identify the IF of the
135
process, the BAT analysis, to propose the most appropriate techniques to improve the sustainability
of the production process, and the Impact Analysis to compare the effects on humans and
ecosystems (fresh water) caused by the activity of a plant in the conventional configuration, and in
the improved one. The method has been validated in a small surfboards production job-shop. The
combination of MEFA and BAT analysis has confirmed to be a very good option for process
evaluation considering sustainability criteria.
The use of USEtox model has permitted to compare the base case scenario with the improved one in
the basis of toxicity impact. The Excel spreadsheet resulted of easy use although the large quantity of
data presented. The results achieved with the calculation of the IS relative to the two scenarios from
the CFs of USEtox, demonstrate consistency with the expected results, and show the reduction of
the impacts after the application of the selected BATs.
This methodology has turned out to be applicable also to a job-shop that apparently does not seem
have impacts because of its restricted and simple industrial metabolism; with MEFA deep
information about the environmental aspects of the process can be extracted to identify the IF
(whether they are inputs, outputs or internal flows), and with BAT analysis and its adoption, which
helps taking into account not only environmental aspects but also economical that may affect the
selection of techniques, the environmental performance can be improved and this job-shop may be
transformed into a “low impact” plant.
These results are very useful to enhance the process efficiency; resources consumption, waste and
emissions generation are reduced, and, at lower level, economical aspects are considered to not
affect them. Due to these reasons the work is endorsed to fall within the Circular Economy model.
REFERENCES
[1] European Commission, 2015. “Closing the loop: Commission adopts ambitious new Circular Economy Package to
boost competitiveness, create jobs and generate sustainable growth”. http://e http://europa.eu/rapid/press-
release_IP-15-6203_en.htm (Accessed, April 2018).
[2] Korhonen, J., Nuur, C., Feldmann, A., Eshetu Birkie, S., 2018. Circular economy as an essentially contested concept.
Journal of Cleaner Production. Vol. 175, pp. 544-552.
[3] European Parliament, 2016. Briefing, “Closing the loop – New circular economy package”
[4] Commission European, 2017. Report from the commission to the European Parliament, the council, the European
economic and social committee and the committee of the regions on the implementation of the Circular Economy
Action Plan.
[5] Council Directive 96/61/EC of 24 September 1996 concerning integrated pollution prevention and control. Official
Journal of the European Communities. Nº257, pp 26-40.
[6] Evrard, D., Villot, J., Armiyaou, C., Gaucher, R., Bouhrizi, S., Laforest, V., 2018. Best Available Techniques: An
integrated method for multicriteria assessment of reference installations. Journal of Cleaner Production. Vol. 176,
pp. 1034-1044.
[7] Bello Bugallo, P.M., Stupak, A., Cristobal Andrade, L., Torres López, R., 2013. Material flow analysis in a cooked
mussel processing industry. Journal of Food Engineering. 113, 100–117.
[8] Torres Lopez, E.R., Doval Leira, R.,Martínez Galera, M., Bello Bugallo, P.M., 2017. Integrated environmental permit
through best available techniques: evaluation of the dairy industry. Journal of Cleaner Production 162, 512–528.
[9] Saavedra, Y.M.B., Iritani, D.R., Pavan, A.L.R., Ometto, A.R., 2018. Theorical contribution of industrial ecology to
circular economy. J. Clean. Prod. 170, 1514–1522.
[10] Verones, F., Bare, J., Bulle, C., Frischknecht, R., Hauschild, M., Hellweg, S., Henderson, A., Jolliet, O., Laurent, A., Liao,
X., Lindner, J.P., de Souza, D.M., Michelsen, O., Pataouillard, L., Pfister, S., Posthuma, l., Prado, V., Ridoutt, B., Fantke,
P., 2017. LCIA framework and cross-cutting issues guidance within the UNEP-SETAC Life Cycle Initiative. Journal of
Cleaner Production. Vol. 161, pp. 957-967.
[11] UNEP & SETAC, 2016. The Life Cycle Iniciative. http://www.lifecycleinitiative.org (accessed 6.04.17).
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[12] Torres Rodríguez, M.T., Cristóbal Andrade, L., Bello Bugallo, P.M., Casares Long, J.J., 2011.Combining LCT tools for
the optimization of an industrial process: Material and energy flow analysis and best available techniques. J. Hazard.
Mater., 192, 1705-1719.
[13] Taboada M.G., Iglesias, A. M., López, R. T., & Bugallo, P. B., 2016. Towards sustainable systems configurations:
application to an existing fish and seafood canning industry. J. Cleaner Prod., 129, 374-383.
[14] Torres Lopez, E.R., Doval Leira, R., Galera Martínez, Bello Bugallo, P.M., 2017. Integrated environmental permit
through Best Available Techniques: Evaluation of the dairy industry. Journal of Cleaner Production. Vol. 162, pp. 512-
528.
[15] Barros, M.C., Bello, P.M., Roca, E., Casares, J.J., 2007. Integrated pollution prevention and control for heavy ceramic
industry in Galicia (NW Spain) J. Hazard. Mater 141, 680–692.
[16] EPA U.S. Environmental Protection Agency, 1991. Guides to Pollution Prevention- The Fiberglass –reinforced and
composite plastics industry.
[17] Kong, E. J., Bahner, M. A., & Turner, S. L., 1996. Assessment of styrene emission controls for FRP/C and boat building
industries. US Environmental Protection Agency, National Risk Management Research Laboratory.
[18] EU, 2007. Reference Document on Best Available Techniques on Surface Treatment using Organic Solvents.
[19] Darryl Davis Chainnan, 1987. Pollution reduction strategies in the fiberglass boat building and open mold plastics
industries. Department of Manufacturing East Carolina University.
[20] EPA U.S. Environmental Protection Agency, 1993. Locating and air emission from source of styrene.
[21] Torres Rodríguez, M.T., Barros, M.C., Bello Bugallo, P.M., Casares Long, J.J., 2006. Pollution prevention and control in
fiberglass-reinforced boat building. 6th ANQUE International Congress of Chemistry Sustainable Development.
[22] Andros, 2016. Resine poliesteri ed epossidiche - cosa sono, come usarle.
[23] EC, 2016, Best Available Techniques (BAT) Reference Document for Common Waste Water and Waste Gas
Treatment/Management Systems in the Chemical Sector), European Commission, JRC IPTS EIPPCB, 2016.
[24] Fantke, P. (Ed.), Huijbregts, M., Margni, M., Hauschild, M., Jolliet, O., McKone, T.E., Rosenbaum, R.K., van de Meent,
D., 2015. USEtox® 2.0 User Manual (Version 2), http://usetox.org
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PEAK-LOAD HIGH-TEMPERATURE CARBONATE STORAGE
C. LANGE1, D. MÜLLER1, J. KARL1

1 University Erlangen-Nürnberg, Nürnberg, Germany.
Abstract
The use of CaCO3 as thermochemical heat storage was first discussed in theory in the 1970s. With the
rise of solarthermal power plants and a request for more flexible steam power plants during German
“Energiewende”, high temperature heat storage came in focus of research again. Through high temp-
erature levels and reasonable reaction enthalpies, carbonate storage systems offer a high storage
density, allowing dynamical charge & discharge. Unfortunately, conventional storages based on fixed
beds are limited by low heat transfer coefficients and will not be adequate for dynamic operation.
Concept
The suggested concept within this project located at the Energy Campus Nürnberg will use high-
temperature sodium heatpipes for the dynamic charge and discharge processes. The use of heatpipes
with optimal heat transfer capacities in fluidized beds allows an isothermal temperature profile in the
reactor and considerably higher heat flux densities than conventional heat storages.
Charging happens through an endothermal calcination of CaCO3 to CaO and CO2. In case of heat
isothermal charge/discharge demand, the temporarily stored CO2 re-enters the reactor
CO2- partial and carbonates CaO with a release of 182,1 kJ/mol heat at
pressure CaCO 3 temperature levels of up to 900°C [1]. An integration of a
1 bar steam generator will provide steam at high temperatures,
discharge
suitable for steam turbines of conventional power plants.
charge
0.2 bar The advantage of this design with heat transfer by means
CaO + CO2
of heatpipes will be an isothermal operation of the
equilibrium reactor. In this case, a dynamically varied CO2 partial
pressure
pressure is able to influence the equilibrium towards
800 °C 896 °C temperature
calcination or carbonation (figure 1).
Figure 1: Equilibrium pressure [1] and isothermal storage concept for CaCO3↔CaO+CO2
Challenges
This conference contribution will present results concerning the reversible capacity of CaO for
capturing CO2, as sintering reduces pore volume and limits reaction surface [2]. These effects will be
investigated in a thermogravimetric analysis, with special focus on the influence of steam-hydration
as a possible regeneration process [3].
In addition, preliminary tests regarding an efficient control of steam generation with heatpipes during
charge & discharge cylces will provide proof-of-concept of the innovative heatpipe design. They will
be an important milestone for the construction of a fully integrated 300 kWh carbonate heat storage.
References
[1] Stanmore, B.R., Gilot, P.: Review - Calcination and Carbonation of Limestone during Thermal Cycling for CO2
Sequestration. Fuel Processing Technology 86 (16), 1707–1743 (2005)
[2] Lu, H., Reddy, E.P., Smirniotis, P.G.: Calcium Oxide Based Sorbents for Capture of Carbon Dioxide at High Temperatures.
Industrial & Engineering Chemistry Research, 45, 3944–3949 (2006)
[3] Han, L., Wang, Q., Ma, Q., Guan, J., Luo, Z., Cen, K.: Hydration Reactivation of CaO-Based Sorbent for Cyclic Calcination-
Carbonation Reactions. Proceedings of the 20th Intl. Conference on Fluidized Bed Combustion, 726–731 (2009)
138
EXPERIMENTAL AND NUMERICAL INVESTIGATIONS OF THERMOCLINE CERAMIC BED

FOR THERMAL STORAGE SYSTEM AT HIGH TEMPERATURE
A.R. SANE 1, D. PHAM MINH1, P. SHARROCK1, A. NZIHOU1

1 Université de Toulouse, Mines Albi, UMR CNRS 5302, Centre RAPSODEE, Campus Jarlard, F-81013
Albi Cedex 09, France.
Abstract
The development of renewable energy resources such as solar, wind, biomass, and wastes is highly
recommended for the 21th century. Among them, solar energy and waste heat from industrial sites
are significantly important. The recovery rate of waste heat is still low, even in developed countries.
According to the International Energy Agency (IEA) [1], by 2050, 9.6% of global electricity could be
produced from concentrating solar power plant (CSP), especially from solar tower power plants [2].
For both CSP and waste heat recovery, energy storage system is needed because of the
intermittence property of these energy sources. Also, it must be able to recover and supply heat up
to high temperature, around 1000°C.
Packed bed thermal energy storage systems with air as high-temperature heat transfer fluid are a
cost effective technology since air is free, non-toxic and non-flammable and can operate at very high
temperature. However, the thermal efficiency of TES system depends on several parameters such as
bed dimension, bed implantation, sharp and size of material particles etc., and the experimental
study of the influence of these parameters on the thermal performance is difficult, mostly due to
high costs required.
In this work, an experimental study was firstly done in order to investigate the thermocline
behaviour of a conventional ceramics packed bed TES system. A pilot-scale thermal storage unit was
used to generate thermocline, using up to around 160 kg of inert ceramic materials. Air was used as
heat transfer fluid.
Secondly, a dynamic 1D numerical heat transfer model is built taking into account the role of air,
solid ceramic and reservoir wall, as well as thermo-physical properties of the material in a large
temperature range of 20 to 1000°C. In addition, this model integrates all the parameters that act on
the temperature profiles in the tank during the charging and discharging phases. This model was
developed in the environment of COMSOL multiphysics@ and was successfully validated with
previous experimental results. The validated model was further used to (1) simulate different
working conditions of TES system and (2) investigate the influence of keys parameters on the
efficiency of the overall heat storage.
References
[1] IEA : Technology roadmap-concentrating solar power, Paris (2014).
[2] Ugo Pelay, Lingai Luo, Yinlin Fan, Driss Stitou, Mark Rood: Thermal energy storage systems for concentrated solar
power plants. Renewable and suistainable Energy Reviews. 79, 82-100 (2017).
139
AIR/CERAMIC PACKED BED THERMOCLINE STORAGE SYSTEM AT PILOT SCALE–

INFLUENCE OF OPERATING CONDITIONS ON SYSTEM BEHAVIOUR
N. LOPEZ-FERBER1,2,4, V. GOETZ1, Q. FALCOZ1, A. NZIHOU2, D. PHAM MINH2, A. MEFFRE3, J.F.

HOFFMANN3
1 PROMES, CNRS, Rambla de la Thermodynamique, Tecnosud, 66100 Perpignan, France
2 Université de Toulouse, Mines-Albi, CNRS UMR 5302, Centre RAPSODEE, Albi, France
3 .Eco-Tech Ceram, Espace Entreprises Méditerranée, Rivesaltes, France
4 Corresponding author: Nicolas.lopez-ferber@promes.cnrs.fr, +33(0)674702718
Abstract
The development of Concentrated Solar Power implies a need for thermal energy storage solutions.
In the same time, industrial waste heat still represents a considerable fraction of the industrial
energetic uptake [1], especially in high-temperature processes found in mineral and metallurgical
industries. Both CSP and energy-intensive industries can benefit from recovering, storing and
delivering heat when needed to increase global plant efficiency.
The packed bed thermocline storage systems could provide an interesting answer to these needs.
Most of the work has been done on the modelling of this kind of systems [2], but there are not
currently widely deployed in the industry. Eco-Tech Ceram is developing a compact and cost-efficient
thermocline packed bed storage of 1-3 MWh. As there’s still a need to study the behaviour of the
system when used in different industrial scenarii a packed bed storage system at pilot scale (45 kWh)
using alumina beads as TESM and air as HTF has been built and operated according different operating
conditions: mass flow rate and inlet air temperature; symmetric and asymmetric charge and discharge;
successive charges and discharges. Influence of degraded thermal input (unstable inlet temperature
and HTF flow rate) during charging phase and influence of CutOff parameters on performances are
currently being investigated. First results exhibit good cycling capabilities of the system, with storage
yields reaching up to 98% depending on operating parameters. The behaviour under repeating cycles
revealed good stability of the thermocline.
Figure 1 : 3D view of the pilot rig Figure 1 State of the packed bed, after each phase when cycled repeatedly
(Charging parameters : Tinlet=590°C, minlet=100kg/h, Tcutoff-charge=150°C,
Discharging parameters : Tinlet=ambiant, minlet=100kg/h, Tcutoff-discharge=450°C
References
[1] I. Johnson et al., Waste Heat Recovery – Technology and opportunities in U.S. industry (2008)
[2] H. Bindra et al., Thermal analysis and exergy evaluation of packed bed thermal storage systems. Journal of applied
thermal engineering, 52, 255-263 (2013)
140
PERFORMANCE OF COUPLING AN AEROBIC PRE-TREATMENT AND SOLID-STATE

ANAEROBIC DIGESTION OF FOOD WASTE
H. FISGATIVA 1, A. TREMIER1, P. DABERT1

1 Irstea, 17 avenue de Cucillé, CS 64427, 35044 Rennes cedex, France.
Abstract
Food loss and wastage lead to major amount of waste that has to be prevented as much as possible.
However, non-preventable food waste (FW) also represents a very interesting bioresource for energy
production through anaerobic digestion (AD). To ensure digestion performance and limit negative
impacts of FW characteristics on biogas production [1], an aerobic pre-treatment has been
investigated.
An experimental design was proposed to test the influence of three parameters on the FW AD
performance: (1) the typological content of FW (paper/no paper); (2) the aerobic pre-treatment (no
pre-treatment/dynamic aeration [2] /static storage); (3) the way to manage the AD process (two
frequencies of leachate recirculation in a batch leach bed reactor (LBR) [3]). The performance of the
digestion was assessed by measuring pH, VFA, biogas production and by modelling the kinetics of
methane production using Gompertz equation. A statistical analyse of variance was performed to
identify the significant impact of studied parameters on the AD performance.
The experimental design showed that FW AD performs well in a LBR without aerobic pre-treatment
and without paper in the FW. The batch test demonstrated a biogas production reaching more than
80% of the biomethane potential with a daily leachate recirculation. A high production of VFA was
noticed (~25 gDCO.L-1) that did not lead to inhibition. A lower frequency of leachate recirculation or
the addition of paper induced a lower production of methane. The introduction of a two-day
aeration step stabilized the production of VFA along the digestion process. Moreover, it enabled a
better degradation of the paper and increased the digestion performance in case of low frequency of
leachate recirculation. Conversely, after a static storage step, a rapid acidification of the waste
medium was observed along with a significant decrease of methane production. Statistical analysis
of variance performed on modelling results shows that AD leachate recirculation condition was the
more impacting parameter on methane production.
Results lead to conclude that optimisation of FW AD conditions may enhance performance better
than aerobic pre-treatments. However, dynamic aerobic pre-treatment lowers average VFA
production during AD without loss of methane production, showing process stabilization potential in
case of high VFA accumulation. Further investigations are on-going to better understand
transformations of the FW during the storage step and on AD FW conditions optimisation within the
DECISIVE project (H2020 Grant N°689229).
References
[1] Fisgativa, H., et al., Understanding the anaerobic biodegradability of food waste: Relationship between the
typological, biochemical and microbial characteristics. Journal of Environmental Management, 2017. 188: p. 95-107.
[2] Berthe, L., et al., Coupling a respirometer and a pycnometer, to study the biodegradability of solid organic wastes
during composting. Biosystems Engineering, 2007. 97(1): p. 75-88.
[3] Degueurce, A., A. Trémier, and P. Peu, Dynamic effect of leachate recirculation on batch mode solid state anaerobic
digestion: Influence of recirculated volume, leachate to substrate ratio and recirculation periodicity. Bioresource
Technology, 2016. 216: p. 553-561.
141
OPTIMIZATION OF BIOGAS PRODUCTION IN A CASSAVA PROCESSING UNIT IN BENIN

BY ANAEROBIC DIGESTION OF WASTE GENERATED FOR THE DEVELOPMENT OF
SUSTAINABLE ENERGY
S. AHOU1,2, E. DUMONT1 , Y. ANDRES1, L.S. BABA-MOUSSA2

1 Université de Nantes, Institut Mines Télécom-Atlantique, GEPEA, UMR 6144, Nantes, France.
2 Université d’Abomey-Calavi, Faculté des Sciences et Techniques, LBTMM, BP : 1604 Cotonou, Bénin.
Abstract
The increase of cassava processing industries poses serious environmental problems because of the
solid residues and the effluents that it releases into the wild. At the same time it puts a strong
pressure on the forest resources to cover the energy needs necessary to cooking food derivatives.
Benin produced more than 4 million tons of cassava in 2014. About 70% of production is processed
by artisanal and semi-industrial methods into many food products such as: gari, fufu, lafun, tapioca,
attieke ... etc. The two main waste products from cassava processing in Benin are peels and
wastewaters. Peels account for about 20-35%[1] of the total weight of cassava, while one ton of
processed cassava consumes about 20 cubic meters of fresh water for washing peeled cassava and it
generates about 12 cubic meters of starch water[2]. Cassava peels have a high content of cyanogenic
glycosides making them uncomfortable in animal feed. As a result, they are generally abandoned on
cassava processing sites, creating nauseating odors and sometimes poisonous air, which is a source
of disease for humans and toxic for the surrounding flora. At present, eliminating cassava peels is a
serious problem for the environment and will become a problem in the future due to the growth of
cassava processing industries. Cassava wastewaters have a very high chemical oxygen demand (COD)
and biochemical oxygen demand (BOD) as well as total solids. According to the literature these
values vary between 4.8-70.42g/L; 1.68-6.82g / L and 3.8-45.9g/L respectively for COD, BOD and
total solids [3]. They also contain a high cyanide concentration of up to 200 mg/L depending on the
cyanogenic glycosides concentration of the cassava varieties. They represent a poison for the aquatic
life of the receiving waters. Studies in Benin have shown that 1kg of garri produced consumes
between 1.30kg and 2.40kg of filao wood mass [4] equivalent to 0.320-0.939 MJ and 1.141-2.749 MJ,
corresponding respectively to 25% of electrical energy and at 75% thermal energy[5]. Anaerobic
digestion presents itself as an interesting alternative that can respond to the environmental and
energy problems faced by the cassava agro-food industries. It converts the organic matter contained
in cassava waste into biogas, that as a renewable fuel that provides factories with a cost-effective
way of feeding grinding engines and heat for cooking cassava pulp. The objective of our study
consists to recover energy from cassava processing waste by anaerobic digestion to cover the
internal energy needs of the cassava agro-food industry. The surplus of biogas can be stored or
resold creating other sources of income. An evaluation of the biochemical methane potential of
cassava peels and wastewaters in a 500 ml batch reactor at 37°C on a laboratory scale prior to
scaling up is considered. Parameters such as pH, T, C/N ratio, sludge /substrate ratio, COD, BOD, dry
matter and total volatile matter in our samples will be evaluated to optimize biogas production.
References
[1] Obadina et al, “Fungal enrichment of cassava peels proteins,” vol. Vol. 5(3), pp. 302–304, Feb. 2006.
[2] A. Kamaraj, N. O. Gopal, P. Venkatachalam, and A. Sampathrajan, “Biofuel production from tapioca starch industry
wastewater using a hybrid anaerobic reactor,” Energy Sustain. Dev., vol. 10, no. 3, pp. 73–77, Sep. 2006.
142
[3] A. S. Sánchez, Y. L. Silva, R. A. Kalid, E. Cohim, and E. A. Torres, “Waste bio-refineries for the cassava starch industry:
New trends and review of alternatives,” Renew. Sustain. Energy Rev., vol. 73, no. Supplement C, pp. 1265–1275, Jun.
2017.
[4] Nago et al, “La préparation artisanale du gari au Bénin : aspects technologiques et physico-chimiques = Artisanal gari
production in Benin : technological and physico-chemical aspects - éditions ORSTOM,” 1995.
143
RELATIONSHIP BETWEEN COMMERCIAL ENZYMES AND NATURAL EXTRACELLULAR

ENZYMES FOR IMPROVED BIOGAS PRODUCTION
J. JANTOVÁ-PATEL1, A. ČERMÁKOVÁ1, R.VILLA1, FARRYAD ISHAQ2, Y. BAJÓN FERNÁNDEZ1

1 Cranfield Water Science Institute, Cranfield University, Cranfield, UK.
2 Severn Trent Water, Coventry, UK.
Abstract
Previous studies have shown the benefits of enzymatic pre-treatment on the hydrolysis step of AD;
however, only some of them were able to show real improvement in biogas yields [1]. In addition,
most of the work published so far refers to quantity of enzymes (ml or mg) rather than the units of
activity (U) added to the system. Enzymatic activity in commercial products (U/ml or U/ml) is very
variable and it will depend on the quality of the enzymes (food vs industrial) and its purity.
Therefore, quantity of enzyme only will not provide the right information to allow the comparison of
previous studies and more so, the translation of this solution at full-scale. Finding the correct
relationship between substrate composition and enzyme addition, in terms of quality and quantity,
will also help to choose the most suitable conditions for the process, lowering treatment cost while
improving its performance. This work aimed at assessing the impact of different types of enzymes on
different AD feedstocks (sludge and energy crops) for biogas yields improvement, taking into
consideration enzymatic activity (U), substrate composition and dosing method.
Initial solubilisation tests (soluble COD release) were performed to understand the enzymatic impact
on hydrolysis and identify the best performing enzymes to be used in biomethane potential tests for
each substrate. The best performing enzyme/dose for each substrate was used for batch anaerobic
tests. Tests were performed using the AMPTS II system by Bioprocess control with working volume
of 700ml at 37˚C.
(a) (b)
Figure 1: (a) Maximum CH4 increase after 48h pre-treatment of sludge; (b) Effect of different enzymatic treatment methods (pre-
treatment and direct addition) on biogas production using industrial powdered cellulase CEL30 (18000 U/gTS) during batch BMP test.
Initial results on sludge showed that biogas yields could be increased by 40% with a cellulase pre-
treatment, and that similar yields could still be achieved by lowering the dose from 18000U/gTS to
2100 U/gTS, with an 80% decrease in cost.
Reference
[1] Roman, H. J., Burgess, J. E., and Pletschke, B. I., Enzyme treatment to decrease solids and improve digestion of
primary sewage sludge. African J. Biotechnol. 5(10), 963-967.
144
ANAEROBIC DIGESTION OF VINASSE AND CFD MODELLING APPROACH
H. CAILLET1, A. BASTIDE1, G. CHUPPA1,2, T. PETIT1,2, L. ADELARD1

1 Laboratoire de Physique et Ingénierie Mathématique pour l’Energie et l’Environnement (PIMENT),
EA 4518, Université de la Réunion, UFR Sciences de l’Homme et de l’Environnement, 117 rue
Général Ailleret, 97430 Le Tampon, France
2 Antenne sud du laboratoire de chimie des Substances Naturelles et des Sciences des Aliments
(LCSNSA), EA 2212, Université de la Réunion, UFR des Sciences et Technologies, 15 Avenue René
Cassin, CS 92003, 97744 Saint‑ Denis
Keywords: anaerobic digestion, computational fluid dynamics (CFD), Newtonian, non-Newtonian,

large-eddy simulation, mechanical mixing
Abstract
The study’s ultimate goal consists of modelling and optimising the co-digestion of particulate
substrates like sewage sludge, biowaste and vinasse from sugar cane. Given these substrates, the
medium is highly heterogeneous and has particular physical characteristics and behaviour.
Moreover, anaerobic digestion could be lead in wet-mode or in dry-mode, thus we want to develop
a model valid for both configurations. In this context, the fluid flow modelling is of interest. Indeed,
the contact between substrates and microorganisms has a significant influence on the anaerobic
digestion process. It is directly correlated to the flow inside the digester. The research question is
therefore the following: Is it possible to predict the spread of microorganisms inside the digester for
both liquid and solid digestion? In this paper, we present the context of the work and the
mathematical model based on Navier-Stokes equations with the Boussinesq approximation. Large-
eddy simulation (LES) is used for the turbulence modelling. The sliding mesh method is used to
characterise the impeller rotation. In further work, we will present the simulation results validated
with the literature data. The differential equations will be solved on OpenFOAM software using the
finite volume method. The flow will be simulated for both Newtonian (vinasse) and non-Newtonian
fluids (manure) and at different total solid (TS) rates for non-Newtonian fluids. The obtained results
will be the velocity and temperature profiles within the digester. It will hence be possible to optimise
the process through both the medium physical properties (TS rate and viscosity) and the digester
configuration. We will also consider the multiphase flow. Alongside numerical simulations,
experiments are carried out on the substrates studied in order to estimate the methane production.
In this article, we present the results of experiments on the vinasse and the development of the CFD
model.
145
1- INTRODUCTION
The development of renewable energies is generally growing in relation to the current context,
particularly, due to the depletion of fossil fuels and the need to limit the negative effects on the
environment. Anaerobic digestion is a widely used process in waste treatment (agro-industrial
waste, biowaste, manure, sewage sludge, vinasse...). The interest of anaerobic digestion is twofold, it
allows organic waste to be treated with energy recovery. Thus, this process meets the particular
needs of Reunion Island, which by its insular character, must call for sustainable solutions in terms of
waste treatment. In fact, the household waste produced in Reunion Island is currently buried while
the landfills are reaching their saturation point. It is therefore urgent to find durable solutions for
waste management. It is in this perspective that studies are funded by the Region to examine the
methanogenic potential of waste produced in Reunion Island (biowaste, sewage sludge, and vinasse)
as well as to optimise the process on an industrial scale. In addition, local renewable energy
production is a real asset for insular territories.
In methanisation industrial plants, the main process parameters are the temperature, the hydraulic
retention time, the biomass and the mixing conditions. These parameters are directly correlated to
the efficiency of the process. The mixing conditions are of utmost importance because mixing allows
the temperature homogenisation and fosters the contact between the substrate and the micro-
organisms. The substrate is naturally crucial in the methane yield because the yield will depend on
the nature of the substrate. In addition, mono-digestion and co-digestion are two means of carrying
out anaerobic digestion. Co-digestion is subject to many studies, in a review published in 2014, the
authors stated that anaerobic co-digestion is a feasible option to overcome the drawbacks of mono-
digestion and to improve the economic feasibility of industrial plants [1].
1- CONTEXT OF THE STUDYWORK CARRIED OUT

1-1- INHIBITION AND FAILURE RISKS IN ANAEROBIC DIGESTION
Various phenomena can destabilise the process of anaerobic digestion lowering it to complete
failure of the biogas production. Anaerobic digestion is subjected to inhibition or failure risks due to
the following reasons:
1. While the hydrolysis phase is largely considered as the rate-limiting phase for complex organic,
intermediate product concentrations like free ammonia, volatile fatty acids and sulphide/sulphate
can lead to inhibitions. Methanogenesis can also be considered like a rate-limiting phase [2] for
easily biodegradable substrates such as wastewater sludge. Total nitrogen concentration measured
on the vinasse is approximately 2000 mg.L-1, which is relatively high for anaerobic digestion.
Although this concentration is relatively high, anaerobic digestion is possible if the micro-organisms
are acclimatised to the substrate [3].
2. For liquid anaerobic digestion (TS < 15%), inhibitions can occur because of an uneven distribution
of biomass and substrates, the intensity and duration of the mixing as well as the retention time,
must therefore be precisely studied to optimise the hydrodynamic behaviour of the process.
Unsuitable mixing conditions can break the flocs of micro-organisms, disturbing the synergetic
effects. Proper mixing conditions also have to be established to control the volume of dead zones
and turbulence.
3. For solid anaerobic digestion, where dry processes are concerned, i.e. if the dry solid content
reaches 15% or for cases of codigestion, high viscosity leads to limited mass and heat transfer among
enzymes, bacteria and substrates in the digester. Mechanical mixing is in this case, considered to be
the most efficient way to optimise the diffusion processes [4]. However, few studies have been
carried out on the hydrodynamics of media.
146
4. Anaerobic co-digestion is often recommended to optimise biogas yield. However, co-digestion can
lead to solid digestion and inhibitions due to the accumulation of volatile fatty acids. In that case, the
development of biofilms among the substrate can disrupt the liquid flows [5].
1-2- ANAEROBIC DIGESTER MODELLING

We have seen a rise in numerical models, especially CFD models in recent years. Regarding the
process modelling, the biochemical and physicochemical processes are taken into account in the
ADM1 model [6]. To meet the needs related to the industrialisation of the methanisation, the
development of models taking the flows into account in a precise way, is necessary. There is
experimental evidence that mixing schemes and intensities have an impact on biogas production [7].
Indeed, all the chemical reactions leading to the complete digestion of the substrates can only occur
when they are in contact with the microorganisms involved in each reaction. To do this, the digestion
medium must be stirred. The agitation mode and type thus influences the quality of the digestion of
the substrates. In fact, vigorous mixing suppresses growth and the propagation of methanogenic
centres if methanogenesis is the rate-limiting step, but also may enhance methane production and
degradation if hydrolysis is the rate-limiting step [8].
In addition, anaerobic digestion can also be carried out by the dry route (TS > 15%). In this case, the
medium agitation is even more significant than in the wet digestion, since the homogenisation of the
medium becomes more difficult. Moreover, the waste treated by this process also has particular
rheological properties which influence the flow and therefore have a role in the optimisation of the
mechanical agitation. Indeed, these fluids can be viscous, Newtonian or non-Newtonian. The
rheology of waste including sewage sludge, manure and biowaste, has been studied in order to
model the flow of these fluids which have a Newtonian or non-Newtonian behaviour according to
the rate of total solid [9]–[15]. It has been shown that the fluid dynamics in the digester can be
affected by the TS [16].
CFD provides accurate results on the flow and is therefore of great interest for anaerobic digestion
modelling and optimisation. The major interest of the CFD is to characterise the flows within the
digester in order to study configurations (digester, impeller) that allow optimal contact between the
substrates and the microorganisms. Ultimately, in our study, we wish to model the displacement of
microorganisms within the digester for both Newtonian and non-Newtonian fluids, in order to
propose stirring optimisation. Indeed, to ensure that all substrates will be digested, it is necessary to
ensure the spread of micro-organisms at any point in the digester. With this in mind, we conducted a
literature review of CFD models applied to anaerobic digesters to identify studies that have already
been carried out using this technique. These models are implemented to optimise the industrial
process. The following table outlines the literature review of the aims of CFD in digesters.
Phase Fluid
References Objectives
model property
[17] Study the impact of the design of the digester (diameter of the Liquid- N
draft tube) on the flows by studying the position and the gas
volume of the dead zones.
[18], [19] Compute the flow with LES techniques. Liquid N
[12] Optimise the power supply and reduce the volume of dead Liquid N-N
zones or weakly stirred area.
[9], [20], Study the liquid homogenisation in stirred tanks and the Liquid N ; N-N
[21] required time for homogenisation (RANS and LES).
[22] Reduce the percentage of poorly mixing zones in gas-lift Liquid N-N
147
digesters by testing configurations of the bottom of the

digesters.
[23] Simulate the characteristics of digesters: the rates of mixing Liquid N
and the slug injection of tracers from the digester volume
turnover time, the mixture diffusion time, and the hydraulic
retention time.
[24] Study different mechanical stirring configurations. Liquid N ; N-N
[25] Investigate the flow fields, power and mixing time in a fully Liquid N
baffled stirred vessel with mechanical agitation (LES).
[26], [27] Investigate turbulence models. Liquid N-N
[16] Simulate mechanical agitation in high solid anaerobic digester. Liquid N-N
[28] Model the flows with mechanical agitation. Liquid N-N
[29] Describe the settling and suspension in anaerobic digester and Three N
evaluate the biomass retention physical process. phases
[30] Model the flows for fluids with variable rheology to study the Liquid N-N
impact on the performance of the digester.
[31] Study the stirring performance of gas recirculation agitation Liquid- N
configurations, and the impact of agitation intensity on gas
biological processes.
[10] Study the hydraulic performance of an existing digester Liquid N
(percentage of dead zones, recirculation volume).
[32] Study the impact of the agitator on suspended particles in Liquid- N
order to optimise the digester. solid
[33] Study the effect of impeller rotational speed and velocity field Liquid N
in the mixing tank.
[34] Study the influence of the behaviour of the sludge on the flow Liquid- N-N
and the consequences on the quality of the agitation. gas
N = Newtonian, N-N = non-Newtonian.
Table 1: Objectives of CFD models.
1-3- TURBULENCE MODELLING

A point of attention is the modelling of turbulence phenomena. The interest comes from the fact
that the mass transfer during the process is dependent on the turbulence phenomena in digesters
[28], and the contact between micro-organisms and substrate is correlated to turbulence [35].
Moreover, studies show that flow predictions are particularly sensitive to the turbulence model
implemented [36]. Thereby, the choice of the turbulence model is important in the simulations.
Mainly Reynolds-average Navier-Stokes (RANS) simulations were conducted on digesters [10], [12],
[13], [16], [17], [24], [26], [29]–[31], [36]–[38]. The SST k-omega model [30], [31], [36]–[38], the
standard k-epsilon model [10], [12], [16], [23], [27], [37] and the realisable k-epsilon model [13], [21],
[24], [27], [29] are recommended by many authors among the RANS models. Furthermore, other
authors claim that the Reynold stress model (RSM) is the most suitable model to predict the
behaviour of this bioreactor [35], [36].
However other studies have been conducted using the large-eddy simulations (LES) to model
turbulence phenomena in anaerobic digesters and stirred tanks [18], [18]–[20], [25], [28], [39]. In
these studies, the outcomes show that LES provide a better flow description than RANS simulations
[18], [18]–[20], [25], [28], [39]. In the study conducted by Wu in 2012, the free subgrid scale (SGS)
148
models investigated are the Smagorinsky-Lilly (LES-SL) model, the wall-adapting local eddy-viscosity
(LES-WALE) model and the kinetic energy transport (KET) model [28]. The three models give very
similar results for flow fields [28]. The comparison between simulated and measured axial velocities
shows that the LES shapes are in general agreement with the experimental data but they differ
clearly in velocity magnitudes [28]. Concerning the impeller power and flow numbers, the SGS
models give excellent predictions and the KET model provides the best results [28]. The author also
compares the results with Reynolds-averaged Navier-Stokes turbulence models (realisable k-e
model, standard k-omega model, Reynolds stress model) [28]. The disadvantage of the LES approach
is the computing cost, but a hybrid simulation approach can overcome this problem on industrial
applications [28].
Given the ultimate goal, which is to predict the displacement of microorganisms within the digester,
the modelling of these flows requires precision, thus we chose the LES turbulence model which
offers the most accurate results. In this work, we use the dynamic Lagrangian SGS model of
turbulence developed by Meneveau et al. (1996) [40]. This approach allows us to optimise the SGS
model coefficients [40]. The Lagrangian model is derived by minimising the error incurred by
inserting the Smagorinsky model into the Germano identity along fluid-particle trajectories [40]. This
method is applicable to complex-geometry and unsteady flows [40].

2-1- THE CHARACTERISATION OF SUBSTRATES
The study examines the biochemical potential (BMP) of the vinasse. The vinasse and the sewage
sludge for the BMP tests come from the active mesophilic biogas plant of the sugar-cane distillery
Rivière du Mât (Saint-Benoit, Reunion Island). The inoculum was sieved through a 900-1000 μm
mesh screen in order to remove coarser materials. No pre-treatment was done on the substrates.
The inoculum is stored at ambient temperature and then incubated at 37°C which is the test
temperature before the BMP tests. The vinasse is stored at 4°C for few days until the tests.
The substrates are characterised with TS, volatile solids (VS) and pH triplicate measurements. The TS
content is obtained after drying 20g of the samples for 24h at 105°C and the VS content after
burning the dried samples for 4h at 550°C. The pH value is determined with a pH metre. The
measured characteristics are the TS, the VS, the pH, the chemical oxygen demand (COD), the total
organic carbon (TOC), the ammonium, the alkalinity and the Kjeldahl azote. The vinasse is autoclaved
for sterilisation. The samples were then homogenised with the Ultra turrax IKA T25 digital at 12,000
rpm for 10 min. The chemical tests were conducted on the Hach Lange DR5000 Spectrophotometer,
using the Hach Lange tests LCK 914 (COD), LCK 381 (TOC), LCK 303 (Ammonium), LCK 362 (Alkalinity)
and LCK 338 (Kjeldahl nitrogen). The values are reported in Table 2. According to the results, the C/N
ratio of the vinasse is 15.23.
Kjeldahl
COD TOC Ammonium Alkalinity
Substrates TS % VS % pH nitrogen
gO2.L-1 mg.L-1 mg.L-1 CaCO3
mg.L-1
Sewage sludge 2.2480 0.9700 4.84 9.93 - 517.67 - -
Vinasse 6.6391 4.0378 7.57 79.67 27646.11 239.00 3651.25 1815.00
Table 2: Physico-chemical characteristics of vinasse and sewage sludge.
149
2-2- THE BIOCHEMICAL POTENTIAL TESTS AND THE PILOT TEST

The BMP tests are done using the Automatic Methane Potential Test System II (AMPTS II - Bioprocess
Control). The BMP tests were performed according to the latest recommendations [41]. The system
includes 15 digesters of 500mL. The substrate quantity is calculated with the ratio of VS from the
inoculum to VS from the substrate (I/S ratio). The recommended ratio is between two and four [41].
In these BMP tests, the ratio used is two. All the tests are carried out in triplicate. Two controls must
also be made, the blank assay and the positive control. The blank assay allows us to estimate the
endogenous methane production. The positive assay enables the inoculum activity to be validated
[41]. The digesters are supplemented with distilled water to obtain identical test volumes. The BMP
tests were carried out under mesophilic conditions at 37°C.
The pilot (10L) test is also carried out with the vinasse in mesophilic conditions for 41 days. The
working volume is 7L and 1.6L are added during the period test because of analysis. The initial pH of
the digestion medium is 7.29. The produced biogas is analysed daily in order to measure the
percentage of methane.
3- CFD MODELLING
3-1- MODEL ASSUMPTIONS
At the beginning, we consider the following hypotheses for the development of the mathematical 3D
single-phase model: digestion is carried out in a mesophilic regime (37°C); vinasse is a Newtonian
fluid; sewage sludge is a non-Newtonian fluid; the digestion medium is isothermal and
incompressible; the digester is heated at its walls; the impeller initial rotation speed N is 500 rpm.
3-2- CONSERVATION EQUATIONS

The conservation of mass and momentum equations with the Boussinesq approximation are used.
The momentum equation and the heat transfer equation are coupled by the Boussinesq term. The
space-filtered equations of an incompressible Newtonian fluid can be written as:
ui
0 (1)
xi
   ui     ui u j  P   ij   ij
     g  ez (2)
t x j xi x j x j
Where t is the time,  is the fluid density, ui is the filtered velocity component in the xi direction, is
the kinematic viscosity, P is the filtered pressure,  is the filtered temperature, g is the gravity
force,  is the thermal expansion coefficient and  ij is the subgrid scale (SGS) stress tensor.
The filtered heat transfer equation in convection-diffusion is:
   2 DT
 ui .  0 (3)
t xi x j x j
Where DT   CP is the thermal diffusion coefficient, C p is the specific heat and  thermal
conductivity .
The stress tensor for Newtonian incompressible fluid is:
150
 ui u j 
 ij      (4)
 x x
 j i 
The SGS stress tensor for incompressible flow is expressed as:
 ij  2t Sij (5)
1  u u j 
Sij   i   (6)
2  x j xi 
Sij  2Sij Sij (7)
Where tSGS   L2S S is the SGS turbulent viscosity, Sij is the rate of strain, Ls  min  d , CS   is the
mixing length,  is the Von Karman constant, d is the distance to the closest wall, CS is the
Smagorinsky constant, and   3 V in which V is the volume of the computational cell.
We use the dynamic Lagrangian model. In this model, the fluid particle trajectory for earlier time t’ <
t is [40]:
z  t    x   u  z  t   , t  dt 
t
(8)
t
3-3- RHEOLOGICAL EXPRESSIONS

The non-Newtonian viscosity for power-law fluids is expressed as:
  k n1 (9)
Where k is the consistency coefficient,  is the shear rate and n is the power-law index.
The consistency coefficient and the power-law index for liquid manure are defined as [42]:
k  8.722e 4830 T 0.58319TS   1010 (10)
n  0.6894  0.0046831 T  273  0.042813  TS (11)
Where T is the temperature.

The density  , the specific heat C p and thermal conductivity  are expressed [12], [43], [44]:
C p  4187.5  28.9  TS (12)
  0.6173  0.0069  TS (13)
  0.0367  TS 3  2.38  TS 2  14.6  TS  1000 (14)
3-4- DIMENSIONLESS NUMBERS

The two dimensionless numbers typically used in a stirred vessel are the power and flow numbers
expressed as [45]:
151
P
NP  (15)
 N 3d 5
Q
NQ  (16)
Nd 3
Where P is the power input, N is the impeller rotation speed, d is the impeller diameter and Q is the
flow rate through the moving zone.
The power and flow numbers are two good indicators for model validation. We will compare their
values, as Wu [28], to measured values in literature data [46]: NP=0.3 and NQ=0.56.
3-5- THE PHYSICAL DESCRIPTION OF SUBSTRATES

Our study is about mesophilic anaerobic digestion whose optimum temperature is 37°C. This is an
important parameter because the physical parameters depend on it. Rheological experimental
measurements at different temperatures (10°C, 25°C, 40°C and 60°C) showed that the viscosity and
the yield stress decrease as the temperature increases [11]. Moreover, this study showed that the
rheological behaviour is irreversibly altered by the thermal history [11].
Firstly, we consider the vinasse. The vinasse has a pseudoplastic behaviour for temperatures
between 10 and 20°C [47]. Indeed, when the temperature is superior to 30°C, the power-law index is
close to 1, indicating an approach to the Newtonian model [47]. In another study, the vinasse is
considered as Newtonian fluid [48]. The sludge treated in a Wastewater treatment plant anaerobic
digester is also considered as Newtonian fluids [10]. The total dissolved solids (TDS) contents sludge
of this plant were 2.5, 5.4 and 9.1% [10]. We will thus perform simulations on the flow of vinasse and
sludge, which are Newtonian. The corresponding physical parameters are given in Table 3.
Fluid Density (kg.m-3) Dynamic viscosity (Pa.s)

Vinasse 1044.69 0.001 009 7
Sludge 999.66 0.065
Table 3: Physical parameter values of vinasse at 35°C (Newtonian model) [10], [48].
Secondly, we study the flow of sewage sludge which is a non-Newtonian fluid. We can use the liquid
manure rheological properties to characterise sewage sludge [10]. In order to compare our results,
we use the same properties as Wu [12], [13], [28] (Table 2). The manure slurry exhibits pseudo-
plastic fluid behaviour when TS is superior to 2.5% [13]. The manure is modelled with a
pseudoplastic model in studies [10], [12], [13], [16], [28], [42], [43]. Moreover, viscosity and shear
stress increase exponentially as TS increases [12]. The lower and upper limits of viscosities are
calculated from the equation (11) [12]. The physical properties for different values of TS are given in
Table 4.
TS T k Density ηmin ηmax 𝜸̇ Cp λ

n
% °C Pa.sn kg.m-3 Pa.s Pa.s s-1 J.kg-1.°C-1 W.m-1.°C-1
2.5 35 0.042 0.710 1000.36 0.006 0.008 4186.78 4186.78 0.6171
5.4 35 0.103 0.639 1000.72 0.009 0.025 50-702 4185.94 0.6169
7.5 35 0.525 0.533 1001.00 0.03 0.17 11-399 4185.33 0.6168
9.1 35 1.052 0.467 1001.31 0.07 0.29 11-156 4184.87 0.6167
12.1 35 5.885 0.367 1001.73 0.25 2.93 3-149 4184.00 0.6165
15 17-24 31.3 0.30 973.0 3.35 44.24 0.61-24.37 4183.17 0.6163
20 17-24 35.4 0.29 1091.8 3.69 48.6 0.64-24.14 4181.72 0.6159
152
Table 4: Physical parameter values of manure (power law model) [12], [15], [28], [42].
3-6- GEOMETRY AND MESHING

In order to compare our results with simulations conducted by Wu [28], we used the same
geometry. This consists of a cylindrical tank with 0.152m diameter (with a 25° slope on the hopper
bottom) and 0.26m liquid height. The agitation is performed by a Lightnin A313 impeller (0.062m
diameter). The digester geometry is given in Figure 1.
Concerning the meshing approach, two main strategies are used for modelling stirred tanks: the
reference frame (RF) (known as the “frozen rotor approach”) and the sliding mesh (SM) [49]. The RF
convergences fast, but it is suitable only for steady-state flows [49]. In contrast, SM is suitable also
for unsteady flows, for which it provides a time-dependent solution, but at the expense of significant
computational effort and time [49]. A comparison between the multiple reference frame (MRF) and
SM techniques showed that the SM technique is more accurate, but it is also much more time-
consuming than the MRF [20]. In recent studies, the MRF is widely used for its simplicity and the
quality of the results [32], [33], [50]–[52]. However, transient simulations require the SM method,
some authors used MRF method for a first approximation and then SM method [25], [53]; whereas
others used SM method directly [19], [39].
In our study, our choice will be based on the SM method to characterise the impeller rotation. The
cylindrical moving zone contains the impeller with 0.98m diameter, and the rest of the digester is the
stationary zone. The cylindrical moving zone is 0.234m height and 0.152m diameter. The two zones
are schematised in Figure 1. The mesh will be then refined at the digester edges, at the interface
between the stationary zone and the moving zone, and at the agitator edges.
Figure 1: Digester geometry (mm).
153

The cumulated BMP curves (Figure 2) shows that vinasse is a complex substrate which can be
difficult to treat in anaerobic digestion. The maximum production of methane is not reached beyond
45 days. The maximum methane production is 284.29 LCH4.kgCOD in the BMP test and 114.64 LCH4 in
the pilot test. The biogas production of the pilot is 270.22 L. The vinasse is composed of complex
molecules like proteins. The COD is also quite difficult to treat, and these curves show why in most
digesters using sugar cane vinasse, only half of the COD is treated by anaerobic digestion.
Figure 2: Cumulative methane production average as a function of time of vinasse in BMP (left) and pilot (right) tests.
The results from CFD simulations of Newtonian and non-Newtonian fluids flow will be presented in
further studies. The simulations will allow us to choose the frequency and the intensity of
mechanical stirring of the pilot digester. Furthermore, the fluid movement allows contact between
the micro-organisms and the substrate. Thus, the flow is linked to the substrate composition and the
digestion rate, which are part of ADM1 parameters. The fluid rheological properties depend on the
substrate composition, but also on the digestion rate. In other words, some ADM1 results, the
digestion rate and the composition, are useful in CFD simulations, and CFD simulations bring results,
the velocities profiles, which are not considered in ADM1 model.
5- CONCLUSION
This article presents the reasons justifying the importance of setting up a CFD model of industrial
digesters. The main purposes being the strong link between the flows and the biogas yield as well as
the physical characteristics of the substrates treated in anaerobic digestion. In conclusion, the CFD
model is naturally based on the Navier-Stokes equations. This model is also coupled with the heat
transfer equation given the impact of temperature on the process. In addition, we use the LES
approach to model turbulence with the Lagrangian dynamic model, to predict turbulent flow
accurately. The modelling of the digester will be carried out for Newtonian fluids and non-Newtonian
fluids, and for different dry matter rates (both wet and dry digestion).
Currently, we develop a single-phase model. Then, we will realise the multiphase model (liquid, gas,
solid), the liquid phase will be the digestion medium, the gaseous phase will be the biogas and the
solid phase will be the microorganisms. It will thus be possible to study the propagation of
microorganisms within the digester. Subsequently, we want to couple the CFD model with the ADM1
model in order to study the impact of flows (influenced by mechanical agitation) on the biogas
production and on the inhibition phenomena. The CFD model is an additional tool for digester
configuration choices. The emphasised inhibition phenomenon will be the detachment of the
biofilm, which is a recurring problem in mechanically stirred anaerobic digesters.
154
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157
RECOVERY OF HUMIC-LIKE SUBSTANCES FROM URBAN DIGESTATES
F. GUILAYN1,2 ,P.M.T. CARRENHO1, J. JIMENEZ1, M. ROUEZ2, M. CREST2, D. PATUREAU1

1 LBE, INRA, Univ Montpellier, 102 avenue des Etangs, 11100, Narbonne.
2 SUEZ, CIRSEE, 38 rue du Président Wilson, 78230, Le Pecq, France.
Abstract
In France, digestates from anaerobic digestion plants have to pass through homologation process or
reach certain specific standards to be commercialized. In this study, valorisation processes regarding
the production of added-value products from urban digestates are being explored. Humic Acids (HA)
extracted from upcycled organic products such as composts have been demonstrated to improve soil
fertility [1] and industrial applications have been proven more recently [2]. However, very few
studies addressed HA-recovery from digestates [3]. Preliminary tests presented in this study were
carried out in order to assess the feasibility of recovering HA from such urban digestates. The
samples were a Food Waste/Cardboard digestate (FW/CB-D) from a pilot reactor and an Organic
Fraction of Municipal Solid Waste digestate (OFMSW-D) from a full-scale plant. HA-extraction was
tested on raw digestates and on its solid fractions after laboratory centrifugation. A practical
approach for HA extraction was performed, adapted from [4]: NaOH 0.1 M was added until pH 12
was reached. The solution was stirred for 24h. After the alkaline extraction was performed, the
digestate was centrifuged. The supernatant was filtered at 0.45 µm and acidified at different pH (1,
2, 3, 5 and 7). This solution was centrifuged to isolate the insoluble fraction containing HA. The
recovered HA were redissolved for Fluorescence 3D analysis. Another acidification at pH 3 was
performed where the precipitate was washed several times with distilled water and freeze-dried for
Mid-Infrared analysis and calculation of recovering yields. Recovered HA were compared to HA
isolated from a leonardite commercial solution and to references from the International Humic
Substances Society (IHSS). Freeze-dried HA yields were low: from 3 to 4% (volatile solids:volatile
solids) and 1 to 2%, for raw mass of FW/CB-D and OFMSW-D respectively. HA extracted from FW/CB-
D were observed to be similar to a river sediment reference from the International Humic
Substances Society. The HA from OFMSW was closer to the HA isolated from the leonardite solution,
but it presented more proteins in the 3D fluorescence spectra. When HAs were extracted from the
solid fraction of digestates, HA extraction yields and spectra were almost unchanged. The pH for
acidification played an important role in HA isolation. pH 1, 2 and 3 were observed to perform
similarly (quality and quantity) but pH 5 and 7 resulted in less extraction of HA and poorer quality.
Industrial feasibility of HA-like extraction from digestate would rely on extraction yields, product
quality and residual matter management options. Experiments will be carried out in order to further
evaluate the quality of the products regarding biodegradability and impact on root growth.
References
[1] Ayuso, M., Moreno, J.L., Hernández, T., García, C., 1997. Characterisation and evaluation of humic acids extracted
from urban waste as liquid fertilisers. J. Sci. Food Agric. 75, 481–488.
[2] Salati, S., Papa, G., Adani, F., 2011. Perspective on the use of humic acids from biomass as natural surfactants for
industrial applications. Biotechnol. Adv. 29, 913–922. doi:10.1016/j.biotechadv.2011.07.012
[3] Li, H., Li, Y., Zou, S., Li, C., 2014. Extracting humic acids from digested sludge by alkaline treatment and ultrafiltration.
J. Mater. Cycles Waste Manag. 16, 93–100.
[4] Quagliotto, P., Montoneri, E., Tambone, F., Adani, F., Gobetto, R., Viscardi, G., 2006. Chemicals from wastes:
Compost-derived humic acid-like matter as surfactant. Environ. Sci. Technol. 40, 1686–1692. doi:10.1021/es051637r
158
EFFECT OF WATER-SOLUBLE ADDITIVES ON THE DENITRIFICATION AND VISCOSITY-

BREAKING OF OIL PRODUCTS OBTAINED FROM HYDROTHERMAL LIQUEFACTION OF
KITCHEN WASTE
D. SHU1, Y. CHI1
1 Zhejiang University, Hangzhou, China.
Abstract
Kitchen waste is considered as a post-consumer waste generated during purchase, preparation and
consumption of meals in households or hospitality sector.1 According to National Bureau of
Statistics, the annual kitchen waste production is approximate 30 million tons in China. The kitchen
waste with high content of moisture and organic matter can be disposed with hydrothermal
liquefaction (HTL) for bio-oil production. The crude bio-oil yield with HHV higher than 30 MJ/kg was
produced by hydrothermal liquefaction, and the HTL was identified to be a promising technology for
bio-oil production. However, the further utilization of obtained bio-oil was limited by the high
content of nitrogen and high viscosity. The N content of oil products were as high as 2~6 wt%, which
resulted from the high content of proteins in the raw kitchen waste. In this research, the effect of
water-soluble additives on denitrification and viscosity-breaking was investigated during HTL of
kitchen waste.
KW was collected twice a day from four canteens in Zhejiang University and stored at 4 °C in a
refrigerator. The hydrothermal liquefaction process was carried out in a 500 ml autoclave purchased
from Parr Instruments. The reactor was heated at a rate of 15 °C/min to reach 320 °C. When the
residence time of 20 min was reached, the reactor was cooled down to room temperature. Each
experiment was done in duplicate or triplicate.
The additives of alkali, inorganic salt, acetic acid,

ethanol, heavy metallic salt, and inorganic acid were
investigated, and the yields of bio-oil and char were
shown in Figure 1. The yield of bio-oil obtained with
addition of NaOH was highest, over 50 wt%, while the
viscosity was highest. The N content and viscosity of
bio-oil obtained with addition of HCl were lowest,
showing high efficient of denitrification and viscosity-
breaking. Figure 1: yields of bio-oil and char obtained from the HTL
of kitchen waste with different additives.
The addition of inorganic acid or heavy metallic salt significantly reduce the N content of oil
products. The addition of organic acid, ethanol, and alkali salt influence little on the HTL. The
addition of inorganic acid, heavy metallic salt, and alkali increase the carbon residuum of oil
products.
References
[1] Deniel, M.; Haarlemmer, G.; Roubaud, A.; Weiss-Hortala, E.; Fages, J.: Energy valorisation of food processing residues
and model compounds by hydrothermal liquefaction. Renewable & Sustainable Energy Reviews, 54, 1632-
1652(2016).
159
CHARACTERISTICS OF BIOCHAR AND HYDROCHAR OBTAINED FROM THERMAL

TREATMENT OF MANURE WASTE
E. CÁRDENAS- AGUIAR1, A. MÉNDEZ1, G. GASCÓ2

1 Departamento de Ingeniería Geológica y Minera. E.T.S.I. Minas y Energía. Universidad Politécnica
de Madrid, C/Ríos Rosas nº21, 28003 Madrid, Spain.

2 . Departamento de Producción Agraria. E.T.S.I. Agrónomos. Universidad Politécnica de Madrid,
Ciudad Universitaria, 28004 Madrid, Spain.
Abstract
Biomass transformation in organic amendments to be used in soils is one of the most sustainable,
clean and renewable waste management techniques1. In the last years, pyrolysis and hydrothermal
carbonization (HTC) have attracted a great attention for the production of biochar and hydrochar.
The hydrochar is produced by HTC of wet biomass using low temperatures (180-260°C) and
autogenous pressures2. In the case of biochar, the solid material is obtained from the pyrolysis of
biomass with limited oxygen (< 1%) and temperatures under 700°C3. The main objective of this work
was to study the main differences of biochars and hydrochars obtained by pyrolysis and HTC of
manure waste. The organic waste was obtained from a rabbit farm located in the practice field of the
Polytechnic University of Madrid (RM). The biochars of RM were prepared with a heating rate of 3 ºC
min-1 up to 450 ºC (BRM450) and to 600 ºC (BRM600). The final temperature was maintained during
1 hour. Also, two hydrochars were produced at 190 ºC (HRM190) and 240 ºC (HRM240). The final
temperature was maintained during 6 hours. Biochars, hydrochars and RM were widely
characterized; i.e. electrical conductivity (EC), pH, easily oxidisable organic carbon (Coxi), extractable
phosphorus (Polsen), cation exchange capacity (CEC), exchangeable elements (Ca, K, Na), UV analysis,
germination test, thermal analysis (TG, dTG and DTA), BET surface area, proximate and elemental
analysis. Experimental results show important differences between hydrochars and biochars. The
highest pH corresponds to BRM600. Also, BRM450 and BRM600 show highest thermal stability, the
lowest Coxi and lowest phytotoxicity. However, hydrochars showed the highest values of micro, meso
and macroporosity.
Authors wish to thank to Spanish Ministerio de Economía y Competitividad for the economic support
(CGL2014-58322-R).
References
[1] Guo, S., Dong, X., Wu, T., Zhu, C. Influence of reaction conditions and feedstock on hydrochar properties. Energy
Conversion and Management, 123, 95–103 (2016).
[2] Ghanim, B. M., Kwapinski, W., Leahy, J. J. Hydrothermal carbonisation of poultry litter: Effects of initial pH on yields
and chemical properties of hydrochars. Bioresource Technology, 238, 78–85 (2017).
[3] Lehmann, J., & Joseph, S. Biochar for Environmental Management: Science and Technology (First). London, Sterling:
Earthscan. (2009).
160
BIOFUEL UPGRADING: ASH REDUCTION AND ENERGY DENSITY ENHANCEMENT OF

OPUNTIA-FICUS INDICA CLADODES VIA HYDROTHERMAL PRETREATMENTS USING
METAL IONS CHEMICAL SEQUESTRATION
M. VOLPE1, M. LUCIAN1, E. WEISS-HORTALA2, L. FIORI1

1 University of Trento, Department of Civil, Environmental and Mechanical Engineering, Trento, Italy.
Abstract
Conversion of residual biomass such as agro-waste into energy can be the key to a circular-driven
economy that could lead to models for sustainable production. In rural and marginal areas large
amounts of agro-waste are produced which are not valorised and whose disposal represents a
hazard to the environment. Converting such organic waste into energy would allow addressing two
important issues: waste management and energy self-production in these areas.
The direct conversion of agro-waste is severely hampered due to their perishability, seasonal
availability, and low energy density. Actually, such wastes are often characterized by a high moisture
and ash content. In order to make such agro-waste suitable for energy production, ad hoc pre-
treatments are mandatory, in particular stabilization and energy densification processes.
Hydrothermal pre-processing of biomass is receiving growing attention due to its ability to directly
treat residues with a high moisture [1] and ash [2,3] content.
Opuntia ficus-indica is a plant belonging to the cactacee family, which is nowadays found and
harvested in many agricultural economies throughout arid and semiarid parts of the world. It is
cultivated for its sweet and nutritious fruits known as prickly pears or cactus pears. Its perennial
shrubs can grow up to 5 m height, with thick, succulent and oblong stems called cladodes. The not
edible cladodes are an excellent source of biomass which can be used for energy purposes and for
the synthesis of bio-based carbon material. Depending on the age of the plant, the moisture content
of cladodes reaches 80-90%, while their ash content and HHV are about 15% and 14 MJ/kgdry.
In this study, we report results of a simple, one pot, mild hydrothermal procedure carried out in
order to pre-treat opuntia-ficus indica cladodes to make them suitable for storage and further
thermo-chemical energy conversion. Cladodes were processed at 120 °C, 0.5 h of residence time,
and solid load (biomass to water w/w) of 20%, with or without the addition in the aqueous phase of
two different chelating agents (2,4 pentanedionate and EDTA salts) giving a pH of 4 to 10.
Raw material and hydrothermal solid residues were characterized by XRF, proximate and elemental
analyses. HHVs and energy yields (EY) were determined by calorimetry and metal ions composition
and chelating agent selectivity in aqueous phase were evaluated by XRF. Depending on the
treatment conditions, hydrothermal solid residues showed an ash content as low as 7.4% with a
corresponding HHV of 16.2 MJ/kg and EY of about 67%. Chelating agents can be recovered by pH
adjustment and recycled into the reactor. In summary, results show that chelating agents are able to
remove structural ash (mainly Mg, S, Cl and K) and enhance the energy properties of the solid
residues thus providing an up-graded biomass for a commercial biorefinery industry.
References
[1] Zhao P., Y. Shen, S. Ge, Z. Chen, K. Yoshikawa, Appl. Energy. 131, 345-367 (2014)
[2] Toufiq Reza M., J.G. Lynam, M.H. Uddin, C.J. Coronella, Biomass and Bioenergy, 49, 86-94 (2013)
[3] Reza T.M., R. Emerson, M.H. Uddin, G. Gresham, C.J. Coronella, Biomass Convers. Biorefinery, 5, 21-31 (2015)
161
HYDROTHERMAL CARBONIZATION OF LIGNIN AND HYDROCHAR ACTIVATION
E. MILIOTTI1, L. BETTUCCI2, S. DELL’ORCO1, D. CASINI2, A.M. RIZZO2, D. CHIARAMONTI1,2

1 CREAR/University of Florence, Dept. of Industrial Engineering, Florence, Italy.
2 RE-CORD Renewable Energy Consortium for R&D, Florence, Italy.
Abstract
The production of ethanol from no-food lignocellulosic material has now achieved full industrial
scale. Together with the main product, ethanol from the fermentation of cellulose and
hemicellulose, a large amount of a very wet lignin-rich stream is also produced, which today is dried
and burnt for heat and power generation. Finding a more profitable way to exploit this co-product
stream is fundamental in order to improve the overall biorefinery efficiency. In this context, the
hydrothermal carbonization technology (HTC) is particularly suited to process this very wet stream of
biomass, as the reaction environment is hot compressed water.
Hydrothermal carbonization of lignin from lignocellulosic ethanol production was performed in a lab-
scale stainless steel batch reactor. The experimental setup and the procedure was similar to the one
adopted in a previous study of the author [1]. Several HTC experiments were carried out by varying
process parameters such as residence time (from 0.5 to 3h) and reaction temperature (from 200 to
300°C) in order to evaluate their influence on the product yield and on the structural characteristics
of the char, in terms of specific surface area, total pore volume and average pore diameter. In
addition, the HTC process water was collected and analysed by GC-MS, GC-FID and HPLC in order to
identify and quantify the major dissolved organic compounds. These analyses were performed
within 1 hour from the aqueous phase production in order to avoid an incorrect characterization due
to degradation reactions. Further hydrochar activation tests were conducted in a tubular furnace by
means of physical (with CO2) and chemical (with KOH) activation in order to increase surface area
and pore volume. The structural characteristics of the produced hydrochar were highly enhanced by
both activation processes, resulting in a large increase in specific surface area.
Figure 1: Hydrothermal carbonization lab-scale test bench (left) and tubular furnace for activation tests (right)
References
[1] Miliotti, E., Casini, D., Lotti, G., Bettucci, L., Pennazzi, S., Rizzo, A.M., Chiaramonti, D.: Valorization of solid
residues from anaerobic digestion through thermal and hydrothermal carbonization process. 25th
European Biomass Conference and Exhibition, Stockholm, 1063–1069 (2017)
162
POLYURETHANE FOAMS PRODUCED FROM PYROLYSIS OIL – THEIR PRODUCTION

AND POTENTIAL APPLICATION AS BUILDING INSULATION
T. SCHULZKE1, S. CONRAD1,2, Q. CAO2, A. IAKOVLEVA1,3, S. ZABELKIN3, A. GRACHEV3

1 Fraunhofer UMSICHT, Institute for Environmental, Safety and Energy Technology, Oberhausen
Germany .
2 Ruhr-University Bochum, Bochum, Germany.
3 Kazan National Research Technological University, Kazan, Republic of Tatarstan, Russian.
Abstract
Rigid polyurethane (PU) foams are widely used for instance in building insulation. Two component
systems comprising of a polyol (either polyether- or polyester-polyol) as component A and a
diisocyanate as component B are generally applied. Both components are produced from fossil oil
resources.
The liquid products from fast pyrolysis of biomass contain a large variety of organic compounds with
–OH functional groups. This gives rise to the idea to substitute the polyol component in PU foams
with such biomass based intermediates. Biooils derived from woody and herbaceous biomass were
produced using a laboratory plant for ablative fast pyrolysis. The biooils were pretreated and more
than 70 samples of PU foams produced with a varying amount of biooil substituting the polyol
component. Samples were characterized by measuring density, thermal conductivity and compres-
sive strength. All samples revealed thermal conductivities in the upper range of commercial insula-
tion materials and especially the biooils produced from straw showed good insulation property
expressed as low thermal conductivity (see Figure 1). The achieved thermal conductivity of 0.0283
W/mK with a substitution degree of 80 % (based on component A/polyol) was 8 % lower than for the
foams produced from commercial components (0.0308 W/mK). These results show high potential for
the application of bio-based intermediates in the building sector. The samples of foams produced
with biooils are more brittle than foams made from commercial components.
Further investigation on other properties is necessary, but the main requirements for thermal
conductivity and compressive strength are already met without optimization of the catalyst/
stabilizer system.
Figure 1: Thermal conductivity as a function of bio-oil content in polyol compound
163
UTILIZATION OF CLASS-C FLY ASH FOR GEOPOLYMER PRECURSOR
Sotya Astutiningsiha* and Dian Adistya,b
a
Department of Metallurgy and Materials Engineering, Universitas Indonesia, Kampus
UI, Depok 16424, Indonesia
*Corresponding author. Email address: sotya.astutiningsih@ui.ac.id

b
Permanent address: Pipeline Operations, DNV GL, Veritasveien 1, 1363 Hovik,
Norway.
ABSTRACT
Class C fly ash containing more than 10wt% of calcium as set by ASTM C618 was
used as geopolymer precursor using NaOH and sodium silicate solution as the
activator. Optimization of mixing composition includes variation in NaOH and sodium
silicate solution content in the paste mixture. This paper describes the effect of mixing
compositions upon compressive strength. It is found that he high amount of calcium
contained in the fly ash caused flash setting resulting in low workability and low
compressive strength. Increasing NaOH content increased strength following an
exponential curve where at certain point the strength remained constant. On the other
hand, strength decreased with sodium silicate solution content. The first was due to the
rapid formation of Ca(OH)2 which caused flash setting. The latter was due to the
increase in viscosity caused by the viscous sodium silicate solution. The Ca(OH)2
formed was the reacted with CO2 in the air forming carbonates. Scanning electron
microscopy (SEM) images of the cured geopolymer fractured surface showed the
formation of crystalline phase in the shape of needle, most probably CaCO3. X-ray
diffraction (XRD) confirmed the presence of CaCO3 together with an obvious
amorphous hump and zeolitic phase on sample with a higher sodium and water content.
However, in conclusion, regardless of the mixing compositions, compressive strength
achieved by these class C fly ash based- geopolymer samples were too low to be used
as building materials.
Keywords: Class C fly ash; geopolymers ; flash set ; compressive strength; calcium.
164
1. INTRODUCTION
Fly ash obtained from a coal power plant in West Papua contains too high amount of
calcium and sulfur as a result of flue gas desulphurization making the overall SiO2 and
Al2O3 content in this fly ash too low to be classified as pozzolanic materials outlined by
ASTM C 618. Class F fly ash, containing less than 10 wt% of calcium has been utilized
as geopolymer precursor for concrete with comparable properties to ordinary Portland
cement concrete. A power plant supplying energy for the operation of a giant copper
mine in Papua wastes 39,417 tons of fly ash every year. This fly ash contains more than
40 wt% of calcium compounds and hence is classified as Class-C fly ash.
The use of class C fly ash for geopolymer has some drawbacks, especially on
workability (Xie and Kayali, 2016; Wongsa et.al., 2017; Guo et.al., 2017). This paper
describes utilization of class C fly ash as a precursor for geopolymer. Variation of
precursor – activator ratios has been performed to increase compressive strength, while
powder x-ray diffraction (XRD) and microstructure examination on the hardened /
cured geopolymeric pastes was done to study the role of calcium.
2. METHODOLOGY/ EXPERIMENTAL
2.1. Materials
X-ray fluorescence was performed on the boiler ash to determine their chemical
composition, which is presented in Table 1. It contains high amount of calcium and
sulfur as a result of flue gas desulphurization. The overall SiO2 and Al2O3 contents are
too low to be classified as pozzolanic materials outlined by ASTM C 618. X-ray
diffraction of the fly ash, presented in Fig. 1 shows the presence of crystalline Ca(OH)2,
SiO2 and aluminosilicates. Due to the high temperature process of coal combustion, fly
ash is very likely to be partly glassy although this is not so obvious in the x-ray
diffraction pattern.
Table 1 Chemical composition of fly ash

Chemical Weight %
Formula
Al2O3 10.6121
SiO2 23.5920
S 10.6506
K2O 1.6513
CaO 44.0250
TiO2 0.7185
MgO 1.0684
Fe2O3 7.6461
ZnO 0.0360
165
intensity
C Data 2
10 20 30 40 50 60 70 80 90
2 theta angle (o)
Figure 1 X-ray diffraction pattern of fly ash
The fly ash will be chemically activated by a mixture of sodium silicate solution (27
wt% SiO2 and 8 wt% Na2O), NaOH pellets of 98.9% purity and distilled water.
Varying the composition of the paste mixture was performed by varying the amount of
NaOH, and sodium silicate solution while maintaining the other ingredients constant.
The mixtures formed viscous pastes which was then casted into cubic samples of ~3
mm3 and cured at 70oC for 5 hours and left at room temperature for 16 days before
compression testing. The paste might set earlier but observation on the accurate curing
time was not performed.
2.2. Testing Methods

Compression testing was performed at PUSPIPTEK, Serpong using Schenk Treble
machine according to ASTM C109 “Standard Test Method for Compressive Strength of
Hydraulic Cement Mortars” on paste cubes of 5x5x5 cm3 with a loading rate of 3
mm/min. The maximum load was then divided by the square area for each specimen to
obtained the compressive strength. Broken specimens after compression test were used
for powder XRD and SEM, both were performed at the Department of Metallurgy and
Materials Engineering, Universitas Indonesia. Monochromatic Cu K (=1,54056Å)
was the radiation source for the wide angle X-ray scattering using Philips x-ray
diffractometer with a step size of 0,02 and time per step of 1 sec. SEM-EDX LEO 420i
was used for microstructure observation, the details of which were printed on the
images shown.

3.1. Effect of Mixing Compositions on Compressive Strength
The compositions of the paste mix and the respective compressive strength are shown
in Table 2 and Table 3.
Table 2 Compressive strength of geopolymer with varying NaOH content

Composition (gr) Load Area Strength
Fly ash NaOH Na2Si3O7 H2O (Kg) (cm2) (MPa)
4.976 402.65 14.22 2.83
20.78 25.804 14
2.976 366.97 13.91 2.64
166
1.976 280.33 13.83 2.03

0.976 163.09 14.39 1.13
0 117.23 14.40 0.81
Table 3 Molar ratio of paste mix with varying sodium silicate composition
Composition (gr) Load Area Strength
Fly ash NaOH Na2Si3O7 H2O (Kg) (cm2) (MPa)
24,804 122,32 14,31 0,85
23,804 214,07 13,95 1,53
14 193,68 14,05
20,78 1,976 22,804 1,38
21,804 377,166 13,95 2,7
20,804 499,49 13,92 3,59
Fig. 2 shows that in general compressive strength increase, exponentially with

increasing NaOH, up to 6 to 8wt% of NaOH where strength remained almost constant.
Sodium ions are required as charge balancers for Al ions substituting Si ions at the
center of oxygen tetrahedra as well as providing high pH for dissolution of the
precursor (Rahier et al., 1996). Excess of sodium and will lead to carbonation of the
sodium ions dissolved in the polycondensation water produced during curing (Barbosa
et al., 2000; Bernal et al., 2013; Puhet & Cyr, 2016). However, in these experiments,
calcium carbonates (CaCO3, calcite) instead of sodium carbonates were formed in the
cured geopolymers which were identified in the x-ray diffraction pattern shown in Fig.
3. This class C fly ash used in these experiments contained very high amount of
calcium as a result of desulphurization in which lime was added to bind Sulphur in the
flue gas. While the fly ash itself, which is the unburnt residue of coal combustion, is
composed mostly of alumina – silica in the form of a multicomponent glassy phase of
aluminosilicates, the calcium is in the form of free oxides as it was not part of the
combustion process. The latter reacted with the excess of NaOH forming calcium
hydroxides, Ca(OH)2 which then reacted with CO2 in the atmosphere producing
CaCO3.
3 sterngth-naoh
Comressive strength (MPa)
2.5
2 D
1.5
0.5
-2 0 2 4 6 8
% NaOH
Figure 2 Effect of NaOH on compressive strength
167
xrd-geo3bb
smooth
q c q = quartz
c = calcite
z = CSH
Intensity
z q
s
10 20 30 40 50 60 70 80 90
2 theta angle (oC)
Figure 3 X-ray diffraction pattern of cured geopolymer
The effect of water ratio on compressive strength is presented in Fig. 4, where strength
decreased with increasing sodium silicate content. It was observed during experiments
that the increase in sodium silicate content increased the viscosity of the fresh paste.
The increase in viscosity, hence decreasing workability increased the tendency of
unfilling of the molds during casting leading to defects in the cured paste.
Compressive strength (MPa)
4
3.5
3
sterngth-nasil
2.5
2
1.5
1 MPa
0.5
35 36 37 38 39 40 41
sodium silicate (wt%)
Figure 4 Effect of sodium silicate on compressive strength
In general, regardless of the compositions, the compressive strength of geopolymer

paste synthesized using a substantially high calcium content were very low, less than ~
4 MPa compared to the ones made from class F fly ash which could achieved as high as
~40 MPa [Astutiningsih, 2016]. This phenomenon was related to the formation of
Ca(OH)2 once the calcium compounds contained in the precursor was in contact with
high alkaline solution causing flash / rapid setting, hindering the geopolymerisation
process.
3.2. Microstructure and Phase Formation

Figure 5 shows the SEM images on the fractured surface of geopolymer samples.
Needle crystals of carbonates were identified on the geopolymer samples having lower
168
strength. The formation of carbonates was preceded by the reaction between calcium
contained in fly ash with alkaline solution forming Ca(OH)2 which then interacted with
CO2 in the air forming calcium carbonates, as detected n samples using XRD. The
formation of Ca(OH)2 is believed to cause rapid setting of the paste resulting in low
workability hence strength achieved.
Figure 5 Scanning electron microscopy images on the fractured surface of geopolymer.
X-ray diffractographs of cured geopolymer samples having various compositions, as

formulated in Table 4, presented in Figure 6 showed an obvious amorphous hump and
the presence of several peaks of crystalline phase(s). It can be noted that CaCO3 was
present on all samples. The compositions are given in molar ratios according to Rahier
et al (Rahier et al., 1996) The formation of this carbonate has been explained in the
previous section. Crystalline quartz, also identified in all samples, was originated from
the fly ash precursor and was not participated in the geopolymerisation process. The
difference between these diffractographs was the presence of crystalline zeolitic phases
in sample having high ratio of water to sodium, as in sample 3. Geopolymer itself was
the crystalline analogue of zeolites. The tendency to form zeolitic phase arose when the
molar ratio of sodium to aluminum (Na/Al) and water to sodium ratio (H2O/Na2O) is
high (Astutiningsih, 2005). Water ratio in the paste mix for making the samples was
much higher compared to the ones made from class-F fly ash. This was due the flash
setting caused by the formation of Ca(OH)2 making the necessary of adding extra water
to improve workability. As a comparison, molar ratio of water to sodium in the class-F
fly ash based-geopolymer was in the range of 20 (Astutiningsih, 2016), while in this
experiments, the molar ratios of sample 3 was 30. The reason why zeolitic phase still
crystallized although Na/Al ratio in this sample was low was explained as follows. The
presence of high amount of calcium oxides that led to flash setting was an obstacle to
geopolymerisation. The available sodium that was supposed to participate in
geopolymerisation became available for the nucleation of zeolitic crystals.
Table 4 Composition variation in molar ratios of geopolymer samples for XRD.

Sample no Na/Al Si/Al H2O/Na2O SiO2/Na2O
169
1 3.96 4.76 20.76 1.45

2 3.30 4.11 19.80 1.35
3 0.62 2.96 30.32 3.46
xrd-gpcomp-qir
1200
q=quartz
q c c=calcite
z z
1000 z=zeolite sample1
q sample2+
sample3+
800 sample3
Intensity
600
sample 2
400
200 sample1
0
16.59 28.19 39.79 51.39 62.99 74.59 86.19
2theta (deg)
Figure 5 X-ray diffraction patterns of cured geopolymer samples with various

compositions
4. CONCLUSION
Class C fly ash contained a very high amount of calcium in the form of free oxide which
when in contact with alkaline solution, i.e. the sodium silicate activator used, formed
Ca(OH)2 that caused flash setting hindering geopolymerisation process. The incomplete
geopolymerisation resulted in the significantly much lower strength achieved by
geopolymer paste samples synthesized using class C fly ash compared to the ones made
from class F fly ash as in the previous study. The calcium hydroxide then reacted with
CO2 in the air forming calcium carbonate, CaCO3, as identified in the x-ray diffraction
patterns of all the samples. Excess of sodium further decreased strength very probably
due to the formation of more carbonates. Carbonate formation as needle crystals could
be observed on the fractured surface of the samples using SEM. There was a tendency
of zeolitic phase(s) formation due to the relatively high sodium and high water content
in the paste mixture. In summary, based on the compressive strength achieved, this class
C fly ash is not suitable for use as geopolymer precursor for structural applications.
5. ACKNOWLEDGEMENT
The authors would like to acknowledge that this project was supported by PT Puncak
Jaya Power and PT Freeport Indonesia in Papua.
170
6. REFERENCES
Astutiningsih, S. (2005), Alkali-activation and curing of aluminosilicate-based
geopolymers, Doctor of Philosophy Thesis, University of Western Australia, pp. 41.
Astutiningsih, S. (2016), Komposisi semen geopolimer dan proses pembuatannya, ID
P000043023.
Barbosa, V.F.F., MacKenzie, K.J.D. and Thaumaturgo, C. (2000), Synthesis and
characterization of materials based on inorganic polymers of alumina and silica:
sodium polysialate polymers, International Journal of Inorganic Material, pp. 309-
317.
Bernal, S.A., Provis, J.L., Walkley, B., San Nicolas, R., Gehman, J.D., Brice, D.G.,
Kilcullen, A.R., Duxson, P. and van Deventer, J.S.J. (2013), Gel nanostructure in
alkali-activated binders based on slag and fly ash, and effects of accelerated
carbonation, Cement and Concrete Research, Volume 53, pp. 127-144.
Guo, X., Shi, H. and Wei, X. (2017), Pore properties, inner chemical environment and
microstructure of nano-modified CFA-WBP (class C fly ash – waste brick powder)
based geopolymers, Cement Concrete Composites, Volume 79, pp. 53-61.
Pouhet, R. and Cyr, M., (2016), Carbonation in the pore solution of metakaolin-based
geopolymer, Cement and Concrete Research, Volume 88, pp. 227-235.
Rahier, H., Van Mele, B., Wastiels, J. and Wu, X. (1996), Low temperature synthesized
aluminosilicate glasses. Part 1 Low-temperature reaction stoichiometry and structure
of a model compound, Journal of Materials Science, Volume 22, pp. 71-79.
Wongsa, A., Boonserm, K., Waisurasingh, C., Sata, V. and Chindaprasirt, P. (2017),
Use of municipal solid waste incinerator (MSWI) bottom ash in high calcium fly ash
geopolymer matrix, Journal of Cleaner Production, Volume 148, pp. 49-59.
Xie, J. and Kayali, O. (2016), Effect of superplasticizers on workability enhancement of
class F and class C fly ash- based geopolymers, Construction and Building
Materials, Volume 22, pp. 36-42.
171
INNOVATIVE CERAMIC THERMAL STORAGE MATERIAL ELABORATED FROM

MUNICIPAL INCINERATOR BOTTOM ASHES
N. LOPEZ-FERBER1,2,5, D. PHAM MINH2, A. NZIHOU2, V. GOETZ1, Q.FALCOZ1, N.TESSIER-DOYEN3, J.F.

HOFFMANN4, A. MEFFRE4
1 Laboratoire PROMES, CNRS, Rambla de la Thermodynamique, Tecnosud, 66100 Perpignan, France .
2 Université de Toulouse, Mines Albi, CNRS UMR 5302, Centre RAPSODEE, Albi, France
3 Laboratoire SPCTS, UMR CNRS 6638, Centre Européen de la Céramique (CEC), Limoges, France
4 Eco-Tech Ceram, Espace Entreprises Méditerranée, Rivesaltes, France
5 Corresponding author: Nicolas.lopez-ferber@promes.cnrs.fr , +33(0)674702718
Abstract
According to the International Energy Agency, the development of Concentrated Solar Power plants
will require important quantities of Thermal Energy Storage Materials (TESM). For industrial purposes,
different criteria are required for a given TESM: easy production, low cost, high availability, low
environmental impact, stability in a wide range of temperatures. Conventional ceramics (Alumina,
Zirconia, Mullite…) are suitable materials for these applications, but they have some drawbacks such
as high cost and low availability. To overcome these issues, it is possible to produce TESM from
industrial by-products [1].
This work is dedicated to the development of a new ceramic material from Municipal Waste
Incinerator Bottom Ashes and waste clay. The main objective being to ease the production process
and lower production costs, all elaboration steps have been conceived so as to be easily implemented
in the building brick industry, using their usual production methods.
After several trials to define the experimental domain, a design of experiment approach has been used
to maximize thermal volumetric capacity and thermal conductivity, using 4 parameters (MWIBA
granulometry, clay content, firing temperature and heating ramp). The best formulation has been
identified. The shaping of the TESM being a critical point, an extrusion protocol is currently under
development.
1,2 1,5
Thermal Conductivity
Thermal capacity
1
[MJ/(m3.K)]
0,8 1
[W/(m.K)]
0,6
0,4 0,5
0,2
0 0
1100-20 1100-30 1100-40 1100-70 1125-20 1125-30 1125-40 1125-70
Firing Temperature [°C] - Clay content [%wt]
Figure 1 Thermal properties of MWIBA-based ceramics as a function of firing temperature and clay content. Firing at 1125°C with 20 or
30% clay appears to be the best strategy to maximise both thermal capacity and thermal conductivity. Samples fired at 1100°C are less
cohesive.
References
[1] Gutierrez et al., Review on industrial waste and by-product materials revalorization as thermal energy storage (TES)
materials, Renewable and sustainable energy reviews, 59, 763-783, 2016
172
ASHES FROM BIOMASS COMBUSTION: RECYCLING AS MORTARS RAW MATERIAL IN

A SUSTAINABILITY PERSPECTIVE
R.C.E. MODOLO1, G. ASCENSÃO2, L. SENFF3, L.A.C. TARELHO4, V.M. FERREIRA5, J.A. LABRINCHA2,
C.A.M. MORAES1, A.S. SILVA6
1 Graduate Program of Civil Engineering, University of Vale do Rio dos Sinos/ NuCMAT, 93022-000,
São Leopoldo, RS, Brazil. *reginaem@unisinos.br (+55 51 980570501)

2 Department of Materials and Ceramic Engineering / CICECO, University of Aveiro, 3810-193 Aveiro,
Portugal
3 Mobility Engineering Center, Federal University of Santa Catarina (UFSC), 89281-000, Joinville, SC,
Brazil
4 Department of Environment and Planning/CESAM, University of Aveiro (UA),3810-193 Portugal
5 Department of Civil Engineering/RISCO, University of Aveiro (UA),3810-193 Portugal
6 Materials Department, National Laboratory for Civil Engineering (LNEC), 1700-066 Lisbon,
Portugal.
Keywords: mortars, bottom ash, fly ash, recycling
Abstract
Mortars were produced in bench scale by replacing conventional sands, namely coarse sand (CS) and
fine sand (FS) with different amount of dry bottom ash (BA-Figure 1) and fly ash (FA) from biomass
combustion. Following a material recycling perspective, BA was treated by sieving and washing, and
then denominated treated bottom ash (TBA). The TBA was tested as replacing raw material. The
ashes were physically and chemically characterized and the effect of both on the mechanical
behaviour was studied in this experimental research. Changes on the water content used to keep the
workability of samples invariable were not significant regarding to reference mortar (REF), since the
CS and FS had similar physical characteristics of BA or TBA and FA. Renderings workability,
unrestrained shrinkage and compressive strength were measured. The results showed that
increasing the amount of ashes in the formulations required extra dosage of water, as result of
particles fineness. A significant weight variation was observed up to 28 days, certainly caused by
intense loss of water out of solid structure in this earlier period. Therefore, the replacement of
biomass bottom and fly ashes affects the hardened state features but do not compromise them
significantly.
173
1- INTRODUCTION
The aim of this study is replacing natural aggregates partially by two types of ashes generated during
biomass combustion for energy production in fluidized bed reactors, namely, bottom ash (BA) and fly
ash (FA). BA is basically composed by a mixture of sand (mainly quartz) particles from the original
bed, and exogenous inorganic components coming from biomass (forest soil and small stones)
contaminants. FA is finer than bottom ash and is richer in inorganic components, typical of the
biomass used as fuel [1-5]. The fly ash and bottom ash collected during fluidized bed combustion of
biomass are classified as industrial waste, with codes 100101 and 100124, respectively, according to
the European List of Wastes [6]. The waste management hierarchy favours strategies that emphasize
first reducing and reusing wastes, then recycling, and energy recovery, and finally, treatment and
correct landfill disposal [7]. Natural aggregates such as crushed stone and sand from crushing
bedrock are major components of the most used construction materials, such as asphalt and
concrete [8]. The siliceous nature of some types of biomass ash makes it a suitable material to
replace natural aggregates in the construction sector, replacing calibrated sand for instance in
industrial mortars [9-11].

The binder used in this research was ordinary Portland cement (OPC type II 42.5). According to
commercial information, it has a specific surface area (SSA) of 0.47 m2/g (Blaine fineness) and a
density of 2.98 g/cm3. The fly ash (FA) was used as received as finer commercial sand replacement
(FS). Two different batches of bottom ash (BA) were prepared; in both batches, the BA (figure 1) was
sieved (< 2.00 mm) to remove coarser inert impurities that come mixed with biomass (e.g. soil, small
stones, tiles pieces), to warranty similar particle size distribution when compared to the coarse sand
(CS) used. Figure 2 shows the location and further processing of BA, TBA and FA coming from the
fluidized bed reactor. In the first BA batch, non-additional pre-treatment (washing) was applied
(further termed as BA), whereas the second BA batch was washed with water to reduce soluble salts
concentration (mainly chlorides), further termed as TBA.
Figure 1: Scanning electronic microscopy image of bottom ash used as raw material.
The chemical composition of ashes from thermal power plant was determined by X-Ray
Fluorescence Spectroscopy – XRF (Panalytical Axios spectrometer) and is presented on Table 1. The
particle size distribution (EN 933-1: 2000) [12] of sands, bottom ash (BA) and sieved and washed
174
bottom ash (TBA), used as mineral aggregates in mortars are shown in the Figure 3. Laser diffraction
(Coulter LS230 analyser) was used to determine the FA particle size distribution due to its finer size,
as shown in Figure 3.
Figure 2: Schematic representation of the ash flows generated in the bubbling fluidized bed combustor (BFBC), including the basic
operations implemented for potential further valorization (Adapted from Modolo et al., 2015) [3].
This paper followed up the behaviour of produced mortars at 7 and 28 days of curing incorporating
10 and 20 wt.% of fly ash (FA), bottom ash (BA) and treated bottom ash (TBA). The reference mortar
(REF) was produced by using two sands with different particle size distributions, named here as
coarser sand (CS) and finer sand (FS), as shown in Figure 3.
Raw Materials
Parameters
FA BA TBA FS CS OPC
SiO2 (% wt, dry basis) 46.30 67.2 81.34 99.4 97.53 20.16
CaO (% wt, dry basis) 11.74 8.31 4.96 0.07 0.28 59.91
Na2O (% wt, dry basis) 1.24 1.15 0.63 0.03 0.07 0.17
Al2O3 (% wt, dry basis) 15.26 9.97 5.11 0.00 1.21 4.82
MgO (% wt, dry basis) 2.23 1.23 0.56 0.07 0.01 2.27
Loss on ignition (% wt, dry basis) 7.34 3.04 3.23 0.09 0.24 2.26
3
Cl- (mg/kg dry basis) ~22x10 472 160 20 10 190
Table 1: Chemical composition of ashes and conventional materials.
The CS and FS were partial replaced by BA or TBA and FA, respectively, to minimize the influence of
such additions on the workability by spread (mm) of mortars (slump test). The workability was fixed
175
in 150 mm and controlled by distinct dosages of water added to the mixtures Table 2. The
preparation of mortars with binder/aggregate weight ratio (B/A) of 1:4 involved the: (i) mixture of
the solid components inside a plastic bag for 1 minute, (ii) a mechanical homogenization for 15
seconds, (iii) resting for 1 minute and (iv) a new mechanical homogenization period of 1 minute and
15 seconds. Three prismatic samples (40×40×160 mm) were cast according to EN 1015-11 methods
[13]. All samples were placed for curing in a chamber with controlled relative humidity (RH=65%) and
temperature (23°C) and then tested in terms of compressive strength [14], water absorption and
apparent porosity [15] at 28 days of curing age.
Figure 3: Particle size distribution of ashes.
Mixture Components (% wt, dry basis)

Spread (mm)
CS FS FA BA Cement CS FS BA FA Water
REF 1.0 1.0 0.0 0.0 100 150 150 0 0 56.0 155
10BA10FA 0.9 0.9 0.1 0.1 100 135 135 15 15 58.8 155
10TBA10FA 0.9 0.9 0.1 0.1 100 135 135 15 15 57.6 145
20BA20FA 0.8 0.8 0.2 0.2 100 120 120 30 30 59.6 155
20TBA20FA 0.8 0.8 0.2 0.2 100 120 120 30 30 58.0 150
Table 2. Mortars formulation and spread on table (workability) result.

The workability of mortars with distinct contents of BA, TBA and FA is shown in Table 2. Changes on
the water content used to keep the workability of samples invariable were slightly different
regarding to REF, due to the CS and FS similar physical characteristics of BA or TBA and FA,
respectively. Consequently, the strategy adopted in this work attenuated eventual influence of such
additions on the results. In practice, the negative impact often observed by using the additional
dosage of water in samples with finer additions tends to be minimized. A weight variation was
observed up to 28 days of curing, certainly caused by the loss of water out of the solid structure in
176
this earlier period. Hence, a contraction of capillary walls in the microstructure is induced [16] and it
is responsible for increasing the unrestrained shrinkage of samples. Beyond this period, the weight
variation was attenuated, meaning equilibrium with the room conditions, while the unrestrained
shrinkage revealed an opposite behaviour (Figure 4). Such results can also be also related to the
carbonation effect that influences the shrinkage evolution, if the room curing is maintained at
relative humidity levels between 50% and 75% [17] and can compensate the weight loss occurrence
caused by the decrease of water in the solid structure.
Figure 4. Results of weight variation and unrestrained shrinkage of formulations.
Therefore, the obtained results again reinforce the importance of the equilibrium relatively to the
amount of FA and BA addition and water content in the mixture. The compressive strength gain of all
samples was just observed at earlier ages (up to 28 days), as a natural hydration evolution, while the
additional increase in compressive strength values observed after this period are of minor
significance (Figure 5).
177
Figure 5. Results of compressive strength of formulations.
Nevertheless, this study has been considered as preliminary work that consolidates the potential use of these
solid wastes tested as raw material for the production of mortars in partial replacement of different types of
sand. From an environmental point of view, this solution could be seen as an opportunity to minimize the
non-renewable natural resources extraction, thus giving an aspect that permeates the sustainability of this
type of product.
4- CONCLUSIONS
This work demonstrates the potential of using BA and FA, generated by thermal power generation
units that burn biomass, as aggregates of cementitious mortars. Since they partially replace (up to 40
wt%) the common aggregate (sand), which is a natural resource showing scarcity risks in several
parts of the globe, this recycling solution shows obvious environmental benefits. Additionally, it
avoids the landfilling disposal, being this aligned with the circular economy paradigm. Values of the
compressive strength in the earlier ages were improved for formulations containing 20%wt ashes,
once the added water content is properly adjusted.
REFERENCES
[1] Vassilev SV, Baxter D, Andersen LK, Vassileva CG. An overview of the composition and application of biomass ash.
Fuel 89 [5] (2012) 913-933.
[2] Steenari B-M, Karlfeldt Fedje, K. Addition of kaolin as potassium sorbent in the combustion of wood fuel – Effects on
fly ash properties. Fuel 89 [8] (2010) 2026–2032.
[3] Modolo RCE, Senff L, Labrincha JA, Ferreira VM, Tarelho LAC, Silva L, Silva T. Characterization of bottom ash from
biomass combustion for its use as aggregate in cementitious-adhesive mortars. Fuel Processing Technology 129
(2015) 192-202.
[4] Modolo RCE, Ferreira VM, Tarelho LA, Labrincha JA, Senff L, Silva L. Mortar formulations with bottom ash from
biomass combustion. Construction and Building Materials 45 (2013) 275-281. doi10.1016/j.conbuildmat.2013.03.093
[5] Tarelho LAC, Teixeira ER, Silva DFR, Modolo RCE, Labrincha JA, Rocha F. Characteristics of distinct ash flows in a
biomass thermal power plant with bubbling fluidised bed combustor. Energy (2015) 1-16.
[6] Decree n.º 209/2004. Portuguese legislation about the European list of wastes in accordance with Commission
Decision 2000/532/EC of 3 May 2000 replacing Decision 94/3/EC establishing a list of wastes pursuant to Article 1(a)
of Council Directive 75/442/EEC on waste and Council Decision 94/904/EC establishing a list of hazardous waste
pursuant to Article 1(4) of Council Directive 91/689/EEC on hazardous waste.
[7] EPA – United States Environmental Protection Agency (2013) Nonhazardous waste management hierarchy. Available
at: http://www.epa.gov/waste/nonhaz/municipal/hierarchy.htm (accessed 15 April 2014).
178
[8] Modolo RCE, Senff L, Ferreira VM, Tarelho LAC, Moraes CAM. Fly ash from biomass combustion as replacement raw
material and its influence on the mortars durability. Journal of Material Cycles and Waste Management, 11
September 2017, Pages 1-10.
[9] Bleischwitz R, Bahn-Walkowiak, B. Sustainable developed in European aggregate industry – A case for sectoral
strategies. Wupertal Institute for Climate, Environment and Energy, Germany 2006. ISBN 978-1-4398-0130-7.
[10] Modolo RCE, Ferreira VM, Tarelho LA, Labrincha JA, Senff L, Silva L. Mortar formulations with bottom ash from
biomass combustion. Construction and Building Materials 45 (2013) 275-281.
http://dx.doi.org/10.1016/j.conbuildmat.2013.03.093
[11] Modolo RCE (2014). Valorization of solid wastes from cellulose and paper industry. PhD thesis, University of Aveiro.
[12] EN 933-1: 2000. Tests for geometrical properties of aggregates, Part 1: Determination of particle size distribution.
[13] EN 1015-11:1999. Methods of test for mortar for masonry – Part 11: Determination of flexural and compressive
strength of hardened mortar
[14] EN 196-1:2005. Methods of testing cement: determination of strength.
[15] Pennings ECM, Grellner W. Precise nondestructive determination of density of porous ceramics. J Am Ceram Soc 72
(1989) 1268–70.
[16] Cachiers du CSTB 2669-4, A3.3: 1993. Certification CSTB unrestrained shrinkage and weight variation.
[17] Nawy EG. Fundamentals of high-performance concrete, 2th ed. New York: Wiley, 2001Hamburger, C.:
Quasimonotonicity, regularity and duality for nonlinear systems of partial differential equations. Ann. Mat. Pura.
Appl. 169, 321–354 (1995)
179
POTENTIAL APPLICATION OF MICROALGAE CULTURE TO WASTEWATER TREATMENT
J. LEGRAND, A. NOUBISSIE YOUALEU, B. LE GOUIC, J. PRUVOST

1 University of Nantes, CNRS, GEPEA, UMR6144, BP406, 44602 Saint-Nazaire Cedex, France
Abstract
The conventional aerobic wastewater treatment plants (WWTP) are the systems generally used to
treat water before to be rejected in the environment. An anaerobic digestion step is sometimes
associated to the WWTP. According to the type of WWTP, a large amount of nutrients (N, P) could be
available, if no physico-chemical treatment exists. Wastewaters can be obtained from several
sources, mainly urban, but also from manure and anaerobic digestates, brewery, paper industry,
olive oil mill. Municipal, industrial and agricultural biowastes can be utilized for the production of
biogas. Then, microalgae couldl be cultivated exploiting CO2 and other gaseous resources from
biogas production and combustion and nutrients and water from the anaerobic digester and
available wastewater, which will result in significantly upgrading the value and energetic content
over the original waste biomass. In parallel, selected microalgal strains will be cultivated for the
treatment of municipal wastewater as a tertiary treatment, again. Microalgae are able to produce
biomass feedstock for advanced biofuels or for others applications, and, at the same time,
recovering nutrients from wastewaters. The microalgae based-wastewater treatment requires solar
radiation, wastewater (minerals/organic matter) and CO2. A ton of microalgae requires about 100-
250 kg of nitrate, 20 kg of phosphate and 1.8 ton of CO2, as well as 200 – 400 tons of water. These
resources seriously affect algal production price and environmental sustainability of algal biomass
production [1]. Then, the recovery of these elements from industrial wastes and wastewaters is also
interesting for microalgae cultivation. For example, a recent report stresses the possibility to
produce sustainable energy economically from microalgae under treatment of wastewater if the
water treatment service is adequately paid for [2].
The substitution of the current inputs for production of the microalgae by recycled industrial waste
has multiple positive impacts: it allows improving the environmental balance, reducing the costs and
increasing the expected income, and to recycle and valorize resources such as carbon and nutrients
from organic industrial wastes under reduction of greenhouse gas emissions and pollution of soils
and water. Moreover, the heat and the CO2 released from the nearby biogas combustion are of
particular value for the cultivation of microalgae.
Low cost culture systems are used, generally raceway bioreactors acting as High-Rate Ponds (HRP).
Raceways can be open or closed (covered) systems. Closed configurations could improve carbon
fixation and productivity. The important parameter is the mean hydraulic retention times (or dilution
rates), which has to be fixed in order to achieve adequate wastewater treatment.
References
[1] Clarens, A.F., Resurreccion, E.P., White M.A., Colosi L.M. (2010), Environmental Life Cycle Comparison of Algae to
Other Bioenergy Feedstocks; Environ. Sci. Technol. 44, 1813–1819.
[2] Lundquist, T. J., I. C. Woertz, N. W. T. Quinn, and J. R. Benemann (2010). "A Realistic Technology and Engineering
Assessment of Algae Biofuel Production" Energy Biosciences Institute; Available at:
http://works.bepress.com/tlundqui/5.
180
COMMERCIAL ADOPTION OF LOW CO2 CEMENT: WHAT IS MISSING?
J.S.J. VAN DEVENTER1

1 Zeobond Pty Ltd, Melbourne, Australia.
Abstract
Despite increased research on low CO2 or alkali-activated cement (AAC), commercial adoption of the
technology is lagging. This paper explores the various hurdles and suggests strategies to unlock the
exciting potential of AAC. Although cement production is expected to contribute more than 20% of
human generated CO2 emissions by 2050 1, this alarming aspect is still not a driver for adoption of
new cement technology, and neither the public nor the industry seems to care.
Substantial materials processing and handling infrastructure is required to implement a new cement
technology, but such infrastructure is rarely available. The reason is that the concrete industry is
used to receive pre-prepared materials from cement suppliers. In contrast, if a new bulk powder has
to be produced at scale, it requires investment that is not justifiable to the concrete producer, hence
the technology does not get demonstrated. A key unit operation not available for bulk testing
purposes is the fine-grinding of materials such as bottom ash, slags and volcanic rock. It is not
feasible for a cement producer with a large mill to stop production, set up special storage facilities,
and then custom grind an experimental material. Therefore, the most innovative mix designs in AAC
never get tested. It is easy to grind and blend materials at laboratory scale, but that is not
commercially convincing. Beyond the 1 m3 scale, bulk materials processing becomes the challenge
rather than new chemistry.
By developing a mini-mill, Loesche in Germany has recognised the limitation of making large vertical
roller mills available for small volume application in remote locations. IMPTEC in Australia has
developed an innovative gyratory crusher with excellent capability for cementitious materials. The
Universal Vortex mobile acoustic grinder produces a shock wave generated in a precisely designed
geometry to shatter brittle materials. These developments will facilitate the pilot grinding of source
materials for use in AAC. Moreover, smaller modular grinding has the potential to revolutionise the
cementitious supply chain; for the first time, it will enable the utilisation of smaller volumes of
source materials in geographically distributed markets. Instead of transporting fine cementitious
powder using pneumatic tankers and ships, it will be possible to transport unground coarse material
using open trucks and bulk carrier ships, which is cheaper and more flexible.
Although a shift from prescriptive to performance-based standards is required, it will be explained

why this is not the main hurdle facing AAC technology. It will be shown that it is possible to enter the
construction market with AAC if innovative commercial strategies are used. For example, certain
bulk powder products like rendering mortar and precast products like building blocks often have only
performance specifications and may provide an entrance point for AAC. It still remains necessary to
apply AAC in iconic projects in view of their high visibility in the market.
References
[1] Beyond Zero Emissions, Rethinking Cement, 2017. http://bze.org.au/rethinking-cement-plan/
181
FOODWASTE FROM AN ENVIRONMENTAL PROBLEM TO A VALUABLE RESOURCE
M. LOIZIDOU1
1 National Technical University of Athens, School of Chemical Engineering, 9, Heroon Polytechniou
Street, Zographou Campus GR-15780 Athens, Greece.
Abstract
182
ROLE OF THE CIRCULAR ECONOMY IN THE SAVING OF RESOURCES
C. BLOCK1, C. VANDECASTEELE2
1 2C Ecosolutions, Duivenstraat 95, 3053 Oud-Heverlee, Belgium.
2 University of Leuven, Department of Chemical Engineering, De Croylaan 46, 3001 Heverlee,
Belgium.
Abstract
In 2015, 7 billion ton of raw materials were consumed in the EU-28 (1). High dependency on
imported resources (ca. 90%) exposes Europe to price volatility and geopolitical uncertainties and
creates a competitive problem for the manufacturing of goods, as materials and imported
components are an important part of the total cost. Current production levels of some “critical
materials” such as Li and Co, are not sufficient to meet the material demand for the production of
sustainable energy in Europe (2). It is consequently important for Europe to optimise its raw material
consumption and to keep these raw materials as long as possible in circulation.
Although in Europe ca. 40 % of the waste is recycled (3), resource consumption can further be
reduced by implementing the principles of Circular economy (CE). Circular Economy aims at
decoupling economic growth from resource constraints by maintaining material and resources as
long as possible in the economy (4). It goes farther than the conventional “reduce, reuse and recycle”
as it also comprises ‘’material repurposing and rethinking’’, ‘’product repair, refurbishing and
maintenance ‘’. To reach the goals of Circular Economy new collaborations between designers,
producers, waste managers, services and consumers are needed. They will result in innovative
production systems based on eco-design, in efficient dismantling methods for end-of-life products, in
thorough selective collection systems for waste, in elaborated procedures for material recycling and
reuse of product parts…but also in a change in mentality, new consumption patterns and new
business models. All these aspects will be illustrated by examples from different sectors.
To facilitate the implementation of CE-principles, the EU introduced in 2015 its CE action plan,
containing a set of general (consumption, product design, production process, secondary raw
materials) and material-specific actions (plastic, food, critical raw materials, construction and
demolition waste, biomess, fertilisers) and a number of legislative proposals (recycling targets).
Some topics of interest are, eco-design, product environmental footprint, labelling system for energy
consumption of household appliances, date marking for food, best waste management, end-of-
waste criteria (5).
References
[1] Eurostat, renewable energy statistics, http://ec.europa.eu/eurostat/statistics-
explained/index.php/Renewable_energy_statistics, accessed in September 2017
[2] WWF, Critical materials for the transition to a 100% sustainable energy future, WWF report 2014,Janury 2014
(wwf.panda.org)
[3] Eurostat, Waste statistics, http://ec.europa.eu/eurostat/statistics-explained/index.php/Waste_statistics, accessed in
September 2017
[4] Wuppertal Institute for climate, environment and energy. Regulatory barriers for the circular economy, Final report,
13 July 2016 (www.technopolis-group.com), accessed in September 2017
[5] European parliament. Circular economy package Four legislative proposals on waste. Briefing EU Legislation in
Progress May 2017, accessed in September 2017
(http://www.europarl.europa.eu/RegData/etudes/BRIE/2017/603954/EPRS_BRI(2017)603954_EN.pdf)
183
IMPROVING CONTINUOUS ANAEROBIC MONO-DIGESTION OF MANURE BY AN

OPTIMIZED AMMONIA PRETREATMENT
A. LYMPERATOU1, H.N. GAVALA1, N.B.K. RASMUSSEN2, I.V. SKIADAS1

1 Department of Chemical and Biochemical Engineering, Technical University of Denmark, Kgs.
Lyngby, Denmark.
2 Danish Gas Technology Center, Hørsholm, Denmark.
Abstract
The anaerobic digestion of livestock manure is a worldwide-expanded practice that permits to

reduce the environmental footprint of livestock production and simultaneously generate renewable
energy in the form of biogas. However, manure mono-digestion often results to economically non-
feasible processes [1] due to the high water and ammonia content in combination to the low
degradation rate of the solid (fiber) fraction. Coupling the Aqueous Ammonia Soaking (AAS)
pretreatment of separated manure fibers with an ammonia recovery step has been identified as a
promising concept for improving the conversion of manure fibers to CH4 [2]. Previous experiments
have shown that a 244% increase of the CH4 yield is possible in batch digestion when manure fibers
are pretreated under optimal AAS conditions [3].
The aim of this study was to evaluate the effects of the optimized AAS pretreatment on the biogas
productivity, methane yield and reduction efficiency of the major organic components of manure
fibers in continuous anaerobic digestion processes. Three continuous mesophilic anaerobic digesters
were run for this purpose: the first fed only with swine manure (Reference digester), the second fed
with swine manure and optimally AAS-treated manure fibers (AAS digester) and the third fed with
swine manure and non-pretreated manure fibers (NP digester). The mixture of manure-to-fibers
ratio was 2:1 (TS basis).
A comparison of the performance of the three processes showed that optimal AAS pretreatment of
the added fibers resulted in the highest biogas productivity and CH4 yield. On the other hand, the NP
digester presented lower TAN (total ammonia nitrogen) concentration, CH4 yield and biogas
productivity even in comparison to the Reference digester, indicating that the low degradation rate
of the manure fibers was more limiting than the TAN concentration for improving manure mono-
digestion. The improved performance of the AAS digester was also indicated by an increased
reduction efficiency of all major organic components of the influent (carbohydrates, lipids, proteins,
and lignin), with the highest, 42 % increase, corresponding to the cellulose fraction.
Overall, it was shown that substituting of 1/3 of the dry matter of manure with optimally pretreated
manure fibers can result in a 17 and 38% increase of biogas productivity and CH4 yield, respectively,
and to an increased efficiency of the reduction of all major organic components of the influent.
Process limitations and economic aspects of the proposed concept are discussed for providing an
insight to the potential of the proposed technology.
References
[1] Asam, Z., Poulse, T.G., Nizami, A., Rafique, R., Kiely, G., Murphy, J.D.: How can we improve biomethane production
per unit of feedstock in biogas plants. Appl.Energy 88, 2013-2018 (2011)
[2] Jurado, E., Gavala, H.N., Skiadas, I.V.: Enhanced methane productivity from manure fibers by aqueous ammonia
soaking pretreatment. Appl.Energy 109, 104-11 (2013)
[3] Lymperatou, A., Gavala, H.N., Skiadas, I.V.: Optimization of Aqueous Ammonia Soaking of manure fibers by Response
Surface Methodology for unlocking the methane potential of swine manure. Bioresour Technol 244, 509-516 (2017).
184
ENHANCEMENT OF METHANE POTENTIAL AND CONVERSION KINETICS OF THE

ANAEROBIC DIGESTION OF AGAVE BAGASSE BY OZONE DELIGNIFICATION
V.K. ARÉVALO-PÉREZ1, O. GARCÍA-DEPRAECT1, E. LEÓN-BECERRIL1*

1
Enviromental Technology Department, Centro de Investigación y Asistencia en Tecnología y Diseño
del Estado de Jalisco A.C., Guadalajara, Jalisco, Mexico, *eleon@ciatej.mx
Keywords: Biochemical methane potential, ozonolysis, biogas, enzymatic hydrolysis, pre-treatment,

lignocellulosic biomass.
Abstract
This study aims to improve the methane yield (YCH4) and conversion kinetics of agave bagasse (AB)
by using ozone pre-treatment followed by enzymatic hydrolysis (EH). The EH of raw and pre-treated
AB was investigated using two enzymatic conditions: i) Celluclast (EH1), and ii) Celluclast + Viscozyme
(EH2). Biochemical methane potential (BMP) tests and kinetics analysis were conducted to evaluate
the impact of six conditions: Raw AB (BST), AB with ozone pre-treatment (BO3), hydrolysates from AB
without pre-treatment (BST-EH1 and BST-EH2), and hydrolysates from pre-treated AB (BO3-EH1 and
BO3-EH2). Compared to BST-EH1 and BST-EH2, higher concentrations of fermentable sugars,
chemical oxygen demand, and volatile solids (VS) were obtained from BO3-EH1 and BO3-EH2.
However, higher hydrolysis efficiency was achieved by using BO3-EH2 as compared to BO3-EH1. The
ozone pre-treatment did not generate furfural and 5-hydroxymethylfurfural. The highest (330. 51
NmL CH4/g VS added) and lowest (75.26 NmL CH4/g VS added) YCH4 were obtained with BO3-EH2 and
BST, respectively. The modified Gompertz model accurately described the experimental data. No
significant lag phase was observed in almost all experiments. BO3-EH2 attained the highest Hmax of
351. 93 NmL/g VS added. Hydrolysates EH1 (BST-EH1 and BO3-EH1) achieved the highest Rmax (3.17–
3.70 NmL/h), while the lowest Rmax (0.27–0.46 NmL/h) was obtained using AB without EH (BST and
BO3). To the best of the authors’ knowledge, this is the first report on evaluating the BMP of raw and
ozonated AB demonstrating the importance of both ozone pre-treatment and EH in the
improvement of YCH4 and conversion kinetics.
185
1- INTRODUCTION
The necessity to develop and implement clean and renewable energy sources is crucial, as the
current fossil fuel energy consumption accounts for more than 80% of total global demand, leading
to several problems of environmental pollution [1]. Lignocellulosic biomass generated by agricultural
activities stands out as suitable feedstock to produce environmental-friendly biofuels. In Mexico,
tequila is a traditional alcoholic beverage with a broad recognition and worldwide demand. In 2017,
the Tequila Regulatory Council estimated production of 271.4 million liters of tequila [2]. The
production of tequila generates a solid by-product called agave bagasse (AB) during the extraction of
juice from the cooked heads of agave. About 1.4–2 kg of AB is generated for each liter of tequila
produced [3]. Thus, the AB annual generation that might be revalorized for biofuels production is
about 3.8 x 105 tons.
The composition of AB (46% cellulose, 23% hemicellulose, and 19% lignin) makes it a potential
feedstock for producing biofuels [4]. Enzymatic hydrolysis (EH) is commonly applied to convert sugar
carbohydrates into monomers such as glucose, xylose, arabinose, galactose, and mannose. These
fermentable sugars contained in the hydrolysate are further subjected to fermentation to produce
biofuels. Among the different biofuels of interest, there is increasing attention in assessing the
hydrolysates for producing methane through anaerobic digestion processes. Unfortunately, the
complex structure, including covalent bonds, several intermolecular bridges, and van der Waals
forces, confers recalcitrant characteristics to AB. Thus, pre-treatments, which are targeted on the
reduction of cellulose crystallinity, depolymerization of both lignin and hemicellulose, and increase in
porosity, are needed to enhance EH efficiency [5].
There are different pre-treatments such as physical, chemical, and biological (including their
combinations); however, there is no ideal pre-treatment because its application depends on the type
of bioprocess and feedstock [6]. This study proposed ozonation as a pre-treatment to enhance the
EH efficiency of AB, and consequently improve its anaerobic digestion. It has been shown that ozone
pre-treatment can be carried out at ambient temperature and pressure, reduce lignin efficiently,
avoid the production of inhibitory compounds such as furfural and 5-hydroxymethylfurfural (HMF),
and significantly improve the yield of fermentable sugars released in the EH of lignocellulosic
biomass [7]. In this regard, to the best of the authors’ knowledge, there is no information concerning
the use of ozone pre-treatment for enhancing the anaerobic digestion of AB.
Therefore, the present study aims to enhance the anaerobic digestion process of AB in terms of
methane yield (YCH4) and conversion kinetics by using ozone pre-treatment followed by EH. To this
purpose, it was investigated the effects of both raw AB and ozonated AB on the EH process and
biochemical methane potential (BMP).

2.1 Agave bagasse preparation
AB was collected from a tequila factory in Tequila, Jalisco, Mexico. The AB was dried at room
temperature (30 ± 2 °C), milled, and then sieved to obtain a particle size of 0.6 mm. The material was
stored at room temperature and without any exposure to sunlight until use.
186
2.2 Ozone pre-treatment

A fixed bed reactor consisted on a glass tube (30 cm length and 6.5 cm internal diameter) containing
a concentric bubble-diffuser was used for ozonation. Ozone was produced by a G11 generator
(Pacific Ozone Technology, USA) at room temperature [8]. The reactor was run with AB at 45% (w/w)
moisture using an ozone dose of 90 mg O3/g AB.
2.3 Enzymatic hydrolysis

The raw AB (BST) and the ozonated AB (BO3) were subjected to EH in a complete mix reactor with a
working volume of 3 L (5% w/v) at 50 °C, 0.1 M sodium citrate buffer (pH 4.8), and 120 rpm. EH was
performed at two different conditions as follows, EH1: Celluclast 68.51 IU/mL (5.7% w/v), and EH2:
Celluclast 68.51 IU/mL (0.2% w/v) and Viscozyme 78.53 IU/mL (5% w/w), both purchased from
Sigma-Aldrich. The EH process was interrupted when the reducing sugars concentration peaked. The
hydrolysates were autoclaved at 90 °C for 1 h to inactivate the enzyme, and then stored in plastic
containers at 4 °C for further use. The hydrolysates were characterized in terms of total volatile
solids (VS), soluble chemical oxygen demand (CODS), reducing sugars, and duration of the EH
process.
2.4 Biochemical methane potential

BMP tests were performed in the Automatic Methane Potential Test System II (AMPTS, Bioprocess
control, Lund, Sweden), following the recommendations described by [10,11]. The operational
conditions were as follows: working volume, 400 mL; temperature, 37 °C; mixing speed, 120 rpm
(mixer on time, 60 s; mixer off time, 180 s); and inoculum to substrate ratio (on a VS basis), 3:1.
Sodium bicarbonate was added to provide buffering capacity (3 g CaCO3/L) to the system. The
operational pH was controlled at 7.2 ± 0.2 using NaOH (5 M) throughout the whole experiment. Each
substrate was evaluated in triplicate. Besides, blank reactors without substrate addition were run to
measure the amount of endogenous methane evolved from the inoculum itself. The reactors were
sealed with rubber stoppers, and then a leakage test was carried out to prevent biogas loss. The
headspace was flushed with inert nitrogen gas (0.5 L/min) during 1 min to ensure free-oxygen
conditions.
2.4.1 Substrate
Six substrates were tested in the BMP tests: raw bagasse (BST), bagasse with ozone pre-treatment
(BO3), hydrolysates from AB without pre-treatment (BST-EH1 and BST-EH2), and hydrolysates from
pre-treated AB (BO3-EH1 and BO3-EH2). To ensure optimum biological activity, only BST and BO3
were supplemented with external nutrients (solutions A and B) according to the recommended by
[9].
2.4.2 Inoculum
Anaerobic granular sludge was used as methanogenic inoculum. The inoculum was obtained from a
stable up-flow anaerobic sludge blanket reactor treating tequila vinasse at mesophilic conditions (35
± 2 °C). The effluent treated had the following characteristics: pH, 7.2 ± 0.2; volatile fatty acids, 0.12
± 0.01 g acetic acid equivalent/L; ammonium, 26.5 ± 0.7 mg/L; alkalinity, 3,032.4 ± 166.2 mg
CaCO3/L; and VS to total solid ratio, 0.8 ± 0.06, indicating good quality characteristics, as
recommended by [11].
187
2.5 Analytical methods

The AB was characterized in terms of hemicellulose, cellulose, and lignin according to the National
Renewable Energy Laboratory (NREL) [12]; reducing sugars for BST and BO3 were considered as the
sum of glucose and xylose. The VS, CODS and pH were measured according to standard methods
[13]. Reducing sugars concentration was measured with the 3,5-dinitrosalicylic acid method [14]. The
concentration of sugars (glucose, xylose) and acid acetic was determined by high-performance liquid
chromatography (HPLC) in a Varian ProStar 230 equipment equipped with a Biorad Aminex HPX-87H
column maintained at 65 °C using a refractive index (RI) detector. The mobile phase consisted of 5
mM H2SO4 at 0.6 mL/min. Furfural and HMF were measured with the same HPLC and column, but
using a column temperature of 60 °C, a Varian 325 UV detector (210 nm), and a mobile phase (0.6
mL/min) composed of 10% pure acetonitrile, 90% 5 mM H2SO4.
2.6 Data analysis

The YCH4 was calculated according to Eq. (1), where BMP is the volume of CH4 produced per gram VS
of substrate added (NmL/g VS added), VS is the accumulated volume of CH4 produced by the sample
(NmL), VB is the accumulated volume of CH4 produced by the blank (NmL), mIS is the total amount of
inoculum in the sample (g VS), mIB is the total amount of inoculum in the blank (g VS), and mVS is the
total amount or organic material (g VS) in the sample [15]. Dixon’s test was used to eliminate single
outliers from measurements [10].
𝑚
𝐵𝑀𝑃 = [ 𝑉𝑆 − (𝑉𝐵 . 𝑚 𝐼𝑆 )] / 𝑚𝑉𝑆 (1)
𝐼𝐵
The BMP was fiited to the modified Gompertz model as is described in Eq. (2) where H (t) is the
cumulative amound of methane (NmL/g VS added) at culture time t (h), Hmax is the maximum
production rate (NmL/g VS added), Rmax is the maximum methane prodcution rate (mL/g VS added-
h), and λ is the lag-phase time (h). The coefficient of determination (R2) was used to assess the
goodness of fit. The kinetic parameters were estimated with the solver function in Microsoft Excel
version 12 (Microsoft, Inc., USA). All data reported are the average and standard deviation of
triplicate experiments. Analysis of variance (Tukey test with a significance level of 5%) was used to
compare mean values.
2.71828 ∙ Rmax
H (t)= Hmax ∙ exp {- exp [ (λ-t)+1]} (2)
Hmax

3.1 Ozone pre-treatment
By applying ozone pre-treatment, lignin is degraded from 35.81 ± 1.02 for BST to 30.88 ± 0.94 for BO3
(% dry weight), provoking the rupture of links, and releasing the sugars. The content of cellulose and
hemicellulose is conserved up to 95% as follows: cellulose 31.23 ± 0.30 for BST and 30.74 ± 0.20 for
BO3, and hemicellulose 7.38 ± 0.19 for BST and 7.29 ± 0.01 for BO3, (% dry weight). The ozone pre-
treatment only affects the lignin avoiding in this way the degradation of carbohydrates.
3.2 Enzymatic hydrolysis

Table 1 shows the physicochemical characterization of the different hydrolysates. The concentration
of reducing sugars, CODs, and VS content was higher when ozonolysis was applied in comparison
with hydrolysates obtained with raw AB. However, BO3-EH2 showed an increase in the reducing
sugars released with respect to BO3-EH1, showing a higher hydrolysis efficiency (higher amount of
188
fermentable sugars in less time) when a combination of two enzymes was used (EH2). As expected,
BST-EH1 and BST-EH2 showed lower values of reducing sugars released, confirming that a pre-
treatment is crucial for maximizing the bioconversion of carbohydrates, cellulose and hemicellulose,
of AB into more easily biodegradable compounds. Furfural and HMF, which are well-known to be
inhibitory compounds for biological processes, were found to be under the detection limit of the
analytical method in both hydrolysates EH1 and EH2, confirming that the ozone pre-treatment
produces little or no inhibitory compounds, as previously reported [7]. It could boost the
performance of subsequent biological processes, e.g., anaerobic digestion to enhance YCH4 and
biodegradability.
Table 1. Physicochemical characteristics of the different enzymatic hydrolysates tested.

Parameter BST-EH1 BO3-EH1 BST-EH2 BO3-EH2
pH 5.03 ± 0.00 5.02 ± 0.01 5.02 ± 0.01 5.01 ± 0.02
VS (g/L) 16.50 ± 0.74 27.56 ± 0.66 28.02 ± 0.70 33.84 ± 3.73
CODS (g/L) 20.61 ±0.12 34.55 ± 1.18 34.55 ± 1.86 46.45 ± 3.15
Reducing sugars (g/L) 7.52 ± 0.11 14.88 ± 0.42 9.82 ± 0.23 19.04 ± 0.01
Acetic acid (g/L) 0.01 ± 0.00 0.76 ± 0.00 0.22 ± 0.91 1.03 ± 0.00
Furfural (g/L) UD UD UD UD
HMF (g/L) UD UD UD UD
Duration (h) 28 48 21 21
-6
UD: under detection limit of 5 x 10 g/L.
3.3 Biochemical methane potential

Fig. 1 shows the profiles of BMP (on VS added basis) over time for the different conditions evaluated.
Table 1 presents the YCH4, duration of the batch test, and kinetic parameters obtained from the
modified Gompertz model. It can be seen from Fig. 1 that the BMP behaviour varied significantly
depending on the substrate used. The highest and lowest YCH4 were obtained with BO3-EH2 and BST,
respectively. Thus, YCH4 obtained with ozone pre-treatment and EH2 resulted 4.5-times higher than
that achieved with raw AB without EH. Also, the extent of the process differed from each other. For
instance, BO3-EH1 and BST-EH1 lasted for 198 h, instead of BO3 and BST which had a duration of 609
h. Interestingly, although there were clear differences in the physiochemical characteristics of
hydrolysates EH1 (BO3-EH1 and BST-EH1), the effect of ozone was less evident in the experiments
conducted under these conditions in comparison to the others. Also, the difference in the BMP
obtained from BO3 and BST accounted for only 100%, indicating that the type of enzyme used had a
relevant role on the hydrolysis efficiency, and the EH had a major impact than ozone pre-treatment
in BMP tests. One explanation for the high BMP values obtained from BST-EH1 and BST-EH2 is that
AB used in this study was collected from a distillery which makes tequila with the autoclave cooking
method. This method used high temperatures (100 °C) for long times (24 h) to cook the agave heads,
and then grinds the agave heads for syrup extraction [4]. It is recommended to perform further
energy and cost analysis on the feasibility of implement ozone pre-treatment to enhance BMP of AB.
For instance, Costa et al. [5] found that the methane derived from thermochemically pre-treated
sugarcane bagasse produced less energy than the direct burning of the feedstock.
189
Figure 1. BMP curves for BO3-EH1 (filled circles), BST-EH1 (open circles), BO3-EH2 (filled triangles), BST-EH2 (open triangles), BO3 (filled
squares), and BST (open squares).
In view of easier comparison among the different conditions tested, the experimental data were
fitted with the modified Gompertz model and kinetic parameters were calculated. Overall, this
model accurately described the experimental data with high R2 values. As expected, the highest
Hmax of 351. 93 NmL/g VS added was observed with BO3-EH2, whereas BST resulted in the lowest
Hmax of 74.14 NmL/g VS added. It must be mentioned that no lag phase was detected in all
experiments, except for BO3-EH1 and BST which had a latency time around 7 and 1 h, respectively.
This suggests that AB contains some readily available compounds for being used by methanogenic
microorganisms in the early stage of the process and that the inoculum to substrate ratio used was
suitable to allow well methanization. The lag phase detected might be a consequence of the
adaptation of inoculum for the new environment which AB conferred to the process. Moreover, the
methane production rate varied according to the condition used. Hydrolysates EH1 (BST-EH1 and
BO3-EH1) resulted in higher rates ranging from 3.17 to 3.70 NmL/g VS added-h, followed by
hydrolysates EH2 (1.34–1.76 NmL/g VS added-h), and finally the lowest methane production rates
ranging from 0.27 to 0.46 NmL/g VS added-h was obtained using AB without EH (BST and BO3). These
values are in accordance with those reported by Lobo-Baêta et al. [16] who applied autohydrolysis to
pre-treated sugarcane bagasse, obtaining the highest methane formation rate of 2.42 NmL/h using
170 °C, 35 min and solid-to-liquid ratio of 0.33. It is difficult to compare findings with those reported
previously in the literature because the differences in operational conditions, feedstock, inoculum,
reactor, pre-treatment, and forms to express YCH4. For instance, Arreola-Vargas et al. [17] reported
260 mL/g COD using acid hydrolysate from AB in an anaerobic sequential batch reactor operated at
32 °C, pH 7.5, and organic loading rate of 1.3 g COD/L-d. Here, the optimum condition was found to
be BO3-EH2, obtaining the highest YCH4 and acceptable methane production rate of 351.93 and 1.76
NmL/g VS added-h, respectively.
190
Table 2. BMP of the six conditions evaluated and kinetic parameters obtained from the modified Gompertz model.
Run YCH4 Duration YCH4 max λ R R2

(NmL/g VS added) (h) (NmL/g VS (h) (NmL/g VS
added) added-h)
BO3-EH1 286.63 ± 5.66 a 198 299.46 7.12 3.17 0.9979
BST-EH1 305.98 ± 6.31a 198 304.17 0.00 3.70 0.9933
BO3-EH2 330.51 ± 4.59 b 409 351.93 0.00 1.34 0.9982
BST-EH2 253.1 ± 14.73c 409 263.77 0.00 1.76 0.9953
BO3 133.39 ± 12.32d 609 133.85 0.00 0.46 0.9801
BST 75.26 ± 4.26e 609 74.14 1.07 0.27 0.9982
Equal letters in the same column indicate no significant difference (α = 0.05).
4- CONCLUSIONS
It can be drawn from results that ozone delignification is a potential pre-treatment to enhance not
only the EH but also the YCH4 and degradation kinetics of AB. The ozone pre-treatment did not
generate inhibitory compounds such as furfural and HMF. However, other factors such as enzyme
composition must be considered for maximizing the revalorization of AB through anaerobic digestion
processes. Also, to the best of the author’s knowledge, this is the first report on evaluating the BMP
of raw and ozonated AB demonstrating the importance of both ozone pre-treatment and EH in the
anaerobic digestion efficiency.
Acknowledgments
This work was supported by CONACYT-SENER-Project -247006. V.K. Arévalo-Pérez acknowledges
CONACYT for the M.Sc. fellowship No. 634555. O. García Depraect acknowledges CONACYT for the
Ph.D. fellowship No. 423963. This work was dedicated to the memory of Dr. Alberto López-López.
REFERENCES
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blue agave bagasse fibers of Mexico. Composites Part A: Applied Science and Manufacturing. 45, 153-161 (2013)
[2] CRT.: Estadísticas oficiales de Consumo de Agave para Tequila y Tequila 100% de Agave. Accessed: 15/03/2018,
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[3] López-López, A., Davila-Vazquez, G., León-Becerril, E., Villegas-García, E., Gallardo-Valdez, J.: Tequila vinasses:
generation and full scale treatment processes. Reviews in Environmental Science and Biotechnology. 9, 109-116
(2010)
[4] Contreras-Dávila, C.A., Méndez-Acosta, H.O., Arellano-García, L., Alatriste-Mondragón, F., Razo-Flores, E.:
Continuous hydrogen production from enzymatic hydrolysate of Agave tequilana bagasse. Effect of the organic
loading rate and reactor configuration. Chemical Engineering Journal. 313, 671-679 (2017)
[5] Costa, A.G., Pinheiro, G.C., Pinheiro, F.G.C., Dos Santos, A.B., Santaella, S.T., Leitão, R.C.: The use of thermochemical
pretreatments to improve the anaerobic biodegradability and biochemical methane potential of the sugarcane
bagasse. Chemical Engineering Journal. 248, 363-372 (2014)
[6] Arenas-Cárdenas, P., López-López, A., Moeller-Chávez, G.E., León-Becerril, E.: Current Pretreatments of
Lignocellulosic Residues in the Production of Bioethanol. Waste and Biomass Valorization. 8, 161-181 (2017)
[7] Travaini, R., Barrado, E., Bolado-Rodríguez, S.: Effect of ozonolysis pretreatment parameters on the sugar release,
ozone comsumption and ethanol production from sugarcane bagasse. Bioresource Technology. 214, 150-158 (2016)
[8] León-Becerril, E. and López-López, A.: MX Patent Application No. MX/a/2015/014521.
[9] Angelidaki, I., Alves, M., Bolzonella, D., Borzaccone, L., Campos, J.L., Guwy, A., Van Lier, J.: Definindg the biomethane
potential (BMP) of solid organic wastes and energy crops: a proposed protocol for batch assays. Water Science and
Technology. 59, 927-934 (2009)
[10] Holliger, C., Alves, M., Andrade, D., Angelidaki, I., Astals, S., Baier, U., …, Wierinck, I.: Towards a standardization of
biomethane potential tests. Water Science & Technology. 74, 2515-2522 (2016)
191
[11] Buitrón, G., Kumar, G., Martinez-Arce, A., Moreno, G.: Hydrogen and methane production via a two-stage processes
(H2-SBR + CH4-UASB) using tequila vinasses. International Journal of Hydrogen Energy. 39, 19249-19255 (2014)
[12] Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J., Templeton, D., Crocker, D.: Determination of Structural
Carbohydrates and Lignin in Biomass. Laboratory Analytical Procedure. NREL/TP-510-42618 (2012)
[13] APHA: Standard methods for the examination of water and wastewater. American Public Health Association,
American water works Association, and water Environment Federation (2005)
[14] Dubois, M., Gilles, K.A., Hamilton, J.K., Rebers, P., Smith, F.: Colorimetric method for determination of sugars on
related substances. 28, 350-356 (1956)
[15] Ruggeri, B., Tommasi, T., Sanfilippo, S.: BioH2 & BioCH4 Through Anaerobic Digestion. Springer, London (2015)
[16] Lobo-Baêta, B.E., Sousa-Lima, D.R., Herrera-Adarme, O.F., Alves-Gurgel, L.V., Francisco de Aquino, S.: Optimization of
sugarcane bagasse autohydrolysis for methane production from hemicellulose hydrolysates in a biorefinery concept.
Bioresource Technology. 200, 137-146 (2016)
[17] Arreola-Vargas, J., Ojeda-Castillo, V., Snell-Castro, R., Corona-González, R.I., Alatriste-Mondragón, Méndez-Acosta,
H.O.: Methane production from acid hydrolysates of Agave tequilana bagasse: Evaluation of hydrolysis conditions
and methane yield. Bioresource Technology. 181, 191-199 (2015)
192
IN STORAGE ANAEROBIC DIGESTION OF PIG MANURE USING A FLOATING COVER,

FROM THE LAB TO THE FARM
P. DABERT1, T. LENDORMI2, F. BELINE1, A. TOUDIC3, K. LAVENAN4

1 Irstea, 17 avenue de Cucillé, CS 64427, 35044 Rennes cedex, France
2 Université de Bretagne Sud, FRE CNRS 3744, IRDL, Allée des Pommiers, 56300 PONTIVY
3 Chambre d’Agriculture de Bretagne, Rue Maurice Le Lannou, CS 74223, 35042 RENNES CEDEX
4 Utilities Performance, 14 rue des Ecoles – Saint-Nicolas-Des-Eaux, 56930 PLUMELIAU
Abstract
Concrete pits used for the storage of pig slurry are producing spontaneously between 0.15 and 0.9
m3 of methane per ton of slurry and per week depending on the season. Catching and burning this
gas would reduce the energy consumption of livestock and reduce greenhouse gas emissions.
However, psychrophilic anaerobic digestion of slurry has been shown to be limited by the long
adaptation time of microbial communities to low temperature, which may last up to almost one year
[1-3]. This work presents the results of three experiments performed in the lab (2L reactors), in pilot
pits (200L plastic tanks) and at the farm scale (10m diameter floating cover on a 300m3 concrete pit).
The goal was to understand the determinant of biogas production at low temperature and validate
the technology.
Incubations carried out in 2 L laboratory digesters showed that methane production is possible at
13°C but requires stable conditions and long adaptation of microorganisms. From the five slurries
tested, fresh pig slurry, pig slurry stored for 2 or 9 months, fresh dairy cows manure, or digestate
from mesophilic anaerobic digester, only this last one did not adapt. Methane production kinetics
differed from one reactor to another producing between 0.25 and 0.5 m3 of methane /m3 of slurry
and per week after 104 days of incubation. At this stage, the digesters expressed 31 to 68% of the
estimated methanogenic potential of the fresh slurry. An analysis of the microorganisms present in
the slurry showed a change in the methanogenic species present in the slurry.
Incubations carried out for 8 months (April to November) in 200 L pilot digesters at ambient
temperature and outside of the laboratory showed that temperature is the main factor that
stimulates methane production. At an average temperature of 12.5°C, methane production was very
low, between 0.1 and 0.2 m3 of methane /m3 of slurry per week. When the temperature rose to
23.8°C, the production reaches 1.1 to 1.4 m3 of methane /m3 of slurry and per week. The
concentration of organic matter in slurry was the second factor directly influencing the production of
methane. Finally, methane production decreased in the fall when the temperature decreases. Thus,
during these tests, there was no adaptation of the methanogenic microorganisms, due to low but
also very variable temperatures.
Finally, we tested the methane production from a half buried pig slurry storage pit equipped with a
floating cover to collect gases from September 2016 to March 2017. The pit of 300 m³ was gradually
filled by 8-24 m3 inputs of sows, piglets or fattening pigs’ slurry, every 15 days. The slurry was mixed
during three to five minutes per day. The biogas produced contained 65±3 % of methane and could
be burn on a boiler. Methane production depended on the quantity and quality of slurry present in
the pit and on the temperature. The production varied from 0.12 to 0.51 m 3 of methane /m3 of
slurry and per week, and the temperature changed from 18.8°C in September to 8.2°C in January.
65 % of the methanogenic potential of the slurry was expressed and 60 % of it was caught by the
193
cover. Despite low temperatures in the pit during winter, inputs of slurry maintained methane
production (9 m3 CH4 per day).
Figure 1: The three systems used to test psychrophilic anaerobic digestion of pig slurry
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194
DRY FRACTIONATION OF OLIVE POMACE FOR BIOGAS PRODUCTION:

MILLING, SIEVING AND ELECTROSTAIC SEPARATION
D.E. ALAMI1,2,3, H. CARRERE1, A. LEBRIHI2, D. DHIBA3, A. BARAKAT2,4

1 LBE, INRA, Univ Montpellier, 102, Avenue des Etangs, Narbonne, F-11100, France
2 AgroBiosciences Department, Mohammed VI Polytechnic Univ. Benguerir, Morocco.
3 R&D OCP, OCP Group, Complexe industriel Jorf Lasfar. BP 118 El Jadida, Morocco.
4 IATE, CIRAD, Montpellier SupAgro, INRA, Université de Montpelier, 34060, Montpellier, France.
Abstract
Olive oil extraction processes are worldwide extended especially in Mediterranean regions, but they
generate huge quantities of olive wastes which show environmental risks [1]. In particular, solid
residues, olive pomaces (OP), are rich in organic matter and lipids, and could be valorized by
anaerobic digestion [2]. The aim of this study was to investigate the effect of dry fractionation
(milling, sieving and electrostatic separation) for OP anaerobic digestion.
Milling at 4 mm and 1 mm, was carried out using knife miller, while smaller sizes (200 µm and 50 µm)
were obtained after ball milling. Samples at 4 mm were sieved using a 0.9 mm screen. Ultrafine
samples (50 µm) were subjected to an electrostatic separation (ES) process [3]. Batch experiments
were conducted in the biochemical methane potential assays, at different particle sizes. Effects of
pretreatments were evaluated by biochemical composition of OP fractions.
Milling at 50 µm increased both soluble chemical oxygen demand and methane yield by 36% and
53% respectively, compared to OP at 4 mm which was due to the increase of surface area and
accessibility to microorganisms [4]. Similarly, samples having size higher than 0.9 mm contained 2
fold lesser lipids which decreased methane production by 19% compared to raw OP. The negatively
charged-ES fraction of milled samples at 50 µm represented the highest polyphenols content (13 mg
equilavent galic acid/gTS) and produced the highest cumulative methane volume (157 ml CH4/gVS), which
was 56% higher than the raw OP.
In conclusion, milling, sieving and separations process are both efficient and clean pretreatments
enhancing methane production from olive pomace without the addition of neither water nor
chemical reagents.
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Biomethane : Impact of Structural Features and Pretreatment and Biomethane , Critical Reviews in Environmental
Science and Technology, 43, 260-322 (2013).
195
EXPERIMENTAL INVESTIGATIONS OF CO2 FEED IN A DOWNDRAFT BIOMASS GASIFIER
D. ANTOLINI1, S. SHIVANANDA AIL1, F.PATUZZI 1 , M. GRIGIANTE2, M. BARATIERI1

1 Faculty of Science and Technology, Free University of Bozen-Bolzano, Italy.
2 Department of Civil, Environmental and Mechanical Engineering, University of Trento, Italy.
Abstract
Gas-fired and coal based power generation plants result in the emission of CO 2, a major greenhouse
gas responsible for climate change. On an average, the flue from such power plants contain
approximately 12 – 17 vol.% CO2, 75 – 77 vol.% N2 and ~4.4 vol.% O2 with fractions of CO, NOx, CO2
and SO2 in ppm range [1]. While the capture and storage of this CO2 stream have been addressed
actively in the literature [2], or even implemented rather unsustainably [3], its application in the fuel
making process is imperceptibly addressed. This work examines the thermochemical biomass
conversion with air and CO2 as gasification media to explore the possibilities and limitations of CO2
capture and its application in the fuel making process. In particular, this work addresses the
employment of the Boudouard reaction in the high temperature char zone to yield carbon
monoxide. While this study revolves around the direct use of CO2 from the flue of diesel engines, the
volumetric composition of the reacting gasification media (N 2, O2 and CO2) are simulated using their
injection into the reactor from pre-calibrated cylinders. The experimental investigations are based
on the configuration of a downdraft reactor made of a cylindrical vessel of 60 mm diameter and
length of 1300 mm utilizing dried biomass pellets as feedstock. The mass flow rates of O 2, N2 and CO2
are measured and controlled using calibrated mass flow controllers and the biomass consumption
rate is measured by placing the reactor over a digital weighing balance.
Preliminary investigations using air gasification studies resulted in producer gas yields of 2.4
kggas/kgbiomass with volumetric gas composition of 15.7% CO, 13.3% H2, 16.1% CO2, 1.7% CH4 and
53.2% N2 accounting to a LHV of 3.4 MJ/kg and an equivalence ratio (ϕ) of 0.3. Introduction of CO 2
into the gasifier with N2/CO2 ratio of 5.5 and maintaining O2 fraction similar to the case of air
gasification studies yielded 3.3 kggas/kgbiomass with a reduced LHV of 3.0 MJ/kg and volumetric gas
composition of 16.9% CO, 10.9% H2, 21.5% CO2, 1.3% CH4 and 49.3% N2. However, propitiously, the
specific power production increased from 2.2 kW/kg-biomass for air gasification to 2.7 kW/kgbiomass for
CO2 co-fed air gasification mode. A complete carbon balance is implemented to analyze the rate of
formation of char and tar under various conditions. This work demonstrates a novel mode of
effective utilization of CO2 from the flue of exhaust gases in the power generation process that can
even be integrated with a bio-refinery plant.
References
[1] Xu, Xiaochun, Chunshan Song, Ronald Wincek, John M. Andresen, Bruce G. Miller, and Alan W. Scaroni.: Separation
of CO2 from power plant flue gas using a novel CO2 ‘molecular basket’adsorbent. Fuel Chem. Div. Prepr 48, 1, 162-
163 (2003)
[2] Aroonwilas, Adisorn, and Amornvadee Veawab.: Integration of CO2 capture unit using single-and blended-amines
into supercritical coal-fired power plants: implications for emission and energy management. International Journal
of Greenhouse Gas Control 1, 2, 143-150 (2007)
[3] Viebahn, Peter, Joachim Nitsch, Manfred Fischedick, Andrea Esken, Dietmar Schüwer, Nikolaus Supersberger, Ulrich
Zuberbühler, and Ottmar Edenhofer.: Comparison of carbon capture and storage with renewable energy
technologies regarding structural, economic, and ecological aspects in Germany. International Journal of
Greenhouse Gas Control 1, 1, 121-133 (2007)
196
PILOT SCALE PYROLYSIS OF SLUDGE FROM MILK PROCESSING FACTORIES
M. KWAPINSKA1, A. HORVAT2, Y. LIU3, JAMES J. LEAHY2

1 Dairy Processing Technology Centre, University of Limerick, V94 T9PX, Ireland.
2 Department of Chemical Sciences, Bernal Institute, University of Limerick, V94 T9PX, Ireland.
3 Dublin Institute of Technology, Kevin Street, Dublin 8, Ireland
Keywords: Dairy processing sludge, pilot scale pyrolysis, pyrolysis gas
Abstract
In Ireland the majority of the sludge from the treatment of wastewater in milk processing plants is
land spread. Drawbacks of land spreading include local oversupply due to high transport costs, which
results in sludge being spread on lands in the vicinity of the dairy factories. Local oversupply can lead
to accumulation of certain substances in soil through annual application over many years. Therefore,
in the long term, there is a need for alternative methods to recover energy and nutrients from
increasing volumes of sludge generated from dairy processing.
Pyrolysis offers a potential alternative to land spreading, which can reduce health and environmental
risks, while providing an avenue for the recovery of energy and nutrients. Pyrolysis allows energy
recovery in the form of a high calorific value pyrolysis gas and a char which may be used as a soil
amendment.
In this study pyrolysis of dried dairy sludge was carried out at pilot scale. Results indicate that a dried
Biological Sludge can be successfully pyrolysed and when mixed with wood the resulting char meets
European Biochar Certificate criteria regarding carbon content.
197
1- INTRODUCTION
The dairy industry accounts for approximately 30% of Irish agri-food exports, with 80 % of milk
products being exported [1]. In order to promote growth within this sector, the Irish government has
adopted strategies that offer scope for significant expansion with the aim to increase milk production
by 50% overall by 2020 using the average of the outputs from 2007 to 2009 as a baseline. An increase
in primary production will inevitably lead to an increase in the generation of processing waste such as
sludge from the treatment of wastewater from milk processing plants. The composition of dairy sludge
depends on the type of products being manufactured and cleaning process deployed at the plant. In
general, there are two main sludge types: i) chemical sludge which is a mixture of fat, grease, oil and
suspended solid particles removed from raw effluent in the waste water treatment plant together
with some proteins and minerals by dissolved air flotation (DAF) and ii) biological sludge which is an
organic material, containing suspended solids and non-biodegradable pollutants such as heavy metals
resulting from biological aerobic, anaerobic or anoxic waste water treatment processes [1,2]. In
Ireland the majority of sludge is land spread, e.g. in 2004 around 120,661 tonnes of dairy sludge was
land spread [3]. Some sludges are sterilised and stabilised by composting and then returned to the
land. DAF sludge is sometimes used as a feedstock for anaerobic digestion, however, milk fat is not
easily bio-degraded and causes technological issues [4,5]. When dairy sludge are used as an organic,
nutrient rich fertiliser [6] a strict code of practice must be complied with for the spreading of organic
dairy sludge once a Nutrient Management Plan has been approved by the Environmental Protection
Agency [7]. Drawbacks of land spreading include local oversupply due to high transport costs, which
results in sludge being spread on lands in the vicinity of the dairy factories, also weather conditions
could constrain the land spreading. Local oversupply can lead to accumulation of certain substances
in soil through annual application over many years.
Therefore, in the long term, there is a need to find alternative methods to recover energy and nutrients
from sludge generated from milk processing plants.
In recent years, pyrolysis has gained increased attention as an alternative disposal method for sewage
sludge [8,9]. According to a study by Samolada and Zabaniotou [8], pyrolysis can be an optimal
thermochemical treatment option compared to gasification and incineration. Pyrolysis can reduce
health and environmental risks from problematic wastes [10-12] while providing an avenue for the
recovery of energy and nutrients [13,8]. Pyrolysis is the thermal decomposition of carbonaceous
material in an inert atmosphere into gaseous, liquid and solid products. Pyrolysis gas contains the non-
condensable low-molecular-mass gases such as H2, CO, CH4, C2H4, C2H6 and CO2. The liquid product
contains the condensable volatile compounds i.e. water and water-soluble organics [14]. The solid
residue obtained (char) is comprised mainly of carbon and ash. Pyrolysis product yields are affected
by the process conditions including temperature, reactor residence time as well as feedstock
properties. Slow pyrolysis is generally characterised by relative mild temperatures (350-700°C) and
heating rates [8]. One of the main concerns related to thermal conversion technologies is the release
of heavy metals and contaminants like NH3, HCl, HCN, H2S [15]. The low pyrolysis temperature is
responsible for the absence of heavy metals in the pyrolysis gas, which remain concentrated mostly in
the resulting carbonaceous solid product. The potential application of all pyrolysis products greatly
depends on the presence of various contaminants [16].
This study is part of project, which investigate the potential of pyrolysis as a conversion technology for
sludge from milk processing factories in the frame of state-founded Dairy Processing Technology
Centre. In this study, dried dairy sludge was pyrolysed in pilot scale to determine the suitability of the
sludge for full scale operation.
198

Sludge from wastewater treatment of an effluent from milk processing plant in Ireland is the focus of
this work. Sludge after biological treatment processes with cationic polyelectrolyte addition was
selected. When received, the moisture content in the Biological Sludge (BS) was at 93 wt. % (solids
content 7 %). The BS was dried outdoors in a simple drying bed (spreading out on polythene film
turned over every 3 - 4 days). After drying, the moisture content was reduced to 20 wt. % (solids
content 80 %).
Analysis of proximate and ultimate properties of the dried sludge, wood and the pyrolysis char were
carried out by Celignis Analytical, Ireland. The moisture content was analysed according to BS EN
14774-1: 2009, the ash content according to BS EN 15403: 2011 and the volatile matter content
according to BS EN 15402: 2011. The elemental composition (C, H, N, S) was determined using a Vario
EL cube elemental analyser. The higher heating value (HHV) was measured with a Parr 6300
isoperibolic calorimeter and the corresponding lower heating value (LHV) was calculated.
The experimental tests were carried out in the pilot scale facility at Premier Green Energy in Thurles,
Ireland. The facility consisted of four main sections: feeding system, pyrolysis reactor with char and
gas separation section, gas conditioning section and a gas engine or flare. The pyrolysis reactor is a
stationary muffle furnace with a rotating retort and when the char leave the reactor it is separated
from the pyrolysis gas. Then the gas is directed to the gas cleaning section, which includes a tar
cracking reactor, scrubber, dehumidifier and a re-heater. A schematic diagram of the experimental
facility is shown in Fig. 1. In Fig. 1 the circles depict sampling and measuring points and each circle
represent one physical property measured, e.g.: mass of the feedstock fed in, mass of the char
produced, gas composition, tar content, NH3 and Cl content in the gas and volumetric flow of the
pyrolysis gas. The solid circles refer to Test 1, patterned points to Test 2 and the open circles to Test
3. Process conditions for pyrolysis experiments at pilot scale for BS and Wood mixture are presented
in Table 1.
Figure 1: Schematic diagram of pilots scale pyrolysis facility.
Feeding Pyrolysis Tar Flow rate of air Syngas

rate, temperature, cracking for cracking, flow rate,
kg/h °C temperature, °C m3/h m3/h
Test 1 77 770 800 37.2 -
Test 2 90 700 890 33.6 65.6
Test 3 78 700 900 26.4 63.3
Table 1: Process conditions for pyrolysis experiments at pilot scale.
199
The pyrolysis gas composition (CO, CO2, H2, CH4, C2H4, C2H6, H2S N2, O2) was determined by gas
chromatography (micro-GC, Agilent 3000) and was used to calculate its heating value. Ammonia was
captured by bubbling the pyrolysis gas through a saturated boric acid solution and its amount was
determined by back titration with 0.1 M HCl. The HCl was captured by bubbling the pyrolysis gas
through 0.1 M nitric acid solution and its amount was measured by ion chromatography.
The Solid Phase Adsorption (SPA) sampling method was used to sample tar. The detiled description of
extraction, and chromatographic analysis of tar was provided by Horvat et al. [17]. During the steady-
state operation two parallel SPA samples were taken at three locations along the pyrolysis process
chain. After SPA sampling the tar compounds were extracted from the sorbent by dichloromethane.
Tert-butylcyclohexane and 4-ethoxy phenol were added as internal standards to the tar solutions. An
Agilent 7890A GC coupled with a triple-axis MSD 5975C was used for identification of the most
abundant tar compounds. A Thermo Scientific Trace 1310 GC with a flame ionization detector (GC-FID)
was used for tar quantification. Calibration curves of naphthalene/tert-butylcyclohexane and
phenol/4-ethoxy phenol were applied to quantify aromatic and phenolic tars, respectively.

3.1 3.1 Properties of dairy biological sludge
In Table 2 the properties of the dried BS are presented. In the tested BS, relatively high volatile matter
content of 60 wt. % and high ash content of 32 wt. % was observed (dry basis). This indicated that
during high temperature decomposition most of the organic content of the dried sludge formed
vapour-phase products (non-condensable permanent gases and condensable compounds) but also
significant amounts remained in the form of solid residue. A high volatile matter is desirable if the
pyrolysis gas is a main product. A fixed carbon of 17 wt. % indicates the amount of unconverted carbon
which will remain in the char after pyrolysis. The nitrogen content was high at 5.8 wt. % which is one
of the typical characteristics of dairy sludge resulting from biological and chemical treatment of
defatted effluent [2]. The sulphur content of 0.8 wt. % was observed while the chlorine content was
much lower at 0.2 wt. %. The bulk density of BS after drying was 550 kg/m3.
Properties, wt. % BS Wood BS/Wood

50/50
Moisture, ar. 93.2 - 89.0
Moisture, after bench 20.0 4.7 10.9
drying
Ash content, db. 31.8 0.42 14.7
Volatile matter, db 59.7 84.1 -
Fixed carbon, db 17.0 15.5 -
C, db. 35.9 50.7 42.9
H, db. 5.6 6.6 6.1
N, db. 5.8 0.2 3.0
S, db. 0.8 0.02 0.4
Cl, db 0.2 0.005 0.1
O, db. 19.9 41.9 32.7
Table 2: Proximate and ultimate properties of Biological Sludge-BS, Wood and mixture of BS with Wood.
When pyrolysing a feedstock, one need to find a potential application/use for all the products. In this
project, the main focus was on the pyrolysis gas which could be directly burned in a boiler or after
200
cleaning used in a gas engine to produce electricity and heat. The presence of elements such as
nitrogen, sulphur and chlorine in the sludge is undesirable since they are highly volatile at pyrolysis
temperatures, and will be released as NH3, HCN, H2S, HCl or NH4Cl, which would need to be removed
from the gas in order to avoid fouling and corrosion in the engine.
The most common applications of pyrolysis chars are as a soil amendment or an adsorptive media. As,
the BS has a relatively high ash content of about 30 wt. %, there will be a significant amount of the
pyrolysis char generated, and given it’s relatively low carbon content (Table 2) the resulting char will
not meet the initial criteria in order to qualify as a biochar for soil applications according to European
Biochar Certificate [18].
To overcome these limitations and increase the carbon content in the char the dried BS was mixed
with wood chips at a ratio of 50/50 by weight. The properties of wood and the mixture are presented
in Table 1.
3.1 Pyrolysis gas composition

The volumetric concentration of the gas components over the Test 3 run time of a typical experiment
is shown in Fig. 2 and 3. It can be seen from the figures that the gas composition profiles for the major
gas components had effectively stabilized after 15 min. However, to ensure steady state had been
reached, an additional 15 min were allowed before sampling the product gas for tars, NH3 and HCl.
55 CO CO2 H2 CH4 55
C2H4 C2H6 N2 O2
50 50
45 45
Volumetric fraction, %
40 40
35 35
20 20
15 15
10 10
5 5
0 0
0 10 20 30 40 50 60 70 80
Time, min
Figure 2: Content of major gas components in pyrolysis gas after tar cracking and conditioning for Test 1.
C2H2 C2H4 C2H6 H2S

1.40 1.40
1.36 1.36
1.0 1.0
Volumetric fraction, %
0.8 0.8
0.6 0.6
0.4 0.4
0.2 0.2
0.0 0.0
0 10 20 30 40 50 60 70 80
Time, min
Figure 3: Content of minor gas components in pyrolysis gas after tar cracking and conditioning for Test 1.
201
The results from pilot scale tests were evaluated and discussed as a two separate cases, when 1)
pyrolysis gas without cleaning is used in a gas boiler and 2) pyrolysis gas is conditioned/cleaned to
meet the specification of gas engine.
In order to measure the pyrolysis gas composition without additional high temperature conditioning
(tar cracking) samples of gas were collected in Tedlar bags from a pipe duct between the pyrolysis
reactor and the tar cracking reactor (see Fig. 1) and then analysed by micro GC. The resulting gas
composition on a nitrogen free basis for Test 2 and Test 3 is presented in Table 3. The calorific value
of the untreated pyrolysis gas was relatively high at 12 and 16 MJ/m3 respectively. The gas contained
mainly carbon monoxide (23 and 40 vol. %), methane (24 and 16 vol. %), hydrogen (6.5 and 12 vol. %)
and carbon dioxide (13 and 20 vol. %). The total tar content of 11 g/m3 was observed. The yield of
pyrolysis gas was of 355 and 472 m3/tonne for Test 2 and 3, respectively.
Gases, vol. % Test 2 Test 3
H2 6.5 11.9
CO 22.7 41.7
CO2 12.6 20.4
CH4 23.6 15.9
C2H2 0.1 0.2
C2H4 2.9 4.9
C2H6 1.1 1.3
H2S, ppm 1220 1340
NH3, ppm 4.51 3.41
Total tar, g/m3 11.1 10.5
LHV, MJ/m3 12.2 16.1
Syngas yield, m3/h 32 37
Table 3: Composition of pyrolysis gas collected before tar cracker on N2 free basis
Gases, vol. % Test 1 Test 2 Test 3

H2 10.2 11.4 12.0
CO 19.4 22.5 21.8
CO2 9.1 11.2 11.7
CH4 7.2 7.9 6.6
C2H2 0.4 0.4 0.3
C2H4 0.9 0.8 0.6
C2H6 0.02 0.03 0.01
N2 38.6 41.9 44.4
H2S, ppm 17.1 31.1 -
NH3, ppm - 0.17 0.12
Total tar, g/m3 - 2.4 3.1
LHV, MJ/m3 6.9 7.7 6.9
Syngas yield, m3/h - 65.6 63.3
Table 4: Composition of pyrolysis gas after conditioning.
202
During all the pilot scale tests the conditioned pyrolysis gas was sampled inline every 10 – 15 min and
analysed by micro GC and the results are presented in Table 4. The calorific value of the conditioned
pyrolysis gas at 6.9 and 7.7 MJ/m3 was lower than the raw/unconditioned pyrolysis gas. Since air was
injected into the cracking reactor (see Table 1), most of the tar compounds were cracked in the
presence of oxygen into carbon monoxide and hydrogen while methane was oxidised as well as the
gas being diluted with nitrogen. The total tar content was also reduced to 2.4 g/m3. Yields of
conditioned pyrolysis gas of 730 and 800 m3/tonne were observed for Test 2 and 3, respectively.
3.2 Impurities in the pyrolysis gas

During pyrolysis Test 2 and Test 3 an attempt was made to quantify the content of NH3 and HCl in the
pyrolysis gas. The measured ammonia concentrations before gas conditioning were 4.5 and 3.4 ppm
(see Table 3). These values are very low, since at the initial content of nitrogen in the BS and Wood
mixture was 3 wt. % (Table 5). The mass balance calculations revealed that about 28 and 19 % of the
initial N was retained in the char thus the remaining 72 or 81 % was released in a gaseous form or as
a condensable fraction - tar. After gas conditioning the NH3 content was significantly lower, 0.12 and
0.17 ppm. While the concentration of ammonia in the water leaving scrubber increased from 59 to
177 and 250 ppm.
An initial sulphur content of 0.4 % was detected in the BS-Wood mixture, while after pyrolysis 44 and
31 % of the sulphur was retained in the char, consequently the balance was released in a gaseous form
or as a condensable or water soluble fraction. The measured concentrations of hydrogen sulphide in
the conditioned pyrolysis gas were 17 and 31 ppm.
N content, % of N S content, % of S Cl content, % of Cl

wt. % retained wt. % retained wt. % retained
dry basis in char dry basis in char dry basis in char
Test-2 3.04 27.7 0.40 44.62 0.11 70.49
Test-3 3.04 19.3 0.40 30.65 0.11 63.62
Table 5: Retention of nitrogen, sulphur and chlorine in the char from pyrolysis of Biological Sludge with Wood.
For chlorine, 64 and 70 % was retained in the char, thus the remainder was released in a gaseous form
or as a condensable or water-soluble fraction.
3.2 Properties of pyrolysis char

The proximate and ultimate properties of chars from pilot scale tests are presented in Table 6. The
pyrolysis chars consisted mainly of fixed carbon contents of 44.5 and 52.5 wt. % on a dry basis. The
volatile matter contents of 11.6 % and 14.8 % indicated that the majority of the organic matter was
decomposed. However, at the laboratory scale almost complete decomposition was obtained with
only 5 % of volatile matter unreleased. The carbon content in the char was from 52 to 57 wt. %, which
meets the criteria set by the European Biochar Certificate (EBC) [10]. Other properties of the pyrolysis
biochar outlined in the EBC [10] should be measured in order to check if the material could be qualified
as biochar.
The yield of pyrolysis char was from 250 to 320 kg/ton of the BS and Wood mixture fed into the
pyrolyser. The bulk density of the char was 135 kg/m3.
203
Properties, wt. % Test-1 Test-2 Test-3

dry basis
Ash content 36.1 40.6 35.9
Volatile matter 11.6 14.8 -
Fixed carbon 52.4 44.5 -
LHV, MJ/kg 20.2 18.5 -
C 57.9 52.3 57.1
H 1.6 1.8 1.8
N 2.4 2.6 2.3
S 0.5 0.6 0.5
Cl 0.3 0.2 -
O 1.2 1.8 2.3
Table 6: Properties of pyrolysis char from pilot scale tests for BS and Wood mixture.
4- CONCLUSIONS
Biological Sludge from milk processing factory was dried to a moisture content of 20 wt. % then mixed
with wood chips at a ratio of 50/50 by weight and pyrolysed at pilot scale.
Three successful pyrolysis tests were carried out at 700°C with the feeding rate of the sludge and wood
mixture from 77 to 90 kg/h. The amount of raw pyrolysis gas generated was at 355 and 472 m3/tonne
with calorific values of 12 and 16 MJ/m3. The raw pyrolysis gas was conditioned in order to reduce the
tar content, and remove ammonia and sulphur compounds. Since air was used as the reagent in the
high temperature cracking reactor higher volume of the final pyrolysis gas diluted with nitrogen were
obtained. The yield of conditioned pyrolysis gas was 730 and 800 m3/tonne with calorific values of 6.9
and 7.7 MJ/m3.
From 250 to 320 kg of pyrolysis char was obtained from a tonne of BS and Wood mixture. The carbon
content in the char meets the criteria set by the European Biochar Certificate.
ACKNOWLEDGMENTS
This work was supported by the Irish State through funding from the Technology Centres programme
- Grant Number TC/2014/0016
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FLUIDIZED-BED GASIFICATION OF VARIOUS SOLID REFUSED FUELS: INFLUENCE OF

THE OPERATING CONDITIONS
M. HERVY1, D. REMY1, G. MAUVIEL1

1 Reactions & Process Engineering Laboratory (LRGP), CNRS, Lorraine University, 1 rue Grandville,
54001 Nancy, France.
Abstract
To cope with the increase of Municipal Solid Waste (MSW) generation, solid recovered fuel (SRF) can
be produced from the non-recyclable MSW, and can be valorised as fuel in waste-to-energy
processes. Among them, the gasification process appears as a promising way to convert SRF into a
rich energy carrier gas named “syngas”, that can be valorised in high energy efficiency applications
(power and heat generation by combustion in gas engines, gas turbines, fuel cells...), and as
precursor in the production of liquid fuel (via the Fischer-Tropsch synthesis) or chemicals. In the past
few years, gasification of SRF in fluidized bed was increasingly studied [1], but several bottlenecks
still prevent the commercialisation of this process. The effect of the operating conditions
(equivalence ratio, temperature) on the gasification efficiency still remains unclear. While the
chemical composition of SRF strongly varied from a sample to another, the influence of the SRF
composition on the gasification performances has scarcely been studied. This study aims at
investigating the influence of the operating parameters on the gasification efficiency of four different
SRF.
Four SRF produced industrially and having different chemical composition were used as gasification
feedstock. Gasification tests were performed in a bubbling fluidised-bed gasifier constructed in the
lab, using olivine as bed material. A constant Air flow rate of (4.505 Nm 3/h) was used in all tests in
order to keep constant fluidisation conditions (U/Umf=4). Downstream of the gasifier, particles were
separated from the syngas with a cyclone. Tar was sampled in propanol scrubbers at 0°C and
analysed with a GC/GC-MS/FID. Acid gases (HCl, H2S, NH3, HCN) were analysed by different methods
(ionic chromatography, potentiometric titration and spectrophotometry). A µ-GC allowed to analyse
online the permanent gases. The influence of the Equivalence Ratio (ER) was investigated at a
temperature of 810-820 °C by varying the SRF flow rate. The ER values investigated were 0.21, 0.25,
0.30 and 0.35. The effect of the temperature was studied in the range 750-900 °C at a constant ER of
0.25. The influence of other parameters was studied, such as the co-gasification of two different SRF,
the SRF feeding position in the gasifier, and the particle size of SRF.
The Cold Gas Efficiency (energy transferred from SRF to syngas) and the syngas LHV (lower heating
value) were proved to increase with decreasing ER, while the carbon conversion slightly rose with
increasing ER. High temperature promoted the gasification efficiency and decreased the tar content.
These trends seem to be similar whatever the chemical composition of SRF. SRF rich in plastics
generated larger amount of light hydrocarbons (C2-C6) and tar. This study is expected to provide a
complete set of parametric data to further improve the gasification conditions depending on the SRF
composition.
Reference
[1] Arena, U., Di Gregorio, F.: Fluidized bed gasification of industrial solid recovered fuels, Waste Management 50, 86-
92 (2016)
206
PLASMA-ASSISTED BIOMASS GASIFICATION IN AN ATMOSPHERIC PRESSURE DROP

TUBE REACTOR
Y. PANG1, TH. HAMMER2, L. BAHR3, P. FENDT3, L. ZIGAN3, S. WILL3,

M. BALDAUF2, R. FLECK3, D. MÜLLER1, J. KARL1
1 EVT, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nuremberg, Germany.
2 Siemens AG, Erlangen, Germany.
3 LTT, Friedrich-Alexander-Universität Erlangen-Nürnberg, Nuremberg, Germany.
Keywords: non-thermal plasma, biomass gasification, drop tube reactor, carbon conversion, reaction
kinetics
Abstract
The major focus of this work is the investigation of non-thermal plasma (NTP) gasification with wood
powder as feedstock, compared to thermal gasification at similar conditions. Key element is a 4 m long
atmospheric pressure drop tube reactor (diameter 100 mm) being equipped with a temperature
controlled heat supply and a glide arc plasma generator with a solid state power supply. The
allothermal gasification between wood powder and conditioned water steam takes place in the
reactor, in which a movable sampling probe is installed. The gas sample is withdrawn from the reactor
and sent for gas analysis. The particle size has been varied in three ranges (125 – 355; 355 – 500; 500
– 710 µm). In case of plasma gasification about 1 kWel power has been fed through plasma generator
into reaction, while the inlet temperature of water steam is increased in case of thermal gasification.
Comparison between NTP assisted and thermal gasification shows that for the same equivalent
temperature level the NTP promotes 12% of carbon conversion calculated from the gaseous products
(CO, CO2 and CH4). Besides, the production of hydrogen has been promoted by at least 40% due to
enhanced tar reforming and dissociation of water. The reaction kinetics is calculated based on one-
step global gasification reaction (CHxOy + H2O → CO + CO2 + CH4 + H2) with first reaction order assumed.
The experimental results showed in case of NTP-gasification an acceleration of reaction rate
coefficient by 30% by extremely high heating rate and presence of reactive radicals (OH, H etc.).
207
1- INTRODUCTION
At the Chair of Energy Process Engineering at the Friedrich-Alexander-Universität Erlangen-Nürnberg
in Germany, biomass gasification with non-thermal plasma is investigated in a drop tube reactor at
atmospheric pressure [1]. The major motivation is to investigate the influence of non-thermal plasma
on fuel conversion and reaction kinetics. The dynamic flexibility of plasma generator offers the
possibility to utilize the excess electricity generated from renewable sources (PV, wind etc.). In this
way, the fluctuated electricity can provide the gasification reaction with the required reaction
enthalpy. The electricity together with chemical energy in biomass is then converted and storage to
chemical energy in form of synthesis gases.

2.1- TEST METHODS
The influence of plasma on the chemical reaction is a mixture of various factors. Among them, two
major parameters are the thermal activation, which is affected by the high temperature species in the
plasma mixture, and the plasma chemistry, which is determined by the ionized particles and radicals.
In this work, a direct comparison between plasma and thermal gasification has been conducted to
minimize the effect of thermal activation and investigate mainly the plasma chemistry.
Figure 1 presents the experimental method of plasma gasification. The main water steam is fed into
plasma generator as working medium. With a defined electrical power, flow rate and feed
temperature of water steam, the final steam temperature Tsteam,1 can be calculated and later measured
optically. The biomass particle is introduced into the generated plasma area so that a direct contact
of plasma filament and particle is guaranteed. The general steps of gasification such as drying, pyrolysis
and char gasification take place in the reactor heated by external furnace. The side water steam can
be fed into reactor for adjustment of steam-to-carbon ratio. The product gas is sampled for gas
analysis.
Electrical power biomass side water

steam
main water steam

Plasma Reactor with Product gas
generator furnace (CO, H2 etc.)
Tsteam,1
Figure 1. Experimental method of non-thermal plasma gasification [1]
A thermal gasification has been performed under similar test condition, s. Figure 2. Instead of plasma
generator, a steam superheater is applied in order to achieve the according steam temperature
Tsteam,2. In this way, the influence of thermal activation can be minimized and mainly the plasma
chemistry is investigated.
208
biomass side water

steam
main water steam

Steam Reactor with Product gas
superheater furnace (CO, H2 etc.)
Tsteam,2
Figure 2. Experimental method of thermal gasification (reference case) [1]
2.2- R&I-SCHEMA
Figure 3 presents the R&I-schema of the whole test-rig, consisting of feeding system, gas system,
steam system, drop tube reactor, cooling system and sampling system. The feeding system consists
mainly of a volumetric screw conveyor (Coperion K-Tron, Typ K-CV-KT20) and nitrogen purge (also as
tracer). The steam control system provides the reaction with conditioned main and side steam flow.
In case of thermal gasification, the main water steam can be heated by a steam superheater to defined
temperature. The reactants (wood powder and water steam) enter the top of reactor equipped with
plasma generator, which is described in detail in the following chapter. The syngas is withdrawn by a
moveable gas probe in the reactor and sent to gas analysis (ABB AO2000 System). The rest of the
syngas enters the flare.
Biomass
Gas control system feeding
system
Steam
control
system
Drop tube reactor with

Plasma Generator
Cooling system
Sampling system
Figure 3. R&I-Schema of the test-rig [2]
209
2.3- DROP TUBE REACTOR
Major component of the test rig is the drop tube reactor with an electrical heater. Figure 4 shows the
structure of the drop tube reactor. For gasification experiments, the electrical furnace can heat the
reactor up to max. 1000 °C. The reactor consists of preheating zone, window zone, reaction zone and
quench zone. In the preheating zone, the furnace conditions the side water steam to the experimental
temperature. After the preheating zone, both water steams joint together in the window zone, where
the non-thermal plasma is ignited and fuel particles fall through the plasma filaments. The window
zone allows an optical access into reactor for temperature measurements with two rectangular quartz
glasses (length 500, width 50 mm) mounted in the front and in the rear part of the reactor. In order to
compensate the heat loss due to the glasses, the furnace heats the window zone to the same
temperature as it in preheating and reaction zone. In the following reaction zone, a vertical adjustable
sampling probe sends the probe gas from different height to gas analysis. This allows a variation of
residence time of fuel particles. The gas sample after suction in the probe is immediately cooled down
avoiding further reactions. After a passive cooling in the quench zone, the synthesis gas containing
carbon monoxide and hydrogen enters the flare. The sampled gas probe, however, is investigated in
gas analyser.
Pre he ating zone
Window zone
Re action zone
Que nch zone
in mm
Figure 4. Structure of drop tube reactor (left); Reactor in operation with dynamic plasma filament/arc using conditioned water steam
as working medium (right) [1]
210
2.4- NON-THERMAL PLASMA
The non-thermal plasma generator is mounted at the top of the drop tube reactor. It operates at the
frequency between 90 and 100 kHz and can provide a maximal electrical power of 1000 W. With a
length of electrode of around 1 m, the plasma is generated in the window zone. Figure 5 shows a
simplified overview of the electrodes. The ignition usually takes place in the section with the smallest
distance.
Once the plasma filament as conductive channel is active, the voltage drops and the current increases
at the same time. The filament is pulled downstream due to a steam flow with an increasing distance
between the electrodes. During the movement, the water molecules dissociate into electrons, ions
etc. The dissociation products diffuse outwards and recombine together. Through the dissociation and
recombination processes, the heat transfer from the plasma filament to the water steam is enhanced.
At the tip of the electrodes, the filament is stabilized and has a normal length of 10 – 15 cm depending
on the operating conditions. If the heat loss is larger than the energy supply, the plasma turns to non-
equilibrium regime. The primary means of dissociation and ionization is then to improve reaction
kinetics due to direct electron impact from high-temperature electrons accelerated by the higher
electric field [3]. The plasma filament vanishes when the growing length cannot be hold by energy
supplier anymore. New ignition will then take place at the smallest gap between the electrodes as
mentioned above and the process starts from beginning again.
Figure 5. Simplified geometry of the non/thermal plasma generator [1]
2.5- TEST CONDITIONS
Test parameters have been summarized in Table 1. The wood pellets are ground from original 6 mm
diameter to wood powder. Three particle sizes have been sieved for gasification. The screw conveyor
feeds the drop tube reactor with a mass flow of 0.2 kg/h based on the volumetric principle with a
nitrogen purge of 3.5 slm. The steam supply system provides a total mass flow of 8 kg/h. In case of
plasma gasification, about 1 kWel is applied through plasma generator as non-thermal plasma, while
the inlet temperature of main water steam is increased to 660°C in case of thermal gasification.
211
Table 1 : Test conditions of plasma and thermal gasification
Plasma gasification Thermal gasification

Particle size of wood [µm] 125 – 355; 355 – 500; 500 – 710;
Mass flow of wood particle [kg/h] 0.2
Mass flow of total steam [kg/h] 8
Flow rate of nitrogen [slm] 3.5
Plasma power [kW] 0.9 0
Inlet temperature of main steam [°C] 350 660
Furnace temperature [°C] 700 – 950 700 – 900
For the purpose of evaluation, the following one-step global gasification reaction (1) is considered:
CHx Oy + H2 O → CO + H2 + CO2 + CH4 (1)
𝐶𝑠𝑦𝑛𝑔𝑎𝑠 𝐶𝐶𝑂 + 𝐶𝐶𝑂2 + 𝐶𝐶𝐻4 (2)

𝐶𝑎𝑟𝑏𝑜𝑛 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛 = =
𝐶𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘 𝐶𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘
In this work, only the gaseous product has been taken into consideration for results evaluation. The
conversion is calculation by the ratio between the carbon content in gaseous product (e.g. CCO: carbon
content in carbon monoxide) and the carbon content in feedstock (2). However, during pyrolysis, the
carbon content in feedstock (Cfeedstock) goes into gaseous products (Csyngas), tar products (Ctar) and char
products (Cchar). Compared to conventional analysis method based on the mass loss of fuel sample
(dm/dt), the major difference lies in the tar product:
Biomass (CHxOy) → gaseous products (CO, H2, CO2, CH4) + tar product + char (3)
𝐶𝑠𝑦𝑛𝑔𝑎𝑠 + 𝐶𝑡𝑎𝑟 𝐶𝑐ℎ𝑎𝑟 (4)

𝐶𝑎𝑟𝑏𝑜𝑛 𝐶𝑜𝑛𝑣𝑒𝑟𝑠𝑖𝑜𝑛𝑡𝑜𝑡𝑎𝑙 = =1−
𝐶𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘 𝐶𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘
The missing tar product (Ctar) indicates that the calculated carbon conversion is lower that the real
carbon conversion. Using the carbon conversion for determination of reaction kinetics, the calculated
value is also lower that the real one. The reaction kinetics k is determined by using data-fitting in an
Arrhenius Equation (7) with first reaction order assumed (n=1):
1 𝑑𝑚 (5)
𝑟= ⋅
𝑚 𝑑𝑡
𝑑𝑚 (6)
= −𝑘 ⋅ 𝑚(𝑡)𝑛 = −𝑘 ⋅ 𝑚(𝑡)
𝑑𝑡
𝐸𝐴
𝑘 = 𝐴 ⋅ 𝑒 −𝑅𝑇 (7)
with r as reaction rate, EA as the activation energy, A as the pre-exponential factor, T as the
temperature and R as the universal gas constant.
212

3.1- SYNGAS PRODUCTION
Figure 6 shows the syngas composition of both plasma (orange dots) and thermal gasification (blue
dots) with three particle sizes. The used temperature, indicating the gas temperature in reactor, is
measured by optical technique, which is explained explicit in a recent published paper from author
[1]. The general trend showed that, with the rising temperature, the hydrogen composition increased
and the content of carbon monoxide deceased. The concentration of methane and carbon dioxide
stayed more or less constant.
125 – 350 µm 350 – 500 µm 500 – 710 µm
H2
Gas concentration [-]
CO
CH4
CO2
Temperature [ C]
Figure 6. Syngas composition of wood gasification at dry-basis with measurement errors at dry-basis (orange: plasma; blue: thermal)
Figure 7 presents the difference in syngas production between plasma and thermal gasification at
760°C gas temperature measured in the reactor. The results clearly showed a promotion of NTP on
the syngas production. In case of hydrogen production, an increase of 40 – 50% in flow rate has been
213
observed, which can be explained by tar reforming and dissociation of water. The production of
methane, carbon monoxide and carbon dioxide has been increased by at least 10 – 20%.
H2 CH4
Flow rate [l/min]
CO CO2
Particle size [µm]
Figure 7. Plasma enhancement in syngas production with systematic errors at dry-basis (orange: plasma; blue: thermal)
3.2- CARBON CONVERSION
In Figure 8, the calculated carbon conversion from the gaseous product (CO, CO2 and CH4) is presented
with systematic errors (s. equation (2)). A rise in temperature increased the carbon conversion in all
cases. However, the difference between plasma and thermal gasification is smaller than the calculated
systematic errors.
d = 125 – 355 µm d = 355 – 500 µm d = 500 – 710 µm

Carbon Conversion [-]
Temperature [ C]
Figure 8. Carbon conversion of plasma (orange) and thermal (blue) wood gasification with systematic errors
Figure 9 shows the plasma enhancement in carbon conversion. The results of particle size 710 – 1400
µm has been obtained by author and published recently in another paper [1]. The smaller the particle
214
diameter, the higher the heating rate inside the particle. Thus, an increasing in heating rate led to an
increasing in conversion. This indicates a reaction-rate limited process. The NTP has increased the
conversion by 12%.
Carbon Conversion [%]
Particle size [µm]
Figure 9. Plasma Enhancement in carbon conversion at 760°C
3.3- REACTION KINETICS
Figure 10 presents the reaction kinetics of plasma and thermal gasification. An increase in temperature
led to an increase in reaction rate coefficient. However, the difference between plasma and thermal
cases is also smaller than the systematic errors.
1000/T [1/K]
lnk
d = 125 – 355 µm d = 355 – 500 µm d = 500 – 710 µm
Figure 10. Reaction kinetics of plasma(orange) and thermal(blue) wood gasification with systematic errors
Figure 11 shows the plasma enhancement in reaction rate. The smaller the particle size, the faster the
reaction rate. The NTP has accelerated the reaction rate by 30% in general.
215
Rate coefficient k [s -1]
Particle size [µm]
Figure 11. Plasma enhancement in reaction rate coefficient with systematic errors (orange: plasma; blue: thermal)
4- CONCLUSIONS
In this work, wood powder with three different particle sizes has been gasified with water steam in a
drop tube reactor at atmospheric pressure. The syngas concentration has been measured and used
for calculation of syngas production, carbon conversion and reaction kinetics. The non-thermal plasma
has promoted the individual syngas production (H2, CO, CO2, CH4) by at least 10 – 20%, the carbon
conversion by 12% and reaction kinetics by 30%.
ACKNOWLEGMENT
This work has been supported by the Campus Future Energy Systems (Campus FES) under the grant
“Biomassevergasung in Nichtthermischen Plasmen”.
REFERENCES
[1] Y. Pang et al., “Plasma-Assisted Biomass Gasification with Focus on Carbon Conversion and Reaction Kinetics
Compared to Thermal Gasification,” Energies, vol. 11, no. 5, 2018.
[2] Y. Pang, D. Müller, J. Karl, T. Hammer, and L. Bahr, “Biomassvergasung mittels nichtthermischen Plasmen im
Fallrohrreaktor,” in 28. Deutscher Flammentag : Verbrennung und Feuerung : Darmstadt, 06. und 07. September
2017 / VDI Energie und Umwelt, 2017, pp. 61–68.
[3] T. Ombrello, X. Qin, Y. Ju, A. Gutsol, A. Fridman, and C. Carter, “Combustion Enhancement via Stabilized
Piecewise Nonequilibrium Gliding Arc Plasma Discharge,” AIAA J., vol. 44, no. 1, pp. 142–150, 2006.
216
CHARACTERISTICS OF PARTICULATE MATTER FROM MUNICIPAL SOLID WASTE

PYROLYSIS, GASIFICATION AND INCINERATION
J. DONG1, A. NZIHOU1, Y. CHI2, Y. TANG1,2, E. WEISS-HORTALA1, M. NI2

1 Centre RAPSODEE, Ecole des Mines Albi, Campus Jarlard, 81013 Albi cedex, France.
2 State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, China.
Abstract
In the transition towards more sustainable development, thermal treatment of municipal solid waste
(MSW) today is increasingly being used to substitute landfill, due to its advantages of waste volume
reduction, destruction of organic pollutants, and energy recovery. However, one of the most serious
issues concerning MSW thermal process is related to the particulate matter (PM) emission. PM is the
microscopic solid or liquid matter suspended in the atmosphere, and is one of the most significant
sources of air pollution. Previous studies have confirmed that the presence of PM is significantly
relevant to health problems, smog formations, acid rain issues, and climate changes [1].
Characterization of PM is challenging, because PM is not only made up of a complex group of
components (mainly including black carbon, organics, sulfate, nitrate, alkalis, trace metals, crustal
material and salt), but also comes in a wide range of sizes from nanoparticles (diameter less than
0.05 m) up to millimetre-sized particles. In addition to this, PM characteristics are also proven to
depend on various factors such as feedstock type, thermal technology, temperature and of others
[2,3]. A detailed knowledge of PM released during MSW thermochemical conversion is essential for
controlling air pollution; however such studies are quite lacking.
In this study, PM characteristics during MSW thermal treatment are carried out, using a lab-scale
fluidized bed as experimental apparatus. The effect of redox atmosphere, temperature and
feedstock types is investigated. Redox atmosphere considered includes pyrolysis, air gasification, CO2
gasification and incineration. The temperature ranges from 700 to 850 oC and different fuel types
(wood waste, RDF and mixed MSW) are tested. PMs are collected using a heated filter, which is
placed at the outlet pipe at a temperature of 350 oC to avoid tar condensation. A settle of physical
and chemical analyses are conducted for the characterization of PM, which include yield, size
distribution/mass size distribution, morphology (SEM/EDX) and composition (XRF, ICP-MS). The
results reveal that the particle size distribution of PM generated from pyrolysis and gasification
processes is bimodal, with the peaks attained at ca. 1 m and 100 m. PM from incineration is
unimodal at ca. 100 m, indicating that the ultra particles at 1 m is mostly by the condensation of
alkali and sulfur compounds. A higher temperature will lead to increasing generation of PM due to
enhanced vaporization of ash elements. The research will be useful to obtain a better understanding
of the PM composition and behavior from different waste thermal processes, with the final aim to
develop a more environmental-friendly MSW treatment option in this regards.
References
[1] Kim, K. H., Kabir, E., & Kabir, S.: A review on the human health impact of airborne particulate matter. Environment
international, 74, 136-143 (2015).
[2] Garcia-Maraver, A., Zamorano, M., Fernandes, U., Rabaçal, M., & Costa, M.: Relationship between fuel quality and
gaseous and particulate matter emissions in a domestic pellet-fired boiler. Fuel, 119, 141-152 (2014).
[3] Park, S. S., Sim, S. Y., Bae, M. S., & Schauer, J. J.: Size distribution of water-soluble components in particulate matter
emitted from biomass burning. Atmospheric environment, 73, 62-72 (2013).
217
CARBONIZED RICE HUSK CHARACTERIZATION FOR SOIL SUBSTRATE APPLICATION
G.KAPPLER1, D. S. MACHADO2, S. B. SCHRÖPFER2, R.C.E. MODOLO*1, C.A.M. MORAES1,2, P.R.

WANDER2, L.A.C. TARELHO3
1 Graduate Program in Civil Engineering, University of Vale do Rio dos Sinos/ NuCMat, 93022-000, São
Leopoldo, RS, Brazil .*reginaem@unisinos.br(+55 51 980570501)
2 Graduate Program in Mechanical Engineering, University of Vale do Rio dos Sinos, 93022-000, São Leopoldo,
RS, Brazil
3 Department of Environment and Planning/CESAM, University of Aveiro, 3810-193 Portugal
Keywords: Rice husks, Carbonized rice husk, Soil substrate
Abstract
The state of Rio Grande do Sul, in Brazil, is the largest rice producer in the country (about 71 % of the
national production). The rice husks generated from the processing of rice grains constitute an
important environmental liability for the producing regions, mainly in terms of landfilling (Figure 1).
So, the aim of this research is to characterize the chemical and physical properties of the rice husks,
before and after carbonization process and analyse the soil behaviour after adding carbonized and
non-carbonized rice husks. The methodology adopted for the study involved the following steps:
chemical characterization of the rice husks samples by XRF, XRD, TGA and loss on ignition (LOI); and
its physical characterization by porosity, granulometry, and optical microscopy (OM) . Samples of
soil mixed with carbonized and non-carbonized rice husks have been analysed for water holding
capacity, cation exchange capacity, pH, and conductivity, for example. The preliminar results showed
that the spontaneous carbonized rice husk (SCRH) addition slightly improved some properties,
mainly related with pH and Cation Exchange Capacity. Nevertheless, the use of crop residue for soil
quality maintenance must be more assessed. Based on the suitable from the SCRH addition on a
farmland soil, this experiment was a first attempt to obtain some beneficial results with the addition
of SCRH in a depleted soil.
218
1- INTRODUCTION
The Green Revolution introduced by Nobel Laureate Norman Borlaug during the 1940s increased
food production in Latin America and Asia. The development of modern or high yielding crop
varieties greatly increased cereal yields, brought down food prices, fed many millions of people, and
is recognized as one of the great technological success stories of the 20th century [1]. However, the
success of Green Revolution mainly consisted of better agricultural technology, such as improved
crop varieties, irrigation, and input of chemical fertilizers and pesticides. Consequently, this practice
raised concerns about the sustainability of intensive cultivation—e.g., the environmental
consequences of soil degradation, chemical pollution, aquifer depletion, and soil salinity [2, 3].
Alongside the aforementioned issues, food supply may also pose risk in the near future. Food and
Agriculture Organization (FAO) estimates that population growth will reach 9 billion people in the
next 30 years and to feed this population it will be necessary to increase food production by 60% [4].
Besides that, crop yields — the number of crops harvested per unit of land cultivated — are growing
too slowly to meet the forecasted demand for food. Additionally, many other factors, from climate
change to urbanization, will also make it challenging to produce enough food [5].
Environmental issues concerning soil degradation, water management and food security from
agricultural activities have recently motivated a ‘Doubly Green Revolution’ that includes
conservation technologies [6, 7]. In this sense, Biochar, which is obtained from crop residues,
provides great opportunities to turn the Green Revolution into sustainable agroecosystem practice
[8]. The recent interest in Biochar is twofold. Biochar is an organic-C rich material [9], and it has
sustained fertility in Amazonian Dark Earths locally known as “Terra Preta de Indio” [10]. These
findings are the basis of recent developments in biochar technology and are the reason why in this
work the association of spontaneous carbonization of rice husks with biochar is made.
Worldwide crop residues represent simultaneously a threat and an opportunity. While they are an
important source of CO2, CH4, and NO2 emissions, the same crop residues are a valuable feedstock
for energy, biochar, and chemical products production. The amount of crop residues produced in the
world was estimated at 2.802 x106 Mg year-1 for cereal crops, 3107x106 Mg year-1 for 17 kinds of
cereals and legumes, and 3758x106 Mg year-1 for 27 food crops from 1991 to 2001 [11]. Singh et al.
(2005) present estimated data of rice-based crop residues at 166x106 Mg year-1 for Asia, 39x106
Mg year-1 for Africa, and 55x106 Mg year-1 for South America, summarizing a world total of 604x106
Mg year-1 [12].
Brazil produced around 291x106 Mg of crop residues from a total production of 854.7x106 Mg for 14
perennial and non-perennial food crops in 2009. Rice crop encompasses 12.6x106 Mg nationwide
with rice husks production of 2.5 x106 Mg, where the State of Rio Grande do Sul was responsible for
9.2x106 Mg of the rice crop and 1.8x106 Mg of rice husks [13].
In this context and based on observations of an in situ application of spontaneous charred and non-
charred rice husks in a farmland, the aim of this study is to compare the use of such feedstock as a
substrate for degraded soil properties amelioration.
Biochar for soil improvement

Charcoal has long been recognized as a normal environmental constituent resulting from fire and
industrial activities. [14, 15, 16, 17]. The discovery of Amazonian Dark Earths in Brazil has aroused a
major scientific interest in studying the benefits of adding charcoal to the soil. It was found that
indigenous settlements maintained and improved soil fertility and crop yields for thousands of years
before Europeans arrived making semi-permanent cultivation possible with only a brief fallowing and
219
as a result of frequent composting, mulching, and in-field burning, whose activities added the
charcoal to the soil [18, 19, 10].
The term ‘biochar’ derives from charcoal, which is produced by the thermal decomposition of
organic material under a limited supply of oxygen (O2) [20, 21]. Biochar definition is relatively recent
[22], and has been distinguished from charcoal considering the end use: charcoal is used as fuel for
energy applications, whilst biochar is directed toward environmental management and carbon
sequestration. Additionally, the term ‘biochar’ emphasizes its biological origin, distinguishing it from
charred plastics or other non-biological materials [23]. Biochar results as a by-product of various
processes, including bio-oil and syngas production. Young et al., (2016) state that priority should be
given to produce biochar as a by-product rather than initially producing biochar due to energy
savings and economic viability [24, 25]. On the other hand, biochar has several environmental
benefits, since it is not merely another type of compost or manure that improves soil properties but
is much more efficient at enhancing soil quality than any other organic soil amendment [8].
Due to environmental constraints biochar production and subsequent application, including in soils,
must be linked to appropriately and robustly deliberated policy guidelines. In this sense, experts
from Empresa Brasileira de Pesquisa Agropecuária – EMBRAPA (Brazilian Agricultural Research
Corporation) occupy central positions and thus exercise most power in the network of the debate,
while science experts are the main players, and policymakers, businessmen, and farmers are
marginally positioned. Despite Brazil is an important player in the international biochar debate,
biochar as a technological discourse has not yet been formally institutionalized. Consequently, the
country lacks an established biochar policy field [26, 27]. Due to the lack of analytical methods
especially tailored for biochar, most laboratories and biochar researchers around the world used and
still use methods originally established for soils, fertilizers, and compost [28]. In Brazil, the Ministério
da Agricultura e Produção Agrária – MAPA (Ministry of Agriculture and Agrarian Production) gives
instructions of minimal requirements of such practices under the INSTRUÇÃO NORMATIVA 35
(NORMATIVE INSTRUCTION 35). Thus, these normative instructions will be used in this study as
guidelines for evaluating the use of crop residues, and its biochar, as a soil conditioner [29].
Rice crop production and its consequent residue generation in the State of Rio Grande do Sul in
Brazil
Estimates from the Instituto Brasileiro de Geografia e Estatística – IBGE (Brazilian Institute of
Geography and Statistics) for the rice harvest indicate 11.65x106 Mg for the year 2017 in Brazil, from
which the State of Rio Grande do Sul (RS) accounts for 71.4 %.
Rice husks are a major concern in the rice value chain. About 20% of the gross weight of the rice
correspond to the husks, generating about 1.66x106 Mg year-1 of rice husks residues in the State of
RS. They are essentially composed of cellulose (50%), lignin (30%) and inorganic matter (20%) [30].
Because of the complex chemical bonds, the decomposition rate is very low, besides that the highly
phenolic composition and low specific weight of rice husks pose several threats to the environment
when the option is to discard on the field [31, 32].
The official entity responsible for environmental regulation in the state of RS is Fundação Estadual de
Proteção Ambiental Henrique Luiz Roessler (FEPAM) (State Foundation for Environmental
Protection). Under the technical directive number 002/2011, the Foundation gives general
orientations for manage residues such as rice husks and ashes, including activities like temporary
storage, incorporation in agricultural soil, composting, use as fuel, disposal in a landfill, among
others. Nevertheless, that directive cites neither biochar nor charcoal production as an
environmental strategy for management of rice husk. Despite most of rice husks are used to fuel
power plants, in some areas it is still landfilled due to logistics and other constraints. Figure 1
220
presents the landfill that receives around 7x104 Mg year-1 of rice husk, which is nearly 4 % of the rice
husks produced in the State of RS.
Figure 1: Rice husks landfill in the State of Rio Grande do Sul, Brazil.
The landfill operates outdoors, on bare soil, subject to inclement weather and releasing airborne
particulate matter naturally entrained by the wind and from machinery operation. Other issues
observed include: i) the risk of self-ignition and combustion of the piles, and when it happens the
responsible managers may suffer penalties from FEPAM, and ii) due to the slow decomposition rate
of the rice husk some piles are stored there for more than five years. Therefore, the landfill is a
possible source of greenhouse gases - GHG, such as, CH4 and CO2 (because of aerobic and anaerobic
decomposition processes) as well as leaching of nutrients [33], which may cause eutrophication and
contamination of superficial and groundwater (see Figure 2).
a b
Figure 2: Eutrophication of a water stream nearby the landfill (a), and collecting a sample for water quality monitoring (b).

A diagnosis by observation was developed in a farmland that uses spontaneous carbonized and raw
rice husks (RRH) (both termed as substrates) in the soil to improving its quality. Photografic register
was fulfilled. In addition, residues obtained from surrounding area where tested in bench scale.
The spontaneous carbonized rice husk (SCRH) resulted from a natural combustion of a rice husks
pile, which was partially carbonized. The substrates were spread with an equipment traditionally
used for adding fertilizers. Immediately after spreading the substrates a ploughing operation took
place mixing soil and substrates at a depth of 0.15 to 0.20 m. The monitoring of the process in the
farmland consisted of visual observations of the plant (Brachiaria) growth for the period of two
years.
As a first attempt to verify the ability of both residues as substrates in soil amelioration, its
interactions with soil was investigated by adding them to a degraded soil. Considering the ratio used
221
on landfarm (a mass of 15 to 20 Mg year-1 of RRH and SCRH by hectare), formulations were prepared
in bench sacle.
To compare the efficacy of the two substrates, Brachiaria decumbens was sown to observe its
growth.
In an attempt to verify the soil amelioration observed on the farmland in a laboratory scale, samples
of rice husks and carbonized rice husks were collected. Characterization of the physical and chemical
properties of the substrates was done. Both substrates were accurately mixed with degraded soil
and the agronomic properties were obtained. A literature review is used to compare the results and
support discussions and conclusion.
Sampling
Rice husks and SCRH samples were collected directly from the landfill cells, homogenized and stored
for further physical and chemical characterization. The formulations are presented in Table 1. The
use of a degraded soil was used to verify whether the addition of the substrates alone may improve
its quality. To do so the CEC (Cation Exchange Capacity) and WHC (Water Holding Capacity) of mixed
soils were checked with and without the addition of substrates.
Soil with substrate sample preparation

Three samples involving the soil were prepared with three replicates of each. The first (Soil) is the
background (raw soil without any substrate), the second sample (Soil + RRH) is a mixture of soil and
raw rice husk, and the third sample (Soil + SCRH) is a mixture of soil and spontaneous carbonized rice
husk. In Table 1, it is shown information about the samples' composition.
Soil RRH SCRH Substrate/soil ratio

3 3 3
Sample cm cm cm (%)
Soil 875 0 0 0
Soil + RRH 875 6 0 0.68
Soil + SCRH 875 0 5 0.57
Table 1: Volumes and ratio of soil and substrates in each sample.
Samples analysis methods

Rice husks and carbonized rice husk characterization involved chemical and physical analysis
following the methodologies and standards shown in Table 2. Soil characterization also included
Normative Instruction 35 – IN35 from MAPA; this instruction gives guidelines for the use of crop
biomass for soil improvement, e.g., water holding capacity of at least 60% and cation exchange
capacity – CEC of at least 200 mmol C kg-1.
222
Parameter Method
RRH and SCRH Soil
Loss on Ignition CEMP 120 (ABIFA, 1985) Not applied
Normative Instruction n° 17 (MAPA, 2007) and Normative Instruction n° 17 (MAPA, 2007) and NP
CEC
NP EN 933-9 (2002) EN 933-9 (2002)
WHC Normative Instruction n° 31 (MAPA, 2007) Normative Instruction n° 31 (MAPA, 2007)
Granulometry CEMP 081 (ABIFA, 2003) - (Adapted) CEMP 081 (ABIFA, 2003) - (Adapted)
Actual moisture. Normative Instruction n° 17
Moisture Infrared moisture analyser – BEL Engineering
(MAPA, 2007)
Calorific value IKA – C200 Equipment identification
XRF EDX 720 HS – Shimadzu EDX 720 HS – Shimadzu
Pycnometer (gas Helium) – AccuPyc II 1340 – Self-compacting method via
Bulk density
Micrometrics Normative Instruction n° 17 (MAPA, 2007)
pH Normative Instruction n° 17 (MAPA, 2007) Normative Instruction n° 17 (MAPA, 2007)
Conductivity Normative Instruction n° 17 (MAPA, 2007) Normative Instruction n° 17 (MAPA, 2007)
Optical
Not applied PLM - Axio Lab, resolutions 10 x and 2,5 x
microscopy
-1
BP engineering – RB 3000, heating rate BP engineering – RB 3000, heating rate 10 °C min
TGA and DTA -1
10 °C min from 25 to 1000 °C from 25 to 1000 °C
Table 2: Chemical end physical parameters analysed in the samples and respective standards used

In this section are presented the field observations and the results obtained from the analysis of the
experiment according to the methodology used. First, some general remarks about the outcomes of
the two areas evaluated are given. The landscape on Figure 3 shows the two cultivated areas under
consideration where Brachiaria was sown at the same time, around four months before the picture
was taken. Both lands received the same amount of substrate, one with rice husk and the other with
SCRH for the period of 2 years. On the reader’s left side is located the area where SCRH was added,
and on the reader right side is located the area where rice husk was added. This research was
performed in the second year, after the second application of substrates, and four months after the
Brachiaria was sown, and the outcomes of the field experiment so far are shown in Fig. 3.
By comparing the areas with SCRH and with RRH addition, by sight observation, it was clear that the
outcome of the area with SCRH if by far better than the one with RRH.
223
Figure 3: Picture of field experiment comparing an area where carbonized rice husk was added (on the reader’s left side) to an area
where raw rice husk was added (on the reader’s right side). This picture is relative to 2 years after the substrates were added to the soil.
-1
Figure 4: macroscopic aspect after 2 years from the addition of SCRH in a proportion of 20 ton Ha (i.e. 0.3% in volume)
SCRH is around 30% finer than RRH. Here, might also be considered the fact of residue fragility in
terms of structure. Due to the intrinsic nature of the material, added to friction conditions, the
material is subject to fracturing. The bulk density can also be related with the granulometry of the
residues. RRH and SCRH presented an endothermic reaction with a mass loss of 9.6% and 2.2%,
respectively, in the range of 25-200°C related with moisture content. Due to the original condition of
RRH, unburned residue, its weight loss between 200-500°C was, considerably, superior (around 58%)
when compared with SCRH (around 7%). This is related with organic matter decomposition.
In terms of chemical characterization, the pH of formulation increased when compared with
reference soil. This fact is relevant when considering that Rio Grande do Sul soils are very acids. Most
crops present good productivity when in the soil pH is obtained between 6.0 and 6.5. Both residues
could slightly contribute to the soil pH regulation maybe actin as a soil correction agent. The CEC was
also slightly amended, but irrelevantly. This fact is due to the low percentage of incorporation of the
residues into the soil.
224
Analysis RRH SCRH

Loss On Ignition (%) 79.46 34.33
>0,075 99.09 66.77
Granulometry
≤0,075 0.91 33.23
Moisture (%) 16.55 40.26
Calorific value MJ/kg 13.80 0
>50% Si Si
XRF qualitative 5%<x<50% Not detected Fe
<5% Al, Fe, K, Mn, Ca, S, Ti, Cu, Zn Al, K, Ca, Mn, P, Ti, Ba, Zn, Cu
-
Bulk density (kg.m ³) 1438.6 1716.5
pH pH 6.51 7.55
Conductivity µs/cm 95.97 175
Table 3: Chemical and physical characterístics of the raw rice husk and of the respective spontaneous carbonized rice husk used as a
substrate.
Macronutrients N, P, K, Ca, Mg and S (also called major nutrients) are absorbed by the plant in a
larger proportion when compared to the micronutrients B, Zn, Cu, Fe, Mo, Cl and Mn (also called
trace elements). Both are constituents of the minerals and organic matter of the substrate where the
plant grows and are also dissolved in the soil solution. Considering that one or more nutrients may
be almost absent in the soil or in a form that the roots cannot absorb, the correct soil management
must be carried out. The organic matter increases soil buffering ability (soil resistance to abrupt pH
changes, requiring higher limestone dosages to achieve the desired values of base saturation or pH).
Soils rich in organic matter and / or with greater cation exchange capacity present greater buffering
and lessens the dangers of mineral imbalances caused by arbitrary fertilization.
The cation exchange capacity of a soil, clay or humus represents the total amount of cations retained
on the surface of these materials in exchangeable condition (Ca 2 + + Mg2 + + K+ + H+ + Al3+). It
represents the graduation of the capacity of liberation of several nutrients, favoring the maintenance
of the fertility for a prolonged period and reducing or avoiding the occurrence of toxic effects of the
application of fertilizers. However, according to the results obtained, both analyzed residues present
a CEC similar to that of a kaolinite-type clay, that is, between 50 and 150 mmol*kg-1. The WHC of
formulations did not present a relevant increasing when compared with the soil results.
Analysis Soil Soil + RRH Soil + SCRH
>0,075 89.57 92.55 91.26
Granulometry
≤0,075 10.43 7.45 8.74
Moisture (%) 7.12 7.29 7.51
>50% Si Si Si
5%<x<50% Al Al, Fe Al, Fe
XRF qualitative
Fe, Ti, K, S, Ti, K, Sn Ti, K
<5%
Ga, V
-
Bulk density (kg m ³) 1044.2 1395.8 1429.4
pH pH 4.81 5.28 5.36
-1
CEC ≤200 mmol C kg 66.5 49.9 50
WHC ≤60% 22.9 24.05 22.76
Table 4: Chemical and physical parameters analysed in the raw soil and in soil mixtures with substrate rice husk and carbonized husk;
CEC value used as soil conditioner according to Normative Instruction n° 17 (MAPA, 2007).
The optical microscopy – OM in Fig. 5 shows a soil constituted predominantly by quartz with
inclusions of zircon and feldspar and traces of iron oxides and hydroxides. The presence of quartz
reduces soil fertility and the CEC because it is a diluent for other minerals [34]. On the other hand,
SCRH might increases, e.g., WHC and CEC due to its high surface area and porosity [35].
225
Figures 6 and 7 illustrate the insertions of RRH and SCRH, respectively, inside the area in detail.
Figure 6: Optical microscopy of Soil + RRH Figure 7: Optical microscopy of Soil + SCRH
Figure 5: Optical microscopy of Soil
(magnifying of 2.5x) (detail with rice husk) (detail with charred husk)
The Figures 5 to 7 show the OM of the depleted soil tested in the attempt to replicate in a laboratory
the soil amelioration conditions observed on the farmland. The purpose was to verify to what extent
the incorporation of the substrates have the ability to ameliorate degraded soils.
Nevertheless, the use of crop residue for soil quality maintenance must be more assessed. Based on
the good from the SCRH addition on a farmland soil, this experiment was a first attempt to obtain
some beneficial results with the addition of SCRH in a depleted soil.
4- FINAL REMARKS
The results obtained in this work showed that the residues spontaneous carbonized rice husk
addition in the soil slightly improved some properties, mainly related with pH and cation exchange
capacity.
According to the results obtained, both analyzed residues present a cation exchange capacity similar
to that of a kaolinite-type clay, that is, between 50 and 150 mmol*kg-1. The water holding capacity of
formulations did not present a relevant increasing when compared with the soil results.
Nevertheless, the use of crop residue for soil quality maintenance must be more assessed. Based on
the suitable from the spontaneous carbonized rice husk addition on a farmland soil, this experiment
was a first attempt to obtain some beneficial results with the addition of SCRH in a depleted soil.
5- ACKNOWLEDGMENTS
The authors acknowledge CAPES (Coordination of the Improvement of Higher Education Personnel),
and CNPq (National Council for Scientific and Technological Development) for financial support.
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228
CO-COMBUSTION OF BITUMINOUS COAL AND PICKLING SLUDGE IN A
HIGH-TEMPERATURE HORIZONTAL TUBE FURNACE SYSTEM: THE
EFFECT OF WATER AND KAOLIN CONTENT ON THE PARTITIONING OF
AS, CR, CU, MN, NI AND PB
S. Zhang1, X. Jiang*1, G. Lv1, A. Nixiang1, Y. Jin1, J. Yan1, X. Deng2

(1State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou
310027, Zhejiang, China
2
Hangzhou Lijia Environmental Services Co., Ltd.)
Key words: co-combustion, pickling sludge, heavy metals, leaching concentration
Abstract
- Purpose: In this work, the effect of water and kaolin addition on heavy metals
As, Cr, Cu, Mn, Ni and Pb partitioning during bituminous coal and pickling sludge
co-combustion were studied.
- Methods: Experiment was carried out in a horizontal tube furnace at 1300 °C.
The pickling sludge amount used in the experiment was 10 wt.% and the
addition rate of water and kaolin was 5, 10, 15, 20 wt.%, respectively.
Thermodynamic equilibrium calculations for different co-combustion conditions
were carried out by Factsage 7.0. Leaching test of bottom ash was carried out
according to Chinese national standard HJ/T 300-2007, and heavy metals
concentrations were analyzed by ICP-AES (Thermo Scientific, iCAP 6300).
- Results: Higher water addition proportion increased As percentage in fly ash,
while reduced Pb percentage in fly ash. With the increasing addition of kaolin, As
partitioning showed a fluctuation trend, while the percentage of Pb and Cu in
bottom ash had an upward trend due to the adsorption capacity of kaolin. The
partitioning of Cr, Ni and Mn were basically not affected by water and kaolin
addition; they existed mainly in bottom ash after co-combustion. The leaching
test results indicated that As and Cr leaching concentrations were enhanced by
water and kaolin addition especially Cr which increased significantly, while the
Mn, Ni, and Pb leaching concentration decreased.
- Main conclusion: Fuel water and kaolin content has an obvious effect on the
partitioning of As, Pb and Cu, and also has a great influence on the leaching of
Cr.
229
1- INTRODUCTION
Due to the development of China, the generation of hazardous waste increased

rapidly in recent years, from 10.8 million tons in 2006 increased to 53.5 million tons
in 2016. Because of the lack of hazardous waste disposal ability, only 16.1 million
tons were disposed and 11.6 million tons were kept in storage in 2016[1]. Pickling
sludge is a kind of hazardous waste[2] (HW17, the seventeenth category of hazardous
waste list), which is generated from the neutralization of acid-pickling waste water
and usually contains lots of heavy metals[3]. Landfill without proper disposal will
cause environmental problems due to the toxic infiltration from the pickling sludge[4].
Due to the advantages of centralized incineration include obvious volume reduction,
wide adaptability and high disposal efficiency[5], it is considered to be the most
appropriate method for hazardous waste disposal in China.
Co-combustion treatment is defined as using waste materials instead of partial
fossil fuels in the industrial boilers to realize the thermal disposal of waste
materials[6]; its greatest advantage is making full use of existing boiler resources and
eliminating the need for specialized wastes incinerators at same time. According to
the electric power development plan in China[7], more than 20 GW outdated thermal
power plants (unit capacity less than 300 MW) will be shut down. Thus, if part of
these outdated power boiler resource could be used for co-combustion of hazardous
waste, the inadequate capacity for hazardous waste disposal will be basically solved.
So far, the research about hazardous waste and coal co-combustion in suspension
firing boilers is few and mainly focus on the effect of co-combustion on the gaseous
pollutants emissions[8-10].
Generally, due to the moisture and ash content of different kinds of coal varying
greatly, it may have a significant impact on the emission and portioning of heavy
metals during co-combustion[11]. Meng’s study indicated that the higher fuel
moisture content can affect the behavior of heavy metals in several ways including
increasing the flue gas moisture, decreasing the combustion temperature and
prolonging the combustion time; besides, the higher moisture will increase the free
H in the system and change some metal chlorides to metal oxides[12]. Some
studies[13-16] point out that the high moisture greatly reduced the volatilization of
heavy metals Cu, Cd, Zn and Pb, while some other studies indicated that effect of
moisture content on the heavy metal partitioning was negligible[17] or only obvious in
the case of high chlorine content[18]. As for the fuel ash content, kaolin was usually
used as additive to simulate high silicon and aluminum content coal ash [19-22], and its
impact on the heavy metals emissions was also studied[23]. Some studies pointed out
that the addition of kaolin had a significant effect on the capture of Pb and Cd [24], and
the reason is that kaolin is an effective physical sorbent and both Pb and Cd appear
to shift from sub-micron particles to macro-particles[25]. Besides, the leaching results
which Pb became insoluble with kaolin addition means that kaolin was also effective
in capturing Pb chemically to form Al–Si-compounds[25].
The purpose of this research is to study the effect of moisture and fuel ash
content on the heavy metals As, Cr, Cu, Mn, Ni and Pb partitioning during
230
co-combustion of bituminous coal and pickling sludge. The experiment was carried
out in a horizontal tube furnace system at 1300 °C high temperature.
2.1 Materials
The pickling sludge used in this study was taken from a hazardous waste
treatment plant in Huzhou, Zhejiang province. A typical bituminous coal was used as
fossil fuel. These two fuels were milled and sieved individually to obtain particle size
less than 74 μm. The properties of the fuels are given in table 1, 2 and 3. Compared
with bituminous coal, the pickling sludge has lower volatile, fixed carbon and heat
value, while the heavy metals content in the sludge is much higher, especially for Cr
and Ni .
Proximate analysis (%) Ultimate analysis (%)
Sample
Mad Aad Vad FCad Qnet,ad(MJ/Kg) C H O N S
Bituminous
4.66 20.65 26.61 48.08 24.584 62.29 3.90 7.17 1.02 0.31
coal
Pickling
1.5 89.15 9.25 0.1 0.075 0.86 0.46 1.32 0.38 6.33
sludge
Table 1: Proximate and ultimate analysis of bituminous coal and pickling sludge (Mass %)
ad, air-dried basis; M, moisture; A, ash; V, volatile; and FC, fixed carbon
Chemical composition (%)
Sample
SiO2 Al2O3 Fe2O3 CaO MgO K2O Na2O
Bituminous coal 50.36 19.20 6.52 8.40 6.65 1.00 0.63
Pickling sludge 6.38 3.53 20.43 32.35 32.49 0.10 0.26
Table 2: Chemical Composition and Ash fusion temperature of bituminous coal and pickling sludge
Heavy metal content (mg/kg)
Sample
Cr Ni Mn As Cu Sb Pb Cd Sn
Bituminous coal 53.4 24.8 161.2 64.7 10.7 94.0 31.2 0.8 1.6
Pickling sludge 24607.7 21086.5 2336.0 82.6 126.6 512.1 33.3 1.6 6.4
Table 3: Heavy metal contents of bituminous coal and pickling sludge
2.2 Setup: high-temperature horizontal tube furnace
valve high-temperature
Horizontal tube furnace
graphene crucible
flowmeter
Heat tracing
filter cylinder
alundum exhaust treatment
air tube
ice bath
5%HNO3+10%H2O2
[26]
Figure 1: Schematic diagram of the high temperature horizontal tube furnace
231
The experiment was carried out in a high temperature horizontal tube furnace
which was described in detail in our previous study[26]. An alundum tube was
installed in the furnace, and the sample was placed in a graphene crucible and fed
into the tube. The flow rate of combustion air was controlled by the valve, and the
furnace temperature could be set ranging from 500 to 1600 °C. The fly ash particles
(diameter > 0.3μm) were captured by the glass fabric filter (capture rate > 99.99%)
which was maintained above 120 °C to prevent the flue gas from condensation, and
the heavy metals in flue gas were absorbed in two gas washing bottles which
contained 10% H2O2 and 5% HNO3 respectively (by volume), according to EPA
method 29.
2.3 Experimental Matrix
The experimental matrix is shown in Table 4. For all conditions, the furnace
temperature was 1300 °C, the mass of the blended fuel was 3 g and the air flow rate
was 3 ml/s. The addition of water (5, 10, 15, and 20%) simulated coal with high
moisture content, while the addition of kaolin (5, 10, 15, and 20%) is on behalf of the
coal with high ash content. The duration of each condition was 30 min.
Experimental Fuel composition/%
No.
condition Bituminous coal Pickling sludge Water Kaolin
Baseline 1 90 10 - -
2 85.5 9.5 5 -
3 81 9 10 -
Water addition
4 76.5 8.5 15 -
5 72 8 20 -
6 85.5 9.5 - 5
7 81 9 - 10
Kaolin addition
8 76.5 8.5 - 15
9 72 8 - 20
Table 4: Experimental matrix
2.4 Heavy Metal Analysis
After experiment, the 10% H2O2 and 5% HNO3 solutions with heavy metals
gathered from flue gas were mixed and diluted to 250 ml. For fly ash and bottom ash,
50 mg ash sample was measured and then digested with mixed acid solution (6 ml
nitric acid, 2 ml hydrofluoric acid and 2 ml hydrochloric acid) respectively in a
microwave digestion system (WX-8000, PreeKem), and the digestion solution was
diluted to 100 ml. The leaching test of bottom ash was carried out according to
Chinese national standard HJ/T 300-2007. At last, the above solutions were analyzed
by ICP-AES (Thermo Scientific, iCAP 6300) to obtain the heavy metals concentrations.
2.5 Thermodynamic Equilibrium Calculations
The thermodynamic equilibrium calculations for different co-combustion
conditions were carried out by Factsage 7.0. C, H, O, N, S and Cl represented the
organic components and atmosphere, and SiO2, Al2O3, Fe2O3, CaO, MgO, K2O, and
Na2O represented the mineral phase; As, Cr, Cu, Mn, Ni and Pb represented the
heavy metals contained in the blended fuels and were calculated one by one. The
reaction temperature was set to 1300 °C and the pressure was set to 1 atm.
232
According to standards for pollution control on hazardous waste incineration

(GB18484-2001) in China, Cr, Ni, Mn, As, Cu, Sb, Pb, Cd and Sn were all studied in this
experiment. However, due to in some conditions the ICP results for Sb, Cd and Sn
content in flue gas and fly ash were lower than the measuring limit, only the
remaining 6 kinds of heavy metals results were analyzed. The partitioning of heavy
metals is defined by the following formula[26]:
𝒎𝒊𝒐𝒖𝒕𝒑𝒖𝒕
partioning rate = 𝑴𝒊 (1)
𝒐𝒖𝒕𝒑𝒖𝒕
𝑖
where i is the species of heavy metals, 𝑚𝑜𝑢𝑡𝑝𝑢𝑡 is the mass of heavy metal i in flue
𝑖
gas, fly ash, or bottom ash after co-combustion, and 𝑀𝑜𝑢𝑡𝑝𝑢𝑡 is the total mass of
heavy metal i in flue gas, fly ash, and bottom ash after co-combustion.
3.1 Water addition
(a) (b) (c)
100 100 100
80 80 80
Partitioning of Cu/%
Partitioning of Cr/%
Partitioning of As/%
60 (a) 60 60
100
40 40 40
20 20 20
80
0 0 0
baseline 5% water 10% water 15% water 20% water baseline 5% water 10% water 15% water 20% water baseline 5% water 10% water 15% water 20% water
(d) flue gas fly ash 60

bottom ash (e) flue gas fly ash bottom ash (f) flue gas fly ash bottom ash
100 100 100
80 80 80
40
Partitioning of Mn/%
Partitioning of Ni/%
Partitioning of Pb/%
60 60 60
40 20 40 40
20 20 20
0
0 baseline 0 5% water 10% water 15% water 20% 0water
flue gas fly ash bottom ash flue gas fly ash bottom ash flue gas fly ash bottom ash
flue gas fly ash bottom ash
Figure 2: Effect of different water added proportion in blend fuels on the heavy metals partitioning during 10%
pickling sludge and bituminous coal co-combustion at 1300 °C in the tube furnace: (a)As, (b)Cr, (c)Cu, (d)Mn, (e)Ni,
and (f)Pb.
The heavy metals partitioning results at different water addition conditions at
1300 °C are shown in fig. 2, and the corresponding thermodynamic equilibrium
calculation results are shown in fig. 3. From fig. 2, it can be seen that the behaviors of
Cr, Mn, Cu and Ni were basically not affected by the addition of water. For Cr, Ni and
Mn, the calculation results were consistent with the experimental results that the
main components were solid substance. While for Cu, an apparent discrepancy
existed between simulation result and experimental data, and the similar results
were found in our previous research that the actual volatilization of copper is much
lower than the theoretical calculation[27]. The possible reason for this phenomenon is
that due to the main Cu compound generated under 900 °C were CuO(s) and
233
CuFe2O4(s), under the limited reaction time decomposition of solid Cu compounds

were incomplete.
For As and Pb, their partitioning characteristics were affected by the addition of
water. For As, with the increasing water added, a higher proportion of As moved into
the fly ash and the percentage in the bottom ash decreased. The possible
explanation is that the higher water content prolonged the initial devolatilization
process of the co-combustion, limited the generation rate of AlAsO4 and resulted in
more As compounds volatilized and captured by filter. For Pb, with higher water
addition the percentage of Pb in the bottom ash and flue gas showed a rising trend,
while the Pb in the fly ash decreased obviously. Similar result that more gaseous Pb
compounds generated by the increasing moisture proportion was also reported by
Zhu[13]. However, it is not reasonable that Pb mainly existed in bottom ash at such
high temperature according to the theoretical calculation result; the probable reason
may be that the initial Pb compounds in the blend fuels was much different from the
simple Pb element used in calculation, and the predicted reaction was kinetically
hindered since thermodynamic equilibrium was not reached[28].
(a) (b) (c)
100 100 100

Cu(g)
CuO(g)
80 80 80 CuCl(g)
AsO(g) CrO3(g) CuS(g)
Cu mass fraction/%
As mass fraction/%
Cr mass fraction/%
AsCl3(g) CrOOH(g)
60 60 60
AlAsO4(s) CrO2OH(g)
AsN(g) Cr(OH)3(g)
40 As(g) 40 CrO2(OH)2(g) 40
AsS(g) CrO(OH)3(g)
20 20
Cr2O3(s) 20
0 0 0
(d) (e) (f)
100 100 100
80 80 80 Pb(g)
NiO(g) PbO(g)
Mn mass fraction/%
Pb mass fraction/%
Ni mass fraction/%
MnCl2(g) Ni(OH)2(g) PbCl(g)

60 60 60
NaMnCl3(g) NiCl(g) PbCl2(g)
KMnCl3(g) NiCl2(g) PbH(g)
40 Mn(g) 40 NiO(s) 40 PbS(g)
Mn2SiO4(s)
20 20 20
0 0 0
Figure 3: Thermodynamic equilibrium calculation results for heavy metals under different water added proportion
co-combustion conditions at 1300°C: (a) As, (b) Cr, (c) Cu, (d) Mn, (e) Ni, and (f) Pb.
3.2 Kaolin added
(a) (b) (c)
100 100 100
80 80 80
Partitioning of Cu/%
Partitioning of Cr/%
60 60 60
40 40 40
20 20 20
0 0 0
baseline 5% kaolin 10% kaolin 15% kaolin 20% kaolin baseline 5% kaolin 10% kaolin 15% kaolin 20% kaolin baseline 5% kaolin 10% kaolin 15% kaolin 20% kaolin
234
(a)
100

80
(d) 60 (e) (f)
100 100 100
80 80 80
40
Partitioning of Mn/%
Partitioning of Pb/%
Partitioning of Ni/%
60 60 60
40 20 40 40
20 20 20
0
0 baseline 0 5% water 10% water 15% water 20%0water
flue gas fly ash bottom ash
Figure 4: Effect of different kaolin added proportion in blend fuels on the heavy metals partitioning under 10%
pickling sludge and bituminous coal co-combustion at 1300°C in the tube furnace: (a)As, (b)Cr, (c)Cu, (d)Mn, (e)Ni,
and (f)Pb.
The effect of kaolin addition on the heavy metals partitioning at 1300°C are
shown in fig. 4, and the related thermodynamic equilibrium calculation results are
shown in fig. 5. As shown in fig. 4, the partitioning of Cr, Ni and Mn were not
influenced by kaolin addition; although under the high kaolin content conditions, the
main solid compounds of Mn and Ni were changed due to the reaction of metal
compounds with SiO2 or Al2O3, they were still existed as solid phase in the bottom
ash and their high temperature stability and low volatility have already been
demonstrated in our previous study[27]. For Cu the proportion in flue gas and fly ash
showed a downward trend with the kaolin ratio increasing; this is because kaolin has
adsorption capacity for halide aerosols[19].
For As, no obvious regular trend was found in this experiment. Owing to the As
content in the blend fuels was at a low level, the original Al2O3 content in the blend
fuels was sufficient for the generation of AlAsO4 and the addition of kaolin didn’t
cause any additional chemical reaction. At the same time, it seems that the kaolin
had no adsorption capacity for gaseous As compounds. The result is that the
partitioning of As with kaolin addition showed a fluctuation trend. For Pb, similar
discrepancy between experiment and calculation was found that most of the Pb
existed in solid form after co-combustion. However, as shown in fig. 4(f), it is certain
that kaolin had an effect on the adsorption of gaseous Pb compounds; with the
increasing proportion of kaolin, the Pb content in the flue gas and fly ash decreased
significantly. However, at 5% kaolin added condition the proportion of Pb in the
bottom ash decreased compared with baseline, which means the volatility of Pb was
enhanced by a small amount of kaolin added in this test.
(a) (b) (c)
100 100 100
80 80 CrO2(g) 80
AsO(g)
Cu mass fraction/%
As mass fraction/%
CrO3(g)
Cr mass fraction/%
AsCl3(g) CrOOH(g)
60 60 60 Cu(g)
AlAsO4(s) CrO2OH(g) CuO(g)
AsN(g) CrO(OH)2(g) CuCl(g)
40 As(g) 40 Cr(OH)3(g) 40
CuS(g)
AsS(g) CrO(OH)3(g)
20 20
Cr2O3(s) 20
0 0 0
235
(d) (e) (f)

100 100 100
80 80 80
NiO(g) Pb(g)
Mn mass fraction/%
Pb mass fraction/%
Ni mass fraction/%
MnCl2(g) Ni(OH)2(g) PbO(g)
60 NaMnCl3(g) 60 60
KMnCl3(g) NiCl(g) PbCl(g)
Mn(g) NiCl2(g) PbCl2(g)
Mn2SiO4(s) Ni2SiO4(s)
40
Mn3Al2Si3O12(s)
40 40 PbH(g)
MnSiO3(s) NiO(s) PbS(g)
20 20 20
0 0 0
Figure 5: Thermodynamic equilibrium calculation results for heavy metals under different kaolin added proportion
co-combustion conditions at 1300°C: (a) As, (b) Cr, (c) Cu, (d) Mn, (e) Ni, and (f) Pb
3.3 Leaching test
Fly ash leaching concentration (mg/L)
Conditions
As Cr Cu Mn Ni Pb
baseline 0.108 23.10 0.145 5.386 4.971 0.043
20% water 0.403 175.0 0.189 4.715 3.930 0.029
20% kaolin 0.117 51.60 0.113 2.452 1.695 0.024
National Standard (GB 16889-2008) 0.3 4.5 40 None 0.5 0.25
Table 5: Bottom ash leaching concentrations
The leaching test results of bottom ash under baseline and two largest addition
proportion conditions are shown in table 5. It can be seen that the addition of 20%
water increased the As, Cr and Cu leaching concentration, while decreased the Mn,
Ni, and Pb leaching concentration. Meanwhile, the addition of 20% kaolin showed
very a similar effect on the heavy metals partitioning, except Cu which showed a
slight decline. A very noteworthy point is that the leaching concentration of Cr under
both 20% water and 20% kaolin conditions increased significantly. The possible
reason for the effect of water addition on the Cr leaching characteristic is that more
water increased the free H in the system, created an oxidizing atmosphere and
changed more metal compounds into metal oxides which might be more soluble. For
the effect of kaolin addition on the Cr leaching characteristic, perhaps some
chromium compounds and aluminosilicates formed some complex compounds which
have a higher leachable property. Compared with the national standard (GB
16889-2008), the co-combustion bottom ash requires further processing to reduce
the heavy metals leaching before landfill disposal as common waste.
4- CONCLUSIONS
Co-combustion of bituminous coal and pickling sludge was performed in a

horizontal tube furnace, and the effect of water and kaolin addition on the
partitioning of heavy metals were studied. Based on the experimental results, the
following conclusions can be drawn:
(1) With the increasing addition of water, a higher percentage of As moved into the
fly ash from bottom ash; while the proportion of Pb in the fly ash decreased
obviously, and the Pb in bottom ash and flue gas had a rising trend. The partitioning
of Cr, Mn, Cu and Ni were basically not affected by water addition.
(2) With the increasing addition of kaolin, the As partitioning showed a fluctuation
trend and no adsorption capacity of kaolin for gaseous As compounds was found;
236
while for Pb and Cu, the adsorption was the main factor and the distribution in
bottom ash had an upward trend. For Ni and Mn, the main solid compounds were
altered by kaolin addition; however the partitioning of Ni, Mn and Cr were
unchanged.
(3) Both 20% water addition and 20% kaolin addition increased the As and Cr
leaching concentration, and decreased the Mn, Ni, and Pb leaching concentration.
While for Cu leaching, it was increased by water addition and decreased by kaolin
addition slightly.
CORRESPONDING AUTHOR
* Tel: +86 571 87952775. Fax: +86 571 87952438. E-mail: jiangxg@zju.edu.cn.
ACKNOWLEDGEMENTS
This study was supported by the Innovative Research Groups of the National Natural
Science Foundation of China (No. 51621005), the National Nature Science
Foundation of China (No. 51676172), the Fundamental Research Funds for the
Central Universities (No. 2016FZA4010), the Special Fund for the National
Environmental Protection Public Welfare Program (Grant 201209023-4), and the
Program of Introducing Talents of Discipline to University (Grant B08026).
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239
CHARACTERIZATION OF INDUSTRIAL WASTES IN RELATION WITH INCINERATION

FUMES AND RESIDUE COMPOSITION
L. LE COQ1, A. JOUBERT1, R. BOUDHAN1, C. DUTOUQUET2, D. VENDITTI3, S. DURECU3, E. FIANI4, O. LE

BIHAN2
1 IMT Atlantique, GEPEA, CNRS, BP 20722, 44307 Nantes cedex3, France.
2 INERIS, Parc Technologique Alata, BP 2, 60550 Verneuil-en-Halatte, France.
3 TREDI - Séché Environnement, BP 20199, 54505 Vandœuvre-lès-Nancy, France.
4 ADEME, BP 90406, 49004 Angers Cedex 01, France.
Abstract
This study is part of the NanoWet project funded by the French Environment & Energy Management
Agency (Ademe) (CORTEA funding scheme Grant 1581C0096). Before performing incineration trials,
our aim was to characterize three industrial wastes potentially harboring nano-fillers, with two out
of three also containing halogenated or sulfur compounds. The wastes are respectively by-products
from i) polyorganosiloxane polymerization processes (PDMS), ii) flexible PolyVinyl Chloride
production (soft PVC) and, iii) soiled strong acid cation exchange resins of sulfonic type (Resin). The
PDMS waste was previously studied in the framework of NanoFlueGas project [1].
The three wastes were first characterized in terms of ultimate and proximate analysis, with a
particular focus on their respective moisture, ash, heavy and alkali metals, halogens and sulfur
contents, as well as on their TGA curves and Higher Heating Values. The nano-fillers contained in the
wastes were evaluated regarding their morphology, size distribution and chemical composition, by
using the Cryo-ultramicrotome-Transmission Electron Microscopy technique.
The PDMS waste contains SiO2 nano-fillers estimated to 24.4% dwt. The soft PVC waste contains 36%
dwt Cl as well as nano-fillers mainly composed of TiO2. The Resin waste exhibits a high sulfur content
of 15.4% dwt, but it does not contain any nano-fillers even though the resin polymer itself is typically
intrinsically nano-structured.
The three wastes were incinerated separately in a custom-built lab-scale incinerator device
composed of a tubular horizontal furnace adapted to control the combustion conditions (within both
the combustion and post-combustion zones) to be representative to the key operating conditions of
a high-temperature incineration process dedicated to industrial wastes. Temperature (T) is equal to
1,100°C in the combustion and post-combustion zones, residence time is maintained to at least two
seconds in the post-combustion zone, sufficient air excess is provided so as to never drop below 11%
O2 content in fluegas, by appropriately feeding primary and secondary air flows, which also
contributes to achieve adequate turbulence conditions (by enabling a good mix between
combustible and oxygen). A fume sampling device allows to characterize O 2, CO2, CO, SO2, HCl
contents as well as particulate matter concentrations in various granulometric ranges. When
present, the solid residue remaining in the furnace at the end of incineration trial is analyzed to
estimate the presence of nano-fillers in this solid fraction.
The results showed in particular significant concentrations of HCl and SO2 in the raw fumes
originating respectively from the incineration of soft PVC and Resin, in full agreement with their
proximate analysis. High content of titanium was found in the soft PVC solid residue. Data from high-
T incineration of PDMS were interestingly compared with previous results obtained at 850°C [2].
References
[1] Tran D.T., Joubert A., Venditti D., Durécu S., Meunier T., Le Bihan O., Fiani E., Le Coq L.: Characterization of polymer
waste containing nano-fillers prior to waste treatment, Waste and Biomass Valo., 8(7), 2463-2471
[2] Ounoughene G., Le Bihan O., Debray B., et al.: Thermal disposal of waste containing nanomaterials: first
investigations on a methodology for risk management, J. of Physics: Conf. Series 838 (2017) 012024
240
MICROSTRUCTURAL TAILORING OF BOF STEEL SLAG FOR CONSTRUCTION

APPLICATIONS: AMORPHOUS CONTENT AND ITS IMPACT ON REACTIVITY AND
MECHANICAL STRENGTH AFTER ALKALI ACTIVATION
P. LOPEZ1, Y. PONTIKES2
1 KU LEUVEN, Leuven, Belgium.
Abstract
Microstructure tailoring of steel slags opens the possibility of creating customized binder precursors
for applications in the construction sector. Previous studies have demonstrated the capability of
alumina additions to generate defined amorphous contents and binding properties in modified slags
[1,2], and explored the impact of different cooling methods [3]. This research evaluates the impact of
the slag’s amorphous content on the reactivity and mechanical properties of alkali activated binders.
Different size fractions of industrial basic-oxygen-furnace slag (BOFS) modified at high temperature
and fast cooled through granulation and water quenching were characterized. BOFS with maximum
particle size around 4mm was sieved into three different fractions (0.063-1mm, 1-2mm and d>2mm).
X-ray diffraction (QXRD) was performed on each fraction to establish mineralogy and quantify the
amorphous content. Further characterization involved secondary electron microscopy (SEM) and
infrared spectroscopy (FTIR) on slag fractions, plus
electron probe microanalysis (EPMA) on amorphous
areas. Sieved fractions were milled ensuring
equivalent specific surface, then paste specimens
were produced mixing the milled fractions with NaOH
solution. Reactivity was quantified through isothermal
calorimetry and hardened binder compressive
strength was measured at 7 and 28 days. The results
show that amorphous content is inversely
proportional to nominal diameter of particle
confirming that a difference in cooling rate during
granulation has appreciable impact on microstructure
developed; such differences generate reactivity
variations, which affect macro-properties of the
binder and can be eventually mapped to link BOFS
processing with binder performance optimization.
Figure 1: Quantified microstructure of slag fractions
References
[1] Ionescu, D. V.: The hydraulic potential of high iron bearing steel slags. PhD Thesis. The University of British Columbia,
Vancouver (1999)
[2] Liu, C.: BOF Slag Hot-stage Engineering towards Iron Recovery and Use as Binders. PhD Thesis. KU Leuven, Leuven
(2017)
[3] Kriskova, L., Pontikes, Y., Pandelaers, L., Cizer, Ö., Jones, P. T., van Balen, K., and Blanpain, B.: Effect of High Cooling
Rates on the Mineralogy and Hydraulic Properties of Stainless Steel Slags. Metall. and Materi. Trans. B 44, 5, 1173–
1184 (2013)
241
FIRING OF ZINC PHOSPHATE SLUDGE – KAOLIN MIXTURE FOR WASTE CONTAINMENT
S. ASTUTININGSIH1, J. MULIAWAN1,2
1 Department of Metallurgy and Materials Engineering, Universitas Indonesia, Depok, Indonesia.
2 Permanent address: PT Dutakimia Berjawa, Puligadung, Indonesia.
Abstract
Zinc phosphate is widely used in metal finishing industries such as automotive, steel furniture,
houseware, electrical equipment, construction to enhance corrosion resistance and paint adhesion
of metal surface. However, the use of zinc phosphate in this process produces waste in the form of
liquid and solid sediment known as zinc phosphate sludge (PS). PS mass consists mainly of, in weight
percentage, ~20 iron, 50-55 phosphorus, and ~10 zinc [1]. The high amount of metal content make
disposal of PS prohibited. Besides recovery of the metal and zinc content (2-6), utilization of PS into
building materials is another option. Extensive research that have been done in the utilization of
waste into building materials can be classified into 3 methods: firing; cementing and
geopolymerisation (7).
Firing is one way to utilize waste while providing metal immobilization. In this paper, firing
temperatures and zinc phosphate sludge (PS) content was optimized to obtain the required strength
of the PS – kaolin mixtures for use as bricks or other building materials. X-ray diffraction, thermal
analysis and scanning electron microscopy were performed to analyze phase transformations and
microstructures upon firing. It is found that specimens containing up to 25 wt% PS fired at 1200 oC
met the required strength. Transformation of quartz into cristobalite indicated vitrification, in certain
extent, in PS added kaolin mixture. While mullite is the strength generator in pure kaolin, vitrified
phase contributed to strength in the kaolin - PS mixture, as well as immobilization of the metals.
References
[1] Narayanan, T.S.N.S.: Surface pretreatment by phosphate conversion coating – A Review. Rev. Adv. Mat. Sci. 9, 130-
177 (2005)
[2] Waite M.D. Process for recovering zinc phosphating make-up feed from zinc phosphate sludge. US Patent 5,376,342
(1993)
[3] Waters R.F., Powell H.E., Ballard L.N.: Recovery of metals and phosphate from water phosphates. US Patent
3,653,875 (1971)
[4] Peters D.S.: Recovery of useful products from by-products of phosphate conversion coating process, US Patent
4,986,977 (1991)
[5] Buchmeier W., Roland W.A.: Method of recycling phosphating sludge. US Patent 5,350,517 (1994)
[6] Baldy C.J.: Recycling zinc phosphate sludge. Metal Finish. 94(11), 23-24 (1996)
[7] Zhang, L.: Production of bricks from waste materials – A review. Constr. Build. Mat. 47, 643-655 (2013)
242
FROM WASTE TO A GREEN CONSTRUCTION MATERIAL: FIRE-RESISTANT CELLULOSE

PANELS FOR CEILINGS
P. MORENO1, N. VILLAMIZAR1, J. PEREZ1, A. BAYONA1, N. MORENO1, J. ROMAN1, N. S. MEDEIROS

CARDOZO2
1 Civil Engineering Department Grupo ambiental de investigación aplicada - GAIA Universidad de
Santander UDES, Bucaramanga, Colombia.

2 Chemical Engineering Department-Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil.
Abstract
In the last century, the use of materials has increased 8 times; nowadays humanity consumes about
60 billion tons (Gt) of materials per year. The construction industry consumes more raw materials
than any other industry, 3000 Mt/year. In order to achieve sustainable development it is necessary
to use construction materials that generate the least possible environmental impacts, as recycled
products. The purpose of this work was to manufacture fire-resistant cellulose panels, with low
density and adequate flexural strength to use as ceilings using recycled newspapers, soy protein as a
binder and acid boric and borax as additives. A central composite design (CCD) was performed in
order to study the influence of the panel components percentage on the following properties of the
panels: flame retardancy, the density and the flexural strength. Flame retardancy was characterized
by UL 94 horizontal burning test. Density measurements were performed according to ASTM D1037-
12. Flexural strength was determined according to ISO 178-2010. Fire-resistant cellulose panels were
successfully made with low densities (120 – 170 kg/m3) and adequate flexural strength (about 0.4
MPa) for ceilings applications. A useful and sustainable construction material with great potential for
use as ceilings is produced while some waste materials are valorised
References
[1] Pacheco-Torgal, F., Labrincha, J.A.: The future of construction materials research and the seventh UN Millennium
Development Goal: A few insights. Constr. Build. Mater. 40, 729–737 (2013)
[2] Lazko, J., Landercy, N., Laoutid, F., Dangreau, L., Huguet, M.H., Talon O. : Flame retardant treatments of insulating
agro-materials from flax short fibres. Polym. Degrad. Stab. 98, 1043-1051 (2013).
[3] López-Hurtado, P., Roully, A., Vandenbossche, V.: A review on the properties of cellulose fibre insulation. Build
Environ. 96, 170-177 (2016)
[4] Binici, H., Eken, M., Dolaz, M., Aksogan, O., Kara, M.: An environmentally friendly thermal insulation material from
sunflower stalk, textile waste and stubble fibres. Constr. Build. Mater. 51, 24-33 (2014).
243
VITRIFIED ASBESTOS WASTE USED AS FILLER MATERIAL IN A THERMOCLINE

STORAGE TANK
M. A. KEILANY1,2, M. MILHÉ1, J-J. BÉZIAN1, T. FASQUELLE2, Q. FALCOZ2, G. FLAMANT2

1 Centre RAPSODEE, Universite de Toulouse; Ecole des Mines d’Albi, CNRS, Albi F-81013, France.
2 CNRS-PROMES, 7 Rue du Four Solaire, 66120 Font Romeu-Odeillo, France.
Abstract
Thermocline systems could be an economically viable solution for thermal energy storage (TES) in
concentrated solar power (CSP) plants. In this work, the use of Cofalit® as solid filler material inside a
thermocline TES in a CSP is studied experimentally with the MicroSol-R pilot-scale facility. Cofalit® is
an inert and low cost post-industrial process rocks (recycled material from asbestos wastes), supplied
by the French company Inertam [1]. The thermal performance of the thermocline filled with Cofalit®
is compared to previous research [2] performed with alumina spheres as filler materials for typical
charge and discharge process. Experimentally, it was first observed that the overall porosity of the
solid bed increased with Cofalit® with respect to Alumina, due to random shapes and distributed size
of the particles. This results in a decrease in volumetric heat capacity from 3.3 MJ/m3K with alumina
spheres to 2.7 MJ/m3K for Cofalit® between 200 and 300 °C. The temperature distribution in the tank
during both charging and discharging phases is also investigated and compared to the reference case.
The development of the temperature gradient and its progression exhibit better performance than
the reference Alumina case, thus showing a very good thermocline behavior. Thermocline thickness
during charge was found 26% of the tank height in Cofalit® case, 7% lower than with Alumina. While
charge efficiency was similar for both materials around 79%, Cofalit® has better discharge efficiency
(8% better than alumina). The good thermal performance of Cofalit® as filler material is attributed
mainly to a greater heat exchange area afforded by its irregular shape. Considering the cost saving of
due to the use of Cofalit® and resulted thermal performance of the thermocline, Cofalit® appear as a
very good candidate as filler material.
1- INTRODUCTION
Concentrated solar power (CSP) is entitled to supply about 10% of the global electricity demand in
2050 (about 620 GWe) according to IEA [3]. One of the main advantages of CSP is the ability to be
integrate a massive and reliable thermal energy storage. The most commercially prevailing technology
is the two tanks molten salt sensible heat TES. Andasol 50MWe is considered a typical trough CSP
power plant with 7.5 h storage (28,000 ton nitrate molten salts) [4]. Thermocline TES systems could
be an economically viable solution for TES in CSP plants because it replaces two-tank TES system with
a single tank. Moreover, cheap solid filler materials are used inside the thermocline tank to increase
the volumetric heat capacity of the TES and decrease the need for expensive heat transfer fluid (HTF).
J.E. Pacheco et al [5] concluded that thermocline filled with cheap filler costs 64% of the two tanks
molten salts total cost (36% cost reduction). However, during charge and discharge a thermal gradient
layer is developed between hot and cold heat transfer fluid (HTF) which is called the thermocline
region or thickness. This region is related to heat diffusion in HTF where the quality of stored energy
is degraded inside it, consequently affecting the efficiency of the process, while this layer is expanding
during the operation it could account up to 33% of total thermocline TES height [6]. A comparison of
the influence of different thermocline design parameters on this thickness, included the thermo-
physical properties of filler materials as well as the HTF, tank height and porosity indicated that the
tank height and thermo-physical properties of the solid filler are the major parameters affecting the
thickness [7].
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When selecting a suitable solid filler materials for TES there are certain desired thermo-physical,
chemical , mechanical , environmental and commercial properties to be considered [8].Py et al [9]
evaluated the use of natural rocks as solid filler materials like granite, gravel and sand in TES. They
found that the contaminations in that filler caused significant declination in the oil’s thermos-physical
properties (HTF). Beside, upon thermal expansion to the tank wall, fin rocks have a potential to
precipitate at the bottom of the tank due to its very small size, preventing the tank’s wall to go back
to its original shape when cooled down, and this puts a serious strain on the mechanical integrity of
the tank wall.
In this study an experimental evaluation of Cofalit®, a cheap filler material (asbestos containing treated
waste) with good thermo-physical properties, is performed, and compared to the reference case of
alumina spheres.
2- COFALIT® AS SOLID FILLER OF TES

Source of Cofalit®: Ceramic from asbestos containing waste (ACW)
Asbestos is a general terminology for naturally available fiber-like minerals: it is known for high tensile
strength, flexibility, resistance to chemical and thermal degradation, electrical resistance and it can be
woven [10]. The main composition of ACW are reported by Gutierrez et al. [11] as follows: O 32 wt%,
Ca 31 wt%, Si 23 wt%, Fe–Mg–Al 13 wt%.
Asbestos was widely used during 20th century, it was found in nearly 4000 products[12]. However, in
1995 asbestos was restricted from use in most industrial countries, after confirming its responsibility
to fatal pulmonary diseases [13], and all asbestos containing waste (ACW) ordered to special recycling
procedures. Out of 250,000 tons per year of ACW produced in France alone, only 6000 tons re-used
after treatment road construction[9] while the rest are placed in highly controlled waste land fill. The
strict rules for treatment of ACW requires melting based operations at about 1400ºC , that allow
complete elimination of the ACW toxicity [11], which implies significant GHG emission and high cost
of energy, this increases the need to find ways to reuse these materials and valorize its use.
Cofalit® is a rocklike treated ACW manufactured by INERTAM [1]. It consists mainly of a calcium
magnesium iron alumino-silicate with various secondary elements based on the waste source such as
Cr, Cu, Zn, Mn, etc..[4]. The French company produces around 3000 tons yearly by subjecting ACW to
plasma torch furnace at 1400ºC, then leaving the molten resultant to cool down to ambient
temperature without specific operation to control the process [14]. The liquid nature of the primary
products allows forming molten Cofalit® in the required shape as molded.
Properties evaluations
Thermo-physical properties:
In order to compare the properties of the HTF with the nominated filler materials, Table 1 summarizes
most cited values of thermo-physical properties for synthetic oil, Alumina spheres and Cofalit® for
quick comparison, along with value obtained from temperature dependent properties in the
temperature range (200 – 300) ºC. This will help assessing the reduction of cost and size of the tank
taking into account important properties such as volumetric heat capacity, heat conductivity and
diffusivity.
Chemical properties:
Chemical stability: Cofalit® had been evaluated as chemically inactive material [15], furthermore, it is
thermally stable up to 1200ºC [1].
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Calvet et al [4] examined the compatibility between Cofalit® and two common molten salts, binary salt
60% sodium 40% potassium nitrate, and the ternary salt 42% calcium, 15% sodium, 40% potassium
nitrate.
Table 1 summarized Thermo-physical properties from literatures and temperature dependent formulas
Type Jarysol ®oil Alumina Spheres Cofalit ®rocks
Shape Liquid 2cm Spheres Irregular
Cost [€/Ton] 6667[16] 1635 [16] 8 [1]

𝑘𝑔 900[17] 3670[18][19] 3100 [9]
Density 𝜌 [ ]
𝑚3 3800-4000[17][20] 3120[1][11][21]
Heat Capacity 755-880[17]
𝐽 800-1043[17][18][11]
2100-2300[17] 750[18]
𝐶𝑝 [ ] 860 [1][21]
𝑘𝑔𝐾 900[20]
Thermal conductivity 18-33[17] 2.7[1][21]
𝑊 0.1[17] 21[18] 1.4[22]
𝑘[ ]
𝑚𝐾 14[16] 2.1-1.4[9][17][11]
Volumetric Capacity
2.831-3.484[17]
𝑀𝐽 1.89-2.07[17] 2.496-3.226[17]
(𝜌. 𝐶𝑝) [ 3 ] 2.752 [18]
𝑚 𝐾
Thermal diffusivity
𝑘 𝑚2 5.79 – 4.29
0.07 – 0.05 0.62 – 0.5
𝛼= [ ] 𝑥 10−6 4.94 – 3.72
𝜌𝐶𝑝 𝑠𝑒𝑐
Temperature range ºC for Temp
200 - 300 200 - 300 200 - 300
Dependent properties below
Temperature Dependent Density 3969 - 3961 [23]
𝑘𝑔 910 - 836 ---
𝜌[ 3] 3973 - 3963 [24]
𝑚
Temperature Dependent heat 1002 – 1059, 770@20ºC[23]
𝐽 2158 - 2476 919 – 964, 787@20ºC [25]
capacity 𝐶𝑝 [ ] 1021 – 1091, 755@20ºC[24]
𝑘𝑔𝐾
Temp. Dependent Thermal 23 – 18, 37@20ºC
𝑊 0.113 - 0.105 1.55 – 1.49; 1.76@20ºC
conductivity 𝑘 [ ] 20 – 16, 33@20ºC
𝑚𝐾
Temp. Dependent Volumetric 3.97 – 4.19
𝑀𝐽 1.9-2.07 2.85 – 2.99
Capacity(𝜌. 𝐶𝑝) [ ] 4.05 – 4.32
𝑚3 𝐾
No corrosion after subjecting the ceramic to 500ºC for 500 h was observed, confirming the
compatibility between Cofalit® and such a binary salt, while further study is recommended to validate
the possibility of use with the ternary salt. Fasquelle et al [18] evaluated the compatibility of Cofalit®
with synthetic oil at 300 ºC for 500 h, and found it stable, but further investigation was recommended
to check how oil properties are actually influenced by cycling operation along with Cofalit®.
Mechanical properties:
Py et al [9] confirmed slightly lower thermal expansion of Cofalit® compared to known high
temperature concrete and ceramic, with (α 8.8 10−6 𝐾 −1), as well as similar value of Young modulus
of 119 GPa. assessing a significant mechanical stability.
Commercial Properties:
Abundant material and very competitive price of Cofalit® was confirmed in different studies, with cost
as low as 8 euro/ton for the as-produced material [1],[9].
Environmental properties:
Various studies reported the low impact of Cofalit®, as it has no toxicity on the environment and (no
is not subject to lixiviation [1][9][26]. Although Jeanjean et al [27] estimated a carbon footprint of
27.48 gCO2/kg for Cofalit® production, the cost of environmental impact is accounted for asbestos
treatment operation and not for the TES[14].
Based on these properties, Cofalit® is as interesting as known ceramic and rocklike materials for
sensible heat, but it has significant advantages of low cost and valorization of waste materials.
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3- EXPERIMENTAL SETUP
Comparison between Cofalit and alumina was carried out in the same experimental setup that was
used by Fasquelle et al [2]. MicroSol-R is a pilot scale CSP plant consisting of 3 parabolic troughs (12m
long, 5.76m aperture, focal length 1.7m 7cm receiver diameter each), with total nominal power
150kW(th). The main TES is a 4m³ thermocline tank with a capacity of 220 kWh, consisting of 4
vertically-arranged baskets, reducing the possibility of thermal ratcheting and allowing easy access to
change the filler materials.
Thermocouples measuring HTF

temperature are distributed in the axial
and radial position as illustrated in
Figure 1.
The solid bed height is 2.64 m, and two
buffer zones allow a good HTF distribution.
In addition to the parabolic troughs, a 70
kW electrical heater is used to charge the
thermocline. Two pumps manage HTF
flow;, for charge and discharge process.
In order to apply similar experimental
conditions on different materials and to
eliminate the intermittent nature of the
solar power, a typical charge/discharge was
selected.
Figure 1 Thermocline tank size and thermocouple positions [2]
A typical charge/discharge consists in applying similar constant mass flow rate was applied at similar
temperature range.

Thermocline dynamic behavior was first compared based on non-dimensional temperature profile
evolution during charge and discharge for both filler materials. , Additional performance parameters
where evaluated to get more insight: thermocline thickness and storage efficiency.
Temperature profile
Taking into account that (Thigh ) is the highest temperature during a process, and (Tlow ) is the lowest
temperature during the same process. Non-dimensional HTF temperature is defined in Equation 1,
non-dimensional axial coordinate is defined in Equation 2:
Tz,t − Tlow
θ=
Thigh − Tlow
Equation 1
z
z∗ =
Htank
Equation 2
Temperature profile during charge

Figure 2 shows the non-dimensional temperature profile inside the thermocline during charge from
248 ºC up to 280 ºC at mass flow rate of 2600 [kg/h] ; where dashed lines represent Cofalit® and solid
lines represent alumina.
Both materials start at constant temperature (horizontal profile), and the high temperature oil
flowing downward results in the propagation of a steep temperature profile top-down (from the
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247
right to the left of the figure). If the behavior is similar for both materials, Cofalit TES is fully charged
(horizontal profile at 𝜃 ≈ 1) faster than alumina. This behavior can be explained by the higher
volumetric heat capacity of alumina compared to Cofalit®, hence alumina needs more time to be
charged. In this experimental setup, there is no limitation on the HTF temperature flowing out of the
tank.
Figure 2 Alumina – Cofalit® non-dimensional temperature profile during charge, mass flow rate 2600 [kg/h] ΔT 32ºC (280 – 248)ºC
However, in a real case a threshold temperature should be taken into account: it is defined as the
highest temperatures that can be sent back to the solar field during charge process, referred as Tthr,c,k𝑐
in Equation 3. This threshold temperature limits the charge state of the TES in real operation.
Tthr,c,k𝑐 = Tlow + k c (Thigh − Tlow )

Equation 3
k c is an arbitrary charge factor related to the operational aspects of the solar field , 20% was
considered in many previous studies [28].
Figure 3 Alumina – Cofalit® non-dimensional outlet temperature evolution during the charge time, mass flow rate 2600 [kg/h] ΔT 32ºC
(280 – 248) ºC
By plotting the non-dimensional outlet temperature over time, (Tthr,c,20% → θthr,c,20% = 20%), it is
observed from Figure 3, that Cofalit® needed around 78 min to reach its maximum charge, while
alumina needed 96 min.
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Temperature profile during discharge

Figure 4 reflects the results during discharge from 290 ºC to 218 ºC at mass flow rate of 2950 [kg/h].
It start from fully charged thermocline at the (θ1 horizontally). The discharge cycle finishes it duration
when non-dimensional temperature reaches( θ = 0.8) at the non-dimensional spatial coordinates
(z*=1), alumina discharged for 12 min more than Cofalit®, this can be attributed to its higher
volumetric heat capacity compared to Cofalit®.
Figure 4 Alumina – Cofalit® non-dimensional temperature profile during discharge, mass flow rate 2950 [kg/h] ΔT 72ºC (290 – 218)ºC
Thermocline thickness
During the discharge process, the operation should stop when the outlet temperature reaches the
discharge threshold temperature, which is lowest temperature that downstream thermal process can
utilize, referred usually as discharge threshold temperature (Tthr,d,k𝑑 ) that calculated from Erreur !
Source du renvoi introuvable.
Tthr,d,k𝑑 = TH𝑖𝑔ℎ − k d (Thigh − Tlow )
Equation 4
k d : is arbitrary discharge factor related to the operation of the downstream process, most of previous
studies consider the value 20% [28], therefore discharge threshold temperatures is represented as
(Tthr,d,20% ). Thus, the non-dimensional discharge threshold temperature equals(Tthr,d,20% →
θthr,c,20% = 80%).
Thermocline thickness Equation 5 is the height of the zone contained between two threshold
temperatures during charge and discharge [28]: it is actually the part of the storage that cannot be
used during operation of the TES in a plant.
𝐻𝑇ℎ𝑖𝑐𝑘 (𝑚) = ℎ(Tthr,d,20% ) − ℎ(Tthr,c,20% )

Equation 5
Thermocline thickness during charge

Figure 5 illustrates the thermocline thickness during charge for both materials. Thermocline thickness
tend to increase sharply at the beginning of charge process until it reaches it maximum value, then it
remains at that high value for a until it start to decrease slowly until it has completely vanished when
thermocline is fully charged.
It should be noted that in real operation scenario charge must be stopped prior to fully charged status,
in order to avoid sending hot HTF back to the solar field. This limitation is set at a certain temperature
explained earlier (charge threshold temperature) θthr,c,20% = 20%. So, thickness must be evaluated
for a targeted non-dimensional threshold temperature, the thickness with Cofalit® was found 25.5%
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compared to 33% in alumina. This could be attributed to the higher thermal diffusivity which found to
lead to bigger thermocline thickness [29], where alumina has value around 5. 10−6 [m²/sec] while
Cofalit® has 0,55. 10−6 [m²/sec] Table 1.
Figure 5 Alumina – Cofalit® normalized charge thermocline thickness against non-dimensional outlet
temperature during charge, mass flow rate 2600 [kg/h] ΔT 32ºC (280 – 248)ºC
Thermocline thickness during discharge

Figure 6 plots the evolution of the thermocline thickness versus time. When the system reaches its
80% threshold temperature, thermocline thickness with alumina expands up to 23%, while with
Cofalit® it increases up to 20% and stabilize until the end of the process. Alumina still has bigger
thickness than Cofalit®, which is attributed to higher diffusivity in similar approach to the thickness
during charge. On the other hand, both materials didn’t reach their maximum thickness value, that
they have during charge process, this could be explained by the faster discharge compared to
discharge, which does not allow the thickness to evolve fast enough.
Figure 6 Alumina – Cofalit® Thermocline Thickness evolution during time for discharge at mass flow rate 2950 [kg/h] ΔT 72ºC (290-218) ºC
Charge Efficiency
The efficiency of charge process Equation 6 [16] is identified by the ratio between the accumulated
stored energy and the total energy that can be stored in the tank.
𝐸𝑎𝑐𝑐
𝜂𝑐ℎ𝑎𝑟𝑔𝑒 ==
𝐸𝑚𝑎𝑥
𝐻
∫0 (𝐴𝑇𝑎𝑛𝑘 𝑖𝑛𝑡 (𝜌. 𝐶𝑝)𝑒𝑓𝑓 + 𝐴𝑤𝑎𝑙𝑙 𝑐𝑟𝑜𝑠𝑠 𝑠𝑒𝑐𝑡𝑖𝑜𝑛 (𝜌. 𝐶𝑝)𝑤𝑎𝑙𝑙 ) . (𝑇𝑧,𝑡(𝐾𝑐) − 𝑇𝑙𝑜𝑤 )𝑑𝑧
[V𝑡𝑎𝑛𝑘 (𝜌. 𝐶𝑝)𝑒𝑓𝑓 + 𝑉𝑤 (𝜌. 𝐶𝑝)𝑤𝑎𝑙𝑙 ](𝑇ℎ𝑖𝑔ℎ − 𝑇𝑙𝑜𝑤 )
Equation 6
Where: (𝜌. 𝐶𝑝)𝑒𝑓𝑓 = 𝜀(𝜌. 𝐶𝑝)𝑓 + (1 − 𝜀)(𝜌. 𝐶𝑝)𝑝 .
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Due the significant contribution of the steel in the stored energy in this pilot storage capacity, the
volumetric heat capacity of the wall and the basket was taken into account. Figure 7 illustrates the
charge efficiency plotted against non-dimensional outlet temperature. Both materials show very
similar efficiency behavior during charge Although, in theory it is possible 100% efficiency based on
above definition, in real case charge scenario the charge should stop atTthr,c,20%.
Figure 7 Alumina – Cofalit® charge efficiency versus non-dimensional charge outlet temperature , mass flow rate 2600 [kg/h] ΔT 32ºC
(280 – 248)ºC
Thus, the charge process should end and the efficiency of charge has to be considered at that non-
dimensional value of outlet temperature 20%.
Hence, charge efficiency in Alumina found a bit lower than Cofalit® by 2%; but this difference cannot
be considered as significant with respect to experimental uncertainty, and both material has around
80% charge efficiency.
Discharge Efficiency
During discharge process, the efficiency can be calculated from Equation 7 as the ratio of discharged
energy to the initial maximum energy stored in the system (HTF, solid filler and tank walls).
𝑡(𝐾𝑑)
𝐸𝑑𝑖𝑠𝑐ℎ𝑎𝑟𝑔𝑒 ∫0 𝑚𝑓 𝐶𝑝𝑓 . (𝑇𝑜𝑢𝑡 − 𝑇𝑖𝑛 )𝑑𝑡
𝜂𝐷𝑖𝑠𝑐ℎ𝑎𝑟𝑔𝑒 = =
𝐸𝑖𝑛𝑖𝑡𝑖𝑎𝑙 [(𝑉𝑓 + 𝑉𝑝 )(𝜌. 𝐶𝑝)𝑒𝑓𝑓 + 𝑉𝑤 (𝜌. 𝐶𝑝)𝑤𝑎𝑙𝑙 ](𝑇ℎ𝑖𝑔ℎ − 𝑇𝑙𝑜𝑤 )
Equation 7
Therefore, by plotting the efficiency of the discharge against the non-dimensional outlet temperature,
discharge has to stop when the out let temperature reaches the threshold discharge
temperatureFigure 8, it can be noted that Cofalit® has a better discharge efficiency than alumina, 80%
and 70% respectively.
Then overall efficiency of alumina can be obtained by multiplying charge by discharge efficiency, which
is about 56% compared to 64% for Cofalit®.
The discharge experiment started from completely charged thermocline which is not possible during
real case scenario, so taking into account a larger thermocline thickness in alumina this is expected to
lower the efficiency for discharge with respect to the calculated one, which will weigh more for Cofalit®
overall efficiency.
Although, thermal conductivity in Cofalit® is lower than alumina, it was found that Cofalit® is
performing better because of its lower diffusivity, which governs the thermocline thickness mainly,
according to Mira-Hernández et.al [29]: higher diffusivity leads to wider thermocline thickness.
Moreover, Cofalit® irregular shape and distributed particle sizes result in greater surface area for heat
exchange and thus a more efficient charge or discharge process.
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251
Figure 8 Alumina – Cofalit® Discharge efficiency evolution in time for mass flow rate 2950 [kg/h] ΔT 72ºC (290-218) ºC
5- CONCLUSIONS
Two materials were experimentally evaluated as solid filler in thermocline thermal energy storage for
concentrated solar power plant. The performance of asbestos contained waste material Cofalit®
compared to alumina as reference ceramic material with spherical shape. Although Cofalit® has lower
volumetric heat capacity of 2.7 [MJ/m³.K] compared to 3.3 [MJ/m³.K] for alumina, Cofalit® has fraction
of the cost with estimated price of 8 [€/ton] when alumina cost around 6670 [€/ton]. The charge
efficiency was very similar for both materials at 80%, thermocline thickness was thinner in Cofalit®
than alumina with 26%, 33%, respectively, while it took almost 20% more time to charge alumina than
Cofalit due to its bigger volumetric heat capacity.
During discharge, both solid filler have relatively similar thermocline thickness of 20%, unlike discharge
efficiency that reached 80% in Cofalit® and 70% in alumina, with overall estimated efficiency 64%,
56%. These results suggest that Cofalit® outperforms alumina ceramic at the temperature level of this
work 300 ºC, while small drawback of volumetric heat capacity can be compensated with the
competitive cost of supply for Cofalit®.
Thermal energy storage for concentrated power plant provides big opportunity to valorize asbestos
treated waste such Cofalit®. It is recommended to test this material for higher temperature range such
as 600 ºC- 800ºC to enable wider applications, consequently benefiting both reducing the impact of
waste material on the environment, and allow wider penetration for CSP as potential renewable
energy.
Acknowledgements
This work was supported by French “Investments for the future” program managed by the National
Agency for Research under contract ANR-10-LABX-22-01 (labex SOLSTICE).
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POTATO PEELS WASTE AS FEEDSTOCK FOR BIOETHANOL PRODUCTION:

A COMPARISON OF CHEMICAL, THERMAL AND ENZYMATIC PRETREATMENT
I. BEN ATITALLAH 1,4, G. ANTONOPOULOU 2,*, I. NTAIKOU 2, M. ALEXANDROPOULOU 2,3, M. NASRI 1, T.

MECHICHI 4, G. LYBERATOS 2,3
1 Laboratory of Enzyme Engineering and Microbiology, National School of Engineers of Sfax,
University of Sfax, BP 1173, 3038 Sfax, Tunisia.

2 Institute of Chemical Engineering Sciences, Stadiou, Platani, Patras, GR 26504, Greece.
3 School of Chemical Engineering, National Technical University of Athens, GR 15780 Athens, Greece
4 Laboratory of Biochemestry and Enzyme Engineering of Lipases, National School of Engineers of
Sfax, University of Sfax, BP 1173, 3038 Sfax, Tunisia.
Keywords: potato peels waste, enzymatic saccharification, chemical and thermal pretreatment,
bioethanol, W. anomalus
Abstract
The present study focuses on the exploration of the potential use of potato peels waste (PPW) as
feedstock for bioethanol production. The saccharification of PPW was performed via thermal and
chemical pretreatment, as well as enzymatic hydrolysis. Thermal pretreatment was conducted for 1
h at 121°C or 24 h at 80°C, while chemical pretreatment was performed through the addition of
H2SO4 and NaOH (0.1 % w/v) at 121°C for 1 h and 80°C for 24 h, respectively. Enzymatic
saccharification was performed using mixtures of a commercial cellulase together with either
commercial amylase or the amylase produced from a Bacillus sp. at the corresponding optimal
conditions. In order to improve PPW hydrolysis and increase the saccharification efficiency,
combinations of the different pretreatment/hydrolysis schemes were studied. Batch experiments
with raw, pretreated and hydrolyzed PPW were conducted, under suspended growth fermentation,
using the newly isolated yeast Wickerhamomyces anomalus strain either through simultaneous
saccharification and fermentation (SSF) or separate hydrolysis and fermentation (SHF). The results
showed that PPW is a very promising feedstock for ethanol production by W. anomalus, leading to
very high yields, close to the maximum theoretical ones.
254
1. INTRODUCTION
Biofuels are gaining an increasing interest as a substitute for petroleum-based fuels. Currently,
bioenergy is regarded as one of the key renewable energy that could be produced from renewable
materials [1]. Among different biofuels, bioethanol has been most widely used during the past
decades as alternative fuel for reducing CO2 emissions, whereas it can also be used in the
automobile sector [2]. Different types of renewable feedstocks, mainly carbohydrate-based, have
been proposed as substrates for ethanol production, including lignocellulosic biomass and
agricultural residues and industrial by-products.
Nowadays, potato is considered as one of the major vegetable crops all over the world. Potato
consumption patterns are gradually changing from fresh to processed formulation (e.g. chips and
french fries). During processing, important fractions of the raw product (20-50 %) are discharged as
wastes especially as peels i.e. potato peels waste (PPW), with its disposal being an environmental
concern for the potato industry sector [3]. The exploitation of PPW towards useful bio-products or
bioenergy such as bioethanol could be a promising alternative, since PPW contains large quantities
of starch and cellulose which are the target molecules during the implicated bio-fermentative
processes.
The conventional methods used to convert starch and cellulose into fermentable sugars include
chemical or enzymatic methods [4, 2]. In this work, various pretreatment methods such as thermal,
chemical (through alkali or acid addition) and enzymatic were applied on PPW in a comparative way,
and the effect of each method on carbohydrates’ fractionation and the structural features of the
substrate, were assessed. The pretreated and enzymatic hydrolyzed PPW were then used for the
first time for bioethanol production, using the newly isolated yeast W. anomalus strain, via the SSF
and the SHF concepts.

2.1. PPW preparation
The PPW used was obtained from local fast food restaurants located in Sfax, Tunisia. Prior to use, the
PPW was initially washed with water to remove undesirable particles and dried at 40 °C for 48 h.
Then, it was chopped with a lab grinder, sieved to obtain particles with a particle size < 1 mm and
the obtained powder was air-dried.
2.2. Chemical and thermal pretreatment conditions

For all pretreatment methods used, the mass/volume ratio of solid (g TS) to aquatic solution (mL)
was 5:100 (solids load 5 % w/v). Acid and alkaline pretreatments were performed through the
addition of H2SO4 and NaOH (0.1 %, w/v) at 121 °C for 1 h and 80 °C for 24 h respectively, while
thermal pretreatment was conducted for 1 h at 121 °C and 80 °C for 24 h without any chemical
addition. All pretreatment experiments were performed in duplicate. Depending on the process
scheme which was followed, either the whole pretreatment slurry or the two fractions obtained
after separation through filtering with 0.7 μm (liquid and solid fractions (solid PPW or SPPW)
obtained after pretreatment), were used for ethanol production.
255
2.3. Enzymatic hydrolysis

2.3.1 Production of a- amylase from Bacilus subtilis
The bacterium B. subtilis was recently isolated from desert soils in southern Tunisia and maintained
at 4 °C on Luria-Bertani (LB) agar slants containing (in g/L): peptone, 10.0; yeast extract, 5.0; NaCl,
5.0 and agar, 18. Amylase production cultures were conducted at 37◦C for 24 h in 250 mL flasks
containing 50 mL of optimized culture medium with the following composition (in g/L): bran, 30.0;
peptone, 2.0; K2HPO4, 0.5; KH2PO4, 0.5; CaCl2, 2.0; NaCl, 0.5. The pH was adjusted to 8.0 prior to
sterilization. The media were autoclaved at 120 °C for 20 min. The culture were centrifuged at 8000
rpm for 15min at 4oC and the supernatants were used for a-amylase activity determination.
2.3.2 Enzymatic hydrolysis of PPW

The hydrolysis was performed in 100 mL Erlenmeyer flasks, using a working volume of 20 mL. Dried
PPW at a solids loading of 5 % w/v was used and treated with a) commercial cellulase (CEL) (Cellic
CTec2-CEL) at pH=4.8, 50oC, 100 FPU/g cellulose, b) commercial a-amylase (C.A.) (from Aspergillus
oryzae) at pH=4.8, 50oC, 100 FAU/g starch and c) a- amylase from B. subtilis (B.A.) at pH=7, 30oC, 100
FAU /g starch, or combination of the cellulotytic and amylolytic enzymes at different conditions such
a) CEL. and C.A. at 100 FPU/g cellulose and 100 FAU/g starch respectively, at pH=4.8, either at 30oC
or 50oC and b) C.A and B.A. at the same conditions. Additionally, a two-step enzymatic hydrolysis
was performed at the optimum conditions for each enzyme, i.e. PPW was initially treated with B.A.
for 24 h (pH=7, 30oC) and then with CEL. (pH= 4.8, 50oC) for another 24 h. To avoid microbial
contaminations, all the experiments were supplemented with 2 % of sodium azide. The samples
were centrifuged and analyzed for the reducing sugars content.
2.4. Fermentation experiments

2.4.1 Preculture preparation
For all experiments the newly isolated yeast W. anomalus was used [5]. One loopful of a single
colony of the yeast was transferred from the agar plate into 50 mL of sterile yeast peptone dextrose
medium (YPD) containing (in g/L): glucose, 20; yeast extract, 10 and peptone, 10. The inoculum was
cultivated overnight in a 250 mL Erlenmeyer flask in a rotator shaker (150 rpm) at 30 °C.
2.4.2 Bioethanol experiments

Bioethanol production experiments using raw, chemical pretreated PPW and SPPW at a solids
loading of 5 % w/v were performed under simultaneous saccharification and fermentation (SSF) or
separate hydrolysis and fermentation (SHF), using the enzymatic mixtures of CEL. and C.A. at pH=4.8,
either at 30oC(SSF) or at 50oC for 24 h(SHF). Τhe liquid fractions obtained after chemical pre-
treatment as well as the chemically pretreated PPW (the whole slurry) were also used for ethanol
production without addition of enzymes. Furthermore, different enzymatic schemes were used for
ethanol production including a) C.A. (pH=4.8, at 50oC) for 24 h and then addition of CEL. at SSF, b)
C.A. and CEL. (pH=4.8, at 50oC) for 24 h and then ethanol production at SHF, c) B.A. (pH=7, at 30oC)
for 24 h and then addition of CEL. at SSF and d) B.A. (pH=7, at 30oC) for 24 h, addition of CEL.
(pH=4.8, at 50oC) for 24 h and then ethanol production at SHF. In all experiments the amylolytic and
256
cellulotytic enzyme loadings were 100 FAU/g starch and 100 FPU/g cellulose, respectively.
Fermentation experiments were carried out in duplicate in 160 mL serum vials with a working
volume of 25 mL and incubated at 150 rpm and 30 °C, in batch mode. The vials were sealed with
rubber stoppers and equipped with 0.22 μm filters for CO2 venting and sterilization. In all
experiments, cells were harvested from pre-culture of the W. anomalus strain (5 %v/v) by
centrifugation at 6000 rpm for 10 min, which was suspended in mineral solution containing KH2PO4,
MgCl2. 6H2O and (NH4)2SO4 each at concentrations of 1 g/L. The initial pH was set to 5.0, by using
NaOH or HCl solution (6 N). For substrate and products analyses, samples were withdrawn at regular
time intervals from the fermentation cultures and were centrifuged at 6000 rpm for 10 min. The
resulting supernatant was used for measurement of ethanol and residual sugars concentrations.
2.5. Analytical methods

Total solids (TS) and volatile solids (VS) were determined according to Standard Methods [6]. Starch
analysis was performed according to the total starch assay procedure (amyloglucosidase/ α-amylase
method, Megazyme AOAC Method 996.11, AACC Method 76.13). The chemical composition of the
raw and pretreated PPW (cellulose, hemicellulose and lignin) was determined by the analytical
methods of the National Renewable Εnergy Laboratory [7]. Detection and quantification of ethanol,
furfural, and hydroxyl-methyl-furfural (HMF) were performed with an HPLC-RI equipped with an
Aminex HPХ-87H column (Biorad) at 60 °C and a Cation H micro-guard cartridge (Biorad) using H2SO4
0.004 N as an eluent at a flow rate of 0.7 mL/min. Soluble carbohydrates content determination was
performed through the phenol-sulfuric acid method described by DuBois et al. [8], while reducing
sugars concentration was estimated by the DNS (3,5-dinitrosalicylic acid) method and was expressed
as glucose equivalents [9].
The surface morphology and characteristics of the raw and pretreated PPW samples were studied
using SEM. SEM micrographs were captured using a Zeiss SUPRA 35VP, after coating the samples
with a homogeneous Au layer by ion sputtering.

3.1. Chemical composition of raw and pretreated PPW
The composition of PPW used in the present study was: TS (%) =84.4 ± 0.10, VS (g/100 gTS)= 90.4 ±
0.20, cellulose (g/100 gTS)= 34.3 ± 0.60, hemicellulose (g/100 gTS)= 5.90 ± 1.90, lignin (g/100 gTS)=
4.30 ± 0.13, starch (g/100 gTS)= 44.8 ± 0.70, extractives (g/100 gTS)= 40.3 ± 1.90 (g/100 gTS),
proteins: 9.00 ± 0.01 (g/100 gTS), ash (g/100 gTS): 11.0 ± 0.10. Comparable compositional analysis
has been reported by other studies [10-11]. Table 1 summarizes the effect of chemical and
enzymatic pretreatment on the fractionation of biomass in terms of lignin, cellulose, hemicellulose
and starch. The values are expressed per kg of initial PPW TS, meaning that the material recovery
due to the loss of weight during pretreatment/hydrolysis has been taken into account (table 1).
257
Table 1: Changes of PPW composition (g/100 gTS initial) after pretreatment approaches applied in this study (commercial amylase = C.A.,
a-amylase from B. subtilis=B.A, cellulase= CEL.)
Pretreatment, Conditions Cellulose Hemicellulose Lignin Starch Material

hydrolysis recovery
o
Thermal 80 C, 24 h 35.5 ± 0.4 2.0 ± 0.0 1.9 ± 0.1 29. 9± 0.1 60.5 ± 0.4
o
Thermal 120 C, 1 h 27.7 ± 0.8 2.0 ± 0.1 4.0 ± 0.2 28.1± 0.2 56.3 ± 0.6
H2SO4 0.1 % w/v 10.6 ± 0.4 0.8 ± 0.0 4.6 ± 0.1 4.0± 0.1 29.9 ± 2.1
NaOH 0.1 % w/v 14.4 ±0.3 1.1 ± 0.1 2.2 ± 0.0 11.5± 0.2 34.9 ± 0.6
o
C.A. +CEL 50 C for 24 h, 8.2 ± 0.8 1.2 ± 0.0 3.6 ± 0.0 3.0 ± 0.0 32.6 ± 0.0
pH=4.8
o
B.A +CEL 30 C, pH=7, for 24h, 14.5 ± 0.1 0.8 ± 0.0 3.1 ± 0.5 8.2 ± 0.0 46.2 ±0.2
o
50 C pH=4.8, 24 h
The loss of biomass increased with pretreatment severity. For example, the percentage material
recovery (gTS pretreated biomass/g TS initial biomass) after thermal treatment was 56.3%, while after
treatment with H2SO4 it was 28.9%. As anticipated, chemical and enzymatic pretreatment resulted in
higher reduction of carbohydrate's fraction compared with the thermal treatment, while alkaline
pretreatment led to partial lignin removal. Thus, pre-treatment with H2SO4 caused a reduction of
cellulose and starch to 10.6 ± 0.4 g/100 gTS and 4.0 ± 0.1 g/100 gTS, respectively, while pretreatment
with NaOH led to a cellulose of 14.4 ± 0.3 g/100 gTS and a starch content of 11.5 ± 0.2 g/100 gTS.
Regarding the cellulotytic and amylolytic enzyme mixtures, the use of commercial a-amylase was
more effective on the reduction of starch content, compared to the a-amylase from B. subtilis.
After all pretreatment/hydrolysis methods, the soluble and reducing sugars were measured and are
presented in table 2. It is obvious that the enzymatic hydrolysis released the highest fermentable
sugars concentration.
Table 2: Analysis of liquid fraction of PPW after pretreatment/hydrolysis (in g/ 100 gTS initial) (commercial amylase = C.A., a-amylase B.
subtilis=B.A, cellulase= CEL.)
Pretreatment, Conditions Sugars Reducing sugars HMF
hydrolysis (g/ 100 gTS initial) (g/ 100 gTS initial) (mg/ 100 gTS initial)
o
Thermal 80 C, 24 h 3.6 ± 0.1 1.8 ± 0.0 4.0 ± 0.0
o
Thermal 120 C, 1 h 41.3 ± 0.3 4.2 ± 0.0 12.0 ± 0.5
H2SO4 0.1 % w/v 53.3 ± 0.9 6.1 ± 0.1 82.0 ± 0.2
NaOH 0.1 % w/v 43.2± 0.1 4.8 ± 0.0 10.0 ± 0.4
o
C.A. +CEL 50 C for 24 h, pH=4.8 98.4 ± 0.0 58.8 ± 0.0 n.d
o o
B.A. +CEL 30 C, pH=7, for 24h, 50 C 67.4± 0.1 21.2 ± 0.1 n.d
pH=4.8, 24 h
n.d.= non detected
Fig. 1 shows SEM images (morphological and structural surfaces) of PPW samples subjected to
different pretreatment methods. The untreated PPW sample showed an even regular and smooth
surface which indicates that the surface is rigid and covered by starch (fig.1a). As shown in fig. 1b, a
fragile and broken surface with complete removal of starch could be observed after acid
pretreatment of PPW. In addition, due to the enzymatic pretreatment, the surface structure of PPW
was strongly modified and disrupted, leading to the formation of pores in the wall surfaces (fig. 1
f,g). This was more evident after the hydrolysis with commercial enzymes, which led to higher starch
and cellulose removal and higher saccharification efficiency.
258
a b c
d e f g
e
Figure 1: SEM images of (a) untreated PPW; (b) acid; (c) alkali; (d) thermal (120 °C; 1h); (e) thermal (80 °C; 24h); (f) enzymatically (CEL
+C.A); (G) enzymatically (CEL +B.A.) pretreated PPW, respectively
3.2.Enzymatic hydrolysis of PPW

In fig. 2, the effect of enzymatic hydrolysis using the amylolytic and cellulolytic enzymes separately
(fig.2a) or mixtures of them (fig.2b), on reducing sugars content, is depicted. It is obvious that the
use of commercial amylase led to higher reducing sugars concentration (45.8 g/100 gTS), compared
to the amylase produced from B. subtilis (19 g/100 gTS) (Fig.2a). In the case of the enzymatic
mixtures (fig. 2b), the use of commercial enzymes also led to more promising results, with the
operational conditions playing a crucial role on the enzymatic hydrolysis efficiency. Thus, at the
optimum conditions for the commercial enzymes (pH =4.8 and 50oC), the reducing sugars
concentration after 48 h of fermentation was 71.2 g/100 gTS, while at 30oC (which is the
temperature of the fermentation during ethanol producing experiments) it was 64.1 g/100 gTS.
Similarly, a higher temperature enhanced the efficiency of the mixture of CEL with B.A. (40.8 g/100
gTS at 50oC and 33.4 g/100 gTS at 30oC).
50 90
45 CEL 80 CEL+C.A. (50oC)
Reducing sugars (g/100 gTS)
B.A. CEL+C.A. (30oC)

40 C.A.
a 70
b
CEL+B.A. (50oC)
35 CEL+B.A. (30oC)
60
30
50
25
40
20
15 30
10 20
5 10
0 0
0 5 10 15 20 25 30 0 5 10 15 20 25 30 35 40 45 50
time, h time, h
90
80
70 c
60
50
40
30
20
10
0
0 5 10 15 20 25 30 35 40 45 50
time, h
Figure 2: Reducing sugars content during enzymatic hydrolysis of PPW using a) cellulose (CEL); amylase from B. subtilis (B.A) and
commercial amylase (C.A) at the optimum conditions for each enzyme, b) CEL. and C.A. at 50 °C; CEL. and C.A. at 30 °C; CEL. and B.A. at
50 °C; CEL. and B.A. at 30 °C and c) the two step enzymatic hydrolysis at the optimum conditions for each enzyme (B.A, pH=7 at 30 °C;.
for 24 h and CEL. pH=4.8 at 50 °C for extra 24 h).
259
From fig.2 c where the reducing sugars concentration from the two-step enzymatic hydrolysis are
presented, it is obvious that the separation of both hydrolytic steps, using B.A. and CEL. at the
optimum conditions of each enzyme enhanced the saccharification from PPW (57.3 g/100 gTS)
3.3. Bioethanol production

In the present study, either the whole slurry obtained after different pretreatment / hydrolysis
schemes or the separate fractions after chemical and thermal pretreatment methods applied to
PPW, were used for ethanol production using W. anomalus. In fig. 3a, the ethanol concentration of
raw, chemically and thermally pretreated PPW without addition of enzymes, is presented, while in
fig.3b and 3c it can be seen the effect of pretreatment on ethanol production at SSF (addition of CEL
and C.A. at pH=4.8 at 30oC) and SHF (addition of CEL and C.A. at pH=4.8 at 50oC for 24 h) mode,
respectively. In all cases, acid pretreatment enhanced ethanol production, due to the higher
solubilisation leading to higher sugars concentration. In addition, the concentration of the HMF
produced during acid pretreatment was low compared with those reported in the literature to cause
yeast inhibition [12-13]. Separation of hydrolysis from the fermentation step (SHF) enhanced ethanol
production from the whole pretreatment slurry of PPW, with the acid pretreated PPW showing the
highest concentration of 21.17 ± 0.77 g/L (16.60 ± 0.21 g/L the respective concentration at SSF). This
can be attributed to the optimum conditions which were applied in both separate processes.
10
raw PPW
9 H2SO4
8 NaOH a
thermal (1h at 120oC)
7
Ethanol (g/L)

6
5
4
3
2
1
0
0 10 20 30 40 50
time, h
20 30
25
15
b c
20
Ethanol (g/L)
Ethanol (g/L)
10 15
H2SO4 (SSF) H2SO4 (SHF)
NaOH (SSF) NaOH (SHF)
thermal (1h at 120oC), (SSF) 10 thermal (1h at 120oC), (SHF)
5 thermal (24h at 80oC), (SSF) thermal (24h at 80oC), (SHF)
5
0 0
0 10 20 30 40 50 0 10 20 30 40 50
time, h time, h
Figure 3: Ethanol production from raw and pretreated PPW a) without enzymes addition, b) at SSF (CEL. and C.A. at 30 °C) and c) at SHF
(CEL. and C.A. at 50 °C for 24 h, prior to fermentation).
From fig. 4, where ethanol production from the separate fractions obtained after pretreatment is
presented, it can be seen that W. anomalus demonstrated higher ethanol production efficiency
when using SPPW at SHF concept than at the SSF, at all pretreatment methods used. Acid pretreated
260
SPPW showed the highest ethanol concentration of 17.27 ± 0.01 g/L (12.94 ± 0.04 g/L the respective
concentration at SSF). From fig. 5, where the effect of enzymatic pretreatment on ethanol
production is presented, it is obvious that except for the saccharification efficiency, C.A. led also to
higher ethanol concentration and yield compared to B.A, when contained in enzymatic mixtures with
CEL. In addition, similarly to the case of chemical and thermally pretreated samples, separation of
the hydrolysis from the fermentation step led to higher ethanol concentration and yields, when
enzymatically treated PPW were used as substrates.
In tables 3 and 4, the ethanol production yields in terms of g /100 gTS initial and g/g consumed sugars, of all
experiments are summarized. From table 3, it is obvious that for all thermal and chemically
pretreated PPW, the whole slurry fermentation led to higher ethanol yields, under the conditions
tested. Acid pre-treatment led to 44.9 ± 0.1 g ethanol/ 100 gTS, which was comparable with the yield
of alkali or thermally treated PPW at SHF (41.9 g ethanol/ 100 gTS).
10
H2SO4 Liquid fractions
9
NaOH
8 thermal (1h at 120oC)
Ethanol (g/L)
6
5
a
4
3
2
1
0
0 10 20 30 40 50
time, h
20 20
H2SO4
SPPW at SSF
NaOH SPPW at SHF
15
Ethanol (g/L)
Ethanol (g/L)
c
10 b 10
H2SO4
NaOH
5 5 thermal (24h at 80oC)
0 0
0 10 20 30 40 50 0 10 20 30 40 50
time, h time, h
Figure 4: Ethanol production from a) the liquid fraction obtained after pretreatment, b) the SPPW at SSF (CEL. and C.A. at 30 °C,
pH=4.8) and c) the SPPW at SHF (CEL. and C.A. at 50 °C for 24 h, prior to fermentation).
20
C.A and CEL. SSF
C.A and CEL. SHF
B.A and CEL. SSF
15 B.A and CEL. SHF
Ethanol (g/L)
10
0
0 10 20 30 40 50
time, h
o
Figure 5: Ethanol production from enzymatic treated PPW using C.A. (pH=4.8, at 50 C) for 24 h and then CEL. at SSF (C.A and CEL, SSF);
o o
CA. and CEL. (pH=4.8, at 50 C) for 24 h (C.A. and CEL, SHF); B.A. (pH=7, at 30 C) for 24 h and then CEL. at SSF (B.A. and CEL. at SSF) and
o o
B.A. (pH=7, at 30 C) for 24 h and CEL. (pH=4.8, at 50 C) for 24 h and then ethanol production at SHF.
261
Similar yields were also observed for enzymatically treated PPW, using commercial enzymes for 24 h
at pH=4.8 and 50oC, indicating that maximum exploitation of carbohydrates was achieved towards
ethanol production. The latter was also confirmed by the values presented in table 4, where it can be
seen that W. anomalus led to very high ethanol yields, given though that the maximum theoretical
ethanol yield is 0.511 g/g consumed sugars. In the case of enzymatic treatment with commercial enzymes,
ethanol production yield was 0.49, corresponding to 96% of the maximum theoretical. These yields
are comparable with those from other studies where ethanol production with Saccharomyces
cerevisae from enzymatically treated PPW was reported [14]. In the case of separation of both
fractions, the ethanol yield from the pretreated SPPW (expressed as g/ 100 gTSinitial) was low, due to
the high solubilization (low material recovery) which was observed during pretreatment, especially
with chemicals. Furthermore, the liquid fractions obtained after pretreatment, despite the fact that
they contained high sugars concentration led to low ethanol yields.
Table 3: Ethanol yields (g/100 gTS initial) of all pretreatment/hydrolysis yields used in the present study (commercial amylase = C.A., a-
amylase B. subtilis=B.A, cellulase= CEL.)
Whole slurry Separate fraction
No enzymes enzymes liquid solid
SSF SHF SSF SHF
o
Thermal (80 C) 10.9 ± 0.1 27.9 ± 0.5 37.4 ± 0.1 8.6 ± 0.0 10.0 ± 0.1 14.1 ± 0.3
o
Thermal(120 C) 12.8 ± 0.0 28.9 ± 1.1 41.9 ± 0.1 11.6 ± 0.0 10.1 ± 0.1 14.5 ± 0.2
H2SO4 19.4 ± 0.1 34.9 ± 0.5 44.9 ± 0.1 10.2 ± 0.0 8.2 ± 0.0 10.9 ± 0.0
NaOH 15.4 ± 0.1 33.4 ± 0.8 41.9 ± 0.2 12.6 ± 0.1 8.9 ± 0.0 11.5 ± 0.1
C.A. +CEL - 30.2 ± 0.5 40.1 ± 0.2 - - -
B.A +CEL - 19.6 ± 0.0 25.5 ± 0.3 - - -
Table 4: Ethanol yields (g/g consumed sugars) of all pretreatment/hydrolysis yields used in the present study (commercial amylase = C.A., a-
amylase B. subtilis=B.A, cellulase= CEL.)
Whole slurry Separate fraction
No enzymes enzymes liquid solid
SSF SHF SSF SHF
o
Thermal (80 C) 0.19 ± 0.0 0.36 ± 0.0 0.35 ± 0.0 0.20 ± 0.0 0.29 ± 0.0 0.30 ± 0.0
o
Thermal(120 C) 0.20 ± 0.0 0.35 ± 0.0 0.36 ± 0.0 0.24 ± 0.0 0.33 ± 0.0 0.31 ± 0.0
H2SO4 0.24 ± 0.0 0.41 ± 0.0 0.44 ± 0.0 0.20 ± 0.0 0.40 ± 0.0 0.40 ± 0.0
NaOH 0.22 ± 0.0 0.37 ± 0.0 0.37 ± 0.0 0.23 ± 0.0 0.37 ± 0.0 0.39 ± 0.0
C.A. +CEL - 0.49 ± 0.0 0.47 ± 0.0 - - -
B.A +CEL - 0.30 ± 0.0 0.40 ± 0.0 - - -
4- CONCLUSIONS
The present study demonstrated that PPW is an attractive agricultural waste to produce bioethanol.
The high starch content of potato peels serves as a great feedstock for fermentable sugars
production, providing raw material for bioethanol production. Results showed that the combination
of acid treatment and enzymatic hydrolysis at SHF or the enzymatic pretreatment alone, led to the
highest ethanol production yield from PPW, corresponding to 90-96 % of the maximum theoretical,
using the newly isolated yeast W. anomalus.
262
Acknowledgements: The authors acknowledge support of this work by the project “Research infrastructure for Waste Valorization
and Sustainable Management of Resources, INVALOR” (MIS 5002495) which is implemented under the “Action for the Strategic
Development on the Research and Technological Sector”, funded by the Operational Programme "Competitiveness, Entrepreneurship
and Innovation" (NSRF 2014-2020) and co-financed by Greece and the European Union (European Regional Development Fund).
Dr. Georgia Antonopoulou acknowledges the financial support of the Stavros Niarchos Foundation within the framework of the project
ARCHERS (“Advancing Young Researchers’ Human Capital in Cutting Edge Technologies in the Preservation of Cultural Heritage and the
Tackling of Societal Challenges”).
REFERENCES
[1] Aditiya, H.B., Chong, W.T., Mahlia, T.M.I., Sebayang, A.H., Berawi, M.A., Nur, H.: Second generation bioethanol
potential from selected Malaysia’s biodiversity biomasses: A review. Waste Management. (DOI: 10.1016/j.wasman.
2015.07.031) (2015).
[2] Ntaikou, I., Menis, N., Alexandropoulou, M., Antonopoulou, G., Lyberatos, G.: Valorization of kitchen biowaste for
ethanol production via simultaneous saccharification and fermentation using co-cultures of the yeasts
Saccharomyces cerevisiae and Pichia stipitis. Bioresour.Technol. 263, 75-83 (2018)
[3] Rezig, M., Sahli, A., Jeddi, F.B., Harbaoui, Y.: Adopting intercropping system for potatoes as practice ondrought
mitigation under Tunisian conditions. Opt.Mediterr. A 95, 329 – 334 (2010).
[4] Vavouraki, A.I., Volioti, V., Kornaros, M.E.: Optimization of thermo-chemical pretreatment and enzymatic hydrolysis
of kitchen wastes. Waste Management. 34, 167–173 (2014)
[5] Atitallah, I.B., Ntaikou, I., Antonopoulou, G., Alexandropoulou, M., Lyberatos, G., Narsi, M., Mechichi, T.: Exploitation
of Tunisian date palm sap as a promising carbon source for bioethanol production by a newly isolated yeast strain.
Proceedings in 5th International Conference on Engineering for Waste and Biomass Valorisation.
[6] APHA, AWWA, WPCF: Standard Methods for the examination of water and wastewater. M.A. Franson, (Eds)
Washington, DC: American Public Health Association (1995).
[7] National Renewable Energy Laboratory (NREL). Chemical Analysis and Testing Laboratory Analytical Procedures: LAP-
002 (1996), LAP-010 (1994) and LAP 017. NREL, Golden, CO, USA (1998).
[8] Dubois, M., Gilles, K.A., Hamilton, J.K., Rebers, P.A., Smith, F.: Colorimetric method for determination of sugar and
related substances. Anal. Chem. 28, 350–356 (1956).
[9] Miller, G.L..: Use of dinitrosalicylique acid reagent for determination of reducing sugar. Anal. Chem. 31, 426 - 428
(1959).
[10] Ben Taher, I., Fickers, P., Chniti, S., Hassouna, M.: Optimization of enzymatic hydrolysis and fermentation conditions
for improved bioerthanol production from potato peel residues. Biotechnology Progress (2016).
[11] Ben Jeddou, K., Maktouf, S., Ghazala I., Donyes, F., Ghribi, D., Ellouz-Ghorbel, R., Nouri-Ellouz, O.: Potato peel as
feedstock for bioethanol production: A comparison of acidic and enzymatic hydrolysis. Industrial Crops and Products.
52, 144 – 149 (2014)
[12] Delgenes, J.P. , Moletta, R., Navarro, J.M.: Effects of lignocellulose degradation products on ethanol fermentations of
glucose and xylose by Saccharomyces cerevisiae, Zymomonas mobilis, Pichia stipitis, and Candida shehatae, Enzym.
Microb. Technol. 19 ,220–225 (1996)
[13] Antonopoulou, G., Vayenas, D., Lyberatos, G.: Ethanol and hydrogen production from sunflower straw: The effect of
pretreatment on the whole slurry fermentation. Biochem. Eng. J. 116, 65-74 (2016)
[14] Arapoglou, D., Varzakas, Th., Vlyssides, A., Israilides, C.: Ethanol production from potato peel waste (PPW) Waste
Management 30, 1898–1902 (2010)
263
BIOMETHANATION OF SYNGAS BY MIXED MICROBIAL CONSORTIA IN A TRICKLE BED

REACTOR
K. ASIMAKOPOULOS1, H.N. GAVALA2, I.V. SKIADAS1

1 Pilot Plant, Department of Chemical and Biochemical Engineering, DTU, Lyngby, Denmark.
2 BIOENG, Department of Chemical and Biochemical Engineering, DTU, Lyngby, Denmark.
Abstract
Syngas is a mixture of gases consisting mainly of CO, CO2 and H2. It may be produced from the
gasification of lignocellulosic biomass and can be used as a substrate in biosynthetic fermentation.
The major bottlenecks of syngas fermentation are the expensive biocatalysts with low growth rates
and the gas/liquid mass transfer phenomena [1]. In order to surpass them we designed a trickle-bed
bioreactor configuration working with enriched anaerobic sludge that can upgrade the syngas
compounds to methane, a valuable fuel for energy production.
The main component of the bioreactor setup is the trickling column where the microbes form biofilm
on the packed bed (135 mL) enhancing the substrate conversion. The operation is in co-current
mode with the gas and the liquid entering from the top of the column and exiting from the bottom.
A liquid reservoir is also used for the recirculation of the liquid phase so that the biofilm is kept wet
and the necessary medium elements are provided. A schematic of the setup can be observed in
figure 1.
Figure 1: Schematic of the bioreactor setup (blue lines – liquid flow, green lines – gas flow and orange line – mixed gas/liquid flow)
The maximum methane productivity achieved with the aforementioned setup expressed per volume
of packed bed is 1.7 mmol/l/h with the liquid recirculation flow rate at 200 ml/min, the HRT
(hydraulic retention time) at 25 d and the EBRT (empty bed residence time) for gasses at 2.25 h. The
substrate yield to methane measured in terms of electron equivalents is 80% of the theoretical one
with acetate being the main byproduct. These results are promising for a scaled up design, however
further optimization of the operational parameters needs to be done. A strategy to avoid channelling
phenomena in the bed so as to achieve uniform biofilm formation is also necessary.
References
[1] Acharya, B., Roy, P., and Dutta, A: Review of syngas fermentation processes for bioethanol. Adv. Biochem. Eng. Biot
5, 551 – 564 (2015)
264
VALORIZATION OF BEER PRODUCTION WASTES:

BIOHYDROGEN PRODUCTION BY DARK FERMENTATION
M. RENAUDIE1,2, C. DUMAS1, B. ERNST1

Z. AAAAA1, Y. BBBBB2, X.W. CCCCC1,2, V. DDDDD1
1 Université de Strasbourg, CNRS, IPHC UMR 7178, Laboratoire de Reconnaissance et Procédés de
Séparation Moléculaire (RePSeM), Strasbourg, France.
2 ADEME, French Environment and Energy Management Agency, Angers, France.
Abstract
France is the 6th beer producer in Europe: 20 million hectoliters per year were produced in 2015 [1],
generating different organic wastes. In this study, beer-production wastes issued from local maltery
and breweries were tested for biohydrogen (bioH2) production by dark fermentation (figure 1). A
process of in situ H2 production by an endogenous fermentation of beer-producing industry wastes
has been developed without any additional energetic consumption. Experiments were carried out to
evaluate the bioH2 production and productivity using a 0.7 L working volume semi-batch reactor at
37°C under anaerobic conditions. Online gas production was analyzed by GC-TCD. The best results
obtained are shown in table 1.
Spent grain showed higher bioH2 productions (84.2 LH2.kg-1TS), productivities (4.2 mmol.L-1.h-1) and
molar ratio H2/CO2 (0.9). Our results with endogenous spent grain microflora are 3 times higher with
those obtained previously in literature by dark fermentation with selected microflorae (25.3 LH2.kg-
1
TS) [3]. Malt sprouts, diatomaceous earth spent cake and yeasts were tested for the first time for
bioH2 production and showed good productions and productivities for malt sprouts and spent yeasts
compared with diatomaceous earth spent cake containing less organic matter. Metabolic pathways,
analyzed though HPLC-UV and GC-FID detected metabolites (organic acids and alcohols), and
bacterial consortia composition, analyzed by 16S DNA sequencing, differ and are correlated to the
biomass tested. This study demonstrates for the first time high bioH2 production from untreated
wastes issued from the malting/brewing processes as the sole source of substrate and microbial
inocula.
Table 1: Hydrogen production performances for
different wastes from beer production industry
Total SolidsProduction Productivity Molar ratio
Biomass
(TS) (%) (LH2.kg-1TS) (mmolH2.L-1.h-1) H2/CO2
Malt sprouts 15.5 20.1 ± 4.4 3.9. ± 2.1 0.3 ± 0.2
Spent grain** 26.6 84.2 4,2 0,9
Spent yeasts 13.2 8.8 ± 1.0 3.6 ± 0.0 0.6 ± 0.1
Diatomaceous earth
32.9 2.1 0.3 0.4
spent cake
Figure 1: Beer production process and wastes

** issued from microbrewery
generation (*biomasses tested for bioH2 production)
References
[1] The Brewers of Europe, 2016. Beer statistics, 2016 edition. The Brewers of Europe. November 2016: 6
[2] Mathias, T.F. et al, 2014. Solid wastes in brewing process. Journal and Brewing and Distilling. 2014, 5(1): 1-9
[3] Bando, Y. et al, 2013. A microbiological study of biohydrogen production from beer lees. International Journal of
Hydrogen Energy. 2013, 38: 2709-2718
265
OPTIMIZATION OF RICE HUSK PARTICLE SIZE ON BIO-HYDROGEN GAS PRODUCTION

USING CO-CULTURE
G.G. TAYLAN1, S. OZMIHCI1

1 Dokuz Eylul University, Environmental Engineering, Izmir, Turkey.
Abstract
The search for eco-friendly, economical, alternative energy sources has begun due to the inadequate
fossil fuels to meet the energy demand caused by industrial development worldwide and also the
negative effects of fossil fuels on environmental pollution. Bio-based energy is a sustainable and
promising alternative to fossil fuel-based energy. Fermentative hydrogen production from
lignocellulosic substrates is a novel and attractive technology because of its sustainability, cost-
effectiveness and eco-friendly nature. Bio-hydrogen production from organic wastes gains
importance, as it can remove organic biomass while simultaneously producing clean hydrogen
energy.
Rice-husk as a lignocellulosic agro-industrial waste can be utilized for bio-hydrogen production. In

this study different rice husk sizes (< 2000µm, <300 µm, <74 µm) were subjected to submerged
fermentation for bio-hydrogen production. Three different sizes of rice husk were tested for
different co-culture ratios (1:1, 2:1, 5.1, 10:1, 15:1, 20:1). In mesophilic, static conditions raw rice
husk with a co-culture ratio of 5:1 gave a good hydrogen production rate of 5.83 mLH 2/gr substrate
and a specific hydrogen production rate of 0.018 mLH2/ gr substrate h with a total 150mL
fermentation media.
266
EXPERIMENTAL INVESTIGATIONS ON AN OPEN TOP DOWNDRAFT GASIFIER

COUPLED WITH A DUAL FUEL COMPRESSION IGNITION ENGINE MICRO-
COGENERATION SYSTEM
C. CALIGIURI1, D. ANTOLINI1, F. PATUZZI1, M. RENZI1, M. BARATIERI1

1 Free University of Bolzano, Bolzano, Italy.
Abstract
The growing importance of alternative fuels for energy conversion purposes is constantly challenging
researchers and technicians on the technological implications of their utilization. Producer gas from
wood biomass represents one of the most promising alternative to traditional fossil fuels. Its
utilization in traditional engines is already solidly established through Spark Ignition (SI) internal
combustion engines; conversely, the coupling of such a gas together with a pilot fuel, i.e. diesel, to
realize a dual fuel compression ignition engine is still facing scientific investigations on both
modelling and experimental sides.
The main purpose of the proposed work is to investigate the feasibility of such a power generation
mode for the micro-cogeneration energy system in operation at the Bioenergy and Biofuels Lab of
the Free University of Bolzano (Italy). Here, an open-top downdraft gasifier coupled with a 4 kW
single-cylinder diesel engine has been optimized to generate heat and power. An initial assessment
of the energy system potentialities has been also carried out through modeling activities [1].
An experimental campaign aimed at monitoring the thermal and electrical power output has been
conducted. Combustion process has been optimized adjusting fuel injection time and providing a
proper air-gas mixing through the use of an internally designed carburetor. Producer gas
composition and flow rate as well as intake air flow rate and diesel consumption have been
monitored. Electrical power output is detected through the use of a power meter, while thermal
power obtained from the recovered heat has been indirectly quantified thanks to the cooling water
flow and temperatures measurements. Exhaust gas emissions have been also monitored.
Experimental tests have been carried out at different diesel substitution rates.
Results show the presence of a diesel substitution peak beyond which dual fuel combustion is not
feasible anymore. Electrical power output faces a 30% derating compared to the 100% diesel
combustion mode. A decrease in PM exhaust emissions has been quantified. High global efficiencies
are reached thanks to the cogeneration mode.
The experimental campaign shows that dual fuel producer gas combustion in a compression ignition
combustion engine represents a solid alternative to the use of spark ignition engines since it can lead
to lower power derating (power derating in a SI engine is quantified as 40 − 50%). Engine control
optimization could leads to relevant performance improvements; in-cylinder measurements would
help to understand dual fuel combustion process.
References
[1] C. Caligiuri, D. Antolini, F. Patuzzi, M. Renzi, M. Baratieri. Modelling of a small scale energy conversion system based
on an open top gasifier coupled with a dual fuel diesel engine. 25th European Biomass Conference and Exhibition,
June 2017.
[2] Pradhan A., Baredar P., Kumar; Syngas as An Alternative Fuel Used in Internal Combustion Engines: A Review, Journal
of Pure and Applied Science and Technology, Vol. 5(2), Jul 2015
267
EXPERIMENTAL STUDY OF SOLID RECOVERED FUEL FLUIDISED BED GASIFICATION
S. VALIN1, S. RAVEL1, PH. PONS DE VINVENT1, S. THIERY1, H. MILLER1

1 CEA, LITEN, Grenoble, France.
Abstract
The purpose of this work is to investigate the influence of process parameters (temperature,
equivalent ratio, …) on solid recovered fuel (SRF) gasification in a pilot fluidised bed, and more
precisely on conversion efficiency and on some pollutant content (tar and H2S/COS).
This study was performed in the frame of the French VaDeO project, which aims at investigating and
optimising preparation and gasification process for energy valorisation of high LHV (Lower Heating
Value) wastes. The project is coordinated by Leroux et Lotz Technologies, the two other partners being
Sibuet Environnement and CEA.
Gasification experiments were performed in an electrically-heated laboratory fluidised bed [1], at 1.5
bars, with SRF pellets as feedstock, as well as beech wood sawdust in one case for comparison. SRF
was prepared from industrial, bulky and furniture wastes. It mainly contains plastics, wood, paper,
cardboards, and textiles.
The feeding rate in the gasifier was about 2 kg/h. Bed material was olivine. Air mixed with N2, as well
as steam in one case, was used as the fluidizing gas. For each experiment, the dry gas, water, tar and
char yields were determined. Gas composition (Ar, O2, CO2, CO, CH4, N2, H2, C2H2, C2H4, C2H6,
C3H6/C3H8, C6H6 (benzene), C7H8 (toluene), C8H10 (xylene), H2S, COS, H2O vapor) was analysed online
using a µGC-TCD. Tar quantification and analysis were performed with tar protocol followed by GC-
MS and GC-FID analyses.
Gas production, carbon conversion rate into gas and cold gas efficiency (CGE) reach about 0.8
Nm3/kgdaf, 70% and 49% respectively in nominal case (850°C, ER=0.24). The dry product gas main
components are CO2 (38 vol%), CO (23 vol%), H2 (18 vol%), CH4 (12 vol%), C2H4 (5.5 vol%) and C6H6 (1.5
vol%). Sulphur measured in gaseous species (essentially H2S) is about 50% of the S input. As ER
increases at constant temperature, CO2 mainly increases as a consequence of a more extended
product oxidation. CGE is then reduced. When temperature increases to 900°C at constant ER, gas
production, carbon conversion rate into gas and CGE all increase – to 0.9 Nm3/kgdaf, 76% and 55%
respectively -, mainly in relation with H2 and CO yield increase. S volatilisation is then also enhanced,
with 71% of S in gas phase. Addition of steam in the fluidising gas (steam over dry SRF mass ratio of
0.5) at 850°C has a similar influence to temperature increase one, with even more S release in gas
phase. The condensable tar content lies between 35 and 50 g/kgdaf for all experiments, with
naphthalene and styrene as major compounds.
The dry gas HHV reaches about 6-7 MJ/Nm3 both for wood and SRF gasification. However, whatever
the experimental conditions investigated with SFR, the gasification efficiency is always significantly
lower than the one obtained with woody biomass in nominal conditions (gas production: 1.0
Nm3/kgdaf, carbon conversion rate into gas: 92% and CGE: 75%). The process parameters should now
be adapted so as to reach better conversion results of SRF.
References
[1] Valin, S., Bedel, L., Guillaudeau, J., Thiery, S., Ravel, S.: CO2 as a substitute of steam or inert transport gas in a fluidised
bed for biomass gasification. Fuel. 177, 288-295 (2016)
268
PERFORMANCE TESTS OF 8 TON/DAY GASIFICATION PROCESS TO GENERATE

ELECTRICITY FROM FLUFF TYPE SOLID REFUSE FUEL
Y.C. SEO1, S.W. PARK1, J.H. OH2, J.H. GU3, Y.S. PARK3
1 Yonsei university, Wonju-si, Republic of Korea
2 SamHo Enviro-Tech, Yongin-si, Republic of Korea
3 .Institute for Advanced Engineering, Yongin-si, .
Abstract
Municipal solid waste (MSW) contains significant amount of paper, food waste, wood and yard
trimmings, cotton, and leather, and considered as a source of renewable energy. Energy can be
recovered from MSW through gasification technology. For our study purpose, we conducted
gasification experiment in a pilot scale plant (8 ton/day) using solid refuse fuel (SRF) as feedstock.
Figure 1 shows whole SRF manufacturing and gasification system.
Figure 1. Whole scheamatic diagram of pilot-scale SRF manufacturing and gasification system
For stable operation of this gasification process, this process was controlled by various factors which
affected operating. These conditions were selected that charging rate of gasifier was 50 to 60 % and
ER was 0.17 to 0.36. Gasification process was operated during 63 hours and shows stable operation
trends about production of syngas and electricity. Average syngas composition (H2, CO, and HC) in
producer gas was about 20 % and heating value of syngas was 1,307 kcal/Nm3. Also, average power
generation by gas engine was 243 kW. MSW gasification shows good performances with stable
operation manner. Specially, in case of power production, even though this plant was pilot scale, gas
engine generator shows good performance using syngas from gasification system.
Acknowledgement
This work was supported by a grant from the Human Resources Development program of KETEP and
the Korea Ministry of Environment (MOE) as a "Waste-to-Energy Technology Development Project"
Reference
[1] Park, SW, Seo, YC, et al. Emission Characteristics of Gaseous Pollutants from Piot-Scale SRF Gasification Process,
Proceedings pf 6th IconSWM 2016, Kolkata, India, p72 (2016).
269
COMBUSTION STUDY OF A MASSIVE POLYETHYLENE HANGED IN AN OWEN
Q.BALME1, F.LEMONT1, P.CHARVIN1, F.MARIAS2

1 Laboratoire des Procédés Thermique Innovant, Commissariat à l'Energie Atomique, BP 17171, 30
207 Bagnols-sur-Cèze Cedex, France

2 .Laboratoire de Thermique, Energétique et Procédé, ENSGTI, Rue Jules Ferry, BP 7511, 64075 Pau,
France
Abstract
Polyethylene (PE) is a simple polymer and one of the most used type of plastic around the world.
Hence, the thermal decomposition of PE has been extensively studied from chemical point of view[1]
(pyrolysis and combustion products, mechanisms) and from kinetic point of view. However, only few
studies deal with the massive sample combustion. Yet, it is necessary to know the burning rate of
this type of sample, especially, in order to do an estimation of the gas flow production. Many
physical phenomena should be taken into consideration for several tens grams of PE sample
combustion. In the plastic phase: heat and mass transfer, melting, pyrolysis, and in the gas phase:
combustion and heat transfer (radiative). Furthermore, there are an important coupling between gas
and condensed phase. In order to study the PE combustion; experimental and simulation (CFD) part
of research are developed. A macro-TGA device has been developed and qualified (Figure 1). Sample
is dropped into a hot oven. Weight loss, sample and oven temperature are recorded over time.
Experimental and modelisation results are compared in this study. The experimental burning rate
shows dependence on initial polyethylene mass (Figure 2).
Figure 1 : expérimental setup Figure 2 : weight loss as function of time and simplified simulation results
(steady-state, 2D axisymmetric) for 50g and 10g (Temperature for mean
burning flow rate)
With small sample, the simulation results show that flam is localized far from PE. The plastic is
heated mainly by upper area. The burning rate depends mainly on this surface. In case of big mass
sample, flam surrounds crucible. Hence polyethylene is also heated by the side and from below. To
conclude, the burning rate is extremely dependent on the initial mass of polyethylene and geometry.
That is why studying of massive polyethylene sample is very useful and necessary.
References
[1] A. Marcilla, M.I. Beltran, R. Navarro, Evolution of products during the degradation of polyethylene in a batch reactor.
J. Anal. Pyrolysis. 86, 14-21 (2009)
270
BALL MILLING AS A TOOL FOR WASTE TREATMENT
M. BALÁŽ1
1 Department of Mechanochemistry, Institute of Geotechnics, Slovak Academy of Sciences, Košice,
Slovakia.
Abstract
Ball milling method (also called mechanochemistry) is an efficient tool for very wide spectra of
applications (Fig. 1). As it can be traced down in recent review papers, it has already penetrated into
fields of inorganic and organic chemistry, co-crystals formation, polymers, catalysis and also waste
management [2-4]. In this contribution, the principles of this eco-friendly method will be briefly
described and the examples of mechanochemical treatment of different kind of waste will be
reviewed. Concretely, the examples of the application of ball milling for human waste (concrete and
building materials, electronic and metallic waste [5], silicon-based waste, fly ash and sludge) and
natural waste [6] (cellulose, shells, clays, and other) treatment will be shown. Furthermore, the
utilization of mechanochemistry for other environmentally beneficial processes (e.g. dehalogenation
[7], sorption and photocatalysis) will be also reviewed.
Figure 1: Applications of mechanochemistry [1]
References
[1] Boldyreva, E.: Mechanochemistry of inorganic and organic systems: what is similar, what is different? Chem. Soc.
Rev. 42, 7719-7738 (2013).
[2] James, S.L., Adams, C.J., Bolm, C., Braga, D., Collier, P., Friščić, T., Grepioni, F., Harris, K.D.M., Hyett, G., Jones, W., Krebs,
A., Mack, J., Maini, L., Orpen, A.G., Parkin, I.P., Shearouse, W.C., Steed, J.W., Waddell, D.C.: Mechanochemistry:
opportunities for new and cleaner synthesis. Chem. Soc. Rev. 41, 413-447 (2012).
[3] Baláž, P., Achimovičová, M., Baláž, M., Billik, P., Cherkezova-Zheleva, Z., Criado, J.M., Delogu, F., Dutková, E., Gaffet, E.,
Gotor, F.J., Kumar, R., Mitov, I., Rojac, T., Senna, M., Streletskii, A., Wieczorek-Ciurowa, K.: Hallmarks of
mechanochemistry: from nanoparticles to technology. Chem. Soc. Rev. 42, 7571-7637 (2013).
[4] Guo, X.Y., Xiang, D., Duan, G.H., Mou, P.: A review of mechanochemistry applications in waste management. Waste
Manage. 30, 4-10 (2010).
[5] Ou, Z., Li, J., Wang, Z.: Application of mechanochemistry to metal recovery from second-hand resources: A technical
overview. Environ. Sci. Processes Impacts 17, 1522-1530 (2015).
[6] Tabasso, S., Carnaroglio, D., Calcio Gaudino, E., Cravotto, G.: Microwave, ultrasound and ball mill procedures for bio-
waste valorisation. Green Chem. 517, 684-693 (2015).
[7] Cagnetta, G., Robertson, J., Huang, J., Zhang, K., Yu, G.: Mechanochemical destruction of halogenated organic
pollutants: A critical review. J. Hazard. Mater. 313, 85-102 (2016).
271
BIODEGRADABLE FILMS PHYSICAL PROPERTIES CHANGE WITH RESPECT TO

DEGRADATION EXPOSURE TO VARIOUS MEDIA
S.M. Al-Salem, A. Al-Nasser, M. Al-Wadi, H. Sultan, M. Al-Foudaree, H. Karam, A. Al-Dhafeeri
Environment & Life Sciences Research Centre (ELSRC), Kuwait Institute for Scientific Research (KISR),
P.O. Box: 24885, Safat 1319, Kuwait
Keywords: Plastic Waste, Polymer, Haze, Biodegradable Plastic.

Abstract
In a state effort to rid the country of accumulated plastic solid waste (PSW), biodegradable plastics
are becoming under the spotlight by various concerned stakeholders. The state of Kuwait generates
over 200 ktpa of PSW and routes of PSW management noted internationally must be undertaken
seriously by concerned parties. In this work, three commercial type biodegradable plastic film grades
available on the Kuwaiti market, have been secured and acquired for further characterization. The
bags which were standardized by cutting them into test specimens where exposed to natural
weathering, accelerated ageing tests and soil burial, all in accordance with internationally recognized
protocols of the American Society of Testing & Materials (ASTM). The samples were then analysed
for colour parameters targeting light/dark, red/green and blue/yellow indices following ASTM D-
2244. Haze (%) and light transmission (%) were also monitored. The degradation profile was
monitored with respect to the change in degradation media and exposure duration in an effort to
have standards that can govern cleaning companies for future reference and use by the
Government. The ANOVA (t-test) performed confirmed some past findings with respect to waste
management and polymeric film exposure conclusions regarding main environmental stressors
effacing the degradation of plastics.
272
1- INTRODUCTION
Plastics are essential to our daily functions and have been used extensively in packaging applications
and consumer products in the past few decades. They are light weight, versatile and cheap to
process and convert; and have replaced classical building and construction materials such as wood,
cement, concrete and metal in many venues. Moreover, PO polymers that constitute the majority of
plastic materials used mainly in film applications; are increasing in production due to the global
increase in both population and demand. The dependency on plastic materials and other
commodities has a notable consequence in increasing the generation of various waste types. It was
reported that in USA, Western Europe and Japan more than 60% of plastic solid waste (PSW) are due
to PO polymers [1]. Solid waste (SW) accumulation is also noted to be a matter that poses a concern
to societies the world over. In addition, the accumulation of SW in landfill ad disposal sites, has also
carried within a number of hazardous and dangerous to the surrounding environment. Past research
has suggested that landfilling SW including plastics has adverse effects on the surrounding
environment due to concern of toxic chemicals migration by leaching, harmful emissions from
additives, bacteria growth and greenhouse gases (GHGs) evolution [2-4].
Furthermore, recycling of PSW is noted to be a priority due to the fact that it can produce desirable
products that can be marketed with ease. Recycling techniques for PSW follow an ascending order of
preference within the PSW management hierarchy [5]. These technologies cover a plethora of
methods from reprocessing of plastics to energy recovery via combustion and power generation.
Enigmatically, in a country with resources such as Kuwait; the infrastructure of SW is still lacking to
have a well-managed and an integrated solid waste management (ISWM) system. Landfilling is still
the main (and can be considered the sole) route of municipal solid waste (MSW) treatment. In
landfill sites within the state of Kuwait, there exists various evidence to support the claim that plastic
solid waste (PSW) is not managed to its optimal manner. It accumulates to a point where the
majority of the plastic film waste is still visible in landfill sites. Also, one should keep in mind that
PSW makes up some 16% of MSW and 13.1% of household solid waste (HHSW) in Kuwait with a
generation rate of over 200 ktpa [6-8].
Henceforth, and as a response to the immediate need deemed by the state government, this work
has been initiated. The aim of this communication is report the preliminary investigation and the
results of the first stages of the research projects aimed at investigating biodegradable plastic carrier
and waste bags standards for the state of Kuwait. This is conducted as a means to reduce the
accumulation of PSW in the country and as a waste management strategy to be implemented by the
concerned parties.

2.1. Samples Acquirement and Assessment
Three types of plastic bags used in the Kuwaiti market were secured from local dealers with their
main characteristics depicted in Table 1. The samples acquired were presumed to be
environmentally friendly and biodegradable, which were secured from various sources within the
state. The samples were cut into standard testing dimension specimens accepted by international
protocols for thin plastic film characterization as described previously [8-9].
Biodegradable Bag Type Application Average Thickness per Test Specimen
Yellow (Type I) Trash Bag 70 m
Blue (Type II) Trash Bag 40 m
Carrier transparent bag (Type III) Carrier Bag 30 m
Table 1: Types of Plastic Bags Considered For Testing.
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2.2. Determination of Biodegradability Extent Using Soil Burial Testing In Controlled Conditions
The determination of the biodegradability extent was conducted in this work under the presumption
that the samples were biodegradable in nature with suitable content of pro-degradants (or oxo-
biodegradable) as declared by the company’s marketing these polymeric products. The
biodegradation extent was investigated via aerobic bacteria in contact with soil under controlled
conditions. The standard testing procedures of ASTM D5998 [10] were followed to determine the
rate of aerobic biodegradation of plastic materials in soil. The test procedure followed is applicable
to all plastic materials covering oxo-biodegradable and starch based products that are not restrained
to the bacteria and fungi presence in soil. Natural soil (particle size < 2mm) was used after reclaiming
it from a local dealer in Kuwait in the amount of 50 kg. The soil originates from the Maqwa’a area
which is the closest to the largest operating landfill site in Kuwait, dug up from 1 to 3 m (top soil)
stored in a cold room storage with a maintained temperature between 1 to 3oC. Compost (sheep
manure) sourced from local dealers was also used in this work. Potato starch (MSDS CAS no. 009005-
84-9) purchased from Loba Chemie Company was used for positive control experimental runs. The
soil was aerated with the compost in laboratory conditions and mixed in a 1:25 ratio (e.g. 18:450 g
compost/g soil) with a moisture content of 80-100% maintained throughout the full duration of the
experiment by adding distilled water. The moisture holding capacity (MHC) of the soil was
determined initially after drying it in an oven for 24 h at 105 oC and was estimated to be 0.6%. Each
experimental run consisted of six air tight 2 litre desiccators. The first was denoted as blank (control)
which contained the soil. A technical control experimental run to make sure that the experimental
setup was free from leakage, was also executed. A positive control experiment was conducted in
conjunction with the first two containing the starch and soil. The remaining three desiccators
contained the samples studied. Plastic bags sample size were used as described in the experimental
protocol of ASTM D5998 [10] and Rudeekit et al.[11] which were 2x2 cm2. The amount of 200 mg for
each type and positive control (starch) sample were used. The carbon (C) to nitrogen (N) ratio was
maintained in the experimental setups after the addition of Ammonium Phosphate ((NH4)2HPO4)
(4.72 g/l, Sigma Aldrich Company reagent >98%) and maintaining the pH 8.2 (Table 2). The C:N ratio
was maintained at 10:1 after addition to the soil. Experimental runs for biodegradable extent
determination were conducted in duplicates for each of the technical control, soil blank, positive
reference material, and test materials. The weight of the vessel and lid were recorded continuously
throughout. The intended total timeframe of each experimental run is six continuous months [10].
Sample Type Total Carbon (%) Average Total (NH4)2HPO4 added to

Carbon (%) Degrading Environment (ml)
73.373
Type 1 72.925 73.04 ± 0.25 328.09
72.925
83.870
Type 2 84.109 84.07 ± 0.18 396.56
84.238
69.026
Type 3 69.708 69.55 ± 0.47 344.69
69.937
39.75
Starch (Reference) 39.75 39.76 ± 0.01 356.45
39.78
Table 2: Carbon Analysis With Respect To Each Sample Type.
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2.3. Carbon Dioxide (CO2) Evolution and Biodegradation (%) Calculation From Biodegradability Extent
The test method described in the previous section aims at the determination of aerobic
biodegradability, obtaining soil as a matrix and source of inoculum, as well as, estimating the degree
of biodegradability [10]. To this end, both barium hydroxide (Ba(OH)2) and deionized water (DI) were
used within each experimental setup, placed inside each of the desiccators used. The Ba(OH)2
solution was prepared by dissolving 4.0 g anhydrous Ba(OH)2 (Aldrich Company, technical grade 95%)
in distilled water and confirmed by manual titration. The solution was sealed and stored to prevent
absorption of CO2 from the air. The amount of 100 ml of 0.025 N Ba(OH)2 and 50 ml of distilled water
were kept constantly throughout the experiments within each of the desiccators used on the
perforated plate inside the vessel. All tested were conducted in dark room in laboratory conditions.
Manual titration was conducted in a frequency of 3 days for the first three weeks and once every
three weeks thereafter as recommended previously by Gomez and Michael [12] and ASTM D5998
[10]. The titration aims at determining the accumulative carbon dioxide (CO2) evolution, conducted
using hydrochloric acid (HCl, 0.05 N) and Ba(OH)2 to a phenolphthalein end-point. The theoretical
total carbon (TC) was determined for each type of plastic bags and starch using dynamic flash
combustion using modified Dumas method [13] in a Thermo-Fisher Scientific (Flash 2000 Model)
CHNS-O analyser. Samples were conducted in triplicates for quality assurance (Table 2). The
theoretical CO2 quantity was calculated thus using reaction stoichiometry
44  Y
CO 2 (th.)  (1)
12
where Y is the net total theoretical carbon (C) charged to each vessel (mg), and CO 2(th.) is the
theoretical CO2 available (mg). The amount of net CO2 produced is calculated by subtracting the
titration readings from the test material titration thus
Z n  Zb  Zt (2)
where Zn is the calculated amount of HCl needed to titrate the CO2 generated solely from the test
material (ml), Zb is the amount of HCl used to titrate the blank vessels with soil only (ml) which is
termed as technical control vessel in this work, and Zt is amount of HCl used to titrate the vessels
containing the soil plus test material (ml). The amount of CO2 produced is calculated as per the
formula given below after accounting for the Normality of HCl [10]
1.1 0.05 N  Z n  44

CO 2 (Produced)  (3)
2
The percentage of CO2 evolution (E) is determined as per the following, which on the other hand is
used to estimate the standard deviation (se) of the experimental runs and biodegradation extent
thereafter.
CO 2 (Produced)
E (%)  100 (4)
CO 2 (th.)
se  s 2
test   
/n 1  s 2blank/n 2 100/C i (5)
where n1 and n2 are the number of replicate test material and blank vessels, respectively, s is the
average standard deviation of the total gaseous carbon produced (mg), and Ci is the amount of
carbon (mg) initially present in the vessel.
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2.4. Natural Weathering of Film Samples

The films intended for characterization post natural weathering were arrayed over non-expanded
metal trays of non-corroding aluminium mesh with openings covering ≈70% of its surface area, in
accordance with ASTM D5272-08 [14] using design for exposure rack ‘A’ with an approximate
individual diameter of openings equal to 0.5 cm. Each rack had seven trays, each divided into two
segments allowing 60 specimens to be mounted on. All racks were placed at a 45 o angle as per ASTM
1435-05 (2005) and ASTM D5272-08 (2013). The first tray was positioned at 90 cm from ground level,
and each tray was of 15 cm in width and 177 cm in length. Two sites were chosen to simulate the
impact of weather in Kuwait. The first was located in an arid area close to the bay (Shwiakh) with a
mean annual ambient temperature of 32oC and relative humidity of 30%. The second, Salmyia area,
is a seafront area with a mean annual ambient temperature of 30oC and relative humidity of 60%.
The start of the natural weathering loading was on the 26th December 2017 and were kept with the
intention of exposing the samples for a continuous period of one year. The film samples were
mounted on the trays with a minimum spacing of 11 mm between each individual specimen [9,14-
15]. The racks were facing southward direction in accordance with ASTM 1435-05 [15]. A minimum
of ten specimens of each type were unloaded of each tray at each site after 1, 3, 6, 9 and 12 months
for further testing and characterization. The unloaded film samples were carefully placed in plastic
bags and rinsed for 3-5 s before drying and conducting the various experiments.
2.5. Accelerated Ageing of Test Specimens

Accelerated (artificial) indoor weathering (ageing) tests are commonly used for studying materials
integrity and were conducted in this work to correlate the results obtained with natural weathering
ones. Films of the study samples were exposed to accelerated weathering (AW) in accordance with
ASTM D 4329 [16]. Samples were mounted on the racks facing the ultra violet (UV) lamps with no
empty spaces in the panels. This is in order to maintain a uniform repeatable test conditions. Cycle A
procedure was used for general applications durability testing, i.e., 8 h of UV exposure at 60 oC
followed by 4 h of condensation at 50oC. At the end of each continuous weathering test, the
chamber was cooled to room temperature and the trays were set to rest on a flat surface for a
minimum of 24 h. Samples were laid to rest for a minimum of 72 hours before characterization
following internationally recognised methodologies and laboratory testing protocols of weathering
[9,16-17]. A minimum of four replicates were exposed to the different exposure durations in the
QUV machine chamber. Ultra Violet (UV) lamps irradiance was also selected according to ASTM D
4329 [16], and the lamp type was set to be 0.68 W m-2 (irradiance) for normal lamp operation, which
was maintained for almost 5000 h of operation. The irradiance sensor was calibrated every 400 h of
lamp operation during the UV cycle under normal test temperature. The equipment used was
cleaned every 800 hrs to remove scale deposits resulting from water evaporation during the
condensation cycles.
2.6. Soil Burial Study Protocol
Soil burial tests in the field were carried out to study the degradation of the plastic bags in the
natural environment. The site for the burial tests was chosen as one of the locations within the
largest operating landfill sites in Kuwait (South 7th Ring Road Landfill) where no presumed landfilling
is to be conducted for the next two years. The site also reflects the type of land used for recent
waste management activities within the state as discussed with Kuwait Municipality (KM) whom are
responsible for such activities. The location is noted as 29.1707 latitude and 47.9085 longitude. Ten
film samples were buried to a depth of 0.3 m so as to allow microorganisms to attack them in
accordance with Muthukumar et al.[18]. Samples were removed after 1, 3, 6, 9 and 12 months for
276
further testing and characterization. The average water absorption ( Wabs ,%) and sample weight loss (
Wloss ,%) were estimated for the test specimens as per the following [19]:
(Wt  Wd )
Wabs (%)   100 (6)
Wo
(Wo  Wd )
Wloss (%)  100 (7)
Wo
Where Wabs is the average water absorption (%), Wt remaining mass at time t, Wd is the mass of the
dried sample, Wo is the initial mass and Wloss is the sample weight loss (%). Samples were removed
from the soil at specific intervals (t), carefully cleansed with distilled water and superficially dried.
Samples were then dried under vacuum at 35oC until constant weight. Samples were washed, dried
and stored in dark laboratory space at 23°C/50% relative humidity between sample collection time
and characterization.
2.6. Haze and Light Transmission Measurements
A Diffusion System MF709 (spherical) haze meter (model BS 2782) was employed to measure the
haze (%) and light transmission (%) at the midpoint of the studied samples, in accordance with ASTM
D1003-11 [20] for samples exposed to the degradation media. Replicates of the tested specimens
were tested for haze (%) and light transmission (%) and the average of the readings were reported.
The difference in haze (%) and transmission (%) were calculated thus [9]:
H  H i  H c (8)
T  Ti  Tc (9)
Where H is the absolute difference for haze (%) with respect to the reference (control) specimen’s
reading (Hc) at a weathering duration (i), and T is the absolute difference for light transmission (%)
with respect to the reference (control) specimen’s reading (Tc) at a weathering duration (i). The
average readings of the replicates for each formulation were measured and all experimental results
conducted resulted from taking a minimum of two readings (runs), having a ±5% error for each data
point (replicate).
2.7. Measurement of Colour Parameters and Total Change in Colour (E)
Standard colour parameters for light/dark ( L*s ), red/green ( a s* ), and yellow/blue ( bs* ) post
degradation will be measured using a Shenzhen Technology 3NH Model colorimeter according to
ASTM D 2244-11 [67]. Parameters measured will be used to calculate the total change in colour (E)
between control samples and each formulation thus [8-9,21]:
E  (L) 2  (a) 2  (b) 2 (10)
Where L , a , and b are the values of the difference between the control specimen
measurements (control samples with no exposure) and those of each tested batch.
2.8. Statistical Analysis
ANOVA testing (F-test) for the comparison of the significant variance between two or more groups
was conducted to analyse the interaction of independent variables considered in this study. These
included physical properties of the different plastic types (haze (%), light transmission (%) and E), as
well as the mechanical properties. Independent one-way ANOVA test was conducted amongst the
studied groups with respect to the different natural weathering durations considered in this work. F
values as a ratio of mean sum of squares due to treatment (MST) to mean sum of squares due to
error (MSE), and p values as the total number of population, were both examined to determine the
277
dependency of the variables with respect to group. F critical taken as upper limits of the normal
distribution was considered as the limit of acceptance/rejection of null hypothesis. The analysis
covered both sites considered in this work. Relevant pollutant levels and metrological conditions
were used to check dependency of variables on each other with respect to the dependent variables.
The variables considered were as per the following to study the extent of pollutant and metrological
conditions impact of exposed samples: Particulate matter (PM10, mg m-3), total hydrocarbon (THC,
ppm), methane (CH4, ppm), non-methane hydrocarbons (NMHC, ppm), ozone (O3, ppb), sulphur
dioxide (SO2, ppb), hydrogen sulphide (H2S, ppb), nitrogen oxides (NOx, ppb), ammonia (NH3, ppb),
benzene (C6H6, ppb), carbon monoxide (CO, ppm), carbon dioxide (CO2, ppm), temperature (oC),
wind speed (m s-1), wind direction (o) and relative humidity (%). The analysis was conducted utilizing
the means of Microsoft Office Excel 2007 - Data Analysis tool as a built-in function. The methodology
has been previously reported in Vikingsson et al.[22], Kacan [23], Kacan et al.[24] and Al-Salem and
Al-Dousari [25].
The various types of plastic film samples were exposed to accelerated weathering in this work. It was
determined that the threshold limit of the samples in the weathering chamber is 11 days, 13 days
and 19 days of continuous exposure, for types 1, 2 and 3, respectively. It is still crucial to correlate
the properties estimated from this project, namely the mechanical properties, between the natural
and accelerated weathering to determine a timeline suitable for comparison between outdoor
weather and accelerated weathering tests. It is essential to note that past investigations have
attempted to establish a correlation between the natural (outdoor) and accelerated (artificial)
weathering studies. It is also recommended that such correlations are considered only as a guideline
for a certain material type [26-27]. This is because of the unpredictability and the number of
variables that govern natural weathering, which cannot be taken under consideration when
performing accelerated weathering tests in controlled environments [9,26-29]. Based on recently
conducted work in Kuwait following similar experimental protocols, 1 hour of exposure in
accelerated weathering is equivalent to 1 day in natural environment [29]. Haze and light
transmission are the main two optical parameters for polymeric samples [30]. Table 3 depicts a
samples of the haze and light transmission measurements extracted from this work for the naturally
exposed samples.
Type 1 Type 2 Type 3
Haze % (0 Days) 47.00±0.42 39.5±0.01 64.9±0.005
Haze % (30 Days) – Site no.1 48.08±6.17 57.80±4.99 78.58±2.2
Haze % (30 Days) – Site no.2 68.43±2.90 59.00±13.58 72.48±2.98
Transmission % (0 Days) 57.85±0.07 52.45±0.005 65.65±0.0
Transmission % (30 Days) – Site no.1 66.45±3.02 61.40±5.44 61.60±2.02
Transmission % (30 Days) – Site no.2 56.98±2.98 58.08±1.26 58.35±2.48
Table 3: Haze (%) and Light Transmission (%) Measurements Conducted Post Natural Weathering at Site No.1.
Typically, haze in polymeric samples are caused by the irregularities at the surface namely due to the
effect of the UV exposure and the loss of amorphous regions within the material’s matrix [31]. The
mechanism of photodegradation of polyolefin (PO) polymers are reported elsewhere [32-33]. The
data in this work are noted to be preliminary at this stage. Further assessment of the type of samples
via thermal characterization and chemical identification is required. However, using
thermogravimetric analysis (TGA) conducted for the samples at hand (not shown), it is suspected
that the samples are of polyethylene (PE) nature. This is due to the degradation (onset) temperature
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being at around 430oC. The degradation of PE is typically initiated under UV exposure with a chain
scission reaction. Branching and cross-linking is followed and the mechanism is terminated with
double bond formation [8,32]. Cross-linking within the polymeric matrix leads to the loss of the
amorphous region, which alters the physical and mechanical properties of the studied samples. A
notable increase was witnessed for all samples with regards to the measured haze (%) after
exposure to natural weathering.
Samples exposed to site no.1 showed a notable increase in haze (%) after 30 days of exposure. At
this stage of the work, it can be concluded that samples were effected with the thickness of the
plastics product. Samples with higher thickness (i.e. type 1) where more resilient than others to
change in haze (%). An increase of 1, 18 and 14% was recorded for the haze (%) after 30 days of
exposure at site no.1 (Table 3). On the other hand, exposure to more humid climate (site no.2)
resulted in more surface irregularities measured as haze (%) in this work. This could be attributed to
the fact that biodegradable plastic favours humid climates for their mechanism rather than more
arid ones (Table 3). Samples exposed to the threshold limit of accelerated weathering showed a
drastic change in haze (%) where for type 1, type 2 and type 3, it was measured as 72.78±8.34%,
58.28±2.28% and 75.50±2.87%, respectively. This indicates that the samples studied in this work
degrade after full length exposure to UV as a result of photodegradation. However, samples buried
in soil at the landfill site showed the largest change in haze(%). This can be attributed to the nature
of the degrading environment favouring surface change with soil burial. A general trend of decrease
was noted with light transmission (%) data as a result of the rearrangement of molecules post
degradation. This hinders the accessibility of light transmitted throughout the polymeric film [8].
Table 4 depicts the water absorption and weight loss after 30 days of soil burial at the field, and
Table 5 shows the total loss in weight for the samples studied. Typically thermoplastic starch (TPS) as
a biodegradable prodegradant in plastic product [19]. The behaviour exhibited by types 2 and 3 of
the samples, indicate that they may be of starch based nature and that the TPS is the agent being
biodegraded. On the other hand, A constant weight was noted for samples exposed natural
weathering (site no.2) after 30 days of exposure. This can be attributed to the fact that at more
humid environments, samples might need more exposure time to the weather for molar mass
reduction to take effect. Ojeda et al.[34] determined the molar mass of exposed PO polymers,
including LLDPE, to natural weathering using size exclusion chromatography (SEC) in a gel
permeation chromatograph. The variation in molar mass reductions were attributed to sample
thickness and amount of additives including antioxidants. It should also be noted that chemical
processes related to degradation phenomena may lead to a reduction of average molar mass due to
macromolecular chain bond scission or to an increase of molar mass due to cross-linking rendering
the polymer insoluble [35]. The loss of weight noted for accelerated weathering samples at threshold
limit can be attributed to the UV exposure and the propagation cross-linking behavior PO polymers
exhibit [36]. The exposure to natural weathering also leads to cross-linking which produces longer
polymer chains, as well as, the oxidation of the polymer matrix from the atmosphere. This alters the
behavior of weight as noted for samples exposed to site no.1 (Table 5). The results of the weight loss
analysis compliments so far the biodegradation extent results determined from this work (Fig.1).
Sample Wabs.(%) Wloss.(%)

Type I -6.81 0.47
Type II 14.46 1.98
Type III 13.28 0.04
Table 4: Measured Water Absorption and Weight After Conducting Soil Burial Test For 30 Days.
279
Weight (g)
Initial 30 NW (Site no.1) 30 NW (Site no.2) AW TL SB (30 Days)
Type I 0.4 0.3 0.4 0.2 0.4
Type II 0.1 0.2 0.2 0.1 0.2
Type III 0.2 0.2 0.2 0.1 0.2
Table 5: Sample Weight After Each Degrading Environment Exposure. Note: NW; Natural Weathering, AW; Accelerated Weathering;
SB; Soil Burial; TL; Threshold Limit.
100
Type I
90
80 Type II
70
Type III
Biodegradation (%)
60
50
40
30
20
10
0
0 2 4 6 8 10 12 14 16
Time (Days)
Figure 1: Biodegradation Extent Rate (%) Determined For The Studied Samples As a Function Of Time.
Type 3 of the studied samples showed a rapid increase in biodegradation and high rate of CO2
generation. All samples increase in their biodegradation extent with time till reaching the 14 days
mark, where afterwards a rapid decrease is detected (Fig.1). Type 3 of the samples studied lost most
of weight by the end of the accelerated weathering runs (Table 5) indicating higher susceptibility to
degradation and biodegradation with moisture in the weathering chamber. Table 6 shows a samples
of the colour parameters and E estimated for the samples considered in this work.
Days L* a* b* E
Type 1
0 56.46 0.62 38.94 0
30 (NW Site no.1) 8.35 0.55 9.96 13.01
30 (NW Site no.2) 10.51 1.52 12.07 16.08
11 (AW TL) 9.08 0.6 12.27 15.28
30 (SB) 8.04 0.76 11.64 14.17
Table 6: Colour Parameters Measured For Type 1. Note: NW; Natural Weathering, AW; Accelerated Weathering; SB; Soil
Burial; TL; Threshold Limit.
It can be deduced that type 1 shows a rapid change in colour after only 30 days in humid
environment of natural exposure. However, by comparison to type 3 (E = 25.91) the change is more
prominent. The moisture in the surrounding environment makes the samples more prominent for
attack by microorganisms. This can be confirmed by the end of the study conducted and comparing
other properties such as thermal and chemical post exposure to the various environment.
280
4- CONCLUSIONS
Three types of biodegradable plastic bags used in the form of standard films, were examined and
characterised in this work. The work indicates that the samples are of polyolefin polymer nature,
with type 2 and 3 having starch as a component. Soil burial and weathering tests shows rapid and
notable change in the surface chemistry of the polymeric samples deduced by change in colour
parameters, haze (%) and light transmission (%). The analysis of the samples will be carried out in the
near future to determine more specifically their type and thermal response and stability.
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282
BIOCHAR AS AN ADSORBENT FOR ODOR REMOVAL
KYOUNG S RO1, OKHWA HWANG3, SANG R. LEE2, DEUG WOO HAN2, SUNGBACK CHO2, MINDY
SPIEHS4, BRYAN WOODBURY4
1 USDA-ARS Coastal Plains Soil, Water & Plant Research Center, Florence, SC, USA.
2 Korean RDA National Institute of Animal Science, Jeonju, Korea
3 USDA-ARS National Laboratory Agiculture and Environment, Ames, IA, USA
4 USDA-ARS Meat Animal Research Center, Clay Center, NE, USA.
Abstract
Malodorous emissions from livestock operations disrupt quality of life in rural and urban
communities. The objective of this study was to evaluate the potential of various biochars to be used
as a sorbent for removing odorants from swine manure storages. Biochar samples were prepared by
pyrolysing pine, oak, solid-separated swine manure, swine compost, coconut shell, and poultry litter
at 350 oC and 500 oC. Some of the biochar samples were also steam activated. All biochar samples
were analyzed for their elemental compositions, volatile matter, fixed carbon, ash contents, size,
density, and surface area. Odorous volatile organic compounds (VOCs) were using Tenax TA® sorbent
tubes and a thermal desorption-gas chromatography-mass spectrometry system. Swine manure was
used as a source for odorants. Sorption capacities of each odorants were calculated from influent
and effluent odorant concentrations, biochar mass and the gas flowrate. The results of these
laboratory experiments such as biochar properties, odor characteristics, and sorption capacities of
different biochar for different odorants will be presented at the conference.
283
SELECTION OF RECOVERY PATHS FOR INDUSTRIAL WASTES:

A MULTICRITERIA ANALYSIS APPROACH
M. BURONFOSSE 1,2, Y. BOUZIDI2, N. ANTHEAUME3, S. LEANG1, F. THERY1

1 EDF R&D, TREE, Technologies et Recherche pour l’Efficacité Énergétique, Groupe Territoires et
Économie circulaire ; EDF Lab Les Renardières, 77250, Moret Loing et Orvanne, France.
2 Université de Technologie de Troyes, CNRS, ICD – CREIDD, UMR 6281, 10 004, Troyes, France.
3 Université de Nantes, LEMNA, Chemin de la Censive du Tertre, BP 52231, 44322 Nantes, France.
Abstract
Waste management is one of the key drivers for the success of the transition from a linear economic
model to a circular one [1]. However, environmental, economic and social pressures involve a multi-
dimensional character with very distinct issues and often divergent solutions in their aims [2]. Nowadays,
most of the methods and tools used for waste management studies focus on the economic [3] and
environmental [4] aspects. Academic literature mainly deals with municipal solid waste (MSW) [3],
whereas industrial waste represents the majority of the output [5]. Companies and local authorities have
the responsibility to organize the correct orientation of their different flows towards the appropriate
recovery paths, while respecting the European regulatory and national valorization targets. To help the
decision maker, EDF's R&D (Electricité De France) works to design a tool in order to compare, with
various criteria, waste management facilities on five considerations namely, technical, economic,
environmental, territorial and regulatory. To build and weight the set of criteria, we propose to adapt
and use a multi-criteria-decision-making (MCDM): Analytic Hierarchy Process (AHP) methodology [6].
This method allows, via a wide panel of experts’ opinions (industrials, academics and from environmental
agencies), the aggregation of qualitative and quantitative criteria to compare waste management
solutions. Each solution obtains a score on the five previous dimensions. It is possible with this standard
to compare several potential recovery facilities and give an in-depth discussion at management level of
the company. Based on the results of many cases studies on asbestos, wood waste, sediments, and
recycled concrete of deconstruction waste, we consider that the tool has many uses and can be applied
to all sorts of wastes in order to evaluate and compare different recovery options. Thus, this guideline
can help the decision maker to understand more clearly the situation and give him the possibility to
choose to a recovery path according to his profile, inclination, values and preferences.
References
[1] ADEME. 2012. « Economie circulaire: notions ».
[2] Marcoux, Marie-Amélie, Franck Olivier, François Thery, et Réseau coopératif de recherches sur les déchets (France).
2016. Déchets et économie circulaire: conditions d’intégration pour une valorisation en filières industrielles. Paris:
Lavoisier : Tec & Doc.
[3] Allesch, Astrid, et Paul H. Brunner. 2014. « Assessment methods for solid waste management: A literature review ».
Waste Management & Research, 0734242X14535653.
[4] C. Bergeron, Francis. 2014. « Assessment of the coherence of the Swiss waste wood management ». Resources,
Conservation and Recycling 91 (Supplement C): 62-70. doi:10.1016/j.resconrec.2014.07.011.
[5] Eurostat. 2016. « Statistiques sur les déchets - Statistics Explained ». Statistiques sur les déchets.
[6] Saaty, Thomas L. 1977. « A Scaling Method for Priorities in Hierarchical Structures ». Journal of Mathematical
Psychology 15 (3): 234-81. doi:10.1016/0022-2496(77)90033-5
284
COMPETITIVENESS OF WASTE PROCESSING CENTERS AND GENERATION OF NEW

COMPANIES AND BUSINESSES IN DEVELOPING COUNTRIES AND EMERGING
ECONOMIES VULNERABLE TO WATER SHORTAGES: A BRAZILIAN PERSPECTIVE
S. A. LUCKE1, A. C. ZUFFO1
1 Unicamp University of Campinas, Campinas-SP, Brazil.
Abstract
The purpose of this study is to investigate feasibility aspects of 4R waste processing plants WPC with
power generation in countries with changing water availability and shortages. Such plants help the
formation of new companies and businesses in municipalities which do not have a big industrial or
commercial structure, or both, to provide a proper consortium supply chain.
Official data was supplied by government agencies and private associations. An array of ten WPC
plant sizes was considered to support calculations. Analysis of water supply and availability for
hydropower generation considered data of Southeast Region of Brazil, where the highest generation
is performed. The authors have applied both quantitative and qualitative approaches for analysis
and calculations.
Results obtained
1) Higher and/or longer water shortages lead to higher prices of hydropower supply;
2) WPC plants may replace more expensive energy from transmission grids;
3) There is good potential for new companies and businesses, in regions with no recovery of
resources discarded in waste dumps and landfills;
4) Organizations may operate in an open configuration or as clusters under the concept of industrial
ecology and circular economy;
5) Strengthening of local/regional economy, with the creation of direct and indirect jobs and
increased financial flows, usually multiplying into a sustainable network;
Long term operation of such a plant provides ground to a long term growth of new product and
services providers and positive multiplying effects.
The increasing vulnerability to weather changes and water shortages lead to more realistic thoughts
about decentralized models and generation of renewable energy.
In times of abundant water supply and availability, hydropower supply is cheaper than energy from
other sources, but global warming and droughts arise as great threats to this condition.
WPC plants have a significant potential of economic feasibility in conditions of water shortages,
leading to sound reduction of direct and indirect expenditures. They also help to create new
companies and businesses to run a growing supply chain with benefits to local economies.
WPC plants become even more competitive generating collateral benefits as to eliminate dumps and
landfill areas and release them to more decent purposes; leading to increased recycling rates and
volumes; to reduce or even eliminate public problems concerning health and sanitation; to increase
local and regional employment rates and economic development.
References
MME 2016, IBGE 2014 and 2015, ABLP 2014, ABRELPE 2016, IBGE 2010 and 2013, CEMPRE 2013a and b, SSEESP 2009,
CAROL 2016 and 2017.
285
PRACTICAL FEASIBILITY ASPECTS OF WASTE PROCESSING CENTERS WITH POWER

GENERATION IN DEVELOPING COUNTRIES AND EMERGING ECONOMIES: THE
BRAZILIAN PERSPECTIVE
S. A. LUCKE1,2,3 , A. C. ZUFFO1
1 UNICAMP University of Campinas, Campinas-SP, Brazil.
2 UNISAL Salesian University, Campinas-SP, Brazil.
3 SAUBER Technologies, Campinas-SP, Brazil.
Keywords: feasibility, waste processing center, power generation, developing countries, emerging
economies, consortium, logistic costs, waste to energy.
Abstract
Purpose
The purpose of this study is to evaluate practical aspects of feasibility when introducing Waste
Processing Centers (WPC) with power generation in developing countries and emerging economies
at initial stages of recycling and energy recovery.
Materials and methods
An array of ten WPC plant sizes was considered to support feasibility calculations covering 645
municipalities of São Paulo State in five-year periods with quantitative and qualitative approaches
for analysis, based on official data supplied by government agencies and private associations.
Results
WPC plants are economically feasible; results are influenced by economies of scale; taxation and
incentive policies have significant influence on bottom lines; bigger cities are able to finance their
own plants; smaller cities should form consortiums or adopt less expensive alternatives; logistic costs
play a significant role for smaller or isolated municipalities;
Conclusions
In most countries recyclables and energy worthy billions are lost in dumpsites and landfills, with
enormous potential for WPC plants and savings.
Size, geographic distribution, topographic conditions, logistics and economic power of the
municipalities influence decision making concerning introduction of WPC plants.
Changes in these countries demand strong drivers like legislation, incentives, taxes, public policies,
education, ease of doing business, less bureaucracy and formalities.
Indirect benefits and operational revenues are savings to cash, and influence bottom line.
Benefits to community are the main goal and plants must be effective, simple and not expensive, as
a solution to problems concerning energy shortages, sanitation, environment, technology and public
management.
286
1- INTRODUCTION
Waste generation and problematic outcomes
During recent decades waste has been considered to be a global problem, demanding joint efforts of
the international community to be properly addressed, as well as increasing international
cooperation between scientists, professionals and multinational companies. [1]. In more recent
years waste has turned out to be a global emergency, demanding urgent efforts to be properly faced
and overcome. [2]. Some of most recent facts and figures showed: [3] Total municipal solid waste
generation 2013 estimated with 1.84 billion tonnes per year; On average, 271.7 kg of municipal solid
waste per person generated in 2013; Municipal solid waste generation levels expected to almost
double by 2025; Recycling rate without informal sector 16.0 % on average; Landfilling and thermal
treatment of waste are the most common methods of municipal solid waste disposal in high-income
countries; Half of the world‘s population has no organized collection of waste.
Health impacts from municipal waste

In most developing countries, healthcare systems and units have difficulties to attend the patients
and resources are reduced, when not available at all. General performance is poor and financial
resources are often limited and mislaid. Clinic examinations take a long time and medical teams have
difficulties to deal with the wide range of symptoms. Hospitals are usually not big and/or good
enough to cope with the daily flow of people coming mainly from towns’ outskirts or poor areas. The
poor population is usually more affected by this kind of situation. [4], [5], [6]
This happens in cities of all sizes, ranging from small villages to mega-cities. In areas where MSW
(Municipal Solid Waste) is not collected, early symptoms appear and diseases develop quickly.
Dengue, zika and chikungunya seem to be the most recent examples of such sanitation problems.
Areas with regular MSW collection also present the same health problems, but in wider range, larger
scale and increased intensity, due to massive waste concentration in dumps and/or landfills, which
offer proper ground to most common resulting health problems. Most frequent diseases
transmitting vectors [7] use to be mice, rats, flies, mosquitoes, cockroaches, pigs and birds, with a
wide range of diseases. Children and elderly are equally affected. [4], [5], [6].
The effects on environment help to worsen the problems through pollution of soil, water and air. In
countries with continental dimensions like Brazil and such extreme variations like tropics and snow,
rainforests and deserts, rainy and dry seasons, such problems are directly influenced by geographic,
seasonal and climate factors. Specific weather conditions also play a significant role and may largely
contribute to unexpected events and accidents with tragic outcomes.
Waste management and treatment solutions

In developing countries and emerging economies, options of waste management and treatment
solutions may vary from “doing nothing” (no collection at all) to “full operating plants with energy
recovery”. Differences are immense, even at developed countries. In all cases it is also evident that
valuable resources (recyclable materials and energy) are lost and there is a huge potential of
recovery and economic benefits to be explored. The resulting savings could be reinvested in public
health services, thus creating a positive circle of benefits. In most developing countries basic
sanitation and public health are the most critical issues to be effectively faced by public authorities.
Economic development and ranking

When trying to fix a ranking of economies today, results may vary according to the promoting
institution and the adopted evaluation criteria. Even though assessments may somehow differ, there
seems to be a broader consensus on this issue.
287
The most accepted ranking lists are issued by the United Nations [8], the International Monetary
Fund [9], the World Bank [10] and the CIA World Factbook [11]. An average figure of these four lists
indicates the world nominal GDP to be around US$ 73.86 trillion. According to the United Nations
and the International Monetary Fund, the terms “developed country”, “industrialized country”, or
"more economically developed country" (MEDC), apply to a sovereign state that has a highly
developed economy and advanced technological infrastructure relative to other less industrialized
nations, and refers to a country with a relatively high level of economic growth and security. [12].
Terms such as "emerging countries," "third world countries" and "developing countries," are
commonly used to refer to countries that do not enjoy the same level of economic security,
industrialization and growth as developed countries.
According to the United Nations Statistics Division [13], there is no established convention for the
designation of "developed" and "developing" countries or areas in the United Nations system. [13].
The designations "developed" and "developing" are intended for statistical convenience and do not
necessarily express a judgement about the stage reached by a particular country or area in the
development process. Most commonly, the criteria for evaluating the degree of economic
development are: Gross Domestic Product (GDP) [9]; Gross Domestic Product per capita (GDP per
capita) [15]; Purchasing Power Parity (PPP) [16]; Level of industrialization and amount of widespread
infrastructure [17]; Human Development Index (HDI) [18].
Globalization and economic interests

According to the World Bank [19], globalization is an inevitable phenomenon in human history that's
been bringing the world closer through the exchange of goods and products, information, knowledge
and culture. But over the last few decades, the pace of this global integration has become much
faster and more dramatic because of unprecedented advancements in technology, communications,
science, transport and industry. Some groups can be acknowledged in this process: Group of Seven
(G7) [20]; Organisation for Economic Co-operation and Development (OECD) [21]; Group of Twenty
(G20) [22]; European Union (EU) [23], [24]; Emerging economies [10]; BRICS [25], [26], [27]
In order to have a more effective approach at project analysis, the World Bank classification for the
current 2015 fiscal year was used. Economies are defined with a GNI per capita range, calculated
using the World Bank Atlas method. [28]
The main research was concentrated on the 85.5% of the economies not considered to be high-
income OECD at the ranking.
Characteristics of Developing Countries and Emerging Economies

According to Jim O'Neill [25] and Wilson [26], the main common characteristics showed by
developing countries and emerging economies, especially the BRICS, are: Economy stabilized
recently; Stable political situation; Labour in large numbers and in qualification process; Increasing
levels of production and export; Considerable reserves of mineral and natural resources; Investment
in infrastructure sectors (roads, railways, ports, airports, power plants, etc.); Increasing GDP (Gross
Domestic Product); Improvements of social indicators; Decrease, albeit slowly, of social inequalities;
Quick access of the population to communication systems like mobile phones and Internet (digital
inclusion); Capital Markets (Stock Exchanges) receiving large foreign investments; Investments of
foreign companies in diverse industries.
Considering present Brazilian conditions as basis for research and calculations, this work has focused
on 1) the profile of waste generating municipalities; 2) investment requirements and conditions; 3)
operational costs of plants during lifespan; 4) behaviour of figures influencing bottom lines; 5)
influence of plant size on bottom lines; 6) influence of taxation policies.
288

Data and methods
Official data was supplied by several government agencies and private associations, concerning
present figures, rates and indexes and future estimations for population, labour, waste generation,
Gross Domestic Product, development, city position coordinates and geographic distribution. [29],
[30], [31], [32], [33], [34], [35]. An array of ten WPC plant sizes ranging between 40 and 1,600 daily
tonnes of waste input was considered to support calculations. The limits refer to practical availability
of machinery and equipment in the Brazilian market in order to cope with legal and environmental
standards and requirements. The analysis of respective investments and costs covered the 645
municipalities of São Paulo State in five-year periods between 2005 and 2020. The authors have
applied both quantitative and qualitative approaches for analysis and conducted a systematic
sequence of linear, nonlinear and statistic calculations for the lifespan of the plants.
Proposed process
The proposed process WPC® ™ (acronym for Waste Processing Centre) utilizes technology and patents
of SAUBER Technologies and partners of Switzerland and Germany. It considers full utilization of the
waste to be treated and an output of by-products like recyclable materials, water and solid mass to
different destinations. In this particular case, the solid mass is used as Refuse Derived Fuel (RDF) in
the following incineration stage. The 4R approach is clearly respected as basis for the process (Figure
1). With removal of main recyclables, the calorific capacity and therefore the power generation are
reduced, increasing the ratio investment per generated power ($ MWh-1).
Figure 1 WPC Plant for MSW processing and energy recovery
The previous separation stage can be either manual or automated, but in Brazil the manual option
should be preferred, thus enhancing the job generation efforts and social inclusion aspects of the
plants desired by legislation in force in the country. This is also recommended in emerging
economies to increase employment, active jobs, economic participation, training of employees and
education of involved families, improving life standards and changing perspectives for poor people,
as well as general spreading of collateral services and activities. In many poor areas such a plant may
create suitable ground for new small enterprises and induce new business opportunities.

Size distribution of municipalities
289
In Brazil 5,262 municipalities out of 5,565 (94.6%) do not reach the minimal plant size (minimal
processing capacity). They generate 11.1% of the total collected waste. The remaining 303
municipalities (5.4%) are bigger and start to reach the processing capacities of the plants, thus
progressively benefiting from the economies of scale. They generate 88.9% of the total collected
waste. This includes the mega-city of São Paulo (26.4% of state population, 44.4% of waste
generation). This profile is common in most developing countries.
State capitals and bigger cities are usually included in this group of municipalities which are big
enough to afford financing their own plants. The smaller cities may have the option of setting up
consortiums as group partners, in order to reach a joint waste generation big enough for a plant. The
critical points of this alternative should be the geographic distribution of the municipalities,
topography and logistics, since the transportation of waste from each municipality to the location
spot of the shared plant should generate new expenditures, thus increasing the final tonnage cost.
The positioning of the common plant itself should be defined based on optimizing calculations to
minimize the final total cost concerning all partners.
Other options may include different sorts of smaller processing plants, which should have difficulties
to be financially feasible and/or reliable concerning environmental standards, or other sorts of
cheaper waste disposal methods acceptable to the legislation in force and environmental
authorities. Damps and open landfills should no longer be an option, due to all sorts of disease
vectors they usually shelter and to gas emissions contributing to global warming effect (GHG).
A first analysis of the distribution of waste generation in relation to the population of the
municipalities indicates that there is a strong alignment between the two variables. It was not
detected any relationship between the areas of the municipalities and their generation of waste
(cloudy or fuzzy profile) [36], [37]. The State is formed by small, medium and bigger municipalities,
what enhances the aggregation in administrative areas and the effect of the average figures in the
analysis by region. This clearly demonstrates the occurrence of the effect of urbanization and
population growth on the individual generation of MSW [38], [39]. As the cities grow and
urbanization takes place, people start to adopt other habits and consumption patterns, thus
changing the generation profile and increasing the generation of household waste [38], [39]. The
curve representing the growth of waste generation due to population growth and consequent
urbanization of the municipalities of São Paulo State is shown in Figure 2. This same profile is to be
found worldwide.
Figure 2 Waste generation based on population growth and urbanization
290
Behaviour of investment
The comparison of total investments and specific investments by generated MWh within this range
of ten plant sizes shows that bigger plants clearly benefit from economies of scale (Figure 3).
Although investment of WPC plant is lower at smaller sizes, specific investment per MWh is higher.
At bigger sizes the relation is the opposite, because the power generation is higher. The ideal
proportion should be at medium sizes four and five (economic ratio).
Figure 3 Investment and specific investment per MWh by plant size
Behaviour of variable costs

As plant size increases, there is a clear increase of taxes and lighter one of disposal costs, while
labour and maintenance tend to decrease, and capital cost remains almost stable (Figure 4).
Figure 4 Behaviour of variable costs
Variable costs breakdown

Variable costs breakdown shows almost stable capital cost figures as size plant increases, while
labour and maintenance figures decrease and disposal costs and taxes increase. Labour costs include
respective charges and taxes are based on revenues (Figure 5).
291
Figure 5 Variable costs breakdown
Behaviour of direct revenues

Direct revenues include sales of energy, recyclables and carbon credits market (Kyoto JI/CDM/IET).
Revenues increase directly with increasing size plants and generated power. Concerning revenues
per generated power, the curves show direct decrease with increasing plant size and generated
power, because of recyclables and carbon credit figures, which do not depend directly on power, but
on processed waste volume (Figure 6).
Figure 6 Direct revenues by plant size
Behaviour of Indirect benefits

Indirect benefits (or revenues) include savings concerning volume of waste disposed of at landfills,
which are charged by processed tonnage, and the amount spent at public health service to attend
patients affected by some kind of impact or disease originated by contact with waste. The third
amount refers to equivalent power generation at plants with non-renewable fuels. Since these
amounts are no longer spent, they may be considered as savings (Figure 7).
292
Figure 7 Indirect benefits by plant size
Bottom line behaviour

Bottom line for operational breakdown is slightly negative for smaller plants and shows a strong and
consistent positive take off at plant size four. In Brazil this is specially caused by high labour charges
of 123,5%, general taxes levels and maintenance costs, which carry the same joint burdens. A
reduction or exemption of taxes and charges could easily make all sizes operationally feasible. Other
developing countries with different taxation levels may present different feasibility scenarios.
General rule is: the less taxation is charged, the better. Considering the indirect benefits the bottom
line is always positive for all plant sizes (Figure 8).
Figure 8 Operational and general results (bottom line)
4- CONCLUSIONS
1. Financial results are positive for general balance of WPC plants.
2. Operational balance has increasing positive figures to WPC plants, showing benefits from
economy scale and a compensation effect at full plant size range.
293
3. Balance bottom line shows an improvement effect favouring WPC plants when including indirect
benefits (savings of health system, power generation based on non-renewable fuels and carbon
credits concerning disposing of at landfills).
4. Mega-cities and bigger cities can afford financing their own plants.
5. Smaller cities must work together and form consortiums to afford a common plant or decide for
cheaper or simpler technologies, for local use.
6. For small processing capacities WPC investment is lower, but specific investment per MWh is
higher. For big capacities the situation is the opposite.
7. Taxes (16,5%) and labour charges (123,5%) are the most significant components of variable cost
breakdown and heavily influence decision making.
8. Interest and attractiveness rates play a significant role at decision making and should be reduced
for a better financing of plants.
9. For imported components, taxes and exchange rates can influence the whole budget and even
make the project unfeasible. Local production may reduce this effect.
10. Indirect benefits must be considered as revenues, in the form of savings to the system, and not
only operational revenues directly to cash. They influence general bottom line.
11. Size, geographic distribution, topographic conditions, logistics and economic power of the
municipalities have a significant influence on decisions concerning introduction of WPC plants.
12. Operational balances and financial results could be improved by government incentives on
taxation and other factors of influence, besides political will from administration.
13. Technology level and deployment quantity seem to balance each other, especially at the
extremes of plant size range.
14. The longer the life span of the enterprise, the more of uncertainty and hedge should be brought
into consideration, as well as increasing rates of interest and attractiveness, while effective
investment per generated MWh decreases.
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295
A MODEL FRAMEWORK FOR EVALUATING SOCIO-ECONOMY CHANGES ON NON-

POINT SOURCE POLLUTION
HAN XIA1, JINGJING XIA1, HONG PENG2, WANSHUN ZHANG1,3

1 School of Resource and Environmental Sciences, Wuhan University, Wuhan, PR China.
2 School of water conservancy and Hydropower Engineering, Wuhan University, Wuhan, PR China.
3 School of Water Resources and Hydropower, State Key Laboratory of Water Resources and
Hydropower Engineering Science, Wuhan University, Wuhan, PR China.
Abstract
Socio-economy strongly affects non-point source (NPS) pollution. How much socio-economic factors
impact NPS pollution is difficult to evaluate [1, 2]. A framework based on the management modules
in Soil and Water Assessment Tool (SWAT) was developed in studying the relationship between
socio-economic changes and NPS pollution in the Three Gorges Basin. The rural population, Gross
Domestic Product and urbanization rate were selected as the indexes of socio-economy [3]. Total
nitrogen and total phosphorus were chosen as indicators of NPS pollution. The coefficient of
determination (R2) ranged from 0.73–0.89 for nutrient yield in the calibration and validation showed
a reliable simulation result. The annual loads of TN and TP were reduced by 71.1% and 21.1% in rural
areas. Because of reductions in arable lands, rural labor flowed out of rural areas seeking economic
opportunities, and agricultural activities decreased. The annual loads of TN and TP increased by
10.4% and 20.1% in urban areas, respectively. When urbanization accelerated, the level of
industrialization increased and urban population density increased, and subsequently the yield of
city garbage and waste water also increased. The framework is helpful for impact evaluation of
socio-economic changes on NPS pollution. It is expected to provide scientific references for
coordinating the management of social and economic development and the water environment at
the basin scale.
References
[1] Deng, K., Yang, S., Lian, E., Li, C., Yang, C., Wei, H., 2016. Three Gorges Dam alters the Changjiang (Yangtze) river
water cycle in the dry seasons: Evidence from H-O isotopes. Sci. Total Environ. 562, 89–97.
[2] Zhang, T., Ni, J., Xie, D., 2016. Assessment of the relationship between rural non-point source pollution and
economic development in the Three Gorges Reservoir Area. Environ. Sci. Pollut. Res. 23, 8125–8132.
doi:10.1007/s11356-016-6344-7.
[3] Hou, Y., Zhou, S., Burkhard, B., Muller, F., 2014. Socioeconomic influences on biodiversity, ecosystem services and
human well-being: a quantitative application of the DPSIR model in Jiangsu, China. Sci. Total Environ. 490, 1012.
296
BIOCONVERSION OF ORGANIC MATTER TO USEFUL CHEMICALS AND FUELS IN A

CIRCULAR BIOECONOMY APPROACH
I. ANGELIDAKI1
1 Dept. of Environmental Engineering, Technical University of Denmark.
Abstract
In biotechnological processes microorganisms, or their enzymes are used as catalysts to convert

components of biomass to products. During their metabolism microorganisms gain energy for their
growth and maintenance, and produce side products which we can use. Already in the 19th century,
there was large scale production of goods based on biomass. Examples hereby were pulp and paper
production from wood, nitration of cellulose from guncotton and viscose silk, production of lactic
acid acetic acid, citric acid and alcohol, are some of the early industrial productions. Nowadays many
of these compounds are produced from fossil fuels, which has put a break in the progress of this
broad application of biotechnology. Biotechnology has been developed in production of more
specialized high value components, as pharmaceuticals, enzymes, etc.
There is however nowadays, a general concern for the extensive use of fossil fuels which are finite
resources, i.e. resources which are not sustainable. Additionally, the political volatility of oil
producing countries, and the fast shifts on the fuel market is putting governments in need to make
long term planning in order to decouple from the fossil fuels dependency. Moreover, environmental
issues have brought circular bioeconomy in to focus, where biotechnology and waste treatment
together, play a significant role. Using waste biomass as raw material has the advantage of working
in a closed sustainable carbon cycle contrary to the open cycle of utilizing fossil fuel with net release
of GHG’s to the atmosphere. In the concept, organic biomass in wastes is converted to an number of
products, with prioritization of the high value products (low volume) and secondary to bulk
production of energy and fuels (high volumes) (Fig. 1).
Figure 1: Valorization of wastes/wastewaters to useful products by biological conversion technologies
297
ALDOL CONDENSATION OF BIOMASS-DERIVED VALERALDEHYDE AND

CYCLOPENTANONE OVER OXIDE CATALYSTS FOR PRODUCTION OF FINE CHEMICALS
AND FUELS
P. MÄKI-ARVELA1, N. SHCHERBAN2, N. KUMAR1, A. AHO1, K. ERÄNEN1, K. VOLCHO3,

D.YU. MURZIN1
1 Johan Gadolin Process Chemistry Centre, Åbo Akademi University, Turku, Finland
2 L.V. Pisarzhevsky Institute of Physical Chemistry, NAS of Ukraine, Kiev, Ukraine
3 Novosibirsk State University, Novosibirsk, Russia
Abstract
Aldol condensation of biomass-derived valeraldehyde (VA), produced from gamma-valerolactone

with cyclopentanone (CP) over basic catalysts to form 2-pentylidene-cyclopentanone used as a
fragrance [1] (Fig. 1) has been very scarcely investigated. The aim of the current work was to
investigate kinetics in cross-aldol condensation of VA with CP over various transition metal oxide
modified basic oxides. In addition, self-condensation of CP to form 2-cyclopentylidene
cyclopentanone, a fuel molecule [2] was studied in this work.
O O
Catalyst
O + CH3 + H2O
H3C
Figure 1: Simplified reaction scheme for aldol condensation of valeraldehyde with cyclopentanone
Several iron and cerium modified oxide catalysts were prepared using evaporation impregnation and
deposition precipitation methods and characterized by nitrogen adsorption-desorption, ammonia
temperature programmed desorption, pyridine adsorption-desorption with FTIR, TEM , XRD and
SEM-EDXA. Aldol condensation was typically performed using 2.7 g VA in 58 ml CP and 1.6 g catalyst
under 1 bar N2 at 130oC in a glass reactor. Periodically withdrawn samples were analysed by GC and
GC-MS.
The results showed that the highest amount of the desired product, 2-pentylidene-cyclopentanone,
maximally 80%, was formed over 14 wt% Fe2O3/CaO catalyst exhibiting 2.2 fold more basic sites
compared to 30 wt % CeO2/MgO, which also promoted formation of heavy side products. The self-
condensation of VA was more prominent, if less volatile mesitylene was used as a solvent. In
addition, selective synthesis of 2-cyclopentylidene cyclopentanone was demonstrated over
Fe2O3/TiO2.
Promising results in aldol condensation of valeraldehyde and cyclopentanone for synthesis of fine
chemicals and fuels exhibited by Fe2O3/CaO and Fe2O3/TiO2, respectively. The catalyst properties will
be correlated in the final work with their performance.
References
[1] [1] Hasni, M., Prago, G., Rouchad, J., Grange, P., Devillers, M., Delsarte, S. Liquid phase aldol condensation of
cyclopentanone with valeraldehyde catalysed by oxynitrides possessing tuneable acid–base properties, J. Mol.Catal.
A, Chem. 247, 116-123 (2006).
[2] [2] Liang, D., Li, G., Liu, Y., Wu, J., Zhang, X., Controllable self-aldol condensation of cyclopentanone over MgO-ZrO2
mixes oxides: Origin of activity & selectivity, Catal. Commun. 81, 33-36 (2016).
298
VALORIZATION OF DIGESTATE THROUGH SOLID STATE FERMENTATION TO PRODUCE

BIOPESTICIDES WITH Bacillus thuringiensis
P. RODRÍGUEZ, A. SÁNCHEZ, A. ARTOLA, X.FONT

Composting Research group, Department of Chemical, Biological and Environmental Engineering,
Escola d’Enginyeria, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193 Barcelona,
Spain.
Keywords: Bacillus thuringiensis, digestate, biopesticides, solid-state fermentation.
Abstract
This research is part of the DECISIVE project, funded by the European H2020 program (grant
agreement N°689229), which aims at proposing and testing a decentralized management scheme for
the valorisation of urban biowaste. The general objective of this research is the production of value
added bioproducts from digestate by using Solid State Fermentation (SSF). The bioproduct to be
explored is a biopesticide from Bacillus thuringiensis (Bt), which is known to have biopesticide
properties. The tests were performed at two scales: lab scale and bench scale, to scale-up the process.
The digestate was tested at lab scale using 500 mL reactors in triplicate with approximately 100 g of
digestate each. The duration of the SSF process was 4 days. Bt growth was successful at lab scale under
sterile and non-sterile conditions, obtaining 1.14·109 CFU g-1 dry matter (DM) and 16.9·108 CFU g-1 DM,
respectively. The process was then performed at bench scale using duplicated 4.5-L (1200 g) and 10-L
(2300 g) reactors operating under non-sterile conditions. The final material contained viable Bt cells
and spores in a number of 9.93·108 CFU g-1 DM and 8.51·108 CFU g-1 DM, and 2.94·109 CFU g-1 DM and
3.03·109 CFU g-1 DM respectively for both reactor volumes. In conclusion, bench scale-up was
performed with good results in terms of Bt growth.
299
1- INTRODUCTION
The increase in population leads to rising energetic and food needs in urban areas and makes urban
waste management increasingly challenging, both in terms of logistics, environmental and health
impacts. In the framework of the European Union HORIZON 2020 programme, the DECISIVE project
wants to demonstrate the capacity to reduce the generation of urban waste and increase recycling
and conversion through decentralized waste management and recovery of the organic fraction of
municipal solid waste (OFMSW). Nowadays, the preferred options to treat this waste are anaerobic
digestion (AD) and/or composting. In addition to these two main forms of valorisation of organic
matter, new biorefinery approaches are being developed aimed at the simultaneous production of
valuable bioproducts through the use of innovative conversion technologies such as solid-state
fermentation (SSF). SSF is a fermentation process that occurs in the absence or near absence of free
water in a substrate that contains sufficient moisture for the growth of microorganisms and their
metabolic activity[1]. SSF is an interesting alternative to conventional biological solid waste treatment
processes, as the final objective of the SSF process is to obtain a bio-product (enzymes, biosurfactants,
biopesticides,…) allowing, at the same time, the stabilization of the organic waste.
Hence, in the DECISIVE project, decentralized micro AD units are proposed for OFMSW treatment
together with the treatment of the obtained solid fraction from AD (digestate) by SSF to produce an
organic amendment with biopesticide effect. This amendment must have final characteristics
according to the fertilizers’ legislation.
In recent decades, the environmental and health risks associated with synthetic pesticides are driving
the creation of other biological insecticide substances. The risk due to the development of populations
of pathogens and pests resistant to the active ingredients of chemical pesticides has provided a great
impetus to look for new alternatives. These insecticide substances should be suitable for the
protection of people and livestock against parasites[2]. Biopesticides are certain types of pesticides
derived from natural materials such as animals, plants, bacteria, and certain minerals[3]. As
biopesticides are commonly biodegradable, they can decompose quickly and do not negatively impact
surface water and groundwater[4]. Like this, Bacillus thuringiensis (Bt) is a Gram-positive rod-shape
bacterium that during its sporulation phase produces a parasporal inclusion formed by Cry proteins
having biological activity against pest insects. Because of these proteins, Bt shows toxicity toward pest
insect larvae of Lepidoptera, Coleoptera and Diptera orders, among others, especially at the forest
habitats [5]. Conversely, they are innocuous for plants, animals and human beings.
There is a novel possibility of obtaining a soil amendment with added biopesticide properties through
waste based SSF processes in presence of Bt. Specifically, digestate from micro AD processes will be
used as substrate for Bt growth obtaining an active, low-cost and locally-produced biological control
agent.
300

Materials
The material used as substrate in SSF was digestate from an OFMSW treatment plant (Consorci per a
la Gestió de Residus del Vallès Oriental, Granollers, Spain). Wood chips were used as bulking agent.
The main properties of the mixture are listed in Table 1.
Parameter Average (±standard deviation) n=8*

Moisture Content (%, wb) 75.60±5.11
Organic Matter (%, db) 63.00±1.62
pH (1:5) 8.31±0.07
Carbon (%, db) 34.14±2.38
Nitrogen (%, db) 4.32±0.33
Hydrogen (%, db) 2.89±0.25
Sulphur (%, db) 0.33±0.14
C/N ratio 11.85±0.70
Hemicellulose (%, db) 10.06±0.90
Cellulose (%, db) 10.42±1.25
Lignin (%, db) 17.54±1.96
Table 1 Average characterisation of the digestate from the municipal solid waste treatment plant used in the fermentation processes.
*n: number of samples analysed.
wb: wet basis, db: dry basis
The digestate was stored at 4°C for a maximum period of one week before its use.
Yeast strain and inoculum preparation
B. thuringiensis var. Kurstaky NRRL HD-73 (CECT 4497) (Bt) used in this study was obtained from
Colección Española de Cultivos Tipo and stored in cryoperls at -80°C. A cryoperl of Bt was used to
inoculate a 500 mL Erlenmeyer flask containing 100 mL of culture media (broth nutrient sterilised at
121°C for 30 min). The flask was incubated in a shaker (180 rpm) at 30°C for 20 h. When the SSF was
carried out at bench scale, the amount of inoculum required was higher. In this case, the liquid culture
was not centrifuged but transferred to a 2-L reactor containing 10% (v/v) of inoculum of this broth
,1.1L of nutrient media, were Bt grew for 24 h at 30°C under static conditions with an airflow of 20 mL
min-1. .These flasks were subsequently incubated in the shaking incubator at 30°C for about 20h. In all
steps, the medium used for inoculum preparation was adjusted to pH 7.5, before sterilisation.
According to the growth kinetics of Bt var Kurstaky, after 20 hours the exponential stage of growth is
reached. At this time, the culture broth was centrifuged at 3500 rpm for 10 minutes and the pellet was
used to inoculate the digestate.
At the end of the fermentation, three analyses were performed routinely to confirm a proper growth
of the inoculum viz. optical density, dry matter and cell count. The values were around 3.5±0.3, 1.6±0.2
g L-1 and (2.35 ±0.04) ·107 CFU mL-1, respectively.
Analytical methods
301
Routine analysis of pH, water content (WC) and organic matter (OM) were performed according to
standard methods [6]. Cellulose, hemicellulose and lignin content were determined according to Van
Soest et al. (1991) using the Ankom200 Fiber Analyzer incubator (Ankom Technology, Macedon, NY).
To determine total cell count (CC), the samples were serially diluted under sterile conditions with
sterile saline solution, NaCl 0.85% (w:v). 0.1 mL of the appropriate dilution were plated on nutrient
agar plate and incubated at 30 °C for 24 h to allow the development of the colonies. For spore count
(SC), the same appropriate dilution was heated at 80 °C for 10 min and then chilled on ice for 5 min.
Then, this solution was also plated in nutrient agar as for cell count. Assays were made in triplicate
and results were expressed as colony forming units per mL (CFU mL -1). 30 to 300 colonies were
enumerated per plate, plates out of this range were discarded.
SSF monitoring parameters
Respiration index expressed as specific oxygen uptake rate (sOUR) was used to indirectly measure the
biological activity during the SSF processes. sOUR in mg O2 g-1 DM h-1 was calculated as Equation 1[7]
(𝑂2,𝑖 −𝑂2,0 )·𝐹·31.98·60· 1000𝑎

𝑠𝑂𝑈𝑅 = (1)
1000𝑏 ·22.4·𝐷𝑀
where, sOUR is the specific oxygen uptake rate (mg O2 g-1 DM h-1); (O2,i-O2,0), the difference in oxygen
content between airflow in and out of the reactor at a given time, in molar fraction; F, the volumetric
airflow measured under normal conditions (1 atm and 273 K); 31.98, the oxygen molecular weight (g
mol -1) ; 1000a ,the conversion factor (mg g-1); 1000b, the conversion factor (mL L-1); 22.4, the volume
occupied by one mol of ideal gas under normal conditions (L); DM, the dry mass of the substrate under
study that is loaded in the reactor (g).
Other process parameters as airflow, temperature and oxygen content were also monitored [7].
SSF reactors
Different fermentation scales have been used in this work: 0.5-L flasks and 4.5-L and 10-L packed-bed
bioreactors consisting of Dewar vessels. In all the fermentation systems, humidified air was
continuously supplied to the reactors by means of an air mass flow meter (Bronkhorst, Spain). The air
entered the bioreactor below the bed, passing through the solid bed and exiting at the top. The oxygen
concentration in the exhaust gases was measured by an oxygen detector (O2A2, Alphasense, UK) and
recorded in a personal computer. These data were used for the calculation of the sOUR.
In the fermentations carried out in 0.5-L reactors, a mixture of digestate and bulking agent in a 1:1
(v/v) ratio was used. The total weight of the sample was 120 g and a ratio of 0.040 g Bt g-1 digestate
was used per batch. Each fermentation was performed in triplicate inoculating the waste with Bt at
the beginning of the test and kept for 4 days (96 hours) at a temperature of 30°C and airflow of 20 mL
min-1. A control reactor was also set, containing the substrate without Bt inoculation. Five samplings
were performed during the process, at the beginning of the SSF process, at 24, 48, 72and 96 hours.
When the fermentations were carried out in 4.5-L and 10-L the total weight of the solid mixtures were
1200 g and 3500 g, respectively. The ratio Bt-digestate was the same as the laboratory scale assays.
Wood chips were added as bulking agent in a ratio of 1:1 (v/v) in order to provide enough porosity to
302
promote proper oxygen transfer[7]. Each fermentation was performed in duplicate inoculating the
waste with Bt at the beginning of the test and kept for 4 days (96 hours). Operational conditions of
the fermentations were: airflow between 400 to 800 mL min-1 in 4.5-L and 10-L reactors. Five
samplings were also performed, one at the beginning of the SSF process and at 24, 48, 72 hours and
another at 96 hours, the end of the fermentation.. Besides the viable cells count, spores quantification,
sOUR monitoring and several physicochemical parameters were measured at these times: pH, dry
matter, organic matter.

SSF experiments at 0.5-L scale
SSF experiments were carried out inoculating Bt on sterilized and non-sterilized digestate on day 0. At
the same time, controls (non-inoculated) were also performed for each case.
Under sterile conditions and non Bt-inoculated process (Figure 1a), the sOUR indicates a low biological
activity. The maximum peak is observed at 35 hours with a value 0.82 mg O 2 g-1 DM h-1. In the Bt-
inoculated process the maximum activity occurs at 20 hours with value of 1.98±0.08 mg O2 g-1 DM h-
1
. In non-sterile conditions (Figure 1b), the activity was higher than under sterile conditions, because
of the presence of more microorganisms. In this case, a maximum peak was observed at 11 hours with
a value 2.79 mg O2 g-1 DM h-1 in the non-inoculated process while increased to 3.23±0.83 mg O2 g-1
DM h-1 when the digestate was inoculated with Bt.
Under sterile conditions (Figure 1a), the initial Bt viable cells was 1.31 ± 0.01 (107) CFU g-1 DM, while
in non-sterile conditions was 9.7±0.5 (109) CFU g-1 DM. Thus, the growth of Bt was more favourable in
sterile conditions, increasing 98% the number of colonies, while in non-sterile conditions the growth
was 40%. Obtaining a maximum viable CC at 72 hours in non-sterile conditions with a value of 1.52 ±
0.24 (109) CFU g-1 DM. Other studies using other substrates working at the same conditions observed
a final CC of 6.6 1010 CFU g-1 DM [8] and 6.2 1011 CFU g-1DM [9], which is higher than the obtained in
the present study using digestate as the substrate. However, it has to be considered that the
substrates were wheat bran[8] and soy fibre[9], respectively, which show less heterogeneity and were
provided with external carbon and nitrogen sources[10]. In this case, the authors observed a viable CC
of 1.9·109 CFU g-1 DM, which is in range of the obtained in the present work.
303
a) Sterile conditions
sOUR, Specific Oxygen Uptake Rate [mg O2 g-1DM h-1 ]

10 1e+10
Cell Count [CFU g-1 DM]

1e+9
6
4
1e+8
0 1e+7
0 20 40 60 80 100
Time [h]
b) Non-sterile conditions
10 1e+10
Cell Count [CFU g-1 DM]

1e+9
6
4
1e+8
0 1e+7
0 20 40 60 80 100
Time [h]
sOUR Digestate
sOUR Digestate inoculated Bt
Viable Cells
Figure 1. Average sOUR and viable cell at laboratory scale 500ml of SSF inoculated at 0h with Bt in reactor R1, a) under sterile
conditions and b) under non-sterile conditions.
SSF experiments at 4.5-L and 10-L
Experiments at bench scale were undertaken under non-sterile conditions and non-controlled
temperature. At the same time, controls (Bt non-inoculated reactors) were performed for each case.
Figure 2 presents the complete operational profile (sOUR, temperature, viable cells and spores) of the
4.5-L reactor inoculated with Bt. The experiments carried out in 4.5-L reactors showed the same trend
than the obtained at lab scale (0.5-L reactors). Fermentations reached the maximum sOUR after 12h
of operation, with a maximum value of 1.2 and 3.67 mg O 2 g-1DM h-1 for the digestate and digestate
inoculated with Bt, respectively. The temperature remained in the mesophilic range reaching a
maximum of 40°C, approximately. This temperature range provided proper growth conditions for Bt,
therefore the survival and colonization of Bt onto the solid matrix was expected. Observed colonies
304
growth sharply through the process, while spores were maintained during the process with values of
9.93±0.12(108) CFU g-1 DM and 8.51±0.54(108) CFU g-1 DM, respectively.
In the case of the inoculated process at 10-L reactor (Figure 3) the oxygen consumption was higher
than in the 4.5-L reactor, as well as the temperature, reaching a thermophilic temperature of 66.8°C.
This factor can explain that Bt growth was less than in 4.5-L reactors. The values of colonies and spores
were practically constant along the process around 5.42±0.04(109) CFU g-1 DM and 3.12 109 ± 1.75 (108
) CFU g-1 DM, respectively.
10 1e+10 80
Cell Count and Spores Count [CFU g-1DM]

8
60
1e+9
Temperature [ºC]
6
40
4
1e+8
20
2
0 1e+7 0
0 20 40 60 80 100
Time [h]

Viable Cells
Spores
Temperature
Figure 2. Average sOUR, temperature, viable cell and spores under non-sterile conditions at bench scale 4.5-L of SSF inoculated at 0h
with Bt.
10 1e+10 80
Cell Count and Spores Count [CFU g-1DM]
8
60
1e+9
Temperature [ºC]
40
4
1e+8
20
2
0 1e+7 0
0 20 40 60 80 100
Time [h]

Viable Cells
Spores
Temperature
Figure 3 Average sOUR, temperature, viable cell and spores under non-sterile conditions at bench scale 10-L of SSF inoculated at 0h
with Bt.
305
Spore count obtained in the present study is comparatively higher than that reported as a cost-
effective method to produce Bt based biopesticides using wastewater sludge as raw-materials under
SSF [11]. In that study, more than 1010 CFU g-1 DM of viable cells of Bt were obtained using sludge or
its mixture with agricultural wastes.
4- CONCLUSIONS
Digestate was used as raw material to produce an organic amendment with biopesticide potential
through solid state fermentation using Bacillus thuringiensis var. Kurstaki. At laboratory scale. Bt was
able to growth with digestate under sterile and non-sterile conditions. Also, bench scale-up was
performed with good results in terms of the growth of Bt. Despite the fact that temperature in 10-L
reactors increased up to the thermophilic range, the growth of Bt was observed in viable cells and
spores with values of 5.42 ± 0.04 (109) CFU g-1 DM and 3.12 ± 0.1 (109) CFU g-1 DM, respectively, at 72
hours of process.
REFERENCES
[1] A. Pandey, “Solid-state fermentation,” Biochem. Eng. J., vol. 13, no. 2–3, pp. 81–84, 2003.
[2] R. Pavela, A. Canale, H. Mehlhorn, and G. Benelli, “Application of ethnobotanical repellents and acaricides in
prevention, control and management of livestock ticks: A review,” Res. Vet. Sci., vol. 109, pp. 1–9, 2016.
[3] EPA, “What are Biopesticides?,” 2015. [Online]. Available: https://www.epa.gov/ingredients-used-pesticide-
products/what-are-biopesticides.
[4] A. Haroun, M. Adam, I. Mohamed, F. Abdalla, M. Abdelkreim, and A. Ibrahim, “Analysis Of Soil NPK , Ph And
Electrical Conductivity At Adham Area- Renk , Upper Nile State,” Int. J. Sientific Technol. Res., vol. 4, no. 12, pp.
341–347, 2015.
[5] M. Mohan and G. T. Gujar, “Characterization and comparison of midgut proteases of Bacillus thuringiensis
susceptible and resistant diamondback moth (Plutellidae: Lepidoptera),” J. Invertebr. Pathol., vol. 82, no. 1, pp.
1–11, 2003.
[6] The US Composting Council, “Field Guide To Compost Use,” pp. 1–94, 2001.
[7] S. Ponsá, T. Gea, and A. Sánchez, “The effect of storage and mechanical pretreatment on the biological stability
of municipal solid wastes,” Waste Manag., vol. 30, no. 3, pp. 441–445, 2010.
[8] P. S. V. Devi, T. Ravinder, and C. Jaidev, “Cost-effective production of Bacillus thuringiensis by solid-state
fermentation,” J. Invertebr. Pathol., vol. 88, no. 2, pp. 163–168, 2005.
[9] C. Ballardo, J. Abraham, R. Barrena, A. Artola, T. Gea, and A. Sánchez, “Valorization of soy waste through SSF for
the production of compost enriched with Bacillus thuringiensis with biopesticide properties,” J. Environ.
Manage., vol. 169, pp. 126–131, 2016.
[10] C. Ballardo, R. Barrena, A. Artola, and A. Sánchez, “A novel strategy for producing compost with enhanced
biopesticide properties through solid-state fermentation of biowaste and inoculation with Bacillus thuringiensis,”
Waste Manag., vol. 70, pp. 53–58, 2017.
[11] L. Zhuang, S. Zhou, Y. Wang, Z. Liu, and R. Xu, “Cost-effective production of Bacillus thuringiensis biopesticides by
solid-state fermentation using wastewater sludge: Effects of heavy metals,” Bioresour. Technol., vol. 102, no. 7,
pp. 4820–4826, 2011.
306
FOOD WASTE PIGMENTS FOR NATURAL HAIR DYES: ULTRASOUND-ENHANCED

ENZYMATIC EXTRACTION AND HAIR DYE APPLICATION
S. TAYLOR1, J. LEE2, M. BUSSEMAKER2

1 Celbius Ltd., Soham, UK.
2 University of Surrey, Guildford, UK.
Abstract
Waste fruit and vegetables are a potential source of naturally derived pigments for various food,
cosmetic and consumer applications. Permanent hair dyeing methods generally involve several
components consisting of harsh chemicals such as ammonia and hydrogen peroxide, and aromatic
amines for which there are significant safety concerns. This work aims to replace the use of these
chemicals with natural alternatives, such as coloured plant pigments. These pigments are inherently
safe for the consumer and provide a sustainable option for the cosmetic industry. However to-date
natural pigments have not achieved significant commercial penetration, even for temporary
colouring of hair.
In this work natural pigments were extracted using ultrasound-assisted enzymatic extraction,
followed by augmentation of hair colouration using ultrasound. In other enzymatic processes,
ultrasound improved the total yield, reaction rate and required enzyme loading. All of which are
dependent on the ultrasonic parameters and enzyme characteristics. [1] Furthermore, ultrasound
has been demonstrated to be effective at enhancing the colouration of wool [2] and nanofibers, [3]
reducing treatment time, and increasing permeability and uptake of the colour.
In this work ultrasound-enhanced extraction of natural pigments was used to create a medium for
application to goat hair as a model for human hair. Then, ultrasound was applied to increase
colourant performance, evaluated using colour fast testing, spectrophotometry and hair damage was
investigated using scanning electron microscopy.
This work will be presented and discussed in the context of literature and the potential development
of environmentally-friendly hair dyes, and technology for the application of natural hair dyes.
References
[1] Kwiatkowska B, Bennett J, Akunna J, Walker GM, Bremner DH. Stimulation of bioprocesses by ultrasound.
Biotechnol. Adv. 29(6), 768-80 (2011)
[2] Ferrero F, Periolatto M. Ultrasound for low temperature dyeing of wool with acid dye. Ultrason. Sonochem. 19(3),
601-6 (2011)
[3] Khatri M, Ahmed F, Jatoi AW, Mahar RB, Khatri Z, Kim IS. Ultrasonic dyeing of cellulose nanofibers. Ultrason.
Sonochem. 31, 350-4 (2016)
307
AN IMPROVED MODEL-FREE KINETIC APPROACH TO STUDY

THE THERMAL DEGRADATION OF SOLIDS
M. GRIGIANTE1*, M. BRIGHENTI1, M. MALDINA1, D. ANTOLINI2

1
Department of Civil, Environmental and Mechanical Engineering, University of Trento, Trento, Italy
2
Faculty of Science and Technology, Free University of Bozen, Bozen, Italy
Abstract
The purpose of this study consists in presenting an improved approach to investigate the kinetics of
thermal degradation of solids including biomasses. This investigation aims to exploit the potentialities
of the “model-free” methods [1] in setting up an innovative computational procedure to completely
describe the kinetics of the indicated process.
The methods adopted in this investigation extend the consolidated “model-free” procedures [2],
usually limited to activation energy determination, by introducing a new kinetic parameter (φα) that
replaces both the Arrhenius pre-exponential factor A and the f(a) reaction function. Furthermore, the
resulting new kinetic equation is solved by implementing a generalized computational method based
on a finite difference scheme.
As main result, the proposed procedure limits the kinetics definition only to two parameters
replacing, therefore, the conventional kinetic triplet. As main consequences, the model presents an
effective “model-free” character and, due to the included computational procedure, can be applied
to any heating program, isothermal or not.
As main conclusions this method can work also in a complete predictive option when applied to
similar types of materials. This has been tested for biomasses for which it reaches an accuracy level
(AAD%) within 1,5%. In any case the setting up of the proposed method requires a limited amount of
experimental data and looks therefore promising to model the thermal degradation kinetics of solids.
References
[1] Berčič, G.: The universality of Friedman’s isoconversional analysis results in a model less prediction of
thermodegradation profiles. Thermochimica Acta 650, 1-7 (2017).
[2] Vyazovkin, S., Wight, CA.: ICTAC Model-free and model-fitting approaches to kinetic analysis of isothermal and non
isothermal data. Thermochimica Acta 340, 53-68 (1999).
308
DISTRIBUTION OF ASH FORMING ELEMENTS DURING PYROLYSIS OF WASTE WATER

TREATMENT SLUDGE FROM MILK PROCESSING FACTORIES
M. KWAPINSKA1, JAMES J. LEAHY2

1 Dairy Processing Technology Centre, University of Limerick, V94 T9PX, Ireland.
2 Department of Chemical Sciences, Bernal Institute, University of Limerick, V94 T9PX, Ireland.
Keywords: Dairy processing sludge, pyrolysis, ash forming elements, heavy metals
Abstract
In Ireland the majority of the sludge from the treatment of wastewater in milk processing plants is
land spread. Drawbacks of land spreading include local oversupply due to high transport costs, which
results in sludge being spread on lands in the vicinity of the dairy factories. Local oversupply can lead
to the accumulation of certain substances in soil through annual application over many years.
Therefore, in the long term, there is a need for alternative methods to recover energy and nutrients
from increasing volumes of sludge generated from dairy processing.
Pyrolysis can provide a viable alternative, which can reduce health and environmental risks, while
providing an avenue for the recovery of energy and nutrients. One of the main concerns related to
thermal conversion technologies is the release and fate of heavy metals and contaminants existing in
the feedstock. Therefore, an understanding of the transformation pathways of problematic
compounds is necessary to assess the suitability of pyrolysis.
In this study pyrolysis of dried dairy sludge was carried out using a laboratory fixed bed reactor. The
mass balance information obtained from the experimental tests was used for an indicative distribution
of major and minor ash forming elements between solid and liquid pyrolysis products.
The results indicate that Ca, Fe, P, Si and Al are predominantly retained in pyrolysis chars (pyrogenic
solids). However, small quantities of non-volatile elements were also detected in pyrolysis oil and in
the aqueous fraction. From 50 to 75 % of K and S in biological sludge BS and dissolved air flotation
sludge DAF and around 50 % of Na in DAF was retained in the solids with significant quantity captured
in the liquid fraction.
309
1- INTRODUCTION
The dairy industry accounts for approximately 30% of Irish agri-food exports, with 80 % of milk
products being exported [1]. In order to promote growth within this sector, the Irish government has
adopted strategies that offer scope for significant expansion with the aim to increase milk production
by 50% overall by 2020 using the average of the outputs from 2007 to 2009 as a baseline. An increase
in primary production will inevitably lead to an increase in the generation of processing waste such as
sludge from the treatment of wastewater from milk processing plants. The composition of dairy sludge
depends on the type of products being manufactured and cleaning process deployed at the plant. In
general, there are two main sludge types: i) chemical sludge which is a mixture of fat, grease, oil and
suspended solid particles removed from raw effluent in the waste water treatment plant together
with some proteins and minerals by dissolved air flotation (DAF) and ii) biological sludge which is an
organic material, containing suspended solids and non-biodegradable pollutants such as heavy metals
resulting from biological aerobic, anaerobic or anoxic waste water treatment processes [1,2]. In
Ireland the majority of sludge is land spread, e.g. in 2004 around 120,661 tonnes of dairy sludge was
land spread [3]. Some sludges are sterilised and stabilised by composting and then returned to land.
DAF sludge is sometimes used as a feedstock for anaerobic digestion. However, milk fat is not easily
bio-degraded and causes technological issues [4,5]. When dairy sludge is used as an organic, nutrient
rich fertiliser [6] a strict code of practice must be complied with once a Nutrient Management Plan has
been approved by the Environmental Protection Agency [7]. Drawbacks of land spreading include local
oversupply due to high transport costs, which results in sludge being spread on lands in the vicinity of
the dairy factories; also weather conditions could constrain the land spreading. Local oversupply can
lead to the accumulation of certain substances in soil through annual application over many years.
Therefore, in the long term, there is a need to find alternative methods to recover energy and nutrients
from sludge generated from milk processing plants.
In recent years, pyrolysis has gained an increased focus as an alternative disposal method for sewage
sludge [8,9]. According to a study by Samolada and Zabaniotou [8], pyrolysis can provide an optimal
thermochemical treatment option compared to gasification and incineration. Pyrolysis can reduce
health and environmental risks from problematic wastes [10-12] while providing an avenue for the
recovery of energy and nutrients [13,8]. Pyrolysis is the thermal decomposition of carbonaceous
material in an inert atmosphere into gaseous, liquid and solid products. Pyrolysis gas contains non-
condensable low-molecular-mass gases such as H2, CO, CH4, C2H4, C2H6 and CO2. The liquid product
contains condensable volatile compounds, water and water-soluble organics [14]. The solid residue
obtained (char) comprises mainly of carbon and ash. Pyrolysis product yields are affected by the
process conditions including temperature, reactor residence time as well as feedstock properties. Slow
pyrolysis is generally characterised by relative mild temperatures (350-700°C) and heating rates [8].
One of the main concerns related thermal conversion technologies is the release of heavy metals and
contaminants like NH3, HCl, HCN, H2S [15]. The low pyrolysis temperature is responsible for the
absence of heavy metals in the pyrolysis gas; these remain concentrated mostly in the resulting
carbonaceous solid product. The potential application of all pyrolysis products greatly depends on the
presence of various contaminants. According to Chen at al [16], heavy metal speciation and
distribution is an important indicator for evaluating pyrolysis as a disposal method and further
application of the char.
This study is part of a project, which investigated the potential of pyrolysis as a conversion technology
for sludge from milk processing factories in the framework of a state-founded Dairy Processing
Technology Centre. In this study, samples of dairy sludge (DS) were pyrolysed using a fixed bed reactor
310
in order to measure the amount of pyrolysis products and determine their ultimate properties and
content of major and minor ash forming elements. The distribution profile of nine major and 15 minor
elements between pyrolysis char and liquid products was investigated.

Dairy processing sludge samples from five milk processing plants in Ireland are the focus of this work.
The dairy sludge samples were of two types collected on the same day from companies: sludge after
biological treatment processes with cationic polyelectrolyte addition to aid coagulation and from a
dissolved air floatation process (DAF). Samples of Biological sludge (BS) were denoted BS-1 to BS-4 and
BS-DAF-5, which was a mixture of Biological and DAF sludge. Samples of DAF sludge were denoted
DAF-1 to DAF-4.
All DS samples were bench dried at ambient temperature and then pyrolysed in a laboratory scale
fixed bed reactor. The pyrolysis set-up consisted of a quartz tube coupled with a condenser cooler and
a twin-neck round-bottom receiving flask where the pyrolysis liquid was collected [17]. The condenser
outer jacket was cooled through circulation of a refrigerated liquid at -5°C. The outlet of the receiving
flask was connected to a rubber tube fitted with a connector, which enabled gas sampling or
connection to an extraction hood, where the permanent gases were discharged. The quartz tube
reactor was wrapped with a heating tape and two layers of woven high-temperature insulation were
wrapped around the outside of the heating tape. An electro-thermal power regulator was used to
supply the heating tape with electricity. A batch of dried sludge in a steel-mesh basket was placed in
the reactor, heated to 700°C, and kept at this temperature for 10 minutes during which the feedstock
was pyrolysed. The product gas generated was cooled to room temperature while passing through the
cooler, and a sample of gas was collected. Then the heating jacket was turned off and the char was
cooled to room temperature while still in the reactor. The char yield was determined as the ratio of
the mass of char after pyrolysis to the initial sample mass. The vast majority of pyrolysis liquid was
collected in the receiving flask; however, some of the oil/tar condensed on the cool parts of the
experimental set-up. Therefore, in order to account for this fraction before and after each series of
pyrolysis runs, the reactor with the heating tape and insulation, the receiving flask, the dry condenser,
the rubber stopper and all of the connected glass ware were weighed to obtain the mass of the liquid
fraction.
Analysis of the proximate and ultimate properties of the dried sludge samples and the pyrolysis chars
was carried out by Celignis Analytical, Ireland. The moisture content was analysed according to BS EN
14774-1: 2009 and the ash content according to BS EN 15403: 2011. The elemental composition (C, H,
N, S) was determined using a Vario EL cube elemental analyser. Inorganic constituents were measured
using inductively coupled plasma optical emission spectrometry (Agilent 5100 ICP-OES fitted with an
SPS4 auto-sampler) after nitric acid and hydrogen peroxide and hydrofluoric acid (HNO 3-H2O2-HF)
digestion in a microwave oven according to BS EN 15290:2011. Before digestion, sludge and char
samples were ashed at 550°C. Duplicate samples of sludge and pyrolysis solids were ashed, digested
and analysed. In order to measure the content of inorganic components in the liquid products, 1g of
pyrolysis liquid was digested using HNO3-H2O2-HF in a microwave oven according to BS EN 15290:2011.
The mass fraction was used to illustrate the retention of major and minor elements in sludge derived
solid and liquid products, and was calculated according to following equation
𝑀
Mass fraction %= 𝑀 𝑖 (1)
0
311
where Mi is the mass of elements in a certain product and M 0 is the mass of elements in a dry sludge
when results on a dry basis are reported (Fig. 5, 6, 7 and 8) or in sludge which contained some moisture
when pyrolysed (Fig. 9, 10, 11 and 12).

3.1 3.1 Properties of dairy sludge
In Table 1 the properties of the different dairy sludge samples are presented. In most of the sludge
samples tested relatively high ash contents (from 30 - 45 wt. %(dry basis)) were observed except for
DAF-1 with the lowest ash content of 13 wt. % and the mixture BS-DAF-5 with 25.4 wt. %. The nitrogen
content was high, between 4 and 5 wt. % for most BS and DAF-3, however it was lower in the remaining
DAF samples at 1-2 wt. % and BS-DAF-5 with 3.3 wt. %. High nitrogen content was one typical
characteristics of dairy sludge resulting from biological and chemical treatment of defatted effluent
[13]. The sulphur content in all BS samples and DAF-3 was from 0.4 to 0.9 wt. % while it was much
lower at around 0.1 and 0.2 wt. % in the other DAF sludge samples.
Properties, wt. BS-1 BS-2 BS-3 BS-4 BS- DAF-1 DAF-2 DAF-3 DAF-4
% DAF-5
Moisture, ar. 88.6 82.5 89.0 83.8 86.5 94.4 60.3 72.3 82.2
Moisture, after 17.9 50.3 12.4 13.5 8.64 3.2 18.3 21.6 17.3
bench drying
Ash content, db. 42.1 44.1 22.6 40.2 25.4 12.9 31.9 42.5 38.8
C, db. 27.4 28.8 40.2 28.9 49.1 63.1 46.9 32.2 36.5
H, db. 4.8 3.6 5.7 3.8 8.0 11.0 6.4 4.6 4.5
N, db. 5.2 6.1 8.5 5.3 3.3 0.9 1.2 5.8 2.0
S, db. 0.9 0.6 0.7 0.4 0.4 0.1 0.2 0.4 0.2
O, db. 19.6 16.8 22.3 21.4 13.8 12.0 13.4 14.5 18.0
Table 1: Ultimate properties of dairy sludge (Biological Sludge-BS and sludge from Dissolved Air Floatation –DAF) .
3.1 Major and minor ash forming elements

The content of the major ash forming elements in dry sludge samples is shown in Fig. 1 and 2. It can be
seen from the figures that the Si content was the highest among all elements for both sludge types, in
the range from 120 to 900 g/kg. The second, most abundant element in the majority of dried sludge
samples was Ca. However, there were substantial differences in Ca contents between particular samples.
The Ca content in BS was in the range from 23 to 90 g/kg and in DAF from 15 to 195 g/kg. On average,
the content of Al was higher in BS samples (around 35 g/kg) while significant difference were observed
in DAF concentrations. The highest Al concentration among DAF samples was in DAF-1 at 25 g/kg while it
was only 3 and 15 g/kg in DAF-3 and DAF-4, respectively. Overall, similar concentration of Na (20 - 30
g/kg) were observed in both sludge type samples. However, in BS-4 and DAF-2 about 75 g/kg of Na was
detected. Generally, the Fe content was similar in BS and DAF samples ranging from 1 to 5 g/kg with the
exception of BS-2 in which 90 g/kg was observed. Slightly higher contents of K was observed in BS than
in DAF samples (7-15 g/kg vs 2-5 g/kg, respectively). The Mg content was similar in most BS and DAF
samples from 2 to 6 g/kg except for BS-4 and DAF-4 in which 13 g/kg was observed. Generally, comparable
concentrations of S was observed for both types of sludge 1 - 3 g/kg. The P content was relatively low
about 1 g/kg in all sludge samples with an exception of BS-1 and DAF-1 (company 1) with 40 and 10 g/kg,
respectively.
312
The differences in the composition of sludge samples arises from the fact that different milk products
were produced by the companies and the composition of the effluent and resultant sludge samples were
different. Moreover, the dosage of flocculants used probably also differed within the wastewater
treatment plants.
BS-1 BS-2 BS-3 BS-4 BS-DAF-5

800000
400000
180000
165000
150000
135000
120000
105000
90000
75000
60000
45000
30000
15000
0
Al Ca Fe K Mg Na P S Si
Elements
Figure 1: Major elements in Biological sludge
DAF-1 DAF-2 DAF-3 DAF-4

800000
400000
195000
180000
165000
150000
mg/kg of dry sludge
135000
120000
105000
90000
75000
60000
45000
30000
15000
0
Elements
Figure 2: Major elements in DAF sludge
The content of minor ash forming elements in dry sludge samples is shown in Fig. 3 and 4. It can be
seen from the figures that in general the content of most heavy metals is low in BS. In particular, the
content of As, Cd, Co, Cr, Cu, Hg, Ni, Pb, Sb, Se and V in BS was below 50 mg/kg with the exception of
Cr and Ni content in BS-3 of around 100 mg/kg and 450 mg/kg of Pb in BS-2. Likewise, a low
concentration of Cr, Cu, Hg, Ni, Mn, Sb, Se and V was observed in all DAF samples while there was no
Cd and Co. In general, the Pb content was also very low, (below 50mg/kg) excluding DAF-14 with 100
mg/kg of Pb in dry sludge. Overall, in BS and DAF the highest concentration of Ti and Zn was observed
313
from 200 - 300 mg/kg and 100-150 mg/kg, respectively. In BS-2 and BS-3 the Mn content was around
200 mg/kg while Ba was high at 400 mg/kg in BS-4 and DAF-4.
BS-1 BS-2 BS-3 BS-4 BS-DAF5

500
mg/kg of dry sludge 400
300
200
100
0
As Ba Cd Co Cr Cu Hg Mn Ni Pb Sb Se Ti V Zn
Elements
Figure 3: Minor elements in Biological sludge.
DAF-1 DAF-2 DAF-3 DAF-4

500
400
mg/kg of dry sludge
300
200
100
0
Elements
Figure 4: Minor elements in DAF sludge
3.2 Retention of major and minor elements in pyrolysis char

The average values and distribution of the pyrolysis products obtained in the laboratory scale
experiments are reported in Table 2. Owing to the relatively high initial ash content, pyrolysis of BS-1
and DAF-2 produced a significant quantity of pyrolysis solids comprising of 42 % and 37 % of the initial
dried sludge mass, respectively. For BS-1 samples, the remaining 58 % was more or less equally split
between liquid (31 %) and gaseous (27 %) products. Relatively low yield of liquid fraction was obtained
for DAF-2 at 15 % while the gas fraction was 48 %. The partitioning of solid and liquid pyrolysis products
showed slight differences for DAF-1, having less solids (15 %) while the gas fraction was the highest
among all tested sludge samples (65 %). The BS-2 Sludge was not sufficiently dried before the
314
experiments (moisture content of 50 wt. %). Therefore, the main pyrolysis product was liquid (water
+ oil) at 70 %.
The experimental uncertainty in the char yield was low because the sludge sample and char were
measured directly. In contrast, the liquid yield had a greater uncertainty because there was always
some oil condensed in the gas sampling bags. This indicates that some pyrolysis products escaped the
apparatus as vapours or aerosols. Thus, based on the conservation of mass, the measured liquid
fraction should be considered the minimum. Consequently, as the gas yield is calculated as the
difference between the solid and the liquid pyrolysis products and the initial sample mass, the gas
yield should be considered the maximum value.
Residue type Solid product, wt. % Liquid yield, wt. % Gas yield, wt. %
BS-1 42.3 30.9 26.8
BS-2 18.5 70.1 11.5
DAF-1 15.2 19.9 64.9
DAF-2 37.5 14.7 47.8
Table 2: Average product distribution from pyrolysis of sludge samples at 700°C for 10 min.
Results of the ultimate analysis of the solid pyrolysis products are presented in Table 3. The solid
product from pyrolysis most often are called chars, but when the ash content in solids is over 50%
according to nomenclature intruded by European Biochar Certificate, term pyrogenic carbonaceous
material is used instead. The solid products, from BS and DAF pyrolysis consisted mainly of ash at about
68 - 81 wt. %, therefore the term pyrogenic carbonaceous material is also used in further discussion.
Properties, wt. % BS-1 BS-2 DAF-1 DAF-2
Moisture, ar. 1.3 1.7 2.2 0.3
Ash content, db. 76.5 81.5 74.2 68.9
C, db. 17.6 14.8 20.7 12.1
H, db. 0.9 0.3 1.0 0.1
N, db. 2.2 1.6 0.9 0.2
S, db. 0.3 0.4 0.1 0.2
O, db. 1.2 -0.4 0.8 18.2
Table 3: Ultimate properties of pyrolysis chars.
150
150 DAF-1
BS-1 DAF-2
BS-2 125
125
100
Mass fraction, %
100
Mass fraction, %
75
75
50
50
25
25
0
0
Al Ca Fe K Mg Na P S Si Elements
Elements
Figure 5: Major elements in Biological sludge. Figure 6: Major elements in DAF sludge.
315
The results for the retention of the major elements in the char (pyrogenic solids) are presented in Fig.
5 and 6. On average over 80 % of initial fraction of all major elements was retained in the char
(pyrogenic solids) for BS except for S and K. For DAF samples, over 90 % of Al, Ca, Fe, P and Si was
retained in the char but only about 50 % of K, Mg, Na and S. Similar findings related to sulphur
release/retention were reported in the literature [15]. Looking at individual BS and in particular DAF
samples it is anticipated that some non-volatile elements like Mg, Si, Ca, Al seems to be released with
the vapour phase during pyrolysis or the mass balance closure is poor in these cases due to errors
associated with analytical procedure.
Most of the minor elements Ba, Cd, Cu, Cr, Mn, Ni, Pb, Sb, Ti, V and Zn, were retained in the char
(pyrogenic solids) of BS (Fig 7). Similar observations for Cu, Cr, Ni, Pb and Zn have been reported [11].
Hen et al. [21] observed that only about 10% of Pb was volatilised during slow pyrolysis at 923K. On
the other hand, for the DAF only a fraction of Ba, Cd, Co, Pb, Sb was conserved in the char (pyrogenic
solids). Dong et al. [22] found that cadmium was more volatile in the reducing atmosphere of the
pyrolysis process. Significant release of Se during pyrolysis at temperatures above 550°C was reported
[23,4].
The most volatile trace element [23], mercury was primarily in the gaseous product, despite significant
amounts retained in the char (pyrogenic solids) of BS-1. Arsenic can also be a mobile element in sludge
[21].
150
150 DAF-1
BS-1 DAF-2
BS-2 125
125
100
Mass fraction, %
100
Mass fraction, %
75
75
50
50
25
25
0
0 Elements
Elements
Figure 7: Minor elements in Biological sludge. Figure 8: Minor elements in DAF sludge.
3.2 Distribution of ash forming elements between solid and liquid products
The content of ash forming elements in the liquid pyrolysis products was determined for two samples,
BS-1 and DAF-2. This was done to investigate the distribution of major and minor compounds between
pyrolysis products.
The liquid fraction obtained from pyrolysis was dark brown in colour and consisted of two visible
phases, the oil and aqueous fraction, and were easy to separate. The latter contained water and
certain hydrosoluble organic compounds while the oil contained the organic fraction. As some
pyrolysis products escaped the apparatus as aerosols or vapours there is some uncertainty associated
with the measurements of total mass of liquids generated during pyrolysis, thus the results presented
in Fig 9, 10, 11 and 12 should be viewed as qualitative. In both, the BS-1 and the DAF-2 pyrolysis oil
beside some quantities of volatile elements like S, K and Na small amounts of non-volatile Al, Fe, and
Si were detected. The same elements were detected in the aqueous fraction with the exception of Ca,
Mg and P. Zhang et al. [15] reported three types of sulphur-containing compounds found in pyrolysis
oil (tar); these are aromatic-S, aliphatic-S and thiophene-S.
316
aqueous oil char

aqueous oil char
150 150
100
100
Mass fraction, %
Mass fraction, %
50
50
0
Al Ca Fe K Mg Na P S Si 0
Elements
Elements
Figure 9: Major elements in DAF sludge.

Figure 10: Minor elements in DAF sludge.
aqueous oil char

aqueous oil char
150 150
100 100
Mass fraction, %
Mass fraction, %
50 50
0 0
Al Ca Fe K Mg Na P S Si As Ba Cd Co Cr Cu Hg Mn Ni Pb Sb Se Ti V Zn
Elements Elements
Figure 11: Major elements in Biological sludge. Figure 12: Minor elements in DAF sludge.
Considerable amounts of Co, Mn, Se, Ti, Ba and were detected together with some Ni, Cr, V, Hg, Ba
and Zn in DAF-1 aqueous fraction. The same elements in smaller quantities were detected in the
pyrolysis oil. In the BS-1 pyrolysis oil some amounts of all tested elements were detected. Likewise ,
the same elements were found in the aqueous fraction except for Cd, Mn and Zn.
There were trace amounts of almost all tested elements in the pyrolysis liquid products, even for non-
volatile elements, which could come from small particles of feedstock elutriated from the bed of
material during rapid release of volatiles causing particle fractionation.
4- CONCLUSIONS
Samples of dairy sludge from five different wastewater treatment were tested. There were substantial
difference in the properties between companies and between the biological sludge (BS) and sludge
from dissolved air floatation (DAF). In general, BS and DAF had high ash content but there were also
samples with very low ash content. The nitrogen content was lower in DAF samples.
The concentration of Si, Al, Mg, K and S was similar between BS samples while the content of P, Ca, Fe
and Na varied significantly. There were significant differences in concentration of Ca and P between
DAF samples. In general, content of Ca was much higher in DAF than in BS. The highest P content was
observed in BS-1 and DAF-1 in all the other sludge samples was very low. In general, the heavy metal
content was very low in all the dairy sludge samples. Among all the analysed heavy metals, the content
of Ti and Zn were the highest from 50 to 300 mg/kg and 50 to 200 mg/kg of dry matter, respectively.
317
For an intermediate pyrolysis at 700°C in a fixed bed reactor, the distribution of pyrolysis products
varied between dairy sludge. The yield of pyrolysis char depends mainly on the initial ash content of
sludge. Both BS and DAF sludge produced a significant quantity of pyrolysis char around 40 % of the
initial residue mass when the ash content was high. Otherwise, for DAF-1, the char yield of 15 % was
observed.
Distribution of major elements between pyrolysis products was similar for DS and DAF, with Ca, Fe, P,
Si and Al predominantly retained in pyrolysis chars (pyrogenic solids). However, small quantities of Al,
Ca, Fe and and Si were detected in pyrolysis oil and in the aqueous fraction. From 50 to 75 % of K and
S in BS and DAF and around 50 % of Na in DAF was retained in the solids with significant quantity
captured in the liquid fraction. The heavy metals and trace elements like Cr, Mn, Ni, Pb, Ti, V and Zn
were mainly retained in the pyrolysis chars with small quantities also detected in the liquid products.
On the other hand, only from 20 to 50 % of Ba, Co, Cu, Hg, Se and Sb was conserved in the pyrolysis
chars.
ACKNOWLEDGMENTS
This work was supported by the Irish State through funding from the Technology Centres programme
- Grant Number TC/2014/0016
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8. Samolada, M.C., Zabaniotou, A.A.: Comparative assessment of municipal sewage sludge incineration,
gasification and pyrolysis for a sustainable sludge-to-energy management in Greece. Waste
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9. Syed-Hassan, S.S.A., Wang, Y., Hu, S., Su, S., Xiang, J.: Thermochemical processing of sewage sludge to
energy and fuel: Fundamentals, challenges and considerations. Renewable and Sustainable Energy
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10. Trinh, T.N., Jensen, P.A., Dam-Johansen, K., Knudsen, N.O., Sørensen, H.R.: Influence of the Pyrolysis
Temperature on Sewage Sludge Product Distribution, Bio-Oil, and Char Properties. Energy & Fuels
27(3), 1419-1427 (2013). doi:10.1021/ef301944r
11. Lindberg, D., Molin, C., Hupa, M.: Thermal treatment of solid residues from WtE units: A review. Waste
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12. Healy, M.G., Fenton, O., Cummins, E., Clarke, R., Peyton, D., Fleming, G., Wall, D., Morrison, L., Cormican,
M.: Health and Water Quality Impacts Arising from Land Spreading of Biosolids. In: AGENCY, E.P. (ed.).
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13. Song, X.D., Xue, X.Y., Chen, D.Z., He, P.J., Dai, X.H.: Application of biochar from sewage sludge to plant
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14. Xu, C., Lancaster, J.: Treatment of secondury pulp and paper sludge for energy recovery. In: DuBois E, N.A.
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15. Zhang, J., Zuo, W., Tian, Y., Chen, L., Yin, L., Zhang, J.: Sulfur Transformation during Microwave and
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319
PRODUCTION OF FIBERBOARD FROM THERMALLY TREATED FURNITURE WOOD

WASTE
P.GIRODS1, B. COLIN1, Y.JANNOT2, Y.ROGAUME1

1 University of Lorraine, LERMAB, EA 4370, Epinal, France.
2 .University of Lorraine, LEMTA, CNRS, UMR 7563, Vandoeuvre-les-Nancy, France.
Abstract
The evolution of French regulations on furniture waste treatment lead to a needed development of
new material recycling sectors since recycling rates of 45% in the public sector and 70% in the
private sector are required.
It is proposed in this work to study the feasibility of producing wood fiberboard from real waste
consisting mainly of particle board waste.
A step of thermal pretreatment through low temperature pyrolysis is envisaged to reduce the
adjuvant content’s (mostly urea formaldehyde resin) and the material hygroscopic properties.
Fibers were then produced by mechanical defibration of the raw and thermally pretreated waste.
Low and medium density fibreboard samples were then made on both types of fibers. These were
then characterized in terms of moisture uptake, swelling and mechanical characteristics. A thermal
conductivity measurement was also performed on the low density samples to broaden the intended
applications for the end products.
The characterization of the thermally treated material reveals a lowering of the nitrogen content,
representative of the glue content and a significant decrease in the hygroscopic nature.
The results obtained during the defibration step reveal that the heat treatment does not have a
negative impact on the quality of the fibers obtained in terms of particle size.
The characterization of the fiber boards show that the previous heat treatment leads to:
• A decrease in the mechanical properties of the panels especially for those of medium density;
• Improved dimensional stability with moisture variations and better resistance to swelling;
• Slight improvement in the insulating properties of low density panels.
References
[1] Mburu, F., Dumarçay, S., Bocquet, J.F., Petrissans, M., Gérardin, P.: Effect of chemical modifications caused by heat
treatment on mechanical properties of Grevillea robusta wood. Polym. Degrad. Stabil. 93, 401-405 (2008)
[2] BC Bal, B.C., Bektaş, I.: The effects of heat treatment on the physical properties of juvenile wood and mature wood
of Eucalyptus grandis. BioResources. 7, 5117-5127 (2012)
[3] Li, H., Liu, X., Legros, R., Bi, X.T., Lim, C.J.: Torrefaction of sawdust in a fluidized bed reactor. Bioresource tech.
[4] 103, 453-458 (2012)
[5] Girods, P., Dufour, A., Rogaume, C., Rogaume, Y., Zoulalian, A.: Thermal removal of nitrogen species from wood
waste containing urea-formaldehyde and melamine-formaldehyde resins. J. Hazard. Mat.159, 210-221 (2008)
320
TECHNICAL-ECONOMICAL FEASIBILITY STUDY ON BIOGAS TREATMENT USING

MUNICIPAL SOLID WASTE INCINERATION BOTTOM ASH
M. FONSERE OBIS1, P. GERMAIN1, H. BENBELKACEM1

1 Université de Lyon, INSA-Lyon, DEEP Laboratory, EA7429, F-69621, Villeurbanne Cedex, France.
Abstract
Purpose
In the context of climate change and deployment of fossil resources, the development of biogas as a
source of renewable energy can play an interesting role. Indeed, the methane content in biogas (40-
60 vol.%) could be used for conversion to electricity, heat, grid injection and biofuel. However, the
biogas contains other detrimental compounds that must be eliminated before biogas valorization.
One of them is hydrogen sulfide, a highly toxic and corrosive gas. Impregnated activated carbons are
usually used in landfills for its elimination (removal capacity of 150-650 g H2S/kg [1]). The use of
these adsorbents leads to a substantial operational costs increase, which restrains biogas
valorization. In this context, the development of new inexpensive materials has recently started on
the basis of circular economy, towards the formulation of alternative adsorbents from waste.
Municipal solid waste incineration bottom ash (MSWI BA) has the physicochemical characteristics
adequate for the H2S adsorption, in particular its basicity and metal oxide content [2]. The purpose
of this study is to evaluate at a pilot scale the potential of BA as an alternative biogas desulfurization
process. From an economic point of view, a comparison with a classical solution (impregnated
activated carbons) is also done for different scenarios.
Materials and Methods

An industrial approach with on-site tests was chosen. Hence, a pilot was installed in a French landfill
in order to carry out the experiments in real field conditions, considering the complexity and the
variability of landfill biogas. The pilot consisted in a 10 kg-BA reactor equipped with a complete
biogas monitoring system. The biogas composition (CH4, CO2, O2, H2O and H2S) of inlet and outlet
biogas was continuously measured using a newly laser infra-red gas analyser called ProCeas®.
Main results and conclusions

The test was performed during 6 months. 1680 m3 of biogas with an average H2S concentration of
1000 ppmv were treated by MSWI BA. Under our specific and controlled experimental conditions, BA
was able to retain close to 250 g H2S/kg dry BA, which is a great adsorption capacity, especially
considering that, at the end of the test, BA was far from being saturated since it still eliminated 80%
of the inlet H2S. Yet, a promising adsorption capacity close to that of commercial adsorbents should
be expected for a longer experiment.
The results showed also that, for all the scenarios done regarding H2S concentration in the biogas, a
lower operational cost will be obtained using MSWI BA instead of impregnated activated carbons.
Hence, 27 to 530 k€ per year could be saved on a 1 kW motor using landfill biogas to produce
electricity.
References
[1] Abatzoglou, N., Boivin, S.: A review of biogas purification processes. Biofuels, Bioprod. Biorefining 6, 246–256 (2009)
[2] Rendek, E., Ducom, G., Germain, P.: Influence of waste input and combustion technology on MSWI bottom ash
quality. Waste Manag. 27, 1403–1407 (2007)
321
BIOGAS BIOREFINERY: TECHNO-ECONOMIC ANALYSIS
A.KUTSAY, L. KRATKY, T. JIROUT1

1 Czech Technical University in Prague, Faculty of Mechanical Engineering, Department of Process
Engineering, Technická 4, Prague 6, Czech Republic, phone +420-224-352-550.
Abstract
As it appears, economic analysis is the reason of why renewable energy plants are not so famous on
the world market. However, biorefinery concept opens new doors for spreading it to the world
commercial production.
As the motivation, the previous studies were taken into account. They were about intensified and
non-intensified (conventional) biogas production [1]. It was concluded that the profit from electricity
selling and residues is simply not enough. However, holding in mind possibilities of increased yield of
biogas production, the attempt would be done in order to implement such a technology with
different other. These attempts must show the sustainability of multi-production. From them: grid
injection, fibre prodduction, algae production. Such a study could be used as a preliminary
estimation of the introduced technologies.
Figure 1: use WasteEng Label style
References
[1] Kutsay, A., Kratky, L., Jirout, T.: Energy-economic analysis of thermal-expansionary pretreatment for its
implementation at biogas plant. Chemical Engineering and Technology. 2016, 39(12). ISBN 0930-7516.
322
SIMULATION OF INTEGRATED SLUDGE ANAEROBIC DIGESTION AND CHP
Y. HU1,2, P. ARLABOSSE1, F. WANG2, M. SAUCEAU1, Y. CHI2

1 Université de Toulouse, Mines Albi, Centre RAPSODEE, Campus Jarlard, Route de Teillet, F-81013

2 Institute for Thermal Power Engineering, College of Energy Engineering, Zhejiang University, China
Abstract
With the increasing production of sewage sludge in China, treatment and disposal of biosolids have
become one of the great challenges in environmental management. Sludge anaerobic digestion (AD)
is the most applied stabilized technology in EU. However, AD is not well established in China, despite
its considerable strengths. Enhancing the biogas production and optimizing the full sludge processing
route is thus a key issue. In this paper, Aspen Plus software is used to simulate an integrated process
that couples AD with cogeneration for the concurrent production of electricity and useful thermal
energy (see Fig.1). The AD model is based on Buswell equation [1]. This theoretical stoichiometric
method estimates products of the anaerobic digestion process by considering energy and mass
balance. After separation, the biogas is sent to the combined heat and power (CHP). The CHP
includes the combustion chamber, 3 gas turbines (HP, IP and LP) to produce electricity at high
efficiency and a heat recovery steam generator (HRSG). The simulation emphasizes that the
efficiency of the process can be improved from about 40% for a single gas turbine to about 60% for a
cogeneration plant. The low grade heat, available as hot water on a 70°C flow basis, is used to heat
the mesophilic digester tank that operates at 35°C. The high grade heat as engine exhaust gas is
available at 509°C. In further developments, this stream will be used for drying the digested sludge.
Figure 1: Simulated biogas CHP unit
References
[1] Nguyen, H.H.: Modelling of food waste digestion using ADM1 integrated with Aspen Plus. University of
Southampton, Department of Engineering and the Environment, Doctoral Thesis 298 p. (2014).
th
[2] Zabihian, F., Fung, A.S., Schuler, F.: Modeling of Gas Turbine-Based Cogeneration System, ASME 2012 - 6
International Conference on Energy Sustainability, San Diego (California, USA), pp. 167–174 (2012).
323
VITRIFICATION OF FLY ASH FROM MUNICIPAL SOLID WASTE INCINERATOR BASED

ON CaO-Al2O3-SiO2 TERNARY SYSTEM BY DC ARC PLASMA
WENCHAO MA1, DONGMEI CHEN1, XIAO HE1, GUANYI CHEN1,2

1 Tianjin Engineering Research Center of Bio Gas/Oil Technology, State Key Laboratory of Engines,
School of Environmental Science and Engineering, Tianjin University, Tianjin 300072, China.
2 School of Science, Tibet University, Lhasa 850012, China.
Abstract
A growing environmental concern has been paid to municipal solid waste incinerator (MSWI) fly ash
in China, due to its toxicity of heavy metals, dioxins and furans. Thermal plasma melting is an
efficient but energy intensive method for vitrifying fly ash. To reduce the energy cost, melting
temperature, heavy metals volatilization and form glass slag after vitrification, the fluxing agent of
CaO, Al2O3 and SiO2 were added to the fly ash . The amount of adding CaO, Al 2O3 and SiO2 was based
on the CaO-Al2O3-SiO2 ternary system, and the behavior of heavy metals in melting process was
studied in a laboratory DC arc plasma furnace. After vitrification, there are obvious changes in
chemical composition, crystalline phases and microstructure between the produced glass slag and
raw fly ash. And, the property of glass slag was affected by the ratio of CaO, Al 2O3 and SiO2. The
possible CaO-Al2O3-SiO2 (CAS) ratio for successful vitrification of fly ash is suggested to be CaO in
range of 20%~48%, Al2O3 in range of 10%~15%, and SiO2 in range of 40%~65%. The residual fraction
(wt.%) of heavy metals in glass slag are in the following sequence: Cr < Ni < Cd < Pb < Cu < Zn.
Moreover, the leaching toxicity characteristic of heavy metals in glass slags was much lower than the
standard limit of toxicity characteristic leaching procedure (TCLP). These produced glass slag with
good quality have potential to serve as a viable alternative for construction materials.
Keywords: Vitrification; MSWI fly ash; Heavy metals; DC arc plasma; CaO-Al2O3-SiO2 (CAS)
324
FUNGAL RESISTANCE OF CELLULOSE PANELS FOR CEILINGS
P. MORENO1, A. BERMUDEZ1, A. GUALDRON2, N. S. MEDEIROS CARDOZO2

1 Civil Engineering Department Grupo ambiental de investigación aplicada - GAIA Universidad de
Santander UDES, Bucaramanga, Colombia.

2 Industrial Microbiology Department Ciencias básicas y aplicadas para la sostenibilidad Universidad
de Santander UDES, Bucaramanga, Colombia.

3 Chemical Engineering Department- Universidade Federal do Rio Grande do Sul, Porto Alegre, Brazil.
Abstract
Cellulose panels made from recycled paper fibres stand up as a sustainable construction material
with great potential use as ceilings. High concentrations of fungi from damp indoor environments
can be serious health hazards to occupants causing allergies and illness (building-related illnesses or
sick building syndrome). Cellulose materials allow fungi growth; in order to prevent fungal attack it
is necessary to add additives as boric acid and borax. The purpose of this work was to assess the
growth of fungal commonly found in indoor environments on cellulose panels made from recycled
paper, soy protein as a binder and acid boric and borax as additives. Out of 16 strains isolated from
different indoor environments, four strains with the ability to use cellulose as sole carbon source
(Chaetomium murorum, Aspergillus niger, Penicillium crustosum, Stachybotrys chartarum) were
chosen and characterized by PCR. These strains causes allergies and in some cases respiratory
diseases. A central composite design (CCD) was performed in order to study the influence of the
panel components percentage on the four-selected fungal growth. Fungal growth measurements
were performed according to ASTM C1338-14. The cellulose panel untreated (control) presented
abundant growth of inoculated strains. All cellulose panels treated with boric acid and borax
preclude the growth of the four common fungal species. These results suggest that cellulose panels
treated with boric acid and borax, precludes fungal growth at high temperatures and relative
humidities.
References
[1] Herrera, J.: Assessment of fungal growth on sodium polyborate-treated cellulose insulation. J. Occup. Environ. Hyg.
2, 626–632 (2005)
[2] Lazko, J., Landercy, N., Laoutid, F., Dangreau, L., Huguet, M.H., Talon O. : Flame retardant treatments of insulating
agro-materials from flax short fibres. Polym. Degrad. Stab. 98, 1043-1051 (2013).
[3] López-Hurtado, P., Roully, A., Vandenbossche, V.: A review on the properties of cellulose fibre insulation. Build
Environ. 96, 170-177 (2016)
[4] Verdier, T., Coutand, M., Bertron, A., Roques, C.: A review of indoor microbial growth across building materials and
sampling and analysis methods. Build Environ. 80, 136-149 (2014).
325
HYGROTHERMAL PERFORMANCE OF A NEW BIO-BASED CONCRETE WALL
N. CHENNOUF1,2,3, B. AGOUDJIL2, A. BOUDENNE1, K. BENZARTI4, F. BOURAS3

1 CERTES, Université Paris Est Créteil Val de Marne, 61 Av. Gén. de Gaulle, 94010 Créteil Cedex,
France.
2 LPEA, Université Batna 1, Les Allées 19 Mai Route de Biskra Batna, Algeria.
3 University Echahid Hamma Lakhdar ElOued,PO Box 789 EL-Oued, Algeria.
4 IFFSTAR IFSTTAR – Département Matériaux ET Structure 14-20 Bd Newton – Cité Descartes 77447
Marne-la-Vallée Cedex 2, France.
Abstract
The environmental quality of a building generally aims to take into account both the stakes of
sustainable development, social and economic. For these reason, several researchers are recently
interested to introduce the bio-based materials in new and renovated buildings to reduce
simultaneously energy consumption, gases emission and agricultural production. Studies carried out
on new bio-based building materials, which contains wastes of date palm fibers (WDPF), have
showed their thermal insulation efficiency and mechanical reliability [1] as well as its height
hygrothermal performance [2]. In results the WDPF is a very good candidate to use in the design of
the bio and modern building.
Figure 1. Experimental device for hygrothermal behavior of WDPF concrete wall.
This work aims to study the hygrothermal behavior of WDPF at wall scale under several conditions of
humidity and temperature. The outdoor climate was generated using a climatic chamber; in the
same time, the indoor climate was maintained at constant value of temperature and humidity. The
temperature and the relative humidity are monitored at different depth with temperature and
relative humidity sensors. Several kinds of hygric behaviors are highlighted such as homogeneous
vapor diffusion and huge vapor pressure variations due to the evaporation condensation and
sorption-desorption phenomena. The temperature and relative humidity profiles of this biobased
concrete wall were obtained at different depth values.
The results show a significant thermal and hygric wall inertia. The response time of the WDPF wall is
short for temperature set points compared for the humidity set points.
326
References
[1] Nadia Benmansour, AbdelkaderGherabli, AbdelhakKareche, AberrahimBoudenne, "Thermal and mechanical
performance of natural mortar reinforcedwith date palm fibers for use as insulating materials in building," Energy
and Buildings, pp. 98-104, 2014.
[2] Bourhaneddine Haba, AbderrahimBoudenne, Karim Benzarti, "Hygric properties and thermal conductivity of a new
insulation material for building based on date palm concrete," Construction and Building Materials, pp. 963–971,
2017.
327
MIXED CULTURE BIOTECHNOLOGY FOR BIOFUELS PRODUCTION IN SYNGAS

FERMENTATION PROCESSES
A. GRIMALT-ALEMANY 1, I.V. SKIADAS1, H.N. GAVALA1

1 Technical University of Denmark, Department of Chemical and Biochemical Engineering, Kgs.
Lyngby, Denmark.
Abstract
Syngas fermentation is one of the most promising approaches among second generation biofuel
technologies due to the benefits derived from the combination of thermochemical and biochemical
conversion processes. In this process, a wide array of feedstocks of different nature can be
converted through gasification into synthesis gas, composed by mainly H2, CO and CO2, which can be
further converted biologically into both gaseous and liquid biofuels. The fermentation of synthesis
gas has been typically carried out by pure cultures. However, using open mixed cultures and taking
thus advantage of their inherent microbial diversity may offer a series of benefits such as high
adaptive capacity, resilience to syngas impurities and non-sterile operation [1, 2]. All the above may
contribute to reducing utility consumption. On the other hand, a poor understanding of the
microbial interactions within microbial consortia usually leads to low product selectivity in
fermentation processes. Thus, gaining a better control on the activity of microbial consortia is
fundamental for the further development of mixed microbial consortia fermentations.
In this work, a number of enrichment strategies were designed for enhancing the microbial activity
of anaerobic sludge towards the production of methane and ethanol. The methanogenic potential of
the anaerobic sludge was assessed through enrichments at different temperatures, developing a
mesophilic (37˚C) and a thermophilic (60˚C) methanogenic consortium. The ethanologenic potential
of the anaerobic sludge was evaluated based on enrichments at different initial pH conditions (6, 5.5
and 5).
The results showed that the enrichments led to less complex microbial consortia with a higher
microbial activity towards the targeted products. The study of the behaviour of the methanogenic
enriched consortia revealed different patterns of activity and inhibition between the mesophilic and
the thermophilic consortia, obtaining a methane yield at the end of the enrichments of 81.4% and
92.6% of the theoretical maximum, respectively. In turn, the ethanologenic potential of the enriched
consortia was observed to increase as the initial pH was lowered, achieving a maximum ethanol yield
of 17.7%, 33.3% and 59.8% of the theoretical maximum in enrichments at pH 6, 5.5 and 5,
respectively.
Overall, controlling the operational conditions of the enrichments enhanced both the product yields
and the activity of certain catabolic routes towards methane and ethanol. This allowed increasing
significantly the overall conversion rate in methanogenic enrichments as well as the product
selectivity in ethanologenic enrichments.
References
[1] Redl S., Diender M., Ølshøj T., Sousa D. Z. and Toftgaard A.: Exploiting the potential of gas fermentation. Ind. Crop.
Prod., 106, 21-30 (2017).
[2] Grimalt-Alemany A., Skiadas I. V. and Gavala H. N.: Syngas biomethanation?: state-of-the- art review and
perspectives. Biofuels, Bioprod. Bioref. (2017). http://dx.doi.org/10.1002/bbb.1826
328
ACIDOGENIC FERMENTATION OF HOUSEHOLD SOLID WASTE: BACTERIAL

ENRICHMENT AT CONTROLLED pH
L. DIGAN1, S. DUBOS1, E. MENGELLE1, E. PAUL1, C. PAGÈS2, E. TRABLY2,

H. ROUX DE BALMANN3, C. DUMAS1
1 LISBP, Université de Toulouse, CNRS, INRA, INSA, Toulouse, France.
2 LBE, INRA, Univ Montpellier, 11100, Narbonne, France.
3 LGC, Université de Toulouse, CNRS, INPT, UPS, Toulouse, France.
Abstract
In order to reduce our dependency to petrochemical resources, valorizing household solid wastes by
producing platform molecules such as volatile fatty acids (VFAs), is an interesting alternative. It is
possible to produce and extract VFAs through solid state fermentation (leach-bed reactors).
Moreover, the VFA-rich broth can be purified and separated with a membrane process (i.e.
nanofiltration).
Hence, this study aimed at evaluating the role of an adapted and enriched inoculum (acidogenic
bacterial populations) at three different pH to assess the effect on population and fermentation
pathways. For this purpose, reactors with a total volume of approximately 1000 mL were operated in
batch mode in a series of three successive runs (Fig. 1b). Tests with (inoculated) and without
(control) inoculation in first batch, were conducted in duplicates. Heat pre-treated wastewater
treatment plant (WWTP) sludge was used as inoculum. The substrate was a reconstituted
fermentable fraction of household solid wastes, including food and green wastes, papers and
cardboard (Fig. 1a). The substrate (and inoculum) quantities were adjusted to obtain a total solids
(TS) content of 5% and a substrate to inoculum ratio of 20 at the beginning of the runs. pH was
controlled and regulated by using HCl (1 to 3 M) and NaOH (0.25 to 0.5 M) solutions. Three pH
conditions were experimented: 4.5, 5.5 and 6.5. Concentrations of fermentation metabolites (such
as VFAs, lactate, and ethanol) and gases were measured daily and when relative pressure was higher
than 5 millibars, respectively. Samples were taken to analyse the evolution of the microbial
populations in the reactors during the tests.
Inoculated
RUN I1 RUN I2 RUN I3

S = fresh substrate S = fresh substrate S = fresh substrate
X = pretreated inoculum X = end of RUN I1 filtrate X = end of RUN I2 filtrate
RUN C1 RUN C2 RUN C3

Control
S = fresh substrate S = fresh substrate S = fresh substrate

X=/ X = end of RUN C1 filtrate X = end of RUN C2 filtrate
Figure 1: a) Substrate: reconstituted fermentable part of household solid wastes. b) Enrichment strategy: three successive runs at
controlled pH and S/X of 20, with heat pre-treated WWTP sludge as initial inoculum.
At pH 4.5 and 5.5, even with no inoculation, the enrichment was successful: the VFA concentrations
increased between the first and the last runs. For instance at pH 5.5, total VFA concentration went
from 5.2 ± 0.2 g/L to 7.0 ± 0.1 g/L in the inoculated reactors, and from 4.2 ± 0.3 g/L to 7.3 ± 0.3 g/L in
the control reactors. At the end of all experiments (RUN I3 and RUN C3), no methane production was
measured. pH had a significant influence on the followed parameters. As compared to pH 4.5,
329
working at pH 5.5 enhanced the VFA production as well as the diversity of VFA and gas produced.
Moreover, other metabolites such as lactate might have been released especially at pH 4.5.
Microbial diversity analysis (sequencing) will provide more information about the evolution of
bacterial populations and their proportions during the enrichments. With the more suitable
inoculum obtained, VFA production will be optimized in leach-bed reactors coupled with a
membrane process (i.e. nanofiltration).
330
HYDROGEN PRODUCTION FROM SEWAGE SLUDGE WITHOUT METHANE

FERMENTATION
J. KANO1, S. NOBORIYA2, Y. SARUYA3, T. NAGAO4

1 Institute of Multidisciplinary Research for Advanced Materials (IMRAM), Tohoku University, Japan
2 Yamato Sanko MFG, Japan
3 Carbon free network, Japan
4 Hirosaki city
Abstract
Much attention has been paid on effective use of hydrogen for fuel cell and fuel cell vehicle.
Unfortunately, hydrogen has currently been produced by steam reforming of fossil fuel, mainly
natural gas. Many researches have been trying to use renewable sources such as biomass. Much
effort is still needed to obtain satisfactory results for replace of fossil fuel.
We have proposed a novel process to generate hydrogen from natural source of biomass and various
wastes including sludge with an aid of mixing processing. These samples are mixed with calcium and
nickel hydroxides and subsequent heating of the mixed samples produces hydrogen at low
temperature of around 600 degrees. Yield of hydrogen generated as high as 50g per dry sewage
sludge has been obtained even from wastes with high impurity. The reasons for the high yield of
hydrogen generation may be attributed to good mixing, which facilitates the solid-state reaction
during heating to form calcium carbonate and also the well dispersion of nickel hydroxide so that an
effective nickel catalyst is formed during heating. We will report fundamental data about the
hydrogen generation from sewage sludge.
A part of this work was performed under the Ministry of Land, Infrastructure, Transport and Tourism
Program of "Breakthrough by Dynamic Approach in Sewage High Technology Project"
331
USING THE CHEMICAL STRUCTURE OF BIOMASS TO INFORM PYROLYSIS MODELLING:

FORMULATION OF PSEUDO-COMPONENTS OF HEMICELLULOSE AND LIGNIN
K. DUSSAN1,2, S. DOOLEY3, R.F.D. MONAGHAN1,2

1 National University of Ireland Galway, Galway, Ireland.
2 Centre for Marine and Renewable Energy MaREI, Galway, Ireland.
Abstract
Kinetic modelling of thermal conversion of lignocellulosic biomass and wastes is approached through
extensive approximations of its composition and reactivity during thermolysis, given their complex
and heterogeneous chemical structure. This study presents a comprehensive methodology for the use
of the chemical composition of lignocellulose based on advanced characterisation techniques, e.g.
carbohydrate content and distribution of aromatic groups, in the formulation of detailed intrinsic
reaction kinetics of pyrolysis of hemicellulose and lignin [1]. Experimental data was gathered from
literature covering the pyrolytic reactivity of several refined polysaccharides and extracted lignins
using low (<1 K s-1) and rapid (>50 K s-1) heating rates. Kinetic models for the 5 hemicellulose and 4
lignin pseudo-components were trained following a trial-and-error routine consisting of (1) the
assumption of the stoichiometry of the pyrolysis reactions, (2) the adjustment of the kinetic
parameters defining reaction rate constants to improve the goodness-of-fit of the model with the
experimental data, and (3) re-adjustment of reaction stoichiometry based on experimental data of
product composition. This approach satisfactorily fitted the training experimental data, demonstrating
a predictive capability similar to that of the state-of-the-art kinetic models of biomass pyrolysis [2].
One of the key features of the new kinetic model is its capacity to capture the high selectivity towards
volatile products observed from biomass under rapid heating conditions in laboratory scale reactors.
This work demonstrates the value of using the chemical composition of lignocellulosic biomass to
formulate advanced and robust kinetic models and proposes a methodology that can advance the
modelling of the intrinsic reactivity of lignocellulosic biomass.
Figure 1: a) Standard reaction scheme of pseudo-components (PCi) of biomass; b) Comparison of experimental and simulated product
distribution of the pyrolysis of xylan in a wire mesh reactor (as reported in [1]).
References
[1] Dussan, K., Dooley, S., Monaghan, R.: Integrating compositional features in model compounds for a kinetic mechanism
of hemicellulose pyrolysis. Chem. Eng. J. 328, 943-961 (2017)
[2] Ranzi, E., Debiagi, P. E. A., Frassoldati, A.: Mathematical Modeling of Fast Biomass Pyrolysis and Bio-Oil Formation. Note
I: Kinetic Mechanism of Biomass Pyrolysis. ACS Sustain. Chem. Eng. 5 (4), 2867-2881 (2017)
332
CHARACTERISTICS OF PYROLYSIS OIL AS RENEWABLE SOURCE OF CHEMICAL

MATERIALS AND ALTERNATIVE FUEL FROM THE SEWAGE SLUDGE TREATMENT
T. CHORAZY1, J. ČÁSLAVSKÝ2, E. ŽVAKOVÁ2, J. RAČEK1, P. HLAVÍNEK1

1 Faculty of Civil Engineering, Brno University of Technology, AdMaS Research Centre, Brno 602 00,
Czech Republic.
2 Faculty of Chemistry, Institute of Chemistry and Technology of Environmental Protection, Brno
University of Technology, AdMaS Research Centre, Brno 602 00, Czech Republic.
Keywords: sewage sludge treatment, microwave pyrolysis, pyrolysis oil, gas chromatography, mass
spectrometry
Abstract
This paper describes the present applied research focused on pyrolysis oil as one of the three
products of sewage sludge (SS) thermal treatment processing – microwave pyrolysis (MP).
Certain MP unit set up uses the microwave radiation technology and it depends on the input
material itself and various parameters. For tests the full-scale MP unit with 3 kW magnetron with the
frequency of 2.45 GHz at low pressure was used.
The aim of this paper is to present a chemical characterization of pyrolysis oil together with the
suitable analytical determination methods. Detailed characterization of pyrolysis oil from SS was
realized by precipitation in n-pentane, fractionation of pentane-soluble part by column
chromatography on activated silica by stepwise elution and analysis of obtained fractions by
comprehensive orthogonal two-dimensional gas chromatography with time-of-flight mass
spectrometric detection.
Substances from several groups have been identified at the pyrolysis oil from SS sample: alkanes
(110 compounds), alkenes and alkynes (184 compounds), cycloalkanes (104 compounds), aromatic
and polyaromatic hydrocarbons (646 compounds), further lower numbers of alcohols, aldehydes,
esters, carboxylic acids and heterocycles.
Comparison of the two chromatographic methods used clearly shows the suitability to be complete
two-dimensional gas chromatography for the analysis of complex mixtures.
The MP seems to be an eco-friendly treatment of SS with three bio-products. If considered all the
outcomes of this MP technology, it could represents a solution from the perspective of circular
economy, carbon footprint reduction, heavy metals fixation, energy recover and water retention.
Further research of detailed characterization of pyrolysis oil from SS will be focused especially on
energy efficiency, ecotoxicity or combustion tests.
333
1- INTRODUCTION
Currently, the sewage sludge (SS) treatment has received a significant attention in the Czech
Republic (CZ) mainly due to planned upcoming legislation changes. It will strictly regulate the present
most popular ways of SS disposal in CZ and other EU countries – landfilling, direct agricultural
applications or composting. Thus, the operators of waste water treatment plants (WWTP) urgently
need to find some new possibilities of its disposal. Disposal of the SS is also one of the most
important issues in terms of circular economy that is a part of the waste management strategy
implemented in the EU.
The growing demand for energy, depletion of viable petroleum reserves and environmental and
socio-political concerns have accelerated the need for the development of sustainable technologies
for utilization of biomass. The European Commission has recently set a long-term goal to develop a
competitive, resource efficient and low carbon bio-economy by 2050 [12].
The landfilling of SS as a non-sustainable disposal is not supported by EU legislation and is strictly
restricted in several EU countries. It is mainly because SS contains a lot of organic matter which
decomposes at the landfill sites and generates CH4 which contributes to the greenhouse effect even
more than standardly calculated CO2. Moreover, the cost of the land needed for landfill is increasing
because of its decreasing availability [13]. Further on, the fees for landfilling disposal is increasing
too.
An alternative SS treatment might be pyrolysis and its variations which could achieve 50% reduction
in waste volume [18], bring stabilization of organic matter, as well as the production of fuels.
Elements such as Na and Mg will be concentrated in the pyrolysis char which can then be used as the
soil amendment or be upgraded to become an adsorbent [2][29]. The produced gas and oil can be
either directly burned as a fuel to provide heat and electricity, or further converted to other
chemicals through subsequent processes [8][26].
Implementation of circular economy strategy postulates a search for new ways of waste recycling
and its material and energy exploitation with/such as incineration and thermal treatment of SS.
Thermal treatment such as torrefaction, gasification and pyrolysis of SS is consequently one of the
most significant challenges in wastewater (WW) management and represents the most suitable
solutions of SS disposal. Based on the data found in the literature, the pyrolysis of SS seems to be a
suitable thermal treatment method to transformation of raw SS to sources with HM fixation in
output product [32][20][22][23][15]. Currently, HM fixation by pyrolysis is addressed in laboratory
research (also at BUT AdMaS), but not in real condition at the WWTPs for agricultural use.
The aim of pyrolysis can be the obtaining of these products: biochar, pyrolysis oil and pyrolysis gas
(Syngas) [4]. The lignocellulosic biomass pyrolysis has balance values for products: the yields
achieved are 60-75 wt % for the liquid, 15-25 wt % for the char and 10-20 wt % for the gas [25]. The
share/ratio of yields depend on raw feedstock characteristics. Char and gas can also be considered as
fuels and be reused in the process itself [13]. Pyrolysis liquid from lignocellulosic biomass has already
been successfully tested as a direct fuel in engines, turbines and boilers [5][6]. However, the
potential direct substitution of pyrolysis oil for conventional petroleum-based fuels in transport
applications requires upgrading processes which are currently under development [13].
Microwave based technology is an alternative heating method and has already been successfully
used in biomass pyrolysis for biofuels production [3][9][31]. Microwave assisted heating has many
advantages over conventional processes which include: (1) Microwave can provide uniform internal
heating of material particles since the electromagnetic energy is directly converted into heat at the
molecular level [30]. (2) Microwave heating is easier to control due to its instantaneous response for
rapid start-up and shut-down. (3) The set-up of microwave system is simple, which facilitates its
adaption to currently available large-scale industrial technologies. (4) It does not require high degree
334
of feedstock grinding and can be used to handle large chuck of feedstock. (5) Microwave heating is a
mature technology and the development of microwave heating system is of low cost. Despite many
advantages of microwave heating over conventional heating methods and some progress made in
biomass pyrolysis, only a few studies have been conducted on sewage sludge pyrolysis using
microwave technology and the effects of catalyst on the pyrolysis process were not examined in
their research [8][24].
In the future, the incineration of biomass seems to be the most used way of its treatment, but it is
not very economically profitable (comparing with economy value of chemical substances, for
example). Thus some other technologies of its processing are under the development included the
pyrolysis and MP. The MP advantage is the energetic balance of the process itself and the wasteless
technology. The output materials can be possibly evaluated – especially the pyrolysis oil or biooil.
Current applied research at Brno University of Technology, Faculty of Civil Engineering, AdMaS
Research Centre (BUT AdMaS) focuses on a low temperature slow MP of SS. This research is
conducted in cooperation with engineering company Bionic E&M. The research is focused first for
energy efficiency use of SS before and after MP (all outputs – biochar, pyrolysis oil and syngas),
second for the transformation of SS to new products for agricultural use (especially because of HM
fixation in the solid outputs after MP) and finally the characterisation and possible utilization of
pyrolysis oil is investigated.
To reduce the climate changes and to increase the energy safety of the country, the contribution of
pyrolysis oil is possible to substitute some fossil fuels for energy and chemicals production or as a
binders (bio-binders) as a suitable alternative for bitumen in asphalt mixture [1].
Pyrolysis oil is actually the product of evaluation of treated waste material as biomass or other
suitable wastes. To be able to suggest the best way of the pyrolysis oil utilization, the detailed
chemical characterization of that complex mixture of substances is very important [33].
The aim of this paper is to describe the methods and provide the characterization of pyrolysis oil
from SS MP processing.
1.1- Pyrolysis oil

The characteristics of pyrolysis oil originated from MP is different in comparison with pyrolysis oil
originated from conventional way of heating. The advantage of oil from MP is higher content of
carbon, higher caloric value and lower content of oxygen [16][17]. Below is stated general properties
of pyrolysis oil originated from MP.
Oxygen content
Due to the presence of 35-40 wt% of oxygen the pyrolysis oil result in different characteristics of
such oil with comparison to fossil fuels. The effect of this high content is lower density of energy,
immiscibility with hydrocarbons and instability [11].
Acidity and corrosivity

Pyrolysis oil contents significant amount of carboxyl acids, especially the acetic and formic acids. This
content has effect with acid pH, which range from 2-3 and it depends on the content of
hemicellulose in the income material and reaction conditions. Due to the high acidity, the pyrolysis
oils are corrosive for current metals such as steal. The corrosivity of pyrolysis oil increases with the
growing process temperature and with the increasing water amount [11].
335
Water content
High water content is the result of two contributions: the water content in the income biomass
which condensate in the oil, and the water which is produced by pyrolytic reactions, especially by
dehydrogenation reactions. The high content of water results in not only low caloric value, but also
in corrosive characteristics. The viscosity of pyrolysis oil is 400 x higher than water viscosity at 25 °C
[11].
Energy efficiency in pyrolysis oil

Pyrolysis oil has a density around 1200 kg.m-3 and the caloric property 16-20 MJ.kg-1. The caloric
value of pyrolysis oil is comparable with that of rare biomass and it corresponds to approximately 40
% of fossil fuels. The lower caloric value is caused by the high content of water as well as the high
content of oxygen [11].
Advantages of pyrolysis oil are simple storage and easy transport possibilities of it. As mentioned,
the oil is possible to use as a quality liquid fuel [14]. Pyrolysis oil has a lot of positive characteristics
comparing with some other oil fuels as is a high caloric property, lower total impact on environment
and lower need of its processing. Some disadvantage of pyrolysis oil is its high viscosity, low
vaporization and high reactivity (due to the high content of unsaturated hydrocarbons). There is
quite complicated direct use at engines due to its polymerization reactions. Pyrolysis oils could
replace the fuels on crude oil basis, but it needs some refining treatment to reach characteristics
enabling its wider applications [33][19].
The pyrolysis oil obtained by the process of quick pyrolysis can be used after the next purification
and treatment either in the chemical production, or as a fuel for mobile diesel engines or directly as
a heating oil for boilers or as a fuel for electricity production at combustion engines or combustion
turbines [14].
Typical characteristics of pyrolysis oil from biomass and conventional crude oil (heating oil) are
summarized in Table 1 [19]. The individual parameters shows the possibility of utilization of pyrolysis
oil instead of heating oil.
Physical characteristics Pyrolysis oil Heating oil

Water content (wt %) 15 - 30 0.1
pH 2.5 -
Specific density (g.cm-3) 1.2 0.94
Carbon 54 - 58 85
Hydrogen 5.5 - 7 11
Elementary structure (%)
Oxygen 35 - 40 1
Nitrogen 0 - 0.2 0.3
Ash 0 - 0.2 0.1

Viscosity (cP) 40 - 100 180
Solid share (wt %) 0.2 - 1 1
Caloric value (MJ.kg-1) 16 - 19 40
Table 1: Typical characteristics of pyrolysis oil from biomass and heating oil [19].
336

2.1- Low temperature slow MP unit
The pyrolysis can be carried out either by using conventional heat transfer via conduction or
microwave heating of pyrolyzed material. The microwave pyrolysis (MP) has already been tested for
lignocellulosic materials, but its application for SS pyrolysis is reported only in a few papers
[4][24][32].
MP represents an eco-friendly treatment of SS resulting in production of biochar, pyrolysis oil and
pyrolysis gas (Syngas) [4]. Importantly, although the nomenclature "biochar" refers only to a charcoal
used as a soil amendment [7] and it is not commonly used for the product produced from 100 % SS,
it is used in following text.
At BUT AdMaS one laboratory and two full-scale MP units using low temperature slow MP are
installed. Two units for test of different samples are used there. The tests were performed by a
laboratory and small unit to simulate real conditions at WWTP [27].
The laboratory scale MP unit represents the experimental apparatus and consists of a procedural
one batch reactor, equipped with two high efficient microwave generators of 3 kW output, 1 x 3 kW
magnetrons, at a frequency of 2.45 GHz. Batches of up to 3 kg/batch can be processed at low
pressure (800 hPa). The temperature was continuously monitored by an infrared thermometer, it
increased maximally up to 250 °C. The attached glass condensation unit allows the separation of the
pyrolysis oils and residues produced in the microwave supported catalytic cracking process for later
analysis. Possible input materials are solid materials with a diameter of less than 8 mm [27].
The small full-scale MP unit has capacity around 10 kg/batch of dried SS, the device works
discontinuously. It consists of one batch reactor equipped with one high efficient microwave
generator of 3 kW output, at the frequency 2.45 GHz. Batches of dried SS were pyrolyzed at low
pressure (800 hPa). The temperature was continuously monitored by an infrared thermometer, it
increased maximally up to 250 °C. The glass condenser attached to the pyrolyzer was used for
separation of the pyrolysis oil and gaseous products. A tuner for incoming and reflected waves was
installed. The pyrolyzed material was a sample of dried SS (SD) from blade drier [27].
For the purpose of the solved sample the pre-treatment was applied, so the final incoming sample to
MP was pelletized and subsequently the pyrolysis oil was characterized.
2.2- Input sample of sewage sludge characterization

From the chemical point of view, SS is a heterogeneous mixture of undigested organic matter (paper,
plant residues, oils, etc.) microorganisms, inorganic materials and water. The content of inorganic
material in the SS is usually higher than 50 %. The undigested organic matter of SS consists of several
compound classes like proteins, peptides, lipids, polysaccharides, phenolic and aliphatic structures
containing macromolecules, polycyclic aromatic hydrocarbons, etc. [13].
Dry SS contains also molecules containing nitrogen and phosphorus, which are nutrients for soils.
The problematic substances for direct application in agriculture are considered xenobiotics,
microplastics and heavy metals.
The testing MP at the BUT AdMaS was carried out with a sample of anaerobically digested (22-day
digestion at 35 °C) and thermally dried SS from municipal WWTP which has a capacity of approx.
531,000 population equivalent, the sludge was dried using a Nara paddle dryer heated to 100 °C with
a retention time of about 3 hours. The basic characteristics of the individual samples of sludge
subject to the microwave technology treatment are as stated in Table 2.
337
Dry solids 91.5-91.9 %

Loss on ignitron 47.1-49.0 %
Fraction approx 1-8 mm (bound finer fractions)
Table 2: Basic characteristics of the individual samples of tested SS.
2.3- Pyrolysis oil sample treatment

Pyrolysis oil is a very complex mixture, which is necessary to analyse by advanced analytical
methods. The composition of pyrolysis oil is as follow: 20 % of water, 40 % of compounds possibly
detected by gas chromatography (GC), 15 % of non-volatile compound, which is possible to detect by
liquid chromatography (HPLC) and 15 % of non-detectable compounds [33].
Chemical characteristics of pyrolysis oil is generally oriented at fractionation into purposive
categories, which are the base to create a method of following final analysis. The segregation into
the categories (so called chemical families) simplify the overview of pyrolysis oil, which changed from
the mixture of dozens of substances into the mixture of several groups [10][28].
It is not possible to determine individual chemical compounds, which are assigned at pyrolysis oil, by
only universal instrumental method, because characteristics of these compounds vary in wide range.
Therefore, fractionation into 4 fractions was applied (see Table 3). These are following: aliphatic
hydrocarbons, polycyclic aromatic hydrocarbons, functional derivatives of polycyclic aromatic
hydrocarbons and polar compounds [33].
Stationary phase Fraction Eluent

Aliphatic hydrocarbons n-pentane
Polyaromates n-pentane / DCM (1:1)
Activated silica gel
Polyaromates derivatives DCM
Polar compounds DCM / MeOH (1:1)
Table 3: Fractionation method.
Extraction
The sample was adjusted first of all by extraction at n-pentane in a rate 1:10, also 1 mL of pyrolysis
oil was mixed with 10 mL of n-pentane. Second, the precipitate was removed by filtration, soluble
fraction was evaporated to dryness under gentle stream of nitrogen.
Column chromatography
Suitable amount of n-pentane soluble compounds (100-200 mg) was dissolved in n-pentane, mixed
with small amount of non-activated silica and carefully evaporated to dryness (the material becomes
loose). This sample containing silica was placed on the top of column filled with activated silica (3
hours at 180 °C). For isolation of individual fractions stepwise elution using eluents presented in
Table 3 was applied. Collected fractions were volume reduced under gentle stream of nitrogen to
final volume of 1 mL.
Analysis of individual fractions

Fractions from column chromatography were analyzed by mass gas chromatography Bruker SCION
436 - GC Detection with MS Detection Triple Quadrupole (TQ) and Autosampler CP-8400. Below
stated as GC – MS analysis.
All fractions were also analyzed by comprehensive orthogonal two-dimensional gas chromatography
with mass spectrometric detection on a LECO Pegasus IVD system equipped with gas chromatograph
338
Agilent 6890A and autosampler Agilent 7683. Primary column used was Rx-5ms, 29 m x 0,25 mm x
0,25 µm (stationary phase 5% diphenyl- 95% dimethyl polysiloxane, Restek), and a secondary column
was BPX-50 (1.5 m x 0.1 mm x 0.1 µm stationary phase 50% phenyl polysilphenylene-siloxane, SGE).
Electron ionization at 70 eV electron energy and Time-of-Flight analyzer (TOF–MS) were employed.
Below stated as GCxGC/TOF-MS analysis.

Individual samples were prepared and measured under the conditions set forth in Section 2.3. The
results were evaluated using the specter libraries. All large samples were successfully identified with
a large number of substances that were broken down by characteristic functional groups into the
following categories: alkanes, alkenes + alkynes, cyclic hydrocarbons, monocyclic aromatic
hydrocarbons and polycyclic aromatic hydrocarbons, alcohols + phenols, esters, aldehydes +
ketones, carboxylic acids, heterocycles, and finally nitrogen-containing or sulphur-containing
compounds.
Pyrolysis oil from sewage sludge Fraction 1 Fraction 2 Fraction 3 Fraction 4

Alkanes 51.3 15.7 22.4 31.2
Alkenes + alkynes 37.6 0.7 --- 0.0
Cyclic hydrocarbons 11.1 1.23 1.0 4.2
Monocyclic aromatic hydrocarbons --- 50.3 38.2 25.1
GROUPS (%)
Polycyclic aromatic hydrocarbons --- 8.9 0.3 1.4

Alcohols + phenols --- 0.8 8.7 35.4
Esters --- 1.6 1.6 4.0
Aldehydes + ketones --- 4.0 3.0 12.3
Carboxylic acids --- 0.1 0.7 0.0
Heterocycles --- 22.3 16.8 22.9
Nitrogen-containing compounds --- 16.0 57.9 23.6
Sulphur-containing compounds --- 6.4 0.1 2.4
Number of identified compounds 398 1183 98 223
Table 4: Relative representation of groups in pyrolysis oil fractions measured with GC × GC / TOF-MS.
Regarding the Fraction 1, the pyrolysis oil from relevant SS sample mainly contained hydrocarbons
with a straight line branched chain, whether saturated or unsaturated. N-alkanes dominated the
largest peaks.
Regarding the Fraction 2, a significant amount of heterocyclic compounds is also to be mentioned. It

closely relates to the increased presence of nitrogen and sulphur-containing compounds. This fact
was also demonstrated by the fact that the largest peaks in the SS sample belonged to sulphuric
heterocycles.
Regarding the Fraction 3, the sample consisted primarily of nitrogen derivatives, mainly of
heterocycles, furthermore of monocyclic aromatic hydrocarbons, iso-alkanes and alcohols. The
largest peaks in the spectrum were nitrogenous substances, and that monoaromatic, aliphatic with
straight saturated chain and heterocycles.
339
Regarding the Fraction 4, the sample consisted mainly of iso-alkanes, alcohols, monoaromatic
compounds, heterocycles, mainly nitrogen and aldehydes. There was also determine a high alcohol
and phenol content.
3.1 GC × GC / TOF-MS and GC-MS measurement methods comparison

Comparison of the analysis performed on two-dimensional gas chromatography with conventional
one-dimensional gas chromatography shows that the detailed characterization of complex mixtures
such as pyrolysis oil appears to be more suitable for two-dimensional GC.
Table 5 shows a considerable difference in the number of identified compounds, which is in most
cases up to several times higher in the measurement on a 2D GC system. The reason is mainly a
significantly higher separation efficiency of this system because every peak eluted in the first
dimension is still separated on the shorter column in the second dimension. Furthermore, the
modulator and TOF-MS as an analyser contribute to lower detection limits, which also positively
affects the results of that measurement.
Fraction 1 Fraction 2 Fraction 3 Fraction 4

Sewage Sludge
2D 1D 2D 1D 2D 1D 2D 1D
Alkanes 110 45 31 0 11 0 5 0
Alkenes + alkynes 184 39 49 0 0 0 0 0
Cyclic hydrocarbons 104 12 63 1 2 5 18 2
Monocyclic aromatic hydrocarbons 0 0 509 78 37 1 39 9
Polycyclic aromatic hydrocarbons 0 0 137 10 2 0 1 0
Alcohols + phenols 0 0 49 6 16 2 41 13
Esters 0 0 73 0 6 1 20 0
Aldehydes + ketones 0 0 116 2 10 0 74 2
Carboxylic acids 0 0 9 0 1 1 0 0
Heterocycles 0 0 362 22 10 1 117 8
Nitrogen-containing compounds 0 0 205 15 58 3 130 10
Sulphur-containing compounds 0 0 173 5 1 2 13 0
Number of identified compounds 398 96 1 183 106 98 12 223 23
Table 5: Comparison of measurement by 2-D and 1-D GC-MS.
4- CONCLUSIONS
The aim of the paper is to provide a detailed characterization of the sample composition of pyrolysis
oil obtained from MP processing of SS including a description of a suitable analytical method.
Comparing the two used chromatographic methods clearly show the suitability of the entire two-
dimensional gas chromatography for the analysis of complex mixtures as the pyrolysis oil.
In summary, substances from all twelve considered groups were found in the sample with the largest
share of alkanes and aromatics and the smallest share of compounds containing sulphur.
The sample of pyrolysis oil from SS originated at Brno Modřice WWTP is characterized by the
following groups of substances: alkanes, aromatics, alcohols, heterocycles, and nitrogen-containing
compounds.
340
Further research at BUT AdMaS of detailed characterization of pyrolysis oil from SS will be focused
especially on energy efficiency, ecotoxicity or combustion tests.
ACKNOWLEDGMENT
This paper has been worked out under the project No. LO1408 "AdMaS UP - Advanced Materials,
Structures and Technologies", supported by Ministry of Education, Youth and Sports under the
„National Sustainability Programme I".
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342
PRODUCTS PROPERTIES AND INTERACTION MECHANISM OF CO-PYROLYSIS OF

WASTE BIOMASS AND PLASTICS
P. LU1, Q.X. HUANG1, Y. CHI1, A.C. (THANOS) BOURTSALAS2, F. WANG1, K. SUN1

1 State Key Lab of Clean Energy Utilization, Zhejiang University, Hangzhou, China .
2 Earth Engineering Center, Columbia University, New York, USA.
Abstract
This paper investigated the co-pyrolysis of typical combustible components of municipal solid waste
(MSW), including waste biomass (pine wood, PW) and plastics (PVC and PE) [1]. Special attention has
been paid on the products (gas, tar and char) distribution, characterization and interaction
mechanism.
PW was co-pyrolyzed with PVC and PE (with a mixing ratio of 1:3, 1:1 and 3:1) both in a lab scale
fixed bed reactor and a thermogravimetric analyzer (TGA). Tar composition was analyzed through a
gas chromatograph coupled with mass spectrometer (GC-MS). Gas products were analyzed with a
gas chromatograph (GC). Char was characterized by scanning electron microscope (SEM), N 2
adsorption-desorption measurement, elemental analyzer and Raman spectroscopy.
The results showed that the interaction between PW and PVC significantly increased the yield (10.1-
27.7%) and carbon content, but decreased the BET surface area of char. The adding of PVC increased
the proportion of tar with 2 and 3 benzene rings (from 1.9 to 82.7%) and decreased the H/C atomic
ratio of tar (from 1.30 to 0.83). The reason may be that the hydrogen chloride (HCl) released from
the PVC affected PW pyrolysis through catalysis as a Lewis acid and suppressed depolymerization [2].
The interaction between PW and PE increased the gas yield (1.4-10.8%) and decreased the liquid
products yield (1.5-21.2%). The adding of PE significantly increased the proportion of tar without a
benzene ring (from 34.8 to 81.6%) and the H/C atomic ratio of tar (from 1.30 to 1.83). The reason
may be that the oxygen containing radicals from PW promoted the scission of polymer chains of PE
during thermal decomposition [3]. Further study concerning the effect of interaction on the catalytic
cracking of tar by activated biochar catalyst (ABC) will be done.
The interaction between PW and PVC produced tar containing heavier hydrocarbons, which were
more difficult to be decomposed by thermal method or catalytic cracking. The interaction between
PW and PE provided oxygen containing radicals, which may contribute to an easier scission of
polymer chains and a larger production of gases.
References
[1] Chen, D.; Yin, L.; Wang, H.; He, P.: Pyrolysis technologies for municipal solid waste: A review. Waste Manage. 34 (12),
2466−2486 (2014)
[2] Kandola, B. K.; Horrocks, A. R.; et al.: Flame-retardant treatments of cellulose and their influence on the mechanism
of cellulose pyrolysis. J. Macromol. Sci. Polym. Rev. 36, 721−794 (1996)
[3] Min, Z.; Asadullah, M.; et al.: Catalytic reforming of tar during gasification. Part I. Steam reforming of biomass tar
using ilmenite as a catalyst. Fuel 90, 1847-1854 (2011)
343
SCALING UP OF A DISRUPTIVE PROCESS FOR HEMICELLULOSE CONVERSION TO

VALUE ADDED PRODUCTS
B. REGO DE VASCONCELOS1, J. BROSSE1, X. DURET1, J. M. LAVOIE1

1 Industrial Research Chair on Cellulosic Ethanol and Biocommodities (CRIEC-B), Department of
Chemical and Biotechnological Engineering, Université de Sherbrooke, Sherbrooke, 2500 Boulevard

de l’Université, Sherbrooke, QC, J1 K 2R1 Canada.
Abstract
Conversion of lignocellulosic biomass into biofuels has shown to be a promising alternative to fossil
fuels. A key goal for the production of lignocellulosic biofuels is that all sugars released during the
first steps should be fermented into ethanol. However, only C6 sugars are easily fermented and the
C5 sugars remains as a waste of the fermentation process. In fact, the kinetics of C5 sugars
fermentation is significantly lower than pure C6 sugars. So, conversion of C5 sugars waste remains a
technical challenge [1, 2]. One pathway for C5 sugars valorization is their conversion into furfural,
which is a platform molecule with a wide range of applications such as in oil refining, plastic and
pharmaceutical industry [1, 2]. Historically furfural has been produced in process involving C5 sugars
conversion but as well as a co-product of different biomass valorization processes. Current industrial
furfural production relies on homogeneous acid-catalyzed processing of xylose-rich lignocellulosic
residues, such as bagasse and oat hulls, under high steam stripping conditions to recover the
products [2]. However, this processes present significant drawbacks related to corrosion of
equipment, catalyst loss and high amounts of acid and toxic waste as well as side reactions that
decrease the furfural yield. It has been reported that furfural yields at industrial scale are around
50% [2]. This work is though focused on the scaling up of a novel process for furfural production
aiming at the production of 15kL/year of furfural. This process has generated so far furfural yields
around 93% at a laboratory scale using C5 solutions as well as a homogeneous acid catalyst in low
concentrations in order to minimize equipment corrosion. The process is based on a biphasic system,
in which an organic solvent is used to recover the furfural as soon as it is produced in the reactor.
The present work will present the challenges encountered to scale up this process and how they
were overcomed. Indeed, problems such as effective mixture, mass and heat transfer, availability
and price of materials as well as the know-how to build the reactor take another proportion at pilot
scale (and at industrial scale) and should be carefully addressed in order to balance the economics of
the process.
Figure 1: P&ID of the pilot for furfural production.
References
[1] Beauchet, R., Berberi, V., Corcos, P.O., Montpetit, G. G., Dion, Y., Eudes, F., Lavoie, J. M.: Fermentation of C6
carbohydrates from triticale straw hemicellulosic fraction as pretreatment for xylose purification. Ind. Crops Prod. 51
(2013) 463-469.
[2] [2] Filiciotto, L. Balu, A. M., Van der Waal, J. C., Luque, R.: Catalytic insights into the production of biomass-derived
side products methyl levulinate, furfural and humins. Cat. Tod. 2017.
344
NOVEL BACTERIAL STRAINS FOR THE DIRECT UPGRADE OF HEMICELLULOSE DERIVED

OLIGOSACCHARIDES
I. TORRADO1,2,3, L. MIL-HOMENS3, N. MARTINS3, P. MARTINS1,3, P. MONIZ2,3, M. T. SANTOS4,

F. CARVALHEIRO3, M. C. FERNANDES2,5, H. PEREIRA1, L.C. DUARTE3
1 Centro de Estudos Florestais, Inst. Superior de Agronomia, Univ. de Lisboa, Lisboa, Portugal.
2 CEBAL - Centro de Biotecnol. Agrícola e Agro-Alimentar do Baixo Alentejo e Litoral /Inst. Politécnico
de Beja, Beja, Portugal.
3 LNEG – Lab. Nacional de Energia e Geologia, Unid.de Bioenergia, Lisboa, Portugal.
4 Escola Superior Agrária Instituto Politécnico de Beja, Beja, Portugal.
5 Inst. Ciências Agrárias e Ambientais Mediterrânicas (ICAAM), Universidade de Évora, Évora,
Portugal.
Abstract
Agricultural, forestry and agro-industrial residues have gained an increased attention as potential
substrates for the biorefineries in the last years. To increase the upgradability of these materials, a
pre-treatment process has to be applied. Hydrothermal processes have substantial advantages over
catalysed processes such as dilute acid, alkali, ionic liquids or solvents and, most noteworthy, they
are highly selective towards hemicellulose, no chemicals other than water are needed and present a
low operational costs (OPEX), turning them as one of the main choices of the emerging biorefinery
installations [1]. However, unlike others processes, the majority of the hemicellulosic sugars is
recovered as oligosaccharides (OS).
The prebiotic properties of hemicellulose derived OS such as xylooligosaccharides have been
investigated yielding promising results. However although the market for prebiotics is growing, it is
quite volatile. Therefore, it is important to achieve alternatives for their upgrade without an
expensive sequential pre-treatment such as acid or enzymatic post-hydrolysis to obtain
monosaccharides from OS.
Currently, there are no industrial relevant microorganisms able to upgrade OS, and hence the need
for the identification of microorganisms able to directly convert these into biofuels, biochemical or
other products. Nevertheless, OS are challenging microbial substrates, because their assimilation
may require additional hydrolytic enzymes and transportation systems.
This work aims to screen the potential to metabolize hemicellulose-derived sugars among bacterial
strains available in culture collections and also in new isolates from agricultural and food sources in
the Alentejo Region, Portugal.
Chemically defined media using a pentose (xylose) or oligosaccharide-rich hydrothermal
hydrolysates based media obtained from several feedstocks were used for the strain
characterization. Bacterial growth was evaluated spectrophotometrically and (oligo)-saccharides
assimilation and products formation were quantified by HPLC.
The strategy enabled the identification of several microorganisms able to assimilate OS with
different chemical structures. Typically, the most promising strains were lactic acid bacteria. Their
potential role as microbial catalysts for the upgrade of OS in the biorefinery framework will be
presented and discussed based on their product yield.
References
[1] Carvalheiro F, Duarte LC, Gírio F, Moniz P. 2016. Hydrothermal/Liquid Hot Water Pretreatment (Autohydrolysis), p
315-347. In Mussatto S (ed), Biomass Fractionation Technologies for a Lignocellulosic Feedstock Based Biorefinery.
Ivone Torrado gratefully acknowledges the PhD grant from FCT SUSFOR doctoral programme PD/BD/114175/2016
345
THE POTENTIAL BIOCONVERSION OF TROPICAL AGRICULTURAL WASTES

PRODUCING VALUE ADDED CHEMICALS (VANILLIN) USING LIGNOCELLULOSE
DEGRADING FUNGUS
I. NURIKA1
1 Agroindustrial Technology Department, University of Brawijaya, Malang, Indonesia.
Abstract
Tropical biomass or agricultural wastes are available which could be converted within a biorefinery
to yield valuable products. Using alternative fungal lignocellulose degrader, the agricultural wastes
such as rice straw, corn stover, sugar cane baggase, and cocoa pod can be degraded into various
number of sugars and other value added chemicals such as ferulic acid and vanillin which can be
separated during the biorefining. The mechanism for lignocellulose decay by the brown rot fungus
Serpula lacrymans has been investigated based on a Fenton-type catalytic system that produces
hydroxyl radicals, which attack lignocellulose. During the growth on biomass substrate the fungus
was capable of promoting the formation of a significant amount of ferulic acid and trace quantities
of vanillin. This study has also emphasis factors influencing the bio-production of ferulic acid and
vanillin, specifically type of substrate and the age of inoculum which could be optimized the release
of vanillin and ferulic acid during bioconversion process. The LCMS/MS method was validated for the
quantification of ferulic acid and vanillin, and the stability of ferulic acid and vanillin were evaluated
in the extract using a variety of extraction solvents. Meanwhile the surface structure modification of
biomass after degradation by the fungus was determined using scanning electron microscope,
indicated the enzymatic or non enzymatic reactions by the fungus damaged surface structure of the
biomass.
Keywords: agricultural wastes ; Serpula lacrymans ; lignocellulose ; vanillin ; ferulic acid ; LCMS/MS.
References
[1] Eastwood D.C, Floudas D, Binder M, Majcherczyk A, Schneider P, Aerts A, Asiegbu FO, Baker SE, Barry K, Bendiksby
M, et al: The plant cell wall-decomposing machinery underlies the functional diversity of forest fungi. Science,
333:762-765 (2011).
[2] Goodell B DG, Jellison J, Qian YH: Iron-reducing capacity of low-molecular-weight compounds produced in wood by
fungi. Holzforschung, 60:630-636 (2006).
346
STUDY OF MATERIALS IN CORROSIVE ENVIRONMENTS USING FUELS WITH HIGH

CHLORINE CONTENT IN OXY-FUEL ATMOSPHERE
ML. CONTRERAS1, I. RODILLA1, M. BENITO1, A. BAHILLO1

1 Unit of valorisation energetic of fuels and wastes, Department of Energy CIEMAT Av. Complutense
40, 28040 Madrid (España).
Abstract
The need to produce energy more sustainably, more efficiently and with less environmental impact
is becoming more and more evident. This leads to increasingly extreme conditions that impose more
demanding features on materials, with higher temperatures and pressures in more corrosive
environments. For these, to maintain good mechanical properties and also to be resistant to
corrosion it is necessary to use protective coatings [1]. Oxy-fuel, which uses a mixture of pure oxygen
and recycled gases instead of air, is recognized as a suitable technology for CO2 capture as it gives
rise to a concentrated stream of CO2 in the flue gases.
The main objective of this work, which is part of the project "Generation and study of coatings for
the protection of materials in aggressive atmospheres: sustainability and energy efficiency" is to
analyse the corrosion behaviour of bare and coated coupons of ferritic steels and a high-alloy
multipurpose austenitic stainless steel facing the increasingly extreme conditions that arise in the
generation of energy in oxy-combustion atmospheres using mixtures of coal and biomass as fuel. The
selected fuels were a subbituminous coal with presence of sulphur and an energy crop, cynara
cardunculus with significant amounts of chlorine, around 1%, and potassium, due to the influence of
the three elements on the corrosion mechanisms.
The effect of different oxy-fuel combustion atmospheres on deposition and corrosion phenomena
has been analysed by means of thermodynamic equilibrium calculations using the HSC Chemistry 6.1
tool, which allows the calculation of equilibrium compositions in heterogeneous systems [2].
The tests have been carried out in a pilot plant, where the core samples are placed. The temperature
at which the core samples are subjected and the flue gases composition are determining factors on
the behaviour and evolution of the materials analysed. The gravimetric evolution and other
characterization techniques like x-ray diffraction (XRD) and scanning electron microscopy with
energy dispersive detector (SEM-EDX) have been used.
There is a tendency to decrease phenomena of deposition as chlorides while sulphates are favoured
at low concentrations in the oxyfuel atmosphere. The ferritic steels have been severely affected
forming non protective oxides. Nevertheless, the austenitic steel has been able to resist and,
therefore it is not necessary to be covered.
References
[1] Berlanga, C., Ruiz, J.A. Study of corrosion in a biomass boiler. Journal of Chemistry, Article ID 272090, 8 pages, 2013.
DOI:10.114472013/272090.
[2] Contreras, M.L., García-Frutos, F.J., Bahillo, A., Oxy-fuel combustion effects on trace metals behavior by equilibrium
calculations. Fuel 108 (2013), pp 474-483
347
SUSTAINABLE PRODUCTION AND USE OF BUILDINGS: A CIRCULAR ECONOMY

PROSPECTIVE
M. C. TABOADA GOMEZ1, F. CULOTTE2, P. M. BELLO BUGALLO1

1
Department of Chemical Engineering, School of Engineering, University of Santiago de Compostela,
Av. Lope Gómez de Marzoa, s/n, E-15782, Santiago de Compostela, Spain.
2
National Institute of Applied Sciences, HVAC and Energy Department,
24 Boulevard de la Victoire, 67000 Strasbourg.
Keywords: Demolition, Waste management, Embodied energy, Life Cycle Thinking (LCT), Best
Available Techniques (BAT).
Abstract
The building construction sector plays an important role in the energy consumption all over the
world. Building accounts for 40% of the total energy consumption of the EU [1]. Concerning material
consumption, over 30% of all waste produced in the EU are construction and demolition wastes [2].
In this study, the demolition stage was analysed from a Life Cycle Thinking (LCT) approach
considering also the Circular Economy principles. The aim was to develop and validate a
methodology to obtain the more sustainable configuration for buildings, defining the environmental
impacts and energy consumption at the end of their life cycle. A methodology combining LCT
indicators and Best Available Techniques (BAT) has been developed, in the basis of previous works
[3, 4, 5]. It has been applied to an existing residential condominium. As a result, 4 Improvable Flows
(IF) have been identified, an inventory of nearly 120 candidate techniques to be BAT has been
established and 19 already implemented BAT have been identified. Then, a series of BAT have been
selected to reduce the effects of the IF.
It can be concluded that to reduce the impact of the demolition stage, we must act over the early
stages of the life cycle. Also, recycled materials are crucial to reduce the impact of the demolition
process. Recyclable and mineral materials will reduce the environmental impact from buildings by
half. The developed methodology allows building planners into selecting the more suitable
modifications to their projects in order to improve them towards a more sustainable system.
348
1- INTRODUCTION
Buildings play a very important role in the consumption of energy and natural resources all over the
world, as well as on the emissions released. In fact, buildings account for 40% of the total energy
consumption of the European Union (EU) [1]. In 2014, the total waste generated in the EU-28 by all
economic activities and households reached to 2,598 million tonnes, this was the highest amount
recorded to date. Construction contributed 35% of the total with 871 million tonnes [2].
Regarding Switzerland, 24 million tonnes of waste were produced in 2013 and demolition wastes
corresponded to 65% of this production with 15.5 million tonnes. Currently, 80% of construction
wastes in Switzerland are sorted, treated, and reused after recycling. The rest is incinerated or
directly landfilled [6, 7].
Considering the importance of this sector, this paper proposes a methodology to obtain more
sustainable buildings by considering sustainable development, life cycle thinking and circular
economy principles. The proposed methodology lies on the basis of an existing methodology
combining LCT tools and Best Available Techniques (BAT) analysis [3, 4, 5], in order to identify the
Improvable Flows (IF) of the system. Once identified the IF, the BAT analysis will help providing
techniques which will minimize the environmental effects of this IF.
1.1- SUSTAINABILITY APPLIED TO THE BUILDING CONSTRUCTION SECTOR

The performance evaluation and the definition of alternatives of existing buildings using Life Cycle
Thinking (LCT) should allow to define more sustainable operating configurations. LCT considers the
range of impacts throughout the life of a product [8]. To consider sustainability in this philosophy,
the life cycle indicators needed to determinate the impact on the environment must been identified.
Many valuable materials scape modern economies trough disposal. To move to a more sustainable
model, our economies shall be circular, recycling all the materials needed to manufacture a product
and thus creating no waste [9].
1.1.1- Embodied energy

Buildings are constructed with a variety of materials consuming energy throughout their stages of
manufacture, use and disposal. Energy is demanded, directly and indirectly through their entire life
cycle. Direct energy is used for construction, operation, renovation, and demolition. Indirect energy
is consumed to manufacture the materials used in its construction and technical installations [10,
11]. The addition of all energy consumed in the production is the “embodied energy”. Building
materials with high-embodied energy potentially produce more carbon dioxide emissions than
materials with low embodied energy [12].
Over 80% of the total energy used during the life cycle of a building is consumed during the phase of
exploitation. CO2 is the main component released by the processes involved in building construction
and its usage [13]. If we analyse the global resource consumption during its construction phase,
buildings consume 40% of stone, sand, and gravel, 25% of wood, 40% of energy from fossil fuels; and
16% of water [14].
To respect the principles of the circular economy and to reduce the embodied energy, the waste
management needs to follow the waste hierarchy, establishing an order of priority that minimises
349
adverse environmental effects and optimises resource efficiency in waste prevention and
management [15]. Among the different waste management strategies, recycling has been found as
the best strategy regarding energy saving potential (53%), while the energy saving potential for
reusing is 6,2% and for incineration is 0,4% [16].
1.1.2- Legislation and standards

The exploitation phase is the stage of the life cycle of a building which demands the highest amount
of energy. To reduce it, European countries set up regulations and standards to limit the
consumption of buildings.
In 1990, Germany created the Passivhaus standard. This voluntary standard seeks to achieve very
low energy consumption. As for Switzerland, since 1994 a similar standard has been developed.
Nowadays, it includes the Minergie (low consumption), Minergie-P (very low consumption) and
Minergie-A (passive house) standards. In addition, the complement Minergie ECO has been created
focussing in the health of inhabitants and the ecology of the construction.
The choice of materials affects the amount of future operational energy. Thormark [17] noted that
the share of embodied energy could be significantly reduced by using recycled materials. To reduce
the waste produced by the building sector and to decrease their embodied energy, the EU created
the “EU Construction & Demolition Waste Management Protocol” [18]. It will contribute to reach the
Waste Framework Directive target of 70% of C&D waste recycled by 2020.
1.2- ENVIRONMENTAL EVALUATION METHODS

The analysis of environmental impacts through the life cycle indicators will allow the identification of
the Improvable Flows (IF) of the system. Being the IF those inputs, outputs, or internal flows that are
remarkable in comparison with the other flows of the process, and which could be improved if
properly managed. This concept has been successfully applied to several previous works to date [19,
20, 21, 22].
Computer software can be used to facilitate this analysis. Calculation tools such as EQUER, ELODIE,
TRIBU, COCON, SméO or Lesosai have been created for the application of dynamic thermal
simulation and can identify the environmental impacts through the life cycle of a building.
To establish more sustainable alternatives, the best available techniques (BAT) for the system should
be identified by a BAT analysis. Since no BATs on construction and demolition processes exist, a BAT
inventory has been elaborated.

2.1- CASE STUDY: LIFE CYCLE OF A BUILDING
LCT tools allow assess all the environmental impacts. For each step, input and output flows are
included, in order to quantify waste, water, energy and CO2. The life cycle of a building is defined in
figure 1. Traditionally, it followed a linear process. To reduce materials consumption and waste
production, it shall be changed to a circular process through recycling.
350
Figure 1: Life cycle of a building.
2.2- METHODOLOGY
An existing methodology [4] has been adapted. The overall methodology includes:
1. Definition of the case study: selection, characterization, and qualitative analysis.
2. Definition of LCT tools applicable to this study.
3. Calculation of sustainability indicators: data acquisition and scenario modelling.
4. Selection of the Improvable Flows.
5. Best Available Techniques analysis.
6. Alternative scenarios definition: existing building vs. alternative scenarios elaborated by selecting
BAT to improve the IF.
7. Sustainability evaluation: selection and calculation of sustainable indicators, as well as election of
the optimal ones.

In this section, the above-mentioned methodology has been applied to a carefully selected case
study.
3.1- DEFINITION OF THE CASE STUDY

3.1.1- Identification of the case study
The developed methodology has been applied to an existing residential condominium in Switzerland.
The complex is distributed in 2 lots of buildings; each one of them composed of 4 buildings of 2
apartments each. The total constructed area is 2,600 m2. They are characterized by a Minergie-P
standard limiting their total consumption to 30 kWh/m2 per year. All buildings are connected by an
underground level which contains the parking and the heating plant. Heat is provided by 2
geothermal heat pumps and a solar thermal installation covering a part (30%) of the hot water
needs. There is an independent double flow ventilation system in each apartment and renewable
electricity (20% of the needs) is provided by a photovoltaic installation.
351
3.1.2- Qualitative analysis of the selected system

Electricity, water, Electricity, water, Electricity, water,
combustible combustible combustible
Preliminary Operations Processing Final Operations Auxiliary Operations
Construction Pre-demolition audit Selective demolition Waste Treatment Hazardous waste

materials, & waste and dismantling removal
products & structure management plan
Wastewater
On site separation Reusable Recyclable Materials Materials management
materials materials for prepared
recovery to landfill Cleaning
Transport Stock
Recycling Recovery Quality control
Recycled Energy & Landfill

material materials
Pollutant: CO2, HAP.. Pollutant: CO2, HAP.. Pollutant: CO2, HAP..

Noise Noise Noise
Figure 2: Flow diagram of the demolition stage.
Preliminary operations: Before starting the demolition process, it is very important to establish a
pre-demolition audit as well as a waste management plan. In Switzerland, the waste management
plan should include: measures to limit and valorise waste, requirements for waste management
facilities, and volume requirements for final disposal [23].
Process: In the demolition stage, the process is focused on the demolition and dismantling as well as
the first waste treatment on site. The objective is to effectuate a first try separating the different
waste by categories: excavation materials, waste from inert buildings site, other construction waste
and special waste. Also, those wastes must be shipped for treatment. The way wastes are
transported is quite relevant; in fact, each type of transport consumes different amounts of primary
energy. That is why trying to keep distances short is primordial. According to the European Union
Construction and Demolition Waste Management Protocol [21], when possible, its preferable to use
waste transfer stations serving as link between a local demolition waste collection point and the final
waste disposal facility.
Final operations: The wastewater is discharged to the municipal sewerage network without
treatment. After separation and sorting, the final operations are focused on the treatment of waste
generated by the demolition stage.
Auxiliary Operations: Several demolition wastes may have hazardous properties and must be treated
separately from other waste, according with the European Regulation [15, 24]. The wastewater
generated on site also needs to be treated. Before the recycled materials can be reuse, they shall go
through two steps: they must be cleaned and go through a quality control for checking if they
respect the environmental and technical requirements. The main wastes of this stage are cleaning
solvents, absorbing materials, and packaging.
352
3.2. CALCULATION OF SUSTAINABILITY INDICATORS

3.2.1. Data acquisition
Data related with the materials used in the construction of the case study have been obtained from
the building planners, as well as technical documents from the materials suppliers. Additional data
have been obtained through databases as Ecoinvent or KBOB [25, 26].
3.2.2. Scenario modelling

Software selection
For the purpose of this work, the software Lesosai has been selected as modelling tool. To calculate
the impacts, four indicators are used [26]:
 Non-renewable energy (NRE): Proportion of non-renewable energy of embodied energy.
 Cumulated energy demand (CED): Total embodied energy that manufacturing needs. It
includes non-renewable and renewable energy.
 Global Warming Potential (GWP): Includes all the gas emissions (kg oil eq).
 Umwelt Belastung Punkten (UBP): Also known as Ecopoints that quantifies the environmental
loads resulting from the use of energy resources, land and freshwater, emissions into the air,
water, and soil, as well as waste disposal (Pts/m²/year).
System modelling
To model the building within Lesosai, it should be characterized, including:
 Weather station, altitude, and emplacement.
 Heated zones, thermal capacity, and type of building.
 Definition of the thermal envelope: volumes, reference areas, thermal bridges.
 Define the structure of the building and the type of materials for each component.
 Define technical installations: heating, ventilation, and air conditioning.
 Define the lifetime of each components of the building.
3.2.3. Results Model 1

The first model considers the materials and characteristics of the real buildings. A detailed analysis
makes possible to compare all the stages of the life cycle. The manufacture of the materials required
for the construction of the building represents more than 50% of the various impacts. In addition,
the replacement of materials that have a shorter lifetime than the building represents 30% of the
overall impacts.
Focusing on the demolition phase and the disposal of materials, this represents only 5% of the
energy impact of the building. However, that impact increases significantly from an environmental
point of view. The objective of this study is to reduce the impact of this phase, based on the
qualitative analysis carried out previously.
3.2.4. Selection of the improvable flows

To develop models with lower impacts than Model 1, it was necessary to determine which were the
Improvable Flows (IF) of the system. Figure 3 shows the impacts of each one of model 1 materials.
Four material categories with comparative higher impacts were identified: reinforced concrete;
polystyrene insulation; ceramic floor tile and finally the type of joinery, especially PVC joinery. To
improve these IF, a BAT analysis should be stablished.
353
Figure 3: Results Model 1 – impacts of the construction materials.
3.2.5. BAT inventory

Using the questionnaire “MINERGIE-ECO New construction” [27], the BREF “waste treatment” [28]
and the green building cards “ECO-CFC” implement by Eco-Bau [25], an inventory of nearly 120
candidate techniques to be BAT has been established (some of them are shown in table 1). Model 1
already uses a certain number of these BATs. Though this work is focused on the demolition stage,
BATs affect all the building life cycle stages.
3.2.6. Alternative scenarios - improvements

BATs from the inventory have been selected to improve the IF previously identified. Two new models
have been established. The new models have been built imagining that the building was constructed
in a more sustainable way. Thus, to reduce the impact of demolition, we must act over the early
stages (design) of the life cycle of a building. For the results to be comparable, the new compositions
have equivalent thermal characteristics than those from model 1.
Model 2 is based on Model 1 but improving the IF. Materials characterized with a high impact were
replaced by other materials. The materials chosen for this model are either recycled materials or
new materials that can be fully recycled. In model 3, the whole concept of the building was replaced.
In this model, the structure of the building is made of wood and only mineral insulation is used.
In parallel with models 2 and 3, an additional scenario has been set up. Model 4 does not use any of
the BATs listed previously. The objective is to show that the BATs implemented have a real interest
in the reduction of grey energy.
3.2.7. BAT analysis

An evaluation of the four models has been carried out based on an analysis of the BATs and the
MINERGIE-ECO questionnaire present on Lesosai. The results are summarized in Table 1.
354
Energy effi ci ency
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Encl os i ng s ys tems wi th extra ction to s ui ta bl e a ba tement pl a nts
Stage Sub-stage Techniques candidate to be BAT Model 1 Model 2 Model 3 Model 4
Si zed extra ction s ys tems for s ome s tora ge a nd trea tments
Preliminary Operations Design Check i f there a re a l terna ti ves to the cons tructi on of a new bui l di ng X X X
Opera tion a nd ma i ntena nce of the a ba tement equi pment
Ai m for a compa ct bui l di ng vol ume X X X
Scrubber s ys tems for ma jor i norga ni c ga s eous rel ea s es
Provi de fl exi bi l i ty of us e X X
Lea k detection a nd repa i r procedures
Groupi ng s a ni ta ry a rea s X X X
Reduci ng emi s s i ons of vol a til es orga ni c compounds a nd pa rticul a te ma tter to the a i r
Ai m for a hi gh-performa nce energy s ta nda rd X X X
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Opti mi zi ng the us e of pa s s i ve s ol a r energy X X X
cri teri a
Li mi ti ng the envi ronmenta l i mpa ct of the bui l di ng X X
Avoi di ng the effl uent by-pa s s i ng the trea tment pl a nt s ys tems
Us e ea s i l y a va i l a bl e ra w ma teri a l s (new or recycl ed) X X X
Col l ecting wa s te wa ters
Choos e ma teri a l s or components tha t a re ea s y to di s ma ntl e a nd reus e or recovery X X
Segrega ting wa s te wa ter
Check tha t the cons tructi on ma teri a l s do not conta i n a ny pol l uta nts X X X
Ha vi ng a ful l concrete ba s e i n a l l the trea tment a rea s
Opti mi ze the i nterna l a rra ngement to ma xi mi ze the us e of na tura l l i ght X X X
Col l ecting ra i nwa ter
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Re-us i ng trea ted wa s te wa ters a nd ra i nwa ter
Choos e the s i te ta ki ng i nto a ccount the phys i cs of the s oi l
Da i l y checki ng on the effl uent ma na gement s ys tem a nd ma i ntena nce of a l og
Total percentage of design [%] 61,54% 84,62% 84,62% 0,00%
Identifyi ng the ma i n ha za rdous content of the trea ted effl uent
Processing Construction Protect groundwa ter a nd s urfa ce wa ter from pol l uti on
Us e the a ppropri a te wa s te wa ter trea tment techni ques for ea ch type
Protect trees by a ppropri a te mea s ures
Increa s i ng the rel i a bi l i ty of control a nd a ba tement performa nce to wa s te wa ters
Compa ct the s oi l i n the s tora ge a rea s
The ma i n cons tituent of trea ted wa s te wa ter
Us e other ma teri a l s tha n pol ys tyrene foa m for i ns ul a ti on, s ea l i ng a nd fi l i ng of ca vi ti es X X
Di s cha rgi ng of the wa s te wa ter
Us e ma teri a l s wi thout l ea d X X X
The emi s s i on l evel s on chemi ca l a nd bi ol ogi ca l oxygen dema nd a nd hea vy meta l s a s s oci a ted
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Impl ement a wa s te ma na gement progra m deta i l i ng reus e, recycl e or el i mi na ti on of
Us i ng re-us a bl e pa cka gi ng X
demol i ti on wa s te a s wel l a s thei r qua nti ty
Re-us i ng drums
Repl a ce extra ct trees by a n equa l qua nti ty of new ones
Ha vi ng a n i nventory of the wa s te on-s i te
Us e few s upporti ng i nner wa l l s X X X
Re-us i ng wa s te
Us e remova bl e a nd ful l y mecha ni ca l fa s teners X X X
Ma rketed before demol i tion ma teri a l s a nd reus a bl e i tems
Ins ta l l s a ni ta ry fi xtures a nd va l ves for effi ci ent wa ter us e X X X
Recover a l l ma teri a l s for PVC fl oori ng a nd roofi ng s heets ma de of PVC or pol yol efi ns
Us e of ra i nwa ter or grey wa ter
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X X X
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desd demol i tion ma teri a l s X X
For a lpercentage
Total l i ns ta l l a tiof
ons , us etreatment
waste ha l ogen-free
[%] ma teri a l s X
0,00% X
0,00% X
0,00% 0,00%
Land reclamation Us e of
Provi maateri
di ng nd amal s wi thout
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s eanil ed
Mi mi s i ng s i te a nd underground equi pment X X X
Total percentage
Total percentage of
of land
construction [%] [%]
reclamation 36,00%
0,00% 72,00%
0,00% 52,00%
0,00% 0,00%
0,00%
Demolition Remove a nd depos
Total percentage i t profes
of BAT [%] s i ona l l y a l l the el ements i denti fi ed a s ha za rdous 14,29% 24,37% 20,17% 0,00%
MINERGIE results Ecological construction Us e enviof
Concept ronmenta l ma na
cons truction gement s ys tems
[%] 75% 100% 100% 75%
Provi s i on of ful
Cons truction mal teri
detaa il lss aof
ndthe a cti vi
proces ti es[%]
s es ca rri ed out on-s i te 79% 100% 100% 47%
Ha
NREvi [MJ/m2.an]
ng a good hous ekeepi ng procedure i n pl a ce 259,5 167 183,1 348
Ha vi [MJ/m2]
NRE ng a cl os e rel a ti ons hi p wi th the wa s te producer/cus tomer 15'570,00 10'020,00 10'986,00 20'880,00
Us e of qua l i fi ed s ta ff
Table 1: BAT analysis.
Conduct a prel i mi na ry a na l ys i s to determi ne the pres ence or a bs ence of pol l uta nts i n
bui l di ngs cons tructed pri or to 1990
3.2.8. Results Devel op a demol i ti on a nd decons tructi on ma na gement pl a n for ma jor projects
Di vi de the ma teri a l s to be demol i s hed i nto di fferent ca tegori es of wa s te
Sustainability indicators have Sort wabeens te on s i tecalculated for all four models and yielded the results shown in
Col l ect s epa ra tel y va l ua bl e ma teri a l s
Figure 4. The results showTotalthat the impact of BATs on our system is important.
percentage of demolition [%] 0,00%
The amount
0,00% 0,00% 0,00%
of
embodied
Final operations energy present in
Waste disposal Ha vi model
ng a concrete 1 knowlisedge
reduced
of the wa s te iby
nput half in model 2, which uses many BATs from de
Impl ementi ng a pre-a ccepta nce procedure
inventory and recycled materials. Impl ementi ng aIt n a is also
ccepta reduced by half in model 3, which is characterized by a
nce procedure
wooden structure. CED indicator is higher in this model than in the model 2 due to a greater amount
Impl ementi ng di fferent s a mpl i ng procedures
Ha vi ng a recepti on fa ci l i ty
of RE in the wood than in the concrete.
Ana l ys i ng the wa s te output The use of recycled materials in model 2 reduces the amount
0,00%
of embodied energy in the manufacture of materials by 53%, whereas the non-use
Total percentage of disposal [%]
of0,00%
these0,00% 0,00%
materials
in model 4 gives rise to a 55% increase.
355
Figure 5: Results: sustainability indicators.
4- CONCLUSIONS
In this work, a methodology combining LCT and BAT has been developed, to get a more sustainable
system. The selected system is the demolition stage within the life cycle of a building.
This methodology has been applied to an existing residential condominium in Switzerland. As a

result, 4 IF have been identified in the process, an inventory of nearly 120 candidate techniques to
be BAT has been established and 19 already implemented BAT have been identified. Then, a series of
BAT have been selected to reduce the effects of the identified IF. On this basis, two new models have
been established, and the sustainability indicators calculated.
It can be concluded that to reduce the impact of the demolition stage, we must act over the early
stages of the life cycle of the building. Also, recycled materials are crucial to reduce the impact of the
demolition process. Recyclable and mineral materials will reduce the environmental impact from
buildings by half. The developed methodology allows building planners into selecting the more
suitable modifications to their projects to improve them towards a more sustainable system.
ACKNOWLEDGEMENTS
The authors would like to thank the collaboration of the buildings planners (the engineering office,
Groupe technique H2, and the architects, Chiché Architectes SA) in providing the data for this paper.
We especially thank, Mr. Antonio Alvarez, CEO of the engineering office, for all his support.
356
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http://eplca.jrc.ec.europa.eu (2012). Accessed 30 November 2017.
9. European Commission: Communication from the Commission. Towards a circular economy: A zero waste
programme for Europe. Brussels (Belgium). COM (2014) 398 final/2.
10. Dixit, M.K., Fernandez-Solis, J.L., Lavy, S., Culp, C.H.: Identification of parameters for embodied energy
measurement: A literature review. Energ. Buildings, 42, 1238-1247 (2010).
11. Cabeza, L.F., Rincón, L., Vilariño, V., Pérez, G., Castell, A.: Life cycle assessment (LCA) and life cycle energy analysis
(LCEA) of buildings and the building sector. Renew. Sust. Energ. Rev., 29, 394-416 (2014).
12. González, M.J., Navarro, J.G.: Assessment of the decrease of CO2 emissions in the construction field through the
selection of materials: Practical case studies of three houses of low environmental impact. Build. Environ., 41, 902-
909 (2006).
13. Sharma, A., Saxena, A., Sethi, M., Shree, V., Varun: Life cycle assessment of buildings: A review. Renew. Sust. Energ.
Rev., 15, 871-875 (2011).
14. Arena, A.P., Rosa C.: Life cycle assessment of energy and environmental implications of the implementation of
conservative technologies in school building in Mendoza-Argentina. Build. Environ., 38, 359–68 (2003).
15. European Parliament and council of the European Union: Council Directive 2008/98/EC of 19 November 2008, on
waste and repealing certain directives. Off. J. European Union L 312/3.
16. Ng, W.Y., Chau, C.K.: New life of the building materials-recycle, reuse and recovery. Enrgy. Proced., 75, 2884-2891
(2015).
17. Thormark, C.: A low energy building in a life cycle – its embodied energy, energy need for operation and recycling
potential. Build. Environ., 37, 429-435 (2002).
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Accessed 10 July 2017.
19. Torres Rodríguez, M., Cristóbal Andrade, L., Bello Bugallo, P., Casares Long, J.: Combining LCT tools for the
optimization of an industrial process: Material and energy flow analysis and best available techniques. J. Hazard.
Mater., 192, 1705 – 1719 (2011).
20. Taboada Gómez, M.C., Magan Iglesias, A., Torres Lopez, R., Bello Bugallo, P.M.: Towards sustainable systems
configurations: application to an existing fish and seafood canning industry. J. clean. prod., 129, 374-383 (2016).
21. Bello Bugallo, P., Stupak, A., Cristóbal Andrade, L., Torres López, R.: Material Flow Analysis in a cooked mussel
processing industry. J. Food Eng., 113, 100 – 117 (2012).
22. Cristóbal, L.: Development and application of the methodologies to get sustainable industrial systems (2012).
23. Swiss confederation: Ordinance 814.600 on the limitation and disposal of waste of 4th December 2015.
24. European Parliament and council of the European Union: Commission Decision 2014/955/UE of 18 December 2014
amending Decision 2000/532/EC on the list of waste pursuant to Directive 2008/98/EC of the European Parliament
and of the Council. Off. J. European Union L 370/44.
25. Association Eco-Bau. Durability of the public constructions. https://www.eco-bau.ch (2016). Accessed 26 December
2017.
26. KBOB. Coordination conference for the construction and building services of public building owners: Data of the
ecobanks in construction 2009/1:2016 (2015).
27. Minergie. https://www.minergie.ch/. Accessed 03 December 2017.
28. European Commission: Integrated Pollution Prevention and Control, Reference Document on Best Available
Techniques for the waste treatments industries (2006).
357
APPLICATION OF MODIFIED BENTONITE AS FOAM STABILIZER IN ENHANCED OIL

RECOVERY
HUI DANG1, ZHIDONG CHANG1, XUE WU1, XINXUE LI1, CHANGYAN SUN1, WENJUN LI1
1 Department of Chemistry and Chemical Engineering, School of Chemistry and Biological
Engineering, University of Science and Technology Beijing, Beijing 100083, PR China
Abstract
After almost two decades when human entered the new millennium, crude oil is still the blood of
modern industry and the global demand keeps increasing. The crude oil crisis is called for nearly half
century and few new deposits can be found now. But actually, only less than half deposit of crude oil
can be displaced from reservoirs by the traditional primary and secondary recovery. In order to
extract the left deposit, enhanced oil recovery (EOR) technologies are developed, among which
water flooding and gas flooding are two of the most widely used. Unfortunately, water flooding
always leads to bypass flow. Reservoir heterogeneity and gravity override contribute to poor sweep
efficiency of gas flooding. To improve sweep efficiency in enhanced oil recovery, foam flooding was
proposed and proved to be a promising technique which has been utilized for several years [1].
Flooding foam is a two-phase fluid system where some gas flow paths are made discontinuously by
thin liquid films called lamellas. When foams are injected into the reservoir, it can quickly block the
high permeability layer and then transfer fluid into a low permeability layer. Nevertheless, foams are
unstable thermodynamically which limits its field applications to a certain extent [2].
In this work, we used modified bentonite and unmodified bentonite mixed with xanthan gum to
stabilize foam with sodium dodecyl sulfate (SDS) as surfactant. The results of foam stability revealed
that modified bentonite can improve the stability of foam greatly which can last more than 3300
seconds with the optimized conditions. XRD data suggested that the silicon plays a pivotal role.
References
[1] Nguyen, P., H. Fadaei, and D. Sinton, Pore-Scale Assessment of Nanoparticle-Stabilized CO2 Foam for Enhanced Oil
Recovery. Energy & Fuels, 2014. 28(10): p. 6221-6227.
[2] Sun, Q., et al., Nanoparticle‐Stabilized Foam for Mobility Control in Enhanced Oil Recovery. Energy Technology, 2016.
4(9): p. 1084-1096.
358
SOPHOROLIPID PRODUCTION FROM FOOD WASTE HYDROLYSATE USING A NATIVE

STARMERELLA BOMBICOLA
HUAIMIN WANG1, GUNEET KAUR1, KRISTIADI UISAN1, CAROL SZE KI LIN1

1 School of Energy and Environment, City University of Hong Kong, Hong Kong, Tat Chee Avenue,
Kowloon, Hong Kong, People’s Republic of China
Abstract
Food waste problem is an increasing problem all over the world. According to the Food Wastage
Footprint model (FWF) published by Food and Agriculture Organization of the United Nations (FAO),
an estimated 1.6 gigatons of food waste is produced annually, accounting for 27% of the 6 gigatons
of total agricultural production for both food/non-food uses.
Sophorolipid (SL) is a promising chemical using in deterrent production and often produced from
microorganisms with a rapidly increasing global market around 27 billion USD. Strain Starmerella
bombicola is a mostly studied strain for SL production. Sophorolipid consist of a hydrophilic
sophorose disaccharide bound to a hydrophobic fatty acid with a typical chain length of 16–18
carbon atoms. The fatty acid may be joined by an ester bond to the second glucose monomer, giving
a lactonic sophorolipid, or joined to only one glucose monomer, giving an acidic sophorolipid due to
the unbound fatty acid.
In our study, food waste was collected from local restaurant in Hong Kong Science Park and
hydrolyzed with glucoamylase, protease and lipase. Food waste hydrolysate (FWH) with 99.1 g/L
glucose and 2430.6 FAN was produced from the food waste and sterilized with membrane filtration.
This FWH was used as sole substrate for SL production with native strain Starmerella bombicola. In 2
L fermentor with 1 L working volume, 91.4 g/L SL was produce at 78 h with a glucose control
around10- 30 g/L.
This result indicate a great potential in converting food waste to sophorolipid with less processing
time and high titer.
Acknowledgement:
The authors are grateful to the financial support from Applied Research Grant (ARG), City University
of Hong Kong.
References:
[1] Geys, R., Soetaert, W., & Van Bogaert, I. (2014). Biotechnological opportunities in biosurfactant production. Current
opinion in biotechnology, 30, 66-72.
359
VALORISATION OF CORN FIBRE: OPTIMISATION OF AN INTEGRATED PROCESS FOR

THE PRODUCTION OF BIO-VANILLIN
R. VALÉRIO1, R. BERNADINO1, C.A.V. TORRES1, M. TAVARES2, M.A.M. REIS1, J.G. CRESPO1, C.

BRAZINHA1
1 Requimte Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de
Lisboa, Campus de Caparica, 2829-516 Caparica, Portugal.
2 Copam-Companhia Portuguesa de Amidos, 2695-722 S. João da Talha, Portugal.
Abstract
Corn fibre, by-product from the starch industry, is commonly incorporated in low value animal feed.
The aim of this project is the development of a sustainable process to maximise the potential of corn
fibre as feedstock for the bioproduction of vanillin, using as a precursor ferulic acid extracted from
corn fibre, which is one of most abundant sources of ferulic acid in agricultural products [1].
The process consists in four main steps:
Step 1- Extraction of ferulic acid from corn fibre
The release of ferulic acid from corn fibre extract under alkaline conditions was optimised, obtaining
an extract containing 2.2 g(ferulic acid)/L. Alternatively, enzymatic hydrolysis using commercial enzymes
is being studied.
Step 2- Separation and concentration of ferulic acid by membrane processing
The arabinoxylans are also released under alkaline conditions from corn fibre [2], which originated
highly viscous extracts. Ultrafiltration is an efficient and suitable option to separate ferulic acid from
arabinoxylans in alkaline extracts, due to the high molecular mass difference of these compounds.
The resultant fraction enriched in ferulic acid was processed by diananofiltration and then
concentrated by nanofiltration obtaining an extract rich in ferulic acid.
The enzymatic hydrolysis, which will consequently destroy arabinoxylans, result in much less viscous
extracts that facilitate further membrane processing.
Step 3- Bioproduction of vanillin using the ferulic acid stream obtained in the previous step
Another challenge in this project is the direct use of the enzymatic and alkaline ferulic acid extracts,
obtained in the previous task, as precursor for vanillin production by Amycolatopsis sp. bacteria.
Optimization of the bioprocess was achieved by assessing the impact of relevant parameters such as
feeding-strategy and composition of the medium.
Step 4- Recovery of bio-vanillin from fermentation broths
The possibility of recovering vanillin in one single step through pervaporation was previously
demonstrated [3], resulting in vanillin with a high purity degree. In this work we also evaluate the
recovery of vanillin by vacuum distillation.
References
[1] Tilay, A., Bule, M., Kishenkumar J., and Annapure U.: Preparation of Ferulic Acid from Agricultural Wastes: Its
Improved Extraction and Purification. Journal of Agricultural and Food Chemistry. 56, 7644–7648 (2008)
[2] Kale, M.S., Hamaker, B.R., Campanella, O.H.: Alkaline Extraction Conditions Determine Gelling Properties of Corn
Bran Arabinoxylans. Food Hydrocolloids. 31,121-126 (2013)
[3] Brazinha, C., Barbosa, D.S, Crespo, J.G.: Sustainable Recovery of Pure Natural Vanillin from Fermentation Media in a
Single Pervaporation Step. Green Chemistry. 13, 2197 (2011)
360
RECOVERY OF VOLATILE FATTY ACIDS FROM WASTE-DERIVED FERMENTATION

BROTH USING NANOFILTRATION
Y. ZHU1, S. GALIER1, C. DUMAS2, H. ROUX-DE BALMANN1

1 Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INPT, UPS, Toulouse, France.
2 LISBP, Université de Toulouse, CNRS, INRA, INSA, Toulouse, France.
Abstract
Nowadays the waste production is growth rapidly especially in developing countries, researchers are
trying to variate waste into resources. This work use household waste as raw material to ferment
volatile fatty acids (VFAs), one kind of useful chemical building blocks. However, in addition to the
targeted VFAs, the fermentation broth contains many other components and further recovery of
VFAs is required.
Nanofiltration (NF) is a pressure-driven membrane process that has been reported to be successfully
used in separation of many organic solutes like lactate and glucose [1]. Only a few reports
concerning VFAs separation have been published [2], showing the necessity to improve the
selectivity. The objective of this work is then to investigate the feasibility of NF for the recovery of
VFAs from waste-derived fermentation broth.
An experimental study is reported, carried out using a dead-end stirred cell with Filmtec NF-45
membrane. The retention of the solutes is measured and the separation factor is calculated in order
to characterize the separation efficiency. Solutions of increasing complexity, single VFAs at different
concentrations, mixtures of VFAs in different proportions, with and without inorganic salts, are
investigated as well as a real fermentation broth. Indeed, it is known that the performances of NF
are very dependent on the broth composition, specially the ionic composition.
The results show that the retention of VFAs (acetate, propionate and butyrate) in single solution
follows their molecular weight but is influenced by the total VFAs concentration. As the total
concentration increase, retentions of all VFAs decrease, due to a screening of the electrostatic
repulsion. However, a higher selectivity is observed for increasing concentration. In the conditions
investigated, the highest retention difference between acetate/butyrate is about 40% and the
highest separation factor is about 2.2. The presence of sulfate improves the retention difference
between the VFAs as well as the separation factor, reaching respectively 72% and 2.5.
Then, it is proved that NF could be used for the recovery of VFAs from waste-derived fermentation
broth. The purity of the recovered fractions strongly depends on the ionic composition of the
fermentation broth and further investigation is required.
References
[1] C. Umpuch, S. Galier, S. Kanchanatawee, H.Roux-de Balmann, Nanofiltration as a purification step in production
process of organic acids: Selectivity improvement by addition of an inorganic salt, Process Biochem. 45 (2010) 1763–
1768.
[2] M.-P. Zacharof, S.J. Mandale, P.M. Williams, R.W. Lovitt, Nanofiltration of treated digested agricultural wastewater
for recovery of carboxylic acids, J. Clean. Prod. 112 (2016) 4749–4761.
361
VALORISATION OF COPPER SLAG FOR THE PHOTOCATALYTYC DEGRADATION OF

ORGANIC POLLUTANTS IN WATER
C.V. MONTOYA BAUTISTA1, R. GARCÍA-ESTRADA1, E.I. AVELLA FERNÁNDEZ1, R.M. RAMÍREZ-

ZAMORA1, R. SCHOUWENAARS 2
1 Instituto de Ingeniería, Universidad Nacional Autónoma de México, 04510 Cd. Méx., México.
2 Facultad de Ingeniería, Universidad Nacional Autónoma de México, 04510 Cd. Méx., México.
Keywords: Copper slag, Photocatalysis, Photo Fenton, Solar Radiation, Wastewater Treatment
Abstract
Copper slag (CS) obtained from a Mexican copper smelting company was evaluated as a
photocatalyst for the degradation of organic pollutants in industrial and urban waste water using
solar irradiation as an energy source. Two lines of investigation were followed, one researching the
capability of CS to catalyse the advanced oxidation process of complex pollutants such as
thiabendazole and ciprofloxacin, the other focusing on the use of waste alcohols as a sacrificial agent
for the production of hydrogen under solar irradiation. This paper summarises the experimental
conditions used in the different experiments, including the physical characterisation of the slag and
the set-up of the degradation tests. Then, an overview of the most important results obtained to
date is given. It is found that the main absorption of light by CS occurs in the blue wavelengths and
can be associated to fayalite, which is the main compound of the material. CS was characterised as
an n-type semiconductor which acts as an electron acceptor. In presence of peroxide, this leads to a
highly efficient degradation of the organic pollutants due to an efficient production of hydroxyl
radicals. The degradation of alcohols used as a sacrificial agent for hydrogen production occurs at
very high quantum yields, but hydrogen production, as determined by the techniques used, is fairly
low. This result seems to suggest that the hydrogen produced remains adsorbed on the negatively
charged surface of the catalyst, which may provide interesting options for its recuperation in future
research.
362
1- INTRODUCTION
Copper slag is an industrial waste material produced in large quantities in the extractive metallurgy
of copper. For each T of metal produced, 2.2 to 3 T of slag is generated [1]. Estimated annual
production is 68 MT [2]. Although it is sometimes classified as a hazardous waste [3], leaching tests
do not show the release of heavy metals [4,5]. An important reason for recycling copper slag is the
recuperation of metal residues [6,7], although with the use of optimised metallurgical processes, this
application is no longer interesting due to low yields. Other applications are the use of aggregates in
cements and concretes [1,8-11], road surfaces and abrasives [12,13].
The main economic and ecological contributions of the latter applications reside in waste reduction,
resulting in lower costs and environmental impact associated to landfilling, as well as a reduction of
the consumption of prime materials in construction applications. This stands into contrast to the
catalytic applications proposed in the present work. Here, the aim is to utilise the electro-optical
properties of the waste material for the treatment of urban and industrial wastewater containing
complex organic pollutants. This allows for the substitution of highly specific and expensive catalysts,
often produced as nanoparticles [14-17] or through expensive modification of nanoparticles [18-24],
using instead a simple non-expensive material, with the goal of enhancing the affordability of water
treatment. By developing applications which operate in the visible spectrum, solar radiation can be
used as an energy source. Further simplification of the processes can be achieved if the process
takes place at the natural pH of the waste water.
The use of CS as a photocatalyst by this research group was originally motivated by the search for
iron-rich solid waste materials to be used in the so-called heterogeneous Fenton reactions. The
original (homogeneous) Fenton reaction is an advanced oxidation process where hydrogen peroxide
is decomposed into hydroxyl radicals under the catalytic effect of Fe+++. The latter ion is soluble in
water at a pH below 2.8, which imposes the use of strongly acidic conditions [25]. At higher pH, the
iron catalyst is lost as dross. The use of solid catalysts containing high levels of iron or iron oxides is
supposed to overcome this disadvantage. The hypothesis used in earlier works was that iron oxides
were responsible for the photocatalytic activity of copper and steel slag [26-28].
Huanosta-Guttierez et al. [26] studied the degradation of phenol using CS and H2O2, with and
without UV-irradiation and reported up to 50% reduction in total organic carbon (TOC). During the
process, toxicity peaks were observed as the result of the formation of intermediate degradation
products. They concluded that the process can be optimised to obtain maximal biodegradability of
the residual products, particularly in presence of the UV-source. Solís-López [27] studied the use of a
heterogeneous photo-Fenton process for the disinfection of water contaminated by Ascaris suum
eggs, where hydroxyl radicals play the role of damaging cell membranes and disrupting the function
of RNA during the cell cycle. They suggested that fayalite was the main actor in the photocatalytic
process and that the strongly negative charge of the CS promoted the efficient formation of ·OH
radicals under solar irradiation at neutral pH. Under optimal conditions, a 90% decrease in the
viabiltiy of the parasite eggs was observed. Arzate-Salgado et al. [28] compared copper slag with
steel slag in the degradation of Diclofenac under simulated solar simulation and in presence of H 2O2.
While steel slag provided rather modest results, CS reduced the concentration of diclofenac to below
the detectability limit of 0.1mg/L in 90 min, with a starting dose of 120 mg/L at neutral pH.
Based on the promising results of the latter three studies, further research was performed on the
degradation of thiabendazole and ciprofloxacin by means of the heterogeneous photo-Fenton
process. On the other hand, CS shows a band gap of 2.5 – 2.7 eV, which is smaller than the band gap
of 3.2 eV observed in TiO2 and hence allows the use of light in the visible spectrum to induce
processes which require UV-irradiation when TiO2 is used. Of particular interest are the dual-purpose
processes where a contaminant is degraded as a sacrificial agent for the production of H 2 [29-33]. A
363
summary of results will be provided of the degradation of waste alcohols from the Mezcal industry
and glycerol, which is a by-product of biodiesel production, the commercialisation of which is not
economically feasible [34-36].
Raw slag was obtained from a smelter in northern Mexico and mechanically ground. The fraction
passing through the 400 mesh was used in the tests. Morphological characterisation was performed
using a a Zeiss AxioImager POL microscope to characterise the microstructure of thin slices of raw
slag, the powdered product was observed with a Philips XL20 SEM equipped with and Oxford 7593
solid state EDX-detector. Chemical composition was analysed by XRF and the crystalline phases
identified through XRD. The Brunauer-Emmet-Teller isotherm was used to characterise the specific
surface area, by adsorption/desorption of N2 in a Belsorp Mini II equipment. The bandgap of CS was
determined by analysis of the Tauc curve using data obtained from UV-Vis diffuse reflectance
spectroscopy with wavelengths in the range of 200 to 800 nm. Electrochemical characterization of the
slag was performed by means of the Mott-Shottky analysis using the techniques described by
Ramírez-Ortega et al. [37].
The full details of the experimental schemes used in the optimisation of the different photocatalytic
experiments are beyond the scope of this brief overview. The designs, as well as their statistical
analysis, will be presented in full-length papers in the near future. A brief description of the main
procedures follows here. All the chemical reagents were reactive grade (ACS). Distilled water was
used in the degradation tests; MilliQ water was used in the electrochemical tests.
Thiabendazole degradation was investigated in distilled water and synthetic urban effluent for
exploratory test and in real effluent after initial optimisation of the procedures. In all cases, 100 g/L
of thiabendazole was added. H2O2 doses were varied in a systematic manner in the range of 4.4 to
0.44 mM. The bottom of the reactor was covered with a thin layer of slag which was not perturbed
during the process. The degradation reaction was executed in natural sunlight for 120 min. For
ciprofloxacin, only preliminary experiments have been performed to date, with a dose of 30 mg/L of
this contaminant in distilled water and varying H2O2 doses from 75 to 85 mg/L, slag doses from 1 to 3
g/L, under simulated sunlight at neutral pH. For both thiabendazole and ciprofloxacin, the residual
concentrations were analysed by HPLC (Agilent 1200 series).
Glycerol degradation, as well as treatment of alcohols representative of mezcal residues (methanol,
propanol, isoamyl alcohol), in absence of H2O2, was studied under UV radiation (Hg-lamp) and
simulated sunlight (Xe-lamp). Hydrogen evolution was measured using a Shimadzu GC-2014 gas
chromatograph and residual contaminant concentration was detected as total non-purgeable TOC. For
glycerol degradation, pH was varied from 2 to 12, slag doses from 0.4 to 2 g/L and glycerol
concentration from 0.06 to 1.74 (%v/v). For the other three alcohols, the slag dose was fixed at 1 g/l,
pH at 6.5 and the initial concentration of alcohols was set at 0.125M. Hydrogen production was
monitored for 6h.
3-RESULTS AND DISCUSSION
The microstructure of the raw copper slag is illustrated in fig. 1. The orthorhombic fayalite phase is
present in the form of long needles separated by opaque zones which consist of a glassy phase.
Magnetite is present as small equiaxed particles. This result coincides to what is observed by XRD
[27]. The morphology of the product after milling is show in fig. 2. Here, the fayalite is seen as grey
elongated zones, the amorphous phase is dark grey and the magnetite is present as white equiaxial
grains on the particle surface. The observed morphology can be explained by the normal cooling
sequence of CS at intermediate cooling speed [38]. No significant porosity was found for the granular
product, which has a specific surface area of 1 m2/g.
364
Figure 1: Polarised light observation of CS. Blue/yellow needles correspond to fayalitie, elongated dark zones are silicate glass and the
equiaxed dark grains are identified as magnetite, based on XRD-analysis.
Figure 2: SEM-image representing the granulometry of the slag as used in photocatalytic experiments. Fayalite is seen as grey
elongated zones, the amorphous phase is dark grey and the magnetite is present as white equiaxial grains on the particle surface.
The band gap associated to CS was measured as 2.7 eV, which roughly confirms earlier results of 2.5
eV [27]. This value corresponds to literature data for fayalite [39,40] and rejects earlier hypotheses
within the research group that the photocatalytic activity could be associated to the magnetite
phase or other iron oxides. The Mott-Shottky analysis demonstrates that CS is an n-type
semiconductor. Hence it acts as a hole donor (electron acceptor).
The advanced oxidation processes showed complete removal of thiabendazole and ciprofloxacin in
preliminary tests and incomplete consumption of H2O2. As the latter reagent increases the cost of
the water treatment process, its dose was lowered during further optimisation of the degradation of
365
thiabendazole. At 1.5 mM, complete degradation is achieved in 120 min with a H2O2 consumption of
55%. At 0.88 mM H2O2, the system evolves toward an approximately steady state in which 90% of
the contaminant is degraded at a consumption of 70% of peroxide. The amount of Fe leached from
the slag into the solution was below the detectability limit (0.25 mg Fe L-1), showing that the process
is heterogeneous catalysis and not a homogeneous Fenton reaction provoked by leached ions.
With respect to the degradation of alcohols as sacrificial agents for hydrogen production, it was
found that the reaction was more efficient under simulated solar light than under UV-irradiation.
Reduction of TOC was 14% for methanol, 3.5% for propanol and 2% for isoamyl alcohol after 6 hrs of
simulated sunlight. The maximal reduction in glycerol was 4% after 5 hours at a pH of 3.7 and a
volumetric content of 1.4% and slag dose of 1.6 g/l. For the case of methanol, an apparent quantum
efficiency of 40% was achieved, expressed in function of TOC-reduction. In all cases, hydrogen
production, as measured by gas chromatography during the process, was very low as compared to
TOC reduction. However, no significant amounts of CO, CO2 or CH4 were detected during the
process, indicating that hydrogen is produced but remains trapped in the system.
The observations can be explained by the semiconductor characteristics of CS. The fact that this
catalyst is more efficient in visible light than UV can be attributed to the measured band gap. The
very high efficiency of photo-Fenton processes using this photocatalyst can be explained by its
nature as an n-type semiconductor (hole donor). The Fenton reaction is initiated by the splitting of
the H2O2 molecule into either ·OH+OH-, with the acceptation of an electron from the Fe-based
catalyst, or ·OOH+H+, donating an electron to the catalyst. At the surface of an n-type
semiconductor, excess holes can be captured and two hydroxyl radicals can be generated instead of
one.
In absence of hydrogen peroxide, the formation of ·OH was observed by Solis-López et al, which can
be explained by the capture of a hole by OH-. This radical can then initiate the degradation of the
organic molecules. For a simple molecule such as methanol, few radicals are required to efficiently
reduce the TOC in the solution. For more complex molecules, more radicals are required and part of
the total equivalent carbon may remain present in the solution as intermediate reaction products,
which are still measured as TOC. This effect was clearly observed in the degradation of highly
complex molecules by heterogeneous photo-Fenton reactions. The one question remaining then is
the fact that the amount of hydrogen produced is not in proportion to the amount of organic
molecules removed, which is particularly striking for methanol, where no intermediate reaction
products could be detected. However, if one considers that the ·OH radicals are generated through
the capture of a hole by OH-, the remaining H+ can be attracted to the negatively charged surface of
the catalyst, and remain as an adsorbed species which is not detected by gas chromatography. This
hypothesis should be confirmed in future research.
4- CONCLUSIONS
Although the original hypothesis behind this research project was that abundant iron oxides in
copper slag would be able to catalyse the heterogeneous photo-Fenton process for water treatment,
it was found that the specific semiconductor properties of fayalite (iron silicate) are responsible for
the observed reactions. This allowed to expand the research into applications which have the dual
purpose of contaminant degradation and hydrogen production, using the organic contaminants as a
sacrificial agent in the water splitting process.
Fayalite was found to possess a band gap of 2.5-2.7 eV, in the blue range of visible light. As a
consequence, natural solar light can be used as an energy source in the photocatalytic process. Its
characteristics as an n-type semiconductor allow for a much higher efficiency in the conversion of
366
H2O2 molecules into ·OH radicals and very efficient degradation of complex organic molecules by the
heterogeneous photo-Fenton process.
In absence of peroxide and for simple organic molecules such as methanol, a high quantum yield was
determined in terms of contaminant degradation. For more complex molecules, the quantum yield is
difficult to determine, unless all intermediate products are characterised. A disproportionally low
hydrogen production was observed. However, considering that ·OH radicals were also created in
absence of H2O2, it was concluded that hydrogen was present in the form of excess H +, which can be
efficiently adsorbed on the negatively charged catalyst surface. This hypothesis must be further
researched and can provide interesting new applications for the valorisation of waste copper slag.
5- ACKNOWLEDGMENTS
This work was supported by DGAPA Grant N° IV100616. C.V. Montoya Bautista, R. García-Estrada
and E.I. Avella Fernández thank CONACYT for the scholarship received during their postgraduate
studies.
REFERENCES
[1] Behnood, A., Modiri Gharehveran, M., Gozali Asl F., Ameri, M.: Effects of copper slag and recycled concrete
aggregate on the properties of CIR mixes with bitumen emulsion, rice husk ash, Portland cement and fly ash, Constr.
and Building Mater. 96, 172-180 (2015).
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368
HYDRODEOXYGENATION OF BIOMASS PYROLYSIS OIL USING HYDROGEN DONOR

SOLVENT AND Co-Mo CATALYSTS
J.K. GANE1, M.A. NAHIL1, P.T. WILLIAMS1

1
School of Chemical & Process Engineering, University of Leeds, Leeds, LS2 9JT, UK
Abstract
Bio-oil produced from the pyrolysis of waste biomass is chemically complex, with high oxygen
content (up to 50 wt.%), acidic properties and tendency to polymerise. These properties restrict the
use of the bio-oil because of end-use issues including filter blocking, oil-pumping issues and
corrosion. The direct substitution of the biomass derived pyrolytic oils for conventional petroleum
fuels is therefore limited and a barrier to the deployment of these next generation biofuels produced
from lignocellulosic feedstocks. Production of a low oxygen content, low viscosity bio-oil produced
from biomass with a composition similar to petroleum crude would enable direct refining of the oil
in existing petroleum refineries. Bio-oil with less than 10 wt.% oxygen content is miscible with
petroleum and reports have suggested that 5 wt.% oxygen is an ideal target for bio-oils to be
incorporated into the existing petroleum refinery system. Hydrodeoxygenation (HDO) is a technology
for upgrading bio-oil where hydrogen is reacted with the bio-oil at high-pressure to remove oxygen
in the form of water. The hydrogen is normally supplied as a gas, but there is interest in using
alternative sources of hydrogen, for example, hydrogen donor solvents which enables transfer of
hydrogen from the donor compound to the acceptor compound.
In this work, fast pyrolysis of waste biomass was used to produce bio-oil using a screw-kiln reactor
system. The product bio-oil was then processed in an autoclave reactor with tetralin (a naphtheno-
aromatic compound of crude petroleum oil) as the liquid phase hydrogen donor and in the presence
of Co-Mo catalyst. The influence of process conditions including reactor temperature and catalyst
composition were investigated in terms of minimising oxygen content of the upgraded oil and
chemical composition in relation to refinery ready petroleum feedstock. The bio-oil was
characterised in terms of oxygen content, and detailed compositional analysis using gas
chromatography-mass spectrometry and Fourier Transform Infrared before and after reaction.
The results showed that the raw bio-oil contained 32 wt.% oxygen but was markedly reduced after
upgrading to < 10 wt.%. The raw bio-oil contained mainly carboxylic acids, ketones, aldehydes and
phenols which were markedly reduced after dehydrogenation and there was a corresponding
increase in aliphatic and aromatic compounds. The influence of upgrading temperature was to
increase the degree of deoxygenation.
References
[1] Elliott, D.C.: Historical development in hydroprocessing bio-oils. Energy & Fuels, 21, 1792-1815 (2007)
[2] Hellinger, M., Baier, S., Mortensen, P.M., Kleist, W., Jensen, A.D., Grunwaldt, J.: Continuous catalytic
hydrodeoxygenation of guaiacol over Pt/SiO2 and Pt/H-MFI-90. Catalysts, 1152-1166 (2015)
[3] Hong, Y., Lee, D., Eom, H., Lee, K.: The catalytic activity of sulphided Ni/W/TiO2 (anatase) for the hydro-
deoxygenation of Guaiacol. Journal of Molecular Catalysis A: Chemical, 392, 241-246 (2014)
369
PRIMARY PYROLYSIS REACTIONS OF LIGNIN
H. KAWAMOTO1
1 Graduate School of Energy Science, Kyoto University, Kyoto, Japan.
Abstract
Purpose Lignocellulosics are the major biomass resources that have the potential for substitution of
fossil-resource-based chemicals/materials and certain amount of world primary energy demand,
because substantial amounts of virgin and waste lignocellulosics exitst in our society. Nevertheless, it
has not been utilized efficiently even in these days. Thermochemical conversion is one way for this
purpose. Under these circumstances, our research group has studied the molecular mechanisms of
pyrolysis of lignocellulosics in order to control the complex chemical reactions involved in the pyrolytic
conversion, aiming at the more efficient production of chemicals, materials and fuels from
lignocellulosics. This paper deals with the primary pyrolysis reactions for the production of monomeric
aromatic compounds and oligomers from lignin, based on our recent investigations, which are
summarized in literature [1]. Lignin is the most abundant renewable aromatic feedstock, since 20-30
wt% of lignin is included in lignocellulosic biomass.
Materials and methods used Lignin model dimers that represent various ether (C-O-C) and condensed
(C-C) type linkages between phenylpropane-units in lignin were used effectively for studying the lignin
primary pyrolysis reactions and molecular mechanisms. The obtained results were carefully discussed
with the data of the pyrolysis of isolated lignins and lignins in wood samples to propose the molecular
mechanisms.
Main results and conclusions Primary pyrolysis reactions took place in the temperature range of 200-
400 C, where the ether-type linkages were cleaved, while the condensed types resisted. Thus, lignin
macromolecules should be depolymerized significantly in the primary pyrolysis stage, because the
ether linkages represent 60-70% of lignin interphenylpropanoid bonds. However, actual yields of
monomeric aromatics from lignin pyrolysis were quite small. This was found to originate from the
condensation reactions of the depolymerisation products, which are preferable to the evaporation of
monomers that stabilize monomers (Figure 1). The ether-cleavage products with conjugated C=C
structures were quite reactive for non-radical Monomers
condensation reactions. In addition, radical Evaporation

coupling reactions account for the
condensation, because most of the ether Ether
linkages other than some of the benzyl ether Lignin
cleavage H-donation
types were suggested to cleave

homolytically, which results in the formation Radical Side-chain conv.
H-donation
of large number of radical species. Thus, this
radical condensation reaction was greatly
influenced by the co-existing substances, i.e., Heating zone
hemicellulose, and the influences were quite (Solid/liquid) Condensation
products Char
different for hardwood and softwood

R: H or OCH , R' : various side-chains
species. 3
Figure 1: Lignin primary pyrolysis reactions.
References
[1] Kawamoto, H.: Lignin pyrolysis reactions. J. Wood Sci. 63, 117-132 (2017)
370
PYROLYSIS OF LOW-GRADE PLASTIC-RICH WASTES TO PRODUCE LIQUID FUELS AND

CHEMICALS
S.T. WAGLAND1, N. JURADO1,2, O. OLUITAN1, M. HARRADINE3, P. O’CALLAGHAN4, L. ORESANWO4, S.

GOMM3, E. J. ANTHONY1
1
Cranfield University, Bedfordshire, UK.
2
University College London, London, UK.
3
Syngas Products, Dorset, UK.
4
WestAfricaENRG, Lagos, Nigeria
Abstract
As waste management practices migrate from a predominately disposal approach to more

sustainable methods, greater emphasis is being placed in the recovery of value from wastes.
Advanced thermal conversion of waste material into high quality renewable products - i.e. clean
syngas, oils and char - represents an attractive and value-added alternative. Advanced thermal
treatment [ATT] technologies offer the potential for higher efficiencies in clean heat and power
production combined with the flexibility to produce gaseous and/or liquid fuels. Such technologies,
which includes pyrolysis, have been suggested as an option for smaller, town-scale, applications with
integrated gas cleaning systems. The Energy Technologies Institute [ETI] recently reported that ATT
operating in the 5-20 MWe range offers the potential for efficient energy from waste solutions [1].
Plastic-rich feedstocks, which are not viable for reuse or recycle, could potentially yield sustainable
alternatives to increasingly expensive fossil-derived fuels, with a growing emphasis on transport
fuels in the UK and as an alternative fuel for diesel back-up generators in developing countries, such
as Nigeria.
A novel approach for modelling pyrolysis is presented here, by defining six stages at specific pressure
and temperature conditions. The model was developed using the software Aspen Plus. In this project
we present results from plastic-rich waste streams and introduce detailed oil production modelling,
building on previous research [2].
Air +
Air Moisture
Semi-dry Heat
Pyrogas Raw Clean Recovery
Feed
Feed
Feed material
material Feed
Feed and Char Ceramic Pyrogas Pyrogas
PYROLYSIS
PYROLYSIS DRUM
DRUM Ceramic Gas Gas
Gas Engine
Engine
composition
composition Conditioning
Conditioning Gas Quench
Quench
Filter
Filter Electricity
Oversize/ Heavy Light

Inerts Char
Oils Oils
Aqueous
Effluent
Figure 1 – Overview of pyrolysis process
This work presents the results generated from the partnership funded by Innovate UK. The core
scientific aim of the project is to develop scientific understanding of the complex chemistry of
organic compound formation. Overall the project team aims to demonstrate the viability of
producing high-value products from the pyrolysis of plastics; having applications in developing
countries as a sustainable diesel fuel alternative.
References
[1] Evans, G., 2017. Targeting new and cleaner uses for wastes and biomass using gasification. Energy Technologies
Institute, Loughborough, UK.
[2] N. Jurado, M. Harradine, S. Gomm, E.J. Anthony, S.T. Wagland., 2017. The Role of Pyrolysis in Distributed Town-scale
Energy Systems and Research Results from a Pre-commercial Facility Processing Waste-derived Feedstocks. IRRC
waste-to-energy symposium, October 2017, Vienna, Austria.
371
CO2 ADSORPTION ON CHEMICALLY ACTIVATED CHARS FROM COMMERCIAL

BIOMASS GASIFIERS
E. CORDIOLI, V. BENEDETTI, F. PATUZZI, M. BARATIERI

Faculty of Science and Technology, Free University of Bolzano, piazza Università 5, Bolzano 39100,
Italy
Abstract
Char is the carbonaceous by-product of biomass gasification processes and nowadays it is treated as
a waste, thus representing an economic and energetic loss for the plant owners. However, due to its
similarities to activated carbons in terms of physical-chemical properties and mechanism of
formation, it can be valorized as cheap precursor for activated carbons in different applications.
Many studies [1] have examined the adsorptive capability of pyrolytic char, while char from
commercial gasification systems has hardly been addressed.
The present study assesses the suitability of char obtained from commercial gasifiers for adsorption
of CO2. Char samples were collected from several commercial biomass gasifiers installed in South-
Tyrol (Italy) and activated using either KOH or ZnCl2 in order to enhance their porosity and thus their
adsorption capacity. Since adsorption is influenced by specific surface area, pore size distribution,
and surface chemistry [2], chars were fully characterized before and after activation. In particular,
elemental analysis, physisorption analysis (BET surface area and BJH theory pore size distribution
and volume) and thermogravimetric analysis (TGA) were conducted in the Bioenergy & Biofuels Lab
at the Free University of Bolzano, while scanning electron microscopy (SEM) and X-ray powder
diffraction (XRD) in the Department of Molecular Sciences and Nanosystems at Ca’ Foscari University
of Venice.
The CO2 adsorption capacity of the char samples was evaluated in a thermogravimetric analyzer
(Jupiter STA 449 F3, Netzsch) following the procedure reported by Rashidi et al. [3]. Different
adsorption temperatures were tested in order to investigate not only the effect of the activating
agent, but also the effect of temperature on the char adsorption capacity. Moreover, the behavior of
the material under regeneration was studied.
Both pure chars and activated chars showed satisfactory CO2 uptakes resembling the ones reported
in the literature for activated carbons [1,3] and proved to be stable under regeneration cycles. The
adsorption capacity of the samples increased by chemical activation and decreased at high
temperatures due to the instability of physical-adsorbed CO2 molecules on the char surface.
In conclusion, chemically activated chars from commercial biomass gasifiers proved to have
remarkable properties that make them suitable adsorbents for CO2 capture and valid candidates to
substitute activated carbons in adsorption applications.
References
[1] Creamer, A. E., Gao, B.: Carbon-Based Adsorbents for Postcombustion CO2 Capture: A Critical Review, Env. Sci. Tech.
50, 7276-7289 (2016).
[2] Di Gregorio, F., Parrillo, F., Salzano, E., Cammarota, F., Arena, U.: Removal of naphthalene by activated carbons from
hot gas, Chem. Eng. J., 291, 244-253 (2016).
[3] Rashidi, N.A., Yusup, S., Borhan, A., Loong, L.H.: Experimental and modelling studies of carbon dioxide adsorption by
porous biomass derived activated carbon, Clean Technol. Environ. Policy. 16, 1353–1361(2014).
372
EGGSHELL AS A POTENTIAL CO2 SORBENT IN CHEMICAL LOOPING GASIFICATION OF

BIOMASS: CALCINATION, CARBONATION AND CHARACTERIZATION STUDIES
S.A. SALAUDEEN1, S. TASNIM1, M. HEIDARI1, B. ACHARYA2, A. DUTTA1

1 University of Guelph, Guelph, Canada. Email: adutta@uoguelph.ca
2 University of Prince Edward Island, Charlottetown, Canada.
Abstract
This work presents an investigation into the potential use of eggshell as CO 2 sorbent in chemical
looping gasification of biomass to enhance carbon negativity. Calcination and carbonation reactions
(Eqns. 1 and 2) were studied with a quartz wool matrix reactor and thermogravimetric analyzer
coupled with a Fourier transform infrared spectroscopy. The sorbent was characterised with a
scanning electron microscope, colorimeter, energy dispersive X-ray and nitrogen sorption analyser.
Pore structures of the samples appear to be of Type II isotherm. Results show that increasing the
calcination temperature enhances decomposition, and improves the calcium content as well as the
specific surface area of the sorbent. As compared to nitrogen, calcination in CO 2 environment is not
effective due to the enhancement of CO2 partial pressure. Samples with low particle size displayed
higher carbonation conversion. The conversion by the sorbent in multiple calcination-carbonation
cycle was also studied. Initial CO2 uptake by the sorbent was highly encouraging. A conversion of
76.41% was realized after the first cycle but due to sintering and attrition, conversion reduces with
increasing cycle. The sorbent exhibited a low conversion of 18% after the seventh cycle and this
corresponds to a decay extent of 76.65%.
Calcination reaction:
𝐶𝑎𝐶𝑂3(𝑠) → 𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(𝑔) + 178.8 kJ/mol (1)
Carbonation reaction:
𝐶𝑎𝑂(𝑠) + 𝐶𝑂2(𝑔) → 𝐶𝑎𝐶𝑂3(𝑠) - 178.8 kJ/mol (2)
References
[1] Acharya, B., Dutta, A., and Basu, P.: Gasification of biomass in a circulating fluidized bed based calcium looping gasifier
for hydrogen-enriched gas production: experimental studies. Biofuels 8 (6), 643-650 (2017)
[2] Acharya, B., Dutta, A., and Basu, P.: Chemical-looping gasification of biomass for hydrogen-enriched gas production
with in-process carbon dioxide capture. Energy & Fuels 23 (10), 5077-5083 (2009)
[3] Acharya, B., Dutta, A., and Basu, P.: An experimental study of calcination/carbonation cycle in a chemical looping
gasifier, ACS Journal of Industrial & Engineering Chemistry Research. 51, 8652−8660 (2012)
[4] Acharya, B., Dutta, A., and Basu, P.: 2010. An investigation on steam biomass gasification for Hydrogen Production
with CaO. Int. J Hydrogen Energy, 35 (4), 1582-1589 (2010)
373
NOVEL CATALYTIC MATERIALS SYNTHESIS FROM INDUSTRIAL SLAGS FOR

APPLICATION IN CATALYTIC FAST PYROLYSIS OF PINE SAWDUST
E. KHOLKINA1, N. KUMAR1, C. LINDFORS2, T. OHRA-AHO2, J. LEHTONEN2, M. PERULA3, J. PELTONEN3,

J. SALONEN3, D. YU. MURZIN1
1 Åbo Akademi University, Laboratory of Industrial Chemistry and Reaction Engineering, Faculty of
Science and Engineering, Biskopsgatan 8, FI-20500 Turku/Åbo, Finland, .2VTT Technical Research
Centre, FI-02044 Esbo, Finland, 3Turku University, FI-20014 Turku, Finland, e-mail: nkumar, tel. +358
2 215 4555
Abstract
Synthesis of value added products from industrial wastes, residuals and side products are important
for efficient use of the limited natural resources available on the planet. Taking into consideration,
need for energy security, nutrisous food, drinking, water, pharmaceutical components and housing,
for the growing population. It is of immense importance that the limited natural resources are
utilized in the best possible way for the welfare of the humanity. Worldwide 450 million tons of
industrial slags: a product of steel industry, are produced every year. Most of these slags are
disposed at the land fillings, quite often using agricultural fertile lands. So far, these industrial slags
have not been transformed to value added products. In this research we report, the wealth creation
strategic by transforming these industrial slags to value added products of novel inorganic materials
for application as catalysts, adsorbents, separation, sensors, membranes and materials for industrial
wastewater treatment. The transformation of industrial slags to novel catalytic materials were
carried out by alkaline pre-treatment and hydrothermal synthesis methods. The physico-chemical
characterization of the as received industrial slag and the produced catalytic materials were carried
out using XRD for structural analyses, nitrogen physisorption for surface area and pore volume
determination. TEM was for the metal particle size measurement and EDX for the quantitative
elemental analyses. The characterization of acid and basic acid sites of the catalytic materials were
carried out using TPD-NH3 and TPD-CO2. The evaluation of the catalysts in catalytic fast pyrolysis of
pine sawdust was carried out with a filament pulse pyrolyzer. The reaction products analyses were
performed using GC-MS. The novel catalytic materials synthesized from industrial slags exhibited
presence of Brønsted and Lewis acid sites. The presence and amount of the acid sites were
influenced by alkaline pre-treatment time, temperature and pH of the sodium hydroxide solution.
The catalysts also showed the presence of weak, medium and strong basic sites. The catalytic fast
pyrolysis of pine sawdust exhibited variations in the compositions of the reaction products in the
presence of catalysts as compared to the non-catalytic fast pyrolysis. In-depth correlation of the
catalyst characterization results with catalytic fast pyrolysis will be discussed. Furthermore, reaction
mechanism regarding the transformation of industrial slags to novel catalytic materials will be
elaborated.
References
[1] N. Kumar, E. Leino, P. Mäki-Arvela, A. Aho, M. Kaldström, M. Tuominen, P. Laukanen, K. Eränen, J.-P. Mikkola, T.
Salmi, D. Yu. Murzin, Synthesis and characterization of solid base mesoporous and microporous catalysts: Influence
of support, structure and type of base metal, Microporous and Mesioporous Materials 152 (2012) 71-77
374
HYDROXYAPATITE AND MAGNESIUM-DOPED HYDROXYAPATITE AS NEW SUPPORTS

FOR DRY REFORMING OF METHANE
S. PHAN THANH 1, D. PHAM MINH1, D.GROUSET1, A. NZIHOU1

1 Université de Toulouse, Mines Albi, CNRS, Centre RAPSODEE, Campus Jarlard, F-81013 Albi Cedex
09, Albi, France.
Abstract
The dry reforming of methane (DRM) consists of the conversion of CO2 and CH4 into syngas (CO and
H2). This process is a promising way to valorise CO2 and CH4, which have high environmental impact.
Syngas could be transformed into many chemical products as liquid fuels, methanol, light olefins and
gasoline.[1] This work focused on the development of new performing catalysts, hydroxyapatite (HA)
and magnesium-doped hydroxyapatite (Mg-HA) supported nickel catalysts for DRM reaction. Mg-HA
could be increase the basicity of support which can enhance chemical sorption of CO 2, inhibit coke
deposition, and therefore, improve the activity and stability of catalyst.
Hydroxyapatite Ca10(PO4)6(OH)2 (HA) and magnesium-doped hydroxyapatite Ca10-xMgx(PO4)6(OH)2

(Mg-HA) were prepared following a precipitation and co-precipitation method [2]. Catalysts based of
nickel carried on HA and on Mg-HA were prepared by dry impregnation method using nickel nitrate
as precursor. High purity Ca(NO3)2.4H2O, (NH4)H2PO4 and Mg(NO3)2.6H2O were used as starting
materials. Catalysts were characterized by using BET, XRD, SEM, TEM, FTIR, TGA and TPD techniques.
Synthetic HA and Mg-HA with high specific area SBET>90m2/g were obtained. Results from DRX and
TEM-EDX indicated the insertion of Mg in the crystalline structure of HA.
Figure 1: CH4 and CO2 conversion with the time of stream
The catalytic tests were done in a fixed-bed reactor at 700°C. Figure 1 shows an example of results.
High catalytic activity was obtained. The conversions of CH4 and CO2 were around 75% and 80%
respectively. High stability was also observed.
Hydroxyapatite-based catalysts seemed to be promising catalytic materials for DRM process.
References
[1] W. Li, Z. Zhao, et Y. Jiao, « Dry reforming of methane towards CO-rich hydrogen production over robust supported Ni
o
catalyst on hierarchically structured monoclinic zirconia nanosheets », Int. J. Hydrog. Energy, vol. 41, n 40, p. 17907-
17921, oct. 2016.
[2] C. Verwilghen, S. Rio, A. Nzihou, D. Gauthier, G. Flamant, et P. J. Sharrock, « Preparation of high specific surface area
o
hydroxyapatite for environmental applications », J. Mater. Sci., vol. 42, n 15, p. 6062‑ 6066, juin 2007)
375
MATERIAL CHARACTERIZATION OF BOTTOM ASH FINE FRACTIION
M. ŠYC1, A. KOPŘIVA2, O. SAMUSEVICH1, Š. VÁCLAVKOVÁ1, B. ZACH, K. SVOBODA, M. PUNČOCHÁŘ

1 Institute of Chemical Process Fundamentals of the CAS, v.v.i., Environmental Process Engineering
Laboratory, Rozvojova 135, 165 02 Praha 6 – Suchdol, Czech Republic.

2 TESCAN Brno, s.r.o., Libusina trida 1, 623 00 Brno, Czech Republic.
Abstract
Waste-to-energy has recently become a leading technology for municipal solid waste (MSW)
treatment in Europe. Waste-to-energy (WtE) plants treat nearly 80 million tons of MSW yearly and
produce approximately 20 million tons of bottom ash (BA). Bottom ash is a very heterogeneous
material and its composition is mainly determined by the composition of MSW. In our previous
studies, we summarized material composition of BA samples from Czech WtE plants [1]. The overall
composition, except for the fraction below 2 mm, is presented in Table 1.
Table 1 Material composition of BA samples from Czech WtE plants
Sample P1 P2 P3 L1 L2 B1
Glass 13.6 22.7 17.2 9.2 12.2 14.8
Porcelain and ceramics 1.8 3.3 5.1 2.2 2.6 3.6
Unburnt organics 0.2 0.3 0.6 1.0 0.6 0.2
Magnetic fraction 16.3 11.1 11.4 15.8 15.6 10.2
Ferrous scrap 8.9 10.3 8.5 7.0 6.1 11.0
NFe metals 1.6 1.9 2.2 1.3 1.3 2.8
Residual fraction 25.4 19.7 25.4 29.0 25.9 20.5
Fraction below 2 mm 32.2 30.7 29.6 34.4 35.7 36.8
Therefore, we focused on detailed characterization and determination of materials composition,

mainly with respect to metals content, of particles below 2 mm. TESCAN Integrated Mineral Analyzer
(TIMA) based on TESCAN VEGA3 LM microscope was used for analyses. Mineralogy of fine fraction
were determined, but main attention were paid on metal content, their speciation, particle size
distribution and liberation analysis. In particles below 2 mm, iron and aluminium were dominant
metals, as expected, however significant content of Cu, Zn, etc. was found. Majority of metallic Al
particles were covered by thin layer of Al2O3. About 10-30 % of Al were in the metallic Al form, the
rest was as Al oxides, and various alumino-silicates. Cu content were found within the range 0.2-0.3
wt .% and more than 2/3 of Cu were as metallic Cu and Cu alloys. Cu particles were partly
agglomerated mainly with various alumino-silicates. Zn content were 0.2-0.5 wt. %, nearly all Zn
were in metallic form and Zn particles were often fully liberated. The presented data, together with
our previous analysis, reveals full potential of bottom ash as resource for metal recovery.
References
[1] Šyc M., Krausová A., Kameníková P., Šomplák R., Pavlas M., Zach B., Pohořelý M., Svoboda K., Punčochář M., 2017.
Material Analysis of Bottom Ash from Waste-to-Energy Plants, Submitted to Waste Management. )
376
LEACHING AND RECOVERY OF TRACE ELEMENTS FROM BOTTOM ASH –

PRELIMINARY STUDY
M. LUPSEA-TOADER1, L. SVECOVA2, D. BLANC1, C. DE BRAUER1

1
University of Lyon, INSA-Lyon, DEEP Laboratory, Villeurbanne, France
2
LEPMI, Grenoble Alpes University, CNRS, Grenoble, France
Abstract
Currently in France, 30% of the annual production of waste is treated by incineration. The main by-
product of incineration is the Municipal Solid Waste Incineration – Bottom Ash (MSWI-BA). The
annual production of bottom ash is estimated to be between 2.7 and 3.2 million tons. In France, the
valorisation of BA is limited to road materials and the French decree of 18/11/2011 fixed the
thresholds related to the metallic content in these ashes and their leachability prior to the
valorisation in such applications. The part of bottom ash which is not valorised (due to small demand
from the road industry), is stored in landfills as non-dangerous waste. However, this alternative is
not environmental friendly, as these ashes are susceptible to leach within the landfill and release to
the environment heavy metals (e.g. Cu, Cr, Pb, Zn) contained in trace concentrations in the bottom
ashes.
The current study focuses on alternative ways of valorisation of the MSWI-BA, namely the recovery
of trace elements is envisaged within this project, with the double objective: (i) to recover
economically important metals and (ii) to pre-treat bottom ash, before further valorisation or
disposal. The obtained MSWI-BA samples from the French Rhône-Alpes region is representative in
terms of composition of common MSWI-BA waste. It is a heterogeneous material, composed of
numerous mineral phases (mainly silicates, metallic oxides and hydroxides, sulphates, carbonates
and metallic alloys formed during incineration). After several treatment steps (removal of iron-based
materials and screening) at the outlet of the furnace, the bottom ash has the shape of gravel,
consisting of fine particles and other fragments of various sizes, e.g. glass and ceramic fragments.
Three particle fractions are obtained after the treatment processes: 0-31.5 mm (global coarse
fraction), 6-31.5 mm (an intermediate fraction) and 3-6 mm (fine fraction). In the current study we
focused on the fine fraction, because it proved to be the most charged in heavy metals.
Hydrometallurgical processes such as leaching, selective precipitation and electro-deposition are
used in order to verify the feasibility of such a treatment. First, the efficiency of classical acid
leaching technique will be compared to the so-called electro-assisted leaching. This innovative
leaching process based on the use of electrochemistry instead of acids has already been tested on
various metal-based materials (ocean nodules, galvanic sludge or industrial solid waste). Two
different experimental set-ups were described in literature. Within the direct electro-assisted
leaching the waste is directly used as sacrificial anode material and the applied potential is chosen as
to obtain the selective oxidation and dissolution of the target metals. On the other hand when the
indirect electro-assisted leaching is used, the solid material is put in suspension into an electrolytic
solution and the leaching species are generated at the electrode-electrolyte interface. The latter
approach is easier to achieve experimentally, nevertheless it seems to be less selective. The
advantage of electro-assisted leaching is on one hand, that no acid is used (unless a diluted acid is
used as electrolyte) and only electrolyte solution is necessary. On the other hand the electro-assisted
leaching process can be easily combined to direct electrodeposition of the desired metal at the
cathode of the same electrochemical cell. In the scope of this work, both acid and electro-assisted
377
leaching steps were tested and compared, followed by electrodeposition or selective precipitation of
leached metals. Several experimental difficulties have been experienced, related mainly to the
complex chemistry of the bottom ash matrix. These difficulties will be discussed here and the most
interesting results of this preliminary study will be presented. The acid leaching seem to give better
results compared to electro-assisted leaching in terms of leaching efficiency, however further
optimization is still needed.
378
BIOCHAR – RECOVERY MATERIAL FROM MICROWAVE PYROLYSIS OF SEWAGE

SLUDGE
J. RAČEK1, J. ŠEVČÍK1, T. CHORAZY1, J. KUČERÍK2, P. HLAVÍNEK1
1 Faculty of Civil Engineering, AdMaS Research Centre, Brno University of Technology, Brno 602 00,
Czech Republic.
2 Faculty of Chemistry, Institute of Chemistry and Technology of Environmental Protection, Brno
University of Technology, Brno 602 00, Czech Republic.
Keywords: sewage sludge, thermal treatment, microwave pyrolysis, biochar.
Abstract
The treatment of sewage sludge (SS) is becoming one of the most important issues of the
wastewater treatment cycle at the European Union. Thermal transformation of SS is typically
accompanied by production of pyrolysis oil, pyrolysis gas (syngas) and solid char product called
either charcoal or biochar, when applied in agriculture. In this work, we used a full-scale MP unit
with 3 kW magnetron with the frequency of 2.45 GHz at low atmospheric pressure. The main aim
was the characterization of the produced sludge-derived biochar. The analyses included
determination of solid yield of biochar, immobilization of heavy metals in SS by production of
biochar, combustion energy and structure of biochar. For evaluation of the surface morphology was
used scanning electron microscopy (SEM) equipped with EDX analyser. The analyser showed
presence of micrometer-sized particles consisting particularly of Al, Si, Ca and Fe. Surface BET
analysis revealed the presence of mesopores and micropores, which are responsible, among others,
for the sorption capacity of biochar. It is concluded that the MP represents as an eco-friendly
treatment of SS giving eco-friendly products, particularly biochar, and therefore it may represent a
solution in terms of circular economy, carbon footprint reduction, heavy metals fixation, energy
recover and water retention.
379
1- INTRODUCTION
1.1 - Disposal of sewage sludge
In 2014, the European Union (EU) countries produced 8.7 million tons of dry solids (DS) of sewage
sludge (SS) which corresponds to around 17 kg DS of SS per capita [1]. Accordingly, the SS
management became one of the most important issues in circular economy connected with carbon
footprint reduction, energy recover and water retention. More specifically, 58 % of the generated SS
was reused, 45 % in agriculture and only 13 % in other way [1]. Currently in 2017, 76 % of the
generated SS was reused, 91 % in agriculture and only 14 % in other way [2]. In the Czech Republic
(CR), where in 2017 was the production 0.18 million tons of DS of SS (approx. 16.8 kg of DS of SS per
capita) [2], has the disposal received significant attention mainly due to new legislation strictly
regulating the SS landfilling and direct application in agriculture.
Based on literature review, the limiting criterion of SS agricultural use is the content of heavy metals
(HM) [3][4]; in the near future the content of xenobiotics (micropollutants) [5][6] and microplastics
[7][8] will also be taken into account. Thus, direct application of SS to agriculture without treatment
will be restricted.
1.2 – Thermal treatment of sewage sludge

At the present, circular economy strategy of wastewater (WW) management postulates a search for
new ways of reusing SS by thermal treatment. Generally, thermal treatment, such as gasification,
hydrothermal carbonation (HTC), torrefaction and pyrolysis, can represent the most suitable
solutions of SS disposal. Pyrolysis technology has recently received considerable attention, namely
slow microwave pyrolysis (MP) producing biochar, pyrolysis oil and pyrolysis gas (syngas) [9]. Some
studies have focused on the MP of SS [9][10][11][12]. However, these studies were conducted in
laboratory scale pyrolyzers. Although, the term "biochar" refers solely to charcoal used as a soil
amendment [13] and it is not commonly used for the product produced from 100 % SS, we use in
following text. There are two main ways for re-used: energy efficiency use of SS and the
transformation SS into new products for agricultural use.
The raw SS has an energy value similar to some low-grade coal, therefore fossil fuel savings would be
possible, thus contributing to overall CO2 reduction [14]. Incineration of SS is carried out directly at
waste water treatment plant (WWTP), or as the co-combustion of SS with coal or other wastes, or
the combustion of SS in cement kilns [15]. The products of pyrolysis were primarily focused on bio-
refinery industries for the production liquid biofuels [16], thus these products are potential
candidates for sustainable energy production and environmental management [17]. The syngas can
be used as a fuel directly, or converted into liquid fuel [18].
Generally, the second way, use biochar of MP for agricultural use, has time complex demands of
resolving issues of biochar of SS especially from the point of view HM fixation, xenobiotics and
microplastics. From the point of view of legislation and environmental protection, two main methods
of SS application in agriculture can be addressed. One limited method is direct application of
stabilized and hygienised SS in accordance with regulation [19], the second way is the conversion of
SS into biochar having similar certified parameters as biomass feedstock [20] and serving as a
fertilizer.
1.3 – Biochar as product of pyrolysis of sewage sludge

Biochar may represent the main product of pyrolysis of SS which can be consequently one of the
most significant challenges in WW management for agricultural use. Based on the literature, several
380
authors [14][21] have compared various yield of biochar between 35 and 80 wt% of DS due to
particular SS quality and composition differences.
The transformation of SS into biochar using MP represents one of the strategies of the conversion of
HM into insoluble form and simultaneously the transformation of the harmful organic compounds
into microbiologically inert amorphous carbon and/or carbonaceous compounds. The authors
[22][23][24][25][26] used an advanced BCR sequential extraction (Commission of the European
Communities Bureau of Reference), which results in four fractions F1-F4 of different bioavailability.
The results confirmed a positive effect of MP on reduction of HM bioavailability.
As Fonts et al. published that the heating value of biochar after pyrolysis is 5-21 MJ∙kg-1 [14].
Furthermore, unlike other thermochemical processes such as combustion or gasification, pyrolysis is
an endothermic reaction and this means that the pyrolysis products may have higher calorific value
than the raw material [14]. Kim and Parker [27] found that the pyrolysis oil and the biochar of
pyrolysis at 300 °C of TWAS (thickened waste activated sludge) had energy content between 0.16
and 1.9 MJ∙kg-1 higher than the raw SS [14].
Other important characteristics are the organic content or surface area. The remaining organic
fraction gives a modest porous nature to the biochar. The highest values of surface area of biochar
after pyrolysis of SS reported from a single pyrolysis step are around 150 m2∙g-1 [14]. However, very
high reaction temperature and high heating rates can destroy the fine porous structure and can
cause the devolatilization/condensation of volatile organic matter in the porous structure of biochar,
resulting in the clogging of pores and reduction in the overall surface area of biochar [17][28]. Thus
the characteristic features of biochar after MP process is a greater pore surface area than the one
available by biochar from conventional heating [29].
Current research at Brno University of Technology, Faculty of Civil Engineering, AdMaS Research
Centre (BUT AdMaS) focuses on a low temperature slow MP of SS. This research is conducted in
cooperation with engineering company Bionic E&M.
Compared with the literature, our research was focused on two different ways, the first for energy
efficiency use of SS and the second for the transformation SS to new product for agricultural use. The
second way is a challenge in research focusing on the pyrolysis products. The aim of this work is to
present a new thermal treatment methodology producing biochar from MP of SS. In our research,
we focus on the investigation mainly on the indicators of MP processes such as pretreatment raw SS
with drying and adding additives, MP process time, maximum temperature of the MP. In this paper,
MP of SS was also investigated with the aim of obtaining data of solid yield of biochar, HM fixation,
energy and structure of biochar.

2.1 – Full-scale microwave unit
At BUT AdMaS there is installed one laboratory and two full-scale units of MP using low temperature
slow MP [30]. The tests presented in this paper were performed using the small full-scale unit with
capacity around 10 kg/batch of dried SS, the device works discontinuously. It consists of one batch
reactor equipped with one high efficient microwave generator of 3 kW output, at the frequency 2.45
GHz. Batches of dried SS were pyrolyzed at low pressure (800 hPa). The temperature was
continuously monitored by an infrared thermometer, it increased maximally up to 250 °C. The glass
condenser attached to the pyrolyzer was used for separation of the pyrolysis oil and gaseous
products. For incoming and reflected waves is installed a tuner. The pyrolyzed materials were
samples of SS produced directly by drying at two municipal WWTPs.
381
2.2 – Samples of dry sewage sludge

The testing of MP at the BUT AdMaS was carried out with samples of anaerobically digested and
thermally dried SS from two different municipal WWTPs.
The WWTP1 has a capacity of around 531 000 population equivalent (PE), the sludge was dried using
a paddle dryer at temperature lower than 100 °C. Tested raw dried samples of SS from WWPT1 had
the content of dry solids (DS) around 91.5-91.9 % and output fraction from dryer was a powder-like
material with particle fraction 1-8 mm.
The WWTP2 has a capacity of around 90 000 PE, the sludge was dried using a belt dryer at
temperature lower than 85 °C. Tested raw dried SS samples from WWTP2 had DS around 90 % and
output fraction from dryer was a noodle shape of around 25 mm in length and around 5 mm in
diameter.
2.3 – Experiments
The raw dried SS was pelletized and its mixing with additives: catalysts, organic matter and other
additives [30]. As catalysts (additive with theoretically catalytic effect), various types of zeolites,
were added and mixed with SS to absorb microwave radiation after evaporation of moisture and to
support catalytic cracking of specific hydrocarbons. The organic matter, such as wood sawdust, lignin
and hay, was mixed with SS in order to adjust physical properties of pellets, to increase the ratio of
organic matter and surface area in the biochar.
We prepared 6 mm diameter samples and before pelletizing these samples were mixed with
additives. SS was mixed with catalyst similar to Zeolite ZSM5, and catalyst similar Zeolite ZSM5 and
organic matter – hay, and with another additive – biochar of wood agromass (biomass represents
agricultural organic waste). Further samples from WWTPs were performed without additives. The
tests of samples from WWTP1 had a longer process time of MP of SS than the samples from WWTP2.
An additive, such as zeolite and biochar of wood with high surface area, was added to SS for HM
fixation in the biochar after MP of SS. The main objective of experiments is to provide an account
data of MP of SS focused on biochar with the main parameters: yield, HM fixation, energy and
structure of biochar.
The input dose ID (g) of SS was weighed and after MP process the product biochar and pyrolysis oil
was measured. The output pyrolysis gas production GP (%) was calculated by following equation:
GP = (ID – BP – CV)/ID ∙ 100 (%) (1)
Where BP represents the weight of the produced biochar (g) and pyrolysis oil (ml).
The HM can occur in two forms such as water soluble (extractable, leachable) and insoluble (non-
extractable, non-leachable). The soluble HM were determined by analysis of water extracts, the total
HM content was determined after digestion of samples in Aqua Regia. Raw SS and biochar samples
were measured by two optimization methods. For the optimization of the AMA and AAS methods for
determination of selected metals were used certified reference materials of calibration standard
solutions ASTASOL® with 5 HNO3, from Analytika Ltd. All other used chemicals were of analytical
reagent grade. Analyses of HM contents were performed using atomic absorption spectrometer with
electrothermal atomization ZEEnit 60 from Analytik Jena with Zeeman background correction and
selected hollow cathode lamp by Photron.
The combustion tests were carried out according to the Czech standard ČSN EN ISO 1716 (7300883)
[31]. The energy efficiency of samples was measured by semi-automatic device (IKA C 200) at
standard laboratory conditions.
382
The energy efficiency was measured by semi-automatic device (IKA C 200) at the laboratory of BUT
AdMaS Research Centre. The contribution tests were performed for raw SS from the WWTP2. After
MP process, the contribution tests were carried out for corresponding samples of biochar.
The surface of biochar of SS depends of appropriate pre-treatment by pelletization, the content of
organic matter or added catalyst. It was investigated by BET (Brunauer–Emmett–Teller) surface
analysis using gas adsorption in Quantachrome Nova 3200e using NovaWin software. For the specific
surface analysis five points were measured and assessed using Multi-Point BET method. For
evaluation of the surface morphology was used scanning electron microscopy SEM (Tescan)
equipped with back scattered detector. The elemental composition Inorganic particles were
detected by EDX analyser.

3.1 – Solid yield of biochar
The dried SS from WWTP1 due to powdery form needed pretreatment using pelletization for MP
process. The tests of samples from WWTP1 had a longer process time of MP of SS than the samples
from WWTP2. The output pyrolysis gas GP was calculated by Equation 1. The yields of MP products
of SS are reported in Table 1.
Pyrolysis
Process
Biochar condensate Gas yield
time of
WWTP Description of SS yield (BP) (oil) yield (GP)
MP (PT)
(CV)
(min) (%) (%) (%)
SS without additive 300 61.0 9.6 29.4
SS with catalyst 180-270 53.5-62.1 13.5-25.2 18.6-28.4
WWTP1
SS with catalyst and org. matter 270 63.4 19.3 17.4
SS with other additive 210-240 57.0-63.7 11.5-20.6 20.5-24.8
WWTP2 SS without additive 40-60 80.4-92.3 4.8-11.7 2.2-10.1
Table 1: Solid yield of biochar after MP of SS.
The pyrolysis condensate (oil) yield after MP was low (4.8-11.7 %) for SS without additive. The
biochar yield was achieved 57.0-92.3 % and the high level of yield was achieved for SS from WWTP2
without additive which corresponds to the short process time of MP of SS and there were not
significant gas vapor and the resulting higher pyrolysis oil production.
3.2 – Heavy metal fixation in biochar

The input dried SS with and without additives before MP and biochar after MP was tested focusing
on HM fixation. The total HM content and soluble HM were determined by digestion of the samples
in Aqua Regia and in water, and in samples before and after MP. Extracts in Aqua Regia represent
the total amount fixed HM in the samples. Extracts in water represent HM biologically available for
plants and other organisms.
Our research focusing on HM fixation after MP of SS presented in a separate publication (paper in
press [32]) demonstrated the significantly low level of biologically available HM after MP process for
383
SS from WWTP1 with pelletization and with additive 2.0 % biochar of wood. HM measurements
revealed a significant structural heterogeneity of the SS [32] and we hypothesized that longer
pyrolysis time process would lead to increasing immobilization of HM in biochar after MP.
3.3 – Energy efficiency of biochar

Our research focusing on energy efficiency of dry SS and biochar before and after MP of SS
presented in a separate publication (paper in press [33]) demonstrated that the average value of
biochar after MP process by small full-scale MP unit represents higher value 13.20 MJ∙kg-1 than
before MP for SS 12.15 MJ∙kg-1, resulting in the difference 1.05 MJ∙kg-1.
3.4 – Structure of biochar

The ratio of organic matter in all input dried samples of SS was around 50 %. After MP process, the
organic matter of pelletized biochar from WWTP1 measured by thermogravimetry was reduced.
Table 2 represents the content of organic matter: up to 22.8 % without additives, 27.5-40.3 % for SS
with catalyst similar to Zeolite, 44.6 for SS mixed with catalyst similar Zeolite and organic matter -
hay. The results 30.5-35.0 correspond to the data based on SS with other additive – biochar of wood
agromass.
SS with
SS with
SS without SS with catalyst
other
WWTP Parameter additive catalyst and org.
additive
matter
(%) (%) (%) (%)
Organic matter (measured
WWTP1 22.8 27.5-40.3 44.6 30.5-35.0
thermogravimetrically)
Table 2: Organic matter in biochar after MP of SS.
The data of surface analysis of biochar of samples without pelletization from WWTP2 are reported in
Table 3. The low values can be attributed to the low amount of organic matter in the input sample
and short process time of MP of SS. In addition, an important role plays also the process
temperature. In particular, for a short period of MP process time, the pores in the biochar may
remain filled with pyrolysis oil.
Process time of MP
WWTP Parameter 40 50 60
2 -1 2 -1
(m ∙g ) (m ∙g ) (m2∙g-1)
WWTP2 Surface analysis 1.24 1.75 0.90
Table 3: Surface analysis in biochar after MP of SS.
The morphology of surface biochar after MP of SS is illustrated in Figure 1, which shows scanning
electron microscopy image obtained by using back scattered electron detector. The light parts in the
Figure 1 represent parts containing elements with higher atomic numbers than the surrounding area.
384
Figure 1: SEM Surface morphology of biochar.
The results of EDX analysis of these lights parts is reported in Figure 2. It can be seen that light parts
contain predominantly Al, Si, Ca and Fe, probably in the form of oxides, sulphates or carbonates.
Figure 2: EDX analysis of light parts.
The dark parts on the photo in Figure 1 represent the carbonaceous part of biochar. Close inspection
of the Figure shows a porous structure. Based on the characteristics of SS and MP process
conditions, the biochar may contain residues of the non-pyrolysis SS and stable condensed aromatic
structures resulting from the high temperature transformation of the original organic matter of raw
SS. Due to the high microscope magnification, Figure 1 illustrated visible cracks indicating
macroporous content.
385
3.5 – Summarizing discussion

The achieved biochar yield was between 57.0-92.3 % when the higher yield was achieved from SS
without additive, which corresponds to a short process time of MP of SS. On the other hand the low
level of biologically available HM was achieved after MP process for SS with additive. The average
energy value after MP process by small full-scale MP unit represents higher value than before MP.
The organic matter content after MP was reduced. The low level of surface analysis 0.90-1.75 m2∙g-1
corresponds to the low amount of organic matter in the input sample and short process time of MP
of SS. The MP process temperature value could also affect the surface area. For evaluation of the
surface morphology scanning electron microscopy (SEM) was used equipped with back scattered
detector. The lighter area that appeared on the surface of biochar were analysed using EDX analyser
and revealed presence of inorganic particles consisting particularly of Al, Si, Ca and Fe. The darker
parts contained carbon, with corresponding properties of biochar. Surface BET analysis revealed the
presence of mesopores and micropores, which cause, among others, the potential sorption capacity
of biochar.
4- CONCLUSIONS
The current research at BUT AdMaS Research Centre is focused on two different ways for re-using of
SS: energy production and the transformation of SS into new products for agricultural use. The
second approach is a challenging research focusing on the pyrolysis product - biochar. MP of SS as
thermal treatment was also investigated in terms of solid yield of biochar, HM fixation, energy and
structure of biochar.
Future basic and applied research leading to certification of biochar after MP can be focused on
content of HM fixation, xenobiotics (micropollutants), energy efficiency, surface area, nitrogen (N),
phosphorus (P), total organic carbon (TOC), and pH according to the agreement with the legislation
for use in agriculture.
ACKNOWLEDGMENT
This paper has been worked out under the project No. LO1408 "AdMaS UP - Advanced Materials,
Structures and Technologies", supported by Ministry of Education, Youth and Sports under the
„National Sustainability Programme I". J. Kučerík acknowledge the financial support of the FCH-S-18-
5331 project of the Ministry of Education, Youth and Sports of the Czech Republic.
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metals in the bio-char produced by co-pyrolysis from municipal sewage sludge and hazelnut shell with zinc chloride.
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and amending Decree No. 294/2005 Coll., on the conditions of landfilling of waste and its use on the surface of the
land and amending Decree No. 383/2001 Coll., on the details of waste management (2016)
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Foundation (EBC), Arbaz, Switzerland. Version 6.3E, DOI: 10.13140/RG.2.1.4658.7043 (2017)
[21] Dominguez A., Menéndez J.A., Inguanzo M. ,Bernad P.L., Pis J.J., Gas chromatographic–mass spectrometric study of
the oil fractions produced by microwave-assisted pyrolysis of different sewage sludges, Journal of Chromatography
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temperature on properties and environmental safety of heavy metals in biochars derived from municipal sewage
sludge, Journal of Hazardous Materials, Volume 320, Pages 417-426, ISSN 0304-3894 (2016)
[23] Liu T., Liu Z., Zhengc O., Lang Q., Xia Y., Peng N., Gai Ch., Effect of hydrothermal carbonization on migration and
environmental risk of heavy metals in sewage sludge during pyrolysis, Bioresource Technology 247 (2018) 282–290.
[24] Liu X., Wang Y., Gui C., Li P., Zhang j., Zhong H, Wei Y., Chemical forms and risk assessment of heavy metals in sludge-
biochar produced by microwave-inducted pyrolysis, RSC Adv. 6, 101960-101967 (2016)
[25] Zhao B., Xu X., Xu S., Chen X., Li H., & Zeng F. Surface characteristics and potential ecological risk evaluation of heavy
metals in the bio-char produced by co-pyrolysis from municipal sewage sludge and hazelnut shell with zinc chloride.
Bioresource Technology, 243, 375-383 (2017)
[26] Huang H., Yuan X., The migration and transformation behaviours of heavy metals during the hydrothermal treatment
of sewage sludge, Bioresource Technology 200, 991–998 (2016)
[27] Kim Y, Parker W. A technical and economic evaluation of the pyrolysis of sewage sludge for the production of bio-oil.
Bioresource Technology, 99:1409–16 (2008)
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[29] Bionic Fuel Knowledge Partners, The bionic μfuel conversion process used with lignocellulosic feedstock:
thermochemical depolymerization facilitated by a combination of catalytic and microwave induced physical and
chemical pathways, Bionic-world, (2015)
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Performed at laboratory and full-scale conditions. In 17 th International multidisciplinary scientific geoconference
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28-7. ISSN: 1314-2704 (2017)
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of Athens, 2018.
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Athens, 2018.
388
SOLID ISSUED FROM TYRE PYROLYSIS: A VALUABLE RECYCLED PRODUCT
C. G. JUNG1, J.-P. BOUYSSET2

1 Université Libre de Bruxelles, Brussels, Belgium.
2 Phenix-Technologies, Versailles-Sancheville, France.
Abstract
Pyrolysis, a well-known thermal treatment (450-650°C) in the absence of oxygen where

decomposition of the organic matter, applied to scrapped used tyres, is leading to hot gaseous
phases (600-700 kg/t) and a stable storable solid phase (300 à 400kg/t). Industrial scale for tyre
pyrolysis furnaces are in the range of 1 to 3 t/h per unit.
The carbonaceous solid phase (commonly named “char”) recovered after magnetic separation of the
steel cord, contains a rich carbon phase mixture mainly with altered initial carbon blacks (30% of the
tyre, steel free basis). This solid phase contains also ashes (8-15%) including mineral fillers (silica,
silicates), rubber additives, sulphur compounds (3-5% S) and ZnO (4% Zn). The calorific value of this
solid is ~29MJ/kg and its specific area is in the range of 30 to 80 m2/g. These characteristics are
mainly depending on the operating parameters (temperature, residence time…) during the pyrolytic
process.
Attempts to commercialise the solid phase issued from tyre pyrolysis has been for many years
unsuccessful mainly because of the loss of surface activity and structure (agglomerates and
aggregate sizes) compared to other reinforcing fillers. Finally, post-treatments of the pyrolytic solid
did generate carbon products with a crucial level of performance and characteristics similar to
several grades of Carbon Black (CB). In consequence, the upgraded (reprocessed) pyrolytic solid
becomes a marketable recovered Carbon Black (rCB) that can be used for the production of a broad
range of commercial products. It is important to note that 100% used tyres as input can produce up
to 24% of r-CB. Appropriate laboratories can perform tests for the evaluation of properties of rubber
Carbon Blacks mainly particle size, structure, surface activity and dispersion as well as the evaluation
of the mechanical properties and abrasion resistance in rubber compounds.
Knowing their characteristics, these rCB can be used for specific applications in a number of
industrial sectors and are particularly useful in a broad array of products and applications associated
directly with the automotive industry including engine mounts, bumpers or fenders, and more
generally technical moulded rubber goods as well as in plastics. Potential markets for rCB are being
evaluated.
ASTM has recently created a D 36 (rCB) sub-committee in order to adapt the existing Carbon Black
Standards to specific standards for r-CB from tyre pyrolysis, especially for the colloidal characteristics
and in-rubber properties.
Under the existing ASTM standard methodology (the ones for CBs), rCB belongs to N300 to N500 CB
series with regards to colloidal properties (specific surface area) and to N600 to N700 CB series with
regards to reinforcing properties in rubber compounds. In consequence, presently, the
characterization of some industrial pyrolytic rCB, has shown that they have properties of semi-
reinforcing fillers with a large particle size distribution and a surface chemistry altered during
pyrolysis.
Conclusion
In order to use rCB from tyre pyrolysis, information should be provided to potential end-users of
these products such as MSD (Material Safety Data sheet) with sectors and scope of use, relevance to
389
EU directives, storage requirements, special permits for use, environmental impacts resulting from
the production process and specifications for uses.
Material valorisation is a real alternative as shown by the latest results of new industrial pyrolytic
realisations. Marketing of these recycled products with their incorporation in a circular economy is
essential in the industrial world.
References
[1] C.G.Jung, European Tyre Recycling Association (ETRA), 24th annual Conference, Pyrolysis Forum, Brussels (2016)
[2] J-P. Bouysset and C.G. Jung, ETRA Pyrolysis Forum - Compendium 2001-2014, CD Publi2 (2015)
[3] Ch. Roy, J-P. Bouysset, J. Fader and C.G.Jung, CSMO du caoutchouc du Québec, Orford, Québec CA (2015)
[4] C.G.Jung, keynote speaker, DEPOTEC Life+ Workshop, Thurles, Ireland, (2015)
[5] J-P. Bouysset and C.G. Jung, Recycled RUBBER Products – Amsterdam (2015)
390
UTILISATION OF FOREST AND AGRICULTURAL BIOMASS IN PELLET MAKING –

HOW FLEXIBLE IS THE PROCESS TO UNCONVENTIONAL FEEDSTOCK?
D. A. AGAR1, M. RUDOLFSSON1, G. KALÉN1, M. CAMPARGUE2, S. H. LARSSON1

1 Swedish University of Agricultural Sciences Department of Forest Biomaterials and Technology, SE-
90183 Umeå, Sweden
2 RAGT Energie SAS, France
Abstract
Continued global growth in the pellet production industry and renewable energy policy targets have
driven interest in under-utilised feedstock from forestry and agriculture. Such raw materials are
typically scattered, seasonally available and differ significantly from spruce and pine species
commonly used in pellet making. This presents challenges for their cost-effective utilisation. An
understanding of how the pelletisation process differs with these feedstock is beneficial for pellet
producers and policy makers. This is among the aims of the MOBILE FLIP Project which investigates
mobile pellet production processes – one approach to a geographically dispersed resource [1].
Pelletisation trials have been systematically carried out on a wide variety of materials from forestry
and agricultural using a 15 kW fixed-die pellet press whose size lends itself to a mobile platform. Raw
materials included logging residues, pine bark, wheat straw, reed canary grass, maize (corn cobs) and
hardwoods not universally utilised in pellet production (willow, beech and poplar). Feedstock have
been dried, milled, sieved and pelletised using four different moisture levels, two pelletising channel
lengths (PCL) and three replicate sampling periods. Sampling was carried out at steady-state
conditions and at a constant rate of pellet production. Eight different batches of 8 mm pellets for
each feedstock type were produced. Pellet were characterised for durability (EN15210), bulk density
(EN15401), moisture content (EN15414) and amount of fines. The energy consumption of the pellet
press was recorded throughout production and the temperature of both die and extruded pellets
was measured.
Optimal pellet properties were observed for most feedstock within the experimental range of
moisture content and PCL. Bulk density of produced pellets was negatively correlated to moisture
content of the feedstock for all materials. For most feedstock, mechanical durability of pellets was
observed to peak within experimental range. The content of fines in production varied from one half
to two per cent across feedstock. The energy density of produced pellets, on a dry basis and using
lower heating value, ranged from 8.2 to 13.3 GJ m-3 representing good energy densification
compared to conventional wood pellets. These and other results are discussed in details, including
their implications for pellet producers.
References
[1] Tamminen, T. Campargue, M., Damerval, F. Da Silva Perez, D., Dupont, C. Englund, F., Kotli, P., Larsson, S.,
Papadopoulou, E., Rasa, K., Raussi, T. and Wallin, M. 2016. Mobile and flexible industrial processing of biomass,
Mobile Flip. 6th International Conference on Engineering for Waste and Biomass Valorisation -May 23–26, 2016 –
Albi, France
391
MULTIVARIATE PREDICTIVE MODELING FOR FLEXIBLE PROCESS CONTROL IN

LIGNOCELLULOSIC BIOMASS PELLETIZING
S.H. LARSSON1, M. RUDOLFSSON1, D. DA SILVA PEREZ2, M. CAMPARGUE3, D.A AGAR1

1 Swedish University of Agricultural Sciencies, Department of Forest Biomaterials and Technology,
Biomass Technology Centre, Umeå, Sweden
2 . Institut technologique FCBA, France
Abstract
Utilization of lignocellulosic biomass as a renewable feedstock for industrial production of materials,

chemicals, and fuels, is globally accepted as a sustainable pathway. However, transport and storage
puts constraints on biomass supply, and thus, compaction through pelletizing (or other compaction
technologies) is, in particular for long-distance transportation and long-term storage, a pre-requisite
for biobased industrial development [1].
In the current study, different biomass materials from forestry, long and short rotation coppice, and
agricultural by-products were pelletized in pilot scale (150 kg/h) to determine optimum process
settings for maximum pellet quality. Obtained results were paired with chemical analysis data to
extract generally applicable patterns and prediction models, and to develop understanding on
underlying mechanisms regarding the interaction of process and biomass main components in the
pelletizing process.
Preliminary results show that it is possible to, by multivariate modelling, from feedstock main
component analysis predict the optimum moisture content for obtaining maximum pellet durability
for unknown biomass materials. This ability is of high relevance for the industrial biomass pelletizing
industry and can, in future applications, be paired with on-line analysis systems for flexible process
control and improved feedstock flexibility.
Figure 1: Principal component analysis score (left) and loading (right) scatter plots for feedstock moisture content at
maximum pellet durability and the biomass main components for five different feedstock assortments
References
[1] Hamelinck, C. N., Suurs, R. A. A., & Faaij, A. P. C. (2005). International bioenergy transport costs and energy balance.
Biomass and bioenergy, 29(2), 114-134.
392
WOODY AND AGRICULTURAL BIOMASS TORREFACTION:

A NEW APPROACH TO MODEL SOLID CONVERSION AND VOLATILES FORMATION
BASED ON BIOMASS EXTRACTED COMPONENTS
M. GONZALEZ MARTINEZ1,2,3, C. DUPONT4, S. THIERY1, D. DA SILVA PEREZ5,

X. MEYER2,3, C. GOURDON2,3
1 Laboratoire de Préparation des Bioressources; CEA, Grenoble, France.
2 Université de Toulouse; INPT, UPS; Laboratoire de Génie Chimique, Toulouse, France.
3 CNRS; Laboratoire de Génie Chimique, Toulouse, France.
4 IHE Delft Institute for Water Education, Department of Environmental Engineering and Water
Technology, Delft, the Netherlands
5 FCBA, InTechFibres, Grenoble, France.
Abstract
Due to its diversity and dispersion, biomass waste is currently underexploited. To face this issue, the
European project MOBILE FLIP proposes to develop mobile conversion processes, among which
torrefaction. This mild thermal treatment (200-300°C, 10min – 1h, default-oxygen atmosphere) gives
rise to a solid with optimized processing properties and condensable coproducts with high-added
value as “green” chemicals.
Up to now, only few studies have characterized and modelled in depth both solid and condensable
species during torrefaction versus biomass type [1]. The biomass macromolecular constituents,
namely cellulose, hemicellulose and lignin, are crucial properties to predict biomass behaviour during
torrefaction [2]. However, torrefaction tests on constituents are scarce and always based on
commercial constituents, which are not representative of the native biomass tested [1], [2].
The objective of this study is therefore to develop a torrefaction model able to predict both solid
volatile species yields versus operating conditions and biomass type thanks to experimental data
obtained on extracted macromolecular components from four families of woody and agricultural
biomasses.
The experiments were performed in a thermogravimetric analyser coupled with a gas chromatography
mass spectrometer device (TGA-GC/MS) through a heated storage loop system. The solid degradation
kinetics and volatile formation profiles showed that the use of the extracted components lead to
strong differences compared to commercial components like Avicel cellulose. Moreover, both solid
transformation and volatiles formation profiles appeared to be correlated with biomass
macromolecular composition. For instance, as expected, furans were produced in higher amount by
biomasses with higher hemicelluloses and cellulose content, while phenols production was favoured
by lignin-rich biomasses.
A kinetic model based on an additive contribution of components was shown to describe satisfactorily
biomass behaviour during torrefaction provided refinements were included to take into account
components impurity as well as interactions between components. In order to assess model
performance as predictive tool, validation was performed on 20 biomasses representative of the
European diversity.
References
[1] Chen, W-H., Peng, J., Bi, X.T.: Renew. Sustainable Energy Rev. 44, 847-866 (2015)
[2] Nocquet, T., Dupont, C., Commandre, J-M., Grateau, M., Thiery, S., Salvador S.: Energy 72, 188-194 (2014)
393
HOW TO CONVERT THE EUROPEAN UNDEREXPLOITED BIOMASS SIDE STREAMS INTO

MARKETABLE PRODUCTS: AN EXTENSIVE STUDY OF SUITABILITY
FEEDSTOCK/PROCESS/PRODUCT UP TO PILOT SCALE
C.DUPONT1, M.MARCHAND2, M.CAMPARGUE3, D.DASILVAPEREZ4, A.KALLI5, S.LARSSON6,

E.PAPADOPOULOU7, K.RASA8, H.WIKBERG5, T.TAMMINEN5
Technology, Delft, the Netherlands.

2 CEA, Laboratory of Preparation of Bioresources, Grenoble, France.
3 RAGT Energie, Albi, France.
4 FCBA, Saint Martin d’Hères, France.
5 VTT Technical Research Centre of Finland Ltd, Espoo, Finland.
6 Swedish University of Agricultural Sciences, Department of Forest Biomaterials and Technology,
Biomass Technology Centre, Umeå, Sweden.

7 CHIMAR HELLAS S.A.,Thessaloniki, Greece.
8 Natural Resources Institute Finland Luke, Jokioinen, Finland.
Abstract
Europe has a large potential of underexploited agro- and forest biomass side streams, mainly because
of their diversity, seasonality and dispersion. The MOBILE FLIP project aims to solve this issue through
the demonstration of flexible and mobile units of conversion based on several advanced processes –
pelletizing, torrefaction, slow pyrolysis, hydrothermal carbonization, hydrothermal treatment before
saccharification – and giving rise to various products, like energy carriers for combustion, particle
board manufacturing, soil amendment and chemicals.
To achieve this goal, one major task is to evaluate suitability between the biomass available, the
processes and the targeted products and then to optimize process operating conditions. In the present
study, more than 15 of the most abundant biomass resources in Europe were therefore extensively
characterized and tested in several laboratory and pilot scale units to supply data for the
demonstration units operation.
This evaluation showed good a good compatibility between most biomasses and process lines despite
their compositional diversity, i.e. moisture content, ash content and composition, and sugar content,
as well as their handling properties, i.e. bulk density and flowability. The optimal raw material and
process was shown to clearly depend on products targeted. For example, woody biomass, possibly
mildly torrefied, appeared as suitable feedstock for particle boards, while the best hydrolysed
products could be obtained when hydrothermal pretreatment was applied on agricultural residues
like corn cob or wheat straw. Hydrothermal carbonization solid products, i.e. hydrochars, seemed to
be particularly promising as soil improving materials, even more than biochars from slow pyrolysis.
Moreover, the significant differences between biomass types in terms of products yield and quality
highlighted the importance of optimizing process conditions versus raw material. For example,
agricultural biomass like corn cob requires shorter residence time compared with hardwood like beech
to get acceptable yield and downstream pellet quality.
394
EXTRACTION OF HUMIC SUBSTANCES FROM RESIDUAL MIXED MUNICIPAL SOLID

WASTE
D. ZINGARETTI 1, M. DI CIOCCO1, A. LIETO 1, F. LOMBARDI1

1 Laboratory of Environmental Engineering, Department of Civil Engineering and Computer Science
Engineering, University of Rome “Tor Vergata”, Via del Politecnico 1, 00133 Rome, Italy..
Abstract
Humic substances are the major constituent of the organic matter of soil and sediments and are
characterised by large amount of functional groups (e.g. carboxylic and phenolic) that allow them to
perform ionic exchange, complex formation and oxidation–reduction processes. For these
characteristics these substances are used in different industrial applications, e.g. as textile
detergents or surfactants. Nevertheless, these substances are also largely present in organic wastes
and recently, applying a Circular Economy model, the research interest is focused on the possibility
of extract these compounds from bio-stabilized wastes, such as compost ([1]-[3]). However, an
interesting option could be to extract humic substances from other organic stabilized wastes that
differently from compost as no further use. Hence, the aim of this study was to evaluate the
possibility of extract Humic Substances (HS) from the output of the aerobic stabilization process of a
Mechanical Biological Treatment (MBT) plant treating mixed residual solid waste, rather than the
commonly used sources, as minerals or other carbon-rich matrices. Namely, the effects of the
different operating conditions (i.e. material particle size, liquid-solid ratio, NaOH concentration and
extraction time) applied for extracting humic acids were assessed.
The waste sample was collected from a MBT plant site near Rome. The humic acids were isolated by
alkaline extraction adopting a modified version of the IHSS method [4]. Namely, the MBT waste
sample was mixed with NaOH solution at 65°C under N 2 gas atmosphere. Then, this slurry solution
containing Soluble Bio-Organics substances was carefully separated from solid residues, mainly
Humin (HU), by a 30min-centrifugation step at 4°C and 12000 rpm and by filtration on glass fiber
membrane. The solution containing SBO was acidified with HCl to pH values lower than 2 in order to
separate the fulvic acids (FA), that are water soluble complexes, from the humic acids (HA), that are
insoluble for acidic conditions. After a precipitation step of about 3 h, a further centrifugation for
30min at 4°C and 12000rpm was performed so to enhance the HA separation yeld. At the end of the
extraction procedure, HA was air dried for 48 h before analysing their properties.
Five different extraction tests were performed on the MBT waste varying the material particle size
(as received waste or d<0.5 mm), liquid-solid ratio (10 or 5 L/kg), NaOH concentration (0.1 or 0.25 M)
and extraction time (4 or 24 h). Then, these tests were also repeated on a MBT waste sample that
underwent a further maturation period in order to assess the effect of the matrix ripening on the
extent of humic substances extraction. Namely, during this 90 days maturation phase the MBT waste
was manually overturned and water was added so to ensure the suitable conditions (aeration and
moisture content) for the further biodegradation phase.
The main properties of the extracted humic acids were evaluated analysing the elemental
composition (i.e. C, H, N, O and S content), the main functional groups (i.e. carboxylic and phenolic
groups) by acid titration with HCl and the E4/E6 ratio by UV–VIS spectrophotometer [5]. As
reference, the same analyses were performed on a sample of the commercial humic acids purchased
by Sigma–Aldrich.
395
Comparing the properties of the different humic acids extracted from the MBT waste before the
ripening period, the operating conditions that showed to improve the extraction extent were the
NaOH concentration and the extraction time. The HA obtained in these specific conditions showed
higher functional group content and aromaticity compared with the substances extracted at the
others operating conditions. The substances isolated from the MBT waste after a 90 days-maturation
phase, instead, showed only slight differences due to the specific operating conditions applied,
suggesting that after the maturation stage also milder operating conditions allow to extract humic
acids with similar chemical properties. These results were also confirmed by the spectrophotometric
analysis that showed higher differences for E4/E6 ratio with the specific operating conditions applied
for the MBT waste before maturation compared with the one obtained after 90 days. On the other
hand, the further maturation period applied on the MBT waste proved to significantly improve the
amount of extracted humic acids, that resulted more than twice. Besides, the humification index (HI)
of the extracted substances, that as defined by Bustamante et al. [6] represent the ratio between the
carbon content of humic acids and the total carbon content of the matrix, prove to significantly
increase. The obtained results showed that the extraction of humic acids from MBT waste could be
an interesting option since the isolated substances present chemical properties comparable with
those observed in the industrial HA or in the ones extracted from compost.
References
[1] Montoneri, E., Boffa, V., Savarino, P., Perrone, D.G., Musso, G., Mendichi, R., Chierotti, M.R., Gobetto, R., 2009.
Biosurfactants fromurban green waste. ChemSusChem2, 239–247.
[2] Savarino, P., Montoneri, E., Musso, G., Boffa, V., 2010. Biosurfactants fromurban wastes for detergents formulation:
surface activity and washing performance. J. Surfactant Deterg. 13, 59–68.
[3] Zingaretti, D., Lombardi, F., Baciocchi, R., 2018. Soluble organic substances extracted from compost as amendments
for Fenton-like oxidation of contaminated sites. Sci. Total Environ. 619-620, 1366-1374
[4] International Humic Substances Society (2018) http://www. humicsubstances.org
[5] Chen, Y., Senesi, N., Schnitzer, M., 1977. Information provided on humic substances by E4/E6 ratios. Soil Sci. Soc.
Am. J. 41, 352–358
[6] Bustamante M.A., Alburquerque J.A., Restrepo A.P., de la Fuente C., Paredes C., Moral R., Bernal M.P., 2012. Co-
composting of the solid fraction of anaerobic digestates, to obtain added-value materials for use in agriculture.
Biomass and bioenergy 43, 26-35
396
THE EFFECT OF BIOCHAR AND HYDROCHAR IN THE METAL PHYTOEXTRACTION FROM
MINING SOILS

E. CÁRDENAS-‐ AGUIAR 1, G. GASCÓ 2, J. PAZ-‐FERREIRO 3, A. MÉNDEZ 1
1 Departamento de Ingeniería Geológica y Minera. E.T.S.I. Minas y Energía. Universidad Politécnica
de Madrid, C/Ríos Rosas nº21, 28003 Madrid, Spain

2 Departamento de Producción Agraria. E.T.S.I. Agrónomos. Universidad Politécnica de Madrid,
Ciudad Universitaria, 28004 Madrid.

3 School of Engineering, RMIT University, GPO Box 2476, Melbourne 3001, VIC, Melbourne, Australia.

Abstract

Soil contamination is a global issue, constituting a threat to ecosystems, farming production and
human wellbeing. When soil contamination is produced by heavy metals, impacts are significant, as
they are non-‐biodegradable compounds1. The main objective of the present work is to determine
the efficiency of manure waste, biochars and hydrochars amendments in the remediation and metal
phytoextraction of two different mining soils from Spain. The two soils were selected from
Gamonedo and Portman mining areas (SPAIN). The manure waste (RM) was obtained from a rabbit
farm located in the practice field of the Polytechnic University of Madrid. The biochars of RM were
prepared with a heating rate of 3 ºC min-‐1 up to 450 ºC (BRM450) and to 600 ºC (BRM600). The final
temperature was maintained during 1 hour. Also, two hydrochars were produced by treatment of
RM solution at 190ºC (HRM190) and 240ºC (HRM240). The final temperature was maintained during
6 hours. Amendment (RM, BRM450, BRM600, HRM190 or HRM240) was added and mixed to each
soil at a rate of 10% (v/v). Two plants species (Sinapsis Alba and Brassica Napus) were grown in
control and amended soils. Pots were maintained in an incubator with 12:12 light/dark cycles at a
controlled temperature of 28 °C for 1-‐2 month. At the end of the experiments the roots and shoots
were sampled and carefully washed with deionized water. Fresh biomass was immediately weighted
and dry mass was assessed. Also, the soil amendment effect was evaluated after the incubation
period determining pH and EC, microbial biomass, dehydrogenase, phosphomonoesterase and β-‐
glucosidase activities. The total content of Fe, Zn, Cu, Cd, Ni, Cr, Pb and As was determined in soil,
roots and shoots in order to study the amendment effect on phytoextraction.

Authors wish to thank to Spanish Ministerio de Economía y Competitividad for the economic support
(CGL2014-‐58322-‐R).

References
[1] Cárdenas-‐Aguiar, E., Gascó, G., Paz-‐Ferreiro, J., Méndez, A. The effect of biochar and compost from urban organic
waste on plant biomass and properties of an artificially copper polluted soil. International Biodeterioration &
Biodegradation 124, 223-‐232 (2017)
397
TOWARDS A REAL MARINE BIOREFINERY FOR THE EFFICIENT MANAGEMENT OF THE

BIOMASS ASSOCIATED TO THE EC LANDING OBLIGATION
LUIS T. ANTELO1, AMAYA FRANCO-URÍA2, JOSÉ ANTONIO VÁZQUEZ1, R. I. PÉREZ-MARTÍN1

1
Marine Research Institute IIM-CSIC. Eduardo Cabello, 6 – 36208 Vigo, Spain.
2
Dept. of Chemical Engineering, School of Engineering, University of Santiago de Compostela - 15782
Santiago de Compostela, Spain.
Abstract
More than 30% of the biomass landed by fishing fleets in the Spanish Atlantic ports constitutes a
waste not usable for human consumption, resulting in hundreds of thousands of tons per year of by-
products that must be managed urgently to avoid serious environmental pollution problems. To this
biomass, we must add, by 2019, the fishing discards that the Common Fisheries Policy of the EC
forces to land in ports. In this new legal framework, vessels must keep on board and landed both
target and those non target species subject to quota regulations and/or below the minimum size.
This fraction represents, in some trawling fisheries, up to 4 tonnes per trip and vessel.
This work, developed in the framework of the LIFE iSEAS project, aims at the establishment of so
colled bionode or iDVP (Integral Discards Valorization Point) that applies a bio-refinery concept to
this important quantity of marine biomass that has to be managed or processed, in the near future,
in an efficient manner to avoid its waste. It is divided in three different rooms: i) Chilled room
storage; ii) Food elaboration area (iDVP1) and; iii) Non-food products area (iDVP3) for materials
considered as category 3. Production lines to be implemented in the iDVP1 (Figure 1) are based in
the use of the muscle for food purposes, including a line of restructured products (Figure 3) and a
line for fish protein hydrolysates and bioactive peptides. In the other hand, the iDVP3 (Figure 2)
includes production lines to obtain valuable bio-compounds such as collagen/gelatin, chondroitin
sulfate or chitin/chitosan, among others, from iDVP1 fish wastes and undersized specimen (Figure 4).
Figure 1: iDVP1 fish fractions Figure 2: iDVP3 operative in the Figure 3: Fish mince blocks Figure 4: Biocompounds
separator Port of Marín (Spain) obtained in the iDVP1 obtained in the iDVP3
The technological developments are integrated and supported by process engineering tools and
mathematical models to define optimal designs and operation conditions of the pilot facilities. In this
aim, economic feasibility and market potential of proposed products/technologies has been also
evaluated and put as a focus, including Material and Energy Flow Analysis (MEFA). This methodology
is applied to optimally manage the discarded biomass resource among the different valorization
process or technological alternatives available in the landing points by modifying/reorganizing flows.
The attained objective is a trade-off between environmental and process yield benefits.
References
[1] Kelloway, A., Daoutidis, P., 2014. Process synthesis of biorefineries: optimization of biomass conversion to fuels and
chemicals. Industrial & Engineering Chemistry Research, 53 (13), 5261-5273.
[2] Martinez-Hernandez, E., Campbell, G., Sadhukhan, J., 2013. Economic value and environmental impact (EVEI) analysis
of biorefinery systems. Chemical Engineering Research and Design, 91(8), 1418-1426.
398
ENERGY CONVERSION OF GASIFICATION RESIDUAL CHAR: COMBUSTION AND

COFIRING SCENARIOS IN NORTHERN ITALY
S. PIAZZI1, XIAOLEI ZHANG2, FRANCESCO PATUZZI1, MARCO BARATIERI1

1 Free University of Bozen-Bolzano, piazza Università 5, 39100 Bolzano, Italy.
2 School of Mechanical and Aerospace Engineering, Queen's University Belfast, Belfast, BT9 5AH, UK
Abstract
Increasing worldwide energy demand needs clean sustainable energy source and gasification char -
which is nowadays disposed of as a waste - could help to decrease the greenhouse gas (GHG)
emissions. Char is the solid by-product of biomass gasification and its disposal typically represents an
economic loss in the management of gasification plants. In the South-Tyrol region (Italy) a large
number of small-scale gasifiers have been recently authorized and more than 350,000 euro are
annually paid in order to dispose the char [1]. Therefore, there is a considerable interest in finding
alternatives for the valorisation of this by-product.
This work is focused on the utilisation of gasification char as a fuel for stationary energy generation.
Although some studies are available in the literature concerning char combustion or co-combustion,
they mainly focus on lab-scale experiments. Analyses on char utilization as energy source in real scale
plants are instead extremely rare. The main purpose of this paper is to assess the potential of char as
an energy source at industrial level, testing different technological solutions for the considered case
study and finding the most profitable.
System models have been developed adopting Aspen Plus package to evaluate different scenarios for
the utilization of char produced in the gasification plants of South-Tyrol. The first scenario considers
the possibility of directly exploit char in a dedicated burner which can be integrated in the gasification
plant, the second scenario assumes that all the char is collected from the different gasification plants
in the region and co-fired with biomass in a centralised biomass combustion plant. The second
scenario considers an existing commercial plant consisting of a biomass boiler connected to an Organic
Rankine Cycle (ORC) [2].
The results reveal that substantial savings in the operating costs of the plants can be achieved. In the
first scenario, depending on the composition of the produced char, the owners of the gasification
plants could save from 50.5 % to 86.5 % of the char disposal costs; in the second scenario the owner
of the ORC plant could save approximately 462,000 euro per year.
The present study provides a basis for further techno-economic studies on char cofiring. The results
can be helpful for the owners of the gasification plants in determining a cost-effective way to dispose
char. Furthermore, it is demonstrated how char could be used as a renewable fuel, with better
performance than using only raw biomass.
References
[1] F. Patuzzi, D. Prando, S. Vakalis, A.M. Rizzo, D. Chiaramonti, W. Tirler, T. Mimmo, A. Gasparella, M. Baratieri: Small-
scale biomass gasification CHP systems: Comparative performance assessment and monitoring experiences in South
Tyrol (Italy). In: Energy 112, 285–293 (2016)
[2] D. Prando, M. Renzi, A. Gasparella, M. Baratieri: Monitoring of the energy performance of a district heating CHP plant
based on biomass boiler and ORC generator. In: Applied Thermal Engineering 79, 98-107 (2015)
399
COMBUSTION AND EMISSIONS CHARACTERISTICS OF PALM ACID OIL-DIESEL MIXED

FUEL AND IMPROVEMENT ON ITS LOW TEMPERATURE FLUIDITY
H. NOGE1, W.J. YAHYA2 AND Y. UENO3

1 Dep. of Mechanical Engineering, National Institute of Technology, Maizuru College, Kyoto, Japan.
2 Advanced Vehicle System Research Group, Malaysia-Japan International Institute of Technology,
Universiti Teknologi Malaysia, Kuala Lumpur, Malaysia.

3 Kyoto Prefectural Technology Center for Small and Medium Enterprises, Kyoto, Japan.
Keywords: Palm Acid Oil, Polyglycerol Fatty Acid Esters, Emulsion, Distribution, Low Temperature
Fluidity, Combustion, Emission.
Abstract
In order to effectively use PAO-diesel mixed fuel for combustion, improvement on the low
temperature fluidity is demonstrated to control the PAO deposition using polyglycerol fatty acid esters
(PFAEs). Combustion experiment using an industrial diffusion burner fueled by the PAO-diesel fuel is
carried out to evaluate the combustion performance and emissions characteristics. The PAO-diesel
fuel with PFAEs or ethanol are made by blending PAO, PFAEs or ethanol and diesel fuel with ultrasonic
irradiation. The PAO mixed fuels are held in cool incubator to examine the PAO deposition and are
burned by the industrial diffusion burner as the combustion fuel. PFAEs with the ultrasonic irradiation
have an effect on reducing the PAO deposition at low temperature definitely in exchange of viscosity
increase. One of the PFAEs: THL-17 puts the aggregation of PAO particles off in the beginning of the
cooling in addition to keep the uniform distribution of the PAO particles, giving the different aspect of
PAO deposit in comparison with the ethanol mixed fuel.
In the industrial diffusion burner experiments, the furnace outlet temperature of THL-17:2wt.%
mixed fuel is 0.6%-2.0% lower than the diesel fuel. On the other hand, the THL-17:2wt.% mixed fuel
decreases NOx by up to 30 % in comparison with the diesel fuel, showing a potential to reduce NOx
without substantial reduction of the furnace outlet temperature.
.
400
1- INTRODUCTION
Palm acid oil (PAO) is the final residue in palm oil refinery process. PAO has a lot of free fatty acid
(FFA) about 30-80% and is inedible. Therefore, PAO is used as only the material for crude soap and
fertilizer. To effectively utilize common vegetable oil as combustion fuel, bio diesel fuel (BDF) is mostly
produced by base catalysed transesterification reaction. This method is the most popular in practical
application and is applied for the materials which have about 2-3 % FFA [1,2]. On the other hand, PAO
which contains much FFA produces soap instead of fatty acid methyl ester if the base catalysed
transesterification reaction is applied. If PAO is really needed as the material for BDF, additional
reaction process such as esterification is necessary, which means the reaction from PAO to BDF is
inefficient because the reaction process may generate much time and cost. Alternative methods of
base catalysed transesterification are also difficult to reduce reaction time and cost simultaneously
[3,4]. PAO might be hard to convert it to BDF because the FFA in PAO is unstable and extensive for
each individual. Conversions from palm fatty acid distillate, which contains around 90% FFA, to BDF
have been reported by Cho et al [4] and Chongkhong et al [5] but there is still no report on a conversion
of PAO to BDF using smart method. Demanded alternative fuel around the world should be evaluated
reliability, cost and environmental performance basically.
Our experiment has been focusing on finding possibility of using PAO as PAO-diesel mixed fuel. The
time required for making the PAO mixed fuel and the cost would be reduced in comparison with base
catalysed transesterification and also it is a very simple method.
Previous studies revealed that the PAO-diesel mixed fuel with organic solvent and ultrasonic
irradiation can reduce PAO deposit at low temperature compare to PAO-diesel mixed fuel without
them [6]. However, PAO is in a solid or slurry state in ordinary temperature. PAO is mainly composed
of palmitic acid and oleic acid. Palmitic acid is also wax component which makes it easy to deposit PAO
in the PAO-diesel mixed fuel at low temperature.
There are also few reports to use PAO as the mixed fuel for combustion.
The main purposes of this study are to control the PAO deposition and to improve the low
temperature fluidity. That is to establish an optimum condition for making the PAO-diesel mixed fuel
where the minimum PAO deposition is obtained or there educe less PAO at low temperature.
The previous study using organic solvent tried to prevent the PAO deposit from dissolving PAO into
the organic solvent. As a result, PAO deposition confirmed under 11℃ shown in Figure 1 and Figure 2
regardless of presence/absence of ultrasonic irradiation and the PAO deposit stuck to bottom of
beaker.
Temp.： 11℃ Temp.： 9℃ Temp.： 2-4℃ Temp.： 11℃ Temp.： 9℃ Temp.： 2-4℃
Period： 3days Period： 3days Period：10days Period： 3days Period： 3days Period：10days
Figure 1 :Deposition behavior of PAO :20%-Diesel :70%- Figure 2 :Deposition behavior of PAO :20%-Diesel :70%-
Ethanol :10% mixed fuel in low temperatures without Ethanol :10% mixed fuel in low temperatures with 50%
ultrasonic irradiation. output ultrasonic irradiation.
This paper explored possibilities of emulsion, distribution of PAO with controlling the crystal growth
in diesel fuel using polyglycerol fatty acid esters (PFAEs), which are open to utilization in various way
such as emulsifying, solubilizer, crystal growth control of oil and fat etc., to avoid outstanding stick
401
deposit on the bottom. PFAEs have been studied as key ingredient in food products for forming
emulsion [7,8] but it never applied to preventing the PAO deposit in the PAO-diesel mixed fuel.
In addition, to estimate the PAO-diesel mixed fuels with PFAEs as the fuel for combustion, combustion
performance and emissions characteristics using a commercial diffusion burner were examined.

2.1- Chemical and Physical Properties of Palm Acid Oil
PAO examined in our study was imported from Indonesia. PAO composition was analysed by Gas
chromatography‐Mass spectrometer (GC/MS, Shimadzu GCMS-QP2010). To improve the accuracy of
qualification, differential scanning calorimeter (Shimadzu, DSC-60) was applied to the measurement
of melting point of main components. Gross calorific value was measured by automatic bomb
calorimeter (Yoshida Seisakusho, 1013-H). Free fatty acid (FFA) was calculated by following equation
where acid value: A is found by neutralization titration experiment (JIS K 0070-1992).
Water content of the PAO-diesel mixed fuel was analysed by Karl Fischer moisture titrate meter
(Mitsubishi Chemical Analytech, CA-21).
FFA=A×Fa (1)
A: Acid value, Fa: conversion factor of FFA
2.2- PAO Mixed Fuel Producing and Evaluation Method

Two kinds of the PAO-diesel mixed fuel were compared. One is composed of
ethanol:10wt.%+PAO:20wt.%+diesel fuel:70wt.% and the other includes each PFAEs (QMP-1, QMP-
5:Taiyo Kagaku and THL-15, THL-17, THL-44: Sakamoto Yakuhin Kogyo):0.5-10wt.%, which are
emulsifying agent, in addition to PAO:20wt.%, diesel fuel:70-79.5wt.%.
On the making method of the PAO-diesel mixed fuel without PFAEs for the PAO deposit experiment
at cool temperature, heated PAO was well blended with ethanol and diesel fuel. The total amount is
80ml. To atomize PAO particles and suspend them homogeneously in the mixture, ultrasonic
homogenizing (Qsonica, Q500) was treated. The output condition of ultrasonic irradiation was 50%
output with pulse for 3 minutes. The homogenized mixture filtered by qualitative filter paper
(Advantec, No.2).
In the case of preparation for the burner combustion fuel, almost 2 liters of the PAO-diesel mixed
fuel were handled with ultrasonic homogenizing. The irradiation was carried out for 20 minutes at 90%
output with pulse while the samples were being kept cool.
On the other hand, the PAO-diesel mixed fuel with PFAEs, only PAO was processed by ultrasonic
irradiation before blending it to PFAEs because we would like to confirm purely the effect of
emulsifying agent to the PAO-diesel mixed fuel. The power and the time for the ultrasonic irradiation
were 70% with pulse and 3 minutes respectively. The prepared PAO below 100ml was being kept cool
during the irradiation.
As soon as the ultrasonic irradiation was completed, the PAO was mixed with PFAEs for 3 minutes at
70℃, after that the diesel fuel was added to the mixture and was stirred for 5 minutes at 70℃. Finally,
filtration was carried out before any experiments.
The PAO mixed fuel was put in the cool incubator (AS ONE, FCI-280) set from 2℃ to 11℃ to evaluate
the PAO deposit and the solidification of the PAO mixed fuel.
For the burner combustion fuel, the same method mentioned above was applied to the making
method.
402
The PAO particles suspended in the PAO-diesel mixed fuel were measured by laser diffraction particle
size analyzer (Shimadzu SALD-2300) and the relation between the PAO deposition in the PAO-diesel
mixed and the duration at cool temperature was analysed by an ultraviolet visible light
spectrophotometer (Shimadzu UVmini-124).
2.3- Diffusion Burner Setup
Some of the prepared PAO mixed fuels were examined. An industrial diffusion burner, which was a
commercial excess air oil burner (YOKOI KIKAI KOSAKUSYO, EOB-1, fuel capacity: 1.0-10 l/h) having
cylindrical combustion chamber (D=850mm, L=1200mm) and flame stabilization mechanism with
multi air holes, was used as experimental setup shown in Figure 3. The diesel fuel was introduced into
the injector at room temperature. The PAO mixed fuels were heated at 50℃ before entering the
injector just in case the PAO form deposit.
Exhaust gases such as NOx, CO, CO2, O2 generated by the combustion at each air excess ratio were
analysed by portable gas analyser (Horiba, PG-350).
Figure 3 :Diffusion combustion burner setup.

3.1- PAO Characteristics and the low temperature fluidity of the PAO-diesel mixed fuel
PAO at room temperature:8-27℃ and heated temperature over 40 ℃ are shown in Figure 4. This
substance is solid state at a room temperature and gives off a smell. Heating is effective method to
liquefy it. GC/MS and DSC analysis show that the PAO contains palmitic acid (CH3(CH2)14COOH, melting
point:62.9℃) and oleic acid (CH3(CH2)7CH=CH(CH2)7COOH, melting point:16.3℃) as main components.
Malaysian palm oil board [9] reports that most of palm oils are composed of palmitic acid:45%, oleic
acid:40% and linoleic acid:11%. As the PAO comes from palm oil, this analysis is carried out in accuracy.
Figure 4 :PAO sample at room temperature (Left) and over 40 ℃ (Right).
403
Table 1 shows gross calorific value, kinematic viscosity and water content. In the PAO analysis, the
gross calorific value of the PAO is lower than the diesel fuel by 30% but the ethanol mixed fuel controls
the reduction ratio within 20%. The gross calorific value of the PAO-diesel mixed fuel with PFAEs might
become closer to the value of diesel fuel when it contains more diesel fuel than ethanol. The value of
kinematic viscosity has no difficulty to be operated at both 30 ℃ and 80℃. PAO contains more water
than diesel fuel.
Gross calorific term Kinematic viscosity[cSt]

Water[mg/g]
[kJ/g] 30℃/80℃
Diesel [No.2 JIS] 40.4 5.37/1.78 0.0487
Palm Acid Oil 28.8 - -
PAO:20wt.%+Diesel:70w
32.1 4.29/0.78 2.15
t.%+Ethanol:10wt.%
Table 1 :Physical properties of PAO and PAO-diesel mixed fuel .
Polyglycerol is made from the dehydrogenation-bond of the glycerin itself and PFAEs has the fatty
acid ester bonded shown in Figure 5. The molecular structure and physical properties of polyglycerol
fatty acid ester depend on the degree of polymerization of the glycerin and the fatty acid chain length.
All of prepared PFAEs which have different composition of the fatty acid.
Figure 5 :Chemical structure of polyglycerol fatty acid ester .
To evaluate the effects of two kinds of PFAEs :QMP-1 and QMP-5 on preventing the PAO deposit in
the PAO-diesel mixed fuel were examined at each 8℃, 7℃, 6℃ for 24h in the cool incubator. On the
chemical composition, the precise differences between QMP-1 and QMP-5 are unclear, however
QMP-1 is slurry and QMP-5 is solid state at room temperature. The PAO-diesel mixed fuels are
composed of QMP-1:10wt.% or QMP-5:10wt.%+PAO:20wt.%+diesel fuel:70wt.% with/without
ultrasonic irradiation. Figure 6 shows the samples examined at 8℃ using QMP-1 are cloudy but
ultrasonic irradiation makes the sample a little bit transparent. Both of the samples using QMP-5 are
clear. In Figure 7 at 7℃, QMP-1 increases viscosity in addition to getting muddy and the effect of
ultrasonic irradiation cannot be confirmed in this figure. QMP-5 without ultrasonic irradiation begins
to deposit the PAO, however there still no observation of the PAO deposit in ultrasonic irradiation
sample.
Both QMP-1 and QMP-5 samples more or less deposit the PAO at 6 ℃ in Figure.8 even if ultrasonic
irradiation is applied. The deposition can be seen around bottom of the bottle. This may be caused by
the deposition of the PAO particles sticking to QMP which are distributed in the mixture.
The experiments using QMP-1 and QMP-5 reveal that PFAEs is solid state at room temperature more
favorable than slurry state to prevent the formation of the layer of the PAO particles. The solid state
emulsifier receives benefit from the ultrasonic irradiation though a limited range of temperature.
Following these results, we prepared three kinds of PFAEs such as THL-15, THL-17, THL-44 which are
solid state at room temperature and the ultrasonic irradiation was applied to the PAO before making
the PAO-diesel mixed fuel.
The initial temperature was set up at 6℃ because the visible PAO deposition was confirmed in all of
conditions using QMP. Figure 9 shows THL-15:10wt.% or THL-17:10wt.% or THL-
404
44:10wt.%+PAO:20wt.%+diesel fuel:70wt.% were held at 6℃ for 24h in the cool incubator. In the
sample using THL-15, thin layer formed by the PAO particles can be seen the bottom of the bottle.
THL-17 and THL-44 also become cloudy similar to THL-15 but they do not generate the precipitation.
All the THLs increase viscosity in comparison with the samples using QMP, which prevents the
conspicuous deposition on the bottom.
The samples examined at 4℃ in Figure 10 are almost same results of Figure 9 except more increase of
the viscosity in which the mixed fuels look like jelly and were kept the solid state when the bottles tilt
up to 90 degrees. These phenomena might be understood that THL puts into the gap between the
PAO particles and the aggregations are suspended uniformly where the PAO-diesel fuel is emulsified
sufficiently, which induces uniform solidification of the PAO particles at low temperature.
Investigations of THL:10wt.% mixed fuel reveal that it is difficult to use them at low temperature in
actual because the viscosity and the cost are too high.
We reduce THL mixing ratio and only THL-17 is selected because it is the highest viscosity in Figure 9
and Figure 10, which suggests the possibility of reducing the amount remarkably. 1. THL-17:0.5wt.%+
PAO:20.0wt.%+diesel fuel:79.5wt.%, 2. THL-17:1.0wt.%+PAO:20.0wt.%+diesel fuel:79.0wt.%, 3. THL-
17:2.0wt.%+PAO:20.0wt.%+diesel fuel:78.0wt.% were examined at 2-4 ℃.
Without ultrasonic irradiation With ultrasonic irradiation
QMP-1 QMP-5 QMP-1 QMP-5
Figure 6 :QMP-1 :10wt.% or QMP-5 :10wt.%+PAO :20wt.%+Diesel :70wt.% at 8℃ for 24h with/without ultrasonic irradiation.
405

THL-15 THL-17 THL-44 THL-15 THL-17 THL-44
Figure 9 : THL-15:10wt.% or THL-17:10wt.% or Figure 10 : THL-15:10wt.% or THL-17:10wt.% or

THL-44 :10wt.% + PAO :20wt.% + Diesel :70wt.% THL-44 :10wt.% + PAO :20wt.% + Diesel :70wt.%
at 6℃ for 24h with ultrasonic irradiation. at 4℃ for 24h with ultrasonic irradiation.
In Figure 11, the THL-17:0.5wt.% mixed fuel, which keeps the lowest viscosity, is two-phase separated.
The others more increase the viscosity than the THL-17:0.5wt.% mixed fuel, however they hold
homogeneous mixture at low temperature with maintaining liquid state.
The THL-17:1.0wt.% mixed fuel in which a little visible small particles are recognized is lower viscosity
than the THL-17:2.0wt.% mixed fuel. To prevent the conspicuous deposition of PAO particles and to
give priority to practical use are better to select THL-17:2.0wt.%.
The pure effects of ethanol and PFAEs on the particle size distributions at room temperature were
studied because the deposition situation at low temperature might be predicted from the PAO
distributions at initial state. The samples, which are 1. PAO:20wt.%+diesel fuel:80wt.%, 2.
ethanol:10wt.%+PAO:20wt.%+diesel fuel:70wt.%, 3. THL-17:2wt.%+PAO:20wt.%+diesel fuel:78wt.%,
were analyzed soon after the making by the laser diffraction particle size analyzer (Shimadzu SALD-
2300). In Figure 12, only the PAO mixed fuel forms the larger particles than the others. Both ethanol
and THL-17 contribute to make smaller particle at least. Remarkable difference between the ethanol
mixed fuel and the THL-17 mixed fuel is that the PAO particles of the ethanol mixed fuel distribute
from 0.2μm to 800μm extensively but 2 distinctive peaks are given in the distribution of the THL-17
mixed fuel. However, to find out elements and characteristics of the PAO deposition from Figure 11,
additional experiments are needed.
The samples in Figure 12 were used to evaluate the growth of the PAO particles at 4 ℃ in Figure 13
and in Figure 14.UV-vis analysis was applied and the absorbance was regarded as one of the
evaluation points. The absorbance of the fuel: 1. PAO:20wt.%+diesel fuel:80wt.% is over 1 after 20
min cooling, which means a lot of PAO particles are easy to aggregate and the agglomerate prevent
the light transmittance. In Figure 14, it can be seen from all of the pictures on the left are the nebulous.
The ethanol:10wt.% mixed fuel keeps low absorbance until 180min at least, however the deposition
406
appears the bottom of the cuvette because the PAO particles generated in the lowest viscosity mixed
fuel are fallen to the bottom easily by the gravity. As a result, center of the cuvette is clear but the
whole the viscosity are increased after the lapse of 24 hours, the PAO particles begin to educe and
easily keep the position in the center of the cuvette.
The THL-17:2wt.% mixed fuel prevents the aggregation of the PAO particles until 40 min. After 40 min,
increase of the viscosity by THL-17 holds the distribution of the PAO particles evenly. THL-17 has an
effect on putting the aggregation of PAO particles off at initial state in addition to keep the uniform
distribution of the PAO particles in exchange of the viscosity increase.
THL-17+PAO20wt.%+diesel fuel
0.5wt.% 1.0wt.% 2.0wt.% 10
THL17-1% 9 TH
PAO-20% 8 P
without ultrasonic irradiation 7
6
5
4
3
2
1
1.2 1.0 0
Figure 11 : THL-17:0.5wt.% or 1.0wt.% or 2.0wt.% + PAO :20wt.% + E-10%
Diesel :79.5wt.% or79.0wt.% or 78.0wt.%
THL17-0.5%
at 4
1.0 PAO-20%℃ for 24h with ultrasonic irradiation.
10 40min 0.8 PAO-20%
9 in 4 ℃ 80min 20min in 4℃ THL17-2%
Relative particle size %
Diesel-80% Ethanol-10%
0.8
8 PAO-20% PAO-20% 0.6 PAO-20%
ABS
7 without ultrasonic irradiation without ultrasonic irradiation without ultrasonic irradiation

6 0.6 180min
ABS
5 0.4
4 0.4 180min
3
2 0.2 0.2
1 20min 80min
40min
0
0 0
0.013000.1 1
400 10 500 100 0.01
600 0.1 700
1 10 300 100 0.01
400 0.1 1
500 10600 100 1000
700
Wavelength nm Particle diameter [μm] Wavelength nm
Figure 12 : The PAO particles distributions which are analysed in fresh state.
1.2
PAO-20% E-10% THL17-2%
180min
1.0 Diesel-80% PAO-20% PAO-20%
0.8 in 4℃ 20min in 4℃ in 4℃
ABS
40, 80, 180min

0.6
80min
0.4 20-80min 180min
20-40min
0.2
0
300 400 500 600 300 400 500 600 300 400 500 600 700
Wavelength nm
Figure 13 : UV-vis analysis on the growth of PAO particles from 20 minutes to 180 minutes. (without ultrasonic irradiation)
PAO :20%+Diesel :80% Ethanol :10%+PAO :20%+Diesel :70% THL-17 :2%+PAO :20%+Diesel :78%
20min 40min 80min 180min 24h 20min 40min 80min 180min 24h 20min 40min 80min 180min 24h
Figure 14 : The growth of PAO particles from 20 minutes to 24 hours. (without ultrasonic irradiation)
407
3.2- Combustion and Emissions Characteristics of the PAO-diesel mixed fuel

The diffusion combustion and the emissions characteristics of 1. diesel fuel:100wt.%, 2.
ethanol:10wt.%+PAO:20wt.%+diesel fuel:70wt.% and 3. THL-17:2wt.%+PAO:20wt.%+diesel
fuel:78wt.% were examined by the industrial diffusion burner.
Figure 15 shows the comparison between the diesel fuel and the ethanol:10wt.% mixed fuel. The
furnace outlet temperature is 2-8% lower the ethanol:10wt.% mixed fuel than the diesel fuel. The
ethanol:10wt.% mixed fuel decrease NOx by 22-26% compare to the diesel fuel. In this experiment,
NOx will be occupied by thermal NO which depends on the combustion temperature. The furnace
outlet temperature is an index of the combustion temperature so it is possible to predict NOx
generation tendency from the furnace outlet temperature. The decrease of the furnace outlet
temperature involves in reducing NOx concentration.
CO concentration and fuel flow rate are almost same between the diesel fuel and the ethano:10wt.%
mixed fuel.
The comparison between the diesel fuel and the THL-17:2wt.% mixed fuel in Figure 16 shows a slight
difference from 0.6% to 2% on the furnace outlet temperature, resulting a little bit higher temperature
the THL-17:2wt.% mixed fuel than the ethanol:10wt.% mixed fuel, however the NOx concentrations
of the both the THL-17:2wt.% and the ethanol:10wt.% mixed fuels are same over air excess ratios
(λ):1.4 and the THL-17:2wt.% mixed fuel decreases NOx by up to 30 % in comparison with the diesel
fuel.
The PAO in the THL-17:2wt.% mixed fuel has a potential to reduce NOx while keeping reduction of the
furnace outlet temperature within approximately 20℃ though there is a restriction on λ. The relative
increase of CO concentration may be caused by reducing supply air.
Furnace outlet temp. ℃
Furnace outlet temp. ℃
1000 5 1000 5
●:Diesel ●:Diesel
□:E10+PAO20+D70 4 □:THL17-2+PAO20+D78 4
Fuel Flow l/h
Fuel Flow l/h

950 Air:660l/min 950 Air:610l/min
3 3
900 900
2 2
850 1 850 1
800 0 800 0
160 160
NOx ppm
NOx ppm
100 100
CO ppm
CO ppm
120 120
80 80
10 10
40 40
1 0 1 0
1.2 1.4 1.6 1.8 2.01.2 1.4 1.6 1.8 2.0 1.2 1.4 1.6 1.8 2.01.2 1.4 1.6 1.8 2.0
Air excess ratio λ Air excess ratio λ
Figure 15 : The diffusion combustion and the Figure 16 : The diffusion combustion and the
emission characteristics of the diesel fuel and the emission characteristics of the diesel fuel and the
ethanol :10wt.% mixed fuel at 660 l/min air flow. THL-17 :2wt.% mixed fuel at 610 l/min air flow.
CONCLUSIONS
This paper demonstrates the possibilities of controlling the crystal growth of the PAO in the diesel
fuel using the PFAEs from emulsification and deposition of the PAO. In addition, the PAO-diesel mixed
fuel with PFAEs as the fuel for combustion is evaluated from the perspective of the combustion
performance and the emissions characteristics using an industrial diffusion burner.
The PAO has lower gross calorific value by 30% compare to the diesel fuel, however, the ethanol
mixed fuel controls the reduction ratio within 20%. The
408
gross calorific value of the PAO-diesel mixed fuel with the PFAEs might have a closer the value to the
diesel fuel when it contains more diesel fuel than ethanol.
The experiments using QMP-1 and QMP-5 reveal that solid condition of PFAEs at room temperature
is favor to prevent aggregation of the PAO particles and also the solid state emulsifier receives benefit
from the ultrasonic irradiation at a limited range of cooing temperature.
THLs, which are solid state at room temperature, increase viscosity in comparison with the samples
using QMPs, which reduces the conspicuous deposition at the bottom.
Considering the prevention of the conspicuous PAO precipitation at low temperature and the priority
to practical use, the THL-17:2.0wt.% mixed fuel is better than the others.
The effects of ethanol and PFAEs on the particle size distributions at room temperature were studied.
Both ethanol and THL-17 contribute to make smaller particle at least. Remarkable differences in the
particulate distribution between the ethanol mixed fuel and the THL-17 mixed fuels in fresh state are
that the ethanol mixed fuel distribute the PAO particles extensively and the THL-17 mixed fuel limits
the range of distribution and shows two distinctive peaks.
The THL-17:2.0wt mixed fuel has an effect on putting the aggregation of PAO particles off at initial
state in addition to keep the uniform distribution of the PAO particles in exchange of the viscosity
increase.
Finally, it is found that the PAO in the THL-17:2.0wt.% mixed fuel has a potential to reduce NOx
without substantial reduction of the furnace outlet temperature.
Acknowledgements
This work has been supported by Kyoto Plant Industry Co., Ltd, Kyoto 3R-Business Support Center
and JSPS KAKENHI Grant Number JP17K14925. Gratitude is also expressed to R. Uemura researcher of
Kyoto Prefectural Technology Center for Small and Medium Enterprises for helpful discussion and
assisting chemical analysis of PAO.
We also would like to express our thanks to Taiyo Kagaku Co., Ltd and Sakamoto Yakuhin Kogyo Co.,
Ltd. to supply polyglycerol fatty acid esters and give some valuable opinions.
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[1] H.J.Berchmans and S.Hirata, Biodiesel production from crude Jatropha curcas L. seed oil with a high content of free
fatty acids, Bioresource Technology, 99, 1716-1721 (2008)
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Industrial Diffusion Burner, International Conference on Chemical and Biochemical Engineering (ICCBE), paper ID, AE-
ICCBEJAK-13037-266, 1-5 (2017)
[7] N.Krog, Food emulsifier and their chemical and physical properties, in Food Emulsions, edited by S.E. Friberg and K.
Larsson, Marcel Dekker, New York, pp. 141–188(1997)
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[9] Official Palm Oil Information Source, MPOB, URL: http://palmoilworld.org/about_palmoil.html
409
A NON‐WASTE, SOLID RECOVERED FUEL FROM MUNICIPAL SOLID WASTE FOR CO‐
FIRING WITH COAL
J.M.JONES1* (J.M.JONES@LEEDS.AC.UK), B.GUDKA1, P. METCALF2, M. GRONNOW3, P. HURST 3, J. RIX4,
STEVE BUTLER5
1
School of Chemical and Process Engineering, University of Leeds. Leeds. LS2 9JT United Kingdom
2
Wilson Bio‐Chemical, Unit 22, Hassacarr Close, Dunnington, York YO19 5SN United Kingdom
3
Biorenewables Development Centre Ltd, 1 Hassacarr Close, Chessingham Park, Dunnington, York
YO19 5SN United Kingdom
4
North Energy Associates, Unit 20, Carlisle Business Centre, 60 Carlisle Road, BRADFORD BD8 8BD,
United Kingdom
5
Sol Environment Ltd, No.10, The Lees, Malvern, Worcestershire, WR14 3HT, United Kingdom

Keywords: solid recovered fuel, MSW, torrefaction…

Abstract
This work reports results of a project funded by Innovate UK concerning the production of a
thermally‐pre‐treated end‐of‐waste fuel from Municipal Solid Waste (MSW) which is high in biogenic
material. The MSW was first steam treated in an autoclave at 160oC to produce a fibre which was
then torrefied to produce a fuel with properties similar to that of lignite. The fibre was produced at
the 20 kg scale in a pilot plant facility. Torrefaction was performed at the laboratory scale in a
bench‐top batch reactor and this was supplemented by thermogravimetric analysis (TGA) studies
and standard fuel characterisation methods. Combustion of both the fibre and torrefied fibre was
assessed in a drop tube furnace and supplemented by TGA studies. Steam treating the MSW makes
it more homogenous and reduces levels of some of the problematic species (Si, K, Cl and N) which
contribute to the slagging, fouling and emission problems in boilers. Subsequent torrefaction
improves the classification of the fibre according to the standards for Solid Recovered Fuels (SRF), BS
EN 15359:2011, and WRAP. The final torrefied product resembles lignite in many respects, and
achieved recognition as “non‐waste”. A lifecycle analysis of the fuel and associated production
indicate that the overall impact of the fuel is very favourable compared to a fossil comparator. The
torrefied solid fuel pellet has been proven to be suitable for a wide range of fuel uses and can be
supplied directly for use or co‐fired with conventional coal as a low carbon ‘green’ coal substitute.

1‐ INTRODUCTION
In order for the UK to meet its target of 15% energy from renewables by 2020, more indigenous
sources of biomass need to be sourced [1], including waste‐derived fuels and solid recovered fuels
(SRF). Autoclaving (Mechanical Heat Treatment (MHT)) is a well‐known process for sterilising waste
and breaking down bio‐waste into a fibre through the action of heat (steam) and agitation. The fibre
produced is relatively benign, although there are possibilities of contamination from heavy metals,
mostly from pigments in coatings and colours [2], which may or may not transfer to the fibre during
autoclaving. Papadimitrio et al [2] report analysis of fibre from six trials and the levels of trace
metals exceeded compost limit values; cadmium and zinc were identified as being particularly
problematic. Increasing temperature and pressure can increase extraction of trace metals (into the
water, and excluding Cr)[3]. Where there is excessive mechanic separation prior to autoclaving [4]
the fibre, has been found to have lower levels of trace metals and was considered to have potential
as an anaerobic digestion feedstock. Recently, there have been investigations of the torrefaction of
MSW [5‐7]. As has been reported for biomass fuels [8‐12], torrefaction of MSW results in a fuel with
410
increased heating value and grindability. There is very little information in the literature on the
impacts of torrefaction on trace metal concentrations for MSW feedstocks. Edo et al [13] observed a
decrease in both chlorine and mercury concentrations during torrefaction of MSW; but statistical
significance was not explored for other trace species. One of the aims of this study is to make the
MSW more homogeneous via MHT, to produce a fibre which could be used as a fuel. In order to
improve the fibre further, it was also torrefied and investigated for its fuel composition, energy
density, grindability and combustion properties. This is the first study of this novel process, which
combines the two pretreatments, namely autoclaving and torrefaction, and also adds to the limited
data available in the open literature on the variability of autoclaved fibre produced from MSW.

2‐ MATERIALS AND METHODS
The “manufactured MSW” used in this study had a composition which matched Defra estimated compositions
of household waste in the UK and this is given in Table 1. Cases with and without glass were studied. In all
cases mean values are reported and the standard deviation indicated where possible. The raw fibre contains
typically 50% moisture and underwent a drying step to 0% moisture (rewetted to 5‐6% prior to pelleting),
before being pelletised at a scale of 30 kg/h into pellets of dimension 90 mm diameter and 180 mm length.
Pellets were milled in a Retsch ball mill before being sieved for analysis according to ISO standard testing
methods. Torrefaction was performed at 270 oC for 20 min using the pellets in a bench‐scale torrefier which
has been described previously [10]. The batch production of torrefied pellets from the pelletised fibre
delivered a mass yield of 78% (daf) and an energy yield of 89% (daf). Pyrolysis and combustion
properties were assessed via thermogravimetric analysis and devolatilisation in a drop tube furnace operating
at 1100oC under a flow of <2%O2/N2 and a residence time of 0.6s. Char combustion characteristics were
assessed via TGA.

Item % Composition kg/batch on 20 kg load
Garden waste 19 3.8
Paper and board 13 2.6
Kitchen and general household waste 26 5.2
Wood 4 0.8
Tin cans 6.5 1.3
Plastic 12 2.4
Textiles 11 2.2
Metal Packaging 2.5 0.5
Glass 6 1.2
Total 100 % 20 kg

Table 1: composition of the manufactured MSW used in the pilot‐scale autoclave

For the life cycle assessment of carbon emissions, the process was modelled from a process flow
mass balance (using data from experiments where available). The scope includes the collection of
MSW (from households and commercial sites), initial processing for removal of most of the non‐
biogenic fractions, and the subsequent processing of the ‘MRF residue’ in an autoclave followed by
drying, pelletisation, torrefaction and finally combustion at a power station. For the counterfactual
situation, the assessment also includes the disposal of the MRF residue in landfill and the production
and combustion of lignite at a power station in place of pelleting and torrefying. The procedures
were consistent with the requirements of ISO 14040:2006 [14] and ISO 14044:2006 [15]

411
3‐ RESULTS AND DISCUSSION
3.1. Fibre characteristics
A statistical analysis was performed on historic data concerning the analysis of 33 representative
samples of fibre generated at a number of pilot scale facilities using black‐bin waste from UK and
Ireland households. The Phyllis2 database was used to generate similar data for typical European
MSW but only 3 analysis points were available, and there was no data for zinc. Similarly, there was
no data for antimony in the historic analysis of the fibre. Figure 1 indicates that autoclaving results
in a fibre which has lower mean concentration of trace metals and also less variability. The trace
metals in the manufactured fibre are also shown in Figure 1 as individual data points; values are
lower. The wt% ash (not shown) is generally unchanged by autoclave treatment, but, based on
mean values, N, S and Cl all decrease during autoclave treatment by approximately 20%, 10% and
35% respectively.

500
Historic Fibre
MSW
400 Manufactured fibre
300
mg/kg (db)
200
100
0
Cd Cr Cu Hg Ni Pb V Zn Sb

Figure 1: Trace metal means and standard deviations in MSW (3 sets of data from Phyllis2) and fibre from treating MSW by autoclave
(33 samples). Also shown as symbols is data for means for fibre from 6 trials on manufactured MSW

3.2. Torrefied fibre properties and classification
Figure 2 compares key properties required for classification of the fibre and torrefied fibre.
Insufficient data was available to present median and 80th percentile values so means and indicative
values are reported here. Ash contents increase slightly during torrefaction, as does net CV, while
heavy metals and moisture decrease. Further work is needed to establish if chlorine is lost during
torrefaction, as reported in some studies in the literature [12].

Based on the compositional data available to date, the dried (raw) fibre is classified according to BS
EN 15359:2011 [16] as Class 4, Class 1, Class 2 (4.1.2) according to the NCV, Cl and Hg contents
respectively. Torrefaction improved the fuel properties and it moves to Class 3, Class 1, Class 1
according to the data available for NCV, Cl and Hg respectively. Note that further measurements
are required in order to report means, medians and 80th percentile values as required by the
standard.

412
0.18
80 0.16
0.14
70
wt%; mg/MJ (ar)
wt%, MJ/kg, mg/MJ
0.12
60 0.1
0.08
50 0.06
0.04
40 0.02
0
30 Cl Hg Cd
20
10
0
Manufactured fibre
Torrefied fibre

Figure 2: Comparison of key properties of raw fibre and torrefied fibre.

3.3 Combustion characteristics
Burning profiles via TGA (not shown) indicate that the fibre begins to decompose at approximately
150oC, while torrefied fibre begins to decompose at approximately 200oC, which is similar to the
onset of combustion for woody biomass. The torrefied fibre (and fibre) is seen to have similar
reactivity as woody biomass, and is slightly more reactive than lignite coal data from the literature
[17]. The temperature for maximum combustion rate of char for the fibre and torrefied fibre are
comparable to torrefied woody biomass and lignite fuels. The char yields from the raw and torrefied
fibres produced in the drop tube furnace were 10% and 20% respectively. The percent nitrogen
partitioned into the collected chars were 13% and 32% respectively. Thus N release approximately
follows C conversion for both fuels, although concentrated in the char to some extent for the
torrefied fibre. The char combustion rates were measured isothermally via TGA and these were
comparable to those reported previously for torrefied willow [18]

3.4.Torrefied fibre as a substitute for lignite coal
In comparison to other co‐firing fuels such as wood or wheat straw, the fibre and torrefied fibre have
much higher ash. However, the ash content of lignite coals has been reported in the range 13‐27%,
[19] and both fuels fall within this range. N‐contents of the fibre are comparable to other fuels
(although higher than typical values for wood), but sulphur is lower than those typically seen in many
fuels. The heating value of torrefied fibre is beginning to approach that of wood chip. Chlorine
contents fall within the range found in lignite fuels of 0.01‐0.49 [20], and are typically lower than
those found in wheat straw. It is possible that the high calcium content of the ash in the fibre and
torrefied fibre (47‐48 wt% CaO in the ash) will act to capture some HCl emissions in situ as reported
in previous trials of lignite combustion [20]. A great advantage of the torrefied fibre fuel in
comparison to lignite is its low moisture content. High moisture adds vastly to transportation costs,
and affects flame temperature, stability and boiler efficiency. The major components in the ash are
CaO, SiO2, Al2O3, Fe2O3, K2O and Na2O. The relative amounts of each of these components is
dependent about the amount of glass, paper etc. in the original MSW. Both raw and torrefied fibres
had ash deformation temperatures above 1400 oC, measured via the ISO standard ash fusion test,
although fouling is predicted to be problematic. The levels of alkali are within the range observed for
413
some low rank coals if considered as a mole equivalent (since the main alkali is Na in coal, and K in
the fibre) [21].)

3.5. Life Cycle Carbon Assessment

The figures in Table 2 are based on primary energy depletion and GHG emissions savings per
functional unit (1MJNCV of torrefied pellets). Empiric data was used where possible. Results indicate
that the torrefied pellet production and use results in a significant reduction in GHG emissions of
143g CO2e/MJ of torrefied pellets combusted compared with the defined counterfactual scenario.
The reduction or ‘saving’ is approximately made up of avoided emissions from lignite combustion of
101g CO2e/MJ, avoided emissions of CH4 from landfill of 67g CO2e/MJ, less additional emissions from
the production of TBFP of 25g CO2e/MJ.

Environmental Impact Saving
Greenhouse gas emissions saving (kg CO2e/MJ) 0.143
Primary Energy Depletion saving (MJPE/MJ) 0.635

Table 2: GHG and primary energy depletion savings per1 MJ (NCV) of torrefied pellets
4‐ CONCLUSIONS
Based on the analysis of composition and the combustion behaviour, the torrefied fibre was
considered to be a promising substitute fuel for lignite which could help off‐set carbon emissions
from fossil fuel, and tackle waste management issues.

ACKNOWLEDGEMENTS
Funding from Innovate UK (Project Number 132123) is gratefully acknowledged.

REFERENCES
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fraction of autoclaved non‐segregated household waste and its compost/digestate. Waste Management & Research
26, 419–430 (2008).
[3] Efstathios K. Papadimitriou, John R. Barton: Report: Factors affecting the content of potentially toxic elements in the
biodegradable fraction of autoclaved household waste . Waste Management & Research 27: 685–692 (2009).
[4] L.I. Blake, F.A. Halim, C. Gray, R. Mair, D.A.C. Manning, P. Sallis, H. Hutchinson, N.D. Gray, Evaluating an anaerobic
digestion (AD) feedstock derived from a novel non‐source segregated municipal solid waste (MSW) product. Waste
Management 59 149–159 (2017).
[5] Haoran Yuan, Yazhuo Wang, N. Kobayashi, Dandan Zhao,and Shiyou Xing: Study of Fuel Properties of Torrefied
Municipal Solid Waste, Energy Fuels: 29, 4976−4980 (2015).
[6] Kingsley L. Iroba, Oon‐Doo Baik, Lope G. Tabil: Torrefaction of biomass from municipal solid waste fractions I:
Temperature profiles, moisture content, energy consumption, mass yield, and thermochemical properties, Biomass
and Bioenergy:105 320‐330( 2017).
[7] Kingsley L. Iroba, Oon‐Doo Baik, Lope G. Tabil: Torrefaction of biomass from municipal solid waste fractions II:
Grindability characteristics, higher heating value, pelletability and moisture adsorption. Biomass and Bioenergy: 106
8‐20 (2017).
[8] PCA Bergman. Combined torrefaction and pelletisation: The TOP process. The Netherlands: ECN: Petten; 2005
414
[9] T.G. Bridgeman, J.M. Jones, I. Shield, P.T. Williams: Torrefaction of reed canary grass, wheat straw and willow to
enhance solid fuel qualities and combustion properties. Fuel 87 844–856 (2008)
[10] T.G. Bridgeman, J.M. Jones, A. Williams, D.J. Waldron: An investigation of the grindability of two torrefied energy
crops. Fuel: 89 3911–3918 (2010).
[11] Raimie H.H. Ibrahim, Leilani I. Darvell, Jenny M. Jones, Alan Williams: Physicochemical characterisation of torrefied
biomass. J Anal Appl Pyrol: 103 21–30 (2013).
[12] Haoran Yuan, Yazhuo Wang, N. Kobayashi, Dandan Zhao,and Shiyou Xing: Study of Fuel Properties of Torrefied
Municipal Solid Waste, Energy Fuels: 29, 4976−4980 (2015).
[13] Mar Edo, Nils Skoglund, Qiuju Gao Per‐Erik Persson, Stina Jansson: Fate of metals and emissions of organic pollutants
from torrefaction of waste wood, MSW, and RDF. Waste Management: 68, 646–652 (2017)
[14] ISO 14040: Environmental Management – Life Cycle Assessment – Principles and Framework' International
Organisation for Standardisation, Geneva, Switzerland, 1997, revised 2006.
[15] ISO 14044: Environmental Management – Life Cycle Assessment – Requirements and Guidelines' International
Organisation for Standardisation, Geneva, Switzerland. 2006.
[16] BSI, Solid recovered fuels —Specifications and classes BS EN 15359:2011. BSI Standard Publications, 2011.
[17] D. Stojiljkovic, M. Radovanovic, M. Ercegovac, J. M. Jones and A. Williams: Devolatilisation of some pulverised
Eastern European lignites. Journal of the Energy Institute: 78, 190‐195 (2005).
[18] P. McNamee, L.I. Darvell, J.M. Jones, A. Williams: The combustion characteristics of high‐heating‐rate chars from
untreated and torrefied biomass fuels, Biomass and Bioenergy: 82, 63‐72(2015).
[19] Fernando, R., Fuels for biomass cofiring, CCC/102. IEA Clean Coal Center, 2005
[20] Sloss, L.L., Halogen emissions from coal combustion, in IEA Coal Research. 1992
[21] Zhu, C., et al., Distribution, occurrence and leaching dynamic behavior of sodium in Zhundong coal. Fuel:. 190: 189‐
197 (2017).
415
FROM BIOMASS AND RESIDUES TO FUELS
A.J. GROOTJES1, B.J. VREUGDENHIL1, R. ZWART2

1 ECN (Energy research Centre of the Netherlands), Petten, The Netherlands.
2 DRT (Dahlman Renewable Technology, Maassluis, The Netherlands.
Abstract
Purpose
Research of the project B2B focusses on cost reduction for the production of biofuels via gasification
by use of low value feedstocks and by valorisation of the product gas (co-production of high value
products). Biomass is a valuable resource and energy products (gas, electricity and heat) as well as
high value products (biofuels and chemicals) can contribute to the optimal valorisation of the
feedstocks. Besides biomass, residues from bio refinery, paper and pulp industry can be employed
for valorisation into high value products, whereas currently these residues are mainly used for
production of heat and/or electricity.
The work presented focuses on efficient gasification of low value biomass feedstocks and residues,
gas cleaning (dust, tar, chlorine-, sulphur- and nitrogen-compounds) and optimisation of (co-)
production strategies towards biofuels.
Used equipment, materials and methods

Laboratory scale, 25 kWth MILENA indirect gasifier, OLGA gas cleaning, catalytic reactors, several
feedstocks like RDF, sludge, lignin, gas analysis (guideline tar, S- and N compounds, HCl).
Results
Product gas composition:
Figure 1: Residue A product gas composition
Other results on the optimal gasification and gas cleaning strategies of residues towards (co-
)production will become available soon and will be presented.
Main conclusions
Initial conclusions of the ongoing project (2017 – 2019) indicate that gasification of residues results
in a medium calorific value product gas, rich in base chemicals/monomers like ethylene, propylene,
styrene and benzene, suitable for various (co-)production schemes towards biofuels and chemicals.
416
CHALLENGES OF FOOD WASTE AVOIDANCE AND COLLECTION ON THE EXAMPLE OF

THE CITY OF HAMBURG
I. KÖRNER1, J. SCHERMULY1, WALK, S.1

1 Hamburg University of Technology, Hamburg, Germany.
Abstract
The project DECISIVE, funded by EU HORIZION 2020 DECISIVE-project (Grant Agreement 689229),
proposes the improvement of the cycle of biogenic substances through decentralized biowaste
management. Besides local valorization units in micro-scale biogas facilities, the collection of waste
from households and commerce’s on local organization level are key elements.
 the purpose
The presentation focuses on food waste from households and catering as resources for decentralized
valorization systems. Food waste inventory, prevention, collection and valorization issues are closely
connected and are discussed for the example of the city of Hamburg, Germany.
 the main materials and methods used
An inventory for Hamburg’s household and catering food waste was carried out and implemented
into a GIS-based system. Models for local collections chain from the local generator to a local micro-
scale biogas facilities were developed considering different urban conditions: densely populated
existing city quarters; new built city quarters; city quarters with dense commercial activity.
 the main results obtained
EU household food waste generation varies (50- 100 kg/capita&a)
[1], but data are rare. In Hamburg 44-59 kg/capita&a are
collected [1] mainly with a combination of residual waste and
biobin. Although separate biowaste collection is obligated by law,
approximately 93% of food waste is incinerated. For transition to
more effective decentralized systems food waste inventories are
the basis and changes in people’s behaviors are necessary. Fig. 1
visualizes the food waste distribution. Model chains considering
avoidance, generation, collection in households and reduction
possibilities for storage and transport are shown. A similar
evaluation was done for catering sector.
Figure 1: Heatmap of Hamburg, Germany, showing the food waste distribution based on the building structure [2]
 the main conclusions of the work

Inventories and close interactions with citizens and commerce’s are most important for the
implementation of efficient food waste valorization systems. A large avoidance potential has to be
considered and a first step is to develop methods to determine local generation of avoidable waste.
References
[1] Manns, D. et al. (2017): Survey on waste collection systems with evaluations for decentralised applications.
Deliverable D3.5 within the DECISIVE-project. http://www.decisive2020.eu
[2] Schermuly, J. (2017): Heatmap of Hamburg. Map developed within the DECISIVE-project: A decentralized
management scheme for innovative valorization of urban biowaste . http://www.decisive2020.eu
417
THE POTENTIAL FOR RECOVERY OF RESIDUAL MUNICIPAL SOLID WASTE:

SUSTAINABILITY OF URBAN MINING STRATEGIES
A. CESARO1, V. BELGIORNO1
1
Sanitary environmental Engineering Division (SEED), Department of Civil Engineering,
University of Salerno, Fisciano (SA), Italy
Abstract
In the last years the concept of solid waste recovery has been widened to the use of anthropogenic
materials that are stocked in different forms in urban areas [1,2]. The reclamation of resources from
urban stocks is referred to as “urban mining”, which represents actions and technologies that can be
implemented to recover resources from residues, as either secondary raw materials or energy [3],
while “closing the loop” of material cycles [4-6].
As pointed out in recent studies, the urban stocks may represent a significant source of materials,
with concentrations of elements often comparable to or exceeding natural ones. However, if the
extraction and processing of anthropogenic stocks is necessary, the generation of an economic
benefit is essential [7]. This depends on several conditions, including the characteristics of the waste,
the available recovery technologies as well as the market for the recovered materials.
Aim of this work was in assessing the potential for recovery of residual municipal solid waste (MSW)
that had been produced and stored in form of bales between 2000 and 2009 in Campania Region, in
Italy. According to the origin of this waste, both materials and energy are expected to be recoverable
[8], so that the management of waste bales has been identified in the framework of urban mining.
As the economic feasibility of this strategy is tightly related to both the characteristics and the
treatability of waste bales, representative samples were collected from a storage site, characterised
by their composition and chemical-physical properties and treated in a full-scale mechanical
selection plant. The output fractions from the processing of waste bales were also characterised to
assess their qualitative suitability for either the recovery of materials or the production of Solid
Refuse Fuel (SRF) in accordance with the European standards. Experimental results showed the
prevailing presence of combustible fractions and recoverable plastics in the treated waste that were
almost completely selected to be further valorised. The qualitative characterization of the output
fractions showed their potential for recovery and allowed to identify the critical aspects in setting up
a sustainable process scheme for the mechanical processing of waste bales.
References
[1] Brunner, P.H.: Urban mining: a contribution to reindustrializing the city. J. Ind. Ecol. 15 (3), 339-341 (2011).
[2] Gutberlet, J.: Cooperative urban mining in Brazil: Collective practices in selective household waste collection and
recycling. Waste Manage. 45, 22-31 (2015)
[3] Urban Mining. Waste Manage. 32 (9), 1737 (2012)
[4] Krook, J., Baas, L.: Getting serious about mining the technosphere: a review of recent landfill mining and urban
mining research. J Clean. Prod. 55, 1-9 (2013)
[5] Ghisellini, P., Cialani, C., Ulgiati, S.: A review on circular economy: the expected transition to a balanced interplay of
environmental and economic systems. J Clean. Prod. 114, 11-32 (2016).
[6] Tesfaye, F., Lindberg, D., Hamuyuni, J., Taskinen, P., Hupa, L.: Improving urban mining practices for optimal recovery
of resources from e-waste. Minerals Eng. 111, 209-211 (2017).
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recoverable material mechanically and physically extractable from residual waste. Waste Manage. 33, 2594-2599
(2013).
418
MUNICIPAL SOLID WASTE FRACTIONS AND THEIR SOURCE SEPARATION –

FORECASTING FOR LARGE GEOGRAPHICAL AREA AND ITS SUB-REGIONS
M. PAVLAS1, R. ŠOMPLÁK1, V. SMEJKALOVÁ2, P. STEHLÍK3

1 Sustainable Process Integration Laboratory – SPIL, NETME Centre, Faculty of Mechanical
Engineering, Brno University of Technology – VUT Brno, Brno, Czech Republic.

2 Institute of Mathematics, Faculty of Mechanical Engineering, Brno University of Technology – VUT
Brno, Brno, Czech Republic
3 Institute of Process Engineering, Faculty of Mechanical Engineering, Brno University of Technology
– VUT Brno, Brno, Czech Republic
Abstract
In this contribution, an approach towards simultaneous forecasting of waste amounts and waste
parameters at different territorial units, which has been first introduced in [1], is further developed.
In general, the approach can be applied to any problem, where forecasts are performed based on
spatially distributed data from previous years. This data is supposed to be incomplete (data for locality
is missing), sometimes even uncertain.
In this paper, the original algorithm is adjusted to handle so called multi-commodity system, where
components overlap between observed streams. Municipal solid waste represents a good example as
it consists of several fractions, such as paper (PAP), plastics (PLAS), glass (GLA) and bio-waste (BIO).
These fractions may be either gathered as separately collected recyclables (SEP, e.g. by kerb-side
collection systems) or they contribute to residual waste quantities (RES) with limited material recovery
possibilities. The algorithm was extended by the following: (1) regression analysis providing models,
which are later on used to get complete information for all nodes, incl. nodes where input data is
missing; (2) extrapolation techniques for data at various levels of details; (3) specification of newly
formulated composition constraints, (4) modification of reconciliation-based balancing model.
The algorithm is demonstrated through a case study inspired by an extensive project for the Ministry
of the Environment of the Czech Republic. Future amounts of residual waste (RES) and recyclable
fractions as paper (RES-PAP), plastics (RES-PLA), glass (RES-GLA) and kitchen bio-waste (RES-BIO)
produced in one country and as well as in its 14 regions and 206 micro-regions is forecasted. The
source-separation efficiency in all of 206 micro-regions is analysed for three different future scenarios.
The developed approach contributes to analysing rational recovery targets by reflecting the current
situation in individual (micro) regions and, at the same time, it exploits examples of good practice from
regions with high recovery rates combining analogy with rigorous regression models (historical data
from one region can serve as one scenario for another region).
References
[1] Pavlas, M., Šomplák, R., Smejkalová, V., Nevrlý, V., Zavíralová, L., Kůdela, J., Popela, P. Spatially Distributed Production
Data for Supply Chain Models - Forecasting with Hazardous Waste. Journal of Cleaner Production 161C (2017) pp.
1317-1328, doi: 10.1016/j.jclepro.2017.06.107
419
COMPOSITION OF MIXED SOLID WASTE USING DEEP NEURAL NETWORKS
C. VRANCKEN1, P. LONGHURST1, S. WAGLAND1

1 Cranfield University, Cranfield, UK.
Abstract
The variable composition of received wastes makes it difficult for producers of waste-derived fuel to
control their processes and ensure certification of their products [1]. This project demonstrates that
by combining optical sensors and neural networks the composition of mixed solid wastes can be
determined to estimate its key fuel properties.
An imaging setup was implemented using 5 digital cameras to take photos of waste materials from 6
categories (paper, cardboard, plastic, wood, textile and inert) using 6 illumination conditions and 5
viewing directions. Colour and greyscale images versions were prepared and used to train and test 3
different network architectures (AlexNet [2], GoogleNet [3] and VGG-16 [4]).
The best mean accuracy of 97.4% was obtained with GoogleNet using colour images, with the worst
classification errors in the wood class (3.5 % classified as cardboard, 1.8% as inert, 1% as paper and
0.5% as plastic). This trained network was then used to classify materials within an image of typical
mixed waste containing paper, cardboard, plastic, and inert materials (Figure 1).
Figure 1. Left: original image, Right: estimated composition. Example determination of mixed materials using the trained GoogleNet
network, indicating obvious errors (red labels) but correctly showing the overall composition distribution.
Once the waste composition is known, fuel properties of such as the calorific value can be estimated
and used to control the mechanical and biological processes to produce more consistent waste-
derived fuels. This approach has the potential to increase the efficiency of solid waste treatment
plants by improving the quality and consistency of refused derived fuels (RDF) and solid recovered
fuels (SRF).
References
[1] Vrancken C., Longhurst PJ., Wagland ST. Critical review of real-time methods for solid waste characterisation:
Informing material recovery and fuel production. Waste Management. March 2017; 61: 40–57.
[2] Krizhevsky A., Sutskever I., Hinton GE. ImageNet Classification with Deep Convolutional Neural Networks. In: Pereira
F, Burges CJC, Bottou L, Weinberger KQ (eds.) Advances in Neural Information Processing Systems 25. Curran
Associates, Inc.; 2012. pp. 1097–1105.
[3] Szegedy C., Liu W., Jia Y., Sermanet P., Reed S., Anguelov D., et al. Going Deeper with Convolutions. arXiv:1409.4842
[cs]. 16 September 2014.
[4] Simonyan K., Zisserman A. Very Deep Convolutional Networks for Large-Scale Image Recognition. arXiv:1409.1556
[cs]. 4 September 2014.
420
PERFORMANCE OF PYROLYSIS AND HTC LIQUIDS IN PLANT PROTECTION
HAGNER MARLEENA1, LINDQVIST ISA1, NIEMELÄ KLAUS2, WIKBERG HANNE2, KÄLLI ANSSI2, RASA
KIMMO1, TIILIKKALA KARI1
1 Natural Resources Institute Finland (Luke), Jokioinen, Finland.
2 VTT Technical Research Centre of Finland Ltd, Espoo, Finland
Abstract
In recent years thermochemical conversion technologies - like pyrolysis and hydrothermal

cabonization (HTC) - have gained much interest due to their flexibility with respect to raw materials
and the range of end-products derived. The industrial exploitation of these technologies is strongly
dependent whether all the produced fractions can be utilized. Especially the produced liquid
fractions have been found to be challenging to commercialize and new ways to utilize these liquids
are needed. Use of especially pyrolysis liquids as herbicide, insecticide and fungicide has long
traditions in Asian countries but scientific evidences concerning their effectivity are still scarce. As
the chemical composition of pyrolysis liquids can vary significantly - depending on feedstock,
processing and storage conditions - their effectivity as a pesticide may also differ a lot.
In current study, various raw materials were pyrolysed to obtain liquid fractions for the experiments:
pine bark (PB-PA), pine forest residue (FR-PA), wheat straw (WH-PA), and willow (WI-PA) which was
also hydrothermally carbonized (HTC-L). The main aim was to identify the efficacy rates of produced
liquids as a i) repellent using the copse snail Arianta arbustorum, ii) herbicide using turnip rape
seedlings (Brassica rapa) and iii) insecticide against aphids (Rhopalosiphum padi). In addition, the
potential effective compounds behind the pesticidal impacts of tested liquids were investigated.
At 100% concentration each pyrolysis liquid induced a clear repellent influence on snails, eliminated
> 85 % of turnip rape seedlings and > 98 % of aphids. At lower concentrations, a clear difference
existed between the products: in all experiments WI-PA was the most effective followed by WH-PA,
PB-PA and FR-PA. Instead, HTC-L had no effect on aphids, barley seedlings or snails. The main
compounds in pyrolysis liquids included acetic acid, methanol, hydroxyacetone, 1-hydroxy-2-
butanone and propanoic acid. PAH concentrations were below 0.4 mg/L. High contents of volatile
fatty acids seems to be the main reason of higher pesticidal activity of the willow-derived pyrolysis
liquid. The reason for lower acetic acid concentration in the FR-PA and PB-PA liquids compared to
WI-PA is the lower content of acetylated hemicelluloses in the raw materials. Certain other
compounds, such as furfural, lactic acid, pentanoic acid, and propanoic acid could also have small
contributions to the observed effects. In conclusion, the pesticidal effect of pyrolysis liquids is highly
dependent on feedstock material. The observed effects are due to a larger set of chemical
constituents rather than due to a specific compound.
References
[1] Fagernäs, L., Kuoppala, E., Tiilikkala, K., Oasmaa, A.: Chemical composition of birch wood slow pyrolysis products.
Energ. Fuels 1275-1283 (2012)
[2] Tiilikkala, K., Fagernäs, L., Tiilikkala, J.:History and use of wood pyrolysis liquids as biocide and plant protection
producthistory and use of wood pyrolysis liquids as biocide and plant protection product. O. Agr. J. 111-118 (2010)
421
ACTIVATED CARBONS FROM VARIOUS BIOMASS RESIDUES VIA HYDROTHERMAL

CARBONIZATION AND ACTIVATION
H. WIKBERG, V. SIIPOLA, T. TAMMINEN

VTT Technical Research Centre of Finland Ltd, Espoo, Finland.
Abstract
Various side-streams generated in forest industry and agriculture are currently poorly utilised,
typically combusted for energy or left on the ground. Challenges in their cost-efficient utilization
for added value products are for example heterogeneity, seasonal availability and remote
locations. In this work, the suitability of several abundant but underutilized biomass residues (corn
stover, corn leaves, coffee cake, grape pomace, green house residues, willow, Scots pine bark,
wheat straw, brewers spent grain) for hydrothermal carbonization (HTC) was studied (1). By HTC,
wet biomass is converted to carbonaceous material, hydrochar, at moderate temperatures (~180-
260°C) using water as the carbonization medium. The results showed that all biomasses were not
equally suited for hydrochar production. Based on high yield, carbon content and solid carbon
recovery level, HTC was found to be most suitable for biomasses having high content of thermally
stable components, such as lignin, and low content of ash (i.e. coffee cake, grape pomace, Scots
pine bark and willow). Selected hydrochars were characterized in detail and further activated with
physical and chemical methods using different impregnation chemicals. Activated carbons having
surface areas between 260-3500 m2 g-1 were obtained. Pore size distributions varied from highly
microporous (up to 95 % micropores) to wider distributions including also meso- and macropores.
The results showed that by using different biomass and activation procedures, the structural and
surface properties (e.g. porosity and the amount of surface oxygen groups) of the activated
carbons can be modified. Chemical activations, for example, were found to be especially suitable
for producing highly surface-active carbons with either narrow or wide pore size distribution. This
gives the opportunity to tailor the activated carbons for specific end-uses by selecting suitable
parameters.
This project has received funding from the European Union’s Horizon 2020 research and
innovation programme under grant agreement No 637020−MOBILE FLIP.
References
[1] Wikberg, H., Grönqvist, S., Niemi, P., Mikkelson, A., Siika-aho, M., Kanerva, H., Käsper, A., Tamminen, T.:
Hydrothermal treatment followed by enzymatic hydrolysis and hydrothermal carbonization as means to valorise
agro- and forest-based biomass residues, Bioresour. Technol. 235, 70-78 (2017)
422
MICRON-SCALE PORE STRUCTURE OF BIOCHARS DERIVED FROM PYROLYSIS AND

HYDROTHERMAL CARBONIZATION PROCESSES
J. HYVÄLUOMA1 J. HEIKKINEN1, S. KULJU1, M. HANNULA2, H. WIKBERG3, A. KÄLLI3, K. RASA1

1 Natural Resources Institute Finland, Luke, Jokioinen, Finland.
2 .Tampere University of Technology, Tampere, Finland.
3 VTT Technical Research Centre of Finland Ltd, Espoo Finland
Abstract
Pyrolysis and hydrothermal carbonization (HTC) have recently gained interest in the field of biomass
conversion into marketable products. This is mainly due to the process flexibility with respect to raw
materials and the wide range of potential applications proposed for the end products. In the
agricultural context the solid end product called biochar has been used to improve soil structure and
fertility, as well as to sequestrate carbon into soils. However, the effects of biochar depend on the
raw material from which biochar is derived as well as on the used processing technology and process
conditions.
One of the commonly highlighted benefits of biochar is its ability to improve water retention
properties of agricultural soil and growing media. Biochar may affect water retention in the direct or
indirect way. In direct mechanism water is stored and held in the biochar pores while the indirect
mechanism is related to soil-biochar-interactions, i.e. the soil structural development (aggregation).
In this work we focused on biochar micron-scale porosity contributing to storage of plant available
water within the biochar particles (direct mechanism). Several biochars were imaged with x-ray
computed microtomography and the obtained images were quantitatively characterized by image
analysis for porosity, specific surface area, pore-size distribution and structural anisotropy [1].
The micron-scale pore characteristics of biochars strongly depend on the used feedstock. It is
notable that biochar pore characteristics may vary greatly due to heterogeneity of feedstock taken
from industrial scale storages (e.g. bark from forest industry), which may challenge development of
designed biochar products for specific purposes. On the contrary, processing technology and process
temperature had only minor effects on the micron-scale porosity of a willow biochar (Salix sp.). The
influence of willow biochar (pyrolysed at 320 °C) on soil water retention was investigated by
measuring the water retention curve for a biochar-amended clay soil. We found that biochar
addition altered the water retention curve. These changes could be explained by the pore-size
distribution of the biochar determined by imaging. Our results highlight that micron-scale porosity of
biochar directly affects the water retention properties of biochar-amended soils.
This project has received funding from the European Union’s Horizon 2020 research and innovation
programme under grant agreement No 637020−MOBILE FLIP.
Reference
[1] Hyväluoma, J., Kulju, S., Hannula, M., Wikberg, H., Källi, A., Rasa, K. Quantitative characterization of pore structure of
several biochars with 3D imaging. Environ. Sci. pollut. Res., doi: 10.1007/s11356-017-8823x (2017)
423
PELLETIZING OPTIMIZATION VERSUS BIOMASS PROPERTIES – DETERMINATION OF

OPTIMAL MOISTURE CONTENT AND COMPRESSION RATE
S. LAVERGNE 1,2, M. ROJAS1, M.CAMPARGUE1,

S.H. LARSSON3, T. MELKIOR2, M. MARCHAND2, C. DUPONT4
1 RAGT Energie, Albi, France.
2 CEA, Laboratoire de Préparation des Bioressources, Grenoble, France.
3 Swedish University of Agricultural Sciencies, Department of Forest Biomaterials and Technology, Biomass
Technology Centre, Umeå, Sweden
Abstract
Pelletizing offers many advantages in biomass treatment, such as obtaining homogeneous and stable
products, facilitating handling and storage, and thus reducing operational costs in biomass conversion
processes. Using various input materials like forestry or agricultural residues as energy source entails
significant socioeconomic and environmental benefits as well as an important role in national economies
by avoiding the import of fossil fuels. Nowadays, this process is well-controlled with wood and animal feed
as feedstock, but remains poorly mastered with other biomasses, were the control of the production
quality is challenging because operational conditions are usually not well anticipated, resulting in non-
optimized costs [1].
The objective of this study, which is part of MOBILE FLIP project that has received funding from the
European Union’s Horizon 2020 research and innovation programme under grant agreement No
637020−MOBILE, was to find optimal operational parameters for various biomasses representative of
available materials in northern Europe. Then, by comparing biomass properties and resulting pellet quality,
the objective is to identify key factors influencing pelletization.
Here, five agricultural and five forestry biomasses were collected, dried, shredded, moisten and finally
pelletized, using at least two different compression rates and three moisture contents, in a flat die pilot
scale setup (~60 kg/h).
Results showed that the optima of pellets durability and bulk density were not found under the same
conditions. While minimum moisture content leads to optimum bulk density in most cases, specific
moisture content should be set for each material in order to reach an optimum durability. Moreover,
compression rate, known to increase friction during pelletization, seemed to make the production of pellet
possible in a wider range of moisture content while increasing (Figure 1). Finally, correlations could be
observed between lignin, hemicelluloses, abrasive elements (Si, K), particle size and pellet quality
parameters, probably due to differences in bonding mechanisms or frictional effects [2].
424
700 Compr. rate = 7 100

Pelletet bulk density
Compr. rate = 5,5 98
Pellet durabiltiy (%)

650
96
600
(kg/m3)
94
550 92
90
500 Compr. rate = 7
88
Compr. rate = 5,5
450 86
10 12 14 16 18 20 10 12 14 16 18 20
Inlet moisture content (%) Inlet moisture content (%)
Figure 1: Difference of impact of moisture content on untreated willow pellets bulk density and durability
References
[1] S. Mani, S. Sokhansanj, X. Bi & A. Turhollow. Economics of producing fuel pellets from biomass. Appl. Eng. Agric. 22,
421–426 (2006).
[2] Stelte, W. et al. Recent developments in biomass pelletization - A review. Bioresources 7, 4451–4490 (2012).
425
COMPARATIVE ENVIRONMENTAL ASSESSMENT OF VINE SHOOTS VALORISATION

STRATEGIES INTO HIGH ADDED COMPOUNDS
B. GULLÓN1, P. GULLÓN2, J. LABIDI2, S. GONZÁLEZ-GARCÍA1

1 Department of Chemical Engineering, School of Engineering, University of Santiago de Compostela.
15782- Santiago de Compostela, Spain.

2 Chemical and Environmental Engineering Department, University of Basque Country, 20018 - San
Sebastián, Spain.
Abstract
The wine industry represents one of the most important economic agro-food sectors in the
Mediterranean countries. This activity generates large amounts of wastes every year. Among these
residues, vine shoots are the main by-product of vineyards as a result of the annual pruning related
activities and they generate a variable amount of lignocellulosic residues. The valorisation of these
residues could be considered as a potential alternative in order to reduce the environmental
burdens from winery activity. In this sense, vine shoots have been proposed as a source of high
added value compounds production (such as oligosaccharides and antioxidants) with multiple
material applications. The goal of this study has been the valorisation of vine shoots into multiple
types of by-products which depends on the biorefinery strategy followed. All these products present
potential industrial applications such hemicellulose, cellulose, lignin, antioxidant extracts and even
bioethanol, being hemicellulosic oligosaccharides the main product with potential uses as
biopolymers. Therefore, three valorisation routes have been proposed for assessment considering
information from a semi-pilot scale. These scenarios differ on the extraction, delignification and/or
hydrolysis routes considered. The assessment has been carried out from an environmental approach
to determine the best scenario considering a cradle-to-gate perspective. Life Cycle Assessment (LCA)
has been the methodology selected to perform the environmental analysis. Thus, the LCA models for
each scenario were developed in accordance with the requirements of ISO 14040 [1]. According to
the results, the environmental profiles are highly dependent on the production yield of the different
compounds as well as on the protocols followed. Among the outstanding differences on the profiles,
it is important to highlight that an increment on the number of valorisation steps included in the
valorisation route involves higher energy and chemical requirements which derives on worse
environmental profiles - when a functional unit based on the amount of valorised residue is
considered. Thus, it must be taken in mind if enhancing “closing the loop” strategies under a
biorefinery concept through better recycling and re-using the waste streams, balances out the worse
environmental burdens obtained as result from their high intensive stages. Further assessment
considering an alternative functional unit, i.e. the one based on an economic revenue should be
performed, since considerably differences on the environmental results should be expected.
This research has been supported by a project granted by Xunta de Galicia (project ref. ED431F 2016/001). Dr. S.
González-Garcia, Dr. B. Gullón and Dr. P. Gullón would like to express her gratitude to the Spanish Ministry of Economy
and Competitivity for financial support (Grant references RYC-2014-14984, FPDI-2013-17341 and FPDI-2013-18748,
respectively). The authors (Dr. S. González-Garcia and Dr. B. Gullón) belong to the Galician Competitive Research Group
GRC 2013-032 as well as to CRETUS (AGRUP2015/02), co-funded by Xunta de Galicia and FEDER).
References
[1] ISO 14040: Environmental Management – Life Cycle Assessment – Principles and Framework (2006).
426
A LIFE CYCLE PERSPECTIVE FOR OPTIMAL DESIGN OF A CLOSED-LOOP SUPPLY

CHAIN : THE CASE STUDY OF LEAD ACID BATTERIES
M. GONZÁLEZ RODRIGUEZ1, C. AZZARO-PANTEL1, A. AGUILAR-LASSERRE2

1 Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INPT, UPS, Toulouse, France, 4 allée
Emile Monso, 31432 Toulouse Cedex 4 – France.

2 Tecnológico Nacional de México, Instituto Tecnológico de Orizaba, DEPI, Av. Instituto Tecnológico
852, Col. Emiliano Zapata, 94300 Orizaba, Veracruz, Mexico.
Abstract
Due to the growing concern for the environment related, in particular, to greenhouse gas
emissions and resource depletion, the design, plan and operation of sustainable supply chains are
challenging for industry. A way of reflecting environmental concerns in logistics decisions is to
integrate and manage both forward and reverse flows in the supply chain, thus creating the so-called
closed-loop supply chain (CLSC). In that context, the objective of this work is to develop a generic
framework for the optimal design of a CLSC for process industries taking into account both
environmental and economic criteria.
The case study of battery recycling is an emblematic example which is particularly consistent with
the projected growth of plug-in electric vehicle (PEV) worldwide. For the sake of illustration, only the
case of lead-acid batteries will be considered in this paper to show that a life-cycle perspective in
evaluating such supply chain networks is essential in fully understanding the environmental
consequences of the infrastructure expansion.
For this purpose, a model for a reverse supply chain network has been developed by connecting the
forward supply chain to the point where the end-of-life products enter the reverse supply chain
taking into account a biobjective optimization approach that simultaneously considers economic and
environmental criteria. The first objective function computes all the cost elements corresponding to
each technological brick and activity within the network, and the second accounts for the CO 2
emissions associated with each entity in the network. For this purpose, a Life Cycle Assessment
methodology that mimics the supply chain process has been carried out and Life Cycle Inventory has
been performed using data collected from dedicated literature [1] and EcoInvent database
embedded in SimaPro software tool. The CLSC design has been formulated as an MILP problem
implemented in the GAMS (General Algebraic Modelling System) environment and solved with
CPLEX. The multiobjective problem is solved by implementing an -constraint method.
The results of the evaluation can provide guidelines for the production and network design on
recycling decision-making issues for the implementation of green supply chains.
References
[1] Yacan Wang ; Jing Yu ; Xinfei Zhao ; Tao Lu ; Jie Du ; Xiaoyan Huang, Research on the Life Cycle Analysis of the
Reverse Supply Chain of the Lead Acid Batteries, 4th International Conference on Bioinformatics and Biomedical
Engineering, 2010
427
ARE BIOMASS, CARBON DIOXIDE AND ELECTRICAL POWER THE MAIN RENEWABLE
FEEDSTOCK OF A SUSTAINABLE CARBON ECONOMY?
T. MARZI1
1
Chemical Energy Storage/Fraunhofer UMSICHT, Germany
Abstract
In order to achieve the global two-degree target, the net emissions of CO2 need to reach a value of
nearly zero in the second half of the century. Thus the fossil based economy of today has to be
transferred into a Sustainable Carbon Economy, where energy and industrial production is solely
based on renewables and sustainable carbon sources. A complete “decarbonisation”, e.g. a
substitution of carbon components in industrial production, is not possible, as the reduction of iron
ores in the steel industry, the production of limestone in the cement industry as well as plastics and
other products in the chemical industry is depending on carbon based compounds. Looking for
sustainable carbon based materials; biomass and CO2 are the only available carbon sources.
“Carbon Capture and Utilisation (CCU) technologies” also called “Power-to-x-technologies” use CO2
as a feedstock for the chemical synthesis of fuels and chemical products. The energy needed for the
activation of CO2 comes from renewable fluctuating sources like wind and solar and with that, low
carbon energy could be transferred from the energy sector to the industrial and transportation
sector. As storing of CO2 in products is only temporary, CCU can not solve the problem of CO 2
emissions by its own. But anyway, CCU is an important linking element in a Sustainable Carbon
Economy, because it allows a cascading utilisation of carbon compounds, so that biomass as a
limited resource could be used more effective and efficient. This requires the cooperation and
coupling of different industrial and energy sectors.
The changing in the German electrical power system from fossil and nuclear to a renewable based
system with its specific characteristics creates interesting innovation conditions for CCU
technologies. Within this paper important aspects of a power and CO 2 related refinery will be
discussed as well as systemic conditions. Finally, two projects will be introduced dealing with this
specific topic. In the project “Carbon2Chem®” a cascading utilisation of carbon is the aim of partners
from steel and chemical industry as well as from plant constructers and researchers. Carbon is
supposed to be used in a first step as a reducing agent in the blast furnace and in a second step as a
raw material for chemical compounds.
428
OVERVIEW AND PERSPECTIVE OF MSW MANAGEMENT BASED ON SOURCE

SEPARATION IN CHINA
JIANGUO LIU1
1 Key Laboratory of Solid Waste Management and Environment Safety, Ministry of Education of
China, School of Environment, Tsinghua University, Beijing 100084, P.R. China
Abstract
Municipal solid waste (MSW) is a highly-concerned waste stream all over the world. With the huge
population and rapidly-growing economy, China has been confronting big challenges of MSW
environmentally-sound management and has made substantial progress in recent two decades. In
2017, 97.1% of the MSW in urban areas was treated in the facilities satisfying to the national
environmental standards, and more than 40% of it was treated through WtE. A primary pattern of
modern MSW management pillared by sanitary landfilling and WtE has been shaped. According to
Chinese national plan, MSW source separation is actively promoted to slow down MSW generation,
to raise resource recovery and to improve pollution control. In 2020, WtE will be the priority of MSW
treatment and will share more than 50% of the technological market, and domestic MSW recycling
will be boosted with favorable policies, e.g., banning foreign waste import, and centralizing domestic
waste recycling. Biological treatment, both anaerobic digestion and aerobic composting will be
reborn to be a solution of source separated organic waste, and landfill will be mainly a sink of inert
residues in many cities. A new pattern of MSW integrated management based on source separation
will be formed in the future in China.
On account of the big differences on natural, social and economic conditions between China and
developed countries, the strength and weakness, the opportunities and challenges of MSW
management should be different from that of the developed countries. The evolution and solution of
MSW management in China could be a good mirror for other developing countries.
Key words: MSW, source saparation, WtE, recycling, biological treatment
429
CONCENTRATION OF HEAVY METALS IN FLY ASH FROM EMPTY FRUIT BUNCHES
COMBUSTION BY PARTICLE SIZE

C. LANZERSTORFER1
1 University of Applied Sciences Upper Austria, Wels, Austria.

Keywords: biomass combustion, fly ash, heavy metals

Abstract

Empty fruit bunches (EFB) are produced during the production of palm oil. This residue is used as
fuel in biomass combustion plants. Beside other ways of utilization, the fly ash from off‐gas de‐
dusting can be utilized as soil conditioner. However, to prevent build‐up of heavy metals in the soil
the heavy metal content of the ash should be low. Yet, in literature only few data on the heavy metal
content of EFB combustion fly ash are available. In this study, the concentration of various heavy
metals in a fly ash as well as their distribution in the different size fractions was investigated.
A cyclone fly ash sample from a grate‐fired combustion plant was split into six particle size classes
using a laboratory air classifier. The concentration of various metals was analysed by ICP‐OES and IC
after aqua regia digestion of the sample.
The results show that the concentration of all heavy metals investigated was quite low in all size
fractions. For several components a considerable dependence of the concentration on the particle
size was observed. Significantly increased concentrations in the fine size fractions were found for the
heavy metals Cd, Cu and Pb. The concentrations in the finest size fractions were up to six times
higher compared to the original fly ash.
The heavy metal contamination of the cyclone fly ash was below the limit concentrations for
utilization of various European countries. Although some heavy metals are significantly enriched in
the finest size fractions their concentrations are still comparatively low.

430
1‐ INTRODUCTION
Empty fruit bunches (EFB) are a residue that is produced during the production of palm oil [1]. The
mass of EFB produced in Malaysia in 2010 was 21.3 Mt [2], the ash content of EFBs is approximately
4% [3]. EFBs can be used as feedstock in the production of biofuels [1‐4]. Another way of utilization is
the production of heat and power by combustion in biomass combustion plants. Thereby,
considerable amounts of bottom ash as well as fly ash, which is separated during de‐dusting of the
combustion off‐gas, are generated. Foo and Hameed [5] reviewed possible ways of utilization of oil
palm ash. Several applications including use as an adsorbent, utilization as a supplementary
cementitious material in the production of concrete, use for sludge treatment and in black soap
processing industries are investigated. Furthermore, the utilization as a geopolymer material has
been suggested [6]. Because of its content of soil nutrients, especially potassium [6,7], the ash can
be utilized as soil conditioner on agricultural land and forest soil [8,9]. However, the concentrations
of heavy metals should be low to prevent build‐up of heavy metals in the soil. In the literature only
few data are available on the heavy metal content of fly ash from EFB combustion [8,10].
In this study cyclone fly ash from a grate‐fired combustion plant using EFB as fuel was investigated.
For the determination of the distribution of heavy metals in the various size fractions the sample was
split into six particle size classes using a laboratory air classifier.

2‐ MATERIALS AND METHODS
The investigated cyclone fly ash sample was collected from the ash discharge of the cyclone
separator of a 4 MW grate‐fired combustion plant using EFB as fuel. In the laboratory the sample
was dried at 105°C for 24h. For the tests the volume of the samples was reduced to a suitable
volume using sample dividers which were applied repeatedly (Haver&Boecker HAVER RT and
Quantachrome Micro Riffler).
The fly ash sample was split into six particle size classes using a laboratory air classifier type 100 MZR
from Hosokawa Alpine. In the first step of the sequential classification procedure the finest size
fraction was separated from the bulk. The coarse material was used in the next classification step as
feed material where the classifier was operated at reduced speed. This procedure was repeated.
Finally, the fly ash was separated into six size fractions. The details of such a sequential classification
procedure are described in the literature. [11]
The particle size distribution of the fly ash samples was measured using a laser diffraction instrument
with dry sample dispersion (Sympatec HELOS/RODOS). A Sympatec SiC‐P600’06 standard was used
to check the calibration of the instrument. The mass median diameters d50 of the size fractions were
obtained from the measured particle size distributions under the assumption of a dust density
independent of the particle size.
After an aqua regia digestion procedure the samples were analysed by inductively coupled plasma
optical emission spectroscopy for Na, K, Mg, Sr, Ba, Ti, V, Mn, Fe, Co, Cu, Zn, Cd, B, Al, Pb, As and Bi
using a Horiba Jobin Yvon Ultima 2 system. Details of the analytical method can be found elsewhere
[12]. The concentrations of Cr, Mo and Ni measured for the size fractions cannot be used because
during the classification procedure the fly ash gets contaminated with these elements due to some
erosion of the classifier wheel [13].
Enrichment in the fine size fractions of fly ash by components volatile during combustion can be
described by a power function: c  1/dN [14]. The exponent N results from the mechanism of
condensation or reaction of the components on the particles. In this study the mass median
431
diameter d50 was used as the characteristic particle size of a size fraction. The mass concentration ci
of a component in size fraction i can be expressed by Eq. (1):

1
ci (d 50 )  K . (1).
d 50,i N

The exponent N can be obtained by linear regression. The higher the value of the exponent, the
more distinct is the increase of the concentration of this component in the fine size fractions and the
depletion of this component in the coarse size fractions.
The enrichment or depletion of a component in a size fraction can also be expressed by the
enrichment factor EFi, which is defined according to Eq. (2):

ci
EFi  (2).
c

3‐ RESULTS AND DISCUSSION
The investigated cyclone fly ash was within the typical size range of cyclone fly ashes from biomass
combustion. Its mass median diameter d50 was 32 µm which is similar to the average d50 of 38 µm
reported for the cyclone fly ashes from ten biomass combustion plants [15].
The mass fractions and the mass median diameters of the size fractions produced are summarized in
Table 1. The sum of the mass fractions of the three finer size fractions is only approximately 13%.
One reason for this is the limited collection efficiency for fine particles of cyclone separators.

Mass fraction Mass median diameter
in % d50 in µm
Fly ash 100 32
Size fractions
1 4.2 2.1
2 3.9 4.6
3 5.1 9.7
4 20.5 19
5 34.7 32
6 31.6 59

Table 1: Data of the size fractions produced

Generally, the concentration of heavy metals in the cyclone fly ash was comparatively low [10,12].
The concentrations of all heavy metals investigated was below the limit concentration for utilization
of the regulations of various European countries [10]. For several components a considerable
dependence of the concentration on the particle size was observed. Significantly increased
concentrations in the fine size fractions were found for the heavy metals Cd, Cu and Pb. The
calculated exponents N were 0.72, 0,82 and 0.59, respectively. In contrast, the side dependence of
the concentration of B was less (N = 0.30) and the concentration of Co was nearly independent of
the particle size (N = 0.12). Figure 1 shows exemplarily the size dependence of the concentrations of
B, Co, Cu and Pb.
432

Figure 1: Size dependence of the concentrations of Cu and Pb (left) and B and Co (right).
The potassium content of the cyclone fly as was 95.1 g/kg. Recycling of low heavy metal content fly
ash from biomass combustion is a common method to return the potassium and other plant
nutrients contained in the ash to the soil [16]. In recent literature also the utilization of fly ash from
wood combustion in potassium fertilizer production has been suggested [17]. Thereby, the
applicability of air classification for fractionation of biomass combustion fly ash for the enrichment of
potassium in the fine fraction has been demonstrated [18]. This process is based on the size
dependence of the potassium concentration. For EFB combustion fly ash this size dependence
(Figure 2) is slightly lower than reported for a cyclone fly ash from a combustion plant using forest
residues as fuel [19].

Figure 2: Enrichment factor for potassium

4‐ CONCLUSIONS
The heavy metal contamination of fly ash from EFB combustion was comparatively low in
comparison to fly ashes from wood combustion. The concentrations of all heavy metals investigated
was below the limit concentration for utilization of the regulations of various European countries.
This was also true for the concentrations of most heavy metals in the fine size fractions although
some of the heavy metals were enriched in these fractions. The heavy metals with the most distinct
enrichment in the fine particles were Cd, Cu and Pb.
433
The potassium concentration of the cyclone fly ash was 9.5%. Potassium is also enriched in the
smaller particles. The enrichment factor for the finest size fraction was approximately 2.0. Thus, use
of this fly ash in fertilizer production could be considered.

REFERENCES
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Conversion Techniques, pp. 479‐490. InTech, Rejeka (2013)
[2] Ng, W.P.Q., Lam, H.L., Ng, F.Y., Kamal, M., Lim, J.H.E.: Waste‐to‐wealth: green potential from palm biomass in
Malaysia. J. Clean. Prod. 34, 57‐65 (20123)
[3] Goh, C.S., Tan, K.T., Lee, K.T., Bhatia, S.: Bio‐Ethanol from Lignocellulose: Status, Perspectives and Challenges in
Malaysia. Bioresource Technol. 101, 4834–4841 (2010).
[4] Fatriasari, W., Anita, S.H., Risanto, L.: Microwave Assisted Acid Pretreatment of Oil Palm Empty Fruit Bunches (EFB)
to Enhance Its Fermentable Sugar Production. Waste Biomass Valor. 8, 379–391 (2017)
[5] Foo, K.Y., Hameed, B.H.: Value‐added utilization of oil palm ash: A superior recycling of the industrial agricultural
waste. J. Hazard. Mater. 172, 523‐531 (2009)
[6] Zarina, Y., Al Bakri, A.M.M., Kamarudin, H., Nizar, I.K., Rafiza A. R.: Review on the various ash from palm oil waste as
geopolymer material. Review on the various ash from palmoil
[7] Al‐mulali, M.Z., Awang, H., Khalil, H.P.S.A., Aljoumaily, Z.S.: The incorporation of oil palm ash in concrete as a means
of recycling: A review. Cem. Concr. Compos. 55, 129‐138 (2015)
[8] Suan, J.D.K., Datta, A., Salam, P.A.: Effect of Oil Palm Fly Ash on Soil Properties and Yield of Sweet Corn in the
Tropical Zone of Thailand. Commun. Soil Sci.Plant Anal. 48, 236‐244 (2017)
[9] Yin, C.Y., Kadir, S.A.A.A., Lim, Y.P., Syed‐Ariffin, S.N., Zamzuri, Z.: An investigation into physicochemical
characteristics of ash produced from combustion of oil palm biomass waste in a boiler. Fuel Process. Technol. 89,
693‐696 (2008)
[10] Lanzerstorfer, C.: Chemical and physical characterization of cyclone fly ashes from five grate‐fired biomass
combustion plants. Carpath. J. Earth Environ. Sci. 9, 129‐135 (2014)
[11] Lanzerstorfer, C., Kröppl, M.: Air classification of blast furnace dust collected in a fabric filter for recycling to the
sinter process. Resour. Conserv. Recyc. 86, 132‐137 (2014)
[12] Lanzerstorfer, C.: Chemical composition and physical properties of filter fly ashes from eight grate‐fired biomass
combustion plants. J. Environ. Sci. 30, 191‐197 (2015)
[13] Lanzerstorfer, C.: Investigation of the contamination of a fly ash sample during sample preparation by classification.
Int. J. Environ. Sci.. Technol. 12, 1437‐1442 (2015)
[14] Linak, W.P., Wendt, J.O.L.: Toxic metal emissions from incineration: Mechanisms and control. Prog. Energy Combust.
Sci.19,145‐185 (1993)
[15] Lanzerstorfer, C.: Flowability of fly ashes from grate‐fired combustion of forest residues. Fuel Process. Technol. 150,
10‐15 (2016)
[16] Maeda, N., Katakura, T., Fukasawa, T., Huang, A.‐N., Kawano, T., Fukui, K.: Morphology of woody biomass
combustion ash and enrichment of potassium components by particle size classification. Fuel Process. Technol. 156,
1‐8 (2017)
[17] Maeda, N., Fukasawa, T., Katakura, T., Ito, M., Ishigami, T., Huang, A.‐N., Fukui, K.: Existence Form of Potassium
Components in Woody Biomass Combustion Ashes and Estimation Method of Its Enrichment Degree. Energy Fuels
(in print) doi:10.1021/acs.energyfuels.7b03090
[18] Nunes, L.J.R., Matias, J.C.O., Catalão, J.P.S.: Biomass combustion systems: A review on the physical and chemical
properties of the ashes. Renew. Sustain. Energy Rev. 53, 235‐242 (2016)
[19] Lanzerstorfer, C.: Cyclone fly ash from a grate‐fired biomass combustion plant: dependence of the concentration of
various components on the particle size. Fuel Process. Technol. 131, 382‐388 (2015)
434
THERMOCHEMICAL ERADICATION OF HEAVY METALS FROM SEWAGE SLUDGE

INCINERATION FLYASH
KANHAR ALTAF, FEI WANG

Institute for Thermal Power Engineering, College of Energy Engineering, Zhejiang University,
Hangzhou, PR China
Abstract
Fly ashes from incineration of sewage sludge can be recycled, recovered and reused for obtaining
environmentally stable materials. However, prior to use they need to be detoxified by eradicating
the heavy metals content. Chlorination has gained paramount importance as effective industrial
technique for eradication of heavy metals. The involvement of chlorides during thermal treatment
greatly slowed down the condensation of metal compounds, which accelerated the volatilization of
heavy metals. In this study three conditions were investigated to estimate the chlorination effect of
various chlorinating agents: confirming the amount and type of chlorinating agents (hydrous and
anhydrous), homogenization of fly ash and chlorinating agents and treatment with thermochemical
method in laboratory-scale tube furnace. In this report we investigated fly ashes from two different
sewage sludge incineration plants and sampled as raw and pretreated fly ash. The obtained four
different samples were subjected to thermochemical treatment (150 g cl/kg of fly ash), at
temperatures of 800-1150°C and residence time of 10 -30 minutes. The heavy metals examined
included Cr, Cu, Zn and Pb in which copper and zinc were mainly focused because of their strong
dependence on treatment conditions. The temperature played a key role during the thermal
treatment of raw fly ash and had significant influence on heavy metal eradication, whereas residence
time had weaker effect. The pretreated fly ashes showed dramatic improvement in heavy metals
evaporation with the addition of chlorinating agents, the eradication rate of heavy metals
augmented with the amount of chlorinating agents increasing. Moreover, the effect of chlorinating
agent’s type on the chlorination of heavy metals differed considerably. Hence we conclude that
hydrous chlorides are the best choice due to their effective eradication.
References
[1] Christian Vogel, Robert M. Exner and Christian Adam Heavy Metal Removal from Sewage Sludge Ash by
Thermochemical Treatment with Polyvinylchloride. Environ. Sci. Technol. 2013, 47, 563−567.
[2] Nowak, B. et al. Heavy metal removal from municipal solid waste fly ash by chlorination and thermal treatment. J.
Hazard. Mater.79, 323–331 (2010).
[3] Zhang, Y. & Kasai, E. Effect of chlorine on the vaporization behavior of zinc and lead during high temperature
treatment of dust and fly ash. ISIJ International 44, 1457–1468 (2004).
[4] Kuboňová, L., Langová, Š., Nowak, B. & Winter, F. Thermal and hydrometallurgical recovery methods of heavy
metals from municipal solid waste fly ash. Waste Manage. 33, 2322–2327 (2013).
435
PRODUCTION OF Mg- AND Fe- CONTAINING COMPOUNDS DURING THE

VALORISATION OF DIAMOND MINE SLIMES VIA THERMOCHEMICAL TREATMENT
B.A. CASTLEMAN1, F.J. DOUCET2, E.M. VAN DER MERWE1

1 Department of Chemistry, University of Pretoria, Lynnwood Rd, Pretoria, 0002, South Africa.
2 Council for Geoscience, 280 Pretoria Rd, Private Bag X112, Pretoria 0001, South Africa.
Abstract
South Africa and other countries face a variety of environmental problems associated with the
management of large volumes of solid mine waste residues [1]. Mine tailings and slimes are a form
of environmental pollution through fine dust dispersal, slope instability, mud slides and possible
contamination to local surface and ground waters, and also take up vast tracks of land that could
possibly be used for other purposes. Mine tailings can, however, represent untapped secondary
mineral resources, which could be processed to promote sustainability through their conversion to
valuable materials or products [2,3,5], and the associated development of treatment technologies to
mitigate environmental problems.
The aim of our study is to develop a process for the valorisation of diamond mine slimes. The
extraction of three components from the slimes and their conversion to produce commercial-grade
products are of particular interest. These include magnesium (for the production of magnesium
carbonate or magnesium oxide nanoparticles, or layered double hydroxides); iron (for the
production of iron nanoparticles) and talc (which can be used in numerous applications). This study
reports on the experimental conditions applied to achieve maximum extraction of Mg and Fe from
the tailings and slimes, using a multistep process which entails the combination of a thermochemical
solid-solid treatment step with ammonium sulphate[3,4], which is followed by aqueous dissolution.
The reactivity of talc, present in the untreated tailings, with respect to the thermochemical and
leaching steps was also investigated. Experimental conditions required to precipitate Mg- and Fe-
containing compounds will be reported. The extent of conversion, from the soluble extracted
minerals to the required products, was monitored using a combination of XRD, DSC, SEM and TGA
analyses.
References
[1] Asif, Z. and Chen, Z. Environ. Sci. Pollut. Contr. (23) (2016) 167 – 179
[2] Frandegard, P., Krook, J., Svensson, N. Waste Management (42) (2015) 137 – 147
[3] Mohamed, S., van der Merwe, E.M., Altermann, W., Doucet, F.J. Waste Management (50) (2016) 334 - 345
[4] Nduagu, E., Björklöf, T., Fagerlund, J., Wärnå, J., Geerlings, H., and Zevenhoven, R. Minerals Engineering 30 (2012)
75–86
[5] Salomão, R., Milena, L.M., Wakamatsu, M.H. and Pandolfelli, V.C. Ceramics International 37 (2011) 3063 – 3070
436
RECOVERY OF IRON FROM PLATINUM GROUP METAL (PGM) TAILINGS AND

SYNTHESIS OF IRON-BASED NANOMATERIALS
S. MOHAMED 1,2, E.M. VAN DER MERWE2, L. PETRIK3, F.J. DOUCET1, 4

1 Council for Geoscience, Private Bag X112, Pretoria 0001, South Africa.
2 . Department of Chemistry, University of Pretoria, Lynnwood Road, Pretoria 0002, South Africa.
3 Department of Chemistry, University of the Western Cape, Robert Sobukwe Road, Cape Town, 7535,
South Africa.
4 Chemical Resource Beneficiation, North-West University, Private Bag X6001, Potchefstroom, 2520,
South Africa.
Abstract
In South Africa, the scale of tailings production associated with the primary production of Platinum
Group Metals (PGMs) in the Bushveld Igneous Complex (BIC) is extensive and approaches 80 Mt
p.a. [1]. These alkaline tailings are regarded as hazardous waste and have been identified as a major
source of environmental impact. Finding routes for recovering additional value from tailings may
assist in minimizing their disposal and in making treatment processes more viable economically.
In recent years, PGM tailings are increasingly being reprocessed for the recovery of additional
primary commodities such as precious and ferrous metals as well as PGM and chromite
concentrates [2]. PGM tailings also contain a significant portion of aluminium (Al), iron (Fe), calcium
(Ca), and magnesium (Mg) bearing silicates which have the potential to serve as a secondary mineral
source.
This study investigates the synthesis of Fe-based nanoparticles from PGM tailings. Elemental
recovery from PGM tailings using a multi-stage process has recently been successfully demonstrated
[3]
. The process involved thermochemical solid-solid treatment of the tailings using ammonium
sulphate ((NH4)2SO4) followed by a dissolution procedure. Extraction efficiencies greater than 50%
for Fe were achieved using this process. Sequential separation and precipitation processes were then
used to successfully synthesize magnetic iron nanoparticles, for potential use in wastewater
treatment. Their detailed characterization was achieved using a set of complementary techniques
(particle size analysis, zeta potential measurements, XRD, ICP-OES, FTIR and TEM) and will be
presented.
References
[1] Vogeli, J., Reid, D. L., Becker, M., Broadhurst, J., & Franzidis, J. P.: Investigation of the potential for mineral
carbonation of PGM tailings in South Africa. Min Eng. 24:1348-1356 (2011)
[2] Ndlovu, S., Simate, G. S., & Matinde, E.: Waste Production and Utilization in the Metal Extraction Industry, pp 80-81.
CRC Press, Taylor and Francis Group, Boca Raton, FL. (2017)
[3] Mohamed, S., van der Merwe, E. M., Altermann, W., & Doucet, F. J.: Process development for elemental recovery
from PGM tailings by thermochemical treatment: Preliminary major element extraction studies using ammonium
sulphate as extracting agent. Waste Manag 50:334-345 (2016)
437
MICROWAVE INDUCED PLASMA GASSIFICATION AS A WASTE MANAGEMENT

STRATEGY FOR KATHMANDU: A CASE STUDY
R. SHRESTHA1, P. PANICKER1
1 New York University Abu Dhabi, Abu Dhabi, United Arab Emirates.
Keywords: Microwave Induced Plasma, Gasification, Solid Waste Management, Nepal
Abstract
The current waste disposal methods used in the Kathmandu Valley, Nepal, are explored from existing
literature, observations made at private and public waste treatment facilities and interviews with
professionals in the industry, and a better and sustainable technology is then proposed. The most
common methods consist of landfilling and incineration of the municipal solid wastes (MSW) but they
are inadequate, have adverse effects on the environment and society, and are hampered by the
mountainous terrain, monsoon rains, and a lack of proper infrastructure and technology. In recent
years, waste-to-energy (WTE) techniques such as biogas production from organic wastes have been
introduced. But the solid waste residue left behind after the bio methanation process and removal of
the fuel gas must be incinerated or landfilled. MSW are not sorted into constituent groups prior to
landfilling, and there are many ill effects such as contamination of water bodies and soil, production
of malodors, and promoting the growth of disease causing vectors at the dump sites. Thus, a
sustainable waste management methodology is required for Nepal that enables a smooth and
economical transition from prevailing social, governmental, and industrial practices, with no negative
impact on the environment. It is proposed that microwave induced plasma gasification of MSW is the
best and most economical solution that would turn MSW into a source of energy and raw materials
while achieving zero-landfill, and thus benefit the national energy security and promote the
preservation of the environment.
438
1- INTRODUCTION
Nepal is a developing country situated in South Asia between India and China, with the Himalayan
mountains on its northern side, elevated valleys in its center and fertile plains on its southern side.
Kathmandu, the capital is in the higher valley region in the center of the country at an altitude of about
1 400 m above sea level. The capital and its surrounding suburbs are home to about 5 million
inhabitants. Waste management is a constant problem for Kathmandu Valley. Historically, Kathmandu
has relied on landfilling as its main waste management strategy. However, this has not been successful
as the city experiences consistent disruptions in waste collection and disposal, due to limitations
caused by technology, geography, and society.
A sustainable solution for waste management would include turning the waste into valuable
resources, such as raw materials for industry, and energy in the form of electricity or fuel. When it
comes to waste-to-energy technologies that can be divided broadly into thermal technologies, such
as incineration and gasification, and non-thermal technologies such as bio methanation for biogas
production, fermentation for ethanol production, and other biological treatments. Biogas production
from organic waste can be performed in small scale units including by private citizens and companies,
and this technology is being applied in the Kathmandu Valley, and will be looked at briefly later in this
paper. Fermentation production and biological treatment can only be feasible on larger scales due to
the economies of scale, and these methods have not been effectively tried in Nepal due to various
natural and economic limitations.
Incineration of MSW has only been applied in a small scale in Nepal by governmental entities as well
as civilians and industries. But, no incineration plant to produce electricity has been established in
Nepal owing to the high costs and large-scale requirements. Incineration plants must be large, with
more than 100s of MWs in power production capacity, to be economically viable. Incineration has
additional drawbacks such as the requirement of a large waste sorting facility, the formation of toxic
emissions such as furans and dioxins, the need for exhaust scrubbers to remove toxic gases, and the
need for landfilling of solid residues. Common incineration techniques can only process specific types
of waste and require pre-processing into smaller sizes. Additionally, hazardous waste must be
separated and handled separately.
Gasification is the process of converting organic waste into a mixture of hydrogen, carbon monoxide
and smaller amounts of carbon dioxide and other gases, called synthesis gas or syngas for short [1].
Thermal gasification, that uses combustion of the organic mass in the feedstock to drive the chemical
conversion of the mass into syngas, has been around for over a century. The syngas can be further
processed into liquid fuels using the well-established Fischer-Tropsch process. Another form of
thermal gasification is the plasma gasification process which employs plasma in a high-energy, high-
temperature reaction to convert all the feedstock mass into gas, with the organic materials
transforming into syngas, and the balance materials including metals and silicates, being captured into
a molten slag that finally solidifies into a glassy substance.
Plasma is the fourth state of matter and consists of ionized gas. It can commonly be found as partially
ionized gas such as in neon lights or fully ionized gas such as in an arc discharge or in the sun. The
temperature of plasma in the arc discharge can exceed 5 000 °C and is thus capable of gasifying all
kinds of waste materials. This is the biggest advantage of plasma gasification waste treatment plants
in that no pre-sorting of waste is required and all manner of wastes can be turned into fuel. Plasma
gasifiers can process organic and inorganic waste with the formation of cleaner and richer syngas that
439
can be used in fuel cells and gas turbines for electricity production or for Fischer-Tropsch process-
based conversion to synthetic fuels, without the need to sort or separate waste materials into similar
groups, unlike traditional thermal treatments like incineration which require considerable pre-
processing, sorting, and separation. The extreme temperatures prohibit the formation of toxic gases
such as furans and dioxins, enables complete tar destruction, and increases syngas production with
minimal production of any residues [3]. The non-hazardous slag obtained as a byproduct can be used
for construction of roads and other infrastructures [4].
However, the critical component of plasma gasification waste treatment plants is the plasma arc torch,
which is very expensive, and requires a considerable amount of electricity to run. Thus, plasma arc
gasification plants tend to be large and costly and are not feasible for many countries. Nevertheless,
many plasma arc waste gasification plants are in operation currently around the world.
The drawbacks of the plasma arc gasifier have been resolved with the application of microwave
sources for producing plasma in the newer microwave induced plasma gasification (MIPG) technology
[1].
Microwave induced plasma generation is already an established technology and has been used in
many industrial processes, such as biomass and solid fuel processing, and bacterial sterilization [5]. A
quick search in the scholarly articles of microwave plasma gasification shows that many research
articles on this topic, and the data presented demonstrates the effectiveness of MIPG in releasing
clean and high-calorific fuel from the feedstocks. Although commercialization of MIPG for waste
treatment is still in the infancy stage, this technology is promising to be the sustainable, optimal and
most economical solution for waste-to-energy conversion. MIPG reactors offer many advantages over
conventional plasma arc reactors and MIPG can be easily adapted to the terrain conditions in Nepal,
as well as scaled to fit the needs of Kathmandu [1,2].
The microwave sources include magnetrons that operate at 2.4 GHz frequency which is the same as
that of a household microwave oven. To scale up the size and power of a reactor, larger powered
magnetrons can be used, but alternatively several magnetrons can be connected in parallel to increase
the power input and the area of coverage of the reaction zone in the reactor to produce microwave
induced plasma. Magnetrons of 1 kW are cheap and readily available in the market due to their
application in household microwave ovens [1,5,6]. Recently, solid state microwave sources based on
semiconductor technology, in the 300 W range, have become available, and their sizes and power
ratings are expected to grow while their prices will come down as they get widely adopted by the
commercial appliances industry. Another advantage of solid state sources is that they require lower
voltage power supplies, at 24 V or 48 V DC [2]. Thus, the MIPG reactors can easily be scaled up to
process waste in an easy and cost-effective manner.
The syngas produced from a MIPG is a pure, clean burning fuel which can be used in fuel cells, internal
combustion engines, and gas turbines or converted into methanol, gasoline, diesel, or other fuels
through the well-established Fischer-Tropsch process. In the context of Kathmandu Valley, electricity
is highly valued product from the gasification process. This is because Nepal suffers from power cuts
that sometimes last up to 16 hours per day. Additionally, recent economic downturns have highlighted
the vulnerability of Nepal’s dependence on energy imports [8]. Hence, MIPG is a solution that would
positively impact the energy security of Nepal while tackling the negative social and environmental
issues of waste management and landfilling.
440

The research was initially conducted through extensive review of literature of solid waste
management of Kathmandu Valley through reports and papers which provided information on the
current practices and infrastructures available in Kathmandu. Additionally, Interviews were conducted
with authorities and industries involved in the waste management sector of Kathmandu, to get
updated information about the current scenario in waste management. The interviews also provided
an opportunity to recognize the perspectives of different stakeholders involved in the waste
management process.
This research evaluates MIPG as a waste management strategy to eliminate landfill and generate
energy for Kathmandu, Nepal. This research evaluates the current waste management methodologies
used in Kathmandu and proposes the MIPG for waste gasification as the solution. This will highlight
the advantages and help demonstrate the feasibility of the technology in the context of existing waste
management practices and infrastructures.

There are no dominant alternatives to landfilling to manage the waste in Kathmandu. In the past, aid
agencies from Germany, Japan and India have supported improving landfilling in Kathmandu by
providing financial and technological support. However, their projects have been unsuccessful due to
issues of sustainability or suitability for Nepal [9]. Landfill sites create an unhygienic and dangerous
environment with the presence of rodents, insects, malodors, and toxic emissions. This creates
problems for the human settlements located close to and around the landfill sites. Disruptions in waste
collection causes waste accumulation on the road sides of Kathmandu [10,11]. As the problems caused
by landfilling constantly increases in Kathmandu valley, other technologies and methods must be
explored to manage the waste of Kathmandu.
The city of Kathmandu has recently shown interest in promoting waste-to-energy technologies by
expanding the biogas plants from a domestic scale to larger commercial scales [12]. Additionally, a bio
methanation plant was installed in the Teku waste transfer station in 2016 which has a capacity to
process 3 tons of organic waste per day and to produce 32 kW of electricity from the waste [13].
However, it is too soon to see their long-term impact on waste management and the energy sector
[12].
A suitable WTE technology must be selected that will fit harmoniously with the existing system of
waste management in Kathmandu. Plasma technologies provide a promising solution for waste
management and energy generation in the context of the currently existing waste collection and
disposal methods applied in Kathmandu, Nepal. However, the plasma arc torch-based gasification
technologies have not been economically viable because of high capital expenses, maintenance
requirements and energy consumption [7,5]. On the other hand, microwave technology is a more
promising and sustainable method for plasma generation.
3.1- Waste Collection Method Kathmandu

Waste collection is done through door-to-door collection in Kathmandu Valley. A garbage truck,
tractor or rickshaw goes to each house door to collect waste. They usually charge between $0.1 and
$2.08 per month for this service [14]. The waste collected from households and commercial
441
establishments is a mixture of diverse types of materials including paper, plastic, food, metals, textiles
and even batteries. After collection, the waste is transported to a local intermediary waste collection
and transfer site. The composition of the waste collected is presented in table 1.
3.2- Composition of collected waste

Waste Composition
Household Institutional Commercial Average
Organic 64.24 % 20.29 % 45.44 % 43.32 %
Plastics 15.96 % 24.55 % 24.29 % 21.69 %
Paper products 8.66 % 44.28 % 23.29 % 25.41 %
Glass 3.75 % 1.37 % 2.86 % 2.66 %
Metals 1.72 % 1.13 % 2.65 % 1.83 %
Textiles 3.40 % 3.89 % 1.03 % 2.77 %
Rubber and Leather 1.12 % 1.14 % 0.00 % 0.75 %
Others 1.15 % 3.35 % 0.45 % 1.65 %
Table 1: Composition of waste collected in Kathmandu, Nepal
Source: Asian Development Bank, Solid Waste Management in Nepal, 2013
Since syngas is produced by the organic portion of the waste through MIPG, it is beneficial to have a
higher organic content in waste. It can be seen from table 1 that majority of waste generated in
Kathmandu is organic in nature. MIPG does not require separating waste into categories before
feeding into the reactor which is advantageous in the case of Kathmandu, where waste is not sorted
into distinct types. Most of the waste produced in Kathmandu consists of organic waste, including
paper, materials of bio-origin such as food, wood, leather, and plants as well as plastic waste, while
other types of waste such as metals are only found in very limited amounts. Thus, a high calorific value
energy can be potentially generated from organic, plastic and paper waste while using MIPG as a waste
management strategy.
3.4- Transfer Site and Secondary Transportation of Waste

The waste transfer site was initially made for the function of waste segregation and pre-treatment.
However, this has not been put into practice due to poor management [15]. The waste accumulated
in the transfer site is then collected by secondary transport vehicles, namely trucks, and taken to the
final disposal sites. Currently waste from Kathmandu Valley goes to the Sisdol landfill site, which is 26
km away from Kathmandu and located in the neighboring district of Nuwakot [15]. Guidelines specify
that roads to landfill sites should have all weather access. However, the road to Sisdol is a narrow
gravel road that is prone to landslides [15]. In some instances, the large garbage trucks struggle to
reach the landfill site due to poor road infrastructures. Drivability on these connecting roads pose a
major problem during the monsoon season due to continual and heavy rains [11].
The waste transporting vehicles cause further damage to the roads that connect to the landfill site.
The vehicles also spread odor, drop and spread waste along the way, and leak leachate from the solid
waste that is being transported. This happens due to overloading the trucks and lack of specialized
waste transportation vehicles. These issues have at times prompted the local inhabitants on the route
to the landfill site to protest and block the roads for the garbage trucks. This then disrupts collection
of waste in the Kathmandu Valley whereby waste accumulates at the transfer sites, riversides, and
roadsides of the city [16].
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Social and infrastructural problems can be identified in the process of transferring waste after
collection. There have been various attempts to help develop the system of landfilling by foreign aid
agencies. However, they have been unsuccessful [9]. Managing waste locally at the transfer site itself
would deal with the issues faced in waste transportation by eliminating the need to transfer waste to
the landfill site. Kathmandu has been working on locally managing waste with the implementation of
a bio methanation plant in the Teku waste transfer station.
Bio methanation still requires separation of organic and non-organic waste, and the disposal of the
solid residue after the fuel gas has been removed. In the past, there have been failures in the
implementation of many technologies in Nepal due to poor waste segregation which are explored
more in section 3.6. With these lessons from the past, it is important to select a waste management
strategy that will provide a smooth transition from the currently existing waste management strategy.
The key advantage of MIPG technology over bio methanation and other WTE technologies such as
incineration is that mixed wastes can directly be processed without any input of additional water, pre-
treatment or drying of waste. No toxins such as hydrogen sulfide, dioxins, etc. are formed and all tar
is consumed. Hence, the syngas produced is cleaner and has higher calorific value than biogas [2].
Implementing MIPG at the transfer site would generate synthetic gas from the mixed waste which can
further be used to generate electricity. The electricity generated can then be connected to the central
power grid and distributed to the communities from which the waste was collected. In the past,
Kathmandu has suffered from power cuts that last up to 16 hours per day [17]. Since, the transfer sites
are within the city, distribution of electricity would also be easier as the power would be distributed
over shorter distances. The production of electricity from municipal waste would be highly beneficial
to the people of Kathmandu.
MIPG technology can be designed and scaled to different capacities that range from 1kW to much
higher according to the amount and type of waste available [2]. This way waste can be managed at
the transfer stations according to the composition of waste collected. This would also utilize the space
dedicated for waste management at the transfer site. Currently, 10 % of the municipality budget is
separated for solid waste management out of which 20 % - 30 % is spent on transportation of waste
[14]. Locally managing the waste would simplify the process of waste management by eliminating the
necessity for secondary transportation of waste to landfills.
MIPG can be further promoted through privatization of the waste management system and promote
local participation in the operations of the waste management and energy production. This is essential
to the success of waste management projects as they increase a sense of responsibility and ownership
amongst the community of Kathmandu.
3.5- Landfilling
The Sisdol landfill site, currently being used by the city of Kathmandu is situated 26 km from the city
in the hills of Nuwakot district. It was initially selected as a temporary landfill site for 3 years, in 2005,
until a long-term landfill site was constructed [15]. However, the Sisdol landfill is still in use today. In
previous years, dumping of waste was being carried out by the public on the banks of the rivers
Bagmati and Bishnumati that flow through Kathmandu [16]. This has severely polluted the rivers within
the Kathmandu Valley. Landfilling is not a sustainable way of managing waste and it has adverse
environmental implications. A better alternative for landfilling must be sought to manage waste
properly in Kathmandu. Locally managing the waste through resource recovery method would be
443
highly beneficial for Kathmandu. Within resource recovery methods, waste to energy technologies are
seen to be preferable for Kathmandu as initiatives have already been taken with bio methanation and
anaerobic digestion technologies.
With the absence of waste treatment at the transfer site, the waste dumped at the landfill site consist
of a mixed composition and contain hazardous wastes, even though these landfill sites were originally
created to handle only municipal solid waste. Analysis has shown the presence of industrial wastes
and biomedical wastes [15,18] which causes additional risks to the environment and the local
inhabitants [16]. An audit of the Sisdol landfill site found that leachate was present and was the main
source of water, land, and air pollution [15]. The runoff and seepage of waste pollutes the ground
water around the landfill site. The polluted water and land affects the aquatic ecosystem, crops,
grazing animals, and scavenging animals. Some of the cattle grazing in the area are farmed for human
consumption. Hence, the toxins can be transferred to the humans as well. Hence, the effect of
landfilling is carried into the ecosystem and to entire food chain.
While waste decomposes in landfill sites, gaseous emissions are released including flammable gases
which poses a danger to the workers and the local inhabitants in the area. Landfill gas contains 50% of
methane (CH4) which greatly contributes to global warming [15]. Furthermore, the presence of waste
poses a threat to the public health of people living in the locality. The fumes produced have a pungent
odor and are poisonous. The disposal sites are usually unhygienic and unsanitary [14] which attract
flies which act as vectors for various disease-causing microbes and contaminant especially when heavy
rainfall and wind can cause the vectors to spread. The landfills have had been a constant source of
problems to the environment and residents of Sisdol and the areas around it.
When landfills for cities are selected close to established residential communities, it is an act of
injustice committed against these inhabitants. Poor practices of the waste collectors also cause waste
to be strewn along the roads leading to the dump sites. Thus, rural communities close to the dump
sites suffer from the waste generated by cities, and this creates ill will between rural and urban
communities. Landfilling is an injustice for the communities living around and en route to the landfill
site. The waste accumulated from cities are dumped into the environments of rural communities. The
reasons given for these rural communities to suffer from the impacts of the urban waste is unjustified.
Hence, waste must be locally managed within the cities, and landfilling must be eliminated.
Residents close to the landfill site have protested because the waste in landfill sites are disposed
without treatment. Due to the pollution caused by the disposed waste, the environment around the
landfill site becomes unbearable to live in. Their protests block off the access to the landfill sites
causing problems in disposal of waste in the city. Landfilling has created tensions amongst citizens
regularly in all the landfill sites of Kathmandu Valley and some landfill sites have been closed due to
continual protests. Although the municipal landfill sites were claimed to be sanitary by the local
government, the Asian Development Bank report on Nepal of 2013 stated that the state of dumpsites
in Nepal were not sanitary [14]. Locally managing the waste would be a clever way to eliminate
landfilling for the sake of environmental preservation and social justice.
3.6- Failure due to poor waste Segregation

According to Asian Development Banks survey only 30 % of surveyed households practiced segregation
of waste [14]. It is known that those people who separate their wastes can sell selected waste
materials to scrap dealers. A few examples are items made of metal, glass, plastic, and electronic
444
items. The scrap dealers pay cash to the sellers, collect the materials, and sell it off to other scrap
agents or export it to India, where the waste will be recycled. However, this waste recycling sector is
very informal, there are no formal records of these scrap dealers and hence their impact on the
management of waste in Nepal is unknown. MIPG does not require separation of waste into various
categories to convert it to energy. Energy will be produced from the organic portion of the waste and
the by-product slag can be used in construction.
In the past, Kathmandu has attempted to use technologies like composting and biogas to locally
manage waste. However, these technologies were not successful because they depended on sorting
waste into organic wastes and inorganic wastes. The government has promoted composting by
providing subsidies and training for small scale composting. There are provisions to provide each
household with their own compost bin at a subsidized price. But, there are no large compost facilities
to handle the enormous amounts of organic waste produced in Kathmandu. Only small numbers of
people have adopted composting in Kathmandu city due to the lack of proper waste segregation
systems and the limited demand for compost. Biogas and biomass energy technologies also require
separating waste into organic and inorganic waste streams. The low adoption rates have led to the
failures in the implementation of composting, biomass, and biogas systems.
There are now a few waste management companies like Heartbeat and Doko that manage waste. A
recycler from Heartbeat recounted that they buy waste from Kathmandu residents worth $150 per
day, and then sort and sell it off to other scrap dealers. He reported that the plastics were converted
into fibres that were then sold. Most of the scraps were sent to the recycling industry of India. Doko
reported that they collect waste in Kathmandu and sells them to recycling factories. These two
companies have been established recently and are not accounted for in recent literature.
3.6- Biomedical Waste and Hazardous Waste

There are limited formalized guidelines to manage biomedical waste and hazardous waste in Nepal,
and no centralized biological or hazardous waste management systems exist in Kathmandu. A few staff
in very few facilities have received written information and training on hazardous waste segregation.
Only a few hospitals practice incineration or decontamination of biological waste through autoclaving.
In the past, hospitals have been unable to use incinerators due to their high costs and they cause
pollution. Incineration cannot be practiced in inner-city clinics and hospitals or at the waste transfer
sites because of their proximity to households. The widespread practice has been to dump untreated
biomedical wastes at the river banks or in landfill sites, and this has resulted in the formation of
contaminated leachate. This seeps into the ground or flows into the river which increases the risk of
spread of infections. Once again, flies act as vectors for various microbes from the biological waste.
MIPG is safely neutralizes hazardous and medical wastes because the plasma ray decomposes
compounds to its elemental stages [1]. This eliminates the need for specialized handling and disposal
of these hazardous wastes. Plasma gasification can decontaminate these wastes even if they are
already mixed and not separated into categories. This would create a centralized system that deals
with all several types of waste.
3.7 – Why MIPG is the Appropriate Waste-to-Energy Technology

Nepal, which is a land-locked country, imports all of its fuel and much of its electricity from its
neighbour India. Having an alternate, indigenous source of energy, preferably a waste-to-energy
solution, would greatly enhance its energy security and reduce the need for fuel and energy imports.
445
Given the mountainous and irregular topography of the land and the wide distribution of the
population over the entire land area within Nepal, obtaining suitable flat grounds for creating
dumpsites that are accessible to cities, yet not too close to high population areas or farms is extremely
difficult in Nepal. Availability of land for creating waste sorting and pre-treatment plants is also short.
Transporting waste over long distances is not practical. Given the wet and humid climate in Nepal,
drying of waste containing moisture on a flat land using sunlight is not feasible. So, moist waste has to
be processed. Thus, MIPG WTE plants of smaller sizes (say, 10 000 tons of waste per day, 1 to 10 MW
of power capacity) can be built at various locations on the outskirts of the city.
Since waste is not pre-sorted, the waste collectors will have to collect all types of wastes from the
collection points, e.g. households and commercial locations. Due to the shortage of waste pre-
treatment facilities, the waste collection agents cannot sort the waste into groups such as papers,
plastics, biomass, woods, etc. at their facility. The waste treatment system should be capable of
processing unsorted wastes. Since there is a shortage of waste treatment facilities and landfills, the
waste treatment facility should be able to process municipal solid waste, biomedical waste from
medical facilities, agricultural waste as well as hazardous wastes.
Imposing waste sorting responsibility on the clients (citizens, commercial enterprises, government
agencies, etc.) will not be very practical, and will increase the improper dumping of waste on public
properties such as parks, side of roads, rivers, etc. Thus, MIPG plants can easily provide a solution that
processes all kinds of waste at one site. MIPG for WTE is the only system of waste management that
can work with all the above constraints.
3.9- Challenges in implementation of MIPG in Nepal

The factors that hinder the implementation of a new and foreign technology as MIPG in a developing
country such as Nepal must also be considered. After the construction of MIPG plants, availability of
technical support and proper upkeep of the facilities are very important and play a huge role in the
wider acceptance of these technologies. The social and cultural factors that affect the adoption of
MIPG by the society should also be further explored as well. MIPG technology is cheaper and more
efficient than traditional plasma technologies. However, an economic feasibility analysis must be done
to explore the impacts of the technology in the context of Nepal. MIPG WTE-based distributed power
generation would work well with smart grid technology to alleviate the power shortage in Nepal.
There are no known industries that use the plasma slag for construction in Nepal, and so the adoption
of this material must be studied. The slag may become more widely used with time as plasma
technologies get established in Nepal or they may be exported to foreign countries where they can be
utilized. With the lessons learned from past failures and after considering the benefits of MIPG for
waste management, the implantation of MIPG based waste-to-energy conversion strategy will help it
successfully solve the ongoing waste management problems that has been plaguing Nepal.
4- CONCLUSIONS
MIPG for WTE has immense potential in a developing country like Nepal where traditionally waste
management methodologies have been poorly implemented. The incorporation of a new waste
management system in a city with a high population density and irregular terrain presents many
challenges such as the embracing of new behaviors by all members of the society in adapting to new
processes and changes to infrastructure. The implementation of MIPG for WTE would enable a
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smoother transition while providing greater benefits to society and the environment. The waste
collection methodology does not require any changes, the waste can be collected and transported in
traditional systems such as waste trucks. The waste treatment plants can be smaller in size (a few MW
in power, as opposed to 100s of MW for the incineration plants) and located closer to urban areas
without fear of harmful emissions. MIPG reactors can be scaled to meet the size and power
requirements easily as the costs of the components scale proportionally with size. Also, MIPG creates
a potential revenue stream for waste management industries who can turn waste into energy, fuel
and raw materials. MIPG for WTE can be phased in within a city and scaled up economically as demand
grows. MIPG also allows the processing of biomedical and hazardous wastes without the need for
waste segregation methods. MIPG does not require large land areas and can achieve zero-landfill, with
no emissions to the atmosphere or water bodies which is the case for landfills and incineration plants,
and thus would greatly benefit public health and protect the environment. As Nepal is actively seeking
sustainable solutions for their waste management problem and testing waste-to-energy methods, we
recommend that MIPG be adopted for a more effective waste management strategy.
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MUNICIPAL SOLID WASTE GASIFICATION TECHNOLOGIES FOR ELECTRICAL ENERGY

GENERATION IN BRAZIL
A. MEDINA1, R. PALACIOS1, S. NEBRA1

1 Centre of Engineering, Modelling and Applied Social Sciences (CECS), Federal University of ABC,
Santo André, SP, Brazil.
Keywords: gasification, MSW, RDF, Energy recovery, efficiency
Abstract
According to the Brazilian Association of Public Cleaning and Special Waste Companies, in 2016
195,452 (tonnes day-1) of municipal solid waste (MSW) were collected, which represents a per capita
waste generation of 0.948 kg per day. Only 58% of the waste has adequate destination in sanitary
landfills, whereas the remaining 42% has inadequate destination in controlled landfills and open
dumps; this situation is a problem to Brazilian government, owing to the inappropriate destination
and the growing generation of waste, which compromises the operating lifetime of sanitary landfills
in the country. Among thermal treatment routes, the gasification of MSW is an interesting alternative
to be studied, because of its versatility, relative low emissions and feasibility to be implemented in a
wide range of capacities. However, assessing the energy potential of this route is hampered by the
limited operational experience and incomplete available data. The aim of this work is to evaluate the
potential of electricity generation through the gasification of the municipal solid waste of Santo André
city comparing three waste gasification technologies. These technologies are TPS Termiska Processer
AB, Carbogas and Energos; these alternatives have operated commercially for a few years, and some
data are available. Specific characteristics of each technology were taken into account, such as the
reactor type and fuel characteristics, to determine MSW pre-treatment, and the synthesis gas cleaning
system. For electricity production, two energy conversion systems were assumed, the former
considers an internal combustion engine, and the latter a power steam cycle. From the process
parameters adopted, the results showed that Carbogas technology presented the highest efficiencies
of electricity generation, which resulted in 30% when the gasifier was coupled to internal combustion
engines, and 25.5%, if a power steam cycle was assumed.
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1. INTRODUCTION
In 2010, the Brazilian government enacted a law establishing its National Solid Waste Policy (PNRS in
Portuguese). This law established the instruments, objectives and guidelines related to the integrated
management and solid waste management that municipalities of the country should follow. Among
the established guidelines, it was defined that the environmentally adequate destination of MSW
should include, in order of priority; reuse, recycling, composting, energy recovery, and finally
environmentally appropriate final disposal in sanitary landfills; however, concerning reuse and
recycling stages only 3% of MSW is recycled [1]. Regarding the other alternatives little has been done.
Therefore, the rest of the MSW is sent to its final destination, and in this way, 58.4% is allocated in
sanitary landfills, 24.2% in controlled landfills and 17.4% in dumps [2]. These numbers represent a
problem for the Brazilian government, as PNRS also instituted that by 2014 controlled landfills and
dumps should be closed, and according to [2] there is still this type of incorrect dispositions that is
practiced along the country. In addition, growing generation of waste is compromising the useful life
of the sanitary landfills of the 2244 cities that use this alternative as final disposal.
In this scenario, energy recovery from MSW through thermal treatment can be highlighted as a viable
alternative, since this technology can reduce approximately 90% of the MSW volume that is deposited
in sanitary landfills. In addition, considering the high MSW energy potential, gasification technologies
can be used to produce fuels, electricity or heat that can be sold and become process revenues. Among
the thermal treatments used for energy recovery from MSW, gasification is an emerging,
environmentally and economically viable technology[3]. Gasification is a thermochemical process that
transforms MSW into a combustible gas, called syngas. Recent interest in gasification process is due
to the fact that it provides an environmentally appropriate MSW destination compared to the
incineration due to the limited formation of dioxins and furans, nitrous and sulphur oxides and the
production of ash that in some cases are produced in a less hazardous form , such as vitrified slag [4]–
[6]. A disadvantage of gasification is that the fuel to be gasified needs a pretreatment to produce a
refuse-derived fuel (RDF) that meets the reactor operating parameters, such as particle size and
moisture; this pretreatment has high costs.
Because of the diverse advantages, in recent years, several authors have studied the MSW gasification
process in order to analyse its feasibility in MSW energy recovery. [7] analysed the gasification of
biomass, MSW and RDF in a newly patented 3-stage fixed bed reactor, the innovation of this reactor
is based on the rotation configuration of 4 fans, which create a new gas flow management model
between the 3 main process stages: pyrolysis, combustion and gasification. The authors concluded
that the reactor could achieve a safe operation at an industrial level, and, at the same time producing
syngas without harmful components, achieving an electrical efficiency of 30% and minimal
environmental impacts below that of those established by the European Union for MSW incineration
plants (Directive 2000/76/EC).
In the study accomplished by [8], the technical-economic feasibility of MSW gasification for Brazilian
cities was analyzed, considering three different economic scenarios using an annual interest rate, of
10.6% in the first scenario, 7.5% in the second and 15% in the third. The concept of net present value
was used to evaluate the economic feasibility, which was positive for cities with more than 60.714
inhabitants for the first scenario, 34.203 for the second and 259.845 for the third. The authors
concluded that the economic viability increases with the installation of larger units, which generate
lower specific costs and higher revenues.
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Considering that the most of the studies reviewed for this work do not analyse different commercial
technologies developed for this process, as well as different arrangements for syngas use, the aim of
this study is to compare three different MSW gasification technologies, TPS, Carbogas and Energos
from energy point of view, for electricity generation in Santo André city, Brazil. The syngas produced
is recovered using two configurations, which are configuration I: internal combustion engine (ICE) and
configuration II: simple Rankine cycle.
TPS Termiska Processer AB supplies a technology, which uses two circulating fluidized bed reactors
(CFB); in the first reactor, the gasification of the RDF occurs at 850 °C, the produced syngas is injected
into the second reactor where the syngas catalytic cracking is carried out at 900 °C by the addition of
dolomite, eliminating certain contaminants. The maximum capacity of this gasifier is 693.5 tonnes d-1
of RDF[9]. Carbogas technology uses an internal circulating fluidized bed reactor (ICFB) where RDF
gasification occurs at 850 °C, achieving a cold efficiency of 75%; in this process limestone is added to
reduce the sulfur content present in the syngas. It has a capacity of 207 tonnes d-1 of RDF [10]. Energos
technology uses two-chamber reactor with the gasification occurring at 900 °C in the first chamber,
which achieves a cold efficiency of 65%; this is a moving grate reactor. The produced syngas follows
to the second chamber where the combustion happens; in this chamber, exhaust gases are
recirculated at a rate of 30%. It has a capacity of 132 tonnes d-1 of RDF.

The composition of the MSW of Santo André city in Brazil was assumed from [11]. Table 1 presents a
simplified MSW gravimetric composition.
Gravimetric Analysis % (wet basis)

Organic matter 50.81
Paper 13.49
Plastic 15.27
Textile 6.20
Rubber 0.93
Wood 0.87
Glass 1.15
Metal 0.51
Aluminum 1.77
Others 9
Source: [11]
Table 1. Simplified gravimetric analysis of MSW - Santo André
From the gravimetric analyses showed in Table 1 and a typical composition given in [12], an
elemental and proximate analysis was calculated for the MSW of Santo André (Table 2). Simulations
were performed using Thermoflex® software [13]. The amount of MSW assumed for calculations was
26.44 tonnes h-1 [14], which corresponds to the mean value of the MSW generated in Santo André
city in 2014. Owing to the high content of recyclable material in the MSW (Table 1), it was assumed
that 20% of these valuable fractions (such as plastics, glass and metals) is recycled; also was assumed
that the population at home does this recycling. Then for the simulation, the amount of MSW
available for the process was 24.74 tonnes h-1 with a moisture content of 39.74% (w.b), this value
was adopted in all the cases simulated. Because of the MSW high moisture content and its particle
size variability, a MSW pre-treatment is required to produce a RDF that complies with the
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characteristics of gasification process. In the Thermoflex® software, the gasifier has been configured
to use as input the operating parameters of each technology, such as, equivalence ratio (ER), cold
efficiency, real air-fuel ratio, operating temperature and pressure, as well as fuel composition and
carbon conversion rate. The software uses the chemical equilibrium model to determined syngas
composition at constant temperature by the equilibrium reactions using the principles of mass
conservation and minimizing the Gibbs free energy [15].
Elemental analysis % (wet basis) Proximate analysis % (wet basis)

Carbon 27.36 Moisture 39.74
Hydrogen 3.48 Volatile matter 45.89
Oxygen 17.34 Fixed carbon 5.13
Nitrogen 0.6 LHV (kJ kg-1) 9701
Sulphur 0.13
Ash 11.36
LHV: lower heating value
Table 2. Elemental and approximate analysis of MSW - Santo André
Gasification technology - Configuration I (Figure 1): the MSW are fed to the plant (Device A), the first
stage of pre-treatment consists of shredding (B) where a mass conservation efficiency of 98% was
assumed. The second stage is the magnetic separation (C); it was assumed that 95% of ferrous fraction
was removed. The last stage is the MSW drying (D) using the exhaust gases exiting the engines (H).
Device E represents the gasification process of each technology adjusted to simulate each gasifier with
their respective operating parameters. Air used as gasifying agent is preheated to 150 °C in the syngas
cooling system (F). Syngas produced passes through purification system (G) used to achieve engines
operating conditions. Subsequently the syngas is burnt in an internal combustion engines (H) to
generate electricity. Drying system gases pass through a cleaning system; filter (K), before being sent
to the environment (L). This configuration assumed internal combustion engines. It was assumed that
engines used in simulations are from General Electric (GE) type JEN JMS620GS-NLC, and according to
their characteristics, these can use fuels with low calorific value, such as syngas, achieving efficiencies
up to 36-37% [16].
A Fuel Feed (MSW)

B Shredder
C Magnetic separator
D Fuel Dryer
E Gasifier
F Air Heat exchanger
G Scrubber
H Engines
I - R Air inlet source
J Fan
K Exhaust gases Filter
L Stack
M Bottom ash disposal
N Coolant water disposal
O – P Water inlet source
Q Scrubber Water
Figure 1. Gasification technology and configuration I: ICE
452
Gasification technology - configuration II, (Figure 2) In this structure the pre-treatment stages (B,C,D)
are the same as those described previously (Figure 1); however, air is preheated at 500 °C in the syngas
cooling system (F) to be used in the drying stage (D). Syngas passes through a second cooling system
(G) where air is preheated to 150 °C; this air is used as gasifying agent in the gasifier (E) and as
combustion air in the boiler (I). A syngas purification system was used to prevent corrosion and fouling
in boiler pipes due to syngas contaminants, reaching higher temperatures and pressures of steam at
the boiler (I).Produced syngas is burnt in a gas boiler (I) to generate superheated steam, which is used
in a steam cycle to generate electricity. Drying system gases pass through a cleaning system composed
of the filter (X) before being sent to the environment (Y).
T Fuel compressor (Syngas)

U Bottom ash disposal
V – C1 Air inlet source
W – B1 Fan
X Exhaust gases Filter
Y Stack
Z Exhaust gases mixer
A1 Air mixer
D1 Water source
E1 Scrubber Water disposal
A Fuel Feed (MSW)
B Shredder
D Fuel Dryer
E Gasifier
F - G Syngas/Air Heat exchanger
H Scrubber
I Thermo Boiler
J High pressure steam turbine
K Low pressure steam turbine
L Water-cooled Condenser
M Deaerator
N-P Pump
O Makeup water
Q Water-cooled Condenser
R Steam splitter
S Valve
Figure 2. Gasification technology and configuration II: Power steam cycle
Energos technology - configuration II, (Figure 3). In this structure the pre-treatment stages (B,C,D) are
the same as those described previously (Figure 1), however in stage B a mass conservation efficiency
of 99% was assumed, due to this reactor accepts larger particle sizes when compared to the other.
The drying stage (D) uses the exhaust gases exiting the boiler (I). Air at 24 °C is used as gasifying agent
in the gasifier (E). Produced syngas is burnt in a gas boiler (I) where 30% of exhaust gases are
recirculated (H). Superheated steam produced is used in a steam cycle to generated electricity. Drying
system gases pass through a cleaning system, filter (X), before being sent to the environment (Y). The
technology developed by Energos is a gasifier and combustor unit; therefore, the syngas can only be
used in this way, without a syngas cleaning system.
Figure 2 and 3 show the same configuration of power steam cycle. In the gas boiler (I), used to burn
the syngas, the conditions of the superheated steam (pressure and temperature) are supplied as input
data, as well as the excess air rate of 10% and the thermal efficiency of 85%. Regarding Figure 2,
superheated steam produced (I) goes to the high-pressure steam turbine (J) where it undergoes an
expansion to 1.6 bar. Part of the exhaust steam (outlet of turbine at 1.6 bar) is sent to the deaerator
(M), while the remaining flow is directed to the low-pressure turbine (K). For both turbines, an
isentropic efficiency of 85% was adopted. After the saturated steam-liquid mixture is sent to the
condenser (L), which operates at 6kPa. Afterwards, the liquid is pumped (N) and mixed with the make-
453
up water (O), and goes to the deaerator (M). The operating pressure of this deaerator was set at 1.6
bar. Water exits the deaerator as saturated liquid. Finally, the saturated liquid is pumped until its
pressure reaches the operating pressure of the boiler (I). For all devices, the properties of inlet and
outlet streams were determined. The mass and energy balances, as well as the thermal efficiency,
were evaluated using Thermoflex® software [13].
K Low pressure steam turbine

L Water-cooled Condenser
M Deaerator
N-P Pump
O Makeup water
Q Water-cooled Condenser
R Steam splitter
S Valve
T Fuel compressor (Syngas)
V Exhaust gases and air mixer
W Bottom ash disposal
X Exhaust gases Filter
Y Stack
A Fuel Feed (MSW)

B Shredder
D Fuel Dryer
E Gasifier
F Fan
G - U Air inlet source
H Exhaust gases mixer
I Thermo Boiler
J High pressure steam turbine
Figure 3. Energos technology and configuration II: Power Steam Cycle
The assumptions and considerations used to accomplish the thermodynamic modelling are presented
as follows: analysis is performed considering steady-state conditions, pressure drop due to the friction
is negligible in heat exchangers, direct heat transfer from the system components to the surrounding
is negligible, effectiveness of the heat exchangers is 80%, the effectiveness of the electric generator is
95%, the temperature of cooling water at condenser inlet is equal to 19 °C and has a 5 °C increase at
the exit, and kinetic and potential energy variations through the devices are neglected. The values
assumed in the simulations, corresponding to the cases mentioned below, are presented in Table 3.
Case a.I: TPS technology plus configuration I (ICE)
Case a.II: TPS technology plus configuration II (Power Steam Cycle)
Case b.I: Carbogas technology plus configuration I (ICE)
Case b.II: Carbogas technology plus Configuration II (Power Steam Cycle)
Case c.: Energos techonology plus configuration II (Power Steam Cycle)
454
Case a.I Case a.II Case b.I Case b.II Case c.

Parameters
TPS TPS Carbogas Carbogas Energos
Dryer
RDF flow rate at dryer inlet 24.15 t h-1 24.15 t h-1 24.39 t h-1
RDF moisture at gasifier inlet 7.5% a 12% f 15% h
GASIFIER
Pressure atmosphere atmosphere atmosphere
Temperature 850 °C 850 °C 900 °C
Equivalence Ratio ER 0.33 a 0.37 a 0.5 i
Real air-fuel ratio 1.8 1.92 2.51
Cold-gas efficiency 50% a 75% f 65.2 j
Carbon conversion efficiency 68% 94.5% 97%
Gasifying agent temperature 150 °C 150 °C 24°C
SYNGAS CLEANING SYSTEM
Relative humidity at the outlet 30% - 30% - -
of scrubber (G-H)b
Internal Combustion Engines
ICE efficiencyc
36-37% - 36 - 37% - -
Engine quantity 6 - 9 - -
BOILER
Air Excess g - 10 % - 10 % 10 %
Boiler efficiency d - 85 % - 85 % 85 %
Superheated steam - 530 °C - 530 °C 440 °C
temperature
Superheated steam pressure - 120 bar - 120 bar 60 bar
RANKINE CYCLE e
Turbine efficiency - 85% - 85% 85%
Deaerator pressure - 1.6 bar - 1.6 bar 1.6 bar
Condenser pressure - 0.1 bar - 0.1 bar 0.1 bar
Pumps isentropic efficiency - 75 % - 75 % 75 %
a
[16] [17] [18] [19] [20] [10] [19] [21] [22] [23]
b c d e f g h i j
Table 3. Simulation parameters used for each technology and configuration

A comparison between the values obtained in the simulation of each gasifier and data found in the
literature was made. Table 4 shows the PCI values and composition of the syngas obtained in the
simulation and the data found in the literature of each technology. For modeling and simulation of
gasification process, certain parameters such as carbon conversion efficiency and exit temperature of
ashes at bottom of the reactor were adjusted to achieve cold-gas efficiency of each gasifier according
to literature data available of each technology [10], [23], [24].
By maintaining compatibility with the cold-gas efficiency literature data, the study attempts to
represent consistently the energy conversion process, as well as to estimate properly the potential of
power generation in the subsequent process of energy utilization of the syngas. For this reason, there
may be some discrepancies between the values obtained in the simulation and those found in the
455
literature. In Table 4 it can be observed that for Carbogas and Energos technologies LHV values are
close to each those reported in literature with a margin of error of less than 10%. However, the
difference in LHV values was excessive for TPS technology, approximately 44%, which suggests that
cold-gas efficiency and LHV data reported to this technology are inconsistent.
LHV Composition (% v/v)

Technology
(MJ Nm3) CO CH4 H2 H 2O N2 CO2
TPS literature a
6.6 6.5 2.9 12.10 16.5 46.4 11.4
TPS simulation 3.64 15.18 - 14.8 15.46 46.5 7.44
Carbogas literature b 4.85 18 3 14 6 49 10
Carbogas simulation 4.45 19.11 0.0013 18.9 9.3 44.42 7.68
Energos literature c 3.52 14 4 5 - - 21
Energos simulation 3.16 14.18 - 12.09 13.43 50.59 9.05
a
[24]b[10]c[23]
Table 4. Syngas simulation composition
Figure 4.a shows the net power obtained for the different technologies. It is possible to observe the
net power higher values in cases using engines, because engines offer higher operating efficiency. Net
power difference between TPS and Carbogas technologies is justified by the fact that gasifiers operate
with cold-gas efficiencies of 50% and 75% respectively. For cases using configuration II: Rankine Cycle,
the differences in net power results are due to the steam production, thus, TPS produces 39.63 (t h-1),
Carbogas 58.63 (t h-1) and Energos 70.3 (t h-1). This can be explained because each technology has a
different amount of RDF, produced in pre-treatment stages, used in syngas production that acts
directly in Steam production (Appendix A).
a. Net power generated by each case b. Thermal efficiency of each case

Figure 4. Net power produced and thermal efficiency
Figure 4.b shows the thermal efficiency of electricity production of each case. Compared to the cases
using configuration I, Carbogas technology (b.I) has the highest thermal efficiency (30%), due to the
cold-gas efficiency of the gasifier, which allows syngas production with better LHV, as well as the
available syngas flow (Appendix A). According to the literature, gasification plants which use
configuration II: Rankine Cycle for energy use of syngas achieve efficiencies between 17% and 28%
[10], [25], and using configuration I: ICE achieves efficiencies between 25% and 37% [26]. Thus,
configurations studied in this work achieve efficiencies close to these values (Figure 4.b).
456
4. CONCLUSIONS
Considering the values used in the simulations, it was possible to indicate that the configurations that
present better performance have electric energy generation efficiencies in the range of 25% to 30% (
For Carbogas case b.I was 30% and for Carbogas case b.II was 25%, while for Energos case c, it was
25%). Comparing the conversion technologies using gasification studied in this work (TPS, Carbogas
and Energos) with others such as incinerations, mainly mass burning, which achieves efficiencies of
less than 28% [20], [25], [27], it is possible to suggested that gasification can be energy competitive
with incineration.
5. Acknowledgement
The authors disclosed receipt of the following financial support for the research, authorship, and/or
publication of this article: The authors would like to thank the Program of Research and Development
of the Electricity Sector Regulated by ANEEL and the financial support provided by PETROBRAS, Brazil,
CAPES, Brazil,[Process:306303/2014-0], CNPq Brazil [Process 306303/2014-0] and UFABC, Brazil.
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Appendix A
Case a.I Case a.II Case b.I Case b.II Case c.
TPS TPS Carbogas Carbogas Energos
RDF production line
MSW mass flow rate (t h-1) 24.74 24.74 24.74 24.74 24.74
MSW LHV at input (kJ kg-1) 9200 9200 9200 9200 9200
MSW thermal input (MW) 63.22 63.22 63.22 63.22 63.22
Energy consumption of RDF production line
Devices (kW) 147.2 147.2 147.2 147.2 86.2
Drying (kW) 6125 6122 5604 5688 5263
Line specific energy consumption (kWh tMSW-1) 253.5 253.5 232.5 235.8 216.2
RDF mass flow rate produced (t h-1) 15.52 15.52 16.3 16.3 17.06
RDF LHV (w.b) (kJ kg-1) 15,649 15,649 14,785 14,785 14,189
RDF thermal energy a (MW) 67.46 67.46 66.95 66.95 67.25
GASIFICATION
Syngas mass flow rate (t h-1) 38.54 38.54 44.41 44.41 56.77
Cold-gas efficiency (%) 50 50 75 75 65
Syngas density (kg Nm3-1) 1.098 1.098 1.04 1.04 1.13
Syngas LHV (kJ kg-1) 3313 3313 4268 4268 2780
Gasifier energy consumption (kW) 342 342 359.3 359.3 375.9
Gasifier specific consumption (kWh tMSW-1) 13.82 13.82 14.52 14.52 15.19
ELECTRICAL ENERGY PRODUCTION
Steam flow rate produced (t h-1) - 39.63 - 58.63 70.3
Steam specific flow rate (tsteam tMSW-1) - 1.6 - 2.37 2.84
Electrical power output (kW) 12,850 12,048 19,480 17,872 18,308
Devices energy consumption b (kW) 316.6 1,136.6 398.2 1,654.2 2,426.7
Devices specific consumption (kWh tMSW-1) 12.8 45.94 16.1 66.9 98.1
Net power (MW) 12.04 10.42 18.56 15.7 15.4
Thermal efficiency (%) 26.14 22.62 30.15 25.5 25.46
Specific net power (kWh tMSW-1) 486.83 421.27 750.82 635.06 623.25
a difference between MSW and RDF energy is due to the energy transfer from the gases to dry the fuel.
b Includes syngas cleaning system devices.
Table 5. Simulation results
458
A STUDY ON SYNGAS ANALYSIS OF HIGH IRON CONTENT INDUSTRIAL SLUDGE BY

FLUIDIZED GASIFICATION PROCESS
Y.T. KUO1
1 AX group, Taipei, Taiwan.
Abstract
The short of land and raising the concept of environmental protection. Many studies are developing
and improving waste treatment technologies to replace the traditional landfilling. The thermal
chemical process such as pyrolysis, gasification or combustion is potential candidates, which can
efficiently reduce the waste by utilizing wastes’ own energy. However, the traditional incineration
process has a very low energy efficiency and side products such as high concentration of NOx in flue
gas and need a serious air pollution control equipment [1]. Many kinds of research are conducting
experiments on the fluidized gasification process, which has advantages of reducing air pollutions
and contamination of soil and water. The high efficiency for waste used as a fuel for power
generation is one of the benefits to develop gasification technology [2]. The study aims to reveal the
relativity of gasification temperature and the effect of reaction between bed material and industrial
sludge to the composition of syngas. Figure 1 shows the aggregation condition of bed materials after
gasification experiments at different temperatures. Table 1 shows that the comprising of the
industrial sludge. Table 2 shows the concentration of H2, CO2, CO, CH4 and, CnHm. The result shows
the temperature is the most impact factor contribute to the aggregation phenomenon. And the XRF
(X-ray Fluorescence Spectrometer) shows that the high content of iron oxide may cause the
aggregation of bed material at a temperature > 850 oC. Even though in the high gasification
temperature could increase tar content and improving the gas yield [3], the risk of aggregation of
bed material is also highly increased. The results can provide the operating parameters and a
reference for the future industrial sludge gasification system design.
Gasification Temperature (oC) 850 760
Feeding inlet condition
Figure 1 condition of feeding inlet
Table 1 XRF analysis of industrial sludge
Composition Na2O MgO Al2O3 SiO2 P2O5 SO3 Cl K2O CaO Cr2O3 Fe2O3
Mass % NA 0.61 8.68 13.25 12.30 5.23 1.29 0.43 18.68 14.60 80.90
459
Table 2 syngas composition at different gasification temperature
Gasification temperature oC Syngas composition vol.%
CO2 H2 CO CH4 O2 N2 *CnHm
850 16.06 3.83 8.69 1.71 1.11 66.28 2.31
760
14.74 1.38 5.48 0.82 3.28 72.94 1.36
References
[1] Thomsen TP, Hauggaard-Nielsen H, Gobel B, Stoholm P, Ahrenfeldt J, Henriksen UB, et al. Low temperature
circulating fluidized bed gasification and co-gasification of municipal sewage sludge. Part 2: Evaluation of ash
materials as phosphorus fertilizer. Waste Manag. 2017;66:145-54.
[2] Zhu J-g, Yao Y, Lu Q-g, Gao M, Ouyang Z-q. Experimental investigation of gasification and incineration characteristics
of dried sewage sludge in a circulating fluidized bed. Fuel. 2015;150:441-7.
[3] Gil-Lalaguna N, Sánchez JL, Murillo MB, Rodríguez E, Gea G. Air–steam gasification of sewage sludge in a fluidized
bed. Influence of some operating conditions. Chemical Engineering Journal. 2014;248:373-82.
460
CO-GASIFICATION OF AGRICULTURAL RESIDUES
M.H. RADANIELINA1, A. EPHRAIM2, D. PHAM MINH2, A. NZIHOU2, J.P. PRAENE3, D. MORAU3, M.S.
RAKOTOMALALA1, H.T. RAKOTONDRAMIARANA1
1
Institute for the Management of Energy (IME), University of Antananarivo PO. Box 566,
Antananarivo 101, Madagascar.
2
Centre RAPSODEE, CNRS UMR 5302, Mines Albi, Campus Jarlard F-81013 Albi Cedex 09, France.
3
PIMENT laboratory, University of Reunion Island, 117 rue du Général Ailleret 97430, Le Tampon,
France.
Abstract
Co-gasification is an efficient alternative for energy conversion and supply in developing

countries like Madagascar, especially in rural and peri-urban areas where biomass feedstock is
widely available. Nevertheless, different biomass types may have different properties, which can
disrupt the continuous operation of the gasifier. The present work aims at analyzing the thermal
decomposition behavior of two types of biomass residues namely rice husk (RH) and rice straw
(RS) which can be used in a co-gasification system. For this purpose, chemical characterization
has been carried out in order to determine the organic and inorganic compounds within these
residues [1]. Next, thermal gravimetric (TG) and differential scanning calorimetry (DSC) analyses
will be conducted on each biomass type and their mixtures in order to study the degradation
behavior of major components (hemicellulose, cellulose and lignin) and the potential
interactions under nitrogen and air atmosphere [2]. Furthermore, pyro-gasification experiments
of these residues will be performed in a bench-scale fixed bed gasifier with the aim to study the
influence of biomass feedstock and operating conditions on the product (syngas, char and tar)
yields and gas calorific values.
References
[1] Y. D. Singh, P. Mahanta, and U. Bora, “Comprehensive characterization of lignocellulosic biomass through
proximate, ultimate and compositional analysis for bioenergy production,” Renew. Energy, vol. 103, pp. 490–
500, 2017.
[2] N. Worasuwannarak, T. Sonobe, and W. Tanthapanichakoon, “Pyrolysis behaviors of rice straw, rice husk, and
corncob by TG-MS technique,” J. Anal. Appl. Pyrolysis, vol. 78, no. 2, pp. 265–271, 2007.
461
EVOLUTION OF ENVIRONMENT PERFORMANCE OF INTEGRATED MUNICIPAL SOLID

WASTE MANAGEMENT SYSTEM IN HANGZHOU, CHINA
ZHAOZHI ZHOU 1, YUANJUN TANG1, YONG CHI1, MINGJIANG NI1

1 State Key Laboratory of Clean Energy Utilisation, Zhejiang University, Hangzhou, China.
Abstract
The continuously increasing amount of municipal solid waste (MSW) gets a lot of attention, and
MSW management system in Hangzhou changes a lot to face the challenge. During the last 10 years,
new MSW incineration plant was built, source-separated MSW collection was launched, food waste
was separated treated [1]. The aim of this study is to present the evolution of environment
performance of MSW management system from 2007 to 2016 in Hangzhou, China. This study use life
cycle assessment to evaluate the environmental impacts: global warming potential (GWP),
acidification potential (AP), nutrient enrichment potential (NEP), photochemical oxidant potential
(POP).
The system boundary is present in Fig 1. According to Fig 1, The system is divided into three periods:
(a) during 2007 and 2009, the MSW was mixedly collected and was sent for landfill or incineration;
(b) during 2010 and 2013, part of food waste was separately collected and transported for separate
landfill, while the rest mixed waste was sent for landfill or incineration; (c) during 2014 and 2016, for
the separate food waste, 73 thousand tonnes of food waste was treated by anaerobic digestion (36.5
thousand tonnes in 2014), and the rest was by separate landfill. [2]
The results show that incineration has the most positive environment impacts and the
environmental performance of MSW management system improves with the MSW incineration rate.
Source-separated MSW collection also benefits the overall environment impacts because of the
MSW with higher heating value and food waste separated treatment. Fig 2 shows the environmental
performance of per MSW treatment in Hangzhou during 2007 and 2016. We find that the MSW
management system in 2010 has the best environmental performance and its weighted
environmental impact is 0.035 Pt/t-MSW; It is because of the source-separated MSW collection and
highest MSW incineration rate. Moreover, anaerobic digestion (AD), with good environmental
performance, should account for bigger percentages in foot waste treatment in the future.
462
MSW generation
Materials
Mixed collection Separated collection

Energy
Emissions Other waste Food waste
Separated Anaerobic
Landfill Incineration
landfill digestion
(a) 2007-2009
(b) 2010-2013
(c) 2014-2016
Fig 1. System boundary of the study.
Fig 2. Environmental performance of MSW management system during 2007 and 2016 (1 tonnes).
References
[1] Dong J, Ni M, Chi Y, Zou D, Fu C. Life cycle and economic assessment of source-separated MSW collection with
regard to greenhouse gas emissions: a case study in China. Environ Sci Pollut Res Int. 2013;20:5512-24.
[2] Hangzhou Municipal Solid Waste Disposal Supervision Center. Hangzhou municipal solid waste physical property
analysis and disposal method. Hangzhou: Municipal Solid Waste Disposal Supervision Center; 2017..
463
UNDERSTANDING FAT, OIL AND GREASE MANAGEMENT IN FOOD SERVICE

ESTABLISHMENTS TO HELP PREVENTING SEWERS’ BLOCKAGES
A. CERMAKOVA 1, P. JEFFREY1, B. JEFFERSON1, R. VILLA1

1 Cranfield University, Cranfield, UK.
Abstract
Fat, oils and grease (FOG) rich wastewaters produced from food processing and cooking activities of
private dwellings and commercial food service establishments (FSEs) are accountable for 80% of the
blockages and overflows in the sewerage system in the UK (Water UK, 2017). FOG deposits are not
just a UK challenge but a more global problem (He, 2017). FOG emissions can be mitigated and
controlled using different technologies (biological and/or physico-chemical) at source or in-sewers.
However, pivotal to all mitigating systems is: (1) awareness of the cause of the problem; (2) kitchen
good management and practice; and (3) staff training. Aim of this work was to assess existing FOG
management practices in commercial premises and to understand restaurants managers’ awareness
of the FOG problem.
Short, face-to-face, semi-structured interviews were used for this survey. Respondents targeted in
this study were people responsible for the kitchen operation, such as restaurant’s managers,
selected in a non-probability convenience sampling
The results show that a lack of at source control was observed in 62% of the 39 FSEs interviewed. In
addition, there was inappropriate maintenance of cooking devices (such as fryers, grills, extraction
hoods) considered the main creator for FOG pollution. Finally, 77% of the interviewees
acknowledged the risk associated with FOG material discharged down the drain but didn’t link it to
kitchen management.
(a) (b)
Figure 1: (a) Cooking devices identified as potentially significant sources of FOG–rich wastewater and their cleaning practice;
(b) number of cooking devices found in the interviewed kitchens
Production linked to kitchen management is not well understood by health inspectors and FSE
managers. The results indicate that ‘technical’ FOG prevention and mitigation needs to be
accompanied trough better training of FSEs staff and environmental health inspectors about FOG
pollution and its impact.
References
[1] He X., de los Reyes F.L. and Ducoste J. A critical review of fat, oil and grease (FOG) in sewer collection systems:
challenges and control. Critical Rev. Env. Sci. Technol. (2017)
[2] Water UK, 2017. https://www.water.org.uk/policy/environment/waste-and-wastewater/fats-oils-and-grease,
accessed on 12th October 2017
464
EVALUATION OF CYNARA CARDUNCULUS FLOWERS ECOTYPES (ALENTEJO,

PORTUGAL) FOR CHEESEMAKING
S. GOMES1, M.J. TRIGO2, A.T. BELO1, N.B. ALVARENGA2, P. LAGE3, C. PINHEIRO4, E. MACHADO5, M.F.
DUARTE4,6, A.P.L. MARTINS2,
1 UEISSPA, INIAV, Polo de Santarém, Vale de Santarém, Portugal
2 UTI, INIAV, Quinta do Marquês, Oeiras, Portugal
3 ESA, I. P. Beja, Beja, Portugal
4 ICAM, ECT - Universidade de Évora, Évora, Portugal
5 ECT - Universidade de Évora, Évora, Portugal
6 CEBAL, Beja, Portugal
Abstract
The use of the cardoon Cynara cardunculus L. as coagulant for cheesemaking is mandatory in
certain portuguese cheeses benefiting from the status of Protected Designation of Origin (PDO).
However the plant continues to grow spontaneously, and the flower picking is free and it is important
to value it as a crop. The aim of this work is to evaluate and compare the potential of cardoon flower
populations from the Alentejo region in Portugal, for traditional cheese production.
After traditional-type coagulant extract preparation (mortar maceration of flower pistils) with
acetate buffer pH 5.5, the extract milk clotting activity was evaluated [1]. The enzymatic coagulation
evolution for each ecotype flower extract, was assessed with the Optigraph (Alliance, France),
according to previous work [2]. The effect on the cheese making potential yield was evaluated
according to Remeuf et al. (1989) [3] and the non-specific proteolytic activity was monitored by NPN
(nitrogen fraction soluble in 12% trichloroacetic acid) [4] release after 1 and 2 hours in milk coagulation
at 32ºC.
Principal componen analysis was used to analyze the similarity of Cynara cardunculus ecotypes
based on the different criteria, allowing also to an interesting speculation about the cardoon natural
variability, which can eventually lead to clarify the influence in cheese production and also to
promising innovation within traditional products.
Aknowledgements: This work is supported by the Program “Alentejo 2020”, through the
European Fund for Regional Development under the scope of “ValBioTecCynara – Economic
Valorization of Cardoon (Cynara cardunculus): Study of natural variability and biotechnological
applications.”.
References
[1] International Standard IDF 199/ISO 23058. Milk and milk products – Ovine and caprine rennets – Determination of
total milk-clotting activity. ISO, Geneva, and IDF, Brussels (2006)
[2] Alves S.M.P., Martins A.P.L., Mourato M.P., Vasconcelos M.M. and Fontes A.M.L.: Effect of technological parameters
on coagulation properties of sheep milk. In: Proceedings of the International Symposium "The Future of the Sheep and
Goat Dairy Sectors", FIL/IDF-CIHEAM, Zaragoza (Spain), 28-30 October 2004, p. 279-280. (2004)
[3] Remeuf F., Lenoir J. and Duby C.: Étude des relations entre les caractéristiques physico-chimiques des laits de chèvre
et leur aptitude à la coagulation par la présure. In: Lait, 69, p. 499-518. (1989)
[4] International Standard IDF 20-4/ISO 8968-4. Milk – Determination of nitrogen content - Part 4: Determination of non-
protein-nitrogen content. ISO, Geneva and IDF, Brussels (2001)
465
THE IMPACT OF LAND USE/LAND COVER CHANGE ON ECOSYSTEM SERVICES IN THE

THREE GORGES RESERVOIR
JINGJING XIA1, HAN XIA1, HONG PENG2, WANSHUN ZHANG1

1 School of Resource and Environmental Sciences, Wuhan University, Wuhan 430079, PR China.
2 School of Water Resources and Hydropower Engineering, Wuhan University, Wuhan 430072, PR
China.
Abstract
Ecosystems provide a wide range of benefits for generating a range of goods and services to human
well-being. Land use/land cover change (LU/LC) was identified as one important driver of change of
ecosystems and their services (Tolessa et al., 2017). The Three Gorges Reservoir (TGR), the world's
largest hydropower project, has experienced the initial stage (begun in June 2003 with the water
level of 135 m), the transitional stage (begun in October 2006 with the water level of 156 m), the
normal stage (begun in October 2008 with the water level of 175 m) (Gao et al., 2016). Together with
growing populations and rapid industrialization, LU/LC has greatly changed in the TGR. Assessing the
impact of land use/land cover change on ecosystem services in the TGR is vital to support decision-
making processes. This study analyzes LU/LC dynamics over the different operation stage and
present situation (2000, 2005, 2010, 2015) to assess its impact on ecosystem services. Ecosystem
Service Values (ESV) was also determined through LU/LC analysis and a data base of biome
equivalents for land use categories (Costanza et al., 1997). LU/LC analysis showed that forest cover
reduced, settlement and water area increased. The study indicates that how ecosystem service
changed through human activities on spatial and temporal scales, and what should be protected and
restored to increase ecosystem services in the TGR. We believe that the results obtained can provide
insights into quantifying the link between ecosystem services and human well-being.
References
[1] Tolessa T, Senbeta F, Kidane M: The impact of land use/land cover change on ecosystem services in the central
highlands of Ethiopia[J]. Ecosystem Services, 23:47-54 (2017).
[2] Gao Q, Li Y, Cheng Q, et al: Analysis and assessment of the nutrients, biochemical indexes and heavy metals in the
Three Gorges Reservoir, China, from 2008 to 2013[J]. Water Research, 92:262, (2016).
[3] Costanza R, D'Arge R, Groot R D, et al: The value of the world's ecosystem services and natural capital [J]. Nature,
1998, 25(1):3-15, (1998).
466
ADSORPTION OF HEAVY METALS BY MICROWAVE-ASSISTED
HYDROTHERMAL MODIFIED MSWI FLY ASH
Q. Qiu, X. Jiang*, S. Zhang, Sh. Lu, M. Ni, Y. Chi, J. Yan

(State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power
Engineering, Zhejiang University, Hangzhou, China)
Keywords: adsorption; MSWI fly ash; hydrothermal treatment; microwave
Abstract
- Purpose: In this work, microwave-assisted hydrothermal was introduced to
modify the municipal solid waste incineration (MSWI) fly ash.
- Methods: The modified fly ash performed a good adsorption capacity of several
mixed heavy metals (Cd, Cu, Mn, Ni, Pb and Zn) at the condition of 1 mol/L
Na2HPO4, 3mL/g, 200 ℃ and 30 min. X-ray diffraction results revealed the
formation of analogous zeolite crystals in the modified MSWI fly ash. The pore
size distribution of raw and modified fly ash was detected.
- Results: The cation exchange capacity (CEC) of fly ash increased from 0.065 to
0.948 meq/g after hydrothermal treatment, about 15 times rising of adsorption
capacity. It revealed that the pore size of the modified fly ash was larger,
compared to the raw one. To study the adsorption mechanism of the modified fly
ash, the adsorption isotherm and kinetics experiments were conducted. The
experimental products could be well described by Freundlich isotherm equation
and the pseudo second-order kinetics.
- Main conclusions: Therefore it will be a good way to dispose MSWI fly as a kind
of adsorbent.
467
1- INTRODUCTION
Accounting for about 34.3% of total municipal solid waste (MSW) was burned in
2015[1], and it reveals that incineration has been a crucial disposal method in China.
Thus the disposal of MSWI fly ash has been a coming problem, because of its harmful
composition[2-4], such as heavy metals, dioxins, etc. For MSWI fly ash, cement
solidification[5,6], chemical stabilization[7-9] are the main methods of fly ash
disposal. However, the disposal difficulty was increased for the high content of heavy
metals in MSWI fly ash, especially for the recycling utilization.
Recently, synthesizing zeolites[10,11], as well as adsorbents [12-14] by the coal
fly ash has been paid much attention to. Nevertheless, the content of SiO2 and Al2O3
is less in MSWI fly ash[15-17] , compared to the coal fly ash, which is the main
composition of the zeolite formation. Thus the idea of adsorbent synthesis is
proposed in our work, as an alternative. According to literatures, the conventional
way to obtain adsorbent is by using hydrothermal treatment, which needs a long
reaction time (even 24-72 h), and obviously plenty of energy consumption is
needed[18-20,14]. Therefore, large-scale application of zeolite formation has not
been realized.
In this work, microwave was introduced to hydrothermal process to decrease the
disposal time, and the heating time was only 30 minutes. After microwave-assisted
hydrothermal process, zeolite-like production was found from the modified MSWI fly
ash, which provided the possibility of application as adsorbent.
2.1. Materials and devices

The raw fly ash in this work was obtained from a CFB boiler of municipal solid
waste incineration plants in Ningbo city of Zhejiang province (China) and the samples
were collected from a fabric filter. Before experiments and tests, samples were all
dried at 105 ℃ for 24 h. The heavy metal solution (Cu, Cd, Mn, Ni, Pb and Zn) was
prepared by deionized water and their nitrate reagents, which were all of reagent
grade. Physicochemical properties of raw and treated fly ash were detected,
including the major elements composition, mineralogy, distribution of pore size, and
adsorption performance, etc. The devices used were X-ray fluorescence (XRF)
spectrometry (Thermo Fisher, Intelli Power 4200, USA), X-ray diffraction (XRD; Rigaku
Rotaflex, Japan) and laser partical analyzer (Coulter LS-230, US). To get the cation
exchange capacity (CEC) of the raw and modified MSWI fly ash, EPA documents (EPA
9081) was referred to.
2.2 Modified fly ash preparation
The MSWI fly ash samples were treated by the microwave-assisted hydrothermal
process to get zeolite-like materials. The condition was fixed at 200 oC, 30 min. The 1
mol/L Na2HPO4 solution was used at a liquid-solid (solution/fly ash) ratio of 3 ml/g.
The microwave apparatus (Sineo MDS-6, China) was applied in this procedure.
468
2.3 Isotherm adsorption and kinetic adsorption experiments

In the isotherm adsorption experiments, the treated MSWI fly ash samples (0.5 g)
were mixed with the heavy metal solution (50 mL) at the concentration of 100 to 500
mg/L, and the contact time was 2 h. In the kinetic adsorption experiments, the
concentration of solution was fixed at 500 ppm, and the contact time was set at each
5, 10, 15, 20, 30, 60, 90 and 120 min. The heavy metal concentration in the solution
after adsorption was detected by the inductively coupled plasma atomic emission
spectrometry (ICP-AES, ICP-6300, US).
3.1 Characteristics of raw and modified fly ash

The chemical compositions of raw fly ash determined by XRF are listed in Table 1.
The major elements were Ca (20.27%), Si(10.14%), Cl(9.98%), C(7.75%), Al (7.09%),
Fe(4.30%), respectively. The content of SiO2 and Al2O3 was obtained about 20.28%
and 13.39% through calculations, respectively, which was pretty low compared to
coal fly ash[21-23]. Usually, the process of zeolites synthesis consisted of four stages,
dissolution, condensation, nucleation, and crystallisation. Thus the content of
aluminosilicates in the samples was the key component for the zeolite formation.
Due to the low content of Si and Al, the amount of zeolites synthesized will be less
and the production will be not pure. Thus, it is proposed that the modified MSWI fly
ash can be used to adsorb heavy metals in waste solution.
The XRD patterns of the raw and modified MSWI fly ash are shown in Figure 1.
The major components in the raw fly ash were detected, such as SiO2, CaCO3, CaSO4,
MgO, NaCl, Al2O3, Fe2O3, and KCl. After the microwave-assisted hydrothermal
treatment, several zeolitic materials (Ca2Al2SiO7, Ca1.5SiO3.5·H2O, CaAl2SiO8·4H2O)
were found in the modified fly ash. It can be seen that the peaks of NaCl and KCl
were not found in the modified fly ash. At the meanwhile, partial SiO2 and Al2O3 were
destroyed. It was suggested that they were transferred into other calcium-zeolite
compounds. The CEC value of the modified fly ash was about 0.948 meq/g, and
increased about 15 times, compared to the raw MSWI fly ash (0.065 meq/g). The
cation exchange capacity was increased for the reason that some substance with the
adsorption property was formed[24]. Furthermore, it was detected that the value of
BET surface area and pore volume of the modified fly ash were higher than those of
the raw MSWI fly ash. As reported, a large number of rough surfaces, as well as a
porous structure formed was due to the dissolvation of alumina and silica during the
hydrothermal process[25].The properties of raw and the modified fly ash are listed in
Table 2. Therefore, the modified MSWI fly ash can be utilized as adsorbents under
promoted condition.
Element Ca Si C Al Cl Mg Fe Na S P K
Content 20.27 10.14 7.75 7.09 9.98 2.10 4.30 3.02 2.19 1.43 2.36
Table 1: Original content of elements in the MSWI fly ash (%)
469
BET surface area Pore volume CEC

(m2/g) (cm3/g) (meq/g)
Raw fly ash 9.122 2.038 0.065

Modified fly ash 24.003 9.992 0.948
Table 2: The properties of raw MSWI fly ash and modified fly ash
Figure 1: The crystalline phases of raw MSWI fly ash (left) and the modified fly ash
(right)
(a SiO2, b CaCO3, c CaSO4, d MgO, e NaCl, f Al2O3, g Fe2O3, h KCl, 1 Ca2Al2SiO7, 2
Ca1.5SiO3.5·H2O, 3 CaAl2SiO8·4H2O)
3.2 Adsorption isotherm studies

The six-metal solution was adsorbed by 0.2 g modified fly ash and the pH value
was adjusted to 3-4, during the whole process of the experiments. The adsorption
equilibrium concentrations are listed in Table 3. Adsorption isotherm is significant for
the analysis of adsorption behavior[24,26]. Langmuir and Freundlich isotherms were
studied in this work.
The Langmuir isotherm[25] can be expressed as Eq.(1):
Ce/Qe=Ce/Qm+1/(Qm*b) (1)
where, Ce (mg/L) is the equilibrium concentration, Qe (mg/g) is the adsorbed amount,
Qm (mg/g) is monolayer adsorption capacity and b (L/mg) is a binding constant
related to the free energy of adsorption.
The Freundlich isotherm[27] can be written as Eq. (2):
logQ＝log K＋1/n * logCe (2)
where, Qe (mg/g) is the adsorbed amount, Ce (mg/L) is the equilibrium concentration,
K is the indicative of the extent of the adsorption and n is the adsorption intensity.
The model parameters are listed in Table 4. For Cd and Zn ions, the adsorption
was better described by the Langmuir isotherm, which assumes that adsorption
occurs at a specific homogeneous surface of the adsorbent. For other 4 heavy metal
ions, the Freundlich model was better, based on the coefficient R2. Totally, the
difference of R2 was not apparent, so the adsorption effect could not be easily
concluded. It was suggested that both ion exchange and adsorption effect on the
adsorption process[28].
470
Original Equilibrium concentration (ppm)

Concentration
(ppm) Cd Cu Mn Ni Pb Zn
100 67.05 51.92 55.05 62.42 31.35 60.13
200 131.22 105.84 127.19 139.73 78.93 128.57
300 221.63 169.25 212.43 222.28 141.18 209.75
400 315.11 228.42 300.42 308.14 201.44 298.88
500 404.22 293.20 382.55 389.79 261.05 390.04
Table 3: The adsorption results (isotherm)
Langmuir Freundlich
Elemen
b Qm K
t R2 1/n R2
(L/mg) (mg/g) (mg/g)
Cd 0.0057 13.72 0.9512 0.5517 0.3754 0.8862
Cu 0.0015 68.49 0.9597 0.8371 0.1808 0.9972
Mn 0.0068 15.55 0.9792 0.4758 0.6856 0.9897
Ni 0.0040 17.21 0.9643 0.5755 0.3482 0.9983
Pb 0.0066 35.84 0.9549 0.5752 0.9519 0.9971
Zn 0.0060 15.80 0.9950 0.5401 0.4711 0.9628
Table 4: The parameters of adsorption isotherm models
3.3 Adsorption kinetics studies

The adsorption kinetics were observed at different contacting times, and the time
was set at 0, 5, 10, 15, 30, 45, 60, 90, 120 min. The concentration of each heavy
metal cations in solution was 500 mg/L and other conditions were fixed. To
determine the kinetic mechanisms of cations adsorbed by the modified fly ash, two
kinetic models were applied: pseudo-first-order[29] and pseudo-second-order[30].
Their linear equations are presented as Eq. (3) and Eq. (4):
The pseudo-first-order equation:
ln(qe-qt) = ln qe - k1t (3)
The pseudo-second-order equation:
t/qt=1/(k2qe2)+t/qe (4)
where, qt (mg/g) and qe (mg/g) are the amount of the cation adsorbed by the
adsorbent at the time t (min) and at equilibrium, k1 (min-1) and k2 (g·mg-1· min-1) are
the equilibrium rate constant.
The equilibrium concentration of heavy metal cations at different adsorption
times is listed in Table 5. The adsorption capacity of modified MSWI fly ash for each
heavy metals removal from aqueous solutions was in the order of Pb2+ > Cu2+ > Mn2+
≈ Ni2+ ≈Zn2+ > Cd2+. The Kinetics parameters of linearized pseudo-first-order and
pseudo-second-order models are shown in Table 6. In terms of the coefficient R2, it
was shown that pseudo-second-order model was the better to describe the
471
adsorption kinetics, which was coincident with the result in other literatures[23,26].
The amount of the ions removed by the adsorbent at equilibrium in experiments was
in good agreement with the model, and the value of coefficient was over 99%.
Concentration (mg/L)
t (min)
Cd Cu Mn Ni Pb Zn
0 500.0 500.0 500.0 500.0 500.0 500.0
5 424.8 392.3 405.8 427.2 293.1 417.2
10 422.0 368.2 403.9 420.8 281.9 412.9
15 425.9 357.3 406.3 419.6 271.3 415.2
20 420.4 340.1 397.9 408.2 268.4 407.8
30 409.8 323.7 386.1 400.3 265.1 396.8
60 409.1 314.1 388.0 403.2 265.8 394.5
90 405.4 303.5 381.0 395.1 262.3 390.0
120 404.2 293.2 382.5 389.8 261.1 390.0
Table 5: Equilibrium concentration of heavy metal cations at different adsorption
times
Pseudo-first-order Pseudo-second-order
Element qm K
K/min-1 -1 R2 qm/mg*g-1 R2
/mg*g /g*mg-1*min-1
Cd 0.0234 4.15 0.8146 0.0137 8.33 0.9920
Cu 0.0315 10.93 0.9262 0.0067 21.69 0.9985
Mn 0.0288 3.78 0.8853 0.0187 11.52 0.9996
Ni 0.0255 1.91 0.7438 0.0343 10.01 0.9989
Pb 0.0186 1.34 0.4254 0.0441 33.00 0.9998
Zn 0.0326 12.40 0.9947 0.0034 16.47 0.997
Table 6: Adsorption kinetics model parameters
4- CONCLUSIONS
Microwave-assisted hydrothermal treatment performed well to modify the

MSWI fly ash. The results are listed as follows:
(1) The cation exchange capacity (CEC) of fly ash increased from 0.065 to 0.948
meq/g after hydrothermal treatment, which rose about 15 times.
(2) The pore size of the modified fly ash was much larger than the raw sample.
(3) The adsorption mechanism of modified zeolites could be well described by
Freundlich isotherm equation and the pseudo second-order kinetics.
CORRESPONDING AUTHOR
* Tel: +86 571 87952775. Fax: +86 571 87952438. E-mail: jiangxg@zju.edu.cn.
472
ACKNOWLEDGMENT
This paper is supported by the Innovative Research Groups of the National Natural
Science Foundation of China(51621005), the National Nature Science Foundation of
China (51676172), the Fundamental Research Funds for the Central Universities
(2016FZA4010),the Special Fund for National Environmental Protection Public
Welfare Program (Grant 201209023-4), the Program of Introducing Talents of
Discipline to University (Grant B08026).
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474
TREATMENT OF INDUSTRIAL WOOD DYEING EFFLUENTS BY ADSORPTION ON PINUS

PINASTER BARK
J. GONZÁLEZ-RODRÍGUEZ, L. VÁZQUEZ-BENGOCHEA, A. MAGÁN, M.S. FREIRE, J. GONZÁLEZ-ÁLVAREZ

1 Department of Chemical Engineering, Universidade de Santiago de Compostela, Santiago de
Compostela, Spain
Abstract
Dyes are employed in the wood industry to manufacture dyed wood veneers. Wood dyeing
significantly improves the final appearance of the products, but colored effluents are generated in
the process, which are very toxic and could cause serious environmental problems. Among the
different techniques available for dye removal (such as coagulation, filtration, ion exchange,
advanced oxidation processes or adsorption), adsorption is considered one of the simplest and most
economical methods to treat dye-contaminated wastewaters [1]. Pinus pinaster bark is an abundant
by-product of the wood industry in Galicia (NW of Spain), where about 2 million m3 of pine wood is
processed each year. Residual biomass provides a renewable, easily available and cheaper
alternative to active carbons. Furthermore, previous work has shown the capacity of pine bark to
adsorb metal cations and phenol from aqueous solutions [2, 3]. The aim of this work is to determine
if pine bark can be effectively used as an adsorbent for the removal of dyes from industrial wood
dyeing effluents. For this purpose, four commercial dyes (acid red 6, acid blue 25, acid yellow 25 and
acid black 172) used by the company Aserpal S.L. (A Coruña, Spain) were studied individually and in
binary mixtures. The maximum absorbance wavelength (λmax) was determined for each dye, as well
as its dependence on concentration and pH, and the dye stability over time was analysed. The bark
was pretreated with a water bath. Later, batch adsorption experiments were performed for each dye
at 25ºC, to study the influence of several parameters on dye adsorption percentage and capacity.
These parameters include initial dye concentration (10-50 mg/L), S/L ratio (0.5/100-1/100 g/mL), pH
(natural and pH=2) and contact time (up to 48 h). The remaining dye concentration was measured by
UV–visible spectrophotometry at λmax. For binary systems, experiments were performed at pH=2
varying S/L ratio (0.5/100-1/100 g/mL) and total initial dye concentration (15 to 150 mg/L). The first-
order derivative spectrophotometric method was applied to determine the remaining dye
concentration. The results show that adsorption is greatly dependent on pH and, to a lesser extent,
on the S/L ratio. Adsorption percentages in the range of 80-90% were achieved for an initial
concentration of 10 ppm operating at pH=2 and with S/L ratio of 1/100. Experimental data were
succesfully fitted to the Ho’s second order kinetic model. It was also observed that adsorption rate
increased with increasing S/L ratio whereas adsorption capacity decreased. The highest adsorption
capacity (7.29 mg/g) was achieved for the yellow dye at an initial concentration of 50 mg/L, pH=2
and S/L=0.5/100. The adsorption capacity for binary mixtures decreases with respect to the
individual dye solution, especially for high dye concentrations and low S/L ratio.
References
[1] Cheng, Z., Zhang, L., Guo, X., Jiang, X., Li, T.: Adsorption behavior of Direct Red 80 and Congo Red onto activated
carbon/surfactant: process optimization, kinetics and equilibrium. Spectroc. Acta Pt. A-Molec. Biomolec. Spectr. 137,
1126-1143 (2015)
[2] Vázquez, G., González-Álvarez, J., Freire, S., López-Lorenzo, M., Antorrena, G.: Removal of cadmiun and mercury ions
from aqueous solution by sorption on treated Pinus pinaster bark: Kinetics and isotherms. Bioresour. Technol. 82,
247–251 (2002)
[3] Vázquez, G., González-Álvarez, J., García, A.I., Freire, M.S., Antorrena, G.: Adsorption of phenol on formaldehyde-
pretreated Pinus pinaster bark: Equilibrium and kinetics. Bioresour. Technol. 98, 1535–1540 (2007)
475
MODELING OF A SMALL SCALE ADIABATIC COMPRESSED AIR ENERGY STORAGE (SS-

A-CAES)
N. MONTOYA ARÉVALO1, M. MARIN GALLEGO1, M. TAZEROUT1

1 CNRS Joint Unit GEPEA, Department of Energy Systems and Environment, IMT Atlantique, 4 rue
Alfred-Kastler BP 20722, 44307 Nantes Cedex 3, Nantes, France
Abstract
Numerous studies have been done so far regarding energy storage technologies due to the rise in
the energy production from alternative sources and the fluctuating nature of the energy obtained.
Compressed air energy storage (CAES) is one of the alternatives of energy storage and it uses the
surplus energy to compress the air and store it in a reservoir. The energy can be obtained by
expanding the compressed air in a turbine or in a pneumatic motor when it is required. The storage
of thermal energy recovered during the compression and its later use during the expansion phase
(adiabatic approach) have been included in Large Scale CAES systems studied in [1]. Most of these
systems consumes fuel. In this sense, the purpose of the present study is to model an experimental
Small Scale Adiabatic CAES (SS-A-CAES) set-up and to develop a sensitivity analysis to determine the
impact of the operational parameters over the system performance in terms of electric and thermal
energy recovery.
The experimental set-up was composed of three intercooled compression stages, a reservoir, an
expansion valve, a pneumatic motor and an alternator. The model was created using the program
ProSim under the hypothesis of steady state and assuming the air as an ideal gas. According to the
comparison with the experimental data, the model accurately represents the set-up in terms of
electric energy consumption and generation. For the sensitivity analysis, four performance indicators
were defined (based on [2]) to evaluate the impact of the variation of the number of compression
and expansion stages, the temperature of the water in the thermal energy storage (TES), the
pressure at the end of the compression stage, the air inlet temperature to each turbine and the
outlet pressure at the expansion valve. The performance parameters included the system electrical
efficiency and a relation between the thermic energy (heating from the compression and cooling
from the expansion), the electric energy generated over the energy consumed for the compression
(Polygenerative Efficiency). The biggest number of compression and expansion stages, the highest
TES temperature are related with the best electric efficiency, as well as the highest air inlet
temperature to the turbines and the largest outlet pressure of the expansion valve. However, the
best conditions for the polygenerative efficiency are the lowest inlet temperatures to the turbines
and the lowest pressure after the expansion valve. The variation of the outlet compression pressure
has any effect over the system efficiency. In the simulated system, the main energy losses are
related to the energy drop in the valve before the expansion phase, thus, the improvements in the
available the technology for the expansion from high pressures such as reached in the SS-CAES
system are required to achieve competitive efficiencies.
References
[1] Zhao, Pan, Yiping, Dai, and Jiangfeng, Wang. “Performance Assessment and Optimization of a Combined Heat and
Power System Based on Compressed Air Energy Storage System and Humid Air Turbine Cycle.” Energy Conversion
and Management 103 (October 2015): 562–72. doi:10.1016/j.enconman.2015.07.004.
[2] Jannelli, E., M. Minutillo, A. Lubrano Lavadera, and G. Falcucci. “A Small-Scale CAES (Compressed Air Energy Storage)
System for Stand-Alone Renewable Energy Power Plant for a Radio Base Station: A Sizing Design Methodology.”
Energy 78 (December 2014): 313–22. doi:10.1016/j.energy.2014.10.016.
476
VALORISATION OF RESIDUAL ENERGY IN COMFORT BUILDINGS: THE RELEVANCE OF

SOLAR INPUTS AND THERMAL INERTIA
A.VILABOA DÍAZ, A. DEL CASTILLO LLAMOSAS, P.M. BELLO BUGALLO

Department of Chemical Engineering, University of Santiago de Compostela,
Keywords
Residual energy, comfort buildings, solar radiation, thermal inertia, resources savings, mathematical
modelling, control system
Abstract
Building stock is the sector with the greatest potential for energy savings, so it is essential to reduce
greenhouse emissions between 80% and 95% by 2050, compared to 1990 for achieving the target of
European Union [1]. Two types of strategies can be proposed to reduce this energy demand. The first
one is creating an envelope with high thermal inertia, which reduces the indoor temperature
variations. The second strategy rides on a good design of the transparent areas, which consist on
elements used to control solar contributions to buildings. The amount of solar gains due to
transparent areas is determined by size of windows, their orientation respect to the sun, external
obstructions, glazing properties and sun-shading devices characteristics [8,9]. These are able to
reduce the energy consumption in summer of about a 20% [10].
On this work a mathematical model is created. This one allows us to predict the temperature inside a
building taking into account both solar inputs and thermal inertia of the envelope. The introduction
of solar radiation on the model makes the system fits better to reality and, furthermore, more
precise results are obtained. Furthermore, it is shown that when the insulation layer is inside (and
therefore the thermal mass is outside), obtained temperatures are more stables. This control system
will permit to valorise that residual energy which would be wasted, maintaining comfort and saving
resources.
477
1- INTRODUCTION
The climate change is one of the main threats that society confronts in the 21st century. Nowadays,
we have already achieved important advances to reduce the greenhouse gases, nevertheless, the
objectives must be more ambitious to mitigate the effects of climate change. For that, the European
Union are looking for cost effective procedures to achieve an economy more respectful with the
environment and consume less energy. In this way, The European Commission suggests a roadmap
towards a low-carbon economy and they establish that, in 2050, the greenhouse emissions should
reduce to 80% below 1990 levels [1].
To achieve the target towards a low-carbon economy, the European Union established and
ambitious framework to 2030 in order to guarantee the long term goals. These targets, whose are
established in climate and energy framework to 2030, set at least: 40% cuts in greenhouse gas
emissions (from 1990 levels), 27% share for renewable energy, and 27% improvement in energy
efficiency [2] [3].
All sectors need to contribute to the low-carbon transition (power generation, industry, transport,
buildings, construction and agriculture) depending on their saving potential. This work is focused in
building sector, which is the one with the greatest energy saving potential. The European
Commission indicates that emissions in this field could be reduced by 90% until 2050. Energy
efficiency will improve dramatically by designing "nearly zero-energy” buildings, renovating old
buildings to improve the energy efficiency and replacing fossil fuels for electricity and renewable
energy [1] [4] [5]. The improvement of energy efficiency provides an essential contribution to the
achievement the main objectives of the EU's policies in the field of climate and energy:
competitiveness, security of supply, sustainability and transition to a low-carbon economy [6].
To achieve a more efficient architecture, we must take advantage of natural resources, especially
solar energy. Solar energy is an important resource for designing buildings with high energy
efficiency. During the winter, the sun can help us to decrease energy demand, however it can also
increase the cooling demand during the summer. Therefore, it is necessary look for an equilibrium
between the glazed surfaces in a building. Thus, we have to be able to build low-energy buildings as
the Passive House, whose energy consumption should be less than 15 kWh [7].
For trying to capture the maximum energy from Sun during the winter it is important a good design
of glazed areas of the building. For this reason, orientation, size, window properties and the external
shadows are very important parameters while designing [8][9], since they significantly affect to
energy consumption. Thus, for windows with South orientation heating needs are lower because
they receive a greater amount of solar radiation. On the other hand, large windows sizes require a
greater power of heating and cooling over the year. Therefore, it is important to look for a balance
between these parameters without affecting home lighting [9].
An excess of solar radiation in summer can generate little comfortable conditions of habitability, so it
is necessary to have passive elements which will improve the thermal comfort of the building. There
are various passive elements which allow us to reduce the amount of solar radiation received in
478
summer. An example of this are the plant barriers, which are one of the best systems to reduce the
cooling demand since they absorb a large amount of radiation to their growth. They may reduce by
20% the cooling loads [10].

The object of this work are buildings, where, based on the elements of their envelope and the solar
radiation received, indoor temperature can be calculated. The building model used in this work is a
cube-shaped one. The outdoor-side elements of the envelope are composed of a 20 cm concrete
layer and 8 cm of insulation. On the other hand, the elements with constant temperature area are
composed of a 20 cm concrete layer.
The dwelling has a surface of 80 m2. Two of its facades and its roof are in contact with outdoors,
while its other two walls and the concrete deck are in contact with a zone having a constant
temperature. These last elements are composed of concrete with a 20 cm thickness. The thermal
properties of the materials are shown in Erreur ! Source du renvoi introuvable. and the responses of
each facade are in Erreur ! Source du renvoi introuvable..
Thickness Heat capacity Density Conductivity Thermal resistance

Layer
[m] [J/(kg∙K)] [kg/m3] [W/(m∙K)] [(m2∙K)/W]
External air - - - - 0,04
Concrete 0,2 1000 2400 2,5 0,08
Isolation 0,08 1404 30 0,032 2,5
Table 1 : Summary of layer properties of the wall.
Thermal mass Oscillation Time Decrement

Type of wall
[J/(m2∙K)] [°C] lag [h] factor
Inner isolation and external thermal
483.369 7,64 7,46 0,3199
mass
External isolation and inner thermal
483.369 0,26 8,01 0,0105
mass
Table 2 : Summary of the results obtained through the simulation of the two walls [11]
The elements in contact with outdoors (including the flat roof) are composed of 20 cm of concrete
and 8 cm of isolation. This type of elements are analysed from two points of view. Firstly, the
thermal mass is placed outside and the isolation is placed in the innermost layer. Secondly, the
isolation is placed outside and, therefore, the thermal mass is inside.
Description Value
Flat roof [m2] 80
Facade 1 (South) [m2] 60
Facade 2 (North) [m2] 60
Concrete deck against ground [m2] 80
Wall 1[m2] 48
Wall 2[m2] 48
Building volume [m3] 480
Number of time renovations [h-1] 1
Table 3 : Summary of the building characteristics
479
To calculate the indoor temperature, we will take into account the thermal mass and the solar
radiation. We will analyse the dynamic behaviour of the building in winter and summer weather. The
study will be realised in the next stages:
1. “Study of the influence of solar radiation through walls”
Firstly, we analysed the influence of solar radiation in the variation of indoor surface temperature.
For doing so, we introduce the sol-air temperature in the model. This temperature oscillation is
affected by thermal inertia [11].
2. “Study of the influence of solar radiation through windows”

In this case, we analyse the influence of input solar through windows. These contributions are the
ones that most affect the interior temperature.

To analyse the influence of the thermal inertia in the indoor temperature in buildings [11], it is
necessary to study how the solar radiation affects to indoor temperature. Firstly, the model which
allowed to calculate the temperature on the inner surface of a wall in contact with the outside was
developed. In this case, we used the analogy between the electric field and the heat and we
achieved the next equation [11]:
Tsur,in (s)⁄Text (s) = 1⁄(R ∙ C ∙ s + 1) [1]

Where:
- C: is the heat capacity of the node [J/m2∙K].

- R: is the thermal resistance of the node [m2∙K/W].
Then, an energy balance was realised taking into account the temperature on the inner surface of a
wall, air renovations and heat contributions of people or electrical equipment.
∑ hin ∙ Ai ∙ (Tsur,in (t) − Tin (t)) + ∑ hin ∙ A0,i ∙ (T0,i (t) − Tin (t)) + 0,32 ∙ n ∙ V ∙ (Text (t) − Tin (t))
i i [2]
dTin (t)
+ Q in (t) = Cp,air ∙
dt
Where:
- hin: is the convection coefficient of air inside [7,69 W/(m2∙K)].

- Ai: is the area of inner surface of the envelope elements against outdoors [m 2].
- Tsur,in: is the inner surface temperature of each envelope element [°C].
- Tin: is the temperature inside a building [°C].
- A0,i: is the area of inner surface of each envelope element against a place with constant
temperature [m2].
- T0,i: is the temperature of each zones at constant temperature [°C].
- n: is the number of air renovations [h-1].
480
- V: is the volume of the building analysed [m3].

- Text: is the external temperature [°C].
- Qin: is the internal loads produced by electronic equipment and by the people living in the
building [W/m2].
- Cp,air: is the heat capacity of the air [J/K].
The transfer function was solved by using the Laplace transformation. This gives as a result
equation [3].
ℎ𝑖𝑛𝑡 ∙ 𝐴𝑖
𝑇𝑖𝑛𝑡 (𝑠) = ∑ ∙ 𝑇𝑠𝑢𝑝,𝑖 (𝑠)
ℎ𝑖𝑛𝑡 ∙ ∑(𝐴𝑖 + 𝐴0,𝑖 ) + 0,32 ∙ 𝑛 ∙ 𝑉 + 𝐶𝑝,𝑎𝑖𝑟𝑒 ∙ 𝑠
𝑖
ℎ𝑖𝑛𝑡 ∙ 𝐴0
+∑ ∙ 𝑇0,𝑖 (𝑠) [3]
𝑖
0,32 ∙ 𝑛 ∙ 𝑉
+ ∙ 𝑇𝑒𝑥𝑡 (𝑠)
1
+ ∙ 𝑄𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑠 (𝑠)
With this equation obtained in the previous study, the influence of the solar radiation will be
introduced through the calculation of sol-air temperature. The sol-air temperature is the outdoor
temperature, which in absence of all radiation exchanges, generates the same heat flow through a
wall that is equal to the combination of the solar incident radiation, the exchange of radiant energy
with the sky and the exchange of heat convection with outdoor air [12,13].
If an energy balance is realised on the outside of a wall, we obtain:

q
= α0 ∙ Gt + h0 ∙ (Text − Tsup,ext ) − ε ∙ ∆R [4]
A
Where:
 α0: absorptivity of the external face subjected to solar radiation.

 Gt: incident solar radiation on the surface, it will depend on its orientation [W/m 2].
 h0: coefficient of heat transfer by radiation and convection from the outside [W/m2].
 Text: outdoor air temperature [°C].
 Tsup,ext: temperature on the outside surface of the wall [°C].
 ε: the emittance of outside surface.
 ∆R: difference between the incident long-wave radiation of the sky and its surroundings and
the emitted radiation by a black body at the same temperature of the outside air [W/m2].
On the other hand, the heat flow between the outside surface and equivalent sol-air temperature
(Tsol-aire) can be expressed as:
𝑞
= ℎ0 ∙ (𝑇𝑠𝑜𝑙−𝑎𝑖𝑟 − 𝑇𝑠𝑢𝑝,𝑒𝑥𝑡 ) [5]
𝐴
481
If equations [4] and [5] are combined:

α0 ∙ Gt ε ∙ ∆R
Tsol−aire = Text + − [6]
h0 h0
Therefore, sol-air temperature allows to know the amount of heat conduction through the wall from
the outside including solar radiation.
Vertical surfaces receive long-wave radiation from the ground, the sky and from other vertical
surfaces, so determine the value of ∆R with precision is complex. When solar radiation is high, the
temperature of objects are higher than air temperature, thus, the long wave radiation compensates
the low emittance of the sky. Therefore, we can assume in vertical surfaces that ε∙∆R=0. On the
other hand, for horizontal surfaces, the long wave radiation is only received from the sky, so the
term ∆R has a value of 20 BTU/h∙ft2 (63,09 W/m2) [12].
The absorptivity of long wave radiation will depend on the colour of the outside surface exposed to
solar radiation. For example, for clear colours we will use 0,60 as value, for dark tones 0,90 and for
surface with medium shades we will use 0,75
Study of the influence of solar radiation through walls

For studying the solar radiation through a wall, we consider two kind of walls: with the isolation by
the outside and by the inside. These walls are composed by 20 cm of concrete and 8 cm of isolation.
As a reference, the climatic conditions that have been used to the simulation correspond to one of
the coldest days recorded in the city of Ourense (the 5 th of February 2012) [14]. The maximum
temperature reached was 8,89ºC and the minimum temperature was -5,85ºC. The influence of solar
radiation on the outside surface of the wall makes that heat flow that occurs will be equivalent to a
maximum temperature of 16,14°C. The sol-air temperature must be calculated for every enclosure
because the value depends on its tilt and orientation. In the Figure 1, the sol-air temperature for a
flat roof (β=0, γ=0) is showed:
Outdoor temperature sol-air temperature on a flat roof

20
15
Temperature [°C]
10
0
0 2 4 6 8 10 12 14 16 18 20 22 24
-5
-10
Time [h]
Figure 1: Graphical representation of the outdoor temperature and the sol-air temperature on a horizontal surface.
482
As a result, a new disturbance is obtained and its effect on the different walls can be analysed. This
new disturbance is the combination of two waves. One of them is outdoor temperature wave
without solar radiation, and the second is the wave disturb the system during the day, taking into
account the solar radiation. In this way, an only disturbance is obtained where the effect of the solar
radiation is showed. The next table shows characteristics of the two waves:
Wave characteristics Outdoor temperature wave Sol-air temperature wave

Maximum temperature [°C] 8,89 15,57
Minimum temperature [°C] -5,8 -5,8
Wave amplitud [°C] 7,35 10,68
Average temperature [°C] 1,55 4,88
Oscillation [°C] 14,69 21,37
Table 4 : Description of sinusoidal waves that disturb the system when the solar radiation is considered.
First, we analyse the wall with outdoor isolation, for that, we have to calculate the perturbation for
the two type of waves and with them, the resulting wave of the system will be obtained. Due to the
gap causing the envelope against the outside elements, solar radiation does not affect the indoor
surface temperature during the hours of sunshine, this peak of temperature is delayed. Thus, the
contribution of energy that enters the building due to radiation is accumulated in the envelope and
subsequently give it to the inside.
indoor temperature without solar radiation

indoor temperature with solar radiation
7,5
7,0
6,5
Temperature [°C]
6,0
5,5
5,0
4,5
4,0
3,5
0 2 4 6 8 10 12 14 16 18 20 22 24
Time [h]
Figure 2: Estimation of the temperature inside when the building has inside insulation considering solar radiation.
The Figure 2 shows that the solar radiation through the walls without taking into account the solar
radiation through the windows. In this case, the indoor temperature increases in 0,5ºC, therefore,
the average temperature in a building is increased and it reaches 5,5ºC. However, the oscillation is
higher when the isolation is in the indoor and the total oscillation reaches the 2,6ºC.
483
20
15
Temperature [°C]
10
0
0 2 4 6 8 10 12 14 16 18 20 22 24
-5
-10
Time [h]
Sol-air temperature [ºC] Indoor temperature [ºC]
Figure 3: Variation of the indoor temperature for walls with inside insulation and taking into account the solar radiation.
When the insulation is in inside (Figure 3), the variation of indoor temperature can reach 3ºC, and
therefore, the minimum temperature is lower than when the insulation is outside (Figure 4). This
type of enclosure produce a constant response, so when solar radiation is introduced is not
appreciated an increase of temperature. The maximum temperature reaches is 5,66ºC and the
minimum is 4,95ºC so the average temperature is 5,30ºC. The average temperature is lower than
with the inside isolation because this configuration is less influenced by solar radiation. However,
temperatures more stables are achieved with the outside insulation.
18
16
14
12
Temperature [°C]
10
8
6
4
2
0
-2 0 2 4 6 8 10 12 14 16 18 20 22 24
-4
-6
-8
Time [h]
Sol-air temperature [ºC] Indoor temperature [ºC]
Figure 4: Variation of the indoor temperature for walls with outside insulation and taking into account the solar radiation.
Study of the influence of solar radiation through windows

The main solar contributions in a dwelling are produced through the windows. Therefore, it is
interesting to analyse the influence of this energy on indoor temperature. These contributions of
484
energy can increase the indoor temperature in winter, however, they can produce an excess of
temperature in summer so it is necessary look for a balance between this two situations. The first
step to study the influence of solar radiation is to add the solar radiation through windows to
equation [3] and solve it using Laplace transformation.
ℎ𝑖𝑛𝑡 ∙ 𝐴𝑖
𝑇𝑖𝑛𝑡 (𝑠) = ∑ ∙ 𝑇𝑠𝑢𝑝,𝑖 (𝑠)
𝑖
ℎ𝑖𝑛𝑡 ∙ 𝐴0
+∑ ∙ 𝑇0,𝑖 (𝑠)
𝑖
0,32 ∙ 𝑛 ∙ 𝑉
+ ∙ 𝑇𝑒𝑥𝑡 (𝑠) [7]
1
+ ∙ 𝑄𝑖𝑛𝑡𝑒𝑟𝑛𝑎𝑠 (𝑠)
ℎ𝑖𝑛𝑡 ∙ ∑(𝐴 𝑖 + 𝐴0,𝑖 ) + 0,32 ∙ 𝑛 ∙ 𝑉 + 𝐶𝑝,𝑎𝑖𝑟𝑒 ∙ 𝑠
1
+ ∙ 𝑄𝑠𝑜𝑙𝑎𝑟 (𝑠)
This new term (Qsolar) depends on the orientation, the tilt and the properties of windows. Thus, solar
contributions are equal to direct solar radiation multiplied by the solar factor of the glass. The solar
factor of the window is the relationship between total energy which enters the room through the
glass and the incident solar energy. This total energy is the sum of solar energy that enters through
direct transmission and energy transferred from the glazing to the interior space [15]. In this case, to
analyse the influence of solar radiation, we will use a glazed surface of 12 m 2 (20% of the surface of
the facade). The window has double glazing with a transmittance of 3,1 W/m 2K and a solar factor of
0,75.
The Figure 5: Variation of the indoor temperature for walls with inside and outside insulation and taking into
account the solar radiation through the window during a winter day.Figure 5 shows the evolution during
the winter of the indoor temperature taken into account the solar radiation. With the inside
insulation, the temperature reaches a maximum of 8,04 ºC. In the other case, with outside
insulation, the maximum peak of temperature is 8,37ºC.
This difference in the maximum temperature reached is due to the wave lag which is produced by
each type of enclosure. When insulation is on the outside and therefore the thermal mass is inside,
the indoor temperature is more stable, and the solar radiation increases the indoor temperature
during the hours of more sunshine. However, when the isolation is in the outside, the wave lag
produces a maximum temperature about 16:00, making this peak reached less than in the previous
case.
485
Outdoor temperature [ºC]

Sol-air temperature [ºC]
Indoor temperature with outside insulation [ºC]
Indoor temperature with inside insulation [ºC]
20
15
Temperature [°C]
10
0
0 2 4 6 8 10 12 14 16 18 20 22 24
-5
-10
Time [h]
Figure 5: Variation of the indoor temperature for walls with inside and outside insulation and taking into account the solar radiation
through the window during a winter day.
4- CONCLUSIONS
The introduction of solar radiation on the model makes the system fits better to reality and,
furthermore, more precise results are obtained. When the insulation is inside (and therefore the
thermal mass in outside) the temperatures obtained are more stables. We are able to obtain higher
temperatures in winter and lower temperatures in summer. Considering the thermal inertia and the
solar contributions in a building, we can design buildings more efficient and obtain more
comfortable temperatures.
Being able to predict the temperature inside a building is useful in the design of HVAC control
systems. From weather predictions you can get an approximation of the evolution of the outside
temperature and thus to design a control system that is anticipated to outdoor temperature
variations, in order to keep the indoor temperature in the comfort area.
To sum up, the installation of this system on a building can help to control and valorise that residual
energy which would be wasted, maintaining comfort and saving resources.
REFERENCES
[1] EC, COM(2011) 112, Communication from the Commission to the European Parliament, the Council, the European
Economic and social committee and the committee of the regions of 8 March 2011. “A Roadmap for moving to a
competitive low carbon economy in 2050”. Brussels, 2008.
Economic and social committee and the committee of the regions of 22 January 2014. “A policy framework for climate
and energy in the period from 2020 to 2030”. Brussels, 2014.
[3] EC, Framework for climate and energy. “Outcome of the October 2014 European Council”. Brussels, 30/10/2014
[4] EC, Directive 2012/27/EU of the European Parliament and the Council of 25 October 2012 on energy efficiency,
amending Directives 2009/125/EC and 2010/30/EU and repealing Directives 2004/8/EC and 2006/32/EC
486
Economic and social committee and the committee of the regions of 8 March 2011. “Energy Efficiency Plan 2011”.
Brussels, 2011.
Economic and social committee and the committee of the regions of 22 January 2014. “A policy framework for climate
and energy in the period from 2020 to 2030”. Brussels, 2014.
[7] Passive House Institute, http://www.passivehouse.com/, 21 February 2018.
[8] Tilmann E. Kuhn, Sebastian Herkel, Francesco Frontinia, Paul Strachan, Georgios Kokogiannakis. “Solar control: A
general method for modelling of solar gains through complex facades in building simulation programs”. Energy and
Buildings 43 (2011) 19–27.
[9] Mari-Louise Persson , Arne Roos , Maria Wall. “Influence of window size on the energy. Energy and Buildings”.
Volume 38, Issue 3, March 2006, Pages 181-188.
[10] K.J. Kontoleon, E.A. Eumorfopoulou. “The effect of the orientation and proportion of a plant-covered wall layer on
the thermal performance of a building zone”. Building and Environment. Volume 45, Issue 5, May 2010, Pages 1287-
1303.
[11] A. Vilaboa, J.C. Álvarez Iglesias, P.M. Bello Bugallo. “Study of the effects of mass and thermal inertia in buildings and
their implications in the indoor temperature”. 6th International Conference on Engineering for Waste and Biomass
Valorisation held from May 23-26, 2016 in Albi, France.
[12] American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc. “ASHRAE Handbook: Heating,
Ventilating, and Air-Conditioning Applications”. Atlanta 2011.
[13] American Society of Heating, Refrigerating and Air-Conditioning Engineers, Inc. “ASHRAE Handbook: Fundamentals”.
Atlanta 2009.
[14] Meteogalicia. http://www.meteogalicia.es/ [Accessed: January 2018].
[15] IDAE 2007, Instituto para la Diversificación y Ahorro de la Energía. “Guía Técnica para la Rehabilitación de la
Envolvente Térmica de los Edificios”. Madrid 2007.
487
EVALUATION OF NOZZLE SYSTEM FOR LATE MOISTURE AND HEAT ADDITION IN

PELLET PRODUCTION
M. RUDOLFSSON 1, T.A. LESTANDER1, D.A. AGAR1, S.H. LARSSON 1

Abstract
In the growing market of fuel pellet production, even small savings in energy consumption is of
importance - to stay competitive and to allow a higher throughput. Within the MOBILE FLIP project,
new methods and equipment for more effective pellet production are developed to handle and
master diverse feedstock from both forestry and agriculture.
In this study, equipment that consists of nozzles placed in the nip between the press roll and die is
evaluated with respect to energy consumption and pellet quality. The equipment has been fitted in a
pellet mill with a rotating die which is most commonly used in the pellet industry. Nozzles enable a
direct and precise addition of additives, such as water or steam, just before the actual compression
of the feedstock. The purpose of such additives is to reduce energy consumption, improve the
binding properties, and/or alter the pellet combustion properties.
Pelletization was performed in parameter setups, varying amounts nozzle water and steam addition
and comparing results to standard procedures, where the same amount of water and/or steam was
added earlier in the process. Pellet quality was evaluated by analysis of moisture content (EN15414),
bulk density (EN15401), durability (EN15210), and amount of fines at production. The energy
consumption and die temperature were recorded during sampling together with pellet temperature.
Results show that the nozzle system works as a method for moisture content adjustment and that
steam addition lowers energy consumption.
References
[1] Rudolfsson M, Larsson S.H. & Lestander T.A. (2017). New tool for improved control of sub-process interactions in
rotating ring die pelletizing of torrefied biomass. Applied Energy, 190:835-40.)
488
COMPARING SUPPLY-CHAIN RELEVANT QUALITIES OF PELLETS MADE FROM NON-

TREATED AND TORREFIED LIGNOCELLULOSIC BIOMASS
D.A. AGAR1, M. RUDOLFSSON1, T. MELKIOR2, M. PEREZ2, C. DUPONT3, M. CAMPARGUE4, S.H.

LARSSON1

2 Commissariat à l'énergie atomique et aux énergies alternatives CEA, Grenoble, France
Technology, Delft, Netherlands

Abstract
Torrefaction is an emerging commercial technology that improves transport and storage properties
of biomass in renewable feedstock supply chains. The key benefits generally stated with torrefaction
are i) better grindability which reduces milling energy requirement and the need for specific grinding
equipment downstream, ii) lower water affinity, which in practice means less humidity sensitive
storage and handling, and iii) - in the case of pellets - greater mass and energy density [1].
In this study, biomass feedstock from forestry and agriculture, non-treated and torrefied, were
pelletised in a pilot scale setup (150 kg/h), resulting pellet qualities were analysed, and results were
put in the context of large scale handling and storage.
Preliminary results from pelletising of non-treated and torrefied beech show differences in pellet
quality which can be attributed to one or more compositional factors. High quality torrefied pellets
are best produced at lower moisture contents than corresponding non-treated pellets. The
difference in optimum moisture content is mainly due to differences in xylans and mannans
composition between non-treated and torrefied biomass – these hemicellulose contain hydroxyl
groups with high moisture affinity. The lower equilibrium moisture content of torrefied pellets is a
substantial share of the higher energy and heating value (as-received basis) of torrefied pellets.
References
[1] Larsson SH, Rudolfsson M, Nordwaeger M, Olofsson I, Samuelsson R. Effects of moisture content, torrefaction
temperature, and die temperature in pilot scale pelletizing of torrefied Norway spruce. Applied Energy.
2013;102:827-32.
489
WET OXIDATION AS A TREAMENT FOR EFFLUENT FROM MOBILE HYDROTHERMAL

CARBONIZATION (HTC) PROCESS
K. MELIN1, J. ALMQVIST2, K. RASA3, H. WIKBERG1

1 VTT Technical Research Centre of Finland Ltd, Espoo, Finland
2 RISE Processum AB, Örnsköldsvik, Sweden
3 Natural Resources Institute Finland, Jokioinen, Finland.
Abstract
Hydrothermal carbonization (HTC) is a promising technology for converting organic raw materials into
biochar suitable for several applications. In the MOBILE FLIP project HTC is employed for converting
unexploited wet biomass residues to soil amendment and activated carbon. However, the liquid
effluent produced in the process is often seen problematic to handle. Typically these effluents contains
high amount of dissolved organic carbon and both biodegradable and non-biodegradable
components. Components such as phenol, HMF, furfural and short chain carboxylic acids are present
in the HTC effluent [1][2].
Wet oxidation is a technology based on treatment of aqueous stream at high temperature and
elevated pressure, which oxidizes the non-biodegradable and toxic compounds into non-hazardous
products such as CO2 and short chain carboxylic acids. The short chain carboxylic acids found in the
effluent after the wet oxidation (e.g. formic, acetic, succinic, propionic and glycolic acid) are not
considered toxic for the environment [1]. Hence, after the treatment, the biodegradable effluent can
be treated in a simple wastewater purification system. Simple wastewater purification systems using
infiltration are currently used for example in household wastewater handling outside sewage pipe
network.
In this study brewer’s spent grain (BSG) and Scots pine bark (SPB) were hydrothermally carbonized.
The effluents were recycled several times in the HTC runs to concentrate them in order to demonstrate
the real environment of mobile HTC container. The concentrated liquid effluents from the last HTC
runs were wet oxidized in a batch reactor at 290 °C for 90 min using oxygen feed.
The analyses results showed that the wet oxidation treatment resulted in a high, approximately 80 %,
reduction of COD for both effluents. Based on the results, the total techno-economic feasibility of the
concept, where both the HTC as well as the wet oxidation treatments would be performed in a mobile
container, was assessed. In addition, the needed amount of oxygen and heat input for the process
were calculated.
References
[1] Reza M. T., Freitas A., X. Yang. Coronella C. J,: Wet Air Oxidation of Hydrothermal Carbonization (HTC) Process Liquid.
ACS Sustainable Chem. Eng., 4, 3250−3254 (2016)
[2] Keskinen R, Hyväluoma J. Wikberg H., Källi A., Salo T., Rasa K. : Possibilities of Using Liquids from Slow Pyrolysis
and Hydrothermal Carbonization in Acidification of Animal Slurry, Waste Biomass Valor.,
https://doi.org/10.1007/s12649-017-9910-4 (2017))
490
USE OF TORREFIED WOOD IN THE PRODUCTION OF PARTICLEBOARDS
E. PAPADOPOULOU1, S. KOUNTOURAS1, T. MELKIOR2, M. PEREZ2, S. THIERY2, P. PONS DE VINCENT2,

A. CHATROUX2, M. GONZALEZ-MARTINEZ2, M. MARCHAND2, C. DUPONT3
1 CHIMAR HELLAS S.A., Thessaloniki, Greece.
2 CEA, Laboratory of Preparation of Bioresources, Grenoble, France
Abstract
Particleboards made from wood are commonly used for furniture and constructions because they
are products with good mechanical properties and of relatively low cost. However, the urea-
formaldehyde (UF) resin that is typically utilized for their manufacturing, offers relatively high
thickness swelling while allows formaldehyde release during the storage life of the product.
In MOBILE FLIP project, one objective of CHIMAR HELLAS S.A. was to evaluate torrefied wood as
substitute of raw wood in the production of particleboards. Both pine and beech were tested after
subjected to torrefaction under varied conditions in the pilot scale multiple-hearth furnace of CEA
biomass platform with a capacity of 150 kg/h of torrefied product. Pine was torrefied at 280 and
300°C during 45 min while beech was torrefied at 250°C during 60 and 75 min, in order to evaluate
the effect of process duration on material performance. All samples were tested as raw wood
substitutes at various levels in the production of particleboards. The torrefied pine material was
tested as wood substitute at the levels of 20% and 40% while the torrefied beech wood was used
for the production of panels throughout of this material. The particleboards were produced at pilot
scale and had dimensions 50x50cm while their target density was 650kg/m3. They were
manufactured following a simulation of the industrial practice using a typical Urea – Formaldehyde
(UF) resin as bonding material. For control, typical panels were prepared with chips from raw wood
of pine and beech. The produced panels were tested and evaluated according to European
standards as per their mechanical properties like internal bond, modulus of rupture and modulus of
elasticity as well as thickness swelling. Their formaldehyde content was determined with the
perforator method.
It was found that the lower the temperature and the duration of the torrefaction process, the best
the performance of the material in the production of panels. All samples had lower mechanical
properties than raw wood but significantly improved thickness swelling and decreased
formaldehyde content (perforator values). Whatever the wood, moderate torrefaction appears
therefore as a promising pretreatment for this application.
This work has received funding from the EU Framework Programme for Research and Innovation
HORIZON 2020 under the Grant Agreement No 637020-MOBILE FLIP.
491
BLENDING BIOMASS: DILUTION OR CHEMICAL REACTION IN COMBUSTION PROCESS
F. DEFOORT1, M. CAMPARGUE2, G. RATEL1, M. MARCHAND1, B. GRANGIER1, H. MILLER1, C. DUPONT3

1 Univ. Grenoble Alpes, CEA, LITEN, Grenoble, France.
2 RAGT Energy, Alby, France.
3 IHE Delft Institute for Water Education, DEEWT, Delft, the Netherlands.
Abstract
Due to the increasing demand for wood pellets in combustion processes, there is an increasing market
for non woody and low-cost biomass feedstock such as agricultural residues. Unfortunately their use
is limited by strong technical issues, in particular related to fouling and ash agglomeration. Solutions
can be implemented downstream the boiler for some of them but there is no cheap industrial solution
for ash agglomeration. Liquid appearance around 900 1150°C is known to be the main cause of ash
agglomeration due to the high amount of alkali, silica and chlorine in ash [1], [2]. One promising
solution to cope with this issue is feedstock blending with an unproblematic fuel like wood [3].
However, blending is always made in an empirical way without any rational optimization.
The present study proposes therefore an innovative modelling tool for biomass blending based on
theoretical predictions assuming thermodynamic equilibrium, ie the ash of each biomass reacts in-
between completely. To this purpose, phase diagrams and the software Factsage [4] were used with
a suitable database [5]. Experimental validation of the calculations was performed by laboratory-scale
annealing of ash or pellet at 1000°C followed or not by quench in air. The samples were characterized
by SEM-EDX and XRD in order to identify the presence of liquid and crystalline phases. Pilot-scale
validation was then performed with combustion tests of the optimal biomass blends predicted in a
50kW moving grid boiler.
One woody and four agricultural residues were selected for the study according to their ash
composition (i.e. Ca, K or Si rich), namely oak bark, rice husk, sunflower hull, grape pomace and wheat
straw. Seven mixtures were selected having a minimum of liquid amount as calculated by
thermodynamic equilibrium. The feedstocks were ground at different particle sizes and mixed. The
different assortments were pelletized using different compaction rates.
Results on mixed ashes showed that chemical reaction was achieved after annealing and that ash
mixing was more than a simple addition. For example wheat straw ash mixed with oak bark ash
showed CaSiO3 or a ternary compound K2Ca6Si4O15 not existing in each single biomass.
Results of mixed biomass as pellets are being performed in order to check if the results are obtained
for pellets and ashes and if particle size and compaction rate have an impact.
In conclusion, this study offers an original methodology to blend biomass in order to solve ash
agglomeration issues during combustion and gives insight on the phenomena involved during
blending, i.e. chemical reaction and not only dilution.
References
[1] Vassilev, S.V. et Al: An overview of the chemical composition of biomass. Fuel 89, 913–33 (2010).
[2] Obernberger, I.: Ash related problems in biomass combustion plants. Technische Universiteit Eindhoven; (2005)
[3] Zeng, T. et Al: Blended biomass pellets as fuel for small scale combustion appliances Fuel 184, 689–700 (2016)
[4] Bale, C.: FactSage thermochemical software and databases, CALPHAD: Computer Coupling of Phase Diagrams and
Thermochemistry 54 35–53 (2016)
[5] Hack, K. et Al: A novel thermodynamic database for slag systems and refractory materials. In 5th International
Congress on the Science and Technology of Steelmaking Dresden, Oct. 1-3 (2012)
492
FEASIBILITY STUDY OF SMALL ANAEROBIC-CO-DIGESTION AT URBAN DISTRICT LEVEL
J-R. BAUTISTA ANGELI1, 2, A. VILLOT2, A. LAKEL1, T. LE FLOC’H1, Y. ANDRES2

1 CSTB, Aquasim, 11 rue Henri Picherit, 44300 Nantes, France
2 . IMT Atlantique, GEPEA (UMR CNRS 6144), 4 rue Alfred Kastler, 44307 Nantes, France.
Abstract
To realize the environmental objectives set by the energy transition policies in Europe, it seems
interesting to study the integration of anaerobic digestion at urban scale, in small and local units.
The co-digestion of several waste sources could be a way to achieve it. [2] The first step consisted on
a panorama of integrated anaerobic digestion European projects at the neighborhood scale and
discussion of their achievements and limits for futur developpments. From this step, a model of
resources conservation, presented in Fig. 1, was etablished as a global context of the study. The
characterization of waste available in district was investigated to determine their relevance for
anaerobic digestion, i.e. the organic matter, the C / N ratio and the lignin composition by TGA. After
BMP tests to ensure the stability of a selected waste mix, the experiment was carried out on a 30 L
pilot reactor at low and medium load, RHT close to 30, 25°C and 35°c. [1] In conclusion of the waste
characterization, we divides deposit in two categories, mains substrates, used as major fractions of
feedstock and secondaries, whose addition in small quantity could increase the reactor stability. The
pilot scale experimentation, it discuted with an focus on performances, biogas production and
energy recovery pathways for the integration of the process at a urban scale.
Figure 1: Model of resources conservation
References
[1] Davidsson, Å., la Cour Jansen, J., Appelqvist, B., Gruvberger, C., Hallmer, M., 2007. Anaerobic digestion potential of
urban organic waste: a case study in Malmö.
[2] Hertel, S., Navarro, P., Körner, I., 2015. Biogas and nutrients from blackwater, lawn cuttings and grease trap
residues—experiments for Hamburg’s Jenfelder Au district.
493
EVALUATION OF CO-DIGESTION OF WINERY SOLID WASTE WITH CASSAVA BIOMASS

FOR OPTIMAL BIOGAS PRODUCTION
U. MKRUQULWA1, V. OKUDOH2, O. OYEKOLA1

1 Department of Chemical Engineering, Faculty of Engineering, Cape Peninsula University of
Technology, Bellville, Cape Town, South Africa.

2 Department of Biotechnology and Consumer Sciences, Faculty of Applied Sciences, Cape peninsula
University of Technology, Cape Town Campus, Cape Town, South Africa.
Abstract
Winery solid waste is a growing problem in South Africa due to high amounts currently being dumped
at landfills. In Southern Africa, a stable and abundant supply of energy is of vital importance to reduce
poverty, stabilize democracy and economic growth. Winery waste in co-digestion with cassava
biomass are considered suitable for anaerobic digestion to produce high amounts of biogas due to
their synergistic chemical properties. This study evaluated the two substrates for enhanced biogas
production using Zebra dung as inoculum. Biomethane potential (BMP) tests were carried out in a
batch, mesophilic (37°C±0.5) reactor using cassava and winery waste separately and in combination
at a ratio of 1:1 for 30 days. Response surface method (RSM) was used to optimize temperature, pH
and co-substrate ratios. The effect of the combined parameters was investigated. The results showed
that cumulative methane yield for cassava, winery waste and in combination were 42, 21 and 38
mLCH4 respectively resulting in 1.62, 0.9 and 1.58 mLCH4/gVS added respectively. The value of
correlation coefficient (R2) was 0.9521 and showed a good fit between the experimental and predicted
values. The maximum methane yield of 396 mLCH4 resulting in 2.20 mLCH4/gVS added was predicted
by the quadratic RSM at the optimal conditions: temperature of 35˚C±0.5, pH 7 and 70:30 ratio of
cassava to winery waste. Each fermentation experiment lasted for 30 days. The RSM model was
successful for biogas production optimization from the co-digestion of cassava and winery waste, a
useful information for the winery industry especially in South Africa.
References
[1] Angelidaki I., Lim J. S., Ho W., Hasahim and Lee C. T. Potential of biogas production from farm animal waste in Malaysia.
Renewable and Sustainable Energy Reviews. [Online]. 60. 714-723 (2016)
[2] Riaño, B., Molinuevo, B. and García-gonzález, M. C. Potential for methane production from anaerobic co-digestion of
swine manure with winery wastewater. Bioresource Technology. 102(5):4131-4136 (2011).
494
OPTIMISING BIOGAS PRODUCTION THROUGH CO-DIGESTION OF SEWAGE SLUDGE

WITH FOOD WASTE AND FOG
AWE OLUMIDE WESLEY1, LIU RABIN1, ZHAO YAQIAN1

Dublin, Newstead, Belfield, Dublin 4, Ireland.
Abstract
This experimental work focussed on the assessment of co-digestion of sewage sludge (SS), FW and
fat, oil and grease (FOG) for enhancing and optimising biogas production. Series of batch
experiments were conducted under a mesophilic condition with different mixtures of SS, FW, and
FOG with 20 days hydraulic retention time (HRT). The aim was to investigate the performances of
mono-digestion of SS, FW, and FOG and, compare with co-digestion effects of mixing different
proportions (ratios) on the bio-methane production of the substrates in order to determine the
optimal mixing ratio per gram of VS added. The performance of the reactors was assessed based on
cumulative methane potential, VFA effects, NH4+-N effects, SCOD, VS and, TS removal efficiency.
Economic and environmental benefits were also assessed in detail with the aims of turning WWTPs
into net energy producers.
Materials and Methods

The food waste and FOG was collected from various source to have a complete outlook of food
waste in Ireland (hotel, restaurants, households etc.), while the primary sludge (PS), waste activated
sludge (WAS) and inoculum was collected from Ringsend wastewater treatment plant, Dublin. The
VS, TS, SCOD, TOC, PH, NH4+-N and, TN, were determined for both influent and effluent following the
standard methods (APHA, 2005). Alkalinity and VFAs were done by titration. The reactor consists of
250 ml serum bottles (13 numbers) with working volume of 200 ml.
Results Obtained
The cumulative methane production of mono-digestion (SS, FW, and FOG) are 346 Nml CH4 g/VSadded,
428 Nml CH4 g/VSadded and 898 Nml CH4 g/VSadded for R2, R3, and R4 respectively. The three reactors
R10, R12 and R13 with a mixture of 5% w/w (oil addition) had the highest methane production with
771, 694 and 725 Nml CH4 g/VSadded respectively.
Conclusion
Anaerobic co-digestion of SS: FW: FOG is feasible because it performed better than mono-digestion
of a single substrate. The three reactors R10, R12 and R13 with a mixture of 5% oil addition had the
highest methane production with 771, 694 and 725 Nml CH4 g/VS added respectively. This translate to
55.12% (2.23 times) higher than SS and 44.49% (1.8 times) than FW alone for R10, while R12 and R13
were 50.14% (2.01 times) and 52.28% (2.1 times) higher than R2 (SS) and, 38.33% (1.62 times) and
40.97% (1.69 times) for R3 (FW). At least 30% of AD unused capacity at WWTP could be available to
treat and handle co-substrate for digestion. Co-digestion can contribute to renewable energy
production, diversion of organic waste from landfill and reduce GHG emissions.
495
Figure 1: (a) Daily methane production, (b) cum. Methane of co-digested substrates, (c) Alkalinity and VFAs before and after AD and,
(d) TS conversion efficiency.
Reference
[1] APHA, 2005. Standard methods for the examination of water and wastewater., Washington DC: Public Health
Association Inc.
496
PRODUCTION OF LACTIC ACID IN BATCH AND FED-BATCH MODE BY LACTOCOCCUS

LACTIS LCL USING DATE WASTE
F. Z. RAS EL GHERAB1, K. ALSAYED MAHMOUD2, O. HASSAINE1, H. ZADI-KARAM1, N.-E. KARAM1, S.

HILIGSMANN2
1 Laboratory of Biology of Microorganisms and Biotechnology, Department of Biotechnology, Faculty

of Sciences of Nature and Life, University of Oran 1, Oran, Algeria.
2 BIO-Bio Tech Unité de Biotechnologie et Bioprocédé, Ecole polytechnique de Bruxelles, Université
Libre de Bruxelles, Brussels, Belgium.
Abstract
The Algerian palm production represents an important pivot for oasis ecosystem. Approximately, 18
million date palm trees are cultivated on a surface of 169.380 ha. Consequently, Algeria is one of the
highest date fruit producers with about 500 000 tons yearly commercialized worldwide. However the
date-processing companies also generates large amounts of sugar-rich wastes e.g. from damaged
fruits. For the last years, attention has been paid on sustainable management of these wastes and on
their valorization with the aim of developing the organic matter recycling. Therefore, the objectives
of our PhD investigations were to optimize a new culture medium containing date juice for the
growth of Lactococcus lactis. This work is a contribution to the valorization of date waste for the
production of lactic acid at industrial scale. Cultures in batch and fed-batch mode were carried out
with different controlled pH in a Sartorius 2L and 15L stirred bioreactors with optical density
(Fundalux probe) and added base monitoring.
The results obtained showed that Lactococcus lactis growth and acid production were not
significantly affected with a pH ranging between 5.8 and 7. In batch culture at pH 7, the reducing
sugars from date juice at an initial concentration of 14 g/l in the culture medium led to 10.9 g/l of
final concentration of lactate. Prolongation of the culture in fed-batch mode with the addition of a
similar sugar content led to maintain a similar yield of lactate with concentration of 20 g/l. Similarly,
lactic acid productivity remains stable with 0.66 g/l/h and 0.62 g/l/h for cultures in mode batch and
fed-batch, respectively. However, no further growth was achieved as measured by the OD probe and
by classical UFC or OD methods in samples.
497
PRODUCTION OF LACTIC ACID FROM WASTE POTATO INDUSTRY
K. ALSAYED MAHMOUD1, M. AOUN2, E. MEJRI2,

F. Z. RAS EL GHERAB3, S. HILIGSMANN1
1 3BIO-Bio Tech Unité de Biotechnologie et Bioprocédé, Ecole polytechnique de Bruxelles, Université

Libre de Bruxelles, Belgium.
2 Université Libre de Tunis, Tunisia.
3 Laboratoire de Biologie des Microorganismes et Biotechnologie, Department of Biotechnology,
Faculty of Sciences of Nature and Life, University of Oran 1 – Ahmed Ben Bella, Oran, Algeria
Abstract
Potato industry is well known for the vast quantities of organic wastes generated in potato-
processing operations. Approximately 8% of potato weight is the typical steam peeling losses, which
presents about one million tons of waste each year. Managing the waste of potato peel causes
considerable concern to potato industries, which implies the need to identify an integrated approach
and an environmental solution. Potato waste could be used in food processing, phyto-
pharmaceutical and biosynthesis industries aiming to increase its added value by recycling with
several advanced processing technologies such as lactic acid, biogas production, and phenolic acids
extraction. Potato industries generate two types of waste: peels and effluents from the peeling and
cooking stage, respectively.
The aim of this study was to reduce this waste by valorization of potato peels and effluents for the
production of lactic acid and cell biomass by Lactococcus lactis. The results of lactic fermentation on
potato peels with different hydrolysis treatments showed that 0.26 IU of α-amylase added in three
steps was the most efficient treatment to achieve acid production reaching 30 g/L. This three-phase
addition was then tested in 2L bioreactors in mixed and pure culture. The results showed that the
culture in presence of the endogenous strains led to a maximum production of lactic acid of 46.4 g/L,
i.e. a yield of 85%.
The fermentation of potato industry effluents particularly rich starch i.e. about 41.7% dry weight
were carried out firstly in a 2L batch bioreactor inoculated with Lactococcus lactis, and secondly in a
15L fed batch bioreactor inoculated by a mixed culture. The results showed that the endogenous
mixed culture system gives a higher production of lactic acid with a yield of 88.84% compared to
those obtained in pure Lactococcus lactis cultures.
Key words: Lactic acid, Waste potato, Fermentation, Lactococcus lactis.
498
THERMOCHEMICAL ENERGY RECOVERY OF MUNICIPAL SOLID WASTE SCENARIO IN

THE STATE OF SÃO PAULO, BRAZIL
SIMÃO. NATHALIA¹,*, DALMO. FRANCISCO¹,², QUEVEDO. HELENO¹, MEDINA. ANA CAROLINA¹, NEBRA.
SILVIA¹, MARTINS. GILBERTO¹, PALACIOS. REYNALDO¹, SANTANA. PAULO¹
1 Federal University of ABC (UFABC), Santo André, Brazil.
2 Federal University of Jequitinhonha and Mucuri Valleys (UFVJM), Teófilo Otoni, Brazil.
*Corresponding author: nathaliamsimao@gmail.com, +55 19 98205-4342.
Keywords: MSW, Waste to Energy, Solid Waste Energy Potential
Abstract
The objective of this paper is to evaluate the potential for electricity generation by thermochemical
energy recovery of Municipal Solid Waste (MSW) in the state of São Paulo, Brazil. São Paulo is the
largest MSW producer of the country, recording 14,568,979 tons in 2016. The electricity consumed in
the state of São Paulo in 2015 was 130,6 GWh, from which the residential sector was responsible for
38 GWh. For the analysis, the landfills that receive MSW from more than one county were considered
individually for the evaluation of the energy generation potential (33 landfills). The other landfills
which receive only the MSW from their own municipalities were divided in 6 populational ranges. For
the analysis of the scenarios, two different thermochemical routes were considered: incineration and
gasification. The incineration presented a slightly higher energy recovery potential (7,683,561
MWh.year-1) than gasification process. Incineration could cover 20.11% of the residential electricity
consumption from São Paulo State, while gasification could cover 20.08%. Considering the total
electricity consumed in the state, the coverage would be of 6.05 and 6.04% respectively. It must be
stressed that for an adequate choice of the most appropriate technological solution, specific
conditions for each municipality must be considered.
499
1- INTRODUCTION
According to the International Energy Agency (IEA), the world generation of municipal solid waste
(MSW) in 2013 has been estimated in 1.3 billion tons, with annual growth projection reaching 2.7
billion in 2050 [1]. Specifically in Brazil, current daily generation is of 13,616 tons.day-1 with projection
of 15,886 tons.day-1 for 2025, for the population of 144.51 and 206.85 million inhabitants respectively
[2].
São Paulo State, whose area extends for 248,222 km², is situated in the southeastern portion of Brazil.
It is the most populous state, with approximately 44.75 million inhabitants (21.7% of the country’s
total), comprising the highest concentration of economical activities of the country.
The waste generated in São Paulo State is annually surveyed by the Environmental Company of São
Paulo State (CETESB), whose data are published in the report called State Inventory of Municipal Solid
Waste (SIMSW). According to the SIMSW published in 2017, based on data collected in 2016, São Paulo
State generated about 40 ktons.day-1, summing up a total of 14,568,979 tons of MSW during the year
2016 [3].
In order to face this high amount of MSW generated in the State, it is necessary to search for
alternatives for the waste treatment and final disposal, as prescribed by the Solid Waste National
Policy (SWNP) [4]. The energy recovery is one of the alternatives foreseen in the SWNP for
environmentally appropriate waste treatment, provided this alternative presents technical, economic
and socioenvironmental feasibility.
The Incineration or combustion of the MSW is one of the thermochemical processes aiming reduction
of the waste volume and mass through its complete oxidation. Energy generation from incineration
takes place through the Rankine cycles, with steam generated in boilers, conducted through steam
turbines, which drive electric generators that generate the electric power.
According to [5], the incineration plants can generate from 0.3 to 0.7 MWh of electricity per ton of
waste , depending on the plant efficiency and the lower heating value (LHV) of the waste.
According to [6], the incineration plants may process from 75 to 1,855 tons of MSW per day. Such data
come from plants that started operation between 2000 and 2013, and are located mainly in Europe,
China and Japan.
Gasification of MSW has been largely studied during the last years. In entrained-flow gasifiers, the
peak gasification temperature is typically in the range 1400 to 1700 °C; however, the exit gas
temperature is much lower; the peak temperature of a fluidized-bed gasifier is in the range of 700 to
900 °C to avoid softening of bed materials[7]. In this process the amount of oxygen is controlled to
avoid the complete combustion and induce the production of a combustible gas, called syngas [8].
The syngas contains minimum amounts of condensables and solid particles , and may be used as
fuel in steam cycles [9]. When passing through a cleaning and purification system, the syngas may
also be used to produce electricity in more efficient systems, such as: gas turbines and internal
combustion engines or, else, as a raw material to produce liquid fuels. Currently, this technology has
commercial plants operating in Europe and Japan [10]. In the gasification process, the fuel should
comply with different characteristics before entering in the reactor; among the most important
characteristics, are the particle size and moisture content [11]. In this study a pretreatment phase
will be considered for this technology.
Having in mind this scenario, the main purpose of this study is to present a panorama of the energy
recovery potential from MSW in São Paulo State using the thermochemical technological route,
comparing the results from different MSW energy recovery technologies: incineration and gasification.
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2- METHODOLOGY
Among the 645 municipal districts of São Paulo State, 367 carry out disposal of their MSW in sanitary
landfills located in their own municipalities, 272 dispose their MSW in sanitary landfills located in other
municipalities within the State, and 6 carry out disposal of their MSW in other states. Among the 367
municipal districts that carry out disposal in their own municipalities there is a wide variation in the
amount of MSW disposed, varying from 0.58 tons.day-1 in Nova Canaã Paulista to 1,470.8 tons.day-1
in Guarulhos.
With the purpose of achieving a better representation of the potential of electricity generation by
these 367 municipal districts, the authors chose to classify them according to their population, as
shown in Table 1, so that the same technologies for energy recovery from MSW may be applied to the
same scale.
Number of Cities mean value

Total Total MSW
Number of Inhabitants Municipal (t y-1)
Population (t y-1)
Districts
0 - 20,000 2,021,986 263 415,644 1,580
20,001 - 50,000 1,951,605 61 485,691 7,962
50,001 - 100,000 1,345,789 20 353,466 17,673
100,001 - 500,000 3,531,141 19 1,121,930 59,049
500,001 - 1,000,000 2,105,123 3 839,522 279,840
>1,000,000 1,337,087 1 536,842 536,842
General Total 12,292,731 367 3,753,094 10,226
Table 1: Municipal districts that carry out MSW disposal in their own local sites, divided according their population range [12] and [13].
The municipal district of Guarulhos was classified separately since it is the only one with more than 1
million inhabitants among those that dispose the MSW in their own municipality.
In these cases, to calculate the energy generation potential, the arithmetic mean of the MSW
produced by all the municipal districts that are in the same group of population range presented in
Table 1 was considered.
For the 272 municipal districts 1 that dispose of their waste in other municipalities, the calculation of
energy generation potential is presented for the total amount of MSW, grouped in 33 landfills of the
State that receive waste from two or more municipal districts, as shown in Table 2.
The first step for planning energy recovery from MSW is the accomplishment of a diagnosis, including
the waste quantification and characterization. For the São Paulo State, quantification is shown in [3],
but there are no available data regarding characterization.
Therefore, to comparatively assess the energy potential of the MSW from São Paulo State, the
gravimetric composition and measurement of the LHV – in a wet base (w.b.) of the MSW from the
municipal district of Santo André – São Paulo State, identified in the study [14] was used.
1
From the 272 municipal districts, four of them dispose their waste in two other municipal sites, nothing in their
own local sites. In this way, the final sum adds up to 268 municipal sites.
501
Population Total MSW

Landfill Municipal Districts
(inhabitants) (t y-1)
1 São Paulo** 7 8,668,883 3,128,758
2 Caieiras* 16 5,945,306 2,112,310
3 Paulínia*** 32 3,402,421 1,125,299
4 Mauá 8 2,140,647 748,874
5 Santos 7 1,649,687 537,163
6 Guatapará 17 1,464,953 501,849
7 Santana de Parnaíba 5 1,212,314 391,203
8 Iperó 11 1,014,983 336,829
9 Itapevi 7 784,284 244,397
10 Jambeiro** 8 833,645 244,284
11 Piratininga**** 17 823,073 232,396
12 Onda Verde 14 626,345 179,854
13 Tremembé 9 564,077 161,326
14 Catanduva 19 458,406 127,108
15 Cachoeira Paulista 12 443,86 120,063
16 Quatá**** 13 421,114 95,809
17 Cesário Lange 7 336,538 95,608
18 Indaiatuba 3 308,943 95,499
19 Rio das Pedras*** 8 238,633 65,255
20 Meridiano 12 207,748 55,381
21 Botucatu 3 167,174 50,516
22 Jardinópolis 5 166,502 44,749
23 Leme 2 104,667 29,437
24 Guará 5 113,529 28,357
25 Sales Oliveira 4 75,723 20,206
26 Tapiratiba 3 79,069 18,816
27 Santa Fé do Sul 2 34,659 9,505
28 Pariquera-Açu 2 32,071 6,161
29 Piacatu 2 10,443 2,456
30 Coroados 2 11,326 2,435
31 Taquaral 2 8,425 1,997
32 Barra do Turvo 2 12,120 1,434
33 Santa Salete 2 3,375 551
Total 268 32,364,941 10,815,884
* The municipal district of São Paulo also disposes of in Caieiras.
** The municipal districts of Suzano and Arujá dispose of in Jambeiro and São Paulo.
*** The municipal district of Piracicaba disposes of in Rio das Pedras and Paulínia.
**** The municipal district of Marília disposes of in Quatá and Piratininga.
Out of the total of 645 municipal districts, six dispose of in other states. Igarapava and Ituverava in
the municipal district of Uberaba, in Minas Gerais State; Arapeí, Bananal and São José do Barreiro
in the municipal districts of Barra Mansa, Rio de Janeiro, in Rio de Janeiro State; and Ribeira in the
municipal district of Rio Negrinho, in Santa Catarina State.
Table 1: Landfills of São Paulo State and Total MSW deposited on a annual basis [3] [12].
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A survey of the generated amount and the MSW and its gravimetric composition are essential to
estimate the energy potential contained in the waste. Table 3 presents data about the gravimetric
composition, the moisture content and the LHV of each fraction of the MSW of the municipal district
of Santo André in 2015. The average LHV that was presented in table 3 was used to calculate
incineration, while for gasification the LHV was calculated using another methodology, due to the need
of MSW pretreatment.
Moisture content
Fraction MSW Fraction (%) LHVf (MJ.kg-1) w.b.
(%)
Organic Matter 44.30 68.21 3.16
Sanitary waste 11.90 52.56 7.67
Plastic 13.80 23.27 23.04
Paper/cardboard/tetrapak 9.90 32.24 9.16
Textile 8.80 31.88 12.9
Inerts (glass. metal and other) 11.30 0.00 0.00
Total 100.00 - -
Table 2: Gravimetric composition from the municipal district of Santo André [14].
ELECTRICITY GENERATION FROM INCINERATION
In order to estimate the theoretical potential of electricity generation from incineration, the LHVf of
each fraction of the MSW, multiplied by their respective percentage in relation to the total
composition, according to data shown in Table 3 was used. Equation 1 presents calculations for the
LHVtotal according to [15].
𝐿𝐿𝐿𝐿𝐿𝐿𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = ∑�𝑀𝑀𝑀𝑀𝑀𝑀 𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 (%) 𝑥𝑥 𝐿𝐿𝐿𝐿𝐿𝐿𝑓𝑓 � /100 (1)
In order to obtain the electricity generated in one year, Equation 2, according to [15], was used,
multiplying the LHVtotal, by the total mass of combustible materials present in the waste composition
in a year. In this case, the inert material fraction was not considered in the calculation.
𝐸𝐸𝑔𝑔 = ∑ 𝑀𝑀𝑀𝑀𝑀𝑀𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝑥𝑥 𝐿𝐿𝐿𝐿𝐿𝐿𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 𝑥𝑥 𝐸𝐸𝑒𝑒 𝑥𝑥 0.28 ( 𝑀𝑀𝑀𝑀ℎ. 𝑦𝑦𝑦𝑦𝑦𝑦𝑦𝑦 −1 ) (2)
Where: ∑ 𝑀𝑀𝑀𝑀𝑊𝑊𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = Total Mass of combustible waste (t.year-1), 𝐿𝐿𝐿𝐿𝑉𝑉𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡𝑡 = mass averaged lower
heating value of the combustible fraction of the MSW (MJ.kg-1), 𝐸𝐸𝑔𝑔 = generated electricity (MWh.year-
1
), 𝐸𝐸𝑒𝑒 = Efficiency of transformation from thermal energy into electricity, assumed as 25% (steam
Rankine cycle) and 0.28 = conversion constant MWh.GJ-1. To calculate the total power, equation 3 is
used:
𝐸𝐸𝑔𝑔
𝑃𝑃 = 8,760 (𝑀𝑀𝑀𝑀) (3)
Where: 𝐸𝐸𝑔𝑔 = generated electricity (MWh.year-1); total operating hours in one year: 8,760 hours.
The generated electricity and the installed total power were calculated for a quantitative of waste
generated along one year; however, for the final calculation of electricity, it was considered 8,000
hours of plant operation, what represents a reduction of about 8.7% in the final generated electricity
503
considering the total installed power. This way, the final generated electricity was calculated by
Equation (4):
𝐸𝐸𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔𝑔 = 𝑃𝑃 𝑥𝑥 8,000 (𝑀𝑀𝑀𝑀ℎ) (4)
Where: P – Total power (MW); Operating hours in one year, considering the maintenance stops: 8,000
hours.
ELECTRICITY GENERATION FROM GASIFICATION
The gasifier chosen to carry out the analysis was a reactor with a moving grate, produced by Energos,
a company with commercial plants installed in Norway and Germany [16]. Due to the fact that the
MSW is composed by different materials, it is necessary to make a pretreatment in order to comply
with several operation parameters required by the reactor with moving grate such as, particles with
150 mm as the maximum size and 15% as the maximum moisture content.
The pretreatment process applied in this work considers the following stages: the first consists of a
separation of 2.5% of the total mass, corresponding to the reciclables portion of the inert fraction, this
value represents the actual average percentage of the waste that is effectively sent for recycling in
São Paulo State [17], assuming that this recycling effort is accomplished by the population (the
generating source of waste), representing a more efficient participation of the population in the
selective separation of waste. The second stage consists of shredding the waste, where the particle
size is reduced up to 150 mm, the maximum size allowed for gasifiers with moving grate [16]. The third
stage is the magnetic separation, where 1.25% of the initial mass is removed, this value corresponds
to the fraction of metals present in the waste [15]. The process of drying is the last stage during the
pretreatment, where the waste moisture is reduced from 51.5% to 15%, which is the required
moisture content for the gasifier [15]. The fuel generated by this process will be called refuse-derived
fuel (RDF).
A Rankine cycle plant to produce electricity was assumed.
Due to the pretreatment carried out in the waste, it is necessary to calculate the LHV of the RDF. The
𝐿𝐿𝐿𝐿𝑉𝑉𝑥𝑥 (MJ kg-1) of each fraction of the RDF is calculated using equation (5) [14], where 𝑤𝑤𝑥𝑥 represents
the final moisture content of each fraction after the drying process, 𝐻𝐻𝐻𝐻𝑉𝑉𝑥𝑥 represents the higher
heating value of each fraction, and ℎ𝑥𝑥 is the hydrogen concentration in dry base (d.b.) (%) of each
combustible fraction.
𝑤𝑤 𝑤𝑤 ℎ 𝑤𝑤
𝑥𝑥
𝐿𝐿𝐿𝐿𝐿𝐿𝑥𝑥 = 𝐻𝐻𝐻𝐻𝐻𝐻𝑥𝑥 𝑥𝑥 �1 − 100 𝑥𝑥
� − 2,444 𝑥𝑥 �100 𝑥𝑥
� − 2,444 𝑥𝑥 �100 𝑥𝑥
� 𝑥𝑥 �8,936 𝑥𝑥 �1 − 100 �� (5)
The 𝐻𝐻𝐻𝐻𝑉𝑉𝑥𝑥 data, as well as data about the hydrogen concentration in dry base (%) from each fraction
were taken from [14], and are presented in Table 4. Table 4 also shows values of the final moisture
contet and 𝐿𝐿𝐿𝐿𝑉𝑉𝑥𝑥 found for each fraction.
The LHV of the RDF was calculated as the mass average of the LHV of all combustible fractions,
resulting in the value of 17.17 (MJ kg-1). Using this value of the 𝐿𝐿𝐿𝐿𝑉𝑉𝑅𝑅𝑅𝑅𝑅𝑅 , the power P (MW) generated
by the gasification plant was calculated using equation (6):
𝑃𝑃 = (𝑚𝑚𝑅𝑅𝑅𝑅𝑅𝑅 𝑥𝑥 𝐿𝐿𝐿𝐿𝐿𝐿𝑅𝑅𝑅𝑅𝑅𝑅 𝑥𝑥 η𝑔𝑔 𝑥𝑥 0.28)/8760 (6)
504
Where; 𝑚𝑚𝑅𝑅𝑅𝑅𝑅𝑅 is the final mass of the RDF generated during the pretreatment phase (ton.y-1), 𝜂𝜂𝑔𝑔 is the
plant’s thermal efficiency, considered equal to 19.3%. Such efficiency considers the consumption of
all the equipment at the plant site, including the pretreatment phase [18]. In addition, 0.28 is the
conversion coefficient (MWhGJ-1). The electricity produced by the plant 𝐸𝐸𝑒𝑒𝑔𝑔 (MWh year-1) is calculated
using equation (7), where 8.000 are the working hours per year of the plant.
Eeg = P x 8,000 (7)
RDF HHVx LHVx

Fraction hx (%) wx (%)
Participation (%) (MJ.kg-1) d.b. (MJ.kg-1) w.b.
Organic Matter 32.1 16.36 5.46 31.06 10.52
Sanitary Waste 10.9 20.10 12.1-4.67 18.87 15.55
Plastic 17.7 33.41 5.4 5.99 29.94
Paper/cardboard/tetrapak 11.6 18.07 5.6 9.08 15.47
Textile 10.3 21.28 5.48 8.95 18.45
Inert (glass, metal and other) 17.4 0.00 - 0.00 0.00
TotalRDF 100.0 - 15 17.17
Table 3: Gravimetric composition and data of the RDF [14]

Table 5 shows the results of the estimates for the annual generation of energy for the respective
technologies, using the landfills listed in Table 2, and for the average values of each population range
shown in Table 1.
This survey has made possible to identify the percentage of the electricity demand that could be
theoretically met by each one of the technologies in São Paulo State, as presented in Table 6.
In accordance with data provided by the Energy Yearbook of São Paulo State [19] for the year of 2016,
the residential consumption of electricity was 38,210,229 MWh.year-1, and for the same year, total
consumption of electricity in SP was 126,981,933 MWh.year-1. Considering the production of
electricity using incineration technology, this cold supply 20.11% of the residential energy
consumption, and 6.05 % of the total energy consumption, while using gaseification technology, it
could supply 20.08% of the residential energy consumption, and 6.04 % of the total energy
consumption.
505
Incineration Gasification Incineration Gasification

Landfills Landfills
MWh.year-1 MWh.year-1 MWh.year-1 MWh.year-1
1 São Paulo 1,650,082 1,647,382 21 Rio das Pedras 34.415 34.358
100,001-
2 Caieiras 1,114,015 1,112,192 22 591.697 590.729
500,000
3 Paulinia 593.473 592.502 23 Meridiano 29.208 29.16
4 Mauá 394.95 394.304 24 Botucatu 26.642 26.598
5 Santos 283.296 282.832 25 Jardinópolis 23.6 23.562
6 > 1,000,000 283.126 282.663 26 Leme 15.525 15.5
7 Guatapará 264.671 264.238 27 Guará 14.955 14.931
Santana de
8 206.317 205.98 28 Sales Oliveira 10.657 10.639
Parnaíba
9 Iperó 177.641 177.35 29 Tapiratiba 9.923 9.907
500,001-
10 442.757 442.033 30 50,001-100,000 186.415 186.11
1,000,000
11 Itapevi 128.893 128.682 31 Santa Fé do Sul 5.013 5.004
12 Jambeiro 128.833 128.622 32 20,001-50,000 256.149 255.73
13 Piratininga 122.564 122.363 33 Pariquera-Açu 3.249 3.244
Onda
14 94.853 94.698 34 Piacatú 1.296 1.293
Verde
15 Tremembé 85.082 84.943 35 Coroados 1.284 1.282
16 Catanduva 67.036 66.926 36 Taquaral 1.053 1.051
Cachoeira
17 63.32 63.217 37 0-20,000 219.207 218.848
Paulista
18 Quatá 50.529 50.446 38 Barra do Turvo 757 755
Cesario
19 50.423 50.34 39 Santa Salete 291 290
Lange
20 Indaiatuba 50.365 50.283 Total 7,683,561 7,670,990
Table 5: Classification of the Technologies for each landfill, considering the energy potential
Electric Power – (%) Electric Power – (%)

Technology Energy (MWh.year-1)
Residential Consumption Total Consumption in SP
Incineration 7,683,561 20.11 6.05
Gasification 7,670,990 20.08 6.04
Table 6: Estimate of the energy potential from the MSW of São Paulo State x real demand
4- CONCLUSIONS
Due to the high amount of MSW that is daily generated in the State of São Paulo, it is necessary to
propose solutions for the waste treatment and final disposal, as foreseen in the Solid Waste National
Policy (SWNP). Energy recovery is among the actions foreseen for environmentally appropriate
disposition of solid waste, since this alternative presents technical and socioenvironmental feasibility.
It is still to be verified the economical feasibility, which was not in the scope of this study.
For the above reasons, this work presented the estimate of the energy potencial from incineration and
gaseification for electricity generation in São Paulo State, considering that all of the MSW generated
in the state were energetically recovered, respecting the present logistic distribution where 33 landfills
506
receive waste from two or more municipal districts of the State, and the average of the municipalitites
that dispose of the MSW in their own landfills grouped in 6 population ranges.
The incineration electricity generation potencial of 7,683,561MWh.year-1, identified in this study,
would be enough to supply 28.00% of the São Paulo City (27,441,478 MWh.year-1), according to data
from the Energy Yearbook of São Paulo State, while the gaseification electricity generation potencial
of 7,670,990 MWh.year-1 would be enough to supply almost the same percentage: 27.95% of the
municipality of São Paulo.
This analysis considers the current situation, but it is important to emphasize that the municipal
districts with low MSW generation can associate in consortial arrangements to obtain benefits of scale
gains in the waste management and energy recovery from the MSW. Management by consortia also
guarantees a better rationalization of the technological resources, cost minimization, optimization
when contracting services, agility in the operation besides technical, managerial and financial gains.
It is important to emphasize that the useful life of the landfills is extremely limited, comparing to a
processing plant, whether incineration or gasification. The use of any of these technologies would
increase the useful life of the landfills studied in this work, decreasing the mass and volume of the
waste that would only be disposed of, since it would be only the final waste produced by these
technologies.
5- ACKNOWLEDGEMENTS
The authors would like to thank the Program of Research and Development of the Electricity Sector
Regulated by ANEEL and the financial support provided by Petrobras, Coordination for the
Improvement of the Higher Education Personnel (CAPES), National Council for Research and
Development (CNPq) (Process PQ 306303/2014-0), Federal University of ABC (UFABC) and Federal
University of the Jequitinhonha and Mucuri Valleys (UFVJM).
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THE ROLE OF WASTE-TO-ENERGY IN THE CIRCULAR ECONOMY
C. VANDECASTEELE1, J. VAN CANEGHEM2, C. BLOCK3

1 Department of Chemical Engineering, KU Leuven, Celestijnenlaan 200F, 3001 Leuven, Belgium.
2 KU Leuven, Campus Group T, Andreas Vesaliusstraat 13, 3000 Leuven, Belgium.
3 2C Ecosolutions, Duivenstraat 95, 3053, Haasrode, Belgium.
Abstract
The aim of the circular economy (CE) is to maintain the value of products, materials & resources for
as long as possible, minimising waste and resource use. In the EU action plan on CE (2 Dec 2015) the
most concrete actions are legislative proposals on waste and targets are set to reduce landfill, and
increase reuse and recycling. For MSW by 2030 prepare for reuse + recycling should exceed 70%,
with prepare for reuse exceeding 5%; disposal should be less than 10% with landfill less than 5%. The
Waste Framework Directive, 2008/98/EC gives a waste hierarchy (WH) with prevention on top,
followed by preparing for reuse, recycling, recovery, disposal. WtE (combustion of waste to give
energy) with high energy efficiency (R1) is to be considered recovery.
WtE is thus lower in the waste hierarchy than prevention, prepare for reuse and recycling, and WtE
does not seem, at first sight, to keep value as long as possible in the economy. Moreover, it can be
asked if WtE does not compete with recycling. Therefore, the purpose of this presentation is to
answer the question ‘Does WtE still have a role to play in the CE?’. In my opinion the answer is yes
for the following reasons:
 WtE combusts only waste that to date cannot be recycled;
 WtE does not compete with recycling, but with landfill (lower in WH);
 WtE Is essential to keep hazardous materials out of the CE;
 A large part of the inorganics in MSW is recycled;
 WtE may generate energy with high efficiency;
 CE needs energy, this may well come from WtE!
These aspects will be considered, discussed and illustrated with e.g. recent data on selective
collection of MSW in Flanders (North of Belgium) and on residual waste, data on MSW treatment in
the EU28, 2015, considerations on the role of waste treatment companies as gatekeeper and enabler
of the CE, recent technological developments on MSWI incineration bottom ash treatment and its
applications [1], information on the Ecluse Industrial Steam Network in Antwerp, Belgium [2], and on
the Keppel Seghers Greater Manchester WtE project (Runcorn, UK), considerations on the energy
need of the CE.
References
[1] Verbinnen, B, Billen, P, Van Caneghem, J, Vandecasteele, C.: Recycling of MSWI Bottom Ash: A Review of Chemical
Barriers, Engineering Applications and Treatment Technologies, Waste Biomass Valor DOI 10.1007/s12649-016-
9704-0
[2] Ecluse: a channel for green energy. Sustainability. http://www.ecluse.be/sustainability/
509
POLY-GENERATION IN BIOMASS GASIFICATION IN SOUTH-TYROL: THE NEXT

GENERATION PROJECT
D. BASSO1, F. PATUZZI1, D. ANTOLINI1, S.S. AIL1, E. CORDIOLI1, V. BENEDETTI1, A. RIZZO2, D.

CHIARAMONTI2, M. BARATIERI1
1 Faculty of Science and Technology, Free University of Bolzano-Bozen, piazza Università 5, 39100
Bolzano, Italy
2 Re-Cord Consortium, Viale Morgagni 40, 50134, Firenze, Italy.
Abstract
South Tyrol is a region in the North of Italy, in which the 42% of the territory is covered by forest. The
small-scale gasification technology has rapidly grown in the last years, representing a viable
alternative for the exploitation of woody residues and their transformation into valuable materials,
such as the syngas. However, the gasification process has a solid carbonaceous by-product (i.e., the
gasification char) that is currently disposed off as waste with an average cost of 145 €/ton. In order
to get insights and to assess the viability of exploiting gasification char as a valuable raw material
under a poly-generation perspective, the NEXT Generation project has been developed and funded
by the Autonomous Province of Bolzano. The main aim of this project was to investigate the
quantity, quality and environmental impacts of the gasification char. During the NEXT Generation
project, a set of representative plants was chosen for the monitoring activity, meaning that both
mass and energy balances were assessed [1]. During the NEXT project, other six plants were
monitored. In this way it was possible both to assess the recent developments in the local
gasification sector and to identify novel or improved technologies. Moreover, the output streams
from the gasification plants were identified and quantified, in terms of total nominal flows. Chars
were collected from the plants and chemically and physically characterized, by means of proximate
and ultimate analysis, BET surface area, calorific value, moisture and ash content. Two possible ways
for char valorization were considered: its utilization for energy production and its utilization as a raw
material for innovative applications (e.g., as a catalyst). For what concerns energy production, two
chars were selected considering their HHV, ash content and humidity, and transformed into pellets,
blended with wood sawdust. Combustion tests were thus performed in lab-scale reactors [2] and the
release of both volatile fuel components and inorganic ash forming elements were determined. The
results were compared to pellets made only by wood sawdust. Char was also studied as an
innovative catalyst. In particular, gasification chars were tested as catalyst materials [3]. The NEXT
Generation project was completed with a thermodynamic analysis of the gasification process,
through which both the gasification products and by-products were assessed qualitatively by their
ability to provide work. The results obtained demonstrate that the gasification process can be
effectively converted into a poly-generation system by using its by-products as a valuable innovative
materials.
References
[1] Patuzzi F., Prando D., Vakalis S., Rizzo A.M., Chiaramonti D., Tirler W., Mimmo T., Gasparella A., Baratieri M.: Small-
Tyrol (Italy). Energy 112, 285–293 (2016).
[2] Carvalho L., Wopienka E., Pointner C., Lundgren J., Verma V.K., Haslinger W., Schmidl C., Performance of a pellet
boiler fired with agricultural fuels, Appl. Energy 104, 286-296 (2013).
[3] Benedetti V., Patuzzi F., Baratieri M.: Characterization of char from biomass gasification and its similarities with
activated carbon in adsorption applications. Applied Energy, In press (2017).
510
Developing waste management systems that recover materials

and energy in the developing world
A.C. (Thanos) Bourtsalas, Nickolas J. Themelis
Earth Engineering Center, Columbia University, New York, USA
The only proven alternative for the management of the post-recycling waste is thermal
treatment for the recovery of energy (waste-to-energy or WTE). The benefits of WTE over
landfilling are mainly associated with the destruction of pathogens, the volume reduction of
the municipal solid waste (MSW) by 90%, the production of about 0.5 MWh of electricity
and more than 0.6 MWh of district heating per ton of MSW combusted; the savings of about
0.5 to 1 ton of Greenhouse Gases emissions per ton of MSW, and the preservation of about 1
sq. meter of land for every 10 tons of MSW. The superiority of WTE over landfilling resulted
in recent regulations in the US able to support WTE projects, the phenomenal growth of
WTE observed in China, the construction of plants announced in Ethiopia, Abu Dhabi, Hong
Kong, and Perth. However, the global picture of waste management indicates that over two
thirds of the global MSW is currently landfilled, mostly in non-sanitary landfills. The
dominance of landfills is mainly associated with the public opposition and the high capital
investment needed for WTE development. The continuing opposition to WTE is based on the
early history of incineration, mainly associated with dioxins and other harmful to public
health emissions. The Earth Engineering Center of Columbia University (EEC-CU)
conducted detailed studies of four nations, i.e. USA, France, S. Korea and China, annual
WTE dioxin emissions and concluded that the emissions were significant below the national
established limits. In addition to this scientific argument, another EEC-CU study found that
the about 1,500 WTE plants worldwide are located on an average distance of 5 km from the
city center that these serve; and therefore, within the city boundaries. A recent study
conducted by the EEC-CU showed that a WTE development is feasible at a significant lower
cost as compared to the past developments, with a high IRR and NPV values.
511
SCREENING THE POTENTIAL OF WASTE-TO-ENERGY PLANTS USING SEWAGE SLUDGE

IN ANDALUSIA (SPAIN)
P. HARO1, A. SINGLITICO2,3, K. DUSSAN2,3, R. MONAGHAN2,3, A. GOMEZ-BAREA1

1 Bioenergy Group, Chemical and Environmental Engineering Department, Escuela Técnica Superior
de Ingeniería, Universidad de Sevilla, Camino de los Descubrimientos s/n, 41092 Seville, Spain.
2 Mechanical Engineering, National University of Ireland Galway, Ireland.
3 Marine and Renewable Energy Research Centre MaREI, Ireland.
Abstract
During the last years, there has been a fast development of wastewater treatment plants (WWTPs)
in compliance with the Directive on Waste-Water Treatment (91/271/EEC). For instance, Spain
achieves an average compliance of 86% of WWTPs with secondary treatment. The large amount of
sewage sludge generated every year might become a problem in regions like Andalusia, where
incineration is not considered a viable option for waste disposal. Currently, the sewage sludge is
used in agriculture. However, there is an uncertainty on how long this situation would continue. The
aim of the study is to analyse the thermal conversion of sewage sludge using gasification as an
alternative treatment, which could provide a sustainable and efficient source of electricity (heat
demand is limited in Southern-Europe). Considering current and foreseeable management in WWTP,
the study is limited to plants with biological stabilization of the sewage sludge using anaerobic
digestion. All WWTP in Andalusia have been identified and characterized, including plant size, type of
treatment, digestate production, use and composition: dry content, organic matter, C/N ratio, heavy
metals, P2O5, K2O, and CaO content. A location-allocation study based on nine potential hubs has
been made for a centralized treatment of the digestate, using capacity (as person equivalent p.e.),
proximity, type of treatment and current use of the digestate as input criteria. The performance of
the gasification plants is assessed based on electricity delivered, characterization of the residues
generated and profitability. The use of conventional (e.g. belt and rotary dryer) and alternative (solar
drying) systems is evaluated. The results indicate that only a banning of agriculture disposal would
make the proposal feasible.
Figure 1: WWTPs in Andalusia (blue) and location of potential hubs for the gasification of sewage sludge.
512
MICRONUTRIENT FERTILIZERS AND FEED ADDITIVES FROM ALFALFA AND

GOLDENROD: TOWARDS THE IMPLEMENTATION OF CIRCULAR ECONOMY
K. CHOJNACKA1, G. IZYDORCZYK1
1 Department of Advanced Material Technology, Faculty of Chemistry, Wrocław. Poland..
Abstract
The purpose: The idea of a circular economy has been very well described in theory. However, there
are no examples of implementations. Interesting direction is the valorization of biomass, so that it
would be possible to use fertilizers extracted from the soil by plants as a source of fertilizer nutrients -
in closed circulation. In addition, alfalfa and goldenrod biomass possesses some unique properties as
it contains functional groups capable of binding and thus concentration of metal cations [1]. Alfalfa
and goldenrod are also butterfly plants, which have capability to fix atmospheric nitrogen. The
purpose of this work was to valorize post-extraction residues of alfa and goldenrod.
The main materials and methods used: The residues originated from the process of supercritical
CO2 extraction, whereby the active components of cosmetics and supplements were obtained. The
direction of utilization was production of micronutrient fertilizers, whereby the biomass served as
biological carrier of nutritionally significant elements [2]. The process was carried out on large-
laboratory scale. All the analyses were carried out in the accredited laboratory according to PN-EN
ISO 17025.
The main results obtained: In this work, we have obtained fertilizers and feed additives based on
alfalfa and goldenrod, by binding micronutrient ions to the surface of cells in the process of
biosorption. The product was obtained on a large-laboratory scale and is an application batch that will
be field-tested. Thus a product containing Cu, Mn and Zn was produced.
The main conclusions of the work: Taking into account the other fertilizer nutrients, the fertilizer can
be classified into micro-element mineral-organic fertilizer.
Acknowledgements
This project is financed in the framework of grant entitled: „Cultivated plants and natural products as
a source of biologically active substances assign to the production of cosmetic and pharmaceutical
products as well as diet supplements” (no. BIOSTRATEG2/298205/9/NCBR/2016) attributed by the
National Center for Research and Development.
References
[1] Rosas-Castor, J.M., Garza-González, M.T., García-Reyes, R.B., Soto-Regalado, E., Cerino-Córdova, F.J., García-
González, A., Loredo-Medrano, J.A.: Methylene blue biosorption by pericarp of corn, alfalfa, and agave bagasse
wastes. Environ. Technol. 35(9-12),1077-90 (2014).
[2] Tuhy, Ł., Samoraj, M., Witkowska, Z., Rusek, P., Chojnacka, K.: Conversion of spent mushroom substrate into
micronutrient fertilizer via biosorption in a pilot plant. Ecological Engineering 84: 370-374 (2015).
513
OPTIMIZATION OF WOOD GASIFICATION CHAIN IN SOUTH TYROL TO PRODUCE BIO-

ENERGY AND OTHER HIGH-VALUE GREEN PRODUCTS TO ENHANCE SOIL FERTILITY
AND MITIGATE CLIMATE CHANGE: THE WOOD-UP PROJECT
D. BASSO1, F. PATUZZI1, T. MIMMO1, G. TONON1, M. BARATIERI1

1 Faculty of Science and Technology, Free University of Bolzano-Bozen, piazza Università 5, 39100
Bolzano, Italy.
Abstract
In South Tyrol, a region in the North of Italy, around 580,000 m 3 of woody biomass are annually used
in more than 70 district heating plants, which altogether produce 724 GWh of heat and 57 GWh of
electricity. During both the GAST Project [1] and the NEXT Generation project [2], more than 40 small-
scale gasification plants were recorded, implementing 13 different gasification technologies,
producing about 7 MW of electrical power and 9 MW of heat. However, the same plants produce more
than 1,000 tons per year of a solid by-product, with chemical and physical characteristics similar to
those of the biochar and which, at present, is treated as a waste, with relevant economic and
environmental costs. A recent national law (G.U. 186 12.08.2015) allows farmers to use biochar as soil
amendment, if it respects a number of physical and chemical parameters. In different experimental
conditions, biochar application to soil proved to have beneficial effects for soil fertility and carbon (C)
sequestration. This double attitude made biochar a globally known and promising material for C
sequestration in terrestrial ecosystems and climate change mitigation. Thus the WOOD-UP project was
developed with the main aim of assessing the characteristics of the gasification char and its effects on
soil fertility and, at the same time, evaluating the quality of the agricultural products and the GHG
emissions. In this work the preliminary results are shown. In particular, an updated map representing
the state of the art of the gasification in South-Tyrol was created, reporting the main characteristics
of the technologies installed in this region. The most promising technologies for the production of char
suitable as soil amendment were selected and on-site continuously monitored, according to the
procedure described in [1]. Chars were collected and characterized. In particular, the pH and electrical
conductivity were measured, proximate and ultimate analyses were performed, and heating value and
ash content of chars were determined. Macro and micronutrients content as well as trace element
content were measured. Finally, char structure was assessed by infrared spectroscopy while the
specific surface and porosity through BET analyser. Phytotoxicity and germination tests were also
performed, using water extracts of six chars and cress (Lepidum sativum L.) as model plant. The results
obtained show that only the double-stage technologies produce a char with values comparable to
those prescribed by the Italian law, although slightly higher than the limits. Hence, to meet the law
requirements post-processing solutions have to be evaluated. Further investigations should be done
to completely assess the possibility to use it in soil and to get insights on the possible soil fertility
enhancements and GHG emissions mitigation.
References
[1] Patuzzi F., Prando D., Vakalis S., Rizzo A.M., Chiaramonti D., Tirler W., Mimmo T., Gasparella A., Baratieri M.: Small-
Tyrol (Italy). Energy 112, 285–293 (2016).
[2] Basso D., Patuzzi F., Gasparella A., Tirler W., Dal Savio S., Rizzo A., Chiaramonti D., Baratieri M., Valorization pathways
for char from small scale gasification systems in South-Tyrol: The “NEXT Generation” project. EUBCE 2017 Conference
Proceedings.
514
UTILIZATION OF WASTE VERSUS COMMERCIAL MG SOURCES TO STRUVITE-BASED

FERTILIZER PRODUCTION FROM SOURCE-SEPARATED HUMAN URINE
J. SANTOS1, T. LLANO1, E. CIFRIAN1, A. ANDRES1

1
Department of Chemistry and Process & Resource Engineering, Green Engineering and Research
Group (www.geruc.es). University of Cantabria, Avda. Los Castros s/n, Santander 39005 Cantabria,
Spain.
Abstract
The biochemical cycles of nitrogen and phosphorous have been radically changed by humans as a
result of many industrial and agricultural processes. Nitrogen and phosphorous are both essential
elements for plant growth, so fertiliser production and application is the main concern. Human urine
contains significant quantities of these macronutrients. On the other hand, such macronutrients
presented in domestic wastewaters cause eutrophication in water bodies and groundwater
resources [1]. The aim of this research is to obtain struvite, a slow release fertilizer through human
urine using different Mg+2 sources: two commercial reagents (MgCl2 and MgO), waste brines and
seawater. The two selected commercial reagents constitute the most common precipitants for
struvite precipitation. Synthetic brine solution and seawater were already studied for struvite
formation, using synthetic and real urine [2]. The novelty of this research was the use of the
wastewater with high brines concentrations from the canning industry as alternative Mg source,
with the aim to carry out the comparative study of commercial and alternatives Mg sources. A
factorial design of experiments was developed to assess the combined effect of stirring speed (30, 45
and 60 rpm), pH value (9, 9.3 and 9.5) and Mg+2:P molar ratio (1:1, 1.5:1, 2:1) with the purpose of
recovering macronutrients (N and P) from source-separated human urine for the struvite formation.
Precipitates collected were dried, weighted and analysed by X-ray diffraction (XRD) and scanning
electron microscopy-energy dispersive spectrometer (SEM-EDS). The optimization of the factors
affect to struvite precipitation from different Mg sources showed that using seawater at 30 rpm
(stirring speed), a pH of 9.5, and 2:1 Mg+2:P molar ratio achieved the highest Phosphorous recovery
(99.96 %). The experimental and simulated data fitted adequately giving a standard deviation less
than 15%.
References
[1] Santos, J., Cifrian, E., Llano, T., Rico, C., Andrés, A., Alegria, C.: Review of potential ways for resource recovery from
human urine. In: WASTES solutions, treatments opportunities II. (eds.) CRC Press, pp. 203-208. Taylor & Francis
Group, London UK (2017).
[2] Liu, B., Giannis, A., Zhang, J., Chang, V.W.C., Wang J.Y.: Characterization of induced struvite formation from source-
separated urine using seawater and brine as magnesium sources. Chemosphere 93, 2738-2747 (2013).
515
EVALUATION OF IN-VESSEL AND PILOT SCALE COMPOSTING AS AN ALTERNATIVE

FOR FOOD WASTE VALORIZATION
I. MICHALOPOULOS1, G.M. LYTRAS1, S. MICHALAKIDI1, S. ZGOURI1, K. PAPADOPOULOU1,

G. LYBERATOS 1, 2
1 School of Chemical Engineering, National Technical University of Athens Iroon Polytechneiou 9,
Zografou 157 80, Athens, Greece.

2 Institute of Chemical Engineering Sciences (ICE-HT), Stadiou Str., Platani, 26504 Patras, Greece.
Abstract
Food Residue Biomass (FORBI) is generated by drying and shredding the fermentable fraction of
household food waste collected door-to-door in the Municipality of Halandri, Greece. The potential
valorization of FORBI for the production of compost is investigated in this work.
Two types of composters were used: an in-vessel composter with an operating volume of 28 L and a
pilot-scale composter with a volume of 280 L. Stirring of both composters was carried out once every
24 hours for the homogenization of the substrate and a temperature sensor continuously recorded
the temperature evolution of the composting mixture. The maximum temperature of the compost
reached up to 52.2 0C for the in-vessel and 67.8 0C for the pilot scale composter, respectively.
Additional parameters, such as moisture, pH, electrical conductivity, FAS, TS, VS and TKN, were
evaluated.
The experimental results obtained were used as a basis for the development of a model by using the
AQUASIM software.
Reference
[1] Kumar, M., Lin, J.G.: Co-composting of Food Waste and Green Waste in Pilot-Scale Systems: In-vessel and Windrow
Investigations Dynamic Soil, Dynamic Plant (Special Issue 2), 127-133, Global Science Books. (2011).
516
EFFECT OF pH ON THE ANAEROBIC FERMENTATION OF FRUIT/VEGETABLES AND

DISPOSABLE NAPPIES HYDROLYSATE FOR BIO-HYDROGEN PRODUCTION
K. TSIGKOU1, P. TSAFRAKIDOU2, S. ATHANASOPOULOU1, C. ZAFIRI 2, M. KORNAROS1

1 Department of Chemical Engineering, University οf Patras, 26504 Patras, Greece.
2 GREEN TECHNOLOGIES Ltd, 26223 Patras, Greece.
Abstract
Purpose: Bio-hydrogen is a promising alternative fuel that could replace efficiently fossil fuels due to
its clean and high-energy yield [1]. Among the parameters that effect bio-hydrogen production
through anaerobic fermentation, pH has been found to be the most important to the distribution of
acidogenic metabolites. The objective of this work was to optimize the anaerobic fermentation of a
mixed waste stream, consisted of fruit and vegetables that have lost their marketing value and a
disposable nappies hydrolysate. More specifically, the aim was to identify the optimal pH value for
maximum hydrogen production and valuable metabolites, such as organic acids and ethanol.
Materials and Methods: A wide range of pH values was tested (from 4.5 to 7.5) using an automatic
controller system in batch fermentations that took place in mesophilic conditions (37°C). The first set
of experiments was carried out with the fruit/vegetable mixture, diluted with water (2:3) and
subsequent trials followed using a fruit/vegetable mixture with disposable nappies hydrolysate at a
2:3 ratio. Physicochemical characterization of waste streams was conducted, as well as
quantification of ethanol, organic acids and hydrogen production during fermentations.
Results: According to the obtained results, pH 6.0 exhibited the maximum hydrogen production
volume (0.52 mol H2 (STP)/mol equivalent glucose consumed) for the fruit/vegetable stream, while
the maximum concentration of ethanol and organic acids (18.16 g/L) was reached at pH 7.5 for the
same substrate. Regarding the mixed waste stream (Fig. 1), both hydrogen production and
metabolites concentration reached a maximum at pH 7.5 with 1.12 mol H2 (STP)/mol equivalent
glucose consumed and 18.28 g/L respectively.
Conclusions: It is evident that with the proper adjustment of operating pH, bio-hydrogen production
can be maximized and this mixed waste stream can be effectively valorized.
H2 CO2
5000
4000
H2, CO2 (mL)
3000
2000
1000
0
6 6.5 pH 7 7.5
Figure 1: Total Hydrogen (H2) and CO2 volume produced as a function of different pH values tested for fruit/vegetable mixture with
disposable nappies hydrolysate (2:3).
Reference
[1] Dareioti, M., Vavouraki, A.I., Kornaros, M.: Effect of pH on the anaerobic acidogenesis of agroindustrial wastewaters
for maximization of bio-hydrogen production: A lab-scale evaluation using batch tests. Bioresour. Technol. 162, 218–
227 (2014)
517
MOLYBDENUM EXTRACTION FROM SPENT CATALYST USING E. COLI:

PRE-TREATMENT AND BIOLEACHING STUDIES
S. DAS1, Q.W. WOON1, Y.P. TING1

1 Chemical and biomolecular engineering department, national university of Singapore, Singapore
117576
Abstract
Spent catalysts contain significant concentration of toxic heavy metals such as molybdenum, nickel
and vanadium, and are categorized as hazardous waste. Due to stringent environmental regulations
governing hazardous waste, spent catalysts must be treated properly before disposal 1. Although
hydrometallurgical and pyrometallurgical processes are commonly used for metal recovery from
these wastes, major drawbacks include high energy consumption and the discharge of toxic by-
products and concomitant costlier downstream treatment. Bioleaching may be used to effect metal
extraction via biogenically produced metabolites and thus provide a green alternative to
conventional leaching methods. Unfortunately, slow reaction rate and low lixiviant concentration are
the major drawbacks of the bioleaching process2. In spent catalysts bioleaching, molybdenum
extraction has typically been lower than other metals such as aluminum and nickel. The main
objective of this study is to enhance molybdenum extraction using the bacterium Escherichia coli.
The growth of the anaerobe is linked to rapid uptake of oxygen and a reducing environment in the
growth media and results in alkaline condition. To reduce the toxic effect of heavy metals on the
growth of the bacteria, two-step bioleaching was adopted where the spent catalyst was added only
after the bacterial culture has reached stationary phase, and maximum pH and metabolite
concentration have been attained. Maximum molybdenum and nickel extraction at 53% and 62%
respectively was obtained with spent catalyst (particles size 100-250 μm) at 1% pulp density in an E.
coli culture (pH 9.5) over 14 days. To improve molybdenum extraction, the spent catalyst was pre-
treated by decoking. Bioleaching of the decoked catalysts resulted in 62.0% Mo extraction under the
same conditions. It is likely that ammonia released during protein metabolism of E. coli and sodium
chloride present in the growth media are main compounds responsible for Mo extraction in the form
of ammonium and sodium molybdates.
References
[1] [1] Srichandan, H., Pathak, A., Singh, S., Blight, K., Kim, D.-J., & Lee, S. W.: Sequential leaching of metals from spent
refinery catalyst in bioleaching–bioleaching and bioleaching–chemical leaching reactor: Comparative study.
Hydromet. 150, 130-143 (2014)
[2] [2] Vyas, S., & Ting, Y. P.: Sequential biological process for molybdenum extraction from hydrodesulphurization spent
catalyst. Chemosphere, 160, 7-12 (2016)
518
OPTIMIZATION OF GOLD BIORECOVERY AND BIOMINERALIZATION OF GOLD

BIOLEACHATE FROM ELECTRONIC WASTE
S. DAS1, G. NATARAJAN1, Y. P. TING1

1 Chemical and biomolecular engineering department, national university of Singapore, Singapore
117576
Abstract
Millions of metric tons of electronic waste (E-waste) are generated worldwide annually due to rapid
technological advancements and shortening life span of electronic devices. Only a small portion of
the waste is recycled; the majority end up in landfills or incinerated 1. E-waste contains toxic heavy
metals that can contaminate the groundwater system causing serious health and environment
problems. Recycling of E-waste and recovery of precious and critical metals from these wastes has
many environmental, economic, and social benefits. This work examines gold bio-recovery from
electronic scrap materials (ESM) using the bacterium Chromobacterium violaceum which produces
and detoxifies cyanide at different growth phases. The strain was genetically modified to increase its
cyanide production for enhanced gold bioleaching efficiency 2. A statistical optimization method,
termed response surface methodology, was employed to optimize the bioleaching process in a 2L-
bioreactor following a two-step bioleaching approach. The effect of four factors (independent
variables), namely pulp density, dissolved oxygen (DO), pH and glycine, on gold recovery (responses)
was investigated. Pulp density and pH were identified as the most significant factors affecting gold
recovery. Optimum conditions for maxmising gold recovery were found to be: Pulp density - 0.5 %
(w/v), DO - 27%, pH - 10 and Glycine – 8 g/L, with the highest gold recovery of 36.5% obtained under
these conditions, compared to 11.3% and 30% recovery using the wild strain and pBAD in shake flask
experiments. Conventionally, metals are recovered from the bioleachate using processes such as
electrowinning, adsorption, ion-exchange extraction or zinc cementation. However, these methods
are costly and have low selectivity in multi-ion solutions. In this study, gold from the bioleachate was
recovered as nanoparticles via biomineralization of the leachate. The bacterium Delftia acidovorans
overcomes Au3+ toxicity through the release of a secondary metabolite (delftibactin) which reduces
and complexes gold as nanoparticles 3. This study demonstrates the application of RSM for the
optimization of bioleaching for precious metal recovery from E-waste, and the subsequent recovery
of gold as nanoparticles.
References
[1] Zhang, L., and Z. Xu.: A review of current progress of recycling technologies for metals from waste electrical and
electronic equipment. J. of Cleaner Production 127, 19-36 (2016)
[2] Tay, S. B., Gayathri N., Muhammad N. A. R., Hwee T. T., Maxey C. M. C., Ting Y.P., and Wen S. Y.: Enhancing gold
recovery from electronic waste via lixiviant metabolic engineering in Chromobacterium violaceum. Sci. rep. 3 (2013)
[3] Johnston, C.W., Wyatt, M.A., Li, X., Ibrahim, A., Shuster, J., Southam, G. and Magarvey, N.A.: Gold biomineralization
by a metallophore from a gold-associated microbe. Nat. Chem. Biology, 9(4), 241-243 (2013)
519
HYDROTHERMAL LEACHING OF CATHODE MATERIAL OF LITHIUM ION BATTERY
D. AZUMA 1, M. WATANABE 1,2, R. L. SMITH, JR.1,2

1 Graduate School of Environmental Studies, Tohoku University, Sendai, Japan
2 Research Center of Supercritical Fluid Technology, Tohoku University, Sendai, Japan.
Abstract
Demand for lithium ion batteries remarkably increased each year because mobility and home energy
supplies are being shifted into on-demand electricity due to eco- consciousness and awareness of
renewable energies. LiCoO2 is one of the main cathode materials of lithium ion batteries and the
price of lithium and cobalt in LiCoO2 is recently rising due to the increase in demand. Cations (Li, Co)
are geographically located in remote areas and geopolitical issues also affect supply. Thus, the price
of Li and Co can be unstable not only due to demand but also due to logistic and political and
reasons. For resource security, technologies for Li and Co must be developed from discarded energy
and mobile.
Commercially available LiCoO2 (0.1 g) and 10 ml of citric acid aqueous solution having a
predetermined concentration (0.01 M to 0.6 M) were placed in a pressure resistant cell and sealed.
After replacing the gas phase with N2 (1.0 MPa), the mixture was heated to a predetermined
temperature (90 ˚C to 175 ˚C) with stirring and allowed to react for a predetermined time (5 min to
30 min). After completion of the hydrothermal treatment, the reactor was cooled and the recovered
solution was filtered off. The metal in the solution was quantified by ICP-AES and the leaching
efficiency was calculated based on the raw material. The presence or absence of a metal complex
was analyzed using UV-Vis. The composition of gas generated was analyzed with GC-TCD and the
amount of citric acid oxidized into carbon dioxide was considered.
At 90 ˚C, the leaching efficiencies of Li and Co were about 60% and 40%, respectively, but as the
temperature increased, the leaching efficiencies increased. At 175 ˚C, both Li and Co were leached
by over 90%. In previous research, H2O2 was added as a reducing agent because leaching efficiency
was improved by reducing trivalent Co in LiCoO2 to divalent, whereas in this experiment H2O2 was
not required [1-3]. According to a report [4] that citric acid forms a complex with Co both divalent
and trivalent, analysis of the reaction solution by UV-Vis confirmed the complexes. The rate of
decomposition of citric acid at 150 ˚C was slow; at 200 ˚C for a reaction time of 30 min, the
conversion rate remained at 0.2% [5], whereas in this experiment 5.3% CO2 production was
confirmed. Therefore, under hydrothermal conditions, citric acid exhibited complex-forming ability
and a reducing action, which gave good leaching results.
References
[1] M. K. Jha, A. Kumari, A. K. Jha, V. Kumar, J. Hait, B. D. Pandey, Waste Manage. 33 (2013) 1890－1897.
[2] C. K. Lee, K. I. Rhee, J. Power Sources, 109 (2002) 17-21.
[3] L. Li, J. Ge, F. Wu, R. Chen, S. Chen, B. Wu, J. Hazard Mater. 176 (2010) 288－293.
[4] G. P. Nayaka, J. Manjanna, K. V. Pai, R. Vadavi, S. J. Keny, V. S. Tripathi, Hydrometallurgy 151 (2015) 73－77.
[5] M. C. Carlsson, Habenicht, L. C. Kam, M. J. J. Antal, N. Bian, R. J. Cunningham and M. J. Jones, Ind. Eng. Chem. Res. 33
(1994) 1989－1996.
520
SELECTIVE HYDROMETALLURGICAL RECOVERY OF Zn AND Pb FROM JAROSITE

RESIDUE
L. HORCKMANS, F. KUKURUGYA, J. SPOOREN, W. VEREYCKEN1

1 VITO – Flemish Institute for Technological Research, Boeretang 200, 2400 Mol, Belgium.
Abstract
Jarosite sludge is an Fe-rich residue obtained during hydrometallurgical Zn production. The

sludge is mainly composed of jarosite, an iron sulphate rich mineral. Yearly, 500,000 tonnes of Fe-
rich sludges from Zn production and recycling are landfilled in the EU. In addition, there is a vast
historical reserve of stockpiled materials. Due to the significant Zn (4-7%), Pb (4-9%), Cu (0-0.3%) and
Cd (0-4%) [1-3] content, jarosite residues are considered hazardous to soil, water and human health
[1].
The formation of jarosite is as follows [1]:
3𝐹𝑒2 (𝑆𝑂4 )3 + 𝑋2 𝑆𝑂4 + 12𝐻2 𝑂 = 2𝑋𝐹𝑒3 (𝑆𝑂4 )2 (𝑂𝐻)6 + 6𝐻2 𝑆𝑂4 (1)
where X represents H3O+; Na+, K+, NH4+, Ag+, Li+ or ½Pb2+.
The jarosite sludge studied in this paper contained Pb incorporated in the jarosite structure,
as described by equation (1), and Zn present as ZnS. FeS2 and CaSO4*2H2O were also identified in the
sample.
The purpose of this work was to selectively recover Zn and Pb from the jarosite residue by a
process based on a combination of thermal treatment followed by 3 leaching steps at atmospheric
pressure and room temperature. The thermal decomposition temperature and used leaching agents’
concentrations were experimentally optimized. In the 1st leaching step, distilled water was used to
selectively leach almost 100% Zn from decomposed jarosite residue. In the 2nd leaching step 90% of
Pb was selectively leached at a close to neutral pH, leaving Fe in the solid residue. Arsenic content,
which accumulated in the solid residue during the treatment, was significantly reduced by a 3rd
leaching step.
The results of the presented work clearly show the possibility to selectively recover Zn, Pb and As
from jarosite residue at room temperature and atmospheric pressure.
This work was carried out in the framework of the METGROW+ project. This project has received
funding from the European Union’s Horizon 2020 research and innovation programme under grant
agreement No 690088.
References
[1] Liu, C. et al.:Recovery of valuable metals from jarosite by sulphuric acid roasting using microwave and water
leaching. Canadian Metallurgical Quarterly, Vol.56, No.1, 1-9 (2017).
[2] Ju, S. et al.:Clean hydrometallurgical route to recover zinc, silver, lead, copper, cadmium and iron from hazardous
jarosite residues produced during zinc hydrometallurgy. Journal of Hazardous Materials, 192, 554-558 (2011).
[3] Han, H. et al.:Anglesite and silver recovery from jarosite residues through roasting and sulfidization-flotation in zinc
hydrometallurgy. Journal of Hazardous Materials, 278, 49-54(2014).
521
LITHIUM RECOVERY FROM SIMULATED PYRO-SLAG OF LITHIUM BATTERY BY

CHLORINATED ROASTING
BENFENG WANG, ZHIDONG CHANG, JIAHUI GUO, XUE WU, CHANGYAN SUN, WENJUN LI
1Department of Chemistry and Chemical Engineering, School of Chemistry and Biological
Abstract
The epoch of electric vehicles seems coming after the announcement of the prohibition of the sale of
fuel vehicles by Germany, France, Netherland, Norway etc. The core of electric vehicles is the
rechargeable Battery in which the lithium battery holds the irreplaceable position to date [1]. The
consumption of the lithium batteries will increase dramatically with the booming of electric vehicles.
The global lithium reserves are 13.5 million tons of pure metal[2]. According to the current
consumption growth rate of lithium, the existing lithium resources can only be maintained to 2038
years, which drive us to recycle the lithium from the end-life-lithium-battery. The current
hydrometallurgical and the pyrometallurgical progresses used in the lithium batteries treatment just
focus on precious metals as Co, Cu, Ni etc [3]. Normally, the lithium is left as a solid waste, a slag
containing Li, Al, Ca and Si, untreated [4].
In this work, we proposed a chlorinated roasting method to recover lithium through the flue gas. The
possibility and efficiency of chlorinated roasting was investigated and evaluated by
thermogravimetric analysis atomic absorption spectrum and XRD analysis in a simulated system. The
simulated slag was calcined with the addition of calcium chloride at 900-1000 degrees and 97.2%
lithium can be evaporated into the flue gas.
Keywords: Lithium recovery chlorination roasting Evaporation recovery Stimulated slag
References
[1] Chagnes, A. and B. Pospiech, A brief review on hydrometallurgical technologies for recycling spent lithium-ion
batteries. Journal of Chemical Technology & Biotechnology, 2013. 88(7): p. 1191-1199.
[2] Swiatowska, J., Lithium Process Chemistry - Resources, Extraction, Batteries, and Recycling. 2015.
[3] Georgi-Maschler, T., et al., Development of a recycling process for Li-ion batteries. Journal of power sources, 2012.
207: p. 173-182.
[4] Ekberg, C. and M. Petranikova, Chapter 7 – Lithium Batteries Recycling. Lithium Process Chemistry, 2015: p. 233-267.
522
SUSTAINABILITY ASSESSMENT - CASE SLOW PYROLYSIS
H. WESSMAN-JÄÄSKELÄINEN.1, K. MELIN1, M. ALAROTU1

Abstract
Research focuses on sustainable solutions for a wide variety of solid residues and biomasses. The aim
is to evaluate the environmental and economic sustainability of different technologies.
Environmental and economic assessments are presented through the case on slow pyrolysis of forest
biomass in a mobile unit. Slow pyrolysis (carbonization) is a thermal conversion process where wood
or other biomass material is slowly heated in the absence of air or oxygen up to final temperature of
about 500ºC. Slow pyrolysis process yields solid char (charcoal), volatile condensable compounds
(distillates) and volatile non-condensable gases (see Figure 1).
Figure 1: Slow pyrolysis batch process and value chain
Environmental sustainability is based on life cycle assessment (LCA) covering the value chain from
the forest to the mobile production phase (cradle-to-gate approach). Economic assessment
evaluates the economic performance of the proposed technology, depending on factors such as
business model and costs. The results of the two subcases are presented. Furthermore, the
challenges and benefits of the mobile concept for slow pyrolysis are discussed.
References
[1] Kujanpää, M., Eggers, J., Verkerk, H., Helin, T., Lindner, M., Wessman, H.: Carbon balance of forest residue collection
and combustion in Southern Finland. 18th European Biomass Conference and Exhibition, Lyon, France (2010).
[2] Dutta, B., Raghavan, V.: A life cycle assessment of environmental and economic balance of biochar systems in
Quebec. Int J Energy Environ Eng 5:106 (2014)
523
ECONOMIC FEASIBILITY AND BUSINESS PLANS FOR SMALL-SCALE FIELD OPERATING

BIOREFINERY UNITS
E. MARKSTRÖM1*, A. BYSTEDT1, F. ENGLUND2, H. HOLMBERG2, K. MELIN3, G. HAARLEMMER4

1 Research Institutes of Sweden, Skellefteå, Sweden.
2 Research Institutes of Sweden, Stockholm, Sweden.
4 Univ. Grenoble Alpes, CEA LITEN DTBH/SBRT/LTCB, 38000, Grenoble, France
Abstract
The economic potential, the business models applied, and the business plans play pivotal roles in the
assessment of the overall feasibility of the biorefinery processes explored in the project MOBILE FLIP
(Mobile and Flexible Industrial Processing of Biomass). Many industrial processes, including
biorefinery plants, typically seek higher profitability through centralisation, conglomeration and
increased plant sizes. However, the basis for the MOBILE FLIP project is the ambition to place the
initial treatment of a variety of biomass feedstock as close as possible to the source, thereby
minimizing the transports of bulky raw materials. The treatment units should thus be mobile and
limited in size, but also flexible and apt to handle different feedstocks, which can enable the
utilisation of certain feedstocks that occur in too small volumes or too scattered to be considered for
a full-size industrial plant. Brewery spent grains (BSG) from small scale breweries, residues from fruit
orchards or wood harvesting residues near roads are examples of such cases to consider.
The degree of mobility, the optimal localisation in relation to transport routes and other forms of
infrastructure, and the ownership and business models are variables to consider in the economic
analyses.
The five technology tracks selected for the project (torrefaction, slow pyrolysis, pelletization,
hydrothermal carbonization, hydrothermal saccharification) have different prerequisites and mobile
treatment units must be evaluated separately for these cases. A main conclusion is that the business
models are highly dependent on transport distances, raw material and owner structure in different
parts of Europe, strongly influencing the business plans and the feasibility of biorefinery processes in
mobile units.
Due to the capacity limitations, personnel costs may play a more pronounced role than in big plants,
which furthermore underlines the need for searching optimal localisation where existing
infrastructure can be co-utilized. In many cases this will be in conjunction with a production facility
like a sawmill, a smaller food industry or a terminal for biomass collection and sorting. Opportunities
for partial remote control of the operation may also be a very beneficial factor.
524
TORREFACTION OF AGRICULTURAL AND FORESTRY FEEDSTOCKS IN A PILOT SCALE

FACILITY: COMPARISON OF MASS AND ENERGY BALANCES.
T. MELKIOR1, M. PEREZ1, S. THIERY1, P. PONSDEVINCENT1, A. CHATROUX1, M. GONZALEZ-MARTINEZ1,

C. DUPONT2
1 Univ. Grenoble Alpes, CEA, Laboratoire de Préparation des Bioressources (LPB), Grenoble, France.
Abstract
This work, which is part of the European project Mobile Flip, is focused on the use of torrefaction to
improve the characteristics of different underexploited biomass side streams from agriculture and
forestry. The main objective is to produce different batches of several hundreds of kilograms of
torrefied material for further pelletization and then use as combustion fuel in particular. This
experimental campaign offers the opportunity to evaluate a torrefaction technology at a pilot scale
and to compare the results obtained under different conditions and with different feedstocks.
The equipment used was the pilot scale furnace of CEA biomass platform located in Grenoble
(France). It is a multiple-hearth furnace (MHF) with 6 hearths and direct heating ensured by 2
burners at each stage. It is 6.5 m in height with an inner diameter of 1.8 m and has a capacity of 150
kg/h of torrefied product. The facility is equipped with several sensors to continuously monitor
temperature at different points, oxygen level, inlet and outlet mass flow rates. Gas composition is
measured online and volatile species can be trapped for further analysis. These data are used to
calculate mass and energy balances.
Conveying and torrefaction tests were performed with two forestry feedstocks, namely beech and
poplar 15 mm-ground chips, and two agricultural residues, namely corn cob and wheat straw ground
below 15 mm or 30 mm. Table 1 summarizes the experimental program and gives the mass losses
measured for each test. Agricultural feedstocks were found to be harder to process because of their
physical aspect but also due to their higher reactivity. The influence of moisture content in different
batches of the same feedstock could also be highlighted.
Biomass AWL (%)
Poplar chips 250 °C 75 min 21
Beech chips 250 °C 75 min 20
Corn cob 250 °C 75 min 14
30mm
15mm
15mm
Figure 1: Scheme of the CEA torrefaction facility
Table 1: Average anhydric weight losses (AWL) measured for
different torrefaction tests
525
DEVELOPMENT OF THE MOBILE DEMONSTRATION UNIT FOR BIOMASS

TORREFACTION FROM PRE-INDUSTRIAL SCALE TESTS
M. HURON1, P. SAJET1, O. LEPEZ1, T. MELKIOR2, M. PEREZ2, S. THIERY2, P. PONSDEVINCENT2, A.

CHATROUX2, M. GONZALEZ-MARTINEZ2, C. DUPONT3, M. MARCHAND2
1
ETIA, Compiègne, France
2
Univ. Grenoble Alpes, CEA, Laboratoire de Préparation des Bioressources (LPB), Grenoble, France.
3
IHE Delft Institute for Water Education, Department of Environmental Engineering and Water
Abstract
The Mobile Flip project aims to develop mobile demonstration units to valorise underexploited
agricultural and forestry biomass waste in Europe. One of the proposed technologies, torrefaction,
consists on a mild thermal treatment (200- 350°C), under an inert atmosphere, producing a solid
with optimized processing and thermal properties. The conception of the mobile demonstration unit
is organised in the project in two interconnected tasks. While the aim of WP2 is to evaluate the
process flexibility and product quality at lab and pre-industrial scales, WP3 is focused on the design,
construction and operation of a mobile demonstration unit. This leads to strong collaboration
between these two work packages. The strategy and the main results of this collaboration are
presented herein.
In the framework of Mobile Flip WP2, lab-scale torrefaction tests in CEA have enabled to
characterize the behaviour of 10 representative dry biomasses, in terms of mass loss kinetics,
products yields and exothermicity during torrefaction, as well as of fire risk. Secondly, preindustrial
scale tests in the CENTORRE torrefaction furnace (CEA) were carried out, in order to set process
operating conditions and derive upscaling. CENTORRE is a multiple hearths furnace with direct
heating, continuously monitoring of temperature at different points, oxygen level, mass flow rates
(inlet and outlet) and a capacity of 150 kg/h of torrefied product. Gas composition was measured
online and volatile species were trapped to be further analysed, in order to calculate detailed mass
and energy balances.
Results of WP2 were used for the conception, design and testing of the mobile torrefaction unit
(WP3). The mobile unit TERMOBIO is composed of three steps: a dryer (allowing moisture content
up to 50%), the torrefaction unit based on TERMOBIO system developed by ETIA and a cooling
system for the torrefied material. It is designed to be included in two containers and is limited to 100
kg/h inlet mass flowrate in the torrefaction unit, so as to fulfil mobility requirements. Thermal
integration is planned by combustion of the torrefaction gases as well as a small part of the torrefied
material to lower drying/torrefaction costs. Several Mobile Flip biomasses will be torrefied in both
CENTORRE and TERMOBIO and their properties will be compared. Operating conditions will be
adapted according to the specificity of each system to fulfil the same targets in terms of mass loss.
Because CENTORRE and TERMOBIO reactors have differing characteristics (particles size limitation,
capacity, mobility), they are complementary and will not address to the same markets. This work
gives a rare occasion to deeply compare the performance of different technologies.
526
EVALUATION AND DEMONSTRATION OF SLOW PYROLYSIS TECHNOLOGY IN

CONVERSION OF VARIOUS BIOMASSES IN MOBILE APPLICATION
A.KÄLLI1, T.RAUSSI2, K.RASA3, S.LARSSON4

2 Raussin Energia Oy, Kouvola, Finland.
3 Natural Resources Institute Finland, Luke, Jokioinen, Finland.
Abstract
The worldwide need for renewable raw materials to produce various products and energy grows
larger year by year. Therefore focus is moving towards utilizing also the more difficult-to-utilize
sources of biomass. To reach and convert these sources into valuable products flexible and mobile
conversion technologies are being developed, and one such technology is slow pyrolysis.
To test the suitability of slow pyrolysis as a process line to convert various species of biomass, a
series of test runs was completed using the following feedstocks; pine bark, forest residue,
salix/willow and wheat straw. A bench scale, batch-operated slow pyrolysis equipment [1] was used
and high mass yields of solid biochar were achieved and valuable product samples were produced
for further application test [2].
A mobile slow pyrolysis demonstration unit was patented, designed, built and operated by Raussin
Energia. The target was to developed a continuously operated unit to improve the operability and
also the economical profitability of the biochar production. Two measuring campaigns were
conducted while the demonstration unit was operated at a steady capacity of 100 kg/h of raw
material feed. During the campaigns high effort was put into determining the amounts and
characteristics of the solid, liquid and gaseous products of the process. The quality of the products
seems promising, and experience from the operation of the demonstration unit shows high potential
for the process line.
References
[1] Fagernäs, L., Kuoppala, E., Tiilikkala, K., Oasmaa, A.: Chemical composition of birch wood slow pyrolysis products.
Energ. Fuels 1275-1283 (2012)
[2] Keskinen R, Hyväluoma J. Wikberg H., Källi A., Salo T., Rasa K. : Possibilities of Using Liquids from Slow Pyrolysis and
Hydrothermal Carbonization in Acidification of Animal Slurry, Waste Biomass Valor.,
https://doi.org/10.1007/s12649-017-9910-4 (2017)
527
STRATEGIC DEVELOPMENT OF EFFICIENT Ni-BASED CATALYSTS FOR BIOMASS TAR

REFORMING
S. KAWI1
1 National University of Singapore, Singapore.
Abstract
Biomass waste has becoming an attractive source of renewable energy and materials. Conversion of
biomass waste into useful products can be performed by using pyrolysis to produce liquid fuels and
chemicals or gasification to produce syngas / hydrogen. Utilization of biomass waste by gasification is
an environmentally beneficial method for the production of syngas, which can be upgraded to
produce a broad range of hydrocarbons such as methanol and ammonia by Fischer–Tropsch process.
Several challenges have to be solved, mainly in the impurities produced such as tar, a mixture of
heavy condensable hydrocarbon compounds including single-ring to five-ring aromatic compounds
such as toluene and naphthalene, which can decrease the efficiency of process operations on
condensation in the particulate filters and pipe outlets, resulting in blockages and reduction of the
effective gas flow. As a result, it can cause significant increases in maintenance and operating costs.
The conventional method to reduce the tar in commercial gasifiers includes the use of high
temperatures above 800°C to burn off the tar, resulting in high cost. The use of catalyst for tar
cracking provides a promising way to make the process more economical and efficient as a catalyst
can reduce the reaction temperature and increase the product yield. Our group has developed
several strategies to solve this problem, designing and preparing stable Ni-based catalyst as shown
below:
• Doping with base metals: alkali metals promotes water dissociation there by enhances steam
reforming reaction at low steam conditions and suppress carbon formation
• Bimetallic catalysts: By forming alloy, the synergetic effect helps to stabilize active Ni species and
promote carbon suppression.
• Catalysts derived from specific structures: we have found that catalysts derived from perovskite,
hydrotalcites and phyllosilicate have a strong metal-support interaction, which helps to
eliminate carbon formation.
• Organic-assistant synthesis: Organic molecules can complex with Ni during impregnation
synthesis which increases dispersion of Ni and decreases Ni particles size, eliminating carbon
formation as a result.
It is believed that effective conversion of tar produced during biomass gasification will continue to be
a concern and developing excellent catalyst to convert the tar is the crucial key to achieve the
gasification technology to be successful industrially.
528
BIOPRODUCTS FROM BIOWASTE: A CIRCULAR ECONOMY CONCEPT
A. DUTTA1
1 Professor and Director of Bio-Renewable Innovation Lab, School of Engineering, University of
Guelph, ON, Canada.
Abstract
The three major challenges in the 21st century are food security, climate change and energy
sustainability. Bioenergy is one promising renewable energy source with low net CO 2 emissions and
potentially sustainable if the economical, environmental and social impacts are properly managed.
The development of clean and economically viable biomass conversion technologies for a domestic
market is thus imperative to promote the local utilization of biomass residues in Canada. Recently
Ontario Government of Canada passed the waste free Ontario, 2016 act which is the Resource
Recovery and Circular Economy act (Bill 151, 2016). In the “Circular Economy act” resource recovery,
and waste reduction strategy will create opportunities and markets of recovered resources. This will
minimize greenhouse gas (GHG) emissions and environmental impacts in the strategy of “Waste-
Free Ontario”.
In this research a hybrid thermochemical and biochemical approach is proposed to produce
biocoal, biomethene and biofertilizer from corn residue (CR) using the concept of circular economy.
In this approach, CR is first pretreated in hydrothermal carbonization (HTC) process to produce solid
biocoal. HTC process water (HTPW), a co-product of HTC processing underwent fast digestion under
anaerobic conditions (AD) to produce biomethene and biofertilizer. Effects of operating conditions
(process temperature and residence time) on both bio-coal and HTPW contents were studied. This
process produced hybrid bioenergy of 15.71 MJ kg-1 of raw CR with an overall energy yield of
86.65%. Biocarbon produced in 240C for 30 min and 260C for 10 to 30 min were comparable to
pulverised coal used in power plants, which contained HHVs of 23.01 MJkg-1 to 24.70 MJkg-1.
Nutrient enriched AD digestate is useable as liquid fertilizer. Biocoal, biomethene and bio-fertilizer
produced at 240C for 30 min HT process can contribute to the circular economy enrichment and
reduction of greenhouse gas (GHG) emission in Ontario.
This novel approach also integrates thermochemical and biochemical conversion processes
through a series of innovative technologies (i.e. hydrothermal pretreatment, supercritical
gasification or anaerobic digestion with dry reforming, gas-to-liquid fuel through fermentation). The
innovative and synergistic integration of design with processing are expected to result in renewable
fuels and value-added products. The resulting biocarbon can substitute fossil resources on a cost-
performance basis with the added benefit of eco-friendliness. This could mean a tremendous
reduction in greenhouse gas emission through the use of bioproduct, reducing our dependency on
petroleum. In addition, the use of hydrothermal, chemical looping and supercritical gasifications,
anaerobic digestion, dry reforming of biogas to produce syngas, and syngas fermentation techniques
in the development and application of biofuels and products would lead to reduced dependency on
petroleum and a sustainable economy.
References
[1] Paul, S., Dutta, A., Defersha, F., Dubey, B.: Municipal Food Waste to Biomethane and Biofertilizer: A Circular
Economy Concept, Waste and Biomass Valorization, 1-11 (2017)
[2] Minaret, J., Dutta, A.: Comparison of liquid and vapor hydrothermal carbonization of corn husk for the use as a solid
fuel. Bioresource Technology 200, 804-811 (2016)
529
[3] Kambo, H., Dutta, A.: Comparative evaluation of torrefaction and hydrothermal carbonization of lignocellulosic
biomass for the production of solid biofuel, Energy Conversion and Management 105, 746-755, (2015)
[4] Kambo, H., Dutta, A.: Strength, storage, and combustion characteristics of densified lignocellulosic biomass
produced via torrefaction and hydrothermal carbonization, Applied Energy 135, 182–191, (2014)
[5] Acharya, B., Dutta, A., and Basu, P.: Chemical-looping gasification of biomass for hydrogen-enriched gas production
with in-process carbon dioxide capture. Energy & Fuels 23 (10), 5077-5083 (2009)
[6] Kambo, H., Minaret, J., Dutta, A.:. Process Water from the Hydrothermal Carbonization of Biomass: A Waste or a
Valuable Product? Waste Biomass Valor, 1-9, doi:10.1007/s12649-017-9914-0 (2017)
[7] Tushar, MSHK., Dutta, A., Xu, CC.: Catalytic Supercritical Gasification of Biocrude from Hydrothermal Liquefaction of
Cattle Manure, published online Feb 21st, in Applied Catalysis B: Environmental, 189, pp. 119–132 (2016)
[8] Gopaul, SG., Dutta, A.: Dry reforming of multiple biogas types for syngas production simulated using Aspen Plus: The
use of partial oxidation and hydrogen combustion to achieve thermo-neutrality, International Journal of Hydrogen
Energy 40 (19), 6307-6318 (2015)
530
CATALYTIC HYDRODEOXYGENATION OF BIODIESEL TO GREEN DIESEL
PALLIGARNAI T. VASUDEVAN1, YE DENG1

1 University of New Hampshire, Durham, NH, USA.
Abstract
The enhancement of biodiesel fuel properties by modifying/optimizing fatty ester composition is an

area of nascent and ongoing research. Chemical upgrading methods include catalytic
hydrodeoxygenation process (HDO), hydrothermal liquefaction, Fischer-Tropsch synthesis (F–T
synthesis), and super-critical modification. Currently, catalytic hydrodeoxygenation process for
converting biodiesel into renewable petrodiesel-like fuels substitutes is gaining considerable
importance [1].
In this paper, catalyst activities of four supported molybdenum catalysts (Mo/Al2O3, Co-Mo/Al2O3,
Mo/Zeolite, and Co-Mo/Zeolite), prepared by the thermal decomposition of ammonium
heptamolybdate, in the hydrodeoxygenation of biodiesel is reported. The effects of two feedstock
sources (methyl oleate and commercial biodiesel B100), five pretreatment temperatures (250, 300,
350, 400, and 450°C), four hydrogen flow rates (20, 30, 40 and 60 mL/min), and five reaction
temperatures (250, 300, 350, 400, and 450°C) were investigated to find the optimal conditions for
hydrodeoxygenation of biodiesel using these catalysts. The effect of cobalt as a promoter for the
reduced molybdenum catalyst was also studied. Additionally, the activities of Co/-Mo catalysts with
different supports (γ-alumina and Y-zeolite) was compared with the activity of a commercial CoMo
catalyst.
The optimal conditions appear to be a hydrogen flow rate of 60 mL/min, and pretreatment and
reaction temperatures of 400°C. The highest overall conversion of biodiesel achieved was 55.8% for
CoMo/γ-alumina and 59.3% for CoMo/Y-zeolite. Factors that affect the catalyst pathway have also
been investigated. Higher hydrogen pressure, the presence of a promoter and optimal support, and
higher reaction temperature can lead to a higher C18/C17 ratio, which results in a better green
diesel product.
References
[1] Arun N., Sharma R., Dalai A., Green diesel synthesis by hydrodeoxygenation of bio-based feedstocks: Strategy for
catalyst design and development. Review and Sustainable Energy Reviews 48, 240-255 (2015).
531
HORMONES OF THE HOLOBIONT: MICROBE-TO-PLANT SIGNALS AS A WAY TO

INCREASE BIOMASS PRODUCTION UNDER CLIMATE CHANGE CONDITIONS
D. L. SMITH 1.
1 Plant Science Department, Macdonald Campus of McGill University 21111 Lakeshore Road,
Ste. Anne de Bellevue, Quebec, Canada H9X 3V9
Abstract
It is now clear that a plant growing under field conditions is not an individual, it is a
community. The plant is always associated with a carefully orchestrated set of microbes –
the phytomicrobiome [1]. The plant plus the phytomicroiome are the holobiont, and this is
the entity that produces plant biomass. Although the phytomicrobiome is not yet well
understood it is certain that there is extensive potential in its exploitation as a source of
low-input, sustainable and environmentally friendly technologies. Over the last few decades
work at McGill University in Montreal has demonstrated that stressful conditions (low root
zone temperatures) can inhibit the signaling that constitutes the initial steps in legume
(soybean) nodulation and nitrogen fixation. Subsequently the microbe-to-plant signals
involved (lipo-chitooligosaccharides – LCOs) were also shown to stimulate the growth of
plants in general (not just legumes) and that this effect is greater when the plants are
experiencing stress (low temperature, high temperature, water deficit, salinity). The
production of the plant-to-microbe signals is triggered by flavonoids, which are often
produced at greater levels when plants are stressed. In addition, jasmonic acid (a plant
stress-management hormone) can also trigger the production of the same LCOs by some
rhizobial bacteria. More recently a strain of Bacillus (a very common genus within the
phytomicrobiome) was shown to produce a small protein (thuicin 17) that also enhances
plant growth, and particularly so when the plants are stressed [2]. The effective
concentrations of LCO are in the 10-6 to 10-8 M range and for thuricin 17 the best
concentrations are in the 10-9 to 10-11 M range. This makes these compounds very
inexpensive to apply, and likely to have little environmental effect. At a time when world
food production must increase to match increasing population and changes in diet, while we
are also looking to plants to provide the biomass to produce the advanced biofuels and
bioproducts that will underpin the growing bioeconomy, inputs of this sort are critical. Being
able to enhance biomass production (both purpose grown biomass feedstock crops and
crop residues associated with food production) in an environmentally harmonious way is
very positive. As climate change conditions develop crop plants will be more stressed more
often, and this will be particularly so for the biomass feedstock crops as they will generally
be produced on more marginal lands, to avoid competition with food crop production, and
crops growning on marginal lands are more likely to experience stressful conditions. Thus,
these signals (the hormones of the holobiont) are able to make our biomass production
systems more climate change resilient and to increase the production of both food and fuel.
References
[1] Smith DL, Gravel, V and Yergeau E 2017. Signaling in the phytomicrobiome. Invited Editorial. Frontiers in
Plant Science https://doi.org/10.3389/fpls.2017.00611
[2] Subramanian S, Souleimanov A, Ricci E and Smith DL 2016. A proteomic approach to lipo-
chitooligosaccharide and thuricin 17 effects on soybean germinationunstressed and salt stress. PLOS One
DOI:10.1371/journal.pone.0160660
532
HYDROTHERMAL CONVERSION OF BIOMASS TO FUELS AND CHEMICALS
P. SAVAGE1,2, J. SHEEHAN,1 J. JIANG1, A, GOLLAKOTA1, D. HIETALA2

1 Pennsylvania State University, University Park, PA, USA.
2 University of Michigan, Ann Arbor, MI, USA.
Abstract
The ability to convert biomass economically and sustainably to fuels and chemicals would allow
society to transition from being hunter-gatherers for our fuels and fuel precursors to becoming
cultivators of our fuels and chemicals feedstocks. All biomass has a high moisture content and drying
the biomass requires significant energy input. Direct conversion of wet biomass in hot, compressed
water is a process concept that could be more economical and more sustainable than competing
process concepts.
This presentation will outline research done to develop and model hydrothermal processes for the
conversion of aquatic biomass (i.e., microalgae) and food waste and to elucidate the reaction
networks and kinetics that govern such conversion [1-5]. More specifically, we will discuss
hydrothermal carbonization, hydrothermal, liquefaction, and hydrothermal gasification.
Carbonization provides a path toward recovery of lipids and valuable fatty acids while
simultaneously producing a fuel precursor with an energy density that exceeds that of the biomass
feedstock. Hydrothermal liquefaction uses the combined action of thermal and hydrolytic reactions
to decompose the biomacromolecules in biomass into smaller molecules approaching those useful
for fuels. Catalytic upgrading of the raw biocrude can then lead to a largely hydrocarbon mixture that
could potentially be blended with petroleum and processed in existing refineries. Hydrothermal
gasification converts biomass feedstocks or organics-laden aqueous streams into fuel gases such as
methane or hydrogen.
In addition to work done with whole biomass, this presentation will provide results from
experiments and modeling with simpler model systems, such as bovine serum albumin, soy protein,
casein, and various model polysaccharides. Research with these model systems provides
opportunities to better understand the chemical reaction pathways and to obtain insights that are
broadly applicable for a wide range of both energy crops (e.g., microalgae) and waste biomass (e.g.,
food waste).
References
[1] Sheehan, J.; Savage, P. E., Bioresource Technology, 239, 144-150 (2017)
[2] Jiang, J.; Savage, P. E. Algal Research, 26, 131-134 (2017)
[3] Xu, D.; Savage, P. E. Bioresource Technology, 239, 1-6 (2017)
[4] Hietala, D. C.; Koss, C. K.; et al., Algal Research 26, 203–214 (2017)
[5] Sheehan, J. D.; Savage, P. E., ACS Sust. Chem. Eng. (2017)
533
FRACTIONATION OF ETHANOLIC ULTRASOUND EXCTRACTS FROM CYNARA

CARDUNCULUS, BY MEMBRANE SEPARATION PROCESSES
T.BRAS1,2, A.PAULINO1, L.A. NEVES2, M.F. DUARTE1,3, J.P.G. CRESPO2

1 Centro de Biotecnologia Agrícola e Agro-Alimentar do Alentejo (CEBAL)/ Instituto Politécnico de
Beja (IPBeja), 7801-908 Beja, Portugal;

2 LAQV/ REQUIMTE, FCT, Universidade Nova de Lisboa, Campus de Caparica, 2829-516 Caparica,
Portugal;
3 ICAAM - Instituto de Ciências Agrárias e Ambientais Mediterrânicas, Universidade de Évora, Pólo da
Mitra, Ap. 94, 7002-554 Évora, Portugal.
Abstract
Membrane technologies have been widely applied for lignocellulosic and hemicellulosic extracts
fractionation [1]. However, the use of this technology in regard to lipophilic and phenolic plant
extracts fractionation, and/or enrichment, is still scarce [2]. Extracts fractionation allows the study of
synergetic and individuals effects of chemical groups, as well as assessment of their biological
potential. Cynara cardunculus belongs to the Asteraceae family, and cynaropicrin is a sesquiterpene
lactone abundantly present in Cynara cardunculus leaves, as recently described by our research
group, carrying interesting biological activities, and unveiling new biopharmaceutical valorisation
routes [3-4].
Mainly composed by sesquiterpene lactones, phenolics, flavonoids and sugars, the ethanolic
ultrasound extract from Cynara cardunculus leaves [5] was, in this study, fractionated by membrane
separation processes in order to obtain a cynaropicrin enriched extract, as well as fractions with
greater biological potential. For that, membrane separation processes were tested. Solvent resistant
membranes with different MWCO were used, in order to assess extraction solvent effect upon
fractionation. Swelling, permeability and solute/membranes interactions were studied, and
biological activities such as anti-inflammatory, were tested for the different fractions obtained.
Complementary membrane processes were applied for a complete removal of low molecular weight
compounds. Results showed that membrane processes are suitable for ethanolic ultrasound Cynara
cardunculus leaves extracts fractionation, getting fractions with larger cynaropicrin quantity, and
biological potential, that can be used for biopharmaceutical products incorporation, such as wound
dressing films.
References
[1] Servaes, K., et al., Purification and concentration of lignin from the spent liquor of the alkaline oxidation of woody
biomass through membrane separation technology. Industrial Crops and Products, 2017. 106(Supplement C): p. 86-
96.
[2] Syed, U.T., et al., Valorisation of grape pomace: Fractionation of bioactive flavan-3-ols by membrane processing.
Separation and Purification Technology, 2017. 172(Supplement C): p. 404-414.
[3] Ramos, P.A., et al., Lipophilic extracts of Cynara cardunculus L. var. altilis (DC): a source of valuable bioactive terpenic
compounds. Journal of agricultural and food chemistry, 2013. 61(35): p. 8420-8429.
[4] Ramos, P., et al., Antiproliferative Effects of Cynara cardunculus L. var. altilis (DC) Lipophilic Extracts. International
Journal of Molecular Sciences, 2017. 18(1): p. 63.
[5] Bras, T et al, Effect of pulsed ultrasound assisted extraction upon cynaropicrin concentration: extraction optimization
using response surface methodology, 10th World Congress Chemical Engineering, Barcelona (Spain), 1 – 5 October
2017.
534
FACTORS AFFECTING THE SUGARS RELEASE IN OZONOLYSIS PRETREATMENT OF

SUGARCANE BAGASSE
D.R. OSUNA-LAVEAGA1, E. LEÓN-BECERRIL1*

1
Environmental Technology Department, Centro de Investigación y Asistencia en Tecnología y Diseño
del Estado de Jalisco A.C., Guadalajara, Jalisco, Mexico, *eleon@ciatej.mx
Keywords: Ozonolysis, particle size, moisture, reducing sugars.
Abstract
The assessment of the effect of particle size, moisture content and ozone dose on the release of
sugars and the chemical structure of sugarcane bagasse was done. Bagasse was pretreated with
ozone in a fixed bed reactor; level factors were: particle size 420-1000 µm, moisture content 30-60%
ww-1 and ozone dose 50-100 mg O3 gb-1 (mg O3 per g of bagasse). After bagasse pretreatment, sugar
release was determined as total and reducing sugars from water extraction of the material; changes
on bagasse structure were assessed in terms of acid soluble lignin (ASL), acid insoluble lignin (AIL),
hemicellulose and cellulose content, as well as by Fourier Transformed Infra Red, X-ray diffraction
and Confocal Laser Scanning Microscopy. Data were treated by ANOVA and response surface. After
the ozone pretreatment the release of sugars increased for all conditions, particle size and ozone
dose were the principal factors, while moisture content has not a statistical significant effect. The
reducing sugars concentration increased from 5.96 to 39.26 mg gb-1 at 420 µm and 100 mg O3 gb-1.
The main chemical structure changes correspond to the maximal removal of AIL and hemicellulose
28.02 and 27.31 %, respectively, meanwhile the recovery for cellulose was up to 92.29 %. Ozone
attacked the crystalline and amorphous fraction of bagasse.
535
1- INTRODUCTION
Lignocellulosic wastes have become very popular due to their potential to produce biofuels because
of their polysaccharides content and their great availability. Nevertheless, the carbohydrates
exploitation is limited due to the complex structure of the material, mainly composed by cellulose,
hemicellulose and lignin. The last one covers the polysaccharides and acts as a barrier against
biological and chemical attacks; besides, cellulose presents crystallinity fractions that provide some
resistance to biological attacks [1]. Therefore, a pretreatment step is required to degrade lignin and
release sugars.
Among the reported pretreatments, ozonolysis has been proven to be an effective way to
depolymerize the lignocellulosic matrix, attacking high electronic functional groups and double
bonds from the aromatic rings like those that exist in the lignin, being affected in a minor grade the
polysaccharides [2,3]. Ozone pretreatment occurs at room temperature, it does not need storage
equipment and it does not generate large volumes of hazard liquid wastes like that generated in
alkali or acid pretreatments. Byproducts of the reaction are biodegradable and furan derivative
inhibitors are not generated [4].
After the ozone pretreatment, the biomass suffers several changes on its structure, as the
solubilization of lignin, in means of the increase of ASL (acid soluble lignin) and the decrease of AIL
(acid insoluble lignin), and the rupture of crystallinity of cellulose. The principal parameters affecting
the ozonolysis of lignocellulosic biomass are the ozone concentration, reaction time, particle size and
moisture content. Particle size is related to the available interfacial area for the reaction, in addition
the smaller the particle size, the lower the crystallinity as a result of the matrix rupture after milling
[5]. Moisture content is associated with the solubilisation and diffusion of ozone through the surface,
interstices and cavities of biomass [6]. Ozone dose in terms of ozone concentration (in parts per
million), gas flow and mass of biomass is a parameter that allow degrading the lignin and remaining
the cellulose.
In this work, the ozone dose (as mass of ozone per mass of bagasse), particle size and moisture
content were evaluated on the changes of the chemical structure of sugarcane bagasse and the
sugar release after the ozone pretreatment, with the aim to preserve the cellulose and degrade the
lignin. The sugar release was determined from water extraction from bagasse and the changes on
bagasse structure were assessed in terms of ASL, AIL, hemicellulose and cellulose content, as well as
by Fourier Transformed Infra Red (FTIR) and X-ray diffraction (XRD), and were associated to the
released organic acids and polyphenolics. Morphological changes were observed by Confocal Laser
Scanning Microscopy (CLSM).

2.1 Substrate
Sugarcane bagasse was collected from a sugarmill from Veracruz, Mexico. Bagasse was dried by solar
radiation for 48 hours, ground, sieved (according particle size of experimental design) and stored at
room temperature until use. Moisture content on raw bagasse was adjusted with distilled water
according to [7].
2.2 Experimental system and operational conditions

The experimental system was composed by an oxygen tank, an ozone generator, a fixed bed reactor,
an acquisition data interphase, an ozone destructor, a gas phase ozone meter and a pneumatic pipe
536
system that allowed directing the gas flow to the ozone meter or reactor inlet. Fixed bed reactor
consisted in a glass tube (30 cm long and 6.5 cm internal diameter) containing a concentric diffuser,
which permitted the axial and radial ozone flow distribution from the bottom to the upper, reacting
with the bagasse. Ozone was produced by a G11 generator (Pacific Ozone Technology, USA) from
oxygen; ozone concentration was determined at the inlet and outlet of the reactor using a 465H
ozone monitor (Teledyne instruments). Bagasse was settled to the moisture content and then it was
ozonated (according to corresponding ozone dose of the experimental design) during a constant
time 30 minutes at 90 L h-1 flow at room conditions [8]. After ozone pretreatment, bagasse was dried
at 35 ± 5 °C during 48 hours and analyzed to determine the structural composition (cellulose,
hemicelluloses, ASL and AIL), then, a soluble compound extraction was done with water at 2.5% w
w -1, 150 rpm agitation during 1 hour for a subsequent analysis of reducing and total sugars,
polyphenolics, organic acids and furan derivatives.

Structural carbohydrates (cellulose, hemicellulose), ASL and AIL were determined according to [9].
Organic acids, furan derivatives and monosaccharides concentrations were determined by high
performance liquid chromatography (HPLC). A Varian Prostar HPLC system with RI detector was
used, with a BioRad Aminex HPX-87H column, at a flow rate of 0.6 ml min-1 of degassed 5 mM
sulphuric acid as mobile phase and a modified temperature 65 °C [9]. Polyphenolics, reducing and
total sugars were determined following the Folin-Ciocalteau, the dinitrosalicylic acid (DNS) [10] and
the phenol-sulfuric method [11], respectively.
2.4 Confocal laser scanning microscopy

Bagasse fibers were observed by a TCS SPE RGBV confocal system equipped with a DM5500B-CS
microscope (Leyca). A 405 nm laser was used for excitation and the emission spectra were acquired
over 420-600 nm.
2.5 FTIR analysis

The bagasse structure was analyzed with a Cary 630 system (Agilent Technologies) at 4000-400 cm-1
region.
2.6 XRD analysis

Crystalline and amorphous fractions of bagasse were determined by a Panalytical X-ray
difractometer (Empyrean) employing Cu Kα radiation (λ=1.542 Å). The crystallinity index was
calculated as the ratio of crystalline peak intensity (I002-IAM) and total intensity [12].
2.7 Experimental design and analysis of data

Particle size, moisture content and ozone dose were evaluated on bagasse structure (hemicellulose,
cellulose and lignin fractions) and on soluble sugars according to a statistical factorial design with
two central points (Table 1). Data were analyzed by an analysis of variance (ANOVA), principal and
interaction effects and response surface at 95% confidence interval, using Statgraphics Centurion XV
(Statpoint) software.
537
Table 1. Statistical factorial design.

Level value
Factor
-1 0 1
Particle size, Ri (μm) 420 700 1000
-1
Ozone dose, D (mg O3 gb ) * 50 75 100
Moisture content, H (%) 30 45 60
-1
*As milligrams of ozone per gram of bagasse (mg O3 gb )

3.1 Composition of sugarcane bagasse
The raw sugarcane bagasse structure consisted in 49.29% cellulose, 18.71% hemicellulose, 3.07% ASL
and 26.6% AIL in dry basis; indicating that almost the half of bagasse mass is constituted by
polysaccharides [13]. Lignin is the target to solubilize, decreasing AIL and increasing ASL.
3.2 Effect of factors on bagasse structure

Structural changes on the sugarcane bagasse were observed after the ozone pretreatment. The
effect of different ozone doses on cellulose, hemicellulose, ASL and AIL fractions on dry basis are
shown on Table 2. AIL was the principal fraction affected, decreasing for all pretreatment conditions.
The minimal AIL removal was 7.98% and a maximal of 28.02%, corresponding to the treatment 10
(T10) and 2 (T2), corresponding to the major particle size with minor ozone dose, and the minor
particle size with major ozone dose, respectively. Therefore it seems there are interaction effects of
these factors. The major AIL removal is close to the 33.44% obtained by [4] in the ozonation of wheat
straw at 120 minutes, 53 mg O3 g-1 and 90% moisture. ASL increased from 3.07 to a maximum of 6.18
% (T5), which is a similar solubilization increasing from 4.46 to 10.25% at 120 minutes, 78 mg O3 gb-1
and 50% moisture in sugarcane bagasse [14]. Cellulose fraction had minor changes, decreasing from
49.29% of raw bagasse to 45.49% (T10), with a recovery up to 92.29%, in agreement with reported
results [2]. Hemicellulose was degraded under 15.63% in all conditions, confirming that the major
effect of factors over polysaccharides was on hemicellulose.
Table 2. Structural composition of raw and ozone pretreated sugarcane bagasse.

Run Ri D H ASL (%) AIL (%) Cellulose (%) Hemicellulose (%)
Raw * - - 3.07 ± 0.32 26.60 ± 1.01 49.29 ± 1.49 18.71 ± 0.99
T1 0 0 0 5.91 ± 0.13 19.24 ± 0.79 47.85 ± 0.69 15.63 ± 1.42
T2 -1 1 -1 5.57 ± 0.36 19.15 ± 0.68 51.43 ± 0.04 14.52 ± 0.07
T3 -1 -1 1 5.73 ± 0.04 22.23 ± 0.27 47.50 ± 1.37 15.62 ± 0.27
T4 1 -1 -1 6.03 ± 0.18 23.40 ± 0.84 45.78 ± 0.17 14.47 ± 0.22
T5 0 0 0 6.18 ± 0.18 20.53 ± 0.29 47.24 ± 0.76 13.60 ± 0.62
T6 1 1 1 5.87 ± 0.39 23.73 ± 0.80 46.21 ± 2.22 14.17 ± 2.61
T7 -1 -1 -1 5.59 ± 0.49 21.89 ± 0.21 48.08 ± 0.27 14.74 ± 0.45
T8 1 1 -1 5.51 ± 0.41 21.18 ± 1.93 49.22 ± 2.18 15.61 ± 1.61
T9 -1 1 1 5.53 ± 0.25 19.50 ± 0.73 50.11 ± 1.03 15.07 ± 0.73
T10 1 -1 1 5.91 ± 0.33 24.48 ± 0.50 45.49 ± 2.69 15.25 ± 2.30
Percentages on dry basis. * Average from different particle sizes.
538
Figure 1 shows the ozone pretreatment effects over the bagasse surface morphology by confocal
laser scanning microscopy (CLSM) images from raw and ozonated bagasse, both of 420 µm. Raw
bagasse presents a natural unreacted physical structure, while bagasse pretreated presents a
disruptive surface due to the ozone oxidation. These superficial changes are attributed mainly to the
lignin solubilization and hemicelluloses degradation.
Figure 1. CLSM images from 420 µm bagasse. a) Raw. b) Ozone pretreated.

Table 3 shows the concentrations of soluble compounds determined from water extractions. After
the ozone pretreatment, reducing and total sugars increased for all conditions, achieving 39.26 and
64.4 mg gb-1, respectively; both corresponding to T9 (the highest ozone dose and moisture content
and the smallest particle size). With the aim to analyze the effect of ozone dose on the sugar
solubilization, the oligosaccharides content was determined as the difference between total and
reducing sugars. Considering the effect of ozone dose and particle size, it seems that 30 and 60%
moisture content release similar oligosaccharides concentrations. T2 and T9 generated an average
oligosaccharides concentration of 25.7 mg gb-1, while T6 and T8 concentrations closer to zero,
indicating that although ozone was in a high dose, the particle size was the limiting factor. Therefore,
at a particle size 1000 µm (T6 and T8), the available interfacial surface was limited, and reducing and
total sugars have similar concentrations; the ozone reacted over contiguous glycosidic bonds of
structural polysaccharides of bagasse, releasing monosaccharides (reducing sugars). For a particle
size 420 µm with more available surface, the ozone reacted generating oligosaccharides.
There are no big differences in polyphenolics concentrations among all the experimental conditions,
obtaining values from 5.1 to 9.1 mg gb-1. The major concentration of plyphenolics was found at the
highest ozone dose (T8), which is related to the delignification of matrix, being a degradation
compound of lignin, as well as organic acids [3, 6]. Acetic, oxalic, lactic and formic acid
concentrations were under 1.04, 6.60, 1.21 and 7.46 mg gb-1, respectively. The major concentrations
were obtained at the major ozone dose, as well as polyphenolics. These organic acid concentrations
are lower than the obtained by [13], in a sugarcane bagasse ozonation at 120 minutes and ozone
doses above 110 mg gb-1. 5-hidroximetilfurfural (data not showed) is related to the hemicellulose
degradation, and was obtained under 30 µg gb-1. The highest glucose and xylose concentrations were
5.12 and 5.99 mg gb-1, respectively, obtained at T9.
539
-1
Table 3. Sugars, polyphenolics and organic acids from water extractions (mg g b ).
Reducing Oligosacch Polyphe- Oxalic Lactic Formic Acetic Gluco- Xylo-
Run Total sugars
sugars arides nolics acid* acid* acid* acid* se* se*
R 420 µm 5.96 ± 0.16 12.70 ± 1.51 6.74 0.20 3.47 0.18 2.33
R 700 µm 6.65 ± 0.04 12.36 ± 1.92 5.71 0.14 0.14 0.22 3.13
R 1000 µm 7.07 ± 0.08 10.40 ± 1.52 3.33 0.09 2.14
T1 29.25 ± 0.08 41.6 ± 0.52 12.36 7.7 ± 0.36 1.90 0.22 0.12 0.82 2.83 3.46
T2 31.96 ± 0.19 58.65 ± 3.51 26.70 8.5 ± 0.06 0.62 1.04 2.27 3.06
T3 22.31 ± 0.35 42.84 ± 0.61 20.53 5.4 ± 0.15 0.96 0.27 5.81 0.07 1.38 2.12
T4 19.51 ± 0.16 35.17 ± 0.65 15.66 5.1 ± 0.07 1.42 0.24 2.80 0.10 1.52 1.14
T5 27.85 ± 0.43 50.54 ± 0.24 22.69 7.0 ± 0.22 1.06 0.28 0.95 1.73 2.30
T6 26.78 ± 0.86 25.46 ± 0.37 -1.32 5.0 ± 0.09 1.83 0.42 3.26 0.32 2.52 2.85
T7 22.50 ± 0.23 44.28 ± 1.66 21.78 7.4 ± 0.01 1.15 0.08 1.35 0.42 1.11 1.36
T8 34.02 ± 0.39 31.53 ± 1.19 -2.49 9.1 ± 0.29 0.67 4.60 0.84 2.37 3.18
T9 39.26 ± 0.23 64.04 ± 1.05 24.77 8.0 ± 0.76 6.60 1.21 7.46 0.68 5.12 5.99
T10 19.17 ± 0.20 33.50 ± 0.20 14.33 5.3 ± 0.87 3.82 0.37 0.32 0.82 2.33 1.72
R: Raw bagasse. *Standard deviation minor to 0.01. Reducing sugars as DNS method result. Total sugars as phenol
sulfuric method result. Oligosaccharides as difference of total and reducing sugars. Glucose and xylose as HPLC result.
Table 4 shows the ANOVA for reducing (as DNS) and total sugars results at 95% level confidence,
with a coefficient of determination (R2) of 94.74 and 89.19%, respectively. The ozone dose has a
statistical significant effect (p-value < 0.05) over the reducing sugars, while particle size over total
sugars; there are no important interaction or quadratic effects among the factors. The moisture
content is important for the ozone diffusion through the bagasse surface and has been reported with
better results at 50% [3, 7]; nevertheless, in this work there is no effect over sugars release.
Table 4. Variance analysis of reducing and total sugars of ozone pretreated bagasse.
Reducing sugars Total sugars
Square Square
F-value P-value F-value P-value
sum sum
A: Ri 42.6426 6.98 0.0775 1088.58 15.24 0.0299
B: H 0.00361 0.00 0.9821 8.3232 0.12 0.7554
C: D 265.075 43.41 0.0071 151.206 2.12 0.2417
AB 17.3166 2.84 0.1908 71.1625 1.00 0.3918
AC 5.16811 0.85 0.4254 423.405 5.93 0.0930
BC 0.30031 0.05 0.8387 26.3538 0.37 0.5865
Error 18.3175 214.319
Total 348.824 1983.35
R2 reducing sugars = 94.74 %. R2 total sugars = 89.19 %.
3.3 FTIR analysis
Among the different conditions of ozonation, bagasse samples showed changes in absorption
intensities in the near infrared spectra. The removed AIL can be related with the vibrational signals
at the 1240-1270 cm-1 band due to syringil rings and C-O bonds among hemicelluloses and lignin [15]
and at the 3300 cm-1 band of hydrogen bonds of lignin and carbohydrates [14]. Ozone can also affect
the polysaccharides, the 1210 cm-1 wave number related with glycosidic bonds (ether) showed
changes, as well as 895-898 cm-1, 1030 and 1160 cm-1, which correspond to amorphous and
crystalline cellulose [16, 17].
540
3.4 XRD analysis
After the XRD analysis, crystalline and amorphous cellulose were detected. Two types of crystalline
cellulose are present in samples, corresponding to 002 peak at 22.5° in 2θ, and 101 peak at 15° in 2θ
[1] while the amorphous region is detected at 18° in 2θ [18]. After ozone pretreatment the 002
peaks intensities increased due to the degradation of hemicellulose, which contributes to an
amorphous fraction [19]. The major crystalline peaks intensities were obtained with dose of 100 mg
O3 gb-1 (T2, T6, T8 and T9) so the ozone reacted over the both amorphous (attributed to
hemicellulose and cellulose) and crystalline fractions (cellulose), in agreement with [20], according
with structural polysaccharides variations on Table 3. Crystallinity index of samples for all the
ozonation conditions remained unchanged, may be due to crystalline and amorphous regions were
affected by ozone in similar fractions. Among the three different particles sizes of raw bagasse, the
420 µm bagasse showed the lowest intensity of 002 peaks [6].
4- CONCLUSIONS
Particle size and ozone dose were the factors affecting the sugar release, while moisture content has
not a statistical significant effect on the sugar release. The reducing sugars concentration increased
from 5.96 to 39.26 mg gb-1 at 420 µm particle size and 100 mg O3 gb-1 dose. The main chemical
structure changes correspond to the decrease of AIL and hemicellulose, affecting the amorphous and
crystallinity fractions of bagasse. Cellulose suffered a slightly degradation with a recovery up to
92.29%. Ozone can hydrolyze the glycosidal bonds among the polysaccharides.
Acknowledgements: This work was supported by CONACYT-Project-133791. D.R. Osuna-Laveaga
acknowledges CONACYT for the Ph.D. fellowship No. 267499. This work is dedicated to the memory
of Dr. Alberto López-López.
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enzymatic digestibility and inhibitory compound formation. Bioresour. Technol. 133, 332-339 (2013)
[14] Barrera-Martínez, I., Guzmán, N., Peña, E., Vázquez, T., Cerón-Camacho, R., Folch, J., Honorato Salazar, J. A., Aburto,
J.: Ozonolysis of alkaline lignin and sugarcane bagasse: structural changes and their effect on saccharification.
Biomass and Bioenergy 94, 167-172 (2016)
[15] Bian, J., Peng, F., Xiao-Peng, P., Xu, F., Run-Cang, S., Kennedy, J.F.: Isolation of hemicelluloses from sugarcane
bagasse at different temperatures: Structure and properties. Carbohydrate Polymers 88, 638-645 (2012)
[16] Harrison, M.D., Zhang, Z., Shand, K., O´Hara, I.M., Doherty, W.O.S., Dale, J.L.: Effect of pretreatment on
saccharification of sugar cane bagasse by complex and simple enzyme mixtures. Bioresource Technology 148, 105-
113 (2013)
[17] Ciolacu, D., Ciolacu, F., Popa, V.I.: Amorphous cellulose - structure and characterization. Cellulose Chem. Technol. 45,
13-21 (2011)
[18] Browning, B.L.: Methods of Wood Chemistry, 2. Interscience Publishers, New York, 561-587 (1967)
[19] Harmsen, P., Huijgen, W., Bermúdez, L., Bakker, R.: Literature review of physical and chemical pretreatment
processes for lignocellulosic biomass. Wageningen, NL (2010)
[20] Perrone, O.M., Souza Rossi, J., de Souza Moretti, M.M., Carreira Nunes, C.C., Bordignon, S.E., Gomes, E., da-Silva, R.,
Boscolo, M.: Influence of ozonolysis time during sugarcane pretreatment: Effects on the fiber and enzymatic
saccharification. Bioresource Technology 224, 733-737 (2017)
542
GRAPEFRUIT WASTE VALORISATION: TOWARD A COST-EFFECTIVE AND LOW-ENERGY

PROCESS CHAIN FOR HIGH-ADDED-VALUE COMPOUNDS RECOVERY FROM PEELS
E. GUE1,2,*, C. BELON1,2, A. SERVENT2, M. CHAPRON1,2, E. RUIZ1,2, M. DELALONDE1,2, C. WISNIEWSKI1,2

1 UFR des Sciences Pharmaceutiques et Biologiques, Université Montpellier, UMR QualiSud, 15
avenue Charles Flahault, B.P. 14491, F-34093 Montpellier Cedex 5, France

2 Cirad, UMR QualiSud, 73 avenue J.F. Breton, F-34398 Montpellier Cedex 5, France.
*Corresponding author: emilie.gue@umontpellier.fr, +33 (0)4 11 75 96 74.
Abstract
In the context of sustainable food systems development, fruit processing is more and more frequently
confronted with waste management and several strategies have been proposed to treat and/or
valorize the various byproducts. In the case of citrus processing, various references about peels
valorization can be found in the literature; research mainly focuses on the relevant choice of extraction
process, with the aim to efficiently extract high-added-value compounds from this type of waste [1-
3]. However, studied processes, considered as intensive processes, are generally not adapted to south
countries, for which green, simple, robust, cost-effective and low-energy consuming processes are
required. Furthermore, a strategy not only focus on the extraction stage but also on the whole waste-
processing line could be a relevant approach. In this waste process chain, several stages were
identified: pre-treatment, extraction, separation, purification. With an overall objective to optimise
the whole waste-processing line, the aim of this study focused first on the relevance of drying step,
highly energy intensive, and conventionally used as pre-treatment ensuring notably stabilisation of
grapefruit peels during storage before extraction. The relevance of drying on extraction efficiency was
examined and assessed through the extraction of two main flavonoids (Naringin and narirutin, that
are anti-inflammatory, anticarcinogenic compounds).
Peels were subjected either to (i) drying (50°C, 16 h) and grinding (blade grinder) or (ii) simply directly
grinding (hand blender) leading respectively to powder or slurry matrix. Water extractions (5 min, 350
rpm), considered as an environment-friendly extraction mode were operated with various dry matter
(DM): liquid (L) ratio. Mixture extractable liquid phase (extract) was obtained by filtration, in a
filtration-compression cell (3 µm, 3 bars). Naringin and narirutin were analyzed in the obtained extract
(HPLC).
For an extraction at the same DM:L ratio (1:54), the naringin extraction was two times more efficient
using powder (52 ± 1 mgnaringin.g-1 DM) than slurry matrix (only 24 ± 1 mgnaringin.g-1 DM) corresponding
to a 96% and 48% extraction yield respectively for powder and slurry. With higher ratio (1:10 for
example), same trend is observed (Table 1).
Naringin Narirutin
DM:L ratio Matrix
(mg/g DM) ± SD (mg/g DM) ± SD
Powder 45.0 ± 3.0 5.4 ± 0.5
1:10
Slurry 14.0 ± 0.5 5.2 ± 1.0
Powder 52.0 ± 1.0 6.2 ± 0.5
1:54
Slurry 24.0 ± 1.0 5.2 ± 1.0
Table 1: Naringin and narirutin content within extracts
543
These results can be essentially attributed to size differences of powder and in slurry aggregates
(Sauter diameter respectively equal to 17.9 ± 0.7 µm and 166.8 ± 7.7 µm, Fig. 1). Actually, slurry
grinding did not allow sufficient cell breakage, leading particularly to low specific/exchange surface
and consequently to a limitation of the naringin extraction.
Figure 1: Particle size distributions of powder (solid curve) and slurry (dotted curve) matrices
It can be noticed that 1:10 ratio is less favourable for slurry, three times lower than powder instead of
two times at 1:54 ratio. In the case of slurry, bioactive compounds have first to diffuse through water-
rich aggregates, before to diffuse toward the liquid phase, final extraction reservoir. If extraction
conditions (especially stirring) can significantly improve compounds diffusion toward liquid phase,
diffusion through water-rich aggregates is more difficult to control. Therefore, this first diffusion step
represents the extraction rate-limiting step, due to lower transfer coefficient. The viscous medium
constituting the slurry aggregate is certainly the seat of intense physical-chemical mechanisms, limiting
the bioactive compounds diffusion rate. This is particularly true for naringin which present a slight
water solubility (1 g.L-1) [4].
Concerning the narirutin, nearly total extraction has been obtained whatever the matrices and the
ratio, 6.2 ± 0.5 vs 5.2 ± 1 mgnarirutin.g-1 DM (1:54) corresponding to a 100% and 83% extraction yield
respectively for powder and slurry; this can be explained by its higher water solubility, in comparison
with the naringin, which promotes its rapid diffusion.
The comparison with the literature data revealing that the measured recovery efficiencies (even for
the slurry) were in the same range of the ones obtained with high-energy processes [1], these previous
results demonstrated that, when a direct peels treatment is sought, without prior storage, a pre-
treatment based only on a grinding, without a drying step highly energy-consuming, could be
envisaged. Further investigations will focus on the optimisation of the slurry grinding as well as water
extraction conditions.
References
[1] Garcia-Castello, E.M., Rodriguez-Lopez, A.D., Mayor, L., Ballesteros, R., Conidi, C., Cassano, A.: Optimization of
conventional and ultrasound assisted extraction of flavonoids from grapefruit (Citrus paradisi L.) solid wastes. LWT –
Food Sci. Technol. 64, 1114-1122 (2015)
[2] Nayak, B., Dahmoune, F., Moussi K., Remini, H., Dairi, S., Aoun, O., Khodir, M.: Comparison of microwave, ultrasound
and accelerated-assisted solvent extraction for recovery of polyphenols from Citrus sinensis peels. Food Chem.,
187(Supplement C): p. 507-516 (2015)
[3] Wang, W., Ma, X., Xu, Y., Cao, Y., Jiang, Z., Ding, T., Ye, X., Liu, D.: Ultrasound-assisted heating extraction of pectin from grapefruit
peel: Optimization and comparison with the conventional method. Food Chem., 178(Supplement C): p. 106-114 (2015)
[4] Trotta, F., etal., 2002, Molecular imprinted polymeric membrane for naringin recognition. J. Membr. Sci., 201(1): p. 77-84.
544
EFFECTS OF AERATION ON MATRIX TEMPERATURE BY INFRARED THERMAL IMAGER

AND COMPUTATIONAL FLUID DYNAMICS DURING SLUDGE BIO-DRYING
D.W. YU1, M.M. LIU2, Y.W. WANG1, Y.S WEI1*

1 State Key Joint Laboratory of Environmental Simulation and Pollution Control, Research Center for
Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China.
Abstract
The effect of aeration on the pile matrix temperature was investigated using thermocouples and
Infrared Thermal Imager (IRI) for temperature sensing, and Computational Fluid Dynamics (CFD) for
modelling of temperature variation during aeration in a full-scale sludge biodrying plant. With
aeration saving of 20%, the improved strategy speeded up biodrying from 21 days to 14 days, while
achieving similar drying effect. A persistent thermocouple recorded the one-dimensional (1D) total
temperature variation of all aeration strategies. The IRI captured the rapid two-dimensional (2D) pile
temperature dropped from 72.5°C to 30.3°C during 6 min of aeration, which mechanism suggested
as the latent heat of moisture evaporation and sensible heat of air exchange. The CFD three-
dimensional (3D) CFD results highlight the importance of latent heat rather than sensible heat.
Therefore, the pile temperature drop inferred is ∆T=5.38°C theoretically and ∆T=5.17±4.56°C
practically, per unit of MC removed. These findings also emphasize the possibility of a pile
temperature valley, due to excessive aeration under unsaturated vapour conditions. Surface
temperature monitored by IRI coupled with 3D temperature simulated by CFD rapidly gives a clear
matrix temperature evolution, empowering biodrying by more accurate temperature and aeration.
INTRODUCTION (the purpose)

Due to its reduction of high moisture content (MC) using bio-generated internal heat instead of
external heat, bio-drying is regarded as a green biofuel pathway from biomass, for example, in the
drying of sewage sludge(Cai et al. 2016). A capacity goal of increasing the treatment rate of sewage
sludge from 20% to 90% was set by the Action Plan for Water Pollution Prevention and Control of
China (State Council of China. 2015). Therefore, sludge bio-drying plants are rapidly being built in
China.
The pile temperature of biodrying changes rapidly during aeration aimed at MC removal, because
this involves rapid phase transformation in which latent heat accounts for 70% to 80% of total
energy output (Haug. 1993). Highly responsive monitoring of the matrix temperature is badly needed
for pile temperature investigation in sludge bio-drying. Therefore, this work focus on the effect of
aeration on matrix temperature of biodrying pile. And the temperature change per unit of MC
removal modelled.
Materials and methods
The full-scale sludge bio-drying plant in this study has the designed capacity for treating 1000 t·d-
1 of excess sludge to reduce MC from 80% to 40%. It is the largest sludge bio-drying plant in China,
and is located in Shenyang (Liaoning Province, China). One-dimensional (1D), two-dimensional (2D)
temperature was recorded with thermocouple (KT B-8A, Kaitai Inc., China) and infrared thermal
imager at all sample points. The 3D temperature was simulated with computational fluid dynamics.
The heat and moisture management were simulated by porous media model (Eq.1) and non-
Equilibrium Thermal Model (Eq.2).
545
(1)
(2)
Results
Fig. 2 shows spatio-temporal pile temperature variation at pile depth of 0.5m and 1.5m, and bio-
drying performance of three piles with three aeration strategies. The pile temperature variations
went through four different stages including temperature increasing stage, thermophilic stage, the
second temperature increasing stage, and cooling stage.
With thermocouple (Fig. 2) and IRI results (Fig. 3 Row 1), another important spatial temperature
variation was revealed, which is related to the heat and moisture exchange between interior and
surface of the pile when the MC of the pile moved from the interior to the surface.
For six different sections of the investigated tunnel, the pile temperature evolution during forced
aeration is shown in Fig. 4 by verified CFD simulation.
The exchange rate for the pile matrix temperatures was DT=5.38°C per unit of MC removed for
both evaporation removal
Conclusions
• Aeration impacts the pile matrix temperature primarily by exchanging MC and latent heat
simultaneously between the interior and surface of the pile. CFD results revealed that the
non-uniform evolution of microscopic temperature was primarily affected by the FAS.
• The exchange rate for the pile matrix temperatures was ∆T=5.38°C per unit of MC removed
for both evaporation removal and condensation acquisition during aeration theoretically.
Practically, the ∆T=5.17±4.56°C was because that high temperature air has high MC holding
capacity and accepts more sensible heat.
• The improved aeration strategy based on IRI and CFD allows for a sludge bio-drying operation
with both shorter period from 21 days to 14 days and similar 40% MC in the bio-drying
product.
Acknowledgments: National Key Research and Development Program of China
(2016YFD0501405), Major Science and Technology Program for Water Pollution Control and
Treatment of China (2012ZX07202-005) and National Natural Science Foundation of China
(21377151).
Figures, Tables Captions
. Fig. 1 Schemes of the sludge bio-drying plant (units: mm).
546
Table 1 Operation conditions for the sludge bio-drying plant
Operation Conditions Pile 0 (Control) Pile 1 Pile 2
Turning Frequency (times/day) 1 1 2 in 1 week, 1in 2nd week

st
Total Solid Retention Time (days) 22 22 14
Quantification Shovel Loader
Mixing BACKHUS Lane Turner, BACKHUS Gmbh, German
Mixing ratio1 1:0.62:0.28 1:0.62:0.28 1:0.62:0.28
Weight (for each pile) ~24.6t
Pile Size L×B×H (m) 4×3×2
Section A (SRT / days) TC, C: 4, T: 45 (2.50) TC, C: 10, T: 40 (2.50) TC, C: 6, T: 45 (1.125)
Section B (SRT / days) TC, C: 8, T: 55 (2.50) TC, C: 15, T: 40 (2.50) TC, C: 6, T: 55 (1.125)
Section C (SRT / days) C: 15 (3.50) TC, C: 10, T: 40 (3.50) C: 12 (1.68)
Section D (SRT / days) C: 17 (4.00) TC, C: 10, T: 35 (4.00) C: 14 (2.00)
Section E (SRT / days) C: 20 (4.00) TC, C: 5, T: 35 (4.00) C: 14 (2.37)
Section F (SRT / days) C: 30 (5.00) TC, C: 5, T: 35 (5.00) C: 30 (5.00)
1 The ratio is weight ratio of raw sludge: back-mixed sludge: husk, respectively.
2 The C mode refers to that aerators of the section were periodically started for C minute per hour.
3 The T mode refers to that aerators were automatically started when monitor temperature over T °C, where the aeration sustained time
was given in the brackets. Sensor was install on the tunnel, monitoring the pile surface temperature.
Fig. 2 Spatial temperature and moisture removal variation under different aeration strategies.
547
Fig. 3 Temporal temperature evolution of microscope pile surfaces by ITI and CFD simulation at aeration time
of 0, 2, 4, and 6 mins.
Table 2 Difference between CFD simulation and IRI thermogram
Location 0 min 2 min 4 min 6 min
left Center right left Center right left Center right left Center right
- -
Top 1.4% 4.6% 9.4% 6.0% 1.4% 1.4% 78.6% 13.8% 11.9% -8.7%
2.4% 6.7%
-
Middle 2.8% -1.4% -1.5% -1.4% -4.2% -1.4% -2.9% 4.4% 2.9% 0.3% -7.1%
6.5%
-
low 0.7% -1.4% 4.3% 1.4% -4.2% -2.9% 7.4% 1.4% 2.9% 5.4% -2.5%
0.5%
548
Fig. 4 Spatio-temporal temperature evolution of macroscopic pile interior by Computational Fluid Dynamics
simulation for Pile 0, 1 and 2.
Fig. 5 Average temperature drop per 1% moisture removed.
References
[1] Cai, L., Chen, T.B., Gao, D. and Yu, J. (2016) Bacterial communities and their association with the bio-drying of sewage
sludge. Water Res 90, 44-51.
[2] State Council of China (2015) The Action Plan for Water Pollution Prevention and Control.
[3] Haug., R.T. (1993) The practical handbook of compost engineering, Lewis publishers, California, USA.
[4] Villegas, M. and Huilinir, C. (2014) Biodrying of sewage sludge: kinetics of volatile solids degradation under different
initial moisture contents and air-flow rates. Bioresour Technol 174, 33-41.
549
ASSESSMENT OF THE BEHAVIOUR OF A COMMERCIAL GASIFICATION PLANT DURING

LOAD MODULATION AND FEEDSTOCK MOISTURE VARIATION: PRELIMINARY
RESULTS OF THE “FLEXI-FUEL-GAS-CONTROL” PROJECT
D. ANTOLINI1, C. HOLLENSTEIN2,3, S. MARTINI2, F. PATUZZI1, C. ZEMANN2,3, W. FELSBERGER4,

M. BARATIERI1, M. GÖLLES2
1 Free University of Bozen-Bolzano, Bolzano, Italy.

2 BIOENERGY 2020+ GmbH, Graz, Austria.
3 Institute for Automation and Control, Graz University of Technology, Graz, Austria.
4 URBAS Maschinenfabrik Ges.m.b.H., Völkermarkt, Austria.
Keywords: biomass gasification, fixed-bed reactor, electric power modulation, fuel flexibility
Abstract
Fixed-bed biomass gasification coupled with internal combustion engines allows an efficient
exploitation of biomass for the combined production of heat and power (CHP) at a scale with increased
economic viability with respect to combustion-based CHP systems. The main barrier on the way
towards a wider market distribution is represented by the fact that a robust practical operation of
state-of-the-art fixed-bed biomass gasification systems is limited to very specific fuel properties and
steady operation.
The aim of this work is twofold. On the one hand, to present the main objectives and methodologies
implemented in the FlexiFuelGasControl project (which stands for “Increased fuel flexibility and
modulation capability of fixed-bed biomass gasifiers by means of model-based control”); and, on the
other hand, to show the preliminary results of the first test runs performed in a monitored commercial
plant selected for the study.
In order to assess the general operational behaviour of the whole gasification system an experimental
one-week-long test run has been performed by BIOENERGY 2020+ and the Free University of Bozen-
Bolzano as round robin test. The plant has been tested under different operating conditions, in
particular, varying the load of the engine and the moisture content of the feedstock. During the test
run, the gas composition has been continuously monitored, as well as the temperature in different
parts of the reactor.
The results shown in the present work provide a unique indication about the behaviour of a small-
scale fix-bed gasifier working in conditions different from the nominal ones.
550
1- INTRODUCTION
Over the last twenty years, considerable improvements have been made to small-scale biomass
gasification technologies and small-scale gasifiers coupled with internal combustion engines. These
systems have been successfully commercialized with electrical and overall efficiency of about 20 %
and 80 %, respectively [1]. The last few years have seen biomass gasification plants become
increasingly used for the combined heat and power (CHP) production [2]; the amount of installations
in Europe is estimated to be around 1000 units [3], with their diffusion mainly driven by favourable
regulatory frameworks and attractive electricity feed-in tariffs.
Small-scale biomass gasification systems can be considered to be robust enough for practical and
commercial application but they are often limited to very specific fuel properties [4] and steady-state
operation. Frequent maintenance operations and required operator supervision [2] are other
important issues impacting the technical and economic viability of this technology.
In order to improve the performance of CHP biomass gasification units, load modulation capability and
fuel flexibility should be enhanced [5]. Fuel flexibility refers to the possibility of using: (a) different
feedstocks (agriculture/forest residual) or (b) the same type of feedstock but with different properties
in term of moisture and size distribution. Load modulation capability refers to appropriately
controlling the fuel fed to the gasification unit according to the energy demand. In both ways, the
economic performance of the plant can be enhanced, producing energy when it is needed (load
modulation) or using several feedstocks (fuel flexibility).
The research project FlexiFuelGasControl, which stands for Increased fuel flexibility and modulation
capability of fixed-bed biomass gasifiers by means of model-based control, is coordinated by
BIOENERGY 2020+ GmbH (BE2020+) and involves Graz University of Technology, Institute for
Automation and Control (TUG), the Free University of Bozen-Bolzano (UNIBZ) and the URBAS
Maschinenfabrik GmbH (URBAS) as project partners.
The overall aim of the project is to develop a model-based control strategy for fixed-bed biomass
gasification systems in order to increase the systems’ fuel flexibility as well as their load modulation
capability. This approach consists of dividing the problem into several interrelated mathematical
models describing all of the system's relevant parts. To the best of our knowledge, this kind of
approach has never been used to control small-scale biomass gasification plants. Conversely, in the
field of biomass combustion, the application of model-based control strategies is a promising approach
for complex systems control and this methodology has already been successfully used to enhance the
operational behaviour of a biomass boilers, e.g. [6].
The development of the model-based control has to be done both experimentally, at a real scale
gasification system, and theoretically, on the basis of theoretical, thermochemical and technical
considerations. In order to assess the general operational behaviour of the entire gasification system
under investigation an experimental one-week-long test run has been performed by BE2020+ and
UNIBZ in the style of a round robin test, investigating the different parts and components as well as
the producer gas properties and their dependence on the different process variables. Experimental
work has been carried out on a real-scale fixed-bed gasifier owned and operated by URBAS, located in
Völkermarkt (Austria). Monitoring data and preliminary results will be presented in this work.

2.1. DESCRIPTION OF THE PLANT AND MEASUREMENTS
The CHP plant selected for monitoring consists of an industrial small-scale fixed-bed downdraft
biomass gasifier using air as gasification agent, a gas cleaning and drying unit and an internal
551
combustion engine to produce heat and electric power (Figure 1). The producer gas exiting the gasifier
first passes through a hot gas filter which removes particulate matter from the gas stream. The
producer gas is then cooled and dried in a heat exchanger and a condensation unit. The dried and
cleaned producer gas enters a suction fan and subsequently the generator unit consisting of an
internal combustion engine and a generator with a nominal electric capacity of 150 kWel.
In terms of automation and control, the CHP plant is equipped with a PLC system, several sensors and
measurement units required for operation. These sensors measure gas temperatures and differential
pressures relative to the ambient between all components along the producer gas stream, the oxygen
content of the exhaust gas and the electric power produced by the internal combustion engine. The
CHP plant has also been equipped with sensors measuring the volume flow rate of air and producer
gas. Due to technical limitations, the mass flow rates of the feedstock and of the discharged char
cannot be measured directly and are estimated by means of mass balance equations.
Figure 1: Simplified structure of the CHP with nominal capacity of 150 kWel
To evaluate the behaviour of the CHP plant outside the nominal conditions, four sampling points have
been selected, as shown in Figure 1. Q1 and Q2 are used to sample the biomass before and after the
drier, Q3 for measuring the gas composition and performing tar sampling, and Q4 to collect char
samples.
The downdraft reactor is designed like an Imbert type reactor using air as gasification agent, compare
e.g. [7]. The gasifier operates slightly below atmospheric pressure, is fully automated and is
autothermal [2].
Externally dried biomass enters the gasifier through a sluice system at the top and moves downwards
while being converted to producer gas. In order to identify the distribution of temperatures and
pressures inside the gasifier, six N-Type thermocouples and two differential pressure sensors have
been installed at different vertical positions near the wall of the gasifier measuring the inside
temperatures and pressures.
The air enters the gasifier in the combustion zone through multiple air nozzles, which are equally
distributed along the diameter of the throat. Performing partial combustion of the biomass char, this
zone on the one hand provides heat necessary for the pyrolysis and drying steps and on the other
hand leads to oxidizing of the pyrolysis gases, which enter from the upper zone [8]. Before exiting the
gasifier, the producer gas flows through a hot char bed. The by-product (char) is disposed as waste
from the gasifier by means of a grate and auger system using water as transportation medium. The
condensable tar components leave the gasifier with the producer gas stream and will be removed by
components downstream.
552
2.2. TEST RUNS PERFORMED
In order to evaluate the behaviour of the fixed-bed biomass downdraft gasifier outside from nominal
conditions two different electrical loads and two different moisture contents of the biomass
feedstocks have been examined. To evaluate the reproducibility two parameter settings have been
tested twice, finally leading to six different test runs. After reaching stable conditions in each test run,
sampling and analyses of biomass, char and producer gas have been performed by BE2020+ and UNIBZ
as round robin tests.
Exact values of moisture content and the electric power produced are given in Table 1, with the two
different loads indicated with Partial load and Full load, and the two different feedstock moisture
contents indicated with dry and wet. Furthermore, the six test runs performed are categorized in pairs,
always indicating two successive test runs, thus including a step-wise change of one parameter while
keeping the other parameter constant. Case A: dry biomass kept and load modulation from partial to
full load; case B: full load kept and moisture variation from dry to wet; case C: partial load kept and
moisture variation from dry to wet.
Test cases Short name Electric power production Feedstock moisture content
Partial load – dry (A) (A) PL-d 120 [kWel] 10.6 [w.t. %] w.b.
Full load – dry (A) (A) FL-d 150 [kWel] 10.6 [w.t. %] w.b.
Full load – dry (B) (B) FL-d 150 [kWel] 11.2 [w.t. %] w.b.
Full load – wet (B) (B) FL-w 150 [kWel] 18.7 [w.t. %] w.b.
Partial load – dry (C) (C) PL-d 120 [kWel] 11.2 [w.t. %] w.b.
Partial load – wet (C) (C) PL-w 120 [kWel] 20.4 [w.t. %] w.b.
Table 1: Test run parameters
2.3. SAMPLING AND CHARECTERISATION OF FEEDSTOCK AND CHAR
During each test run, different samples of the biomass feedstock and char residues have been
collected at the sampling points Q1, Q2 and Q4 respectively (see Figure 1). Since the particle size
distribution of the biomass feedstock corresponds to the class P100 according to EN 14961, the
collected samples have been finely chopped directly at the CHP plant in a first preparation step. All
the collected samples have then been analysed both from UNIBZ and BE2020+ separately. BE2020+
used the following analysis methods:
• sample preparation according to EN 14780 (mixing and milling);

• determination of the moisture content according to EN 14774 (weight loss during drying at
105°C until a constant weight is reached);
• determination of the ash content according to EN 14775 (loss of ignition at 550°C);
• determination of the Carbon, Hydrogen and Nitrogen mass fractions according to EN 15104;
• determination of the bulk density according to EN 15103.
Whereas UNIBZ used the following analysis methods:
• moisture and ash content according to EN ISO 18134-2:2015 and UNI EN 14775:2010;
• elemental analysis (C, H, N, O) according to UNI EN ISO 16948:2015;
• calorimetric analysis according to UNI EN 14918:2010.
553
A comparison of the results from UNIBZ and BE2020+ will be described in section 3.
2.4. MEASUREMENT OF FLOW RATES
Three Prandtl-type pitot tubes have been used to measure the volume flow rate of the gasification air,
the engine air and the producer gas. In addition, an orifice plate flow meter is used to measure the
volume flow rate of the gasification air and a fluidistor gas flow meter is used to measure the volume
flow rate of the producer gas.
The mass flow rate of the biomass fed to the gasifier and the resulting char residue have been
calculated from a mass balance what will be described in more detail in section 2.6. In addition, the
estimation of the mass flow rate of the biomass fed to the gasifier has been complemented by using
the number of feeding cycles, the volume of biomass per one feeding cycle and the bulk density of the
biomass. In order to estimate the volume of biomass per feeding cycle, the volume of wet biomass
consumed (before the external dryer) was monitored during a defined period. Subsequently, this
volume of wet biomass was converted to a volume of dry biomass (before entering the gasifier) and
then divided by the total number of feeding cycles performed within this period.
2.5. PRODUCER GAS ANALYSIS
The sampling point Q3 (after the cleaning and drying step in the CHP plant, see Figure 1), was used for
producer gas and tar sampling. Both have been performed as round robin test by BE2020+ and UNIBZ,
applying slightly different methods. BE2020+ continuously analysed the producer gas on dry basis
using a gas analyser (ABB AO2020), which is operating with an equidistant sampling rate of 1 s. This
gas analyser measures CO, CO2 and CH4 with an infrared measuring principle, H2 with a thermal
conductivity measuring principle and O2 with an electrochemical measuring principle. N2 is assumed
to be the rest of the volume fraction to sum up to 100 vol % d.b. In addition, the cross sensitivity of
the individual gas components are internally balanced.
In contrast, UNIBZ has used a portable gas chromatograph (microGC 490 Agilent, SRA instruments)
able to detect H2, O2, N2, CH4 and CO in a Molsieve column and CO2, C2H4, C2H6 and C3H6/C3H8 in a Plot-
U column and analysed the producer gas each 3 min (corresponding to the time required for the
chromatographic separation and analysis of the extracted gas samples).
The net calorific value of the dry producer gas was estimated using the producer gas composition and
the corresponding standard heat of combustions of each component.
2.6. STRATEGIES FOR THE MASS BALANCE
In order to estimate the mass flows of biomass, air (gasification agent), producer gas and char, three
different strategies have been performed.
In the first strategy, an overall mass balance was carried out using
• measured mass flow rate of the producer gas and gasification air (assumption: reliable),
• calculated char mass flow rate using ash balance (ash content analysis of biomass and char),
• and estimated mass flow rates of biomass fed to the gasifier as the difference between the
mass flow rate of the product gas and the sum of the mass flow rates of the air and char.
In the second strategy, an atomic balance solver was developed in order to minimize the least squares
error of the estimation using an overdetermined set of equations formed by
554
• C, H, N, O and ash mass balances,

• mass flow rate correlations between air/biomass, producer gas/biomass and char/biomass,
calculated using the measured product gas composition, the elemental composition of the
biomass and char (laboratory analysis results) and the composition of the gasification air,
• one of the measured mass flows; in particular, the producer gas mass flow was considered to
be the most reliable measure (the biomass flow rate was assessed indirectly from volumetric
measurements and the air measurement signal was characterized by a high level of noise due
to mechanical vibrations close to the blower).
In the third strategy, a linear system was built in order to calculate a single solution using
corresponding balances for
• N, relating the air (gasification agent) and the producer gas,

• ash, connecting biomass and char mass flows,
• C for biomass, char and producer gas connection, and
• one of the measured mass flows; in particular, as for the second strategy, the producer gas
mass flow was considered to be the most reliable measure.
In the third strategy, nitrogen, carbon and ash content were selected because they represent the
highest fractions in the mass flows of air, biomass and char, respectively; therefore, they result to be
the most relevant for the correlation between air/producer gas, biomass/producer gas and
biomass/char.

The preliminary results will be presented in terms of gasification outputs for load modulation and
moisture content variation as well as a comparison between the results achieved by BE2020+ and
UNIBZ. In order to have a complete description of the gasification process, a biomass and char
characterization analysis has been performed. Average values are presented in Table 2.
Elemental analysis Wood chips Char

Ash [w.t. %] d.b. 0.74 31.65
C [w.t. %] d.b. 50.36 65.78
H [w.t. %] d.b. 6.09 0.55
O [w.t. %] d.b. 42.38 1.19
N [w.t. %] d.b. 0.13 0.31
S [w.t. %] d.b. 0.31 0.53
Calorific value Wood chips - average Char - average
LHV [MJ/kg] d.b 17.92 -
Table 2: Average biomass and char characterization
The biomass samples were collected before every run test and moisture analysis was determined using
an on-line moisture transmitter.
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3.1 COMPARISON OF RESULTS ACHIEVED BY UNIBZ AND BE2020+ (ROUND ROBIN TEST)
Biomass and char sampling were collected at the same time and divided between the two research
groups for separate lab analysis. In the same way, the producer gas was collected using a common
heated line. Then the flow was split in two independent lines and it was analysed using different
equipment. The results of gas analysis were examined and compared. The same methodology of round
robin tests has been performed for all the measurement campaigns. A period of 8 hours of analysis is
presented in Figure 2 as an example of this procedure.
Figure 2: Gas analysis - comparison of round robin test
The separate results of gas analysis present a good agreement, the average error of all gases is less
than 3% related to the maximum error recorded. However, the error regarding methane (CH4) is
significantly but almost constant over time, thus just an offset. After correcting the offset error the
maximum error regarding CH4 is less than 7%. In any case, the CH4 content in the producer gas is quite
constant during the gasification and it is around 2% in terms of molar fraction.
3.2 EFFECT OF LOAD MODULATION
During the monitoring campaign, the electricity production was set either to nominal load or to partial
load in order to investigate the corresponding behaviour of the gasification plant. One test was
performed using the same biomass in terms of moisture content, modulating the power load from 120
kWel to 150 kWel. On the contrary, moisture content was varied from dry to wet biomass imposing a
constant electric load. In Figure 3 the corresponding desired and produced electric power signals are
shown exemplarily for the operation with dry biomass (case A).
The measured electric power matches the desired value sufficiently well, indicating a reasonable load
control. Furthermore, the producer gas composition does not change significantly, going along with
an average decrease of the LHV of 4.1% d.b. This could be explained by the control system
appropriately adjusting the pressure before the gas engine and thus adjusting the air mass flow
entering and the product gas mass flow leaving the gasifier. This only slight influence of the load on
556
the equivalent ratio was also verified by the experimental data collected during the test runs belonging
to case B and C.
In Figure 4 the reactor structure and the average temperatures inside the reactor are shown. The
positions of the thermocouples type-N and the differential pressure sensors are presented
respectively using the abbreviations TG1 to TG5. As can be seen from Figure 4, there is no significant
variation of the temperature inside the reactor while varying the electric load, except for the
temperature close to the nozzle zone TG3 what is already damped at the next temperature
measurement TG4.
The temperatures recorded at TG1, TG2 and TG5 are almost the same for the two load levels. As already
mentioned, the producer gas composition (Figure 5) is characterized by some minor variations. In
particular, a slight decrease of carbon monoxide and hydrogen and a slight increase of carbon dioxide
and nitrogen could be detected, while the methane content remained constant, when the load was
increased from 120 kWel to 150 kWel. These trends are confirmed comparing the data of case B and
case C at the same moisture content and different loads.
Figure 3: Electric power desired (Psetup) and monitored (PGE) – case A
average temperature
1000
(A) PL-d
900 (A) FL-d
(B) FL-d
(B) FL-w
800
(C) PL-d
(C) PL-w
700
600
500
[°C]
400
300
200
100
T T T T T T
G1 G2 G3 G4 G5 G6
Figure 4: Structure of the fixed-bed biomass downdraft gasifier – average temperature inside the reactor
557
average gas composition d.b. average product gas LHV d.b.

50 6
5
40
30
3
[%vol]
[MJ/kg]
20
(A) PL-d
2
(A) FL-d
(B) FL-d
10 (B) FL-w
1
(C) PL-d
(C) PL-w
0 0
CO CO CH H N LHV
2 4 2 2
Figure 5: Average producer gas composition and LHV value d.b. – all cases presented
3.3 EFFECT OF MOISTURE CONTENT VARIATION
In order to compare the effect of varying the moisture content in biomass gasification at different
electric loads, four periods of steady state gasification were selected. In the cases B and C, the moisture
content was changed keeping the power load constant (full load in case B, partial load in case C). The
results in terms of average electric power generated as well as gas composition and temperatures
inside the reactor are shown in Figure 4, Figure 5 and in Table 3.
It should be noted that the use of dry biomass leads to an increase in the amount of carbon monoxide
and, in contrast, a decrease in the amount of carbon dioxide. However, the methane content is quite
stable in any condition. On the contrary, hydrogen grows very slightly with increasing moisture content
and decreasing the power load. Nitrogen presents the same trend with respect to the biomass
moisture content and the opposite trend reducing the load.
As far as the nozzle temperature is concerned, it is correlated to both moisture content and electric
load. The nozzle temperature is higher at full load than at partial load, both in the case of dry and wet
biomass. Moreover, increasing biomass moisture tends to reduce the temperature in the core of the
reactor, as it can be expected. Furthermore, the highest temperature monitored at TG4 has the same
trend, increasing the moisture content the temperature decreases. In this case, the same result was
obtained decreasing the electric load.
moisture CO CO2 CH4 H2 N2

TG3 TG4 TG5 LHVpgas
[w.t.%] [%vol] [%vol] [%vol] [%vol] [%vol]
[°C] [°C] [°C] [%vol] d.b
w.b d.b d.b d.b d.b. d.b.
(A) PL-d 10.6 712 847 774 21.9 11.7 2.5 21.5 42.4 5.58
(A) FL-d 10.6 817 871 772 20.9 12.2 2.4 21.0 43.4 5.35
(B) FL-d 11.2 803 863 772 22.4 10.8 2.3 21.0 43.1 5.53
(B) FL-w 18.7 745 853 785 18.8 13.7 2.4 21.6 43.5 5.13
(C) PL-d 11.2 717 837 785 22.8 11.3 2.4 22.2 41.3 5.79
(C) PL-w 20.4 673 833 760 19.0 13.6 2.4 22.5 42.4 5.29
Table 3 : Comparison of average electric power generated, temperature and producer gas composition
558
4- SUMMARY AND CONCLUSIONS

The preliminary results of the project FlexiFuelGasControl were presented in this work. The project
aims at increasing the systems’ fuel flexibility and the load modulation capability developing a model-
based control strategy for fixed-bed biomass gasification systems combined with an internal
combustion engine for CHP generation. The results of a monitoring campaign performed on a real-
scale fixed bed gasifier owned and operated by URBAS located in Völkermarkt (Carinthia, Austria) was
presented and discussed.
In particular six test runs have been performed, testing the performance of the plant in several
operational conditions. Two different electrical loads and two different moisture contents of the
biomass feedstocks have been examined. The electrical load was changed from 150 kWel (nominal
load) to 120 kWel (partial load) and the water content of the biomass feedstock was varied between
10-11 w.t. % w.b., i.e. dry conditions and 18-20 w.t. % w.b., i.e. wet conditions.
The main result observed is that the current control system of the plant modulates air to meet the
power load request with the constraint of keeping a stable value of the equivalent ratio.
Both load modulation and moisture variations influence the temperature profile inside the reactor
and in particular in the zone close to the nozzles where the air is fed into the gasifier. As a result, the
producer gas quality changes in terms of gas composition and calorific value.
The load modulation from 150 kWel to 120 kWel results in a small increase in the producer gas LHV,
which is equal to approximately 4.3 % and 3.0 % when running with dry and wet biomass respectively.
On the other hand, the moisture variation has a higher effect. In fact, a variation from 10-11 w.t. %
w.b. (dry biomass) to 18-20 w.t. % w.b. (wet biomass) of feedstock moisture content causes a
reduction of the producer gas LHV of about 7.2 % at full load and 8.6 % at partial load.
REFERENCES
[1] Bocci, E., Sisinni, M., Moneti, M., Vecchione, L., Di Carlo, A., Villarini, M.: State of art of small scale biomass
gasification power systems: A review of the different typologies. Energy Procedia. 45, 247–256 (2014)
[2] Patuzzi, F., Prando, D., Vakalis, S., Rizzo, A.M., Chiaramonti, D., Tirler, W., Mimmo, T., Gasparella, A., Baratieri,
M.: Small-scale biomass gasification CHP systems: Comparative performance assessment and monitoring
experiences in South Tyrol (Italy). Energy. 112, 285–293 (2016)
[3] IEA Bioenergy task 33 - gasification of biomass and waste: workshop: small scale gasification for CHP. , Innsbruck
(2017)
[4] Basu, P.: Chapter 8 - Biomass Handling. Elsevier Inc. (2010)
[5] Urchueguía, J.F., Alakangas, E., Berre, I., Cabeza, L.F., Grammelis, P., Haslinger, W., Hellmer, R., Mugnier, D.,
Papillon, P., Stryi-Hipp, G., Helden, W. van: Common Implementation Roadmap for Renewable Heating and
Cooling Technologies, http://www.rhc-platform.org/fileadmin/Publications/RHC_Common_Roadmap.pdf
[6] Zemann, C., Heinreichsberger, O., Gölles, M., Brunner, T., Dourdoumas, N., Obernberger, I.: Application of a
Model Based Control Strategy at a Fixed Bed Biomass District Heating Plant. 22nd Eur. Biomass Conf. Exhib. Proc.
1698–1705 (2014)
[7] Reed, T.B., Golden, A. Das: Handbook of Biomass Downdraft Gasifier Engine Systemss. (1988)
[8] Basu, P.: Chapter 8 - Design of Biomass Gasifiers. Academic Press (2013)
559
ANALYTICAL CHARACTERIZATION OF OLIVE OIL SOLID RESIDUES FOR THEIR

POTENTIAL USE AS A GASIFICATION FUEL
G. DUCOM1, M. GAUTIER1, M. PIETRACCINI1,2, R. GOURDON1

1 Université de Lyon, INSA-Lyon, DEEP, F-69621 Villeurbanne, France.
2 Politecnico di Torino, Torino, Italia.
Keywords: gasification, characterization, residues from olive oil production, TG-DSC, Py-GC-MS
Abstract
Organic waste gasification is a promising waste-to-energy technique providing an attractive

alternative to combustion. The technology however is adapted to a relatively limited panel of solid
waste fuels of defined specifications, which must therefore be characterized properly to assess their
adaptation. The purpose of this research was to assess the relevance of thermochemical methods to
analyze organic solid residues from olive oil production with respect to their potential use as a waste
fuel for gasification, notably in Mediterranean countries.
Solid residues from Tunisia were used in this study. After grinding, two fractions of visibly distinct
natures were separated. One fraction (S) was apparently made of olive stones and kernels. The other
one (P) was probably made of olive pulp and peal. Each fraction and the initial mixture (M) were
analyzed separately by thermogravimetry (TG), differential scanning calorimetry (DSC) and pyrolysis
coupled to gas chromatography and mass spectrometry (Py–GC–MS).
The results obtained underlined the complex nature of the residues. Total mass loss in TG analyses
was in the order of 97-98%, indicating that the residues were mainly organic, with very little mineral
matter. TG-DSC analyses revealed the presence of several types of organic constituents, including
cellulose, hemicellulose and lignin. Py–GC–MS technique allowed to identify the nature of some of the
organic constituents, such as phenolic compounds or oleic acid and derivatives. The presence of
residual olive oil in the P fraction was clearly revealed by the thermochemical analyses.
560
1- INTRODUCTION
Organic waste gasification is an attractive alternative to combustion. Gasification is a thermochemical
process that converts a solid carboneous fuel into gaseous components (syngas, mainly composed of
carbon monoxide, hydrogen, methane, and some other inert gases) at high temperature. The whole
process of gasification is very complex and generally described as a four-step process occurring in
different zones within the gasifier. These steps are namely drying, pyrolysis, oxidation and reduction.
The oxidation and reduction involve several simultaneous chemical reactions. The technology
however is adapted to a relatively limited panel of solid waste fuels of defined specifications, which
must therefore be characterized properly to assess their adaptation.
Classical analyses include overall parameters (such as moisture, volatile matter, fixed carbon, and ash
contents), elemental analyses (C, H, N, O and other elements contents), heating value and physical
parameters such as bulk density or particle size distribution. Other analytical techniques may provide
however more specific information on the considered waste material with respect to its treatability
by gasification.
The purpose of this research was to assess the relevance of thermochemical methods to analyze
organic solid residues from olive oil production with respect to their potential use as a waste fuel for
gasification, notably in Mediterranean countries. The used characterization methods were thermo-
gravimetry coupled with differential scanning calorimetry (TG-DSC) and pyrolysis coupled to gas
chromatography and mass spectrometry (Py–GC–MS). It is expected that these methods may give
insights into phenomena happening in the gasifier.
One specificity of the solid residues from olive oil production is that they contain residual oil. This can
affect the gasification process and the syngas composition. Moreover, in order to be treated by
gasification, solid residues from olive oil production have to be pre-treated by means of drying and
pelletization or briquetting operations. However, residual oil content in the solid waste has an adverse
effect on pellet quality and must therefore be quantified. Consequently, residual oil will be of
particular interest.

Solid residues collected from a three-phase olive oil extraction plant located in Tunisia were used in
this study. For analytical purposes, the dry samples of solid residues were grinded down to below
1 mm prior to the analyses. This operation generated 2 fractions of visibly distinct natures. One
fraction, referred to as S in this paper, was made of hard particles, probably olive stones and kernels.
The other fraction, named P, was milder, probably made of olive pulp and peal. The fractions were
well separated by sieving at 0.3-1 mm. The raw sample comprising the 2 fractions was named M.
2.1- Thermogravimetry and differential scanning calorimetry

The three samples (M, P and S) were analyzed individually. Thermogravimetry (TG) and differential
scanning calorimetry (DSC) were performed using a Mettler Toledo TGA/DSC 2 thermal analyzer in
either nitrogen or air atmosphere. This apparatus, equipped with a thermobalance, recorded, as a
function of temperature, both the weight sample evolution (TG) and the heat flow variation between
the sample and a reference material (DSC). Samples of approximately 20 mg were introduced in an
alumina crucible and heated from 25 °C to 800 °C at a rate of 10 °C/min. All analyses were at least
duplicated.
561
2.2- Pyrolysis coupled to gas chromatography and mass spectrometry

The S and P fractions were characterized with pyrolysis (Py) coupled to gas chromatography (GC) and
mass spectrometry (MS). The mass sample was in the order of 1-1.5 mg. After a flash pyrolysis at
550 °C (Pyrolyzer EGA/PY-3030D), the gas emitted was analyzed with a gas chromatograph and a mass
spectrometer (qualitative analysis) from Agilent. The GC oven program temperature was: 50 °C for 5
minutes, heating rate of 15 K/min (50 to 280 °C), 280 °C for 5 minutes. The method allowed the
identification of the main compound families in the pyrolysis gas.

3.1- Thermogravimetry and differential scanning calorimetry (TG-DSC)
As mentioned in the introduction, the gasification process is a four-step process, including a pyrolysis
step and an oxidation step. For this reason, TG-DSC analyses were performed in both oxidative (air)
and inert (N2) atmospheres.
a/ In air
Figure 1 shows the TG and DSC profiles obtained in air for the raw olive oil residue (M) after grinding
(1 mm).
0 14000
exo
-10 12000
-20
DSC : Heat flux (mW/g)

10000
TG : Weight loss (%)
-30
-40 8000
-50 6000
-60 4000
-70
2000
-80
-90 0
-100 -2000
0 100 200 300 400 500 600 700 800
Temperature (°C)
Figure 1: TG (blue curve, left axis) and DSC (red curve, right axis) profiles of the raw olive oil residue (M) in air.
The blue curve represents the mass loss (y-axis on the left) and the red curve represents the heat flux
(y-axis on the right). The TG curve showed a first weight loss associated with an endothermic peak
centered at 80 °C assigned to water vaporization of the residual water in the residue (about 10%). A
second weight loss was associated with an exothermic peak centered at 320-325 °C showing the
oxidation of some organic matter. A third weight loss was then observed, apparently associated to 4
superimposed exothermic peaks. This observation revealed the complex nature of the residue,
composed of several groups of organic constituents which are oxidized at different temperatures. The
cumulated weight loss was in the order of 97-98% and mainly occurred below 550 °C, indicating that
the residue was mainly organic, with small content in inorganic matter.
562
Figures 2a and 2b show the TG and DSC profiles obtained in air for the 2 fractions obtained after sieving
(respectively S and P).
exo exo
Figure 2a: TG and DSC profiles of the S fraction in air. Figure 2b: TG and DSC profiles of the P fraction in air.
Fraction S, containing the stones and kernels (Figure 2a), revealed a first weight loss (associated with
an endothermic peak), assigned to water vaporization of the residual water which represented about
8% of overall weight loss. Then, 2 main weight loss zones associated to exothermic peaks were
observed, corresponding to the oxidation of organic constituents. These peaks were centered at about
330 °C and 490 °C. The first exothermic peak may be attributed to the oxidation of relatively easily
degradable organic matter such as primary cellulose and hemicellulose [1]. A shoulder can be noted
on this peak, indicating at least 2 different types of organic matter. The second exothermic peak may
be attributed to the oxidation of more complex organic matter such as lignin. It can be noted that two
“maxima” seem to be observed on this peak. The overall weight loss was about 98-99%.
The analysis of fraction P (Figure 2b) containing the pulp and peel showed a first endothermic weight
loss of about 9% associated to water vaporization. Then, three main exothermic weight loss peaks
associated with the oxidation of different groups of organic constituents were observed. They were
centered at about 310, 415 and 460 °C, respectively. It was observed that exothermic peaks 1 and 3
were shifted to lower temperatures. The second exothermic peak at about 415 °C was not present in
S fraction and may be attributed to residual olive oil. This is quite consistent with results obtained by
Vecchio et al. [2] who studied the thermal decomposition of 12 monovarietal extra virgin olive oils
from different geographical origins and observed by TG-DSC a complex multistep decomposition
pattern, with a first decomposition step occurring in the range of 200-367 °C (mass loss of 35-40 %),
followed by a second decomposition step occurring in the range of 377-497 °C (mass loss of 15-20 %).
b/ In N2
Figure 3 shows the TG and DSC profiles obtained in N2 for the raw olive oil residue (M).
An overall weight loss in the order of 97% was measured. This result appeared high since usually more
char remains at the end of thermal analyses in nitrogen. The TG profile was very similar to the one
observed in air (3 main weight losses), but the degradation occurred at higher temperatures for the
last weight loss, indicating that the corresponding organic constituents were more difficult to degrade
in pyrolysis.
563
0 3000
exo
-10 2500
-20
DSC : Heat flux (mW/g)

2000
TG : Weight loss (%)

-30
-40 1500
-50 1000
-60 500
-70
0
-80
-90 -500
-100 -1000
0 200 400 600 800
Temperature (°C)
Figure 3: TG and DSC profiles of the raw olive oil residue (M) in N2.
The first endothermic weight loss assigned to water vaporization was about 9%. The second weight
loss (exothermic) was centered at 325 °C, whereas the third weight loss zone seemed to cover two
exothermic peaks (centered at 500 and 715 °C). Heat fluxes were logically smaller than in air.
Yang et al. [3] investigated the pyrolysis characteristics of the three main components of biomass
(hemicellulose, cellulose and lignin) separately by TG-DSC in N2. The temperature range of observed
weight losses are reported in Table 1. They observed that the pyrolysis of hemicellulose and cellulose
occurred quickly whereas lignin was more difficult to decompose (wide temperature range). They also
observed that the pyrolysis of cellulose was endothermic while the pyrolysis of hemicellulose and
lignin was exothermic.
Hemicellulose Cellulose Lignin

220-315 °C 315-400 °C 160-900 °C
Table 1: Temperature range of weight losses observed by TG-DSC in N2 according to [3].
In our results, it seems that degradation of hemicellulose, cellulose and lignin were superimposed,
making it difficult to identify clearly the thermic phenomena. Moreover, it is possible that some other
phenomena occur, such as vaporization of fatty acids or degradation of residual olive oil.
3.2- Pyrolysis coupled to gas chromatography and mass spectrometry

Figure 4 shows the results of the Py-GC-MS of the stone/kernel (S) fraction in black and of the
pulp/peel (P) fraction in blue. As the needed sample is very small (1-1.5 mg), only the separated
fraction were analyzed (and not the raw sample M). The y-axis is abundance and the x-axis is the
retention time.
From 0 to 8 min, no major peak can be observed. From 8 to 17 min, numerous peaks are observed and
are mainly attributed to substituted phenols. These substituted phenols probably come from the
degradation of lignin. No major difference can be observed between the S and P fractions in this range
of retention time. However, difference is observed for high retention time (> 17 min) where peaks are
attributed to oleic acid and derivatives (retention time of 17-21 min) and squalene (retention time of
24 min). These peaks are mainly present in the P fraction. Oleic acid and derivatives come from the
degradation of residual oil and there is some squalene in the olive oil. These results show the presence
564
of residual oil in the P fraction. This observation could partly explain the small differences observed in
thermal analyses.
Figure 4: Py-GC-MS of the S fraction (black) and the P fraction (blue).
4- CONCLUSIONS
The results obtained underlined the complex nature of the residues. Total mass loss in TG analyses
was in the order of 97-98%, indicating that the residues were mainly organic, with very little mineral
matter. TG-DSC analyses revealed the presence of several types of organic constituents, including
cellulose, hemicellulose and lignin. Py–GC–MS technique allowed to identify the nature of some of the
organic constituents, such as phenolic compounds (coming from the pyrolysis of lignin) or oleic acid
and derivatives (coming from the pyrolysis of residual olive oil). The presence of residual olive oil in
the P fraction was very well revealed by the thermochemical analyses.
ACKNOWLEDGEMENT
This study was part of an ERA-NET MED research program (BIOSOL) aiming at the development and
demonstration of a hybrid renewable electricity production mini-power plant, composed of a
concentrated solar power system and a biomass gasification boiler operated with solid residues from
olive oil production. The authors wish to thank the French Agence Nationale de la Recherche (ANR)
for financial support.
REFERENCES
[1] Garcia-Ibañez, P., Sánchez, M., Cabanillas, A.: Thermogravimetric analysis of olive-oil residue in air atmosphere. Fuel
Processing Technology 87, 103–107 (2006)
[2] Vecchio, S., Cerretani, L., Bendini, A., Chiavaro, E.: Thermal decomposition study of monovarietal extra virgin olive oil
by simultaneous thermogravimetry/differential scanning calorimetry: relation with chemical composition. Journal of
agricultural and food chemistry 57(11), 4793–4800 (2009)
[3] Yang, H., Yan, R., Chen, H., Lee, D. H., Zheng, C.: Characteristics of hemicellulose, cellulose and lignin pyrolysis. Fuel,
86(12-13), 1781–1788 (2007)
565
POWER-TO-GAS: DYNAMIC MODELING OF A CATALYTIC

METHANATION REACTOR
A. FACHE 1, F. MARIAS1, V. GUERRE2, S. PALMADE2

1 Univ Pau & Pays de l’Adour, Laboratoire de thermique, énergétique et procédés – IPRA, 64000 Pau,
France.
2 ENOSIS, 12 rue Louis Courtois de Viscose, 31100 Toulouse, France
Abstract
The product gas from waste and biomass gasification usually contains high amounts of CO, CO2 and
H2. In order to complete the production of combustible gas, the CO/CO2/H2 mixture can be
converted into CH4 thanks to a catalytic reactor (CO2 + 4 H2 = CH4 + 2 H2O; CO + 3 H2 = CH4 + H2O).
The advantage is that CH4 is more convenient to store/transport/use, in existing devices, than H2.
A complementary H2 supply is required to convert all the carbon compounds. This supply should
preferably be obtained by electrolysis, based on renewable electricity. The latter undergoes
temporal variations. Therefore, the reactor has to enable dynamic operation.
In this context, a dynamic mathematical model of a reactor performing methanation on a nickel-
based catalyst is built. The simulated reactor is a multitubular, wall-cooled, fixed-bed reactor. 1-D
model is used in each reactor component (coolant, gas mixture, tubes walls). The catalytic section is
modelled as a pseudo-homogeneous reactive medium. Kinetics from Xu & Froment1 are used.
Thermal losses through the whole reactor walls are taken into account. The computation code is
used to simulate an on-off operation, and to determine a range for conception parameters values,
with regards to a couple of complementary (and possibly conflicting) issues:
- catalyst preservation: local temperature should not exceed a given value,
- industrial specifications to reach an economically viable solution: high conversion yield, fast start-
up after a standby period to avoid using CO/CO2/H2 at loss.
Figure 1 shows an example of restarting simulation, in the case of CO2/H2 methanation.
Figure 1: evolution of axial temperature in the reaction medium, after a 10 h standby, when re-injecting feed gas
Conclusion: Many quantities of interest (temperatures, mixture composition along the axial
position…) are calculated from start-up to steady-state. The next step is to build a pilot unit, in order
to adjust the model thanks to experimental data. It will then be possible to design and to size an
industrial reactor.
References
[1] Xu J, Froment G F. Methane steam reforming, methanation and water-gas shift: I. intrinsic kinetics. AIChE Journal
1989, vol. 35, No. 1 : 88-96.
566
VALORIZATION OF CHAR FROM BIOMASS GASIFICATION AS CATALYST SUPPORT IN

DRY REFORMING OF METHANE: PRELIMINARY INVESTIGATIONS
V. BENEDETTI, S. SHIVANANDA AIL, F. PATUZZI, M. BARATIERI

Faculty of Science and Technology, Free University of Bolzano, piazza Università 5, Bolzano 39100,
Italy
Abstract
This study aims at demonstrating the feasibility of using char derived from biomass gasification as
catalyst support for Co-catalyst in Dry Reforming of Methane (DRM). DRM, the catalytic conversion
of a mixture of CO2 and CH4 into syngas, was selected as the test reaction because of its potential
benefits on manipulating the H2/CO ratios for downstream industrial processes as methanol,
dimethyl-ether or Fischer-Tropsch synthesis.
The foremost reason for such an application of char includes the ability to tune its physico-chemical
properties (surface area, pore characteristics, acidity) similar to that of conventional catalyst
supports like Al2O3, SiO2, TiO2, or activated carbon. Moreover, it has been observed that an inert
carbon based support like char, can reduced the metal support interactions that are predominantly
present in the conventional supports, resulting in a potential increase of the catalytic conversion
efficiencies [1]. Additionally, carbonaceous catalyst supports exhibit the advantage of easy recovery
of the active metals from the deactivated catalysts by simply burning off the support [1].
Char from a commercial biomass gasifier currently in operation in South Tyrol, Italy, was collected
and characterized. Part of the char was acid treated in boiling HNO3 in order to remove, at least
partially, any surface contaminants and to reduce the ash content. 10% Co-catalysts were
prepared by wetness impregnation using both pure char and pre-treated char. Although noble metal
catalysts (especially Rh and Ru) exhibit very high activity and low carbon deposition in the process,
also Co and Ni are used due to their lower price and ease of availability. In addition, since
deactivation of catalysts can be attenuated by the presence of metal oxide with a strong Lewis
basicity as for example alkaline earth metal oxides [2], MgO effects on the stability of the catalyst
were investigated. Approximately, 0.2 g of catalyst was placed in a quartz tubular reactor, radiatively
heated in an electric furnace. After being reduced in situ by flowing H2 (50 ml/min) at 500°C for 4 h,
the catalysts were tested for DRM activity at T = 850 °C, P = 1 atm and WHSV = 6500 mL/(g h) using a
gas mixture of 49% CO2, 49% CH4 and 2% Ar. The composition of the gas exiting the reactor was
analyzed using an on-line gas chromatographer (3000 micro-GC, SRA Instruments). Preliminary
studies with pure char showed high initial activity and rapid deactivation. However, HNO3 treated
char displayed positive effect on the process with increased catalytic activity and decreased
deactivation. Also MgO hindered catalyst deactivation changing the nature of CO2 and CO
chemisorbed species and thus inhibiting carbon deposition by the Boudouard reaction on the
working catalyst. Conclusively, according to the preliminary investigations conducted in the
Bioenergy & Biofuels Lab at the Free University of Bolzano, there is room for biomass gasification
char to be used as an effective catalytic support in DRM reactions.
References:
[1] Rodrìguez-Reinoso, F.: The role of carbon materials in heterogeneous catalysis. Carbon 36, 159–175 (1998).
[2] Guerrero-Ruiz, A., Sepulvèda-Escribano A., Rodrìguez-Ramos, I.: Cooperative action of cobalt and MgO for the
catalytic reforming of CH4 with CO2. Cat. Tod. 21, 545-550 (1994).
567
USING VINE SHOOTS-DERIVED BIOCHAR FOR THERMAL CRACKING OF EUGENOL (A

MODEL COMPOUND OF PYROLYSIS VOLATILES)
C. DI STASI, B. GONZÁLEZ, J. J. MANYÀ

Aragón Institute of Engineering Research (I3A), Technological College of Huesca, University of
Zaragoza, Spain.
Abstract
The purpose of this work is to test the capacity of a biochar-based porous material to enhance the
thermal cracking of pyrolysis vapors. Biochar is a sustainable material that is obtained from
renewable resources and a relatively low cost alternative to the metal-containing catalysts used in
catalytic cracking.
The biochar used in this work was obtained from the slow pyrolysis of vine shoots at a peak
temperature of 600°C. Different biochars were produced at two levels of absolute pressure (0.1 and
1.1 MPa) and using two different carrier gases (N2 and CO2). Biochar produced in this way did not
present appropriate textural properties to be used as an adsorbent. Thus, biochars have to be
activated to improve their specific surface areas and pores size distributions. It was reported that the
optimal pore sizes for the adsorption of volatile organic compounds (VOC) was around 0.7 nm [1].
For this purpose, a physical activation method, which consists of heating the biochar up to 800 °C in
a CO2 atmosphere [2], was selected. Two different residence times at the final temperature (30 and
120 min) were established to evaluate the influence of the percentage of burn-off on the properties
of the biochar-based activated carbon. The textural properties of the produced adsorbents will be
evaluated by measuring the specific surface areas and micropore volumes from the adsorption
isotherms of CO2 at 273 K and N2 at 77 K and the pores size distributions (from the CO2 adsorption
data for micropores below 1.0 nm using NLDFT or GCMC methods).
The compound chosen as tar model was eugenol, a phenolic compound which is one of the major
components present in the condensable phase of the effluent stream from the slow pyrolysis of
biomass [3]. The performance of biochar-based adsorbents will be evaluated in a bench-scale plant
equipped with a fixed-bed reactor (10 mm internal diameter of 30 mm length). The eugenol will be
added to a gas stream (N2) by means of a HPLC pump. Using this experimental set up, we will be able
to study the influence of the gas hourly space velocity (GHSV), the influence of absolute pressure (in
the range of 0.1–1.0 MPa) and bed temperature (650–750 °C). The effluent gas stream will be
analyzed using a GC-FID analyzer.
We have already produced all the biochar samples. The activation with CO 2 is already done for the
biochar produced with N2 as carrier gas and at atmospheric pressure. From the characterization of
the textural properties of this activated carbon, a high volume of ultra-micropores (lower than 0.8
nm) was observed. This preliminary result is promising and we’ll be glad to present the final results
during the course of the conference.
References
[1] Lillo-Ródenas, et al.: Competitive adsorption of a benzene-toluene mixture on activated carbons at low
concentration. Carbon 44, 1455–1463 (2006).
[2] Liu, W. J. , et al.: Development of Biochar-Based Functional Materials: Toward a Sustainable Platform Carbon
Material. Chem Rev. 115, 12251–12285 (2015).
[3] Ledesma, E. B., et al.: Vapor-Phase Cracking of Eugenol: Distribution of Tar Products as Functions of Temperature
and Residence Time. Energy Fuels 27, 868–878 (2013).
568
AROMATIC ENRICHED OIL PRODUCTION FROM MIXED PLASTICS USING DIFFERENT

ZINC-ACTIVATED BIOCHAR CATALYSTS
KAI SUN1, CHEN SUN1 QUNXING HUANG1, YONG CHI1, JIANHUA YAN1
1 State Key Laboratory Clean Energy Utilization, Zhejiang University, Hangzhou, Zhejiang 310027,
People’s Republic of China
Abstract
Catalytic pyrolysis of mixed waste plastics into aromatic enriched oils is a promising technology to
realize waste disposal and resource reusing. In this paper, zinc-activated biochars produced by one-
step (impregnated by 40% ZnCl2 solution, defined as Zn/C-I) and two-step (impregnated by 40% ZnCl2
solution and 40% ZnCl2 microemulsion, defined as Zn/C-II and Zn/C-III, respectively) activation-
loading methods were used to catalyse the pyrolysis of mixed plastics to comparatively study the
effect of different preparation methods on catalyst characteristics, oil compositions and aromatic
compositions, meanwhile the possible catalytic mechanism was discussed. The specific surface areas
of Zn/C-I, Zn/C-II, and Zn/C-III were 984.6, 736.4, and 636.5 m2/g, and the loading amount of Zn were
7.69, 12.5, and 7.73 wt.%, respectively. Compared with direct thermal pyrolytic oil, Zn/C showed
high selectively towards aromatics, and the proportion of aromatics in oils could be up to 47.6%,
46.8%, and 39.0% by Zn/C-I, Zn/C-II, and Zn/C-III, respectively. In aromatic compositions, bicyclic
aromatics were significantly enriched, which could reach 91.7% by Zn/C-I. Addition of Zn/C led to the
production of tricyclic aromatics, and Zn/C-II with highest Zn loading amount even catalysed the
formation of 9.2% tetracyclic aromatics. Benzene, 1, 1'-(1, 3-propanediyl) biswas the main
composition in oils, the proportion of which could be up to 20.2% by Zn/C-I. High specific surface
areas can provide more attachment sites for catalytic reactions, improving the catalytic effect, while
high loading amount of Zn species could significantly enhanced the aromatization and condensation
processes. Zn (II) introduced on char surface could form a large number of Lewis acid sites (Zn-L),
which significantly promoted the dehydrogenation, cyclization, and aromatization of alkanes and
alkenes by carbonium ions reaction mechanism. Zn-L could also catalyse hydrogen transfer reaction
and Diels-Alder reaction, which were also important pathways for aromatics formation.
References
[1] Miandad, R., Barakat, M. A., Aburiazaiza, A. S., Rehan, M., Nizami, A. S.: Catalytic pyrolysis of plastic waste: A review.
Process. Saf. Environ. 102, 822-838 (2016)
[2] Uemichi, Y., Makino, Y., Kanazuka, T.: Degradation of polyethylene to aromatic hydrocarbons over metal-supported
activated carbon catalysts. J. Anal. Appl. Pyrol. 14, 331-344 (1989)
[3] Gonzalez, Y. S., Costa, C., Marquez, M. C., Ramos, P.: Thermal and catalytic degradation of polyethylene wastes in
the presence of silica gel, 5A molecular sieve and activated carbon. J Hazard Mater. 187, 101-12 (2011)
[4] Nakagawa, Y., Molina-Sabio, M., Rodríguez-Reinoso, F., Modification of the porous structure along the preparation
of activated carbon monoliths with H3PO4 and ZnCl2. Micropor. Mesopor. Mat. 103, 29-34 (2007)
[5] Biscardi, J. A., Meitzner, G. D., Iglesia, E.: Structure and Density of Active Zn Species in Zn/H-ZSM5 Propane
Aromatization Catalysts ☆. J. Catal. 179, 192-202 (1998)
[6] Fanchiang, W. L., Lin, Y. C.: Catalytic fast pyrolysis of furfural over H-ZSM-5 and Zn/H-ZSM-5 catalysts. Appl. Catal. A-
Gen. 419-420, 102-110 (2012)
[7] Escande, V., Olszewski, T. K., Grison, C.: Preparation of ecological catalysts derived from Zn hyperaccumulating plants
and their catalytic activity in Diels–Alder reaction. CR. Chim. 17, 731-737 (2014)
569
MODELING THE REACTION KINETICS OF AGRO-WASTE DURING HYDROTHERMAL

CARBONIZATION
M. LUCIAN1, G. PIRO1, M. VOLPE1, L. FIORI1

1 University of Trento, Department of Civil, Environmental and Mechanical Engineering, Trento, Italy..
Abstract
This paper presents an original reaction kinetics model as a tool for estimating the carbon yield and
distribution among the product phases originating from hydrothermal carbonization (HTC) of
biomass. The kinetics model, developed in MATLABTM, was used in a best fitting routine with HTC
experimental data obtained for a representative ligno-cellulosic biomass (Opuntia-ficus indica
cladodes [1]) and it is easily applicable to any kinds of feedstock. Levenberg–Marquardt algorithm
was used for best fitting. The HTC reaction pathway was described through the lumped model shown
in Fig. 1, in which biomass is converted into solid (primary and secondary char), liquid and gaseous
products. Runge-Kutta method was used to solve the system of 6 differential equations - mass
balances - accounting for the different HTC lumped reactions, through the estimation of 5 Arrhenius
kinetics parameters (k1, k2, k3, k4, k5). The ki parameters were used to graphically determine the pre-
exponential factors (k0,i) and the activation energy (Ei) values for each reaction. The carbon yields of
hydrochar and gaseous phase produced by HTC are shown in Fig. 2 for a HTC temperature of 220 °C
and for reaction times until 3.5 h. Fig. 2 reports both modelling predictions and experimental data,
which were obtained considering mass yield and composition of both hydrochar and gaseous phase
[1]. Similar curves were obtained for HTC temperatures of 180 and 250 °C. Modelling predictions are
in very good agreement with experimental data. For all the examined conditions (T=180-250 °C, t=0-
3.5 h), the model fitting errors resulted lower than 8%. The developed reaction kinetics model is
therefore a reliable tool for the prediction of carbon distribution among HTC products.
Figure 1: the lumped-model used to describe the HTC reaction paths Figure 2: carbon recovery in hydrochar and gaseous
phase; both experimental data and model predictions are
reported
References
[1] Volpe, M., Goldfarb, J.L., Fiori, L.: Hydrothermal carbonization of Opuntia ficus-indica cladodes: Role of process
parameters on hydrochar properties. Biores. Techn. 247, 310-318 (2018)
570
FROM RDF TO CHEMICALS: AN EFFECTIVE EXAMPLE OF CIRCULAR ECONOMY
G.IAQUANIELLO1, A. SALLADINI2],[ E.AGOSTINI3

1 KT-Kinetics Technology S.p.A., Rome, Italy
2 .Processi Innovativi srl, Rome, Italy]
3 Bio-P, Rome, Italy
Abstract
The concept of circular economy is becoming dominant in the society, modifying the use of resource
towards more future sustainable processes. Circular economy is strictly connected to the use of
waste as feedstock and this scenario requires efforts in the development of new technology and new
approach in the waste management. On this regards the EU waste policy aims to ensure that waste
is used wherever possible as raw material to make new products. The EU Renewable Energy
Directive (RED) infact promotes the use of wastes and residues feedstock for the production of the
so called advanced biofuels by establishing that a minimum of 10% biofuels or other renewable fuels
for transport shall be used in every Member State by 2020.
Moving from this scenario an innovative process scheme aiming to valorize waste feedstock into
chemicals has been developed.
A suitable gasification technology allowing to convert Refuse Derived Fuel into a syngas reach in
hydrogen and Carbon monoxide and free of tar, char and harmful compounds like dioxins appears a
promising root in producing methanol and other chemicals such as hydrogen and urea.
High temperature gasification process validated on industrial scale has been adopted as core step of
this innovative process scheme. The overall process scheme from RDF high temperature gasification
up to syngas purification and chemicals synthesis, has been modelled and optimized through
customized process simulation tools. Heat and material balance performed around the proposed
scheme showed very high conversion efficiency.
Techno-economic analysis demonstrated the technical feasibility of methanol, urea and hydrogen
production from a waste feedstock like RDF. Compared to conventional incinerator, the proposed
technology allows for an important reduction of carbon dioxide emission (up to 50%) and for a more
sustainable approach towards waste management.
The evaluation of Capex and Opex, showed infact that thanks to the negative cost paid for waste
disposal, the proposed technology may be competitive with traditional production route.
Valorization of RDF into a valuable product like methanol/urea, may be considered a good example
of circular economy. The assessment of technology, showed interesting results both from technical
and economical point of view.
Bio-Methanol
BIO-FUEL Bio-MTBE
Refuse Derived Fuel
RDF Bio-chemicals Bio-Urea

Bio-Ad-Blue
Figure 1: RDF to chemicals conversion
571
References
[1] Antonetti, A., Iaquaniello G., Salladini A., Spadacini L, Perhatoner S., Centi G.: Waste to chemicals for a circular
economy: the case of urea production. ChemSusChem (2017)
[2] Iaquaniello G., Centi G., Salladini A., Palo E., Perhatoner S., Centi G., Spadacini L.,: Waste-to-methanol_Process and
economics assessment, Bioresource Technology 243, 611-619 (2017)
[3] Arena U.,: Process and Technological aspects of municipal solid waste gasification. A review, Waste Management 32,
625-639 (2012
[4] Iaquaniello, Centi G., Salladini A, Palo E., Spadacini L., Chapter 3 - Waste as a source of carbon for methanol
production, Methanol Science and Engineering, 2017)
572
OVERVIEW OF DRYING OF FAECAL SLUDGE FROM ON-SITE SANITATION
S. SEPTIEN 1, S. TENAW1, D. NAIDOO1, T. ONABANJO2, A. KHOLIOS2, I. MABBETT3, C.A. BUCKLEY1

1 Pollution Research Group, University of KwaZulu-Natal, Durban, South Africa.
2 Center for Combustion, Carbon Capture & Storage, Cranfield University, Cranfield, United Kingdom.
3 Chemistry Department, Swansea University Prifysgol Abertawe, Swansea, United Kingdom.
Abstract
According to figures from the World Health Organization, 2 billion people worldwide does not have
access to decent sanitation in 2017 [1]. As a result, important quantities of excreta are annually
generated from unimproved sanitation facilities or open defecation practice, which represent a
public health threat and pollution source for the environment. The treatment of the excreta is
indispensable for a sustainable sanitation, as it enables a suitable disposal of the waste without risks
for the population and the environment, and with the possibility of resource recovery in an
ultimately goal. Different products can be obtained from faecal sludge as fertilizer, soil container,
biofuel, animal protein and building material [2].
Drying represents a critical part of several treatment processes. It enables to remove the moisture
from the sludge and to kill the pathogen population found in the faecal material. The loss of
moisture leads to the decrease of the mass and volume of the material, reducing costs related to
transportation and storage. The deactivation of pathogens leads to a product safer to handle. Drying
can be the final treatment before reuse or a pre-treatment step before further processing (example:
pyrolysis or combustion).
This work presents a landscape study of drying in the context of faecal sludge management. The
different drying technologies employed for faecal sludge treatment will be reviewed. For this, a few
case studies will be described, including drying technologies being part of a faecal sludge treatment
plant and those integrated into the reinvented toilets funded by the Bill & Melinda Gates
Foundation. The first case study will consist in an infrared dryer developed within the eThewkini
municipality (Durban, South Africa). This process leads to the treatment of faecal sludge from
ventilated improved pit latrines as dried and pasteurized pellets. In the second case study, a faecal
sludge dehydration system will be the presented as a pre-treatment step before the pyrolyzer unit
that aims at producing bio-char from faecal sludge. The third case study will explain the central of
drying in some of the reinvented toilets.
Afterwards, the challenges and technological gaps to overcome will be outlined, and the laboratory
work conducted for this purpose will be displayed. This includes but it is not limited to: kinetic and
thermal analysis; characterization of the emission during drying; the rheological, consistency and
morphological evolution of the faecal material with the removal of moisture; the pasteurization of
the material; identification of the different type of bonding of the moisture with the dry bone.
References
[1] WHO: Progress on drinking water, sanitation and hygiene: 2017 update and Sustainable Development Goal
baselines. Switzerland (2017)
[2] Kengne, I., Diaz-Aguado, B., Strande, L.: Enduse of Treatment Products. In: Strande, L., Brdjanovic, D. (eds.) Faecal
Sludge Management: Systems approach for implementation and operation, pp. 203-226. IWA publishing, London
(2014)
573
BIOREMEDIATION OF BOVINE WASTEWATER

USING A PRETREATMENT AND MICROALGAE
C. VIEGAS1, M. GONÇALVES1, V. JORGE1, B. MENDES1

1 MEtRICs, Faculty of Sciences and Technology, New University of Lisbon, Caparica, PORTUGAL
Keywords: microalgae, agro-industrial effluents, bioremediation, bovine manure effluent, Chlorella

vulgaris, C. protothecoides and Scenedesmus obliquus
Abstract
Animal production is a source of effluents with high loads of macro and micronutrients and therefore
with a huge potential for eutrophication of water bodies. The treatment of these effluents generally
requires multiple methods to efficiently decrease their chemical oxygen demand (COD) and
microbiological contamination thus constituting a significant economic load for animal producers.
Microalgae have been used in the bioremediation of various effluents as an alternative to more
complex and expensive processes [1] [2].
In this work, bovine manure was treated by a combination of a physical-chemical pre-treatment and
remediation with three types of microalgae. Bovine manure was diluted 1:10 in tap water and biomass
ash was added under agitation until a pH around 12 was achieved. This pre-treatment allowed the
precipitation of suspended materials and compounds, and also eliminated the microbiological
population of the manure that is not viable at this pH value. The mixture was fractionated by
decantation to yield a liquid fraction and a solid precipitate both of which contain components of the
manure and of the added ash. The liquid effluent was used as growth media for the microalgae
Chlorella vulgaris, C. protothecoides and Scenedesmus obliquus leading to biomass productivities of
64, 68 and 67mg.L-1.d-1, respectively. The microalgae growth contributed to an important reduction
on the optical density at 540 nm of the effluent, by adsorption or consumption of suspended materials.
The nutrient removal efficiency was 100% for nitrogen and more than 30% for phosphorus,
evidentiating the ability of these microalgae to remove eutrophication-related species. This method is
coherent with the principle of circular economy because the produced microalgae could be
incorporated in animal feed and the solid by-product obtained in the pre-treatment with ash could be
valorised as a component for fertilizers.
574
1- INTRODUCTION
The growing of the human population and the need to feed it, places a significant pressure on natural
resources such as soil and water, namely by accumulation of wastes produced by different activities.
Effluents from agro-industries including animal production units contain large amounts of nutrients
and microorganisms that have a huge potential to contaminate soils and eutrophicate water bodies
[3]. Dairy farms daily produce massive quantities of manure and wastewaters from cleaning activities
that cannot be drained for conventional wastewater treatment neither be totally incorporated into
the soil, in fertilizer applications [4].
Currently the two most used solutions are the deposition of manure in open ponds and subsequent
deposition in the soil and the anaerobic digestion of the produced effluents. The deposition in the soil
causes high risks of soil and ground water contamination and is a source of considerable gaseous
emissions. Anaerobic digestion implies tight control of the operating parameters and a high dilution
ratio of the effluents, so that microorganisms are not inhibited, so it is a limited solution for processing
large volumes of manure [5].
Bioremediation with microalgae could be an alternative for the treatment of those effluents because
microalgae are ubiquitous and not very demanding microorganisms, they are also resistant and easy
to handle and have been tested in the remediation of different agro-industrial effluents with very
encouraging results [6] [7] [8]. This solution could be simpler than the anaerobic digestion and does
not involve significant costs. Nevertheless, the high solids content of manure and its high degree of
microbial contamination require the use of adequate pre-treatment processes before microalgae
could be successfully grown.
The approach proposed in this work aims to find a sustainable solution for the treatment of solid cattle
effluents, using a pre-treatment with a residue (biomass ashes) and the subsequently growth of
microalgae.
The manure is subject to dilution, pre-treatment with biomass ash and phase separation by
decantation or filtration. The liquid effluent was then bioremediated with microalgae from three
different species and the removal of nitrogen, phosphorus, and other components contributing to
CQO and turbidity was evaluated. The tested process enables the production of microalgae and of an
ash-rich precipitate that can be used as feed and fertilizer, respectively. The water used in the dilution
step is treated by the microalgae and can be recirculated for dilution of another batch of manure. To
our knowledge this is the first example of the application of microalgae in the remediation of raw solid
manure and of the coupling of a physical-chemical treatment by pH-induced protein denaturation and
bioremediation with microalgae.

The manure effluent used in the experiment was a solid cow manure from a dairy farm located in the
north of Portugal. This manure was diluted 1:10 in tap water and a pre-treatment was conducted
consisting in adding 80g/L of biomass ash in the diluted effluent, with agitation by air flow for 12 hours.
In the end of this process the pH was neutralized and it was obtain a solid residue (from ashes and
suspended solids) and a manure effluent for the microalgae growth.
In this work we used three species of microalgae Chlorella vulgaris (INETI 58, LNEG_UB, Portugal) (Cv),
Chlorella protothecoides (UTEX # 25 - INETI, LNEG_UB, Portugal) (Cp) and Scenedesmus obliquus (ACOI
204/07, Coimbra University Algotec, Portugal) (Sc).
The microalgae growth experiments were conducted during 32 days at room temperature (20°C ± 1°C),
under artificial lighting (LED fluorescent lamps of 6500°K, ± 8000 lux, digital luxmeter ROLINE, model
RO 1332A) with cycles of 12 h light/12 h dark and using 1000mL of effluent agitated by air bubbling
575
(air pump Stellar 380D, 50L/h) and sealed with hydrophobic cotton. The inoculations were performed
similarly independently of the microalgae specie, using approximately 50 mL of stock solution
(inoculum). The microalgae controls were grown in synthetic culture medium. C. vulgaris and C.
protothecoides grown in Chlorella medium [9] and Scenedesmus in Bristol medium [10]. Algal growth
was followed by measuring the culture optical density at 540nm using a spectrometer (Biocrome S4
Libra) and dry weight by filtered the samples through a Whatman GF/C 47mm filter. The parameters
evaluated in the effluents before and after microalgae growth were: total and suspended solids, total
nitrogen, total phosphorus, chemical oxygen demand (COD) and biological oxygen demand (BOD 5). All
the tests were performed with replicates and according to the methodology described in Standard
Methods Examination of Water and Wastewater [11].
After the microalgae culture reached the stationary phase, the culture was harvested by centrifugation
at 7000 rpm for 5 minutes. The liquid phase was used to make the determinations described above
and the algal biomass was dried in an oven at 45°C for 48h.

The physical-chemical pre-treatment allowed to reduce significantly the optical density of the
medium, through the deposition of suspended solids. In Figure 1 it is possible to observe the evolution
of the manure effluent throughout the remediation process.
a) b) c) d) e)
Figure 1: Evolution of manure effluent during the remediation process: a) cow manure; b) manure diluted (1:10);
c) manure diluted (1:10) with ashes; d) manure filtered after pre-treatment; e) treated effluent after algal growth.
At a pH of 12 or higher, most proteins denaturate and other molecules also suffer structural changes,
what contributes to break micellar structures and destroy microorganisms. These materials precipitate
forming a solid layer that contains components of the manure and excess ash, leaving on the top, a
liquid phase (Fig1-c) less turbid than the diluted manure (Fig1-b). This bovine effluent subject to pre-
treatment was filtered by a cotton cloth to separate the higher granulometry solids and the clarified
liquid was inoculated with the selected microalgae. The three microalgae were able to grow in the
treated effluent and reached productivities of 64, 68 and 67mg.L-1.d-1 for C. protothecoides, C. vulgaris
and S. obliquus, respectively (Figure 2). The growth of the three microalgae was not significantly
different between them, however the growth in the effluent was higher than in the synthetic medium,
for the three algae. Similar productivity of 53mg.L-1.d-1 were achieved by Beevi et al. for Chlorococcum
in dairy effluent [12]. Although Hena et al. could attained productivities of 144 and 231mg.L-1.d-1 for
Chlorella sorokiniana in dairy farm effluents [13] and Franchino et al. achieved 195mg.L-1.d-1 for C.
576
vulgaris grown in digestate from anaerobic digestion of agriculture wastes diluted in tap water 1:10
[7].
Their growth caused a decrease on the optical density of the effluent (Figure 3) and they were also
effective in removal of nitrogen and phosphorus and other components contributing to CQO (Table
1). The removal efficiency was 100% for nitrogen and that may be a limiting factor to algae growth
since they are depleted of nitrogen at a certain moment. The removal rate for phosphorus was more
than 29%. The three tested microalgae have a high potential to remove the nitrogen and total solids,
although C. protothecoides has a greater ability to remove phosphorus.
80
Productivity (mg.L-1.dia-1)
60
40
20
0
Control - C. Manure - C. Control - C. Manure - C. Control - S. Manure - S.
vulgaris vulgaris protothecoides protothecoides obliquus obliquus
Figure 2: Productivity in control medium and manure effluent in the three algae.
Figure 3: Optical density in the beginning, after pre-treatment and in the end of the experiment for manure effluent in the three algae.
577
Total COD BOD5 Ashes

Total Nitrogen
Phosphorus Removal Removal Removal
Removal
Removal Efficiency Efficiency Efficiency
Efficiency (%)
Efficiency (%) (%) (%) (%)
Manure effluent - C. vulgaris 100 29 76 99 54
Manure effluent - C. protothecoides 100 64 91 99 48
Manure effluent - S. obliquus 100 37 77 97 49
Table 1: Removal rates for the three algae in manure effluent.
The biomass ashes dissolved in the liquid fraction during the pre-treatment were removed by the
microalgae at removal rates from 48% to 54%. According to Franchino et al. a 64% ammonium
reduction was achieved for C. vulgaris grown in digestate from anaerobic digestion of agriculture
wastes diluted in tap water 1:10, and a 93% reduction for phosphate [7].
In the synthetic media the nitrogen removal was also 100% for all microalgae. The phosphorus removal
rate was 59%, 56% and 89% for C. vugaris, C. protothecoides and S. obliquus, respectively. The removal
rate for S. obiquus is expected to be higher because the Bristol medium has a much lower amount of
phosphorus in its composition.
The COD reduction was higher than 75% for all algae but C. protothecoides was the one with better
performance (91%). For BOD5 the efficiency of removal was nearly 100% for all.
Beevi et al. had reported an analogous reduction for COD (93%) and a 82% reduction for BOD5 in dairy
effluent for Chlorococcum [12].
4- CONCLUSIONS
The novelty of this work is to propose a microalgae bioremediation process for raw bovine manure,
which is a material with a very high solids content, and to demonstrate that the process allows to
obtain a by-product that can be valorised as fertilizer and does not have the same environmental
impact of the manure in terms of gaseous emissions. The effluent presented a high rate of
remediation, which means that the liquid after the growth of the microalgae, can be reused in the
dilution of another batch of manure. In this method the manure valorised as a raw material instead of
constituting only a residue that must be treated.
This process is an alternative or complement for the existing methods of manure processing by
composting or anaerobic digestion, and has the advantage of promoting CO2 absorption during the
microalgae growth.
The proposed process allows manure to be used as a source of nutrients for the growth of microalgae,
and produces algal biomass that can be incorporated in animal feeds or used as fertilizer. The liquid
effluent after remediation can be recirculated in the system to lower water requirements of the
process. The process also creates an additional application for biomass ashes, produced in the
combustion of solid biofuels, and yields an ash-rich precipitate, that could also be used as a crop
fertilizer or as a soil pH corrector.
REFERENCES
[1] A. Patel, B. Gami, P. Patel, and B. Patel, “Microalgae: Antiquity to era of integrated technology,” Renew. Sustain.
Energy Rev., vol. 71, no. 2017, pp. 535–547, 2017.
[2] T. Suganya, M. Varman, H. H. Masjuki, and S. Renganathan, “Macroalgae and microalgae as a potential source for
commercial applications along with biofuels production : A biorefinery approach,” Renew. Sustain. Energy Rev.,
vol. 55, pp. 909–941, 2016.
[3] A. I. Zouboulis, E. N. Peleka, and P. Samaras, “Chapter 17 – Removal of Toxic Materials from Aqueous Streams,” in
578
Mineral Scales and Deposits Scientific and Technological Approaches, Z. Amjad and K. Demadis, Eds. 2015, pp. 443–
473.
[4] G. Markou, L. Wang, J. Ye, and A. Unc, “Using agro-industrial wastes for the cultivation of microalgae and
duckweeds: Contamination risks and biomass safety concerns,” Biotechnol. Adv., p. Accepted Manuscript, 2018.
[5] N. I. Siddique and Z. A. Wahid, “Achievements and perspectives of anaerobic co-digestion: a review,” J. Clean.
Prod., 2018.
[6] J. I. Labbé, J. L. Ramos-Suárez, A. Hernández-Pérez, A. Baeza, and F. Hansen, “Microalgae growth in polluted
effluents from the dairy industry for biomass production and phytoremediation,” J. Environ. Chem. Eng., vol. 5, pp.
635–643, 2017.
[7] M. Franchino, V. Tigini, G. C. Varese, R. Mussat Sartor, and F. Bona, “Microalgae treatment removes nutrients and
reduces ecotoxicity of diluted piggery digestate,” Sci. Total Environ., vol. 569–570, pp. 40–45, 2016.
[8] M. Singh, D. L. Reynolds, and K. C. Das, “Microalgal system for treatment of effluent from poultry litter anaerobic
digestion,” Bioresour. Technol., vol. 102, no. 23, pp. 10841–10848, 2011.
[9] A. Vonshak and H. Maske, “Algae: growth techniques and biomass production,” in Techniques in Bioproductivity
and Photosynthesis, J. Coombs and D. O. Hall, Eds. Oxford: Pergamon Press, 1980, pp. 66–77.
[10] UTEX, “Bristol Medium Recipe,” UTEX Culture Collection of Algae, 2018. [Online]. Available:
http://web.biosci.utexas.edu/utex/Media PDF/bristol medium.pdf. [Accessed: 22-May-2018].
[11] APHA, AWWA, and WPCF, Standard Methods for the examination of water and wastewater, 16th editi. Washington
D.C.: American Public Health Association, 1980.
[12] U. S. Beevi and R. K. Sukumaran, “Cultivation of microalgae in dairy effluent for oil production and removal of
organic pollution load,” Bioresour. Technol., vol. 165, pp. 295–301, 2014.
[13] S. Hena, N. Fatihah, S. Tabassum, and N. Ismail, “Three stage cultivation process of facultative strain of Chlorella
sorokiniana for treating dairy farm effluent and lipid enhancement,” Water Res., vol. 80, pp. 346–356, 2015.
579
A DYNAMIC INTENSIFIED PROCESS AND MECHANISM OF WASTEWATER

PRETREATMENT FOR INTERNAL MICRO-ELECTROLYSIS
QIN GANG1, YE YAPING1, TANG MU1, ZHANG ZHAOCHANG2

1 Department of Chemistry and Chemical Engineering, University of Science and Technology Beijing,
Beijing, China.
2 .Beijing Weiwente Environment Tech-development Co., Ltd., Beijing, China.
Abstract
A dynamic intensified internal micro-electrolysis process was developed for wastewater

pretreatment. The intensified process comprised dissolving iron chips as anode in the presence of
non-soluble granular carbon particles as cathode and precipitating organic and inorganic impurities
on the resultant compounds that was formed in the rotary drum by applying weak voltage. The
chemical oxygen demand (COD) removal efficiency and the color removal efficiency of the simulated
dye wastewater were 80%~85% and 95%~98%, respectively after the treatment by the dynamic
intensified internal micro-electrolysis device. The experimental results revealed that the color
removal mechanism was based on the breaking down the unsaturated chemical bonds of
chromophore in dye molecules through reduction processes of hydrogen which was produced at the
cathode, the COD removal mechanism was absorption, coagulating sedimentation and co-
precipitation around the flocculation center of colloid Fe2+ being intensified as a result of the
reducing in dissolubility of dye due to its molecule structure changed by reduction processes. The
device effectively treated actual high COD wastewater of 26,000 mg∙L-1 from printing ink plant,
where the applied voltage was 30V, pH was 2-3, the reaction time was 100 minutes, the COD and the
color removal efficiency were 71.2% and 78%, respectively.
References
[1] Linares-Hernández,I.: Barrera-Díaz, C.: Roa-Morales,G.: Bilyeu, B.: Ureña-Núñez,F. : A combined electrocoagulation–
sorption process applied to mixed industrial wastewater. J. Hazard. Mater. 144, 240–248 (2007)
[2] Barrera-Díaz,C.: Linares-Hernández, I.: Roa-Morales, G.: Bilyeu, B.: Balderas-Hernández,P.: Removal of biorefractory
compounds in industrial wastewater by chemical and electrochemical pretreatments. Ind. Eng. Chem. Res. 48,1253–
1258 (2009)
[3] Canizares,P.: Martinez,F.: Jimenez,C.: Saez, C.: Rodrigo,M.A.: Coagulation and electrocoagulation in oil-in-water
emulsions, J. Hazard. Mater. 151, 44–51 (2008).)
580
BIOCONVERSION OF CELLULOSIC MATERIALS INTO SUCCINIC ACID USING YARROWIA

LIPOLYTICA PSA 02004
KHAI LUN ONG 1, NENGXIONG WANG1, CHUN YIN YAP1, CHONG LI1, XIAOTONG LI1, CAROL SZE KI LIN 1
1 School of Energy and Environment, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong
Kong, China..
Abstract
Cellulosic materials are most abundant biomass in the Earth [1]. Burning of cellulosic materials will
release greenhouse gases that cause global warming. Alternative treatment of cellulosic materials
biomass should be applied to prevent pollution. On the other hand, succinic acid is one of most
desirable chemical with industrial application. Succinic acid can be used as precursor of many bio-
based chemicals and polymers [2]. Yarrowia lipolytica PSA 02004 could converted glucose to succinic
acid through fermentation [3]. In this study, we focus on bioconversion of cellulosic materials into
succinic acid using Yarrowia lipolytica PSA 02004 through fermentation. Firstly, cellulosic materials
underwent alkaline pretreatment. After that, pretreated cellulosic materials were adjusted to pH 7
prior for enzymatic hydrolysis. Optimization of enzymatic hydrolysis of pretreated cellulosic
materials was performed to obtain optimum concentration of glucose. Parameters for enzymatic
hydrolysis optimization included pH of buffer, temperature and concentration of enzymes. Next, pH
adjustment and filtration of cellulosic materials hydrolysate were done prior to fermentation.
Fermentation of cellulosic materials hydrolysate using Yarrowia lipolytica PSA 02004 for 4 days.
Fermentation broth was analyzed using HPLC to determine succinic acid concentration produced.
Results showed that optimum pH, temperature and concentration of enzymes for enzymatic
hydrolysis of cellulosic materials were found. Fermentation of cellulosic materials hydrolysate using
Yarrowia lipolytica PSA 02004 resulted in a succinic acid yield of 0.264 g/g. In conclusion,
bioconversion of cellulosic materials into succinic acid using Yarrowia lipolytica PSA 02004 was
successfully achieved.
References
[1] Isikgor, F. H., Becer, C. R.: Lignocellulosic biomass: a sustainable platform for the production of bio-based chemicals
and polymers. Polym. Chem. 6, 4497-4559(2015)
[2] Cheng, K.K., Zhao, X.B., Zeng, J., Zhang, J.A.: Biotechnological production of succinic acid: current state and
perspectives. Biofuels, Bioprod, Biorefin. 6(3), 302-318 (2012)
[3] Yang, X., Wang, H., Li, C., Lin, C.S.K. Restoring of glucose metabolism of an engineered Yarrowia lipolytica for succinic
acid production via a simple and efficient adaptive evolution strategy. J. Agri. Food Chem. 65(20), 4133-4139 (2017)
581
MUNICIPAL SOLID WASTE AS A SUSTAINABLE BIORESOURCE TO PRODUCE CULTURE

MEDIA
J.K. IZAGUIRRE1, I. URRETA1, S. SUAREZ1, S. CASTAÑÓN1

1 Neiker-Tecnalia, Vitoria-Gasteiz, Spain.
Abstract
In recent years municipal solid waste (MSW) has contributed significantly to the total amount of waste
generated by our society [1]. Traditionally, anaerobic digestion and composting have used to the
reduction of the biodegradable fraction of MSW sent to landfills. However, the low economic value of
compost and biogas demands new alternatives to find an outlet for this type of bio-waste [2]. Within
the bioeconomy strategy waste is considered as a resource and the conversion of that biomass into a
reliable source of raw materials is of paramount importance to contribute to the environmental
sustainability and at the same time maximize the economic return.
In this work it was development a laboratory-scale process (0.2-1 litre) to the production of
concentrates rich in carbon and nitrogen from MSW-derived compost. Depending on which composting
stage is found the residue, it is richer in polysaccharides (initial phase) or proteins (final phase). In this
way, the initial phase was used for the development of a process to produce free-amino acids
concentrates. The procedure is based on the combined action of various enzymes to hydrolyse the
proteins presents in the bio-residue and thereby increasing the degree of hydrolysis [3]. In order to
reduce the viscosity of the solution and promote the action of proteases the glucanase Viscozyme L®
(1%; 50°C; pH 4.5) was used. Thirty minutes later Alcalase 1.5® (1 AU-A·g-1; 50°C; pH 7), an
endoprotease, was used and finally after 150 minutes the exoprotease Flavourzyme 500 MG® (208
LAPU·g-1; pH 7) was added continuing with the hydrolysis up to 270 min. Finally, the obtained
concentrates were used to carry out some tests of growth with lactobacillus.
The obtained hydrolysates contain 19 g/L or AA (0.1% of total nitrogen) and resulted suitable as
nutritive components in culture media for the production of microorganism. Currently a more
exhaustive characterization of the hydrolysates is being conducted to discards presence of heavy metals
and other pollutants and ensure their safety for alternative uses. Similarly, with the initial phase of
composting it was possible to obtain hydrolysates rich in carbohydrates. This way, it may be considered
mixing both MSW hydrolysates in order to reduce the production cost for a culture medium.
In conclusion, the procedure described in this work could be used to develop a suitable strategy for the
reduction of MSW, which in turn could decrease the environmental impact of these residues.
References
[1] Fernandez, Y.: Life cycle assessment of different municipal solid waste management options: a case study of Asturias
(Spain). Journal of Cleaner Production, 81. pp. 178-189, (2014).
[2] Sawatdeenarunat, C.: Anaerobic biorefinery: Current status, challenges, and opportunities. Bioresource Technology,
215. pp. 304-313, (2016).
[3] Romero, J.M.: Development of a process for the production of L-amino-acids concentrates from microalgae by
enzymatic hydrolysis, Bioresource Technology. 112, pp. 164-170, (2011).
582
THE EFFECT OF INITIAL pH ON THE BACTERIAL COMMUNITY DURING DARK

FERMENATION OF KITCHEN WASTES
R. SLEZAK1, J GRZELAK1, L. KRZYSTEK1, S. LEDAKOWICZ1

1 Department of Bioprocess Engineering, Faculty of Process and Environmental Engineering, Lodz
University of Technology, Wolczanska 213, 90-924 Lodz, Poland.
Abstract
Since the natural resources has been depleting, scientists aim to convert waste into other valuable
substrates (Katikaneni and Cheryan, 2002). From an economic standpoint the production of volatile
fatty acids (VFAs) and H2 in the dark fermentation process is more reasonable from biodegradable
waste rather than from pure substrates (Pan et al., 2008). The kitchen wastes (KW) are
uncontaminated source of substrate for dark fermentation.
The present paper focuses on the dark fermentation of KW in batch bioreactors to evaluate the
effect of the initial pH on the process performance in terms of VFAs and H2 production. The bacterial
community at the end of the process was also characterized. Initial pH was ranged from 5.5 to 9.0.
The substrate for the production of VFAs through the dark fermentation was selectively collected
from the household KW (Lodz, Poland). In the fermentation process, the digested sludge (after
anaerobic treatment) from the Waste Water Treatment Plant in Lodz, Poland was used as the
inoculum. Batch fermentation tests were carried out over for 4 days in bioreactors of 1.2 L volume.
Acetic and butyric acids were produced in the largest amount. At the initial pH of 8.0 the highest
concentration of VFA was 14.0 g/L. The maximum production yield of H2 (82.4 mL/gVS) was found for
the initial pH at 7.0. The carbon balance calculation showed that the maximum CO2 yield of 0.095
gC/gC was attained in the bioreactor with the initial pH of 9.0.
The microbiological analysis revealed that the predominant microorganisms in the dark fermentation
process were Bacteroidetes, Firmicutes, Spirochaetes and WWE1 at phyla level. In the bioreactor, in
which the greatest production of VFAs was reported (initial pH 8.0), the highest occurrence of
Bacteroidetes (11.7%), Firmicutes (35.9%), Spirochaetes (17.0%) and WWE1 (11,0%) at phylum level
was noted. At the smaller concentration of VFAs (initial pH = 6.0), Firmicutes dominated (67.1%) at
phylum level.
References
[1] Katikaneni, S.P., Cheryan, M.: Purification of fermentation-derived acetic acid by liquid-liquid extraction and
esterification. Ind. Eng. Chem. Res. 41, 2745–2752 (2002)
[2] Pan, J., Zhang, R., El-Mashad, H.M., Sun, H., Ying, Y.: Effect of food to microorganism ratio on biohydrogen
production from food waste via anaerobic fermentation. Int. J. Hydrogen Energ. 33, 6968–6975 (2008)
583
ASSESSING THE ENVIRONMENTAL PROFILE OF NUTS SHELLS VALORISATION INTO

VALUABLE PRODUCTS
B. GULLÓN1, P. GULLÓN2, J. LABIDI2, G. FEIJOO1, M.T. MOREIRA1, S. GONZÁLEZ-GARCÍA1,*

1 Department of Chemical Engineering, School of Engineering, University of Santiago de Compostela.

2 Chemical and Environmental Engineering Department, University of Basque Country, 20018 - San
Sebastián, Spain.
Abstract
The awareness of environmental pressures derived from waste management and the
implementation of a bioeconomy based on renewable feedstocks have focused the attention on the
integration of the biorefinery concept helping to develop more sustainable processes. Thus, the
valorisation of agri-food residues into added value products is a crucial role of society. This study
centered on the valorisation of peanut shells (Arachis hypogaea) for the recovery of added value
compounds using a biorefinery cascade processing has been evaluated from an environmental point
of view. Life Cycle Assessment (LCA) has been the methodology selected to perform the
environmental analysis. Nutshells are residues from the nut peeling process, present a composition
essentially lignocellulosic and up to 46 million tons are annually produced all over the world [1]. The
proposed valorising scenario displayed in Figure 1 consists of 8 main steps and renders 3 main co-
products: fermentable sugars, lignin and hemicellulosic rich stream, all of them with market value
and potential applications. Inventory data corresponding to the foreground system has been
gathered from activities performed at a semi-pilot plant. Data corresponding to the background
system has been taken from literature. Results indicate that both energy requirements and enzymes
consumption in the enzymatic hydrolysis can be considered as environmental hotspots.
Contributions to the environmental profile from the autohydrolysis and alkaline delignification are
also outstanding due to the high electricity requirements. This initial study could provide a major
insight for the concept of the cascade fractionation of valuable products from other food wastes
such as these from chestnut industry. Further research should be performed on the environmental
comparison of this scenario with the current nut shells management practice based on direct
burning for heat production.
RAW MATERIALS
SYSTEM BOUNDARIES
Background system
Peanut
production and ELECTRICITY TAP WATER CHEMICALS ENZYMES
consumption PRODUCTION PRODUCTION PRODUCTION PRODUCTION
Hemicellulosic
Electricity stream
Nut shells Electricity
Step 1
AUTOHYDROLYSIS chemicals
Step 2
CENTRIFUGATION
Tap water Step 6
Solid fraction SULFURIC ACID
PRECIPITATION
Electricity
Step 3 Liquid fraction Lignin
ALKALINE DELIGNIFICATION
Tap water and
Chemicals Electricity
Step 7
Solid fraction WASHING WITH WATER & FILTRATION
Tap water
Electricity Black liquors

Step 4 Black liquors
WASHING WITH WATER & FILTRATION Fermentable
Tap water sugars
Cellulose
Electricity
Step 5 Step 8
Tap water, chemicals & enzymes ENZYMATIC HYDROLYSIS WWTP
Foreground system
Figure 1: Flowchart corresponding to the nut shells based valorising scenario .
584
Acknowledgements
This research has been financially supported by Xunta de Galicia (project ref. ED431F 2016/001) and
the Spanish Ministry of Economy and Competitiveness (CTQ2016-81848-REDT and CTQ2016-75136-
P). S.G-G., B.G. & P.G. would like to express her gratitude to the Spanish Ministry of Economy and
Competitiveness for financial support (Grant references RYC-2014-14984, FPDI-2013-17341 and
FPDI-2013-18748, respectively). The authors (S.G-G., B.G., G.F. & M.T.M.) belong to the Galician
Competitive Research Group GRC 2013-032 as well as to CRETUS (AGRUP2015/02), co-funded by
Xunta de Galicia and FEDER).
Reference
[1] Carneiro, A.P., Rodríguez, O., Macedo, E.A.: Dissolution and fractionation of nut shells in ionic liquids. Biores.
Technol. 227, 188-196 (2017).
585
BROMINE RECOVERY FROM COMBUSTION GASES OF BROMINE-CONTAINING

PLASTICS
S. HIPPMANN1, T. WOLFF1, U. ŠINGLIAR1, M. BERTAU1

1
Freiberg University of Mining and Technology, Institute of Chemical Technology, Freiberg, Germany
Abstract
The plastic claddings of all electronic devices contain flame-retardants, in order to impede ignition in
case of fire. Brominated flame-retardants, such as hexabromocyclododecane (HBCD), are a
significant and widely distributed class of these additives. Once the period of use has expired, the
plastic claddings are usually burnt. If they contain brominated flame-retardants, hydrogen bromide
(HBr) is released in this process. At the moment, exhaust gas purification systems aim only at the
removal of HBr, but not for a bromine recovery. Please provide a structured
At the Institute of Chemical Technology, Freiberg University of Mining and Technology, a new
process is developed in cooperation with Dresden University of Technology, which removes bromine
from the combustion gas and transforms it to a useful product. During the process, released
hydrogen bromide reacts with a suspension of nanostructured ferric oxyhydroxide particles (Figure
1) to give iron(III) bromide (FeBr3). The nanoparticles, which are produced by different mixing
systems (microjet, impinging-steam-mixer), are fully characterised by grain size distribution, X-ray
structure analysis (XRD), specific surface analysis (N2-Adsorption Isotherm), electron microscopy
(SEM), thermogravimetric analysis (TGA). The dissolved iron bromide can be separated from
unreacted iron oxide and hydroxide particles afterwards by means of filtration or centrifugation. The
aim of the process is to produce iron bromide in a quality that it can be used e.g. for removal of
mercury from exhaust gases in coal power stations.
Within the scope of the conference, we wish to present the results of the studies on the influence of
mixing systems and production conditions on particle properties. Furthermore, first results on
hydrogen bromide removal from synthetic exhaust gases are presented, which were obtained by
means of two specially prepared gas purification systems.
586
THE ENVIRONMENTAL CHARACTERISTICS OF USING REFUSED DERIVED FUELS IN

PRODUCTION OF CERAMIC MATERIALS: CO2 EMISSIONS AND DISTRIBUTION OF
CHLORINE
R. SANI1, D. PHAM MINH1, T. CUTARD2, A. NZIHOU1

1 Mines Albi, centre RAPSODEE CNRS UMR-5302, Campus Jarlard, F-81013 Albi, France.
2 Mines Albi, Institut Clément Ader CNRS UMR-5312, Campus Jarlard, F-81013 Albi, France.
Abstract
Fired-clay ceramic fabrication belongs to the industrial sectors having high environmental impact.
The development of new formulations for ceramic fabrication appears as a promising alternative [1,
2]. The incorporation of wastes such as Refused Derived Fuel (RDF) contributes not only to the
improvement of thermal and mechanical properties of fired products, but also to the energetic
balance of the global process. This paper is focused on the investigation of CO 2 emissions and
chlorine distribution during firing of clay-sand-RDF mixtures. Two types of RDF of different chemical
composition were chosen. RDF1 was rich in organic components such as paper, wood, plastics and
contained small amounts of inorganic elements (Al, Si, Ca…) while RDF2 contained more inorganic
elements. Both RDF1 and RDF2 contained chlorine of 0.3 and 0.1%.wt, respectively. Three
formulations were studied: clay-sand mixture without additives (C), clay-sand mixture with 8%.wt of
RDF1 and 8%.wt. of RDF2 (C/8%.wtRDF1 and C/8%.wtRDF2), respectively. These mixtures were
submitted to the fabrication of plate’s samples by a defined industrial extrusion process. Then, the
firing of extruded plates was carried out in a lab-scale fixed-bed reactor at 5°C/min and heating from
30 to 1000°C. The composition of gas emitted from the firing step was determined by different
analytical techniques such as micro-GC and ion chromatography while SEM-EDS was used for the
analysis of solid products. The results showed that, 10.6%.wt and 5.6%.wt of CO2 emissions were
found for C/8%.wtRDF1 and C/8%.wtRDF2, respectively. This CO2 was related to the decarbonation
of clay matrix and the thermal decomposition of organic matter coming from RDF. The distribution
of chlorine showed that 90%.wt of chlorine was remained as CaCl2(s) and NaCl(s) in solid products.
And only 10%.wt was emitted to the gas phase under HCl(g) form. In conclusion, adding RDF into clay
matrix was contributed to increase CO2 emissions during firing. But part of this CO2 could be
considered as “green CO2” thanks to its biogenic origin. The inorganic elements (Na, Ca) initially
present in RDFs helped to stabilize chlorine inside the solid phase. The results obtained allowed
evaluation the possibility of incorporation of RDFs in the fabrication mixture of fired-clay products.
Acknowledgement
The authors would like to acknowledge the TERREAL and PAPREC SUD OUEST Companies for
scientific contribution
References
[1] C. M. F. Vieira, R. M. Pinheiro, R. J. S. Rodriguez, V. S. Candido, et S. N. Monteiro, « Clay bricks added with effluent
sludge from paper industry: Technical, economical and environmental benefits », Appl. Clay Sci., vol. 132‑133, p. 753
‑759, nov. 2016.
[2] A. N. Adazabra, G. Viruthagiri, et N. Shanmugam, « Management of spent shea waste: An instrumental
characterization and valorization in clay bricks construction », Waste Manag., vol. 64, p. 286‑304, juin 2017.
587
CALCIUM PHOSPHATES AS A NEW SUPPORT MATERIAL FOR CATALYSIS IN FISCHER-

TROPSH SYNTHESIS
R. MUNIRATHINAM1, D. PHAM MINH1, A. NZHIZOU1

1 Centre RAPSODEE, UMR CNRS 5302, Ecole des Mines d’Albi, Campus Jarlard, 81013, Albi CT Cedex
9, France.
Abstract
Limited petroleum reserves have renewed research activities on Fischer-Tropsch (FT) synthesis, a
heterogeneous catalytic process, which aims to produce synthetic fuels and value-added chemicals
from synthesis gas (syngas, mixture of CO and H2) obtained from non-petroleum resources such as
coal, natural gas and diverse biomass. FT catalysts usually consist of Co or Fe nanoparticles, which
are dispersed on a support material such as alumina, silica, titanium oxide, zirconium oxide, niobium
oxide, SiC, or carbon. Tuning of chemical nature (acid-base properties) of these conventional
supports is not very trivial. In recent years, calcium phosphates (CaP), has been investigated as
porous support. The presence of phosphate groups in CaP not only stabilize the structure of active
sites, but also allow for easy tuning of acid-base properties by varying the calcium/phosphate ratio.
This interesting property of CaP would enable to tune the activity/selectivity of the product
distribution in FTS. Further, industrially used conventional supports like alumina and silica often
interact with the metal precursors leading to the formation of refractory compounds (e.g. Co
aluminates) that are catalytically inactive, thus, decreasing the reducibility of metals. However, using
CaP, the detrimental metal-support interactions can be minimized drastically. In this study, we
intend to investigate for the first time, the textural, structural chemistry and catalytic behavior of
CaP-supported cobalt samples and compared with their counterparts supported on commercial
alumina (-Al2O3) in the FT synthesis process.
Alumina and CaP supports were procured from commercial supports. The CaP- and alumina-
supported cobalt catalysts (Co/CaP and Co/alumina) were dry impregnated with 10 wt% (w/w)
nominal loading of cobalt metal. Thus obtained catalysts were analysed by a series of techniques,
namely, BET, elemental (ICP-OES), XRD, TPR, TPD and TEM analysis to determine their textural
properties, elemental composition, different crystalline phases of Co, reduction behaviour of cobalt
and cobalt oxide nanocrystallites size distribution, respectively.
The results obtained from different characterization techniques showed that the metal-support
interactions are totally reduced on Co/CaP catalysts when compared to that on Co/alumina catalysts,
leading to enhanced Co reducibility. Consequently, the Co/CaP catalysts displayed better activity by a
factor of two in FT synthesis reaction when compared their counterparts on alumina. Further, good
product selectivity (~83%) to long chain hydrocarbons and low methane selectivity (~10%) were
obtained on Co/CaP catalysts. STEM analysis on tested catalysts showed the presence of small Co
particles (nm) and Co particle aggregation on alumina support. On the contrary, less Co aggregation
and no small Co particles (<5 nm) were detected on CaP support. In conclusion, we have showed
that CaP could be used as a potential alternative support material for developing efficient FT
catalysts.
Reference
[1] Tsuchida, T., Kubo, J., Yoshioka, T., Sakuma, S., Takeguchi, T., Ueda, W.: Reaction of ethanol over hydroxyapatite
affected by Ca/P ratio of catalyst. J. Catal. 259, 183-189 (2008)
588
PY-GC-MS STUDY OF TAR FORMATION CHARACTERISTICS FROM MAIN MSW

COMPONENTS
Y.J. TANG 1, K. SUN, Q.X. HUANG 1*, Y. CHI 1, J.H. YAN 1

1 State Key Laboratory of Clean Energy Utilization, Institute for Thermal Power Engineering of
Zhejiang University, Hangzhou, China..
Abstract
It is of great interest and importance to understand the characteristics of tar derived from municipal
solid waste (MSW) to guide gasification syngas cleaning and upgrading. In this work, rice husk,
camphor pine wood, bamboo (chopsticks), paper, corrugated paper, polyethylene (PE),
polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), rubber and nylon were selected as
main MSW components and analytical pyrolysis-gas chromatography/mass spectrometry (Py-GC-MS)
investigations were performed to examine their tar formation characteristics. The results were
compared with Py-GC-MS study of lignite and bitumite. Results indicate that tar formation varies
with the feedstocks. The tar derived from herbal biomass mainly comprises of oxygenated
compounds, such as ethers, esters and furans while tar generated from woody biomass consists
primarily of phenols and its derivatives. When it comes to the polymers, the pyrolysis of PE and PP
will yield alkane and alkene while the pyrolysis of PS and PVC trends to yield BTEX and polycyclic
aromatic hydrocarbons (PAHs). Amide takes up the dominant proportion in tar derived from nylon.
The most components in tar derived from lignite are phenols and its derivatives while for tar
generated from bitumite, the most components are PAHs. What’s more, it is observed that the tar
composition shifted toward higher molecular weight substances as the final temperature rises from
400 to 600 °C. This work described here favors us control the tar production in the pyrolysis process
of MSW.
589
STATISTICAL ANALYSIS OF THE SIGNIFICANT PARAMETERS AFFECTING NITROUS

OXIDE EMISSION DURING MANAGEMENT OF ORGANIC SOLID WASTES
R. AFFES1, R. GIRAULT1, A. TREMIER1

1 IRSTEA, UR GERE, 17 avenue de cucillé, CS 64427, F-35044, Rennes Cedex, France.
Abstract
Nitrous oxide (N2O) emission strongly contributes to global warming and also to stratospheric ozone
depletion. The number of researches assessing N2O emissions from solid organic waste management
processes has thereby notably increased in the last decade. Before land spreading, emissions mainly
occur during composting and storage. And, a large range in emission factors (EF) is observed due to
the complex nature of the process and the heterogeneity of waste piles. Indeed, many factors can
impact the magnitude of N2O emissions such as management practice, experiment conditions and
waste characteristics [1]. In this context, the objective of this study was to investigate the main
control factors affecting N2O emissions during storage and composting of solid organic wastes. For
that purpose, a bibliographic review was carried out to implement a database combining measured
N2O emission factors and investigated variables. The dataset contained the results of 26 research
articles involving 88 observations published between 2000 and 2015. We explored the effect of 9
variables: organic waste category, management type (storage, composting), measurement duration,
experiment scale, C/N ratio, addition of bulking agent, the application or not of phase separation,
mixing and aeration conditions. Information about the measurement method of the EF was also
gathered. Then, the effect of studied variables on N 2O emission factors was investigated through
multiple correspondence analysis. This statistical method allows the analysis of a dataset containing
nominal (qualitative) variables.
Results indicated that the most significant control factors affecting N 2O emission were: management
type, experiment scale, mixing, measurement duration and aeration conditions. Forced aeration
system and turned system, unlike static aeration system (storage system), showed potential for
increasing N2O emissions. Aeration and mixing practices increased the nitrification/denitrification
alternation and thus promoted N2O production. A recent study proved that pile turning promoted
N2O production through nitrification near the surface and denitrification near the area under micro-
aerobic conditions [2]. Moreover, measurement duration strongly impact N 2O EF, highlighting that
that this parameter have to be taken into account for an accurate estimation emissions. In addition,
studies carried-out at lab-scale systems (< 100 L) lead to higher N2O emission factor than pilot-scale
experiments and field measurements.
Our statistical analysis presented a synthesis of the pattern of relationships of the significant
operational factors with N2O EF, being a guideline for Scientifics and farmers to refine the
management of organic solid waste. From an operational point of view, these results highlight
storage and composting practices that can mitigate N 2O emissions. From a scientific point of view,
they allow the identification of parameters that have to be taken into account by models to allow an
accurate prediction of N2O emissions.
References
[1] Pardo, G., R. Moral, E. Aguilera, A. del Prado: Gaseous emissions from management of solid waste: A systematic
review. Global Change Biology. 21, 1313–1327 (2015).
[2] Ahn, H. K., W. Mulbry, J. W. White, S. L. Kondrad. Pile mixing increases greenhouse gas emissions during composting
of dairy manure. Bioresource Technology. 102(3), 2904-2909 (2011).)
590
NANOWET PROJECT: CHARACTERIZATION OF NANOPARTICLE EMISSION FROM HIGH

TEMPERATURE INCINERATION OF NANO-/HALOGEN-/SULFUR-CONTAINING WASTES
AND PERFORMANCES OF WET-SCRUBBER UNITS
A. JOUBERT1, R. BOUDHAN1, C. DUTOUQUET2, D. VENDITTI3, S. DURECU 3, E. FIANI4, O. LE BIHAN2, L.

LE COQ1
1 IMT Atlantique, GEPEA, CNRS, BP 20722, 44307 Nantes cedex3, France.
2 INERIS, Parc Technologique Alata, BP 2, 60550 Verneuil-en-Halatte, France.
3 TREDI - Séché Environnement, BP 20199, 54505 Vandœuvre-lès-Nancy, France.
4 ADEME, BP 90406, 49004 Angers Cedex 01, France.
Abstract
In order to address the health and environmental problems potentially raised by the incineration of
nanowastes, the NanoWet project (supported by the French Agency for Environment and Energy
Management -ADEME- CORTEA funding scheme - Grant No. 1581C0096) focuses on the treatment of
nanowastes by high-Temperature (T) incineration required when halogen- and sulfur-containing
wastes are disposed of. The objectives of the project are i) to assess the effect of both high post-
combustion T of 1,100°C and presence of acid gases in raw fumes, on the potential emission and
behaviour of nanoparticles originating from nanowaste incineration, and ii) to quantify downstream
nanoparticle capture by the wet-scrubbers equipping the fume treatment lines before the exhaust.
First, three wastes were selected and characterized: PDMS waste from polyorganosiloxane
polymerization processes containing 24.4% dwt of SiO2 nano-fillers (waste previously studied in the
framework of NanoFlueGas project [1]); soft PVC from flexible PolyVinyl Chloride production
containing 36% dwt of Cl and nano-fillers mainly composed of TiO2; Resin waste from soiled strong
acid cation exchange resins of sulfonic type exhibiting 15.4% dwt of S, but no nano-filler type
identified.
A lab-scale incinerator device composed of a tubular horizontal furnace was designed to operate in
representative key conditions of a high-T incineration process dedicated to industrial wastes (T of
1,100°C in both combustion zones, residence time at least of two seconds in the post-combustion
zone, air excess from primary and secondary air flows contributing to achieve adequate turbulence
conditions). A fume sampling device allows to characterize O2, CO2, CO, SO2, HCl contents as well as
particulate matter concentrations in various granulometric ranges. When present, the solid residue
after incineration is analyzed to estimate the presence of nano-fillers. Incineration tests were carried
out in single-waste or mixed loads. The interactions between the PDMS nanowaste and the halogen-
/sulfur- wastes will be discussed in terms of behavior/fate of particles in the fumes.
In order to study the performances of wet-scrubbers regarding nanoparticle capture, a lab-scale
spraying scrubber will be developed based on real data inferred through a measurement campaign
which was carried out on a full-scale industrial unit (TREDI - Groupe Séché Environnement), out of
specific incineration of nanowastes but in prevalence condition of halogen-/sulfur-containing wastes.
In particular, the particle concentration and size distribution were measured in the core-process, at
the inlet of the wet-scrubber columns (after dedusting by electrofiltration).
The lab-scale spraying scrubber will thus operate in realistic conditions of temperature, humidity,
particle load, liquid/gas ratio, height/diameter ratio of the column, residence time, turbulent flow
regime, droplet diameter and relative velocity between particles and droplets.
References
[1] Tran D.T., Joubert A., Venditti D., Durécu S., Meunier T., Le Bihan O., Fiani E., Le Coq L.: Characterization of polymer
waste containing nano-fillers prior to waste treatment, Waste and Biomass Valo., 8(7), 2463-2471
591
PURIFICATION OF BIODIESEL BY THE USE OF A STACKED BED OF SAWDUST AND ION

EXCHANGE RESIN
M.A. KADI1, K. LOUBAR1, S. AWAD1, M. TAZEROUT1

1 IMT Atlantique, Nantes, France.
Abstract
The production of biodiesel has increased considerably over the years and is considered as an
alternative fuel to diesel in order to reduce gas emissions (CO2, CO, SOx, NOx) and particles that are
harmful to the environment and human life [1].
Purification is a very important step after biodiesel production. It consists of eliminating all
impurities from biodiesel such as excess alcohol, catalyst, residual glycerin and soap in order to meet
international standards (EN14214, ASTM D6751). In general this treatment is carried out by wet
(water, acid) or dry method (adsorption by the ion exchange resin, silica, activated carbon,
membrane filtration).
In this work, biodiesel was synthesized from various vegetable oils (waste cooking oil and rapeseed
oil) by the transesterification reaction with oil / methanol at molar ratio of (1: 6) in the presence of 1
wt. % of the homogeneous KOH catalyst [2].
After the separation by gravitational decantation of the glycerin and the biodiesel, the feed of
biodiesel was purified through a column containing a bed of 30 g sawdust followed by 30 g of ion
exchange resin (Amberlyst 15 dry) supported by a glass tube. These quantities were able to purify 30
l of biodiesel before saturation.
The biodiesel production resulted in 96% biodiesel yield with a conversion rate of 99%. Several
analysis (GC-FID, GC-MS, flash point, viscosity, acidity .........) were applied to filtered biodiesel in
order to quantify biodiesel and residual impurities. A remarkable decrease in the amount of
impurities was observed after filtration, where the residual alcohol was reduced from 3 wt. % to 0.1
wt. %, the glycerin from 0.26 wt. % to 0.024 wt. % and the amount of catalyst from 3000 mg/kg to
0.50 mg/kg.
The purification media made of sawdust and ion exchange resin, satisfied international standards.
References
[1] Hadis Bashiri , Nastaran Pourbeiram, Biodiesel production through transesterification of soybean oil: A kinetic Monte
Carlo study, Journal of Molecular Liquids. 223, 10–15 (2016).
[2] Umer Rashid, Farooq Anwar, Production of biodiesel through optimized alkaline-catalyzed transesterification of
rapeseed oil, Fuel. 87, 265–273(2008).)
592
REUSE OF ALUMINUM-BASED WATER TREATMENT SLUDGE AS COAGULANT FOR

ANIMAL FARM WASTEWATER TREATMENT
C. KANG1, Y.Q. ZHAO1, C. TANG1,2

1 UCD Dooge Centre for Water Resources Research, School of Civil Engineering,University College
Dublin, Dublin, Ireland.

2 2 Key Laboratory of Subsurface Hydrology and Ecology in Arid Areas, Ministry of Education,
Chang’an University, Xi’an 710054, PR China.
Abstract
This study aims to reuse the aluminum-based water treatment sludge (Al-WTS), collected from the
Irish biggest water treatment plant, to replace the traditional chemicals as the coagulant in the
coagulation-flocculation process of an animal farm wastewater treatment.
The study was designed for a lab-scale trial to explore the optimum condition of coagulation and
flocculation process so that the removal efficiencies of the total suspended solids (TSS), total organic
carbon (TOC) and PO43- concentration of the wastewater can be maximized. The experiments were
conducted in a series of jar-test apparatus with magnetic stirring to simulate the coagulation-
flocculation process. The effects of initial pH and the dosage of Al-WTS on the removal efficiencies of
the three parameters of farm wastewater were examined and discussed. Moreover, a Box-Behnken
statistical experimental design (BBD) by Design expert 8.0 was used to optimize the experimental
condition.
At the optimum initial pH value of 7.0 and the Al-WTS dosage of 1588 mg/L, the removal efficiencies
of TSS, PO43-, and TOC were 87.76 ± 2.2%, 96.88 ± 2.9%, and 62.14 ± 1.8%, respectively.
(a)
(b) (c)
Figure 3D response surfaces plots described for contaminant removal

(a) TSS removal (%); (b) PO43- removal (%); (c) TOC removal (%).
It’s concluded that the alum sludge could be reused for the treatment of animal farm wastewater
with great removal efficiencies. Thus, reuse of the Al-WTS could substantially reduce even replace
the chemical coagulant requirements in coagulation process for animal farm wastewater treatment,
thereby reducing the economical consumption of chemicals coagulant and sludge treatment.
References
[1] Yang, Y., Zhao, Y., Babatude, A., Wang, L., Ren, Y. and Han, Y. (2006a). Characteristics and mechanisms of phosphate
adsorption on dewatered alum sludge. Separation and Purification Technology, 51(2), pp.193-200.
[2] Zhao, Y., Sun, G. and Allen, S. (2004). Anti-sized reed bed system for animal wastewater treatment: a comparative
study. Water Research, 38(12), pp.2907-2917
593
ENHANCING OIL PALM YIELD USING THERMALLY ASSISTED MECHANICAL

DEWATERING (TAMD)
H. HASHIM1, P. ARLABOSSE2, S.YUSUP1
1 Universiti Teknologi PETRONAS, Bandar Seri Iskandar, Perak, Malaysia.

2 Université de Toulouse, Mines Albi, Centre RAPSODEE, Campus Jarlard, Route de Teillet, F-81013
Abstract
The thermally assisted mechanical dewatering (TAMD) is a new technology for the separation of
solid/liquid. When applied to “nature-wet” biomass, the TAMD process shows significant impact on
the separation yield. In the present study, TAMD was used to extract the crude palm oil (CPO) from
the palm mesocarp (Elaeis guineensis). The operating conditions investigated were pressure of 3 to
12 bar with varied temperature ranging from 30 to 105 °C through batch process for total extraction
time of 45 min. Response Surface Methodology was utilized to create the design of experiment
based on central composite design (CCD). The CPO yield, carotene concentration and free fatty acids
(FFA) content through TAMD was analysed. The maximum yield of 73.69 w/w% with averaged FFA of
0.98 ±0.08% was obtained at the optimum operating parameter of 10.45 bar and 77.30°C.
Substantial oil yields at relative lower pressure for short extraction time proved that TAMD is viable
Design-Expert® Software
alternativeFactor
method for the extraction of palm oil.
Coding: Actual
Yield (%)
Design points above predicted value
Design points below predicted value
73.312
38.155
80
X1 = A: Temperature
X2 = B: Pressure
70
60
Yield (%)
50
40
30
10 92
8.9 79
7.8
66
6.7
53
B: Pressure (bar) 5.6 A: Temperature (C)
4.5 40
Figure 1: Response surface from TAMD statistical modeling
References
[1] Harrison, L. L., Chuah, C. H., Choo, Y. M., Ma, A. N.,: Characterization and supercritical carbon dioxide extraction of
palm oil (Elaeis Gunineensis), Journal of Food Lipids. 210-221, (2006)
[2] Teixeira, C. B., Macedo, G. A., Macedo, J. A., da Silva, L. H. M., Rodrigues, A. M. d. C.,:Simultaneous extraction of oil
and antioxidant compounds from oil palm fruit (Elaeis guineensis) by an aqueous enzymatic process, Bioresource
Technology, 129, 575-581, (2013).
[3] Md Sarip, M. S.,Morad, N. A. , Yamashita, Y., T. Tsuji, T., Yunus, M. A. C., Aziz, M. K. A., et al., :Crude palm oil (CPO)
extraction using hot compressed water (HCW), Separation and Purification Technology, 169, 103-112, (2016
594
OBTAINING AND CHARACTERIZATION OF PELLETS BASED ON WALNUT SHELLS AND

WASTE PAPER AND PAPERBOARD
Y. PÉREZ1, A. GONZALEZ1, A.H. ROJAS1

1 Facultad de Ingeniería, Universidad Católica de Temuco, Temuco, Chile.
Abstract
Several southern cities of Chile experience in winter a high concentration of particulate material
(PM) in the air. In the regions near Chilean Patagonia, the values of PM2.5 (peak: 956 µg/m3) have
exceeded peak values reported by Chinese cities like Beijing (peak: 886 µg/m3) [1]. The deterioration
of air quality is mainly caused by non-decentralized wood combustion of thousand households, low
quality of the wood combustion systems, poor insulation inside households and high moisture of
wood. One of the measures taken by Ministry of the Environment of Chile to counteract the PM
emissions is the replacement of the conventional wood stoves for pellets stoves [2]. Pellets are
mainly composed by residues and byproducts from silviculture activities with high content of water.
To decrease moisture content (<10%), it is recurred to a drying process resulting in a more expensive
pellet. In addition, forest plantations are treated with pesticides which could lead to contamination
problems with heavy metals and volatile organic compounds.
This study proposes the production of pellets based on solid wastes and a byproduct with lower
moisture content like as: (i) walnut hells, (ii) waste paper, (iii) waste paperboard and (iv) wheat bran.
All raw materials were physiochemical characterized. The pelletization process was performed by
semi-industrial pelletizer using commercial lignin as binding material (≤10%). For the pellets
production was tested different proportions of the raw materials and the resulting pellets were
characterized according to the European standard EN-14961-1. Moreover, results were also
compared with the values reported for a commercial pellet.
The results indicate that the structural chemical composition of the raw materials does not allow the
production of pellets composed by 100% of each. The best results were obtained for pellets with
55% of walnut shells and 5% of lignin, with 34% and 6% of wheat bran and waste paper and
paperboard, respectively. The characterization of the resulting pellets showed a moisture and ash
content below 1.9% and 7.9%, and a high calorific value between 18.2 and 21.3 MJ/kg. All
parameters analyzed in the resulting pellets meet the values set by the EU in EN 14961-1. In
addition, it was possible to obtain pellets with moisture content less than 0.6%; 10 times lower than
the moisture content of the regional commercial pellet and much lower than the value set by the
EN-14961-1 (10%). The pellets produced in this study could compete with the commercial pellet.
Moreover, it is possible to produce pellets with lower content of commercial lignin and no-additional
dry process.
References
[1] Díaz-Robles L., Fu J.S., Vergara-Fernández A., Etcharren, P., Schiappacasse, L.N., Reed, G.D. and Silva, M.P. Health
risks caused by short term exposure to ultrafine particles generated by residential wood combustion: A case study of
Temuco, Chile", Environ. Int. 66:174-181 (2014)
[2] Gómez, W., Salgado, H., Vásquez, F., Chávez, C. Using stated preference methods to design cost-effective subsidy
programs to induce technology adoption: an application to a stove program in southern Chile. J. Environ. Manage.
132, 346-357 (2014).
595
SOLID-LIQUID PHASE EQUILIBRIA AND THERMODYNAMIC PROPERTIES OF MIXTURES

OF 20 Α-AMINO ACIDS IN A MODEL SYSTEM OF INDUSTRIAL RESIDUES
N.A. BOWDEN1,2, J.P.M. SANDERS1,3, M.E. BRUINS3

1 Biobased Chemistry and Technology Group, ASFG, Bornse Weilanden 9, 6708WG Wageningen,
Wageningen UR, The Netherlands

2 School of Life Sciences, Lovensdijkstraat 61-63, 4818AJ Breda, Avans University of Applied Science,
The Netherlands
3 Wageningen Food & Biobased Research, Bornse Weilanden 9, 6107WG Wageningen, The
Netherlands.
Abstract
Bio-based products made from proteins and α-amino acids, such as bioplastics, pharmaceuticals, and
fine chemicals, could become increasingly important if an effective way of separating them from
solution is found [1-2]. One of the challenges is to find a way to separate proteins and α-amino acids
that are dissolved in liquid industrial residues or produced through fermentation [3]. Understanding
the solubility of α-amino acids in mixtures is integral to designing technologies for solid-liquid
separation of individual α-amino acids from mixtures of α-amino acids in these residue streams.
Although, crystallizing individual α-amino acids from a mixture of α-amino acids would improve their
separation in a bio-refinery, no knowledge is available on the solubility of the 20 α-amino acids in a
mixture of 20 α-amino acids. In order to understand the solubility of α-amino acids in mixtures of 20
α-amino acids, we first modeled the solubility of the 20 α-amino acids in single solution using the van
‘t Hoff and Sober equations and data available in the literature.
The results of these equations were compared and their coefficients are reported. Then we
measured the solubility of the 20 α-amino acids in a model system of an industrial residue containing
all 20 α-amino acids and found that only L-tyrosine, L-tryptophan, L-aspartic acid, L-glutamic acid and
L-asparagine dissolved in higher concentrations in the model system of 20 α-amino acids than in
aqueous solution by themselves. The solubility of all of the aliphatic α-amino acids was lower in the
mixture. The longer the side chain length of the aliphatic α-amino acids, the greater the decrease in
solubility in the mixture as compared to being in solution by itself. The maximum solubility of L-lysine
and L-glutamine showed the most decrease when in the mixture in comparison to in aqueous
solution alone.
Our results demonstrate that α-amino acids with similar physical structures have similar changes in
solubility when in a mixture of α-amino acids. We assert that α-amino acids can be grouped by their
physical structure.
References
[1] E.L. Scott, F. Peter, J.P.M. Sanders, Appl. Microbiol. Biotechnol. 75 (2007) 751-762.
[2] T.M. Lammens, M.C.R. Franssen, E.L. Scott, J.P.M. Sanders, Biomass Bioenergy 44 (2012) 168-181.
[3] Widyarani, N.A. Bowden, J.P.M. Sanders, R.C. Kolfschoten, M.E. Bruins, Ind. Eng. Chem. Res. (2016).
596
FEASIBILITY OF ANAEROBIC DIGESTION OF TAR-LADEN CONDENSATE FROM SMALL

SCALE BIOMASS GASIFICATION PLANTS
D. CASINI1, A.M. RIZZO1, G. LOTTI1, S. PENNAZZI1, D. BASSO3, F. PATUZZI3, M. BARATIERI3, D.

CHIARAMONTI1,2
1 Consorzio RE-CORD, Florence, Italy.
2 CREAR/University of Florence, Florence, Italy
3 Free University of Bozen-Bolzano, Bozen, Italy
Abstract
Distributed CHP from biomass gasification has attracted considerable attention in EU in past decade
for the business opportunities connected to generous feed-in tariffs and incentives schemes for
small-scale plants. By-products of gasification plants are a solid residue, called char and, depending
on process configuration, a dirty water stream, i.e. the Tar-Laden Condensate (TLC). Though largely
dependent from the originating process technology, TLC generally exhibits very high COD and
significant amount of phenols, benzene-derivatives, mono- and poly-cyclic organic hydrocarbons and
a broad spectrum of other organics [1,2]. Because of its composition, currently TLC has to be
disposed of, as it is classified as a waste being contaminated by several organic compounds,
including toxic or carcinogenic substances.
This work investigate the possibility to convert the organic content of TLC into a valuable energy
carrier, i.e. methane, by means of anaerobic digestion (AD). TLC samples from distinct gasification
plants have been sampled on site during plant operation and therefore characterized in terms of
COD and main compounds content (e.g. PAHs).
An experimental method for the acclimation of AD microorganisms to the challenging environment
of TLC was adapted from published results on the AD of the water phase from intermediate pyrolysis
of biomass [3], which share broad similarities with the TLC composition. The inoculum for biological
degradation was prepared by mixing an inoculum from an AD plant, operating with a conventional
diet under mesophilic conditions, and a sewage sludge samples, recovered from three distinct
process steps of a large wastewater treatment plant, operating on the by-products of textile
industries and municipal wastewater. After a starvation phase, the inoculum underwent an
acclimation period in which the amount of organic contaminants were progressively added to reach
a target food to microorganism ratio (F/M, gCOD_substrate/gCOD_inoculum) of 0.2-0.3, in order to
promote the natural selection of autochthonous strains, more tolerant toward TLC’s constituents.
TLC AD tests were conducted with acclimated inoculum with a target F/M ratio of approximately 0.6
and 2.
Qualitative results of the microbial activity of different trophic groups after the acclimation phase
and the AD production tests are reported, compared and discussed.
References
[1] Tian, S., Qian, C., Yang, X.: Biodegradation of Biomass Gasification Wastewater by Two Species of Pseudomonas
Using Immobilized Cell Reactor. Appl. Biochem. Biotech. 128.2, 141-147 (2006)
[2] Jeeswani, H., Mukherji, S.: Batch studies with Exiguobacterium aurantiacum degrading structurally diverse organic
compounds and its potential for treatment of biomass gasification wastewater. Int. Biotdet. & Biodegr. 80, 1-9,
(2013)
Torri, C., Fabbri, D.: Biochar enables anaerobic digestion of aqueous phase from intermediate pyrolysis of biomass.
Bioresour. Technol. 172, 335–341 (2014)
597
NITROGEN REMOVAL AND CHARACTERISTICS OF ANAEROBIC AMMONIA OXIDATION
BACTERIA IN NUA–DAS ECOFILTERS

L. M. WANG1, M.Y. ZHOU1,2
1 Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection, Nanjing, China.
2 College of Environment, Hohai University, Nanjing, China.

Abstract

Industrial by‐products such as neutralized used acid (NUA) and dewatered alum sludge (DAS) are
used to remove nitrogen from contaminated wastewater [1,2]. However, the substrates that
combine with DAS and NUA in ecofilters for high nitrogen removal in livestock wastewater treatment
are not well understood. Knowledge on the characteristics and diversity of anaerobic ammonia
oxidation bacteria (Anammox) in matrix, as well as their effect on NH+ 4 –N treatment potential in
ecofilters, is also limited. This study analyzed the NH+ 4 –N and total nitrogen (TN) treatment
performance of novel NUA‐ and DAS‐based ecofilters (Figure 1) for the removal of synthetic NH+ 4 –N
in livestock sewage. The spatial (top, middle, and bottom layers of DAS and NUA) and temporal
(three sampling time points, 180 days) diversity (Shannon index), and similarity (principal component
analysis, PCA) of Anammox for both substrates were examined using PCR‐DGGE. The Anammox
potential associated with NH+ 4 –N removal was further determined using Pearson correlation. Results
showed that the NUA–DAS ecofilter achieved high and stable nitrogen removal, and that the average
removal efficiencies of NH+ 4 –N and TN were 75% and 70%, respectively. DGGE image analysis
revealed that Anammox existed only in DAS and not in NUA, and that the diversities of Anammox in
DAS did not change with time and space (Figure 2). PCA results demonstrated that the structures of
the Anammox community of the initial DAS were inconsistent with those in treated samples, and the
structures of all processed DAS did not exhibit distinct differences except D22 (sample from the
middle layer of DAS in 180 days) (Figure 3). The relationships between NH+ 4 –N removal and diversity
of Anammox confirmed that the reducing NH+ 4 –N was not determined by the Shannon index of
Anammox at substrates, which had no significant Pearson correlations with effluent NH + 4 –N
concentration. Overall, the combination of NUA and DAS in the ecofilter effectively removed NH+ 4 –N
in livestock wastewater, and these findings on Anammox indicated that NH+ 4 –N removal cannot be
predicted from only the genetic property of Anammox in the NUA–DAS system.

Figure 1: Structure of NUA‐DAS ecofilter. Figure 2: Anammox DGGE in NUA and DAS. Figure 3: PCA based on DGGE fingerprint.

References
[1] Wendling, L.A.: Nutrient and dissolved organic carbon removal using mining and metallurgical by‐products. Water.
Res. 46, 2705‐2717 (2012).
[2] Hu, Y.S.: High Rate Nitrogen removal in an alum sludge‐based intermittent aeration constructed wetland. Environ.
Sci. Technol. 46, 4583‐4590 (2012).
598
IMPROVED DEWATERING OF DEINKING SLUDGE BY ENZYMATIC PRETREATMENT

B. SAAKE1, R. JANZON1, F. STEFFEN1
1 Chemical Wood Technology, Department of Wood Science, University of Hamburg,
21031 Hamburg, Germany.

Abstract

Recovered paper is the most important raw material for the paper industry of industrialised
countries. However, the recycling process by deinking results in large volumes of waste such as
deinking sludge (DS). The dominating disposal strategy for DS is mechanical dewatering and
subsequent incineration. The high moisture content of dewatered DS considerably affects its
disposal and reduces the possibility of recovering energy [1]. Any improvement in DS dewatering
would lower the disposal costs and increase energy recovery. DS from most recovered paper grades
contain a high amount of fibre fines, which usually negatively affects the dewatering ability [2]. The
hypothesis was that cellulase treatment should be able to modify fines and reduce their negative
effect on dewatering. Yet, many cellulases are not effective under the pH (7-‐8) and high inorganic
load of DS [3]. The objectives of this work were:
− To identify cellulases which are effective on DS without buffer or pH adjustment;
− To determine the effect of suitable enzymes on DS from different processes;
− To correlate the effect of enzyme treatment on DS fibre properties and dewaterability.
Three DS samples were obtained from pulp mills producing recycled graphic and tissue paper from
100% recovered paper. From all samples, carbohydrate and lignin content, ash content, metal profile
and calorific value were determined. A screening of 12 enzyme preparations was performed
regarding their activity towards cellulose under the conditions of technical DS. A suitable enzyme
product was selected for treatments of DS with different dosage and incubation time. The drainage
behaviour of untreated and enzyme-‐pretreated DS was tested regarding drainage speed (drainage
jar) and regrading final dry content by filtration compression cell (FCC) tests. DS fibre properties,
such as fibre length distribution, fibre fines content and number of fibres, were measured before and
after enzyme treatment. Furthermore, the release of carbohydrates and the COD of filtrates were
determined.
The composition of DS samples depends strongly on the recycling process (newsprint, office paper,
tissue) and the applied recovered paper grade. Inorganic fillers account for a main fraction of DS. The
screening of enzyme preparations could identify 5 cellulase products which were suitable for the
treatment of DS. Enzymatic treatment of the various DS samples could reduce the fibre length and
increases the amount of fibre fines. Our results show that the shorter fibre fragments can be packed
more efficiently in a cake when the fibre is pressed and considerably higher dry contents are
obtained after dewatering as a result. Through enzymatic treatment of DS before dewatering,
substantial increases in dry contents (e.g. from 58.5% to 72.4%) were achieved which would result in
a 20% reduction of the annually generated amount of DS and considerable disposal cost savings.
References
[1] Lähdeniemi, A., Mäkelä, M., Dahl, O.: Drying/fractionation of deinking sludge with a high-‐velocity cyclone. Dry.
Technol. 31, 378–384 (2013)
[2] Hubbe, M.A., Heitmann, J.A.: Review of factors affecting the release of water from cellulosic fibers during paper
manufacture. BioResources. 2, 500–533 (2007)
[3] Min, C.M., Ramarao, B.V.: Mechanisms of the inhibition of enzymatic hydrolysis of waste pulp fibers by calcium
carbonate and the influence of nonionic surfactant for mitigation. Bioprocess Biosyst. Eng. 40, 799–806 (2017)
599
A NOVEL PROCESS “ADVANCED THERMAL TREATMENT + HSAD” TO TREAT SWINE

MANURE: KINETICS AND MICROBIAL COMMUNITY ANALYSIS
YUYING HU1, JING WU1, ZHONGHUA LI1, HUAI-ZHI LI2, JIANE ZUO1, KAIJUN WANG1
1 State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment,
Tsinghua University, Beijing 100084, China.

2 .Laboratory of Reactions and Process Engineering, Université de Lorraine, CNRS, 1, rue Grandville,
BP 20451, 54001 Nancy cedex, France.
Abstract
Huge amount of swine manure is produced each year and raise severe environmental problem. High
solid anaerobic digestion (HSAD) is a promising solution with advantages of low heating energy,
small both digestate and digester. However, its methane production is poor. Though thermal
treatment could enhance HSAD’s methane production rate [1], few applications are on swine manure.
In this study, an advanced thermal treatment process on swine manure without any dilution at
21.3% solid content (70±1 °C, 3 days) combined with HSAD was proposed. Results showed that
methane production rate of the pretreated manure at 11.7% solid content (158 mL CH4/g VS) could
reach up to 89.2% of that at low solid content (4.4%). The kinetics analysis revealed that only the
readily biodegradable organics was utilized in HSAD, while both the readily and poorly biodegradable
organics was consumed at low solid content. This agreed with the microbial community. It was worth
noting that the hydrogenotrophic methanogens predominated in HSAD with the relative abundance
˃ 99%. This study firstly combined kinetic analysis and microbial analysis to reveal “advanced
thermal treatment + HSAD”, and was of great practical importance.
Table 1 Kinetics parameters
Solid 𝑀𝑚𝑎𝑥1 k1 ( k ) 𝑀𝑚𝑎𝑥2 k2 R2

content ( 𝑀𝑚𝑎𝑥 ) d-1 mL CH4/g d-1
% mL CH4/g VS VS
4.4 141 0.1230 65.2 0.0908 0.999
11.7 152 0.1098 - - 0.975
14.1 143 0.0969 - - 0.995
17.6 150 0.0780 - - 0.999
Fig1. Simulation of (a) low solid anaerobic digestion and (b) HSAD
References
[1] [1] Val del Rio, A., Morales, N., Isanta, E.,et al. 2011. Thermal pre-treatment of aerobic granular sludge: impact on
anaerobic biodegradability. Water Research, 45(18), 6011-20.
600
MASS BALANCE AND PERFORMANCE OF COMMON DIGESTATE MECHANICAL

SEPARATION EQUIPMENT AND FERTILIZING-VALUE TYPOLOGY OF LIQUID AND SOLID
FRACTIONS
F. GUILAYN 1,2, J. JIMENEZ1, M. ROUEZ2, M. CREST2, D. PATUREAU1

1 LBE, INRA, Univ Montpellier, 102 avenue des Etangs, 11100, Narbonne.
2 SUEZ, CIRSEE, 38 rue du Président Wilson, 78230, Le Pecq, France.
Abstract
Whether to enhance nutrients management for land spreading or as a previous-step for advanced
treatments, digestate mechanical phase separation is present in many Anaerobic Digestion (AD)
plants. A wide range of equipment is available including screw presses, centrifuges, belt presses and
rotary drums. Up-to-date, few or maybe no study has critically regarded a database of digestate
separation efficiency, mass balances and quality of outputs for different separators. To fill-up this
gap, data from literature was gathered with an INRA’s database and operational data from SUEZ.
From this database, two different analysis approaches were carried out. The first consisted to
perform clustering analysis on complete fertilizing-value data of liquid fractions (LF, n = 38) and solid
fractions (SF, n = 47) separately. The second approach consisted to calculate mass balances and
separation efficiency indicators [1] when characterization of raw digestate and its associated LF and
SF were available. The later consisted in digestate data from over 50 industrial scale digesters. The
first approach resulted in a typology for LF (Figure 1A), and SF (Figure 2B). LF and SF were observed
to be grouped according to AD feedstock (fibrous/non-fibrous) and separation equipment (low/high
performance), with significant distinct fertilizing-values. The second analysis approach is still
ongoing. Early results highlight the distinguishable performances of previously observed groups. A
recurring lack of consistency on the mass balances of some elements such as nitrogen is observed
and will be discussed.
Figure 1: Principal Component Analysis biplots of LF (A) and SF (B). DM: Dry matter. VS: Volatile Solids. C/N: Carbon/Nitrogen ratio. TN:
Total Nitrogen. TAN: Total Ammoniacal Nitrogen. TP: Total Phosphorus. TK: Total Potassium. BW: Source-separated biowaste. FAI:
Food/Agri-industrial waste. GW: Green Waste. OFMSW: Organic Fraction of Municipal Solid Waste. SS: Sewage sludge.
References
[1] Hjorth, M., Christensen, K.V., Christensen, M.L., Sommer, S.G., 2010. Solid-liquid separation of animal slurry in
theory and practice. A review. Agron. Sustain. Dev. 30, 153–180.
601
BREAKING THE CHAIN: THE ROLE OF DEGREE OF POLYMERISATION ON THE

THERMAL DECOMPOSITION OF XYLAN
J. TOUITOU1, K. DUSSAN2,3, R. F. D. MONAGHAN2,3, S. DOOLEY1

1 School of Physics, Trinity College Dublin, the University of Dublin, Dublin, Ireland.
2 Mechanical Engineering, National University of Ireland Galway, Galway, Ireland.
3 Centre for Marine and Renewable Energy MaREI, Galway, Ireland.
Abstract
Xylan is one of the most abundant polysaccharides found in hemicellulose of hardwoods and
herbaceous plants. The use of model compounds, such as 4-O-methyl-glucuronoxylan refined from
biomass, provides a substrate for the consolidation and validation of the inherent thermal
decomposition kinetics of hemicellulose in experimental studies. Previous studies have shown that
hexose carbohydrates with various degrees of polymerisation, such as glucose, cellobiose and
cellulose, have distinct thermolysis selectivity [1]. Compared to glucose, cellulose produces a larger
amount of levoglucosan and lower amounts of permanent gases, water and other low molecular
weight oxygenated products at 500 oC [1]. This work will present the distinct reactivity of pentose
carbohydrates with various degrees of polymerisation (chain length in polymer) during pyrolysis and
will cross-validate the experimental data with state-of-the-art kinetic models [2,3]. For this purpose,
the mass conversion rate during the pyrolysis of xylose, xylobiose, xylotriose and xylan is
investigated using thermogravimetric analysis ranging from 30 to 600 oC using several heating rates
(0.2-3 K s-1). Time-resolved product distribution is using a coupled mass spectrometer coupled with
the thermogravimetric analyser informing of the pyrolytic selectivity of these carbohydrates. This
work will provide valuable features of reaction mechanisms of hemicellulose pyrolysis and the
involvement of the polymer chain-length in the selectivity of depolymerisation against dehydration
and fragmentation.
References
[1] Zhou, X., Nolte, M. W., Mayes, H. B., Shanks, B. H., Broadbelt, L. J.: Experimental and Mechanistic Modeling of Fast
Pyrolysis of Neat Glucose-Based Carbohydrates. 1. Experiments and Development of a Detailed Mechanistic Model.
Ind. Eng. Chem. Res. 53, 13274-13289 (2014)
[2] Ranzi, E., Debiagi, P. E. A., Frassoldati, A.: Mathematical Modeling of Fast Biomass Pyrolysis and Bio-Oil Formation.
Note I: Kinetic Mechanism of Biomass Pyrolysis. ACS Sustain. Chem. Eng. 5 (4), 2867-2881 (2017)
[3] Dussan, K., Dooley, S., Monaghan, R.: Integrating compositional features in model compounds for a kinetic
mechanism of hemicellulose pyrolysis. Chem. Eng. J. 328, 943-961 (2017)
602
FUELS FROM RELIABLE BIO-BASED REFINERY INTERMEDIATES – BIOMATES
T. SCHULZKE1, S. CONRAD1, D. KUBICKA2, S. BEZERGIANNI3, U. PFISTERER4, N. RETTENMAIER5,

R. DIAZ-CHAVEZ6, M. MULDER7, M. MARTIN8
1 Fraunhofer UMSICHT, Institute for Environmental, Safety and Energy Technology, Oberhausen,
Germany.
2 University of Chemical Technology, Prague, Czech Republic.
3 CERTH/CPERI, Thessaloniki, Greece.
4 BP Europe SE, Bochum, Germany.
5 Ifeu, Heidelberg, Germany.
6 Imperial College London, London, United Kingdom.
7 HyET BV, Arnhem, The Netherlands.
8 Ranido sro, Prague, Czech Republic.
Abstract
Co-feeding lignocellulosic-biomass-derived intermediates into conventional refineries is a promising

option to decarbonise automotive, aviation and bunker fuels and to reduce import-dependence of
mobility. Of course, this strictly requires compatibility of the intermediates with the refining process
and, the reliability of the intermediates’ properties. In the end, fuel qualities meeting the standards
and fuel yields not diminished by intermediate-caused off-spec batches are the explicit goal.
This defines the idea behind the BioMates concept, which is depicted in Fig. 1: a fast pyrolysis
converts lignocellulosic feedstock to bio-oil (exemplarily, an ablative fast pyrolysis [AFP] processes
straw and miscanthus). Furthermore, implementing an in-line-catalysis in the AFP-reactor already
optimises the bio-oil with respect to the later refinery application. In a second step (optionally at
another location), mild hydrotreatment over a tailor-made catalyst converts the bio-oil into
intermediates with reliable properties to be fed into refineries. Applying solar-generated renewable
make-up hydrogen and electrochemical compression of recycled gas of the mild-hydrotreatment
step even improves carbon footprint and production costs of the bio-based intermediates.
This concept will be put into practice in the Horizon 2020-project BioMates, starting in October,
2016. The project receives funding from the European Union’s Horizon 2020 research and innovation
programme under grant agreement No 727463. It will include validating the technology in a
Technology Readiness Level 4-5. Pilot-scale refinery testing and quality assessment by an
international refinery company will ensure the applicability of the generated results.
Figure 1: Project steps in the context of classical refinery – scope of project and refinery integration of products
603
CARBONACEOUS MATERIALS FROM LIGNOCELLULOSIC BIOMASS UNDER

HYDROTHERMAL CONDITIONS
D. WUEST1,2, D. JUNG2, M. LUCIAN1, A. KRUSE2, L. FIORI1

1 University of Trento, Trento, Italy.
2 University of Hohenheim, Stuttgart, Germany.
Abstract
Rising environmental concerns and the need for cost-effective competitive products are becoming two major
guidelines in modern material research. As a consequence the main effort in this field is primarily directed
towards the production of new and effective materials, which can be synthesized from a low-cost and
sustainable feedstock such as waste biomass which is widely available and with a high potential around 22
billion ton (70 wt.-%) year-1 from agricultural cycles [1]. Usually, these waste streams have a high moisture
content which prevents an efficient utilization. Therefore hydrothermal treatment without pre-drying of a
variety of biomass are being focused [2]. Amongst these, hydrothermal carbonization (HTC) as a technology
for the production of carbonaceous materials termed “hydrochar” (HC) has attracted interest [1]. HCs are
formed through two reaction pathways: a solid-to-solid-conversion which results in the “primary char” with a
similar structure and morphology of the feedstock and “secondary char” or “coke” with a sphere-like
geometry is formed by polycondensation/ -merization of dissolved organic compounds such as
Hydroxymethylfurfural (HMF) and Furfural (FU) [1, 3]. An example of the resulting geometry can be seen in
the SEM picture (Figure 1). The aim of this study is to better understand the formation mechanism of HC from
lignocellulosic biomass. For this purpose process water (PW) from the HMF-production was mixed with
brewer’s draff so that a total dry matter of 16 wt.% was obtained. Afterwards, the suspension was converted
at HTC conditions (T = 220 °C, t = 5 h) in a batch autoclave (V = 250 mL; S.S.: 1.4571).
Figure 1: SEM picture illustrating primary and secondary char of hydrothermal carbonized brewer’s draff (T = 220 °C, t = 5 h)
Compared to the conversion of brewer’s draff in distilled water, the use of PW from HMF-production leads to
a higher HC yield, corresponding to decrease of dissolved organic compounds in the aqueous phase. This
indicates the formation of a secondary char which has a higher carbon content, due the formation of aromatic
structures [3].
In order to get more detailed information on the transformation mechanism of lignocellulose into HC, kinetic
experiments to quantify the formation of secondary char from dissolved organic compounds were finally
performed and modelled.
References
[1] Titirici, M.-M. Sustainable Carbon Materials from Hydrothermal Processes. WILEY-VCH, Book (2013), 4, 102-110.
[2] Kruse, A.; Dahmen, N. (2015) Water - A magic solvent for biomass conversion, The Journal of Supercritical Fluids, 96,
36–45. DOI: 0.1016/j.supflu.2014.09.038.
[3] Volpe, M., Fiori, L., 2017. From olive waste to solid biofuel through hydrothermal carbonisation: the role of
temperature and solid load on secondary char formation and hydrochar energy properties. J. Anal. Appl. Pyrolysis.
124, 63–72. http://dx.doi.org/10.1016/j.jaap.2017.02.022.)
604
CHARACTERIZATION OF ODOROUS GAS EMISSIONS DURING COMPOSTING ACTIVE

PHASE OF EIGHT SOLID WASTES AND FOUR DIGESTATES
C. RINCON1, A. DE GUARDIA1, A. COUVERT2, S. LE ROUX1, I. SOUTREL2, M. DAUMOIN1.

1 Irstea, Rennes, France.
2 École Nationale Supérieure de Chimie de Rennes, Rennes, France.
Abstract
Digestates and raw wastes are composted for later uses in agriculture. Despite of contributing to a
proper waste management, composting and methanization sites face a crucial challenge regarding
odour nuisances affecting plant workers and neighbours [1]. The critical operations responsible for
malodours in biological treatment plants include the storage and composting steps as active phase,
turning, screening and curing [2, 3]. Monitoring of major odorants involves mainly instrumental
methods and odour concentration (OC) measurements [4].
In this study, a total of 141 gas samples were comprehensively analysed in order to characterize the
chemical composition and OC of odorous gas emissions produced during the active phase under
forced aeration of 8 solid wastes and 4 digestates. Wastes used to this purpose comprised raw and
pre-conditioned substrates (turkey manure, dehydrated pig slurry, pre-fermented households waste,
sludge from wastewater treatment plant, green bio-waste and food-waste from restaurant,
restaurant’s kitchen and households) and digestates from different origins (bio-wastes from
supermarkets, pig slurry, bio-wastes and households waste). Active phase was conducted over 30
days period in lab-scale pilots of 300 L with positive and continuous aeration rates ranging from 6.4
to 1.4 L/h/kg and ratios bulking agent (wood chips) to waste, when needed, from 2.9 to 0.9 (vol/vol).
Gas emissions were sampled at the composting reactors outlets 3 or 2 times per week and analysed
by gas chromatography-mass spectrometry (organic volatile compounds), gas chromatography-
electrochemical detection (reduced sulphur compounds) and acid traps (ammonia). OCs from gas
samples were measured by dynamic olfactometry according to the standard EN13725 in odour
European units (OUE) with a trained and screened human panel [5].
The odour activities values (OAVs), defined as the ratio of the chemical concentration of a single
chemical compound to its respective odour detection threshold, were used as basis to identify the
major odour contributors. The OCs profiles showed as common trend a pick emission along the first
10 days of process and a clear drop of OCs after 20 days of treatment. The odour emission factors
(∑OC) fluctuated from high values for raw and pre-conditioned substrates (586000-12800 OUE/kg)
and relatively low values for digestates (6100-1400 OUE/kg). 60 gaseous compounds were identified
and categorized into 12 different chemical families: esters, alcohols, terpenes, sulphur compounds,
alkenes, aromatic hydrocarbons, aldehydes, nitrogen compounds, ketones, organic heterocycles and
acids. The chemical substances with the highest OAVs (or OAVmax) were hydrogen sulphide (44.7%),
methanethiol (31.2%), dimethyl sulphide (6.4%), acetic acid (6.4%), limonene (2.8%), 2,3-
butanedione (2.1%), ethanethiol (2.1%), dimethyl disulphide (1.4%), ammonia (1.4%), p-cymene
(0.7%) and alpha-pinene (0,7%). The comparison of both data sets, OCs and OAVmax, revealed that
42% of OAVmax values were inside the confidence level of OC measurements as per standard
EN13725. Sulphide compounds were the most odorous substances of active phase gas emissions
accounting for an occurrence frequency of 86.3% of OAVmax. The integrated evaluation of malodours
emissions during composting process provided valuable information to seek for suitable odour
control strategies.
605
References
[1] Krzymien, M., Day, M., Shaw, K., Zaremba, L.: An investigation of odors and volatile organic compounds released
during composting. J. Air Waste Manage. Assoc. 49, 804–813 (1999).
[2] Rosenfeld, P. E., Suffet, I. H.: Understanding odorants associated with compost, biomass facilities, and the land
application of biosolids. Water Sci. Technol. 49, 193–199 (2004).
[3] V. Blazy, A. de Guardia, J. C. Benoist, M. Daumoin, F. Guiziou, M. Lemasle, D. Wolbert, S. Barrington.: Correlation of
chemical composition and odor concentration for emissions from pig slaughterhouse sludge composting and
storage. Chem. Eng. J. 276, 398–409 (2015).
[4] Kim, K. H., Park, S. Y.: A comparative analysis of malodor samples between direct (olfactometry) and indirect
(instrumental) methods. Atmos. Environ. 42, 5061–5070 (2008).
[5] EN 13725, Air Quality- Determination of odour concentration by dynamic olfactometry. European Committee for
Standardization (CEN), Brussels (2003).
606
CATALYTIC DEGRADATION OF POLYETHYLENE AND POLYPROPYLENE WASTES OVER

USY ZEOLITE INTO GASOLINE AND DIESEL-LIKE FUELS
C. KASSARGY1,2, S. AWAD1, K. KAHINE2, M. TAZEROUT1

1 GEPEA, UMR 6144, DSEE, IMT-Atlantique, Nantes 44307, France.
2 Modeling Centre, Lebanese University, Beirut, Lebanon.
Abstract
The world’s annual production of plastic materials has increased from around 1.7 million tons in the
1950s to nearly 311 million tons due to rapid urbanization and economic development. Polyolefin,
namely, high density polyethylene (HDPE), low density polyethylene (LDPE) and polypropylene (PP)
represent around half of the overall plastic production [1].
Several methods are used for wastes disposal including incineration and landfilling. However these
methods can contribute to health and environmental problems [2].
Pyrolysis is an alternative treatment of plastic waste, with low negative environmental impacts,
which consists on converting plastic wastes into fuel oil and valuable chemicals by heating at
temperature range of 300-600⁰C in the absence of oxygen [3]. The main disadvantages of thermal
degradation are wide product distribution and requirement of high temperatures. Therefore,
catalysts were added in order to improve the quality of the liquid fuel produced and reduce the
energy demand [4].
In this work, the main objectives were to produce useful fuels from PE, PP and their mixtures over
ultra-stable Y (USY) zeolite. Furthermore, the influence of using USY zeolite on the yield and
composition of products from catalytic degradation of Polypropylene (PP), polyethylene (PE) and
their mixtures was studied in a bench-scale plant at 500°C, with a plastic/catalyst ratio of 10:1.
Non-catalytic pyrolysis of PE produces a high yield of wax with a wide range carbon numbers. While
polymers were converted to liquid products with high yields in presence of USY zeolite. The liquid
fraction derived from the catalytic pyrolysis of PP and that of PE was dominated by a (C5-C7)
hydrocarbons fraction. The liquids obtained contained a wide range of components which suggests
the separation of the oils into three phases: gasoline-like fraction, intermediate fraction and a diesel-
like fraction.
Different temperature of separation were tested and 160°C was found to be the temperature where
the boiling range distributions and physical properties of the light fraction meet the gasoline
standards and 220°C is the temperature where the boiling range distributions and physical
properties of the heavy fraction meet diesel fuel standards.
References
[1] Plastics – the Facts 2015 An analysis of European plastics production , demand and waste data 2015.
[2] Shent H, Pugh RJ, Forssberg E. A review of plastics waste recycling and the flotation of plastics. Resour Conserv
Recycl 1999;25:85–109.
[3] Miandad R, Barakat MA, Aburiazaiza AS, Rehan M, Ismail IMI, Nizami AS. Effect of plastic waste types on pyrolysis
liquid oil. Int Biodeterior Biodegrad 2017;119:239–52.
[4] Al-Salem SM, Antelava A, Constantinou A, Manos G, Dutta A. A review on thermal and catalytic pyrolysis of plastic
solid waste (PSW). J Environ Manage 2017;197:177–98.
607
IMOGOLITE FROM CEMENT KILN DUST AS CATALYST IN BIO-OIL UPGRADING
A. GONZALEZ1, A. MONTECINOS1, M.A. PLACENCIA1, N. ARANCIBIA-MIRANDA3

1 Facultad de Ingeniería, Universidad Católica de Temuco, Temuco, Chile.
2 Center for the development of Nanoscience and Nanotechnology, CEDENNA, Chile.
Abstract
Imogolite (Imo) is an hydrated aluminosilicate ((HO)3Al2O3SiOH) that exhibit short-range order. Their
structure corresponds to a single-walled nanotube with an outer and inner surface mainly
constituted by aluminol groups (Al-OH and Al2-OH) and silanol groups (Si-OH), respectively. The
composition of its surface and their porous structure (specific surface area: 300~800 m2g-1) has been
aroused a great interest in its use for catalytic applications [1]. According to Garrone and Bonelli
(2016) the catalytic properties of Imo in gas phase are limited by its thermal stability and also by
diffusion limitations of reactants and products within the Imo nanotubes (inner diameter around 1
nm). Nevertheless, it has been observed that the thermal collapse of Imo (<600°C) increase also
acidic sites which is of great concern for catalytic pyrolysis in the upgrading of bio-oil [2]. The
synthesis of Imo has been tested with diverse sources of silica with high purity [3]. However, as we
know, research about the synthesis of Imo from cement kiln dust (Imo-CKD) and their application as
catalyst in the upgrading of bio-oil has not been performed, up to date.
For the experimental procedure, Imo-CKD was characterized by XRD and FT-IR analyses, and
compared with Imo. Bio-oil was obtained by slow pyrolysis of oat hulls at 300 and 500°C. Two fixed
bed reactors were used for the pyrolysis and the catalytic upgrading of the gas phase, respectively.
For the recovering of bio-oil, a condensation unit was inserted. The pH values and water content by
Karl-Fisher titration method of bio-oils were performed. In order to facilitate the detection of main
compounds in bio-oil, a fractioning was also performed. The method was based on the liquid-liquid
extraction of the aqueous phase of bio-oil with organic solvents (chloroform, acetate ethyl and
hexane). Posterior, fractions were analyzed by GC-MS. As main results, it was detected that Imo-CKD
presented similar XRD and FT-IR pattern as Imo. Oat hull bio-oils indicated low values of pH, being
for all samples below 3.0. Nevertheless, the lowest value (1.8) was at 350°C and with no addition of
imogolite, whereas the highest pH value was at 500°C with the addition of imogolite (2.6). The water
content of bio-oils followed non similar trend as pH, increasing parameter value with an increase of
temperature. Moreover, the addition of Imo-CKD implies also an increase of water content in bio-oil
(10%) which could be a consequence of the catalytic mechanism by means of the acidic sites. The
information obtained from GC-MS indicate that the relative content of aldehydes and ketones
decrease in 3%, whereas derived compounds from furfural, furans, phenol and benzene increase in a
5.4% in almost fractions analyzed. This result could indicate that Imo-CKD interact with carbonyl
groups in similar pathway as acidic zeolites. Based on this statement, it is proposed the experimental
study of a model compound in order to gain more information about catalysis mechanism of Imo-
CKD. Nevertheless, the preliminary results indicate potential use of Imo-CKD as catalyst for the
upgrading of bio-oil.
Acknowledgements for the support of CONICYT through FONDECYT 11150088 and FB0807
References
[1] Arancibia-Miranda, M., Lilo, S., Escudey, M. Nanotubular aluminosilicates a case study for science and industry. J.
Chil. Chem. Soc. 58, 2061-2066 (2013).
st
[2] Garrone, E. Bonelli, E. Imogolite for catalysis and adsorption, In: Nanosized Tubular Clay Minerals, 1 Edition
Halloysite and Imogolite, Yuan, P., Thill, A., Bergaya, F. (eds) pp. 672-707, Elsevier, Amsterdam (2016)
608
IN-SITU HYDROTREATMENT OF SPENT COFFEE GROUNDS USING A NICKEL

MOLYBDENUM GAMMA ALUMINA CATALYST
R. VENTER1, S. MARX1
1 Energy Systems, School of Chemical and Mineral Engineering, North-West University, Hoffman
Street, Potchefstroom, South Africa.
Abstract
Renewable hydrocarbons produced from bio-oil is more expensive compare to petrochemical

hydrocarbons with the production of bio-oil through pyrolysis or hydrothermal liquefaction as
feedstock for renewable hydrocarbons production being significant contributors to the cost of this
hydrocarbons. In situ hydrotreatment of spent coffee grounds in the presence of different solvents
was evaluated in this study in terms of liquid product composition, degree of deoxygenation and
liquid product yield. The aim was to establish whether liquefaction bio-oils are forming besides the
fatty acid present in the SCG at the given hydrotreatment conditions used in this project and what
degree of deoxygenation takes place.
A cylindrical bench scale batch reactor with an inside volume of 350 cm3 was used to conduct the
experiments. Reactions were carried out at a reactor temperature of 390˚C and an initial hydrogen
pressure of 9 MPa with a retention time of 1 hour after the desired temperature was reached. A
commercially procured NiMo/Al2O3 hydrotreating catalyst was used in this experiments. The catalyst
was sulphided using 15% H2S in Argon at 3 MPa and 400 ˚C for 1 hour prior to the hydrotreatment
step. After activation the reactor was depressurised to just above atmospheric pressure and a
solvent was injected through a septum to minimise the exposure of the catalyst to oxygen. The
solvent compared in this study were iso-octane, ethanol, methyl naphthalene and acetone. After the
introduction of the solvent to cover the activated catalyst, the reactor was slightly opened to
introduce a specific amount of spent coffee grounds. After further purging with nitrogen the reactor
was pressurised using hydrogen to the desired pressure and the hydrotreatment commenced. After
the reaction the reactor was cooled down, depressurised and the contents separated using a
Buchner funnel. Both the liquid and solid phase were weighed to determine the liquid product yield
and degree of carbonisation. The liquid product was analysed using GC-MS from Agilent.
Hydrotreatment results of SCG in the presence of iso - octane showed an increased naphtha and
kerosene fraction in the liquid product at lower solvent to biomass ratios which is an indication of
the formation of bio-oil through liquefaction during the hydrotreatment process. At higher solvent to
biomass ratios the liquid product mainly consists of alkanes in the C15 to C18 range. The presence of
a significant concentration of C16 and C18 alkanes in the liquid product suggests that the
hydrodeoxygenation pathway is dominant. At lower solvent to biomass ratios it is also evident that
isomerisation of the n-alkanes are more prominent. A liquid product yield of up to 35% was obtained
and from GC-MS data it is clear that oxygenated functional groups are removed.
References
[1] Wang, Y.: Lin, H.: Zheng, Y.: Hydrotreatment of lignocellulosic biomass derived oil using a sulfided NiMo/Al2O3
catalyst.Catalalysis Science and Technology 4, 109 – 119 (2014)
[2] Huber, G.W.: Iborra, S.: Corma, A.: Synthesis of transportation fuels from biomass: Chemistry, Catalyst and
Engineering. Chemical Reviews 106, 4044 – 4098 (2006)
609
EFFECT OF PORE STRUCTURES ON CATALYTIC FAST PYROLYSIS OF SACHA INCHI

RESIDUES USING MICROPOROUS AND MESOPOROUS ZEOLITES
S. VICHAPHUND1, V. SRICHAROENCHAIKUL2, D. ATONG1

1 National Metal and Materials Technology Center, Thailand Science Park, Pathumthani, 12120,
Thailand.
2 Department of Environmental Engineering, Faculty of Engineering, Chulalongkorn University,
Bangkok, 10330, Thailand.
Abstract
Sacha inchi (Plukenetia volubilis L.), known as Inca peanut, is a climbing plant mainly originated from
the Peruvian Amazon region. In the present, it is widely cultivated in the northern part of Thailand as
a promising new valuable crop in the food, pharmaceutical and cosmetic industries. Additionally, it is
considered as an alternative resource for biodiesel production [1]. Sacha inchi seeds are a good
source of oil (35-60%), protein (25-30%), essential amino acids, mineral and vitamin E [2]. After oil
extraction, the sacha inchi residues (oilseed cakes) are by-product which caused the disposal
problems. Some research has reported the utilization of this residues, however, to our knowledge,
there is no report to utilize Sacha inchi residues in catalytic fast pyrolysis application. In this work,
therefore, Sacha inchi residues were utilized as biomass feedstock in catalytic upgrading fast
pyrolysis with microporous (ZSM-5 with 3D structure, pore size 5.2-5.7 Å) [3] and mesoporous
catalysts (SBA-15 with 2D, pore size 50 -300 Å) in order to investigate pyrolysis vapor products using
analytical pyrolysis-GC/ MS (Py-GC/MS) technique. The effect of pore size and structure of both
porous catalysts were studied. The pyrolysis was performed at 500C with the biomass residue to
catalyst ratio of 1:1-1:10. The major compositions from non-catalytic fast pyrolysis were fatty acids,
mainly linoleic acid (C18:2). Other organic compounds were aliphatic hydrocarbon (26%) and
nitrogen containing compounds (13%), esters (9%), alcohols (7%), aldehydes (1%), and phenols (
1%). The presence of both catalysts contributed to eliminate the undesirable oxygenated compounds
such as fatty acids which could alleviate problem regarding acidity and instability in bio-oil. They also
enhanced significantly the yields of desirable hydrocarbon compounds. Results suggest that the
difference in pore structure has influence on the product selectivity, especially hydrocarbon
compounds. The medium pore zeolite with microporous pore size range (ZSM-5) produced the
highest aromatic selectivity of 90% including mainly toluene and xylene, which are valuable products
because of their high heating value properties. In contrast to the medium pore zeolite, large pore
zeolite with mesoporous pore size range (SBA-15) showed the ability to improve aliphatic selectivity
(C6-C23) up to 64%. Moreover, the increase in catalyst contents had an effect on the enhancement of
hydrocarbons yields, and tended to promote deoxygenation and denitrogenation.
References
[1] Rawdkuen,S., Murdayanti, D., Ketnawa S., Phongthai, S.: Chemical properties and nutritional factors of press-cake
from tea and sacha inchi seeds. Food Bioscinnce. 15, 64-71 (2016)
[2] Gutiérrez, L.-F., Quiňones-Segura, Y., Sanchez-Reinoso, Z., Díaz, D.L., Abril, J.I.: Physicochemical properties of oil
extracted from -irradiated Sacha Inchi (Plukenetia volubilis L.) seeds. Food Chemistry. 273, 581-587 (2017)
[3] Vichaphund, S., Aht-ong, D., Sricharoenchaikul, V., Atong, D.: Effect of crystallization temperature on the in situ
valorization of physic nut (Jatropha curcus L.) wastes using synthetic HZSM-5 catalyst. Chemical Engineering
Research and Design. 92, 1883-1890 (2014))
610
BIOREFINERY CONCEPTS WITHIN THE AGRI-FOOD SUPPLY CHAIN: A ROAD TO

SUCCESS
M.E. BRUINS1
1 Wageningen University and Research centre, Food and Biobased research, Wageningen, The
Netherlands.
Abstract
“Twice the food production at half the ecological footprint” is the EU goal for 2050 that combines
the ambition for less human impact on the environment with the rapidly growing world population
and living standards. Rather than improving crop-production yield, developing biorefinery
technology with unused biomass from the agri-food supply chain may be the crucial factor to reach
sustainable global food security.
Residues from food industry have very specific advantages that make them especially suited as
cheap and easy starting materials for biorefinery. First, they are already collected and therefore
costs on transportation are limited. Secondly, they have often been pre-treated in the factory. This
can either be an advantage or a disadvantage as pre-treatment may make components more
accessible, but may also cause degradation of valuable components. The last important point is that
food driven biorefinery adds a new outlet within the context of an existing process and product
outlet, which is already cost competitive. This is in contrast to new biorefinery concepts, where both
new technologies in combination with multiple new outputs have to be developed.
A successful example of food-driven biorefinery is the extraction of protein from green tea residues.
These residues are left after tea lemonade production, and are currently at best used for energy by
burning them. We developed a cost efficient method for protein extraction, and determined
parameters that are important for the protein yield and to tune cost efficiency [1]. The concept was
supplemented by a process for pectin production [2] and optimised for sustainable alkali usage
through reuse or recycle.
Another example is in the better use of product waste streams from vegetable processing [3].
Vegetable residual flows have significant potential value in terms of functional ingredients for food
or pharmaceutical applications. Onion and carrot residues in the Netherlands, Belgium and the west
of Germany, for example, annually represent a value of ten million euros for flavonoids, an anti-
oxidant. In our study, first the logistics were investigated. Within the focus area of our research, one
processing location per product or product group is the most profitable as transport costs are low
compared to the construction and operation costs of a processing plant. Cost can even be made
lower when products are combined. Current research, therefore, focusses on the co-production and
applicability of different fractions, again for protein and possibly pectin.
While we now still focus on using already available residues, the future will also bring redesign of
entire factories for high quality output of multiple components without residues, and re-design of
entire chains for better logistics and integration of new products.
References
[1] Zhang, C; Sanders, JPM; Bruins, ME (2014) BIOMASS & BIOENERGY 67: 466-472
[2] Zhang, C; Sanders, JPM; Xiao, TT; Bruins, ME (2015) PLOS ONE 10(7): e0133046
[3] Vollebregt, HM (2015) Project Infinity https://www.wageningenur.nl/en/newsarticle/Project-Infinity-confirms-
Vegetable-residual-flows-full-of-valuable-ingredients.htm
611
PROFITABILITY OF FOOD WASTE BIOREFINERY CONCEPT IN EUROPE
J. CRISTOBAL1, C. CALDEIRA1, S. CORRADO 1S. SALA1.

1 European Commission, Joint Research Center, Directorate D-Sustainable Resources, Bioeconomy
Unit, Ispra, Italy.
Abstract
The European Commission has identified food waste (FW) as one of the priority areas of the
European circular economy action plan [1] and it is highly committed to establish strategies and
policies to reduce the FW along the food supply chain. In parallel with the implementation of FW
prevention measures and good management practices, the valorisation of FW in biorefineries
focused on value-added products and chemicals will contribute simultaneously, to reduce the
amount of FW and the use of fossil and bio-based resources. Most of the biorefineries proposed in
the literature are focused on the production of bioenergy or biofuels. In these cases, the TRL
(Technology Readiness Level) is high and some of them are even at the commercial level, being the
cost estimation of the new biorefinery concept relatively easier since real costs are available for the
escalation and the validation of the results. On the other hand, biorefineries focused on value-added
products and chemicals are scarcer in literature and usually present a low TRL, being the cost
estimation difficult and uncertain. Due to this, up to now, very few studies have performed techno-
economic analysis at the European level. Besides, the use of FW as feedstock for biorefineries is at an
early stage of development and there is a strong need to reduce uncertainty about the volume of FW
available and the economic viability of the plants [2].
This paper presents a techno-economic and profitability analysis of a biorefinery concept in Europe
to produce value-added products from FW. To that end, we firstly identified relevant agri-food
products and estimated the total quantity available in Europe; secondly, we selected a valorisation
technology; thirdly, we estimated the total investment capital and manufacturing costs; and, finally,
calculated revenues and profitability ratios. This work was focused on the industrial wastes (i.e. food
processing residues) due to their high homogeneity and the fact that their high generation quantity
is located in specific industrial plants [3]. Results were obtained for the valorisation of industrial
waste of the tomato, potato, citrus and olive processing into bioactive compounds for a different
number of plants installed across Europe (i.e. from 7 to 70). Since the market price of those bioactive
compounds is very uncertain, three scenarios considering low, medium, and high market value were
analysed. A sensitivity analysis of the most important parameters (i.e. ISBL calculation, market value
of the products) in the study was included to see its relevance. Preliminary results of this study
suggest that the economic viability of the biorefinery concept using FW as input depends on the
number of plants installed (large number of plants is less profitable than small number) and also the
market value of the valorised product.
References
[1] European Commission (EC), Closing the loop - An EU action plan for the Circular Economy, COM (2015) 0614
[2] Imbert, 2017. Food waste valorization options: opportunities from the bioeconomy. Open Agriculture, 2: 195 – 204.
[3] Ravindran et al., 2016. Exploitation of food industry waste for high-value products. Trends in Biotechnology, 34: 58 –
69
612
VALORISATION OF WASTE WOOD FOR ENERGY
B.GUDKA1*, J.M.JONES1, A.WILLIAMS1, A.R.LEA-LANGTON2, E.J.S MITCHELL1, J.GANE1, G.STAMMERS3,

R.KIRKMAN4, P.FOWLER4
1
School of Chemical and Process Engineering, University of Leeds. Leeds. LS2 9JT United Kingdom
2
School of Mechanical, Aerosoace and Civil Engineering, Manchester University. Manchester M13
9LP United Kingdom
3
Consultant, Wadsley Hall Farm, Sheffield, S6 4FD United Kingdom
4
Veolia Energy Solutions, Operational Services, Lumley Street, Sheffield S4 7ZJ United Kingdom
Keywords: waste wood, washing, combustion
Abstract
31 samples of Grade B/C waste wood were analysed before and after rapid washing in water and a
statistical analysis was carried out to determine the effect of washing. It was found that washing reduces
the ash content of the fuel by nearly 50%. The washed waste wood was both less variable in composition,
and had a higher specification. An important conclusion is that the rapid washing of the wood removes a
lot of the fines which are very high in soil, grit, paint flakes and other contaminants. Combustion trials
conducted on a multi fuel domestic stove showed that washing and the use of a high calcium additive
help to reduce the SOx and HCl emissions significantly.
613
1- INTRODUCTION
Currently large amounts of wood biomass are being imported in the UK for electricity generation.
The need for affordable, clean, secure and reliable energy is leading to interest in biomass of lower
grade, particularly that available at a local or National level [1]. In 2010, the UK generated
approximately 4.3 Mtonnes of waste wood of which 2 Mtonnes was recycled. Waste wood is
currently an unattractive fuel for large and small scale power generation due to its high levels of
contamination which result in both plant performance and emission issues. Waste wood can be
graded according to the levels of contamination as in the standard provided by Waste and Resources
Action Programme (WRAP) [2]. The low grade biomass can be valorised to a more attractive fuel via
pre-treatment methods such as water washing. This removes some of the inorganic species from the
fuel which contribute to slagging, fouling, and corrosion problems in boilers which leads to
downtime on the power plant, and potentially reduces emissions including SO x, NOx, HCl and trace
metals. A number of studies have shown the effects of water washing on biomass fuels [3]

2.1 Materials
A typical Grade B/C waste wood which is composed of building and demolition materials (untreated
and chemically treated hardwood and softwoods) and DIY materials like plywood, OSB (Oriented
Strand Board), MDF (Medium Density Fibreboard), chipboard and fibreboard, was used to carry out
the washing experiments. The waste wood was separated into 6 different fractions and a typical
composition was calculated as shown in Figure 1.
3.87
7.42
7.63
39.59
23.35
18.15
Light Wood Chipboard

Hardwood/MDF OSB/Plywood
Dark Wood Red Wood
Figure 1 Typical Composition of Grade B/C Waste Wood
2.2 Washing Experiments
Rapid wood washing experiments were carried out on a demonstration washing plant with a built in
stone separator. 1-2 tonnes/hour waste wood was introduced into the plant and the stone separator
was used to remove the glass, stones and metals from the waste wood. The wood was then passed
614
through a rotating drum. After a rapid wash in the drum the waste wood was collected and the fines
and surface contaminants are separated via holes in the drum.
2.3 Statistical Analysis
31 samples of the unwashed and washed wood were then collected randomly from the bulk sample
and sent to an external accredited laboratory to be analysed for the proximate, ultimate and metal
analysis according to the British Standard Methods. Statistical analysis was carried out on this data at
Leeds using the statistical program SPSS. The means and the standard deviations of some of the
problematic species have been plotted to look at the effect of washing on the removal of species and
sample variability.
2.4 Briquetting
Combustion tests were carried out on the Grade B/C waste wood (pre and post wash and a pre-wash
sample with a high calcium additive). Grade B/C waste wood without any glass, metal or stones was
washed rapidly as in Section 2.1 in a vertical drum washing machine at Leeds. The samples were
dried to <10% moisture and milled to a particle size of <4mm in a Retsch Cutting Mill. Cylindrical
briquettes with a 5cm diameter, 2 cm height and weighing approximately 39g each were made in a
die pre-heated to 130oC and the milled wood was compressed with a pressure of 26MPa for 10
minutes.
2.5 Combustion Tests
A Waterford Stanley Oisin multi fuel stove was used for all fuels. The appliance is technically rated
having a maximum non-boiler thermal output of 5.72 kW and an efficiency of 78.8%. The dimensions
are 535 x 408 x 415 mm (HxWxD). There is just one (primary) air supply which is manually controlled
via a damper. The general arrangement of the test equipment was based on BS EN 13240. Sampling
ports were installed in the flue at a height of 1.43m. A batch of approximately 700-800g of briquettes
were tested on each run. Flue gas composition was measured on a wet basis using a Gasmet
DX400FTIR gas emissions analyser. Relative percentage errors were =/-5%

3.1 Fuel Characteisation and Ash Behaviour
The means and standard deviations of the ash content, ultimates and inorganic metal of the 31
unwashed and washed waste wood samples are plotted in Figure 2. The ash and Cl contents in the
waste wood decrease by >50% after rapid washing, while the inorganic metals decrease by >25%.
The standard deviation of all these species in the waste wood also decreases after washing, making it
less variable, hence tightening the fuel specification.
615
0.80 2500
0.70
2000
0.60
0.50
ppm (db)
1500
0.40
% db
0.30 1000
0.20
500
0.10
0.00 0
-0.10
-0.20
Unwashed Wood Washed Wood (a) Unwashed Wood Washed Wood (b)
* Divided by 10
** Divided by 100
Figure 2 Means and standard deviations (error bars) of (a) ash content and ultimates and (b)
inorganic metals of unwashed and washed waste wood.
The inorganic metals in the ash tend to cause slagging and fouling in the boilers and heat exchanger
tubes hence leading to downtime of the plant. The tendency of the fuel to cause fouling and slagging
in boilers was calculated using the Alkali Index (AI) and the base to acid ratio (R b/a) as shown in
Equations 1 and 2 respectively [4, 5].
AI = kg (K2O + Na2O)/GJ (Equation 1)
Rb/a= % (Fe2O3 + CaO + MgO + K2O +Na2O)/% (SiO2 + TiO2 + Al2O3 + P2O5) (Equation 2)
The waste wood exhibits a low fouling tendency due to the low alkali content but certain trace
metals like lead and zinc can strongly influence fouling [6]. The Rb/a however predicts a high tendency
to cause slagging when compared to the literature [4, 5]. Washing of the waste wood reduces the
ash content by 50% hence reducing the tendency of slagging and fouling by 50% leading to less
downtime on the plant.
3.2.2 Emissions
Combustion tests on the multi-fuel domestic stove of the unwashed and washed waste wood and
unwashed waste wood with a high calcium additive produce a typical temperature and emissions
(HCl and SOx) profile as shown in Figure 3. Washing the wood and the use of a high calcium additive
with the unwashed wood significantly reduce the SOx and HCl emissions. After washing the waste
wood, SOx and HCl emissions reduce by 7 and 29% respectively and by using an additive with the
unwashed wood, these emissions reduce by 40 and 56% respectively. Ca in the additive can scrub
out some of the HCl and SO2 emissions during combustion [7].
616
Flue Gas Temperature SO2 (ppm) HCl (ppm)

50 350
300
40
Concentration (ppm)
250
Temperature (oC)
30
200
150
20
100
10
50
0 0
0 5 10 15 20 25 30 35 40 45
Time (mins)
Figure 3 Typical temperature and emissions’ profiles from the flaming stage of combustion of
unwashed waste wood in a domestic multi-fuel burner
4- CONCLUSIONS
Pretreatment of the waste wood via water washing removes some of the problematic species hence
improving fuel properties and helps to tighten the fuel specification. Both washing and the use of the
high calcium additive helps to reduce the SOx and HCl emissions significantly during combustion.
ACKNOWLEDGEMENTS
The authors are grateful for funding from three sources: EPSRC Impact Acceleration Account, the
EPSRC Centre for Doctoral Training in Bioenergy and the EPSRC Supergen Bioenergy Hub
REFERENCES
1. Phillips, D., et al., The use of conservation biomass feedstocks as potential bioenergy resources in
the United Kingdom. Bioresource Technology, 2016. 212: p. 271-279.
2. BSI, Specification for the requirements and test methods for processing waste wood. PAS 111.
2011.
3. Gudka, B., et al., A review of the mitigation of deposition and emission problems during biomass
combustion through washing pre-treatment. Journal of the Energy Institute, 2016. 89(2): p. 159-
171.
4. Bryers, R.W., Fireside slagging, fouling, and high-temperature corrosion of heat-transfer surface
due to impurities in steam-raising fuels. Progress in Energy and Combustion Science, 1996. 22(1):
p. 29-120.
5. Jenkins, B.M., L.L. Baxter, and T.R. Miles, Combustion properties of biomass. Fuel Processing
Technology, 1998. 54(1-3): p. 17-46.
6. Bankiewicz, D., P. Yrjas, and M. Hupa, High-Temperature Corrosion of Superheater Tube Materials
Exposed to Zinc Salts. Energy & Fuels, 2009. 23(7): p. 3469-3474.
7. Rebbling, A., et al., Waste Gypsum Board and Ash-Related Problems during Combustion of
Biomass. 2. Fixed Bed. Energy & Fuels, 2016. 30(12): p. 10705-10713.
617
WASTE-TO-BIOFUELS: VALORIZATION OF FOOD RESIDUE BIOMASS (FORBI) FOR

HYDROGEN AND METHANE PRODUCTION
G.M. LYTRAS1, I. MICHALOPOULOS1, D. MATHIOUDAKIS1, T. DIMITRIOU1, I. ZACHAROPOULOS1, C.

LYTRAS1, K. PAPADOPOULOU1*, G. LYBERATOS1,2
1 School of Chemical Engineering, National technical University of Athens, Iroon Polytechneiou 9,
Zografou, 15780, Athens, Greece

2 Institute of Chemical Engineering Sciences (ICE-HT), Stadiou Str., Platani, 26504, Patras, Greece
*corresponding author: Konstantina Papadopoulou

e-mail: kpapado@chemeng.ntua.gr
Keywords: FORBI, biofuels, methane, hydrogen, AQUASIM, Household Food Waste
Abstract
This research work concerns the production of Hydrogen and Methane from a Food Residue Biomass
(FORBI) product, generated from pre-sorted Fermentable Household Food Waste in a Continuous
Stirred Tank Reactor (CSTR). FORBI is generated by drying and shredding the fermentable fraction of
household food waste, collected door-to-door in the Municipality of Halandri, Greece.
Hydrogen production from FORBI through anaerobic fermentation under acidogenic mesophilic
conditions was carried out using a 4L CSTR (H2-CSTR), operated at 4 hr and 3 hr Hydraulic Retention
Times (HRT), with a feed concentration of 15 g TS/L. Volatile fatty acids (VFAs), Total and Volatile
Suspended Solids (TSS and VSS), Total and Soluble Chemical Oxygen Demand (tCOD and sCOD), Total
and Dissolved Carbohydrates, pH and hydrogen content in the biogas were monitored. The H2-CSTR
operated for 32 days. During its operation, the biogas productivity reached 7.78 L/d, out of which
4.13 L/d was hydrogen (60%). This corresponds to a yield of 22Lbiogas/kgFORBI.
The conversion of FORBI into methane was carried out through the operation of a CSTR (CH 4-CSTR)
with working volume 4L (CH4-CSTR). the reactor operated under mesophilic methanogenic
conditions at 20,15 and 10 days HRT and an organic loading of 15 g TS/L. TSS, VSS, tCOD, sCOD, pH,
alkalinity, VFAs and methane content in the biogas were monitored. The mean methane percentage
in the biogas was up to 65%, with an average biogas productivity of 0.5Lbiogas/Lreactor/day, during the
optimum operational conditions. The biogas productivity corresponds to a productivity of 477
Lbiogas/kgFORBI.
The experimental results obtained were used as a basis for the development of a model by using
AQUASIM [1] software, which was able to adequately simulate the operation of the bioreactors.
Conclusively, FORBI was proved as a suitable feedstock material both for hydrogen and methane
production, resulting in high biogas yields in both cases.
618
1- INTRODUCTION
The recent urbanization trends throughout the world are expected to lead to a dramatic increase in
the Municipal Solid Waste generation [2]. The most promising, in terms of valorization opportunities,
and in the same time less exploited fraction is the biodegrable MSW. The quantity of the
biodegradable MSW corresponds to a 30-50% of the total MSW quantities generated, and
dramatically up to 95% is ultimately landfilled [3]. The lack of sufficient management and valorization
of the generated food waste leads to high freshwater and fossil fuels consumption, as well as
methane and CO2 emissions from the decomposition processes, enhancing global warming [4].
Hence, the need to develop and apply innovative and environmentally sound valorization
alternatives is urgent.
In the Municipality of Halandri [5], in Attica, Greece an innovative food waste valorization approach
was developed and implemented in pilot-scale within the framework of the Horizon2020 project
WASTE4think [6]. The waste management scheme implemented includes the source-separated
collection of the kitchen waste from 250 households. The kitchen waste collected, was then led to a
drying/shredding facility, located within the Municipality. The drying/shredding process of the food
waste leads to a homogenized biomass product called FORBI (Food Residue Biomass). FORBI, apart
from its homogeneity, has a variety of benefits compared to the raw food waste: its volume and
weight is reduced by up to 80% in comparison with the starting kitchen waste and odours are
removed, while it can be stored for prolonged periods without deteriorating.
The potential of a wide range of potential valorisation alternatives is being currently examined. The
current working paper focuses on the potential generation of gaseous biofuels, namely biohydrogen
and biomethane. There are numerous research works focusing on the anaerobic generation and dark
fermentation of food waste [7]–[16]. However, the idea of using previously dried and shredded food
waste as feedstock for these processes, is not yet widely explored.
This paper is focusing on the operational parameters optimization of the dark fermentation and
anaerobic digestion processes of FORBI. Moreover, the ADM1 modelling framework was used to
develop a model adequately describing the anaerobic digestion process [17].

Determination of soluble (sCOD) and total chemical oxygen demand (tCOD), total (TSS) and volatile
(VSS) suspended solids, total alkalinity and temperature were carried out according to Standard
Methods [18]. The pH was measured using a digital pH-meter (WTW INOLAB PH720). The biogas
production rate was measured using an oil displacement technique [19]. For the quantification of
VFAs, 1 mL of sample acidified with 30 μL of 20% H2SO4 was analyzed on a gas chromatograph
(Shimadzu GC-2010), equipped with a flame ionization detector and a capillary column (Agilent
technologies, INC. 30 m 0.53 mm). The oven was programmed from 105 to 160 oC at a rate of 15oC/
min, and subsequently to 235oC (held for 3 min) at a rate of 20oC/min. Helium was used as the
carrier gas at 15 mL/min, the injector temperature was set at 175 oC and the detector at 225oC. The
produced hydrogen and methane were quantified with a gas chromatograph (Shimadzu GC-2014),
equipped with a thermal conductivity detector and a 12390-U SUPELCO Metal Packed GC Column.
Helium and Argon were used as carrier gases for the measurement of methane and hydrogen
respectively.
619
2.2. Feedstock
FORBI is produced through drying and shredding of food waste using a GAIA GC-300 food waste
dryer. The main characteristics of FORBI are shown in Table 1.
Table 1 main characteristics of FORBI
Ingredient % w/w (In dry base)
Proteins 13.70+0.44
Lipids 12.26+0.11
Glucose 0.00
Sucrose 0.51+0.04
Total reducing sugars 4.96+0.94
Starch 10.68+0.07
Pectin 3.27+0.082
Cellulose 10.31+0.07
Hemicellulose 11.32+0.17
Lignin 6.75+0.15
Ash 7.16+0.27
2.3. Experiments for hydrogen production
Α Continuous Stirred Tank Reactor (H2- CSTR) with a working volume of 4L was used for the
assessment of use of FORBI as feedstock for the production of biohydrogen through dark
fermentation. The H2- CSTR was made of stainless steel and the temperature control (35 ± 0.5 oC)
was achieved via recirculation of warm water in the outer jacket of the bioreactor. The H2-CSTR
operated under anaerobic conditions at different Hydraulic Retention Times (HRTs) (4 and 3 hours).
During start-up, the CSTR was inoculated with 4 L of thermally treated (100 oC for 20 minutes)
activated sludge. The thermal pretreatment is necessary for the inhibition of methanogens and
domination of hydrogen producing microorganisms such as bacteria belonging to the class of
Clostridia [20]. The H2- CSTR was fed using a peristaltic pump with an aquatic suspension of FORBI
(15g FORBI/L) operating in continuous mode. The tCOD of the feedstock was 17.6 g/L on the
average. The dark fermentation experimental procedure lasted 35 days. During day 25 of the
experimental procedure 50 ml of methanogens from the CH4-CSTR were added to the bioreactor in
order to test whether the reactor can stably overcome methanogen contamination. Throughout the
operation of the H2- CSTR no pH regulation took place and the pH remained stable at 4.6- 4.7.
620
During the experimental procedure, gas and liquid samples were taken regularly to measure biogas
composition, TSS, VSS, pH, VFAs, soluble and total COD.
2.4 Experiments for methane production
A conventional CSTR-type bioreactor (CH4- CSTR) was used to investigate the methane production
potential of FORBI. The anaerobic digestion experimental procedure lasted 202 days, including three
different phases based on the operational parameters. During the first phase (days 1-138) the HRT
was set to 19.3 days, while the tCOD of the feedstock was 17.6 g/L on the average. After steady state
was reached, the HRT was reduced to 14.9 days, while the inflow tCOD was essentially the same
(16.9 g/L on the average). This second phase lasted 51 days. Finally, the HRT was reduced to 10 days
(the inflow tCOD was again 16.5 g/L on the average). This last phase of the experimental procedure
lasted for 14 days, before the process failed with biogas production and pH dropping due to VFA
accumulation.
During the experimental procedure, gas and liquid samples were taken regularly to measure biogas
production rate, TSS, VSS, VFAs, pH, Alkalinity, soluble and total COD.
2.5 Mathematical simulation
The experimental results from (CH4- CSTR) were used as the basis for developing a mathematical
model. AQUASIM 2.0 was used to develop the model.

3.1 H2-CSTR
The biogas productivity and the composition of the biogas produced by the H2-CSTR are given in
Figures 1 and 2, respectively. The bioreactor operated in continuous mode immediately after the
inoculation of the bioreactor. During the first four days the biogas productivity and the percentage of
hydrogen increased steeply and then remained almost stable for 18 days. During this 18-days period
of operation, an average biogas productivity rate of 1.15 Lbiogas/Lbioreactor/day was achieved, which
corresponds to 0.0129 Lbiogas/gFORBI (in wet base). The mean percentage of hydrogen during this
period was equal to 49.4% while it reached up to 59%, indicating a robust, stable, long-term
operation over time. The mean removal of soluble carbohydrates was 57.7% (Data not shown). Iso-
valeric, iso-butyric and valeric acids were produced in small quantities. As presented in Fig. 3, the
dominant metabolic products were butyric and acetic acid. This observation verified that the
hydrogen production was related to the production of butyrate and acetate [reactions (1) and (2)]
[20]. The low concentrations of propionic acid (Fig. 3) indicate an efficient hydrogen production
process, as the formation of propionate consumes hydrogen [reaction (3)] [21].
(1) Acetic acid production: C6H12O6 + 2H2O → 2CH3COOH + 2CO2 + 4H2

(2) Butyric acid production: C6H12O6 → CH3CH2CH2COOH + 2CO2 + 2H2
(3) Propionic acid production: C6H12O6 + 2H2 → 2CH3CH2COOH + 2H2O
621
In order to test the sustainability of the bioreactor, we intentionally contaminated the H 2-CSTR with
methanogens by feeding 50 ml of the mixed culture from the anaerobic CH4- CSTR. We have shown
(unpublished data) that the production of hydrogen can be significantly impaired by the domination
of hydrogen consuming methanogens. Despite the fact that the methanogens that are added to the
H2-CSTR cannot be “washed-out”, as methane is produced-even in low quantities- (Fig. 2), the biogas
productivity of the bioreactor remained stable and the percentage of hydrogen high.
The operation of the H2-CSTR with even lower HRT, equal to 3 hours, led to an increase of biogas
productivity, whereas the percentage of hydrogen remained stable. During this period of operation,
an average biogas productivity rate of 1.505 Lbiogas/Lbioreactor/day was achieved, which corresponds to
0.0125 Lbiogas/gFORBI (on wet basis). In addition to this, the amount of produced VFAs decreased
(Fig.3). Therefore, despite the fact that the decrease of HRT led to the increase of biogas
productivity, the operation of H2-CSTR with an HRT of 3 hours was not investigated further as the
biogas productivity per gram of feedstock decreased substantially.
Figure 1. Biogas productivity by H2-CSTR during its operation.
622
Figure 2. Composition of the biogas produced by the H2-CSTR during its operation.
Figure 3. Production of VFAs during the operation of H2-CSTR.
3.2 CH4-CSTR
The methane production process worked smoothly throughout the experimental procedure. During
the first experimental phase (HRT=19.3 d) an average biogas productivity rate of 0.303
L/Lbioreactor/day was achieved, which corresponds to 0.382 Lbiogas/gFORBI, while the mean methane
content of the biogas was up to 65%.
623
During the second experimental phase (HRT= 14.9 days) the biogas productivity rate increased to
0.451 L/Lbioreactor/day, which in turn corresponds to 0.467Lbiogas/gFORBI. The average methane content
of the biogas produced during phase 2 was 62%.
Finally, the HRT decrease to 9.77 days led to process failure. More specifically, the concentration of
Volatile Fatty Acids increased gradually, as shown in Figure 3.
The most important experimental results for the methane production are presented in Figures 4 & 5:
Figure 4 For all the three experimental phases of the Anaerobic Digestion process, biogas productivity rate is presented.
Figure 5 For all the three experimental phases of the Anaerobic Digestion process, the metabolic products concentration is presented.
The sharp increase of the concentration during the final -third- phase of the procedure indicates process failure.
Aquasim modeling with ADM1
Based on the experimental results obtained throughout the experimental process, an ADM1 model
was developed for the simulation of the process. The modeling results are presented in Figs. 6-12:
624
Figure 6 Biogas productivity experimental Figure 7 pH experimental data and model simulation
data and model simulation
Figure 8 sCOD experimental data and model Figure 9 Acetic acid experimental data and model simulation
simulation
Figure 10 Butyric Acid experimental data and model Figure 11 Propionic acid experimental data and model simulation
simulation
625
Figure 12 Volatile Suspended Solids
The model is adequately simulating the experimental process. The deviation observed during the
first 70 days between the experimental data and the modeling outcome in sCOD and VSS, is probably
related to the time needed for the process to reach steady-state conditions, given the fact that the
initial reactor state was not sufficiently known..
4- CONCLUSIONS
The present work investigated the potential valorization of FORBI, an innovative biomass product,
for the production of gaseous biofuels, methane and hydrogen. FORBI was generated by drying and
shredding of pre-sorted door-to-door collected household kitchen waste in the Municipality of
Halandri. The development and implementation of the specific bio-waste management scheme
aspires to revolutionize the way the Fermentable Municipal Solid Waste is being managed.
Hydrogen productivity using FORBI as feedstock reached 1.15 Lbiogas/Lbioreactor/day with an HRT
of 4 hours. The mean percentage of hydrogen during this period was 49.4%. Methane productivity
through FORBI, using a conventional CSTR, reached a productivity of 0.467Lbiogas/gFORBI with an HRT of
15 days. The mean methane content of the biogas produced was 62%. The anaerobic digestion
process failed when the HRT was decreased to 10 days. An ADM-1 model was developed -using
AQUASIM- based on the experimental results of the anaerobic digestion process. The modelling of
the process was satisfactory.
ACKNOWLEDGMENTS
This work is produced under research project Horizon 2020, Grant Agreement No 688995. «Moving
towards Life Cycle Thinking by integrating Advanced Waste Management Systems-[WASTE4THINK].
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626
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627
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628
VALORISATION OF CELLULOSE, HEMICELLULOSE, AND LIGNIN USING SUPPORTED
METAL CATALYSTS

A. YAMAGUCHI1, N. MIMURA1, M. SHIRAI1,2, O. SATO1
1 Research Center for Compact Chemical System, National Institute of Advanced Industrial Science
and Technology (AIST), Sendai, Japan.
2 Department of Chemistry and Biological Sciences, Faculty of Science and Engineering, Iwate
University, Morioka, Japan.

Abstract

Conversion of nonedible biomass into valuable chemicals has greatly attracted attention for
establishing the sustainable society because of its renewability, abundance, and inedibility.
Lignocellulosic biomass is composed of cellulose, hemicellulose, and lignin. Direct catalytic
conversion of cellulose and hemicellulose in lignocellulosic biomass to valuable chemicals is highly
desirable to open new possibility for the use of lignocellulosic biomass. In this paper, we have
succeeded in converting hemicellulose, cellulose, and lignin into useful chemicals using supported
metal catalysts in step‐by‐step procedures. At first, we found a technique for the conversion of
cellulose and hemicellulose in biomass chips to sugar alcohols by supported metal catalysts with
hydrogen [1, 2]. Without a delignification pretreatment, the cellulose and hemicellulose in the wood
chips were converted to sugar alcohols and lignin could be obtained as solid after the reaction.
Next we investigated the chemistry for intramolecular dehydration of the sugar alcohols in high‐
temperature liquid water into valuable chemicals. The intramolecular dehydration of sorbitol and
mannitol can provide valuable diols, isosorbide and isomannide, by bimolecular dehydration.
Isosorbide and isomannide have attracted a great deal of attention because poly(ethylene
terephthalate) (PET) containing isosorbide has higher glass transition temperatures than pure PET.
We found that isosorbide and isomannide could be produced from sorbitol and mannitol
dehydration in high‐temperature liquid water without adding any acid catalysts [3‐5], which could
enhance the prospect for biomass‐based monomers.
At last, the lignin, which remains mostly as solid after the direct conversion of biomass chips into
sugar alcohols, can be converted into chemicals. Conversion of lignin into valuable aromatic
compounds requires the cleavage of C–O ether bonds and C–C bonds between lignin monomer units.
We found cleavage of the aromatic C–O bonds in lignin model compounds using supported metal
catalysts in supercritical water without adding hydrogen gas and without causing hydrogenation of
the aromatic rings [6].
References
[1] Yamaguchi, A., Sato, O., Mimura, N., Hirosaki, Y., Kobayashi, H., Fukuoka, A., Shirai, M.: Direct Production of Sugar
Alcohols from Wood Chips using Supported Platinum Catalysts in Water. Catal. Commun., 54, 22‐26 (2014)
[2] Yamaguchi, A., Sato, O., Mimura, N., Shirai, M.: Catalytic production of sugar alcohols from lignocellulosic biomass.
Catal. Today, 265, 199–202 (2016)
[3] Yamaguchi, A., Hiyoshi, N., Sato, O., Shirai, M.: Sorbitol dehydration in high temperature liquid water. Green Chem.,
13, 873‐881 (2011)
[4] Yamaguchi, A., Sato, O., Mimura, N., Shirai, M.: Intramolecular dehydration of mannitol in high‐temperature liquid
water without acid catalysts. RSC Adv., 4, 45575‐45578 (2014)
[5] Yamaguchi, A., Muramatsu, N., Mimura, N., Shirai, M., Sato, O.: Intramolecular dehydration of biomass‐derived
sugar alcohols in high‐temperature water. Phys. Chem. Chem. Phys., 19, 2714‐2722 (2017)
[6] Yamaguchi, A., Mimura, N., Shirai, M., Sato, O.: Bond Cleavage of Lignin Model Compounds into Aromatic Monomers
in Supercritical Water using Supported Metal Catalysts. Scientific Reports, 7, 46172 (2017)
629
HYDROTHERMAL LIQUEFACTION FOR VALORISING WET BIO-WASTE – TUNABLE

KINETICS ENABLES OPTIMUM BIO-PRODUCT MIX
CONTRIBUTION TITLE
A. SAPRE, R. BHUJADE
1 Reliance Industries Limited, Mumbai, India.
Abstract
Wet bio-waste such as food processing waste, dairy waste, waste water sludge form effluent
treatment plants typically have over 80% water. HTL, an emerging technology, is a thermo-chemical
conversion process that converts wet biomass to oil and gas, using water as a solvent at high
temperature and high pressure. It essentially expedites the natural process of oil and gas formation
from biomass— instead of millions of years as taken by nature, HTL achieves the process in a few
minutes. It not only avoids energy-intensive drying to convert biomass to biofuel but also recovers
water, minerals, nutrients, and co-products.
Biomass organics essentially contain protein, carbohydrates, lipids and lignocellulose depending on
the source of bio-waste. HTL is inherently feedstock agnostic. All the major biomass components
undergo chemical transformation individually, and intermediate molecules interact cross-
functionally to form various bio-oil components, such as alcohols, amines, acids, long-chain
hydrocarbons, amides, furans, polycyclics, and aromatics, via dehydration, condensation,
decarboxylation, amidation, deamination, cyclization, and aldol splitting.
On further investigation of HTL reactions at the molecular level, it has been observed that the
kinetics of the reactions can be tuned in such a way that the desired product mix can be obtained to
suit the market demand and economics. This potential of tuning the HTL reactions kinetics makes it a
most promising technology not only for wet biomass but also for relatively dry agricultural residues.
Although HTL has the potential to be the most promising technology for converting bio-waste and
biomass, most research has been performed at the laboratory scale. Reliance Industries, as part of
algal biomass to oil project, built a large-scale pilot plant and it is commissioned in 2016.
In the presentation, we will share and discuss our experience gained during the journey of concept
to commissioning this large scale pilot plant, for further scale up towards commercialization.
Reference
[1] Bhujade, R., Chidambaram, M., Kumar, A., Sapre, A.: Algae to Economically Viable Low-Carbon-Footprint Oil, pp. 335-
357, Annual Reviews (2017).
http://www.annualreviews.org/eprint/XQnbqQcBgRKhDpPwnCZS/full/10.1146/annurev-
chembioeng-060816-101630.
630
SOLID ANAEROBIC DIGESTION: CURRENT TRENDS AND SCIENTIFIC HURDLES
L. ANDRE1, A. PAUSS2, T. RIBEIRO1

1 Institut Polytechnique UniLaSalle, UR Transformations & Agroressources, Beauvais, France.
2 Sorbonne Université, EA 4297 TIMR, Compiègne, France.
Abstract
In 2017, only 11% (representing 57 biogas plants – 45 operating in discontinuous way and 12 in
continuous way) of solid anaerobic digestion plants for farms can be found in France, showing a low
level of such installation in comparison with the large amount of agricultural feedstock like manure,
estimated between 68 and 89 Mt.y-1 [1]. But farm anaerobic digestion cannot be only performed
with agricultural byproducts like manure, with a methane potential equal to 203 à 240 Nm3CH4.TVS-1
varying with the TS amount [1]. In order to propose a solution to solve this situation, the codigestion
is fully adapted for such installation (i.e. solid AD). Operating digesters working with codigestion used
mix of substrates like agri-food and agricultural byproducts [2]. Solid AD process is the most adapted
solution for degradation of byproducts with high TS content, especially with lignocellulosic materials
like straw or manure. By this way, this process should be optimized and research works are required
in order to solve scientific and technological hurdles.
Many processes are available for solid AD, essentially operating in discontinuous way and with
technologies approved for household waste. In many case, the digesters are silos, containers or
garages. The first solid AD process described was the Isman and Ducellier process (1939), several
times patented. At this time, the solid AD sector in France is at a low level of development, maybe
due to the lack of manufacturers for such technology. Solid anaerobic digestion should be a fully
adapted solution for anaerobic digestion, especially in farms but its development must be enforced,
because of some scientific and technical problems have to be solved. There’s a lack of knowledge for
example about liquid transfers and rheology of such system operating with high TS content.
Solving the scientific and technological hurdles of solid AD is the key factor of success, especially in
order to understand the phenomena involved in such process, moreover for management of biogas
plants and improvement of profitability. Most of these hurdles were mentioned in different studies
[3, 4]; but there’s few research works in literature. These hurdles could be listed as following: (i)
heterogeneity of substrates; (ii) measurement of realistic BMP; (iii) implementation of reliable
codigestion; (iv) management of inhibition; (v) better knowledge of microbial population dynamics,
(vi) management of inoculum; (vii) better knowledge of hydric transfers and rheology; (viii)
development of adapted monitoring tools; (ix) pretreatment of substrates; (x) lack of manufacturers.
When not solved, such scientific and technological locks provoke many consequences like
dysfunction of installation with loss of profitability, low level of methane and biogas, low level of
degradation, financial losses.
References
[1] Degueurce, A., Capdeville, J., Perrot, C., Bioteau, T., Martinez, J., Peu, P., 2016a. Fumiers de bovins, une ressource à
fort potentiel pour la filière de méthanisation en France ? Sciences, Eaux et Territoires. Hors-série n°24 2016.
[2] Béline, F., Girault, R., Peu, P., Trémier, A., Téglia, C., and Dabert, P., 2012. Enjeux et perspectives pour le
développement de la méthanisation agricole en France. Sciences Eaux et Territoires. 7, 1-10.
[3] Viard, N., Meier-Wawrzyniak, V., 2009. La méthanisation en voie sèche : fonctionnement biologique, technique et
état des lieux des technologies disponibles. TRAME. 1-106.
[4] André, L., Pauss, A., Ribeiro, T. 2017. Solid anaerobic digestion: state-of-art, scientific and technological hurdles.
Bioresource Technol. In press..
631
CONVERSION OF AQUEOUS ETHANOL AND ABE MIXTURES TO THE BIO-GASOLINE

BLENDING STOCK WITH Zn(Cd)-Zr BASED CATALYSTS
M.V. LANDAU, T. HOS, B. PORGADOR, R. VIDRUK NEHEMYA, M. HERSKOWITZ

1 Blechner Center for Applied Catalysis and Process Development, Chemical Engineering Department,
Ben-Gurion University of the Negev, Beer-Sheva, Israel.
Abstract
Purpose
Fermentation is the main route for production of ethanol and butanol from waste organic biomass
delivered by food industry. Ethanol and acetone-butanol-ethanol (ABE) mixtures are obtained as
aqueous products after separation of fermentation broth which further dehydration is economically
not feasible. But the known catalytic materials for conversion of ethanol and ABE to bio-fuels suffer
from fast deactivation as zeolites or lose their activity at hydrothermal conditions. The purpose of
the present work was development of novel hydrothermally stable catalytic materials for conversion
of aqueous ethanol and ABE to hydrocarbons suitable as bio-blending stock for gasoline according to
their carbon numbers and chemical composition.
Main materials and methods
The ethanol and ABE mixtures containing 4-65% water were converted in a fixed-bed reactor at
elevated pressure of 2-15 bar, temperature 430- 480oC and WHSV = 0.3-1.5 h-1 in presence of mixed
oxide catalysts with acid-base functionality. The catalysts contained zirconium oxide where part of
Zr-ions were substituted by Zn or Cd with addition of promoters Mo,W,V,In,Sc,Ga,Mn, Cu,Fe, Al, Si,
Ca, Mg adjusting the acid-base and redox properties.
It was found that ethanol at concentrations >50% is converted with Zr-based catalysts to liquid
hydrocarbons, C2-C4 olefins, hydrogen and CO2 according to complicated multistep process including
dehydrogenation, decarboxylation and condensation reactions. The yield of liquid hydrocarbons with
Zn-Zr catalyst reaches 48% and after oligomerization of light olefins with commercial ZSM-5 based
catalyst and mixing both liquid products became 70%. The liquid contains C 4-C22 hydrocarbons
including olefins (65-72%), paraffins, aromatics and oxygenates. Hydrotreating of this liquid product
with Pt-SAPO-11-Al2O3 catalyst yields an excellent bio-blending stock for gasoline with density 0.735
g/cm3 consisting of 75% paraffins (i-/n- =2.8) and 20% aromatics. The catalyst is not sensitive to
water displaying stable operation in a 700 h run. Promotion of catalyst with Cd and basic
components removes oxygenates from the liquid product and allows to get 70% yield of liquid
hydrocarbons in one step excluding oligomerization of light by-products. Similar results were
obtained converting aqueous ABE mixture to high quality bio-blending stock for gasoline with 86-
89% yield.
Main conclusions
Application of promoted Zr-based mixed oxide catalysts permits conversion of aqueous ethanol and
ABE to liquid hydrocarbons yielding qualified bio-blending stock for gasoline after its hydrotreating.
Hydrotreating uses hydrogen produced at the main condensation process step.
Acknowledgement
The project WASTE2FUELS leading to this presentation has received finding from the European
Union’s Horizon 2020 research and innovation programme grant No 654623.
632
MONITORING OF CARBON AND NITROGEN BIODEGRADATION AND GAS EMISSIONS

DURING STORAGE AND COMPOSTING OF DIGESTATES TO DEVELOP MODELS
A. TREMIER 1 R. AFFES, R. GIRAULT1

1 IRSTEA, UR GERE, 17 avenue de cucillé, CS 64427, F-35044, Rennes Cedex, France.
Abstract
The development of anaerobic digestion at the farm and territorial scale leads to the production of
digestate whose management has to avoid greenhouse gases and ammonia emissions and to
promote fertilizing value and carbon recycling into agricultural soils. Thus to develop digestate
products with specific agronomic needs, the digestate post-treatment value chains have to be
optimized. Among possible post-treatments, storage and composting lead to aerobic transformation
of the organic matter through interconnected physical and biological phenomena. Numerical models
of these processes could be useful as predictive tool to assess the risk of loss of fertilizing value and
gas emissions during treatment and to simulate the quality of the post-treated digestates depending
on the process parameter management. In order to develop and validate these models, this study
aimed at experimentally measuring the aerobic transformation of different types of digestate and
the linked emissions under storage and composting conditions.
The study of 5 types of solid digestates has been planned. They differ in terms of chemical
composition (nitrogen and carbon distribution) and in terms of the type of separation process they
arise from. The impact of aeration and mixing on biodegradation and emissions are studied in three
300L cylindrical reactors with the objective of simulating storage and composting systems
environment: simulation of storage system (3 months with passive aeration); simulation of windrow
system (3 months with passive aeration and mixing once per month); simulation of forced aerated
composting (45 days with forced aeration between 150 and 300 L/hour and mixing twice per
month). The in-coming air flow, the mass variation and temperatures are continuously monitored.
Ammonia is trapped in sulphuric acid (H2SO4, 1 N) and quantified. Concentrations of O2, CO2, CH4,
and N2O are continuously measured in both incoming and out-coming air-flows using continuous gas
analyser systems.
First results were obtained using solid digestate, separated from anaerobically digested beef manure
(screw press) and pig manure (decanter centrifuge). Solid digestates had a high aerobic residual
biodegradability. Either in storage and composting conditions, temperatures of more than 70°C were
reached for several days. Kinetics of biodegradation was higher in composting conditions. Ammonia
and N2O emissions demonstrated to increase with forced aeration but also with mechanical mixing.
In static storage, N2O emissions stopped as soon as temperature reached 60°C. It confirms the high
impact of aeration and temperature on nitrogenous emissions during digestates post-treatment.
These results will be further used to develop numerical models. For composting, the model proposed
by Denes [1], describing carbon and nitrogen biodegradation, thermal and mass transfers will be
improved. In parallel the same model will be adapted regarding transfers phenomena in order to
simulate storage conditions with passive aeration.
References
[1] Denes J.. Modelisation couplée des phases de traitement par compostage et de recyclage agricole des matieres
organiques. Doctorat en Sciences de l'Environnement, Université de Rennes 1 (2014)
633
EXPLOITATION OF TUNISIAN DATE PALM SAP AS A PROMISING CARBON SOURCE

FOR BIOETHANOL PRODUCTION BY A NEWLY ISOLATED YEAST STRAIN
I. BEN ATITALLAH1,4, I. NTAIKOU 2, G. ANTONOPOULOU 2, M. ALEXANDROPOULOU2, G. LYBERATOS2,3,

M. NASRI 1, T. MECHICHI 4
1 Laboratory of Enzyme Engineering and Microbiology, National School of Engineers of Sfax,

2 Institute of Chemical Engineering Sciences, 11 Stadiou st., Platani, Patras, GR 26504, Greece.
3 School of Chemical Engineering, National Technical University of Athens, GR 15780 Athens, Greece.
4Laboratory of Biochemestry and Enzyme Engineering of Lipases, National School of Engineers of Sfax,
Keywords: Date palm sap, bioethanol, Wickerhamomyces anomalus, microaerobic and anaerobic
fermentation, batch culture, fed-batch culture, scale-up.
Abstract
Among the so called clean fuels, bioethanol is considered to be one of the most promising, whereas it
can also be used as fuel additive. However, in order to be sustainable bioethanol production has to be
based on renewable carbon sources as well as robust microbial strains exhibiting advanced
performance and high yields under various conditions. The present study investigated the efficient
utilization of natural date palm sap (DPS) for direct, low cost bioethanol production.
For all experiments the newly isolated yeast Wickerhamomyces anomalus X19 was used in batch and
fed batch mode. Batch experiments were conducted using synthetic media and the DPS based
medium at different initial substrate concentrations whereas the effect of low oxygen concentration
on the performance of the stain was assessed under microaerobic or anaerobic conditions (both
pressurized and non-pressurized). Fed batch experiments with DPS were also conducted in order to
improve ethanol yield. The scale-up of alcoholic fermentation was performed in batch mode under
anaerobic non-pressurized condition. Growth, total and reduced sugars, ethanol and pH were
monitored over time.
It was shown that strain W. anomalus X19 was able to grow sufficiently producing significant ethanol
concentrations even in media with low pH values and initial concentration of sugars up to 200 g/L. The
highest ethanol concentration achieved was 61 g/L, using DPS in batch-mode non-pressurized cultures
of 48 hours incubation, whereas in all cases ethanol yields were quite high reaching up to 80 % of the
theoretically estimated values. This study provides promising results for the possible exploitation of the
DPS as a new renewable, non-cellulosic feedstock for bioethanol production.
634
1. INTRODUCTION
The date palm trees are widely cultivated in various arid and semi arid regions throughout the world,
including North Africa and Arabian Gulf countries, where it plays significant socio-cultural, economic,
and ecological roles. The cultivated surface of date palms in 2006 was estimated at 1.18 million
hectares in the world. In Tunisia, for instance, date palm oases covers an area of about 46,000 hectares
with around three million trees [1]. Tunisian date palm culture provides annually about 4 % of the total
value of agricultural production and 13 % of the total value of agricultural exports. In addition to date
fruits, palm trees offer several other derivatives (such as leaves, trunks, and seeds), which are used for
various traditional and industrials activities such as roofing, fencing, basket making, and animal feeding
[2]. Date palm sap (DPS), known in Tunisia as “legmi”, is one of the popular derivatives of date palm
trees. During one tapping season, a date palm tree may offer a total sap yield up to 500L [3].
Composition analysis of fresh sap revealed that sugars are the major components (92 – 95 % dry
matter basis) with the dominance of sucrose with small amounts of glucose and fructose [4]. In spite of
the availability and the typical properties of DPS, the exploitation of this resource is still limited and no
study has so far reported its potential as a promising carbon source for alcoholic fermentation. Thus, to
the best of our knowledge, this is the first report describing the possible exploitation of the natural DPS
extracted from palm trees as a renewable feedstock for direct bioethanol production. Batch
experiments were conducted using DPS based medium under microaerobic or anaerobic conditions,
followed by fed-batch and scale-up fermentations to evaluate growth and ethanol production profile of
the newly isolated yeast W. anomalus X19. The isolated strain was taxonomically characterized and its
ability to grow and produce ethanol at various concentrations of sugars, at low pH and under anaerobic
conditions was tested.

2.1. Yeast isolation
In the present study, the yeast strain W. anomalus X19 (MH237950.1) was recently isolated from a
sample of decaying wood collected from a forest located in the north west of Tunisia. The sample of
decaying wood was transported in sterilized plastic bags and brought to the laboratory without further
exposure to the external environment. 2 g of the sample were inoculated to 50 mL of yeast peptone
dextrose medium (YPD) containing: 10 g/L yeast extract, 10 g/L peptone and 20 g/L glucose and
incubated at 30 °C on an orbital shaker at 150 rpm. When growth was detected, successive serial
dilutions was performed in sterilized physiological water (NaCl 0.9 %, w/v in water). Aliquots of each
dilution (0.1 mL each) were spread on YPD agar (5 g/L yeast Extract, 5 g/L peptone, 10 g/L glucose and
20 g/L agar, pH 5.5) plates supplemented with 50 mg/L Chloramphenicol to avoid bacterial
contamination and incubated for 48 h at 30 °C. The purified isolates were stored on YPD agar plates at
4 °C. For long-term preservation, the strain was stored in 20 % glycerol at − 80 °C.
2.2. Molecular Identification of the selected yeast

The yeast isolate was identified by sequence analysis of the D1/D2 domain of the 26S rRNA and the ITS
region [5]. The D1/D2 domain and the ITS region were amplified as described before by Kurtzman and
Robnett [6] and Fell et al. [7]. Sequencing of the PCR products was done by Seqlab GmbH, Göttingen,
635
Germany. The generated sequences were compared to the sequences of related species retrieved from
the NCBI database using BLAST search in GenBank. The optimal tree with the sum of branch length =
0.42557607 is shown. The percentage of replicate trees in which the associated taxa clustered together
in the bootstrap test (1000 replicates) are shown next to the branches. The phylogenetic tree was
inferred using the Neighbor-Joining method excluding positions with gaps [8]. The evolutionary
distances were computed using the Maximum Composite Likelihood method [9] and are in the units of
the number of base substitutions per site. Evolutionary analyses were constructed with MEGA7 [10].
2.3. Feedstock used
The DPS was tested in this study as a suitable substrate for bioethanol production. Fresh DPS was
kindly provided from palm trees planted in the region of Gabes “South east of Tunisia” in March 2017.
The juice was collected from a shallow depression scooped out at the top. The samples were
immediately stored in an ice box (4 °C) to avoid fermentation during transportation to the laboratory.
Prior to use, the juice was centrifuged at 8000 rpm for 15 min at 4 °C to remove solid particles and the
supernatant was sterilized for 121 °C for 20 min then stored at 4 °C until further use.
2.4. Bioethanol production

2.4.1 Inoculum preparation
One loopful of a single colony of the yeast W. anomalus X19 was transferred from the agar plate into
50 ml of sterile YPD proliferation media containing: 20 g/L glucose, 10 g/L yeast extract and 10 g/L
peptone. The inoculum was cultivated overnight in 250 ml Erlenmeyer flask on a rotator shaker (150
rpm) at 30 °C.
2.4.2 Small scale he batch and fed batch experiments

The fermentation was carried out comparatively in batch and fed-batch systems. In both fermentation
systems, experiments were carried out in 160 mL serum vials with an initial working volume of 25 mL at
30 °C with orbital shaking at 150 rpm.
In batch experiments, the efficiency of the isolated yeast W. anomalus X19 to produce ethanol was
assessed in various defined media containing 30 - 120 g/L of sugars (i.e. sucrose, sucrose /D-glucose
mixture, D-xylose, D-xylose/D-glucose mixture, L-arabinose, L-arabinose/D-glucose mixture, cellobiose
and cellobiose/D-glucose mixture) with 2 g/L of yeast extract or NH4Cl supplementation. The
fermentations were performed during 96 h.
DPS based medium was evaluated as economic culture medium. The effect of diluted oxygen on the
performance of the yeast strain was assessed in batch mode using this substrate under microaerobic
and anaerobic conditions. Aerobic experiments were performed in 100 ml flasks plugged with
hydrophobic cotton and incubated at 30 °C with mechanical agitation at 150 rpm. For anaerobic
fermentations under pressurized condition, experiments were carried in serum vials sealed with rubber
stoppers. While anaerobic fermentations under non-pressurized condition were conducted in serum
vials capped with rubber stoppers pierced with a needle to allow the release of the carbon dioxide
produced during the fermentation.
The fed-batch fermentation was performed under anaerobic non-pressurized condition with sterile
DPS based medium. The feeding regime used was stepwise feeding. Feeding of the DPS was performed
as described in Table 1. The initial total sugars concentration and initial cell mass concentration were
636
the same in all the experiments. The fermentations were performed during 144 h.
Starting batch First feeding Second feeding Third feeding Forth feeding
0h 24 h 48 h 72 h 96 h
FB1 25 ml DPS + 5 ml DPS + 5 ml DPS + 5 ml DPS + 5 ml DPS
FB2 25 ml DPS - + 10 ml DPS - + 10 ml DPS
FB3 25 ml DPS - - + 20 ml DPS -
Table 1: Addition of fresh medium in fed-batch mode during the fermentation of DPS
In all experiments, cells were harvested from pre-culture of the yeast W. anomalus X19 equal to 5 %
inoculum by centrifugation at 6000 rpm for 10 min, suspended in mineral salt solution containing the
following nutrients (g/L): NH4Cl, 2.0; KH2PO4, 0.05; and MgSO4.7H2O, 0.05. The initial pH of DPS was
not adjusted for fermentation. At selected time intervals, samples withdrawn from the fermentations
were centrifuged at 6000 rpm for 10 min, filtered through 0.7 µm filters and then analyzed for ethanol
and sugars quantification. Microbial growth and pH were monitored over time. All experiments were
carried out aseptically and analyses were performed in duplicate.
2.4.3. Scale-up batch experiment

In order to investigate the scaling up of alcoholic fermentation, experiments were performed in batch
mode under anaerobic non-pressurized condition using a 1.2 L bioreactor with 200 mL working volume.
The substrate and the bioreactor were sterilized at 121 °C for 20 min before inoculation. Inoculum was
prepared with centrifuged cells from pre-culture of W. anomalus X19 corresponding at 5 % v/v. NH4Cl,
KH2PO4, and MgSO4.7H2O at concentrations of 2.0, 0.05 and 0.05 g/L respectively, were also added, for
nutrients supplementation. pH of the DPS was not adjusted. During the fermentation, the temperature
was set at 30 °C and the agitation was maintained at 150 rpm. Samples were periodically withdrawn at
regular time intervals for analyses of sugars, ethanol contents and biomass. The pH values were also
reported. Duplicate runs were performed and the average values of the two runs are reported.
2.5. Analytical methods

Total solids (TS), volatile solids (VS) and Τotal Kjeldahl Νitrogen (TKN) quantified according to Standard
Methods [11]. Crude protein content was determined by multiplying TKN by a factor of 6.25 [12].
Phosphorous content was determined by vanadomolybdophosphoric acid method [11]. Total sugars
concentration was measured by the phenol-sulfuric acid method described by DuBois et al. [14].
Reducing sugars concentration was determined in the growth media according to the DNS (3, 5-
dinitrosalicylic acid) method as described by Miller [15] and was expressed as glucose. The minerals Na,
K, Mg, Ca, Cu, Zn, Co and Fe were quantified by atomic absorption spectrometry. In order to estimate
biomass, optical density (OD) was measured at 600 nm and subsequently biomass concentration
(Cbiomass) was determined through the equation:
Cbiomass (g/L) = 1.0858 * OD − 0.1376 (R2 = 0.993).

Ethanol was quantified via HPLC-RI (Shodex) with an Aminex HPΧ–87H column (Biorad) at 600C and a
Cation H micro-guard cartridge (biorad Laboratories), with H2SO4 0.006Ν mobile phase at a flow rate of
0.7mL.min-1. The standard curve for ethanol was plotted using standard ethanol sample.
637
Bioethanol yield (Y), volumetric productivity and fermentation efficiency (FE) were determined using
the following equations as described by Laopaiboon et al. [16]:

3.1. Identification of the isolated yeast: molecular characterization and taxonomy
The selected yeast strain X19 was identified by analysis of the sequence of its 26S rRNA D1/D2 domain
and compared with sequence of type strains from the database of the NCBI (accession number
indicated in Figure 1. Alignment results of the rRNA sequences of the isolate showed that the sequence
of strain X19 (MH237950.1) have 100 % similarity with Wickerhamomyces anomalus strain H7
(KM655847.1). To confirm the position of each strain in phylogeny, a number of sequences were
selected from the NCBI database and the phylogenetic tree was contracted using the MEGA7 software.
As shown in Figure 1 the isolate X19 share the same clade cluster of the phylogenetic tree of D1/D2 26S
rDNA sequences corroborating all they belong to the genus Wickerhamomyces.
Figure 1: Phylogenetic tree obtained by the Neighbor-joining method, based on the analysis of 26S rDNA and the ITS region of the
isolate strain X19. The optimal tree with the sum of branch length = 0.42557607 is shown. The strain was identified within the genus
Wickerhamomyces. Access number type strain is in parentheses.
3.2. Composition of DPS

Chemical composition of DPS is shown in Table 2. It can be seen that DPS had high total sugar content.
It is mainly composed of a mixture of sugars and other minor substances. It contained 92 total
carbohydrate, 1.4 proteins and 2.56 mineral (g/100 g dry matter basis). Analysis revealed that dry
matter represents 17.32 %. The pH of the sap was approximately 5.0. This result could explain the fact
that the sap may be used as substrate for ethanol fermentation.
638
3.3. The batch and fed batch small scale experiments

In order to study the ability of the yeast W. anomalus X19 to utilize DPS based medium as the sole
renewable carbon source, we examined the effect of diluted oxygen concentration on the
performance of the yeast for bioethanol production in batch culture under both anaerobic and
microaerobic conditions. The results are shown in Figure 2.
It can be noted that a similar ethanol production pattern was observed in anaerobic fermentation
under both pressurized and non-pressurized condition and the amount of ethanol produced was also
comparable. At the beginning of fermentation, there was a rapid increase in ethanol production and a
rapid decrease in sugar concentration. This behavior can be attributed to two factors, first the active
structure of the yeast which does not take much time to react, second the rich substrate that contains
most of the nutrients which cause rapid adaptation and development of microorganisms. The
maximum yields of ethanol concentrations were 61.08 and 61.07 g/L after 48 h of fermentation under
anaerobic pressurized and non-pressurized fermentations respectively. For microaerobic
fermentation, the ethanol concentration reaches its maximum value (51.62 g/L) after 48 h of
fermentation and then showed a rapid decline.
Characteristics Data
pH 4.8
Dry matter (%) 17.32 ± 0.4
Ash (g /100 g dry matter) 2.56 ± 0.13
Reducing Carbohydrates (g/L) 18.345 ± 0.08
Total Carbohydrates (g/L) 200.013 ± 0.12
TNK (g /100 g dry matter) 0.224 ± 0.076
Protein (g /100 g dry matter) 1.4 ± 0.02
P* 40.14 ± 0.30
Na * 11.04 ± 0.19
Mg* 297.88 ± 0.21
K* 484.57 ± 0.03
Ca * 14.55 ± 0.08
Fe * 1.44 ± 0.41
Cu * 0.74 ± 0.12
Zn * 0.34 ± 0.07
Co * < 0.01
Values are the means ± standard errors of three determinations. *mg /100 g dry matter basis.
Table 2: Physicochemical characteristics of the date palm sap used in this study.
It is evident from Figure 2.C that the strain W. anomalus X19 is capable of growing both with and
without oxygen supply, although the growth was much faster in aerobic condition when oxygen was
present. The cell mass increased rapidly during the first 48 h of fermentation followed by a period of
much slower growth. Maximum biomass values of 8.3 g/L were obtained after 24 h of fermentation
under aerobic fermentation, while the respective value of biomass during growth of the strain was
639
equal to 6.018 g/L and 7.035 g/L after 48 h of fermentation under anaerobic pressurized and non-
pressurized fermentations respectively.
Figure 2.b shows the effect of pH on ethanol production. It can be seen that the pH gradually
decreases in all cultures during the 24 h. Then, it tends to fluctuate between 2.5 and 2.8.
Figure 2 : Kinetics of pH and cell growth during ethanol production from DPS based medium in batch mode under microaerobic and
anaerobic conditions.
Three fed-batch experiments under anaerobic non-pressurized conditions were performed with DPS
based medium in order to improve ethanol yield. Cell growth, pH, sugar consumption and ethanol
production results are shown in figure 3. The effects of feeding on ethanol fermentation were
investigated for fed-batch culture. All fermentations were compared at 96 h.
Figure 3: Kinetics of pH, cell growth, sugar consumption and ethanol production from DPS based medium in fed-batch fermentations.
640
The fist fed-batch cultivation (FB-1) was performed by feeding 5 ml of DPS every 24 h. In this case,
figure 3.a-1 shows that the ethanol production was 63.73 g/L giving 0.484 g/g bioethanol yield per
consumed sugar. The fermentation efficiency reached 94.866 %. The second fed-batch culture was fed
with 10 ml of DPS every 48 h. As observed in figure 3.a-2, the ethanol concentration was 70.1 g/L
resulting from the maximum ethanol yield and fermentation efficiency of 0.5 g/g consumed sugar and
97.94 % respectively. The third fed-batch cultivation was fed with 20 ml of DPS after 72 h. Figure 3.a-3
shows that the ethanol yield was slightly lower compared to other fed-batch cultures.
3.5 .The scale-up experiments

The experimental profile of bioethanol production by W. anomalus X19 cultivated in DPS based
medium at scale-up condition under anaerobic non-pressurized condition is depicted in Figure 4.a it
can be seen that bioethanol production started immediately from the first hours of fermentation. The
ethanol concentration increased gradually until reaching a steady state after about 48 h of
fermentation. The sugar consumption showed down and the fermentation medium becomes more
acidic after the production of both ethanol and carbon dioxide. Higher bioethanol production (61.51
g/L) has been obtained after 48 h, giving 0.41 g/g bioethanol yield per sugar consumed.
The variation of pH during alcoholic fermentation is given in Figure 4.b. It showed a rapid decline from
5 to 2.5 during the first 24 h. Then, it tends to stabilize around 2.5. The decrease in the pH was due to
the production of carbon dioxide that acidifies the medium, followed by ethanol formation and a small
amount of carboxylic acids. The yeast W. anomalus X19 has great tolerance to low pH values which is in
agreement with the description of the yeasts of the Wickerhamomyces genus.
Figure 4: Kinetics of pH, cell growth, sugar consumption and ethanol production from DPS based medium in scale-up condition.
Kinetics of W. anomalus X19 were performed using DPS based media in scale-up condition and several
parameters including ethanol concentration, ethanol yield and fermentation efficiency were estimated
(Table 3).
641
Fermentation parameters
Medium t (h) PE (g/L) Y E/S (g/g) FE (%)
DPS based medium 12 16.6 0.16 32.34
24 29.67 0.23 45.9
48 61.51 0.41 80.16
72 63.00 0.41 81.01
Table 3: Quantitative data originated from kinetics of W. anomalus cultivated in DPS based medium at scale-up condition. Fermentation
time (t, h), ethanol production (PE, g/L), ethanol yield (YE/S, g/g) and fermentation efficiency (FE, %). Values represent the means of
double independent experiments. Culture conditions: temperature, 30 °C ± 1 °C; agitation rate 150 rpm.
4. CONCLUSION
This study provides that the newly isolated yeast strain W. anomalus X19 can be employed efficiently in
bioethanol production. Results showed that promising ethanol yields obtained from different
fermentation cultures of DPS based medium were quite high reaching up to 80 % of the theoretically
estimated values. This demonstrated that the fresh DPS is a complete medium for alcoholic
fermentation. In addition, the unnecessary pretreatment and enzymatic hydrolysis of the sap has
promoted this substrate as an attractive feedstock. Therefore, a large amount of unexploited DPS could
serve as a new renewable feedstock for bioethanol production.
ACKNOWLEGMENTS
Dr. Georgia Antonopoulou acknowledges the financial support of the Stavros
Niarchos Foundation within the framework of the project ARCHERS (“Advancing
Young Researchers’ Human Capital in Cutting Edge Technologies in the
Preservation of Cultural Heritage and the Tackling of Societal Challenges”).
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[3] Barreveld, W. H.: Date palms products. Rome: FAO. 101 (1993).
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date palm sap (Phoenix dactylifera L.) by a proteomic approach. Food Chemistry. 123, 765-770 (2010).
[5] Brysch-Herzberg, M., Seide,l M.: Yeast diversity on grapes in two German wine growing regions. International journal of
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[6] Kurtzman, C.P., Robnett, C.J.: Identification and phylogeny of ascomycetous yeasts from analysis of nuclear large subunit
(26S) ribosomal DNA partial sequences. Antonie Van Leeuwenhoek. 73, 331–371 (1998).
[7] Fell, J.W., Boekhout, T., Fonseca, A., Scorzetti, G., Statzell-Tallman, A.: Biodiversity and systematics of basidiomycetous
yeasts as determined by large-subunit rDNA D1/D2 domain sequence analysis. Int. J. Syst. Evol. Microbiol. 50, 1351–1371
(2000).
[8] Saitou, N., Nei, M.: The neighbor-joining method: A new method for reconstructing phylogenetic trees. Mol. Biol. Evol. 4,
406–425 (1987).
[9] Tamura K., Nei M., and Kumar S.: Prospects for inferring very large phylogenies by using the neighbor-joining method.
Proceedings of the National Academy of Sciences (USA). 101, 11030-11035 (2004).
[10] Kumar S., Stecher G., Tamura K.: MEGA7: Molecular Evolutionary Genetics Analysis version 7.0 for bigger
datasets.Molecular Biology and Evolution. 33, 1870-1874 (2016).
642
[11] APHA, AWWA, WPCF: Standard methods for the examination of water and wastewater, 17th edn. APHA, AWWA,
WPCF, Washington (1989).
[12] Monlau, F., Barakat, A., Steyer, J.P., Carrere, H. Comparison of seven types of thermo-chemical pretreatments on the
structural features and anaerobic digestion of sunflower stalks. Bioresour. Technol 120, 241–247 (2012)
[13] Dubois, M., Gilles, K.A., Hamilton, J.K., Rebers, P.A., Smith, F.: Colorimetric method for determination of sugar and
related substances. Anal. Chem. 28, 350–356 (1956).
[14] Miller, G.L. Use of dinitrosalicylique acid reagent for determination of reducing sugar. Anal. Chem. 31, 426 - 428 (1959).
[15] Laopaiboon, L., Nuanpeng, S., Srinophakun, P., Klanrit, P., Laopaiboon, P.: Ethanol production from sweet sorghum
juice using very high gravity technology: effects of carbon and nitrogen supplementations. Bioresour. Technol. 100, 4176–
4182 (2009).
643
VALORISATION OF EDIBLE OIL WASTEWATER SLUDGE: BIOETHANOL AND BIODIESEL

PRODUCTION
W. NGOIE ILUNGA1,2, P. J. WELZ2, O. O. OYEKOLA1, D. IKHU-OMOREGBE1

1 Cape Peninsula University of Technology, Department of Chemical Engineering.
2 Biocatalysis & Technical Biology Research Group, Cape Town, 7585, South Africa.
Abstract
Currently, most sludge from the wastewater treatment plants of edible oil factories is disposed to
landfills, but landfill sites are finite and potential sources of environmental pollution. Production of
biodiesel from wastewater sludge can contribute to energy production and waste minimization.
However, conventional biodiesel production is energy and waste intensive. Generally, biodiesel is
produced from the transesterification reaction of oils with alcohol (i.e. Methanol, ethanol) in the
presence of a catalyst [1]. Homogeneously catalysed transesterification is the conventional approach
for large scale production of biodiesel as reaction times are relatively short. Nevertheless,
homogenous catalysis presents several challenges such as high probability of soap formation in the
presence of water and free fatty acids and difficulty of separation and reusability [2]. The current
study aimed to reuse wastewater sludge from the edible oil industry as a novel feedstock for both
monounsaturated fats and bioethanol to produce biodiesel. Preliminary results have shown that the
fatty acid profile of the oilseed wastewater sludge is favourable for biodiesel production with 48%
(w/w) monounsaturated fats and that the residue left after the extraction of fats from the sludge
contains sufficient fermentable sugars after steam explosion followed by an enzymatic hydrolysis for
the successful production of bioethanol [29% (w/w)] using a commercial strain of Saccharomyces
cerevisiae. A novel nano-magnetic catalyst was synthesised from mineral processing alkaline tailings,
mainly containing dolomite originating from cupriferous ores using a modified sol-gel technique [3].
The biodiesel produced through this green process exhibited its flash point at 61ºC with a higher
heating value (HHV) of 45.7 MJ/kg and a viscosity of 3*10-6 m2/s at 40ºCBoth the catalytic
properties and reusability of the catalyst were investigated. A maximum biodiesel yield of 78% was
obtained, which dropped to 57% after the fourth transesterification reaction cycle. The proposed
approach has the potential to reduce material costs, energy consumption and water usage
associated with conventional biodiesel production technologies. It may also mitigate the impact of
conventional biodiesel production on food and land security, while simultaneously reducing waste
[4].
References
[1] Morales et al., 2014
[2] Kiss and Boskovic, 2012
[3] (Shengyang et al., 2011
[4] Kumar et al., 2015
644
ON THE MEASUREMENT OF MAIN INORGANIC CONTAMINANTS (HCl, H2S AND NH3)

IN WASTE-DERIVED SYNGAS
V.F. DE ALMEIDA1, J. ARROYO-CAIRE 1, M. SUARÉZ-ALMEIDA 1, I. PARDO-ARIAS 1, S. NILSSON 1, P.

HARO 1, A. GÓMEZ-BAREA 1
de Ingeniería, Universidad de Sevilla, Camino de los Descubrimientos s/n. 41092 Seville, Spain.
Abstract
Solid waste gasification is a challenging process due to the high heterogeneity and high
concentration of contaminant species in these fuels [1]. From the main inorganics in the fuel (S, Cl
and N), the main pollutants found in waste-derived syngas are H2S, HCl, and both NH3 and HCN,
respectively. These contaminants should be properly measured to design a gas cleaning section able
to guarantee both legal requirements and a smooth performance of equipment (corrosion). There
are many studies in the literature that quantify HCl, H2S and NH3 and HCN during waste gasification
[2,3]. However, in most works, small amounts of these species are reported in syngas, compared to
the total contaminant input (i.e. entering with the fuel), suggesting that there might be
inconsistencies in the quantification of these species during the tests.
In this paper, the measurement of HCl, H2S and NH3 during gasification of wastes are assessed by
analysis of pilot plant data from the literature and from dedicated tests conducted in a lab-scale
reactor using a synthetic gas doped with contaminants. Data from selected papers [2-4] are used to
calculate the partitioning of the above mentioned contaminants. The lab-scale tests were conducted
at 800°C, doping the gas with typical concentrations of H2S, HCl and NH3 in syngas from gasification
of solid wastes [5] (H2S: 1000 ppmv, NH3: 50 – 300 ppmv and HCl: 30 – 250 ppmv). The influence of
the measurement method, experimental setup and reactor material (SS316, SS310, alloy C-276,
HR160, Kanthal-APM and quartz) on the quantification of the contaminants is studied. HCl and NH3
in the gas phase were collected in impingers with a proper capture solution for each species and
evaluated by ion chromatography. H2S were analyzed using a UV analyzer.
Results from the dedicated tests evidence inconsistencies with the data from the literature for the
measurement of contaminants concentrations in waste-derived syngas. Recommendations for
proper sampling and measurement of these contaminants are provided, including a method of
sampling, analysis, and for the selection of reactor material.
References
[1] Van Paasen, S.V., Cieplik, M.K. and Phokawat, N.P.: Gasification of non-woody biomass. Energy Research Centre of
the Netherlands (ECN). (2006). 
[2] Arena, U. and Di Gregorio, F.: Gasification of a solid recovered fuel in a pilot scale fluidized bed reactor. Fuel. 117,
528 – 536 (2014).
[3] Berrueco, C., Recari, J., Abelló, S., Farriol, X. and Montané, D.: Experimental Investigation of Solid Recovered Fuel
(SRF) Gasification: Effect of Temperature and Equivalence Ratio on Process Performance and Release of Minor
Contaminants. Energy & Fuels. 29, 11, 7419 – 7427 (2015).
[4] Recari, J., Berrueco, C., Abello, S., Montane, D. and Farriol, X.: Gasification of two solid recovered fuels (SRFs) in a
lab-scale fluidized bed reactor: influence of experimental conditions on process performance and release of HCl, H 2S,
HCN and NH3. Fuel Processing Technology. 142, 107 – 114 (2016).
[5] Van Paasen, S.V.B., Cieplik, M.K. and Phokawat, N.P: Gasification of non-woody biomass. Energy research Centre of
the Netherlands, ECN. (2006)
645
PYRO-GASIFICATION OF BIOMASS, BIOWASTES AND INDUSTRIAL CO-

PRODUCTS: A REVIEW ON THE PURIFICATION AND UTILIZATION OF SYNGAS
WITH DEMONSTRATIONS AT INDUSTRIAL SCALE
D. PHAM MINH1, A. NZIHOU1

1 Centre RAPSODEE, UMR CNRS 5302, Ecole des Mines d’Albi, Campus Jarlard, 81013, Albi CT
Cedex 9, France
Abstract
The valorization of biomass, biowastes and industrial co-products plays important role in the
context of the sustainable development. Up-to-date, biological and thermo-chemical
processes are the two main routes to convert these feedstocks into energy, as illustrated in
Figure 1. Biological route needs longer time and larger lands compared to thermo-chemical
route. On the other hand, thermo-chemical route consumes more energy because it is an
endothermal process.
Figure 1. Scenarios of waste and biomass valorization; (1) pyro-gasification; (2) biological treatment; (3) biogas reforming;
(4-8) syngas utilizations; (9) biogas upgrading.
During the last decades, much work has been remarked on the thermo-conversion
processes, in particular the gasification for syngas production. Syngas cleaning appears as
the first challenge for the deployment of gasification technology. As a function of
downstream applications, syngas purification has to meet strict requirements on the
composition and the quality. This work reports progress of the main processes in syngas
purification with some demonstrations at the pilot and/or industrial scale. This will helps the
scientific community to have a panorama on the current state of this research field.
646
TOXIC ANIONS REMOVAL USING LAYERED DOUBLE HYDROXIDES SYNTHESIZED FROM

SERPENTINE ORE TAILINGS AND STEEL SLAG
J. LUMSDEN1, M. VALIX1, N. MURAYAMA2

1
The University of Sydney, Sydney, NSW 2006, Australia
2
Kansai University, Osaka, 5648680, Japan
Abstract
Layered Double Hydroxides (LDHs) with high anion exchange capacities have traditionally been
synthesised from standard laboratory reagents [1]. This study investigated the production of LDHs
from industrial wastes, specifically serpentine tailings and steel slag. Millions of tonnes of solid and
liquid tailings are generated each year [2]. These are stored in heaps retained by dams in tailing
storage facilities (TSF). Failures of such dams have resulted in lasting environmental and socio-
economic consequences. Regulatory bodies and mining industries are thus seeking long term and
cost effective technologies to reduce, reuse and detoxify and stabilise these wastes [3]. The
conversion of these waste to value-added products such as LDH constitute an important initiative in
the management of mineral tailings. Two types of waste-LDHs were prepared from serpentine and
slag tailings using the co-precipitation method; Mg-Al-SO4 (serpentine-LDH) and Ca-Al-Cl (slag-LDH)
and compared with standard LDHs prepared from pure reagents. Crystal structures were compared
by thermogravimetric analysis and X-ray diffraction. Adsorption properties were established using
chromate and selenate solutions. Serpentine-LDH, at natural pH removed approximately 70% and
98% whereas reagent-LDH was able to remove 98% and 100% of chromate and selenate
respectively, Anion removal of the slag-LDH was even lower at 40% and 55% for chromate and
selenate respectively. The poorer adsorption of waste-LDHs demonstrates the importance of the
type of LDH and metal impurities (e.g., Fe) in the reaction product. Nonetheless, this study has
demonstrated that LDHs can be synthesised from mineral tailings with properties for adsorption
suitable for environmental protection application.
(a) (b)
Figure 1. Chromium adsorption at natural pH (1.5-2.0) on: a) Serpentine-Al-LHD; b) Slag-Al-LDH
References
[1] Murayama, N., Maekawa, I., Ushiro, H., Miyoshi, T., Shibata, J., Valix, M., International Journal of Mineral Processing,
2012. 110: p. 46-52.
[2] Houri, B., Legrouri, A., Barroug, A., Forano, C., Besse, J. P., Journal De Chimie Physique Et De Physico-Chimie
Biologique, 1999. 96(3): p. 455-463.
[3] Li, C., Sun, H. H., Bai, J., Li, L. T., Journal of Hazardous Materials, 2010. 174(1-3): p. 71-77.
647
VALORISATION AND EFFECTIVENESS OF USING TWO WATERWORKS RESIDUES FOR

GAS PURIFICATION
B.M. REN1,2, Y.Q. ZHAO1, N. LYCZKO 2, A. NZIHOU2

1 Centre for Water Resource Research, School of Civil Engineering, University College Dublin, Dublin,
Ireland.
2 Université de Toulouse, Mines Albi, UMR CNRS 5302, Centre RAPSODEE, Campus Jarlard, F-81013
Albi cedex 09, France.
Abstract
The Purpose of this study is to explore the reuse of alum sludge as low-cost sorbent for gas impurities
purification, thus diverting alum sludge from disposal. Alum sludge is derived from the water
treatment process when aluminium sulphate is used as coagulant for raw water purification. It is an
easily, largely, locally available by-product in waterworks in towns, cities and metropolis regions and
it has been treated worldwide as a waste for landfilling [1]. Notwithstanding it has been explored for
different reuses in recent years [2], including wastewater treatment, building & construction material,
land-based application etc., none of it was reported in the literature for its use in gas purification.
Additionally, hydrogen sulfide (H2S) is formed as a gas pollutant in different processes such as syngas
produced from gasification of biomass, particularly, it is considered the most important reason for
odour emission and corrosion in wastewater collection and treatment facilities [3].
Two sources of alum sludges were collected from the local waterworks in Dublin (Ireland) and Carmaux
(France), respectively, dried and sieved. First, syngas (40%CO + 30%H2 +15%CO2 +15%CH4) containing
200 ppmv of H2S passed through the sorbent bed with relevant flow rate. The output H2S
concentration was monitored every 10 mins using gas analyser (Micro GC). The quantity of
accumulated H2S into different sorbents was calculated. First results showed Carmaux sludge presents
better performance than Dublin sludge which is 0.71mg/g and 0.32mg/g after 140 mins, respectively.
Due to the fact that Carmaux sludge has a larger surface area (257 m 2/g) and contains various metal
elements like Al, Ca, Fe, etc. experiment will be carried out in the same operating conditions with air
contaminated with H2S. The formulation of sorbents from calcium phosphate and sludge will be
optimized and will be tested to clean the gas contaminated
In conclusion, alum sludge presents its feasibility of a low-cost sorbent as well as a proper media for
H2S adsorption. Moreover, using the waste to treat waste could be an indispensable solution for the
sustainable development. It not only opened the new prospects for the waterworks sludge
management but also in the circular approach of using in a useful way the waste from an industry for
the pollutants treatment from the same industry.
References
[1] Zhao, Y.Q., Ren, B.M., O’Brien, A. and O’Toole, S.: Using alum sludge for clay brick: an Irish investigation. International
Journal of Environmental Studies. 73 (5), 719-730 (2016)
[2] Liu, R., Zhao, Y., Sibille, C., Ren, B.: Evaluation of natural organic matter release from alum sludge reuse in wastewater
treatment and its role in P adsorption. Chemical Engineering Journal. 302, 120–127 (2016)
[3] Talaiekhozani, A., Bagheri, M., Goli, A., Talaei Khoozani, M.R.: An overview of principles of odor production, emission,
and control methods in wastewater collection and treatment systems. Journal of Environmental Management. 170,
186–206 (2016)
648
STEAM-THERMOLYSIS OF USED TIRES: INFLUENCE OF THE PROCESS OPERATING

CONDITIONS ON THE RECOVERED CARBON BLACK BULK AND SURFACE PROPERTIES
L. MOULIN1,2, E. WEISS-HORTALA2, Y. SOUDAIS2, S. DA SILVA1, R. BARNA2

1 Alpha Recyclage, 4 rue Jules Védrines, 31400 Toulouse, France.
2 Université de Toulouse, IMT Mines Albi, CNRS, Centre RAPSODEE, 81013 Albi, France.
Abstract
According to the European Tyre Recycling Association (ETRA), nearly 300 millions of waste
tires are treated in Europe each year and are subjected to legislation and regulation policies for the
re-use and recycling of 95% of the total mass of end-of-life vehicles [1]. For many years now,
thermolysis technologies have been targeted as some of the most promising alternatives for the
treatment of tires. Steam-thermolysis, a hybrid of pyrolysis and solvolysis processes, is an efficient
alternative among the thermochemical methods treating waste tires for materials recovery. The
process uses superheated steam at atmospheric pressure as an additional factor of heating the
waste tires within the reactor. This technology provides an economical and viable solution to valorize
waste tires. Recovered Carbon Black (rCB), which can be reintroduced in rubber industry as
reinforcing filler, is a more economical added value material than shredded tires.
Steam-thermolysis experiments have been performed using an original semi-continuous

laboratory-scale pilot reactor (PRITherm) developed by MARVAPOL joint laboratory between the
RAPSODEE Center of Mines Albi and ALPHA RECYCLAGE and based on previous established studies
for carbon fiber reinforced composites and waste tires [2,3]. In the present work, feedstock samples
under investigation include model laboratory N330 carbon black filled rubbers and industrial
shredded waste tires from light vehicles.
This paper aims to investigate the impact of the steam-thermolysis treatment of model
rubbers and raw waste tires on the rCB filler characteristics depending on the process operating
temperature, residence time, and carrier gas flow rate conditions. After evaluation of the
thermolysis efficiency regarding the yield, thermal behavior and toluene discoloration, the rCB
samples are characterized through their textural and structural properties, morphological features,
as well as their bulk and surface chemical composition. More conventional ASTM (American Society
for Testing and Materials) analytical techniques have also been performed. This study tends to assess
the rCB chemical surface and structural state discrepancies arising from the steam-thermolysis
process, which could lead to a modified in-rubber performance (from both rheological and
mechanical behavior).
References
[1] Shulman, V.L., European Tyre Recycling Association Conference, Introduction to tyre recycling, March 2016
[2] Sheng, Y.Y., Bounaceur, A., Soudais, Y., Barna, R.: Parameter optimization of the steam thermolysis: A process to
recover carbon fibers from polymer-matrix composites. Waste and Biomass Valor. 4(1), 73-86 (2013)
[3] Moulin, L., Da Silva, S., Bounaceur, A., Herblot, M., Soudais, Y. : Assessment of recovered carbon black obtained by
waste tires steam water thermolysis: an industrial application. Waste and Biomass Valor. (2017)
649
PRODUCTION OF FUEL BRIQUETTES FOR IMPROVED COOKING SYSTEMS: THERMO-

PHYSICAL CHARACTERIZATION, COMBUSTION, EMISSIONS AND ENERGY EFFICIENCY
OF BIOMASS CO-PRODUCTS FROM CASAMANCE REGIONS
M.S. BA1, J. DONG2, L.G. NDIAYE1, E. WEISS-HORTALA2, I. YOUM3, A. NZIHOU2

Laboratoire de Chimie et de Physique des Matériaux, Université Assane Seck, Ziguinchor, Sénégal.
. Université de Toulouse, Mines Albi, CNRS, Centre RAPSODEE, Albi, France.
2Centre d’études et de recherches sur les énergies renouvelables de Dakar, Dakar, Sénégal.
Abstract
The development of alternatives energies illustrates the common interest of all countries in reducing
greenhouse gas emissions and combating climate change. Thermochemical treatment of municipal
solid waste, agricultural and forestry wastes is a major challenge for this XXIst century to replace
petroleum fuels. Biomass (wood, agricultural residues, charcoal, etc.) and waste are the main energy
sources (70% - 90%) of West Africa population [1], depending on the country, as well as the location.
Indeed, rural and urban population accesses differently to the power grids, especially rural population
mainly uses biomass. In this context, upgrading the biomass co-products for heat production by
manufacturing combustible briquettes will preserve the environment and the ecosystem. However,
the direct use of briquettes for combustion in cooking system should be safe regarding toxic emissions
of organics, minerals and fine particles. The key issue is to design briquettes, from local resources,
which will provide healthy use.
The selected resources for the study are peanuts shells (PNS), cashew nut shells (CNS), palm nut shells
(PLS) and millet stems (MS) which are estimated to represent 159 411 – 652 655 tons of waste per
year in Senegal [2]. These resources are particularly enriched in endogenous metals (2.12wt. % -
5.47wt. % of ash for raw feedstocks). Chars have been prepared by torrefaction at 300 °C during 40
min. As the first objective is to get solid biofuel higher heating values have been determined for
feedstocks and their resulting chars. The goal of the study is to compare the emissions (CO, COV, SOx,
NOx, HCl, and dust) resulting from combustion in air atmosphere of the four chars. During combustion,
gaseous phase was bubbling into acidic solution to dissolve minerals and then the gaseous phase has
been analyzed using a micro-GC. In addition, fine particles have been collected in order to determine
their size (PM1, PM2.5 and PM10), and therefore their involvement in lung disease. Consolidating the
data of energy potential (HHV), fine particles amount and size, as well as toxic emissions, the objective
is to determine the most favored options between feedstocks to be used as solid biofuel. It has been
observed that the ashes rate, the lignocellulosic content, and the oily content have a significant impact
on emissions.
Keywords: combustion, co-products, emissions, energy delivered, char briquettes.
References
[1] J.-P. Favennec et al., « L’Energie en Afrique à l’horizon 2050 », 2009.
[2] FAOSTAT, 2015.
650
MECHANOCHEMICAL TREATMENT OF FLY ASH
Y. PENG1, M. TANG1, S. LU.1

1 Institute for Thermal Power Engineering, Zhejiang University, Hangzhou, China.
Abstract
Purpose. Mechanochemical (MC) methods have been proposed to destruct PCDD/F in the waste,
which require no heating or off-gas treatment and do not generate secondary pollution. In the
present study, the MC treatment of fly ash was carried out and the destruction efficiency was
estimated, also de novo experiments to explore the chemical reactivity of the residual carbon were
performed.
Materials and methods. The fly ash used in this experiment was sampled from the baghouse filter of
an externally circulating fluidised bed municipal solid waste incineration plant. The MC reactor is an
all-dimensional planetary ball mill and after running for specific time the sample was taken. The
concentration of PCDD/F was detected by HRGC/HRMS refer to method USEPA 1613.
Results. After 6 h of milling total concentration and I-TEQ finally reduced by 41.7% and 30.6%,
respectively. During degradation different trends appeared for PCDD/F and I-TEQ. Fig.1 shows the
tetra-octa chlorinated PCDD/F homologue profiles, both for original and MC treated FA. For the de
novo test, the total concentration and I-TEQ value for fly ash milled after 6h attains just 36.8% and
45.4%, respectively, of that obtained from raw fly ash.
FA0
2000 FA1.5
FA3
FA6
concentration(pg/g)
1500
1000
500
0
F
F
F
D
F
D
D
D
D
D
D
D
D
D
6C
7C
8C
C
C
6C
7C
8C
C
C
P5
T4
P5
T4
O
H
H
O
H
Figure 1: Homologue pattern of PCDD/F for original fly ash (FA 0) and MC treated fly ash
Conclusions. Most of the PCDD/F were removed from the fly ash by MC treatment due to the
dechlorination. And in this process amorphous and graphite-like carbon were formed, decreasing the
possibility to synthesis PCDD/F again.
References
[1] WEI, Y., YAN, J. Mechanochemical decomposition of pentachlorophenol by ball milling. JES. 21.12: 1761-1768(2009).
[2] Nomura, Y., Nakai, S., Hosomi, M.. Elucidation of degradation mechanism of dioxins during mechanochemical
treatment. ES&T, 39(10), 3799-3804(2005).
651
PCB REDUCTION/REFORMATION IN MILLED MODEL FLY ASH
ISHRAT MUBEEN1, ALFONS BUEKENS1,2, SHENGYONG LU1*, JIANHUA YAN1

1
State Key Laboratory for Clean Energy Utilization, Institute for Thermal Power Engineering,
Zhejiang University, Hangzhou 310027, China.
2
Formerly: Chemical Engineering Department, Vrije Universiteit Brussel, Brussels, Belgium.
Abstract
Polychlorinated biphenyls (PCB) are environmental pollutants and are important precursors of
polychlorinated dibenzo-p-dioxins and dibenzo-furans (PCDD/F) [1]. In present work, de novo
formation of PCB in Cu-doped model fly ash (MFA) milled for selected time, 0 (original sample), 1, 2,
4 and 8 h was studied in simulated conditions, prevailing in deposits in the heat-recovery zone of an
incinerator, where PCB and dioxins are formed and destroyed [2]. ∑PCB, ∑dl-PCB (dioxin like PCB)
and corresponding ∑I-TEQ (International Toxic Equivalents) concentrations were greatly reduced
after 8 h treatment both in gas and solid phase of MFA (see table 1). The homologue and isomer
signatures of PCB were variable in concentration, while chlorination degree (dc) successively
decreased with prolonged milling augmentation (Table 1). MFA still exhibits de novo activity after
long 8 h MC treatment and reformation of some PCB congeners was also observed, among dl-CB
erratic reformation of penta-CB, #81 was found with 1296.6% increase in concentration in solid
phase, compared to 4 h milled sample.
Table 1. dl-PCB, I-TEQ concentration and Cl-PCB of 0, 1, 2, 4 and 8 h milled samples.
–1
dl-PCB concentration (ng g )
gas solid
Time, h 0h 1h 2h 4h 8h 0h 1h 2h 4h 8h
Tetra-CB (#81) 1.4 11.2 1.0 0.1 0.0 1.6 9.4 1.2 0.0 0.3
Tetra-CB (#77) 6.2 3.4 5.5 0.3 0.2 7.4 9.6 5.9 0.4 0.1
a
Penta-CB (#123) 2.3 0.7 2.5 0.1 0.0 0.9 0.8 0.8 0.0 n.d
Penta-CB (#118) 20.0 2.3 13.5 0.7 0.5 9.0 2.6 9.0 0.4 n.d
Penta-CB (#114) 0.1 0.4 0.4 0.0 0.0 4.3 0.5 0.5 0.0 0.0
Penta-CB (#105) 8.9 2.1 2.8 0.1 0.1 5.6 2.6 8.3 0.1 0.2
Penta-CB (#126) 15.9 3.5 4.3 0.1 0.0 18.7 3.7 5.0 0.1 0.1
Hexa-CB (#167) 4.8 1.0 0.6 0.0 0.0 4.3 1.0 0.8 0.0 n.d
Hexa-CB (#156) 11.4 2.4 1.8 0.1 0.0 12.1 2.5 2.0 0.0 n.d
Hexa-CB (#157) 5.8 1.5 0.9 0.0 0.0 6.1 1.3 1.1 0.0 n.d
Hexa-CB (#169) 6.9 1.5 1.0 0.0 0.0 11.8 1.5 1.1 0.0 n.d
Hepta-CB (#189) 15.1 1.4 1.3 0.1 0.0 22.2 1.1 1.4 0.0 n.d
–1
Sum 12 dl-PCB, ng g 98.9 31.3 35.7 1.6 1.0 104 36.7 37.1 1.3 0.8
b –1
WHO-TEQ, ng TEQ g 0.8 0.1 0.7 0.0 0.0 0.4 0.2 0.4 0.0 0.0
dc (Cl-PCB) 4.3 3.3 3.2 2.9 2.8 4.6 3.0 3.1 2.6 2.6
∑PCB 2353 1174 1472 138 85 2833 809 1649 99 83
a
n.d = not detected.
b
TEQ values were calculated using WHO-TEF [3] (Van den Berg, 2006).
References
[1] Vogg, H., Stieglitz, L.: Thermal behavior of PCDD/PCDF in fly ash from municipal incinerator. Chemosphere, 15, 1373–
1378 (1986)
[2] Mubeen, I., Buekens, Chen, Z., A., Lu, S., Yan, J. : De novo formation of dioxins from milled model fly ash. Environ.
Sci. Pol. Res., 24, 19031-19043 (2017)
[3] Van den Berg, M., Birnbaum, L.S., Denison, M., et al.: The 2005 World Health Organization re-evaluation of human
and mammalian toxic equivalency factors for dioxins and dioxin-like compounds. Toxicol. Sci. 93, 223–241 (2006)
652
UNVEILING THE CONTRIBUTION OF BIOECONOMY TO CIRCULAR ECONOMY

THROUGH LIFE CYCLE THINKING
S. CORRADO1, C. CALDEIRA, 1S. SALA1.

1 European Commission, Joint Research Center, Directorate D-Sustainable Resources, Bioeconomy
Unit, Ispra, Italy.
Abstract
European policies are advocating a transition toward “bioeconomy”, an economy aiming at reducing
the dependence from fossil-based resources, limiting greenhouse gas emissions, safeguarding food
security and ensuring a sustainable economic growth. Besides, circular economy policies are aiming
at closing loop of resources as much as possible. The application of circular economy principles to
bioeconomy, namely the cascading use of bio-based waste, could represent a valuable contribution
to bioeconomy performance optimisation. However, different pathways exist for the valorisation of
a single waste [1], e.g. as energy or bio-material, and the choice of the preferable one should be
based on various criteria, e.g. economical and environmental, and may not be straightforward.
The present study aims at proposing a conceptual framework to support the selection of the most
preferable pathway for bio-waste valorisation in a circular economy perspective. The framework is
consistent with the European hierarchy for waste and with the legislative context [2]. Its
underpinning concept is the minimisation of the dissipative use of bio-resources and the
maximisation of their cascading use. The selection of the preferable pathways is based on a set of
criteria, namely compliance to the legislation, technical feasibility, environmental preferability and
economic profitability. The framework complies with the European Waste Framework directive [2]
and poses life cycle thinking at the core of the assessment processes for all the for aspects
investigated.
The proposed framework is applicable both at a plant and at the regional scales. At both levels it may
represent a valuable tool for strategic decisions and can support the challenge of unveiling the
potential of reuse and recycle of bio-waste, which is currently still little exploited, above all
concerning the use of bio-waste as source of biomaterials [3].
References
[1] Mirabella M., Castellani V., Sala S., 2014. Current options for the valorization of food manufacturing: a review.
Journal of Cleaner Production, 65: 28-41
[2] European Commission, 2008. Directive 2008/98/EC of the European Parliament and of the Council of 19 November
2008 on waste and repealing certain Directives
[3] Girotto F., Alibardi L., Cossu R., 2015. Food waste generation and industrial uses: a review. Waste Management, 45:
31-41
653
COMBINING PROCESS SIMULATION AND LIFE CYCLE ASSESSMENT FOR THE ECO-
DESIGN OF BIOREFINERY PROCESSES.
R. JULIO1, C. SABLAYROLLES1, C. VIALLE1, J. ALBET1

1 Laboratoire de Chimie Agro-industrielle (LCA), Université de Toulouse, INRA, INPT, Toulouse, France.
Abstract
Fossil resources depletion leads to base industry on sustainability and circular economy [1]. So, it is
relevant to work on the eco-design of biorefinery processes to valorize renewable resources [2], but
it requires to determine the best functioning parameters. The main limit is certainly the lack of
specific data. To face this, it is possible to couple the fields of process modelling/simulation and Life
Cycle Assessment (LCA). Simulating a process leads to obtain detailed mass and energy balances
which can be used to perform an environmental LCA, but also an economic analysis and to predict
production yields. This innovative assessment can be relevant to facilitate decision support based on
Life Cycle Thinking [3].
This innovative methodology is applied with a tool based on ProsimPlus and Simapro and is tested on
a process which valorizes wheat bran and straw by extracting and purifying hemicelluloses, used to
create biofilms. The process is composed of extrusion, centrifugation, filtration, chromatography,
precipitation and freeze drying steps. It is simulated by combining existing unit operations, such as
distillation, and newly created technologies, based on polynomial or mathematical models, such as
extrusion. Polynomial equations are obtained thanks to experimental design. LCA method is Recipe
(H) Endpoint. The functional unit is to produce 1 kg of hemicelluloses. Background data come from
Ecoinvent and Agribalyse databases. A significant improvement is that foreground data are obtained
thanks to process simulation.
Performing LCA helps to determine the most contributive steps, which are precipitation,
ultrafiltration, freeze drying and extrusion. The improvement is the determination of the best
operating conditions. For instance, extruding at low water flowrates leads to a reduction of the
environmental impacts, and to the highest production rates. Moreover, this method can be used to
quickly test and validate operating parameters sets by launching a simulation, and obtaining detailed
data on production yields, economic viability and environmental performance. Nevertheless, some
operating conditions give antagonist results in function of the objective. Highest screw rotation
speeds minimize the production costs but also reduce the production yields and increase the
environmental impacts. It highlights the importance of choosing one particular objective, because
the operating conditions of the extrusion process could strongly differ.
Coupling process modelling/simulation to LCA appears as a major accomplishment to develop
sustainable processes. It gives the potential to perform simultaneous assessments of economic,
environmental performances and productivity. It also leads to a better understanding of links
between process flowrates and environmental impacts. By predicting specific data with models
especially developed for the assessed processes, a significant progress could be performed in the
data quality.
References
[1] Clark JH, Farmer TJ, Herrero-Davila L, Sherwood J. Circular economy design considerations for research and process
development in the chemical sciences. Green Chem. 18(14):3914–34. (2016)
[2] Kamm B, Kamm M. Principles of biorefineries. Appl Microbiol Biotechnol. 64(2):137–45 (2004)
[3] Azapagic A. Sustainability considerations for integrated biorefineries. Trends Biotechnol. 32(1):1–4 (2014).
654
EMBEDDING THE PRODUCTION OF HMF INTO THE BIOREFINERY ROUTE
MARÍA TERESA MOREIRA, SARA BELLO, GUMERSINDO FEIJOO1

1
Dept. of Chemical Engineering Universidade de Santiago de Compostela
Abstract
The degradation of C6 sugars (hexoses), such as glucose, galactose or fructose gives rise to 5-
hydroxymethylfurfural (HMF). HMF is a potential substitute of petroleum based building blocks of
polymers such as polyethylene terephthalate (PET) or polybutylene terephthalate (PBT). HMF can as
well yield versatile compounds such as levulinic acid or 2,5-furandicarboxylic acid (FDCA), which is
one of the top 12 chemical building blocks according to the US Department of Energy 1.
Glucose is an abundant feedstock that can be obtained from cellulose. A reliable large-scale
production of HMF can be guaranteed if a feasible feedstock is largely available. In this sense, the
use of residual woody biomass does not compete with other markets such as food-like feedstocks
(corn, wheat, etc.).
The production pathway of this study is the synthesis of HMF within the processing of lignocellulosic
material in a biorefinery. In the case of woody biomass, the separation of wood main components
through Organosolv digestion yields cellulose, lignin and hemicelluloses. The lignocellulosic
biorefinery becomes highly resourceful, generating a wide range of value added sustainable
products, if all the wood fractions are exploited.
The HMF production route studied though life cycle assessment methodology (LCA) includes a
process with three main sections. After pretreatment of the biomass, based on Organosolv digestion
and enzymatic hydrolysis of cellulose to glucose, HMF is synthesized from the glucose solution in a
reactor with a solid catalyst (Sn20-γ-Al2Ο3) and the presence of an organic solvent (Dymethyl
sulfoxide, DMSO). Downstream processing includes a liquid-liquid extraction column with the use of
DMC (dichloromethane) and distillation unit for solvent recovery. Finally, the solid biomass residue
from the process (biotar) and natural gas are burnt in a boiler to fulfill process energy requirements2.
Inventory data considered is based on process simulation with Aspen Plus TM and covers a cradle to
gate approach. Results display the hotspots of the process, which are clearly the use of DMSO in the
synthesis section and the use of DMC in the recovery section. On the other hand, the repurpose of
the process generated solid waste, decreases environmental impacts otherwise associated to natural
gas consumption; however, the generation of heat in the boiler does not contribute greatly to global
results regarding impact categories.
One of the considerations to acknowledge, under the point of view of an integrated biorefinery, is
the percent of retrieved glucose which would be destined to HMF production and the percent
destined to fermentation for bioethanol production. Equilibrium of both processes may result in an
optimal combination, minimizing total environmental impact for an economically feasible process.
Acknowledgements
This research was supported by EnzOx2 BBI JU-Project. The authors belong to the Galician Competitive Research Group
GRC2013-032 and to the CRETUS Strategic Partnership (AGRUP2015/02). All these programmes are co-funded by FEDER
(EU).
References
[1] Top Value Added Chemicals from Biomass Volume I—Results of Screening for Potential Candidates from Sugars and
Synthesis Gas. Washington, D.C: United States. Department of Energy, 2004.
[2] M.A. Kougioumtzis, A. Marianou, K. Atsonios, C. Michailof1, N. Nikolopoulos, N. Koukouzas, K. Triantafyllidis, A.
Lappas, E. Kakaras. Production of HMF from cellulosic biomass: Experimental results and integrated process
simulation, 2017.
655
SUSTAINABILITY ANALISYS OF BIOREFINERIES FOR HIGH VALUE BIOPRODUCTS AND

BIOFUELS PRODUCTION
G. MAGAÑA1, L. AMAYA1, A. SANCHEZ2

1 Centro de Investigación y Asistencia en Tecnología y Diseño del Estado de Jalisco A.C., Unidad de
Biotecnología Industrial, Zapopan, Mexico.

2 Centro de Investigación y de Estudios Avanzados del IPN, Laboratorio de Futuros en Bioenergía,
Zapopan, Mexico.
Abstract
Purpose
Tequila industry in Mexico generates an important quantity of residues (agave bagasse and vinasses)
[1] considered as potential feedstocks for bioproducts and biofuels production due to their sugar
content and location. The implementation of biorefineries schemes for their conversion is currently
under development. Moreover, according to [2], biorefineries must be competitive, sustainable and
eco-efficient. Therefore, the assessment of these schemes takes a relevant role since their design
stage. In the present work, different perspectives were integrated for the evaluation of 4
biorefineries for bioethanol and xylitol production using the tequila industry residues.
Main materials and methods used
Based on mathematical models, a technoeconomic analysis was performed to evaluate the
biorefineries feasibility. Then, a sustainability analysis was performed applying a method based on a
process engineering approach and created for prospective technologies [3]. Economic,
environmental and social impacts were assessed with 15 indicators. The capacity for all biorefineries
was 500 ton/day. All biorefineries are based on biochemical platform (BIO1-BIO4). Two different
fermentation strategies for bioethanol and xylitol were evaluated. All schemes include an anaerobic
digester for biogas production which fuels the cogeneration stage. The generated electricity is used
in the process. BIO4 includes a biohydrogen production stage using vinasses as feedstock.
With respect to the technoeconomic analysis, BIO1 and BIO3 are considered the most feasible
biorefineries since their capital costs are significantly lower (40-50%) than those for BIO2 and BIO4,
affecting directly to the production cost. For the sustainability assessment, partial results show small
differences between BIO1 and BIO3 in the economic domain, since these indicators are associated to
the energy yields, which are higher for BIO1 (10% more). For the environmental and social domains
results favor to BIO1. The global sustainability value will define the most sustainable biorefinery.
Main conclusions of the work
Since the obtained results are not yet conclusive it is necessary to calculate the global sustainability
value. This result will also show the impact (positive or negative) of the xylitol production stage to
the biorefinery.
References
[1] Consejo regulador del tequila. Producción Total: Tequila y Tequila 100%,
https://www.crt.org.mx/EstadisticasCRTweb/. (2017).
[2] International Energy Agency. IEA Bioenergy Task 42 Biorefinery.
http://www.biorefinery.nl/fileadmin/biorefinery/docs/Brochure_Totaal_def initief_HR_opt.pdf. (2009).
[3] Sanchez, A., Magaña, G., Partida, M.I., Sanchez, S. Bi-dimensional sustainability analysis of a multi-feed biorefinery
design for biofuels co-production from lignocellulosic residues and agro-industrial wastes, Chem Eng Res Des. 107,
195-217 (2015).
656
HEALTH AND CLIMATE CO-BENEFITS OF THE RURAL RESIDENTIAL ENERGY

TRANSITION IN CHINA
S. TAO1, M.Y. RU1, W. DU1, X. ZHU1, Q.R. ZHONG1, B.G. LI1, G.F. SHEN1
1 College of Urban and Environmental Sciences, Peking University, Beijing 100871, China
Abstract
Although solid fuels are still widely used in rural China for cooking and heating, significantly
contributing to the emissions and adverse health and climate effects, a rapid transition towards
clean energy is occurring in China. However, this trend was not well recorded in mainstream
literature, leading to possible misestimations. To fill the data gap, we conducted a nationwide survey
to collect energy mix data for 34,489 households and fuel weight data for 1670 households. Here, we
present the results of the survey and a full assessment of the relative contributions of rural
residential energy consumption on emissions of various air pollutants, ambient air PM 2.5 (particulate
matter with an aerodynamic diameter of less than 2.5 m) associated premature deaths and climate
forcing in China. We found that the rural residential energy mix and consumption changed rapidly
when clean cooking energy increased from 8% to 59% and heating energy from 2% to 15% from
1992 to 2012, resulting in a significant reduction of air pollutant emissions. Among other factors, per
capita income is the leading driving force causing such changes. Consequently, the relative
contributions of rural residential emissions to mean ambient exposure PM 2.5 concentrations,
premature deaths, and climate forces decreased from 16.110.4 to 7.25.1 g/m3, from 271 (201-
417 as semi-quartile range) to 61 (47-131) thousand, and from 0.058 to 0.030 W/m2 from 1992 to
2012, respectively. Such changes vary extensively among regions and months.
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MINIMIZATION OF THE RESOURCE CONSUMPTION AND CARBON FOOTPRINT OF A

CIRCULAR ORGANIC WASTE VALORIZATION SYSTEM
S. COBO1, A. DOMINGUEZ-RAMOS1, A. IRABIEN1

1 University of Cantabria, Santander, Spain.
Abstract
The design of Circular Integrated Waste Management Systems (CIWMSs) that link resource
processing and waste treatment will enable the transition to a circular economy [1]. The goal of this
work is to determine the optimal configuration of a CIWMS that aims at valorizing the organic
fraction of the waste generated yearly in Cantabria, a region located in the northern coast of Spain,
by means of the implementation of technologies designed for nutrient and energy recovery. The
developed model describes the complete life cycle of the organic waste; it is assumed that all the
products generated from the organic waste (compost, digestate, struvite and ammonium sulphate)
are applied to land in order to grow corn. The closed-loop perspective of the system is given by the
land application of these products, which results in a reduction in the consumption of industrial
fertilizers required for the production of food, a fraction of which becomes organic waste in a later
life cycle stage.
A superstructure comprising different technologies to manage organic waste was designed, and a
Mixed Integer Linear Programming problem was formulated in GAMS v24.8.1 for the subsequent
optimization of the flows of organic matter that are sent to each technology according to the
following objective functions to be minimized: the carbon footprint, the consumption of non-
renewable raw materials and the landfill area. The mathematical model was fed with the output
data from i) the EASETECH v2.3.6 software, which enables to carry out the Life Cycle Assessment of
the waste treatment technologies based on the waste composition, and ii) the DNDC v9.5 software,
which models the carbon and nitrogen flows in agricultural ecosystems.
After verifying that a trade-off must be found to simultaneously minimize the three objective
functions, a multi-objective optimization based on the epsilon-constraint method was performed for
scenarios with different source separation rates. The results show that the combination of different
technologies is essential to achieve the optimal configuration of the system.
Future research should look into the possibility of considering economic criteria. However, it has
already been proved that the proposed methodology is a valid strategy to assist decision-makers in
the design of CIWMSs.
Reference
[1] Cobo, S., Dominguez-Ramos, A., & Irabien, A. (2017). From linear to circular integrated waste management systems:
A review of methodological approaches. Resources, Conservation and
Recycling, doi:10.1016/j.resconrec.2017.08.003.
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HOMOGENOUS HYDROTHERMAL SYNTHESIS OF CALCIUM PHOSPHATE WITH

CALCIUM CARBONATE AND CORBICULA SHELLS
H. ONODA1, S. YAMAZAKI1
1 Kyoto Prefectural University, Shimogamo-Nakaragi, Sakyo, Kyoto, 606-8522, Japan.
Abstract
Interest in new means to effectively recycle and reduce waste has increased in recent years. With
this goal in mind, researchers have previously attempted to use seashells as raw materials for
various industrial materials. Generally, the edible portion of shellfish is small, leaving a large amount
of waste after processing the animal. Seashells are also easy to gather, a favorable trait of any raw
material. At present, relatively light-toned seashells with little pigmentation (such as scallops) are
used as a calcium source. However, darker seashells with higher pigmentation (such as Corbicula, a
common food clam in Japan about 3 cm in size) are more difficult to use in this manner.
Calcium phosphate is an important substance used for many applications, such as in ion exchangers
and adsorbents. Calcium phosphates have been previously prepared from sea urchin shells and
artificial phosphorus waste fluids, where the main component of the obtained precipitate was
CaHPO4•2H2O. These precipitates contained organic coloring materials when sea urchin shells were
pre-treated through heating at low temperatures. While the coloring in sea urchin shells is very
strong, calcium phosphate produced with corbicula shells feature less coloring. Therefore, we
prepared calcium phosphate from corbicula shells and phosphoric acid in order to avoid issues
related to pigmentation [1].
The addition of urea to a solution and subsequent heating increases its pH value, as urea
decomposes to ammonia and carbon dioxide upon heating which then dissolve into the solution. As
a result, any precipitates are expected to form in a homogenous manner. In this work, this
homogenous process was used to synthesize calcium phosphate using a hydrothermal method [2,3].
Calcium carbonate and corbicula shells were treated using this homogeneous hydrothermal process
with phosphoric acid, and the obtained materials were examined in terms of chemical composition.
Calcium hydrogen phosphate and hydroxyapatite were synthesized by a homogeneous hydrothermal
process, using both commercial calcium carbonate and corbicula shell precursors. Hydroxyapatite
was easily formed under these high-temperature conditions, because the addition of urea increased
the pH of the reaction solution. The crystalline phase changed from calcium hydrogen phosphate to
hydroxyapatite in samples prepared from commercial calcium carbonate at 160 °C for 3 h. Samples
prepared from corbicula shells had weaker XRD peaks for hydroxyapatite than those prepared from
commercial calcium carbonate. These results were related to the pH of the solution after processing.
References
[1] Onoda, H., Nakanishi, H., Takenaka, A., Preparation of calcium phosphates with corbicula shells. J. Ecotech. Res.,
16(3), 85-89 (2012).
[2] Galea, L., Alexeev, D., Bohner, M., Daebelin, N., Studart, A. R., Aneziris, C. G., Graule, T., Textured and hierarchically
structured calcium phosphate ceramics blocks through hydrothermal treatment. Biomater., 67, 93-103 (2015).
[3] Faghihi-Sani, M., Arbabi, A., Mehdinezhad-Roshan, A., Crystallization of hydroxyapatite during hydrothermal
treatment on amorphous calcium phosphate layer coated by PEO technique. Ceram. Intern., 39(2), 1793-1798
(2013).
659
HYDROTHERMAL OXIDATION OF FERMENTATION SLUDGE FOR USE IN A

REGENERATIVE LIFE SUPPORT SYSTEM
D. ZHANG1, F. RONSSE1, A. LUTHER2, P. CLAUWAERT2, D. LÓPEZ BARREIRO1, W. PRINS1, D.W.F

BRILMAN3
1 Department of Biosystems Engineering, Ghent University Gent, Belgium.
2 Center for Microbial Ecology and Technology (CMET), Ghent University Gent, Belgium.
3 Sustainable Process Technology Group (SPT), Faculty of Science and Technology, University of
Twente, Enschede, the Netherlands.
Abstract
A regenerative life support system is required for its capacity to recycle carbon, nutrients and water
from waste streams in long-term human space missions. The crew and the food production from
living organisms generate several liquid and solid waste streams that, if not recycled, represent
significant sinks of carbon and (inorganic) nutrients. The European Space Agency’s Life Support
System, envisioned by the MELiSSA project, utilizes anaerobic thermophilic fermentation to degrade
organic waste. Hydrothermal oxidation was considered to further decompose these recalcitrant
constituents which end up in the digestate from anaerobic fermentation (i.e. fibers). Organic carbon
can be converted to reusable carbon dioxide by means of hydrothermal oxidation in a continuous
tubular heated reactor, operation in subcritical or supercritical water oxidation conditions, during
which nutrients are retained in the liquid effluent and nitrogen is mainly converted to ammonia.
The temperature (300 to 500℃), the residence time (tR) (1-10min) and the oxidizer equivalent ratio
(OER) (0.5 to 2) were the experimental variables. Hydrogen peroxide solution was used as the
oxidizer. A sludge obtained from the anaerobic fermentation of a model feed (wheat straw, red beet,
lettuce, fecal material and toilet paper) was used as feed to these experiments, and the
concentration was set to 2 wt% dry matter (DM). The purpose of this study was to optimize the
process conditions for complete oxidation of carbon, while retaining the nutrients in the liquid
effluent. Non-condensable gases were analysed by gas chromatography and the liquid effluent was
analysed by means of total organic carbon (TOC), nitrogen content and volatile fatty acids
concentration. GC-MS was also applied to identify any remaining organic compounds in liquid
effluent.
The highest total organic carbon removal and oxidation efficiency achieved in our tests were 98.6%
and 97.1%, respectively, with most of the nitrogen being converted to ammonia. Carbon oxidation at
supercritical conditions performed much better than at subcritical conditions. Subcritical water
oxidation resulted in the formation of char and tar. Higher temperature and OER were needed to
suppress this. However the increasing net gain in carbon removal slowed down when temperature
was raised to above 400℃ and the OER was higher than 1.5. Longer residence time(>60s) was
required only at low temperature (i.e. 300°C). Temperature just above the supercritical point was
beneficial for the ammonia recovery, while longer residence times increased carbon dioxide
formation but also enhanced ammonia decomposition. The carbon recovery from original wastes
could reach almost 100% by combining anaerobic fermentation with hydrothermal oxidation.
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Figure 1 Liquid effluents of digestate oxidation at 400°C, tR = 1min, OER being 2.0, 1.5, 1.0 and 0.5 from left to right
661
POTENTIAL OF WOOD WASTE IN PORTUGAL – A BIO-BASED ECOSYSTEM MODEL
J. COSTA1,2, A. L. FERNANDO1,*
1 MeTriCs, FCT-Universidade NOVA de Lisboa, Caparica, PortugaL.
2 Instituto Superior de Educação e Ciências, Lisboa, Portugal.
Keywords: wood wastes, bioenergy, circular economy, recycling
Abstract
The overall objective of this work was to identify, develop and fully unlock the unused wood waste
potential in Portugal, namely in Lisbon and Alentejo regions. An update of the scientific and practical
knowledge on wood waste including statistics, state of the art and best practices was performed and
based on this, a general classification of a model wood waste ecosystem was proposed.
Based on the inventory of the wood wastes in those regions, the model proposed focused on wood
recycling and cascading use in order to provide products, with added benefits towards the green and
the carbon economy and the circular economy. The model also indicates that only non-hazardous
waste wood that cannot be recycled should be used as a source of energy. Recycling through the
incorporation of more waste wood in biomaterials (such as those produced by panel manufacturers)
is promising, especially because we are assisting to a boom in the building sector along with
consumer preferences for more ecological options. Regarding contaminated waste wood, currently,
those wastes after being collected and redirected to CDR (waste-derived fuels) production units
where industrial pellets are produced. After, they are delivered to cement factories that use them in
their furnaces. Yet, additional solutions to this contaminated waste are needed once the societal
acceptability is keen on solutions addressing the bio refinery concept and not the incineration option
currently in place. Ultimately the proposed model, the knowledge, tools, mechanism and practices
identified, in close cooperation with key stakeholders, will be transferred to the studied regions
(Alentejo and Lisbon).
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1- INTRODUCTION
Wood is a versatile raw material that can be used for various applications in the paper, packaging,
furniture, and timber industries, building sector, etc. After the original use, wooden products can be
reused and recycled, and combusted in a heat and power installation or in a heat boiler. Wood
should be produced sustainably and used in the best possible way. Wood waste valorisation includes
fossil/mineral product substitution, product reuse and material recycling. Each of these aspects
present specific impacts to targets in the field of CO2 reduction, carbon storage, resource efficiency
and resource productivity.
Therefore, the overall objective of this work was to identify, develop and fully unlock the unused
wood waste potential in Portugal, namely in Lisbon and Alentejo regions. Both regions are focused
in the circular economy, to reduce wastes, and on the green and carbon economy, to develop energy
production systems from renewable sources and to create added value to wastes in a biorefinery
concept. The information collected in both regions, and based on identified best practices and
success factors among other European regions, a model wood waste ecosystem will be proposed.

An update of the scientific and practical knowledge on wood waste in the regions of Lisbon and
Alentejo, in Portugal, including statistics, state of the art and best practices was performed and
based on this, a general classification of a model wood waste ecosystem was proposed. Figure 1
shows the map of the studied regions.
Figure 1: Map of the regions of Portugal that will be studied: Lisbon and Alentejo.

Concerning wood waste management activities, there is not a clear panorama of how those wastes
are being managed by each region and how these wastes are treated. Most of the information
related with wood waste is given for the country, but some estimation can be done for each region
based on the sectorial activities linked with wood. However, given the structure of the current waste
management activities in each region, it is plausible that wood waste management activities follow a
similar pattern to the one described for the entire country. There is also not a clear strategy in each
region for the management of wood waste. As it is also observed for other wastes, each region
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follows a national strategy described in the national plan for the management of wastes (PNGR -
Plano Nacional de Gestão de Resíduos).
3.1-Wood waste characteristics

The total amount of wood waste produced in Portugal, in 2014, was 0.27 million tons, which
corresponds to only 3.3% of the total waste being collected in Portugal. In the region of Lisbon, 67
thousand tons of wood waste were produced (equivalent to 0.81% of the total waste produced in
Portugal and to 25% of the total wood waste being produced in Portugal). In the region of Alentejo,
only 27 thousand tons of wood waste was produced (equivalent to 0.32% of the total waste
produced in Portugal and to 10% of the total wood waste being produced in Portugal 1 .
Most of the wood waste source in Portugal comes from the commercial and industrial use (150
thousand tons, equivalent to 55% of the total wood waste produced). But there is no precise
knowledge on the amount of the commercial and industrial wood waste being produced in the
regions of Alentejo and Lisbon. It was estimated, based on the number of industries and activities in
both regions, that Lisbon region produces 42 thousand tons of commercial and industrial wood
waste (62% of the total wood waste being produced in Lisbon), and that Alentejo region produces 10
thousand tons of commercial and industrial wood waste (39% of the total wood waste being
produced in Alentejo). The amount of wood waste from municipal collection in Portugal accounts for
44 thousand tons (16% of the total wood waste being produced in Portugal). In Lisbon region the
amount of wood waste from municipal collection is only 4 thousand tons (6% of the total wood
waste being produced in Lisbon). In Alentejo region the amount of wood waste from municipal
collection is 11 thousand tons (41% of the total wood waste being produced in Alentejo). The source
of municipal wood waste in each region is known because it is linked with companies that collect
wastes. Wood waste from construction and demolition activities is residual, only 11 thousand tons
were produced in Portugal in 2014 (4% in total wood waste produced in Portugal). However there is
no clear information on the amount of these wood wastes being produced in Alentejo and Lisbon.
Based on the business activities in this sector it was estimated a production of 3 thousand tons of
wood waste from construction and demolition activities in Lisbon region (4% of the total wood waste
produced in this region) and 750 tons in Alentejo region (3% of the total wood waste produced in
this region). Wood waste from other sources accounts for 68 thousand tons in Portugal (25% of the
total wood waste being produced in Portugal). There is also no information on the amounts being
produced by other sources in Lisbon and Alentejo region. So, an estimation was made based on the
business activities. The estimation accounts for 19 thousand tons being produced in Lisbon (28% of
the total produced in this region) and only 5 thousand tons in Alentejo (17% of the total wood waste
being produced in this region). There is some information on the collection of the wood waste per
sectorial activity in Portugal but not in the regions of Alentejo and Lisbon. Table 1 provides this
information.
The information about the wood waste from packaging is inconsistent when looking into the
different data obtained by several administrative offices, and at this stage it was decided not to
provided it. The information about the municipal wood waste is not defined per code, however the
statistics indicate a total of 44 thousand tons being produced (equivalent to 16% of the total wood
waste produced in Portugal).
Regarding the quality of wood wastes the only classification that currently exists is the separation
between non-hazardous and hazardous wood wastes. The production of hazardous wood waste
(wood waste that needs treatment or that it goes to landfill) is low. In Portugal a total of 299 tons of
hazardous wood waste were produced. In the regions of Lisbon, 83 tons, and in Alentejo region only
21 tons. The percentage of hazardous wood wastes is therefore also very low, only 0.1%, either in
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average Portugal and in the regions of Lisbon and Algarve, regarding the total amount of wood waste
being produced.
Sectorial activities Waste wood (t) Percentage to total

wood waste produced
in Portugal
Wood transformation: 03 01 01 47 925 17.5
sawmill, panel industry, 03 01 04 248 0.1
carpentries, joineries… 03 01 05 30 347 11.1
78 520 28.8
Building, demolition 17 02 01 10 902 4.0
17 02 04 12 0.004
10 914 4.0
Waste management 19 12 06 21 0.008
plant 19 12 07 67190 24.6
67211 24.6
Table 1: Wood waste generated in 2014 in Portugal per sectorial activities 1 (in red the hazardous wood wastes)
3.2- Available art technologies related to the different uses of wood waste
The recovery of the wood wastes is high. On average in Portugal, 89% is being recovered. But
information relating the amount being recovered per region is lacking. However, there is no
knowledge on how the wood waste is being reused to more than half of the wood waste recovered
(156 thousand tons, 57% of the total wood waste). Yet, knowledge of the behaviour of the
Portuguese population, indicates that part of those wastes and being reused either for household
storage or in home heating systems. Reuse of wood waste as material represents 28% of the total
wood waste being produced in Portugal (77 thousand tons). Statistics of Portugal indicate that 10
thousand tons of wood waste are being recovered for energy (3.5% of the total wood waste) 1 . Yet,
part of the collected wood waste with unknown use is in fact being used for energy (especially in
households).
Regarding the treatment options, especially to the hazardous wood waste, there is currently a survey
being done to obtain this information in the processing units that are receiving and collecting these
type of wastes.
3.2.1-Operational knowledge
There is in Portugal several facilities that can receive wood waste and provide added value to it and
when no other reuse is possible, landfill is also an option [2].
In 2014, 32 landfills were active in Portugal with a capacity of 23.3 billion tons. In Lisbon region there
are 4 active landfill and in Alentejo 5 active landfill.
To receive the wood wastes for recycling and treatment there are in the country several ecocenters.
In the region of Lisbon there are 17 ecocenters, in the region of Alentejo there are 24 ecocenters.
To organically valorize the wood wastes, there are currently in Lisbon region five units working and
in Alentejo 3 units working. In Lisbon, 2 units are centers for mechanical and biological treatment of
wastes (anaerobic digestion and compost), 2 units are centers for mechanical and biological
treatment of wastes (compost), and 1 unit is a center for biological treatment of wastes (anaerobic
digestion and compost). In Alentejo, 1 unit is a center for mechanical and biological treatment of
665
wastes (anaerobic digestion and compost) and 2 units are centers for mechanical and biological
treatment of wastes (compost).
To treat the hazardous wastes there are 2 enterprises in Portugal that have competences to do it.
Both are located in the central part of the country (Chamusca, Santarém), located 50-150 km to
Lisbon and Alentejo regions. In the region of Lisbon 4 incinerators are active to receive and
incinerate hazardous wastes. In the region of Alentejo there are no facilities to incinerate hazardous
wastes.
In order to valorize the wood waste to materials there are currently in Lisbon region 4 pellet and
briquettes companies and 29 wood panel industries. In Alentejo, there are 3 pellet companies and 2
wood panel industries. In the North of Portugal (Mortágua), located 200 km to Lisbon and Alentejo
region, there is a biomass power plant (10MW) that receives mostly forest residues. In Lisbon and
Alentejo region there are other biomass power plants (0.1 MW) but those power plants are linked to
companies are functioning with biomass wastes from those companies (e.g, in Alentejo, with olive oil
wastes).
The most problematic issues encountered in Portugal, regarding wood waste, is the reuse of
hazardous wood waste as non-hazardous wood waste. Deleterious emissions can be a problem and
population health can be affected.
3.3-Most developed sector in wood waste management

Wood waste management is not well developed in both regions and in Portugal. However, it is well
known that wastes (non-hazardous) from wood transformation: sawmill, panel industry, carpentries,
joineries…are collected and reused for the production of pellets, briquettes as well as wood panels.
This sector is well organized in order to reuse as much as possible and add value to the wastes.
3.3- Bio-based ecosystem model

According to national rules, there are commitments to recycle wood packaging and to make use of
wood waste. Concerning non-contaminated wood waste, traditionally, those are reused for pellets
and energy or incorporated in new materials (such as panel board). Concerning contaminated wood
waste: it is mandatory that those wastes are channeled to CDR (waste-derived fuels) production
units where industrial pellets are produced. These industrial pellets are delivered to cement factories
that have the licence, and are certified, to use them in their furnaces. The aim is not to deliver those
wastes to landfill. Several companies work in this field (collecting, reusing and recycling) but at the
national level not at the regional level, due to the dimension of the country. The collected wood
waste is mostly coming from municipal or industrial sources.
Potential for development effective industrial wood waste ecosystem in Lisbon and Alentejo regions
is high. Either in Lisbon and in Alentejo, there are several academic and scientific institutions that can
help municipalities and entrepeneurs to improve management of wood waste. Both regions are
focused in the circular economy, to reduce wastes, and on the green and carbon economy, to
develop energy production systems from renewable sources and to create added value to wastes in
a biorefinery concept.
In both regions but especially in Alentejo region due to its rurality, there is still potential to collect
more waste wood waste from households. To improve the household collection of wood waste, the
BioReg project in partnership with both municipalities, associations and entrepeneurs will address
this issue.
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Regarding the industrial and municipal wood waste, options for improvement are not so much
related with amount collected (although still it can be improved) but to how it can be reused,
recycled and valorized.
There are still options for improvement regarding the knowledge on how the wood waste that is
being collected is reused and recycled. Knowledge on the regional status of those wood wastes
would help to define strategies. Moreover, concerning the non-hazardous wood wastes, and based
on the information obtained from the model regions (in Germany, Italy, Sweden, Austria and
England), it was identified that the current use of wood wastes for pellets, energy and materials
(such as panel board), can be also improved. It was identified also that wood recycling and cascading
use are some topics that are wide open to innovative solutions that can provide excellent products,
with added benefits towards the green and the carbon economy and the circular economy.
However, these new and innovative solutions should be sustainable, not only from the economic
point of view but also environmentally and socially. Only non-hazardous waste wood that cannot be
recycled should be used as a source of energy and this information should be better transmitted to
the different stakeholders and nationwide. Stressing that recycling is mandatory to prolong the life
of the forest, and allows carbon to be kept preserved should be campaigned to reach a wider
audience. Recycling through the incorporation of more waste wood in biomaterials (such as those
produced by panel manufacturers) is promising, especially because we are assisting to a boom in the
building sector along with consumer preferences for more ecological options. It can be also
highlighted that some objectives for the sector should be imposed. If the municipalities adhere,
objectives could be given per region. BioReg project could be a tool to link stakeholders and to
improve discussions in this field.
Regarding contaminated waste wood, the information gather indicates that, currently those wastes
after being collected they are channelled to CDR (waste-derived fuels) production units where
industrial pellets are produced. These industrial pellets are delivered to cement factories that have
the licence, and are certified, to use them in their furnaces. Yet, experts are warning to the necessity
to find additional solutions to this contaminated waste. In fact, the amount of hazardous wastes
(where wood wastes are included) exceed the capacity and the needs of the cement factories and
incinerators available in the country which causes market prices to be controlled by those
incinerators and cement factories. Representatives of entrepreneurs from CDR’s production units
are already in association trying to overcome this problem. Suggestions made are linked with the
hypothesis to resuse those wastes in a cascading use. In addition, societal acceptability is keen on
solutions addressing the bio refinery concept and not the incineration option currently in place.
The BioReg project and the solutions presented by the model regions can also provide additional
information for the different stakeholders. But those solutions presented by the model regions need
to be further evaluated by the different stakeholders with care, in order to understand if they fit the
Alentejo and Lisbon regions situation. Adjustments of some regulatory frameworks adapted to wood
waste are also highlighted as hypothesis following some examples from other countries in the
European Union limits.
Barriers to improve solutions to recycle and reuse more wood waste are majorly connected with the
investments needed and the operating costs. On the other hand, innovative solutions require
specialized personnel which can also contribute to reduce the exodus of skilled persons from regions
such as Alentejo.
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4- CONCLUSIONS
Lisbon and Alentejo regions present a great potential for bio-economy development. They have
available plants for the exploitation of the wood, either for material, energy or to landfill. But,
management of those wastes in each region needs to be improved.
Knowledge on the amount of wood wastes being produced in both regions, either non-hazardous
and hazardous wastes is existing. But, information related with the wood waste sources in each
region, as well as the type of recovery in each region, is missing. Information on what type of
recovery is being used for each type of wood waste source exits but this information is given to the
country and not to each region. Knowledge about the treatments applied to hazardous wastes is also
needed. The better knowledge of the wood waste panorama in each region, will help to suggest
options for improvement regarding wood waste use and applications. For that reason the regions
studied in Portugal can use and effectuate good practices and solutions from the model regions. For
this, it is mandatory that more data of wood wastes in those regions need to be collected, a task that
will be continuously updated until the end of the BioReg project, by cross linking data from
companies with data from statistics.
REFERENCES
[1] INE: Estatísticas dos Resíduos 2014 (2016), available at www.ine.pt
[2] APA: Relatório Anual de resíduos Urbanos 2015. Agência Portuguesa do Ambiente (2016), available at
www.apambiente.pt)
ACKNOWLEDGEMENTS
This work was supported by the European Union (BIOREG - Absorbing the Potential of Wood Waste
in EU Regions and Industrial Bio-based Ecosystems (Project Number: 727958, H2020-BB-06-2016).
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OPTIMISATION OF A DISSOLVING PULP BLEACHING SEQUENCE TOWARDS ITS

VALORISATION
C. ARCE1, T. LLANO1, G. RUIZ1, N. CHENNA2, A. COZ1

1 Department of Chemistry and Process & Resource Engineering, Green Engineering and Research
Group, University of Cantabria, Avda. Los Castros s/n, Santander 39005 Cantabria, Spain.
2 MillWide NCG Solutions group, Valmet Technologies Oy, Tampere, Finland.
Abstract
Dissolving pulp is a high-purity cellulose (90 to 98 %) and can achieve very high brightness (> 90 %
ISO). The market demand for dissolving pulp has been constantly growing around the world for the
past decade, particularly in China [1]. Dissolving pulp can be also valorised to produce several
different raw materials that can be used in applications such as food packaging, additives, filters,
clothing and paints, among others [2]. In the production of dissolving pulp, bleaching is a critical
process that not only increases brightness, but also increases purity, adjusts the viscosity and
molecular weight distribution of the cellulose [3] and allows it to meet the requirements of end-use
products such as viscose, acetates, cellulose nitrate or cellulose ether [4].
The aim of the present work is to investigate the optimal bleaching conditions for the dissolving pulp
that can be used as raw material for valorisation. The cellulose raw material was obtained from a
sulphite pulp mill and a two-stage bleaching sequence was applied, which were: alkaline extraction
(EOP) and hydrogen peroxide (PO). To achieve the objective, bleaching experiments were done
varying four process variables: NaOH and H2O2 dosages, time and temperature. Bleaching
experiments were performed in two stainless-steel 1L reactors. Bleached pulp quality were
performed as specified in Tappi and ISO standards. Alfa-celullose, lignin (as kappa number), viscosity
and brightness were analysed.
The obtained bleaching sequence parameters were optimised with Aspen Custom Modeler and
GAMS. Two regenerated cellulose products: viscose and cellulose acetate were considered as
valorisation alternatives, to fix the restrictions of the mathematical model.
The results fitted well with the second-order polynomial equations, giving R2-values between 0.88
and 0.987. Pareto charts were plotted so, it was possible to obtain which variables influenced the
pulp quality the most. With the results obtained, it was possible to determine the most influencing
variables in both stages of the bleaching process which were NaOH and H 2O2 dosages in the EOP
stage; time and temperature in the PO stage. However, the response variables viscosity and
brightness, in the PO stage, were most influenced by time and H2O2 dosage and temperature and
H2O2 dosage respectively. Finally, the optimisation was obtained based on the final quality
parameters of pulp that is required for cellulose acetate and rayon production.
References
[1] Llano, T., Arce, C., Coz, A. Dissolving pulp quality during alkaline extraction and peroxide bleaching steps. COST
ACTION FP 1205 Training School. Postdam (2017)
[2] Strunk, P. Characterization of cellulose pulps and the influence of their properties on the influences of their
properties on the process and production of viscose and cellulose ethers. (2012)
[3] Liu, Y., Shi, L., Cheng, D., He, Z. Dissolving Pulp Market and Technologies: Chinese Prospective A Mini Review.
Bioresources, 11, 7902-7916 (2016).
[4] Ji, L., Zhao, L. Current situation and future trend of the dissolving market in domestic and international. China Pulp
Paper Industry, 36, 41-45 (2015).
669
CATALYTIC HYDRODEOXYGENATION OF NAPIER GRASS PYROLYTIC OIL VIA IN-SITU

HYDROGEN GENERATION
I.Y. MOHAMMED1, 4, Y.A. ABAKR1, F.K. KAZI2, R. MOKAYA3
1 Department of Mechanical, Manufacturing and Materials Engineering, the University of
Nottingham Malaysia Campus, Jalan Broga, Semenyih 43500, Selangor, Darul Eshan, Malaysia.
2 Department of Engineering and Mathematics, Sheffield Hallam University, City Campus, Howard
Street, Sheffield S1 1WB, United Kingdom.

3 School of Chemistry, University of Nottingham, University Park, Nottingham NG7 2RD, United
Kingdom
4 Department of Chemical Engineering, Abubakar Tafawa Balewa University Bauchi Nigeria.
Keywords: Napier grass, Pyrolytic oil, Catalyst, hydrogenation
Abstract
The global concerns over the emission of greenhouse gases from the use of fossil-based fuels and their
impacts on the environment is an unresolved issue. Biomass from non-food crops cultivated on lands
that are increasingly marginal for more favoured major crops are potential source of sustainable
renewable energy. Pyrolysis of biomass produces liquid product called pyrolytic oil, a complex mixture
of oxygenated organic compounds with traces of nitrogen and sulfur containing chemical species. The
high level of the oxygenated compound in the oil makes it unsuitable in most cases for direct
application as fuel or refinery-ready feedstock for fuel production. Hydroprocessing of pyrolytic oil
generally requires a significant amount of hydrogen to produce deoxygenated oil. This makes the
process expensive for industrial scale application. This study presents transformation of crude organic
phase pyrolytic oil derived from Napier grass into high-grade biofuel precursors via
hydrodeoxygenation reaction over platinum and palladium catalysts with in-situ hydrogen generation
from methanol. The reaction was conducted in a high-pressure stainless steel batch reactor (50 mL
stainless steel Swagelok double-ended, 98.6 mm and 2.4 mm wall thickness) at 350 oC, 20 wt%
methanol ratio, 2 wt% catalyst loading and 60 min reaction time. Analysis of the organic liquid products
collected over palladium showed superior fuel quality compared to similar product obtained with the
platinum catalyst. Carbon monoxide, carbon dioxide, hydrogen and methane were the major
components in the gas products. This suggests that the upgrading process proceeded via multiple
reactions such as hydrodeoxygenation, hydrogenation, hydrocracking, decarbonylation and
decarboxylation. The overall characteristics of the upgraded organic liquid products processed with
both catalysts are much comparable to that of fuel oil. Consequently, this study has demonstrated
that deoxygenation of pyrolytic oil over palladium and platinum catalysts with 20 wt% methanol is
sufficient to produce deoxygenated pyrolytic oil with high fuel quality.
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1- INTRODUCTION
Bioenergy systems offer significant possibilities for reducing greenhouse gas emissions due to their
immense potential to replace fossil-based fuels in energy production. Lignocellulosic biomass from
non-food crops cultivated on lands that are increasingly marginal for more favoured major crops are
potential source of sustainable renewable energy. Napier grass is one of the underutilised energy
crops with high biomass yield and low establishment cost. It requires little or no nutrient input with
typical biomass yield of 25-35 oven dry tonnes/hectare [1], making it one of the most promising
bioenergy feedstocks. Biomass conversion via thermochemical process such as pyrolysis represent a
sustainable approach towards reducing the reliance on fossil fuels as it can handle any biomass
feedstock and capable of producing high liquid yield [2]. Valorisation of Napier grass into pyrolytic oil
has been reported in the literature. The results from these studies showed the yield of pyrolytic oil
typically in the range of 35-60 wt% depending the type of pyrolysis process, reactor type and process
variables used [2-4]. Generally, pyrolytic oil is produced in two phases, organic phase and aqueous
phase. The organic phase contains water-insoluble high molecular weight components and represent
the most valuable precursor for the production of liquid biofuel. Upgrading of Napier grass pyrolytic
oil via catalytic cracking has been reported recently [5, 6]. The results revealed that the upgrading
process proceed via decarboxylation, decarbonylation, dehydration, cracking, aromatization and
oligomerisation reactions, which produced about 38 wt% light fraction and 48 wt% middle distillate
biofuels with physicochemical characteristics comparable to similar fossil-based fractions. The authors
reported that process variables such as reaction time, temperature and catalyst loading represent the
key parameters for the production of high quality biofuel.
Catalytic hydroprocessing on the other hand modifies pyrolytic oil into biofuel via catalytic
hydrocracking, hydrodeoxygenation and hydrotreatment with improved physicochemical properties.
Studies by Ahmadi et al. [7] on hydrodeoxygenation of fast pyrolysis oil in supercritical ethanol over
nano-structured CoMo catalysts revealed that high liquid yield of approximately 58-62 wt% with high
hydrogen and carbon contents can be obtained at reaction temperature between 300 and 350 oC.
Mortensen et al. [8] reported hydrodeoxygenation of phenol as a model bio-oil compound over
Ni/SiO2. The author revealed that hydrodeoxygenation reaction proceeds via hydrogenation of the
aromatic ring into cyclohexanol followed by deoxygenation reaction. They investigated the effect of
nickel particle size on the hydrodeoxygenation reaction and found that intermediate nickel particle
size is required for optimal phenol hydrodeoxygenation over Ni/SiO2 at temperature below 300 °C.
Recent review by Patel and Kumar [9] has highlighted production of renewable diesel through the
hydroprocessing of lignocellulosic biomass-derived bio-oil. However, the authors identified catalyst
deactivation and lack of comprehensive techno-economic assessments of the whole pathway remains
a challenge. Hydroprocessing of pyrolytic oil requires significant amount of hydrogen to produce
deoxygenated bio-oil with high fuel quality. This makes the process expensive for industrial scale
application [10]. Upgrading of pyrolytic oil via catalytic hydrodeoxygenation with in-situ hydrogen
generation has been proposed in the past decade. Most researchers have focused on the use of
synthetic or model pyrolytic oil compounds as a basis for evaluating the catalyst performance. Tan et
al. [11] reported upgrading of phenol and furfural as bio-oil model compound over Pd and Pt based
catalysts using formic acid and acetic acid as in-situ hydrogen sources. Cyclohexene was identified as
the major product and they concluded that phenol can be transformed into hydrocarbon with in-situ
hydrogen generation from formic acid and acetic acid. The authors stated that the conversion pathway
proceeded through formation of cyclohexanone followed by hydrogenation to cyclohexanol and
subsequent dehydration to cyclohexene. Feng et al. [12] reported in-situ hydrodeoxygenation of
biomass-derived phenolic compounds with methanol-water as hydrogen donors over Raney Ni and
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HZSM-5 as bifunctional catalysts. They observed that more than 90 % conversion of the phenolic
compound was achieved with high selectivity of 70-90 % for cyclohexanes and hydrocarbon formation.
The reaction pathway was said to have proceeded via stepwise metal-catalysed hydrogenation, acid-
catalysed dehydration, and metal-catalysed hydrolysis. Xu et al. [13] studied in-situ hydrogenation of
both model compounds and a typical raw bio-oil over Ni/CMK-3 catalyst with hydrogen donors from
methanol, ethanol and formic acid. They reported that alcohol hydrogen donors promoted
esterification reaction while formic acid enhanced the conversion of phenol. They observed that most
carbonyl compounds such as ketones and aldehydes in the raw bio-oil were converted to alcohols and
more than 50 % conversion of acids and phenols was archived. In-situ hydrodeoxygenation pyrolytic
oil derived from pine sawdust to hydrocarbon biofuel over Pd/C catalyst was recently reported by
Cheng et al. [14]. The authors observed that the physicochemical properties such as calorific value,
total acid number and chemical compositions of the produced biofuels improved significantly relative
to the characteristics of the feed bio-oil. To date, studies on catalytic hydrodeoxygenation of a typical
Napier grass pyrolytic oil has not been reported in the literature. The objective of this study was to
evaluate hydrodeoxygenation of Napier grass pyrolytic oil over Pd/C and Pt/C into high-grade biofuel
with in-situ hydrogen generation from methanol.

The crude organic phase pyrolytic oil used in this study was obtained from pyrolysis Napier grass in a
vertical fixed bed reactor at 600 °C, 50 °C/min under 5 L/min nitrogen atmosphere and its
physicochemical properties and chemical composition are summerised in Table 1.
Physicochemical property Value

Density (g/cm3) 0.98
HHV (MJ/kg) 29.18
Carbon (wt %) 53.87
Hydrogen (wt %) 6.45
Nitrogen (wt %) 1.35
Sulphur (wt %) 0.76
Oxygen (wt %) 37.57
Chemical composition (% Area)*
ALHC 4.67
ARHC 2.53
PHOL 28.15
MTPHOL 37.87
MARHC 2.18
AAK 16.88
IMDZL 3.05
EST 4.68
Table 1: Physicochemical property and chemical composition of raw pyrolytic oil. *Chemical composition of the pyrolytic oil is based on
GC-MS percentage peak area. (ALHC) Aliphatic hydrocarbon, (ARHC) aromatic hydrocarbon, (PHOL) normal phenol, (MTPHOL) methoxy
phenol, (MARHC) methoxy aromatic, (AAK) acids, ketones, aldehydes, (IMDZL) imidazole and (EST) esters [2,5,6]
Palladium and platinum catalysts, 10% on carbon each were purchased from Merck Sdn. Bhd.
(Selangor, Malaysia). Scanning electron microscopy-energy dispersive x-ray (SEM-EDX) (FEI Quanta
400 FE-SEM, Hillsboro, USA) and physisorption analyser (ASAP 2020, Micrometrics, Norcross, USA)
were used to establish the structural, surface and compositional characteristics of the catalysts. In-situ
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catalytic hydrodeoxygenation study was performed in a laboratory scale upgrading rig as shown in
Figure 1.
Figure 1: Schematic diagram of a laboratory scale pyrolytic oil upgrading rig.
The system consist of a 50 mL (98.6 mm and 2.4 mm thickness) high-pressure stainless steel Swagelok
double-ended tube reactor. Pyrolytic oil sample (30 g) was mixed with 2 wt% methanol (99.9 % purity,
Merck Sdn. Bhd. Malaysia), 2 wt% catalyst and the mixture was transferred in to the reactor. The
system was purged with nitrogen (99.9% purity, Linde Gases Sdn. Bhd. Malaysia) for few minutes and
later sealed up with fittings. The reactor was heated electrically at 50 oC/min to 350 oC for 60 minutes
reaction time. Subsequently, the power supply was shutdown and the setup allowed to cool to room
temperature. The reactor was depressurised and its contents were collected, weighed and analysed
accordingly. Phase separation was carried out using centrifuge (Eppendorf™ 5430, Fisher Scientific
Sdn. Bhd. Malaysia) at 6500 rpm for 12 min. The reactor was carefully cleaned with solvent (acetone)
and the material recovered was mixed with remnant semi-solid (solid and tar) in the separation tube.
Solid component was separated in vacuum filtration assembly with the aid of sartolon polyamide filter
paper (0.45µm pore size), washed with acetone and oven dried at 60 oC overnight. The total liquid,
organic, aqueous, solid and gas yield were computed using according to the individual equation below.
The experiment was repeated three times and standard deviations were computed.
𝑊𝑇𝐿𝑃 = (𝑊𝑅2 − 𝑊𝑅1 ) + 𝑊𝐴𝐶𝑄 − 𝑊𝑇𝑆𝐿𝐷 (1)
𝑊𝑇𝐿𝑃
𝑌𝑖𝑒𝑙𝑑 (%) 𝑇𝐿𝑃 = [ ] × 100 (2)
𝑊𝑇𝐿𝐹
𝑊𝐴𝐶𝑄
𝑌𝑖𝑒𝑙𝑑 (%)𝐴𝐶𝑄 = [ ] × 100 (3)
𝑊𝑇𝐿𝐹
673
𝑌𝑖𝑒𝑙𝑑 (%)𝑂𝐿𝑃 = 𝑌𝑖𝑒𝑙𝑑 (%) 𝑇𝐿𝑃 − 𝑌𝑖𝑒𝑙𝑑 (%)𝐴𝐶𝑄 (4)
𝑊𝑇𝑆𝐿𝐷 − 𝑊𝐼𝐶
𝑌𝑖𝑒𝑙𝑑 (%)𝐶𝑂𝐾𝐸 = [ ] × 100 (5)
𝑊𝑇𝐿𝐹
𝑌𝑖𝑒𝑙𝑑 (%)𝐺𝑃 = 100 − [𝑌𝑖𝑒𝑙𝑑 (%) 𝑇𝐿𝑃 + 𝑌𝑖𝑒𝑙𝑑 (%)𝑆𝐿𝐷 ] (6)

Where W is the weight (g) and the subscript TLP, R2, R1, TLF, ACQ, OLP, TSLD, IC and GP is the total liquid product, reactor and its
content, empty reactor, total liquid feed (pyrolytic oil + methanol) , aqueous phase, organic liquid product, total solid product, coke
yield, initial catalyst and gas product respectively.
Liquid product characteristics using standard analytical instruments. Calorific value was determined
with an oxygen bomb calorimeter (Parr 6100, Parr Instruments, Molin, USA). Elemental composition
was determined using a CHNS/O analyser (2400 Series II CHNS/O analyser, Perkin Elmer Sdn Bhd,
Selangor, Malaysia) Analysis of the gas products was carried out in a gas chromatography (PerkinElmer
Clarus 500, Akron, USA) equipped with a stainless steel column (Porapak R 80/100) and thermal
conductivity detector (TCD). Helium was used as a carrier gas and the GC was programed at 60 °C oven
temperature and injector and TCD temperature was maintained at 80 °C and 200 °C respectively.

Textural characteristics of the catalysts are summerised in Table 2. Pd/C has larger BET and micro
surface area compared to Pt/C with a better mesoporous surface area. Both catalysts exhibited
relatively similar pore volume and pore diameter. Figure 2a shows the nitrogen adsorption-desorption
isotherms from the physisorption analysis, which indicate that both catalysts have combination of type
I and IV isotherm based on the IUPAC classification with initial region of reversible micropore filling,
and multilayer physisorption and capillary condensations at relative pressure above 0.45, a typical
characteristics of a mesoporous material with micro structures [15]. Both materials also displayed a
type H4 hysteresis loop, usually associated with narrow slit-like pores [16-18]. This observation is in
good agreement with the SEM images in Figure 2b, showing the individual active specie (Pd, Pt)
dispersed on the carbon slit-like pores Elemental mapping (figure 2c) from the EDX study confirmed
that the material constitute majorly carbon and the active species.
Catalyst (SBET)1 (Smicro)2 (Smeso)3 (Vmicro)2 (Vmeso)3 Dpore

Surface area (m2/g) pore volume (cm3/g) pore diameter(nm)
Pd/C 851.47 458.73 344.25 0.21 0.44 5.11
Pt/C 780.99 381.49 369.07 0.18 0.50 5.45
Table 2: textural characteristics of the catalyst. 1Brunauer–Emmett–Teller (BET) method, 2t-plot method, 3Barrett, Joyner and Halenda
(BJH) method
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Figure 2: Characteristics of Pd/C and Pt/C catalyst obtained from (a) physisorption, (b) SEM and (c) EDX.
In-situ hydrodeoxygenation product distribution is shown in Figure 3. Thermal hydrodeoxygenation of

the pyrolytic oil was first conducted under the same condition without any catalyst loading and is used
as a control for evaluation of thermal effect on the process. Under this condition, the total liquid (TLP),
organic liquid (OLP), aqueous (ACQ), gas (GP) and coke yield was 87.55, 72.75, 14.80, 9.02 and 3.43
wt% respectively. Generally, decomposition of methanol is an endothermic reaction, which produces
hydrogen and carbon monoxide with an equilibrium reaction temperature between 250 and 350 oC
[19]. This suggests that thermal in-situ hydrodeoxygenation of the pyrolytic oil has taken place via
thermal decomposition of methanol solvent and methanol derivative such as furan-methanol initially
present in the raw pyrolytic oil, which may have contributed greatly to the production of aqueous
phase and gas product. With 2 wt% Pd/C loading, the TLP reduced by approximately 16 w% with a
drastic reduction in the OLP of about 3.2-fold lower relative to the thermal OLP while ACQ and GP
recorded was 3.3 and 2.5 times higher compared to corresponding product obtained under the
675
thermal condition. Studies on in-situ hydrodeoxygenation of pine wood with Pd/C catalyst reported
by Cheng et al. [14] showed that a decrease in the organic phase product with corresponding increase
in aqueous phase and gas production at higher temperature (300 oC) compared to lower temperature
investigations. This observation was ascribed to high activity of the Pd/C promoted by hydrogen rich
environment at high temperature, which enhanced conversion of more oxygenated compounds into
hydrocarbons and gas products via multiple reactions such as hydrodeoxygenation, hydrogenation
and decarbonylation. The products distribution over 2 wt% Pt/C loading relative to the thermal
treatment is similar to those obtained over the Pd/C. The TLP and OLP is nearly 20 wt% and 2.5 times
lower whereas the ACQ and GP are 2.5-2.9 times higher. Catalytic activity of Pt/C produced 7 wt% OLP
and 3.8 wt% GP more compared to Pd/C. This is not surprising since Pt/C is known to favour
decarbonylation reactions, which may be responsible for the higher gas yield recorded [20]. The coke
formation, product of polymerisation and polycondensation reactions over both catalyst is about 7
wt%, which is approximately 3.64 wt% higher than thermal coke. This can be linked to the high
hydrogen pressure in the reactor which prevent excessive catalyst coking.
Figure 3: Effect of Pd/C and Pt/C catalyst on the in-situ hydrodeoxygenation of Napier grass pyrolytic oil at 350 oC, 20 wt% methanol, 2
wt% catalyst loading and 25-30 bar reactor pressure. Values are the average of three replicates. (TLP) total liquid product,
(OLP) organic liquid product, (ACQ) aqueous phase, (GP) gas product
Physicochemical characteristic of the upgraded pyrolytic oil is summerised in Table 3. The density
(measured at 20 oC using Anton Paar density meter DMA 4500 M, Ashland, VA, USA) of pyrolytic oil
decreased from 0.98 to 0.90 and 0.89 after of the upgrading over Pt/C and Pd/C, suggesting
improvement in the property of the upgraded oil. Higher heating value of the oil increased by 12 %
after thermal treatment while 30 % and 35 % increase was recorded for the sample upgraded oil over
Pd/C and Pt/C catalyst. The characteristics of the upgraded oil also shows reduction in nitrogen and
sulphur content, which eliminate the fear of NOx and SOx emission when use as fuel in combustion
facility. The carbon and hydrogen contents of the oil increased from 53.83 wt% to 58.22, 70.28, 71.55
wt% and 6.45 to 7.02, 9.74, 10.01 wt% after thermal treatment and catalytic upgrading over Pt/C and
Pd/C. A significant reduction in oxygen content was also observed particularly for the catalytic
upgraded samples. The molar ratio of hydrogen/carbon increased from 1.44 in the raw pyrolytic oil
sample to 1.66-1.68 while the oxygen/carbon molar ratio reduced to 0.18-0.20 after catalytic
676
upgrading. This indicate that the upgraded oil samples from the catalytic process have high
combustibility tendencies and low content of acidic components since a high H/C of fuel is an
indication of its combustibility and lower O/C ratio depict less acidity. Furthermore, since the
upgrading process of HDO is believed to include both hydrogenation and deoxygenation reactions, the
degree of hydrogenation (DH, %), deoxygenation (DOD, %) and the overall extent of upgrading (OEU,
%) is computed according to the equation (7), (8) and (9) respectively. The upgraded oil collected over
Pd/C catalyst shows a superior quality with DH, DOD and OEU value of 66.64, 54.06 and 60. 35 %
relative to 62.30, 50.28 and 56.29 % recorded for the oil upgrade with Pt/C catalyst. This observation
could be linked to the characteristics of individual catalyst (Table 2). Higher surface area (BET, Smicro)
exhibited by Pd/C may have promoted more upgrading reactions since larger surface area means more
active site for reaction. The presence of excess microporous surface area in the Pd/C relative to Pt/C
signifies more conversion of small oxygenates such as short chain ketones and aldehydes during the
upgrading. According to Cheng et al. [14], these small chemical species are converted to alcohols in
hydrogenation reactions. Similarly, Volkov et al. [21] reported conversion of ketones and aldehydes
over Pd/C catalyst. They stated that the carbonyl groups are first reduced to alcohols and thereafter
converted into saturated products via deoxygenation reaction.
(𝐻/𝐶)𝑂𝐿𝑃 − (𝐻/𝐶)𝑂𝑃𝑂
𝐷𝐻 (%)𝑂𝑃𝑂 = [ ] × 100 (7)
(𝐻/𝐶)𝑚𝑎𝑥 − (𝐻/𝐶)𝑂𝑃𝑂
(𝑂)𝑂𝑃𝑂 − (𝑂)𝑂𝐿𝑃
𝐷𝑂𝐷 (%)𝑂𝑃𝑂 = [ ] × 100 (8)
(𝑂)𝑂𝑃𝑂
𝐷𝑂𝐷(%)𝑂𝑃𝑂 + 𝐷𝐻(%)𝑂𝑃𝑂
𝑂𝐸𝑈 (%)𝑂𝑃𝑂 = (9)
2
Where OPO, OLP, O and (H/C) max is organic pyrolytic oil, organic liquid product, oxygen content (wt %) and gasoline hydrogen/carbon
molar ratio (1.8)
Physicochemical properties Raw pyrolytic oil Thermal Pd/C Pt/C

Density (g/cm3) 0.98 0.95 0.89 0.91
HHV (MJ/kg) 29.18 32.69 39.32 38.07
Carbon (wt %) 53.87 58.22 71.55 70.28
Hydrogen (wt %) 6.45 7.02 10.01 9.74
Nitrogen (wt %) 1.35 1.12 1.01 1.10
Sulphur (wt %) 0.76 0.27 0.17 0.20
Oxygen (wt %) 37.57 33.37 17.26 18.68
Hydrogen/carbon(mole ratio) 1.44 1.45 1.68 1.66
Oxygen/ carbon (mole ratio) 0.52 0.43 0.18 0.20
Degree of hydrogenation, DH (%) 0.00 2.79 66.64 62.30
Degree of deoxygenation, DOD (%) 0.00 11.18 54.06 50.28
Overall extent of upgrading, OEU (%) 0.00 6.98 60.35 56.29
Table 3: Calorific value and elemental composition of raw and upgraded pyrolytic OLP
The composition of gas product evaluated using gas GC-TCD is summerised in Table 4. High content of
hydrogen was detected in the gas stream. This implies the upgrading reaction proceeded in hydrogen
sufficient environment, which is a requirement for suppressing the formation of solid product as
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rightly observed in the products distribution section above. The gas collected over both Pt/C and Pd/C
catalysts contain mainly carbon monoxide and carbon dioxide but in different proportions, which are
indications of decarbonylation and decarboxylation reactions during the upgrading. Pd/C produced
higher carbon dioxide while carbon monoxide was the dominant component in the gas stream
collected over Pt/C. This suggests that the upgrading of pyrolytic oil with Pd/C proceeded with more
decarboxylation reaction compared to Pt/C, which produced more carbon monoxide, an indication of
high decarbonylation reaction. Studies reported by Wang et al. [22] on hydrodeoxygenation furfural
revealed that decarbonylation is the primary reaction pathway of Pt/C catalyst. In a separate studies,
Cheng et al. [14] reported higher content of carbon dioxide in the gas product obtained during in-situ
hydrodeoxygenation of pine sawdust bio-oil over Pd/C catalyst. These observations are in good
agreement with the result obtained in this study. The traces of methane detected in the gas product
can be attributed to decomposition and demethoxylation reactions of long hydrocarbon chain and
scission of methoxy groups, which are one of the components present in the feed pyrolytic oil.
Gas component (vol %) Pd/C Pt/C
Hydrogen 52.25 54.67

Carbon dioxide 28.77 18.55
Carbon monoxide 15.34 22.51
Methane 3.64 4.27
Table 3: Gas composition from GC-TCD analysis.
4- CONCLUSIONS
Upgrading of Napier grass pyrolytic oil was carried out in a high-pressure batch reactor via
hydrodeoxygenation over platinum and palladium catalysts with in-situ hydrogen generation from
methanol. Upgrading over palladium catalyst produced 22.52 wt% organic liquid product, 48.59 wt%
aqueous phase and 22.0 wt% gas product compared 29.51, 37.64 and 25.81 wt% of organic liquid
product, aqueous phase and gas product obtained with platinum catalyst. Analysis of the organic liquid
products collected over palladium showed superior fuel quality compared to similar product obtained
with the platinum catalyst. Carbon monoxide, carbon dioxide, hydrogen and methane were the major
components in the gas products. This suggests that the upgrading process proceeded via multiple
reactions such as hydrodeoxygenation, hydrogenation, hydrocracking, decarbonylation and
decarboxylation. The overall characteristics of the upgraded organic liquid products with both
catalysts are much comparable to that of fuel oil. Consequently, this study has demonstrated that
high-grade biofuel can be produced from catalytic upgrading of Napier grass pyrolytic oil with in-situ
hydrogen generation.
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of Pd/C catalysts in aqueous phase hydrodechlorination through doping of carbon supports. Catalysis Science &
Technology 8, 2598-2605 (2018).
[17] Wei, Q.: Ma, Q.: Zuo, P.: Fan, H.: Qu, S.: Shen, W.: Hollow Structure and Electron Promotion Effect of Mesoporous
Pd/CeO2 Catalyst for Enhanced Catalytic Hydrogenation. ChemCatChem 10(5), 1019-1026 (2018).
[18] Gonzalez, G.: Sagarzazu, A.: Cordova, A.: Gomes, M. E.: Salas, J.: Contreras, L.: Noris-Suarez, K.: Lascano, L.:
Comparative study of two silica mesoporous materials (SBA-16 and SBA-15) modified with a hydroxyapatite layer for
clindamycin controlled delivery. Microporous and Mesoporous Materials 256, 251-265 (2018).
[19] Bai, Z.: Liu, Q.: Lei, J.: Jin, H.: Investigation on the mid-temperature solar thermochemical power generation system
with methanol decomposition. Applied Energy 217, 56-65 (2018).
[20] Wang, C.: Luo, J.: Liao, V.: Lee, J. D.: Onn, T. M.: Murray, C. B.: Gorte, R. J.: A comparison of furfural hydrodeoxygenation
over Pt-Co and Ni-Fe catalysts at high and low H2 pressures. Catalysis Today 302, 73-79(2018).
[21] Volkov, A.: Gustafson, K. P.: Tai, C. W.: Verho, O.: Bäckvall, J. E.: Adolfsson, H.: Mild Deoxygenation of Aromatic Ketones
and Aldehydes over Pd/C Using Polymethylhydrosiloxane as the Reducing Agent. Angewandte Chemie International
Edition 54(17), 5122-5126 (2015).
[22] Wang, C.: Luo, J.: Liao, V.: Lee, J. D.: Onn, T. M.: Murray, C. B.: Gorte, R. J.: A comparison of furfural hydrodeoxygenation
over Pt-Co and Ni-Fe catalysts at high and low H2 pressures. Catalysis Today 302, 73-79 (2018).
679
THERMO-CATALYTICAL OPTIMIZATION OF FORESTRY WASTE PYROLYSIS VAPOURS
J. SOLAR 1, B.M. CABALLERO1, I. DE MARCO1, J. ALONSO1, A. LOPEZ-URIONABARRENECHEA1, N.

GAZTELU1
1 Chemical and Environmental Engineering Department (UPV/EHU). Bilbao. Spain.
Abstract
In a world with ever-growing greenhouse gas emissions, biomass and its derivatives have shown
many advantages compared to conventional fossil fuels, being the closed carbon loop (net CO2
emissions equal zero) it’s most regarded characteristic [1]. Due to the chemical nature of biomass,
pyrolysis has been proved to be a suitable technique to transform biomass waste into more useful
materials such as a carbonaceous solid fuel known as charcoal and hydrogen rich pyrolysis gases.
In this research, woody biomass waste (pinus radiata) coming from forest activities carried out in the
north of Spain has been pyrolyzed in a laboratory scale auger reactor connected to a secondary
tubular reactor. In every experiment 90 g h-1 of biomass are pyrolyzed in the screw reactor while
advancing through an oven with 4 sequential temperature zones: 300, 500, 700 & 700°C. At the end
of the screw reactor the charcoal and vapours are separated and the latter are thermo-catalytically
treated at 800°C in the tubular reactor which promotes further cracking, thus enhancing gas yield
and quality. Non condensable gases and bio-oils are then split up and analyzed separately. A
complete description of the pyrolysis system can be found in [2]. Nickel containing catalysts have
been introduced in the tubular reactor for biomass pyrolysis vapors treatment since Ni catalysts
greatly promote tar cracking if the appropriate operating conditions are used [3]. Concerning
supports alumina has been selected since it is one of the most widespread supporting carrier of
active metals. In addition to Ni containing catalyst ZSM5 zeolite (in its hydrogen form, HZSM5) has
also been used due to its cracking ability [4].
The pyrolysis products obtained were characterized. As expected, charcoal yield and composition is
independent of the catalyst used. Concerning the gas and liquid fractions, all the catalysts used
increase gas yield to the detriment of liquids, markedly in the case of high Ni containing catalyst. The
composition of the gas is affected by the catalyts, the higher the Ni content the higher H2 and CO
share in the gas, while there is no clear effect in the composition of liquids. The charcoal obtained
can be utilized for heating purposes and, as reducing agent, while gases are valuable products as
energy or chemical sources (syngas, hydrogen, syntetic natural gas...).
References
[1] Babich, A., Senk, D.: Biomass use in the steel industry: back to the future? Stahl Und Eisen. 153, 57-67 (2013)
[2] Solar, J., de Marco, I., Caballero, B.M., López-Urionabarrenechea, A., Rodriguez, N., Agirre, I.: Influence of
temperature and residence time in the pyrolysis of woody biomass waste in a continuous screw reactor. Biomass
Bioenergy. 95, 416-423 (2016)
[3] Pinto, F., André, R.N., Franco, C., Lopes, H., Gulyurtlu, I., Cabrita, I.: Co-gasification of coal and wastes in a pilot-scale
installation 1: Effect of catalysts in syngas treatment to achieve tar abatement, Fuel. 88, 2392–2402 (2009)
[4] Adrados, A., Lopez-Urionabarrenechea, A., Acha, E., Solar, J., Caballero, B.M., de Marco, I.: Hydrogen rich reducing
gases generation in the production of charcoal from woody biomass carbonization, Energy Convers. Manag. 148,
352–359 (2017)
680
EFFECTS OF CAO ADDITIVE ON MUNICIPAL SOLID WASTE PYROLYSIS
Y. TANG 1,2, Y. CHI1, J. DONG1,2, A. NZIHOU2, E. WEISS-HORTALA2, M. NI 1

1 State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou, China.
Abstract
Thermal treatment of municipal solid waste (MSW) attracts increasing attention due to the
associated environmental and energy advantages of both waste volume reduction and energy
recovery. However, MSW incineration receives significant resistances from the general public
because of the hazardous pollutant emissions (dioxins, furans, chlorine, and heavy metals) and the
low energy efficiency. Pyro-gasification of MSW is among the potential alternatives to realize clean
and efficient MSW thermal conversion. By pyro-gasification, MSW is converted into useful products
(i.e. raw gas, char, and tar) while incineration provides sensible energy. Therefore, the high added-
value products can be further utilized in a more environmental friendly and energy efficient
downstream system.
In order to increase the quality of the pyro-gasification products, catalysts or additives are commonly
used. Calcium oxide (CaO) is established as a potential in-furnace additive for produced gas
reforming, since it can serve as a CO2 sorbent to enhance hydrogen production [1]. CaO is also an
effective catalyst for tar cracking [2] that increases the syngas yield. Besides, it is also one of the
most attractive candidates for the in-situ removal of chlorine by either adsorption or chemical
reaction [3]. Accordingly, the aim of the present study is to investigate the effects of temperature
and CaO additive on (1) MSW pyrolysis product yields (mass distribution of produced gas, tar, HCl,
and solid residues); (2) MSW pyrolysis produced gas composition (i.e. combustible gas yield, H2 yield,
etc.); (3) HCl removal efficiency; and (4) tar reduction efficiency and tar composition.
As illustrated in Fig.1, more gaseous product is yield with the increasing temperature and the use of
CaO additive; while the emission of HCl gas declines dramatically when CaO is added. CaO favours
the production of H2 in produced gas and catalyses the decomposition of aromatic compounds.
(a) (b) (c)

Fig.1 (a) Products mass distribution; (b) Produced gas composition; (c) Tar composition from GC-MS
References
[1] Zhou C, Stuermer T, Gunarathne R, et al. Effect of calcium oxide on high-temperature steam gasification of municipal
solid waste[J]. Fuel, 2014, 122: 36-46
[2] Jordan C A, Akay G. Effect of CaO on tar production and dew point depression during gasification of fuel cane
bagasse in a novel downdraft gasifier[J]. Fuel processing technology, 2013, 106: 654-660.
[3] CLi Y, Wang W, Cheng X, et al. Simultaneous CO 2/HCl removal using carbide slag in repetitive adsorption/desorption
cycles[J]. Fuel, 2015, 142: 21-27.)
681
EFFECT OF POTASSIUM ON THE THERMAL DEGRADATION OF BIOMASS EVALUATED

USING THERMOGRAVIMETRIC ANALYSIS
M. SAFAR1,2, WEI-HSIN CHEN2, D. LANGAUER1,2, H. RACLAVSKA1

1 . VŠB-Technical University of Ostrava, Faculty of Mining and Geology, Institute of Enviromental
Engineering, 17 listopadu 15, 708 33, Ostrava, Czech Republic

2 Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan
Abstract
Biomass is considered a renewable and eco-friendly energy source that contributes to the reduction
of carbon dioxide emissions. It can be utilized for electricity, heat, bio-fuels and chemical materials
via thermochemical processes [1]. Potassium is a well-known alkali catalyst in the thermal reactions
of biomass. The presence of potassium also affects bio-oil properties, water content and viscosity.
This type of pre-treatment can improve the properties of biomass for thermal conversion by
improving grindability, heating value, reducing the hydrophilic nature, and increasing its resistance
to biodegradation [2,3]. The influence of potassium on the volatiles releasing behavior was
dependent on the amount of loading potassium. The gas yield was significantly increased with the
increasing the potassium concentration.
To figure out the effect of potassium on the thermal degradation of biomass, the rubber wood
sawdust was adopted as the feedstock, and the biomass sample was crushed and then dried in an
atmospheric oven. Impregnation was used to prepare samples with different potassium ion content
equably and adequately. Thereafter, the sample was analysed by TG-FTIR analysis. [3] Accordingly,
the effect of potassium on the biomass degradation, kinetics, and gas production behaviour could be
understood.
References
[1] Hyewon Hwang, Shinyoung Oh, Tae-Su Cho, In-Gyu Choi, Joon Weon Choi, Fast pyrolysis of potassium impregnated
poplar wood and characterization of its influence on the formation as well as properties of pyrolytic products, In
Bioresource Technology, Volume 150, 2013, Pages 359-366, ISSN 0960-8524,
https://doi.org/10.1016/j.biortech.2013.09.132.
[2] Jason Kramb, Nikolai DeMartini, Magnus Perander, Antero Moilanen, Jukka Konttinen, Modeling of the catalytic
effects of potassium and calcium on spruce wood gasification in CO2, In Fuel Processing Technology, Volume 148,
2016, Pages 50-59, ISSN 0378-3820, https://doi.org/10.1016/j.fuproc.2016.01.031.
[3] Feiqiang Guo, Yuan Liu, Yan Wang, Xiaolei Li, Tiantao Li, Chenglong Guo, Pyrolysis kinetics and behavior of
potassium-impregnated pine wood in TGA and a fixed-bed reactor, In Energy Conversion and Management, Volume
130, 2016, Pages 184-191, ISSN 0196-8904, https://doi.org/10.1016/j.enconman.2016.10.055.
682
SYNTHESIS AND CHARACTERIZATION OF ZrO2-Bi2O3 CATALYSTS FOR CONVERSION OF

N. OCULATA MICROALGAE LIPID TO BIODIESEL
NURUL JANNAH ABD RAHMAN1, ANITA RAMLI1, KHAIRULAZHAR JUMBRI1, YOSHIMITSU UEMURA2
1 Fundamental Applied Science Department, Universiti Teknologi PETRONAS, 32610 Bandar Seri
Iskandar, Perak, MALAYSIA.

2 Chemical Engineering Department, Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar,
Perak, MALAYSIA.
Abstract
Heterogeneous catalyst has become a recent focus for production of third generation biodiesel [1].
In this study, ZrO2 have been synthesized by hydrothermal method using zirconium oxynitrate and
cetyltrimethylammonium bromide as template. ZrO2-Bi2O3 were then prepared via incipient wetness
impregnation of bismuth nitrate (5, 15 and 30%) on the synthesized ZrO 2. Various characterization
techniques (XRD, XPS, BET and CO2-TPD and NH3-TPD measurements) were used to evaluate the
physico-chemical properties of the ZrO2-Bi2O3 catalysts. The performance of the ZrO2-Bi2O3 catalysts
were studied in the transesterification of green microalage lipid of Nannochloropsis oculata to
biodiesel. XRD diffractogram of ZrO2 shows the presence of monoclinic (M) and tetragonal (T) phases
and the intensity of the monoclinic (M) phase at 2θ = 28○ increases with increasing content of Bi2O3
in ZrO2-Bi2O3. The total surface area of ZrO2 is 69 m2/g and the total surface area decreases with
increasing Bi2O3 loading down to 44 m2/g at 30% Bi2O3 loading. CO2-TPD and NH3-TPD indicate that
all the catalysts possess both acidic and basic properties. Results indicate that the Bi2O3 content
significantly influence the properties of the catalysts and the interaction between ZrO2 and Bi2O3.
The effect of different reaction parameters including methanol to oil ratio, catalyst loading, reaction
time and reaction temperature were studied in the transesterification of Nannochloropsis oculata
lipid to biodiesel on the catalytic activities of ZrO2-Bi2O3. The composition of FAME produced were
determined using GC-FID.
Figure 1: XRD diffractogram of ZrO2, ZrO2-Bi2O3 5%, ZrO2-Bi2O3 15% and ZrO2-Bi2O3 30%
Reference
[1] Galadima, A., Muraza, O.: Biodiesel production from algae by using heterogeneous catalysts : A critical review. Energy
78, 72-83 (2014).
683
THE ELIPSE PROCESS: AN UNDERWATER PLASMA TECHNOLOGY FOR HAZARDOUS

ORGANIC LIQUID TREATMENT
F. LEMONT, M. MARCHAND, R. MAGNIN, M. MABROUK

1 CEA, DEN, DE2D, SEVT, LPTI, F-30207 Bagnols sur Cèze, France
Abstract
Hazardous liquid organic wastes are very various and produced in different quantities. Some of them
are treated through specific processes when others are still waiting from outlet to be destroyed and
stabilized. Their different composition (chlorinated, phosphate, sulfated, fluorinated, …) make their
treatment difficult in a same technology.
The ELIPSE process has been design to propose an innovative solution leading to a global treatment
of what is usually called “orphan liquids”. This brand new technology involved a non-transferred
plasma torch working under a water column ensuring the cooling, the filtration and the scrubbing of
the gases coming from the combustion of the liquids. Furthermore, the water that ensures the global
cooling of the system leads to low or to avoid the corrosion in a compact process. Only the nozzle of
the torch may be affected by the corrosion and may become a wearing part of the system of
treatment.
After giving a detailed description of the ELIPSE process, the present paper will focus on the results
obtained for the treatment of such different liquids as tributyl phosphate, perfluorinated oil and
trichloroethylene. In addition to obtaining destruction efficiency upper than 99%, the corrosion
seems to have been significantly limited. These features lead to the first conclusion that the ELIPSE
process could be a solution for the future to the problem of the hazardous liquid treatment.
Furthermore, if the main objective of the ELIPSE process is the destruction of hazardous waste
through instantaneous combustion in oxygen plasma, their gasification could be envisaged through
argon and/or water plasma in order to produce Syngas for energy recovery.
Exhaust gas
Cheminée
Filtre
Filter
NaOH
Filter
Filtre
Heat exchanger
Echangeur
Torche à plasma
Plasma
d’arc
torch
Purge
Purge
O2 or H2OO2 Ar
(Mineral charge)
Liquides
Organic
organiques
liquids
ELIPSE process principle and image of underwater plasma
684
TECHNO-ECONOMIC ASSESSMENT FOR IMPLEMENTING GASIFICATION

TECHNOLOGIES TO PROCESS MSW REFUSE IN SPAIN
M. SUÁREZ-ALMEIDA1, V.F. DE ALMEIDA1, J. ARROYO-CAIRE1, P. HARO1, A. GÓMEZ-BAREA1

de Ingeniería, Universidad de Sevilla, Camino de los Descubrimientos s/n, 41092 Seville, Spain.
Abstract
According to Eurostat, almost 55% of generated municipal solid waste (MSW) in Spain is landfilled.
The figure is even larger in regions as Andalucía, where landfilling rises up to 80%. This situation, far
from the targets of the European Directive, is leading landfill’s owners to consider new schemes for
MSW management. The European waste hierarchy establishes that only the refuse fraction of MSW
can be used as feedstock in WtE plants, and that the use of any other fraction must be justified from
a life cycle thinking (Directive 98/2008). MSW refuse is the unsorted fraction of MSW that cannot be
further processed (for recycling) and therefore is incinerated or landfilled.
This paper assesses the techno-economic feasibility of applying thermochemical conversion methods
to valorise MSW refuse in landfilled-dominated regions, taking the MBT plant with largest capacity in
Andalucía as reference (Centro Integral de Tratamiento de Residuos Sólidos Urbanos de
Montemarta-Cónica, CITMC). The CITMC processes approximately 600 kt/y of MSW and produces
around 470 kt/y of refuse waste. A review of thermochemical technologies was conducted to select
the best two available processes (technological maturity and market potential in Spain). Selected
technologies are Nippon Steel Direct Melting System (DMS), with more than thirty plants mainly in
Japan [1]; and Valmet technology with only one demonstration plant (Lahti II) in Finland [2]. The
study was carried out in collaboration with EDIFESA, a company managing the CITMC, so real waste
samples taken from the plant were used for the performance assessment cost estimations (Table 1).
Nippon Steel DMS M€ M€/año €/t M€/MWe Valmet M€ M€/año €/t M€/MWe
CAPEX 378 - 807 12.4 CAPEX 188 - 769 4.9
OPEX - 34.9 74 - OPEX - 20.4 84 -
Table 1: Cost estimation for Nippon Steel DMS and Valmet technologies for CITMC MBT plant
The main conclusions are: (i) the proposed treatment of MSW refuse by gasification in Spain is not
competitive compared to incineration (and, obviously, to landfill, which is by far the cheapest
method); and (ii) Valmet’s concept, in which pretreated MSW refuse is gasified in large CFB and the
syngas produced is cleaned at high temperature to achieve clean combustion and high electrical
efficiency, has the best prospects for a future implementation. However, this concept still faces up
technical challenges, which were analysed by developing a simulation model. The results from the
model enabled predicting the syngas quality for different SRF/RDF, and then to estimate the removal
efficiencies necessary in the gas cleaning sections (high temperature filter and APC) to fulfil the
Waste Incineration Directive (WID) regulations. Technical and scientific challenges were identified as
well as the main lines of research to be developed.
References
[1] Tanigaki, N., Manako K., & Osada, M: Co-gasification of municipal solid waste and material recovery in a large-scale
gasification and melting system. Waste Management, pp. 667-675. Tokyo (2012)
[2] Bolhar-Nordenkampf, M. & Isaksson, J.: Operating Experiences of Large Scale CFB-Gasification Plants for the
Substitution of Fossil Fuels. Tampere, 2016
685
THERMO-CATALYTIC REFORMING OF DIGESTATE
M. HEBERLEIN 1 F. STENZEL 1, A. HORNUNG1,2,3

1 Fraunhofer Institute for Environmental, Safety, and Energy Technology UMSICHT Sulzbach-
Rosenberg, Germany.
2 Friedrich-Alexander University Erlangen-Nuremberg, Faculty of Engineering, Department of
Chemical and Biological Engineering, Erlangen, Germany.

3 University of Birmingham, School of Chemical Engineering, Birmingham, UK.
Abstract
The material use as fertilizer is the most appropriate use of digestate and manure. However, in some
regions in Germany, particularly in regions with high livestock farming as well as anaerobic digestion
plants a competition can arise regarding the disposal of the contained nutrients on the available
arable land. For identifying such regions a scenario based model, down to community level, linked to
a map for visualizing was created to balance the nutrient amounts against the available arable land
in the federal state of Bavaria, Germany. Although there is enough agricultural land in Bavaria as a
whole, in about 14 % or respectively 30 % of the individual communities exists an excess of nitrogen
as example for one main nutrient in the here used 2 main scenarios (two various cattle manure
amounts) and used parameters. In such excess regions nutrient management or alternative
utilizations are needed to protect the waters and environment against eutrophication. One could be
the usage as feedstock for conversion technologies for heat and power production like the Thermo-
Catalytic Reforming (TCR)1.
The TCR technology is an endothermic two stage process developed by Fraunhofer UMSICHT, able to
process biomass and biomass residues, also with high ash and moisture contents as well as with low
ash melting points. The process is a combination of an intermediate pyrolysis reactor and a
reforming stage. The pyrolysis stage is typically running at temperatures between 400 and 500 °C
and the reforming stage between 600 and 700 °C. In the first stage pyrolysis vapors and biochar are
produced. In the second stage the vapor phase has to pass a continuous removed biochar bed in the
reformer where it (the permanent gas as well as the gaseous oil) is upgraded. The temperatures can
be varied to modify the products yield, quality and properties in specific ranges. Various test trials
were performed with a 2 kg/h TCR unit at lab scale, but also a scale-up up to 30 kg/h TCR unit was
performed in Sulzbach-Rosenberg, Germany.
The products are a synthesis gas, biochar, oil and process water. The oil and process water can be
separated easily from each other just through gravity. The products have high quality and can be
used without any further treatment. The synthesis gas is rich in hydrogen (30 - 50 % depending on
the input) and with a LHV at about 14 MJ/kg. The oil has a low viscosity (< 5 mm²/s), low oxygen
content (< 10 %) and a low acid number (about 2 mg KOH/g) with a LHV of 31 - 34 MJ/kg. The
biochar has very low O:C and H:C ratios - in the same ranges as anthracite - by high C content (mainly
depending on the feedstock and the contained ash content) with a LHV of 16 - 23 MJ/kg.
The basic suitability was shown as well, as the first scale-up from a 2 kg/h into a 30 kg/h unit. The
next step would be the scale-up into an industry scale unit with a 300 kg/h.
References
[1] Neumann, J., Jäger, N. Apfelbacher, A., Daschner, R., Binder, S., Hornung, A.: Upgraded biofuel from residue biomass
by Thermo-Catalytic Reforming and hydrodeoxygenation. Biomass and Bioenergy 89, 91-97 (2016)
686
COMBINED PRODUCTION OF HYDROGEN AND ELECTRICITY FROM

HOSPITAL SOLID WASTE: TECHNOLOGY
J. RAMOS1, A. INGA2, S. QUESNEL1, E. GONZALES2, Y. CARHUARICRA3, G. ROMAN3, W. HUACCACHI2

1 University of Engineering and Technology (UTEC), Lima, Peru.
2 National University of Engineering (UNI), Lima, Peru.
3 National Major University of San Marcos (UNMSM) Lima, Peru.
Abstract
In Peru, the Ministry of the Health and hospitals are responsible for the hospital’s waste treatment
and disposal. At a national level, in 2013, 12.755 tons of bio contaminated solid waste were
generated [1]. Some hospitals choose the incineration as an option for waste treatment, but it can
generate toxic components (CH4, CO2) for the environment and health of people living or working
close to these hospitals. In this context, the transformation of the hazardous solid waste to hydrogen
is the solution to generate an adequate fuel in order to meet the energy demand of the cities,
chemical and automotive industries [2].
A combined production of hydrogen & electricity (CPHE) energy system from hospital-solid-waste is
proposed. A CPHE energy facility is based on three processes: (1) production of syngas (including
solid waste treatment and solid waste gasification); (2) production of hydrogen
(washing/separation/purification process of the syngas), and (3) production of electricity (with
hydrogen fuel cells). In this paper, a CPHE energy system state-of-the-art technology is developed.
Chemical reaction of solid-waste gasification with oxygen, or air or steam vapor produces syngas
containing significant amounts of hydrogen, light components (CO 2, CO, etc.) and tars [3-4].
Hydrogen streams should be cleaned and purified to eliminate the impurities and tars using
membranes (polymers, porous, high density or proton exchange). Pure hydrogen (from syngas) will
drive fuel cells to generate electricity. Fuel cells could be SOFC technology because of its reliability
and aptitude to accept CO as a fuel [5], or PEM technology fueled by hydrogen from gasification [6].
Finally, two conditions are required in order to keep this co production plant economically feasible :
(i) the power must be equal or higher than 1 MWe, and (ii) it must operate at full load in order to
produce electricity and sell the surplus electricity to reduce the payback.
References
[1] Ministry of Environment of Peru, «Sixth national report about the solid wastes and the environmental management
municipal and no municipal 2013,» 12 2014. [On line]. Available:
http://redrrss.minam.gob.pe/material/20160328155703.pdf. [Last access: 24 03 2017].
[2] N. Abas, A. Kalair y N. Khan, «Review of fossil fuels & future energy technologies,» Futures, vol. 69, pp. 31-49, 2015.
[3] C. Vargas, « theoretical and experimental comparative study between downdraft fixed bed and bubbling fluidized
bed to generate electricity for low potential application», thesis, energy engineering institute of Valencia.
[4] A. Bridgwater, «Renewable fuels and chemicals by thermal processing of biomass» Chemical Engineering Journal,
vol. 91, pp. 87-102, 2003.
[5] U.S. Department of Energy, «Types of fuel cells» [En línea]. Available: https://energy.gov/eere/fuelcells/types-fuel-
cells. [Último acceso: 09 06 2017].
[6] J. Ramos-Saravia, P. Muñoz, C. Ames, A. Sancho, E. Gonzales, F. Valencia y C. Zavala, «Microsistema energético de
respaldo para hospitales basado en pilas de combustible accionadas con biohidrógeno a partir de bagazo de caña de
azúcar». XXVIII Congreso Interamericano de Ingeniería Química, Cusco, 2016..
687
PREPARATION AND AIR GASIFICATION OF BIO THERMO STABILIZED MUNICIPAL

SOLID WASTE
V. PÉREZ1, R. RAMOS1, R. BADOS1, L. ESTEBAN1, R. BARRO1, I. ORTIZ2, Y. TORREIRO2, J.M. SÁNCHEZ2

1 CEDER-CIEMAT, Lubia (Soria), Spain.
2 CIEMAT, Madrid, Spain
Abstract
The generation of Municipal Solid Waste (MSW) in EU-28 was 242,258 thousand tons and the
landfilling rate was 25.3% in 2015 [1]. The gasification process could be an alternative to reduce this
rate more economically and environmental friendly than incineration [2]. The produced gas could be
used not only to obtain thermal energy but also electric power, chemicals and biofuels, as in a
biorefinery [3]. Thus, MSW would be turned into resources contributing to circular economy
schemes, which is one of the goals of the RETOPROSOST Community of Madrid (CM) project
(P2013/MAE-2907). The project seeks to promote the sustainable industrial development in the
Community of Madrid and foster the generation of new business opportunities through the
innovative use of waste flows.
Preparation and pilot-scale gasification of a fraction designated as Bio Thermo Stabilized Municipal
Solid Waste was studied to evaluate the potential of this waste to obtain gas by means of
gasification. The preparation of municipal solid waste for thermochemical process has been studied,
making a special focus on reducing humidity and increasing its density. On the other hand, air
gasification of municipal solid waste has been done to determine gas quality, tar production, low
heating value, gas yield, carbon conversion and efficiency.
The fuel preparation included drying, milling and pelletizing using a pelletizing plant of 300 kg/h
capacity. The evaluation of the milling and pelletizing energy demand was performed, as well as the
quality of the pellets obtained.
Air gasification tests of the dried pelletized municipal solid waste were carried out focusing on the
influence of the equivalence ratio used. The tests were performed in a bubbling fluidized bed gasifier
at atmospheric pressure and autothermal operation, without the use of any external heating.
Gasification tests were conducted at 150 kWth and temperatures around 800 ºC, using silica sand as
bed material.
High quality pellets were obtained, regarding some physical parameters such as durability, fines and
bulk density. The produced gas is made up of 3.5-4.0 % H2, 6.0-7.0 % CO, 2.2-4.0 % CH4 and 1.2-2.5 %
C2H4, as the main components which contribute to its heating value of 2.8-3.1 MJ/Nm3. Its tar
contents are 12-14 g/Nm3.
An appropriate fuel was obtained to be used in the air gasification process where the gas produced
can be used to obtain energy.
References
[1] Eurostat: Municipal Waste Statistics. Available on line http://ec.europa.eu/eurostat
[2] Leckner, B., 2015. Process aspects in combustion and gasification Waste-to-Energy (WtE) units. Waste Manage. 37,
13–25.
[3] Arena, U., 2015. From waste-to-energy to waste-to-resources: the new role of thermal treatments of solid waste in
the Recycling Society. Waste Manage. 37, 1–2.
688
SULFOALUMINOUS CONCRETE: AN ADVANCED WAY OF WASTES REDUCTION

AND REUSE
J. NOUAIRI1, W. HAJJAJI2, J.A. LABRINCHA3, F. ROCHA2, M. MEDHIOUB1

1 Dept of Geology, Faculty of Sciences of Sfax, 3018, Sfax-Tunisia
2 Geobiotec, Geosciences Dept, University of Aveiro, 3810-193 Aveiro. Portugal
3 Department of Materials and Ceramic Engineering / CICECO – Aveiro Institute of Materials,
University of Aveiro, Aveiro, 3810-193, Portugal
Abstract
Several processes have been developed to reduce the greenhouse gas emissions responsible
for the global warming. Sulfoaluminous clinkers are considered as environmentally friendly
materials since they include small amounts of carbonate and then lower CO2 emissions.
This contribution reports the use of low cost materials (mine wastes) containing huge
amounts of metallic elements as clinkers. Two samples of mine wastes were studied. The
chemical analysis was carried out by X-ray fluorescence (XRF) and the mineralogy by X-ray
diffraction (XRD). After sintering in presence of commercial CaCO3 and alumina, the
presence of the targeted crystalline phases: trialuminate sulfate (C4A3Š), belite (C2S), and
ferrite (C4AF) in the desirable amounts and as predicted by the phase diagram was
confirmed.
Heat flow generated during the hydration of different cement pastes showed a slower
reaction for clinkers with higher amounts of C4A3Š or constituted by coarser particles. After
28 days curing, the best mechanical resistance (24.34 MPa under compression) was obtained
for the clinker calcined at 1350ºC and showing a suitable particle size distribution.
Concerning heavy metals, 75 to 85% of Pb, Zn and Cu were immobilized in the mortars
formulated with the produced clinker/cement, posing no hazardous risks to the
environment.
689
INORGANIC POLYMERS FOR OUT OF THE BOX APPLICATIONS USING BIOMASS FLY
ASH WASTE

RUI M. NOVAIS1, P. SEABRA1, J.A. LABRINCHA1
1 Department of Materials and Ceramic Engineering / CICECO-‐ Aveiro Institute of Materials,
University of Aveiro, Campus Universitário de Santiago, 3810-‐193 Aveiro, Portugal.

Abstract

The replacement of Portland cement by inorganic polymers (also known as geopolymers) is
promising due not only to their lower carbon footprint but also to performance benefits. Indeed the
majority of studies considering inorganic polymers are focused on their mechanical performance.
However inorganic polymers possess other exciting properties that may allow their use as low
thermal conductivity materials [1], pH buffering materials [2] or as adsorbents in wastewater
treatment systems [3, 4]. In this work, biomass fly ash, produced by a Portuguese pulp and paper
industry, as used as aluminosilicate source in inorganic polymer production. Then the possibility of
using them in distinct applications was evaluated: i) as pH regulators; ii) as adsorbents for
wastewater treatment (e.g. methylene blue extraction). Results show remarkable pH buffer ability
for the produced waste based geopolymer. The inorganic polymers can also efficiently remove heavy
metals or dyes from industrial wastewaters.

References
[1] Novais, R.M., Buruberri, L.H., Ascensão, G., Seabra, M.P., Labrincha, J.A., 2016. Porous biomass fly ash-‐based
geopolymers with tailored thermal conductivity, Journal of Cleaner Production 119, 99-‐107.
[2] Novais, R.M., Seabra, M.P., Labrincha, J.A., 2017. Geopolymer spheres as novel pH buffering materials. Journal of
Cleaner Production 143, 1114-‐1122.
[3] Novais R.M., Buruberri L.H., Seabra M.P., Labrincha J.A., 2016. Novel porous fly ash-‐containing geopolymer
monoliths for lead adsorption from wastewaters. Journal of Hazardous Materials 318, 631-‐640.
[4] Novais, R.M., Ascensão, G., Tobaldi, D.M. Seabra, M.P., Labrincha, J.A., 2018. Biomass fly ash geopolymer monoliths
for effective methylene blue removal from wastewaters, Journal of Cleaner Production 171C, 783-‐794.
690
DEVELOPMENT OF A BINDER MATRIX BASED ON GROUND GRANULATED

BLAST-FURNACE SLAG AND FLY ASH AS A REPLACEMENT OF CEMENT IN
MORTARS
S. SEIFI1, D. LEVACHER2, M. BOUTOUIL1, N. SEBAIBI1

1
Ecole supérieur d’ingénieurs des travaux de la construction, 1 rue Pierre et Marie Curie,
14610 Epron, France.
2
Normandy University, Unicaen, UMR 6143 CNRS - M2C, 24 rue des Tilleuls, 14000 Caen,
France.
Abstract
One of the main concerns of recent years is the high consumption of non-renewable
resources followed by the CO2 emission which is the most cause of global warming and part
of this amount of CO2 comes from cement production. In the other hand the high content of
waste is producing every day by industries. New environmental regulations have been
provided to protect the natural sources and recycle the wastes left behind by several
industries. In present study, wastepaper sludge ash (WSA) and ground granulated blast
furnace slag (GGBS) are by-products reused, mixed and activated so as to provide a binder
matrix for manufacturing dry mortars in construction industry, like standard mortars for
manufacturing blocks. Considering sustainable approach, the aim is to replace and to
substitute cement quantity by this new binder matrix in usual dry-mortar formulation.
Two types of binder matrix for dry mortar manufacturing are investigated, a non-cement
and a cement based binder. Non-cement matrix is composed of 73% of wastepaper sludge
ash and 27% of GGBS, considering that GGBS should be 7% of total mass of the mixture
without cement addition. In this latter case for having the maximum reactivity, sodium
carbonate and sodium silicate are considered as activators. A second binder matrix is
composed of 70% of WSA fly ash, 20% of GGBS and 10% of cement CEM I 52.5. WSA fly ash
contains 20% SiO2 and 50% CaO which are very close to the one of cement and encouraging
the pozzolanic properties in the absence of cement. This high amount of CaO contained in
WSA fly ash will absorb large quantity of water and therefore find the optimum ratio
between water amount and binder in the mixture is essential for non-cement binder matrix.
Curing is carried out at 20°C, 70% RH for 24h for all the 4*4*16 samples. The specific weight
has been calculated, this value increases with the water/binder ratio. The specific weights
are ranged from 19 to 20 kN/m2. Mechanical tests (compression and bending) are performed
after 2, 7 and 28 days to determine the mechanical resistance comparing to usual type of
mortars. The maximum compressive strength for non-cement based binder matrix is
obtained 10.5 MPa after 28 days and for a cement based binder is 24.5 MPa.
Keywords
Dry mortar, Non-cement mortar, Fly ash, Ground granulated blast furnace slag, Recycling,
Alternative material, Valorization
691
OBTENTION OF ALUMINUM ZINC ALLOYS FROM RECYCLED ALKALINE BATTERIES:

EFFECT OF FLUXING ADDITIVES ON MELT TREATMENT
J. CABALLERO-JAIMES1, P. DELVASTO2
1 Universidad Industrial de Santander, Bucaramanga Colombia.
2 Universidad Industrial de Santander, Bucaramanga Colombia.
Abstract
In recent years, the problem of the final disposition of spent batteries in Latin-American countries
has gained attention, due to the modification of their environmental legislation in order to enforce
the valorization and recycling of the metals contained in this kind of electrical devices [1]. The main
issue to establish recycling procedures for the locally-available spent batteries is the relatively small
tonnage of this special waste generated in such countries, which is not enough as for justifying the
construction of state-of-the-art battery recycling plants. A possible way to overcome this situation,
consists in identifying locally-existing industrial processes, in which spent batteries residues could be
incorporated as raw materials. Among the several feasible options, the aluminium metal casting
industry seems to offer an interesting advantage, since aluminium is an active metal, which can be
used as reducing agent for the heavy-metal oxides contained in the electrode materials of the spent
batteries [2]. Taking into account the above-mentioned situation, in this work we studied the direct
incorporation of the zinc-bearing fraction of spent alkaline batteries into molten aluminium to obtain
Al-Zn alloys. To accomplish this objective, several fluxing salt mixtures were used in the treatment of
the molten metal and the impact of such treatments in the incorporation of Zn into the alloy was
measured through optical emission spectrometric chemical analyses in combination with a
microstructural characterization by metallographic techniques. The melting batches had a mass ratio
composition of aluminium, anode Zn powder and fluxing mixture of 100:20:40, respectively. Melting
was performed in fire-clay crucibles in an electric resistance furnace in air atmosphere. The fluxing
salt mixtures used were: NaCl/KCl; KCl/ZnCl2 and borax. As negative controls, batches of only
aluminium and aluminium plus anode Zn powder were melted under the very same conditions. It
was found that when borax and KCl/ZnCl2 are employed as fluxing aids in the melting process, the
incorporation of Zn into the alloy increases from 0.011 wt% up to 1.50 wt%. These results show
that the direct incorporation of the Zn-bearing fractions from spent alkaline batteries into molten
aluminium is feasible to produce Al-Zn alloys if proper fluxing agents are incorporated during such a
process.
References
[1] Blanco, S., Orta-Rodriguez, R., Delvasto, P.: Influence of Na+, K+ , Mn2+, Fe2+ and Zn2+ ions on the electrodeposition
of Ni-Co alloys: Implications for the recycling of Ni-MH batteries. J. Phys.: Conf. Ser. 786 012033 (2017).
[2] Ochoa, R., Flores, A., Torres, J. Escobedo, J.: Manufacture of Al-Zn-Mg alloys using spent alkaline batteries and cans.
Mater. Today Proc. 10, iss. 10, part A, 4971-4977 (2015).
692
ASSESSMENT OF MATERIALS AND RECYCLING IN ANCIENT TIMES: MODELS OF

HUMAN BEHAVIOUR
A. ČIVILYTĖ 1
1 Lithuanian Institute for History, Vilnius, Lithuania.
Abstract
This paper deals with the assessment and recycling of materials in the ancient human past. Having
already learned to make any items needed in everyday life, people very quickly understood that they
could extend their useful life of raw materials by transforming finished items into refurbished or new
goods. The assessment of how ancient peoples reutilized different materials and their methods of
recycling has been the topic of recent archaeological investigations [1] [2]. However, there is still a
gap between the archaeological practices and modern materials science, especially in fields of waste
management and recycling.
This study explores organic and non-organic archaeological materials such as bone, pottery
(ceramics) and metals. The ancient assessment of materials and the process of reuse and recycling
extends through several levels of economic systems: circular economy, trade economy and ritual
economy. All of the transformations of materials within economic systems were based on an
ingenious, successful and rational background of innovation and invention in recycling technology.
The most important invention and technological change in the ancient history of recycling was the
development of Bronze, an alloy of copper and tin. Unlike stone, Bronze could be melted, poured
into a huge range of shapes. These objects could then be easily re-melted and re-poured into any
number of different molds to create different functional its. Bronze was the first material that could
easily be 100 % recycled. Thus with its adoption humankind came closer to what has been referred
to as “economic rationality”.
Bones of wild and domestic animals were selected from the remains of meals for utilization in the
creation of tools. This is clearly a form of secondary use of materials in order to make new objects.
Pottery was made first to execute a primary function for cocking, eating and drinking. It also had the
potential to be re-used as other objects, and had multiple functions in society such as the
transmission of information via decoration. Thus the secondary use and recycling of pottery is
multifunctional and often has not only practical but also psychological reasons.
The purpose of this presentation is to show that by looking back into the ancient past we are able to
create the models of human behaviour and to recognise patterns with which we can assess the
recycling of materials in ancient cultures. The archaeology of reuse and recycling can show us how
complex economies could be very efficient. It can also show us the transformation of value in
materials during the recycling processes. The ways in which ancient peoples thought about recycling,
their engineering innovations, and the practical as well as psychological reasons for reuse and
recycling process can act as a connecting bridge between the past and our modern society.
References
[1] Lene Melheim, Recycling Ideas: Bronze Age Metal Production in Southern Norway. BAR International Series 2715
(2015).
[2] Dragos Gheorghiu, Paul Mason (Edt.), Working with the Past: Towards an Archaeology of Recycling. Oxbow Books
2017.
693
VARIATION OF FOOD WASTE CHARACTERISTICS DURING AEROBIC STORAGE:

CONSEQUENCES FOR SOLID-STATE ANAEROBIC DIGESTION PROCESS
A. DEGUEURCE 1, P. PEU1, A. TREMIER1

1 UR OPAALE, Irstea, 12 avenue de Cucillé 35000 Rennes, France..
Abstract
The DECISIVE project, founded by European H2020 program (grant agreement N°689229),
aims at proposing and testing a decentralized management scheme for the valorisation of urban
biowaste. The strategy involves the development of a network of micro anaerobic digestion units in
urban and peri-urban areas that will mostly be fed with food waste (FW) from nearby
neighbourhood (mass catering, citizens…) and green waste. This scheme implies a storage period
between the FW collection phase and the micro-AD unit feeding. However, previous work showed
that FW storage could lead to the inhibition of solid-state anaerobic digestion (SSAD) process [1].
Consequently, the present study focuses on the variation of FW characteristics during different
storage periods to identify which elements could be involved in the inhibition of the SSAD process.
The experiments were performed at two scales, representing two FW storage cases. The first
one consisted in six reactors of 10L, equivalent to the volume of a home compost bucket. The second
one consisted in two reactors of 300L that correspond to the FW storage volume needed by a mass
catering. The lower part of each reactor was designed to allow the percolation of a liquid phase and
ease its separation from the solid FW for further analysis. Gaseous emissions (CO2, CH4, alcohols) of
all reactors were recorded along the 14 days of experiment. A chemical trap was also added to
monitor NH3 emissions. Every two days, one small reactor was stopped and both liquid and solid
phases were sampled to follow the variation of FW characteristics. At the end of the experiment, all
samples were analysed for total and volatile solids, pH, volatile fatty acids, ammonia and alcohols.
Gaseous emissions observed during the aerobic storage of FW mainly consisted in CO2 and
alcohols. Each reactor showed two peaks of alcohols emissions always coupled with a CO2 emission
peak of varying intensity that can be attributed to the degradation of organic matter (see fig.1).
Moreover, analysis of the liquid phase produced during the storage period, showed the presence of
ethanol, methanol and an important concentration of lactic acid. After one day of storage, 4 g/L of
lactic acid were measured. Then, the concentration increased to 7.4 g/L at day 6, and started to
decrease until a complete disappearance at the end of the experiment.
These results pointed the start of an alcoholic fermentation during FW storage that could
lead to the production of inhibitory compounds for batch mode solid-state anaerobic digestion.
Further experiments will be done to quantify them.
694
Figure 1 – Example of gaseous emissions profiles
References
[1] Fisgativa, H. : Study of the impact of aerobic pretreatment on anaerobic digestion of food waste, PhD Thesis from
the University of Rennes I (2016)
695
BIOCHAR ASSISTED THERMOPHILIC CO-‐DIGESTION OF FOOD WASTE AND WASTE

ACTIVATED SLUDGE UNDER HIGH ORGANIC LOADING

QIAN LI1, XIAOCHANG WANG1
1 Xi’an University of Architecture and Technology, Xi’an, China.

Abstract

The purpose: Thermophilic anaerobic digestion (TAD) is considered more efficient for the treatment
of organic waste. However, the instable performance at high OLR limits its application. Therefore, to
enhance the capacity of TAD to resist the pH drop caused by excessive VFA generation and
accelerate the degradation of generated VFAs are likely to be the key strategies. In this study,
biochar (BC) was used to stimulate methane production during the thermophilic co-‐digestion of food
waste (FW) and waste activated sludge (WAS) at different OLR in batch mode. Main attentions were
paid on the effects of BC on buffer capacity, the syntrophic oxidation of accumulated VFAs, and
variation of microbial community structure.
The main materials and methods used: Biochar was made from sawdust, and pyrolyzed under 500oC
for 1h. Seed sludge was obtained from a full-‐scale upflow anaerobic sludge blanket reactor (UASB)
treating brewery wastewater. Co-‐substrate of FW and WAS was prepared according to previous
study [1]. Batch testing was conducted in 120 mL serum bottles with different feedstock/seed sludge
(F/S) ratios of 0.25, 0.75, 1.5, 2.25, 3 (based on VS), experimental procedure followed previous study
[1].
Te main results obtained: The results showed that the presence of BC dramatically shortened the lag
time of CH4 production by 21.4%, 79.5%, 83.0%, 86.1% and 87.4% and increased the methane
production rate by 20.2%, 59.6%, 72.9%, 75.0% and 125% at F/S ratios of 0.25, 0.75, 1.5, 2.25 and 3,
respectively. The higher buffer capacity and large specific surface area of BC promoted
microorganism growth and adaption to VFAs accumulation. Additionally, the electron exchange in
syntrophic oxidation of butyrate and acetate as intermediate products was significantly facilitated by
BC possibly due to the selective succession of bacteria and methanogens which may have
participated in direct interspecies electron transfer, in contrast with the control group with low-‐
efficient electron ferried between syntrophic oxidizers and methanogens using hydrogen as the
electron carrier.

Figure 1: Accumulative methane production at F/S ratio of 0.25, 0.75, 1.5, 2.25, and 3 in the control group (FS) and biochar-‐amended
group (FS+BC)
The main conclusions obtained: BC could ensure the stable and efficient CH4 production during TAD of FW
and WAS at extremely high organic loading by enhancing buffer capacity and facilitating the VFAs degradation by
stimulating interspecies electron transfer between syntrophic oxidizers and methanogens.
696
References
[1] Li Q., Li H., Wang G.J., Wang X.C. (2017). Effects of loading rate and temperature on anaerobic co-‐digestion of food
waste and waste activated sludge in a high frequency feeding system, looking in particular at stability and efficiency.
Bioresource Technology, 237, 231-‐239
697
DEVELOPMENT AND CHARACTERIZATION OF ADSORBENTS FOR NEW ANAEROBIC

DIGESTION BIO-REFINERY CONCEPTS
M. AYIANIA1, F. M. CARBAJAL-GAMARA2, A. DUMSOR1, M.GARCIA-PEREZ1

1 Department of Biological Systems Engineering, Washington State University, L.J. Smith Hall, 1935 E.
Grimes Way, Pullman, Washington 99164-6120, United States

2 Faculty Gama, University of Brasília, DF St. Leste Projeção A - Gama Leste, Brasília - DF, 72444-240,
Brasil
Abstract
Purpose: Although, anaerobic Digestion (AD) is an efficient technology to convert the carbon
contained in farm animal manure into methane, it does not have the capacity to separate or
transform the nitrogen and the phosphorous. Thus, high contents of these nutrients remain in the
AD liquid effluents. The presence of H2S in the biogas is another hurdle for the wide adoption of this
technology. In this work we developed and tested a biochar from anaerobically digested fiber and
Douglas fir for nutrients (N and P) removal from liquid efluents and H2S from bio-gas. The biochar
was prepared and activated under CO2 utilizing slow pyrolysis conditions, and the adsorption
capacity of the biochar toward hydrogen sulfide (H2S) and phosphate (PO43-) and ammonia (NH3)
were evaluated.
Main materials and methods: Here we used anaerobic digester fiber from George DeRuyter and
Sons Dairy Farm in Outlook, WA, USA. Another adsorbent with low ash content was developed from
a woody material with low ash content activated with phosphoric acid for adsorbing ammonia gas.
Some of the analytical techniques used were: Elemental analysis, proximate analysis, gas
physisorption analysis for biochar surface area and porosity, topographic and microstructural
analysis and ICP MS analysis. Batch equilibrium studies of phosphate and breakthrough curves of H2S
and NH3 were studied.
Main results obtained: Biochars produced at high temperatures (above 500°C) from anaerobic
digestion fiber adsorbed hydrogen sulfide from biogas at levels that were comparable to those of
commercial activated carbon. Phosphate recovery of 97.62% was also observed. The biochar
activated with phosphoric acid also showed a high capacity for ammonia removal, adsorbing
approximately ten times more ammonia than the activated carbon (170.1 mg of ammonia per g of
biochar vs. 16.2 mg of ammonia per g of activated carbon).
Main conclusions of the work: This work discusses the advances in the design and use of biochar to
adsorb and retain nutrients and H2S. We developed an engineered biochar adsorbent made from
anaerobic digestion fiber that fulfills two important roles: adsorbing hydrogen sulfide from biogas,
and removing phosphorus from the liquid effluent. The acidified adsorbent prepared from Douglas
fir was effective on ammonia removal.
698
HYDROLYZED ORGANIC RESIDUES AS SOURCES OF SECONDARY RAW MATERIALS
D. PLEISSNER1, J. C. PEINEMANN1
1 Sustainable Chemistry (Resource Efficiency), Leuphana University Lüneburg, Germany.
Abstract
It is expected that the production of municipal solid waste (organic content of 46%) will increase to
2.2 billion t by 2025 [1]. In accordance with the composition of mixed food waste collected from
restaurants [2], the following shares of the components were assumed: 450-750 g/kg total
carbohydrates (300-600 g/kg starch), 50-100 g/kg protein, 70-400 g/kg lipids and around 2 g/kg
phosphorus. Furthermore, enormous amounts of lignocellulosic material, including grass clippings,
leaves, bushes, etc., is produced, which additionally can serve as a source of carbohydrates and
other functionalized molecules. Hardwood for example comprises 250-400 g/kg hemicelluloses, 450-
470 g/kg celluloses and 200-250 g/kg lignin [3]. With this composition organic waste is a promising
carbon and nitrogen source in many fermentative processes [4]. The recovery of phosphate,
however, has been ignored due to low quantities and strong dilution after
fermentation/downstream processing.
The present study addresses the coupling of efficient phosphate recovery and
fermentation/downstream processing. Calcium carbonate-rich seashell powder (SP) has been used
for phosphate adsorption from filtrated lactic acid (LA) fermentation broth. Experiments with pure
phosphate solution (PPS), artificial (AFB) and real fermentation broths (RBS) have been carried out.
AFB and RBS contained authentic concentrations of 50 mg/L phosphate and 50 g/L LA. Adsorption
kinetics and the effect of time, SP load and mode of operation (batch (flask) and continuous
(column)) on the adsorption performance were investigated on PPS and AFB. Optimized conditions
were eventually applied on RBS.
Experiments revealed that in the presence of LA, phosphate adsorption follows the Langmuir
isotherm indicating a monolayer of phosphate on the SP particles. In PPS the Freundlich isotherm
described best the data, suggesting a higher influence of pore diffusion on the adsorption process.
More than 80% of the phosphate in PPS and 50% of the phosphate in AFB were removed after 20
min when 4.8 g SP was applied. With increasing SP amount adsorption capacity declined from 2.57
mg phosphate/g to 0.50 mg/g in PPS and 0.57 mg/g to 0.34 mg/g in AFB. Using a column with 0.6 g
SP (flow: 2 mL/min), the adsorption capacity was 1.12 mg/g (PPS) and 0.79 mg/g (AFB). Conclusively,
it was shown, that SP is well suited to adsorb phosphate in the presence of LA and can be used to
remove phosphate from fermentation broths. This approach contributes to the utilization of organic
waste, the production of fertilizer and eventually the production of new biomass.
References
[1] Campuzano, R., González-Martinez, S.: Characteristics of the organic fraction of municipal solid waste and methane
production: A review. Waste Manag. 54, 3-12 (2016)
[2] Pleissner, D., Kwan, T. H. and Lin, C. S. K.: Fungal hydrolysis in submerged fermentation for food waste treatment
and fermentation feedstock preparation. Bioresour. Technol. 158, 48-54 (2014)
[3] Limayem, A., Ricke, S. C.: Lignocellulosic biomass for bioethanol production: Current perspectives, potential issues
and future prospects. Prog. Energy Combust. Sci., 38, 449-467 (2012)
[4] Koutinas, A. A., Vlysidis, A., Pleissner D., Kopsahelis, N., Lopez Garcia, I., Kookos, I. K., Papanikolaou, S., Kwan, T. H.,
Lin, C. S. K: Valorization of industrial waste and by-product streams via fermentation for the production of chemicals
and biopolymers. Chem. Soc. Rev., 43, 2587-2627 (2014)
699
VALORISATION OF MOLASSES FOR THE PRODUCTION OF BIOLUBRICANTS VIA

FERMENTATION USING OLEAGINOUS YEASTS
A. PAPADAKI1, E. BOVIATSI1, M. KYRIAKOU1, G.J. NYCHAS1, J.A.C. DA SILVA2,

D.M.G. FREIRE3, A. A. KOUTINAS1,
1 Agricultural University of Athens, Department of Food Science and Human Nutrition, Iera Odos 75,
11855 Athens, Greece.

2 Cenpes, Centro de Pesquisas Leopoldo Américo Miguez de Mello, Petrobras, Rio de Janeiro, Brazil.
3 Department of Biochemistry, Institute of Chemistry, Federal University of Rio de Janeiro, Cidade
Universitária, Centro de Tecnologia, BL A, SL 549, Ilha do Fundão, 21949-900, Rio de Janeiro, Brazil.
Abstract
Molasses is considered the major by-product derived from the sugar cane industry (more than
65,000 t in 2015) [1]. This study focuses on the efficient production of microbial oil and its further
conversion into biolubricants. Rhodosporidium kratochvilovae Y-43, a newly isolated yeast strain, and
Rhodosporidium toruloides NRRL Y-27012 were initially cultivated using various carbon sources. Both
strains could assimilate sucrose, fructose, glucose and mannose. Furthermore, R. kratochvilovae
could assimilate galactose, whereas R. toruloides assimilated xylose. The high potential of the red
yeasts R. kratochvilovae and R. toruloides for microbial oil production was initially determined in
batch fermentations using cane sugar as substrate. The biomass production and lipid content
achieved were up to 22 g/L and 47% (w/w), respectively. Submerged fermentations were
subsequently carried out using molasses as substrate for the production of microbial oil, which was
then served as raw material for the production of bio-based lubricants through enzymatic
biocatalysis. The highest lipid content (42%, w/w) and biomass concentration (22 g/L) were achieved
by R. kratochvilovae when the medium contained a minimal mineral supplement. The yeast R.
toruloides achieved the highest biomass (17.2 g/L) and lipid content (49%, w/w) when the medium
contained only molasses, without any mineral addition. Subsequently, the microbial oil was
extracted from the yeast cells and was enzymatically hydrolysed in order to produce a free fatty
acid-rich fraction. A solvent-free catalysis, as an environmentally friendly method, was performed
using Lipomod 34-MDP, free fatty acids and neopentyl glycol as substrate at 40°C for 24 h under
agitation. The results showed that free fatty acids derived from microbial oil were efficiently
converted into biolubricants with a conversion yield of 76% within five minutes. Nowadays, although
90% of lubricant production is based on petroleum, there is significant environmental and societal
concerns to increase the utilisation of biolubricants.
Acknowledgements
The project was funded by CNPq (Special Research Visitant – Line 2) and Petrobras (Brazil).
References
[1] Avramenko, S.: World: Molasses - Market Report. Analysis And Forecast To 2025.
(http://www.indexbox.co.uk/blog/which-countries-produce-the-most-molasses/) (2017), (accessed on 10/2017)
700
VALORISATION OF MUNICIPAL SOLID WASTE FOR SUCCINIC ACID PRODUCTION BY

BASFIA SUCCINICIPRODUCENS
E. STYLIANOU1, C. PATERAKI1, D. LADAKIS2, A. VLYSIDIS2, A. KOUTINAS1

1 Department of Food Science and Human Nutrition, Agricultural University of Athens, Iera Odos 75,
11855, Athens, Greece.

2 Department of Chemical Engineering, University of Patras, 26504, Patras, Rio, Greece.
3 School of Chemical Engineering, National Technical University of Athens, Iroon Polytechneiou 9,
Abstract
The utilisation of renewable resources for the production of bio-based products is essential in
order to develop sustainable bioprocesses and biorefineries. Municipal solid waste (MSW) could be
used for the production of succinic acid, one of the most important platform chemicals in the bio-
economy era. According to Eurostat, the amount of MSW produced in 2014 was ca. 475 kg/capita
[1]. The composition of the organic fraction of MSW varies depending on the origin and the applied
process. It contains significant quantities of polysaccharides (30-40%), proteins (5-15%) and lipids
(10-15%). Treatment and management of MSW is currently limited in landfilling, incineration and
composting. Valorisation of MSW for the production of succinic acid and simultaneous separation of
value-added co-products (e.g. proteins, lipids) could result to a sustainable biorefinery concept.
The main objective of this study was the valorisation of MSW for the biotechnological
production of succinic acid using Basfia succiniciproducens, a natural succinic acid producing strain,
and Escherichia coli AFP184, a genetically engineered strain. Optimisation of the fermentation
medium was firstly applied in Duran bottle fermentations using Plackett-Burman experimental
design in order to limit the number of the medium components. Subsequently MSW was used as
fermentation feedstock in order to evaluate the production of succinic acid in bench-top bioreactors.
Preliminary experimental results demonstrate that succinic acid production from MSW hydrolysates
could be utilised for succinic acid production.
References
[1] [1] Matsakas, L., Gao, Q., Jansson, S., Rova, U. and Christakopoulos, P. (2017) ‘Green conversion of municipal solid
wastes into fuels and chemicals’, Electronic Journal of Biotechnology. Elsevier España, S.L.U., 26, pp. 69–83.
701
METHANOL SYNTHESIS THROUGH CO2 HYDROGENATION OVER Cu/ZnO/Al2O3

CATALYSTS UNDER FLUCTUATING CONDITIONS
M. KRAFT1, A. ZURBEL1, Q. ROODE-GUTZMER1, M.BERTAU1

1
Freiberg University of Mining and Technology, Freiberg, Germany
Abstract
At present, methanol is produced on an industrial scale predominantly through the conversion of

fossil resources to syngas as the intermediate for catalytic methanol synthesis. An alternative
ecologically friendly method to produce methanol is to use a feed gas mixture of CO2 captured from
large point emitters and H2 obtained via electrolysis using renewable sources [1]. The advantages of
this process include the reduction of CO2 emissions and chemical storage of the excessive
regenerative energy. Since the operation conditions vary over time due to the dynamic availability of
the resources, an evaluation of the effects of fluctuating conditions on the performance of the
methanol synthesis catalysts is needed.
In this respect, we investigated the effect of fluctuating conditions on methanol synthesis through
CO2 hydrogenation over an industrially relevant Cu/ZnO/Al2O3 catalyst in an integral reactor. The
catalyst was first examined at temperatures between 503 and 563 K (230 and 290 °C) and pressures
between 4.0 and 8.0 MPa to define the best parameters under steady state conditions. CO2
conversion rates up to 50 % and methanol yields up to 42 % were achieved. The non-steady state
experiments were conducted by startup/shutdown cycles as well as changing the H2/CO2 ratio
frequently over a period of 100 hours. It is found that, although the phase transformations were
more pronounced under dynamic conditions, the long term stability of the synthesis process was still
satisfying in terms of methanol yield. A thorough analysis of catalyst deactivation as well as
operational optimisation possibilities with regard to catalyst lifetime will be discussed throughout
this paper.
References
[1] M. Bertau, H. Offermanns, L. Plass, F. Schmidt, H.J. Wernicke, Methanol: The Basic Chemical and Energy Feedstock of
the Future (Asinger’s Vision Today), Springer Verlag, Heidelberg, 2014, ISBN 978-3-642-39708-0
702
CHARACTERIZATION OF BIO-OIL PRODUCED BY HTL OF BINARY MIXTURE OF

PHENYLALANINE AND GLUCOSE
Z A. MATAYEVA. 1 F. BASILE1, F. CAVANI1, D. BIANCHI2, G. CHIABERGE2

1 Dipartimento di Chimica Industriale, University of Bologna, Bologna, Italy.
2 Renewable Energy & Environmental R&D Eni spa, Novara, Italy.
Abstract
Hydrothermal liquefaction (HTL) is an effective technique to obtain bio-oil from advanced waste
biomass without any drying step. However, bio-oil produced from HTL cannot be used directly as a
liquid transportation fuel due to its significant heteroatoms content. While oxygen is easy to remove
by hydrotreating, nitrogen is more recalcitrant making the bio-oil difficult to integrate in
conventional refinery processes. To overcome this problem it is necessary to study the chemical
behavior of nitrogen containing compounds during HTL in order to reduce their formation.
Doubtless, for optimization and selection of appropriate upgrading strategy the chemical
characterization of heteroatom and functionality distribution in bio-oil is crucial. Therefore, in the
present study phenylalanine and glucose were employed as representative biomass model
compounds of protein and carbohydrate macromolecules. Their interaction behavior during the HTL
process was investigated considering the molecular level characterization of the nitrogen-containing
species in bio-oil by means of positive electrospray high resolution mass spectrometry (FTICR –MS).
Most attention is paid for the carbon and nitrogen transferring into oil products produced from
hydrothermal liquefaction.
References
[1] H Y. He et al. Algal Research, 17, 185 (2016).
[2] Chen Yu-peng et al. Journal of Fuel Chemistry and Technology, 42, 61 (2014).
[3] E. Kendrick et al. Anal. Chem., 35, 2146 (1963).
[4] S. Chiaberge et al. Energy Fuels, 23, 4486 (2009). amburger, C.: Quasimonotonicity, regularity and duality for
nonlinear systems of partial differential equations. Ann. Mat. Pura. Appl. 169, 321–354 (1995)
703
3DOM CERIA ECOCERAMICS FROM SUSTAINABLE CORK TEMPLATES FOR SOLAR

THERMOCHEMICAL HYDROGEN PRODUCTION
RUI M. NOVAIS, ROBERT C. PULLAR1

1 Department of Materials and Ceramic Engineering / CICECO- Aveiro Institute of Materials,
University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal.
Abstract
Climate change and renewable energy sources are two of the major technological and societal
challenges of the millennium, with increasing public and political awareness regarding energy
production and its sustainability. As a result, the European Union has implemented demanding
directives [1] to change the paradigm from fossil fuels to renewable sources, and by 2020 a fifth of
the EU total energy needs should be produced using renewable sources. One emergent technology
that can contribute to this target is thermochemical energy production using solar power. This
process uses very high temperatures (1600 oC) to split water and produce hydrogen. Nevertheless,
current solar-to-energy efficiency levels are modest which is a major challenge limiting this
technology. Among the different materials that have been investigated for thermochemical fuel
production (TCFP), cerium oxide (CeO2) is the benchmark material [2]. CeO2 has excellent redox
properties and oxygen storage / release capacity [3]. However, its low reduction and oxidation rates
hinder the efficiency of thermochemical fuel production [4]. Process kinetics can be modified by
increasing CeO2 surface area and porosity [5, 6], suggesting that three-dimensionally ordered
macroporous (3-DOM) CeO2 could further enhance systems efficiency. In this work cork, a unique
sustainable resource, was used as a template for producing lightweight and porous ecoceramics
using a simple and green-chemistry procedure [7, 8]. The ceria ecoceramics preserved the
microstructure of cork, but the cell rear walls were ruptured, thus increasing the open porosity and
surface area, which may allow their use in TCFP.
References
[1] Directive 2009/28/EC of the European parliament and of the council of 23 April 2009 on the promotion of the use of
energy form renewable sources and amending and subsequently repealing Directives 2001/77/EC and 2003/30/EC
(Document: 32009L0028). Official Journal of the European Union, L140/16-L140/62. Available from: http://eur-
lex.europa.eu/homepage.html.
[2] Bulfin, B., Call, F., Lange, M., Lubben, O., Sattler C., Pitz-Pall, Shvets , R. Thermodynamics of CeO2 thermochemical
fuel production. Energy & Fuels 29, 1001-1009 (2015).
[3] Huang, H., Liu, J., Sun, P., Ye, S., Liu, B. Effects of Mn-doped ceria oxygen-storage material on oxidation activity of
diesel soot. RSC Advances 7, 7406-7412 (2017).
[4] Chueh, W. C., Falter, C., Abbott, M., Scipio, D., Furler, P., Hail, S. M., Steinfeld, A. High-Flux Solar-Driven
Thermochemical Dissociation of CO2 and H2O Using Nonstoichiometric Ceria. Science 330, 1797-1801 (2010).
[5] Venstrom, L. J., Petkovich, N., Rudisill, S., Stein, A., Davidson, J. H. The effects of morphology on the oxidation of
ceria by water and carbon dioxide. Journal of Solar Energy Engineering 134, 011005(1-6) (2012).
[6] Furler, P., Scheffe, J., Marxer, D., Gorbar, M., Bonk, A., Vogt, U., Steinfeld, A. Thermochemical CO2 splitting via redox
cycling of ceria reticulated foam structures with dualscale porosities. Phys. Chem. Chem. Phys. 16, 10503-10511
(2014).
[7] Pullar, R.C., Marques, P., Amaral, J., Labrincha, J.A. Magnetic wood-based biomorphic Sr3Co2Fe24O41 Z-type
hexaferrite ecoceramics made from cork templates. Mater. Design 82, 297-303 (2015).
[8] Pullar, R.C., Novais, R.M. Ecoceramics - Cork-based Biomimetic Ceramic 3-DOM Foams. Materials Today 20 (2017)
45-46.
704
IMPACT OF MUNICIPAL SOLID WASTE INCINERATORS ON HEAVY METALS IN THE

SURROUNDING SOILS BY MULTIVARIATE ANALYSIS AND Pb ISOTOPE ANALYSIS
H. ZHANG1,2, Y. LI1,2, L.M. SHAO1,2, P.J. HE1,2

1 Institute of Waste Treatment and Reclamation, Tongji University, Shanghai, China.
2 Centre for the Technology Research and Training on Household Waste in Small Towns & Rural Area,
Ministry of Housing Urban-Rural Development, Shanghai, China.
Abstract
Municipal solid waste (MSW) incineration has become an important anthropogenic source of heavy
metals (HMs) to environment. However, it can be a challenging task to assess the impact of MSW
incineration on HMs in the environment, especially soils, because of various sources. To investigate
this impact, the contents of eight HMs and the Pb isotope ratios in the surrounding soil samples with
different distances from four MSW incinerators in Shanghai, China, were analyzed. Source
identification and apportionment of HMs in the soils were studied by using principal component
analysis and Pb isotope analysis. The result indicated that the relatively high contents of Cd, Pb, Sb,
and Zn in the soils at 250 or/and 750-1250 m away from the MSW incinerators were related to MSW
incineration, while the elevated contents of most HMs were associated with other anthropogenic
activities. Pb isotope analysis suggested that for the MSW incinerators that have been operated for
more than 10 years, MSW incineration was estimated to contribute to approximately 10% of soil Pb
in average, which was less than coal combustion, while for those MSW incinerators that have been
operated for only several years, their influence on the HMs in the surrounding soils was not
significant.
Reference
[1] Li, Y., Zhang, H., Shao, L. M., He, P. J.: Tracing source and migration of Pb during waste incineration using stable Pb
isotopes. J. Hazard. Mater. 327, 28-34 (2017)
705
MERCURY EMISSIONS CONTROL IN HAZARDOUS WASTE INCINERATION PLANTS
X. CHAUCHERIE1, M. BACQUET1, T. GOSSET1, B. VOSTEEN2

1 SARPI-VEOLIA, Limay, France.
2 VOSTEEN Consulting GmbH, Cologne, Germany.
Abstract
The control of mercury emissions from incineration plants has become an important issue in Europe
in recent years and may become so in the US and elsewhere in the future. In the framework of the
actual revision of the EU BAT (Best Available Techniques) Reference Document (BREF) [1], it is very
likely that incineration plants will have to meet more stringent requirements, including the
continuous mercury emission measurement and a lower emission limit value in the 10 – 25 µg/Nm3
dry basis range instead of 50 µg/Nm3 dry basis (at 11% O2) at the moment.
The presentation reports about 600-hours trials performed at two hazardous waste incineration
plants with dry and semi-dry gas cleaning to test and validate the patented Bromine-Enhanced
Mercury Oxidation (BEMO) technology from Vosteen Consulting GmbH. This BEMO technology was
initially developed in hazardous waste incineration plants with wet gas cleaning and proved to be
flexible, reliable and effective at a reasonable price.
During the trials, it was demonstrated that the more mercury is oxidized, the higher the removal
efficiency is (up to 99.9 %) - also in case of dry gas cleaning with normal activated carbon injection
(ACI) only.
Mercury emission peaks caused by "hidden mercury" (simulated by the discontinuous injection of
"Hg bombs") can be effectively suppressed by adequat CaBr2 injection into the post-combustion
chamber.
In case of semi-dry gas cleaning (dry air pollution control system with ACI, followed by wet tail-end
neutral scrubber), the combination of CaBr2 injection into the post-combustion chamber and PRAVO®
addition into the wet tail-end neutral scrubber did show highly promising results. PRAVO® is an
inorganic alkaline precipitation agent of Vosteen Consulting GmbH, based on sodium sulfide, sodium
thiosulfate and bromide.
Three SARPI-VEOLIA hazardous waste incineration plants implemented recently the BEMO
technology to control mercury emissions in industrial conditions.
References
[1] European Commission. Waste Framework Directive. Directive 2008/98/EC (2008)
[2] Vosteen, B.W., et al. Bromine-enhanced mercury abatement from combustion flue-gases. Recent industrial
applications and laboratory research. VGB PowerTech. Volume 86, Issue 3/2006, pages 70-75 (2006)
706
REDUCING CHLORINE CONTENT IN PYROLYSIS GAS FROM RDF
M. HURON1, P. SAJET1, O. LEPEZ1

1 ETIA, Compiegne, France.
Abstract
Pyrolysis is an attractive alternative to landfilling or incineration for the valorisation of Refuse

Derived Fuel (RDF). With proper operating conditions, pyrolysis can produce a high calorific synthetic
gas which can be used in various energetic applications and a low final char residue. However, RDF
may contain high amount of chlorine. During pyrolysis, part of this chlorine is released as HCl or
other chlorinated gaseous compounds. This is a major hindrance for the process as it leads to
corrosion problems and environmental issues. As a consequence, capturing as much chlorine as
possible in the char is a challenge that has to be fulfilled in order to optimize gas valorisation.
Use of calcium oxide and calcium hydroxide has been widely investigated in literature in order to
limit chlorine emission during combustion of waste [1, 2] and its efficiency has been demonstrated.
Nevertheless, only few studies have been carried out on the use of Ca(OH) 2 during pyrolysis process,
and are often limited to lab scale experiments.
In this study, RDF was co-formulated with different amount of Ca(OH)2 (5 ; 10 ; 15%) and pyrolyzed
in Biogreen’s continuous pyrolysis process developed by ETIA. Its scalability ranges from 5 kg/h to 1
t/h and it is already a proven technology since 2013. Pyrolysis was carried out at 750°C with
residence time of 20 minutes in a bench unit with mass flow rate of 8 kg/h.
Impact of Ca(OH)2 addition on mass yield, energy balance, gas composition and repartition of
chlorine was investigated. It was shown that formulation of RDF with Ca(OH)2 is an efficient way to
decrease the chlorine emission in gas and can be used in industrial units.
References
[1] Fundamental study of the behavior of chlorine during the combustion of single RDF, Gui-Qing Liu, Yoshinori Itaya,
Ryohei Yamazaki, Shigekatsu Mori, Masataka Yamaguchi, Motohiro Kondoh, Waste Management, Volume 21, Issue
5, August 2001, Pages 427-433
[2] The effects of calcium hydroxide on hydrogen chloride emission characteristics during a simulated densified refuse-
derived fuel combustion process, Kung-Yuh Chiang, Jer-Chyuan Jih, Kae-Long Lin, Journal of Hazardous Materials,
Volume 157, Issue 1, 30 August 2008, Pages 170-178)
707
CHARACTERIZATION OF NANOMATERIAL’S FROM BIO-WASTES
S. THOMAS1, N. KALARIKKAL1
1 Mahatma Gandhi University, Kottayam, Kerala, India.
Abstract
Agro-wastes are eco-friendly starting materials to produce typical nanoparticles with well-defined
chemical composition, size, and morphology. Cellulose, chitin, chitosan and starch are the most
abundant biopolymers from agro-waste around the world. Cellulose nanoparticles(fibers, crystals
and whiskers) can be extracted from agro-waste resources such as jute, coir, bamboo, pineapple
leafs, coir etc and nanoparticles of chitin (fibers, whiskers) can be extracted from shrimp and crab
shells. Starch nano particles can be extracted from tapioca and potato wastes. These nanoparticles
can be converted into smart and functional biomaterials by functionalization through chemical
modifications (esterification, etherification, TEMPO oxidation, carboxylation and hydroxylation etc)
due to presence of large amount of hydroxyl group on the surface. Transmission electron microscopy
(TEM), scanning electron microscopy (SEM) and atomic force microscopy (AFM) are used to
investigate the morphology of these nanoscale biopolymers. Fourier transform infra-red
spectroscopy (FTIR) and x ray diffraction (XRD) can be used to study the functional group changes,
crystallographic texture of nanoscale biopolymers respectively. Zeta potential measurements are
used to investigate the suspension stability and surface charge of these nano scale materials. Further
utilization of cellulose, starch and chitins can be done after functionalization and can be easily
incorporated into polymer matrices to produce smart nanocomposites like membranes for various
applications. Several characterization techniques can be employed to characterize these bio
nanocomposites. These include: BET to investigate average pore size and specific surface area,
contact angle studies to investigate the wettability of these membranes, morphological analysis,
thermal studies etc. The reinforcing effect of these nanoparticles resulting from the formation of a
percolating network based on hydrogen bonding forces can also be analyzed through various
characterization techniques. The role of nano particle dispersion, distribution, interfacial adhesion
and orientation on the properties of the ecofriendly bio nanocomposites can also be evaluated
through various characterization techniques being discussed in this talk.
References
[1] Meldrums Acid Modified Cellulose Nanofiber-Based Polyvinylidene Fluoride Microfiltration Membrane for Dye
Water Treatment and Nanoparticle Removal, Gopakumar D. A., Pasquini, D., Henrique, M. A., Luis, de Morais., C.
Grohens Y. and Thomas, S.,(2017) ACS sustainable chemistry and Engineering, DOI:
10.1021/acssuschemeng.6b02952
[2] Revalorization of sunflower stalks as novel sources of cellulose nanofibrils and nanocrystals and their effect on
wheat gluten bionanocomposite properties Fortunati, E., F. Luzi, A. Jiménez, D. A. Gopakumar, D. Puglia, S. Thomas,
J. M. Kenny, A. Chiralt, and L. Torre (2016). Carbohydrate polymers 149 (2016): 357-368.
[3] Chitin nanowhisker (ChNW)-functionalized electrospun PVDF membrane for enhanced removal of Indigo carmine.
Gopi, S., Balakrishnan, P., Pius, A., & Thomas, S. (2017) Carbohydrate Polymers, 165, 115-122.)
708
SYSTEMATIC AND INTEGRATED APPROACH IN HAZARDOUS MEDICAL WASTE

TREATMENT
V. MÁŠA, M. TOUŠ, E. KONEČNÁ, P. STEHLÍK

Brno University of Technology, Faculty of Mechanical Engineering, Institute of Process Engineering,
Brno, Czech Republic
Abstract
The management of hazardous waste, especially medical waste, is an important topic that can't be
avoided. Treating medical waste in a correct manner can prevent possible dangers when moving or
disposing the waste [1]. Moreover, the amount of medical waste will rise with the increase in
healthcare [2]. Medical waste can contain a high percentage of infectious waste that has to be
treated under special requirements. The best way to avoid dangers from the medical waste is to
separate the infectious waste and then decontaminate it directly in the medical facility.
This paper focuses on various methods for treating medical waste. There are a number of different
methods to decontaminate infectious waste. For this paper, the three most promising methods were
chosen: steam sterilization, incineration and shredding. These methods will be described technically
and compared with each other. Various indicators will be observed and studied, such as the possible
type and amount of input waste, energy and time demands, output waste conditions and
possibilities for further treating the output material.
The main target is to provide a complete description of each method with its characteristics, and a
list of advantages and disadvantages. A couple of examples from recent period is shown. With a
detailed characterization of the selected methods, an overall balance can be created for future work.
Also, the potential in waste heat can be determined and its use can be considered in other existing
systems (e.g. a hospital laundry) in the medical facility as well as a potential export of energy.
Utilizing this information, the integration of a particular system can be evaluated.
References
[1] PRÜSS A., GIROULT E., RUSHBROOK P.: Safe management of wastes from health-care activities. Geneva: World
Health Organization, 1999. ISBN 9241545259.
[2] WINDFELD, E.S., BROOKS, M.S.L.: Medical waste management – A review. Journal of Environmental
Management. 2015, Volume 163, Pages 98-108. ISSN 0301-4797.
709
THE INFLUENCE OF PLANT CULTIVATION METHODS ON BIOGAS PRODUCTION:

ENERGY EFFICIENCY
L. KRZYSTEK1, K. WAJSZCZUK2, A. PAZERA1, M. MATYKA3, R. SLEZAK1, S. LEDAKOWICZ1

1 Lodz University of Technology, Faculty of Process and Environmental Technology,
Department of Bioprocess Engineering, 213 Wolczanska St., 90-924 Lodz, Poland.

2 Poznan University of Life Sciences, Department of Management and Law,
28 Wojska Polskiego St., 60-637 Poznan, Poland.

3 Institute of Soil Science and Plant Cultivation – State Research Institute,
8 Czartoryskich St., 24-100 Puławy, Poland.
Keywords: plant cultivation, biomass, biogas, economics efficiency, energy efficiency
Abstract
The aim of the paper was to determine the influence of the fertilization level, soil type and climate
conditions on the energy efficiency of the biogas production from maize, sorghum and reed canary
grass silages.
The plant material used to prepare silages was obtained from a field experiments located on light,
medium and good soil. Depending on the plant investigated and allowing for fertilization
requirements the following levels of nitrogen fertilization were assumed in the research: for reed
canary grass 40, 80 and 120 kgN·ha-1, for maize and sorghum: 80, 120 and 160 kgN·ha-1.
Increasing of nitrogen doses had little effect on the yield of these plants. The highest yield of maize
green mass was obtained at the level of about 50 t ha-1. The yield of sorghum was above 70 t ha-1,
and reed canary grass about 40 t·ha-1.
High yields of biogas were obtained from maize silage with the lowest fertilization level of 80 kgN·
ha-1 from 194.5 m3·t-1 green mass up to 315,33 m3·t-1 depending on soil quality. The highest biogas
yield of 1 ton of sorghum green mass (115 m3·t g.m.-1) was obtained for the highest fertilization level
of 160 kgN·ha-1. In turn, for reed canary grass the highest biogas yield 126 m3·ha-1 was obtained
when 80 kgN·ha-1dose was applied.
Depending on the soil type, the Energy Return on Energy Investment index (ERoEI) and the Net
Energy Value (NEV) values for maize ranged from 5.05 and 189,000 MJ ha-1 (light soil), obtained at
the level of 120 kgN ha-1 to 9.76 obtained at the level of 80 kgN ha-1 and 433,000 MJ ha-1 obtained at
the level of 120 kgN ha-1(good soil). For sorghum (light soil) values of about 5.2 and 200,000 MJ ha -1
were appropriately obtained at the level of 160 kgN ha-1. In the case of reed canary grass the highest
ERoEI and NEV values obtained at the level of 80 kgN ha-1 - they were amounted to 3.8 and 74,000
MJ ha-1 (light soil), respectively.
710
1- INTRODUCTION
When the world in XXI century faces problems with growing energy consumption and reducing fossil
fuels it is essential to develop suitable cultivars of crops being renewable sources in order to obtain
maximum yield of methane production per hectare, all the more so because in recent years more
and more attention has been paid to the usefulness of crops for industrial purposes [1-3]. Therefore,
it is necessary to conduct research aimed at the evaluation of the energetic efficiency of the
technologies related with the production of biomass for energetic purposes [4, 5].
The most important parameter in choosing crops for methane production is the net energy yield per
hectare, which is defined mainly by biomass yield and convertibility of the biomass to methane. This
may result in different harvesting strategies when growing energy crops for anaerobic digestion.
Specific harvest and processing technologies and specific genotypes are required when crops are
used as a renewable energy source. Ideally, energy crops should offer a high dry biomass yield at a
low cost, a composition with the least contaminants such as soil and should require low nutrient and
energy inputs [6]. It should also offer a low sensitivity to pest and a good soil cover, while not
decreasing the biodiversity.
However, the use of those energy crops which are used as food products for biofuel production is an
important issue which must be considered in terms of the current food safety. Nowadays, the
development of specific crops dedicated to energy has been proposed as a strategy to produce
energy without affecting food security and the environment. Improving biomass yield of dedicated
energy crops on a limited area of land is cited as one of the possible strategies for achieving an
effective and sustainable use of bioenergy [7]. For bioenergy cropping systems, N fertilizer use is a
key agricultural management practice for improving productivity and profitability [7, 8]. Nitrogen (N)
availability has been reported as the most frequently limiting factor for growth of native grasses,
suggesting that N fertilization can be an important management practice for energy crops biomass
production and feedstock quality [9, 10]. Yet, there is still a lack of information regarding impacts of
N fertilization on biomass yield of energy crops, growing on soils in different localisations.
Modern cultivation programs seek to increase the digestibility of plants, as there are still great
opportunities to improve this feature. It is therefore important to assess the suitability of potential
energy crops for biogas production in order to achieve the best possible output, since the
justification for the economics of biogas production depends on the high productivity of its
production. Apart from cost accounting energy efficiency costing is an important element in the
assessment of production of biofuels. The advantage of energy costing is its independence of price
relations, which enables a comparison of findings in different research centres.
In this paper the effect of nitrogen fertilization level, soil type and climate conditions on the yield
and production of biogas from maize, sorghum and reed canary grass silages was determined. In
order to assess the energy efficiency of the investigated crops, the Energy Return on Energy
Investment index (ERoEI), also known as the Energy Return on Investment (ERoI), and the Net Energy
Value (NEV) ratio were used.

Field experiments
The field experiments of selected maize (Zea mays L.), sorghum (Sorghum Moench) and reed canary
grass (Phalaris Arundinacea L.) were carried out in this study.
The plant material used to prepare maize and sorghum silage was obtained from a field experiment
located on light soil (5-6 complex) in Mochełek locality, Poland ( N: 53 ° 13'23.63 "E: 17 ° 52'21.41").
On the other hand, from experiments on light soil (5-6 complex) in the location of Jelcz-Laskowice,
711
Poland (N: 51 ° 2'35.27 "E: 17 ° 21'23.59); on medium soil (4-5 complex) in the locality of Osiny,
Poland (N: 51 ° 27'59.98 "E: 21 ° 39'44.28") and on good soil (2 complex), in the locality of Grabów,
Poland (N: 51 ° 20'58.23 "E: 21 ° 39'44.28") maize silage was harvested. Plant material used for the
preparation of reed canary grass silage was obtained from a field experiment located in the medium
soil (4-5 complex) in Osiny, Poland (N: 51°27’59.98”, E: 21°39´44.28”). The experiments were
conducted in a randomized complete block design in "split-plot" system, with 4 replications.
Depending on the plant investigated and allowing for fertilization requirements the following levels
of nitrogen fertilization were assumed in the research: for reed canary grass: 40, 80 and 120 kgN
ha-1, for maize and sorghum: 80, 120 and 160 kgN ha-1.
The seeds were sown with a single seed drill at a rate of 130 thousand ha-1 for maize – 130 thousand
ha-1, from April 26 to May 12, and sorghum - 220 thousand ha-1 from 9 May to 8 June. Before
sowing, the seeds were treated with insecticides and fungicides. There was also applied chemical
weed control. Maize was harvested on 7–11 September, and sorghum on 19–28 October. Reed
canary grass seeds, were sown in the amount 25 kg ha-1 in row with spacing of 12 cm to a depth of
1.5-2.0 cm. Yields were collected in the second decade of June.
The evaluated species were grown for silage, which was the material for further research on the
potential of biogas production. The yields of green and dry mass were determined. Dry matter
content in silage was determined on the basis of Standard Methods [11].
BMP analysis
Based on the results of preliminary studies for silage dry matter and organic matter initial load of the
bioreactor was selected. Weighed portion of the silage with the anaerobic sludge was placed in a
sealed fermentation vessels with a working volume of 1 dm3 in order to perform Biochemical
Methane Potential (BMP) analysis. Then bioreactors were placed in a shaker with thermostat
maintaining the temperature of 370,1°C. The contents of the bioreactors were flushed with N2/CO2-
gas for 5 minutes and then were then sealed with rubber stoppers. Daily methane production from
each digester was measured by using a water displacement. The level of gas in the collector was read
every 24 hours and its composition was analyzed using a SRI 8610C gas chromatograph (SRI
Instruments, USA) equipped with TCD detector and two chromatographic columns: a column packed
with Silica Gel No. 8 and 5A molecular sieve mesh 80/100. The reactors ran until no further methane
production was detected. Each sample was performed in triplicate and the arithmetic average was
taken for data interpretation. At the beginning and end of batch fermentation, the contents of the
bioreactors were analyzed for dry matter, according to Standard Methods [11]. As an inoculum
anaerobic sludge obtained from an active biogas plant in Konopnica, Poland, and incubated for a
period of 56 days in bioreactor with a capacity of 100 dm3 was used. Significant differences between
the examined parameters were evaluated by the analysis of variance, setting Tukey’s confidence
half-intervals at significance level α = 0.05.
Energy efficiency analysis
In order to assess products with the characteristics of energy carriers or fuels, the Energy Return on
Energy Investment index (EroEI), also known as the Energy Return on Investment (ERoI), will be used
and calculated according to the following formula (1) [12]:
ERoEI (ERoI ) = Eout / Ein (1)
where: Eout - energy gained (useful), Ein - energy intake, energy input.
Apart from the ERoEI ratio, the Net Energy Value (NEV) ratio is also used in the assessment of the
energetic efficiency of the product. The ratio is defined as the difference between the amount of
energy gained (Eout ) and the amount of energy consumed to make the product (Ein).
712
After determining an amount of biogas obtained from the aforementioned plants the methane
content was determined. As far as biogas is concerned, its calorific value depends on the content of
methane, whose high calorific value (HCV) is 39.72 MJ/m3 at 0oC and 101.325 kPa [13, 14]. Then the
result per 1 ha of the plantation was calculated.
In general, two components of the outlay can be listed. The first concerns the outlay related with the
production of the raw material (Einp), whereas the other one concerns the outlay related with the
raw material processing (Eint). Thus, the general formula for determination of the energy input into
the production of biogas looks as follows (2):
Ein = ΣEinp + ΣEint (2)
where: Ein - as in formula (1), ΣEinp – total accumulated energy related with the production of plant
raw material, ΣEint – total accumulated energy related with the processing of plant raw material into
biogas.
Due to the substantive scope of the project, as far as the energy intake is concerned, this paper will
assess the first element related with the production of raw material and supplying it to the place
where it will be processed into biogas. The accumulated energy related with the production of plant
raw material is composed of four basic streams of energy [15, 16]. It is calculated according to the
following formula (3):
ΣEinp = ΣEmat + ΣEmt + ΣEf + ΣEhl (3)
where: Einp – as in formula (2) [MJ·ha–1], ΣEmat – total energy consumption of the applied materials
and raw materials [MJ·ha-1], ΣEmt – total energy consumption of the machines and tools applied
[MJ·ha-1], ΣEf – total energy consumption of the fuel consumed [MJ·ha-1], ΣEhl – total energy
consumption of the human labour [MJ·ha-1].

Biogas production
In the studies on the effect of fertilization on the quantity and composition of biogas produced and
the yield of biogas production, three plants were analyzed: maize, sorghum and reed canary grass.
Tables 1 and 2 present the results of the biomass yielding and the biomethane potential (BMP)
analysis of maize silage from Grabów, Osiny, Jelcz-Laskowice and Mochełek locations and sorghum
from Mochełek location for three different nitrogen fertilization levels: 80, 120 and 160 kgN ha -1, and
also reed canary grass silage from Osiny location with 40, 80 and 120 kgN ha-1 fertilization.
In the studies conducted, the highest yield of green mass of maize was obtained on good soil in
Grabów (about 50 t ha -1). The yield of sorghum was higher than 70 t ha-1, and of the reed canary
grass was about 40 t ha-1. Increasing nitrogen doses resulted in a slight increase in green mass yield
from 1ha. The highest green mass yield was obtained for the highest nitrogen fertilization of 160N.
Analysis of the results showed that the degree of nitrogen fertilization had a significant effect on the
biogas yield of maize silage from different locations, which were characterized by their different
quality.
The highest yield of biogas per hectare of Bosman maize silage from Grabów (good soil) and Osiny
(medium soil) locations was obtained for middle fertilization level: 120N, Table 2. Comparing the
maize silage by location, silage from Grabów appeared to be the most efficient since the yield of
biogas per hectare was 15595 m3 ha-1 year-1 (120N fertilization rate). Much lower biogas yields were
obtained for Vitras maize silage from Jelcz Laskowice and Mochełek (light soil) sites, the yields of
713
which were in the range of 9751-11412 m3 ha-1 year-1 and 7810-8690 m3 ha-1 year-1, respectively.
BMP analysis was repeated 3 times and each time such low yields of biogas were obtained. It should
be noted that in this case the highest yield was obtained for maize silage from the Jelcz-Laskowice
location with the highest fertilization level (160N) amounting to 11412 m3 ha-1 year-1.
Level of nitrogen Yield of Yield of dry Share of Yield of

Crop Localisation fertilization green mass mass dry mass silage*
(kgN·ha-1) (t·ha-1) (t·ha-1) (%) (t·ha-1)
80N 48.0 15.37 32.03 36.0
Maize Grabów
120N 51.3 15.29 29.81 38.5
Bosman Good soil
160N 51.5 17.95 34.85 38.6
80N 45.9 12.24 26.66 34.4
Maize Osiny
120N 44.3 13.14 29.66 32.2
Bosman Medium soil
160N 45.2 12.38 27.39 33.9
Jelcz- 80N 37.6 9.38 24.94 28.2
Maize
Laskowice 120N 43.9 8.87 20.20 32.9
Vitras
Light soil 160N 46.9 9.72 20.72 35.2
80N 44.7 21.31 47.69 33.51
Maize Mochełek
120N 44.3 19.54 44.10 33.23
Vitras Light soil
160N 46.3 19.9 42.96 34.74
80N 71.8 22.69 31.60 53.85
Sorghum Mochełek
120N 71.9 29.58 41.13 53.94
Rona 1 Light soil
160N 73.5 23.91 32.52 55.14
Reed canary 40 32.0 8.8 27.4 24.0
Osiny
grass 80 37.6 10.2 27.0 28.2
Medium soil
Bamse 120 46.3 12.3 26.5 34.7
* silage yield specified on the basis of green mass yield
Table 1:. Yielding of maize, sorghum and reed canary grass.
Comparing individual silages due to biogas yield from 1ton of green mass, it was observed that the
highest yields of biogas production were obtained from the maize silages with the lowest fertilization
level (80N): for Bosman maize silage from Grabów location 315.33 m3 t-1 green mass (g.m.), Vitras
from Jelcz Laskowice locality 259,33 m3t-1 g.m. and Vitras from Mochełek 194.5 m3 t-1 g.m. On the
other hand, for Bosman maize from Osiny locality with middle fertilization level: 318.67 m3 t-1 g.m.
Dry matter content during maize harvest was 27 to 35% for the Bosman cultivar, and 20% to 48% for
the Vitras cultivar, Table 1. The highest dry matter content was found for Vitras maize from
Mochełek locality (light soil), being 43-48%, which was associated with low biogas production from
7810 to 8790 m3 ha-1 year-1. Almost twice higher biogas yield (about 16000 m3 ha-1 year-1) was
obtained for Bosman maize from Grabów location (good soil) the dry matter content of which was
about 30%.
The optimum nitrogen dose for maize found by various authors [17] varies between 90-180 kg ha-1.
Such different effect of nitrogen doses on maize yield is mainly due to different cultivation methods,
and hence the use of different doses, different planting density, harvesting date, limiting the length
of vegetation period. None of the authors, however, examined the effect of nitrogen fertilization
level on biogas production. Comparison of the results of BMP analysis of three maize silages and
three sorghum silages fertilized with 80, 120 and 160 kgN ha-1 from Mochełek location (light soil)
showed much higher biogas yields for maize silage than for sorghum. The highest biogas yield of
194.5 m3 t-1 green mass was obtained from maize silage with the lowest level of fertilization (80 kgN
ha-1). On the other hand, in the case of sorghum, the highest amount of biogas (115 m3 t-1 g.m.) was
obtained from silage fertilized with the highest dose of 160 kgN ha-1 (Table 2).
714
By analyzing the effect of nitrogen fertilization on the susceptibility of selected silages to

decomposition in the processes of methane fermentation and biogas production, the difference in
biogas yield was higher for sorghum. However, higher production of biogas and methane from 1
tonne of green mass and higher yield per hectare of these gases were obtained in the present work
from maize silage as compared to sorghum silage, which is confirmed by results of other authors: [18
- 21]. Methane content in biogas for both maize and sorghum was high and ranged from 73 to 79%
and from 66 to 73%, respectively.
Level of
Biogas Biogas Methane Energy gained
nitrogen Biogas Methane
Crop Localisation (Nm3 from (Nm3 ha-1 (m3 ha-1 Eout
fertilization (dm3) (%)
1 t g.m.*) year-1) year-1) (MJ ha-1)
(kgN ha-1)
80N 4.73 315.3 15136 75 11352.00 450674.40
Maize Grabów
120N 4.56 304.0 15595 78 12164.10 482914.77
Bosman Good soil
160N 3.07 204.0 10506 77 8089.62 321157.91
Osiny 80N 3.84 255.3 11720 73 8555.60 339657.32
Maize
Medium 120N 4.78 318.7 14117 74 10446.58 414729.23
Bosman
soil 160N 4.58 305.0 13786 76 10477.36 415951.19
Jelcz- 80N 4.10 259.3 9751 74 7215.74 286464.88
Maize
Laskowice 120N 3.96 234.7 10302 76 7829.52 310831.94
Vitras
Light soil 160N 2.97 243.3 11412 73 8330.76 330731.17
80N 3.89 194.5 8690 79 6865.10 272544.47
Maize Mochełek
120N 3.53 176.3 7810 76 5935.60 235643.32
Vitras Light soil
160N 3.65 182.5 8453 78 6593.34 261755.60
80N 1.79 89.5 6426 70 4498.20 178578.54
Sorghum Mochełek
120N 2.06 103.0 7408 66 4889.28 194104.42
Rona 1 Light soil
160N 2.30 115.0 8455 73 6172.15 245034.36
Reed canary Osiny 40N 2.46 123.0 3936 53 2086.08 82817.38
grass Medium 80N 2.52 126.0 4738 54 2558.52 101573.24
Bamse soil 120N 0.91 45.5 2107 49 1032.43 40987.47
Table 2: The energy gained from the production of maize, sorghum and reed canary grass for silage processed into biogas
at different levels of nitrogen fertilization.
For Mochełek location dry matter content in case of sorghum harvest was lower than for maize and
was from 31 to 41% and from 43 to 48% , respectively, Table 1. Comparing the effect of fertilization
on maize and sorghum yield from Mochełek location, it was found that increasing nitrogen doses
had little effect on both maize and sorghum yields. Sowinski and Liszka-Podkowa [22] also suggested
that nitrogen fertilization did not significantly affect the yield of fresh and dry matter of sorghum and
maize. At the highest level of fertilization 160N, the yield of green mass of both maize and sorghum
was the highest. The yield of sorghum was almost one-and-a-half times higher than that of maize,
but that did not translate into the yield of biogas produced.
The field experiments of reed canary grass Swedish variety Bamse (Osiny locality, medium soil)
cultivation showed the increase of green mass yield depending on the fertilization level (Table 1).
The highest difference was noticeable when comparing the lowest (40 kgN ha-1) and highest (120
kgN ha-1) dose of nitrogen. While for dry matter yield there was no statistically significant differences
depending on applied dose of nitrogen fertilization. This however was not reflected in the
production of biogas (Table 2). The best yield of biogas 126 m3 t-1 g.m. was obtained from canary
grass with applied 80 kgN ha-1 and the lowest one 45.5 m3 t-1 g.m. from the highest level of
fertilization (120 kgN ha-1). Allison et al. [23], stated that the use of nitrogen fertilizers can cause an
715
increase in lignin content. In the case of reed canary grass, this increase can affect the growth of the
calorific value and improve crop yields. On the other hand it may have a negative effect on the
susceptibility of grass to the conversion process such as anaerobic digestion. This can be the reason
of low biogas production from the silage with the highest dose of nitrogen (120 kgN ha -1).
Comparing the effect of fertilization on the yield and biogas production from maize and reed canary
grass from Osiny location (mean soil), it was found that the yield of maize green mass was higher and
was 45.9 t ha-1 at nitrogen fertilization level of 80 kgN ha-1, however at fertilization level of 120N
higher green mass yield was obtained for reed canary grass (46.3 t ha-1). The yield of biogas from 1t
maize green mass was more than double than that of green canary grass and nearly 7 times higher
for nitrogen fertilization of 120 kgN ha-1. Biogas yields from 1 hectare had similar character of
changes as for yield from 1ton green mass.
Energy efficiency calculations

In Table 2 the amount of biogas gained, including the content of methane and the energy gained per
1 ha (Eout) based on calorific value of methane are presented. Comparing the data obtained in Table
2, it results that regardless of the level of fertilization and the type of soil, the highest amount of
methane obtained from the unit of area and, as a consequence, the energy obtained, is
characterized by the production of maize. For this plant, methane productivity ranged from 5935.60
m3 ha-1 year-1 to 12164.10 m3 ha-1 year-1. This enabled obtaining energy from 235643.32 MJ ha-1 to
482914.77 MJ ha-1, respectively. This variation depends primarily on the type of soil. The highest
rates of energy gained were obtained on good and medium soils. On good soils, an average of 37%
to 65% more energy was obtained compared to light soils. On the other hand, on medium soils, the
difference in obtaining energy in relation to light soils ranged from 26% to 53% in favor of medium
soils.
The level of nitrogen fertilization was the second factor affecting the amount of energy obtained. On
light and medium soils there were no visible differences in the amount of energy obtained.
Fluctuations in the indicator ranged from 14% in light soils to 18% in medium soils. In both soil types,
the highest amounts of energy were obtained at the highest level of N fertilization (160 kg). A slightly
different relationship was revealed in good soils. Here, in turn, the lowest index of obtained energy
was recorded at the highest fertilization level N (160 kg). The highest energy was obtained at the
second fertilization level (120 kgN), where the indicator was 50% more than the highest level of N
fertilization (160 kg). Similarly, with the lowest fertilization level N, this difference was over 40%.
In the case of the other two plants - sorghum and reed canary grass, generally the amount of energy
obtained is lower in relation to maize. In the case of sorghum, which was grown on light soils, the
decrease in energy efficiency in relation to maize cultivated on the same type of soil averaged from
25% to 50%. However, in the case of reed canary grass, which was grown on medium soils, the
decrease in energy efficiency in relation to maize cultivated on the same soil type averaged as much
as 420%.
The energy intake (Ein) is the other aspect of the energy balance. As was earlier shown in the
methodology, this publication will present the amount of accumulated energy related with the raw
material production and transport to the place of processing (Einp). Table 3 shows the results of
investigations into this matter. The volumes of four basic streams of energy were calculated for each
of the plants under investigation, allowing for the level of nitrogen fertilisation. In view of the fact
that the level of nitrogen fertilisation was the chief factor differentiating the technologies for a
particular plant, the stream of energy related with fertilisation was enhanced in the stream of
accumulated energy related with materials and raw materials.
716
Upon the analysis of the data presented in Table 3 it is noticeable that the technologies with the
highest level of nitrogen fertilisation (160N) are characterised by the highest energy inputs – from 50
GJ ha-1 to 53 GJ ha-1 in case of maize, around 46 GJ ha-1 in case of sorghum and around 31 GJ ha-1 in
case of reed canary grass (120N). In the case of maize, regardless of the quality of the soil, the
differences in energy inputs were similar. Energy inputs at the level of fertilization 160 kgN was
higher on average 17% compared to the level of fertilization 80 kgN. In the case of 120 kgN the
difference was approximately 8%. In the structure of energy streams the highest inputs are related
with the stream of fuel consumed (Ef) and it makes between 60% and 68% of the total energy inputs.
The works related with the preparation and transport of silage were the dominant outlay in this
stream. The same trend is also confirmed by a Pepliński study [24].
Level of Emat
Crop nitrogen Emt Ef Ehl Einp NEV
fertilisers others ERoEI
Localisation fertilization
(kgN·ha-1) (MJ ha-1) (MJ ha-1) (MJ ha-1) (MJ ha-1) (MJ ha-1) (MJ ha-1)
Maize Bosman 80N 8242 225 4498 31473 1729 46169 9.76 404505
Grabów 120N 11322 228 4565 31782 1752 49651 9.73 433263
Good soil 160N 14402 231 4632 32092 1775 53132 6.04 268025
Maize Bosman 80N 8242 223 4463 31233 1713 45876 7.40 293781
Osiny 120N 11322 226 4530 31543 1736 49358 8.40 365371
Medium soil 160N 14402 229 4560 31852 1759 52803 7.88 363147
Maize Vitras 80N 8242 219 4086 28713 1553 42814 6.69 243650
Jelcz-Laskowice 120N 11322 222 3483 30075 1594 46698 6.66 264133
Light soil 160N 14402 224 3560 31178 1629 50995 6.49 279735
Maize Vitras 80N 8242 219 4086 28713 1553 42814 6.37 229729
Mochełek 120N 11322 222 3483 30075 1594 46698 5.05 188945
Light soil 160N 14402 224 3560 31178 1629 50995 5.13 210760
Sorghum Rona 1 80N 8242 85 2771 25447 1252 37797 4.72 140780
Mochełek 120N 11322 88 2851 26909 1294 42466 4.57 151638
Light soil 160N 14402 91 2924 28089 1330 46837 5.23 198196
Reed canary 40N 4280 20 2928 13637 1108 21974 3.77 60842
grass Bamse
80N 7785 22 3123 14628 1182 26741 3.80 74831
Osiny
Medium soil 120N 11290 24 3265 15354 1241 31175 1.31 9811
Table 3. The energy efficiency and accumulated energy inputs in the production of maize, sorghum and reed canary grass
for silage processed into biogas at different levels of nitrogen fertilisation.
As for the two remaining plants, in the case of sorghum grown on light soils, the level of energy
inputs compared to maize cultivated on the same type of soil does not differ. On the other hand,
within sorghum, slightly greater differences occur due to the fertilization levels of N. The energy
inputs at the fertilization level of 160 kgN were higher by an average of 24% compared to the
fertilization level of 80 kgN. In contrast, in case of the 120 kgN level, this difference amounted to
approximately 12.5%. In the case of reed canary grass grown on medium soils, the level of energy
inputs compared to maize cultivated on the same type of soil differs significantly - it is lower by
about 50%. Also, higher variation of energy inputs occurs at different fertilization levels of N. The
energy inputs with the highest fertilization level of 120 kgN were higher by an average of 42%
compared to the fertilization level of 40 kgN. In contrast, in case of the 80 kgN level, this difference
was around 22% . As results from the data shown in Table 3, the highest ERoEI (Energy Return on
Energy Investment) ratio could be observed in the technologies of plants produced for biogas
717
processed from maize. The ratio ranges from 5.05, in the production of maize on the light soil at the
level of nitrogen fertilisation 120 kgN, up to 9.76 – the highest efficiency, which is achieved at the
lowest level of nitrogen fertilisation, i.e. 80 kgN on the good soil.
In general, the diversity of ERoEI and NEV indicators due to the fertilization level of N was low for
sorghum grown on light soils and maize cultivated on light and medium soils. In these cases, the
fluctuation of the indicators ranged from 2% - 9%. However, significant differences occurred in the
case of maize cultivated on good soils and reed canary grass grown on medium soils. In the case of
reed canary grass, the highest levels of indicators were obtained with an average fertilization level of
80 kgN. However, it should be noted, that from the point of view of the ERoEI and NEV indicators,
this plant proved to be the least efficient from the point of view of energy gained.
In the case of maize cultivated on good soils, with the fertilization level N of 120 kg and 80 kg, the
highest levels of both indicators were obtained. The highest level of ERoEI - 9.76 was obtained at the
lowest level of fertilization, ie 80 kgN - over 60% more than the level of 160 kgN. In turn, the highest
NEV level - 433263.48 MJ ha-1, was obtained with average fertilization level of N - 120 kg, it was
more than 60% obtained energy in relation to the obtained energy at the highest level of N - 160 kg.
4- CONCLUSIONS
Studies carried out in this work indicate that both fertilization level and soil quality influence the
susceptibility of selected silage to decomposition in the processes of methane fermentation and
biogas production.
The highest biogas yield (over 300 m3 from 1 tonne green mass) produced from maize silages from
Grabów locality (good soil, 80N) and Osiny (medium soil, 120N) was observed by analyzing the
susceptibility of maize silages from four different locations with differentiated quality, on methane
fermentation and biogas production. The yield of biogas from maize silage derived from light soil at
the location of Jelcz-Laskowice (259.33 m3 t-1 g.m., 80N) and Mochełek (194.5 m3 t-1 g.m., 80N) was
lower.
In most locations, the lowest fertilization level of 80 kgN ha -1 fostered the efficient production of
biogas from 1 t green mass. Increasing the application of fertilization dose to 160 kgN ha -1 did not
significantly reduce the yield of biogas from 1 tonne green mass except for the Grabów location
(good soil), where significant reduction was observed. The highest yields of biogas per hectare of
maize silage of Bosman Osiny and Bosman Grabów were obtained in case of 120N level of
fertilization, respectively 15595 m3 ha-1 year-1 and 14117 m3 ha-1 year-1. On the other hand, on the
light soil in Jelcz Laskowice location, the highest yield of biogas per hectare was obtained for the
highest degree of fertilization of 160N (11412 m3 ha-1 year-1) and in Mochełek with the lowest
fertilization rate of 80N (8690 m3 ha-1 year-1). Comparing the effect of fertilization on yield of maize,
sorghum and reed canary grass, it was found that increasing nitrogen doses had little effect on the
yield of these crops. The highest yield of green mass of maize was obtained on good soil in Grabów
(about 50 t ha-1). The yield of sorghum was higher than 70 t ha-1, and the reed canary grass about
40 t ha-1. Increasing nitrogen doses resulted in a slight increase in green mass from 1 ha. The highest
green mass yield of was obtained for the highest nitrogen fertilization of 160N (maize and sorghum)
and 120N (reed canary grass). High yield of sorghum green mass did not contribute to high
production and biogas yield. The highest biogas yield from 1 tonne of green mass of sorghum (115
m3 t-1 g.m.) was obtained for the highest fertilization level of 160 kgN ha -1. In the case of reed canary
grass the potential biogas yield of 1 tonne green mass was small and was about 125 m 3 t-1 g.m. for
40N and 80N fertilization levels, however, the increase of nitrogen caused a significant reduction of
biogas production and its yield to about 45 m3 t-1 g.m. Methane content in biogas from maize and
sorghum was high and was above 70% and for reed canary grass it was about 50%.
718
The investigations proved that in general, the production technologies of crops where the low levels
of nitrogen fertilization were applied proved to have the highest energy efficiency. Depending on the
soil type, ERoEI and NEV values for maize ranged from 5.05 and 188,945 MJ ha-1 (light soil), obtained
at the level of 120 kgN ha-1 to 9.76 obtained at the level of 80 kgN ha-1 and 433,263 MJ ha-1 obtained
at the level of 120 kgN ha-1 (good soil). The obtained levels of indicators turned out to be higher by
as much as 60% in relation to the level of indicators obtained at the highest level of fertilization –
160 kgN. For sorghum (light soil) values of about 5.2 and 200,000 MJ ha -1 were appropriately
obtained at the level of 160 kgN ha-1. In turn, in the case of reed canary grass the highest ERoEI and
NEV values obtained at the level of 80 kgN ha-1 - they were amounted to 3.8 and 74,000 MJ ha-1
(light soil), respectively.
Acknowledgement
The work was funded by the European Union under the Operational Programme “Innovative
Economy” 2007-2013: POIG.01.03.01-00-132/08-00 (European Regional Development Fund), “The
Development of a Species Index and Optimization of Production Technologies for Selected Energy
Crops”.
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USING OF NATURAL BENTONITE CLAY FOR FLUORIDE REMOVAL

FROM SYNTHETIC AQUEOUS SOLUTION
J. ASSAOUI1, A. KHERIBECH1, Z. HATIM1

1 Chouaïb Doukkali University, Faculty of Science, Biomaterials and Electrochemistry Team,
Laboratory “Water and Environment”, El Jadida, Morocco.
Abstract
The contamination of wastewater by fluoride ions has been recognized as one of the environmental
problems worldwide [1] imposing a serious threat to human health [2]. The discharge of industrial
wastewater containing such as pollutant into the surface water would lead to groundwater
contamination, considered as one of the important sources of drinking water. Thus, the consumption
of this latter can be classified as the major path of human exposure. Among various treatment
technologies developed for the purpose of reducing the hazardous impacts generated by fluoride
ions, adsorption process has been exploited widely and offers satisfactory results. It has been proved
to be a robust and an effective technology for industrial wastewater treatment. In this study, natural
bentonite clay was used to test its adsorption potential of fluoride ions from wastewater using batch
adsorption experiments (Figure 1). The aim was to implement the optimal parameters leading to
maximum fluoride removal efficiency. The compositional, structural and textural characteristics of
the natural bentonite clay were determined using accurate physicochemical and mineralogical
characterizations. The analysis of fluoride ions in the liquid phase was performed using the
potentiometric method with a fluoride-specific ion electrode. The effect of various operational
parameters such as contact time, initial fluoride concentration, adsorbent dose and initial aqueous
pH solution were evaluated under atmospheric conditions. The results obtained from batch
adsorption experiments showed a pH dependency of the natural bentonite clay toward the fluoride
adsorption. Maximum fluoride removal efficiency exceeded 50% under acidic conditions. It was
obtained at the pH value of initial aqueous solution comprised between 1 and 4, taking a few tens of
minutes for attaining equilibrium. Batch adsorption data was better described by Freundlich model.
Figure 1: Graphical illustration of wastewater defluoridation by adsorption on natural bentonite clay
References
[1] Chen, N., Zhang, Z., Feng, Ci., Li, M., Chen, R., Sugiura, N.: Investigations on the batch and fixed-bed column
performance of fluoride adsorption by Kanuma mud. Desalination 268, 76-82 (2011)
[2] Vinati, A., Mahanty, B., Behera, S.K.: Clay and clay minerals for fluoride removal from water: A state-of-the-art
review. Applied Clay Science 114, 340-348 (2015)
721
EXPERIMENTAL STUDIES ON SOLIDIFICATION OF HEAVY METALS IN MUNICIPAL

SEWAGE SLUDGE BY ALKALINE THERMAL HYDROLYSIS
YING ZHOU1, YONGCHUN ZHAO1, JUNYING ZHANG1

1 State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan,
Hubei, China.
Abstract
With the rapid development of economic, the production of municipal sewage sludge (MSS) has
increased sharply year by year. Land use is the most common way for MSS disposal because it can
provide high content of organic matter, nitrogen and phosphorus [1]. However, accumulated heavy
metals (e.g Cr, Co, Ni, Cu, Zn, Cd, Pb) in MSS can increase environmental problems and secondary
pollution if not properly treated. Therefore, it is urgent to research methods that can reduce the eco-
toxicity of MSS to the environment [2]. Thermal hydrolysis of MSS is considered as a simple, efficient,
low consumption technology which can stabilize heavy metals of MSS [3]. Three kinds of MSS were
tested to investigate the quality change of MSS and migration characteristics of heavy metals. The
alkaline thermal hydrolysis of MSS was conducted by means of a high pressure and high temperature
autoclave. Parameters, including hydrothermal temperature and pH value on migration behaviors of
heavy metals in the treatment have been analyzed in detail. The leachability of heavy metals from
solid products was further tested by horizontal vibration method after the thermal hydrolysis.
The results showed that the quality of sludge was greatly reduced by 63％ after alkaline thermal
hydrolysis. The higher temperature promoted the dissolution of MSS. The sludge residue increased
after hydrothermal with the higher pH value and it is highly suspected to link to the addition of
Ca(OH)2. After alkaline thermal hydrolysis, the content of heavy metals in solid residue increased
compared to the untreated MSS. The main reason is the reduction of MSS quality. There was only a
small fraction of heavy metals dissolving into liquid phase, which showed alkaline thermal hydrolysis
was a promising method on immobilization of heavy metals. The increase of temperature and pH
value had some positive effect on heavy metals accumulating in solid phase. After hydrolysis the
leaching toxicity of heavy metals in sludge was greatly decreased and a higher temperature and pH
value led to the lower leaching rate. In view of heavy metal’s stabilization, temperature of 250°C or
pH of 12 corresponded to the lowest migration rate and to the least heavy metal leaching toxicity.
Therefore temperature of 250°C and pH of 12 were the best choice of alkaline hydrothermal
temperature and pH value to treat municipal sewage sludge.
References
[1] Shi, W., Liu, C., Ding, D., et al.: Immobilization of heavy metals in sewage sludge by using subcritical water
technology. Bioresour Technol. 137, 18-24(2013)
[2] Wang, X., Li, C., Zhang, B., et al.: Migration and risk assessment of heavy metals in sewage sludge during
hydrothermal treatment combined with pyrolysis. Bioresour Technol. 221, 560-567(2016)
[3] Appels, L., Degrève, J., Bruggen, B.V.D., et al.: Influence of low temperature thermal pre-treatment on sludge
solubilisation, heavy metal release and anaerobic digestion. Bioresour Technol. 101, 5743-5748(2010)
722
UTILIZATION OF SANDY TAILINGS FROM IRON ORE BENEFICIATION IN

CEMENT MORTARS
A.E.C. PERES1, M.A.M. AGUIAR2, K.C. FERREIRA3

1
UFMG, Belo Horizonte, Brazil
2
CEFET, Araxá, Brazil
3
UEMG, João Monlevade, Brazil
Abstract
The concentration of iron ores via cationic reverse flotation yields huge environmental
passive. The weight of concentrate produced equals roughly the amount of wastes. The
reject fraction consists of sandy tailings and slimes, at the ratio 80%:20%. A typical large iron
ore concentrator producing 30 million tons of pellet feed per year yields 24 million tons of
sandy tailings. The major mineral in the sandy tailings is quartz (“sand”), in the size range
<0.150 mm >0.010mm. Sandy tailings are inert and are not contaminated by chemicals. The
reagents utilized are corn starch (biodegradable edible species) and decyl ether amine. Ether
amine is not toxic and is strongly adsorbed onto quartz. The mineralogy of the slimes is more
complex. Goethite (iron oxyhydroxide) and kaolinite (aluminum silicate) are the major
species, in the size range <0.010 mm. The motivation for this study was to investigate the
exploratory utilization of sandy tailings in the production of cement mortar. Different mortar
mixes were produced by varying the cement/tailings ratio and water/cement ratio. For each
sample the setting time, viscosity, and density were determined in the fresh state. Density
and compressive strength were determined in the hardened state. The mortar produced
with the highest content of tailings (cement:tailings ratio of 1:2.5) and lowest water:cement
ratio (0.95) presented the shortest setting time and the highest compressive strength. It is
worthwhile noting that, irrespectively of the sophistication of the product and/or cost of
production, it is impossible to turn several million tons of an environmental passive such as
sandy tailings into economic active. Nevertheless, all contributions, especially the low cost
ones, are relevant towards enhancing the awareness of the mining companies regarding
environment protection and sustainability.
Keywords: waste recovery, iron ore sandy tailings, cement mortar
723
1. INTRODUCTION
Itabirite is a metamorphic rock constituted of quartz and iron oxides (hematite and goethite)
layers. The beneficiation of itabirites, from the Brazilian Iron Quadrangle, via froth flotation,
yields a concentrate (mostly hematite) and two reject fractions, sandy tailings (mostly
quartz) and slimes (predominance of goethite, containing also kaolinite) [1]. The ratio
concentrate:reject fraction is approximately 50%:50%. In the reject fraction, the ratio sandy
tailings:slimes is 80%:20%. The designation sandy tailings arises from the visual aspect and
composition similar to those of sand. The size range is <0.150mm >0.010mm and hematite is
always present. The size range of the slimes is <0.010mm. The brown to dark orange color is
characteristic of the predominance of goethite. The sandy tailings settles rapidly in water
and the slimes stay in suspension for a long time.
Sandy tailings are inert and are not contaminated by chemicals. The reagents utilized are
corn starch (biodegradable edible species) and decyl ether amine. Ether amine is not toxic
and is strongly adsorbed onto quartz [2].
Both fractions are currently disposed and stored in tailings ponds. The costs of construction,
raising, and monitoring the damns are high and there is always risk of failure. A fraction of
the sandy tailings may be stored in the final pit at the end of the mine life.
The physical and chemical characteristics of sandy tailings and slimes are uniform and the
production is huge. Only one company yields 24 million tons of sandy tailings and 6 million
tons of slimes per year. The availability and uniformity of these materials render them
attractive concerning investigations aiming at the production of concrete and cement based
materials (mortars, paving blocks, ducts, etc.)
The motivation for this study was to investigate the exploratory utilization of sandy tailings
in the production of cement mortar. It is worthwhile stressing that irrespectively of the
sophistication of the product and/or cost of production, it is impossible to turn several
million tons of an environmental passive such as sandy tailings into economic active.
Nevertheless, all contributions, especially the low cost ones, are relevant towards enhancing
the awareness of the mining companies regarding environment protection and sustainability
and encouraging professionals from all areas to search for different applications. The cost of
production of cement mortar is low and the throughput may be fairly large.

The sandy tailings sample, supplied by a mine in the Iron Quadrangle, Brazil, was dried at
70ºC, homogenized and quartered in 3 kg bags.
Figure 1 illustrates the aspect of the sandy tailings after preparation. The chemical analysis is
SiO2 80.7% and Fe 13.1% (Fe2O3 18.7%). The particles size distribution is +10 µm -0.150 µm.
724
Figure 1. Sandy tailings after the preparation.
The first step was the determination of the unit weight (1.27 kg/L), required for the
calculation of the ratio cement:tailings (C:T) in volume.
Exploratory laboratory experiments were conducted prior to the selection of cement:tailings
(C:T) and water/tailings (W/T) ratios, listed in Table 1.
Parameters - +
C:T 01:02 01:2.5
W/T 0.95 1.00
Table 1. Low and high levels of the cement:tailings (C:T) and the water/tailings (W/T) ratios.
Four mortar mixes were prepared for replicate experiments presented in Table 2. The
sequence was randomized with aid of the program Minitab® 15.
Mixes
Experiments Sequence
C:T W/C
1 01:02 0.95 5
2 01:02 1 7
3 01:2.5 0.95 6
4 01:2.5 1 8
5 01:02 0.95 3
6 01:02 1 2
7 01:2.5 0.95 4
8 01:2.5 1 1
Table 2. Mortar mixes tested.
Five cylindrical test specimens (5 cm diameter, 10 cm height) were molded for each
experiment.
The properties setting time, viscosity, and pulp density were determined in the fresh state
and density and compressive strength were measured in the hardened state.
725
The setting time was measured in the apparatus Resistance Machine Unificate (RMU), model
M-23, operated with T shape rotors at 5RPM.
Viscosity was determined in the analogical apparatus Brookfield, model RVT, operated with T
shape rotors, 17 readings at 15 s each.
The density of the fresh state mortar affects directly its workability. Fresh state density was
calculated via direct measurement of the weight of a known volume of mortar. For the
calculation of the hardened state density the specimen was weighted and the volume was
calculated (four determinations of the height and two of the diameter of the test specimen).
The compressive strength was determined with the use of an automatic EMIC press, model
PCI 150.

The results achieved for the properties of mortar mixes in the fresh and hardened states are
presented, respectively, in Tables 3 and 4.
Mixes Properties of fresh state mortar

C:T W/T Setting time (s) Viscosity (Pa.s) Density (kg/m³)
0.95 24060 13.98 ± 0.62 1866 ± 4.0
01:02 1 31620 14.04 ± 0.77 1830 ± 7.0
0.95 21420 414.71 ± 109.00 1906 ± 10.7
01:2.5 1 - 283.41 ± 54.01 1892 ± 10.2
0.95 26880 49.33 ± 3.02 1807 ± 1.7
01:02 1 32760 17.02 ± 0.73 1832 ± 10.0
0.95 22260 474.94 ± 120.67 1839 ± 3.4
01:2.5 1 22140 289.76 ± 48.20 1918 ± 7.4
Table 3 - Results of setting time, viscosity, and density of mortars, determined in the fresh state, at 95% statistical
confidence level.
Mixes Properties of hardened state mortars

C:T W/C Density (kg/m³) Compressive strength (MPa)
0.95 1823 ± 14 15.4 ± 1.5
01:02
1 1799 ± 35 14.8 ± 1.5
0.95 1864 ± 11 16.3 ± 1.4
01:2.5
1 1869 ± 12 14.9 ± 1.5
0.95 1782 ± 17 13.9 ± 1.5
01:02
1 1793 ± 15 13.1 ± 1.2
0.95 1877 ± 15 15.4 ± 1.6
01:2.5
1 1833 ± 12 14.6 ± 1.4
Table 4 – Results of density and compressive strength, determined in the hardened state, at 95% statistical confidence level.
726
The variance analysis (ANOVA), at 95% statistical confidence level, presented in Table 5,
indicated that both variables, C:T and W/C, are significant and their interaction is also
significant. The mortar produced with C:T = 1:2.5 and W/C = 0.95 presented the lowest
setting time.
Source of variation DF SS MS Fc Ft(0.05; 1; 8) P

C:T 1 25992 25992 75.18 0.001
W/T 1 6844 6844 19.8 0.011
C:T x W/C 1 5725 5725 16.56 5.32 0.015
Residue 4 1383 345.7
Total 7 39944
Initials: DF=degree of freedom; SS=sum of squares; MS=mean squares; Fc=calculated factor;
Ft=tabulated factor; P value
Table 5 – Variance analysis for the response setting time.
Fc > Ft indicates significant difference between the levels of the variables.

The variance analysis (ANOVA), at 95% statistical confidence level, presented in Table 6,
indicated that both variables, C:T and W/C, are significant. The mortar produced with C:T =
1:2.5 and W/C = 0.95 presented the highest compressive strength.
Source of variation DF SS MS Fc Ft(0.05; 1; 8) P

C:T 1 10.3022 10.3022 10.36 0.003
W/T 1 8.4424 8.4424 8.49 0.006
C:T x W/C 1 0.3733 0.3733 0.38 5.32 0.544
Residue 36 35.8007 0.9945
Total 39 54.9186
Table 6 - Variance analysis for the response compressive strength after 28 days cure.
4. CONCLUSIONS
The production of mortars with the use of sandy tailings in the mix is technically viable. The
mortar produced with C:T at the high level (1:1.25) and W/C at the low level (0.95)
presented the shortest setting time and the highest compressive strength.
The standard deviation of the measured values of density in the fresh state is within
acceptable limits to prevent segregation of the components.
The standard deviation of all measured values of compressive strength is within the
established limit (20%).
ACKNOWLEDGEMENTS
To CAPES/CNPQ/FAPEMIG for the support to PPGEM.
REFERENCES
[1] Araujo, A.C., Viana, P.R.M., Peres, A.E.C.: Reagents in iron ores flotation, Minerals
Engineering, v. 18, p. 219-224 (2005).
[2] Peres, A.E.C., Agarwal, N., Bartalini, N.M., Beda, D.: Environmental impact of an
etheramine utilized as flotation collector. In: 7th International Mine Water Association
Congress. Mine Water and the Environment. Ustron, Poland, p. 464-471 (2000).
727
NOVEL INORGANIC POLYMER SPHERES FOR METHYLENE BLUE EXTRACTION FROM

WASTEWATERS

RUI M. NOVAIS1, J. CARVALHEIRAS1, D.M. TOBALDI1, P. SEABRA 1, J.A. LABRINCHA1
1 Department of Materials and Ceramic Engineering / CICECO-‐ Aveiro Institute of Materials,
University of Aveiro, Campus Universitário de Santiago, 3810-‐193 Aveiro, Portugal

Abstract

Methylene blue (MB), one of the most used dyes, is known to severely affect humans causing
blindness and respiratory distress [1]. In this context, its removal from wastewaters is of the
foremost importance. Adsorption is probably the most cost effective technique and activated carbon
has been extensively used as adsorbent material. Nevertheless its very high production cost limits its
widespread use [2]. The use of powdered inorganic polymer (e.g. geopolymer) for adsorption has
received increasing attention, not only due to their lower production cost, but also due to the
possibility of distinct unexplored wastes in their production. Nevertheless these powdered materials
cannot be easily retrieved neither regenerated and for that reason novel adsorbents capable of
multiple adsorption cycles are eagerly pursued. In this study the feasibility of using biomass fly ash-‐
based geopolymer spheres as methylene blue adsorbents was evaluated. The influence of contact
time, MB and spheres concentration on the MB adsorption by the porous inorganic polymer spheres
was evaluated. Adsorption results were fit using Langmuir and Freundlich isotherm models, while
FTIR, XDR and SEM/EDS characterization were also performed. Additionally desorption and
regeneration tests were performed. Results show a very high MB removal efficiency for these novel
adsorbents: up to 96% removal efficiency was observed when the MB concentration in the synthetic
wastewater reaches 100 mg/L. These results demonstrate the spheres potential for treating
industrial wastewaters. Furthermore the spheres can be easily handled and used directly in packed
beds, while powdered adsorbents cannot. The latter enhancing the simplicity of wastewater
treatment systems.

Figure 1: Photograph of the biomass fly ash-‐based geopolymer spheres before and after MB adsorption.

References
[1] Khan, M.I., Min, T.K., Azizli, K., Sufian, S., Man, Z., Ullah, H.. Effective removal of methylene blue from water using
phosphoric acid based geopolymers. RSC Advances 5, 61410-‐61420 (2015).
[2] Rafatullah, M., Sulaiman, O., Hashim, R., Ahmad, A.. Adsorption of methylene blue on low-‐cost adsorbents: a review.
Journal of Hazardous Materials 177, 70-‐80 (2010).
728
ANALYSIS OF THE STATE OF COMBUSTION IN SRF CO-FIRING IN 2MW CFB
JUSOO HYUN1, KEUNHEE HAN1, YUNTAE HWANG1, JEONGMIN KIM1

1 Korea Institute of Energy Research, Daejeon, Korea
Keywords: CFBC, Solid Refused Fuel, Dual Fuel, Flue Gas
Abstract
“Flue Gas R&D Demonstration Facility” constructed in KIER is the only power plants in Korea for
research. It is equipped with CFBC, steam turbine and flue gas cleaning system. The scale of facilities
is 2.0 MWe class, coal feed rate is 1.4ton/h and steam(46kg/cm2, 453℃) generating rate is 12,000
kg/h. In this research, for the purpose of the demonstration test that SRF is used for fuel in CFBC,
combustion experiment is carried out for 20 ~ 50 hours, 6th times of experiment in co-firing of coal
and SRF. On the same condition of power generation electricity of 1,100 kW, the combustion
temperature distribution, the flue gas concentration were measured, and then was compared and
analysed with data of the experiment.
729
1- INTRODUCTION
“Flue Gas R&D Demonstration Facility” constructed in KIER is the only power plants in Korea for
research. It is equipped with CFBC, steam turbine and flue gas cleaning system. The scale of facilities
is 2.0MWe class, coal feed rate is 1.4ton/h and steam(46kg/cm2, 453oC) generating rate is 12,000
kg/h.
In recent, existing coal supply system was changed from the belt conveyor type into screw
conveyor type. The new fuel supply system is prevented from being compressed or clumped for low
density, relatively large volumes of solid fuel by using screw feeder. Features a stirring wing to
prevent bridge phenomenon, which is the flow of solid fuel lower. A gas and air supply device for
supplying gas or compressed air to prevent entanglement of raw materials. Solid fuel is discharged
through an exhaust control device for controlling the amount of fuel. Besides, coal and SRF inlet
diameter was extended from 4 inches to 8 inches. In order to prevent high temperature fusion when
SRF fuel is input, double inlet pipe is used to supply cooling water
Figure 1. Coal Conveyor Feeder Figure 2. SRF Screw Feeder
Figure 3. Before modification Figure 4. After modification
730
Figure 5. Existing Fuel Inlet Drawing Figure 6. Modified fuel inlet drawing

In this research, for the purpose of the demonstration test that SRF is used for fuel in CFBC,
combustion experiment is carried out for 20 ~ 50 hours, 6th times of experiment in co-firing of coal
and SRF. On the same condition of power generation electricity of 1,100 kW, the combustion
temperature distribution, the flue gas concentration were measured, and then was compared and
analysed with data of the experiment.
Higher heating value of bituminous coal is 6,480 ~ 6,800 kcal/kg, SRF is 3,950 ~ 4,410 kcal/kg.
Sulfur content of SRF is less than bituminous coal. Therefore, it is analysed that the concentration of
SOx in flue gas is less than in comparison of bituminous coal firing. Specific gravity of SRF is also less
than bituminous coal. So, It is thought that the combustion occurs at the bottom and the
recirculation is not performed well in CFBC, so that the post combustion occurs well.
SRF Co-firing(Heat, Temperature) SRF Co-firing

1 200 1075 1108 (Flue gas Concentration)
1 000 866 855
745 748 150
800 626,8 636,0 571 611 115 119
600
400 203 222 100 81
122 127 66
200 53
0 50
4
0
CO(ppm) SOx(ppm) NOx(ppm)
Coal SRF pallet Coal(6.2%O2) SRF(6.6%O2)
Figure 1: Co-firing SRF (Heat, Temp.) Figure 2: Co-firing (concentration in flue gas)
731

In CFB boiler typically bed temperature maintains constantly by increasing the amount of fuel supply,
on the other hand, the temperature of center, top and outlet of boiler will tend to rise combustion
temperature by increasing the amount of fuel supply.
Fig. 9 is the distribution of combustion temperature in dual fuel of SRF 5%, and Fig. 10 is the
distribution of combustion temperature measured in dual fuel of SRF 10%. When is dual fuel of SRF
5%, the mean temperature measured in bed, center, top and outlet of boiler is 930℃, 877 ℃, 798℃
, 777 ℃, respectively, when is dual fuel of SRF 10%, is 919℃, 884℃, 797℃, 757℃, respectively.
In comparison with all bituminous coal burned down, it was measured to be lower at about 6℃ ~ 12
℃ in dual fuel of SRF. There was no significant difference in bed temperature, but was more than 10
℃ in outlet temperature. It is thought that the combustion temperature in bed is high because the
volatile ingredients of the SRF is more and rate of combustion reaction is faster, and the
temperature in top of boiler is low because of the relatively small amount of heat.
Fig. 11 shows the comparison of power output with fuel input of bituminous coal 100%, dual fuel of
SRF 5%, dual fuel of SRF 10%. In comparison with power output when the fuel input is converted into
heat input, it was calculated to be 99.1% in dual fuel of SRF 5%, 93.3% in dual fuel of SRF 10%, when
compared to 100% of bituminous coal.
Fig. 12 shows the comparison of combustion temperature inside boiler in 100% of bituminous coal,
dual fuel of SRF 5% and dual fuel of SRF 10%. It was lower 10℃ ~ 20℃ in combustion temperature of
center, upper of boiler when dual fuel of SRF considering 100% of bituminous coal, it was thought to
be due to that heat input was reduced to 99.1% in dual fuel of SRF 5% and 93.3% in dual fuel of SRF
10%. In bed temperature, temperature difference of bed A supplied with bituminous coal was only 3
℃ and those of bed B supplied with SRF in dual fuel was 8℃, it was a relatively great difference.
1400
1272
1243
1200 1168
1000
876
Coa l, Powe r
865
806
800
600
400
200
0
Coa l(kg/hr) Power(kWh)
Coal SRF 5% SRF 10%
Figure. 9: distribution of combustion Figure. 10: distribution of combustion Figure. 11: Comparison of fuel input and
temperature in dual fuel of SRF 5% temperature in dual fuel of SRF 10% power output
732
Fig. 13 is the comparison with the concentration of O2 and SOx emissions in flue gas. Because the
sulfur content of bituminous coal is only about 0.2%, the concentration of SOx was 148 ppm in 100%
of bituminous coal. On the other hand, in case of SRF dual fuel, the concentration of SOx was 157 ~
182 ppm, that was increased to 6 ~ 23 %, because the sulfur content of SRF is 1.1~ 1.3%, 5th times
more than the bituminous coal.
In CFB boiler, after combustion of coal the remaining ash is discharged from the bed in the form of
bottom ash, from the bag filter in the form of fly ash. The analysis of bottom & fly ash that sampled
in demonstration test is as Table 1. The average unburned carbon of bottom ash was within 1%, that
was almost completely burned, and it was analysed to be similar with each other in 100% of
bituminous coal and dual fuel of SRF. The average unburned carbon of fly ash is 5.3~6.6 wt% in case
that all bituminous coal burned down, 8.04 wt% in case of dual fuel of SRF 5%, 6.68 wt% in case of
dual fuel of SRF 10%, respectively, it showed an increase of about 23~26%.
950 250
Com b u st ion Te m p e ra t u re ( C)
919 916
o
SOx, NOx, CO(p p m ), O2 (%)
906 907
900 896
905
897 200
182
Unburned Carbon(wt%)
884 884
148
157 Sample Bottom
150
Fly Ash
850
Ash
813 100
808
800
797
788
Coal 0.70 6.55
777
50 SRF 5% 0.72 8.04
757
750
Bed A Bed B Center Upper Exit 0
6.4 6.9 5.8 Coal 0.40 5.29
Coal SRF 5% SRF 10% Coa l SRF 5% SRF 10% SRF 10% 0.48 6.68
SOx O2
Figure. 12: Comparison of CFBC Figure. 13: Comparison of SOx Table 1: Analysis of unburned carbon
combustion temperature concentration
4- CONCLUSIONS
For using SRF as fuel, that is the solid renewable fuel dried and mixed the pig excrement and the
flammable organic material, demonstration test was performed with bituminous coal, dual fuel of
SRF 5% and SRF 10% in 2MWe scale CFBC power plant owned by KIER. Regarding SRF, volatile
material is 1.5th times more than bituminous coal, ash content is 2.5th times more, sulfur content is
5th times more, fixed carbon is only a one-sixth and higher heating value is about 3,360kcal/kg.
In comparison of combustion temperature between 100% of bituminous coal and dual fuel of SRF in
demonstration test, bed temperature maintains constantly, but the combustion temperature had a
tendency to lower of about 10~20℃ toward the upper boiler. Thus, in case of SRF dual fuel
compared with 100% of bituminous coal, heat input was about 1.1% less and the power output was
a decrease of about 2.0%. The composition of NOx, CO, CO2 and O2 out of flue gas was similar to, but
SO2 was increased by about 15%. Also, there was no difference that unburned carbon in bottom ash
733
was less than 1%, but unburned carbon in fly ash was about 8.0%, that was increased about 25%
compared to 100% of bituminous coal.
In conclusion, for combustible waste to energy, SRF 5 ~ 10% in the existing bituminous CFBC was
judged to be a dual fuel as possible, even though fine output reduction, temperature difference in
combustion chamber and symptoms of increased SO2 has happened.
ACKNOWLEDGEMENT
This work was conducted under the framework of Research and Development Program of the Korea
Institute of Energy Research.(B7-2435-02)
This work was supported by the National Research Council of Science & Technology(NST) grant by
the Korea government MSIP). (No. CRC-15-07-KIER).
REFERENCES
[1] Han Keunhee, Hyun Jusoo, Choi Wonkil, Lee Jongseop, “A Study of Co-Combustion Characteristics of North Korean
Anthracite and Bituminous Coal in 2 MWe CFBC Power Plant”, Korean Chem. Eng. Res., Vol. 47, No. 5, pp580-586
(2009).
[2] Shun D., Jin K. T., Yi C. K., and Han K. H., "Development of Circulating Fluidized Bed Combustion and Emission Control
Technology", Research Report, KIER-A03707, KIER, 7~12(2000).
[3] D. W. Shun, D. H. Bae, K. H. Han, J. E. Son, Y. Kang, Y. H. Wee, J. S. Lee, P. S. Ji, "Circulating Fluidized Bed Combustion
of Korean Anthracite", HWAHAK KONGHAK, 34(3), 321~326(1996).
[4] Leckner, B., "Fluidized Bed Combustion: Mixing and Pollutant Limitation", Prog. Energy Combustion Science, 24,
31~61(1998).
[5] Ake, T. R., Dixit, V. B. and Mongeon, R. K.,: Proc. of 12th International Conference on Fluidized Bed Combustion,
81(1993).
[6] Han Keunhee and Hyun Jusoo, “The Development of Energy Infra”, KIER-A72422, Research Report, (2006).
734
STUDY ON PURIFICATION EFFICIENCY OF TAIL WATER IN BAFFLED VERTICAL-FLOW

CONSTRUCTED WETLANDS USING BROKEN BRICKS AS SUBSTRATE
ZHANG GUOZHEN 1, SHANG XINGBAO1, WU FUPING1

1 Lanzhou Jiaotong University, Lanzhou, China.
Abstract
In recent years, with the accelerated process of urbanization in China, the emission of construction
waste has been increasing. In each of the ten thousands of square meters building construction
process, construction waste alone occupied more than 100 million tons, according to statistics. The
buildings were eliminated so that a large amount of masonry waste was produced, when the
building gets close to the service life. Hence, we can realize that construction waste could give rise to
serious environment problem every year, if we don't reuse of these resources. Not only will it lead to
a plenty of resource wastes, but causes pollution of the ecological environment and the terrible
ecological appearance. For instance, waste bricks, as an important part of the construction waste,
account for 30% -50% of the total amount of construction waste, and most of them are taken soil as
raw material to burn, which possess the surface of the porous structure, feature of the less-
environmental pollutions, and non-toxic substances. Regarding the concept of "usage of waste to
treat waste"(treatment wastewater with construction waste), a new fangled application is studied so
that the removal pollutants, using broken brick as the matrix of vertical flow constructed wetland.
Bricks are made from loess, shale, coal gangue and fly ash. After the demolition of the building,
becoming construction waste, the waste brick made of different particle size (10 ~ 20mm, 5 ~ 10mm,
2 ~ 5mm) filler.
The variation of pollutants along the experiment flow under three hydraulic loading rates (0.15, 0.25
and 0.35m3/(m2∙d)) and the wetland system was run continuously from June to September in 2016.
During the experiment, the system was run continuously and the water was controlled through the
valve. The water samples were collected every 3 days. The temperature, DO and pH were measured
in the field. The water samples were taken back to the laboratory to measure CODcr, NH 4+-N, TN and
TP and other indicators.
The results showed that the broken bricks of construction waste could serve for the carrier for the
developing biofilm and were suitable for the normal growth of wetland plants, which had a positive
effect on the removal of pollutants in the tail water. The baffled vertical-flow constructed wetlands
could significantly reduce the influent pollutants loading under the condition of three different
hydraulic loading conditions, and effluent concentration of nitrogen and phosphorus was elevated
with the increase of hydraulic loading rates. Under low hydraulic load condition of 0.15m 3/(m2∙d),
the average removal efficiency of 66.52%, 72.10%, 56.53% and 91.55% were achieved for CODcr,
NH4+-N, TN and TP, respectively. The effluent concentrations of CODcr and TP were less than the III
standard of GB 3838-2002”Surface Water Environment Quality Standard”.
The baffled vertical-flow constructed wetland system used broken bricks as a filler has a high
capacity for denitrification in the treatment of secondary biogenic tail water, indicating that the
construction waste (waste bricks) as constructed wetland filler has a strong practical significance and
promotion value.
References
735
[1] Yu D,Piotr RW,Mawuli D et al.Impact of hydraulic loading rate and season on water contaminant reductions
integrated constructed weylands.wetlands,2011,31(3):499-509.Geddes, K.O., Czapor, S.R., Labahn, G.: Algorithms for
Computer Algebra. Kluwer, Boston (1992)
[2] Deblina G,Brij G.Effect of hydraulic retention time on the treatment of secondary effluent in a subsurface flow
constructed wetland.Ecological Engineering,2010,36(8):1044-105)
736
COMPARISON OF FILTRATION PERFORMANCE WITH ROUNDED FILTER BAGS AND

PLEATED FILTER BAGS IN PILOT SCALE TEST UNIT USING SIMULATED FLUE GAS OF
WASTE INCINERATOR FOR APPLICATION OF WASTE TO ENERGY INDUSTRIES
KWANG-DEUK KIM 1, KANG-SAN LEE1, SEONG-MIN JEON1, NAIM HASOLLI1, JAE-RANG LEE1, YOUNG-
OK PARK1
1 Solar Thermal Convergence Laboratory and Clean Fuel Laboratory, Korea Institute of Energy
Research, Daejeon, Korea.
Abstract
Filter bag replacement can be one of the largest operating expense for a baghouse system. Selecting
a filter media and filter shape on price can be costly. A low priced media with short bag life could
actually be more expensive over the lifetime for the system.
Analysis filter failures and short bag life time often reveals system problems and shape of filter bags
that are easy to correct with field operating data and test data. Using knowledge of filtration
material properties and shapes of filter bag, alternatives can be specified that are more compatible
with operating conditions. Combining laboratory test results with field operating data, it is possible
to find a solution that outperforms the current baghouse configuration. While bag life and filter bag
cost determine bag repacement expense, improved filter bag performance (lower emissions, higher
airflow, etc.) can also have a large impact on the total system operating cost.
This paper examines the problems and solutions found during operation of pilot scale test unit with
rounded filter bags and surface flexible pleated filter bags using simulated flue gas of waste
incinerator. The solution may be changing to a high performance filter bag. In other cases, system
conditions create problems that greatly limit the performance of the filter bag. Attention to
operation and periodic checks of the shape of filter bags provide opportunities for significant cost
savings.
We tested filtration performance of different shapes of filter bags with same filter media in the pilot
scale test unit using simulated flue gas of waste incinerator. The flow rate and operating
temperature of the test unit are 2,600 Nm3/hr in maximum and 160 oC, respectively. Test dust is fly
ash that collected from the electrostatic precipitator at coal-fired power plant and classified in the
jet-mill. The concentration of inlet test dust and mean particle size are 20 g/Nm3 and 5.0
micrometers, respectively. Test results shows that the bag cleaning interval of surface flexible filter
bags increased up to 2 times than that of the rounded filter bags at same test conditions. Also, the
initial pressure drop of surface flexible filter bags is lower compared to rounded filter bags and rigid
cartridge shape of filter bags. Especially, the fractional collection efficiency of surface flexible filter
bags at 3.0 micrometers of particle size increased up to 2.0 %, from 97.0 to 99.0 % than that of two
different shape of filter bags.
References
[1] Wey, M.Y, Ou, W.Y., Liu, Z.S., Tseng, H.H., Yang, W.Y., Chiang, B.C., Pollutants in Incineration Flue Gas, J. Hazard.
Mater. B82, pp. 247-262(2001)
[2] P. Biswas and Ch.-Y. Wu, Nanoparticles and the Environment, Journal of the Air & Waste Management Association,
55 pp.708-746(2005)
737
BIMETALLIC GOLD-COPPER CATALYSTS FOR GLYCEROL CONVERSION TO LACTIC ACID
D. HERNANDEZ1, D. LOPEZ1, R. PALACIO1.

1 Química de Recursos Energéticos y Medioambiente, Instituto de Química, Facultad de Ciencias
Exactas y Naturales, Universidad de Antioquia UdeA, Medellín, Colombia.
Abstract
Selectively converting glycerol, a by-product generated during biodiesel production, to valuable

chemicals is a process of significant importance both for fundamental research and potential
industrial applications [1, 2]. Conversion of glycerol into lactic acid is interesting because lactic acid is
considered one of the 12 key chemical platforms from which valuable chemical products can be
generated [3].
In this work, heterogeneous catalysts containing bimetallic gold-copper species as active phases,
supported on cerium oxide, were obtained using the deposition-precipitation method. After
deposition of gold and copper precursors, the powders were dried under vacuum and then
calcination was carried out at 400 oC in a muffle oven. Before the catalytic reaction the powders
were reduced under H2 flow at 400 oC.
SEM-EDS analysis showed that copper and gold species are both, rather homogeneously distributed
throughout the whole analysis area of the powder after calcination step at 400 oC.
The catalytic reaction was performed at 250 oC with a NaOH/Glycerol mole ratio of 0.8, 600 mg of
catalyst during 8 h reaction and mechanical stirring of 650 rpm.
The glycerol conversion reached 87.2 % with the main product formed being lactic acid with a
selectivity of 84.4 % followed by pyruvaldehyde (7,6% selectivity), 1,2-propanediol (4.1% selectivity).
Other identified products were acetic acid and hydroxyacetone.
References
[1] Behr, A., Eilting, J., Irawadi, K., Leschinski, J., Lindner, F.: Improved utilization of renewable resources: New important
derivatives of glycerol. Green Chemistry. 10, 13-30 (2008)
[2] Yang, F., Hanna, M. A., Sun, R.: Value-added uses for crude glycerol – a byproduct of biodiesel production.
Biotechnol. Biofuels. 5, 13-22 (2012)
[3] Datta, R., Henry, M.: Lactic acid: Recent advances in products, processes and technologies — A review. J. Chem.
Techno. Biotechnol. 81, 1119-1129 (2006)
Acknowledgements: The authors thank the Universidad de Antioquia and Colciencias for the project: “Sustainable
products from biomass”, financed by the 2006 Newton Funds Institutional link.
738
RECOMBINANT EXPRESSION OF A XYLANASE VI (GH30) FROM TRICHODERMA REESEI

WITH POTENTIAL APPLICATION IN THE XYLAN EXTRACTION FROM SUGARCANE
BAGASSE
B.F. FERREIRA1, A.M.F. MILAGRES1

1 Escola de Engenharia de Lorena, USP, Lorena-SP,Brazil
Abstract
Sugarcane bagasse is a material with a high potential to be employed in a sustainable platform for
fuels and chemicals production. The components present in the cell wall of sugarcane bagasse have
been intensively studied, for its conversion into high value products. This work focused in the
extraction of the second most abundant molecule in the cell wall of sugarcane, composed of
arabinoglucuronoxylan (GAX). Sugarcane bagasse was chemithermomechanically treated with an
alkaline/sulfite solution followed by disk refining as described by Mendes et al. [1]. The choice of a
pretreatment technically feasible for reducing the recalcitrance without significant modification of
carbohydrates could increase the portfolio of products derived from sugarcane bagasse. For this, a
recombinat xylanase from family 30 was used in alkaline sulfite pretreated bagasse with aiming to
hydrolyze part of the residual xylans. Trichoderma reesei gene coding for a GH30 xylanase was
cloned in Aspergillus nidulans strain A773. Strains with higher expression were cultivated in maltose.
GH30-xylanase is an appendage-dependent enzyme that cleaves glucuronoxylan main chain at the
second glycosidic linkage to the MeGlcA substituents [2]. Relatively small amounts of xylanase (5
IU/g of substrate) and incubation times (24 h) were sufficient for removal of 15% of the accessible
xylan and 32% after cold alkaline extraction with NaOH 10% (m/m). Xylooligosaccharide fraction was
absent in the profile of xylanase GH30 incubated on bagasse xylan. The hydrolysis products obtained
after 30 h reaction were analyzed by thin-layer chromatography (TLC) and by size exclusion
chromatography (SEC). The average molecular weight of xylan (MW) before and after incubation
with GH30 was quite different, indicating its action in several cleavage sites. Xylanase GH30
hydrolyzed xylan and released 53% products with molecular weight around 30 kDa and 47% of
xylooligomers mixture around 6 kDa. This product could be a highly attractive material for deposition
onto cellulosic pulps for increasing their xylan content, thereby providing added value to xylan-
bagasse.
References
[1] Mendes, F. M. et al. Biotechnology Progress, 29: 890–895 (2013)
[2] Biely, P., Singh, S., Puchart, V. Biotechnology Advances 34: 1260–1274 (2016).
739
HCl REMOVAL CHARACTERISTICS OF CALCIUM HYDROXIDE AT THE REAL SCALE DRY-

TYPE SORBENT REACTION ACCELERATOR IN THE MUNICIPAL WASTE INCINERATION
PLANT
YOUNG-OK PARK1, KWANG-DEUK KIM1, SEONG-MIN JEON1, NAIM HASOLLI1, KANG-SAN LEE1, JAE-
RANG LEE1, JAE-WON HAN2, HEE TAIK KIM2, JIN-DO CHUNG3
1 Solar Thermal Laboratory and Clean Fuel Laboratory and Clean Fuel Laboratory, Korea Institute of
Energy Research, Korea.

2 Department of Fusion Chemical Engineering, Hanyang University, Korea.
3 Department of Environmental Engineering Hoseo University, Korea.
Abstract
Most incinerator exhaust gases contain toxic organic compounds, heavy metals, and acid gases. As a
method of properly removing HCl, the wet method has relatively high removal efficiency compared
to the dry method. Dry method has the advantage of using the energy of flue gas, reducing the
generated gases, and removing other compounds, such as heavy metals. Using a baghouse with the
dry method can increase such method’s removal efficiency. The existing sorbents were replaced with
the highly reactive Ca(OH)2 to increase the removal efficiency of the pilot-scale dry sorbent reaction
accelerator. HCl removal characteristics with secondary reaction of the unreacted sorbent in a
baghouse according to the stoichiometric ratio (SR). In the dry sorbent reaction accelerator, the acid
gas contained flue gas moves through a cylindrical from the bottom to the top. The fresh Ca(OH) 2 is
injected into the conical zone at high velocity. HCl concentrations were measured using the GASMET
Dx-4000 analyzer. The average HCl concentration at the inlet of the reactor was maintained at 878
ppm. The HCl removal efficiency was maintained at over 99.9%, and the HCl emission concentration
was maintained at below 5 ppm under the conditions that the flow amount of the flue gas was
40,000 Nm3/hr, the SR was below 2.0, and the pressure loss at the baghouse was 150 mmH 2O.
The SRx can maximize the removal efficiency of acid gas when linked with a baghouse, and can
simplify the flue gas disposal process without any need for water treatment.
Reference
[1] K.D. Kim, S.M Jeon., HCl Removal Characteristics of Calcium Hydroxide at the Dry-type Sorbent Reaction Accelerator
Using Municipal Waste Incinerator Flue Gas at a Real Site, Korean J. Chem. Eng, 34(3) pp.747-757(2017)
740
HEAVY METALS PARTITIONING DURING THERMAL DEVOLATILIZATION OF SOLID

WASTES IN A FLUIDIZED BED REACTOR
V.F. DE ALMEIDA1, A. RONDA1, J. ARROYO-CAIRE1, M. SUAREZ-ALMEIDA1, I. PARDO-ARIAS1, D.

FUENTES1, P. HARO1, A. GOMEZ-BAREA1
de Ingeniería, Universidad de Sevilla, Camino de los Descubrimientos s/n. 41092 Seville, Spain.
Abstract
Thermal valorization of solid waste has become an active research field during the last few years,
due to its capacity of generating energy while processing a residue that would be otherwise
landfilled. However, the use of solid wastes as fuel in thermochemical processes still presents several
economic and technical drawbacks, making their conversion more challenging than for coal or
biomass. The main reason is that waste fuels like municipal solid wastes (MSW) and dried sewage
sludge (DSS) contain high amounts of potentially pollutant species, generated during gasification (Cl,
S, N and heavy metals –HM–). Specifically, the HM content in these solid wastes is much higher than
in a clean biomass. Therefore, there is a special concern to understand HM partitioning between the
solid residue and syngas during thermochemical conversion. The assessment of HM partitioning
enables syngas cleaning design and proper disposal/valorization of the solid residue generated. The
tendency of an HM to volatilize changes with process conditions and fuel composition [1,2].
Volatilization indicates the trend of HM to be released to the gas phase, calculated as:
(𝑚𝑖0 −𝑚𝑖𝑓 )
𝑉𝑖 = ∙ 100 Equation 1
𝑚𝑖0
In a fluidized bed test, the final solid residue may not be fully recovered, due to mixing and potential
combination/reaction with the inert material, leading to the indetermination of solid residue mass
remaining after conversion and so, preventing accurate calculation of volatilization. In those cases,
the HM concentrations in the solid residue is measured though, through the analysis of a solid
residue sample. By taking a key HM with very low volatilization as reference (zero) - for instance, Ni,
Fe, Cu, etc. - the mass of the final solid residue can be estimated, enabling the determination of the
volatilization for the rest HM.
In this paper, tests were performed in a dedicated fluidized bed reactor, using solid wastes in a N 2
atmosphere at typical pyrolysis and gasification temperatures. The fuels and process solid residues
composition in HM were analyzed by Inductively Coupled Plasma (ICP). For some cases, in which the
solid residue mass was successfully measured, the result calculated from the key component method
was validated. Results show great accordance between measured and calculated solid residue mass,
and therefore, volatilization of HM was satisfactorily calculated for most cases, presenting a high
accordance level to literature data. The key component method shows to be advantageous,
especially in cases in which it is impossible to determine the mass of the final solid residue, i.e.
fluidized bed thermal conversion of solid wastes.
Nomenclature: Vi (%) = volatilization of metal I; mi0 (g) = initial mass of metal i (mass of metal in the fuel); mif (g) = final
mass of metal i (mass of metal in the solid residue).
References
[1] Konttinen, J., Backman, R., Hupa, M., Moilanen, A. and Kurkela, E.: Trace element behavior in the fluidized bed
gasification of solid recovered fuels–A thermodnamic study. Fuel. 106, 621 – 631 (2013).
[2] Niessen, W.R.: Combustion and incineration processes: applications in environmental engineering. (2010).
741
MATERIAL, ENERGY AND EXERGY FLOW ANALYSIS TO REDUCE THE ENERGY

CONSUMPTION IN AN OPTIMIZED CERAMIC PLANT
T. GRONIER1, M. C. TABOADA GÓMEZ2, P. M. BELLO BUGALLO2

1
Ecole de Mines d’Albi-Carmaux, 1 Allée des sciences, F-81013, Albi, Cedex 9, France
2
Department of Chemical Engineering, School of Engineering, University of Santiago de Compostela,
Av. Lope Gómez de Marzoa, s/n, E-15782, Santiago de Compostela, Spain
Keywords: Ceramic industry, Drying, Energy efficiency, Material and Energy Flow Analysis (MEFA),
Best Available Techniques (BAT), Exergy Analysis (EA).
Abstract
Spain is the fourth producer and the second exporter of ceramic goods worldwide. In the European
Union (EU), the ceramic industry is directly affected by the communitarian energy and environment
policies, especially due to its huge energy consumption. The EU Emissions Trading Scheme [1] taxes
energy consumption, representing 30% of the costs of this industry [2]. To preserve their
competitiveness and to prevent carbon leakage, it is essential for the industry to reduce its energy
consumption [3].
The main goal of this work is searching for alternatives to reduce the energy consumption in a tile
factory. The study focuses on the drying stage, the second most energy consumer stage. To this end,
existing methodologies combining Material and Energy Flow Analysis (MEFA), Best Available
Techniques (BAT) analysis [4] and Exergy Analysis (EA) [5] were applied. This way, this study includes
an EA to identify other losses than those given by the MEFA.
For the first time, EA has been applied to a high energy-consuming stage from an intensive energy-
consuming industry. Also, as Life Cycle Thinking (LCT) has proved its effectiveness regarding energy
efficiency, the study examined also some upstream and downstream flows that impact significantly
the energy consumption.
The analysis identified 4 Improvable Flows (IF) and 10 relevant BAT to reduce the effects of the
identified IF and build a more sustainable configuration for the drying stage. The study underlined
important energy losses concerning the air-flow rate, which needs to be measured and controlled,
as well as in the recirculation system [6].
742
1- INTRODUCTION
European Union requirements regarding ecology, are one of the strictest in the world. Regarding the
ceramic activities, in the one hand, the ceramic industry found the impact of such requirements
positive, as it leads to apply the Best Available Techniques (BAT) and increases productivity [7]. In
the other hand, it threatens the European ceramic industry because it creates extra costs compared
to countries with low environmental requirements: as energy represents about 30% of the
production costs [2], any increasing in costs has a significant impact.
From an ecological point of view, the implementation of too strong local environmental policies can
eventually lead to carbon leakage: as the production become too expensive, the production is
delocalized to other countries and this could increase the global amount of pollution [8, 3]. Thus, it
is essential for the ceramic industry to improve both its competitiveness and its ecological impact.
Spain is the fourth largest producer of ceramics worldwide, with 440 million of m², and the second
world exporter, with almost 14% of the world exports [9]. It is also the first European producer of
ceramics. The turnover of the sector in 2015 was 3 billion euros only in Spain.
In Spain, the ceramic industry is a cluster-based sector. The production is concentrated in three
areas: the north-western coast (where Galicia is), the Valencian Community, and the Southern coast.
1.1- LIFE CYCLE THINKING
From the concept of Sustainable Development, the Life Cycle Thinking (LCT) philosophy has
emerged. LCT considers the range of impacts throughout the life of a product, aiming to reduce the
ecological impact of industrial processes. All phases of the product life-cycle are studied, beginning
with raw material extraction and conversion, then manufacture and distribution, through to use
and/or consumption. It ends with re-use, recycling of materials, energy recovery and ultimate
disposal.
This approach reveals integration possibilities, i.e. actions on one or several phases that impact
another phases. As LCT aims to Sustainable Development, it considers ecological, but also economic
and social aspects of the industrial process. Therefore, LCT leads to concepts like circular economy.
In circular economies, all the materials needed to manufacture a product are wastes recycled from
another process, creating no waste.
LCT has been promoted by the European Commission, especially through Life Cycle Assessment, to
help European industries reaching the European ecological objectives. Furthermore, the European
Integrated Pollution Prevention and Control (IPPC) Bureau (EIPPCB) published the BREFs. BREFs are
freely-available documents indexing the Best Available Techniques (BAT) to achieve ecological and
energetic efficiency for a given industrial field or activity. According to the EU, BAT are ‘the most
effective and advanced stage in the development of activities and their methods of operation which
indicates the practical suitability of particular techniques for providing the basis for Emission Limit
Values and other permit conditions designed to prevent and, where that is not practicable, to
reduce emissions and the impact on the environment as a whole [10]. In addition to BAT, BREFs
provide descriptions of the field, of the processes used and data about the expected ecological
impact of the studied industry, with estimates of emissions and energy consumption.
743
BAT are difficult to use, as it is not easy to identify nor the most relevant stages to improve, nor the
most efficient techniques to apply on them. Therefore, many methods have been used to identify
where and how to apply the BAT, and many works have been published [5, 11, 12, 13, 14, 15, 16].
Most BREFs are currently being reviewed, as they were published in the 2000’s. Unfortunately, the
BREFs applied in this study (Ceramic Manufacturing Industry and Energy Efficiency) have not been
reviewed yet.
1.2- OBJECTIVES
This study had two objectives. The first one was to reduce the consumption of a ceramic tile factory,
focusing on the drying stage as requested by the company. The second one was to upgrade an
existing methodology [4] used to identify the most relevant Improvable Flows (IF) and the more
suitable BAT to improve them. Being the IF those inputs, outputs, or internal flows that are
remarkable in comparison with the other flows of the process, and which could be improved if
properly managed [17].
The existing methodology was based on a combination of MEFA and BAT analysis. In this work, it has
been adapted, including a reflexion on irreversibility. In fact, though MEFA reveals the losses in the
quantity of energy, it does not reveal the losses in quality. This kind of losses can be revealed and
quantified by an Exergy Analysis (EA). Exergy, also called “available work”, is defined as the
maximum theoretical useful work (shaft or electrical work) obtained if the system is brought into
complete equilibrium with the environment. The ratio of exergy to energy in a substance can be
considered a measure of energy quality. Forms of energy such as kinetic and electrical energy are
100 % recoverable as work, and therefore have an exergy equal to their energy. However, forms of
energy such as radiation and thermal energy cannot be converted completely to work and have
exergy content less than their energy content [18, 19].
1.3- STATE OF THE ART
The techniques used by the ceramic industry have known few evolutions since the publication of the
Ceramic BREF [20]. According to several studies, the industry will never be able to reach the EU
objectives for 2050 without some technological breakthroughs [3, 7]. In this context, the European
Commission started the DREAM project (Design for Resource and Energy efficiency in cerAMic kilns)
in October 2016 [21]. This focus is easy to understand knowing that kilns represent about 90% of the
energetic consumption in the ceramic industry.
One of the main changes expected in the following decades is the transition to electricity-powered
dryers and kilns, as it would decrease significantly the ecological footprint of this stages [22].
Nevertheless, optimization is still possible, and some new techniques have been successfully applied
in the industry, such as the use of solar thermal energy as an auxiliary source of energy in the dryer
[23] or the use of thermal oil to recover heat from the tubes [24].
2- METHODOLOGY
The overall methodology includes the following stages.
744
1. Case study definition

 Definition of the process under study. Some downstream and upstream stages have been
analysed.
2. Qualitative analysis
 Qualitative analysis of the selected industrial system.
 Qualitative analysis of the selected stage (drying): analysis of the inputs, outputs, and internal
flows, including exergy.
 Identification of the most influencing upstream and downstream stages.
 Identification of the irreversibilities: qualitative analysis of the energy flows to identify the most
important losses in energy quality.
3. Quantitative analysis
 Data acquisition: compilation of data using direct measurements as well as based on previous
works. Where data were not available, use of estimations, bibliography, interviews, etc.
 Software selection.
 Modelling: using a MEFA and the identified irreversibilities.
 Identification of the Improvable Flows (IF): the results obtained from the MEFA and the EA are
analysed to identify the IF.
4. BAT analysis
 Recompilation and inventory of the candidate techniques to be BAT for the selected industrial
system.
 Identification of the already implemented BAT.
 Proposal of alternatives to the process: for each IF, selection of the most efficient BAT.
3- APPLICATION OF THE METHODOLOGY

3.1- DEFINITION OF THE CASE STUDY
The above-mentioned methodology has been applied to Cerámica Verea SA. It is a Spanish
enterprise located in Galicia (NW Spain), and it is exemplary regarding energy efficiency and
pollution. A study using BAT has already been performed in this plant [4].
The company specialises in the production of tiles with local clay -all the quarries are situated less
than 10 km away from the plant- and sells them mainly in Spain, but also in France and in the USA. It
produces hundred million of tiles per year, using highly automated processes. The enterprise
produces almost 200 different types of tiles. The composition of the clay is mostly the same in all of
them, but there are differences in shape and aspect (old aspect or grey colour for example).
As already mentioned, the plant managers wished to reduce the energy consumed inside the dryer.
According to the LCT approach, the study will also consider some of the downstream and upstream
flows as potential improvable flows.
3.2- IDENTIFICATION OF THE INDUSTRIAL PLANT

The methodology has been applied to the factory of Cerámica Verea SA, a ceramic installation in the
NW of Spain that produces tiles.
3.3- QUALITATIVE ANALYSIS

3.3.1- Analysis of the selected industrial system
745
The milled clay is a mix of four types of clays extracted from the quarries. Some additives are mixed
with the clay. The first one of them, the Barium Carbonate (CO 3Ba), it is always added to block
efflorescence (apparition of salt on the surface of the tile). The other, Manganese Oxide (Mn 3O4), is
optional and used as a colorant.
Then, the clay is extruded. Once extruded, the shape of the tile is cut from it. A worker removes
manually the non-conform tiles. They are recycled as shown on the flow-diagram. Next, the tiles are
loaded on shelves and the shelves are piled up on a trolley. The trolleys are then conduced to the
drying stage. Once dried, non-conform tiles are identified by a robot and recycled. Then, the
remaining tiles are stocked and cooked. The post-processing includes the palletizing and packaging.
The entire process is illustrated on Figure 1.
Figure 1: Process description.
3.3.2- Analysis of the selected stage (drying)

The drying stage lasts 24 hours, therefore, the dryers and the furnace are always on.
There are two dryers, with two lines each one of them corresponding to the two types of water
present in the tile (Fig. 1). The trolley enters in the first dryer via a lock, to limit heat losses. In this
first dryer, the “contraction water” is removed from the tile. Then, as the second dryer is hotter
746
than the first one, tiles must pass a second lock. In the second dryer, it is the “porosity water” that is
removed. To be extracted, the “contraction water” needs more air flow and less temperature than
the “porosity water”.
The distribution of the air along the dryers is complex (Fig. 2). The air in the second dryer is a mix
between fresh air and air coming from the furnace, both heated in a heat exchanger (number 3).
This air goes through the second dryer and then, it is mixed with fresh air, heated (heat exchanger
number 2), and sent through the first dryer. At its exit, it is mixed with fresh air, heated (heat
exchanger number 1) and recirculated into the first dryer. All this process is automated.
Figure 2: Drying stage.
In the heat exchangers, the air is heated with hot air. Heat comes from a burner fuelled with natural
gas. In each one of the heat exchangers, some air is purged, and some fresh air is introduced to the
process (Fig. 2). Even though three locks are in place to prevent heat losses, some air inevitably
escapes the dryers through the locks.
The temperature in the dryers never goes over 90°C. Temperature is known in the dryer for each
entry point for the air. It is measured at two heights, because there is a gradient of temperature
between the floor and the ceiling. There are also moisture sensors inside the dryer (so the moisture
of the air, not the tile, is known).
Temperature upstream and downstream of the burner are always known, but not moisture.
Moisture of the air (fresh and hot) is known right before the first dryer, but not the second. The air
flow rate is not measured.
3.3.3- Identification of the most relevant upstream and downstream flows
747
Inputs of the drying stage include: wet raw tiles, fresh air, hot air from the kiln, natural gas, and
electricity. Outputs of the drying stage include: humid air, dry raw tiles and gas emissions from the
combustion of the natural gas: VOC, PM 10, CO, CO2, NOx [4].
The moisture of the wet raw tiles is a key parameter. Moreover, it has been proved that reducing
the moisture of the tiles allows significant energy savings [25]. Consequently, it has been considered
as an important upstream flow.
In the drying step, energy used is mainly thermal energy used to heat the air [4]. Consequently, both
fresh air and air from the kiln are significant flows for the drying stage.
3.3.4- Identification of irreversibilities

Irreversibilities are source of energy losses that cannot be seen by classical energy balances, as it is
not the quantity, but the quality of energy that change. To maximize energy efficiency, the concept
of exergy has been established: it represents the maximum energy that a system can give before
reaching the equilibrium with its environment. Such equilibrium is often named “dead-state”.
There are three types of irreversibility’s: thermal, mechanical, and chemical [18]. Thermal
irreversibilities comes from all heat transfers, mechanical irreversibilities are created by friction and
chemical irreversibility’s come from mixture of substances. The irreversibilities identified in the
drying stage are listed in Table 1.
Irreversibility’s Nature Description

Heat exchanger Thermal, mechanical Heat transfer and head losses are great sources of
irreversibility.
Joule effect Thermal Joule effect transforms electric energy into heat energy, which
is often not valorised. So, it creates irreversibility.
Mixing of air Thermal Mixing of air, in the dryer, is also a thermal irreversibility, as
the temperature become quickly homogeneous once air is
mixed.
Pipe Mechanical Pipes create head losses and frictions, known sources of
irreversibility, as this energy is usually taken from pressure.
Water addition to the tiles Chemical As energy needed to extract water is far more important
than energy needed to mix, it creates irreversibility.
Table 1: Irreversibilities in the dryer.
3.4- QUANTITATIVE ANALYSIS

3.4.1- Data acquisition
The data used in this work was mainly provided by the selected industrial plant. Most of the data
were obtained from technical visits or given by the staff during personal interviews. Extra data were
obtained through meteorological services, articles from scientific journals and reference books.
3.4.2- Software selection

A combination of Excel and MATLAB has been used to perform the calculations. Excel was used to
standardize all the data and Matlab to calculate. One script has been made for each heat exchanger,
recirculation system and area of the dryer. These scripts calculate mass, energy, and exergy flows.
748
3.4.3- Modelling
The following assumptions have been made:
 Creation of dust is neglected.
 Steady-state supposed.
 Pressure is equal to atmospheric pressure (very low variation).
 Moisture of the air coming from the kiln is supposed to be null (low according to the staff).
 Variation of potential energy is neglected (only 6 m of difference).
 Heat losses in the circuit are neglected (about 2°C lost over 50 m);
 Radiation energy neglected (the dryer is inside a plant and no temperature exceed 200°C).
Mass balances have been performed. Then, energy balances have been performed in two parts.
Firstly, enthalpy balances of the different species involved have been calculated. The changes in
kinetic energy have been also calculated for the air flows. This first part corresponds to the energy
received by the system and the equations have been solved for each flow. Secondly, thermal energy
balances have been calculated using the natural gas and electric consumptions.
3.4.4- Results of the quantitative analysis

The results of the material and energy analysis are represented on figure 3. Exergy losses in the
different stages of the process are shown in table 2.
Figure 3: Sankey diagram.
749
Irreversibility’s Value [MJ/d]

Heat exchanger 1 23300
Areas 1&2 9200
Area 3 2100
Recirculation 1 1600
Recirculation 2 3500
Recirculation 3 800
Table 2: Irreversibilities in the dryer.
3.4.5- Identification of the Improvable Flows

According with the results of MEFA and EA, four flows have been proved to be improvable.
The air flows have been highlighted as the major carriers of energy of the process. Heat exchanger 1
is where energy exchanges were the most important. Consequently, the air flow between area 1 and
heat exchanger 1 and the purged air flow have been considered as IF. Then, as fresh air is the
coldest air flow in the process, the three fresh air flows have been identified as IF, for two reasons:
first, they are the flows driving natural gas consumption, and, secondly, their air flow is not
optimized.
Exergy analysis underline that in the recirculation, there were a lot of exergy destroyed, especially
through minor head losses (about 85% of head loss), which leads to overconsumption of electric
energy. Exergy lost in heat exchangers could seem important, but as it is generated by the heat
exchange itself (which is the goal of the stage), it is not an IF.
The cooking stage consumes much more energy than the drying stage: between 5 and 10 times
more, according to the director of the plant as well as previous studies [4, 12]. Addition of organic
wastes to clay, according to numerous studies, should lead to a significant diminution in energy
consumption. For these reasons, even if it is not related to the dryer, the flow of thermal energy in
the kiln is also identified as an IF.
Tiles often have enough water for the process and it is only added occasionally, in very little
quantity. Moreover, addition of water is realized manually, as no software able to calculate its need
has been found by the enterprise. Consequently, addition of water is not an IF.
3.5- BAT ANALYSIS

3.5.1- BAT inventory
Table 3 indexes BAT relevant to the case study: BAT aiming energy efficiency and applicable to the
drying stage. They are mostly taken from the European Union BAT reference documents (BREF), as
well as other literature.
Technique Involved stage Description Source

Cogeneration system Dryer and furnace Utilization of the smokes of the natural gas to create electricity 20
Heat recovery from flue gases Dryer and furnace Utilization of the heated air of the kiln in the dryer to reduce energy 4, 11, 16,
and recirculation to dryer consumption 20
Modification of ceramic bodies Mixing and/or shaping Either reduce the amount of water added, either modify the shape of 20, 26, 27,
the tile, either utilization of additives 28, 29, 30
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Improved design of kiln and dryer Dryer and furnace Automation of the process, better sealing, high velocity burners, 5, 11, 20
optimization of the passage time between dryer and kiln, finish the
drying in the pre-heating
Superheated steam Dryer Use of superheated steam instead of air 20
Radiation processes Dryer Using microwaves, energy losses are reduced, as energy is directly 20
applied to the tile
Insulation All stages Insulation of the installations to limit heat losses 5, 20
Optimization of the All stages Improvement of the controlling and of the monitoring system, to 18, 20
monitoring and of the control reduce energy consumption
system
Optimization of electric All stages Use well-sized energy efficient motors, use direct coupling or 18
motors installing high efficiency transmission system
Improving ventilation system All stages Use well-sized high efficiency fans, use ducts of large size with 18
limited head losses (long runs, obstacles)
Maintenance All stages Instituting regular and efficient maintenance, to prevent 18
degradation of the equipment’s and to avoid breakdowns
Table 3:BAT inventory.
Some emerging techniques found during the bibliographic review are not ready-to-use today but
can become BAT later. They are listed in table 4.

Solar-assisted drying Dryer Use of a fluid heated by the sun to heat the air flows 23
Use of fluid to recover heat Dryer and furnace Setting up a counter current flow of fluid surrounding the heat 16
transfer tubes to recover some energy (see figure 1)
Transition to electricity- Dryer and furnace Replace natural gas by electricity to reduce drastically emissions 3
powered dryers and kilns
Table 4: Emerging technique.
3.5.2- Identification of the already implemented BAT

The considered plant has already implemented 4 BAT, which are listed in table 5.
Technique Description
Heat recovery from flue gases and A tube leads the air exiting the kiln into the dryer
recirculation to dryer
Improved design of kiln and dryer Three locks have been installed
Reprocessing of wastes The clay is recuperated at three different points of the process to be recycled
Insulation All the conducts are recovered by 100 mm of rock wool
Table 5: Already implemented BAT.
3.6- PROPOSAL OF ALTERNATIVES TO THE PROCESS

Some candidate techniques to be BAT from the inventory are proposed for those IF identified for
the process.
 Air flows in heat exchanger 1: to optimize the quantity of air, the BAT “Optimization of the
monitoring and of the control system” is proposed. Installing flow sensors and linking them to the
current monitoring process will allow to control the air flow and to avoid heating air not
necessary for the process. It should be rather efficient to fix maximum and minimum air flows in
the monitoring system.
 Fresh air: To reduce the amount of fresh air drained from the plant, the BAT “Optimization of
the monitoring and of the control system” is also relevant here. Furthermore, the BAT “Heat
recovery from flue gases and recirculation to dryer” can be applied: as fresh air is only used to
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control the depression in the dryer, replacing it by air coming from the locks, which is hotter,
should reduce the need of thermal consumption.
 Recirculation: the main problem here are head losses. To enhance the IF, the BAT
“Optimization of the monitoring and of the control system” can be efficiently used with
anemometers limiting the celerity of the air in the tube, as head losses are proportional to the
cube of celerity. Once implemented, another BAT, “Improving ventilation system” and
“Optimization of electric motors”, must be used to be applied to earn energy efficiency: it
consists in reducing the size of the motors and of the fans according to the new energetic needs
(and potentially buying more efficient ones, if relevant). Then, as minor heat losses are
important, the circuit should be improved to suppress right-angled corners and abrupt narrowing
of section.
 Cooking stage: as said before, the BAT Modification of ceramic bodies should permit
significant economy, but it creates few problems. Firstly, as it changes the reaction in the tile,
cooking and drying stage must be adapted: for example, addition of bio wastes increases the
global humidity of the tile, forcing the parameters of the drying to be changed. Secondly, it
creates normative problems, as adding more than 1% of organic matter to a tile force to test its
fire resistance to be conform with EU legislation [31]. Moreover, as it increases porosity, it can
create problems of permeability.

The methodology used in this work succeeded in identifying IF and proposing BATs to implement.
4 IF have been identified. As air is the main conveyor of energy, it is not surprising that 3 IF concern
directly the air flows inside the dryer. One of them concern fresh air, the most important input
regarding to its quantity. Another IF concern head losses, which is not obviously an important
matter in this stage. Moreover, these 3 IF work on electric consumption, as gas consumption is well
optimized in the process. Lastly, the fourth IF concern the cooking stage. Even if it should be outside
of the study, it has been considered as it participates to the main objective of the industrial, i.e.
reduction of its energetic consumption.
BAT analysis permitted to index 11 candidate BATs and 3 techniques still under development. 4
already applied BATs have been identified and 5 BATs have been proposed. Exergy analysis and
integration of outer stages provided each one IF. The already applied BAT justify that there are no
significant improvements to do.
The most relevant proposed BAT is the monitoring of the debits of air in the dryer, as it is the
simplest to implement and should be the most efficient in energetic reduction. Changing the motors
and the fans is costlier, but can be implemented gradually, when they break. Recuperation of air in
the locks should only be implemented if not too costly, as it does not reduce that much the
consumption. Lastly, adding organic wastes to the tiles mixing could be the most efficient BAT to
implement, but it imposes to modify all the thermal treatment, i.e. drying and cooking.
5- CONCLUSIONS
This study has applied a methodology combining MEFA, EA and BAT analysis with a limited
perspective: reducing the energetic consumption of a single process, the drying stage of a ceramic
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tile plant. Considering the effectiveness of the LCT approach, outer stages strongly linked to the
drying stage or to the energetic consumption of the plant have been also considered.
This limited perspective explains that the number of IF (4) and BAT proposed (5) is low compared to
previous studies using similar methodologies. For example, in 2016 a similar methodology was
applied to a tuna canning industry, identifying 16 IF and proposing 14 BAT [5].
The study proved that this methodology is also suitable on a smaller scale. Moreover, it confirmed
the effectiveness of using exergy analysis and proved that it is relevant to consider outer stages in
the study.
ACKNOWLEDGEMENTS
The authors would like to thank the collaboration of the company, Céramica Verea SA. We especially
thank, PhD José Miguel Rodríguez Blas for the assistance provided in the measurements.
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ASSESSMENT OF THE PHYSICO-CHEMICAL PROPERTIES OF RESIDUES AND

EMISSIONS GENERATED BY BIOMASSES COMBUSTION UNDER N2/O2 AND
CO2/O2 ATMOSPHERES IN A DROP TUBE FURNACE (DTF)
G. CRUZ1, P.M. CRNKOVIC2

1
Federal University of Maranhão, Department of Mechanical Engineering, São Luis (MA),
Brazil.
2
University of São Paulo, Department of Mechanical Engineering, São Carlos (SP), Brazil.
Keywords: renewable sources, energy production, lignocellulosic materials, metallic parts.
Abstract
This study evaluates gases CO, CO2, NO and SO2 emitted from five in natura Brazilian biomasses: pine
sawdust, sugarcane bagasse, coffee and rice husks, and tucumã seed and the residues generated
when the biomasses are applied to combustion atmospheres (N2/O2: 80/20) and oxy-fuel
combustion (CO2/O2: 80/20) in a Drop Tube Furnace (DTF). The in natura samples and residues
generated were evaluated by TG/DTG (Thermogravimetry/ Derivative Thermogravimetry), SEM
images (Scanning Electron Microscopy) and EDS analysis (Energy Dispersive Spectroscopy). The SEM
images revealed some of the main morphological differences of the in natura materials. However,
for the residues under both atmospheres, a large part of the lignocellulosic matrix was degraded,
indicating the good efficiency of the thermal process. The TG/DTG curves for the in natura and
residues samples of both thermal processes enabled the quantification of the contents of remaining
moisture, total organic materials consumed and ashes produced. The emissions for both
atmospheres (80% N2 and 80% CO2) ranged between 90-6,200 mg Nm-3 g-1 for CO, 5-210 mg Nm-3 g-1
for CO2, 10-170 mg Nm-3 g-1 for NO, and 25-870 mg Nm-3 g-1 for SO2 and are directly related to the
chemical composition of the lignocellulosic materials, oxidizing atmospheres and furnace conditions.
The O2 consumption (6-77 mg Nm-3 g-1) inside the furnace for the oxidizing atmospheres and
different biomasses exhibited an 80% CO2 > 80% N2 trend. The chemical composition (EDS) for the in
natura and residues samples and both atmospheres revealed different proportions of organic,
inorganic and metallic elements in the samples and that the individual behavior of the biomass is a
consequence of the diversity of its properties.
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1- INTRODUCTION
The several agricultural cultures in Brazil, has been characterized by its large-scale production,
presenting in its vegetation a wide variety of lignocellulosic materials, which can be used as
feedstock sources for bioenergy production. In terms of using alternative sources of energy, Brazil
has a privileged position compared to other countries [1,2].
Several materials, such as harvest residues and energy crops or even the leftovers of processed
products have been discarded in rural environments. These materials negatively contribute to
pollution and degradation of soil and water and facilitate the proliferation of diseases [1]. An
alternative to avoid the burning of agricultural residues in fields, which causes emissions of pollutant
gases into the atmosphere, is to use them as fuel feedstock in thermal conversion processes, such as
biomass combustion for bioenergy production [2].
Bioenergy from biomass is a clean technology, safe and renewable resource, and is considered as a
potential alternative to partially replace fossil fuels, which will decrease in the future [3]. The
replacement of fossil fuels by renewable sources, as well as biomass, for a clean energy production
has gained great concern. These fuels are responsible for most of the gaseous emissions into the
atmosphere and have caused several problems to the environmental, animals and humans.
Second Wang et al. (2006) [4], thermochemical and biochemical processes are used to convert
biomass in energy useful form. Due to high efficiency in the conversion into solid, liquid and gaseous
products, technology of biomass conversion has found wide application under specific thermal
conditions. Some researchers [5-8] have conducted studies to elucidate, what occurs with the main
constituents of the biomass in thermal degradation steps (mass loss thermal events) during the
several thermal conversion processes.
For example, the conventional combustion process of biomasses comprises the burnout in an
ambient rich in oxygen or air, which considers types and fuel properties, particles size, air flow rate
and fuel moisture. Such characteristics affect combustion, reaction rates and generation and heat
transfer [9,10].
According to Yang et al. (2007) [11], the main constituents of the biomass (hemicellulose,
cellulose and lignin) present mass loss thermal events, which occur in determined temperatures and
specific thermal conditions, because each one of them has its particularities. During the direct
combustion processes, hemicellulose, cellulose and lignin have its reactivity influenced directly by
chemical differences between them. Knowledge of the each component amount is important to
predict the efficiency of the biomass thermal conversion processes [12].
Other combustion process well actual addressed in this study involves clean energy technologies
by use of high CO2 concentrations generated in the fossil fuels power plants. Is case of the oxy-fuel
combustion, where the fuel is burnt in a mixture of pure oxygen and recycled flue gases. Because
nitrogen is eliminated from the oxidizing atmosphere, the flue gas leaving the combustion chamber
is highly enriched in CO2, which means that the combustion process takes place in a CO2/O2
atmosphere. Partial recycling of flue gas helps to control the flame temperature in the combustion
chamber [13] or Drop Tube Furnace [14].
Although many characteristics of the combustion processes and pollutants formation (CO, CO2,
NO and SO2) are known, some details still lack for the oxy-fuel combustion process and their
emissions gaseous in a DTF. Within the context presented, this study evaluates gases CO, CO2, NO
and SO2 emitted from five in natura Brazilian biomasses: pine sawdust, sugarcane bagasse, coffee
and rice husks, and tucumã seed and the residues generated, when the biomasses are applied to
conventional combustion atmospheres (N2/O2: 80/20) and oxy-fuel combustion (CO2/O2: 80/20) in a
Drop Tube Furnace (DTF). The in natura samples and residues generated also were evaluated by
TG/DTG curves (Thermogravimetry/ Derivative Thermogravimetry), SEM images (Scanning Electron
Microscopy) and EDS analysis (Energy Dispersive Spectroscopy).
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Biomass Origin
The five in natura biomass samples used in this study were collected from different regions of
Brazil, namely: sugarcane bagasse, pine sawdust and coffee husk samples (São Paulo State,
Southeast region); rice husk (Maranhão State, Northeast region) and tucumã seed (Pará State, North
region). It is interesting to note that each region exhibits vegetation and climate has been clearly
defined and differentiated. These features facilitate the plantation of several native species, which
require very specific natural conditions.
Biomass preparation
The samples have been received in natura from their respective regions and underwent pre-
treatments that comprised: washing in running water to remove impurities, grinding in laboratory
knives mill to decrease particle size and subsequent sieving for separation in the required
granulometric range. The biomass samples in natura have been pulverized using a household
blender and thereafter sieved. For all the biomass samples, average sizes of 0.46 mm particles were
selected. The biomass samples used in this research were prepared and established by standard
ASTM (D 2013-72) [15].
Biomass samples characterization
Elemental analysis and calorimetry

Instruments equipment (Elemental Analyzer), EA1110-CHNS-O model. The moisture and ash
content were determined by thermogravimetry (TG curves) under oxidizing atmosphere (carbon
dioxide) and controlled temperature ≈ 600 °C [16]. The High Heating Value (HHV) of the samples was
measured in an adiabatic oxygen bomb calorimeter IKA C 2000 model, according to the standard
ASTM E-711 [17].
Table 1 show details of the physical-chemical properties of the biomasses, which can be used for
the biofuels or bioenergy production. Such properties are elemental analysis, moisture and ash
content, and High Heating Value (HHV) of the samples.
-1
Sample Moisture Ash C (%) H (%) N (%) S (%) O*(%) HHV (MJ kg )
Sugarcane bagasse 6.4 ± 0.2 4.8 ± 1.9 45.05 5.57 0.25 n.a. 37.93 17.5 ± 0.1
Pine sawdust 7.2 ± 0.1 1.2 ± 0.1 46.60 6.17 0.40 n.a. 38.43 18.3 ± 0.2
Coffee husk 8.2 ± 0.3 8.3 ± 2.8 43.13 5.93 1.55 0.67 32.22 16.8 ± 0.1
Rice husk 7.1 ± 0.4 11.2 ± 2.4 39.11 4.91 0.31 0.59 36.78 15.4 ± 0.1
Tucumã seed 5.3 ± 0.3 5.3 ± 0.1 48.83 6.71 0.88 n.a. 32.98 20.8 ± 0.1
*Difference at 100%; n.a. - not available.
Table 1: Moisture and ash content, elemental composition and High Heating Value of the in natura biomass samples.
Thermal analysis (TG/DTG curves)

The TG/DTG curves for the in natura and residues samples were carried out using Shimadzu
analyzer, TGA-50H model. The oxidizing atmosphere was promoted by synthetic air (80% N2/20% O2)
with a dynamic flow rate of 100 mL min-1, which was kept constant during the experiments. For
these experiments, the constant heating rate utilized was of 10°C min-1 from room temperature up
to 700 °C. The mass of the samples used was 10.0 ± 0.5 mg and crucible of alumina. The tests were
carried out in duplicate and the mean values and standard deviations were considered.
Scanning electron microscopy (SEM images)
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The morphological analysis of all the biomass samples in natura and residues were analyzed by
mean of images produced in a Scanning Electron Microscopy (SEM); it was obtained with a Scanning
Electronic Microscope equipment, LEO 440 model, with amplitude of 1,000 times.
Energy Dispersive Spectroscopy (EDS analysis)

The in natura and residues samples were prepared by sintering for a best adherence on the
surface of the aluminum support for the EDS analysis, which was also performed under a Scanning
Electron Microscope, LEO 440 model. No metallization type (gold or graphite bath) was used for this
analysis, as it may hide or show regions of some elements (organic and inorganic) more common in
lignocellulosic materials.
Combustion and oxy-fuel combustion in a Drop Tube Furnace (DTF)

A Drop Tube Furnace (DTF) electrically heated (3.5 kVA maximum power) (Figure 1) was used for
the biomass termal processes, i.e. combustion and oxy-fuel combustion. The basic dimensions of the
experimental apparatus are 60 mm outer diameter, 400 mm uniform zone and 200 mm heated
zone. The biomass particles were introduced into the reactor (DTF) by a feeding system with
vibratory mechanical transport and controlled by PWM (Pulse Wide Modulation), where the optimal
rotational velocities and frequency were achieved for each material. The sample mass used was 3.0
± 0.5 g for a 10-minute experiment. An air primary flow rate of 1.5 L min-1 with 20% oxygen
concentration was applied to keep the biomass particles in suspension, during the combustion
process in DTF. After burning at 950 °C, the residues were collected for evaluation by TG/DTG
curves, SEM images and EDS analysis.
Figure 1: Schematic representation of the Drop Tube Furnace (DTF) and feeding system for the biomass combustion
Gases analyser
Equipment of the SICK brand (GMS 810 model) is able of detect and capture the emitted
concentrations by main atmospheric pollutants, during biomasses combustion and oxy-fuel
combustion in a DTF, such as SO2, CO, NO and H2O measured in ppm, and CO2 and O2, in %. It was
used a computational program - SOPAS Engineering Tool - coupled to the analyzer for
communication, data capture from gaseous emissions and equipment calibration.

Thermal analysis (TG/DTG curves)
758
Figures 2 to 6 presents the TG/DTG curves for the in natura samples and residues generated of
pine sawdust, sugarcane bagasse, coffee husk, rice husk and tucumã seed generated after
conventional combustion (80% N2) and oxy-fuel combustion (80% CO2) processes.
Figure 2 (a-b) shows TG/DTG curves in natura pine sawdust and residues generated after
different thermochemical processes (conventional and oxy-fuel combustion) in DTF.
100 0.00
(a)
80
-0.01
Mass loss (%)
DTG (mg s-1)

60
40 -0.02
20 in natura in natura
air (80% N2) -0.03 air (80% N2)
80% CO2
80% CO2 (b)
0
100 200 300 400 500 600 700 100 200 300 400 500 600 700
Temperature (ºC) Temperature (ºC)
Figure 2: (a) TG and (b) DTG curves of the in natura samples and pine sawdust residues after conventional combustion (80%
-1
N2) and oxy-fuel combustion (80% CO2) in DTF. Experimental conditions: 25 up 700 C; heating rate: 10 C min , sample
-1
mass: 10 mg and 100 mL min of synthetic air flow rate
DTG curve (Figure 2b) of the in natura sample displays peaks well defined at 328 and 460 °C,
which correspond to maximum combustion rates and can be attributed to thermal decomposition of
holocellulose and residual lignin. Thin peaks and elongated are a strong characteristic of crystalline
samples [7,18].
In both thermoconversion processes, pine sawdust residues presented low moisture contents (≈
2%). For the conventional combustion, it was observed original structure loss, i.e., mainly the
holocellulose was totally degraded in thermal process, and presence of a small intensity peak around
340 °C confirm such information, but still remained residual lignin and this effect can be proven for a
high intensity peak being displacement for 434 °C. For the residues under oxy-fuel combustion
atmosphere, it was verified a wide oxidation of biomass organic materials, but still exits some
remaining material, mainly residual lignin, which can be confirmed by the peaks at 340 and 532 °C.
Comparing the TG/DTG curves profiles of the residues for both atmospheres, it was perceived a
higher difference in the maximum decomposition rate of the main constituents of biomasses
between 200 and 500 °C.
100 0.00
(a)
80
-0.01
Mass loss (%)
DTG (mg s-1)
60
40 -0.02
air (80% N2) -0.03 air (80% N2)
80% CO2 80% CO2 (b)
0
100 200 300 400 500 600 700 100 200 300 400 500 600 700
Temperature (°C) Temperature (°C)
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Figure 3: (a) TG and (b) DTG curves of the in natura samples and sugarcane bagasse residues after conventional combustion
-1
(80% N2) and oxy-fuel combustion (80% CO2) in DTF. Experimental conditions: 25 up 700 C; heating rate: 10 C min ,
-1
sample mass: 10 mg and 100 mL min of synthetic air flow rate
TG/DTG curves (Figure 3a-b) of the sugarcane bagasse residues after different oxidative
processes (combustion and oxy-fuel combustion) were similar, i.e., showed the same thermal
profile. In general, it was observed a wide consumption of the total organic materials (hemicellulose,
cellulose and lignin). The in natura sugarcane bagasse sample (Figure 3a) present a “shoulder”
around 310 °C, which is indicative of high hemicellulose content [18] and also that hemicellulose and
celullose are decomposed simultaneously [19]. For the residues after conventional combustion and
oxy-fuel combustion (Figure 3b) this “shoulder”no was identified. For the in natura samples, other
peak was observed at 445 °C, which is attributed to the residual lignin decomposition. However, for
the residues under both atmospheres this event no was observed.
100 0.00
(a)
80
-0.01
Mass loss (%)
DTG (mg s-1)

60
40 -0.02
air (80% N2) -0.03 air (80% N2)
80% CO2 80% CO2 (b)
0
100 200 300 400 500 600 700 100 200 300 400 500 600 700
Figure 4: (a) TG and (b) DTG curves of the in natura samples and coffee husk residues after conventional combustion (80%
-1
-1
Orsini et al. (2011) [1] stated that high amount of inorganic compounds in the coffee husks,
mainly potassium element, made them more resistant to the deformations and, consequently,
combustion processes. This information is agree with observations made in this study, because
evaluation of the residues showed that inside of the particles no presented burning process or was
deficitary, but only carbonization in more external regions. Comparision to residues under both
atmospheres, the difference more pronounced was observed under 80% CO2 atmosphere, for which
DTG curve (Figure 4b) presented only one thermal event at 432 °C, probably caused by the presence
of residual lignin and inorganic materials oxidation no burned in temperatures relatively lower ≈
1,000 °C, such as K, S, Cl among other elements, which can conducte to the corrosives species
formation and environmental dangerous [1,6,20].
760
100 0.00
(a)
80
-0.01
Mass loss (%)
DTG (mg s-1)

60
40 -0.02
air (80% N2) -0.03 air (80% N2)
80% CO2 80% CO2 (b)
0
100 200 300 400 500 600 700 100 200 300 400 500 600 700
Temperatue (°C) Temperature (°C)
Figure 5: (a) TG and (b) DTG curves of the in natura samples and rice husk residues after conventional combustion (80% N 2)
-1
and oxy-fuel combustion (80% CO2) in DTF. Experimental conditions: 25 up 700 C; heating rate: 10 C min , sample mass:
-1
10 mg and 100 mL min of synthetic air flow rate
TG/DTG curves (Figure 5a-b) for the rice husk residues generated after tests carried out under
synthetic air (80% N2) and dioxide carbon (80% CO2) atmospheres showed a degradation almost that
total of the organic materials (holocellulose and ligin) present in the biomasses. Such information
can be made with base in the ash contents presented in the TG curves final, resulting average value
around ≈ 90%.
100 0.00
(a)
80
-0.01
Mass loss (%)
DTG (mg s-1)
60
40 -0.02
air (80% N2) -0.03 air (80% N2)
80% CO2 80% CO2 (b)
0
100 200 300 400 500 600 700 100 200 300 400 500 600 700
Figure 6: (a) TG and (b) DTG curves of the in natura samples and tucumã seed residues after conventional combustion (80%
-1
-1
From TG/DTG curves (Figure 6a-b) for the in natura tucumã seed was possible to observe three
events well defined of mass loss. The first, with peak in around 185 °C, due to release of lighter
volatiles [21] or by the fast thermal decomposition of fatty compounds present in oilseed between
150 and 200 °C [22]. The maximum combustion rate was observed in ≈ 300 °C, for the thermal
degradation of holocellulose and, at 450 °C for the residual lignin decomposition. However, DTG
curves (Figure 6b) for the residues in both combustion processes exhibited events of mass loss
between 220 and 512 °C, with mass loss maximum in ≈ 290 °C. Tucmã seed samples no presented
satisfactory yield in the different thermal processes, possibly, because this samples presented a high
oiliness content, which was harmful to feeding system and, consequently, burning process.
761
Scanning Electron Microscopy (SEM images)
Figures 7 to 11 shows the SEM micrographics for the in natura samples and residues of pine
sawdust, sugarcane bagasse, coffee husk, rice husk and tucumã seed generated after conventional
combustion (80% N2) and oxy-fuel combustion (80% CO2) processes.
(a) in natura (b) 80% N2
(c) 80% CO2
Figure 7. SEM micrographics of the pine sawdust: (a) in natura samples and residues generated under typical atmospheres:
(b) conventional combustion (80% N2) and (c) oxy-fuel combustion (80% CO2), with magnitude of 1,000 times
Figure 7 (a-c) shows the SEM images for the in natura pine sawdust and residues generated in
DTF, after different thermochemical processes. It was noted that morphological structure of the pine
sawdust residues after 80% N2 atmosphere (Figure 7b) in comparison to in natura sample (Figure 7a)
presented agglomerate of particles, structures that seem cenospheres [23] and particles shrinkage
[24]. However, for the 80% CO2 atmosphere (Figure 7c), was verified presence of some particles with
diameters higher, broken structures and a pattern of reticulated type or nanowhiskers [23]. By
means of the distinct structural characteristics observed for the pine sawdust residues in different
atmospheres, it is understood that each thermal process employed affected the biomasses
morphology of specific ways.
762
(c) 80% CO2
Figure 8. SEM micrographics of the sugarcane bagasse: (a) in natura samples and residues generated under typical
atmospheres: (b) conventional combustion (80% N2) and (c) oxy-fuel combustion (80% CO2), with magnitude of 1,000 times
Figure 8 (a-c) presents the SEM images for the in natura sugarcane bagasse and generated
residues in DTF after 80% N2 and 80% CO2 processes.
The sugarcane bagasse residues presented morphological structures different of the in natura
samples (Figure 8a), mainly regards to the fibrous characteristics loss. It was noted that for the
samples under containing CO2 atmosphere (Figure 8c), the particles presented a crystalline format,
which is characteristic of the silicon oxides presence or iron oxides [25], and confirmed by Figure
12b. Already in sample under synthetic air atmosphere (Figure 8b) it can also be noted the presence
of crystalline and spongeous structures. According to Cruz (2015) [26], spongeous structures are
indicative of possible deficiency in the burning process, where part of the samples were undergoing
the devolatilization process, i.e. fast volatiles release and other gases, which are trapped inside
samples, therefore, no reaching the complete combustion.
763
(c) 80% CO2
Figure 9. SEM micrographics of the coffee husk: (a) in natura samples and residues generated under typical atmospheres: (b)
conventional combustion (80% N2) and (c) oxy-fuel combustion (80% CO2), with magnitude of 1,000 times
Figure 9 (a-c) shows the SEM images for the in natura coffee husk and residues generated in DTF
after conventional combustion and oxy-fuel combustion processes. For the combustion processes of
coffee husk, it was observed that both residues (Figure 9b-c) exhibited a disruption in relation to the
in natura sample (Figure 9a), and presented several breaks, meso and micropores superficial. The
formation of these structures, it was due to high volatiles materials release, which for this biomass is
around 75%, during the combustion process.
(e) 80% CO2
Figure 10. SEM micrographics of the rice husk: (a) in natura samples and residues generated under typical atmospheres: (b)
Figure 10 (a-c) shows the SEM images for the in natura rice husk and residues generated in DTF
after conventional combustion and oxy-fuel combustion processes.
For the rice husk samples, it was observed that remaining residues from several thermochemical
processes under both atmospheres presented differences in regards to the in natura material (Figure
764
10a). The two residues (Figure 10b-c) showed highly porous structures (mesopores and macropores),
and apparently, without there being the possibility of distinction among them, and presented in
common structures with initial condition ruptures, but also maintained part of the original
lignocellulosic matrix.
For Luan et al. (2014) [24], the thinner particles deposited on the rice husk samples, after
conventional combustion processes can be mainly, alkali-aluminum silicates compounds and/or
alkaline chlorides.
It was noted that in natura tucumã seed structure is composed of a set of axial and radial
microchannels, which appear to cross its entire structure (Figure 11a), whereas for the other in
natura biomasses, occurred the prevalence of a more fibrous structural. After submitted to the
several thermal processes, tucumã seed residues maintained some of its physical characteristics and
still presented the microchannels and, apparently no disruptions in relation to in natura sample,
which also differ of other biomasses, and can be effect of its rigidity and hardness [26].
(c) 80% CO2
Figure 11. SEM micrographics of the rice husk: (a) in natura samples and residues generated under typical atmospheres: (b)
Energy Disperse Spectroscopy (EDS analysis)
Figure 12 shows the EDS analysis in terms of mass percentage (concentrations) for the in natura
and, residues generated for the pine sawdust, sugarcane bagasse, coffee husk, rice husk and tucumã
seed samples after combustion processes. This technique was used to determine the elemental
composition and compare its compositional evolution in thermal processes, in order to predict the
possible impacts caused by use of these biofuels in combustion equipments.
For Fernández et al. (2012) [27], chemical elements such as sodium (Na), potassium (K),
magnesium (Mg), phosphorus (P) and calcium (Ca) among others, which are present in biomasses
samples forms oxides, hydroxides and carbonated of alkaline metal and earth alkaline and, are
problematic constituents in combustion process, avoiding the good functioning of the operation
plant of thermal processes.
765
Senneca (2007) [10] related that biomasses are a biofuels special class, because contain less
aluminum (Al), iron (Fe) and titanium (Ti) and more silicon (Si), potassium (K) and sometimes more
calcium (Ca) than coal. The nitrogen, chlorine (Cl) and metals content, also ranges significantly
among biomasses. These compounds are directly related to the NOx emissions, corrosion and ash
deposition in thermal systems, which also exists a great variation in the biomasses elemental
composition.
After the burn under 80% N2 atmosphere, pine sawdust residues presented 77.5% of carbon in its
composition, while, tucumã seed, 55.2%. These samples presented the higher carbon contents in its
residues, regarding the other biomasses, i.e., an indicative that for these samples there was a lower
efficiency in the burn process. In addition, oxygen contents for both samples also were lower, 17.5
and 29%, respectively.
It was verified that sugarcane bagasse residues generated under 80% CO2 atmosphere no
exhibited carbon contents (Figure 12b), a strong clue that all organic material was consumed in this
process, which can be confirmed by SEM images (Figure 8c). The high Si presence in sugarcane
bagasse residues, no is due to their in natura composition, but contamination by impurities
incorporated in harvest process of the sugarcane or storage of the sugarcane bagasse, after juice
extraction, mixturing it with land or sand [28]. For the in natura samples, rice husk presented in
average 8.1% of Si, and sugarcane bagasse, 0.4%. After burning under 80% CO2 atmosphere, the
sugarcane bagasse showed average values of 44.5% for Si content, while for 80% N2 atmosphere,
23.5%. The rice husk residues in both atmospheres presented Si average content of 34.8%.
80 80
(a) Pine sawdust in natura (b) Sugarcane bagasse in natura
80% N2 80% N2
80% CO2 80% CO2
60 60
Concentration (%)
Concentration (%)
40 40
20 20
0 0
C O Na Al Si K Ca Mn Fe Cl Cu Zn Mg P S C O Na Al Si K CaMnFe Cl Cu ZnMg P S Ti Cr Ni
Elements Elements
80 80
(c) Coffee husk in natura (d) Rice husk in natura
80% N2 80% N2
80% CO2 80% CO2
60 60
Concentration (%)
Concentration (%)
40 40
20 20
0 0
C O Na Al Si K Ca Mn Fe Cl Cu Zn Mg P S C O Na Al Si K Ca Mn Fe Cl Cu Zn Mg P S
Elements Elements
766
80
(e) Tucumã seed in natura
80% N2
80% CO2
60
Concentration (%)
40
20
0
C O Na Al Si K Ca Mn Fe Cl Cu Zn Mg P S
Elements
Figure 12. Elemental composition obtained by EDS analysis of the in natura biomasses and generated residues under
conventional combustion (80% N2) and oxy-fuel combustion (80% CO2) atmospheres - (a) pine sawdust, (b)sugarcane
bagasse, (c) coffee husk, (d) rice husk, and (e) tucumã seed
Another element present in the in natura biomasses in relevant quantities is potassium (K),
mainly in the coffee husk, which for this study was detected around 4% (Figure 12c), forming
primarily potassium oxides (K2O) and located in the ashes, but for other biomasses this content were
lower at 0.5%.
According to Akinrinola et al. (2014) [29], K concentrations in biomasses superior 30%, decrease
combustion temperature of the volatiles and char, and indicate high fuels reactivity. However, for
this work the K contents in biomasses were lower than 5%, no being possible to establish a
correlation between K concentration and samples reactivity.
Potassium present in ashes is a main precursor in slurry formation, agglomeration and
incrustation in thermal systems [20]. After conventional combustion in DTF, K content in coffee husk
residues were in average 18.9%, i.e., 367% superior in relation to the in natura biomass. For 80% N2
atmosphere the quantity of this chemical element present in the coffee husk was intensified by
means superficial broken and exposition of its layers more internal [2,26].
For the different in natura biomasses, other elements, such as Na, Mg (magnesium), Cl, Ca, Mn
(manganese), Al, P, Fe and S (sulfur) were found in inferior amounts (< 0.7%), and are known as trace
elements, participating several reactions during combustion [30]. It is interesting note that, tucumã
seed residues in 80% N2 presented 8% Fe, i.e. considerably above of the other biomasses, whose
average value was ≈ 0.25%.
An important aspect to be evaluated in biomasses is Cl content, because when metallic materials
are submitted to thermal processes containing such element in ambient, this can cause corrosion
problems in metallic parts of the chamber combustion and air pollutant emissions [27]. Besides, the
Cl can also react with alkaline metals, such as Na and K, forming chlorides, which are deposited in
boiler surfaces and heat exchanger, leading to the corrosion and also affecting the heat transfer in
these systems [23].
As regards the S content, these also should be quantified in biomasses, because in thermal
processes forms sulfates, causing incrustations and depositions, which compromise the combustors
and gasifier performance. Moreover, this element forms undesirable pollutants such as sulfur oxides
(SO2) in combustion processes and H2S (sulfuric acid) in the gasification. In this research the S
contents found in natura biomasses were in average 0.27%. Second Croiset and Thambimuthu
(2001) [31], approximately 0.3% of S for the different biomasses keep retained in the ashes. For this
study, the S contents in residues of the different thermal processes were in average 0.25%,
confirming such affirmation.
767
Other elements, such as P, Ca and Na also are found into biomasses and in amount lower than
0.5%, which interfere in low yield in the volatiles compound combustion. Elements as Mg, Mn, Al
and Fe also are commonly found in the biomasses for making part of its nature composition, and can
bring consequences undesirable to the thermal processes.
Finally, it is understood, that a study more in-depth is need for obtaining more information about
the possible biomass applications and/or residues that contains some inorganic elements
environmentally undesirable. A possible suggestion to solve these problems would be the utilization
of the ashes generated by the different thermochemical processes by the concrete industry,
composites, among others [2,26,27,32].
Emissions gaseous (air pollutants)
Figure 13 shows the average values of the main air pollutants (SO2, CO, CO2 and NO) generated
under conventional combustion (80% N2) and oxy-fuel combustion (80% CO2) atmospheres in DTF
for the samples of pine sawdust, sugarcane bagasse, coffee husk, rice husk and tucumã seed. The O2
concentration was used as criteria for the evolution verification from respective processes.
Although pine sawdust and tucumã seed samples no presented sulfur detectable limits in its
composition, this exhibited the higher (873 mg Nm-3 g-1) and lower (25 mg Nm-3 g-1) of SO2 emissions
values under conventional combustion and oxy-fuel combustion, respectively.
The higher SO2 emissions in thermal systems are an indicative of complete combustion or
partially complete, because this gas participate effectively of the combustion global reaction and, is
released totally in the volatiles form in the char combustion [33,34]. For explaining the lower SO 2
emissions under oxy-fuel combustion, Toftegaard et al. (2010) [35] and Normann et al. (2009) [36]
also observed that this reduction is a common characteristic waited in this process type.
Croiset and Thambimuthu (2001) [31] revealed that variation in SO2 concentration is mainly, due
to volume change in the combustion ambient. For instance, in higher oxygen concentrations, other
gases total flux inside of the thermal system is inferior, because less nitrogen and CO 2 are present,
increasing SO2 concentration.
For some pollutants species, for example, carbon monoxide (CO) the formation and destruction
reactions are intimately coupled, and compression from formation of these pollutants to require a
perfect knowledge of the combustion chemical, which is very complex [37]. In oxy-fuel combustion
(80% CO2) atmosphere, the higher CO emissions were observed for sugarcane bagasse (6,200 mg
Nm-3 g-1). Roy and Corscadden (2012) [38] found results similar for several woods species and
briquettes burned in domestic oven.
80% N2 80% N2
6000
800 80% CO2 80% CO2
5000
SO2 (mg Nm-3 g-1)
CO (mg Nm-3 g-1)
600
4000
400 3000
2000
200
1000
0 0
Sawdust Bagasse Coffee Rice Tucumã Sawdust Bagasse Coffee Rice Tucumã
768
80% N2 80% N2
200 80% CO2 150 80% CO2
NO (mg Nm-3 g-1)

CO2 (mg Nm-3 g-1)
150
100
100
50
50
0 0
Sawdust Bagasse Coffee Rice Tucumã Sawdust Bagasse Coffee Rice Tucumã
80
80% N2
80% CO2
60
O2 (mg Nm-3 g-1)
40
20
0
Sawdust Bagasse Coffee Rice Tucumã
Figure 13. Main air pollutants generated by biomasses under conventional combustion (80% N2) and oxy-fuel combustion
o -1
(80% CO2). Experimental conditions: furnace temperature: 1.000 C, primary airflow rate: 1.5 L min and mass flow rate: 0.3
-1
g min
Probably, this increase in CO emission can be due to Boudouard equation, which is presented in
equation (1) [36,39,40].
C + CO2 2 CO (1)
According to Toftegaard et al. (2010) [35], in high partial pressures and temperatures, CO2 can be
dissociated in CO and O2, by means of strongly endothermic reactions. In the reactor flame zone
under oxy-fuel combustion process, both conditions above are present.
Sugarcane bagasse also presented the higher CO2 emissions (210 mg Nm-3 g-1) under 80% CO2
atmosphere. For Aghamohammadi et al. (2011) [41], differences in formation rates of the
combustion gases, for example, CO2 are due to the hemicelluloses, cellulose and lignin compositions.
Oxygen excess and a better mixture can be useful in the organics emissions control in this
combustion stage. Finally, the unburned biomasses are naturally decomposed for CO2 releasing.
For Winter et al. (1999) [42], nitrogen (N) content is relatively low for the biomasses of
agricultural residues and these produce low NO and N2O emissions. However, NO emitted during
combustion process depend of other parameters, besides the compositional nitrogen, from low
fixed carbon content and also take into account operating mode, burner design and combustion
chamber [43]. Consequently, agricultural residues can emit higher NOx concentrations, when
compared to coal with same nitrogen content [44].
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Coffee husk presented the higher elemental nitrogen content (1.55%) and sugarcane bagasse, the
lower (0.25%) (Table 1). The first sample exhibited the higher NO emissions under conventional
combustion (172 mg Nm-3 g-1) and 80% CO2 (144 mg Nm-3 g-1), probably by the total oxidation of its
nitrogen content under oxidizing atmospheres. It is interesting to highlight that coffee husk, tucumã
seed and sugarcane bagasse samples presented under oxy-fuel combustion atmosphere a gradual
increase in their NO emissions, while that rice husk and pine sawdust, a decrease.
Finally, by means O2 concentration was possible to observe the combustion process performance
inside the DTF under different atmospheres and biomasses. It was observed a decreasing trend in
the O2 consumption: 80% CO2 > 80% N2, where sugarcane bagasse presented the higher O2
consumption rate for conventional combustion, and tucumã seed for oxy-fuel combustion
atmosphere.
4- CONCLUSIONS
In this study was evaluated gases CO, CO2, NO and SO2 emitted from five in natura Brazilian
biomasses: pine sawdust, sugarcane bagasse, coffee and rice husks, and tucumã seed and the
residues generated when the biomasses are applied to combustion atmospheres (N2/O2: 80/20) and
oxy-fuel combustion (CO2/O2: 80/20) in a Drop Tube Furnace (DTF). The in natura samples and
residues generated were evaluated by TG/DTG (Thermogravimetry/ Derivative Thermogravimetry),
SEM images (Scanning Electron Microscopy) and EDS analysis (Energy Dispersive Spectroscopy).
TG/DTG curves showed and confirmed that performance and combustion efficiency are functions
of the biomass type, feeding system used and operating conditions of the DTF. By means of this
technique was also possible to observe the quantities of moisture, volatiles materials, fixed carbon
and ashes remaining in the biomass samples after thermochemical processes in DTF.
The SEM images revealed some of the main morphological differences of the in natura materials,
such as presence of tubes, medullas, lamellas, ordered structures and more compacted, and porous
structures. However, for the generated residues under conventional combustion and oxy-fuel
combustion atmospheres, a large part of the lignocellulosic matrix was degraded, which indicates
the good efficiency of the thermal process, although some biomasses still retained their original
structures.
From EDS analysis, was possible observe that some inorganic elements, such as S, Si, Fe, Cl, Ca,
Cu, K, P and Na can damage the metallic parts of the thermal systems, thermal changes during
burning and the environment, when they are released into the atmosphere.
The gaseous emissions for both atmospheres (80% N2 and 80% CO2) ranged between 90-6,200 mg
Nm-3 g-1 for CO, 5-210 mg Nm-3 g-1 for CO2, 10-170 mg Nm-3 g-1 for NO, and 25-870 mg Nm-3 g-1 for
SO2 and are directly related to the chemical composition of the lignocellulosic materials, oxidizing
atmospheres and furnace operating conditions. The O2 consumption (6-77 mg Nm-3 g-1) inside the
furnace for the oxidizing atmospheres and different biomasses was also an indicative performance
and combustion efficiency and exhibited an 80% CO2 > 80% N2 trend.
And finally, our findings have proven the perfect knowledge of some behavioral trends of
lignocellulosic materials is mandatory, so that generalizations of proceedings are not applied when
different biomasses and atmospheres are employed in thermochemical processes.
5- ACKNOWLEDGEMENTS
The authors gratefully acknowledge FAPEMA for the financial support, Mechanical Engineering
Faculty from University of Campinas (FEM-Unicamp), University of São Paulo (EESC-USP) and Federal
University of Maranhão (UFMA).
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772
TOWARDS SUSTAINABLE RECONSTRUCTION SYSTEMS: FROM RUINS TO ECO-

EFFICIENT BUILDINGS
A. DEL CASTILLO LLAMOSAS, P.M. BELLO BUGALLO

Department of Chemical Engineering, University of Santiago de Compostela,
Keywords: Zero-Energy Building, Reconstructed building, Waste Ruins, Eco-efficient building
Abstract
Building reconstruction projects are mainly motivated by social factors, without a deep evaluation of
the Best Available Techniques. The main aim of this work is to analyse the advantages of defining
sustainable re-constructed buildings, previously building the edifice, by using methodologies towards
sustainable systems [1].
A real re-constructed building located in Ourense (North West Spain) was considered as case study.
Three scenarios have been considered to analyse its sustainability, including: the waste ruins of the
old building, the current re-constructed building, and a defined hypothetic sustainable re-
constructed building. Firstly, the energy consumption and operational costs of the existing building
which was reconstructed from another building ruins, has been analysed. Secondly, a new scenario
was proposed adding passive solutions to this existing building, with the purpose of improve its
energy efficiency as to achieve a Zero Energy Building; also energy consumption and costs of the
refurbishment were analysed.
After having carried out this study, considering not only economic factors, but environmental and
social ones, it can be concluded that it is more sustainable and profitable constructing an efficient
building from the beginning by using waste ruins in spite of refurbishing a re-built one. Related to the
definition of the sustainable scenario, even though thermal isolation gives positive results on high
energy efficiency, the use of “green materials” and/or biomass (e.g. compressed straw) in the re-
construction stage [2], could increase the sustainable behaviour of the building.
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1- INTRODUCTION
Even the term sustainability has not a universal accepted definition, most of the discussions about its
meaning are focused on the triple bottom line (TBL) which deals with the positive results regarding
economic, social and environmental dimensions [3]. Even though, recent years many authors started
to introduce the governance as the fourth pillar of Sustainable Development [4]. Sustainable
construction concerns the four main fields of sustainability: environment, society, economy and
governance. On this context, environment can refer to the responsible exploitation of sources as
well as the control of emissions during the construction, the use and the possible demolition of the
edifice. Society is related, for example, with people’s comfort inside the building. Economy can
concern about how much would cost the construction or the refurbishment, and above all, the
economical profitability during its lifetime. And finally, governance has an important role by writing
regulations and by raising public awareness.
Buildings are dynamic systems, being in this case very relevant to consider not only the proper
activity in the use of building (with the typical inputs and outputs), but also the activities in the
stages of edifice construction, demolition, and others such as re-construction. To perform a
complete analysis of the energy efficiency, the good manage of its waste of these stages must be
also included. This sustainable meaning of construction integrates also the circular economy which
rides to a better manage building stocks in terms of waste processing and urban mining, as well as
reducing embodied environmental requirements [5]. Any architecture to be identified as bioclimatic
(also called “energy efficient building”, or “green building”) must be in compliance with people who
will inhabit in order to be healthy with them and consume as less as possible resources: combining
passive and active resources for the purpose of getting an optimal building design and an efficient
control of the indoor climate [6].
Global energy consumption is increasing over time, and global primary energy consumption has
grown by 85% from 1980 to 2012 as also has done CO2 emissions by 75%, what would resume steady
growth through 2035 [7]. European Union leaders agreed to reduce the European Union’s projected
energy consumption reducing on a 40% the emissions of greenhouse gas, an improvement of a 27%
in energy efficiency and having a 27% of energy recovered by renewable energy systems; all by year
2030 [7,8,9].
In Spain, the Technical Edification Code (TEC) [10] published in 2007 and modified in 2013, aims at
the particular issue of energy saving in buildings [11]. This last modification is closely related with the
Royal Decree 235/2013 [12], which is associated with Energetic Certification in Buildings. On the
reported entitled Implementation of the EPDB in Spain [13] it is explained the calculation
methodology of the Energy Performance Certificate (EPC derived from Energetic Certification in
Buildings). This calculation can be performed through the official software Unified Tool Lider-Calener
(UTLC). On the other hand, as to promote and to contribute with a sustainable development in the
activity of construction, Spanish legislation takes also into account the management of the
construction waste in the Royal Decree 105/2008 [14], in way of its reuse, recycle, elimination and
valorisation.
Implementation of passive and energy saving technologies is a fundamental way to improve building
energy efficiency, which includes advanced building envelopes, passive heating or cooling and
thermal energy storage [6]. There exist located areas on the building structure where the heat flow is
different in comparison with adjacent areas, where temperature between inside and outside is
774
different; these elements are called thermal bridges. The energy losses incurred by a linear thermal
bridge are quantified by the linear thermal transmittance (ψ) and measured in W/mK (watts per
square metre kelvin). Also point thermal bridges can be considered [15]. In general, thermal bridges
would result in higher energy use for heating and cooling and discomfort due to cold surfaces, even
deriving also on mould growth and its associated health concerns.
In the building sector, the concept of “net energy” has not been included into the calculation and
certification methods; energy evaluation of buildings typically only considers the energy use in the
form of electricity or fossil fuels for the operation of a building, without considering the other energy
inputs from building construction process as the manufacturing of materials.
Was the Norwegian Zero Energy Building (ZEB) centre [16] which defined the most relevant aspects
of the ZEB concept, such as the ambition level, the rules of calculation, the system boundaries, CO 2
factors, energy efficiency, mismatch and indoor climate [17]. To achieve this ZEB, it becomes
necessary to understand the work’s limitations: if it is a new edifice, or an existing one. There are a
wide variety of solutions depending on these two situations, as those explained by Chwieduk [18].
The main aim of the present work is to analyse the sustainability of a case study based on a real re-
constructed building, where the re-construction project was motivated by social factors (a usual
practice in the last decades), without a deep evaluation of the Best Available Techniques. The idea is
to analyse the advantages of defining sustainable re-constructed buildings by using methodologies
towards sustainable systems [17,19] previously building the edifice.

Case study
The case study of this work is the public building called La Molinera located in Ourense (Spain),
which was a flour manufacturing and storage building. After years of production the edifice was
abandoned, and its ruins were disposed at the street for years; this stage of ruins defines the
Scenario 1 on this work. In 2011 Ourense’s Council decided to rebuild a new public edifice by reusing
many of its ruins. Nowadays this four-floors building is a Digital Social Innovation Centre where
many workshops are developed based on new technologies, social media and electronic sciences.
Methodology
Three scenarios were considered:
- Scenario 1: waste ruins of the old building,
- Scenario 2: the current re-constructed building,
- Scenario 3: a defined hypothetic sustainable building based on Scenario 2 but adding some
passive solutions.
Two processes were compared: from Scenario 1 to Scenario 3 including scenario 2, and the process
that builds scenario 3 directly from Scenario 1.
With the purpose of studying the characteristics of the existing building (Scenario 2), the thermal
envelope was defined. This thermal envelope refers to all the elements of the exterior of the edifice
including walls, floors and roofs in contact with the exterior, against underground or against those
775
unheated surfaces which do not belong to the building itself. To characterise La Molinera, the
software Auto-CAD was selected.
Energetic Surface Reference (ESR) refers to the sum of all the floor surfaces included at the thermal
envelope which need to be heated or conditioned. This ESR was defined on the software using floor
plans as basis. Surface of floors, facades and roofs were delimited and drawn on Auto-CAD using
both floor and elevated plans as basis.
A data base was created using Microsoft Excel with information about floors, facades and roofs
defined and classified by their orientation, slope and material composition based on information
taken also from constructive section plans. This information was treated on a spreadsheet to
calculate the total surface and volume of the building, the area of all the basic elements belonging to
the envelope (floors, roofs and facades) as well as the walls surface (m2) occupied by windows and
doors.
Even though scenarios could have been performed by a dynamic model [17], a steady state model
was used for the case study considering the main objectives of this work. The simulation of this
steady state model has been performed considering the less favourable conditions: an exterior
temperature about -3,3ºC (degrees Celsius). The software selected was Lesosai, because it permits
the creation of a data base where general data of different envelope elements can be introduced:
floors, facades, roofs, and thermal bridges values. Later, these data were exported to the project
where envelope elements are characterised with its own specific properties (orientation, surface,
slope…). Materials of each floor, facade and roof were added to Lesosai following the compositions
defined on constructive section plans, and windows and doors were added on each corresponding
wall. Although each facade was characterised with its own specific materials, it was supposed that all
floors belonging to the envelope had the same composition: suspended floor with 25 cm of
reinforced concrete with 1% steel.
Thermal bridges were modelled, simulated and calculated to know their value, as well as it was
calculated the condensation risk. For modelling and simulating them it was used the software
THERM, and for calculation of thermal bridge’s U-value and condensation risks, it was used Microsoft
Excel once again. Calculation of Ψ-value (in W/mK) was performed following formulas (1) and (2).
∅ = Uvalue, t · ΔTt · Lt (1)
Where:
- ∅ : relation between the general information of the thermal bridge in W/m.
- Uvaluet: exported from THERM simulation (W/m2K)
- ΔTt exported from THERM simulation (ºC)
- Lt: exported from THERM simulation (m)
Ψ = ∅ - Uvalue1 · ΔT1 · L1 - Uvalue2 · ΔT2 · L2 (2)
Where:
- Ψ: value of thermal bridge in W/mK
- Uvalue1,2 : U-value calculated by Lesosai (W/m2K)
- ΔT1,2: result exported from THERM simulation (ºC)
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- ΔT1,2 : difference of temperature between the boundary conditions of one of the walls object
of study (1 or 2) (ºC)
- L1,2: length of the element object of study (1 or 2) (m)
To calculate condensation risks, it was considered as basis of calculation the sea level altitude of
Ourense, the critical month for moulds growth, and f Rsi value from the SIA 180:2014 [20] taking also
into account its correction [21]. Next formulas (3) and (4) were used for calculation:
∅ si,min = fRsi,min x (∅ i - ∅ a,e,min) + ∅ a,e,min (3)

Where:
- fRsi,min: minimal temperature’s factor aceptable
- ∅ a,e,min: minimal outdoor temperature per year (ºC)
- ∅ a,e,m: minimal outdoor temperature per month (ºC)
- ∅ i: indoor air temperature (ºC)
- ∅ si: surface temperature of indoor air (ºC)
The final value of the thermal bridge (Ψ) was upload on Lesosai on the inventory of the
corresponding facade to complete the model, and it was simulated. This software exports a result in
terms of heating demand of the building, measured in kWh/m2.
The existing building was simulated on CATE DMELECT, a calculation program of thermal loads in
buildings based on graphic design. To perform the model, walls were drawn using floor plans. Every
enclosure was defined with its constructive characteristics, with its properties of floor, ceiling,
heating-cooling system, illumination and occupation; and windows and doors were created taking
into account its surface as well as its transmittance and proportion glass/frame. Once carpentry was
placed on each corresponding wall, the calculation was performed. This simulation was exported to
HULC, software recommended by CTE [10]. This program calculates if there exist any non-
compliance with guidelines HE-1 and HE-0 of the CTE specification and exports a certification about
building’s energy efficiency in terms of CO2 and non-renewable primary energy consumption.
Considering these simulations and the real budget of performing the existing building from the
original building waste ruins, scenario 2 was defined.
Scenario 3 was defined following the same stages developed on Scenario 2, based on energy
efficiency and studying economic savings. The Swiss Minergie Standard was chosen as a part of the
methodology towards sustainable systems. This Standard has more restrictive limitations than
Spanish legislation, and supports passive and simple solutions as to achieve a high energy efficiency
in buildings. Some authors study Minergie limitations [22].
Besides analyse how environmentally friendly are Scenario 2 and 3, cost savings could be studied: as
less heating demand, more economic savings. The budget to perform the refurbishment of Scenario
2 to achieve the Scenario 3 was calculated using software PRESTO, which permits to calculate the
project cost. The database of CYPE [25] was used for doing a best estimate of materials and
operational costs. Later, the real budget of the project (Scenario 2) was analysed with the main
objective of comparing both budgets: economic costs on process 1 (from Scenario 1 to Scenario 3
including the refurbishment to perform the Scenario 3) and on process 2 (from Scenario 1 directly to
Scenario 3).
777
Once scenarios 1, 2 and 3 were defined and characterised, its sustainability was studied in terms of
social, environment, economy, and governance.

Once all facades of the existing building (Scenario 2) were classified by their orientation and material
composition following the information acquired by construction section plans, they were named
with correlative numbers from 1 to 28, and the ERS was calculated (Table 1).
Element High (m) Partial Surface (m2) Volume (m3)
Cellar/Basement 2 Floor I 2,6 269,01 699,426
Total: 2,6 269,01 699,426
Cellar/Basement 1: Floor II 3,15 575,69 1813,4235
Total: 3,15 575,69 1813,4235
Ground floor: Floor III 3,55 768,69 2728,8495
Total: 3,55 768,69 2728,8495
First flat: Floor IV 5,13 84,81 435,0753
Total: 5,13 84,81 435,0753
Total E.R.S.: 1698,2 5676,7743
Table 1: Calculation of the ERS
Thermal envelope of Scenario 2 was studied considering its thermal bridges (Table 1). Those thermal
bridges located on the suspended floor of the Basement 2 (characterised as against exterior) were
not considered due to the high valour they would achieve.
Thermal Bridges Ψ (W/mK) Condensation Risk

TB 1 0,5209 None
TB 2 0,6658 None
TB 2 B) 0,817 Yes
Table 2: Summary of thermal bridges of Scenario 2. TB: Thermal Bridge; Ψ valour of thermal bridge.
These results were introduced on Lesosai software and results of the simulation shown that Scenario
2 had a heating demand of 250,6 kWh/m2. The existing building was also modelled on CATE
DMELECT and imported to HULC. Results of HULC simulation related with the certification exported
about its energy efficiency can be observed on Figure 1.
Figure 1. Energy Certification exported from HULC software (Scenario 2).
Figure 1 shows that Scenario 2 was qualified with a letter D in terms of Primary non-renewable
energy (measured in kWh/m2year), and with a C in emissions of CO2 (kgCO2/m2year).
778
Important reductions on heating and cooling demand can be achieved using a combination of well-
established technologies such as glazing, shading, insulation, and natural ventilation [23]. The air
source heat pump (ASHP) integrated on the existing building (Scenario 2) does complain with TEC
conditions [10] because it is based on aerothermal energy. Due to that fact, the improvement on
heating and cooling demand proposed is just to recommend to building’s users the natural
ventilation of the edifice. This natural ventilation refers to the flow of air from an indoor space to the
outside without using mechanical systems (opening windows and/or doors). Moreover, existing glass
windows with U-value of 1,2 W/m2K were replaced for glazing with 0,8 W/m2K to reduce heat losses
assuring more comfortable enclosures. Due to the many benefits that provide passive solutions
[21,23,24], the main improvement was about to improve the thermal envelope of La Molinera.
Following this tendency, facades, floors and roofs of Scenario 2 were simulated on Lesosai adding a
layer of 14 cm of PUR as isolation material (as can be seen on Figure 2; Scenario 2 at the left hand,
Scenario 3 at the right hand).
Figure 2. (a) Wall composition of Scenario 2 (modelled by Lesosai); (b)

Wall composition of Scenario 3 adding a 14 cm PUR layer (modelled by
Lesosai).
To ensure that the refurbishment of construction elements was in compliance with Minergie
Standard, thermal bridges based on new walls composition were simulated on THERM and
calculated again with a spreadsheet in Excel to assure that condensation risk was eradicated (Table
3). New thermal bridges were modelled related with Basement 2 floors (TB 0.1, TB 0.2 and TB0.3).
Thermal Bridges Ψ (W/mK) Condensation Risk

TB 0.1 -0,140 None
TB 0.2 0,065 None
TB 0.2 B) 0,934 None
TB 0.3 1,693 None
TB 0.3 B) 0,324 None
TB 1 0,472 None
TB 2 0,2535 None
TB 2 B) -0,182 None
Table 3: Summary of thermal bridges of Scenario 3. TB: Thermal Bridge; Ψ valour of thermal bridge.
Comparing these results, in Scenario 3 it was clearly eradicated the condensation risk on Thermal
Bridge TB 2 B). All U-values (Ψ) were also improved, even disappearing Thermal Bridge TB 2 B) which
does not exist on Scenario 3 (with a value of -0,182 W/mK).
These results were added to Lesosai simulation, which finally reported a value of 27,4 kWh/m2 for
Scenario 3. From Scenario 2 to Scenario 3 it was observed an 89,1% of heating energy savings, which
is traduced on high economic savings in terms of electricity costs.
About the energy efficiency qualification (Figure 3), Scenario 3 was defined with a letter B in Primary
non-renewable energy and A in CO2 emissions.
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Figure 3. Energy Certification exported from HULC software (Scenario 3).
Figure 3 shows that passive solutions proposed on this methodology increased the energy efficiency
of the existing building, also being in compliance with Swiss Minergie Standard. On Figure 4 the
three scenarios can be observed: Scenario 1 Figure 4(a); Scenario 2 Figure 4(b); Scenario 3 Figure
4(c).
Figure 4. (a) Scenario 1 (source: Faro de Vigo, 2014); (b) Scenario 2 (source: Gomez Crespo, 2018); and (c) Scenario 3
(modelled by CATE Dmelect).
The first process to analyse is from Scenario 1 to Scenario 3 including Scenario 2: budget to perform
this process was about to build the first edifice 1.491.114€ and to refurbish it as to achieve a
sustainable building in compliance with Swiss Minergie Standards, which would cost 65.506,18€.
Thus, process 1 is traduced in an approximately 1.556.620,85€.
The second process is from Scenario 1 directly to Scenario 3: the hypothetic budget for building a
sustainable edifice directly from construction waste ruins would be of about 1.509.860,25€.
From the social point of view, knowing that a public building is committed to protecting the
environment (Scenario 3), it can improve the image of governance in front of society, and to arise
different governments to promote sustainable systems as re-constructed buildings. Valuating
Scenario 1, construction waste ruins do not suppose any economic cost, but it is true that it does not
meet with environmental and social “standards”. All these results are summed up in Table 4.
Scenario 1 Scenario 2 Scenario 3

- 1.556.620,85 1.509.860,25 Economic cost (€)
- 250,6 27,4 Space heating demand (kWh/m2)
No No Yes Meets with Swiss Minergie Standard
- D B Energy Qualification: Primary non-
renewable energy
- B A Energy Qualification: CO2 Emissions
Table 4: Summary of three scenarios studied
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4- CONCLUSIONS
In this work the advantages of defining sustainable re-constructed buildings by using methodologies
towards sustainable systems [17,19] previously building the edifice, was analysed. The selected case
study is a real re-constructed building, where the re-construction project was motivated by social
factors (a usual practice in the last decades), without a deep evaluation of the Best Available
Techniques.
Results show that even having construction ruins disposed at the street (Scenario 1) does not entail
any expenditure, it is true that this scenario leads to a bad image of the city involving environment
and social fields. Second scenario adds a high value in society and environment to the city, but
construction and refurbishment of the building as well as current electricity bills are traduced on
expensive operational costs. On the other hand, the third scenario, even more environmentally and
socially friendly, results on an approximately 90% of cost savings in heating energy demand, which
would be traduced on high economic savings. Related to the definition of the sustainable scenario,
even though thermal isolation gives positive results on high energy efficiency, it could have been
taken into account “green materials” and/or biomass (e.g. compressed straw) in the re-construction
of the building [2].
After having carried out this study, considered not only economic factors, but environmental social
and governmental ones, it can be concluded that it is more sustainable and profitable constructing
an efficient building from the beginning by using waste ruins in spite of refurbishing a re-built one.
Thus, the proposed methodology helps to develop a construction project, towards sustainable
construction systems, considering the circular economy focus in terms of well waste management by
re-using edifice ruins.
It was observed that in Spain exists a potential of improvement in terms of energy efficiency in
buildings. This can be demonstrated developing methodologies which show that applying more
restrictive standards from other European countries it could serve as a support to strengthen and
improve our own legislation.
REFERENCES
[1] Torres Rodríguez, M.T., Cristóbal Andrade, L., Bello Bugallo P.M., Casares Long, J.J. Combining LCT tools for the
optimization of an industrial process: Material and energy flow analysis and best available techniques. Journal of
Hazardous Materials 192 (2011) 1705–1719.
[2] Cascone, S.; Catania, F.; Gagliano, A.; Sciuto, G. Energy performance and environmental and economic assessment of
the platform frame system with compressed straw. Energy and buildings, 166, 83-92, (2018).
[3] Bartocci, L.; Chiappetta, C.J.; Lopes de Sousa, A.B.; Kannan, D. Sustainability as a dynamic organizational capability:
as systematic review and a future agenda toward a sustainable transition. Journal of Cleaner Production, 142, 308 –
322, (2017).
[4] Taboada, M.C.; Magán, A.; Torres, R.; Bello P.M. Towards sustainable systems configurations: Application to an
existing fish and seafood canning industry. Journal of Cleaner Production, 129, 374 – 383, (2016).
[5] Stephan, A.; Athanassiadis, A. Quantifying and mapping embodied environmental requirements of urban building
stocks. Building and Environment, 114, 187-202, (2017).
[6] Serra, B.; Verdejo, P.; Díaz, A.; Merí, R. Assembling sustainable ideas: The construction process of the proposal SML
system at tech Solar Decathlon Europe 2012. Energy and Buildings, 83, 186 – 194, (2014).
[7] Cao, X.; Da,i X.; Li,u J. Building energy-consumption status worldwide and the state-of-the-art technologies for zero-
energy buildings during the past decade. Energy and Buildings, 128, 198 – 213, (2016).
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[8] EC, COM (2014) 15, Communication from the Commission to the European Parliament, the Council, the European
Economic and social committee and the committee of the regions of 22 January 2014, A policy framework for
climate and energy in the period from 2020 to 2030. COM, Brussels, 2014.
[9] EC, Framework for climate and energy. “Outcome of the October 2014 European Council”. Brussels, 30/10/2014.
[10] ETC, 2007. Technical Edification Code, in Spanish “Código Técnico de la Edificación”.
[11] García-Sanz-Calcedo, J.; López-Rodríguez, F. Analysis on the performance of a high efficiency administrative building
in Spain. International Journal of Green Energy, 14, 55-62, (2017).
[12] RD, 2013. Royal Decree 235/2013 of 5 April, of Basic procedure of energetic certification in buildings, in Spanish
“Procedimiento básico para la certificación energética de edificios”.
[13] EPBD, 2010. Implementation of the EPDB in Spain in November 2010. Available at http://www.epbd-
ca.org/Medias/Downloads/CA_Book_Implementing_the_EPBD_Featuring_Country_Reports_2010.pdf (Accessed on
03/07/2017).
[14] RD, 2008. Royal Decree 105/2008 of 1 February, of Regulation of production and management of construction and
demolition waste, in Spanish “Por el que se regula la producción y gestión de los residuos de construcción y
demolición”.
[15] Theodiosiou, T.; Tsikaloudaki, K.; Bikas, D. “Analysis of the Thermal Bridging Effect on Ventilated Facades.
International Confrence on Sustainable Synergies from Buildings to the Urban Scale, SBE16. Procedia Environmental
Sciences, 38, 397 – 404, (2017).
[16] ZEB, 2014. Research Center on Zero Emissions. Available at http://www.zeb.no/index.php/en/conference/item/554-
the-norwegian-research-centre-on-zero-emission-buildings-%E2%80%93-zeb (Accessed on 03/07/2017).
[17] Wiberg, A.H.; Georges, L.; Dokka T.H.; Haase, M.; Time, B.; Lien, A.G.; Mellegard, S.; Maltha, M. A net zero emission
concept analysis of a single-family house. Energy and Buildings, 74, 101 – 110, (2014).
[18] Chwieduk, D.A. Towards modern options of energy conservation in buildings. Renewable Energy, 101, 1194 – 1202,
(2017).
[19] Soares, N.; Costa, J.J.; Gaspar, A.R.; Santos, P. Review of passive PCM latent heat thermal energy storage systems
towards buildings’ energy efficiency. Energy and Buildings, 59, 82 – 103, (2013).
[20] SIA, 2014. Thermal Protection, protection against moisture and climate inside buildings, in French “Protection
thermique, protection contre l´humidité et climat intérieur dans les bâtiments”; 2014-06 Edition.
[21] SIA, Corrective. Corrective C1 to the norm SIA 180:2014, in French “Correctif C1 à la norme SIA 180:2014”.
[22] Hall, M.; Geissler, A.; Burger, B. Two years of experience with a net zero energy balance – analysis of the Swiss
MINERGIE-A. Energy Procedia 48, 1282 – 1291, (2014).
[23] Omer, A.M. Renewable building energy systems and passive human comfort solutions. Renewable and Sustainable
Energy Reviews, 12, 1562 – 1587, (2008).
[24] Sadineni, S.B.; Madala, S.; Boehm, R.F. Passive building energy savings: A review of building envelope components.
Renewable and Sustainable Energy Reviews, 15, 3617 – 3631, (2011).
[25] CYPE, 2017. Construction prices generator, in Spanish “Generador de precios de la construcción CYPE”. Available at:
http://www.generadordeprecios.info/ (Accessed on 12/07/2017).
782
ONSITE SORTING AND PYROLYSIS OF COFFEE RESIDUES FOR BIOCHAR PRODUCTION

– A CASE STUDY
S. VAKALIS 1, 2, V. BENEDETTI 1, E. CORDIOLI 1, F. PATUZZI 1, M. BARATIERI1

1 Free University of Bolzano, Faculty of Science and Technology, Piazza Università 5 – 39100 Bolzano,
Italy.
2 National Technical University of Athens, School of Chemical Engineering, Unit of Environmental
Science & Technology, 9 Iroon Polytechniou Str., GR-15780 Athens, Greece.
Abstract
The production process of coffee beverages from grained coffee beans creates a significant waste
stream, i.e. the spent coffee grounds. Their treatment/ disposal presents several difficulties due to
characteristics like high phenol content and high biochemical oxygen demand during decomposition
[1]. In addition, the sheer volume of the waste creates additional issues, since coffee is one of the
top traded products worldwide [2]. This study aims, on the one hand, to develop an onsite sorting
campaign for collecting pure streams of spent coffee grounds and, on the other hand, to valorize
spent coffee grounds by converting them into biochar. This approach takes into consideration that
coffee beans are already torrefied (roasted) and as a result the final yield of the biochar after
pyrolysis will be significantly higher than in the case of pyrolysis of other competing streams like
agricultural waste or plain woody biomass [3]. In addition, the end product has a particularly high
selling price and can return significant profits. The first basic step of the program is the collection of
coffee (and filter paper) waste from selected coffee shops in Bolzano (Italy). The collection will be
done onsite in cooperation with local coffee shops in specialized waste bins and the waste mass
flows will be identified. The collected samples will be transferred to a central facility and converted
into biochar by pyrolysis/ gasification. Finally, end uses will be identified and assessed for the final
product and this will be done in accordance to the quality of the produced biochar. Also, the
products will undergo further analysis for the identification of the conditions for optimal biochar
production. Coffee imports in EU are very high in respect to mass but also on an economic basis. The
goal is to manage a pure and underutilized stream which would otherwise end up in landfills or
would be composted. The proposed approach denotes a solution with higher potential in respect to
economic viability and sustainable practices.
References
[1] Liu, Y., Tu, Q., Knothe, G., Lu, M.: Direct transesterification of spent coffee grounds for biodiesel production, Fuel
199, Pages 157-161 (2017)
[2] Minten, B., Dereje, M., Engida, E., Kuma, T.: Coffee value chains on the move: Evidence in Ethiopia, In Food Policy,
https://doi.org/10.1016/j.foodpol.2017.07.012. (2017)
[3] Tsai, W-T.: Chapter 10 - The potential of pyrolysing exhausted coffee residue for the production of biochar,
Handbook of Coffee Processing By-Products, edited by Charis M. Galanakis,, Academic Press, pp. 299-322, ISBN
9780128112908 (2017)
783
ENERGETIC POTENTIAL OF PULP AND PAPER INDUSTRY SOLID WASTES FOR

THERMOCHEMICAL CONVERSION PROCESSES
B. F. M. L. GOMES1, C. M. MEDEIROS2, P. C. R. FERNANDES2, S. L. F. ANDERSEN²

1 Department of Civil and Environmental Engineering, Federal University of Paraíba, João Pessoa,
Brazil
2 . Department of Renewable Energy Engineering, Federal University of Paraíba, João Pessoa, Brazil
Keywords: Energy, biomass, thermochemical conversion, pulp and paper industry waste.
Abstract
This work purpose was to physico-chemically characterize solid wastes from paper and mill industry
for energy purposes through thermochemical conversion processes. The selected biomasses were:
thickener fiber (T. Fiber), pond fiber (P. Fiber), decanter cleaning residue (DCR) and clean bark (C.
Bark). They were characterized as solid fuels and their physicochemical properties were measured by
proximate analysis, thermal behavior, higher heating value (HHV), ash composition and its fusibility
probability. P. Fiber and T. Fiber have shown higher volatile matter content than others (80.25% and
80.14% respectively) and also presented lower ash content (16.05% and 17.30%). The HHV of
samples were calculated and their values were close to the sugarcane bagasse and other wood,
agricultural and farming wastes already applied to energy purposes. It was observed that ignition
temperatures for all four samples ranged from 164 to 214 °C. C.Bark presented the lowest ignition
temperature, indicating a high reactivity of it, when compared to the others. The biomasses studied
in this piece of work have shown to be a promising energy potential for its use in thermochemical
conversion processes, such as combustion or gasification.
784
1. INTRODUCTION
An energetic matrix based on pollutant energy will never lead to a sustainable development.
Amongst global challenges, reduce of fossil fuels usage as energy feedstock is, certainly, one of the
most urgent causes on global agenda. Trying to find an environmental friendly alternative to truly
substitute fossil fuels, a big advance on bioenergy research has been noted and taken all over the
world [1].
Biomass energy conversion processes have emerged on scientific and technology field to supply the
growing demand for energy causing less damage to the atmosphere, by providing methodologies
capable to reduce CO2 emissions by 70–90% [2]. Biomass can be defined as a renewable energy
source and it evolves any organic material (household waste, domestic effluent sludge, etc.), organic
by-products (agricultural effluents, industrial wood and vegetable fiber processing residues, etc.)
dedicated energy crops (eucalyptus, pinus, sugarcane, sorghum, soy, etc.), industrial waste (such as
sludge from industrial effluents) or any other organic material which can be processed; having as
main composition cellulose, hemicellulose, lignin and extractives [3].
Biomass can be converted into energy by a lot of processes and thermochemical conversion is one of
them. It uses heat and chemical processes to produce energy from biomass and it includes
combustion, pyrolysis, gasification, and liquefaction [3]. In order to utilize lignocellulosic wastes in
any conversion processes, it is imperative to know their physicochemical properties. Knowing it, it is
possible to understand the process involved and select the convenient conversion route to attend a
maximum efficiency for a specific biomass [4].
Brazil has been outstanding worldwide for its high forestry production. However, the products and
by-products of these activities generate enormous amounts of solid wastes. On the latest National
Solid Waste Plan released by the Federal Government [5], it was estimated that the forestry sector,
together, generated more than 10 million tons of waste per year. In most cases, such wastes are not
destined properly, and because of its low value added, they are also not reused. This scenario, yet,
offers an enormous potential to a development of high value bio-based materials and products,
aggregating value to the residues and providing a proper disposal.
Analyzing Brazilian industrial sector, the pulp and paper industry corresponded, on 2016, to an
industrial Gross Domestic Product (GDP) of 6.2% and it is internationally recognized for its use,
almost entirely, of planted forests in an area of 7.84 million hectares. Although considered
sustainable, this industry, only in the year 2016, produced over 47.8 million tons of solid wastes, of
which, 33.7 million tons were from the forestry activity and 14.1 million tons from the industrial
activity. From these, the main solid wastes are bark, fiber from the effluent treatment plant, fibers,
but also residue from producing lumber like chips and sawdust [6].
The evaluation of the properties of any biomass for its use in thermochemical conversion processes,
are the main and first step to be taken. From its characterization, its energetic potential can be
applied to adequate processes in which its constituent properties will be favorable. Given the large
amount of solid waste generated by the pulp and paper industry in Brazil, this work aims to physico-
chemically characterize solid wastes from the paper and pulp industry to evaluate their potential to
be used as energy sources specially in thermochemical conversion processes.
785
In this work four solid wastes from a pulp and paper industry (located in São Paulo, Brazil) were
selected and characterized. Their physicochemical properties were evaluated by proximate analysis,
thermal behavior and ash composition. The Higher Heating Value (HHV) and ash tendency toward
fouling and slagging were calculated and predicted by methodologies proposed in the literature.
The selected biomasses were: thickener fiber (T. Fiber), pond fiber (P. Fiber), decanter cleaning
residue (DCR) and clean bark (C. Bark).
Prior to the analysis, the residues were dried at 105 ± 5 °C for 24 hours, crushed and sieved through
100 mesh (<150 μm) granulometry.
The proximate analysis (moisture, ash and volatile material content) was performed according to
ASTM E1755 and ASTM E872 [7, 8], respectively. Fixed carbon content was calculated by equation 1,
on a dry basis.
𝐶𝐹 = 100 − (𝑉𝑀 − 𝑍) (1)

Where, CF, VM and Z are the fixed carbon, volatile material and ash given in mass percentage.
The HHV was determined theoretically using the Nhuchhen and Salam [9] equation (equation 2)
based on concentrations obtained in proximate analysis.
𝑉𝑀 𝐹𝐶 𝑍
𝐻𝐻𝑉 = 19.2880 − 0.2135 ∙ ( 𝐹𝐶 ) + 0.0234 ( 𝑍 ) − 1.9584 (𝑉𝑀) (2)
Where, HHV is given in MJ.kg-1 and Z, FC and VM in mass percentage.
Thermogravimetric experiments were carried out to predict the thermal behavior during the selected
biomasses pyrolysis or combustion. For that, 10 mg of each sample was used, with controlled heating
rate of 10 °C.min-1, and temperature ranging from 25 to 900 °C. The analysis were performed under
inert atmospheres (N2 at 99.997% v/v purity) and synthetic air (21% v/v O2 and 79% v/v N2), both at a
flow rate of 50.0 mL.min-1.
The samples ashes were obtained using a muffle furnace according to ASTM E1755 [7]. The
composition of those was determined using the X ray fluorescence analysis (XRF), by the elements
method, with opening mask of 10 mm. Samples were pressed using boric acid as a substrate. Prior
analysis samples were dried for 24 hours.
The ashes fusibility was estimated using a correlation, equation 3, established by Pronobis [10].
Fe2 O3 + CaO+MgO+Na2 O+ K2 O+ P2 O5
B/A(+P) = (3)
SiO2 + Al2 O3 + TiO2
Where, Fe2O3, CaO, MgO, Na2O, K2O, P2O5, TiO2 and Al2O3, are the amount percentage (m/m) of
these compounds in the biomasses ash.
The correlation above indicates the tendency of fouling and slagging, predicting a low temperature
786
ash fusion. The higher the value of B/A(+P), the higher these tendency [10]. For results around 0.75,
there is slagging possibility, i.e., when biomasses are rich in Fe2O3, CaO and MgO compounds, the ash
melt is imminent when using thermochemical processes, since these compounds volatilize at
temperatures below 750 °C [11, 12].
SEM analyses were carried out to observe the samples morphology before and after the combustion
process.
3. RESULTS AND DISCUSSIONS
3.1. Biomass and ash composition
Table 1 shows the biomasses properties and its ashes composition. It can be observed that P. Fiber
and T. Fiber have shown the highest volatile material content between the four samples, 80.25% and
80.14%, respectively, values commonly found for lignocellulosic biomasses. They also presented the
lowest ash content, 16.05% and 17.30%, which are results close to the acceptable for the use of
wood for biofuels purposes, 15% [13]. Samples presented low fixed carbon content, probably due to
the pulp industry processes for long fibers production, which requires the lignin chains break [14].
The samples presented HHV close to sugarcane bagasse, 15.54 MJ.kg-1, indicating a similar stability
during the burning [15]. The higher the volatile matter content the faster the biomass burnt, and
such condition, together with the low ash content implies on lower probability of losses in boilers and
furnaces. P. Fiber and T. Fiber can be considered, then, potential fuels for thermochemical conversion
[15, 16].
T. Fiber P. Fiber C. Bark DCR

Proximate Analysis (% m/m)
U 8.35 7.85 6.42 6.97
*
CF 2.56 3.70 9.41 21.72
MV* 80.14 80.25 34.90 40.21
Z* 17.30 16.05 55.69 38.06
HHV (MJ.kg-1) 12.19 14.27 15.38 17.05
Ash composition (% m/m)

Al2O3 36.24 40.25 47.06 40.07
SiO2 24.04 29.01 33.04 40.75
CaO 21.30 15.63 0.41 3.20
Fe2O3 7.96 9.13 14.95 8.67
SO3 2.60 0.91 0.22 0.52
TiO2 2.00 1.67 2.62 1.46
P2O5 1.42 0.63 0.59 1.65
K2O 1.22 1.08 0.67 2.31
MgO 1.19 0.85 0.19 0.64
Na2O 0.80 0.43 - -
Others 1.23 0.41 0.25 0.7
787
R(b/a) 0.50 0.37 0.20 0.15

*dry basis.
Table 1: Proximate analysis, HHV, ashes composition and fusibility ratio (R(b/a)) of biomasses.
The HHV determined for C. Bark and DCR were the highest, 15.38 and 17.05 MJ.kg-1, respectively.
They were similar to those known for materials such as Acacia Magiu (16.96 MJ.kg-1), wood
pellets (18.21 MJ.kg-1), residues of soy (16.47 MJ.kg-1), sorghum (11.87 MJ.kg-1), poultry
manure (14.58 MJ.kg-1) and palm kernel shell (16.66 MJ.kg-1), which makes it possible to say that
C.Bark and DCR are potentially interesting for applications in thermal processes [4, 15, 18-20].
However, each biomass presents distinct peculiarities in its composition, it is possible that it may be a
material capable to offer good conditions to be used in thermal processes. Another important point
to be observed toward the composition of materials is that the volatile products refer to cellulose
and hemicelluloses while lignin presents almost entirely in solid (fixed carbon) form [17]. Therefore,
they can be interesting fuels to conversion technologies based on combustion and gasification
processes [4].
The biomasses origin and composition influence directly on the fouling and slagging tendency. Alkali
metals and sulfur in their composition, for example, as well as calcium, magnesium, iron and
phosphorus, on P2O5 form, are related to such problem on thermal conversion systems [21]. In order
to estimate the tendency toward fouling and slagging, the equation developed by
Pronobis (2005) [10] was applied, for which, for values around 0.75, the tendency is extremely high.
For values lower than 0.75, chances are unlikely, but in the other hand, the system temperature tend
to be higher.
The T.Fiber, P.Fiber, C.Bark and DRC ashes are rich in acid oxides (Al2O3 and SiO2) (Table 1) resulting,
in fusibility ratio values lower than 0.75, indicating that the melting temperature is probably high.
Furthermore, they could be mixed to other residues for co-pyrolysis process [22], or be a feedstock of
Al2O3, SiO2 and Fe2O3 for catalysis purpose [23]; once they can supply needed compounds to another
wastes to improve its thermochemical conversion efficiency.
3.2. TG/DTG
The TG/DTG results are given as plots of total mass loss (TG) and mass loss rate (DTG) with
temperature. Figures 1 and 2 show the biomasses TG/DTG curves under inert and oxidizing
atmospheres respectively. Similar behavior is observed, but different mass loss (three peaks); except
for C.Bark (four peaks). Table 2 presents the mass loss for all samples, under N2 and synthetic air
conditions, its ignition and peak temperature.
100
10
T. Fiber
90 P. Fiber
80 C. Bark 8
DCR
DTG (%/min)
70 T. Fiber
60
6 C. Bark
P. Fiber
TG (%)
50 DCR
4
40
30 2
20
0
10
0 0 200 400 600 800 1000
0 200 400 600 800 1000
Figure 1: TG/DTG curves from C.Bark, T.Fiber, P.Fiber and DCR under N2 condition.
788
T.Fiber 1,8
100 P.Fiber 1,6 T.Fiber
C.Bark C.Bark
1,4 P.Fiber
80 DCR
1,2 DCR
DTG (%/min)
TGA (%)
60 1,0
0,8
40 0,6
0,4
20
0,2
0 0,0
0 200 400 600 800 1000 0 200 400 600 800 1000
Figure 2: TG/DTG curves from C.Bark, T.Fiber, P.Fiber DCR under synthetic air condition.
The first peak, from room temperature to 150 °C, is attributed to the moisture loss and some volatile
compounds. On the second peak, 230-400 °C, the highest mass loss is observed, varying from 19.07%
to 57.29%, for T.Fiber, P.Fiber and DRC under both different atmospherics conditions (Table 3). It can
be attributed to the thermal degradation of the hemicellulose (from 250 to 300 °C), followed by
cellulose (300–350 °C), characteristic of volatile matter in biomasses. The residual volatile and fixed
carbon content are degraded at temperatures above 400 °C. Peaks in T.Fiber and P.Fiber curves has
shown peaks at temperatures higher than 600 °C, which can be related to the residual lignin
decomposition [4, 24-26]. The smaller peak found above lignin zone of degradation (500 °C) can be
attributed to inorganic matter decomposition as carbonates [26].
Unlike other samples presented, the C.Bark burning profile has shown four peaks. The first one
represents the moisture loss, under 100 °C. The second peak, 170-270 °C, indicates there was not a
complete volatile matter release and the beginning of hemicellulose degradation; it is easily
pyrolyzed due to its random amorphous structure with low strength. The third, 270-370 °C, points to
the cellulose degradation. The last peak can be attributed to complete cellulose degradation and the
lignin chains break [4, 21, 28].
Under synthetic air condition P.Fiber and DCR were quicker consumed and reached higher value of
DTG than under nitrogen atmosphere (Figures 1 and 2) [29]. It occurred possibly due to most of C-C
bonds were oxidized to CO and C-O bonds at second stage [30] and because in oxygen presence the
force of the fusion layer is reduced, leading to the quicker volatile matter liberation [13].
Ignition temperatures were determined under oxidizing atmosphere: they were taken as the
temperatures at which the mass loss curves deviates [31]. It was also observed that ignition
temperatures for all four samples range from 164 to 214 °C (Table 2). The highest peak for T.Fiber,
P.Fiber and RDC were found to be occurring in the cellulose zone of degradation (250 – 350 °C).
C.Bark presented the peak at the lowest temperature (164 °C), indicating the high reactivity of it,
when compared to the others and also more reactive biomasses as coffee grounds (179 °C) and meat
industry wastewater sludges (185 °C) [32]. The more reactive the biomass, the lower the process
temperature and the processing time required for complete conversion, which helps to control
residence time and contributes to minimize problems related to ash in thermochemical conversion
processes, however, it cannot be the unique parameter, since a good performance of those
conversion process will depend on homogeneity and particle size range as well [18].
Samples Atmosphere Temperature Range (°C) Tpeak Tignition
789
(°C) (°C)
<100 100-250 250-350 350-500 >500 Ash
N2 6.21 2.64 34.97 34.59 11.25 10.34
T.Fiber 329 214
S.Air 6.87 3.04 44.03 21.38 6.13 18.55
Mass Loss (%)

N2 6.37 1.97 22.11 23.96 16.04 29.55
P.Fiber 333 202
S.Air 6.53 2.73 56.05 27.28 1.59 5.82
N2 4.47 4.55 13.94 15.81 13.96 47.27
C.Bark 319 164
S.Air 5.84 4.38 16.47 19.72 2.92 50.67
N2 4.62 3.53 14 12.41 12.52 52.92
DCR 324 202
S.Air 7.6 4.73 23.6 18.21 11.9 33.96
Table 2: Mass loss for T.Fiber, P.Fiber, C.Bark and RDC under N2 and synthetic air conditions and Ignition Temperature.
3.3 Scanning electron microscopy (SEM)
Figure 2 (a - h) presents the SEM images for the biomasses studied and their respective ashes. The
fibers (T.Fiber and P.Fiber), shown in Figures 2a and 2c, present a uniform appearance of fairly
irregular particles, caused by fiber disintegration; this disaggregation is perceived by sample peeling
(or simply by the detachment of the smaller particles from the large ones). As for its ashes, Figures 2b
and 2d, there is a change in the morphology and size of the particles (visibly smaller) due to their
thermal degradation.
Figure 2: SEM images for a) T.Fiber; b) T.Fiber ashes; c) P.Fiber; d) P.Fiber ashes; e) C.Bark; f) C.Bark ashes; g) RDC; h) RDC ashes.
C.Bark structure, Figure 2e, shows uniformity with few pores. It is also verified on its the ashes,
Figures 2f, due to the high percentage of ashes, their structures are practically preserved, without
great morphologic differences, only a mass decrease.
790
RDC, Figure 2g, show morphology predominantly in hives form, indicating the presence of voids,
while its ashes, Figure 2h, indicate that the structure practically disintegrates itself, presenting
irregular particles.
4. CONCLUSION
In this work, solid wastes from a paper and pulp industry were investigated and have shown high
energy content, ranging from 12.19 to 17.05 MJ.kg-1. From these, T.Fiber and P.Fiber were considered
as potential fuels to be used in boilers and furnaces, due its HHV close to wood materials caused by
the high volatile material, low ash and high fixed carbon content. C.Bark and RDC showed the highest
HHV values, 15.38 and 17.05 MJ.kg-1, being therefore interesting fuels to conversion technologies
based on combustion and gasification processes.
The samples thermogravimetric behavior observed was common to solid fuels already found in the
literature and the ignition temperature for the samples ranged from 164 to 214 °C.
The biomasses studied present promising energy potential for their use in thermochemical
conversion processes. And it could contribute to the reduction of energy costs and emissions in paper
and pulp industry.
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792
PHOSPHATE RELEASE AND AFFECTING FACTORS ANALYSIS DURING SLUDGE

THERMAL HYDROLYSIS
Z.Q. XU1, C.Z. YAO1, L. YAO1, R.R. LIU1, A.Z. ZHOU1

1 Xi'an University of Technology, State Key Laboratory Base of Eco-Hydraulic Engineering in Arid
Area, Xi'an, China.
Keywords: Excess sludge 1, Thermal hydrolysis 2, Phosphorus release 3, Influencing factors 4
Abstract
The phosphorus (P) in excess sludge (ES) which produced by the sewage treatment plant has huge recycling
value.The most important step of P recovery from the ES is to release as much P as possible into the solution.
In this work, the ES with a solid content of 5% was used to study the thermal hydrolysis of P release.. The
results showed that when the ES was treated with low-temperature and pretreated with acid, the floc of the
sludge was destroyed, and the release of P increased significantly. When the temperature was 75 °C for 1 h, ,
the release of the total P (TP) and dissolving of the inorganic P (IP) in the liquid phase of raw sludge reached
the maximum level, 311.9 mg/L and 293.8 mg/L, respectively Increased 7.9 times and 8.4 times compared
with raw sludge. When the sludge mixture was allowed to stand for 24 h at 35°C, the concentration of
ammonia nitrogen (NH4+-N) increased from 96.0 mg/L to 318.7 mg/L, accompanied by a significant decrease in
the concentration of soluble chemical oxygen demand (SCOD). These results demonstrated that the
combination of low-temperature and short-time thermal and acid pretreatment can significantly increase the
P and NH4+-N release in the sludge, which can create favorable conditions for P recovery by struvite
precipitation.
793
1- INTRODUCTION
Phosphorus (P) is one of the most essential nutrients for all living organisms. It is also an important
resource that cannot be regenerated and will be depleted [1,2]. Therefore, the recovery of P from
various P-rich residues，the development of methods to promote the release and recovery of P are
receiving widespread attention [3,4]. The Excess sludge (ES) produced by the sewage treatment
plant (STP) is rich in P. In traditional activated sludge processes, sludge usually contains 1-2% P. In
sludge discharged from enhanced biological P removal (EBPR)processes, a much higher content of P
(5 -7 %) has been found [5]. Therefore, the ES has a huge value of P recovery and utilization.
P can be recovered from the ES through crystallisation of struvite, MgNH4PO4·6H2O. Crystallisation is
profitable since the nitrogen (N) can also be recovered at the same time. As compared to chemical
and biological P removal method, recovering P through struvite crystallisation method can not only
reduce sludge and resource, but also be reused in agricultural production [6,7].
To increase the efficiency of P recovery, the first and foremost step is to release as much as possible
P from the sludge into the liquid phase Therefore, it is necessary to study the P release conditions ,
to avoid the combination of P with metal ions such as calcium, magnesium, iron in the sludge, and
also to increase the release rate of NH4+-N and reduce the amount of NH4+-N dosing during struvite
crystallisation.
Most of the P in the ES is stored within phosphorus accumulating organisms (PAOS) and extracellular
polymer substances(EPS) [8]. To promote the P release in the sludge and enhance the solid
hydrolysis rate, some pretreatment technologies (thermal, mechanical, and chemical) have been
applied [9,10]. Among these pretreatment, low-temperature is regarded as a relatively low energy
process that can enhance the biodegradability of sludge, and simultaneously release P from sludge
[11,12]. P release by low-temperature thermal pretreatment is 3.7 times greater than biological [13].
Kuroda et al. (2002) [14] reported that approximately 87% of the total P (TP) could be released from
P accumulating flocculent sludge (PFS) simply by heating it at 70° C for 1 h. Zhang and Kuba (2014)
[15] reported that only about 29% TP could be released into the water phase from PFS after thermal
pretreatment at 70°C for 80 minutes. In addition, the P release process is significantly affected by the
pH in the water phase. Xu and Hu (2017) [16] reported that the TP in the solid release percentages
were 36.2% and 12.4% at pH=2.0 and pH=12, respectively. The released P comes mainly from
dissolved inorganic P (IP) in acidic condition, and from non-apatite inorganic P (NAIP) and organic P
(OP) in alkaline condition.
Due to various factors such as heating temperature, heating time, and pH in the liquid phase, there is
a large difference in the P release process during the thermal hydrolysis of sludge. At the same time,
there is also great uncertainty in the struvite crystallisation, due to the influence of the soluble
chemical oxygen demand (SOCD) and ammonia nitrogen (NH4+-N) release. Therefore, the aim of this
work is to analyze the factors such as heating temperature, heating time, and pH to obtain the
optimal conditions for the phosphate release from the sludge, to investigate the effects of SCOD and
NH4+-N concentration on the P recovery in water phase, and to lay the foundation for improving
efficiency of struvite recovery from the ES.

2.1 Experimental Materials
The was obtained from the secondary sedimentation tank of a municipal WWTP in Xi'an, China. This
plant was designed to treat municipal wastewater using an inverted A2/O activated sludge process.
After retrieving the sludge, the remaining sludge with a solids content of 5% (the ratio of phosphorus
in the dry sludge is 1.1%) was used. The sludge parameters are shown in Table 1:
794
Index Unit Value

pH - 6.41~6.81
SCOD mg·L-1 106~265
TCOD mg·L-1 44707~48303
TP mg·L-1 573.2
IP mg·L-1 406.5
TP（1） mg·L-1 35.2~37.3
IP（1） mg·L-1 34.5~37.1
NH4+（1） mg·L-1 36.2~41.8
(1) denotes: supernatant liquid.
Table 1: Various parameters of sludge mixture.
2.2 Experimental Methods

The single factor rotation method is used in the experimental method. The operation method is as
follows: fixed sludge heating time was 1h, sludge pH was 6, and thermal hydrolysis treatment was
carried out at 45, 60, 75, 90, 105, 120, 135 and 150°C respectively ,then the optimum thermal
hydrolysis temperature was selected; At the optimum thermal hydrolysis temperature, the fixed
sludge pH was 6 and the heating time was 0.5, 1, 2, 3, 4, 5, and 6 h respectively, then the optimum
heating time was determined; The pH of the sludge mixture was adjusted to 3, 4, 5, 6, 7, 8, 9, 10, and
11 with the temperature of the hydrolysis and the heating time. The change of pH was adjusted by
HCl(1mol/L) and NaOH(1mol/L),then the optimum pH was determined.
2.3 Analysis Methods

The determination methods of TP, IP, NH4+-N, SCOD, and Ca2+ were all measured by the standard
method [17]. TP and IP were measured by molybdenum and antimony spectrophotometry; NH 4+-N
was measured by Nessler's reagent spectrophotometry; SCOD was determined: the organic matter
contained in the filtrate was dissolved after the sludge sample was vacuum-filtered through a 0.45
μm filter. Chemical oxygen demand (SCOD) was determined by rapid digestion spectrophotometry;
Ca2+ was determined by flame atomic absorption spectrometry.
The phosphorus content of various forms in the sludge adopts the SMT protocol proposed by the
European standard test and measurement organization. The SMT method [18,19] divides the
extracted phosphorus into 5 types: non-apatite inorganic phosphorus (NAIP: phosphorus combined
with Fe, Mn, Al oxides and their hydroxides, and unstable phosphorus is also included in the Among
them), apatite inorganic phosphorus (AP: calcium phosphorus, including various phosphorus
combined with Ca), inorganic phosphorus (IP), organic phosphorus (OP) and total phosphorus (TP).
After measuring the total phosphorous content in the dry sludge and the phosphorous content of
each component, convert the phosphorus content of the 5% solids-containing sludge mixture.
According to the SMT extraction method, TP = OP + IP, IP = NAIP + AP. In, the recovery rate of TP is
between 97.2% and 103.2%, and the recovery rate of IP is between 95.5% and 104.7%. The contents
of various forms of phosphorus in the original sludge are shown in Table 2.
Each form phosphorus（mg·L-1） NAIP AP IP OP TP

Value 291.6 116.0 406.5 168.4 573.2
Table 2: The content of total phosphorus and phosphorus in sludge mixture.

3.1 The release of phosphorus under different conditions
795
Under the condition of pH=6, the residual sludge (solid content is 5%) was heated and hydrolyzed,
while the heating time was maintained for 1 h. The temperature range was from 45°C to 150°C.
Figure 1 shows the evolution of phosphorus released from the sludge into the liquid phase at
different heating temperatures. As the temperature increases, the content of phosphorus released
into the liquid phase increases and then decreases. When the heating temperature was 75°C, the
release of TP and IP in the sludge reached the maximum, which were 249.7 mg/L and 246.0 mg/L,
respectively. The release rates were 43.6% and 60.3%, respectively, while the release rate of OP was
only 2.2%; After 75°C, with the increase of temperature, the concentration of TP and IP released into
the liquid phase gradually decreased, and the concentration of OP gradually increased. When the
heating temperature was 150°C, the release amounts of TP and IP were 179.9 mg/L and 154.0 mg/L,
respectively. The release rates were 31.4% and 37.9%, respectively, while the release rate of OP
increased to 15.4%. However, the release of phosphorus under heated and hydrolyzed was still IP-
based, the released IP accounted for 85.6% of TP, while OP accounted for only 14.4%. After the
temperature exceeds 75°C, the decrease of phosphorus release rate is mainly due to the
concentration of metal ions such as Ca2+ and Mg2+, which is recombined with the released PO43--P to
form precipitates. Therefore, the IP release of the sludge after heat treatment at 75°C is the highest,
which is more conducive to the subsequent recovery of struvite phosphorus.
600 70 600 70
IP TP OP IP TP OP
IP TP OP 60 IP TP OP 60
Phosphorus release rate/%

500 500
Phosphorus release/mg·L-1
50 50
400 400
40 40
300 300
30 30
200 200
20 20
100 100 10
10
0 0 0 0
45 60 75 90 105 120 135 150 0 1 2 3 4 5 6
Temperature/℃ Time/h
Figure 1: Effect of different heating temperature on Figure 2: The effect of heating time on phosphorus
phosphorus release. release.
600 90
IP TP OP Ca2+
IP TP OP Ca2+ 80
500
70
400 60
50
300
40
200 30
20
100
10
0 0
3 4 5 6 7 8 9 10 11
pH
Figure 3: The effect of pH on phosphorus release.
The above experimental study showed that the optimum treatment temperature for the release of
phosphorus from sludge was 75°C. With heating time maintained at 75°C and pH=6, the effect of
continuous heating on the release of phosphorus from the sludge was further investigated(see
Figure 2). As can be seen from Fig. 2, at the heating time of 0.5 h, the release amounts of TP and IP
were 210.0 mg/L and 207.0 mg/L, respectively, the release rates were 36.6% and 50.7%,
796
respectively; when the heating time was 1 h, TP and the release of IP increased to 230.0 mg/L and
226.8 mg/L, respectively. The release rates were 40.1% and 55.8%, respectively, while the release
rate of OP was only 1.9%. At the heating time of 2 h, the release of TP and IP decreased significantly.
With the heating time, the release of phosphorus increased. At the heating time of 5 h, the release
of TP and IP increased to 230.0 mg/L and 220.0 mg/L, respectively. The release rates were 40.1% and
54.1%, respectively. The release rate of TP is similar to the heating time were 1 h, but the release
rate of IP decreased, the release rate of OP increased. The IP released from sludge is an effective
part of phosphorus recovery, so the heating time of 1 h is the best condition for phosphorus
recovery.
The above experimental study shows that when the heating temperature is 75° C and the heating
time is 1 h ,the IP release efficiency is highest, but the pH value also has a great influence on the
phosphorus release intensity of the sludge[16]. The experiment further examined the effect of pH on
the release of phosphorus (Figure 3). As can be seen from Figure 3, with the increase of pH, IP
release gradually decreased. However, when pH value is greater than 7, the release of OP gradually
increased, resulting in the release of TP reaches its lowest value at pH=7, after which the release
increased as the pH increased. At pH=3, the highest levels of TP and IP were released in sludge,
reaching 311.9 mg/L and 293.8 mg/L, respectively. The release rates of TP and IP were as high as
54.4% and 72.3% respectively.
As the sludge contains more Ca2+ and other cations, Ca2+ is more easily combined with IP to form
calcium phosphate precipitate under alkaline conditions[20]. By analysing, the concentration of Ca2+
in the experimental sludge mixture (solid content is 5%) was 1681.2 mg/L, and as the pH value
increased, a large amount of Ca2+ in the liquid phase combined with IP to form calcium phosphate
which has a smaller solubility, while Ca2+ content in the liquid phase of the sludge showed a
significant decrease (Fig. 3). This resulted in a decrease in the IP content in the liquid phase after pH
value is greater than 7 (Figure 3). This will affect the efficiency of subsequent struvite phosphorus
recovery. Under acidic conditions, IP does not easily form crystalline products with Ca2+ and other
cations, which are generally present in the liquid phase as phosphate ions. Therefore, at pH=3, the IP
release is maximum, which is more conducive to the subsequent recovery of phosphorus.
3.2 Release patterns of NH4+-N and SCOD and their effects on phosphorus recovery
Figure 4 shows the effect of temperature change of the thermal hydrolysis on the NH 4+-N
concentration in the liquid phase of the sludge at a pH of 6 and a heating time of 1 h. The
concentration of NH4+-N in Figure 5 is the difference between the amount of ammonia released and
the amount of volatilization. There is a certain balance between the amount of ammonia in the liquid
phase and the volatilization of ammonia[21]. As the temperature rises, the sludge releases a large
amount of ammonia, resulting in an increase in the concentration of residual NH4+-N in the liquid
phase, while a substantial increase in the volatilization of ammonia. When the temperature is 75°C,
the residual NH4+-N concentration in the liquid phase is 145.8 mg/L, while at 150°C, is 194.7 mg/L,
there is 1.3 times higher than at 75°C. It also indicate that the amount of ammonia volatilization is
much greater than 75°C at 150°C. If the temperature is higher, the loss of ammonia will be greater,
and it will be more detrimental to the recovery of nitrogen and phosphorus in the sludge. At a
temperature of 75°C, although the concentration of residual NH4+-N in the liquid phase is not high,
the loss of volatilization is small, and a large amount of ammonia can be released from the sludge
into the liquid phase by means of standing at an intermediate temperature (see subsequent
experimental results).
797
200 150
+
NH4+ NH4
180
NH4+ release/mg·L-1 140
160
-1
NH4 release/mg·L
140 130
120
120
100
+
110
80
60 100
45 60 75 90 105 120 135 150 0.5 1 2 3 4 5 6
Temperature/℃ Time/h
Figure 4: The effect of temperature on the Figure 5: The effect of heating time on the
+ +
concentration of NH4 -N in liquid phase. concentration of NH4 -N in liquid phase.
180 400 7000
NH4+ SCOD
+
170 NH4 350 6750
SCOD release/mg·L-1
160
NH4+ release/mg·L-1
300
-1
6500
NH4 release/mg·L
150
250
140 6250
200
130 6000
150
+
120
100 5750
110
100 50 5500
3 4 5 6 7 8 9 10 11 0 10 20 30 40 50
pH Time/h
+
Figure 6: The effect of pH on the concentration of NH4 Figure 7: 35 ℃ let stand conditions, the sludge
+
-N in liquid phase. concentration of NH4 -N in liquid phase change
Fig. 5 shows the effect of heating time on the concentration of residual NH4+-N in the liquid phase at
a pH of 6 and a heating temperature of 75°C. As can be seen from the figure, when the heating time
is 0.5 h, the residual NH4+-N concentration in the liquid phase is 118.6 mg/L. When the heating time
was 1 h, the concentration of residual NH4+-N increased to 139.0 mg/L, and the heating time
continued to increase. The concentration of residual NH4+-N in the liquid phase remained at
approximately 135.0 mg/L, while there is a balance between the NH4+-N concentration and the
volatilization of ammonia. When the heating time is 1 h, the concentration of residual NH4+-N in the
liquid phase is basically the same as the condition of heating for a long time. It can also pass through
the subsequent medium temperature static method without consuming too much heat energy. A
large amount of nitrogen is released (see subsequent experimental results).
Figure 6 shows the effect of pH on the concentration of residual NH4+-N in the liquid phase at a
heating temperature of 75°C and a heating time of 1 h. As can be seen from Fig. 7, the residual NH4+-
N concentration in the liquid phase is lower (less than 120 mg/L) under acidic conditions (pH=3-7),
and residual NH4+-N in the liquid phase at pH=7-9. At pH=9, the concentration of residual NH4+-N
reached the maximum (173.2 mg/L); the pH was in the alkaline condition (pH=9-11), and the residual
NH4+-N concentration in the liquid phase is decreased again. At pH=7-9, due to the continuous
increase of SCOD release in sludge (see Figure 11), the protein is further hydrolyzed after dissolution
to form a large amount of NH4+-N, which also promotes the volatilization of ammonia. Under the
alkaline conditions, NH4+-N is more likely to combine with OH- to form NH3·H2O state, it is easily to
volatilize from the liquid phase, resulting in the loss of ammonia. Therefore, under the partially acidic
condition, although the concentration of residual NH4+-N in the liquid phase of the sludge is small, a
large amount of released nitrogen can be recovered and used in the form of struvite by subsequent
intermediate temperature static method (see subsequent experimental results).
798
Figure 6 shows the effect of pH on the concentration of residual NH4+-N in the liquid phase at a
heating temperature of 75°C and a heating time of 1 h. As can be seen from Fig. 7, the residual NH4+-
N concentration in the liquid phase is lower (less than 120 mg/L) under acidic conditions (pH=3-7),
and residual NH4+-N in the liquid phase at pH=7-9. The concentration of NH4+-N increased. At pH=9,
the concentration of residual NH4+-N reached the maximum (173.2 mg/L); the pH was in the alkaline
condition (pH=9-11), and the residual NH4+-N in the liquid phase. At pH=7-9, due to the continuous
increase of SCOD release in sludge (see Figure 11), the protein is further hydrolyzed after dissolution
to form a large amount of NH4+-N, which also promotes the volatilization of ammonia. Under the
alkaline conditions, NH4+-N is more likely to combine with OH- to form NH3·H2O state, it is easy to
volatilize from the liquid phase, resulting in the loss of ammonia. Therefore, under the partially acidic
condition, although the concentration of residual NH4+-N in the liquid phase of the sludge is small, a
large amount of released nitrogen can be recovered and used in the form of struvite by subsequent
intermediate temperature static method (see subsequent experimental results).
At the optimum conditions of 75°C heating, heating time 1 h, pH=3, the residual NH4+-N
concentration in the liquid phase was lower (90 mg/L-130 mg/L), affecting birds. The efficiency of
phosphorus recovery from the sedimentation of manure. After a short time of acid-hydrolysis, the
sludge mixture could stand at 35° C. As the standing time increased, the concentration of NH4+-N in
the liquid phase increased significantly (as shown in FIG. 7). After standing for 24 h, the
concentration of NH4+-N in the liquid phase increased from 96.0 mg/L to 318.7 mg/L, much higher
than the concentration of NH4+-N in the liquid phase at the heating temperature of 150°C (194.7
mg). /L), while the SCOD concentration in the liquid phase decreases. Some microorganisms may be
present in the liquid phase. The organic substances such as proteins released during the thermal
hydrolysis process may be further hydrolyzed to ammonia nitrogen at 35°C, resulting in a significant
increase in the concentration of NH4+-N in the liquid phase. At a heating temperature of 75° C., a
heating time of 1 h, and a pH of 3, high levels of phosphorus can be obtained in the liquid phase of
the sludge, and then the NH4+-N in the liquid phase can be greatly increased by the method of
standing at medium temperature. The concentration of nitrogen and phosphorus in the process of
using struvite precipitation to recover nitrogen, no need to add nitrogen, you can meet the recovery
requirements, to achieve the simultaneous recovery of nitrogen and phosphorus.
Figure 8 shows the effect of heating temperature on the release of SCOD at a pH of 6 and a heating
time of 1 h. As can be seen from Figure 8, the amount of SCOD released increases with increasing
temperature. When the temperature was 75°C, the SCOD release was 5003.6 mg/L, and at 150°C,
the SCOD release was 11353.2 mg/L, which was 2.27 times higher than that at 75°C. The higher the
concentration of organic matter in the liquid phase, the more it will affect the phosphorus recovery
of struvite, which will reduce the efficiency of phosphorus recovery and affect the purity of the
product [22]. Therefore, relatively low heating temperature conditions should be selected, which is
more conducive to improving the subsequent phosphorus recovery efficiency and product purity.
20000 30 20000 20
SCOD SCOD SCOD SCOD
17500 17500
25
SCOD Release rate/%
15000 15000 15
SCOD Release rate/%
-1
SCOD release/mg·L
20
12500 12500
10000 15 10000 10
7500 7500
10
5000 5000 5
5
2500 2500
0 0 0 0
45 60 75 90 105 120 135 150 0 1 2 3 4 5 6
Temperature/ ℃ Time/h
799
Figure 8: The effect of heating temperature on SCOD Figure 9: The effect of heating time on SCOD emission.
release.
20000 30
SCOD SCOD
25
SCOD release rate/%

15000
20
10000 15
10
5000
5
0 0
3 4 5 6 7 8 9 10 11
pH
Figure 10: The effect of pH on SCOD release.
Figure 9 shows the effect of heating time on the release of SCOD at a pH of 6 and a heating
temperature of 75°C. When the heating time was 1 h, the SCOD release was 5130.4 mg/L, the
heating time was extended to 5 h, the SCOD release was 7311.9 mg/L, which was 1.4 times of 1 h,
but there was no heating temperature for the release of SCOD. The effect is significant. Different
from the release characteristics of IP and TP, the SCOD concentration in the liquid phase of the
sludge gradually increased with the heating time. This may be due to an increase in the degree of
cracking of cells in the sludge mixture as heating time increases. Similarly, too high concentration of
SCOD in the liquid phase will affect the efficiency and purity of subsequent phosphorus recovery,
and the heating time will also consume a lot of energy, so from the economic point of view, the
heating time is chosen as 1 h, and more Facilitates the recovery of phosphorus
Under different pH conditions, the release of SCOD in sludge is different from the release of
phosphorus (as shown in Figure 11). At pH=7, the lowest concentration of SCOD in the liquid phase
was only 5451.5 mg/L. Under acidic conditions, the SCOD concentration in the liquid phase was
higher, and at pH=3, the SCOD concentration was 8229.2 mg/L. Under alkaline conditions, the
release of SCOD in the liquid phase was higher than the release of SCOD under acidic conditions as
the pH value increased. When pH = 11, SCOD release reached a maximum of 10420.4 mg/L, 1.3 times
higher than pH = 3. The results showed that under the alkaline conditions, the sludge cells were
more destructive [23], but the released OP content also increased (Figure 3), and the released IP was
more easily combined with Ca2+ and other metal ions to form a precipitate, resulting in liquid the
content of IP in the phase is reduced. Therefore, under acidic conditions, more IP is released and the
content of SCOD is lower. The follow-up is more conducive to the recovery of struvite phosphorus.
4- CONCLUSIONS
(1) The method of low-temperature thermal hydrolysis and acid treatment can significantly increase
the release of IP in sludge. When the hydrolysis temperature is 75°C, the release rate of IP is higher
than that at 150°C. At the heating temperature of 75°C for 1 h, the IP release at pH 3 was 1.7 times
higher than that at pH=11 and 8.4 times higher than that of the raw sludge. Therefore, for the ES
with a solid content of 5% (the ratio of P in dry sludge is 1.1%), the optimum conditions of P release
are heating temperature 75°C for 1 h and at pH=3.
(2) The sludge mixture treated at pH=3 and the heating temperature 75°C for 1 h was placed at
35°C for about 12 h. The concentration of NH4+-N in the liquid phase increased from 96.0 mg/L to
318.7 mg/L, which was 2.3 times of the concentration of IP (molar ratio). The release of high-
800
concentration NH4+-N was more conducive to the recovery of P without the addition of a nitrogen
source.
(3) The higher concentration of SCOD in the liquid phase would reduce the efficiency of P recovery
and affect the purity of struvite [22]. Under the optimal conditions of P release, the SCOD
concentration only accounted for 18% of TCOD, which had little effect on subsequent P recovery.
(4) The P release conditions of the short-term and low-temperature thermal hydrolysis determined
through the test had lower heat energy consumption. At this stage, it is suitable for pretreatment of
P recovery from SE.
REFERENCES
[1] Cordell, D., Drangert, J.O., White, S.: The story of phosphorus: global food security and food for thought, Global
Environ. Change-Hum. Policy Dimens. 19, 292–305 (2009)
[2] Burns, R.T., Moody, L.B., Celen, I.: Optimization of phosphorus precipitation from swine manure slurries to enhance
recovery. Water Science and Technology, 48(1),139-146 (2003)
[3] Rittmann, B.E., Mayer, B.P., Edwards, M.: Capturing the lost phosphorus, Chemosphere 84, 846–853 (2011)
[4] Liang, W., Cheng Z., Hui H,:Phosphorus and short-chain fatty acids recovery from waste activated sludge by
anaerobic fermentation: Effect of acid or alkali pretreatment. Bioresource Technology 240, 192–196 (2017)
[5] Yuan, Z.G., Pratt, S., Batstone, D.J., Phosphorus recovery from wastewater through microbial processes. Curr. Opin.
Biotechnol. 23 (6), 878–883 (2012)
[6] Shu, L., Schneider, P.V.: An economic evaluation of phosphorus recovery as struvite from digester supernatant.
Bioresource Technology 97, 2211–2216 (2006)
[7] Wu, Q., Bishop, P.L.: Enhancing struvite crystallization from anaerobic supernatant. Journal of Environmental
Engineering and Science 3, 21–29 (2004)
[8] Cloete, T.E., Oosthuizen, D.J.: The role of extracellular exopolymers in the removal of phosphorus from activated
sludge. Water Research, 35(15):3595-8 (2001)
[9] Zou, J., Li, Y.M.: Anaerobic fermentation combined with low-temperature thermal pretreatment for phosphorus
accumulating granular sludge: Release of carbon source and phosphorus as well as hydrogen production potential.
Bioresource Technology. 218, 18–26 (2016)
[10] Daniel, S., Christian, V., Christian, A.: Effect of various types of thermochemical processing of sewage sludges on
phosphorus speciation, solubility, and fertilization performance. Waste Management 62, 194–203 (2017)
[11] Val del Río, A., Morales, N., Isanta, E., Mosquera-Corral, A., Campos, J.L., Steyer, J.P., Carrere, H.: Thermal pre-
treatment of aerobic granular sludge: impact on anaerobic biodegradability. Water Res. 45 (18), 6011–6020 (2011)
[12] Kuroda, A., Takiguchi, N., Gotanda, T., Nomura, K., Kato, J., Ikeda, T., Ohtake, H.: A simple method to release
polyphosphate from activated sludge for phosphorus reuse and recycling. Biotechnol. Bioeng. 78 (3), 333–338
(2002)
[13] Xue, T., Huang, X., Hao, W.J.: Characteristics of phosphorus, nitrogen and total organic carbon release in thermal
excess sludge treatment process. China Water & Wastewater, 22,(23):22-25.(2006)
[14] Kuroda, A., Takiguchi, N., Gotanda, T., Nomura, K., Kato, J., Ikeda, T., Ohtake, H.: A simple method to release
polyphosphate from activated sludge for phosphorus reuse and recycling. Biotechnol. Bioeng. 78 (3), 333–338
(2002)
[15] Zhang, M.Y., Kuba, T.: Inhibitory effect of metal ions on the poly-phosphate release from sewage sludge during
thermal treatment. Environ. Technol. 35 (9), 1157–1164 (2014)
[16] Xu, Y.F., Hu, H., Liu, J.Y.: pH dependent phosphorus release from waste activated sludge:contributions of
phosphorus speciation. Chemical Engineering Journal 267, 260–265 (2015)
[17] Monitoring and analysis of water and wastewater, China environment publishing house, beijing, 2002
[18] Ruban, V., López-sánchez, J.F., Pardo, P.: Selection and evaluation of sequential extraction procedures for the
determination of phosphorus forms in lake sediment. Journal of Environmental Monitoring, 1:51-56 (1999)
[19] Ruban, V., López-sánchez, J.F., Pardo, P.: Harmonized protocol and certified reference material for the
determination of extractable contents of phosphorus in freshwater sediments-a synthesis of recent works.
Fresenius Journal of Analytical Chemistry, 370:224-228 (2001)
[20] Cheng, Z.M., Wei, Y.S., Liu, J.X.: Effect of acid - base pretreatment on the release of residual activated sludge from
microwave radiation. Journal of environmental engineering, 30(4):1111-1114 (2009)
[21] Weiler, R.R.: Rate of Loss of Ammonia from Water to the Atmosphere. Journal of the Fisheries Research Board of
Canada, 36(6):685-689 (2011)
[22] Tao, F.F., Tian, Q., Li, F.: Study on the effect of coexisting impurities on the recovery of phosphorus from ammonium
801
phosphate crystallization. Journal of environmental engineering. 05(11):2437-2441 (2011)

[23] Xu, D.C., Zhou, L.J., Yin, K.H.: The analysis of low organic sludge and phosphorous morphology of low - organic
sludge. Journal of environmental engineering. (10):5621-5629 (2017)
802
LIGNOCELLULOSIC BY-PRODUCTS FROM BRAZILIAN SUGARCANE AGROINDUSTRY

FOR BIOTECHNOLOGICAL PRODUCTION OF XYLITOL: STUDY OF OXYGEN SUPPLY AND
SUPPLEMENTATION WITH SUCROSE
A. HERNÁNDEZ-PÉREZ1, F.M. SIMÕES1, M.G.A. FELIPE1*

1 Departamento de Biotecnologia, Escola de Engenharia de Lorena – Universidade de São Paulo,
Lorena, Brasil, *mgafelipe@usp.br.
Abstract
PURPOSE. This work aimed to study the valorisation of the mixture of sugarcane bagasse and straw in
the context of a biorefinery, through the use of the hemicellulosic fraction for xylitol bioproduction, a
sugar-alcohol with growing market and important applications in food and pharmaceutical industries.
MATERIALS AND METHODS. A 1:1 mixture of sugarcane bagasse and straw was submitted to dilute
acid hydrolysis in a 80 L reactor (solid:liquid ratio 1:10, 1% w/v H2SO4, 121 oC, 20 min). The
hemicellulosic hydrolysate obtained was vacuum concentrated (70 oC), to raise xylose concentration
up to approximately 75 gL-1, and detoxified by pH adjustment and activated charcoal adsorption, in
order to reduce concentration of potentially toxic compounds for the fermentation process. The
hemicellulosic hydrolysate was supplemented with rice bran extract (20.0 gL -1), (NH4)2SO4 (2.0 gL-1)
and CaCl2·2H2O (0.1 gL-1). Batch fermentations with Candida guilliermondii FTI 20037 were performed
in a 1.5L bench scale fermenter with 600 mL of working volume, 30 oC, initial pH 5.5 and 72h.Two
fermentation parameters were evaluated: oxygen supply (KLa 10 and 30 h-1), which is considered the
most influencing parameter in xylose-to-xylitol bioconversion by native yeast, and supplementation
with sucrose (5 and 15 gL-1), based on previous results of our research group that demonstrated that
sucrose addition to the sugarcane straw hemicellulosic hydrolysate favoured xylitol production [1].
RESULTS. It was verified a higher xylose consumption rate (1.56 gL-1h-1) with KLa was the maximum (30
h-1) and sucrose addition the minimum (5 gL-1), than in the experiment with minimum KLa (10 h-1) and
maximum sucrose addition (15 gL-1) (1.03 gL-1h-1). It is worth noting that xylose and sucrose were
consumed simultaneously independently of the fermentation conditions. Utilization of lower KLa (10
h-1) and higher sucrose supplementation (15 gL-1) improved xylose-to-xylitol bioconversion, as verified
in higher efficiency (73.85%) and xylitol volumetric productivity (0.54 gL-1h-1) than in the experiment
with higher KLa and lower sucrose addition (53.95% and 0.36 gL-1h-1, respectively).
CONCLUSIONS. The important influence of oxygen supply as well as the possibility of supplementation
of the hemicellulosic hydrolysate from the mixture of sugarcane bagasse and straw with sucrose to
improve xylitol production by C. guilliermondii FTI 20037 were demonstrated.
(Acknowledgments FAPESP Processes 2016/22179-0 and 2016/05971-2, and CNPq).
References
[1] Hernández-Pérez, A.F., Costa, I.A.L., Silva, D.D.V., Dussán, K.J., Villela, T.R., Canettieri, E.V., Carvalho Jr., J.A., Soares
Neto, T.G., Felipe, M.G.A. Biochemical conversion of sugarcane straw hemicellulosic hydrolyzate supplemented with
co-substrates for xylitol production. Bioresour. Technol. 200, 1085-1088 (2016).
803
NANOFIBER PREPARATION FOR ADSORPTION OF LOW LEVEL CO2 THROUGH

ELECTROSPINNING
D. W. JEONG 1 J. M. OH1, S. B. KIM2, Y. G. PARK3, A. ADELODUN4, Y. M. JO1

1 Kyung Hee University, Yongin, Korea.
2 .Korea Institute of Industrial Technology, Ipjang, Korea.
3 Kangwon National University, Samcheok, Korea.
4 The Federal University of Technology, Akure, Nigeria.
Abstract
Freshly electrospun nano-sized fibres were chemically modified for selective adsorption of low
concentration CO2 frequently found in public indoor spaces such as subway, classrooms, buses etc.
Upon chemical activation, the fibres were 250 - 350 nm thick, with pore sizes distributed between
0.6 and 0.7 nm and an average specific surface area of 569 m2/g as could be seen in Fig. 1. The KOH
activation reduced the amount of pyrrole and increases that of quaternary-N (Fig. 2). The pure (100%)
and indoor (0.3%) CO2 adsorption capacities at the ambient condition were improved from 1.08 and
0.013 to 2.2 and 0.144 mmol/g, respectively. It was found that the adsorption amount of CO2
adsorbed by the chemically activated carbon nanofiber prepared through chemical activation would
vary depending on the specific surface area and micropores ratio.
Raw Intensity
Peak Sum
8500 Background
8000 Pyridine
Intensity (counts/s)
7500 Pyrrole
7000 Quaternary
6500
6000
5500
5000
4500
4000
394 398 402 406 410
Binding Energy (eV)
Figure 1: SEM plate of electrospun fiber adsorbent. Figure 2: Deconvoluted XPS peaks
Acknowledgement
This research was supported by Basic Science Research program through the National Research
Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (NRF-
2015R1D1A1A01060182)
References
[1] Adelodun A., Lim Y. H., Jo Y. M.: Surface oxidation of activated carbon pellets by hydrogen peroxide for preparation
of CO2 adsorbent, J. of Ind. and Eng. Chem. 20, 2130-2137 (2014)
[2] Adelodun A., Ngila J. C., Kim D. G., Jo Y. M.: Isotherm, Thermodynamic and Kinetic Studies of Selective CO2
Adsorption on Chemically Modified Carbon Surfaces. Aerosol and Air Quality Research 16, 3312-3329 (2017)
[3] Kim D. W., Jung D. W., Adelodun A., Jo Y. M.: Evaluation of CO2 adsorption capacity of electrospun carbon fibers
with thermal and chemical activation. J. of Applied Polymer Sci., 434-455 (2017)
804
PROCESS GAS PURIFICATION BY CENTRIFUGAL COOLING DEVICE
S. B. KIM1, J. H. KIM1 J. M. OH2, Y. G. PARK3, A. KIM4, Y. M. JO2

1 Korea Institute of Industrial Technology, Ipjang, Korea.
2 .Kyung Hee University, Yongin, Korea.
3 Kangwon National University, Samcheok, Korea.
4 Chungryu FnS Co.,Ltd, Seoul, Korea.
Abstract
Renewable energy has been of interests in the area of modern alternative fuels. A typical renewable
energy, biogas is produced through the anaerobic digestion processes in wastes landfill sites
including hydrolysis, acidogenesis, organic acid fermentation (acetogenesis), and methane
fermentation (methanogenesis). High contents of fine dust and moisture limited its utilization for
direct combustion, manufacture of town gas and vehicle fuel. Thus this study proposed a new design
of a cooling device using a centrifugal cyclone for simultaneous removal of fine dust and moisture as
a pretreatment of purification processes. A heat exchanger and an I.D fan, which were installed
inside and outside of the cyclone as seen in Fig. 1, facilitated to cool the humid gas down to the
below of the freezing point and formed foggy mist. Such an atmosphere enhanced to capture fine
dust as recirculating the cold mist flow. The water removal rate was 80.8% at a relative humidity of
95%, and the particle removal efficiency was 98.3% for 2.5 μm. Simultaneous removal efficiency was
70.8% and 99.6% for particle and moisture respectively.
Figure 1: Schematic of cyclone cooler.
References
[1] Castellani B., Rossi F., Filipponi M., Nicolini A. : Hydrate-based removal of carbon dioxide and hydrogen sulphide
from biogas mixtures : Experimental investigation and energy evaluations, J. of Biomass and Bioenergy, 330-338
(2014)
[2] Soreanu G., Be´land M., Falletta P., Edmonson K., Svoboda L., Al-Jamal M., Seto P. : Approaches concerning siloxane
removal from biogas, Canadian biosystems eng., 53, 8.1 –8.18 (2011)
[3] Park Y.O. : Cybag filter, The magazine of Soc. of Air-conditioning and Refrigerating Engineers of Korea, 36, 4-12
(2007)
805
ETHANOL PRODUCTION FROM HIGH SOLIDS LOADING OF RICE STRAW BY

SIMULTANEOUS SACCHARIFICATION AND FERMENTATION USING A NON-
CONVENTIONAL REACTOR
R.C.A. CASTRO1, S.I. MUSSATTO2, I.C. ROBERTO1

1 Departamento de Biotecnologia, Escola de Engenharia de Lorena, Universidade de São Paulo,
CEP:12602-810, Lorena, São Paulo, Brazil.
2 . Novo Nordisk Foundation Center for Biosustainability, Technical University of Denmark,
Kemitorvet, Building 220, 2800, Kongens Lyngby, Denmark.
Abstract
A non-conventional reactor, specifically a Vertical Ball Mill (VBM) reactor equipped with a three-disk
impeller (Fig 1) was recently employed to assess the profile of rice straw enzymatic hydrolysis as well
as the ethanol production from glucose by Kluyveromyces marxianus (Castro, et al. 2017). In the
present work, the efficiency of the VBM reactor for simultaneous saccharification and fermentation
process (SSF) at high solids content by K. marxianus was evaluated. Initially, an experimental design
was performed to optimize the conditions of temperature (40-46 °C) and number of glass spheres (0-
30 units) employing pre-treated rice straw at 8% w/v initial solids and 1.0 g/L of cells. Under the best
SSF conditions (41.5 °C, 18 glass spheres, 200 rpm) assays were also carried out at 16 and 24% (w/v)
biomass loading, in batch mode, aiming to increase the final ethanol titre. The results showed that
the performance of the process was similar at 8 and 16% biomass loading (Q P ~1.4 g/L.h and ethanol
yield ~86%). However, by increasing the solids to 24%, all the parameters evaluated decreased
dramatically (QP ~0.7 g/L.h and ethanol yield ~43.5%) suggesting a mass transfer limitation. In order
to overcome this drawback, three different feed profiles were investigated in fed-batch SSF using
24% pre-treated rice straw. Gradual feeding of substrate (starting with 16% + 4% at 10 h + 4% at 24
h) resulted in high ethanol concentration (52.3 g/L) with an overall productivity of 1.1 g/L.h and
ethanol yield of 67.5%. These findings demonstrate that the VBM reactor has an efficient and
promising configuration for use on the cellulosic ethanol process at high solid loadings.
//
//
Figure 1: Illustration of the Vertical Ball Mill (VBM) reactor (Castro et al. 2017)
References
[1] Castro, R.C.A., Mussatto, S.I., Roberto, I.C.: A vertical ball mill as a new reactor design for biomass hydrolysis and
fermentation process. Renewable Energy. 114, 775–780 (2017).
Acknowledgments: FAPESP (2013/13953-6 and 2015/24813-6) and CNPq.
806
THE USE OF CASSAVA HARVEST RESIDUES (MANIHOT ESCULENTA CRANTZ) IN

THERMAL CONVERSION PROCESSES FOR BIOENERGY PURPOSES: A
LITERATURE REVIEW
A.L.P. RODRIGUES1, M.E.P. SOUZA2, G. CRUZ,1,2 W.C. GOMES1

1Ceuma University - Master Science in Environmental, São Luís - MA, Brazil.
2Federal University of Maranhão - Department of Mechanical Engineering, São Luís - MA,
Brazil.
Abstract
Bioenergy is regarded as an attractive, low-carbon energy source because it supports

environmentally friendly conversion of biomass to bioenergy, and has low CO2 emissions.
Several studies about determination of the physico-chemical characteristics of crop
residues, such as olive seeds, rice husks , soy, sugarcane bagasse between others. There is
still a lack of detailed information on the use of cassava residues for energy applications.
This research evaluates the "state-of-art" of the characterization of residues cassava harvest
and use in the bioenergy industry. Regarding the available literature for this biomass,
several pretreatment techniques including mechanical, chemical, thermal, ultrasonic and
wet blast were observed. Structural and compositional analyses revealed that cassava
residues were discussed. Authors studied the use of cassava residues for described the
characteristics and behavior of this residues as biofuel, through thermal processes
(combustion, oxy-fuel combustion, gasification and pyrolysis). However, a problem
identified in use of agricultural biomasses in thermal processes is the high ash content (≈
25% to 35%), where 60% of these ashes contains metals or oxides. Use of cassava residues
in thermal processes can increase the viability of this raw material for the production of
biofuels and/or in power cogeneration units. Further studies are recommended and should
carried out to evidence the use of cassava residues in thermal conversion processes.
Key-words: characterization of residues; cassava; thermochemical conversion
807
1. INTRODUCTION
According to International Energy Agency (IEA), biomass energy accounts for about
14% of the world's total primary energy supply [29]. Lignocellulosic biomass is the most
abundant and renewable material in the world for the production of biofuels, which can be
used as a fuel alternative resource to replace fossil resources[54] ;[69]. The biomass
conversion into energy is an alternative that will help reduce dependence on fossil fuels, as
well as mitigate negative social and environmental impacts, such as rural unemployment
and global warming [55].
With the growth of research into alternative energy sources, the use of biomass is
an attractive option and attracted considerable interest since the 1990’s, as a way to
mitigate global climate changes [25] ;[55]. The bioenergy production from biomasses or
agricultural wastes has gained significant interest also because of rising and prices fossil
fuelscarcity. Several studies on the determination of the physicochemical characteristics of
crop residues, such as corn cobs and straws, rice husk, olive seeds, sugarcane bagasse
among others [64];[21]; [22]; [16]). Detailed informations on the use of cassava residues for
the energy applications are still missing.
Cassava is a perennial plant of the genus Manihot esculenta Crantz. The main
producer countries of cassava in world are Nigerian, Brazil, Thailand and Ghana in order[78].
Cassava is a shrub cultivated extensively as an annual crop in tropical and subtropical
regions, and their root is an edible starchy tuberous [21].Cassava residues are available in
the fields after harvest[83];[32]). This crop is the 5th most important staple crop in the
world, with a production about 285 million tons/year of unprocessed roots [24]; [11].
It is noted that few papers discuss the use of cassava residues as an energy source.
Pattiya [58,59]characterized the cassava wastes for its use as fuel in Thailand, and classifying
the stalks and seed stem as residues, and characterized them physically and chemically. [84]
quantified and characterized the cassava residues by thermogravimetric analysis at oxidizing
and inert atmospheres for studying the residues behavior as biofuel. [2] recently conducted
a review on the use of pre-treated cassava residues in biological and thermal processes.
Within the above, this research addresses the "state–of-art" for the residues
characterization - from cassava harvest and use in the bioenergy industry. Regarding the
available literature for this biomass, several pretreatment techniques, including mechanical,
chemical, thermal, ultrasonic and wet blast were observed. It is also discussed the use of
cassava harvest residues for the bioenergy production by thermal processes (combustion,
gasification, pyrolysis and oxy-fuel combustion).
2. CHARACTERISTICS CASSAVA
2.1 What is cassava?
Cassava (Manihot esculenta Crantz) is an edible tubercle rich in starchy and other
carbohydrates (Fig. 1). It is produced in almost all tropical countries and grows in degraded
soils, where almost nothing else can grow [37]. Furthermore, cassava can be harvested
anytime after planting, e.g., between 8 to 24 months [17]; [55].
808
Fig. 1. Cassava husk
The cassava starch, it has several industrial applications that create a huge global
business and can be found in the manioc roots (raw material). The starch content present in
the cassava roots varies from region, climate, soil and crop type, ranging from 20 to 32%,
while water content in the roots is about 60% [13].
After removal of the tuberous roots, cassava harvest residues and plant branches are
estimated from 144 to 257%. Use of cassava stems, leaves as forage or addition of roots
wastes to prepare animal feed flour, is due their high nutritional value (Bose et al., 1984).
Several steps are involved in cassava roots processing to obtain industrial products, such as
starch and cassava flour (tapioca): peeling and washing, grating, pressing, disintegration,
sifting, drying, milling and screening [80].
2.2. Cassava Composition
The main composition of the cassava is starch and carbohydrates, with proteins,
vitamins and minerals traces ([28]). Carbohydrate contents of in natura cassava were
estimated at 35% [27]. [50] evaluated the carbohydrate contents of the whole cassava root,
peeled roots as 37.9% and 28.8%, respectively. Cassava samples also contains significant
amounts of calcium (Ca), phosphorus (P), zinc (Zn), magnesium (Mg), copper (Cu), iron (Fe),
manganese (Mn), potassium (K) and vitamins, such as C, folates, thiamine, pyridoxine (B6
vitamin), ribofin and pantethenic acid. [84]
[84] presented results of elemental analysis for the different crops and cassava varieties
and observed that few variations were found between the different plant parts, except for
nitrogen content (N), which presented highest amounts, i.e. 1.7% for thin stems and 0.27%
for thick stems. In another cassava variety, for example, in the samples of IAC 14, IAC 90 this
concentration ranged between 0.55 and 0.80%. It was observed that knowledge of the N
content is necessary for estimating the nitrogen oxides (NOx) formation through the NO-fuel
mechanism in waste combustion processes [59].
2.3 Characterization of Cassava Residues
The cassava residues are mainly composed of holocellulose, i.e. hemicellulose and
cellulose together (46.7 wt%) and starch (38.4 wt%), with relatively low contents of lignin
809
(5.7 wt%), ash (1.9 wt%) and other components (7.3 wt%). Therefore, from the composition
point of view, the use of low lignin cassava residues (5.7% by weight) would be favorable for
applications in thermal processes [59].
The physical-chemical properties of the cassava ashes content ranged from 2.5% to
3.5%, reaching about 6.0% in unwashed samples. Approximately 60% of the ashes are
formed by alkaline oxides, especially P2O5 (phosphoruspentoxide), K2O (potassiumoxide)
and CaO (calcium oxide), which have low melting points, approximately XX °C [84].
Most of the energy contained in the roots (about 120 kcal 100 g-1) is recovered as starch,
totaling about 70% of the initial energy content [84]. Bagasse contains 15% of the root's
edible calories, with an energy content of 29 kcal 100 g-1 along with residual fibers and lignin
[11].The use of such residues also contributes to prevent pollution and represents a possible
source of income (Ki et al.2013).
[82]) carried out the proximate analysis of the cassava husk and results found were:
21.4% for fixed carbon, 74.5% for volatile matter, 2.3% of ash and moisture of 1.8%. High
Heating Value for this biomass was 17.9 MJ kg-1.Table 2 summarizes the main characteristics
of the cassava plants [81].
Table 2. Characteristics of the residues from cassava plants [81].
Proximate Cassava
Cassava stalk hizome
analysis (%)
Volatile matter 79.9 77.7
Fixed carbon 14.1 18.2
Ash 6.0 4.1
Moisture 15.5 8.3
Heating value (MJ kg-1, dry basis)
HHV 17.6 23.7

LHV 18 18.5
3. MAIN TECHNIQUES OF PRETREATMENTS FOR THE CASSAVA BIOMASS - AN OVERVIEW
Agricultural biomasses present physical-chemical properties that must be considered for

thermal engineering applications, such as: density, fluxability, grindability, moisture
sorption, ash and volatile materials content, thermal properties and energy content [10].
Cassava stems, for example, residues after harvesting starchy roots, are a potential
biofuels resource. However, high concentrations of ash and some elements, such as Cl, K, P,
S, among other in the cassava stems samples may cause severe deposition, corrosion and
particle emissions, in addition to slagging during combustion process [27].Therefore,
adequate pretreatment is necessary to reduce such problems.
3.1. Mechanical Pretreatment
810
The mechanical methods need an initial energy to disrupt non-covalent forces between
the cassava cells.[53]In these cases, chemical modifications in the organic matrix rarely are
observed, and when they occur, may not be significant [3].Peltola et al. (2004) observed an
increase of approximately 60% in soluble content by using mechanical pretreatment for the
municipal solid wastes samples.
[61] performed the pretreatment of the cassava basket by mechanical activation, using a
self-designed agitator ball mill. This activation significantly altered the properties of the
cassava residues, causing an increase in amorphism and hydrogen bonding energy, which
decreased crystallinity index and crystallite size, but not alter the cellulose crystal type.
Some advantages and disadvantages to this pretreatment technique were observed. For
example, an advantage by use of an agitated ball mills, can be obtaining of a solubilization
among 10 and 30% and an increase from 10 to 20% in the biogas production ([8];, [42]. On
the other hand, disadvantages for using of this technique are capital and operational costs
[67].
3.2. Chemical Pretreatment
Chemical pretreatments such as acid, alkaline or ozone can be used (Silverstein, 2007).
Ozone treatment produced a 4100% increase in the biogas production, while alkaline
treatment produced from 25 to 100% increase in biogas yields, as well as in the methane
production)[21].
The use of these pretreatments also presents some advantages and disadvantages. For
instance, with the alkaline method, solubilization ranged from 30 to 60%[79]), although the
increase of non-biodegradability is main disadvantage for using this technique. Whereas
ozone technology can improve on 30% of solubilization, but this pretreatment causes the
structure destruction [52].
[90] investigated the cassava residues pretreatment by thermally diluted sulfuric acid
hydrolysis through of statistically designed experiments. Results obtained indicated that the
hydrolysis, using dilute sulfuric acid, is adequate to predict the ideal pretreatment condition,
which showed be effective for cassava wastes pretreatment, increasing the methane
yield.[73]) submitted the cassava bagasse and husk samples to alkaline treatment with 5%
w/v KOH (potassium hydroxide) solution (1:18 ratio) at 25 °C and suspensions were shaken
mechanically for 14 h.
[47] carried out chemical characterization of cassava stems from different origins from
South China and Xinxuan. The autors submitted the cassava stems to a saccharification,
including starch hydrolysis, pretreatment with sulfuric acid or 1-ethyl-3-methylimidazolium
acetate and cellulose enzymatic hydrolysis. Pretreatment resulted in 20% higher glucan
conversion than pretreatment with sulfuric acid.
[40] characterized cassava bagasse nanofibers and peels, for isolating of the nanofibers,
were used a pretreatments combination (alkaline treatment and chelating treatment, and
bleaching), acid hydrolysis and a final step of ultrasonic disintegration. The acid hydrolysis
was conducted at constant temperature of 60 °C and acid concentrations of 30, 40 and 50%.
811
3.3. Thermal Pretreatment

According to [23] thermal pretreatment can increase the biogas production and
methane yield of certain substrates, but is not an effective technique in all cases. For
example, thermal pretreatment of hyacinth water at 80 °C increased slightly their solubility
to xx%, with few or no effect on the anaerobic digestion. Pasteurization process of abattoir
wastes at 70 °C for 1 h, produced a fourfold increase in methane yields, however the
application of this pretreatment not can be generalized when different biomasses are
employed[1].
[12] temperatures below 100 oC are used to breakdown plant cells, increasing
membrane fluidity and hydrolyzing polymers, resulting in a soluble COD release of
approximately 35%. This thermal method causes modifications in the exopolymers chemical
equilibrium in the lignocellulosic biomasses.
Thermal pretreatment was applied by [1] for the optimal release of fermentable sugar
from cassava husks. Used the response surface design method to investigate the effect of
immersion temperature, immersion duration and autoclave, acid concentration and solid
loading on the sugar yield reduction, obtainig optimal pretreatment conditions and
immersion temperature of 69.62 °C.
3.4. Ultrasonic Pretreatment
Pretreatments based to ultrasound irradiation has been employed as isolated technique
or combined with other technologies. Such combinations include acid pretreatments,
alkaline, ionic liquid and ozone or with a physical technique, for example, microwave
irradiation, thermal and supercritical carbon dioxide, for the pretreatment of lignocellulosic
biomasses and wastes for improving biofuel production [80].
Ultrasound present a spectrum ranging between 20 and 10 MHz and their tone is above
of human hearing, which can detect sounds up to 16 kHz [51]. This process catalyzes the
biopolymers depolymerization, emulsification, vegetables tanning oils extraction from
almond, ginger, and wood seeds [9]. Electron beam and gamma-irradiation, microwave and
ultrasound energies present certain advantages over energy conventional source, and there
is an opportunity that these energies can be exploited for biomass pretreatment
[9].However this may not be suitable for energy crops such as cassava wastes.
3.5 Wet explosion pretreatment
The wet explosion process was developed as a combination of thermal and chemical
oxidation [12]. [85] used wet explosion pretreatment for enhancing methane production
from energy crops, such as cassava wastes and other agricultural residues. The results
showed an increase in the sugars release after pretreatment, but not implying at higher
methane yield.
4. THERMOCHEMICAL CONVERSION PROCESSES
Thermochemical conversion of biomass includes a great processes number, such as
direct combustion, liquefaction, gasification, pyrolysis and oxy-fuel combustion [57]. From
812
techniques presented, pyrolysis is the more usual in the biomass thermochemical

conversion processes, to produce solid and liquid fuels, both are easy to handle and
transport [57].
Direct combustion is major thermal conversion route to provide heat, liquid fuel and
other elements, for generation processes of thermal heat and electricity. Fig. 2 summaries
the main processes used for this production [56].
Fig. 2. Thermochemical conversion routes for biomasses or solids fuels (Panwar; Kothari; Tyagi, 2012).
Regarding to thermal characterization, [33] analyzed the thermo-oxidative degradation

of cassava starch, using thermogravimetric analysis (TGA) and derived thermogravimetry
(DTG). [57]analyzed thermal degradation of hemicellulose and cellulose of cassava wastes
occurred at temperatures between 200 and 350 °C, while residual lignin was decomposed at
higher temperatures, typically between 280 and 500 °C.
4.1 Direct combustion
Combustion is a process widely used to convert stored chemical energy in the biomass
into heat, mechanical energy or electricity, using various processes and equipments, such as
stoves, ovens, boilers, steam turbines and turbo generators [18].This is a known technology,
although improvements in performance are still possible).
Several studies have been devoted to the agricultural wastes combustion in fluidized
bed systems, using sand as fluidizing ([45];[60]). These studies focused mainly on fluorinated
gaseous emissions, efficiency and ash related problems, such as fouling and bed
agglomeration [78]. Combustion performance in efficiency terms and emissions has been
reported to depend heavily on fuel properties as well as on system design characteristics
and operating parameters, such as fluid velocity, bed temperature and fuel feed rate[12;
34].
Fixed or fluidized beds and drag reactors are three typical combustion systems, with an
increase in the velocity of the carrier gas inside the reactor.A higher gas velocity imply into
an intensive mixing of the feedstock, which improves combustion efficiency and heat
exchange rate [45].The flushed flow systems are expected to exhibit the best performance
813
among these three types of combustion systems [78]. However, none study about direct
combustion of cassava harvest residues in reactors was found during our research.
4.2 Pyrolysis
Pyrolysisto convert biomass into solid charcoal, liquid (bio-oil) and gases at elevated
temperatures ([45]). This process can be divided into three subclasses, i.e. slow, flash and
fast pyrolysis[86]. Thermogravimetric analysis is essential for understanding the
decomposition behavior of the raw material, before pyrolysis of the laboratory scale is
performed [72].
[51] investigated the pyrolysis process of cassava rhizome, utilizing the flue gas in a
laboratory scale metal kiln. Reported that charcoal yield of the dry cassava rhizome ranged
from 26 to 35%, depending on the pyrolysis temperature and fast pyrolysis time was found
from 19 to 38 minutes.
Fast pyrolysis is a process that needs high heating rate and short residence time. In
particularly, favors the liquid products formation, but inhibits the solid chars formation[48]).
Their liquid products (bio-oils) are composed of an aqueous phase, which contains several
organo-oxygen compounds of low molecular weight, and a non-aqueous phase (tar), which
includes a variety of insoluble aromatic organic compounds of high molecular weight [77])
[72] and [73] studied the utilization of cassava residues for the bio-oil production by
pyrolysis process. Also used rhizome and cassava stalk as feedstock to obtain bio-oil by fast
pyrolysis process in two reactors types: fluidized-bed reactor [72] and free-fall reactor [73].
[36] used the cassava husk as raw material to produce bio-oil through slow pyrolysis
process in a fixed bed reactor. The yield percentage of solid, liquid, and gas products
obtained from slow pyrolysis of cassava peel at temperatures ranging from 400 to 600 °C
are shown in Table 3. How can be observed the char yield diminished from 37.5% to 20.8%,
while gases yield continuously raised from 23.8% to 37.6% with increase of the
temperatures from 400 to 600 °C.
Table 3. Yield and products distribution from slow pyrolysis process of cassava peel [36]
T (°C) Experimental Simulation

Solid (wt.%) Liquid (wt.%) Gas Solid (wt.%) Liquid (wt.%) Gas
(wt.%) (wt.%)
400 37.5 38.7 23.8 41.3 34.6 24.1
425 34.3 41.8 23.9 37.9 38.0 24.2
450 29.6 46.9 23.5 32.7 43.0 24.4
475 26.8 48.2 25.0 29.5 46.0 24.5
500 25.1 50.3 24.6 27.6 47.8 24.6
525 24.3 51.2 24.5 26.7 47.5 25.7
550 22.9 48.7 28.4 25.4 47.4 27.4
575 21.4 45.4 33.2 23.2 43.6 32.8
600 20.8 41.6 37.6 22.9 43.4 33.7
Mean squared error (MSE) 13.37 16.24 0.
49
Determination coefficient 0.96 0.95
(R2) 0.99
814
The physicochemical properties of the bio-oil resulting from cassava residues

pyrolysis are shown in Table 4. The flash point of the resulting bio-oil was 1.73 times greater
than the ASTM requirement, indicating handling and storage safe of the liquid fuel in a high
temperature ambient [67].
Table 4. The physicochemical properties of resulted bio-oil of cassava residues [67]
Properties Bio-oil ASTM

D7544
High Heating Value (MJ 27.43 15 min
kg-1)
pH 4.26 –
Kinematic viscosity (cSt) at 35.8 125 max
40 °C
Density (kg dm-3) at 20 °C 1.27 1.1–1.3
Pyrolysis solids content 0.12 2.5 max
(%)
Water content (%) 23.74 30 max
Sulfur content (%) 0.01 0.05 max
Ash content (%) 0.08 0.25 max
Flash point (°C) 78 45 min
4.3 Gasification
Gasification process is conversion of solid fuel into gaseous fuel, chich can be used in
wide applications. This thermochemical conversion process is carrid out at elevated
temperature range of 800–1300 ◦C, occurring under various chemical reactions [15].
[19] reported that optimum operation of a gasifier was found of approximately 1.50 Nm3
kg-1 of the air-fuel ratio, for a wet feed rate of 4.48 kg h-1, which produces a gas with High
Heating Value of about 5 MJ m-3 at a volumetric flow of 9 N m3 h-1.
An experimental apparatus used for biomass gasification experiments is illustrated in
Figure 3.
Figure 3. Experimental schematic apparatus for the biomasses gasification [19]
Most commercial gasifiers are downdraft type, fluidized bed systems and upstream,
such classification depends on the biomass feed way, which can be from top, bottom or side
of the gasifier [65].One reactor specific type is not necessarily suitable for all power ranges,
815
i.e. each reactor is operated in an adequate range. For example, fixed bed is suitable for
smaller scales, ranging from 10 to 10 MW; fluidized bed is more suitable for intermediate
units from 5 to 100 MW; while drag bed reactors are used for large scale power plants
higher to 50 MW [4].
[73] proposed cobalt catalysts for the catalytic gasification of cassava rhizome, which
represented an important stage in the hydrogen rich gas production, suitable for internal
combustion and direct industrial gas turbine. Also compared the production of non-catalytic
synthesis gas from cassava rhizome at temperatures from 873 to 1073 K. Lower Heating
Value (LHV) of the gas produced was 8.11 MJ m-3 compared to the non-catalytic LHV of 4.12
MJ m-3.
4.4 Oxy-fuel combustion
Second [62] the CO2 emissions can be reduced of different ways i.e., water absorption at
high pressure, combustion in the presence of calcium oxide, oxy-fuel combustion, and
electrical absorption. Among the CO2 reduction methods cited, oxy-fuel combustion is
considered one of the more important and promising options for CO2 sequestration, due to
their ability for a significant reduction in the operating costs [66].
Some researchers ([78] [79], [12], [24]) focused their attentions on the mathematical
models development to predict the coal combustion, gaseous emissions and combustion
chambers performance. It was observed in this research that biomass are not extensively
investigated and applications of oxy-fuel combustion using cassava residues not were found.
5. CONCLUSIONS
After extended research about the several know ways for the termoconversion
(conventional combustion, pyrolysis, gasification and oxy-fuel combustion) from cassava
harvest residues and agricultural wastes in bionergy or biofuels, it was observed that still
lack many information and specific applications for such biomass, which leads the
researchers to the developing of studies more applied to the reality of each Country.
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ENERGY VALORIZATION OF GRASSES BY DRY PROCESS
J.F. LARGEAU1, M. TAZEROUT1

1 IMT Atlantique GEPEA UMR 6144, Département Systèmes Energétiques & Environnement. 4, rue
Alfred Kastler, BP 20722, 44307 NANTES Cedex 3, France.
Abstract
Background:
Currently grasses in Europe, are not valorised in energetic point of view (as fuel). They are mainly
abandoned on the ground or used for compost. In all cases, without treatment, internal moisture of
grass will quickly start the fermentation and decomposes carbon molecules (48h are enough).
The aim of this work is to explore in one hand, technical solutions for conditioning grasses (energy
storage) and other hand, processes in order to convert this biomass energy into fuel by dry way
(pyrolysis/gasification). Even if grasses are an abundant resources, all this conversion chain must be
also economically acceptable.
Materials/Methods:
The energetic potential of garden grasses was evaluated (moisture, ashes rate, lower heating value,
elementary chemistry (CHNS)). Different approaches were study to decrease the moisture level in
order to obtain a good stabilization of the grasses biomass and to obtain something compliant with
energy storage or pyrolysis/gasification processes.
The thermo-kinetic decomposition behaviour was studied with TGA and DSC analysis methods in
order to determined kinetic parameters: activation energy and pre-exponential factor (Kissinger and
Flynn/Wall/Ozawa).
Results:
The lower heating value is evaluated at 4,6kWh/kg with an ashes rates of 7%, so grasses are
interesting for energetic valorization but the level of moisture is until to 80%. With air drying system
and compression process, moisture could decrease to 20% for the pebble and the pellet shapes
studied.
Analysis of experiments in term of kinetic model give an energy of activation about 7.3 KJ/mol for
the main degradation (Kissinger Model’s). Conditioned grasses biomass is being studied by pyrolysis
in order to link Flynn/Wall/Ozawa activation energy parameters with the formation of major gas
components.
A macro-TGA is being developing in order to take into account of the inhomogeneous properties of
the biomass and check the validity of kinetic models. Results are being compared with other studies
on herbs valorisation ([1], [2] for example).
References
[1] Guo, F.,Dong, Y., etal “Pyrolysis kinetics of biomass (herb residue) under isothermal condition in a micro fluidized
bed,” Energy Convers. Manag., vol. 93, Pages 367–376, 2015.
[2] Wang, P., Zhan, S. etal, “The effects of temperature and catalysts on the pyrolysis of industrial wastes (herb
residue),” Bioresour. Technol., vol. 101, no. 9, Pages 3236–3241, 2010.
823
ASSESSMENT OF THERMAL PROPERTIES OF DRIED FISH WASTE
B. GCOBO*1, D.I.O IKHU-OMOREGBE1

1
Department of Chemical Engineering, Cape Peninsula University of Technology, Cape Town 8000,
South Africa
*
Corresponding author: busigcobo@gmail.com; Tel. +2721 9596130
Keywords: Dried fish waste, Higher heating value, Ultimate analysis, and Proximate analysis
Abstract
The increasing consumption of fish products, owing to its nutritional value and the diet
consciousness of consumers has led to high fish waste generation. The high volume of fish waste
generated and the current disposal methods have become problematic as it poses serious human
health and environmental risks such as unpleasant odour, emissions of obnoxious gases,
groundwater contamination and oxygen depletion in the marine environment. The composition of
fish waste e.g. organic compounds, lipid and protein makes it a potential waste material for energy
production, however, the exploitation of this resource as fuel in thermal application requires
knowledge of its higher heating value (HHV) and physicochemical characteristics. The present work
explored the possibility of using fish waste for energy production by determining its energy content,
proximal and ultimate analysis. This was achieved by drying the fish waste up to an average of 8wt %
moisture, subsequent to evaluating the HHV and the proximate analysis. The data obtained was also
compared with the reported studies. The HHV was determined experimentally by combusting dried
fish waste (DFW) under higher pressure oxygen (3000Kpa) in a bomb calorimeter. The
thermogravimetric analysis (TGA) was used to assess the weight loss behaviour of the sample and
obtain the proximate compositions in terms of volatile matter, fixed carbon, ash and moisture
content of dried fish waste. The results obtained showed an average HHV of 20.31 MJ/kg, which is
comparable to catering food waste (21.65 MJ/kg), and the MSW (19 MJ/kg) from Cape Town, South
Africa. The study also found a maximum waste degradation averaged of 85 wt%, achieved at
temperature above 500 °C. Findings from this study demonstrated the potential of fish waste as a
source of energy with significant HHV.
824
1. INTRODUCTION
Global fish consumption has increased by over 100% from 1990 to 2014 [1]. This rapid increase has
been attributed to the growing recognition of fish nutritional value and the diet consciousness of
consumers shifting towards a healthy lifestyle. Fish products, in addition to its important health
benefits, are often the cheapest and most frequently consumed animal protein food source,
therefore, play a vital role in eliminating hunger and malnutrition in poor communities [2, 3]. Despite
the high demand of fish products, the global supply for human food has been sustained and growing
steadily at an average rate of 3.2 % annually [1]. According to FAO [1] estimate, world fisheries and
aquaculture production currently supplies about 167.2 million tonnes of fish. In South Africa, about
600 000 tonnes of fish are produced every year, with an estimate of 312 000 tonnes being destined
for human consumption [4]. The expansion in global fish supply and consumption has led to high
amount of wastes generation.
Fish processing industries generate a significant amount of waste, which has become detrimental to
both human health and the environment globally. During fish processing operations, waste materials
composed of heads, tails, bones, viscera and sometimes whole fish rejects are produced. These
materials are highly perishable and decompose rapidly at uncontrolled conditions; therefore, the
safe disposal of fish processing waste is necessary to prevent hygienic problems and pathologically
transmissible diseases. Currently, fish waste is disposed in landfills and the marine environment, and
in few developed countries, it is also converted into animal feed products such as fishmeal. In South
Africa, there is insufficient information documented on fish waste management, however, it is
reported that landfilling is the most practiced method for waste management in the country [5–7].
These disposal methods, apart from health issues, also create environmental pollution such as
unpleasant odour, emissions of obnoxious gases, groundwater contamination and oxygen depletion
in the marine environment.
Although landfilling is generally considered the most practical and the cheapest waste management
method in many countries, including South Africa, the scarcity of land as well as environmental
impacts (landfill gas emission) caused by disposal of organic waste (including fish waste) have made
this method a less attractive management system [8]. Thus, the development of effective treatment
technologies and environmental protection strategies have become necessary, mainly to achieve
changes required in addressing the impacts of global warming. Alternative treatment technologies
such as Waste to Material and Waste to Energy have been investigated worldwide, with a focus to
divert waste from landfills. Among alternative resources, Waste to Energy Technology has received
global attention and it is seen as a promising clean and environmental friendly strategy to reuse
waste and improve its economic value, reduce disposal costs, and simultaneously achieve a
renewable energy supply [9] This method, particularly combustion technology, has been used to
convert various types of biomass such as wood, wood crops, agricultural wastes and animal waste
into energy to heat up homes, especially in rural areas [10]. Recently, studies on the waste materials
such as municipal solid waste (MSW), refused derived fuel (RDF) and wastes from food processing as
825
important sources of energy has gained growing interest because of their high content of organic
matters and the accumulation rate [11]. Arena [12] reported the conversion of MSW components to
fuel via thermochemical approach. Caton et al. [9] explored the possibility of utilising food waste for
energy recovery. However, the exploitation of waste resources as fuel feedstock in thermal
applications requires knowledge of its physicochemical characteristics and the understanding of
waste degradation behaviour during thermal processing to ensure optimisation and maximise their
energy efficiency [10, 13, 14]. Numerous studies report on essential characterisation, including
proximate analysis, energy content determination and ultimate composition, mainly for
understanding, predicting and evaluating the thermal performance and the use of wastes as an
energy source [10, 15].
In the design of thermal systems for the conversion of solid fuels and the optimisation of their
operating conditions, information on proximate composition is essential [14, 16–19]. Proximate
analysis measures the contents of moisture and ash, volatile matter as well as the fixed carbon
present in a fuel. These variables are important in predicting the material behaviour as a fuel in
thermal conversion, for example, moisture and ash contents affect the ignition and heat available for
combustion, resulting to lower process yield [16, 20], while presence of high volatile matter signifies
good ignition point and lower excess oxygen demand for a complete combustion [21].
The higher heating value (HHV) is the measure of total chemical energy released during combustion
of the fuel and it is strongly influenced by the amount of moisture contained in the material [22].
Determination of HHV is important for defining the energy content of a fuel in order to evaluate its
suitability as an energy source and for the design of thermal process to extract its energy. The study
by Carton et al. [9] explored the food waste potential for energy recovery. The study measured the
chemical composition, moisture and higher heating value (HHV) (21.7MJ/kg) of food waste, and
compared with the same analysis of wood. In another study by Shi et al. [14], the HHV of MSW was
determined using a developed empirical model based on ultimate analysis. Hlaba et al. [23], assessed
the calorific value of MSW from the city of Cape Town’s landfills.
Apart from the above mentioned factors, HHV is also influenced by the elemental composition of a
fuel. The composition of carbon (C), hydrogen (H), and oxygen (O) are the most considerable
components of solid fuels, and they strongly contribute to the heating value. According to Garcia et
al. [15], fuels with high ratio of H to C implies a high volatile content, thus contributes positively to
their HHV. In contrary to high O to C or O to H ratio, this implies a low volatile matter content and
lower heating value. This theory is confirmed by Lewandowuski & Kicherer and Gracia et al. [15, 24]
stating that greater oxygen concentration influences the heating value of a fuel as it decreases nearly
linearly with the increasing oxygen content. Although a considerable amount of research has been
performed on characterisation of solid wastes and assessing their potential for thermal application,
surprisingly, little discussion has been made on fish waste materials. This study aimed to explore the
potential of utilising fish waste as an energy source material by determining its energy content and
proximate and ultimate analysis, and compare the data with different biomass. The study first
826
conducted proximate and energy content analysis to compare the data with typical biomass fuels
(wood, MSW, RDF and food waste). The thermal loss behaviour of fish waste under nitrogen
condition was also evaluated in a thermogravimetric analyser (TGA) and compared with the same
data of typical biomass.
2.1. COLLECTION AND PRE-TREATMENT OF FISH WASTE
The fish waste used in this study was collected from Oceana Group Pty.Ltd Cape Town, South Africa.
Subsequent to drying, the fish waste was collected in iced and insulated container in order to
prevent sample deterioration due to decomposition. Using a laboratory tunnel dryer, the fish waste
was subjected to a temperature of 105 oC until a constant weight of the dried fish waste was
achieved. The dried fish waste was then finely grounded using a miller (Trapp Animal ration shredder
Hammer Miller TRF 400) at ambient temperature into homogeneous particles. The grinded dried fish
waste was then stored (at moderated temperature) in sealed plastic bags until further use.
2.2. ANALYTICAL METHODS
2.2.1. HIGHER HEATING VALUE (HHV)
The HHV was determined experimentally by combusting a mass of 0.5 g of the milled dried fish
waste under high pressure oxygen (3000 kPa) in a bomb calorimeter (e2k, version 3.3, digital data
system). The analysis was conducted in three replicates and the average value was used for HHV.
2.2.2. ULTIMATE ANALYSIS
The determination of elemental composition (carbon, hydrogen, nitrogen and sulphur) of milled
DFW was carried out using CHNS Vario EL Cube elemental analyser. The content of oxygen was
subsequently determined as the percentage difference to the sum of C, H, N, S contents. This study
followed the procedure used by various authors [10, 25].
2.2.3. THERMOGRAVIMETRIC ANALYSIS
In this study, thermogravimetric analysis (TGA) was performed to determine the proximate
composition of the fish waste using thermogravimetric analyser (TG PerkinElmer Pryis). The
derivative thermogravimentric (DTG) analysis was also determined in order to evaluate the
degradation behaviour of the sample. The DFW sample was heated from 20-600 o C under nitrogen
(N2) atmosphere at the rate of 10 o C/min. Thereafter, the temperature was increased to 900 o C at a
heating rate of 20 o C/min and was held for 7 min under nitrogen environment. The carrier gas was
827
o
then switched to oxygen at the same rate held for 30 min at the temperature of 900 C for
combustion process.
3.1. HIGHER HEATING VALUE AND ULTIMATE ANAYSIS
In this work, HHV and ultimate analysis were carried out on DFW and the results are summarised in
table 1. The results obtained were compared with the data found in literature for different types of
biomass. This study showed an average HHV of 20.31 MJ/kg which is not significantly different from
the expected range, of 14-23 MJ/kg reported by other researchers. The elemental composition of
the main components carbon (44.70 wt%) hydrogen (9.25 wt%) and oxygen (38.05 wt%) of the
sample were also in the expected range of general biomass reported in literature. The high
concentration of H and C in the dried fish waste could be attributed to the presence of carbonaceous
materials such as lipids, carbohydrates and protein, which make DFW a potential source of energy
recovery.
Energy
Organic elements (wt %) content
HHV Reference
Biomass materials C H O N S (MJ/kg)
Fish waste 44,70 9,25 38,05 7,65 0,35 20,31 This study
Food waste 50,70 7,10 31,50 3,78 0,27 21,70 [9]
Agri-food waste (grape marc) 42,20 3,50 39,30 3,00 0,25 16,97 [26]
Agri-food waste (tomato residues) 59,40 7,60 23,40 1,60 0,35 21,17 [26]
MSW - - - - - 19,00 [23]
Biomass (Khasiana) 41,26 5,38 52,09 1,25 - 13,29 [27]
Table 1: Ultimate analysis and HHV of the dried fish waste compared with different biomass (wt% on
dry basis) Where: C=carbon, H=hydrogen, O=oxygen, S=sulphur content
The HHV of the dried fish waste as seen in table 1 was found very comparable to that of food waste
(21.7 MJ/kg), with slightly lower carbon and high oxygen content as reported by Caton et al. [9]. This
value is also in agreement with the findings by Agrawal et al. [16] for various cellulosic materials such
as paper, food waste and garden waste, which gave an HHV of approximately 20 MJ/kg. However, in
comparing fish waste with lignocellulose biomass (Khasiana), Singh et al. [27] reported a lower HHV
with slightly lower carbon and hydrogen content but greater oxygen content. From these presented
studies, it can be deduced that HHV of these biomass materials was positively influenced by carbon
and hydrogen content, while decreases linearly with the increase of oxygen content. These
observations are in line with the statements made by various researchers [13, 15, 24].
828
3.2. THERMOGRAVIMETRIC ANALYSIS OF DRIED FISH WASTE
In this study, thermal degradation behaviour and proximate composition of the dried fish waste
were also investigated using TGA method. The aim of this analysis was to evaluate the
decomposition behaviour of the dried fish waste in thermal conversion processes by observing the
significant weight loss of the material during the conversion. The experimental data from TGA was
used to generate the thermogravoimetric (TG) and derivative thermogavimetric (DTG) curves as
shown in figure 1. These curves were then used to estimate the proximate composition (moisture
content, volatile matter, fixed carbon and ash content) and inspect the rate of weight loss of the
sample. From figure 1, it can be seen that four stages of DFW decomposition were exhibited during
heating. The first minor decomposition occurred at temperature between 108-142.2 oC, which
indicated the evaporation of water from the sample. The remaining three stages displayed significant
weight loss, which represent the decomposition of volatiles after the removal of moisture. Out of
these three distinct decomposition stages, it can be deduced that the first and the second peaks
could be attributed to the decomposition of carbohydrates and proteins, and the third
decomposition stage between temperatures of 210-500 oC could represent the decomposition of
lipids. Similar observation based was reported where the maximum decomposition of lipids was
achieved at temperature of 550 oC [28].
TGA Curves
100 -6
Derivative weight %/min

80 -5
Sample weight %
TG
-4
60 DTG
-3
40
-2
20 -1
0 0
0 100 200 300 400 500 600 700 800 900 1000
Temperature ᵒC
Figure 1: Thermogavimetric (TG) and derivative thermogravimetric (DTG) curves describing the
thermal degradation of dried fish waste and the rate of weight loss of the sample during thermal
conversion
The proximate analysis of dried fish waste in comparison to different biomass reported from
literature is shown in table 2. The results obtained indicated a low moisture content (6.9 wt%) of the
sample on dry basis, which makes the fish waste a suitable source of fuel feedstock in thermal
processes. The volatile matter of DFW was very high, up to 73.4 wt% similar to biomass based
829
products. This fraction showed a good ignition point of DFW and lower oxygen demand to complete
the combustion process [21, 24].
Organic elements
Biomass materials M VM FC Ash Reference
Fish waste 6,99 73,74 4,33 15,40 This study
Food waste - 83,20 12,70 5,50 [9]
Agri-food waste (grape marc) 10,00 50,00 28,00 12,00 [26]
Agri-food waste (tomato residues) 8,00 76,00 8,00 8,00 [26]
Table2: Proximate analysis of the dried fish waste compared with different biomass (wt% on dry
basis)
Where: M=Moisture content, FC= fixed carbon, VM= volatile matter
The fixed carbon content of DFW was relatively lower compared to other biomass materials used as
reference in this study, but significant ash content was detected. This can be attributed to the
presence of fish bone.
4. CONCLUSION
Based on the requirements for a waste material to be considered for energy recovery in thermal
systems, DFW, in comparison to MSW, agro-food waste and food waste showed a significant higher
heating value. The carbon and hydrogen content of the DFW were found to be the main contributors
to the waste as potential energy source material.
830
5. REFERENCES
1. FAO: Food and Agriculture Department. 2016. The State of World Fisheries and Aquaculture.
Food and Agriculture Organisation of United Nations Rome, 2016. (2016)
2. FAO: Food and Agriculture Department. 2010. The State of World Fisheries and Aquaculture.
Food and Agriculture Organisation of United Nations Rome, 2010. (2010)
3. Tacon, A.G.J., Metian, M.: Fish Matters: Importance of Aquatic Foods in Human Nutrition and
Global Food Supply. Rev. Fish. Sci. 21, 22–38 (2013).
4. FAO: Food and Agriculture Department. 2014.The State of World Fisheries and Aquaculture.
Food and Agriculture Organization of the United Nations Rome, 2014. (2014)
5. Rorbet Gumisiriza, A.M.M. and K.K.: Nile perch fish processing waste along Lake Victoria in
East Africa: Auditing and characterization. African J. Environ. Sci. T echnology. 3, 013–020
(2009)
6. Department of Environmental Affairs: National Waste Information Baseline Report. (2012)
7. Oelofse, S.H., Nahman, A.: Estimating the magnitude of food waste generated in South Africa.
Waste Manag. Res. 1–28 (2013).
8. Hartmann, H., Ahring, B.K.: Strategies for the anaerobic digestion of the organic fraction of
municipal solid waste: An overview. Water Sci. Technol. 53, 7–22 (2006).
9. Caton, P.A., Carr, M.A., Kim, S.S., Beautyman, M.J.: Energy recovery from waste food by
combustion or gasification with the potential for regenerative dehydration : A case study.
Energy Convers. Manag. 51, 1157–1169 (2010).
10. García, R., Pizarro, C., Lavín, A.G., Bueno, J.L.: Characterization of Spanish biomass wastes for
energy use. Bioresour. Technol. 103, 249–258 (2012).
11. Miodrag Belosevic, M.G.E.D.Z.S.J.R.B.: Degradation of Alizarin Yellow R using UV / H 2 O 2
Advanced Oxidation Process. Environ. Sci. Technol. 33, 482–489 (2014).
12. Arena, U.: Process and technological aspects of municipal solid waste gasification. A review.
Waste Manag. 32, 625–639 (2012).
13. Parikh, J., Channiwala, S.A., Ghosal, G.K.: A correlation for calculating HHV from proximate
analysis of solid fuels. Fuel. 84, 487–494 (2005).
14. Shi, H., Mahinpey, N., Aqsha, A., Silbermann, R.: Characterization , thermochemical conversion
studies , and heating value modeling of municipal solid waste. Waste Manag. 48, 34–47
(2016).
15. García, R., Pizarro, C., Lavín, A.G., Bueno, J.L.: Spanish biofuels heating value estimation. Part
II: Proximate analysis data. Fuel. 117, 1139–1147 (2014).
16. Ravindra K. Agrawal: A RAPID TECHNIQUE FOR CHARACTERIZATION AND PROXIMATE
ANALYSIS OF REFUSE-DERIVED FUELS AND ITS IMPLICATION FOR THERMAL CONVERSION.
Waste Manag. Res. 6, 271–280 (1988)
17. Dixon, N., Jones, D.R. V: Engineering properties of municipal solid waste. Geotext.
Geomembranes. 23, 205–233 (2005).
18. García, R., Pizarro, C., Lavín, A.G., Bueno, J.L.: Bioresource Technology Biomass proximate
analysis using thermogravimetry. Bioresour. Technol. 139, 1–4 (2013).
831
19. Gillespie, G.D., Everard, C.D., Fagan, C.C., Mcdonnell, K.P.: Prediction of quality parameters of
biomass pellets from proximate and ultimate analysis. Fuel. 111, 771–777 (2013).
20. Vargas-moreno, J.M., Callejón-ferre, A.J., Pérez-alonso, J., Velázquez-martí, B.: A review of the
mathematical models for predicting the heating value of biomass materials. Renew. Sustain.
Energy Rev. 16, 3065–3083 (2012).
21. Cosmin Marculescu, Gabriela Ionescu, Simona Ciuta, and C.S.: Energetic Analysis of Meat
Processing Industry Waste. In: Sustainable Food and Beverage Industry:Assessments and
Methodologies. pp. 221–234 (2016)
22. Tilay, A., Azargohar, R., Drisdelle, M., Dalai, A., Kozinski, J.: Canola meal moisture-resistant fuel
pellets : Study on the effects of process variables and additives on the pellet quality and
compression characteristics. Ind. Crop. Prod. 63, 337–348 (2015). d
23. Hlaba, A., Rabiu, A., Osibote, O.A.: Thermochemical Conversion of Municipal Solid Waste —
An Energy Potential and Thermal Degradation Behavior Study. Int. J. Environ. Sci. Dev. 7, 661–
667 (2016).
24. Lewandowski, I., Kicherer, A.: Combustion quality of biomass: Practical relevance and
experiments to modify the biomass quality of Miscanthus x giganteus. Eur. J. Agron. 6, 163–
177 (1997).
25. Ghetti, P., Ricca, L., Angelini, L.: Thermal analysis of biomass and corresponding pyrolysis
products. Fuel. 75, 565–573 (1996).
26. Kraiem, N., Lajili, M., Limousy, L., Said, R., Jeguirim, M.: Energy recovery from Tunisian agri-
food wastes : Evaluation of combustion performance and emissions characteristics of green
pellets prepared from tomato residues and grape marc. Energy. 107, 409–418 (2016).
27. Singh, Y.D., Mahanta, P., Bora, U.: Comprehensive characterization of lignocellulosic biomass
through proximate, ultimate and compositional analysis for bioenergy production. Renew.
Energy. 103, 490–500 (2017).
28. Shuo Yang, Robin S. Simmonds, E.J.B.: Physicochemical Characterization and Thermal
Properties of Lipids From R. opacus PD630. Food Public Heal. 4, 87–92 (2014).
832
EVALUATION OF ANTIOXIDANT ACTION OF PEELS OF ANNONA MURICATA L. TO

APPLICATION ON BIODIESEL
P. DETLINGER1, G.A.R. MAIA 1, L.A.C. MATOS,1 M.A. MOLINARES1, P.R.P. RODRIGUES1, E.P. BANCZEK1
1 Universidade Estadual do Centro Oeste,Guarapuava,Brasil.
Abstract
Biodiesel has been gaining space in the world energy sector due to its environmental
advantages, compared to petroleum diesel. However, it has low oxidation stability due to the
presence of unsaturated fatty acids. The main antioxidants used on the prevention of biodiesel
oxidation are the BHT (butyl-hydroxytoluene), the BHA (butylhydroxyanisol) and the TBHQ (t-butyl-
hydroxyquinone), that are synthetic compounds and has proven carcinogenic effects [1]. The Annona
Muricata.L is a fruit cultivated in various world regions, and has excellent antioxidant properties,
besides high concentration of phenolic acids [2]. In this sense, the objective of this work is to
investigate the antioxidant action of peels of Annona Muricata L. (consumption waste) in soybean
biodiesel. To the extraction of possible antioxidant compounds of the peels, it was used three
solutions: acid, (pH=1), basic, (pH=14) and neutral, (pH=7). The concentration of the used extracts
was varied from 1 to 5 g L-1. The obtained extracts were used to biodiesel preparation and the
accelerated oxidation assays were realized three times, according to the EN 14112 European
standard, employing the Rancimat 873 device, from Metrohm®.
120
Results: According to the results obtained for
100
Biodiesel
the three extraction methods and the tested
Biodiesel + AM (5gL/pH14)
concentrations, the basic extraction and with

80
concentration of 5 g L-1 presented the best

Conductivity (µS)
60
results of induction times: (11.95 ± 0.285)h,

40
Figure 1, overcoming the National Agency of
Petroleum (ANP- Brazil) requirement [3].. To
20
0
0 3 6neutral and acid medium, the best
8 11 14
Time (s)
concentrations also were of 5 g L-1, with
Figure 1. Induction times for biodiesel without induction time of (8.64±1.745)h and
antioxidant and with 5 g L-1 extract (pH=14). (10.29±0.657)h, respectively.
Conclusion: The induction time obtained to the soybean biodiesel sample using the extract of
Annonna Muricata L. peels in the concentration of 5 g L-1 with pH=14 was (11.95±0.285)h. This value
agrees the ANP regulation with suggests an induction time superior to 8 h.
References
[1] ITO, N.et al. Carcinogenicity and modification of the carcinogenic response by BHA, BHT, and other antioxidants. Critical Review
Toxicology, v. 15, p. 50–109, 1985.
[2] Gavamukulya, Y. et al. Phytochemical screening, anti-oxidant activity and in vitro anticancer potential of ethanolic and water
leaves extracts of Annona muricata. Asian Pacific Journal of Tropical Medicine, v. 7, n. S1, p. S355–S363, 2014.
[3] ANP. Resolution nº 51 de 25.11.2015. In 10.02.2017:http://nxt.anp.gov.br/NXT/gateway.dll?f= templates&fn=
default.htm&vid=anp:10.1048/enu.)
833
ASSESSMENT OF ALKALINE PRETREATMENT FOR LIGNIN EXTRACTION FROM PEANUT

SHELLS
BEATRIZ GULLÓN1, GEMMA EIBES1, JALEL LABIDI2, MARÍA TERESA MOREIRA1*, SARA GONZÁLEZ-
GARCÍA1, PATRICIA GULLÓN2
1
Department of Chemical Engineering, School of Engineering, University of Santiago de Compostela.
2
Chemical and Environmental Engineering Department, University of Basque Country, 20018 - San
Sebastián, Spain.
Abstract
Due to the depletion of fossil resources, in recent years there has been an increasing interest for the
use of renewable feedstock to obtain a wide range of chemicals and energies in replacement of the
fossil-based ones [1]. In this context, lignocellulosic biomass (an abundant and renewable resource)
is a suitable feedstock for obtaining value added chemicals. The integral valorization of
lignocellulosic biomass (which consists of a selective fractionation of cellulose, hemicellulose and
lignin) is a key tool to develop a sustainable biorefinery. In this sense, peanut shells (PS) are residues
from agro-food industry and can be considered as a suitable raw material for obtaining several
compounds [2]. In this work, we investigated the suitability of PS as feedstock to obtain lignin using
alkaline delignification. For this purpose, we carried out a first stage of hydrothermal treatment at
210 ºC to obtain a liquid phase with a high content of oligosaccharides, and a solid containing lignin
and glucan. The autohydrolyzed solid was subjected to an alkaline treatment yielding a delignified
solid (enriched in cellulose) and a liquid phase with the isolated lignin. The conditions of the
delignification process were optimized using Box-Behnken design. The independent variables studied
were %NaOH (2-12%), time (60-240 min) and temperature (105-124 ºC), and the solid yield and the
percentages of delignification and retained glucan were evaluated as response variables. The alkali
lignin obtained under optimal conditions was characterized by FTIR, TGA, HPSEC, and Py-GC/MS.
Additionally, phenolic compounds and antioxidant activity (measured as DPPH, ABTS and FRAP) of
this fraction were also evaluated. The compositional data determined for PS showed that the lignin
was the main component (42.7%), followed by glucan (20.9%) and hemicelluloses (19.3%). In the
most severe conditions tested (12% NaOH, 300 min and 124 ºC), a removal of 80% of lignin was
obtained. Therefore, the PS can be considered as a suitable resource to obtain their isolated
constituents, which may be further used as platforms to produce added value products.
Acknowledgements
This research has been supported by a project granted by Xunta de Galicia (project ref. ED431F 2016/001) and Spanish
Ministry of Economy and Competitiveness (CTQ2014-58879-JIN and CTQ2016-81848-REDT). Dr. B. Gullón, S. González-
Garcia, and Dr. P. Gullón would like to express her gratitude to the Spanish Ministry of Economy and Competitivity for
financial support (Grant references, IJCI-2015-25305, RYC-2014-14984 and IJCI-2015-25304, respectively). The authors
(Dr. B. Gullón, Dr. Gemma Eibes, Prof. M.T. Moreira and Dr. S. González-Garcia) belong to the Galician Competitive
Research Group GRC 2013-032 as well as to CRETUS (AGRUP2015/02), co-funded by Xunta de Galicia and FEDER).
References
[1] R. Liguori; V. Faraco.: Biological processes for advancing lignocellulosic waste biorefinery by advocating circular
economy. Bioresource Technol. 215, 13-20 (2016).
[2] Carneiro, A. P., Rodríguez, O., & Macedo, E. A. Dissolution and fractionation of nut shells in ionic liquids. Bioresource
Technology, 227, 188-196 (2017).
834
CHARACTERIZATION OF BIOMASS BY MEANS OF ELUTRIATION AND SEDIMENTATION
D.A. RAMIREZ-QUINTERO, W.A. BIZZO

University of Campinas, Faculty of Mechanical Engineering, Campinas, Brazil.
Keywords: biomass sieving, biomass elutriation, drag velocity, irregular particles, particle shape size
effect, bamboo, cassava branch.
Abstract
Density, shape and size are three characteristics that combine in the fluid dynamics of the particles
to produce unpredictable results so far. In irregular particles, as in biomasses, the interaction of
these three characteristics of the particle in the upward fluid has a great influence on the drag force,
therefore at particle velocity as well. Some traditional methods for characterizing biomasses, such as
sieving, do not consider the irregular shape of the particles. Form factors are used to complement
the data obtained by sieving. But this data obtained in conjunction with the different theoretical,
empirical correlations or in the combination of both; for determination of drag velocity produce
results with great uncertainties. This work aims to present a comparison between a traditional
procedure, sieving, to characterize the biomass particles (bamboo and cassava branch) with the
results found with the separation of the material using the elutriation. The material was separated
into ten Tyler mesh sizes. A device was built to separate the biomass particles at different drag
velocities. The drag velocities were determined with the diameters found in the sieving and the
correlations proposed by different authors. The differences between drag velocities found and
measurements are high, deviations greater than 90% on average. The use of biomass separation by
elutriation and sedimentation of the particles provides import parameters in the reactors design that
combine homogeneity of size, shape and density.
835
1- INTRODUCTION
Since Wadell showed that with the particle size classification based on the arithmetic or geometric
mean of its diameters, two particles, one having diameters on its axes with very different values and
the other being a sphere with its diameters on its axes of same length, may have the same "size"
value [1]. A challenge was posed that different authors have tried to approach in different ways
through of theorical and empirical methodological proposals, or a combination of both, to predict
the effect of these considerations. The question becomes more complex if one of the particles is
porous and presents some variation with the value of the density between the particles of its same
species. Thus, in the fluid-dynamics behaviour of irregular particles, such as biomasses, considerable
uncertainty has arisen due to the techniques used to classify and determine the representative
dimensions of the irregular particles. These feature influence the prediction of parameters, such as
velocity, force and drag coefficient; which involve the design of systems that use fluidized bed
technology, such as the combustion, gasification and pyrolysis of biomasses.
Given the wide particle size distribution used in the fluidized beds, it is expected that the air velocity
will be higher than the terminal velocity of the lighter particles, resulting in particles entrainment [2].
While this loss of material from fluidized bed reactors is considered a disadvantage, some process
takes advantage of the loss of fines, e.g. fluid bed classifiers [3].
Currently, fluidized bed applications operate with materials having a wide range of granulometric
distribution. In Brazil, sugarcane bagasse with small amounts of straw, is only used as fuel in boilers
to produce steam in processes that include electricity generation. Studies involving bamboo have
been encouraged by the government of Brazil, in 2011, by a law that provides on the national policy
of incentive to sustainable management and bamboo cultivation seeking to stimulate researchers of
institutions to develop studies that make possible the use of this raw material in the different
industrial processes. Bamboo is a biomass with a wide variety of uses that grows on all continents,
except in Europe, with a wide range of applications in the areas of architecture, civil engineering,
medicine, chemical industry, among others. Different species of bamboo grow naturally in the world
(20 to 1 cm in length daily) and are used as human food, clothing, medicinal compounds, animal
fodder, energy biomass, construction material for multiple purposes, raw material for various
industrial sectors (including pulp and paper), handicrafts, tools, furniture manufacture and musical
instruments [4, 5, 6, 7, 8, 9]. Cassava is a plant native to the Americas with a large number of species,
used in various fields of economic activity, mainly in food; Although it is not attractive as an export
product, domestic consumption in the different developing countries is high [10, 11, 12]. According
to [13] world cassava production in 2010 and 2014 increased from 243 million to 270 million tons of
root. Brazil is the third largest producer of cassava in the world [10] with 24 to 25 million tons [13].
This works presents aims to present a comparison between a traditional procedure, sieving, to
characterize the biomass particles (bamboo and cassava branch) with the results found with the
separation of the material using the elutriation.
Terminal or drag velocity

From an extensive evaluation of the correlations reported for the determination of the drag
coefficient, CD, of particles falling at their terminal velocities, Ut, Haider and Levenspiel [14]
developed a procedure for estimating Ut, Eq. (2), from the determination of the particle
dimensionless diameter, d*, Eq. (1), and the terminal velocity dimensional, Ut*, Eq. (2), for regular
particles, Eq. (3), and irregular particles, Eq. (4).
1⁄3
𝑔𝜇(𝜌𝑠 −𝜌𝑓 )
𝑢𝑡 = 𝑢* ( ) (1)
𝜌𝑓2
836
1⁄3
𝑔𝜌𝑓 (𝜌𝑠 −𝜌𝑓 )
𝑑* = 𝑑𝑠𝑝ℎ ( ) (2)
𝜇2
−1
18 0.603
𝑢* = (𝑑2 + ) (3)
* 𝑑*0,5
−1
18 2.3348−1.7439∅
𝑢* = (𝑑2 + ) 0.5 ≤ ∅ ≤ 1 (4)
* 4𝑑*0,5
Where dsph is the equivalent spherical diameter, g is the acceleration due to gravity, μ is the dynamic
viscosity of the fluid, ρs and ρf are the density of the particle and the fluid, respectively; and ∅ is
sphericity.
Chien [15] developed a correlation, Eq. (5), to predict the settling velocity of irregular particles, (Vs)t,
in Newtonian and non-Newtonian fluids for all types of slip regimes. The correlation was derived
from extensive data on the drag coefficients and Reynolds particles of irregularly shaped particles.
(𝑉𝑠 )𝑡 = 32.355√𝑑[(𝜌𝑠 − 𝜌𝑓 ) − 1] (5)
Where d is the equivalent diameter of the particle, equal to 𝑑𝑠𝑝ℎ but in cm.

The bamboo used is the giant species, Dendrocalamus giganteus Munro, popularly known as giant
bamboo, collected from the School of Agricultural Engineering, on the campus of the University of
Campinas. The bamboo stems were cut manually into small pieces and later milled in hammer mills.
Thick and thin branches of the cassava plantation were collected in a producing region in the São
Paulo state. The branches were initially ground in a hammer mill used for animal feed production.
The material was dried in the sun for one week to equilibrate moisture to the environment, samples
were taken for the experiments. For the measurement of each measured quantity (including
separation) three tests were made, the value presented is the average value. The characterization of
the basic properties (density, humidity, equivalent spherical diameter and sphericity) of the previous
biomass was carried out in order to estimate the terminal velocity of the particles.
The biomasses were separated by sieving and elutriation. Ten mesh sizes were used for sieves
separation. The separation experiments by elutriation were carried out in the SESY -sedimentation
elutriator separator system, illustrated in Figure 1. SESY is composed of a tube riser (R) with a glass
section for visual inspection of the particles behaviour, internal diameter of 0.1 m and 1.8 m in
height. The riser is followed by a U-bend downward to end in a sedimentation chamber (SC). Air
suction is performed by an air exhaustor (AE). A filter is placed between the sedimentation chamber
and the air connection to avoid the output of the material. Air velocity was controlled by valve (V).
The material to be separated by elutriation is spread in a vibrating feeder system (VS) to dose the
biomass into the riser. The dragged material is collected in the sedimentation chamber and the
settled material is collected at the bottom of the riser to be feed in the vibrating system at the next
speed. The air flow rate was measured with an orifice plate system (OP) constructed in accordance
with ASME MFC-14M/2003 standard and pressure was measured with Smar LD301 transducers (P).
The air temperature of the system was measured to determine the air density. The device is able of
producing superficial air velocities between 0.5 and 6.5 m/s.
Using atmospheric air at ambient pressure and temperature as the working fluid, an airflow was
generated in the riser at different velocities, where biomass particles were feed in the airflow. The
837
feeding of the particles was done continuously and in small quantities, preventing a large amount
from being simultaneously arranged in the riser, in order to minimize the agglomeration of particles.
The density of biomass samples were measured with water pycnometry. The Sauter diameter was
calculated based on weight fraction of the separated material by sieving. The projected area of the
particles were obtained by image scanning. The ImageJ program was used to measure this
dimensions, as well as major and minor axis length for the calculation of sphericity, Eq. (6), based on
Wadell’s original definition. These dimensions are described by [16]. The plugins developed for the
ImageJ program become a striking option for particle size measurement. ImageJ is a public domain
Java processing program, freely available, open source, platform independent and analysis program
developed at the National Institutes of Health (NIH) [17, 18].
𝑑 2
∅ = (𝑑𝑣 ) (6)
𝑠
Where dv is the surface area of a sphere of the same volume as the particle, and d s is the actual
surface area of the particle.
Figure 1: Experimental bench SESY. Air exhaustor (AE), elutriated material collector (Ce), sedimentary material collector (Cs), pressure
gauge (P), riser (R), sedimentation chamber (SC), temperature gauge (T), valve (V) and vibratory feed system (VS).
The bamboo was separated with velocities of 0.6 to 6.1 m/s and the cassava branch at 0.6 to 5.5
m/s. For the terminal velocities predicted by correlations the results obtained by sieving was used.
Three correlations were used: the correlations of Haider and Levenspiel (1989) for spherical and non-
spherical particles and Chien’s correlation.

The biomass properties are presented in Table 1. Ten Tyler mesh sizes were used for biomass
separation. It was separated by elutriation 98% of the bamboo and 99% of the cassava branch.
838
Figure 2 shows the results of the separation by sieving (up) and elutriation (down). From Figure 2, It
can be seen that for sieving separation the bamboo particles size distribution presents a first peak in
the fines, then falls off and then has a rapid growth with a maximum peak at Tyler's 32 mesh.
However, for elutriation, the distribution is more homogeneous, almost normal, with the maximum
peak at approximately half of the maximum velocities used (≈3 m/s). In the case of cassava branch,
the particle size distribution has a gradual growth up to Tyler's mesh 20, then falls and then has the
maximum peak in Tyler's 14 mesh, showing higher concentration in coarse particles. For the
elutriation separation, cassava has a more homogeneous distribution, with a slight concentration at
the rate of 1.3 m/s (fines particles).
Specific mass Sauter mean diameter W

Biomass Φ
(kg/m³) (µm) (%)
Bamboo 1152 ± 47 563 ± 15 0.67 5%
Cassava branch 625 ± 17 927 ± 10 0.76 3%
Table 1: Biomass sample properties.
Figure 2: Distribution of particle size by sieving (up) and elutriation (down).
839
Figure 3 shows the lengths of the major axis of the biomass particles for both sieving (up) and
elutriation (down). From figure 3, clearly the behaviour of the lengths of the major and minor axes of
the bamboo particles presents greater variability. Interestingly, bamboo presents three peaks in the
size distribution both in sieving and elutriation, but with very different trends. On the other hand,
the particle size distribution of cassava exhibits a similar behaviour, with a tendency of the minor
axis length that seems to follow a little more closely in the sieving separation.
Figure 3: Major and minor axis length of particles of biomass for the separation by sifting (up) and elutriation (down).
From Figure 2 and 3, we notice that the behaviour of particles separated by elutriation and the
particles separated by sieving is different, showing the combined influence of the irregular shape and
size of particles. Particles shape may attenuate or increase the differences between the results
obtained by these two characterization methodologies. For example, the needle-like shape of the
bamboo particles seems to present a greater degree of difference between the size distribution by
sieving and elutriation, in comparison with the effect of the cylindrical pellet shape of the cassava
particles (closer to a sphere), Figure 4. From Figure 4, it is showed the 2D images obtained from the
separated particles both by sieving and by elutriation. It was difficult to compare the 2D morphology
840
between the particles separated by sieving (up Figure 4) and by elutriation (down Figure 4) for both
the bamboo and the cassava branch. It is easier to see the continuous growth of the length of the
bamboo particles separated by sieving (upper left) than for the particles separated by elutriation
(upper right); but in the case of the cassava branch, it is easier to see this growth in the separation by
elutriation (lower right) than by sieving (lower left). In the previous one, it is clear the significant
influence of the particle thickness and density -given that the plants have different parts that present
differentiated in their properties and in their constitution, e.g., bamboo has leaves, culm, nodes
(diaphragms), etc. These aspects that are difficult to consider with the current techniques of
characterization.
Figures 5 and 6 show the accumulated mass fraction as a function of the terminal velocity of the
particle both measured in the elutriator and predicted by correlations for the bamboo and the
cassava branch, respectively. From Figures 5 and 6, a pattern can be observed between the Haider
and Levanspiel and Chien correlations. All of them with deviations from 10% to 1600 % of the speeds
measured.
In the case of bamboo, Figure 5, the Haider and Levenspiel equation for non-spherical particles
matches the measured velocities slightly, with deviations between 92 and 100%. The results
obtained by the Chien equation for Tyler meshes 32, 35 and 42 (550, 460 and 387.5 µm) approaches
36%, 13% and 40%, respectively, at measured separation velocity values.
Figure 5: Mass fraction accumulated versus terminal velocity of bamboo particles, measured and predicted by correlations of some
authors.
For cassava, Figure 6, the Haider and Levenspiel equation for spherical particles, in general, timidly
follows the behavior at measured separation velocities values, with deviations from 9% to 958% for
the fine particles. The results obtained by the Chien equation for meshes 24, 28, 32 and 35 (775, 655,
550, and 460 µm) of Tyler approach at 23%, 1%, 15 and 25%, respectively, to the measured
separation velocities values.
841
Figure 4: Bamboo separated by sieving (upper left) and elutriation (upper right), cassava branch separated by sieving (lower left) and elutriation (lower right).
842
Based on the above results we can conclude that the correlations described for the determination of
the terminal or settling velocity of the irregular particles does not provide a clear indication of the
biomass fluid dynamic behavior with large aspect-ratio. It is necessary to find a way to correlate the
influence of shape, size and density on the fluid dynamics of irregular particles, since the use of the
results obtained for the determination of the terminal velocity of the biomass particles could lead to
high deviations in the design of reactors.
Figure 6: Mass fraction accumulated versus terminal velocity of cassava branch particles, measured and predicted by correlations of
some authors.
4- CONCLUSIONS
The results showed great difference between separation techniques by sieving and elutriation for
characterization of size particles, especially for bamboo. Terminal velocity values obtained
experimentally differ, with deviations greater than 90% on average, of the value calculated by
classical correlations of literature, due to the variety and irregularity of the particle shape and size
distribution from biomass.
REFERENCES
[1] Wadell, H.: Volume, shape and roundness of rock particles. Journal of Geogoly, 40, 443-451 (1932)
[2] Londoño, X.: Evaluation of bamboo resources in Latin America. A Summary of 92the Final Report of
Project No. 96-8300-01-4, Internatinoal Network for Bamboo and Rattan, Cali (1998)
[3] Scurlock, J. M. O.: Bamboo: an overlooked biomass resource?. Biomass and Bioenergy, 19, 229–244
(2000)
[4] Kalher, C. G.: Report on bamboo thematic study in the framework of Forest Resources Assessment
Program 2005 for Latin America. Global forest resources assessment, working paper 123 (2005)
[5] Pereira, M. A. R., Beraldo, A. L.: Bambu de corpo e alma. Canal 6, projetos editoriais, Bauru (2007)
[6] Ramón-Mercedes, J.: Guía Técnica Cultivo del Bambú. Centro para el Desarrollo Agropecuario y Forestal,
Inc. (CEDAF), Santo Domingo (2006)
[7] Ramirez-Quintero, D. A. ; Pécora, A. A. B. : Fluidizing velocities of bamboo/sand mixtures. In: 22th
International Conference on Fluidized Bed Conversion, Proceedings of the 22nd International Conference
on Fluidized Bed Conversion, Turku (2015)
843
[8] Hillocks, R.J., Thresh, J. M., Bellotti, A.C.: Cassava: Biology, Production and Utilization. CABI Publishing,
New York (2002)
[9] Souza, M. L., Menezes, H. D.: Processamentos de amêndoa e torta de castanha-do-brasil e farinha de
mandioca: parâmetros de qualidade. Ciênc. Tecnol. Aliment., 24, 120-128, Campinas (2004)
[10] Pereira, J. M., Aquino, A. C. M., Oliveira, D. C., Rocha, G., Francisco, A., Barreto, P. L. M., Amante. E. R.:
Characteristics of cassava starch fermentation wastewater based on structural degradation of starch
granules. Ciência Rural, 46, 732-738 (2016)
[11] Departamento de Economia Rural (DERAL), Secretaria de Estado da Agricultura e do Abastecimento
(SEAB). PROGNÓSTICO MANDIOCA 2017/18 (2017)
[12] M. COLAKYAN, M., LEVENSPIEL, O,: Elutriation from fluidized bed. Powder Technology, 38, 223 - 232
(1984)
[13] Yang, W. C.: Handbook of Fluidization and Fluid Particle Systems. Marcel Dekker Inc., Pittsburgh (2003)
[14] Haider, A., Levenspiel, O.: Drag Coefficient and terminal velocity of spherical and nosplherical particles.
Podwer Technology, 58, 63-70 (1989)
[15] Chien, S. F.: Settling velocity of irregularly shaped particles. SPE, Texaco Inc. (1994)
[16] Baxes G. A.: Digital Image Processing: Principles and Applications. John Wiley & Sons, New York (1994)
[17] Igathinathane C., Pordesimo L.O., Columbus E.P., Batchelor W.D., Methuku S.R.: Shape identification and
particles size distribution from basic shape parameters using ImageJ, Computers and Electronics in
Agriculture, 63, 168-172 (2008)
[18] Bailer W.: Writing ImageJ Plugins – A Tutorial, Version 1.71 (2006)
<http://rsb.info.nih.gov/ij/download/docs/tutorial171.pdf> accessed July 29.07.2010
844
HOLISTIC APPROACH FOR THE MANAGEMENT OF DOMESTIC WASTEWATERS VIA

CONSTRUCTED WETLANDS AND EXPLOITATION OF BIOMASS AND EFFLUENTS FOR
NUTRIENTS, WATER ANG ENERGY RECOVERY
I. NTAIKOU 1, G. ANTONOPOULOU 1, S. DAILIANIS2, V. DRAKOPOULOS1, F. HARIZAJ3, P. LAZE3, J.

SHEHU3, I. VYRIDES4, G. LYBERATOS1,5
1 Institute of Chemical Engineering Sciences, Foundation for Research and Technology, 10 Stadiou st.,
Platani, Patras, GR 26504, Greece.

2 Department of Biology, University of Patras, Patras, GR 26 500, Greece.
3 Department of Environmental Science and Technology, Cyprus University of Technology 30
Archbishop Kyprianou St. 3036 Lemesos, Cyprus.

4 Faculty of Agriculture and Environment, Agricultural University of Tirana, Koder Kamez, 1000
Tirane, Albania.
5 School of Chemical Engineering, National Technical University of Athens, GR 15780 Athens, Greece.
Abstract
A considerable ratio of the total population in Balkan and Mediterranean countries is dispersed in
rural areas and organized in small communities that are often spaced apart, and therefore the
management of their wastes and wastewaters in a centralized system is not feasible. Indeed,
wastewater treatment via typical biological wastewater treatment plants might not be the most
appropriate in the case of small communities since it has high manufacturing and maintenance costs
and its presence within the community limits, is not acceptable by the residence for fear of odors
and safety. On the other hand, constructed Wetlands (CW) constitute a cost efficient and highly
effective practice for the treatment of domestic/household wastewaters in rural areas since they do
not require complex mechanical and expensive equipment and their maintenance and operation
costs are minimal. Moreover, CWs do not contribute to natural environment degradation; on the
contrary they can be aesthetically pleasing and they also provide habitat for wildlife and human
enjoyment, and thus can be easily accepted by the residence.
In the framework of the present study two CWs located in one Greek and one Cypriot community,
were studied as real laboratories. The two CWs were systematically monitored under different
conditions, their performance efficiency was evaluated, and the response to operational factors that
have hardly been studied before, such as supply variations and recirculation, were recorded. As such
water quality parameters data (DO, conductivity, pH, BOD, SS, metals, chlorophyll, bacteria, bio-
toxicity, xenobiotics, etc.), biotic parameters data (plant activity and symbiotic relationships in the
roots, zooplankton etc.) and meteorological data (T, rainfall, light intensity) that highly affect CWs
performance were used in order to develop a mathematical model capable to predict the
performance of free surface flow CW systems.
The exploitation strategy of the CW effluents was also evaluated via the reuse of the effluent for the
irrigation of citrus trees and maize crops as well as via the establishment of an industrial forest of
Paulownia trees. Moreover, the exploitation of cropping (residual plant biomass) for energy and
nutrients recovery was evaluated via Biochemical Methane Potential (BMP) tests and composting for
organic fertilizer production, respectively.
The ultimate goal of the study was the creation of a generic assessment tool via which the feasibility
of CW technology application in different rural areas could be evaluated based on minimal initial
data, and also to prove the management of domestic wastewaters can be successfully combined
with remarkable nutrients and water recovery in a cost- and eco-efficient manner.
845
TRANSFORMATION MECHANISM OF NITROGEN IN A BIOCHAR ‘PREPARATION-

APPLICATION’ SYSTEM
ZHONGXIN TAN, LIYUN LIU, ZHIXIONG YE

1 College of Resources and Environment, Huazhong Agricultural University, Wuhan, 430070, P. R.
China
Abstract
Elemental analysis-stable isotope ratio mass spectrometry (EA-IRMS) and X-ray photoelectron
spectroscopy (XPS) were conjointly employed to investigate the migration and transformation
mechanism of biochar N in a ‘preparation-application’ system. EA-IRMS data indicated that during
the preparation process, the N retention rate in biochar first dropped sharply (300–400 °C), then
became stable (400–500 °C), and finally decreased slowly (500–800 °C) with increasing pyrolysis
temperature. With the combined action of ammonification, nitrification, denitrification, and biochar
adsorption on nitrogen, the nitrogen mass distribution rate was of the order: biochar after
application (88.40–90.42%) > soil (8.81–10.07%) > plants (0.77–1.53%). In addition, the pyrolysis
temperature was positively related to the nitrogen mass distribution rate in biochar and negatively
correlated to that in soil and wheat. The pyrolysis atmosphere had little effect on nitrogen retention
in biochar before application and the nitrogen mass distribution rate in biochar after application. The
XPS results suggested that alkaloid-N, free amino acid-N, protein-N, and NH4+-N in wheat straw were
gradually transformed into pyridine-N, amino-N, pyrrole-N, quaternary-N, NH4+-N, NO2--N, and NO3--
N in biochar during the biomass pyrolysis process. Among these species, biochar produced at 300 °C
was found to be in a transition stage that included all nitrogen species in wheat straw and biochar
produced at lower temperatures (≤ 500 °C). Higher temperatures impelled inorganic nitrogen species
to be more abundant and more high content level. For pyrolysis temperatures ≤500 °C, biochars
prepared under both N2 and CO2 atmospheres comprised similar nitrogen species and contents and
the changes in nitrogen species and nitrogen release patterns did not differ significantly.
Keywords: biochar; pyrolysis temperature; pyrolysis atmosphere; nitrogen speciation; isotope tracer
method
846
EFFECT OF CaO LOADING ON TRANSESTERIFICATION OF JATROPHA OIL TO BIODIESEL

IN THE PRESENCE OF SAPO-34 SUPPORTED CATALYSTS
BASHIR ABUBAKAR ABDULKADIR1, ANITA RAMLI1*, LIM JUN WEI1, YOSHIMITSU UEMURA2
1
Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, 32610 Bandar Seri
Iskandar, Perak, MALAYSIA
2
Chemical Engineering Department, Universiti Teknologi PETRONAS, 32610 Bandar Seri Iskandar,
Perak, MALAYSIA
Abstract
Attaining a very high degree of active metal distributions on the surface of catalyst support at the
required loading of the metal becomes a serious challenge in the area of catalyst and in biodiesel
production. Hence, the influence of calcium oxide (CaO) loading on performance of SAPO-34
supported catalysts for biodiesel production from Jatropha oil. The SAPO-34 was purchased from
ACS Materials, Inc while calcium nitrate was supplied by Merck. CaO/SAPO-34 catalysts were
prepared by wet impregnation method with 5 – 30 wt% CaO loadings following the method reported
by Farooq et al. [1]. The physicochemical properties of the catalysts were characterized using XRD,
BET, FESEM, EDX and TPD. The performance of the catalysts was tested in the transesterification of
jatropha oil to biodiesel. XRD and EDX results show the presence of CaO in the prepared catalyst
confirming the successful incorporation of the active metal into the support. The BET results show
that total surface area of the catalysts decreases with increasing loading of CaO while the average
pore size and total pore volume increases with increasing CaO loading. 15 wt% CaO/SAPO-34 shows
the highest FAME yield of 97.8% at 70 oC, methanol to oil ratio of 15, catalyst loading of 2.5 wt% and
reaction period of 100 minutes. In addition, the catalyst could be used for up to seven (7) runs
without significant loss in catalytic activity.
Figure 1: FESEM and EDX image representative of CaO/SAPO-34.
Reference
[1] [Farooq M., Anita R, and Duvvuri S.: Physiochemical Properties of γ-Al2O3-MgO and γ-Al2O3-CeO2 Composite Oxides.
Journal of Chemical Engineering Data, 57:26–32 (2012)]
847
STRATEGY FOR THE DESIGN OF WASTE TO ENERGY PROCESSES BASED ON

PHYSICOCHEMICAL CHARACTERISATION
I. ORTIZ1, J.M. SÁNCHEZ-HERVÁS1, Y. TORREIRO1, M. MAROÑO1, V. PERÉZ2, R. RAMOS2, M.

FERNANDEZ2, R. PIÑEIRO2
1 Energy Valorisation of Fuels and Wastes, CIEMAT, Madrid, Spain.
2 CEDER-CIEMAT, Soria, Spain.
Abstract
Energy recovery from wastes is needed for cost-effective and sustainable management, while it
contributes in addition to renewable energy generation or production of high-value chemicals [1].
For a given waste, the definition of suitable thermochemical conversion process schemes relies on
devising a strategy based on several variables among which feedstock characterization is crucial.
Depending on the properties of the fuel, the available waste resource may not be suitable for a
specific application, for technical and sometimes for environmental reasons [2]. Nonetheless synergy
and symbiosis can be found between wastes from different sources which is one of the goals of the
RETOPROSOT-CM project. Within this framework, agro-industrial wastes (grape stem, beer bagasse
and orange juice residues) were characterized and the results are being used to design a strategy for
their effective integration in waste to energy processes. Energy content, proximate and ultimate
analysis, composition, ash fusibility and thermal behavior were determined. For the physicochemical
analysis UNE and/or ISO standard methods were used. Thermochemical analysis was conducted in a
Mettler Toledo TGA/DTG at three different heating rates: 5, 10 and 20 ºC/min. Characterization
results show that the three wastes have good quality for thermochemical conversion with energy
contents between 19 MJ/Kg (beer bagasse) and 16 MJ/Kg (orange juice residue) and ash contents
below 10 % in all cases. However, some drawbacks were found: high moisture (76%), nitrogen (3.5%)
and sulphur (0.2%) content for beer bagasse; elevated nitrogen (1.1%) and sulphur (0.15%)
concentration for grape stem and nitrogen (1%) content for orange juice residue. Regarding
thermogravimetric analysis, orange juice residue showed a more differentiated thermal behaviour
with two important mass losses of 20% and 23%. Although grape stem has the maximum mass loss
at higher temperature (297 – 386 ºC), beer bagasse presented the most difficult degradation pattern
with a final step at 320 – 380 ºC (19%) and the highest apparent activation energy calculated with
the Kissinger method.
Even though the three wastes exhibit good potential for thermal valorization, several considerations
should be kept in mind before their use, such as the moisture content of beer bagasse which might
require a previous drying step or its sulphur and nitrogen content which dictate strong gas cleaning
requirements. All this information is being used to design a smart strategy to use them in sustainable
and environmental friendly waste to energy processes as part of a circular economy approach. The
strategy includes the definition of the conversion process steps but also blending with cleaner
feedstocks so that acceptable solid recovered fuels can be produced.
References
[1] Gumisiriza, R., Hawumba, J.F., Okure, M. & Hensel, O. Biomass waste-to-energy valorisation technologies: a review
case for banana processing in Uganda. Biotechnol. Biofuels 10 (2017).
[2] Virmond, E., Rocha, J.D., Moreira, R.F.P.M. & José, H.J. Valorization of agroindustrial solid residues and residues from
biofuel production chains by thermochemical conversion: a review, citing Brazil as a case study. Braz. J. Chem. Eng.
30, 197-230 (2013).
848
A NEW AND ACCURATE METHOD TO MEASURE SURFACE TEMPERATURE AND SIZE

OF SOLID PARTICLES DURING FUEL CONVERSION IN FLUIDIZED BEDS
J. SALINERO, D. FUENTES, A. BERDUGO, P. HARO, A. GÓMEZ-BAREA

Bioenergy Group, Chemical and Environmental Engineering Department, Escuela Técnica Superior
de Ingeniería, Universidad de Sevilla, Camino de los Descubrimientos s/n. 41092 Seville, Spain
Abstract
Fluidized bed convertors (FBCs) are recognized as one of the most suitable technologies to thermally
convert heterogeneous solid fuels. FBCs provide flexibility and a smooth operation even with
changes of fuel quality and load. FBCs, i.e. combustors/boilers and gasifiers, have been installed over
the world with relatively success during the last decades. The control of temperature is probably one
of the most important aspects for FBC optimization, especially for difficult fuels like wastes. Optimal
bed temperature is normally between 800 and 900 ºC, considering the balance between benefits
and drawbacks associated with the thermal load. While increasing the temperature enhances tar and
char conversion in FB gasifiers and enables optimization of pollutant emissions in FB boilers, it also
increases the risk of sintering/agglomeration of char/ash in the bed. Therefore, a maximum process
temperature is set. The mechanisms controlling these phenomena are intimately related to the local
surface temperature of the burning solids. Moreover, the temperature of the fuel particles can be
higher than that of the bed, depending on the surrounding gas. In addition, there is experimental
evidence of rapid oscillations of the fuel particle (char) temperature during combustion and
gasification, resulting from the movement of the char between phases. From this, it is clear that
careful measurement of the char surface temperature oscillations are of paramount importance to
smoothly operate and optimize FBC.
In this work, a new method to accurately measure the char surface temperature during conversion in
FBCs is presented. The method is based on pyrometry with a digital camera. It applies one-color
pyrometry sequentially for three wavelength bands (red, green, and blue), changing from one band
to another automatically as a function of the radiation intensity received on the sensor of the digital
camera. The method allows following the evolution of the size and temperature during particle
conversion. In particular, the measurement of the magnitude and frequency of temperature
oscillations is captured significantly better than using thermocouple or pyrometry with optical probe
(common techniques used in FBCs). Dedicated single char particles combustion experiments were
conducted in a two-dimensional FBC (made of quartz) showing the capability of the method. A
combustion model has been developed to predict the evolution of temperature and char size of char
particles during conversion allowing good estimation of the measurements and explaining the main
rate-controlling mechanisms during combustion and gasification.
849
FOOD WASTE: ANALYSIS AND PROPOSAL OF A QUANTIFICATION METHODOLOGY
M. BAQUERO 1, A. ANDRÉS1, E. CIFRIÁN1

1 University of Cantabria, Santander, Spain..
Abstract
About one-third of the food produced for human consumption, is wasted globally each year [1].
Regrettably, this quantity is expected to rise gradually for the next twenty-five years [2]. Due to
moral, social and environmental issues that this situation entails, reduction plans and strategies are
being developed at different levels. Assessing the progress of taken measures, checking the
achievement of the proposed objectives, comparing data from different regions and quantifying the
generation of food waste are paramount tasks. Therefore, it is necessary to quantify food waste
adequately and homogeneously, but, the required methodology does not exist at present. There are
several studies, in which very different quantification methodologies are used for different purposes,
which means that waste flows measured vary depending on the authors, the country where the
study is conducted and the available data [3, 4]. This makes data comparison impossible.
Consequently, the aim of this study is to collect, analyze and compare existing quantification
methodologies, to stablish the foundation of a comprehensive methodology. To achieve these
objectives, an extensive literature review has been executed, through several databases and specific
browsers.
The main differences among methodologies have been identified: Food waste definition and food
categories considered, scope of the quantification, estimation methods used, mass flows considered
as food waste and exclusions of the quantification. Subsequently, the foundation of a comprehensive
methodology has been stablished in line with the food waste definition given by the EU FUSIONS’
PROJECT Quantification manual to monitor food waste amounts and progression [5], that provides a
definitional framework and practical guidelines on how to quantify food waste. The proposed
methodology considers the whole food supply chain, all food categories and every measurable waste
flow generated during production, processing, retail and consumption. Only flows excessively
difficult to measure and those which do not meet the food waste definition are not included in the
quantification. This methodology can be used to monitor the effectiveness of the measures taken to
avoid food waste.
References
[1] FAO. FAO y Messe Düsseldorf lideran SAVE FOOD: Global Initiative on Food Loss and Waste Reduction. 2017.
[2] Brancoli P., Rousta K., Bolton K. Life cycle assessment of supermarket food waste. 2017. Resour.Conserv.Recy.
118:39-46.
[3] Stenmarck A., Jensen C., Quested T., Moates G: Estimates of European food waste levels. FUSIONS EU Project. (2016)
[4] Gustavsson J., Cederberg C., Sonesson U., Otterdijk R., Meybeck A. In FAO (Ed.), Global Food Losses and Food Waste;
Extent, Causes and Prevention. 2011.
[5] EU FUSIONS. Quantification manual to monitor food waste amounts and progression. 2016. (https://www.eu-
fusions.org/) )
850
A COMPARISON OF ALUM SLUDGE WITH IRISH PEAT FOR AQUEOUS GLYPHOSATE

REMOVAL WITH SPECIAL FOCUS TO MAXIMIZE THEIR VALUE IN PRACTICAL USE
Y. WANG1, B. REN2,3, Y. ZHAO1,2, A. ENGLISH2, M. CANNON2

1 School of Environmental and Municipal Engineering, Lanzhou Jiaotong University, Lanzhou 730070,
Gansu, P.R. China
Dublin, Belfield, Dublin 4, Ireland

3 Université de Toulouse, Mines Albi, CNRS UMR 5302, Centre RAPSODEE, Campus Jarlard, Albi
81013, Cedex 09, France
Abstract
This study compares and contrasts the glyphosate removal efficiency of alum sludge (waterworks
residue) and Irish peat in aqueous. Alum sludge is an easily, largely, locally by-product of potable
water production and in towns, cities and metropolis, and is currently disposed of as a waste
worldwide. It has been gaining considerable attention during the last decade and so far it has been
preliminarily studied as a potential adsorbent for the removal of various pollutants and metals in
wastewaters [1,2]. On the other hand, peat is an abundant natural resource in Ireland (the third
largest peat deposit worldwide) and is an accumulation of partially decayed vegetation or organic
matter that is unique to natural areas called peatlands, bogs (ref. please here).Brooks [3] firstly
proposed the use of peat for residential wastewater treatment. Since then peat had been tested for
the adsorption of phosphate [4], thallium ions [5], arsenic [6] etc. from domestic and industrial
effluents. Regarding P adsorption in aqueous, published data showed that the capacity for peat is in
the range of 0.097 to 8.91 mg/g [4] while for alum sludge followed the order: orthophosphate >
pyrophosphate > triphosphate > organic phosphate and the range is from 3.3 to 85.9 mg/g [2,7,8].
However, it is noted that the individual studies were based on different experimental conditions and
there is no report on the comparison purpose of using these two low-cost materials. Thus,
knowledge of comparing the two cost-effective adsorbents for pollutant immobilization is not only
necessary for the materials choosing but also useful for the beneficial reuse to maximize their value
in practice. Therefore, the objective of the study was to compare and contrast of the two abundant
and indigenous low-cost materials, i.e. Irish peat and alum sludge, addressing on their Glyphosate
removal capacity via pot tests.
Organic phosphate was removed in pot tests filled with peat and alum sludge separately, while
effluent samples were taken from each pot to analysis the concentration of phosphorus (P) and COD
(chemical oxygen demand); physical and chemical analysis for both media before and after use was
carried out subsequently. The results show that the P removal capacity of alum sludge was
significant (99.8%), while the removal capacity of peat was considerably less than 10% after ten
weeks. Both materials significantly reduced the levels of COD, but it was noted that peat had a
marginally greater initial P removal capacity (74.9%) and did perform better than alum sludge (57%).
Moreover, pre-treatment is a crucial step to harness the full potential of peat. Overall, this study
provides a scientific clue for sorbents selection when considering alum sludge and peat to maximize
their value in practice.
Keywords: Adsorption, Alum sludge, Glyphosate, Irish peat, Phosphorus
851
References:
[1] Liu, R., Mao, Y., Shen, C., Zhao, Y. Can biofilm affect alum sludge adsorption: An engineering scope in a novel biofilm
reactor for wastewater treatment. Chemical Engineering Journal 328, 683–690, 2017.
[2] Maqbool, N., Khan, Z., Asghar, A. Reuse of alum sludge for phosphorus removal from municipal wastewater.
Desalination and Water Treatment 57, 13246–13254, 2016.
[3] Brooks J. L. A Field Study of the Efficiency of Sphagnum Peat as a Medium for the Treatment of Residential
Wastewater. PhD thesis, University of Maine, Orono, U.S. 1980.
[4] Xiong J. B. & Mahmood Q. Adsorptive removal of phosphate from aqueous media by peat. Desalination, 259(1-3),
59-64, 2010.
[5] Robalds A., Klavins M. & Dreijalte L. Sorption of thallium (I) ions by peat. Water Science and Technology, 68(10),
2208-2213, 2013.
[6] Oliveira L. K., Melo C. A., Goveia D., Lobo A. F., Hernandez M. A. A., Fraceto L. F. F., Rosa A. H. Adsorption/desorption
of arsenic by tropical peat: influence of organic matter, iron and aluminium. Environmental Technology, 36 (2), 149-
159, 2015.
[7] Babatunde, A.O., Zhao, Y.Q., Zhao, X.H. Alum sludge-based constructed wetland system for enhanced removal of P
and OM from wastewater: Concept, design and performance analysis. Bioresource Technology 101, 6576–6579,
2010.
[8] Ippolito J. A., Barbarick K. A., Heil D. M., Chandler J. P., Redente E. F. Phosphorus retention mechanisms of a water
treatment residual. Journal of Environmental Quality, 32, 1857-1864, 2003.
852
IMPACT OF TROPICAL LIGNOCELLULOSIC BIOMASS COMPOSITION IN STEAM

GASIFICATION CHAR PROPERTIES
L. M. ROMERO MILLAN1,2, F. E. SIERRA VARGAS1, A. NZIHOU2

1 Facultad de Ingeniería, Universidad Nacional de Colombia-Sede Bogotá, Bogotá, Colombia.
Abstract
Purpose: Agroindustrial lignocellulosic residues are diverse and have different physico-chemical
characteristics according to their origin and handling. This work aims to evaluate the impact of
tropical lignocellulosic agrowaste composition on steam gasification products. Special attention is
given to char properties.
Materials and methods: Three agricultural residues with different macromolecular and inorganic
composition, and H/C and O/C ratios near 1.5 and 0.8 were chosen: coconut shells (CS), oil palm
shells (OPS) and bamboo guadua (BG). Steam gasification tests were performed using a laboratory
scale fluidized bed reactor. Different gasification parameters were analyzed in order to determine
their influence in the produced gas quantity and the char properties. In particular, steam to biomass
ratio (S/B) varied from 0 to 5, gasification temperature from 750°C to 850°C, and gasification time
from 1 to 3 hours. The product yield was established for each gasification condition. Chars were
collected and analyzed, in order to determine their physico-chemical and structural characteristics.
The organic and the inorganic composition, as well as the specific surface area (S BET) and surface
functional groups of chars were determined.
Results: For the three studied biomasses, a maximum of gas production was observed for an S/B ratio
of 2. Moreover, an augmentation in the gasification temperature and time enhanced the gas
production and reduced the char yield. The char characterization highlighted that for the studied
experimental conditions, produced chars have high specific surface areas from 500 m 2/g to 1000
m2/g, and are highly microporous, with pore diameters between 4Å to 7Å. In all cases, CS chars
developed higher surface areas compared to OPS and BG. Similarly, higher amounts of oxygen
surface functional groups were found in coconut shells chars compared to other two feedstocks.
Conclusion: The differences observed between the properties of chars are mainly related to the
inorganic composition of raw materials. Coconut shells are rich in potassium (K), which is known to
be a catalyst element of steam gasification reactions [1]. In contrast, oil palm shells and bamboo
guadua are rich in silicon (Si), aluminum (Al) and phosphorous (P), which tend to inhibit the K
catalytic effect, and then, the biomass reactivity to steam gasification [2,3]. The inorganic
composition of raw biomasses has then an important influence in gasification chars properties and
can impact their possible valorization pathways.
References
[1] Dupont C, Jacob S, Marrakchy KO, et al (2016) How inorganic elements of biomass influence char steam gasification
kinetics. Energy 109:430–435. doi: 10.1016/j.energy.2016.04.094
[2] Nzihou A, Stanmore B, Sharrock P (2013). A review of catalysts for the gasification of biomass char, with some
reference to coal. Energy 58:305–317. doi: 10.1016/j.energy.2013.05.057
[3] Hognon C, Dupont C, Grateau M, Delrue F (2014) Comparison of steam gasification reactivity of algal and
lignocellulosic biomass: Influence of inorganic elements. Bioresour Technol 164:347–353. doi:
10.1016/j.biortech.2014.04.111)
853
ASSESSMENT OF THE ENERGY PRODUCTION POTENCIAL FROM PHYTOREMEDIATION

DERIVED BIOMASS
A.P.G.C. MARQUES1,2, P.M.L. CASTRO1, N.S. CAETANO2,3

1 CBQF – Centro de Biotecnologia e Química Fina, Escola Superior de Biotecnologia, Centro Regional
do Porto da Universidade Católica Portuguesa, Rua Arquiteto Lobão Vital, 4200-072 Porto, Portugal
2 .LEPABE – Laboratory for Process Engineering, Environment, Biotechnology and Energy at the
Faculty of Engineering of Porto (Lepabe-Feup), Rua Dr Norberto Frias, 4200-465 Porto, Portugal.
3 CIETI/ISEP (School of Engineering, Polytechnic of Porto), Rua Dr António Bernardino de Almeida
431, 4249-015 Porto, Portugal
Abstract
There are presently more than 3 million contaminated sites all over EU, according to the EEA (report
25186 EN). Heavy metal (HM) contamination is of particular concern, as metals are not degradable
and only transferable form one matrix to another [1]. Phytoremediation, a biologically based
technology, is gaining attention from the public and is an attractive low cost alternative for soil
requalification, by establishing a vegetation cover which will stabilize the site, avoiding dispersion of
contamination and simultaneously removing pollutants present in the brownfield [1]. Although the
fate of harvested biomass is a common obstacle for its implementation, it may represent an
opportunity for producing energy. However, and although it has been proposed theoretically as an
excellent option, the information available in literature concerning practical applications is scarce,
despite the considerable degree of success reported [2,3,4].
The use of biomass grown in degraded and abandoned soils, not involving agricultural soils for
energy crop cultivation, may increase the sustainability of utilizing biomass for energy generation,
while it may allow for increasing the available agricultural soil through the consequent gradual
decontamination of such brownfields.
This work presents a novel integrated strategy comprising the utilization of all plant parts (maize and
sunflower) parts for the generation of several energy products. Combinations of the selected
energetic plants and plant growth promoting microbiota was assessed, and the soil and plant status
was monitored to further understand the effects on crop productivity and soil remediation. At this
stage harvested plant tissues were used for oil extraction and bioethanol production. The quality of
the generated products was assessed and is discussed in this work to understand the effect of the
HM soil contamination in the quality of the final products.
References
[1] Marques A.P.G.C., Rangel AOSS, Castro PML (2009) Remediation of heavy metal contaminated soils:
phytoremediation as a potentially promising clean-up technology. Critical Reviews Environmental Science
Technology 39:622-654
[2] Syc, M., Pohorely, Kamenikova, P., Habart, J., Svoboda, K., Puncochar, M. (2012). Willow trees from heavy metals
phytoextraction as energy crops. Biomass and Bioenergy 37,106-113
[3] Ljung, A., Nordin, A. (1997) Theoretical Feasibility for Ecological Biomass Ash Recirculation: Chemical Equilibrium
Behavior of Nutrient Elements and Heavy Metals during Combustion. Environmental Science Technology 31: 2499–
2503
[4] Chami, Z.A., Amer, N., Smets, K., Yperman, J., Carlee, R., Dumontet, S., Vangronsveld, J. (2014) Evaluation of flash
and slow pyrolysis applied on heavy metal contaminated Sorghum bicolor shoots resulting from phytoremediation.
Biomass and Bioenergy, 63: 268-279)
854
GRAPHENE SPONGES FOR OIL REMOVAL
GEORGE Z. KYZAS1, ATHANASIOS C. MITROPOULOS

1 Hephaestus Advanced Laboratory, Eastern Macedonia and Thrace Institute of Technology, Kavala,
GR-654 04, Greece.
Abstract
Many different types of materials have been proposed or tested for use in cleaning up oil spills, including
zeolites, polymers, activated carbon, and even sawdust. Selective absorption capacity of the oil layer is of
paramount importance in such an application, and the toxicity of the absorbent itself is also an important
consideration. Based on our research, some graphene-sponges were in order to achieve a morphology with a
high surface area. Briefly, the fabrication of GN@PU (graphene/polyurethane) sponge was achieved via a
simple dip-coating method. The raw PU (polyurethane) sponge with dimensions of 40×40×20 mm3 was
washed respectively with the ethanol and deionized water to remove impurities of the sponge. Different mass
ratios of GN (1 g) to CNWs that was 1:5 (GN@PU-1), 1:10 (GN@PU-2), 1:20 (GN@PU-3) and 1:30 (GN@PU-4)
were fabricated, respectively. The mixture of GN and CNWs was dispersed in deionized water (400 mL) with
the assistance of ultrasonication for 36 h. Then the sponge was put into the disperse solution followed by
ultrasonication for 40 min. 4 samples were prepared for each dip coating process. The dip-coated sponges
were taken out and put in the oven for drying for 24 h at 50°C. After that, the process of both dip-coating and
drying was repeated once to make sure the GN was uniformly coated on the PU sponge surface. In order to
eliminate the effect of hydrophilic CNWs (cellulose nanowhiskers) on the wetting behavior of sponges,
GN@PU-5 was selected to be dip coated firstly in GN/CNWs suspension (CNWs/GN = 1:20) and drying for 24 h
at 50°C. Then the dried sponge was put into pure GN suspension and dried. Thus the outer surface layer is
only covered with neat GN sheets without CNWs. This sponge was named GN@PU-5. GN@PU-6 sponge was
fabricated by putting PU sponge in pure GN suspension and drying, this process was repeated to compare
with other sponges. All dip-coating process was lasted 40 min following ultrasonication and drying processes
were continued for 24 h at 50 °C.
(a) (b)
Fig. 1. (a) SEM images of the morphology of GN@PU-6 (b); the exterior of
GN@PU-6 (b) Absorption capacity of GN@PU (1:20) sponge for various oils and
organic solvents.
855
The GN@PU-3 sponge (the mass ratio of CNWS to GN was 1:20) was optimum ratio for the oil
absorption. GN@PU sponges were fabricated with a simple dip-coating method, where PU sponges
functioned as a basic continuous framework. The GN@PU sponges can be continuously conducted the
experiment of oil-water separation more than 100 cycles. The GN@PU sponges can effectively separate oils
and organic solvents in water, and absorption capacity of lubricating oil was 28 g/g. Moreover, according to
thermal and mechanical analysis, the GN@PU sponges exhibited excellent elasticity of PU sponge and good
thermal and chemical stability. Furthermore, even conducting oil-water separation experiment 50 times,
GN@PU-5 still kept super-hydrophobicity with water contact angle over 150°. It exhibited excellent
performance with adsorption capacity for toluene, acetone, and lubricating oil of 34, 46, and 31 g/g,
respectively. In conclusion, the GN@PU sponges were fabricated with dip-coating method, which simplified
the process of preparation and saved production cost. And the GN@PU sponges possessed excellent
functional performance and a broad application future due to excellent oil-water separation capacity and
notable cycle performance.
References
[1] Luo, Y., Jiang, S., Xiao, Q., Chen, C., Li, B.: Highly reusable and superhydrophobic spongy graphene aerogels for
efficient oil/water separation. Sci. Rep. 7, (2017)
[2] Xiao, J., Zhang, J., Lv, W., Song, Y., Zheng, Q.: Multifunctional graphene/poly(vinyl alcohol) aerogels: In situ
hydrothermal preparation and applications in broad-spectrum adsorption for dyes and oils. Carbon 123, 354-363
(2017)
[3] Ao, C., Yuan, W., Zhao, J., He, X., Zhang, X., Li, Q., Xia, T., Zhang, W., Lu, C.: Superhydrophilic graphene
oxide@electrospun cellulose nanofiber hybrid membrane for high-efficiency oil/water separation. Carbohyd. Polym.
175, 216-222 (2017).)
856
WASTE AGRICULTURAL SUGAR CANE BIOMASS FOR THE RECOVERY OF GOLD (I)
THIOUREA COMPLEXES
N. SYNA, A.W. CHEUNG, M. VALIX

1 The University of Sydney, Sydney, NSW 2006, Australia
Abstract
The extraction of gold is based on hydrometallurgical routes that use lixiviants such as cyanide in an
alkaline solution and chlorine and thiourea in an acidic medium [1,2]. Although cyanide has been
favoured commercially, it is disadvantaged by slow dissolution kinetics, poor selectivity and its
toxicity [3]. Among the complexing agents, thiourea (CS(NH2)2) is of considerable interest because it
offers faster dissolution rates, greater selectivity and its current EPA status is medium hazard
ranking. The gold leaching reaction with thiourea can be described in its simplified form as:
+
2𝐴𝑢 + 2𝐶𝑆(𝑁𝐻2 )2 + 𝑜𝑥𝑖𝑑𝑖𝑠𝑖𝑛𝑔 𝑎𝑔𝑒𝑛𝑡 → 𝐴𝑢[𝐶𝑆(𝑁𝐻2 )2 ]2 + 𝑒 (1)
Most commercially available carbons for gold extraction, however, have been developed only for the
recovery of gold cyanide complex. This paper reports on an investigation on the potential to use
sugar cane bagasse as a precursor for the manufacture of biochar and activated carbons suitable for
the recovery of gold-thiourea complexes. Activated carbons were prepared from waste sugar cane
bagasse by thermal and chemical methods. These carbons were tested for the adsorption of
thiourea- gold (I) chloride complexes which is an important alternative gold lixiviant to cyanide with
the potential to address current ecological and safety concerns in the extraction of gold. The
textural and surface chemical properties of the carbons were analysed and their effects on gold
adsorption examined. Gold adsorption increased with carbon surface area, alkalinity and
microporosity. The optimum gold adsorption obtained from activated carbon derived from bagasse
was 336 mg/g of carbon. This was comparable to gold adsorption from commercially available
carbons of 195-249 mg/g of carbon demonstrating the potential of sugar cane bagasse as precursor
for manufacture of activated carbon for gold recovery.
400
350
300
Adsorption Capacity
(mg Au/g carbon)
250
200
+
150 Figure 1. [Au-Tu]n adsorption as a function of
100 total surface area
50
0
0 500 1000 1500 2000
TSA (m 2 /g)
15% PCO2, 900°C 100% PCO2, 900°C

Commercial carbons Chemically activated carbon
References Fig. 5. [Au-Tu]n+ adsorbed at various carbon

[1] Lee, H.Y., S.G. Kim, and J.K. Oh,surface areas
Canadian Metallurgical Quarterly, 1997. 36(3): p. 149-155
[2] Deschenes, G., Cim Bulletin, 1987. 80(902): p. 103-103
[3] Lawrence, R.W. and P.B. Marchant, Cim Bulletin, 1987. 80(902): p. 89-89
857
AN EXPERIMENTAL STUDY ON EMULSIFICATION OF LIQUEFACTION BIO-OIL, DIESEL

AND ALCOHOLS
D. LÄNGAUER1,2, W.-H. CHEN2, M. ŠAFÁŘ1,2, V. ČABLÍK1

1 VŠB – Technical University of Ostrava, Faculty of Mining and Geology, Institute of Environmental
Engineering, 17.listopadu 15, 708 33 Ostrava-Poruba, Czech Republic.

2 Department of Aeronautics and Astronautics, National Cheng Kung University, Tainan 701, Taiwan.
Abstract
Liquefaction bio-oils are a sustainable and renewable energy resource. Emulsification is the only
physical upgrading technology that blends immiscible liquids into homogenous emulsions, through
the addition of emulsifiers. In this way, stable emulsions of bio-oil and diesel can be prepared.[1,2]
Emulsification characteristics of liquefaction bio-oils, diesel, emulsifier and alcohols at various
operating conditions are analyzed. Surfactants is investigated, emulsion stability and minimum
emulsifier usage.
Atlox polymeric surfactants are medium molecular weight nonionic materials which use steric
mechanisms to stabilize emulsions and dispersions. The hydrophilic portion is polyethylene oxide
(PEG) and the hydrophobic portion is poly 12-hydroxystearic acid (pHSA) or alkyd resin. The
mechanism of stabilization involves the solvated pendant side chains extending far into the
continuous medium with the polymeric backbone adsorbing to the solid or liquid internal phase. [3]
The functional groups in the emulsifiers, bio-oils, alcohols and diesel are analyzed by a Fourier
transform infrared spectroscopy (FTIR) to recognize the characteristics of emulsions. It is found that
FTIR is a fast and effective tool to examine the stability and homogeneity of emulsified fuels, even
though no stratification is observed.
References
[1] ZHANG, Le, Ronghou LIU, Renzhan YIN a Yuanfei MEI. Upgrading of bio-oil from biomass fast pyrolysis in China: A
review. Renewable and Sustainable Energy Reviews [online]. 2013, 24, 66-72 [cit. 2017-10-11]. DOI:
10.1016/j.rser.2013.03.027. ISSN 13640321.
[2] GUO, Zuogang, Shurong WANG a Xiangyu WANG. Stability mechanism investigation of emulsion fuels from biomass
pyrolysis oil and diesel. Energy [online]. 2014, 66, 250-255 [cit. 2017-10-11]. DOI: 10.1016/j.energy.2014.01.010.
ISSN 03605442.
[3] LIN, Bo-Jhih, Wei-Hsin CHEN, Wojciech M. BUDZIANOWSKI, Cheng-Ting HSIEH a Pei-Hsun LIN. Emulsification analysis
of bio-oil and diesel under various combinations of emulsifiers. Applied Energy [online]. 2016, 178, 746-757 [cit.
2017-10-11].DOI: 10.1016/j.apenergy.2016.06.104. ISSN 03062619.
858
STEAM-THERMOLYSIS OF THERMOPLASTIC AND THERMAL RESISTANT CARBON

FIBER COMPOSITES. FORMULATION OF NEW COMPOSITES WITH RECOVERED
CARBON FIBERS
P.FONTAINE12, E. WEISS2, Y. SOUDAIS2, R. BARNA2

1 ADEME (Agence de l’environnement et de la maitrise de l’énergie), France.
2 Ecole des Mines Albi-Carmaux, France.
Abstract
Carbon Fiber Reinforced Composites (CFRC) are high technical materials applied in various fields such
as aerospace and automotive sectors, construction or sport. Recently, the demand of CFRC has
increased significantly and is expected to grow to over 120,000T by 2020. Nowadays, residues of
composite materials are currently grinded or incinerated, and these solutions do not let the recovery
of the carbon fibers, the added-value material. Due to new European directives, and strategies along
EU Waste hierarchy, new options that minimize the environmental impact and reduce the cost of
manufacturing should be developed. The best solution consists in recovering the carbon fibers and to
recycle them in new cheaper formulations.
The recovery of carbon fibers from waste composite is currently studied with dry and wet
thermochemical processes, such as pyrolysis, steam-thermolysis, or solvolysis ([1]YE,2012, [2]OLIVEIRA
NUNES,2015, [3]CHAABANI, 2017). Actually, pyrolysis and steam-thermolysis are the most developed
processes at industrial scale. However, such as in the field of biomass thermoconversion, the variability
of the resources is a key point in the technology development. Therefore the objective is to study the
recycling of carbon fibers from thermosetting and thermoplastic organic resin composites and their
mixtures. The efficiency of the process is based on the resin removal and obviously the mechanical
properties of the recovered carbon fibers for subsequent formulation. The experiments are carried
out with a 1L semi-continuous reactor feed with 50-100 g of waste composite. The operating
conditions such as the steam flow rate (40-160 g/h), the temperature (300-550°C) and the nature of
feedstock (thermoset and thermoplastic resins) are the core of this study. Among the resins
investigated, a thermoplastic and thermoresistant resin has been used. The impact of its presence on
the reaction temperature was significant, increasing the reaction temperature requested (550°C) for
achieving the resin removal, while the other resin removals were achieved at 500°C. The
steam/composite ratio is also a key aspect, since a too high steam ratio could attack the carbon fibers
that will result in a degradation of mechanical properties. In the mixture, the “optimal” reaction
temperature defined with each composite (500°C) was only modified in presence of the
thermoresistant resin. Overall, the conversion was achieved for each resin for an equimassic mixture
containing 2 thermosetting and 2 thermoplastics resins, under the following conditions: 500°C,
steam/composite ratio 2 during 2 hours. Keeping the same parameters and adding the
thermoresistant resin (20 wt.% in the mixture), the efficiency of the resin removal decreased to 97%.
References
[1] YE S.Y.: Valorisation de déchets composites à matrices polymériques renforcées de fibres de carbone par un procédé
de vapo-thermolyse. thesis, Institut National Polytechnique de Toulouse, France (2012)
[2] OLIVEIRA NUNES A.: Carbon fiber reinforced composites: recovery of carbon fiber by steam-thermolysis, optimization
of the process. thesis, Ecole des Mines d’Albi-Carmaux, France (2014)
[3] CHAABANI C.: Carbon fibers reinforced composites: recovery of carbon fibers solvolysis. Impact on carbon fiber quality
and liquid phase valorization. thesis, Ecole des Mines d’Albi-Carmaux, France (2017)
859
MODELING AND DESIGN OF AN INDUSTRIAL REACTOR FOR TAR THERMAL CRACKING

AND SYNGAS UPGRADING
F. MARIAS1, J.P. ROBERT-ARNOUIL2, A. BLOAS2

1 Univ Pau & Pays Adour, Laboratoire de Thermique Energétique et Procédés-IPRA, Pau, France.
2 Europlamas, Pessac, France.
Abstract
Tars production during waste and biomass gasification is an important bottleneck in the
development of thermochemical conversion processes of these resources. These tars are heavy
aromatics components (with several possible rings) for which the high dew point values might lead
to fouling and corrosion in the downstream use (and valorization) of the gas leaving the gasifier.
Separation of these species from the syngas lead to a decrease in the energetic content of the gas,
their thermal cracking allows for converting them into lighter molecules which keeps their energetic
content in the gas to be further valorized. It is in that context that French company Europlasma
develops high temperature reactors (Turboplasma). This high value is reach using plasma torch. The
design of these reactors has been possible thanks to a partnership between the company and a
French academic Laboratory (LaTEP, University of Pau) who has strong experience in the modeling of
reactors for thermochemical conversion. The goal of the present paper is to show how modeling has
been a very efficient tool in the final building of the industrial reactors.
860
HYDROTHERMAL CARBONISATION OF POULTRY LITTER: EFFECTS OF INITIAL pH ON

YIELDS AND CHEMICAL PROPERTIES OF HYDROCHARS
B. M. GHANIM 1, W. KWAPINSHI 1, J. J. LEAHY 1,

1 Carbolea Research Group, Department of Chemical Science, University Of Limerick, Ireland..
Abstract
Poultry litter (PL) has been described as a complex mixture. Notwithstanding, the advantages of PL
for increasing soil fertility, there are environmental concerns about its over application on
agricultural sites. Disposal technology for biowaste has clearly indicated that thermochemical
conversion processes have the capability to convert animal by-products into valuable products.
Among the disposal alternatives, the hydrothermal carbonization (HTC) process is considered to be a
very effective thermal treatment which typically is performed in water at moderate temperatures
between 180 and 260 °C for various residence times under self-generated pressures. In this study,
HTC of PL was carried out at 250 °C for 2 h and at various initial pH using acetic acid (CH 3COOH) or
sulfuric acid (H2SO4) to evaluate the impact of initial pH on the yields (HY) and fuel properties of
hydrochar (HC). The results indicated that undertaking HTC in the presence of acids (CH 3COOH,
H2SO4) significantly affects the HY and energy contents of HC. The C content and HHV of the HC
increased with decreasing initial pH. In the presence of H2SO4, the HY increased while the ash
content was significantly reduced. However, in the presence of CH3COOH, the ash recovery
decreased while carbon and energy recoveries were relatively constant. From the obtained results, it
can be concluded that the changes in initial pH affected the yields and chemical composition of the
produced hydrochar. Also the results showed that the type of acids, organic or mineral, was
important in terms of their effects.
References
[1] Ghanim, B.M., Pandey, D.S., Kwapinski, W., Leahy, J.J., 2016. Hydrothermal carbonisation of poultry litter: Effects of
treatment temperature and residence time on yields and chemical properties of hydrochars. Bioresour. Technol.
216, 373–380.
[2] Kambo, H.S., Dutta, A., 2015. A comparative review of biochar and hydrochar in terms of production, physico-
chemical properties and applications. Renewable Sustainable Energy Rev. 45, 359–378.
[3] Reza, M.T., Rottler, E., Herklotz, L., Wirth, B., 2015. Hydrothermal carbonization (HTC) of wheat straw: Influence of
feedwater pH prepared by acetic acid and potassium hydroxide. Bioresour. Technol. 182, 336–344.
[4] Wikberg, H., Ohra-aho, T., Pileidis, F., Titirici, M.-M., 2015. Structural and morphological changes in Kraft lignin
during hydrothermal carbonization. ACS Sustainable Chem. Eng. 3, 2737–2745.)
861
COMBINED PRODUCTION OF HYDROGEN AND ELECTRICITY FROM

HOSPITAL SOLID WASTE: APPLICATION
J. RAMOS1, A. INGA2, S. QUESNEL1, E. GONZALES2, M. RIVERA2

1 University of Engineering and Technology (UTEC), Lima, Peru.
2 National University of Engineering (UNI), Lima, Peru.
Abstract
In Peru, the Ministry of the Health and hospitals are responsible for the hospital’s waste treatment
and disposal. At a national level, in 2013, 12.755 tons of bio contaminated solid waste were
generated [1]. Some hospitals choose the incineration as an option for waste treatment, but it can
generate toxic components (CH4, CO2) for the environment and health of people living or working
close to these hospitals. In this context, the transformation of the hazardous solid waste to hydrogen
is the solution to generate an adequate fuel in order to meet the energy demand of the cities,
chemical and automotive industries [2].
In this paper, a combined production of hydrogen & electricity (CPHE) energy system from hospital-
solid-waste is proposed. A CPHE energy facility is based on three processes: (1) production of syngas
(including solid waste treatment and solid waste gasification); (2) production of hydrogen
(washing/separation/purification process of the syngas), and (3) production of electricity (with
hydrogen fuel cells).
The CPHE energy system proposed in this work uses PEM fuel cells fueled by hydrogen [3] from
gasification process [4]. Low electricity prices affecting the economy of a CPHE energy facility. In
Peru, this kind of energy system is economically feasible when the power plant capacity is higher
than 1 MWe [4]. Medium scale projects of power plant generation (3 to 5 MWe) based on fuel cells
fueled by hydrogen (from hospital-solid-waste gasification) demonstrate an economic feasibility with
a payback of 5 years. In Peru, the public hospitals with 500 beds managed by the Health
Administration could implement this technology (CPHE energy facility) because of their energy
consumption may be supplied using a mix of hospital solid wastes and other residues.
Overall, this concept of electricity production from hydrogen fuel cells would contribute to reduce
the environmental impact of the national energy system. Solid waste from city of Lima (9.080 t/day)
and a CPHE energy system could generate 1.869 GWh/year. It means a 10 % of the electricity
demand of Lima Region.
References
[1] Ministry of Environment of Peru , «Sixth national report about the solid wastes and the environmental management
municipal and no municipal 2013,» 12 2014..
[2] N. Abas, A. Kalair y N. Khan, «Review of fossil fuels & future energy technologies,» Futures, vol. 69, pp. 31-49, 2015.
[3] J. Ramos, A. Inga, S. Quesnel, Y. Carhuaricra, E. Grandy, G. Fuentes, W Huaccachi, «Plantas de producción combinada
de hidrógeno y electricidad a partir de residuos sólidos hospitalarios no peligrosos. Parte I: Tecnología.»..
[4] J. Ramos-Saravia, P. Muñoz, C. Ames, A. Sancho, E. Gonzales, F. Valencia y C. Zavala, «Microsistema energético de
respaldo para hospitales basado en pilas de combustible accionadas con biohidrógeno a partir de bagazo de caña de
azúcar». XXVIII Congreso Interamericano de Ingeniería Química, Cusco, 2016..
862
SUSTAINABILITY OF THE VALORISATION OF DISCARDED CARTILAGINOUS BIOMASS
X. GARCÍA-SANTIAGO1, A. FRANCO-URÍA1, L.T. ANTELO2, J.A. VÁZQUEZ2, G. FEIJOO1

1 Department of Chemical Engineering, School of Engineering, Universidade de Santiago de
Compostela, 15782 Santiago de Compostela, Galicia, Spain.
2 Marine Research Institute IIM-CSIC, Eduardo Cabello, 6, 36208 Vigo, Spain.
Abstract
Current fishing practices generate discards which are usually dumped overboard, resulting in the
waste of valuable resources. However, the new legal framework established by the Common
Fisheries Policy [1] oblige to keep on board and land both target and non-target species. Therefore,
the quantity of marine biomass to be efficiently managed inland is expected to increase in the near
future. Once in land, this biomass is processed according to its characteristics to obtain high-added
value products. From cartilaginous species, cartilage and chondroitin sulphate can be obtained [2].
The impacts related with the production of both cartilage and chondroitin sulphate with a purity of
90% (CS90) were assessed and quantified by Life Cycle Assessment (LCA). In this analysis, solid by-
products are considered to be sent to other processes. Thus, the muscle is sent to the production of
fish protein hydrolysate (FPH) and the rest of the solids to the production of fish meal. The
wastewater is treated in an appropiate wastewater treatment plant. A summary of the inventory
data from a pilot plant can be seen in table 1.
Table 1: Summary of the inventory data used in the LCA.
Functional unit Inputs from technosphere Outputs to technosphere

1 kg cartilaginous fish Tap water Electricity NaOH HCl Product Wastewater By-products
Cartilage 1.6 L 0.9 kWh - - 0.1 kg 1.6 L 0.8 kg
CS90 2.3 L 1.6 kWh 0.01 kg 0.1 kg 0.01 kg 2.3 L 0.9 kg
The hot spot identified in the cartilage production was the drying step, with a contribution to the
total impact around 40%. For CS90, the contribution of the hydrolysis and drying stages implies 33%
and 19%, respectively. These impacts are mainly related with the consumption of electricity.
Comparing both processes, the global impact increases by a factor of 3 when the process continues
from cartilage to CS90. The identification of the critical steps is crucial to optimize these processes
and convert them in alternatives to the valorization of marine biomass.
Acknowledgements. Project Life ISEAS LIFE13 ENV/ES/000131. X. García-Santiago, A. Franco-Uría

and G. Feijoo belong to CRETUS (AGRUP2015/02).
References
[1] European Commission: Regulation (EU) No 1380/2013 of the European Parliament and the Council of 11 December
2013 on the Common Fisheries Policy. Available at: http://ec.europa.eu/cfp/indexen.htm (2013)
[2] Antelo, L.T., de Hijas-Liste, G.M., Franco-Uría, A., Alonso, A.A., Pérez-Martín, R.I. : Optimisation of processing routes
for a marine biorefinery. J.Clean.Prod. 104, 489-501 (2015)
863
TREATMENT OF OSMIUM WASTEWATER FOR RECOVERY OF OSMIUM TETROXIDE
T. NUNOURA1, H. HIRAI2, R. MIYOSHI2, O. SAWAI1

1 Environmental Science Center, The University of Tokyo, Chiba, Japan.
2 Department of Environment Systems, The University of Tokyo, Chiba, Japan.
Abstract
Osmium (Os) is a scarce metal element and its completely oxidized form, osmium tetroxide (OsO4), is
often used in scientific research as a powerful oxidizer and as a staining reagent. OsO4 is extremely
toxic but its treatment method has not been developed yet due to its high fugacity into gas phase
[1]. Considering its high volatility (i.e., difficulty in immobilization) and scarcity (i.e., high price),
recovery and reuse of OsO4 is favourable rather than stabilization and landfill which is commonly
applied for hazardous metals. The final goal of this study is to develop a treatment method of Os
wastewater to recover OsO4. The proposed system consists of two parts: supercritical water
oxidation (SCWO) and supercritical carbon dioxide (SCCO2) extraction. By SCWO Os-compounds in
wastewater are totally oxidized to OsO4 while co-existing organic matters are converted to CO2.
Subsequently, SCCO2 is applied to the SCWO-effluent to extract OsO4 and as a result Os-free water is
obtained. The purpose of this study is to investigate the behaviour of Os-compounds in SCWO and
SCCO2 extraction.
For the SCWO experiment, potassium hexachloroosmate (K2OsCl6) was used as a reactant. Aqueous
solutions of K2OsCl6 and H2O2 were preheated and introduced to the reactor (made of SUS316) by
high-pressure pumps. The reaction conditions were kept at 673 K and 22.5 MPa by a molten salt
bath and a back-pressure regulator. The effluent samples were analysed by UV-vis and ICP-MS for
OsO4 and total Os concentrations. Effect of co-existing organic matter was also studied. As a result,
K2OsCl6 was successfully oxidized to OsO4 (its yield reached 100%) within 50 s. However, when
methanol was present in the reactor, OsO4 yield dropped drastically while methanol oxidation was
highly promoted, implying that OsO4 is produced but is immediately consumed (reduced) for
methanol oxidation. Results suggest that elimination of organics is necessary to achieve complete Os
oxidation.
For the SCCO2 extraction study, aqueous solution of OsO4 (200 mg/L) was put in the extractor
(SUS316) and deionized water was put in the collectors. The extractor was maintained at 308-328 K
and 8-12 MPa by a heater and a SCCO2 pump. After stabilization, SCCO2 was flowed through the
extractor for a desired time. Samples in both the extractor and the collectors were analysed for OsO 4
and total Os concentrations. As a result, OsO4 was successfully extracted and recovered by the SCCO2
system, and the extraction percentage exceeded 99.9% within 60 min at 10 MPa and 318 K with
SCCO2 flowrate of 3 mL/min. Higher temperature and flowrate resulted in higher extraction, but the
influence of pressure was not monotonic, suggesting the competing effects of residence time,
solubility, and dielectric constant. Change of the OsO4 solution’s pH (pH: 3-11) did not affect the
extraction performance.
In summary, the proposed treatment system was capable of oxidizing Os-compound and recovering
OsO4, though the effects of various parameters and co-existing matters are still under investigation.
Detailed results including reaction mechanism will be discussed at the presentation.
Acknowledgments
This work was supported by JSPS KAKENHI Grant Numbers JP15K20925, JP17K00593.
Reference
[1] Švorc, L., Tomčík, P., Durdiak, J., Rievaj, M., Bustin, D.: Analytical methods for the detection of osmium tetroxide: A
review. Pol. J. Environ. Stud. 21(1), 7–13 (2012)
864
PROCESS SCALE-UP FOR A COMPLETE VALORIZATION OF WINEMAKING WASTE

USING SUPERCRITICAL CO2
K. DUBA1, L. FIORI2
1 East Carolina University, College of Engineering and Technology, Greenville, NC 27858, USA.
2 University of Trento, Department of Civil, Environmental and Mechanical Engineering, Trento, Italy.
Abstract
Winemaking industry produces throughout the world more than 3 Mt of grape marc [1], the primary
winemaking solid by-product, consisting of grape seeds, skins and stalks. The potential for valorising
grape marc is enormous, in particular concerning innovative food applications [2]. Grape seed oil
extraction is already established, but the actual production processes present drawbacks:
mechanical extraction by pressure allows for a high quality oil, but the extraction yield is low;
conversely, solvent extraction (using, for instance, n-hexane) allows for high yield at the expenses of
oil quality. Supercritical CO2 (SCO2) extraction represents an interesting alternative, allowing for both
high quality oils and extraction yields [3,4]. Unfortunately, the use at industrial scale of the SCO2
extraction process is limited by its high investment costs.
In this framework, the aim of this study is to provide a bio refinery scheme, at industrial scale, to
valorise grape marc for grape seed oil production. Data obtained at lab-scale [5] are duly used to
model the SCO2 extraction plant at a larger scale. The bio refinery plant is then designed, and the
involved costs (both operating and investment costs) are quantified. SCO2 is used to extract grape
seed oil while grape skins and stalks are burned to provide the necessary energy for the process. A
plant with a total capacity of 15000 ton of grape marc per-year has a rate of return on investment of
8.25% and a payback period of 5 years at the current minimum retail-selling price of grape seed oil.
Investing in such a complete SCO2 extraction plant provides attractive socio-economic and
environmental benefits and generates substantial revenues. Besides, it creates an opportunity for
wine-makers to sell sustainably wet grape marc at a price of up to US$ 10/ton.
References
[1] www.faostat3.fao.org
[2] Lavelli, V., Torri, L., Zeppa, G., Fiori, L., Spigno, G.: Recovery of winemaking by-products for innovative food
applications. Ital. J. Food Sci. 28, 542–564 (2016)
[3] Fiori, L., Lavelli, V., Duba, K.S., Sri Harsha, P.S.C., Mohamed, H.B., Guella, G.: Supercritical CO2 extraction of oil from
seeds of six grape cultivars: modeling of mass transfer kinetics and evaluation of lipid profiles and tocol contents. J.
Supercrit. Fluids 94, 71-80 (2014)
[4] Mohamed, H.B., Duba, K.S., Fiori, L., Abdelgawed, H., Tlili, I., Tounekti, T, Zrig, A.: Bioactive compounds and
antioxidant activities of different grape (Vitis vinifera L.) seed oils extracted by supercritical CO 2 and organic solvent.
LWT - Food Science and Technol. 74, 557-562 (2016)
[5] Duba, K.S., Fiori, L.: Supercritical CO2 extraction of grape seed oil: effect of process parameters on the extraction
kinetics, J. Supercrit. Fluids 98, 33-43 (2015)
865
THERMAL DEGRADATION AND TAR REMOVAL TESTS WITH CHAR FROM

COMMERCIAL GASIFICATION SYSTEMS
E. CORDIOLI1, F. PATUZZI1, M. BARATIERI1

1 Free University of Bolzano, Piazza Università 5, Bolzano 39100, Italy.
Abstract
The formation of tar during gasification of biomass is still a major hindrance for the development and
application of gasification technologies on a wide scale. The condensation of tar can cause the
blocking of pipelines, engines, fuel lines, and nozzles, thus damaging process equipment. Catalytic
cracking is the most efficient technique for tar removal, allowing for the retrieval of chemical energy
through conversion of tar into useful products. Many studies have shown that char is a potential
catalyst for tar removal [1]. However, the main research has only concerned chars derived from
pyrolysis of biomass under controlled conditions. The present work assesses the potential catalytic
activity of chars collected from commercial gasifiers installed in South-Tyrol (Italy). First, thermal
degradation tests at high temperature (up to 900 °C) were performed in a tubular fixed-bed reactor
in the Bioenergy and Biofuels Lab of the Free University of Bolzano. The tests carried out in inert
atmosphere (N2) resulted in very low mass losses, proving that char is suitable for high temperature
applications like the ones required for the catalytic cracking of tars. The degradation of char was
tested also in reactive atmosphere (CO2), showing negligible mass loss up to 700 °C, but degrading
rapidly at higher temperatures. The test rig for inspecting the suitability of char for tar removal was
then designed and set up. Previous works tested char-based catalysts for the removal of model tars,
trying to determine the reactivity of char for tar adsorption and cracking. Burhenne and Aicher [2]
tested benzene adsorption capacity of pyrolytic char, as well as its reactivity for catalytic removal of
benzene. Bhandari et al. [3] studied the catalytic activity of biochar for removal of toluene,
comparing its catalytic activity with that of activated carbons. Similarly, toluene was chosen in the
present work as model tar for preliminary experiments. Tar adsorption tests at ambient temperature
and tar cracking tests at high temperature (700-900 °C) were carried out by leading toluene through
a bed of char in a quartz reactor and analyzing the released gaseous products. The tar removal
efficiency of the char samples was calculated based on inlet and outlet concentrations of toluene. A
full characterization of the chars was performed before and after each test, in terms of elemental
analysis, BET surface area, and pore volume size and distribution, in order to identify which physical-
chemical properties led to higher tar removal efficiencies. The tests confirmed that biomass char has
high potential as adsorbent and catalyst for the removal of tars. The results with toluene are, in fact,
comparable to those found in literature for activated carbons. Further experiments are envisaged
with other model tars (e.g. naphthalene, phenol), and with real producer gas in order to test the
activity of char under real operating conditions and, hence, to evaluate its commercial potential.
References
[1] J. Lee, K.-H. Kim, E. E. Kwon: Biochar as a Catalyst. In: Renewable and Sustainable Energy Reviews, 77, 70–79 (2017)
[2] L. Burhenne, T. Aicher: Benzene removal over a fixed bed of wood char: The effect of pyrolysis temperature and
activation with CO2 on the char reactivity. In: Fuel Processing Technology, 127, 140–148 (2014)
[3] P.N. Bhandari, A. Kumar, D.D. Bellmer, R.L. Huhnke: Synthesis and evaluation of biochar-derived catalysts for
removal of toluene (model tar) from biomass-generated producer gas. In: Renewable Energy, 66, 346–353 (2014)
866
LOAD MODULATION CAPABILITY OF AN OPEN TOP GASIFIER BY VARYING THE

SECOND STAGE AIR FLOW RATE
D.ANTOLINI 1, S. SHIVANANDA AIL 1, C. CALIGIURI1, F. PATUZZI 1, M. RENZI 1, M. BARATIERI 1

1 Free University of Bolzano, Faculty of Science and Technology, Bolzano, Italy.
Abstract
During the last years, small-scale gasifiers coupled with internal combustion engines have been
successfully commercialized with electrical and cogeneration efficiencies of about 20% and 80%,
respectively [1]. The increasing installation and operation of biomass gasification based CHP plants in
the past few years, suggests a robust performance such systems [2].
However, the operation of these plants are rigidly governed by the specific fuel properties (moisture
fraction, shape and size of biomass and its availability). In addition, CHP biomass gasification units
typically lack on load modulation capability, which refers to the ability of controlling the feed load to
generate electrical and thermal power as a function of its demand. In this way, the effectiveness of
the plant can be enhanced, producing energy when it is needed (load modulation).
This work is based on a pilot CHP system set up at the Bioenergy and Biofuels Lab of the Free University
of Bolzano. The experimental system couples an open-top downdraft gasifier with a 4kW single-
cylinder dual-fuel diesel engine. The configuration of the gasifier is based on a double-stage single line
reactor, wherein the primary air required for gasification is partly drawn from the (open) top, and the
secondary air from the nozzles that are located at the combustion zone. The hot gas exiting from the
reactor bottom passes through a clean-up section composed of a cyclone, two scrubbers, a chilled
water scrubber and a fabric filter. Finally, the gas is sent to a burner or used in an internal combustion
engine.
This biomass gasification system was designed in order to increase the residence time within the
reactor at elevated temperatures (1273 – 1373 K) in the char zone, resulting in enhanced conversion
efficiencies and negligible tar concentrations. During the experimental tests, the modulation capability
was obtained varying and controlling the airflow rate provided to the reactor.
In order to maintain high conversion efficiency and high temperature in the char combustion zone,
different airflow rates were tested through the nozzle in the char combustion zone. In order to assess
the effect of the load modulation on the performance of the entire CHP system, the experimental
results in terms of syngas heating value and flow rate were used as input in a 0-D thermodynamic
model describing a dual fuel combustion engine [3].
This approach confirmed the possibility of modulating the load of the gasifier using the airflow rate as
a guide parameter by simultaneously enabling the preservation of elevated temperatures at the
reduction zone resulting in higher gas conversion efficiencies.
References
[1] E. Bocci, M. Sisinni, M. Moneti, L. Vecchione, A. Di Carlo, and M. Villarini: State of art of small scale biomass gasification
power systems: A review of the different typologies. In: Energy Procedia 45, 247–256 (2014)
[2] F. Patuzzi, D. Prando, S. Vakalisa, A.M. Rizzo, D. Chiaramonti, W. Tirler, T. Mimmoa, A. Gasparella, M. Baratieri: Small-
Tyrol (Italy). In: Energy 112, 285–293 (2016)
[3] C. Caligiuri, M. Renzi: Modelling a dual fuel diesel – producer gas compression ignition engine. In: 9th International
Conference on Applied Energy ICAE2017 (2017)Broy, M.: Software engineering — from auxiliary to key technologies.
In: Broy, M., Denert, E. (eds.) Software Pioneers, pp. 10–13. Springer, Heidelberg (2002)
867
EXPERIMENTS AND MOLECULAR DYNAMICS SIMULATIONS ON THE INTERACTION OF

TRIOCTYLAMINE/SULFURIC ACID/WATER SYSTEM
NA LI1, ZHIDONG CHANG1, XUE WU1, CHANGYAN SUN1, WENJUN LI1

1 Department of Chemistry and Chemical Engineering, School of Chemistry and Biological
Abstract
The treatment industrial waste acid with low concentration is a traditional and tough topic, in which
solvent extraction with trioctylamine (TOA) as extractant has been widely regarded as a cost
effective, low-energy-consuming technique and received extensive applications in the metallurgical
industry [1]. However, TOA is prone to aggregate and form something like viscoelastic material
during the process of the waste acid [2], which greatly damages the potential usage of TOA.
Therefore, it is meaningful to investigate and disclose the aggregation mechanism.
Based on the possible molecular interaction model proposed in our previous work [3, 4], we are
going to probe the interaction of TOA and the sulfuric acid as well as to obtain a chemical structure
corresponding to various molar ratios through molecular dynamics calculations together with a
specific distance distribution function. The results show that the hydrogen bonding of the whole
system strengthens with the increase of the molar ratio of sulfuric acid to TOA. Furthermore, the
portion of the shared free water and sulfuric acid decreases. When the molar ratio of sulfuric acid to
TOA is comparatively low, the interaction between TOA and water was predominated by hydrogen
bonds. When it is high, TOA will reaction with sulfuric acid through protonation.
References
[1] Kirsch, T., H. Ziegenfuß, and G. Maurer, Distribution of citric, acetic and oxalic acids between water and organic
solutions of tri- n -octylamine. Fluid Phase Equilibria, 1997. 129(1): p. 235-266.
[2] Guo, F., et al., Reversed micelle formation in a model liquid-liquid extraction system. Journal of Colloid & Interface
Science, 2008. 322(2): p. 605-610.
[3] Qiu, X., et al., Effect of hydroxyl on formation of viscoelastic scum during solvent extraction of sulfuric acid with
trioctylamine. Separation & Purification Technology, 2012. 86(86): p. 137-142.
[4] Qiu, X., et al., Structural analysis of N H⋯O in viscoelastic scum formation during solvent extraction of sulfuric acid
with trioctylamine. Separation & Purification Technology, 2012. 95(95): p. 196-201.
868
INFLUENCE OF THERMAL TREATMENT ON THE MINERALOGY AND THE LEACHING

BEHAVIOUR OF HEAVY METALS IN BOTTOM ASH
O. HAMMOUD1, M. LUPSEA-TOADER1, D. BLANC1, C. DE BRAUER1, F. EL HASSOUNI1

1 University of Lyon, INSA-Lyon, DEEP Laboratory (Waste Water Environment Pollution) 20 avenue
Albert Einstein, F-69621 Villeurbanne, France.
Abstract
France produces about 37.6 million tons of non-hazardous household waste per year. 30% of this
waste is treated by incineration. The main by-product of incineration is the Municipal Solid Waste
Incineration – Bottom Ash (MSWI-BA). The valorisation of MSWI-BA plays an important role in the
waste management system because of increased landfill costs. The high leaching potential of
pollutants from BA (mainly heavy metals) makes their valorisation difficult. One way towards
valorisation, is the stabilisation of metallic pollutants in the chemical structure of bottom ash.
In this paper, we studied the influence of thermal treatment on the mobility of heavy metals in the
MSWI-BA. The pollutant potential of bottom ash is evaluated by leaching tests performed according
to the EN 12457-2 standard [1]. For a better understanding of the physico-chemical mechanisms
taking place during the thermal treatment in the mineralogical phases of BA, the characterization of
the solid matrix has been performed by X-ray diffraction, infrared spectroscopy and
thermogravimetric analysis.
The experimental results show that the leaching of different elements varies in function of the
temperature used during the thermal treatment. Heating at lower temperatures, i.e. 400 °C,
decreased the leachability of copper and chromium. On the other hand, the leaching of chromium
increased after treatment at higher temperatures, i.e. 700 °C.
In conclusion, the thermal treatment seems to be effective for reducing the leachability of some
heavy metals. However, the choice of temperature is important, because not all elements have the
same behaviour in function of the temperature used.
References
[1] European standard. EN 12457-2: Characterization of waste – Leaching – Compliance test for leaching of granular
waste materials and sludges – Part 2: One stage batch test at a liquid to solid ratio of 10 L/kg for materials with
particle size below 4 mm (without or with size reduction) (2002)
869
WASTE TRANSPORTATION COST IN ADVANCED NETWORK FLOW MODELS
J. GREGOR1, F. JANOŠŤÁK1, M. PAVLAS1,2, R. ŠOMPLÁK1,2

1
Institute of Process Engineering, Faculty of Mechanical Engineering, Brno University of Technology –
VUT Brno, Technická 2896/2, 616 69 Brno, Czech Republic
2
Sustainable Process Integration Laboratory – SPIL, NETME Centre, Faculty of Mechanical
Engineering, Brno University of Technology – VUT Brno, Technická 2896/2, 616 69 Brno, Czech
Republic
Abstract
Irrespective of whether it is material or energy recovery, transport of waste from producers to pre-
processing and final treatment facilities represents an important subject in waste management. It
contributes to total chain cost, and therefore, it should be addressed carefully, even in the phase of
conceptual development of such a chain or its sub-systems.
In this contribution, the most common transportation systems for waste are reviewed shortly first.
Then a complex techno-economic model is used to compare transportation cost for various waste-
based commodities and related transportation systems. Special focus will be separately collected
fractions from municipal solid waste as inputs to sorting and other refining plants. The most
influencing parameters as waste density, transported amount and distance are highlighted.
The cost model is further used in a comprehensive analysis focused on network flow problems.
These problems, often denoted as reverse logistic in waste management, propose optimum
locations of capacities and allocate transported amounts across edges of which the network
consists. Simplified cost models with constant price are often used, which is justified by keeping the
model linear and having computation times short. The aim of this paper is to investigate the effect of
applying more complex transportation cost models on the proposed solution. Models are applied on
a network consisting of more than 200 nodes and 50,000 edges and the optimisation is performed.
The outputs are analysed (statistically) to describe their influence on result. Several scenarios are
included in the calculation, impact of an advanced model is investigated for each scenario.
Finally, the obtained results are generalized in form of commenting on a trade-off between cost
model quality and result stability.
870
RESEARCH ON THE EXTRACTION BEHAVIOR OF OIL SANDS AND GROUND CRUDE

OILS BY AQUEOUS TWO-PHASE EXTRACTION
LI LIU 1, PIJIAN GONG1, XINXUE LI 1,

1 Department of Chemistry and Chemical Engineering, School of Chemical and Biological Engineering,
University of Science & Technology Beijing, Beijing, China..
Abstract
The research focused on the mechanism of extraction and separation of oil sand and ground crude
oil by aqueous two-phase system constructed by glycol ethers and NaCl. The solution system was
designed for recycling. The hydrophilic and lipophilic property of ethylene glycol alkyl ether is tuned
by using of different molecular structure, different operation temperature and / or different salinity.
The extraction process can be divided into two steps, the first step is the separation of oil and sand,
as shown in Figure 1.The second step is the separation of oil and glycol ether solution. The latter can
be reused for the next extraction of oil sand. To achieve this goal, it is necessary to understand the
the formation of aqueous two-phase extraction for separating crude oil and sand efficiently. At the
same time, the effects of temperature, salinity, interfacial wettability and the interfacial tension,
interfacial electrical double layer on the stripping process of oil drop from the surface of solid
particle. The obtained results can supply theoretical basis for the optimization of aqueous two-phase
system.
Figure 1: Static stratification in oil sand aqueous two-phase extraction
References
[1] Abramov OV, Myasnikov SK, Mullakaev MS. Extraction of bitumen, crude oil and its products from tar sand and
contaminated sandy soil under effect of ultrasound, Ultrason Sonochem 2009, 16(3): 408-416.
[2] Geramian M, Osacky M, Ivey DG, Liu Q, Etsell TH. Effect of Swelling Clay Minerals (Montmorillonite and Illite-
Smectite) on Nonaqueous Bitumen Extraction from Alberta Oil Sands, Energy & Fuels 2016, 30(10): 8083-8090.
[3] Huang R, McPhedran KN, Sun N, Chelme-Ayala P, Gamal El-Din M. Investigation of the impact of organic solvent type
and solution pH on the extraction efficiency of naphthenic acids from oil sands process-affected water, Chemosphere
2016,146: 472-477
871
CHARACTERIZATION OF SOLID PRODUCTS FROM THERMOCHEMICAL CONVERSION

OF MUNICIPAL AND TEXTILE WASTES
M.A.AYIANIA1, R. NICHOLSON2, A.P.P. PIRES1, E. TERRELL1, J. MEISSNER3, K. ENGLUND2, M. GARCIA-

PEREZ1
1 Biological Systems Engineering, Washington State University, Pullman, WA, USA
2 Department of Agricultural and Biological Engineering, The Pennsylvania State University, PA, USA
Annex IO, USA

3 Composting Materials and Engineering Center, Washington State University, Pullman, WA, USA
Abstract
Municipal solid waste fractions containing wood and textiles have the potential to be used for the
development of value added products. The main purpose of this work was to produce and
characterize biochar from municipal solid waste (MSW) woody fractions and torrefied pellets from
textiles. Our carbonization work focused on compost overs, molded wood pallets, treated wood,
sawmill cut ends, wood derived fuels and furniture, painted wood, playwood. oriented strand board
and particle boards from Washington State recycling facilities. Eleven biochar samples were
produced from MSW and compost overs at two temperatures (400 and 600°C) in a lab-scale
pyrolysis spoon reactor. The yield of solid residue left decreases linearly with pyrolysis temperature
between 350 and 500 °C. Our goal was to use these bio-chars as soil amendments. However, there
are concerns with both the potential presence of condensed organic pollutants and heavy metals.
The presence of heavy metals and polycyclic aromatic hydrocarbons (PAH) in all the biochars
produced were examined. Bio-chars produced at high temperature were enriched in recalcitrant
polyaromatic structures rich in carbon. High temperature chars contained less volatiles, hydrogen,
and oxygen. Our GC/MS analyses of liquid extracts did not reveal the presence of soluble PAH
compounds. High concentrations of mercury (Hg) and Arsenic (As) were found in the biochar made
from painted wood and treated wood respectively. Among the methods tested for the removal of
heavy metals, acid wash was found to be the most effective. The volatiles released from the
analyzed MSW fractions were also analyzed in Py-GC/MS studies. Several hundred compounds were
identified. Among them 83 contained Cl, N, or S which could be potential sources of pollution if the
pyrolysis vapors are combusted. Our studies with textiles, confirm that high grinding energy is one of
the major challenges to process these materials. Torrefaction is a well-known approach to reduce
grinding energy. A new strategy for the production of textile torrefied pellets and the
characterization of resulting product will be discussed in the conference.
872
HYDRATION OF LIGNOCELLULOSIC BIOMASS. NON-LINEAR MODELING WITH

MODIFIED LANGMUIR ISOTHERMS
A. SÁNCHEZ1, P. HERNÁNDEZ-SÁNCHEZ1, R. PUENTE1

1 Laboratorio de Futuros en Bioenergía, CINVESTAV, Unidad Guadalajara, Jalisco, México.
Abstract
PURPOSE
Developing improvements or innovations in new or existing processes for the pre-treatment of
biomass (e.g. steam explosion, diluted acid, AFEX, alkaline pre-treatment, ionic liquids) is an important
area for the production of biofuels [1]. As all pre-treatments recover the fermentable fraction with
water or aqueous solutions and the biomass are hydrophilic, the hydration properties play an
important role in the pre-treatment performance. In this work, we study the hydration capacity of four
different lignocellulosic biomasses (LB) as a function of particle size.
MAIN MATERIALS AND METHODS
The hydration experiments were performed by Robertson and Eastwood method [2] using wheat
straw, corn stubble, sorghum straw and sugar cane bagasse. The hydration medium was 40 cm3 of
distilled water. Absorption kinetics (i.e. Water Holding Capacity and Water Retention Capacity)
experiments were carried out for particle sizes of 3.36, 2.00, 0.595 and 0.250. pH decay and sugars
release (glucose and xylose) for a hydration time of 0, 1, 2, 4, 5, 12, 24, 48, 60 and 96 hours were also
recorded.
MAIN RESULTS OBTAINED
The experimental data was modelled using a modified Langmuir equation (1) as a function of hydration
time for the absorption phenomena, which uses two absorption constants (alpha and beta).
𝛼𝑡
𝜃= (1)
𝛽+𝑡
The extended paper will present the results for the four LB studied. The experimental data fits the
proposed Langmuir modified model within 0.9882 as its lower value and 0.9980 as its higher value of
correlation. However, steady-state hydration values differ for each LB and particle size, demonstrating
that the differences in its absorption capacity are directly associated by the process of surface increase
and the structure of the biomass. Otherwise, the degradation of the LB by microbial activity produced
a decrease in the pH up to 3.98, reaching maximum concentrations of 1.497 g/L (glucose) in the
kinetics of sugar release and degradation.
CONCLUSIONS OF THE WORK
Hydration capacity of LB can be reliably modelled by a simple empirical model, which proposes that
the absorption phenomena increase in a non-homologous way with the particle size and the time
required to reach equilibrium. Fermentation can also take place by a variety of bacteria present in LB.
A first stage of LB hydration could increase the effectiveness of the subsequent treatments.
References
[1] Mosier, N., Wyman, C., Dale, B., Elander, R., Lee, Y. Y., Holtzapple, M., & Ladisch, M. (2005). Features of promising
technologies for pretreatment of lignocellulosic biomass. Bioresource Technology.
https://doi.org/10.1016/j.biortech.2004.06.025
[2] J. a Robertson y M. a Eastwood, “A method to measure the water-holding properties of dietary fibre using suction
pressure.”, Br. J. Nutr., vol. 46, núm. 2, pp. 247–255, 1981.
873
CHARACTERIZATION AND DEGRADATION OF AGRICULTURAL RESIDUES OF SINALOA

MEXICO FOR BIOETHANOL PRODUCTION
L.I. BELTRAN-ARREDONDO1, I. CONTRERAS1, M.G. AGUILAR-USCANGA2, C. CASTRO-MARTÍNEZ3

1
Universidad Autónoma de Sinaloa - FCQB, Culiacán, México
2
Instituto Tecnológico de Veracruz – UNIDA, Veracruz, México
3
Instituto Politécnico Nacional - CIIDIR Sinaloa, Guasave, México.
Keywords: Agricultural residues, acid pretreatment, enzymatic hydrolysis, bioethanol
Abstract
The northwest region of Mexico generates a large amount of residues from crops that have the
potential of becoming a central focus for bioethanol production. One of the crucial steps in biomass
degradation is enzymatic hydrolysis; however, the lack of an effective pretreatment can negatively
affect the efficiency of saccharification. The objective of this work was to evaluate the structural
composition of the biomass and to compare the efficiency of enzymatic hydrolysis through the
release of fermentable sugars after a dilute acid pretreatment of five agroindustrial residues: corn
stover (cs), poplar waste (pw), bean (bs), wheat (ws) and chickpea straw (chs). Sulfuric acid (2%v/v)
was used for the acid pretreatment. Then, enzymatic hydrolysis was carried out using the pretreated
biomass and a commercial cellulase. Efficiency was evaluated measuring the release of the total
reducing sugars. The lignin content was similar for cs, bs and ws. Regarding cellulose content, results
showed that ws>chs>pw>bs>cs. After the pretreatment with sulfuric acid, the amount of lignin in the
residues increased while the cellulose decreased. A subsequent enzymatic hydrolysis of the
recovered solids after pretreatment was performed. The highest amount of reducing sugars was
obtained at 72 h of hydrolysis, being corn-stover the residue with the highest amount of sugar with
159.96±2.16 mg/g of dry biomass. In conclusion, results revealed that sulfuric acid pretreatment has
a great effect in the reducing sugars recovered from agricultural residues. Moreover, it showed that
corn stover is the biomass with the foremost potential for bioethanol production in Sinaloa, México.
874
1- INTRODUCTION
Currently, the use of agricultural waste is an attractive option for the obtainment of second
generation biofuels like bioethanol. Second generation bioethanol is produced from lignocellulosic
biomass like stems, leaves and straw of agricultural crops, herbs, woody crops and paper waste [1].
Its northwest is known to be the main producer of crop residues such as corn, bean, chickpea,
wheat, etc. Therefore, this area has the potential to become a central focus of attention for the
production of bioethanol [2].
Bioethanol production from lignocellulosic biomass involves five different steps: pretreatment,
enzymatic hydrolysis, fermentation, product separation and purification [3]. Structural and chemical
characteristics of lignocellulosic biomass make possible its degradation possible through physical,
chemical and enzymatic processes that convert the biomass into fermentable sugars for bioethanol
production [4]. Lignocellulosic biomass is composed of cellulose, hemicellulose, lignin, extractives
and several inorganic materials. The variation of each component is dependent of the origin of the
biomass. Cellulose is a linear, crystalline polymer of D-glucose units linked by ß-1, 4 glycosidic bonds.
Cellulose is the most abundant polysaccharide in plant cell wall. The rigid structure of plant cell wall
makes it difficult to break down; however, this fraction can be converted into glucose by enzymatic
hydrolysis or by chemical methods. Hemicellulose is composed of linear and branched
heteropolymers of D-xylose, L-arabinose, D-galactose, D-glucose and D-mannose. This structure is
not crystalline; therefore, it is easier to hydrolyze. Lignin is a three-dimensional polymer molecule
consisting of three different phenyl-propane monomer units that are particularly difficult to
biodegrade [5].
Enzymatic hydrolysis is a critical step in biomass degradation; however, due to the complexity of the
cell wall, the efficiency of saccharification without a prior effective pretreatment is extremely low
[6]. Pretreatment is performed to disrupt the compact structure of lignocellulosic material with the
aim of overcoming the recalcitrance of lignin, increasing the fraction of amorphous cellulose,
improving the total yield of the monomeric sugars in hydrolysis, limiting the formation of inhibitory
compounds and reducing the cost of bioethanol production [7].
Various pretreatments methods are now available to fractionate, solubilize, hydrolyze and separate
cellulose, hemicellulose and lignin. This process can be mechanical, physical, chemical,
physicochemical or biological. The most widely used method is a chemical pretreatment under acid
conditions. Sulfuric acid is the most commonly used chemical pretreatment used in industry due to
its efficiency and low cost [8]. Acid pretreatment can be performed with concentrated or diluted
acid; however, due to the formation of inhibiting compounds like furfural an HMF, the employment
of concentrated acid is less attractive [9]. Dilute acid pretreatment is commonly used for the
pretreatment of a wide variety of lignocellulosic biomass. The concentration of acid tends to be
lower than 4% (v/v). There are two types of dilute acid pretreatment processes: high temperature
(more than 180°C) during short period of time and lower temperature (for instance 120°C) for longer
retention time (30-90 min) [7]. Sulfuric acid pretreatment has been used successfully for the
degradation of agricultural residues such as cane bagasse, corn cob, rice straw [10], corn stover [11],
sorghum stalks [12], among others.
875
The aim of this work was to evaluate the structural composition of the biomass and to compare the
efficiency of enzymatic hydrolysis through the release of fermentable sugars after a dilute acid
pretreatment of five different agricultural residues of Sinaloa, Mexico.
2.1 Materials
The experiment was conducted using five of the main agricultural residues from crops grown in
Sinaloa, Mexico. This residues were: corn stover (cs), poplar waste, bean (bs), wheat straw (ws) and
chickpea straw (chs). The biomass was obtained from the northern region of Sinaloa, Mexico. It was
collected from the remnants on ground during the harvest of grains. Dust was removed using
distilled water followed up by dying at 60°C for 72 h. The dried biomass was subsequently milled and
sieved to a 1 mm particle size using a blender and it was stored in an air tight bag at room
temperature for further analysis.
2.2 Dilute acid pretreatment
All experiments were carried out with 4% moisture. Sulfuric acid (H2SO4) in low concentration was
employed for acid pretreatment. Glass flasks containing 10 g of dry material (10% w/v) with H2SO4 at
2% were placed in autoclave at 121°C for 60 min. After the acid hydrolysis, the reaction mixture was
cooled to room temperature. The recovered samples were centrifuged and filtered. The supernatant
was subjected to a total reducing sugars analysis using dinitrosalicylic acid (DNS) method [13]. The
solid residue was washed with distilled water until it reached pH of 5. Then, it was dried and stored
for biomass compositional analysis and enzymatic hydrolysis [10].
2.3 Biomass compositional analysis
The biomass compositional analysis of corn stover, poplar waste, bean straw, wheat straw and
chickpea straw was evaluated in raw material as well as in the acid pretreated biomass. Lignin
content was determined using the standard laboratory analytical procedures provided by the
National Renewable Energy Laboratory (NREL), Golden, CO, USA [14]. Lignin content in extractive
free samples was determined by performing a two-step acid hydrolysis with 72% (v/v) H2SO4 for one
hour and quantitative post hydrolysis with 4% H2SO4 at 121 °C. The solid residue from post
hydrolysis process was recovered by filtration considering it as Klason lignin. Cellulose content in
biomass was measured by Kürschner-Hoffer modified method [15]. A mixture of ethanol: nitric acid
(4:1) was added to one gram of extractive free biomass for 30 minutes in water bath. This process
was repeated twice. The solid residue was washed with hot distilled water and a sodium acetate
solution. Afterwards, it was dried at 105 °C overnight and the weighted to calculate the cellulose
percentage.
2.4 Enzymatic Hydrolysis
The enzymatic saccharification of corn stover, poplar waste, bean straw, wheat straw and chickpea
straw was realized with the H2SO4 2% (v/v) pretreated biomass to compare the fermentable sugars
876
obtained for the five residual biomass. For enzymatic hydrolysis, the cellulase produced by
Trichoderma reesei ATCC 26921 (Sigma, USA) was added at the rate of 20 FPU/g of biomass.
Enzymatic hydrolysis of pretreated samples (one gram each) was carried out in 50 mM citrate buffer
(pH 5) at 5% (w/v) substrate for 72 h [16]. Progress of the enzymatic hydrolysis was monitored at
regular intervals of 24 h by estimating the reducing sugars content by DNS method [13].
3.1 Acid pretreatment effect on the structural composition of lignocellulosic residues
Acid pretreatment is considered as one of the most important techniques for high sugar yields from
lignocellulosic biomass. In this research, corn stover, poplar waste, bean straw, wheat straw and
chickpea straw were pretreated with dilute sulfuric acid and hydrolyzed with cellulases for
fermentable sugar production. The compositions of raw material and acid pretreated biomass were
evaluated in the five agricultural residues (Table 1). The lignin content was similar for corn stover,
bean straw and wheat straw (16.05±1.28, 16.88±0.81 and 16.23±0.27 %). The lignin content of
chickpea straw and poplar waste was higher than the rest of the stubbles. For cellulose content, the
results showed that wheat straw was the biomass with higher cellulose content (64.6±0.48%)
followed by chickpea straw, poplar waste, bean straw and corn stover.
After pretreatment with dilute sulfuric acid, the amount of lignin content in all lignocellulosic
residues increased. Cellulose content in wheat straw and poplar waste increased with acid
pretreatment making it available for enzymatic hydrolysis. On the other hand, cellulose content
decreased in corn stover (from 45.08±0.16 to 38.63±1.49%), bean straw (from 56.7±0.89 to
37.60±0.95%) and chickpea straw (from 61.6±0.90 to 38.64±1.05%). This effect may be due to the
sulfuric acid pretreatment. Since it hydrolyzes hemicellulose, it may have hydrolyzed a small fraction
of cellulose into monomeric sugars [6]. The hydrolysis of hemicellulose can be demonstrated in the
amount of reducing sugars released in the liquid fraction of the acid pretreatment. This effect in
pretreated biomass structure was observed by Chen et al [17] in corn stover pretreated with dilute
sulfuric acid. The study showed that acid pretreatment removes a considerable amount of the
hemicellulose fraction and increases the amount if lignin and cellulose. Therefore, the pretreated
corn stover can achieve efficient enzymatic hydrolysis with high sugar yields and low by-products
concentration.
Table 1: Structural composition of five biomass residues
877
3.2 Enzymatic Hydrolysis of pretreated lignocellulosic residues
Subsequent enzymatic hydrolysis of the recovered solids obtained after pretreatment of the five
lignocellulosic residues was performed at solid loading of 5% (w/v) for 72 h (Figure 1). The highest
amount of reducing sugars in each residue was obtained at 72 h of enzymatic hydrolysis. Corn stover
was the residue with the highest release of sugar with 159.96±2.16 mg/g of dry biomass, followed by
bean straw and wheat straw (142±1.73 and 129.95±0.79 mg/g of dry biomass). The lignocellulosic
biomass that released the lowest amount of fermentable sugars were chickpea and poplar waste
with 103.27±1.36 and 84.28±1.40 mg/g of dry biomass, respectively.
In the structural composition analysis, chickpea straw and poplar waste without pretreating
presented the highest lignin content (Table 1). Hence, their structure is more recalcitrant and
difficult to break through acid pretreatment resulting in difficulty for the access of the enzyme;
therefor, the amount of sugar released is lower. On the contrary, corn stover has a lower lignin
content resulting in a more efficient removal of hemicellulose and a redistribution of lignin; thus,
enhancing enzymatic digestibility. Chen et al. [17] evaluated enzymatic hydrolysis after sulfuric acid
pretreatment in corn stover in similar conditions as the ones in this study, obtaining a higher glucose
concentration (326 mg/g of dry biomass) at 72 h of hydrolysis. Other biomass like wheat straw [18],
rice straw [19] and alfalfa steam [20] have been pretreated with dilute sulfuric acid improving
enzymatic digestibility of the lignocellulosic residues compared with the non-treated biomass.
Figure 1: Enzymatic hydrolysis of pretreated biomass residues.
4- CONCLUSIONS
This study aimed to evaluate the effect of dilute acid pretreatment of corn sotver, poplar waste,
bean straw, wheat straw and chickpea straw in structural composition and its subsequent enzymatic
hydrolysis for fermentable sugars production. In conclusion, results revealed that sulfuric acid
pretreatment has a great effect in the reducing sugars recovered from the different agricultural
residues evaluated improvement of the cellulose digestibility as observed in the enzymatic hydrolysis
assays. Overall, corn stover demonstrated to be the biomass with the greatest potential for
bioethanol production in Sinaloa, Mexico.
878
REFERENCES
[1] Chandel, K.A., Singh, O.V.: Weedy lignocellulosic feedstock and microbial metabolic engineering: advancing the
generation of Biofuel. App Microbiol Biotechnol. 89, 1289-1303 (2011)
[2] Mosier, N., Wyman, C., Dale, B., Elander, R., Lee, Y., Holtzapple, M., Ladisch, M.: Features of promising technologies
for pretreatment of lignocellulosic biomass. Bioresour Technol. 96, 673–686 (2005)
[3] Rios, M ., Kaltschmitt, M.: Bioenergy potential in Mexico: status and perspectives on a high spatial distribution.
Biomass Conv. Bioref. 3, 239–254 (2013)
[4] Galbe, M., Zacchi, G.: A review of the production of ethanol from softwood. Appl Microbiol Biotechnol. 59, 618–628
(2002)
[5] Prasad, D., Singla A., Negi S.: An overview of key pretreatment processes for biological conversion of lignocellulosic
biomass to bioethanol. 3Biotech. 5, 597–609 (2015)
[6] Li, P., Cai, D., Luo, Z., Qin, P., Chen, C., Wang, Y., Zhang, C., Wang, Z., Tan, T.: Effect of acid pretreatment on different
parts of corn stalk for second generation ethanol production. Bioresource Technology 206, 86–92 (2016)
[7] Bhutto, A. W., Qureshi, K., Harijan, K., Abro, R., Abbas, T., Bazmi, A. A., Karim S., Yu, G.: Insight into progress in pre-
treatment of lignocellulosic biomass. Energy. 122, 724-745 (2017).
[8] Van Eylen, D., Van Dongen, F., Kabel, M., Bont, J.: Corn fiber, cobs and stover: Enzyme-aided saccharification and co-
fermentation after dilute acid pretreatment. Bioresource Technology. 102, 5995–6004 (2011)
[9] Mesa, L., Martínez, Y., Barrio, E., González, E.: Desirability function for optimization of Dilute Acid pretreatment of
sugarcane straw for ethanol production and preliminary economic analysis based in three fermentation
configurations. Applied Energy. 198, 299-311 (2017)
[10] Sumphanwanich, J., Leepipatpiboon, N., Srinorakutara, T., Akaracharanya, A.: Evaluation of dilute-acid pretreated
bagasse, corn cob and rice straw for ethanol fermentation by Saccharomyces cerevisiae. Annals of Microbiology. 58,
219-225 (2008)
[11] Avci, A., Saha, B.C., Kennedy, G.J., Cotta, M.A.: Dilute sulfuric acid pretreatment of corn stover for enzymatic
hydrolysis and efficient ethanol production by recombinant Escherichia coli FBR5 without detoxification. Bioresour.
Technol. 142, 312-319. (2013)
[12] Deshavath, N.N., Venkata Dasu, V., Goud, V.V., Srinivasa Rao P.: Development of dilute sulfuric acid pretreatment
method for the enhancement of xylose fermentability. Biocatalysis and Agricultural Biotechnology. 11, 224-230
(2017)
[13] Miller, G.L., Blum, R., Glennon, W.E., Burton, A.L.: Measurement of carboxymethylcellulase activity. Anal Biochem. 2,
127–132 (1959)
[14] Sluiter, A., Hames, B., Ruiz, R., Scarlata, C., Sluiter, J., Templeton, D., Crocker, D. NREL/TP-510-42618. (2008)
[15] Kurschner, K., Hoffer, A.: A new quantitative cellulose determination. Chem. Zeit. 55, 1161-1181 (1931)
[16] Karthika, K., Arun, A.B., Rekha, P.D.: Enzymatic hydrolysis and characterization of lignocellulosic biomass exposed to
electron beam irradiation. Carbohydrate Polymers. 90, 1038-1045 (2012)
[17] Chen, L., Li, J., Lu, M., Guo, X., Zhang, H., Han, l.: Integrated chemical and multi-scale structural analyses for the
processes of acid pretreatment and enzymatic hydrolysis of corn stover. Carbohydrate Polymers. 141, 1–9 (2016)
[18] Zheng, Q., Zhou, T., Wang Y., Cao, X., Wu, S., Zhao, M., Wang, H., Xu, M., Zheng, B., Zheng, J., Guan, X.: Pretreatment
of wheat straw leads to structural changes and improved enzymatic hydrolysis. Nature. 8, 1321 (2018)
[19] Zhang, H., Wang, Y., Lu, F., Chai, L., Shao, L., Pin-Jing, H.: Effects of Dilute Acid Pretreatment on Physicochemical
Characteristics and Consolidated Bioprocessing of Rice Straw. Waste Biomass Valor. 6, 217–223 (2015)
[20] Zhou, S., Yang, Q., Runge T. M.: Ambient-temperature sulfuric acid pretreatment to alter structure and improve
enzymatic digestibility of alfalfa stems. Industrial Crops and Products. 70, 410–416 (2015)
879
GEOGRAPHIC INFORMATION SYSTEM AS AN AUXILIARY TOOL OF DATA COLLECTION

FOR THE LIFE CYCLE INVENTORY PHASE
M.R. RIGON1, C.A.M. MORAES 2, M. MANCIO3, R.C.E. MODOLO 4

1 Polytechnic School, Graduate Program in Civil Engineering, Unisinos University (Unisinos/NuCMat),
São Leopoldo, Brazil.
Keywords: GIS, Life Cycle Assessment, biomass.
Abstract
Brazil is one of the largest rice producers in the world, currently occupying the ninth position in the
world production ranking, with an yearly harvest of about 12 million tons of the grain. The
production is mainly distributed in the southern region, namely in the state of Rio Grande do Sul, by
far the largest producer within the country, and statistics point to a trend of increasing rice
production. A consequence of increased grain production is the large generation of rice husk, the
main agricultural waste coming out of the process. Therefore, the proper use or disposal of the
waste generated is one of the main challenges faced by the rice industry. Rice husk has been used
for energy generation and has received attention since it does not threaten food supplies and it is a
vital source of renewable energy [1]. In Brazil, according to the Generation Information Bank of the
National Electric Energy Agency (Aneel), until October 2017, there were 536 biomass-fuelled
thermoelectric power plants, corresponding to a total of 14 million kilowatts (kW) installed. From
this total, 12 plants are exclusively powered by rice husk, eight of which are located in Rio Grande do
Sul [2]. In this context, the objective of this study is to use a geographic information system as an
auxiliary tool in the evaluation of the rice husk life cycle and its potential use for energy purposes in
Rio Grande do Sul, as well as to characterize the generation of rice husk ash - a by-product that has
great potential for use in several applications. Mapping was developed by using the Software ArcGis
version 10.0. The boundaries of rice producing regions in the state of Rio Grande do Sul was carried
out considering the IRGA (Rice Institute of Rio Grande do Sul) Geographical Information System. The
ranking of the 50 largest industries in the state of Rio Grande do Sul, representing approximately
84% of the total amount of rice processed, was considered for the mapping of the rice producers,
which generate the rice husk as one of the process wastes. The address of each company was
obtained from their institutional websites and they were located through Google Earth. The
geographic mapping enabled the identification of the main rice producers and thermoelectric power
plants in the state of RS, as a tool to support the decision-making to conduct a Life Cycle Assessment
(LCA) study involving the rice husk ash by-product, and could be useful as a supporting method for
further studies focused on the LCA of rice husk ash. It was also possible to observe that the
thermoelectric power plants are centered in the West Frontier region and the Campanha region in
the state. Furthermore it was possible to verify that there is a large potential for energy generation
from the combustion of rice husk in this and other regions.
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1- INTRODUCTION
The demand for energy will increase by 56% between 2010 and 2040. As consequence of the
population and economic growth, the prospect is that. Although the fossil fuels, oil, natural gas and
coal will remain as the main energy sources until 2040, one of the sources with greatest growth
potential in the next years are those based on different types of biomass [2,3].
Biomass corresponds to any organic matter that can be transformed into mechanical, thermal or
electric energy [2]. This energy source is considered one of the best alternatives for the
diversification of the energetic matrix since the dependence on fossil fuels has been raising concerns
regarding the exhaustion of this resources and the climate change [1].
In addition, biomass has been considered a promising energy source due to its potential to neutralize
CO2, and its broad availability from several sources [2,4]. Besides, most of the biomass fuels contain
little or no sulphur on their composition; therefore, the SO2 emissions could be reduced if fuels such
as coal, which contains high percentage of sulphur, were replaced [4].
In Brazil, according to the Generation Information Bank of the National Electric Energy Agency
(Aneel), until October 2017, the country had 536 biomass-fuelled thermoelectric power plants,
which correspond to a total of 14 million kilowatts (kW) installed. From this total, 12 units are
exclusively powered by rice husk, and 8 of these units are in Rio Grande do Sul, the largest national
rice producer, accounting for 66.5% of the total production in 2013 [5,6].
Rice husk, one of the wastes of rice processing has been used for energy generation and has gained
attention since it doesn’t threaten the food supply and it’s a vital renewable energy source [1]. It is
the most expressive by-product generated in the rice processing, and its volume represents around
20% of the rice mass as husk and straw, which is produced in mass approximately equivalent to the
grain yield [7]. Among the 21 types of residue identified by Saidelles et al. (2012) in a processing unit
in Rio Grande do Sul, the rice husk and the ashes generated in the drying process were the wastes
observed in higher amounts.
It is worth noting the estimates that predict an 11% raise in the rice production in the next 10 years,
period from 2012/2013 to 2022/2023 [5]. Therefore, a consequence of the increase in grain
production will be the generation of the agricultural waste involved in the process. As a result, the
adequate use or disposal of the by-products produced is one of the main challenges faced by the rice
industry [1].
In this context, the objective of this study is to use the geographical information system as an
auxiliary tool for data collection in the life cycle inventory phase, allowing the evaluation of the rice
husk generation cycle and its potential use for energetic purposes in Rio Grande do Sul. In addition,
be able to identify the generation of the by-product rice husk ash (RHA).

Data collection was conducted through the application of a questionnaire to two companies in the
municipality of Alegrete, state of Rio Grande do Sul (RS), southern Brazil to obtain technical
information regarding the biomass combustion technology. The two companies are rice processing
units that sell the product as food and burn the husk as a by-product for energy generation. One of
the companies uses the technology of grate combustion and another uses technology of fluidized
bed. As a result, two types of RHA were generated by combustion of rice husk in a bubbling fluidized
bed reactor (RHA-FB) and by a moving grate furnace (RHA-GF).
RHA-FB is produced by burning rice husk in a bubbling fluidized bed at temperatures below 800 °C.
Briefly, rice husk is loaded onto the fluidized bed chamber and instantly burned on a sand bed and
an ascending air flow. The company that produces RHA-FB is the only one in RS that operates with a
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fluidized bed system to combust rice husk for energy. Similarly, RHA-GF is produced by burning rice
husk on a moving grate furnace system that includes air feed and ash removal modules. Additionally,
data collected from the literature and obtained through document analysis were used.
To elaborate of the generation cycle maps and application of RHA as a by-product, the ArcGis version
10.0 was the tool utilized. All maps generated were geo-referenced to the Geodesic SIRGAS System
(Geocentric Reference System for the Americas).
The division of the rice producing areas in the state of Rio Grande do Sul was conducted considering
the Geographical Information System from IRGA (SIG IRGA).
For the mapping of the processing units, which generate rice husk as a waste of its process, we
considered the ranking of the 50 largest industries of the state of Rio Grande do Sul, which represent
around 84% of the total processed rice [9]. The address of each company was obtained from their
institutional website and the companies were located using Google Earth. Consequently, a KML file
was generated from markers. The same procedure was used to obtain the location of the concrete
batchers in the state of RS. However, the RHA by-product absorption capacity wasn’t evaluated by
the companies since their size is unknown.
The Thermoelectric Power Plants (TPPs) powered by the combustion of rice husk biomass in
operation in the state of Rio Grande do Sul were located through the National Electric Energy Agency
(ANEEL).

The production of rice in Rio Grande do Sul is divided in six regions, represented in Figure 1. The
regions are: Fronteira Oeste, Campanha, Depressão Central, Planície Costeira Interna, Planície
Costeira Externa e Zona Sul.
Figure 1: Division of the rice producing regions of the state of RS.
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Considering the rice producing regions of the state of Rio Grande do Sul, the municipalities located in
each region with their respective number of rice processing companies and generators of rice husk
waste are represented in Figure 2. The municipality of Pelotas with 8 companies accounts for the
highest number of processing units in the state, followed by the municipalities of São Borja and
Camaquã with 5 and 4 companies, respectively. Only the municipality of Itaqui has 3 processing
units. The most common occurrence corresponds to one or two processing companies located in
each municipality.
Figure 2: Rice processing companies in the state of RS.
According to data collected of harvest 2013/2014 on the rice production, available from IRGA, the
major producing regions of the grain are the Fronteira Oeste region, with approximately 2.6 million
of tons, the Zona Sul region with 1.3 million of tons and the Campanha region with 1.2 million of
tons, as it can be observed in Table 1. Table 1 also presents the rice husk estimated production in
each region, which was calculated from considerations found in the literature, from 20% of the grain
mass [7].
The amount of husk processed for energy generation in the TPP with installed capacity of 5 MW and
fluidized bed combustion system represents approximately 13.8% of the husk consumed in the
region in the Fronteira Oeste region. They are located the TPPs in which the data was collected by
on-site survey. The rice husk combustion by grate system, in which the TPP has installed capacity of
3.8 MW and effective production of 3 MW, represents around 7.8% of the husk consumed for
energetic purposes in the Fronteira Oeste region.
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Region Rice production (t) Estimate CA production (t/year)

Fronteira Oeste 2,609,789 521,957.80
Zona Sul 1,366,142 273,228.40
Campanha 1,240,172 248,034.40
Depressão Central 1,023,667 204,733.40
Planície Costeira Interna 992,885 198,577.00
Planície Costeira Externa 884,014 176,802.80
Table 1: Rice production by region, harvest 2013/2014.
Source: IRGA (2015)
The thermoelectric power plants powered by rice husk biomass in operation in the state of Rio
Grande do Sul are presented in Figure 3. It is possible to observe that the TPPs are centered in the
Fronteira Oeste and Campanha regions of the state, where the largest production of rice takes place,
as mentioned previously.
Figure 3: TPPs in the state of RS.
It was possible to estimate the amount of rice husk to be used by the TPPs for energetic purposes
from the amount of rice husk processed by the fluidized combustion and grate systems (The results
are presented on Table 1. The estimate quantities of biomass for each TPP are shown in Table 2. The
effective energy production by the grate system (3 MW) and the amount of processed husk from
Alegrete enterprises were used as parameters for the estimation of production from other
companies, since this system is commonly used by other TPPs in the state. The last TPP to be put in
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to operation is located in Capão do Leão and began its operation in December 2015, after the data
for this research were collected.
Installed Estimate amount Total amount of

Region TPP capacity of processed processed husk/ %
(MW) husk/ (t/year) (t/year)
Alegrete LF 5 72000
Alegrete GR 3.8 52440
410,100
Fronteira Oeste Itaqui 4 55200 71.4%
Itaqui 4.2 57960
São Borja 12.5 172500
Dom Pedrito 1.2 16560
Campanha 362,940 133%
São Gabriel 25.1 346380
Table 2 – Estimate rice husk production, harvest 2013/2014.
Source: IRGA (2015)
Therefore, considering that all the rice produced in the Fronteira Oeste region is processed in the
municipalities that constitute this region, it is possible to verify that the TPPs consumes around
71.4% of the rice husk produced in the region. It is possible to verify that the demand for biomass is
33% superior to the husk processed in the municipalities which integrate the region in the Campanha
region, where are located other two TPPs for energy generation. Although, as observed in Figure 3,
the municipality of São Gabriel where one of the TPPs is located, borders the municipalities of Santa
Maria and São Sepé, with two processing units installed, which could supply the demand for biomass
from these two TPPs.
Lim et al. (2013) highlights that one of the main challenges faced by the rice industry is related to the
inadequate use or disposal of its byproducts, especially in underdeveloped countries. The author
also observes that most of the times, the rice processing companies sell their byproducts at very low
prices. In the short term, the sale of by-products can be the easiest way for the companies to obtain
a subsistent income. Even though, in the long term, it might be more profitable to invest on
technology to convert the byproducts in value-added products.
From the environmental perspective, to some companies the waste from the industrial rice
processing becomes a fuel for energy generation, contributing to reduce the dependence on oil
products by using renewable sources. Consequently, reducing the environmental impacts and costs,
since the disposal of what is still considered a waste to be managed adequately by other companies
is avoided.
In addition, it is possible to affirm that there is potential for energy generation from rice husk
combustion in the other regions of the state of Rio Grande do Sul, such as the Planície Costeira
Externa and the Planície Costeira Interna. When not used as a biomass fuel, rice husk presents some
negative features such as low nutritional properties and resistance to degradation and takes up large
volumes in the waste areas [10]. In Figure 4 it is possible to observe the challenge yet faced in some
regions of Rio Grande do Sul where rice husk is not used as a fuel for energy generation.
4- CONCLUSIONS
The SIG tool allowed, the visualization of the distribution of the rice processing companies in the
state of Rio Grande do Sul, as well as the companies that generate energy from rice husk biomass,
through the geographical representation, demonstrating to be an auxiliary tool for decision-making
to conduct a study on LCA involving the by-product RHA, and it can be used as a support to further
studies conducted in the LCA range.
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In addition, the content generated in this assessment found the considerations related to the
regional specificities of the product evaluated, and it is extremely necessary to the conduction of LCA
studies.
REFERENCES
[1] Lim, J. S.; Manan, Z. A.; Alwi, S. R. W.; Hashim, H. A review on utilisation of biomass from rice industry as a source of
renewable energy. Renewable and Sustainable Energy Reviews, 16, 3084-3094 (2012)
[2] Agência Nacional de Energia Elétrica (ANEEL). Biomassa: fontes renováveis: parte II. In: ______. Atlas de energia
elétrica do Brasil. 3. ed. Brasília, DF, 2008. cap. 4.
[3] UNITED STATES. Energy Information Administration (EIA). Office of Energy Analysis U.S. Department of Energy.
International energy outlook 2013: with projections to 2040. Washington, July 2013. Disponível em:
<http://www.eia.gov/forecasts/ieo/pdf/0484(2013). pdf>. Acesso em: 10 jun. 2014.
[4] Yin, C., Rosendahl, L.A., Kær S.K.: Grate-firing of biomass for heat and power production. Progress in Energy and
Combustion Science. 34, 725- 75 (2008)
[5] BRASIL. Ministério da Agricultura, Pecuária e Abastecimento (MAPA). Brasil projeções do agronegócio 2012/2013 a
2022/2023. Brasília, DF, 2013
[6] AGÊNCIA NACIONAL DE ENERGIA ELÉTRICA (ANEEL). Disponível em:
<http://www2.aneel.gov.br/aplicacoes/capacidadebrasil/OperacaoGeracaoTipo.asp >. Acesso em: 10 out. 2017.
[7] Pandey, S., Byerlee, D., Dawe, D., DobermanN, A., Mohanty, S., Rozelle, S., HARDY, Bill (Edit.). Rice in the global
economy: strategic research and policy issues for food security. Los Baños (Philippines): International Rice Research
Institute - IRRI. 477 p. (2010)
[8] Saidelles, A.N.F. et al.: Gestão de resíduos sólidos na indústria de beneficiamento de arroz. Revista Eletrônica em
Gestão, Educação e Tecnologia Ambiental. 5, 904-916 (2012)
[9] INSTITUTO RIO GRANDENSE DE ARROZ (IRGA). Produtividades municipais - safra 2013/14. Porto Alegre, 2013-2014.
Disponível em: <http://www.irga.rs.gov.br/upload/20140903105722produtividade_municipios_safra_13_14_
versao_final.pdf>. Acesso em: 13 dez. 2014
[10] Calheiro, D. Influência do uso de aditivos na moagem de cinzas de casca de arroz para sua adequação como
coproduto. São Leopoldo, 2011. 99 f. Dissertação (Mestrado em Engenharia Civil) - Universidade do Vale do Rio dos
Sinos - UNISINOS. São Leopoldo, RS, 2011.
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CELLULASE PRODUCTION USING AGRICULTURAL RESIDUES
L.D. CASTRO-OCHOA1, S.R. HERNÁNDEZ-LEYVA1, L.I. BELTRÁN-ARREDONDO2, M.G. AGUILAR-

USCANGA3, C. CASTRO-MARTÍNEZ1
1 Instituto Politécnico Nacional - CIIDIR SINALOA, Guasave, México.
2 Universidad Autónoma de Sinaloa - FCQB, Culiacán, México.
3 Instituto Tecnológico de Veracruz - UNIDA, Veracruz, México.
Keywords: cellulase, agricultural, residues
Abstract
Improvements in the development of economically viable technologies for the production of

saccharifying enzymes are essential for optimizing the biofuel production process. In this context,
the purpose of this study was to analyze celullase production by native microorganisms using
different lignocellulosic agricultural residues by submerged fermentation to decrease the
environmental and cost impacts. Bacillus subtilis RS-351, Penicillium sp. and Cladosporium sp. were
isolated from agricultural residues of corn stover and Moringa oleifera. For cellulase production, the
strains were cultivated using different agricultural residues: corn stover, chickpea straw, soya straw
and moringa straw, as a sole carbon source (1%). Submerged fermentation were carried out in 250
mL Erlenmeyer flaks containing 50 mL of basal medium (A or B). The inoculated flasks were then
incubated on a rotatory shaking incubator for 5 days. Culture conditions for Bacillus and Penicillium
were 30°C, 200 rpm, and for Cladosporium 25°C, 150 rpm. Cellulase activities were determined using
CMC, filter paper and p-nitrophenyl-glucopiranoside (pNPG) as the substrates. The enzymatic
activities for both fungi were higher than those produced by the bacteria. The maximum cellulase
activity for Bacillus subtilis RS-351 and Cladosporium sp. were obtained when they were cultivated in
the medium containing untreated corn stover as a sole carbon source, using basal A and B media
respectively. Penicillium sp. showed the highest enzymatic activity in medium A, supplied with
moringa as the carbon source.
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1- INTRODUCTION
Cellulases are a group of enzymes involved in the hydrolysis of cellulose, one of the most important
natural polymers and the major component of the plant cell wall. Chemically, cellulose is a linear
homo-polysaccharide consisting of anhydrous glucose units linked by β-1,4-glycosidic bonds[1].
Based on their mode of catalytic action, cellulases are classified into three main types: endo-
glucanases, exo-glucanases and β-glycosidases, which act in synergy to complete the hydrolysis of
cellulose to glucose [2].
The catalytic properties for cellulases are considered of great interest in various industrial processes.
For many years, cellulases have been used in the paper and pulp manufacturing, food and feed, wine
and beverages, detergent and textile industrial processes, this last one being the most successful and
popular application of cellulases [3]. Furthermore, cellulose have wide applications in the biofuel
industry. Recently, there has been a growing demand in the use of these enzymes for hydrolysis of
lignocellulosic substrates for to produce second generation bioethanol. Production of liquid biofuels,
such as bioethanol, has been promoted as a sustainable option to address the challenges associated
with rising crude oil prices, global warming and diminishing fossil fuel reserves [4].
Cellulases have been commonly obtained from diverse organisms, mainly fungi, bacteria, and
protozoans, although plant and animal cellulases are known [5.6]. Among organisms, fungi and
bacteria have become the focus of the cellulase industry.
Production of cellulase is the third area of research around the world for cost-effective production of
biofuels. Therefore, many researches are consistently looking for cellulases sources to be used in
this. In order to overcome these barriers novel and versatile approaches are required [7]. Cellulase
production by microorganisms is a complex system due to many factors affecting enzyme
production. The successful strategy to industrial production of cellulolytic enzymes includes both the
choice of microorganisms and the process strategy [8]. In this sense, utilization of inexpensive
agricultural residues offers the potential for reducing production cost and for increasing the use of
enzymes for industrial purposes [9].
The aim of this study was to investigate the effect of different low-cost agricultural residues on
extracellular cellulase production by three native microorganisms: Bacillus subtilis RS-351,
Cladosporium sp. and Penicillium sp.

Biological material
Bacillus subtilis RS-351, Penicillium sp. and Cladosporium sp. were obtained from the culture
collection of the Laboratory of Bioenergetics, Department of Agricultural Biotechnology, CIIDIR-
Sinaloa (México). The strains were isolated from agricultural residues: either from corn stover or
Moringa oleifera. The fungi were maintained on Potato Dextrose Agar (PDA) at 4°C and transferred
to a fresh medium every two months. For Bacillus subtilis, the strain was kept at -80°C in glycerol (15
%) stocks.
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Inoculum preparation
Bacillus subtilis RS-351. To prepare the inoculum, one isolated colony was inoculated in 5 mL of LB
broth, and incubated at 30°C and 200 rpm overnight. Then, we transferred the overnight culture
(1%) into a 250 mL Erlenmeyer flasks containing 50 mL of LB and incubated for 4 h at the conditions
as indicated. The inoculum consists of 10% (v/v) of the pre-culture.
Penicillium sp. Potato dextrose agar (PDA) plates incubated at 30°C for 7 days were used for the
production of spores. The spore suspension (1x 106 spores/mL) was prepared in sterile 0.1 % (v/v)
Tween 80 solution.
Cladosporium sp. Fungi was grown in potato dextrose agar (PDA). Plates were incubated at 25°C for
7 days. The inoculum consisted of 5 mm diameter discs cut from the grown fungus.
Media and substrate
Medium A. Basal medium composition per liter: (2 g) KH2PO4, (0.5 g) MgSO4, (0.5 g) NaCl, (0.2 g)
FeSO4.H2O, (0.3 g) NH4NO3, (0.3 g) MnS04.H2O, and (10 g) carbon source.
Medium B. Prepared according to Maeda et al. [11], composition per liter: (1 g) KH2PO4, (0.2 g)
CaCl2.2H2O, (0.15 g) urea, (0.97 g), yeast extract, (0.36 g) (NH4)2SO4, (0.0025 g) FeSO4.H2O, (0.008 g)
MnS04.H2O, (0.007 g) ZnSO4.7H2O, (0.01 g) CoCl2.6H2O, (0.15 g) MgSO4.7H20, (0.5 mL) Tween-80, and
(10 g) carbon source.
Substrates for fermentation. For cellulases production, the media were supplemented with synthetic
cellulose: CMC (Sigma), or lignocellulosic agricultural residue from: corn stover, soja, chickpea and
moringa straw (1% w/v). Agricultural residues were collected from local fields of Guasave, México.
The residues were washed with water and, dried at 60°C overnight in a heat air oven to remove
moisture before being ground and sieved to 1 mm particle size. Each sample was placed individually
in a separate sealed bag and stored under appropriate conditions until further use.
Submerged fermentation (SF)
The submerged fermentation was performed using both, synthetic and agricultural residues as sole
carbon sources (1%). SF was carried out in 250 mL Erlenmeyer flaks containing 50 mL of basal
medium, the pH was adjusted to 5 before sterilization at 121°C for 15 min. The inoculated flasks
were then incubated in an orbitary shaker for 5 days. Culture conditions for Bacillus and Penicillium
were 30°C, 200 rpm, and for Cladosporium 28°C, 150 rpm.
Determination of cellulase activity

CMC-agar diffusion method detection of cellulase activity
Extracellular cellulase activity of microorganisms was evaluated with Congo red plate [11]. The agar
plate was prepared with carboxymethyl cellulose (1 % w/v) and agar (2% w/v). After solidification,
wells (5 mm diameter) were formed aseptically. The wells were filled with supernatant sample (100
µL) and incubated at 30°C for two days. Then plates were stained with 1% w/v Congo red solution for
15 min and discolored with 1M NaCl for 15 min.
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CMCase activity. CMCase activity was determined according to Chiranjeevi et al. [12]. with some
modification by incubating 0.25 mL of the assay mixture containing 0.20 mL of 1% CMC in acetate
buffer, pH 5.0 and 0.05 mL of enzyme extract at 50°C for 50 min. Enzyme and substrate blanks were
simultaneously incubated with the samples. The reaction was stopped by adding 0.250 mL of dinitro
salicylic (DNS) reagent, followed by 5 min boiling. After cooling, the absorbance was read at 540 nm
using glucose as a standard, following, the protocol reported by Miller [12]. One unit of endo
cellulase activity was defined as the amount of micromoles of glucose liberated per milliliter of
enzyme solution in one minute.
FPase activity. Filter paper activity (FPase) was determined by the modified method of Ghose [14]. At
first, 0.2 mL of 0.1 M acetate buffer, pH 5.0 and 12.5 mg of filter paper strips (Whatman No.1) were
added to the test tube. Then 0.05 mL of cellulase extract was added to the tube. The mixture was
incubated at 50°C for 50 minutes. The reducing sugar released were estimated by DNS method of
Miller [12].
β-glucosidase activity. β-glucosidase activity was determined by a spectrophotometric assay using p-

nitrophenyl-glucopiranoside (pNPG) as the substrate as described by Joo et al. [15]. The reaction
mixture consisted of: 0.05 ml enzyme extract, and 0.2 ml 0.01M pNPG in 0.1 M phosphate buffer (pH
6.0). The hydrolytic reaction was carried out at 50 °C for 30 min, after which 0.25 ml of 0.1M Na2CO3
was added. The absorbance of liberated p-nitrophenol was measured at 420 nm. One unit of β-
glucosidase activity was defined as the amount of enzyme that caused the release of 1 μmol of p-
nitrophenol per minute.

First, we analyzed the ability of native microorganisms to degrade non-crystalline cellulose (CMC) as
substrate. Enzyme activity was tested through CMC hydrolysis by cell free supernatant in solid
media. As shown in Figure 1, different cellulolytic activity were exhibited by strains after . All
microorganisms supernatant showed halo diameters of CMC hydrolysis. This halos increased with
time up to 72 h. The largest halo diameter, was seen for fungal species of Cladosporium sp. and
Penicillium sp. indicating a higher activity, compared with those obtained in Bacillus subtilis RS-351.
Other authors have also reported hydrolysis of amorphous cellulose by Bacillus, Cladosporium and
Penicillium strains [16-18]
Figure 1. Detection of cellulase activity by congo red staining method. Cell free superantants of: A) Bacillis subtilis RS-351, B)
Cladosporium sp. and C) Penicillium sp. after 0-3 days of growth with CMC as a sole carbon source. Sample were incubated for 2 days
at 30°C before staining. Clear zone halo around wells indicate extracellular cellulase activity.
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Since, the use of synthetic substrates in the production of cellulases increases production cost, we
analyzed four different lignocellulosic residues as inducer substrate. Figure 2 shows the production
profiles of CMCase activity by Bacillus subtilis RS-351 cultivated in basal medium A. Higher CMCase
activity was observed when corn stover was the carbon source, followed by soja straw. Enzyme
activity was detected on the first day of culture, and it was increased with time of incubation until
maximum production was reached at 3 days. On the other hand, moringa and chickpea straws
produced lower cellulolitic activity than with the other residues.
The production of cellulase from agricultural wastes by Bacillus species has been increasing in last
years. Meng et al [19] reported that B. subtilis BY-3 can produce cellulase when grown on rice straw,
corn stover and wheat bran. In accordance with our results, the maximum cellulase activity of the
strain was up to 4.323±0.065 U/mL when cultivated in the medium containing untreated corn stover
as a sole carbon source.
Figure 3 shows the time course of CMCase activity by Cladoporium sp. grown in basal media A and B.
The highest production of CMCase (3.2 U/mL) was obtained when fungus was cultivated in B
medium supplied with corn stover as a sole carbon source. The enzyme production progressively
increased and reached its maximum level after 3 days of fermentation. The cellulase enzyme
production by Cladosporium sp. grown in medium A, showed lower activity values using the same
carbon source (Fig. 3A). On the contrary, higher activity was obtained in basal medium A, when
moringa and soja were de carbon sources evaluated. For chickpea straw, the maximum values of
CMCase activity were similar in both basal media. Chiranjeevi et al. [12] studied the utilization of rice
straw on cellulase production by Cladosporium cladosporoides. They evaluated the impact of critical
fermentation factors at different levels using statistical experimental design. Rice straw showed
maximum impact on production of CMCase (50%). Cellulase production noticed maximum on 3 rd day
for endo-glucanase (2.6 IU/mL).
Figure 2. CMCase activity production by Bacillus sp. grown in basal medium A, using different agricultural residues as a sole carbon
source. The microorganism was cultivated at 30°C and 200 rpm for 5 days. Data are mean of three replicate. Bars indicate standard
errors.
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Figure 3. CMCase activity production by Cladosporium sp. grown in basal media A y B using different agricultural residues as a sole
carbon source. The microorganism was cultivated at 28°C and 150 rpm for 5 days. Data are mean of three replicate. Bars indicate
standard errors.
Extracellular cellulase systems secreted by various Penicillium species showed to be efficient in
cellulose hydrolysis, thus, they are very promising candidates to be use in bioconversion processes of
lignocellulosic feedstock to liquid fuels [20]. In the present study, we investigated the cellulase
production by an endemic Penicillium sp. strain using lignocellulosic residues. The results showed
that higher cellulase activity was obtained after three days of incubation, using medium A with
moringa straw as the carbon source (Figure 4A). Lower CMCase was obtained in medium B. As
shown in Figure 4, corn stover was the second best substrate for the production of cellulase,
achieving similar results in both media (A and B).
A study published by Ghoshal et al. [21] investigated cellulase production using selected agricultural
wastes such as wheat bran, rice hust and rice bran as substrate using Penicillium citrinum MTCC 9620
during solid state fermentation. Among these three substrates and their three pretreatment
conditions, was observed that alkali treated wheat bran was the most suitable substrate to maximize
cellulase production.
Figure 4. CMCase activity production by Penicillium sp. grown in basal media A and B using different agricultural residues as a sole
carbon source. The microorganism was cultivated at 30°C and 2000 rpm for 5 days. Data are mean of three replicate. Bars indicate
standard errors.
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As mentioned before, the maximum CMCase activity for Bacillus subtilis RS-351 and Cladosporium
sp. was obtained when the microorganims were cultivate in the medium containing untreated corn
stover as a sole carbon source using medium basal A and B respectively. While for Penicillium sp.
higher CMCase activity was obtained in medium A, supplied with moringa as carbon source. In order
to characterize cellulolytic activities in this crude extract (cell free supernatant), we also evaluated
Fpase and β-glucosidase activity. Table 1 showed the results. Cladosporium produced the highest
Fpase activity, while β-glucosidase activities were very similar in enzymatic extracts of Cladosporium
sp. and Penicillium sp.
Table 1. Cellulase activities produced by native microorganisms using agricultural wastes. Numbers indicate the average of three
replicate, ± standard deviation.
basal medium/ Cellulolytic activity (U/mL)

Microorganism carbon source
CMCase FPase β-Glucosidase
Bacillus subtilis RS-351 A/corn stover 1.350±0.013 0.089±0.010 0.600±0.002
Cladosporium sp. B/corn stover 2.355±0.056 1.071±0.048 1.08O±0.010
Penicillium sp. A/moringa straw 3.715±0.025 0.288±.002 1.020±1.001
4- CONCLUSIONS
The native strains: Bacillus subtilis RS-351, Cladosporium sp. and Penicillium sp. were able to grow
and produce higher cellulolytic activities using cheap agroindustrial residues as carbon source.
In this sense, corn stover and moringa straw showed a great potential for cellulase production. Both
fungi evaluated produced a higher CMCase activity compared to that obtained by the bacteria.
REFERENCES
[1] Menéndez, E., García-Fraile, P., Rivas, R.: Biotechnological applications of bacterial cellulases. AIMS Bioengineering.
163-182 (2015)
[2] Sadhu, S., Maiti, T.K.: Cellulase production by bacteria: a review. British Microbiol. Res. J. 3, 235-258 (2013)
[3] Ahmed, A. & Bibi, A.: Fungal cellulase; production and applications: minireview. LIFE: Int. J. of Health Life Sci. 4, 19-
36 (2018)
[4] Saini, R., Saini, J.K., Adsul, M., Patel, A.K., Mathur, A., Tuli, D., Singhania, R.R.: Enhanced cellulase production by
Penicillium oxalicum for bio-ethanol application. Bioresour. Technol. 188, 240-246 (2015)
[5] Obeng, E.M., Siti, N.N.A., Budiman, C., Ongkudon, C. M., Maas, R.; José, J.: Lignocellulases: a review of emerging and
developing enzymes, systems, and practices. Bioresour. Bioprocess. 4, 16 (2017)
[6] Kuhad, R.C., Deswal, D., Sharma, S., Bhattacharya, A., Jain, K.K., Kaur, A., Pletschke, B.I., Singh, A., Karp, M.: Revisiting
cellulase production and redefining current strategies based on major challenges. Renew. Sustain. Energy Rev. 55,
249–272 (2016)
[7] Srivastava, N., Singh, J.P., Ramteke, P.W., Mishra, P.K., Srivastava, M.: Improved production of reducing sugars from
rice straw using crude cellulase activated with Fe₃O₄/alginate nanocomposite. Bioresour. Technol. 183, 262-266
(2015)
[8] Biswas, R., Persad, A., Bisaria, V.S.: Production of Cellulolytic Enzymes. In: Bioprocessing of Renewable Resources to
Commodity Bioproducts. V.S. Bisaria, A. Kondo (Eds.), John Wiley & Sons Inc. pp. 105–132 (2014)
[9] Bharathiraja, S., Suriya, J., Krishnan, M., Manivasagan, P., Kim, S.K.: Production of enzymes from agricultural wastes
and their potential industrial applications. Adv. Food Nutr. Res. 80, 125–148 (2017)
893
[10] Maeda, R.N., Barcelos, C.A., Santa Anna, L.M., Pereira, N.: Cellulase production by Penicillium funiculosum and its
application in the hydrolysis of sugar cane bagasse for second generation ethanol production by fed batch operation.
J. Biotechnol. 163(1), 38-44 (2013)
[11] Carrasco, M., Villreal, P., Barahona, S., Alcíno, J., Cifuenes, V., Baeza, M.: Screening and characterization of amylase
and cellulase activities in psychrotolerant yeasts. BMC Microbiol. 16, 21 (2016)
[12] Chiranjeevi, T., Baby Rani, G., Anuj, K., Chandel, Prakasham, R.S., Uma, A.: Optimization of holocellulolytic enzymes
production by Cladosporium cladosporioides using Taguchi-L16 orthogonal array. J. Biobased Mater Bioenergy. 6, 1-
10 (2012)
[13] Miller, G.L.: Use of Dinitrosalicylic Acid Reagent for Determination of Reducing Sugar. Anal. Chem. 31(3), 426–428
(1959)
[14] Ghose, T.K.: Measurement of cellulase activities. Pure Appl. Chem. 59, 257-268. (1987)
[15] Joo, A., Jeya, M., Lee, K., Lee, K., Moon, H., Kim, Y., Lee, J.: Production and characterization of f-1,4-glucosidase from
a strain of Penicillium pinophilum. Process Biochem. 45, 851-858 (2010)
[16] Abrha, B., Gashe, B.A.: Cellulase production and activity in a species of Cladosporium. World J. Microbiol. Biotechnol.
8, 164 (1992)
[17] Reddy, K.V., Lakshmi, T.V., Reddy, A.V.K., Bindu, V.H., Narasu, M.L.: Isolation, screening, identification and optimized
production of extracellular cellulase from Bacillus subtilis Sub.sps using Cellulosic Waste as Carbon Source. Int. J.
Curr. Microbiol. App. Sci. 5(4), 442-451 442 (2016)
[18] Prasanna, H.N. Ramanjaneyulu, G. Reddy, B. R.: Optimization of cellulase production by Penicillium sp. 3 Biotech.
6(2), 162 (2016)
[19] Meng, F.M., L. Ji, S., Yang, W., Cao, B.: Isolation and characterization of Bacillus subtilis strain BY-3, a thermophilic
and efficient cellulase-producing bacterium on untreated plant biomass. Lett. Appl. Microbio. 59(3), 306-312 (2014)
[20] Gusakov, A.V., Sinitsyn, A.P.: Cellulases from Penicillium species for producing fuels from biomass. Biofuels. 3(4),
463–477 (2012)
[21] Ghoshal, G., Banerjee, U.C. Shivhare, S.: Optimization of Cellulase (E.C. 3.2.1: 4) Production using Penicillium citrinum
MTCC 9620 in solid state fermentation. Br. Biotechnol. J. 3(4), 509-523 (2013)
894
PREPARATION OF SOLUBLE PEPTIDE FROM DEFATTED SOYBEAN IN THE PRESENCE

OF BASE ADDITIVES IN HYDROTHERMAL CONDITION AND EVALUATION OF ITS
FUNCTION
MASARU WATANABE1,2, MASAYOSHI WAGATSUMA1, RICHARD LEE SMITH, JR.1,2

1 Graduate School of Environmental Studies, Tohoku University, Sendai, Japan
Abstract
Denatured soluble proteins (DSP), or hydrothermal soluble proteins (peptides) were treated at
hydrothermal conditions and their characteristics (foaming property, antioxidant activity and
hypotensive effect) were evaluated. To enhance the yield of DSP, base additives and microwave
heating were found to be effective. The maximum yield of DSP at 190˚C by microwave heating in the
presence of base additive for 1 h was 80% based on the original amount of protein in a defatted
soybean. The peak of molecular weight distribution of DSP by GPC was around 10 kDa. The foaming
capacity and foaming stability of DSP were higher than that of alkali soluble (60 ºC, 30 min, pH 8
NaOH solution) soybean protein. Antioxidant activity (AA) was 63% and that of commercially
available soluble protein isolated (SPI) was 64%. AA is closely related to the order of amino acid
polymerized (such as histidine, proline and hydrophobic amino acid) and thus DSP probably
consisted of histidine and proline in its structure. Hypotensive effect of DSP was measured by
angiotensin converting enzyme (ACE) inhibition effect and was found to be positive while IC50 of DSP
was 0.66 mg/L compared with 3.3 mg/L of SPI and thus DSP is superior to SPI in view of hypertensive
effect.
895
EFFECT OF TEMPERATURE, TIME AND ZnCl2 ADDITION ON FORMATION OF

OXYGENATED FUNCTIONAL GROUPS ON THE SURFACE OF FLEXIBLE CARBON OF
PSEUDOTSUGA MENZIESII PREPARED BY HYDROTHERMAL CARBONIZATION
TAIGA WATANABE1, MASARU WATANABE1,2, RICHARD LEE SMITH, JR.1,2

1 Graduate School of Environmental Studies, Tohoku University, Sendai, Japan.
Abstract
To increase amount of oxygenated functional groups that contribute hydrophilicity of flexible carbon
surface, hydrothermal carbonization was applied: 20wt% Pseudotsuga menziesii slurry was
hydrothermally treated at 200～250 °C for 0.5～24 h in the presence of 0～100 g of zinc chloride
(ZnCl2). Hydrochar yield, Residual Cellulose Ratio, H/C and O/C, and amount of oxygenated functional
groups (OFGs) were evaluated. The amount of OFGs decreased due to dehydration of cellulose and
so on, while increased due to hydrolysis in a molecular structure such as lactone ring-opening by
prolonging reaction time and by addition of ZnCl2. Through the studies, it was found that ZnCl2 was
effective additives for promotion of carbonization and increase of OFGs formation at 250 ºC
hydrothermal carbonization of woody biomass.
896
EXPERIMENTAL DETERMINATION OF SELF-HEATING AND SELF-IGNITION RISKS OF

INDUSTRIAL HAZARDOUS WASTES
K. PAPANIKOLA1, K. PAPADOPOULOU1, V. RONDOGIANNI1, A. KORKOLIS3,

G. LYBERATOS 1, 2
1
School of Chemical Engineering, National Technical University of Athens Iroon Polytechneiou 9,
Zografou 157 80, Athens, Greece
2
Institute of Chemical Engineering Sciences (ICE-HT), Stadiou Str., Platani, 26504 Patras, Greece
3
Polyeco S.A. –Headquarters, 16th km of Athens-Korinthos Ntl Road, Aspropyrgos, 19 300, Attica –
Greece
Abstract
Solid and semi-solid (sludges) waste materials are often used as alternative fuels e.g. in the cement
industry. When stored in piles before their use ,they may undergo spontaneous combustion (self-
ignition) causing a fire hazard. By addition of inert substances, the probability of such a fire hazard
can be decreased.
A series of experiments with different types of industrial hazardous wastes (polyurethane, filters, ink
sludge’s, color powder residue, oil sludge etc.).were carried out in order to study the effect of the
composition on the self-ignition temperature. Measurements i.e. water content, Al, Cl, F, SO4, Ash,
VS, NCV, GCV, pH, %Hd, TC, and microorganisms were used in order to select the most hazardous
and highly self-ignition materials.
The ability of the materials to undergo oxidative self-heating was evaluated by using self-heating
apparatus following UN recommendations. The self-ignition temperature was determined using a
self-ignition apparatus according to the standard EN 15188:2007.
References
[1] Yasuhara, A., Amano, Y., Shibamoto, T.: Investigation of the self-heating and spontaneous ignition of refuse-derived
fuel (RDF) during storage. Waste Management 30 (2010) 1161–1164
[2] Shimizu, Y., Wakakura, M., Arai, M.: Heat accumulations and fire accidents of waste piles. Journal of Loss Prevention
in the Process Industries 22 (2009) 86–90
897
PRODUCTION OF AN ADSORBENT FROM FOOD RESIDUE BIOMASS (FORBI):

EVALUATION OF ITS PHYSICAL, CHEMICAL AND ADSORPTION PROPERTIES
E. PAPADOPOULOU1, H. PAVLOPOULOS1, P. GEORGIOU1, A. PEPPAS2, L. ZOUMPOULAKIS1, G.

LYBERATOS1,3
1 1School of Chemical Engineering, National Technical University of Athens Iroon Polytechneiou 9,

2 2School of Mining and Metallurgical Engineering of the National Technical University of Athens,
Iroon Polytechneiou 9, Zografou 157 80, Athens, Greece.

3 3Institute of Chemical Engineering Sciences (ICE-HT), Stadiou Str., Platani, 26504 Patras, Greece.
Abstract
Food Residue Biomass (FORBI) is generated by drying and shredding the fermentable fraction of
household food waste collected door-to-door in the Municipality of Halandri, Greece. The
production of an adsorbent by pyrolysis of FORBI was investigated as a chemical activation
procedure was employed in order to assess its impact on the properties of the adsorbent. Pyrolysis
conditions (temperature, pyrolysis time) and activation parameters used influence the properties of
resultant adsorbent significantly.
Preparation of adsorbent from FORBI was studied using chemical activation with KOH at 800˚C. The
sample was initially pyrolysed at 800˚C, then impregnated with the chemical agent and subsequently
activated at the same temperature under constant N2 flow. Impregnation ratio used was 1:4
(gCarbon to gKOH) and pyrolysis/activation time was 1h.
The adsorbent prepared from FORBI by chemical activation was characterized by SEM, FTIR and BET,
in order to determine its physical and chemical properties. The adsorbent was also tested for the
removal of Cr(VI) and COD from wastewater.
898
EXTRACTION OF CONTAMINANTS FROM HDPE WASTES: IS A RINSE SUFFICIENT ?
E. HÉLIAS, F. J. ESCUDERO SANZ, D. GROUSET

RAPSODEE Laboratory, IMT Mines Albi, Albi FRANCE.
Keywords: Plastic wastes, HDPE, Contaminants, ASE, GC-MS
Abstract
The issue of plastic waste valorisation or recycling has become urgent lately. With China’s
decision to recycle plastic wastes only if those are thoroughly cleaned and decontaminated, EU faces
an impasse. Some European waste collectors use solvents or lye while grinding wastes to ensure
decontamination. Nevertheless, that method has not be proven to be efficient enough. The goal of
the following study is to evaluate the decontamination effects of a rinse and consequently assess if
chemical migration into plastic takes place in the plastic jar lifetime.
Present work dealt with real plastic waste provided by a waste collector. Consequently, it a
blend of chipped jerry cans that had contained several chemicals.
In order to evaluate the solvent rinsing decontamination capacity, an Accelerated Solvent
Extraction (ASE) was performed (110 bars for 120°C) on plastic wastes ground to 1 mm particles (HDPE-
1mm). As a results, 21 molecules were extracted, quantified an identified with GC-MS analysis. A
comparison with clean HDPE showed that this method did not extract organic additives at required
levels to be detected. The quantification of minerals was not performed. Same not grounded plastic
wastes (HDPE-2cm) were also rinse for 24h with several solvents: either pure acetone, acetonitrile,
dichloromethane or mixtures of acetone / acetonitrile, acetone / dichloromethane and acetonitrile /
dichloromethane at different proportions (9:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:9). Using GC-MS analysis, the
contaminants in the rinse solutions were identified and quantified to be compared with the analysis
performed after ASE.
Firstly, as expected, 24h rinsing process performance was lower than ASE. Best observed
extraction performance was 57% of ASE. Besides, not every molecules were extracted with a simple
rinse, this method is not selective and thorough enough. Secondly, some mixtures were more efficient
than pure solvents: acetone/acetonitrile 1:1.
As a result, those contaminated plastics cannot be cleaned thoroughly by rinsing. They must
be excluded from recycling in favour of valorisation.
899
1- INTRODUCTION
Plastics are fossil materials widely used in several sectors such as packaging (39.9% in 2016 in
EU), building and construction (19.7%) or automobile (10%) [1]. The demand in Europe for plastics
increases each year and reached 49.9 Mt in 2016 [1], [2]. In the context of the environmental and
energy global issue, those plastic wastes are reconsidered as a new source of power. Indeed, the
European Union Directive 2008/98/CE [3] demands to limit the landfilling of wastes. Therefore, two
solutions are considered: recycling or energy recovery. In 2016, for the first time recycling overcame
landfill with respectively 31.1% and 27.3% of the 27.1 Mt of collected plastics post-consumption [1].
The rest was used for energy purposes. The tendency to recycle or valorise is mainly due to some
policies, pushed for in Northern Europe, limiting landfilling [1], [2].
In October 2017, China announced that it refuses from now on to import the plastic wastes [4],
[5], considered uncleaned. Indeed, they couldn’t ensure a proper recycling and guarantee the safety
of the workers. With this operation, called “Blue Sky”, 9 million of tons of post-consumption plastics
are concerned. As a result, EU must find a new way to valorise wastes on its own territory. Only China
possesses the appropriate infrastructure to treat the amount of plastic wastes collected by Europe.
Furthermore, several standards limit the presence of contaminants (metals, halogens, etc.) in
the polymer matrix [6]–[11]. That is why some studies quantify the amount of contaminants in the
plastic matrix which have diffused from the contained product toward the container. Some focus on
the additives’ quantification [12]–[17] while others characterise the amount of organics and volatiles
[18]–[23]. Both types may be qualified as contaminants as they are not the polymer itself. Several
methods of extraction are commonly used such as Solid Phase Micro-Extraction (SPME) [19], [22],
Microwave Assisted Extraction (MAE) [17], Supercritical CO2 Extraction (SCCO2) [14], [16], [18], [23]
and Accelerated Solvent Extraction (ASE) [20], [21]. The cited methods use high pressure, high
temperature or both to enhance the natural diffusion of contaminants within the polymer matrix.
After the extraction, the solvent is analysed through Gas Chromatography (GC) or High Performance
Liquid Chromatography (HPLC).
Before any recycling, the plastic wastes are rinsed with an organic solvent for decontamination.
Although, this method may eliminate the surface contaminants, it has not be proven to be efficient in
the core of the polymer. The following study is composed of two parts: firstly an extraction of the
additives was attempted, secondly a characterisation of the rinse for several solvents was made, and
compared with the results of the ASE.

2.1 – Samples
For the following study, contaminated High Density PolyEthylene (HDPE) was compared with
clean and unused HDPE. The former was a mix of different plastics which had been formerly chipped
to 2 to 3 cm thick flat particles (about 10 cm2) and rinsed with lye by a waste collector. Each type of
plastic in the mix contained unknown products, which have migrated within the polymer jar lifetime.
The second studied HDPE came from new jerry cans, which had never contained any product. Each
one’s contamination was characterised using ASE extraction, and/or simple solvent extraction,
coupled with GC-MS. In order to quantify the amount of each contaminant extracted, 1.36 µmol of
heptane was injected into each solution before GC-MS analysis.
2.2 – ASE method
900
The ASE method consists in enhancing a solvent extraction by increasing the pressure and the
temperature to approximately 100 bars and 100°C. As a result, the time of extraction can be reduced
to 15-30 min; decreasing by extension the amount of used solvent [24], [25]. ASE may extract low
polarity molecules but has a tendency to solubilise oligomeric fractions of the polymer matrix [26]. A
filtering is often required after the extraction. The figure 1 represents the ASE system.
Figure 1 : ASE System from [24]
For the following study, the ASE tests were performed at 120°C for 110 bars. Two cycles of
extraction were executed, lasting 5 min each. The solvent used was pure acetone. Each sample was
ground to approximately 1 mm beforehand, to enhance the contaminants’ diffusion.
2.3 – Rinse method

For the contaminated mix of plastics, a study of the influence of the rinse solvent was
performed. Between 2 to 4g of HDPE-2cm were plunged into approximately 10mL of a solvent for 24h,
at room temperature, and removed afterwards for the liquid to be analysed by GC-MS. The solvents
were pure acetone, acetonitrile, dichloromethane, or mixes of acetone/acetonitrile,
acetone/dichloromethane and acetonitrile/dichloromethane at different proportions (9:1, 3:1, 2:1,
1:1, 1:2, 1:3, 1:9). For each solvent, 3 samples were prepared and analysed.
2.4 – Comparison method

A first comparison between the ASE performed on the clean and the contaminated HDPE was
used to determine if organic additives could be extracted by this method (no quantification of minerals
was performed). Afterwards, the contaminants of the mix of plastic wastes were identified and
quantified, ruling out the organic additives, if extracted.
The ASE was used as a reference for extraction. The number of extracted molecules, noted 𝑠𝐴𝑆𝐸
was measured. It represents a reference for the selectivity of the rinse. If the rinse i extract 𝑠𝑖 > 𝑠𝐴𝑆𝐸
molecules, then it has a lower selectivity than the reference: the ASE performed with acetone. The
selectivity factor defined as such does not take into account any molecule which was not extracted by
the ASE, but, having a better affinity with a solvent i, appeared on its GC-MS analysis.
901
Another parameter to take into account is the quantity extracted. For that, as the tracer is
injected with a known quantity, the GC-MS analysis allowed to determine the quantity extracted for
each contaminant j. We chose to represent the quantity extracted by doing a mean of the molar
quantities, for each j contaminants, for a fixed solvent i. As ASE is the reference, the mean, called
extraction factor, is calculated on a basis of 𝑠𝐴𝑆𝐸 possible contaminants:
1
µ𝑖 = 𝑠 ∑𝑠𝑗=1
𝑖
𝑛𝑗𝑖 (1)
𝐴𝑆𝐸
with 𝑛𝑗𝑖 the molar quantity of the extracted contaminant 𝑖 for the solvent 𝑗.
Finally, to compare each factor with the chosen reference, a relative extraction factor 𝐸𝑖−𝐴𝑆𝐸
and a relative selectivity factor 𝑆𝑖−𝐴𝑆𝐸 were defined as such for each solvent i:
µ𝑖
𝐸𝑖−𝐴𝑆𝐸 = µ𝐴𝑆𝐸
(2)
𝑠𝑖
𝑆𝑖−𝐴𝑆𝐸 = (3)
𝑠𝐴𝑆𝐸

3.1 – Extraction of additives and contaminants with ASE for unused and contaminated HDPE
After the ASE performed on clean and contaminated HDPE, the solvents were analysed by GC-
MS. The extract from the unused plastic showed no contaminants, whereas 21 species were identified
for the mix of plastic wastes, presented in table 1.
Contaminant Retention time (min) Quantity extracted (µmol)

Toluene 3.825 0.173 (s.d. 0.033)
3-penten-2-one, 4-methyl- 4.436 2.31 (s.d. 0.42)
Eucalyptol 9.142 0.202 (s.d. 0.021)
Benzoic acid, ethyl ester 11.426 0.145 (s.d. 0.057)
Octanoic acid, ethyl ester 11.791 0.301 (s.d. 0.083)
Decanoic acid, ethyl ester 14.613 0.472 (s.d. 0.13)
Tetradecane 14.721 0.274 (s.d. 0.05)
2-propenoic acid, 3-phenyl-, ethyl ester 15.616 0.283 (s.d. 0.10)
Unidentified alkane or alkene 17.14 0.361 (s.d. 0.076)
2-ethylhexyl salicylate 19.56 0.258 (s.d. 0.077)
Table 1: The 21 contaminants identified in the mix of HDPE wastes, identified and quantified by GC-MS after ASE
902
As a result, the two factors characterising ASE could be calculated: 𝑠𝐴𝑆𝐸 = 21 and µ𝐴𝑆𝐸 =
0.417 µmol. To synthesise, the ASE method, used as such with acetone, could not extract additives
from the polymer matrix. The procedure could, however, extract various organic compounds and they
have been quantified and identified using GC-MS. The large variability of the resource may explain the
wide standard deviation. Besides, species might have been adsorbed by the oligomeric fractions of
polymer and washed out of the solution during the filtering. Some other methods of extraction might
be less selective like SCCO2 or MAE. To complete the identification of contaminants, an Inductively
Coupled Plasma (ICP) analysis would be required.
3.2 – ASE/rinse comparison for contaminated HDPE

The second part of the study aims to characterise the efficiency of a rinse for different solvents.
For each solution, the factors 𝑠𝑖 and µ𝑖 were calculated and compared with their equivalent for ASE.
The results are presented in the table 2 and figure 2. As heptane is not miscible with acetonitrile, for
high concentrations of that particular solvent, the results were not relevant. Indeed, the tracer was
shared between the two solvents and the quantity injected varied, depending of the homogeneity. For
pure acetonitrile, however, an agitation before injection was enough to obtain coherent results.
Solvent 𝑭𝒊−𝑨𝑺𝑬 𝑺𝒊−𝑨𝑺𝑬

Acetone 7.32% 38.10%
Acetonitrile 2.67% 33.33%
Dichloromethane 57.17% 57.14%
9:1 27.75 % 33.33 %
3:1 17.70 % 28.57 %
Acetone / Acetonitrile
2:1 18.88 % 42.86 %
1:1 5.12 % 33.33 %
3:1 14.15 % 47.62 %
2:1 7.68 % 38.10 %
Acetone / Dichloromethane
1:1 17.86 % 52.38 %
1:2 1.45 % 47.62 %
1:1 2.41 % 38.10 %
1:2 21.46 % 47.62 %
Acetonitrile / Dichloromethane
1:3 32.18 % 52.38 %
1:9 37.54 % 57.14 %
Table 2: Extraction and selectivity factors for the rinse solvent, for contaminated HDPE-2cm, for 24h
903
Fi-ASE Si-ASE
70.00%
60.00%
50.00%
40.00%
30.00%
20.00%
10.00%
0.00%
A1 A2 D A1/A2 A1/D A2/D

Figure 2: Extraction and selectivity factors for each mix of solvent for 24h rinse (A1=Acetone, A2=Acetonitrile,
D=Dichloromethane)
Each solvent has extraction and selectivity factors lower to 1. In other words, whichever the
solvent used for rinse, the plastic wastes contained residual contaminants after the experiment. Those
have not been extracted from the core of the matrix. To enhance the rinse’s effects, one could grind
the HDPE to 1mm or use alternative methods such as ASE, MAE, SCCO2 and so forth.
Furthermore, some solvents are more relevant to an extraction, being less selective and
extracting a larger amount of contaminants. For example, pure dichloromethane is the more efficient
solvent in regard to the quantity extracted (𝐹𝐷𝑖𝑐ℎ𝑙𝑜−𝐴𝑆𝐸 = 57.17%) and to the number of species
identified (𝑆𝐷𝑖𝑐ℎ𝑙𝑜−𝐴𝑆𝐸 = 57.14%). Besides, the GC-MS analysis on pure dichloromethane rinse
allowed to identify other alkanes that had not been extracted by the ASE.
Another observation, confirmed by the literature [21], is the effect of a mix of solvent
compared with a pure solution. The mixture acetone / acetonitrile has extracted more contaminants
than the pure solvents. As a result, a mixture of different solvents could improve the extraction
compared with the effect of each one of them taken separately.
4- CONCLUSIONS
Plastics recycling or valorisation is becoming a priority for the European waste treatment
sector. Given the Chinese decision concerning the import of plastic wastes, a solution must be
proposed in Europe. This study was performed on HDPE wastes which have been contaminated by the
contained products. As a result, those plastics cannot be recycled as they might contain toxic or
polluting molecules.
Indeed, the result shows that even a complete rinse of 24h at room temperature could not
penetrate entirely within the polymer. A possible improvement could be to optimize the solvent used,
or grind the wastes. Solvents, however, are pollutants and limiting their use would be beneficial.
Besides a too intensive grinding may deteriorate the quality of the plastics for reuse.
904
Furthermore, an intense extraction method such as ASE was inefficient to extract some
additives. Yet, in some applications, plastics are reinforced with flame retardants, containing halogens
like brome. Such an endocrine disruptor should not be recycled if the new application could endanger
humans.
For all the cited reasons, recycling should not be promoted for plastic wastes which could
contain dangerous contaminants. That particular category of waste may be valorise for energy
purposes. One solution is the incineration, producing heat, electricity or both while eliminating the
contaminants. Another developing solution is the gasification of the wastes. Indeed, gasification would
convert any organic contaminant into syngas. This high-value-added product might be converted into
hydrogen, methane, and so forth for chemical or energetic purposes.
REFERENCES
[1] PlasticsEurope, ‘Plastics - the Facts 2017 : an analysis of European plastics production, demand and waste data’,
2017.
[2] PlasticsEurope, ‘Plastics - the Facts 2016 : an analysis of European plastics production, demand and waste data’,
2016.
[3] Conseil de l’Union Européenne, Directive 2008/98/CE du Parlement Européen et du Conseil du 19 novembre 2008
relative aux déchets et abrogeant certaines directives, vol. 2008/98/CE. 2008.
[4] M. Combe, ‘La Chine interdit l’importation des plastiques en mélange’, Techniques de l’Ingénieur, 11-Oct-2017.
[5] M. Delamarche, ‘Opération Ciel bleu en Chine, recyclage en berne en Europe - L’Usine Matières premières’, L’Usine
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Ultraviolet Stabilizers, Plasticizers and Photoinitiators in Plastic Food Package by Accelerated Solvent Extraction
Coupled with High-Performance Liquid Chromatography’, J. Chromatogr. Sci., vol. 53, no. 6, pp. 1026–1035, Jul.
2015.
[13] Y. Zhang, Z. Du, A. Li, A. Tu, W. Yu, and J. Zou, ‘Rapid qualitative and semi-quantitative determination of polymer
additives in polymer matrix by electrospray ionization-triple quadrupole mass spectrometry with accelerated
solvent extraction (ASE-ESI-MS/MS)’, Anal. Methods, vol. 5, no. 19, pp. 5112–5120, 2013.
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using SFE/HPLC’, J. Appl. Polym. Sci., vol. 76, no. 6, pp. 938–946, May 2000.
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of Organic Flame Retardants in Acrylonitrile Butadiene Styrene’, Anal. Lett., vol. 48, no. 14, pp. 2319–2328, Sep.
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905
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chromatography mass spectrometry to evaluate the efficiency of recycling processes’, J. Chromatogr. A, vol. 1218,
no. 10, pp. 1319–1330, Mar. 2011.
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rings of gingko (Gingko biloba L.): Determination of PAHs by GC/MS after accelerated solvent extraction’,
Microchem. J., vol. 97, no. 2, pp. 138–143, Mar. 2011.
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906
REVIEW ON BIOMETHANATION OF SYNGAS TO BIOGAS
W. ZHANG1
1 Mid Sweden University, Sundsvall, Sweden.
Abstract
Biogas as a heat and power resource as well as a vehicle fuel has been commercialized well in many
countries such as Germany, Sweden etc.. However, further development of the biogas market is
limited by the amount of available organic waste as well as the number of biogas filling station. On
the other hand, biomass can be gasified into syngas and then synthesized into bio-SNG through
catalytic methanation, or biomass gasification can be integrated into the biogas system to produce
methane through biological methanation. In this way, biomethane can give a significant contribution
to the energy market to replace natural gas. Biogas can be an important energy carrier in the future
smart energy grids. By means of biogas system for electricity and vehicle fuel production, the
increased proportion of variable renewable electricity (solar and wind) on the grid can be balanced.
More importantly for the countries with rich biomass residues, biogas production can be increased
to a full scale to meet heat & power and transport fuel demand by integrating biomass gasification
into biogas system. For this purpose, a novel pathway is proposed to be studied in this project:
Biomass gasification > H2+CO > Biogas digester > Upgrading > Natural gas network
The review paper emphasizes 1) to develop suitable biomass gasifier for production of a good quality
syngas, and 2) to study the biogas production from biological methanation or bio-methanation of
syngas. The technology feasibility, the bioreactor design, the process synergy and the integration of
the gasification plant with the biogas plant will be addressed. It can be concluded that the dual-
fluidized bed gasifier can be a good choice to produce high concentration hydrogen syngas. It is
possible to convert the most of CO2 in biogas from digesters into biomethane when syngas is added
in the digesters. The commercialization of syngas biomethanation is discussed.
907
IN-RUBBER PERFORMANCE OF THE RECOVERED CARBON BLACK REINFORCING

FILLER OBTAINED FROM THE STEAM-THERMOLYSIS OF USED TIRES
L. MOULIN1,2, E. WEISS-HORTALA2, Y. SOUDAIS2, S. DA SILVA1, R. BARNA2

1 Alpha Recyclage, 4 rue Jules Védrines, 31400 Toulouse, France.
2 Université de Toulouse, IMT Mines Albi, CNRS, Centre RAPSODEE, 81013 Albi, France.
Abstract
According to the European Tyre Recycling Association (ETRA), nearly 300 millions of waste
tires are treated in Europe each year and are subjected to legislation and regulation policies for the
re-use and recycling of 95% of the total mass of end-of-life vehicles [1]. Steam-thermolysis, a hybrid
of pyrolysis and solvolysis processes, uses superheated steam at atmospheric pressure as an
additional factor of heating the waste tires within the reactor. The process is an efficient alternative
among the thermochemical methods for the treatment of waste tires allowing materials recovery.
Recovered Carbon Black (rCB), which can be reintroduced in rubber industry as reinforcing filler, is a
more economical added value material than shredded tires.
Steam-thermolysis experiments have been performed using an original semi-continuous

laboratory-scale pilot reactor developed by MARVAPOL joint laboratory between the RAPSODEE
Center of Mines Albi and ALPHA RECYCLAGE and based on previous established studies for carbon
fiber reinforced composites and waste tires [2,3]. In the present work, samples under investigation
include N330 rCB from model laboratory N330 filled rubbers and industrial rCB from shredded waste
light vehicles tires.
This paper aims to investigate the application of rCBs in rubber compounds in substitution
with conventional carbon blacks. The study focuses on the comparison between respectively: a N330
commercial carbon black, a model N330 rCB and an industrial rCB filled NR/SBR vulcanizates, in
terms of rheological and mechanical properties (viscosity, in-rubber dispersion, tensile strength,
elongation at break, M300% and compression set).
Recovered fillers in-rubber performance will be assessed and compared to the conventional
N330 filler, taking into consideration the influence of their chemical surface and structural state
discrepancies arising from the steam-thermolysis recycling process. The overall properties of the rCB
obtained from the steam-thermolysis of used tires is proven to be an interesting reinforcing filler in
rubbers.
References
[1] Shulman, V.L., European Tyre Recycling Association Conference, Introduction to tyre recycling, March 2016
[2] Sheng, Y.Y., Bounaceur, A., Soudais, Y., Barna, R.: Parameter optimization of the steam thermolysis: A process to
recover carbon fibers from polymer-matrix composites. Waste and Biomass Valor. 4(1), 73-86 (2013)
[3] Moulin, L., Da Silva, S., Bounaceur, A., Herblot, M., Soudais, Y. : Assessment of recovered carbon black obtained by
waste tires steam water thermolysis: an industrial application. Waste and Biomass Valor. (2017)
908
ACTIVATED PYROLYSED CORK RESIDUES FOR METHYLENE BLUE REMOVAL FROM

WASTEWATERS
RUI M. NOVAIS, ANA P.F. CAETANO, ROBERT C. PULLAR1

1 Department of Materials and Ceramic Engineering / CICECO- Aveiro Institute of Materials,
University of Aveiro, Campus Universitário de Santiago, 3810-193 Aveiro, Portugal.
Abstract
The presence of dyes in industrial wastewaters is a long-lasting environmental concern. Among

these, methylene blue (MB) is one of the most problematic due to its toxicity. In fact, MB can cause
blindness, respiratory distress and abdominal disorders [1], and for that reason its removal from
industrial wastewaters is mandatory. Activated carbon presents very high adsorption capacity.
However, its very high production cost hinders its widespread use [2]. In this context, new adsorbent
materials with lower production cost should be developed. One interesting possibility is the use of
waste materials as precursors. In this work, industrial cork residues coming from wine stopper
production were first activated, by using several commercial alkaline materials, or a mixture of these
and an alkaline waste effluent coming from pulp and paper production. These were then pyrolysed
to produce the adsorbent material. Afterwards, the feasibility of using the activated pyrolysed cork
residues as MB adsorbents was evaluated. Results show that these innovative adsorbents present a
rapid, high methylene blue uptake capacity, demonstrating their potential for wastewater
decontamination. Moreover, this novel adsorbent material was produced using cork, which is a
natural and sustainable material, and any CO2 emitted during its pyrolysis will be absorbed by the
cork oak tree to regenerate the cork bark. The latter greatly reduces the environmental footprint of
the produced adsorbent.
References
[1] Khan, M.I., Min, T.K., Azizli, K., Sufian, S., Man, Z., Ullah, H.. Effective removal of methylene blue from water using
phosphoric acid based geopolymers. RSC Advances 5, 61410-61420 (2015).
[2] Rafatullah, M., Sulaiman, O., Hashim, R., Ahmad, A.. Adsorption of methylene blue on low-cost adsorbents: a review.
Journal of Hazardous Materials 177, 70-80 (2010).
909
METHANE DECOMPOSITION TO HYDROGEN AND CARBON BLACK

USING SOLAR ENERGY
H.J. KIM1, J.G. KIM1, K.H. SONG1,2, K.T. PARK1, S.K. JEONG1
1 Korea Institute of Energy Research,Daejeon, Republic of Korea.
2 Korea University, Seoul, Republic of Korea.
Abstract
Biogas produced from municipal waste typically contains methane and carbon dioxide as main
products. Since methane concentration in the biogas is generally around 50%, it is combusted as a
fuel for heating or cooking. Combined with the removal process of CO2, methane can also be used in
a gas engine to convert its energy into electricity and heat or compressed as CNG to power motor
vehicles.
Since methane is combusted in the gas or motor engines, production of CO 2 is inevitable. The
thermal decomposition of methane (TDM) to hydrogen and carbon black using renewable energy is
considered as a promising route to use efficiently the energy of methane without emitting
greenhouse gas CO2. The carbonaceous solid product can be either sequestered without CO2 release
or used as a valuable material commodity in different applications. It can also be applied as reducing
agent in metallurgical industry. The generated H2-rich gas mixture can be directly used as fuel for
internal combustion engines or further processed to high purity H2 for being used in fuel cells [1].
TDM (non-catalytic) typically requires temperatures higher than 1,300 oC in order to achieve
reasonable reaction rates. Consequently, the use of catalysts (either metallic or carbonaceous
catalysts) was investigated in order to operate at lower temperature and improve the process
kinetics [2].
In this work, Ni-containing alloy catalysts were prepared by co-precipitation and thermal reduction
process. The nitrate precursors of transition metals were dissolve in DI water and co-precipitared
with Na2CO3 aqueous solution. The obtained precipitates were washed with DI water and dried at
100oC overnight. The alloy catalysts were obtained by further reducing the samples with H2 at 700 oC
for 4h. The catalysts were characterized by SEM, XRD, BET, TGA, FT-IR and TPR. The activity of the
catalysts toward methane decomposition was evaluated in a conventional fixed bed reactor. The
catalysts, under a stream of CH4/Ar (10%vol CH4/Ar at a total flow of 100mLmin−1), were heated from
RT up to 1,200 oC at 10 oC min−1 and kept constant at 1,200 oC for 2h. Activity results have been
evaluated in terms of the quantity of the produced H2, given in Table 1. Ni-Fe alloy catalyst showed
the best activity among the prepared catalysts.
Table 1. Catalytic activity of Ni-containing alloy catalysts toward methane decomposition
H2 Produced (mmol/gcat)
Catalyst o o o o
900 C 1,000 C 1,100 C 1,200 C
Ni-Cu 21.3 101.3 127.5 153.7
Ni-Ga 35.2 98.7 167.3 287.9
Ni-Fe 98.7 198.5 312.8 420.8
Ni-Co 73.7 132.9 257.9 393.7
Ni-Mo 43.1 145.8 275.2 317.8
References
[1] Abanades, S., Kimura, H., Otsuka, H., : Hydrogen production from CO2-free thermal decomposition of methane:
Design and on-sun testing of a tube-type solar thermochemical reactor. Fuel Proces. Tech. 122, 153-162 (2014)
[2] Guil-Lopez, R., Botas, J.A., Fierro, J.L.G., Serrano, D.P., : Comparison of metal and carbon catalysts for hydrogen
production by methane decomposition. Appl. Catal. A Gen. 396, 40-51 (2011)
910
THE ROLE OF SECONDARY TAR REACTIONS ON THE PRODUCT YIELDS AND GAS
COMPOSITION DURING SOLAR-DRIVEN FAST PYROLYSIS OF BIOMASS PELLETS
J. SORIA*,1, R. LI2, D. GAUTHIER2, G. FLAMANT2, G. MAZZA1

1 Institute for Research and Development in Process Engineering, Biotechnology and Alternative
Energies (PROBIEN, CONICET - UNCo), 1400 Buenos Aires St., 8300 Neuquén, Argentina. Tel: +54
(0)2994490300 ext.456; *Corresponding author e-mail: jose.soria@probien.gob.ar
2 Processes, Materials and Solar Energy Laboratory (PROMES-CNRS, UPR 8521), 7 Rue du Four
Solaire, Odeillo 66120 Font-Romeu, France.
Keywords: Biomass, Solar pyrolysis, Intra-particle tar decomposition, Particle size influence
Abstract
Biomass is a renewable energy source that can aid relieving the energy crisis and environmental
problems. Pyrolysis is one of the most attractive thermochemical processes to convert biomass into
biofuels. Even more, by using concentrated solar radiation as the energy source, the process efficiency
is upgraded.
The objective of this work is to experimentally study and compare the effect of pellet size (5 and 10
mm height) on the product yields (tar, char and gas), gas composition (H2, CO, CO2, CH4) and secondary
tar reactions under fast solar pyrolysis (800, 1200 and 1600°C and heating rates of 10 and 50°C/s ).
Solar pyrolysis experiments are carried out in transparent Pyrex® spherical balloon reactor, with argon
used as the working flow medium in order to take out the volatiles products. The pellet is placed in a
graphite crucible insulated with graphite foam and placed and fixed at the focus of a 1.5 kW vertical
axis solar furnace. Also, a characteristic time and a dimensionless number study is performed so as to
estimate the rate-controlling phenomena.
The experimental results show that, for temperatures above 1200°C, there are almost no differences
between product yields as well as for the gas product distribution, for the two pellet heights. The
differences are within the error bars.
It can be considered that at high heating rates and high final temperature, the pellet size seems to be
not relevant for improving tar decomposition. This behaviour can be explained by the low residence
time of tar in the pellet, evidencing that secondary tar reactions reaches a maximum potential
occurrence. Thus, further increase in the operating conditions along with the pellet height will result
in an almost negligible effect on product yields.
911
1- INTRODUCTION
The increasing demand of energy along with the need of diminishing greenhouse gas emissions has
led the attention towards renewable fuels. Biomass is a renewable energy source that can partly
relieve the energy crisis and environmental problems, since it represents a carbon neutral fuel with
extra benefits such as low content of nitrogen and sulphur.
Pyrolysis and gasification are the most attractive thermochemical processes to convert biomass into
biofuels due to reasons of feedstock flexibility and conversion efficiency. Pyrolysis represents the first
(main) chemical step in gasification, and combustion, amongst others processes. It can also be a stand-
alone process. Pyrolysis produces three main products: char, condensable gases (tar and water) and
non-condensable gases (H2, CO, CO2, CH4). Depending on the operating conditions and feedstock
properties, pyrolysis will produce different distributions and yields and, consequently, will affect the
behaviour of the succeeding steps.
Conventional gasifiers (fixed or fluidized beds) usually treat centimetre sized biomass particles, since
they cannot be economically processed into very fine sizes due to its high volatile content and
moisture level. These large biomass particles may provide sufficient residence time for tar to
decompose homogeneously and heterogeneously inside the particle to give secondary gas, tar and
char, which can also affect the product yields. Moreover, the average thermal conductivity of biomass
is very low. Then both the biomass size and the effective thermal conductivity (λeff) along with the high
operating values of temperature and heating rates (HR) encountered in these units could make intra-
particle heat transfer mechanism to play an important role on product distribution from pyrolysis.
Most of the experimental and modelling research regarding tar intra-particle secondary reactions
were performed under slow heating rate and low temperature. Nonetheless, up to the authors’
knowledge, no results have ever been reported concerning pyrolysis of thermally thick particles at
both high heating rate and final temperature.
Okekunle et al. [1] studied experimentally (by macro TGA) and numerically the effect of biomass aspect
ratio in tar cracking. The final reactor temperature was 700ºC and the heating rate was 30ºC/s. Results
showed that tar yield decreased with increasing biomass length while the particle diameter was held
constant. They stated that according to the numerical analysis, the optimum aspect ratio for achieving
intra-particle tar decomposition is 1.1. Pattanotai et al. [2] performed macro TGA experimental essays
to study intra-particle secondary reactions of tar during biomass pyrolysis of a centimetre wood
cylinder. They compared the product yields of sawdust and wood cylinder at 0.5ºC/s (low heating rate,
kinetic controlled regime). Therefore, a comparison of the sawdust and wood cylinder revealed the
occurrence of intra-particle secondary reactions. They concluded that tar intra-particle decomposition
is important when slowly pyrolyzing “thermally thick” particles. Bennadji et al. [3] conducted an
experimental study and compared the pyrolysis behaviour of two different sizes of wood spheres.
Pyrolysis was performed at atmospheric pressure in a bench-scale tubular reactor designed to pyrolyze
solids at a maximum temperature of 482ºC. A numerical model was also formulated and validated
against the experimental data. Kenarsari and Zheng [4] formulated a model validated by comparing
experimental data found in bibliography. More recently, Shi et al. [5] formulated a 3D particle model
accounting for transport phenomena along with primary pyrolysis and homogeneous and
heterogeneous tar decomposition. The model was validated with experimental data from literature.
In this frame, the objective of this paper is to experimentally study the effect of pellet size on the
product yields, gas composition and intra-particle secondary tar reactions (homogeneous and
heterogeneous, since they cannot be separated during the experiment) under moderate and fast
pyrolysis at high temperature (800, 1200 and 1600°C and 10 and 50°C/s). A comparison of product
yields as well as permanent gas composition (H2, CO, CO2, CH4) is carried out for two different heights
912
of pellets (5 and 10 mm). Also, a characteristic time study is performed so as to estimate the rate-
controlling phenomena and explain the product yields obtained

2.1. Biomass feedstock characterization
The feedstock used in this study was pine sawdust from forestry industry generated at a wood
processing installation in Aluminé, Patagonia (southern region from Argentina). The particles were
dried in an oven (105ºC for 24 hours) to remove their moisture content, and then compressed into
cylindrical pellets with 10 mm in diameter and 5 and 10 mm height. The pellet composition and its
properties are given in Tables 1 and 2, respectively. In Table 1, CELL stands for cellulose, HCE for
hemicellulose, LIG for lignin. In Table 2, ε0 represents the initial pellet porosity, L0 the initial bed height,
R0 the pellet radius and ρp,0 the initial pellet apparent density.
Proximate Analysis Biochemical Analysis

Ultimate Analysis (wt.%, d.b)
(wt.% d.b) (wt.%, d.b)
Volatile Fixed
C H O N S Ash CELL HCE LIG
Matter C
50.93 6.03 42.36 0.11 0.05 82.4 17.07 0.53 42.96 19.99 26.8
Table 1: Pine sawdust composition.
Sample ε0 L0 [m] R0[m] ρp,0 [kg/m3]

Pellet 1 0.43 5·10-3 5·10-3 850
Pellet 2 0.43 1·10-2 5·10-3 850
Table 2: Pellet properties
2.2. Experimental procedure

A single particle solar reactor is used to carry out pyrolysis experiments. A detailed description of the
reactor and peripheral systems can be found in Zeng et al. (2015) [6]. Briefly, the reactor consists of a
transparent Pyrex® spherical balloon, with argon used as sweeping gas. The pellet was placed in a
graphite crucible insulated with graphite foam and placed at the focus of a 1.5 kW vertical-axis solar
furnace (parabolic mirror of 2 m). Fig. 1 depicts the setup applied for carrying out the solar pyrolysis
experiments. Also the pellet remained static during the whole experiment. The sample surface
temperature was measured by a solar-blind optical pyrometer. The heating rate and the final
temperature were controlled by a PID controller that mastered the incident radiation by means of a
shutter. A vacuum pump was used to take out the pyrolysis gas and tar along with argon. Tar was
condensed and gas was collected in a sampling bag. Finally, off-line gas chromatography was used to
analyse the species in the non-condensable gaseous phase. Pyrolysis were carried out at three
temperatures: 800, 1200 and 1600ºC and two heating rates: 10 and 50ºC/s. Each condition was
performed by triplicate assays.
2.3. Characteristic time analysis

The characteristic time theory is adopted as a first approach in order to estimate the rate controlling
process. The characteristic time of a phenomenon is the theoretical time needed for pyrolysis
conversion when this is only controlled by the involved phenomenon [7]. It should be pointed out that
during the pyrolysis process, the structure of the solid (e.g. porosity, permeability, density) changes as
913
well as its thermo-physical properties. Therefore, there is a degree of variability and uncertainty in the
estimation of the properties of the phases, particularly the solid properties, which influences the
characteristic time scales. Consequently, only the order of magnitude of the characteristic time is
taken into account. The characteristic time of main phenomena during pyrolysis, physical and
chemical, are calculated by the equations given in Table 3.
Figure 1: Experimental setup for solar driven pyrolysis
Phenomenon Characteristic time [s]

Pyrolysis chemical kinetic, 𝑡𝑡𝑝𝑝𝑝𝑝 1/𝑘𝑘𝑝𝑝𝑝𝑝
External heat transfer, 𝑡𝑡𝐻𝐻,𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝜌𝜌𝑝𝑝 𝑐𝑐𝑝𝑝,𝑝𝑝 𝐿𝐿𝐶𝐶 /ℎ𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
Conductive heat transfer, 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 𝜌𝜌𝑝𝑝 𝑐𝑐𝑝𝑝,𝑝𝑝 𝐿𝐿2𝐶𝐶 /𝜆𝜆𝑒𝑒𝑒𝑒𝑒𝑒
Intra-particle mass convection, 𝑡𝑡𝑀𝑀,𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 µ 𝐿𝐿2𝐶𝐶 /(𝛥𝛥𝑃𝑃 ∙ 𝐵𝐵)
Intra-particle mass diffusion, 𝑡𝑡𝐷𝐷𝐷𝐷𝐷𝐷𝐷𝐷 𝐿𝐿2𝐶𝐶 /𝐷𝐷𝑒𝑒𝑒𝑒𝑒𝑒
Dimensionless number Definition

Pyrolysis number 𝑃𝑃𝑃𝑃 = 𝑡𝑡𝑝𝑝𝑝𝑝 /𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
Damkhöler number 𝐷𝐷𝐷𝐷 = 𝑡𝑡𝑝𝑝𝑝𝑝 /𝑡𝑡𝐻𝐻,𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
Thermal Biot number 𝐵𝐵𝑖𝑖 𝑇𝑇 = 𝑡𝑡𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 /𝑡𝑡𝐻𝐻,𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
Table 3: Characteristic times and relevant dimensionless numbers
The pellet is externally heated by radiation. Also, convective heat transfer is considered to take place
between the pellet surface and argon flow, since the pyrolysis gas is highly diluted. Inside the particle,
the heat transport occurs by effective conduction and chemical reactions of pyrolysis take place. Mass
transport inside the pellet is due to convection and diffusion. The generated gases (both condensable
and non-condensable) inside the pellet cause a sudden increase of pressure, creating a pressure
gradient between the interior and exterior of the pellet, which causes a convective outflow of the gas.
914
The pellet physical properties and transport properties are taken from literature (Table 4). The
external heat transfer coefficient is estimated based on a calorimetric tests carried out in a similar
parabolic mirror (diameter of 1.5 m).
Properties Reference
−5 2 −1 Shi et al. [5]
𝐷𝐷𝑒𝑒𝑒𝑒𝑒𝑒 = 1.10 𝑚𝑚 . 𝑠𝑠
𝛥𝛥𝑃𝑃 = 300 𝑃𝑃𝑃𝑃 Soria et al. [8]
𝜌𝜌𝑝𝑝 = 850 𝑘𝑘𝑘𝑘/𝑚𝑚3 Measured, this work
µ = 3.10−5 𝑘𝑘𝑘𝑘. 𝑚𝑚−1 . 𝑠𝑠 −1 Shi et al. [5]
−12 2 Soria et al. [8]
𝐵𝐵 = 1.10 𝑚𝑚
−1 −1
𝜆𝜆𝑠𝑠 = 0.255 𝑊𝑊. 𝑚𝑚 𝐾𝐾 Okekunle et al. [9]
−1 −1
𝑐𝑐𝑝𝑝,𝑠𝑠 = 2300 − 1150 exp[−0.0055. 𝑇𝑇] 𝐽𝐽. 𝑘𝑘𝑔𝑔 . 𝐾𝐾 Blondeau and Jeanmart [10]
8 −1
𝑘𝑘𝑝𝑝𝑝𝑝 = 1.10 exp[− 140000⁄𝑅𝑅𝑅𝑅] 𝑠𝑠 Chan et al. [11]
𝜔𝜔 = 0.9 Gronli [12]
−2 −1 Estimated
ℎ𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐 = 150 − 530 𝑊𝑊. 𝑚𝑚 . 𝐾𝐾
Table 4: Thermo-physical properties for sawdust pellets
2.4. Dimensionless number analysis

The pyrolysis behaviour is also usually described by means of two dimensionless numbers: the thermal
Biot number (BiT), which relates the characteristic time for internal and external heat transfer; and the
Pyrolysis number (Py) that accounts the ratio of characteristic time between kinetics and conductive
heat transfer. A third relevant non-dimensional number is the Damköhler (or external Pyrolysis
number, Py’), which represents the ratio between the chemical kinetic mechanism and the external
heat transfer process. Based on Py and BiT values, four different regimes can be defined [13]. The first
regime is known as kinetically controlled pyrolysis, where the rate of pyrolysis is determined
exclusively by the chemical reactions. This regime is usually typical of very fine particles. Small particles
(BiT < 0.2) are pyrolyzed under thermally thin regime (region 2). In this region, the particle can be
considered to have a uniform temperature profile and pyrolysis takes place in the whole particle
domain at the same rate. Large particles are usually pyrolyzed in region 3, which are referred as
“thermally thick particles” (0.2 < BiT < 10). In this regime, a temperature gradient appears and both
the kinetics as well as the heat transfer may control pyrolysis. The last regime corresponds to the
thermal wave regime (BiT > 10): A well-defined pyrolysis front (1-3 mm size) is developed, as a result
of the thermal wave, which travels from the surface toward the interior of the pellet at a nearly
constant velocity. [13].

3.1. Characteristic times
The calculated characteristic times for a heating rate of 50°C/s are presented in Table 5. At the lowest
temperature studied on the 5 mm pellet, internal heat transfer as well as external heat transfer time
scales are comparable, and 3-4 orders of magnitude slower than tpy. The influence of internal heat
transfer increases as the pellet height also increases. For both pellets and temperature above 1200°C,
the limiting process is given by internal heat transfer and the behavior can be considered as a thermal
wave regime.
The outflow of gas reaction products due to convection is quite similar to mass transport by diffusion,
regardless the temperature and pellet size. Also it is important to remark that, based on the values of
915
tM,conv and tDeff, it appears that the intra-particle residence time for both pellets is quite similar. This
observation is crucial to evaluate the effect of secondary chemical reactions during pyrolysis process.
800ºC 1200ºC 1600ºC

Phenomenon
L0 = 0.005 m L0 = 0.01 m L0 = 0.005 m L0 = 0.01 m L0 = 0.005 m L0 = 0.01 m
𝒕𝒕𝒑𝒑𝒑𝒑 7·10-2 7·10-2 9·10-4 9·10-4 8·10-5 8·10-5
𝒕𝒕𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄 4·101 7·101 1·101 3·101 1·101 2·101
𝒕𝒕𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄 2·102 8·102 2·102 8·102 2·102 8·102
𝒕𝒕𝒄𝒄𝒄𝒄𝒄𝒄𝒄𝒄 3·100 8·100 3·100 8·100 3·100 8·100
𝒕𝒕𝒅𝒅𝒅𝒅𝒅𝒅𝒅𝒅 3·100 1·101 3·100 1·101 3·100 1·101
Table 5: Characteristic time scales comparison for 50°C/s
3.2. Dimensionless numbers

On the one hand, the BiT calculated for both pellets are in the range 3.58-36.68. Therefore, it can be
considered that the process is limited by the external/internal heat transfer at the lower limit and
purely controlled by internal heat transfer at the highest temperature [13]. In both cases, an internal
temperature gradient is will be present.
On the other hand, the Py values obtained, always lower than 0.001 (at the lowest temperature
studied), indicate that kinetics play a negligible role as a controlling phenomenon. A similar trend is
observed for Damköhler number. On this basis, both pellets behave non-isothermally and pyrolysis
will be controlled by the convection and conductive heat transfer until 1200ºC in the case of the 5mm
pellet. Further increase in the final temperature causes the pellet to pyrolyze under the thermal wave
regime. These results are in agreement with the observations reported by Soria et al. [8]. The authors
formulated a CFD model and showed a non-uniform temperature profile in the 5 mm pellet.
Dimensionless 800ºC 1200ºC 1600ºC

number L0 = 0.005 m L0 = 0.01 m L0 = 0.005 m L0 = 0.01 m L0 = 0.005 m L0 = 0.01 m
Py 3.4·10-4 8.5·10-5 4.8·10-6 1.2·10-6 4.2·10-7 1.1·10-7
Da 1.8·10-3 9.2·10-4 6.3·10-5 3.2·10-5 7.7·10-6 3.8·10-6
BiT (50°C/s) 5.36 10.73 13.15 26.30 18.34 36.68
BiT (10°C/s) 3.58 7.15 8.77 17.53 12.23 24.45
Table 6: Dimensionless numbers comparison
3.3. Pyrolysis products yield

Char yield
It can be seen from Table 7 that, for each pellet and same heating rate, as temperature increases the
char yield diminishes. This behavior is in accordance with [14]. Also, for each pellet and at a fixed
916
temperature, the decrease in the heating rate causes the char yield to increase, as expected [9]. As
the pellet size increases, the char yield tends also to increase. Thus, the higher the pellet, the higher
the char yield. In fact, the heating rate inside the particle decreases towards the center of the pellet
[8, 15], which favors the char yield. This effect is more evident in the case at 800°C and 10°C/s, where
thermally thick regime may occur. Consequently, the highest pellet will produce more char, especially
at its bottom part, where lower heating rates might occur.
When comparing both pellets, it is noticed that the char yield difference tends to decrease as
temperature increases (ie. 3.15 at 10ºC/s and 800ºC against -0.14 at 10ºC/s and 1600ºC). This may lead
to a regime transition from thermally thick (800°C) to thermal wave regime (above 1200°C). However,
for HR = 50ºC/s, the difference in the char yield remains almost constant (around 1%) for the
temperature range studied. The slightly difference can indicate the presence of a thermal wave
regime, with a similar heating rate inside both pellets. Therefore, pyrolysis may be controlled by the
heat transport inside the pellet and char produced by secondary tar reactions is similar for both pellets.
Gas yield
From the analysis of Table 7, some observations regarding the gas yield can be indicated. The general
trend of gas yield against temperature is in accordance to studies reported in literature [8], whereas
an increase in temperature level produces more gas. However, as temperature increases (above
1200ºC), the gas yield increases but at a lower rate. An increase in the heating rate also produces more
gas. Additionally, the influence of the heating rate on the gas yield is more important as temperature
increases.
For both pellet sizes, the increment in gas yield, at 800ºC, from a HR=10ºC/s to 50ºC/s is about 3%;
while for the same heating rate change the gas yield at 1200ºC and 1600ºC is around 10%. When
comparing the gas yield between both pellets, the 10 mm pellet produces more gas only at the highest
temperature. At 800ºC and 1200ºC, the smaller pellet yields more gas. Although, the differences are
within the error bars.
HR T GAS YIELD [%] TAR YIELD [%] CHAR YIELD [%]

[°C/s] [°C] L0 = 5mm L0 = 10mm Diff L0 = 5mm L0 = 10mm Diff L0 = 5mm L0 = 10mm Diff
10 800 21.37 19.68 -1.69 60.14 58.68 -1.46 18.49 21.64 3.15
10 1200 29.38 25.43 -3.95 56.72 59.65 2.93 13.90 14.92 1.02
10 1600 34.93 36.32 1.39 52.33 51.08 -1.25 12.74 12.60 -0.14
50 800 24.58 22.61 -1.97 57.93 58.23 0.30 17.50 19.16 1.67
50 1200 39.42 35.68 -3.75 48.75 50.72 1.97 11.83 13.60 1.78
50 1600 44.53 45.66 1.13 45.77 43.57 -2.20 9.70 10.77 1.07
Table 7: Product yields
Tar yield
Experimental results (Table 7) show that the total tar yield decreases with increasing temperature.
Higher values of temperature favors tar decomposition rate, yielding less tar. Additionally, an increase
in the heating rate seems to reduce the tar yield. This observation is in agreement with results
obtained from [9]. The lowest tar yield takes place at both the highest heating rate and temperature.
An increase in the pellet length may reduce tar by secondary tar reactions. In this case, the tar yield is
similar for both pellets. For similar conditions (HR = 30º/s and T = 700ºC) and particle size as dealt with
in this work, Okekunle et al. [1] reported that tar yield decreases as the length increases, but a further
length increase (above 5 mm) resulted in a tar yield plateau. This similar behavior might be explained
as follows: the high values of heating rates dealt with in this work may reduce the intra-particle
917
residence time of tar, leading to similar values of �TAR for both pellets and resulting in an almost
negligible difference on effect of homogeneous and heterogeneous tar reactions. A similar trend was
reported by Shen et al. [16], that for biomass particles larger than 1.5 mm, the tar yield remained
constant.
3.4. Gas composition

Figure 2 depicts the yields of main gaseous products: H2, CO, CO2 and CH4. CO and H2 are the most
abundant products from pyrolysis, especially at temperature above 1200°C. With an increase in the
final operative temperature, more H2 is produced; while CH4 and CO2 are reduced. CO yield remains
almost constant for both pellet at the heating rate and temperature ranges studied in this work.
Regarding H2, it can be seen that higher values of both heating rate and temperature generates more
H2. However, when analyzing the influence of pellet size, different behaviors were observed. At 10ºC/s,
an increase in the pellet height increases the H2 molar fraction. This trend is not reproduced at 50ºC/s,
where the pellet size seems not to influence H2 production.
Figure 2: Gas product distribution
4- CONCLUSIONS
A characteristic time analysis as well as a dimensionless number analysis was performed in order to
estimate the controlling process during the solar pyrolysis of sawdust biomass pellets. Results indicate
that for temperatures lower than 1200ºC, the pyrolysis rate is controlled by external and internal heat
transfer, while the thermal wave regime occurs for temperatures above 1200ºC.
It can be considered that at high heating rates and high final temperature, the pellet size seems to be
non-relevant for improving tar decomposition. This behavior can be explained by the low residence
time of tar in the pellet, evidencing that secondary tar reactions reaches a maximum. Thus, further
918
increase in the operating conditions along with the pellet height will result in an almost negligible
effect on product yields.
Consequently, product yields will result from the competition between the influence of both main
operating variables, temperature and heating rate. On the one hand, a higher heating rate causes the
gas product to form rapidly, which increases the intra-particle pressure gradient and expels the gas
out of the surface, diminishing the gas intra-particle residence time and, therefore, reducing tar
cracking. On the other hand, the char layer formed at the particle surface is at a higher temperature
than the interior, thus favoring tar cracking.
Future work will include the CFD modelling of the pyrolysis of both pellet sizes and comparison with
experimental data. The numerical model will be able to obtain a better insight of the rate controlling
process as well as the gas residence time inside the pellet, instead of using characteristic time scales
to estimate the main aspects.
REFERENCES
[1] Okekunle, P.O., Watanabe, H., Pattanotai, T., Okazaki, K.: Effect of Biomass Size and Aspect Ratio on Intra-Particle Tar
Decomposition during Wood Cylinder Pyrolysis. J. Therm. Sci. Technol. 7, 1–15 (2012).
[2] Pattanotai, T., Watanabe, H., Okazaki, K.: Experimental investigation of intraparticle secondary reactions of tar during
wood pyrolysis. Fuel. 104, 468–475 (2013).
[3] Bennadji, H., Smith, K., Serapiglia, M.J., Fisher, E.M.: Effect of Particle Size on Low-Temperature Pyrolysis of Woody
Biomass. Energy & Fuels. 141204065221004 (2014).
[4] Kenarsari, S.D., Zheng, Y.: Fast Pyrolysis of Biomass Pellets Using Concentrated Solar Radiation: A Numerical Study. J.
Sol. Energy Eng. 136, 041004–041007 (2014).
[5] Shi, X., Ronsse, F., Pieters, J.G.: Finite element modeling of intraparticle heterogeneous tar conversion during pyrolysis
of woody biomass particles. Fuel Process. Technol. 148, 302–316 (2016).
[6] Zeng, K., Gauthier, D., Li, R., Flamant, G.: Solar pyrolysis of beech wood: Effects of pyrolysis parameters on the product
distribution and gas product composition. Energy. 93, 1648–1657 (2015).
[7] Septien, S., Valin, S., Dupont, C., Peyrot, M., Salvador, S.: Effect of particle size and temperature on woody biomass
fast pyrolysis at high temperature (1000–1400°C). Fuel. 97, 202–210 (2012).
[8] Soria, J., Zeng, K., Asensio, D., Gauthier, D., Flamant, G., Mazza, G.G.: Comprehensive CFD modelling of solar fast
pyrolysis of beech wood pellets. Fuel Process. Technol. 158, 226–237 (2017).
[9] Okekunle, P.O., Pattanotai, T., Watanabe, H., Okazaki, K.: Numerical and Experimental Investigation of Intra-Particle
Heat Transfer and Tar Decomposition during Pyrolysis of Wood Biomass. J. Therm. Sci. Technol. 6, 360–375 (2011).
[10] Blondeau, J., Jeanmart, H.: Biomass pyrolysis at high temperatures: Prediction of gaseous species yields from an
anisotropic particle. Biomass and Bioenergy. 41, 107–121 (2012).
[11] Chan, W.-C.R., Kelbon, M., Krieger, B.B.: Modelling and experimental verification of physical and chemical processes
during pyrolysis of a large biomass particle. Fuel. 64, 1505–1513 (1985).
[12] Gronli, M.G., Melaaen, M.C., Grønli, M., Melaaen, M.C.: Mathematical model for wood pyrolysis - Comparison of
experimental measurements with model predictions. Energy & Fuels. 14, 791–800 (2000).
[13] Bryden, K.M., Ragland, K.W., Rutland, C.J.: Modeling thermally thick pyrolysis of wood. Biomass and Bioenergy. 22,
41–53 (2002).
[14] Li, R., Zeng, K., Soria, J., Mazza, G., Gauthier, D., Rodriguez, R., Flamant, G.: Product distribution from solar pyrolysis
of agricultural and forestry biomass residues. Renew. Energy. 89, 27–35 (2016).
[15] Zeng, K., Soria, J., Gauthier, D., Mazza, G., Flamant, G.: Modeling of beech wood pellet pyrolysis under concentrated
solar radiation. Renew. Energy. 99, 721–729 (2016).
[16] Shen, J., Wang, X.-S., Garcia-Perez, M., Mourant, D., Rhodes, M.J., Li, C.-Z.: Effects of particle size on the fast pyrolysis
of oil mallee woody biomass. Fuel. 88, 1810–1817 (2009).
919
A TEXTILE-BASED BIOREFINING STRATEGY FOR POLYESTER RECYCLING FROM

BLENDED FABRICS VIA BIOLOGICAL METHOD
XIAOTONG LI 1, KAI-JEN HSIAO 2, SHI-KUANG HWANG 2, ZHI-FENG JUE 2, YUNZI HU 1, CHENYU DU3,
SHAO-YUAN LEU 4, HOUDE JING 4, CAROL SZE KI LIN 1,*
1 School of Energy and Environment, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong
Kong
2 Department of Fiber Materials Synthesis & Application, Division of Fiber & Textile Chemicals
Technology, Material and Chemical Research Laboratories, Industrial Technology Research

Institute, Taiwan, R.O.C.
3 School of Applied Sciences, University of Huddersfield, Huddersfield, HD1 3DH, United Kingdom
4 Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University,
Kowloon, Hong Kong
Abstract
In the past few decades, there is a constant increase of global fiber production for textile application,
around 100 million tonnes in 2016 [1]. The lifetime of textile was shortened dramatically with the
increase of living standard and thus a growing amount of textile wastes were generated. In the
United States alone, exceeding 16 million tonnes of textile wastes have been generated in 2014 [2].
In Hong Kong, 306 tonnes of textile waste were generated per day, and 95% of textile waste ended
up in landfills [3], which exerts more pressure on the limited landfill space. Therefore, it is urgent to
find an environmentally and economically sustainable process to recycle textile waste. In this work, a
novel process for blended textile fabrics recycling was developed with the blended fabrics
cotton/polyester 40/60 as feedstock. Firstly, the textile waste was mixed with NaOH and urea at -20
℃ for 6 h and neutralized to pH 7, followed by rinsing with tap water for 3-5 times and drying in
oven for 48 h. Next, the pretreated materials were hydrolyzed with addition of cellulase and ß-
glucosidase under optimized conditions for 96 h. The final glucose yield was 85% and the purity of
polyester fiber was 98.2%. Finally, the recovered polyester was further processed by melt spinning in
order to be re-spun into new polyester fibers. The re-spun fully oriented yarn was produced with a
tenacity over 3 g/den and an elongation of 20%-40%. The present study demonstrates a novel
circular textile waste-based biorefinery strategy with recovery of glucose and polyester as value-
added products.
References
[1] The Fiber Year, The Fiber Year 2017: World Survey on Textiles & Nonwovens (The Fiber Year GmbH, 2017).
[2] United States Environmental Protection Agency, 2016. Advancing sustainable materials management: 2014 fact
sheet.
[3] EPD, 2015. Monitoring of Solid Waste in Hong Kong: Waste Statistics for 2015.
920
ACTIVITY OF FLY ASH-DERIVED ZSM-5 AND ZEOLITE X ON FAST PYROLYSIS OF

MILLETTIA (PONGAMIA) PINNATA WASTE
K. SOONGPRASIT1, V. SRICHAROENCHAIKUL2, D. ATONG1,

1 National Metal and Materials Technology Center, Thailand Science Park, Klong 1, Klongluang,
Pathumthani, 12120, Thailand.

Bangkok 10330, Thailand.
Abstract
This research aims to investigate catalytic fast pyrolysis of Millettia (Pongamia) pinnata seed wastes
in the presence of ZSM-5 and Zeolite X catalysts. The catalysts were successfully prepared by alkali
hydrothermal and alkali fusion method using coal fly ash as aluminum and silicon sources. Lignite fly
ash (LFA) is a major by-product from coal power plant, however, most of FA is considered as waste
due to its high lime (CaO) and other impurities contents. Utilization of these waste as starting
materials for zeolite catalysts synthesis is a promising solution. Meanwhile, De-oil Millettia
(Pongamia) pinnata seed wastes (PPW) is produced in large amount from bio-oil extraction process.
This waste is of no value due to its toxicity, namely karanjin and di-ketone pongamol, which limited
its further utilization. Proximate and ultimate analysis shown that PPW mainly contained 91%
combustible compound (volatile matter and fixed carbon) and 45-51% carbon contents thus it may
be promising hydrocarbon feedstock [1]. Thus, fast pyrolysis of PPW was performed using single shot
Pyrolyzer interfaced with Gas chromatography-Mass spectrometry (Py-GCMS) with various biomass
to catalyst ratios (1:1, 1:5, and 1:10). The result demonstrated that pyrolysis temperature has strong
influence on chemical composition of pyrolysis vapours while particle size of biomass has only a
minor effect. Pyrolysis vapours of PPW have high content of undesirable components, carboxylic
acid, oleic acid, and others oxygenated compound (67.24%), whereas aliphatic and aromatic
hydrocarbon contents were markedly lower. The presence of the synthesized ZSM-5 and zeolite X
showed major improvement in the pyrolysis vapour quality. Selectivity on total hydrocarbon
(aliphatic and aromatic) was significantly increased with greater catalyst contents for both ZSM-5
(90.58%) and zeolite X (84.90%). ZSM-5 exhibited high selectivity for aromatic hydrocarbon (82.64%)
while zeolite-X showed a higher selectivity towards aliphatic structure at 71.03%. Oxygenated
compound decreased sharply to 1.12% and 21.92% at optimum condition for ZSM-5 and zeolite X,
respectively. In addition, ZSM-5 reduced nitrogenated compound content from 24.83% (thermal
condition) to 8.29% while zeolite X completely eliminated these compounds. Overall, the results
suggest that ZSM-5 synthesized from fly-ash has higher selectivity on hydrocarbon and has been
shown to be more effective in promoting deoxygenation reaction whereas zeolite X enhances
significantly the denitrogenation reaction.
References
[1] Soongprasit, K., Sricharoenchaikul, V., Atong, D.: Catalytic fast pyrolysis of millettia (pongamia) pinnata waste using
zeolite Y. J. Anal. Appl.Pyrol. 124,696-703 (2017)
921
ZRO2-SUPPORTED TRANSITION METALS IN SUPERCRITICAL WATER CONVERSION OF

PULPING WASTE FOR FUEL GAS GENERATION
Y. HAWANGCHU1, V. SRICHAROENCHAIKUL2
1 International Program in Hazardous Substance and Environmental Management, Graduate School,
Chulalongkorn University, Bangkok, Thailand.
Bangkok, Thailand.
Abstract
Enhanced conversion of pulping wastes under supercritical water (SCW) condition with addition of
ZrO2-supported transition metals for syngas production was investigated in this study. Two types of
liquid wastes from pulp and paper manufacturers (kraft and soda black liquors, KBL and SBL) were
subjected to rigorous SCW reaction at 400-600°C and 25 MPa for 10 minutes in a batch reactor.
Transition metals (nickel, palladium, and ruthenium) were impregnated on zirconium dioxide (ZrO 2)
and applied with proportion of waste and catalyst of 1:1 and 1:10 to enhance the reaction.
Generally, addition of catalysts promote formation of H2 as major gaseous species while the
conversion to CO and CH4 was minor. At higher catalyst proportion, the H2 generation was improved
for KBL but declined for SBL as raw materials. Higher CH4 formation during catalytic process with KBL
indicated greater cleavage of aromatic groups in its structure. Addition of catalysts also yielded
greater H2 generation which suggested the availability of CO for water gas shift reaction generated
from the effective methanation reaction. Ru catalyst exhibited superior performance on H2
production and followed by Ni catalyst. Comparing with non-catalytic reaction at 500-600°C, Ru
catalyst enhanced H2 yield as 2.2 times for KBL at 1:10 ratio and 1.5 times for SBL at 1:1 ratio, while
Ni catalyst at 1:1 ratio could promote 1.5 and 1.3 times for KBL and SBL, respectively. Positive
influence of ZrO2-supported catalysts on H2 generation was evident and nickel based catalyst might
be the most promising option with regard to efficient and cost-effective provision.
References
[1] Wen, C., Changqing, C., Liejin, G., Hui, J., Xiangdong, Y.: Hydrogen production from supercritical water gasification of
chicken manure. Int. J. Hydrogen Energy. 41, 22722–22731 (2016)
[2] Reddy, S.N., Nanda, S., Dalai, A.K., Kozinski, J.: Supercritical water gasification of biomass for hydrogen production.
39, 6912-6926 (2014)
[3] Sricharoenchaikul, V.: Assessment of black liquor gasification in supercritical water. Bioresour. Technol. 100, 638-643
(2009)
922
HIGH EFFICIENT SUPERPARAMAGNETIC SOLID EXTRACTION FOR HEAVY METAL IONS

REMOVAL
L. YANG 1, H. XING1, J. YU1, H. LIU1

1 Institute of Process Engineering, Chinese Academy of Sciences, Beijing, China.
Abstract
Water pollution by heavy metal ions such as Cr(VI) and Cd(II) has become one of the most important
issues of the world because of its great threat to the environment and human beings[1]. The solid
extraction technology which based on adsorption principle is the most promising method for the low
concentration heavy metal ions removal. However, the traditional adsorption method faces many
challenges such as the low adsorption capacity, low selectivity, and batch/batch continuous
operation mode which will lead to the low efficiency. Focus on these problems, we investigated the
effect of composition and structure on the separation selectivity and adsorption capacity[2,3]. On
this bases, we explored a serial of magnetic adsorbents with high capacity and selectivity such as
amine, -C=S, or extractant modified magnetic polymer/inorganic particles for Cr(VI) and Cd(II) ions
removal[4,5]. In addition, novel gas-assisted superparamagnetic extraction technology was proposed
for continuous separation of ions uploaded magnetic particles [6].
Figure 1: Effect of PGMA-D2EHDTPA dose on Cd(II) and Zn(II) removal
References
[1] Fowler, B.A., Monitoring of human populations for early markers of cadmium toxicity: A review, Toxicology and
Applied Pharmacology, 238 (2009) 294-300
[2] Sun, X.T., Yang, L.R.*, Xing, H.F., Zhao, J.M., Li, X.P., Huang, Y.B., Liu, H.Z.*, Synthesis of polyethylenimine-
functionalized poly(glycidyl methacrylate) magnetic microspheres and their excellent Cr(VI) ion removal properties.
Chemical Engineering Journal, 2013. 234: p. 338-345.
[3] Dong, T.T., Yang, L.R.*, Pan, F., Xing, H.F., Wang, L., Yu, J.M., Qu, H.N., Rong, M., Liu, H.Z.*, Effect of immobilized
amine density on cadmium(II) adsorption capacities for ethanediamine-modified magnetic poly-(glycidyl
methacrylate) microspheres. Journal of Magnetism and Magnetic Materials, 2017. 427: p. 289-295.
[4] Sun, X.T., Yang, L.R.*, Li, Q., Zhao, J.M., Li, X.P., Wang, X.Q., Liu, H.Z.*, Amino-functionalized magnetic cellulose
nanocomposite as adsorbent for removal of Cr(VI): Synthesis and adsorption studies. Chemical Engineering Journal,
2014. 241: p. 175-183.
[5] Sun, X.T., Yang, L.R.*, Xing, H.F., Zhao, J.M., Li, X.P., Huang, Y.B., Liu, H.Z.*, High capacity adsorption of Cr(VI) from
aqueous solution using polyethylenimine-functionalized poly(glycidyl methacrylate) microspheres. Colloids and
Surfaces a-Physicochemical and Engineering Aspects, 2014. 457: p. 160-168.
[6] Dong, T.T., Yang, L.R.*, Zhu, M.H., Liu, Z.N., Sun, X.T., Yu, J.M., Liu, H.Z.*, Removal of cadmium(II) from wastewater
with gas-assisted magnetic separation. Chemical Engineering Journal, 2015. 280: p. 426-432.
923
NUMERICAL STUDY OF HEAT AND MOISTURE PROPERTIES OF WALL BASED ON

WASTE DATE PALM FIBERS CONCRETE
T. ALIOUA1,2, B. AGOUDJIL1, N. CHENNOUF1,2, A. BOUDENNE2, K. BENZARTI3

1 Batna 1 university, LPEA laboratory, 05000, Algeria.
2 Université Paris Est Créteil (UPEC)/CERTES, 61 Av. du General de Gaulle, 94010 Créteil cedex,
France.
3 IFSTTAR – Département Matériaux et Structure 14-20 Bd Newton – Cité Descartes77447 Marne-la-
Vallée Cedex 2 France
Abstract
The increasing demand for energy accompanying growing human

activities implies an urgent recur to sustainable renewable resources
in all sectors. The housing sector represents one of the major energy
sinks nowadays, where thermal insulation and interior comfort can
still be achieved in much better ways. In this work we study the
hygrothermal performance of a new biobased building material
constituted with Waste Date Palm Fibers and Concrete (WDPFC).
A mathematical model describing heat and mass transfers on
porous materials using for buildings was developed and solved
numerically. The numerical results obtained were compared with Figure 1: WDPFC wall with T&RH sensors
the measurements values of our WDPFC wall.
A wall of WDPFC was built in laboratory and subjected to different conditions of temperature and
relative humidity using a climatic chamber. Measurements were taken at different depths of the wall
(figure1).
The model below [1,2] is solved numerically with the finite elements method using WDPFC
properties which were already performed [3]. Several scenarios of temperature and moisture
variation were applied to the wall according to the experimental protocol.
Moisture transfer:
𝒅𝝋
𝝃𝝋 = 𝜵[𝜹𝒗 𝜵( 𝝋𝒑𝒔𝒂𝒕 ) + 𝑫𝒍 𝜵𝝋]
𝒅𝒕
Heat transfer:
𝒅𝑻
(𝝆𝟎 𝒄𝟎 + 𝒄𝒍 𝒘) = 𝜵 [𝝀𝜵𝑻 + (𝒍𝒗 + 𝑪𝒗 (𝑻 − 𝑻𝒓𝒆𝒇 )) [𝜹𝒗 𝜵( 𝝋𝒑𝒔𝒂𝒕 )]] + 𝜵[𝑪𝒍 (𝑻 − 𝑻𝒓𝒆𝒇 )𝑫𝒍 𝜵𝝋]
𝒅𝒕
As expected, there is a variation of both relative humidity and temperature at different depths of the
wall as function of time while exposed to climatic variation. Values estimated by the model were
slightly different from those obtained during the experiment. Nevertheless, the developed model
can be used for further studies to predict the behavior of biomass based materials under various
thermal and hygric conditions.
References
[1] Künzel, Hartwig M. "Simultaneous heat and moisture transport in building components." One-and two-dimensional
calculation using simple parameters. IRB-Verlag Stuttgart (1995).
[2] Oumeziane, Yacine Ait. Evaluation des performances hygrothermiques d'une paroi par simulation numérique:
application aux parois en béton de chanvre. Diss. INSA de Rennes, 2013.
Haba, Bourhaneddine, et al. "Hygric properties and thermal conductivity of a new insulation material for building
based on date palm concrete." Construction and Building Materials 154 (2017): 963-971.
924
INFLUENCE OF PROMOTER MGO ON NI/AL2O3 CATALYSTS FOR THE STEAM

REFORMING OF VOLATILES DERIVED FROM BIOMASS PYROLYSIS
L. SANTAMARIA1, G. LOPEZ1, M. AMUTIO1, J. ALVAREZ1, M. CORTAZAR1, E. FERNANDEZ1, M. OLAZAR1

1 University of the Basque Country, Department of Chemical Engineering, 48080 Bilbao, Spain.
Abstract
The growing demand of H2 as energy carrier, fuel and raw material has promoted an increasing
interest for the development of renewable sources for its production. Hydrogen from biomass can
be generated through promising termochemical methods. Among them, the most effective and
feasible method for its industrial implementation is the catalytic steam reforming of volatile
products from biomass pyrolysis. [1] The aim of this research was to study the influence of the
addition of MgO promoter on the Ni/Al2O3 catalyst, and analyzed the catalyst performance for
maximizing the hydrogen production as well as enhancing the catalyst stability.
Pine sawdust (1-2 mm) has been used as raw material. The biomass pyrolysis and in-line catalytic
steam reforming has been studied in a bench scale plant provided with a conical spouted bed reactor
(CSBR) and a subsequent fluidised bed reactor, where the pyrolysis and catalytic steam reforming of
volatiles take place at 500°C and 600°C, respectively. The experiments were carried out by
continuously feeding 0.75 g·min-1 of biomass, with a steam/biomass (S/B) mass ratio of 4 and a
space time of 0.28 gcatalyst·h·(gbiomass)-1. These conditions were determined as the optimum one in a
previous study [2]. The volatile stream was quantified on-line by means of a GC Varian 3900,
whereas the permanent gases were analyzed on-line in a microGC (Varian 4900). The catalysts
selected in this research have been Ni/Al2O3 and Ni/MgO-Al2O3. Both of them were synthesized by
wet impregnation method, being the Ni loading fixed at 10%wt. In addition, fresh catalysts have
been characterized by N2 adsorption-desorption, X-ray fluorescence (XRF) and Temperature
Programmed Reduction (TPR) in order to ascertain the catalysts performance during the process.
Thus, physical properties of the catalyst, the metallic properties (Ni content) and the reduction
temperature of the different metallic phases present in the catalyst have been analyzed.
The results at zero time on stream evidenced a full carbon conversion as well as a hydrogen yield
over 90% when both catalysts are tested. Carbon conversion decreased from 100% to 73.0% in 100
min on stream with the Ni/Al2O3 catalyst, while the hydrogen yield gradually dropped from 92.4% to
62.6% that indicates notable deactivation due to the coke formed on the catalyst. Moreover, when
Ni/MgO-Al2O3 was tested, the activity and stability was not improved during the reaction, being the
results similar to those when Ni/Al2O3 was used. This is probably due to the small amount of active
phase reduced on Ni/MgO-Al2O3 (30%) compared with the reduction degree on Ni/Al2O3 (54%).
In view of these results, it can be concluded that the calcination temperature when Ni promoted
catalyst was synthesized was inadequate and leaded to a small amount of reducible nickel active
phase, hindering an improvement in the activity and stability of Ni/Al 2O3 catalyst
References
[1] A. Arregi, M. Amutio, G. Lopez, M.Artetxe, J. Alvarez, M. Olazar. Energy Conversion and Management,(2017), 136,
192-201
[2] A. Arregi, G. Lopez, M. Amutio, I. Barbarias, J. Bilbao, M. Olazar. RSC Adv., (2016), 6, 25975–25985
925
PYROLYSIS-CATALYTIC STEAM REFORMING OF PLASTICS AND MIXED PLASTIC IN A

TWO STAGE REACTION SYSTEM
I. BARBARIAS1, G. LOPEZ1, M. AMUTIO1, M. ARTETXE1, J. ALVAREZ1, A.ARREGI1, E. FERNANDEZ1, M.

OLAZAR1
1 University of the Basque Country, Department of Chemical Engineering, 48080 Bilbao, Spain.
Abstract
The challenges of plastics waste management and its reduction should be directed towards its
recycling and valorization. In 2014, 26 million tones of post-consumer plastics waste were recovered
in Europe, of which 70 % were treated by recycling and energy recovery process and 30 % were still
land filled [1]. Tertiary recycling of waste plastics by means of pyrolysis is considered the most
attractive strategy to valorize these residues. The pyrolysis of waste plastics has been studied with
the objective of producing fuels, chemicals, monomers and H2 and, although interesting technologies
have been developed at laboratory and pilot plant scale, their full scale implementation is a pending
matter. The conical spouted bed reactor (CSBR) performs very well for plastics flash pyrolysis, since
the vigorous cyclic movement of the particles, characteristic of this reactor, minimizes bed
agglomeration problems caused by the fused plastics [2].
This study approaches the continuous steam reforming of pyrolysis volatiles obtained in the pyrolysis
of polystyrene (PS), polyethylene terephthalate (PET), high density polyethylene (HDPE),
polypropylene (PP) and a mixture of them, for the production of hydrogen. The experimental
conditions have been selected based on the previous studies on the flash pyrolysis of PS and PET in a
conical spout bed reactor [3, 4] and the reforming of HDPE pyrolysis volatiles using a commercial Ni
catalyst in a fluidized bed reactor [5]. The pyrolysis has been carried out at 500 ºC and the steam
reforming at 700 ºC. It has been fed 0.75 g min-1 of each plastics and the mixture, and 3 mL min-1 of
water continuously, accordingly the steam/plastic ratio equal to 4. It has been studied two space
times 4.1 and 16.7 gcat min gPlastic-1.
With 16.7 gcat min gPlastic-1 of space time, pyrolysis-reforming strategy gives way to full conversion of
pyrolysis volatiles, with yields being high for H2, CO2 and CO and negligible for CH4, and C2-C4
hydrocarbons and non-converted C5+ hydrocarbons fractions for all the plastics and mixture studied.
By decreasing the space time, the yields of H2, CO2 and CO decrease significantly whereas the yield of
non-converted C5+ fraction increases considerably, given that the reforming reaction is disfavored.
The pyrolysis in CSBR and in line reforming of different plastics and a mixture of them in a fluidized
bed reactor has been revealed as a feasible alternative for the production of H2 from plastics.
References
[1] Plastics, Plastics Europe, Plastics-the Facts, 2016; An Analysis of European plastics production, demand and waste
data (2016).
[2] R. Aguado, M.J. San José, M. Olazar, S. Alvarez, J. Bilbao. Chem. Eng. Process. 44 (2005) 231-235.
[3] M. Artetxe, G. Lopez, M. Amutio, I. Barbarias, A. Arregi, R. Aguado, J. Bilbao, M. Waste Manage. 45 (2015) 126-133.
[4] M. Artetxe, G. Lopez, M. Amutio, G. Elordi, M. Olazar, J. Bilbao. Ind. Eng. Chem. 49 (2010) 2064-2069.
[5] I. Barbarias,G. Lopez, J. Alvarez, M. Artetxe, A. Arregi,J. Bilbao, M. Olazar. Chem. Eng. J. 296 (2016) 191-198.)
926
CATALYTIC STEAM REFORMING OF PLASTIC PYROLYSIS MODEL COMPOUNDS
I. BARBARIAS1, G. LOPEZ1, M. ARTETXE1, A. ARREGI1, L. SANTAMARIA1, M. CORTAZAR1, M. OLAZAR1

1 University of the Basque Country, Department of Chemical Engineering, PO Box 644, 48080 Bilbao.
Abstract
Plastic materials have contributed to the development and progress of the society for the last 150
years. The annual increase in plastic consumption has caused an increasingly environmental issue
associated with their management. Although gasification is the most usual thermochemical process
for plastic waste valorisation, the lower temperature used in the pyrolysis strategy improves energy
efficiency of the process [1]. In the pyrolysis of different plastics, the circumstances and composition
of the volatiles are considerably different. Polystyrene (PS) pyrolysis stream is mainly composed of
aromatic hydrocarbons [2], that of polyethylene terephthalate (PET) pyrolysis is heterogeneous and
composed of CO, CO2, oxygenated compounds and aromatics [3]. In the case of high density
polyethylene (HDPE) and polypropylene (PP) pyrolysis, the streams of volatile obtained are mainly
composed of waxes (C21+) and diesel fraction (C12-C20) in both cases [4]. Consequently, two paraffins,
one olefin and one aromatic compound have been chosen as model hydrocarbons in order to study
the effect of type of hydrocarbon on conversion and H2 yield.
Thus, the effect of paraffin chain length and hydrocarbon nature (olefins and paraffins) on steam
reforming has been studied (reactivity at zero time on stream) using n-hexane, tetradecane and 1-
hexene. Besides, toluene has been used as a model compound for the aromatic compounds in the
pyrolysis volatiles stream, which are the main hydrocarbons in PS and PET pyrolysis. The reforming
has been carried out in a fluidized bed reactor in which a commercial Ni catalyst has been placed, at
700 ºC, with space time of 10 gcatalyst min gcompound-1 and steam/feedstock ratio of 4. The volatile
stream leaving the reforming reactor has been analyzed on-line by means of a gas chromatograph
and moreover, the analysis of non-condensable gases has been carried out in a micro gas
chromatograph.
Steam reforming of different model compounds, representative of plastic pyrolysis volatiles, has
shown that the composition in the reaction medium has great influence on the conversion and H2
yield obtained. Thus, a conversion higher than 92 % and H2 yield higher than 76 % are achieved for
linear hydrocarbons. As the paraffin molecule is longer the reforming rate is lower, but a comparison
of the paraffin (n-hexane) with the olefin (1-hexene) shows that olefin susceptibility to thermal
cracking leads to a decrease in the reforming reaction rate, obtaining a conversion and H2 yield of 92
% and 76 %, respectively. Nevertheless, in the case of toluene reforming, lower conversion (82 %)
and H2 yield (65 %) is observed, which evidences a lower reactivity of aromatic hydrocarbons
compared to linear hydrocarbons.
References
[1] T. Namioka, A. Saito, Y. Inoue, Y. Park, T. Min, S. Roh, Appl. Energy 88 (2011) 2019-2026.
[2] M. Artetxe, G. Lopez, M. Amutio, I. Barbarias, A. Arregi, R. Aguado, J. Bilbao, M. Waste Manage. 45 (2015) 126-33.
[3] M. Artetxe, G. Lopez, M. Amutio, G. Elordi, M. Olazar, J. Bilbao, Ind. Eng. Chem. 49 (2010) 1089-1094.
[4] I. Barbarias,G. Lopez, J. Alvarez, M. Artetxe, A. Arregi,J. Bilbao, M. Olazar. Chem. Eng. Process. 296 (2016) 191-198.)
927
INVESTIGATION ON THE EVOLUTION OF POLYCYCLIC AROMATIC

HYDROCARBON (PAHS) IN BIO-OIL DURING WASTEWATER SEWAGE SLUDGE
CATALYTIC PYROLYSIS
Yanjun Hu 1, Wenjing Yu 1, Fan Yu 1,Linjie Wang 1, Jiang Chen 1

1
Zhejiang University of Technology, Institute of Energy and Power Engineering, Hangzhou, China.
2
.
Abstract
Pyrolysis bio-oils were complex mixtures made up of a group of aromatic clusters with one to three
aromatic rings connected by long straight chain hydrocarbons with hydroxyl groups [1]. As reported
by some researchers, the composition of pyrolysis bio-oils from different urban sewage sludge
consistently contained polycyclic aromatic hydrocarbons (PAHs) [2-3]. PAHs remain a widely
distributed health, ecological and environmental concern, which makes it necessary to know both
their residue levels and their distribution in the process of wastewater sewage sludge disposals.
Different kinds of catalysts are usually studied to improve the chemical quality of pyrolysis products.
Especially, catalytic pyrolysis could decrease the environmental risk of organic pollutants contained
in bio-fuels.
Sewage sludge was sampled after mechanical dewatering using a filter press and without using
any additives in Linàn Urban wastewater plant, Hangzhou, China. The mass ratio of the selected
catalyst and the dried sludge is 1:5 for collecting bio-oil sample by a pyrolysis test. Distribution and
toxicity equivalent (TEQ) of 16 kinds of PAHs defined as priority pollutants by USEPA are investigated.
The selected catalysts are muriate, soda, calcium oxide and ferric oxide. The mass variation of sludge
was monitored by thermogravimetric analyser. Chemical composition of pyrolysis bio-oil and
residues were further analysed by infrared spectrum technique. PAHs in bio-oil was quantitatively
and qualitatively measured by GC-MS. The results show that adding 4 kinds of catalysts can reduce
the production of 16 kinds of EPA-PAHs and decrease TEQ. The catalyst type influenced the yield and
TEQ of PAHs with different ring number violently. A decreasing content of PAHs in the different bio-
oil is as followed: from the pyrolysis of sludge and potassium chloride （ 4.23 g/Kg ） > from the
pyrolysis of sludge and sodium carbonate （ 4.36 g/Kg ） > from sludge and calcium oxide
（ 6.74g/Kg ） > sludge and ferric oxide （ 7.73g/Kg ） . PAHs evolved into pyrolysis bio-oil with
addition of catalyst were majorly consisted of two rings, three rings and four rings of PAHs, which
their amount is accounted for more than 95% of the total concentrated PAHs. With the addition of
catalysts, three rings and four rings of PAHs were obviously decreased. The present results may be
valuable for the evaluation of sewage sludge thermal treatment and for gaining knowledge of PAHs
formation during pyrolysis of sewage sludge with different type of catalyst.
References
[1] Shen L， Zhang D K, An experimental study of oil recovery from sewage sludge by low-temperature pyrolysis in a
fluidized-bed, Fuel. 82: 1465-1472(2003)
[2] Tsai WT., Lee MK, Chang JH, Su TY, Chang YM, Characterization of bio-oil from induction-heating pyrolysis of food-
processing sewage sludges using chromatographic analysis, Bioresour. Technol.. 100: 2650–2654(2009)
[3] Broy, M.: Software engineering — from auxiliary to key technologies. In: Broy, M., Denert, E. (eds.) Software
Pioneers, pp. 10–13. Springer, Heidelberg (2002 Tsai WT, Mi HH, Chang JH, Chang YM, Levels of polycyclic aromatic
hydrocarbons in the bio-oils from induction-heating pyrolysis of food-processing sewage sludges, J. Anal. Appl.
Pyrolysis. 86: 364–368(2009)
928
CYNARA CARDUNCULUS EXPERIMENTAL FIELD INSTALLATION: A SOURCE OF

NATURAL VARIABILITY

A. PAULINO1, T. BRAS1,2, E. MACHADO3, D. ROSA1, M. CASTRO1, A.M. FERRO1,3, L. MARUM1,3, A. F.
BELO3,4, M.P. SIMÕES3,4, C. PINTO-‐CRUZ3,4, J. PORTUGAL5, S. RAMOA5, P. NOZES5, I. GUERREIRO5, M.
REGATO5, M.F. DUARTE1,3
1 Centro de Biotecnologia Agrícola e Agro-‐Alimentar do Alentejo (CEBAL)/Instituto Politécnico de Beja
(IPBeja), 7801-‐908 Beja, Portugal.

2 LAVQ/REQUIMTE, FCT, Universidade Nova de Lisboa, 2829-‐516 Caparica, Portugal
3 ICAAM -‐ Instituto de Ciências Agrárias e Ambientais Mediterrânicas, Universidade de Évora, Pólo da
Mitra, Ap. 94, 7002-‐554 Évora, Portugal.

4 Departamento de Biologia, Escola de Ciências e Tecnologia, Universidade de Évora, Pólo da Mitra,
7002-‐554 Évora, Portugal

5 Escola Superior Agrária, Instituto Politécnico de Beja (IPBeja), 7801-‐908 Beja, Portugal

Abstract

Cynara cardunculus (Cc) is an herbaceous crop of the Mediterranean region that naturally grows in
harsh habitat conditions. In South part of Portugal, within Alentejo region, there is a great Cc
phenotipic variability, which urges to be explored as a source of morphological, genetic, and
chemical variability, for further crop economic valorization, based on desired biochemical profiles. Cc
is widely known for the use of its flower, as cardosin natural source, used in cheese making industry,
however, other parts of the plant, such as the leaves, are rich in several bioactive compounds, such
as cynaropicrin [1]. Therefore, knowledge regarding natural genetic variability as well as the
occurence of different biochemical profiles are the essential keys for creation of wider Cc database,
useful, in the near future, for designing new breeding programs to select desired production
parameters, potentiate certain genetic and chemical profiles, among many other outcomes.Thus,
our research team implemented two Cc experimental irrigated and a non-‐irrigated fields, with
selected ecotypes from 20 different natural occuring populations spread within Alentejo region.
From that, 7 plant individuals per population were selected, genetic populations/individuals diversity
was studied using 10 microsatellite markers (SSRs), and evaluated in terms of cynaropicrin leaves
content (mg/gDW), cardosin profiles and flower proteolytic capacity. Seeds were then colected,
germinated in a growing medium soil, with 7 hours light exposure. Germinated plants were kept in
the seedling trays until reaching 50 days, being then transfered into pots/bags, and growth for
approximately 4 months, before going to the field. Ecotypes were installed in two fields in the south
of Portugal, Beja (drip irrigation system) and Évora (without irrigation). Results demonstrated the
reprodutibility of chemical profiles within the installed plants, in terms of cynaropicrin content, as
well other biochemical profiles. Furthermore, preliminary results reveal interesting relationship
between genotypes, with desired biochemical profiles. Installation of the two experimental Cc fields,
allows the availability of different Cc plants with different genetic, morphological and chemical
profiles, turning it more suitable for Cc genes conservation as well as the provide of feedstock for
prior studies and applications.

References
[1] Ramos P., Guerra A., Guerreiro O., Freire C., Silva A., Duarte M.F., Silvestre A.J.D.. Lipophilic Extracts of Cynara
cardunculus L. var. altilis (DC): A Source of Valuable Bioactive Terpenic Compounds. J. Agric. Food Chem., 61,
8420−8429 (2013)
929
USE OF AGRO WASTES AND FORESTRY MATERIALS IN THE PRODUCTION OF

PARTICLEBOARDS
E.PAPADOPOULOU1, S.KOUNTOURAS1, C.STATHOPOULOS1, M. NTALIARI1, G. KALEN2, S.H.LARSSON2

1 CHIMAR HELLAS S.A., Thessaloniki, Greece
Abstract
In MOBILE FLIP project, CHIMAR HELLAS S.A. evaluated various agricultural materials and forestry
residues as alternatives to virgin wood in the production of particleboards. The materials tested
were Scots Pine bark, Forestry residues, Reed canary grass, Salix, Corn Cobs and Sunflower seeds.
All materials were provided by SLU in the form of chips. CHIMAR tested all of them separately and
in mixtures in order to find their optimum use. Two fractions of them were evaluated (1-7mm long
and 7-15mm long) as well as the effect of the storage life of Salix to the properties of
particleboards. The particleboards were produced at pilot scale and had dimensions 50x50cm while
their target density was 650kg/m3. They were manufactured following a simulation of the industrial
practice using a typical Urea- Formaldehyde (UF) resin as bonding material. For control, typical
panels were prepared with chips from virgin wood of pine, poplar and beech. The produced panels
were tested and evaluated according to European standards as per their mechanical properties like
internal bond, modulus of rupture and modulus of elasticity as well as thickness swelling. Their
formaldehyde content was determined with the perforator method. It was found that amongst the
materials tested Salix gave panels with the best mechanical properties while Forestry residues
improved the thickness swelling. The formaldehyde content of these experimental panels were at
levels close to that of typical panel produced with chips from pine wood. The dimensions of chips
had not significant effect to the comparison of materials. Hence, Salix and Forestry residues may be
considered as wood substitutes for particleboards suitable for interior applications.
This work has received funding from the EU Framework Programme for Research and Innovation
HORIZON 2020 under the Grant Agreement No 637020-MOBILE FLIP.
930
LIFE CYCLE ASSESSMENT OF WASTE BIOMASS TREATMENT IN MOBILE CONTEXT
ALAROTU, M.1, WIKBERG, H.1, ARPIAINEN, V.1

1 VTT Technical Research Center of Finland Ltd, Espoo, Finland.
Abstract
The aim of the research was to study the environmental performance of mobile slow pyrolysis and
hydrothermal carbonisation (HTC) processes utilising waste biomass. Several mobile concept options
were evaluated by means of life cycle assessment (LCA) and in accordance with the standards ISO
14040 and ISO 14044.
The biomass raw materials studied were forest residues, wheat straw, pine bark, and brewery spent
grain. The solid product output from the treatment processes was biochar, which was assumed to be
used as soil amendment, activated carbon, or metallurgical coal. The system boundaries covered the
life cycle from raw material extraction to transportation of the product to the assumed use location.
Thus, the use phase and end-of-life of the product were excluded. The LCA model of one slow pyrolysis
case can be seen in Figure 1.
Figure 1. Life cycle model of a slow pyrolysis case, where energy for the mobile unit is produced with a diesel generator and the end
product is soil amendment which is transported and spread to a field. In this case, the mobile unit is located next to the raw material
source, thus no tranportation is needed for the raw material.
The data for the biomass treatment processes was acquired from the process designers. Energy
production and transportation data was sourced from Ecoinvent 3.4 database. The life cycle systems
were modelled with the LCA software SULCA. Life cycle impact assessment was conducted based on
the CML 2001 methodology. The study focused on three impact categories: acidification, climate
change, and eutrophication.
References
[1] Nyström, M.: Mobile biomass HTC-processing unit. Aalto University, School of Chemical Technology. Espoo, Finland
(2016) )
931
COMPOSITION OF MUNICIPAL SOLID WASTE IN ATHENS - GREECE
T. ARVANITIS1, RAZIS 1, D.F. LEKKAS2

1 HERRCo SA, Athens, Greece
2 .Waste Management Laboratory, Department of Environment, University of the Aegean, Lesvos,
Greece.
Abstract
The estimation of MSW composition is crucial in order to design and build any waste management
system or infrastructure [1,2,3]. In this work, the composition of Municipal Solid Waste in Athens
(Greece), emphasizing on the Packaging Waste material, is determined. Results are compared to
previous sampling periods (S1: 2013, S2: 2014, and S3: 2015) as well as the recoveries measured in
32 Material Recovery Facilities (MRFs) in Greece. The Direct Sampling Method (Protocol
Lekkas/HERRCO) was used as described by Lekkas et al. [4], according to which the sampling area
was divided into sectors. Sectors were identified using as a criterion the homogeneity of the MSW
quality and production, which mainly depends on the social characteristics of each sector.
The municipal solid waste collection practice in Greece, in most municipalities, is based on a dual
stream system. The mixed wastes are collected into green (or grey) bins and the recyclable wastes
(mainly packaging material) into blue bins. The recyclable materials (glass, plastic, paper and metal)
are separated and recovered in MRFs. The management of mixed solid wastes is more complicated;
despite the operation of dual-stream system, large amount of recyclables are disposed with the
households biodegradable wastes in the green bins.
For the purpose of this paper, samples were collected from blue and green bins in parallel, at unified
points of disposal i.e. disposal points containing blue and green bins. The experiment run for 7 days
in a row so as to monitor the weekly variations. The sampling was repeated in four different seasons.
The sampling area was the city of Athens with a population of 2.486.729 inhabitants. In each
sampling point blue and green bins were considered as one sample in order to estimate the
aggregate MSW.
Table 1. Overall composition of MSW in Attica (mean weighing values - S4, July 2017)
MSW Total Blue Bin Green Bin
Packaging Materials 23,0% 39,3% 10,8%
Other recovered materials 10,0% 19,0% 4,0%
Residue 67,0% 41,7% 85,1%
Total 100% 100% 100%
An important finding is that blue bins create a stream in which the concentration of plastic (all types)
is twofold the concentration in the MSW whereas the total recoverable materials are approximately
60% pw. That supports the argument that a dual system diverts significant amounts of recyclable
materials even though there are impurities. The green bin stream contains a large amount of PW. In
order to divert these materials to blue bin stream there are several actions that need to be made;
public engagement, upgrade of blue bin network and more important to collect more vigorously.
The conclusions are considered of great importance, especially for Greece, as many MSW treatment
systems are under construction at this moment.
932
References
[1] Maklawe Essonanawe Edjabou, Morten Bang Jensen, Ramona Götze, Kostyantyn Pivnenko, Claus Petersen, Charlotte
Scheutz, Thomas Fruergaard Astrup: Municipal solid waste composition: Sampling methodology, statistical analyses,
and case study evaluation, Waste Management 36, 12-23 (2015)
[2] Guillermo Díaz-Villavicencio, Simone Regina Didonet, Alexander Dodd: Influencing factors of eco-efficient urban
waste management: Evidence from Spanish municipalities, Journal of Cleaner Production 164, 1486-1496.
[3] E. Gidarakos, G. Havas, P. Ntzamilis: Municipal solid waste composition determination supporting the integrated
solid waste management system in the island of Crete, Waste Management, 26, 668-679 (2006).
[4] Lekkas TD Razis, Y., Komis, I., and Arvanitis T. (2016), Recycle for what its worth, CRETE 2016 – 5TH International
Conference in Industrial and Hazardous Waste Management
933
EVALUATION OF THE EFECTIVENESS OF THE IPPC LEGAL FRAMEWORK BY LIFE CYCLE

THINKING TOOLS: THE CASE OF SLAUGHTERHOUSES IN GALICIA
F. GONZÁLEZ DURÁN, A. GARCÍA RELLÁN, E. R. TORRES LOPEZ, P. M. BELLO BUGALLO

Department of Chemical Engineering, School of Engineering, Universidade de Santiago de
Compostela,
Av. Lope Gómez de Marzoa, s/n, E-15782, Santiago de Compostela, Spain
Keywords: slaughterhouses, IPPC (Integrated Pollution Prevention and Control), Best Available
Techniques (BAT), environmental permit, industrial emissions, life cycle thinking, impact assessment
Abstract
Slaughterhouses are an industrial activity affected by Industrial Emissions Directive (Integrated

Pollution Prevention and Control – IPPC), so specific Best Available Techniques (BATs) must be
applied to achieve a high level of environmental protection as a whole. This work analyses the
degree of implementation of the IPPC Directive in the Galician slaughterhouses (a region in
Northwest of Spain) and their environmental behavior.
The methodology is based on tools derived from the Life Cycle Thinking (LCT): BAT Analysis and
Impact Assessment. For this purpose, five industrial installations of this type affected by the IPPC
legal framework have been selected as case study. The degree of implementation of BATs and the
qualitative and quantitative consumptions and emissions, have been analyses considering their
environmental permits and data from Spanish Pollutant Release and Transfer Register (PRTR). Then,
using these data to perform a life cycle inventory, an environmental impact evaluation of each plant
is developed using a free software.
The results provide an updated inventory of Best Available Techniques for obtaining around a
hundred of candidate techniques to be BAT, with a high degree of implementation in selected plants.
The environmental impact analysis evaluation shows the quantitative relevance of slaughterhouses
in terms of impact category, as well as the specific impact of each plant. Among other aspects, this
work concludes that it would be necessary to develop previous studies (as the present one) to
implement the appropriate techniques to prevent or/and reduce impacts from any specific activity.
934
1- INTRODUCTION
Galician food industry represents more than 16% of the region’s economic activity, been meat
industry the most important subsector, after the fishing sector [1]. Galician production represents
the 6% of the total in Spain in 2016 with a volume of 385190 tons of meat and a value of over €1
million [2].
Slaughterhouses represent the first step of the meat production and processing value chain and their
potential environmental aspects are the water and energy consumption as well as the discharge of
wastewater with a high organic concentration [3].
Currently, Directive 2010/75/EU on Industrial Emissions, from now on IPPC Directive, is the main
European instrument regulating pollutant emissions from industrial installations. It is based on an
integrated approach, flexibility and public participation with the aim of reaching a high level of
protection of the environment as a whole by laying down measures to prevent or, where not
practicable, to reduce emissions to air, water and land, including measures concerning waste [4]. The
IPPC Directive, meaning Integrated Pollution Prevention and Control, sets down the necessity of
avoiding waste generation by implementing Best Available Techniques (BAT) [5]. According to
Karavanas et al. [5], in addition to the information about environmental performance provided
through environmental permits (Emission Limit Values (VLE) and implemented BAT), the data from
European Pollutant Release and Transfer Register (E-PRTR) gives a coherent and interesting picture
of the degree of BAT implementation and an indication of IPPC obligations fulfilment.
BAT Analysis [6, 7] is a tool that evaluates the techniques candidate to be BAT following the
methodology set by the EIPPCB (European IPPC Bureau). It is a sustainability-oriented methodology
involving a deep knowledge of the process considered to develop an inventory of candidate
techniques. Each technique has its own data sheet including all the information recommended by
the EIPPCB. The BAT Analysis has already been validated in the fish and seafood canning industry [8]
and in dairy industry [9] with rather success. On the other hand, the LCIA (Life Cycle Impact
Assessment) is used to understand and to evaluate both the magnitude and the significance of the
potential environmental impacts of a system. Its purpose is to convert the LCI (Life Cycle Impact)
results into the related environmental impacts - effects on natural resource use, natural
environment and human health, collecting them in impact categories [10]. The goal of the LCIA is
provide a global life cycle impact assessment methodology for the three main areas of protection
(human health, ecosystem quality, resources) [11].
The importance of the meat industry sector makes it necessary to study their sustainability and how
can it be improved. The aim of this work is the analysis of the Galician slaughterhouse activity. The
analysis follows the focus of the IPPC policy and their environmental behavior based on pollutant
emissions regarding the installed BAT. The applied methodology is based on LCT (Life Cycle Thinking)
focus and combines BAT Analysis and IA (Impact Assessment) to identify the degree of implemented
BAT and to assess their influence on the overall environmental performance of the installation.

The methodology developed in this work is based in previously works [8, 9] and includes a set of
sequential steps which are described in the Figure 1.
935
1. Definition of the systems under study.

Identification of the industry plants.
2. Qualitative analysis.
Brief description of the generic process and identification of the derivative environmental effects.
3. Quantitative analysis.
Presentation of the main consumptions of each plant; calculation of the main emissions to air and to
water using emissions factors; recompilation of data about generated waste.
4. BAT analysis.
Inventory of techniques candidate to be BAT and identification of the already implemented BAT.
5. Impact assesment.
Data from a life cycle inventory is used to evaluate the activity in terms of impact categories.
Figure 1. Flowchart of the applied methodology.
3- DEVELOPMENT, RESULTS AND DISCUSSION

3.1- DEFINITION OF THE SYSTEM UNDER STUDY
Five Galician slaughterhouses have been selected, all affected by IED (Industrial Emissions Directive)
[4, 14] and by PRTR Regulation [15], with their environmental permit in force [16]. Galician
slaughterhouses of poultry, pigs and cows have been selected, with different production capacities
and different commercialized products. Two of them, in addition to having catalogued their activity
as animal’s sacrifice, are also installations for the disposal or recycling of animal carcasses and animal
waste by means of the by-product treatment. All of them are enrolled in the register of producers
and manager of hazardous waste and these plants got their first environmental permits between
2011 and 2015.
3.2. QUALITATIVE ANALYSIS

According to the flow diagram published by Bello Bugallo et al. [15], the general slaughterhouses
productive process can be classified in four main stages, which differ significantly depending on the
type of animal to be sacrificed.
- Previous operations. The process starts with the reception and uploading of animals,
maintaining the animals as calmed and relaxed as possible under a good hygienic and welfare
conditions, so these influence on final quality of meat. Next, animals are stunned and hanged
to continue with their slaughter.
- Processing. It is the most meticulous stage, as the hygiene and quality of the carcass can be
affected by it performance. The first and last operation, bleeding and evisceration, are
approximately the same and common to all cattle. The intermediate operations concern the
preliminary preparation of the carcass according to the type of cattle (removal of hair, skin,
head, hooves and feathers). Finally, the meat carcase is split, refrigerated or frozen and
packed according to the requisites of the final product.
- Post-processing. This stage consists in the wastewater treatment and waste and by-products
management.
936
- Auxiliary operations. It includes the cleaning and disinfection of the equipment and the
maintenance of the installation, to guarantee the hygienic and technical conditions of the
machinery and facilities.
3.2.1. MAIN ENVIRONMENTAL ASPECTS
The key environmental issues for slaughterhouses are water consumption, the discharge of liquid
effluents with HOL (High Organic Load), the energy consumption associated with refrigeration and
water heating, and infectivity in relation to TSE risk materials (Transmissible Spongiform
Encephalopathy). Odours from animal by-product storage and handling, the WWTP and noise from
equipment and animals can also be local issues [16]. Figure 2 shows an overview of all potential
emissions to the different media from slaughter activity, based on the environmental impacts
identified in previous works [17]. It also includes their environmental effects, which may be harmful
to human health or to the quality of the environment, resulting in damage to material property, or
interfering with amenities and other legitimate uses of the environment.
Figure 2. Summary of potential emissions to different media and their associated environmental impacts from slaughter industries.
3.3- QUANTITATIVE ANALYSIS

The environmental performance of these plants will be analysed using the environmental permits of
each plant, which have been used to compile data about processing, consumptions, emissions and
the degree of implementation of the BAT. By other hand, the public information available at PRTR -
Spain is also used [11]. A compared overview of the environmental performance of each plant
referred to 1 ton of processed meat carcase is given in Figure 3 according to main consumptions,
emissions to air and to water.
Gaseous emission to air from the following sources have been considered: electricity (kg CO2/MWh),
fossil fuels (kg of pollutant/GJ), wastewater treatment plant (kg of pollutant/m3), manure
937
management and enteric fermentation from animals (kg of pollutant/animal*year). An example of

used the emission factor to know the emission to water is given in Table 1. These emission factors to
water have been multiplied per the volume of wastewater treated per ton of processed meat
carcase for each plant, using the respective changes of units.
Emission factors
Pollutant Unit All kind of cattle References
BOD mg/L 42,5 [3] Table 3.22
[3] Estimated from emission level associated to BAT and
COD mg/L 106,25
BOD
TN mg/L 40 [3] Average from Table 3.22 and Table 5.1
TP mg/L 2,75 [3] Table 3.22
TSS mg/L 45 [3] Table 3.22
NH3 mg/L 10 [3] Table 3.22
Table 1: Emission factors to water.
The results of this part are shown in Figures 3. Porcine and bovine slaughterhouses have the higher
energy and water consumption. In the case of water and electricity consumption, these are
equitable for all plants. The use of fuels depends on the plant and each of them use a different
source of energy (Plant A only uses fuel oil; Plant B uses fuel oil and natural gas; Plant C uses fuel oil,
natural gas and gasoil; Plant D only uses natural gas; Plant E uses fuel oil and gasoil). Paying attention
to emissions, poultry slaughterhouses (Plant A and E) are the least polluting. The most significant
pollutants are CH4, NH3, CO2 and PM10 for air, and COD, BOD and TSS for water. The CH4 and NH3
emission are higher for plants B and C due to manure management and enteric fermentation is
major from pigs and cows. Related to a possible transfer of pollutants, only a transfer of suspended
particles from air to water is observed since they follow the same trend in both media. For NH 3,
there is no transfer.
Figure 3b: Energy consumption per ton of processed meat

Figure 3a: Water consumption per ton of processed meat carcase
carcase for each plant.
for each plant.
938
Figure 3c: Emission to air for each plant (kg of pollutant/ton of Figure 3d: Emission to water for each plant (kg of
processed meat carcase). pollutant/ton of processed meat carcasses).
Based on data provide from Spanish PRTR, Plant B generates 0,35 kg of hazardous waste per ton of
carcase and 18,88 kg of non-hazardous waste. The Plant E generates 0,10 kg and 10,60 kg,
respectively. Due to the uncertainty of these data, the rest of the amounts have not been estimated.
3.4- BAT ANALYSIS

Candidate techniques to be BAT are inventoried according to the methodology developed by Barros
et al. [6, 7], which was successfully applied to the study cases (Table 2). The final inventory includes
91 candidate techniques to be BAT according to the stages of the slaughter process described in
qualitative analysis, most of them taken from the bibliography [3, 16] and others are the result of a
previous analysis of the Galician sector [15, 17].
Most of them are related to consumption and emissions to water. It includes “process integrated”
techniques related to prevention, control and minimization of consumptions, as well as “end-of-
pipe” techniques applied to wastewater treatment and air pollution. Some of them are very
technical and others are good operating practices called Best Environmental Practices (BEP),
covering management techniques.
Candidates Implemented BAT

to be BAT Plant A Plant B Plant C Plant D Plant E
BEP 10 4 4 2 4 5
Previous operations 18 3 2 8 1 2
Processing 9 3 3 4 3 1
(all kind of cattle)
Pig processing 9 - 2 7 - -
Bovine processing 7 - - 3 2 -
Poultry processing 9 6 - - - 5
Post-processing 19 6 3 14 7 9
Auxiliary operations 10 8 6 6 4 4
Table 2: Number of available and implemented BAT for each plant by steps.
The degree of implementation of these techniques is high as global, 75% of all candidate BAT are
implemented; plant E has turned out to be the one implementing more techniques with a 95% of
implementation related to all available BAT, closely followed by plant A (88%) and D (78,1%). Plants
939
B and C have a poor degree of implementation, with a percentages of BAT implementation of the
27% and 54%, respectively.
An example of the procedure accomplished to analyse the already implemented BAT for each plant
is showed in Table 3, in this case the considered BAT are related to good practices.
CANDIDATE TECHNIQUE A B C D E
Environmental management system
Training provision
Implement water management systems
Implementing energy management systems (Optimization of the efficiency
of the ventilation and cooling system)
Implement light management systems
Implement a noise management system
Use of environmentally friendly fuels and refrigerants, as well as more
efficient machinery
Re-use heat and/or power produced in one activity in other activities and
export any heat and/or power produced which cannot be used on-site.
Utilization of heat / electricity from renewable energy sources when will
be economically viable
Odours and quality controls
Table 3: Candidate techniques related to good practices for slaughterhouses and their implementation for each plant.
Each one of the techniques of the inventory has a data sheet showing all considered aspects to help
in the decision making process. Following the methodology set by the European IPPC Bureau [18],
data sheet includes environmental aspects, technical description, benefits, side effects,
implementation, applicability and economical aspects. Figure 4 shows an example.
OPTIMIZE COOLING SHOWERS FOR PIGS [3]

Environmental impacts
Water consumption.
Technical description
Pigs are showered during hot, dry periods, for animal welfare reasons. It helps to
calm them and to prevent them from becoming stressed. The shower nozzles can be
designed and installed so that they are only activated when there are pigs present.
The flow and the operation time are controlled automatically. Showering also
improves the environment for people entering the lairage, by reducing respirable
and total dust levels.
Benefits/environmental data
Less water consumption than if manual or continuous showering is carried out.
Secondary effects
Reduces dust by 60 %, whereas an electrostatic filter reduces both total and
respirable dust by 40 - 45 %.
Implementation
Installation of a control system that activates the water supply for two minutes
every half hour.
Applicability and characterization
All pig slaughterhouses.
940
Economic aspect
The costs necessary for the application of this measure are those derived from
installing a water supply control system for the showers.
Figure 4: Example of data Sheet.
3.5- IMPACT ASSESSMENT
The evaluation of environmental impact is developed using data from the inventory of selected
Galician slaughterhouses (presented previously in the quantitative analysis) and the OpenLCA vs 1.6
software, considering the ReCiPe midpoint (E) method [19]. Only the most representative categories
of impact for this sector have been represented. The obtained results show in Figure 5.
Figure 5a: Contribution to climate change for each plant. Figure 5b: Contribution to water ecotoxicity for each plant.
Figure 5c: Contribution to fossil depletion for each plant. Figure 5d: Contribution to water depletion for each plant.
These results do not exactly reflect the data obtained in the quantitative analysis, although the plant
B and C continue having the highest consumption and emission values. This may be because the LCIA
also considers the emissions derived from the manufacture of raw materials.
4- CONCLUSIONS
The applied methodology has been proved to be appropriate to evaluate the effectiveness of the
IPPC legal framework and to know the environmental performance of any slaughterhouse affected
by this directive. In addition to give practical solutions to improve their environmental performance,
and to help in the design of a more sustainable process configuration. So it seems possible to extend
it to the whole industry, optimizing the global environmental performance of such a relevant sector
for the Galician economy.
941
In the case of analysed slaughterhouses, the degree of implementation of BAT reflects the results of
the calculated emissions. However, it can be concluded that the degree of implementation of BAT is
not enough. The stages with a less degree of implementation are previous operations and processing
of cows. Owing to poor implementation of BAT found, further work should be focussed on
identifying the main limitations of these plants regarding BAT. It is necessary to analyse whether the
already implemented techniques are the appropriate ones or if they are correctly working.
Accordingly, corrective measures could be proposed, and the environmental performance of the
plants could be improved. It is a long-term task, as it involves economic investment and
technological modifications. By other hand, the main pollutant focus should be identified for each of
them, so that proper BAT could be recommended and implemented.
Finally, a relevant conclusion of this work is also that it is necessary to develop previous studies (as
the present one) to implement the appropriate techniques to prevent or/and reduce impacts from
any specific industrial activity.
REFERENCES
[1] Xunta de Galicia, 2015. Galician Statistics Institute. Accessed 4 January 2018 from:
http://www.ige.eu/web/index.jsp?idioma=gl
[2] MAPAMA (Ministry of Agriculture, Fishing, Food and Environment), 2017. Statistical annual directory 2016.
Government of Spain European Union: Directive 2010/75/EU on industrial emissions (integrated pollution
prevention and control). OJ L 334, 17.12.2010, pp. 17-119.
[3] EC, 2005. Integrated Pollution Prevention and Control. Reference Document on Best Available Techniques in the
Slaughterhouses and Animal By-products industries. Directorate – General: JRC (Joint Research Centre), Institute for
Prospective Technological, European IPPC Bureau.EU, 2010. Directive 2010/75/EU on industrial emissions
(integrated pollution prevention and control). Official Journal of the European Communities L334, 17-119.
[4] EU, 2010. Directive 2010/75/EU on industrial emissions (integrated pollution prevention and control). Official Journal
of the European Communities L334, 17-119.
[5] Karavanas, A., Chaloulakou, A., Spyrellis, N.: Evaluation of the implementation of best available techniques in IPPC
context: an environmental performance indicators approach. J. Clean. Prod. 17, 480-486 (2009).
[6] Barros, M.C., Bello, P.M., Roca, E., Casares, J.J., 2007. Integrated pollution prevention and control for heavy ceramic
industry in Galicia (NW Spain). Journal of Hazardous Materials 141, 680-692
[7] Barros, M.C., Torres, M.T., Bello, P.M., Roca, E., Casares, J.J., 2008. Integrated pollution prevention and control in the
surface treatment industries in Galicia (NW Spain). Clean Technologies and Environmental Policy 10, 175-88.
[8] Bello Bugallo, P.M., Cristóbal Andrade L., Iglesias Magán, R., Torres López, R., 2013. Integrated environmental
permit through Best Available Techniques: evaluation of the fish and seafood canning industry. Journal of Cleaner
Production 47, 253-264
[9] Torres López, R. Doval Leira, E.R., Galera Martínez, M., Bello Bugallo, P.M., 2017. Integrated environmental permit
through Best Available Techniques: Evaluation of the dairy industry. Journal of Cleaner Production 162, 512-528
[10] UNE-EN ISO 14040:2006.Environmental Management – Life cycle assessment. Principles and framework.
International Organisation for Standardisation (ISO).
[11] LC-Impact, 2018. . Accessed 09 May 2018 from: http://www.lc-impact.eu/methodology-home.
[12] Spanish Government, 2013. Spanish Law 5/2013, whereby the Law 16/2002 of Prevention and Control Integrated of
the Pollution and the Law 22/2011 of Residues and Contaminated Soils are modified. Official Gazette 140, 44257-
44288.
[13] EC, 2006. Regulation 166/2006/EC of the European Parliament and of the council concerning the establishment of a
European Pollutant Release and Transfer Register and amending Council Directives 91/689/EEC and 96/61/EC.
Official Journal of the European Communities L33, 1-16.
[14] Xunta de Galicia, 2018. Environmental Permits. Accessed 20 January 2018 from. http://cmaot.xunta.gal/busca-de-
expedientes-da-autorizacion-ambiental-integrada
[15] Bello Bugallo, P.M., Cristóbal Andrade L., Agrelo de la Torre, M., Torres López, R., 2014. Analysis of the
slaughterhouses in Galicia. Science of Total Environment 481, 656 – 661.
[16] EPA (Enveriomental Protection Agency), 2008. BAT Guidance Note on Best Available Techniques for the Slaughtering
Sector (1st Edition). Ireland.
942
[17] Xunta de Galicia, 2006. Environmental permit: application guide for slaughterhouses. Ed. Xunta de Galicia -
Department of the Environment and Sustainable Development.
[18] EC, 2018. Joint Research Centre - The European IPPC Bureau. Accessed 28 January 2018 from:
http://eippcb.jrc.ec.europa.eu/about/
[19] GreenDelta, 2017. LCIA methods. Impact assessment methods in Life Cycle Assessment and their impact categories.
943
STRAW XANTHATE AS A HEAVY METAL SORBENT IN BIOGAS SLURRY - SYNTHESIS,

CHARACTERIZATION AND APPLICATION
JUNHAO CHEN1, JUNHAO CHEN1, YING SUN1

1 Beijing Key Laboratory of Farmland Soil Pollution Prevention and Remediation, College of Resources
and Environmental Science, China Agricultural University, Beijing 100193, P.R. China.
Abstract
Biogas slurry and residue contaminated with heavy metals are widely used as fertilizers in vegetable
crop planting. To better use biogas slurry as a resource and to reduce its environmental impact, in
this study, straw xanthate, prepared by wheat straw, was used as an absorbent to remove heavy
metal irons from biogas slurry. Based on the orthogonal experimental design method (L25(54)), the
best xanthates synthetic condition was determined. The adsorption characteristic and the
mechanism of xanthate showed that the adsorption of Cu on straw xanthate could be better fitted to
the pseudo-second order kinetic equation and the Langmuir Isotherm model. At 298K, the maximum
equilibrium adsorption amount was found to be 17.61 mg•g-1. Straw xanthate removed more than
90% Cu from biogas slurry.
Acknowledgments
This study was supported in part by the National Key Research and Development Program of China
(2016YFD0501404)
944
ASSESSING THE POTENTIAL OF DIGESTATE FROM BIOWASTE FOR CELLULASE AND

XYLANASE PRODUCTION
L. MEJIAS1,2, A. CERDA1, R. BARRENA1, T. GEA1, T. SÁNCHEZ1

1 Composting Research Group, Department of Chemical, Biological and Environmental Engineering,
Escola d’Enginyeria, Universitat Autònoma de Barcelona, 08193 Bellaterra, Barcelona, Spain
2 Aeris Tecnologías Ambientales S.L., Carrer Santa Rosa, 38, local, 08290 Cerdanyola del Vallès,
Barcelona, Spain
Abstract
This study assesses the potential valorization of digestate from biowaste to produce cellulase and
xylanase through solid state fermentation (SSF), in the framework of the DECISIVE project, funded by
the European Horizon 2020 Programme (grant agreement Nº 689229). To achieve this goal,
inoculation requirements are studied, evaluating the production of these hydrolytic enzymes at lab
scale using different strategies: i) the potential production by autochthonous microbiota and ii)
bioaugmentation with Trichoderma reesei. The nutrient supplementation effect in autochthonous
microbiota and the mixing effect when inoculating T. reesei were also evaluated.
Hygienised non-sterile digestate (95 g) and toothpicks in a 1:1 (v/v) ratio conformed the solid matrix.
The monitoring parameters were the oxygen uptake rate (OUR) and the cumulative oxygen
consumption (COC). Four set of reactors where run in quadruplicates: a) digestate without
inoculation, i.e autochthonous microbiota (AM), b) digestate without inoculation and supplemented
with nutrients (AMS), c) supplemented digestate inoculated with T. reesei pellets in a 7% (w/v) under
static conditions (TSS) and d) supplemented digestate inoculated with T. reesei with daily manual
mixing (TSM). Cellulase and xylanase activity were determined at 0, 48, 72, 96 and 120 hours.
AM reactors showed a maximum cellulase activity value of 1.2 ± 0.2 FPU g-1 DM at 72 hours, a low
value than expected [1]. However, a peak of xylanase activity was observed at 84 hours with a value
of 81 ± 7 UA g-1 DM. Nutrient supplementation in AMS reactors led to an increase of nearly 20% in
OUR but a lower enzymatic production. This may be attributed to the fact that the hemi-cellulolytic
microorganisms could not beneficiate of the added nutrients. A peak of xylanase activity was
observed in the TSS reactors at 66 hours (31 ± 16 UA g-1 DM), however, cellulase activity during
fermentation was not higher than initial activity (1.1 ± 0.3 FPU g-1 DM). Finally, mixing in TSM
reactors neither improve cellulase nor xylanase production.
Main conclusions are that digestate is not an appropriate substrate for producing cellulase under
conditions tested. However, autochthonous microbiota showed a good potential for xylanase
production that will be explored in further research. Inoculation with T. reesei did not improve the
production of these enzymes, being the main hypothesis that alkaline pH of digestate hindered fungi
growth, as its optimum pH is between 5-7.
References
[1] Cerda, A., Mejías, L., Gea, T., and Sánchez, A.: Cellulase and xylanase production at pilot scale by solid-state
fermentation from coffee husk using specialized consortia: The consistency of the process and the microbial
communities involved. Bioresour. Technol. 243, 1059–1068 (2017)
945
SCREENING OF SUPPORT MATERIALS FOR THE PRODUCTION OF SOPHOROLIPIDS

THROUGH SOLID STATE FERMENTATION
A. RODRIGUEZ1, T. GEA1, X. FONT1

1Composting Research Group, Department of Chemical, Biological and Environmental Engineering,
Escola d’Enginyeria, Universitat Autònoma de Barcelona, Cerdanyola del Vallès, 08193 Barcelona,
Spain Barcelona, Spain.
Abstract
Surfactants are an important class of molecules widely used in modern household and industry [1].
Most of these compounds are chemically synthesized from petroleum derivates [2]. Most of them are
harmful to the environment and have not feasible biodegradability. Biosurfactants, or microbial
derived surfactants, are an alternative to replace these chemical/synthetic surfactants. Sophorolipids
(SLs), which are produced by nonpathogenic yeast, are probably one of the most promising
biosurfactants [3]. SLs are produced through submerged fermentation with the yeast Starmerella
Bombicola. However, Solid State Fermentation (SSF) is being investigated as an alternative.
The main goal of this study was to evaluate 10 different materials (rice husk, wheat straw, pine bark,
coconut fiber, wood chips, clay, perlite, volcanic clay, black foam and yellow foam) as a support to
produce SLs with Starmerella Bombicola ATCC 22214 by SSF using food-industry wastes as substrates
(Winterization Oil Cake (WOC) and sugar beet molasses (MOL)). A complete physicochemical
characterization of the target materials was performed. This characterization included, besides the
most usual parameters (dry and organic matter, pH, Water Holding Capacity, Bulk Density or Porosity)
an elemental analysis and surface roughness with Scanning Electron Microscope (SEM).
Materials with Water Holding Capacity above 1 g H20 per g of Material were chosen for SSF process
using 1:4 MOL:WOC mass ratio and 0.30 L kg−1 min−1 aeration rate [4]. Experiments were performed
at 400 ml scale reactor carried out under static conditions and monitored for 7 days. The Oxygen
Uptake Rate (OUR) and the Cumulative Oxygen Consumption (COC) were used to monitor the
biological activity of the SSF process [4]. The highest SL yields and biological activity were obtained
using natural materials as a support compared to the inert ones, due to a better fixation of the
microorganism and an increased availability of nutrients needed to produce SLs. This study describes
an alternative to valorize agro-industrial wastes and use it as an alternative to produce biosurfactants.
References
[1] Z. Velioglu and R. Ozturk Urek, “Optimization of cultural conditions for biosurfactant production by Pleurotus
djamor in solid state fermentation,” J. Biosci. Bioeng., vol. 120, no. 5, pp. 526–531, 2015.
[2] R. M. S. Cameotra, “An update on the use of unconventional substrates for biosurfactant production and their new
applications,” Appl. Microbiol. Biotechnol., vol. 58, no. 4, pp. 428–434, Mar. 2002.
[3] I. N. A. Van Bogaert, J. Zhang, and W. Soetaert, “Microbial synthesis of sophorolipids,” Process Biochem., vol. 46,
no. 4, pp. 821–833, 2011.
[4] P. Jiménez-Peñalver, T. Gea, A. Sánchez, and X. Font, “Production of sophorolipids from winterization oil cake by
solid-state fermentation: Optimization, monitoring and effect of mixing,” Biochem. Eng. J., vol. 115, pp. 93–100,
2016.
946
BIOMASS HYDROLYSIS BY A CARBON-BASED SOLID CATALYST
WEI-CHUN HUNG1, CHIUNG-FANG LIU1, HOU-PENG WAN1

1 Industrial Technology Research Institute, Hsinchu, Taiwan, R.O.C.
Abstract
Cellulose is the main ingredient of lignocellulose, which is a polymer generated from combination of glucose
monomers through β-1,4 glycosidic bonds.[1,2] β-1,4 glycosidic bond can be destroyed by acid, causing
cellulose hydrolysis and generating compounds such as glucose or oligosaccharides, etc. The first acid used in
cellulose hydrolysis to produce sugar was an inorganic acid.[3-5] However, the existence of these inorganic
acids causes problems, including difficulty separating products, reactor corrosion, difficulty reusing the
catalyst, and wastewater treatment. These problems urgently need to be overcome.
In this study, a carbon-based solid catalyst bearing sulfonic acid groups and hydroxyl groups, which was
synthesized by sulfonation of active carbon, lignin, and the residue from sugarcane bagasse hydrolysis, was
investigated for potential application in cellulose hydrolysis. Sulfonic acid groups and hydroxyl groups on the
surface of carbon-based solid catalyst serve as catalytic domains and cellulose-binding domains,
respectively.For the study of the real biomasss hydrolysis, corn stover was hydrolyzed into sugars in the
formic acid/n-hexane azeotrope system with sulfonated residue from sugarcane (BRS) as a catalyst. The yield
of total reducing sugar was 86.8 wt.%, and the molar fractions of glucose and xylose in the product were 64.6
and 78.8 mol.%, respectively. Preliminary results indicated that the carbon-based solid catalyst has good
stability. Further improvement on developing a strategy to separate/recover the catalyst from the hydrolysis
residue is required before homogeneous acids can be replaced with carbon-based solid catalysts.
References
[1] Sun, Y.; Cheng, J. Y.: Hydrolysis of lignocellulosic materials for ethanol production: a review. Bioresour. Technol. 83,
1-11 (2002).
[2] Isikgor, F.H.; Remzi Becer, C.: Lignocellulosic biomass: a sustainable platform for the production of bio-based
chemicals and polymers. Polym. Chem. 6, 4497-559 (2015).
[3] Stein, T.V.; Grande, P.; Sibilla, F.; Commandeur, U.; Fischer, R.; Leitnera, W.; Pablo, M.: Salt-assisted organic-acid-
catalyzed depolymerization of cellulose. Green Chem. 12, 1844-49 (2010).
[4] Rinaldi, R.; Schüth, F.: Acid hydrolysis of cellulose as the entry point into biorefinery schemes. ChemSusChem 2,
1096-1107 (2009).
[5] Kumar, S.; Dheeran, P.; Singh, S.P.; Mishra, I.M.; Adhikari, D.K.: Kinetic studies of two-stage sulphuric acid hydrolysis
of sugarcane bagasse. Renewable Energy 83, 850-858 (2015).
947
CONVERSION OF SHRUB BIOWASTE THROUGH TORREFACTION

MOBILE UNITS FOR REDUCING FIRE RISK IN THE SOUTHERN EUROPE
M. GONZALEZ MARTINEZ1,2,3, C. DUPONT4, L. MIGUEZ RODRIGUEZ5, S. THIERY1, M. GRATEAU1, D. DA

SILVA PEREZ6, X.M. MEYER2,3, C. GOURDON2,3
1 Laboratoire de Préparation des Bioressources; CEA, Grenoble, France.
2 Université de Toulouse; INPT, UPS; Laboratoire de Génie Chimique, Toulouse, France.
3 CNRS; Laboratoire de Génie Chimique, Toulouse, France.

5 Consellería de Educación e Ordenación Universitaria, Xunta de Galicia, Spain.
6 FCBA, InTechFibres, Grenoble, France.
Abstract
In the last decades, unusual high temperatures and lacking precipitation during abnormally long dry
seasons have contributed to increase the incidence of forest fires, especially in the Southern Europe.
This was enhanced by the accumulation of a growing vegetal mass in forests and mountains,
presumably because of the decline in agricultural and farming activities. In this context, the
European project MOBILE FLIP aims at developing and demonstrating mobile conversion processes
to valorise underexploited agro- and forest-based biomass resources. One of the proposed processes
is torrefaction, a mild thermal treatment, typically between 200 and 300°C during a few tens of
minutes in a default-oxygen atmosphere. Torrefaction produces a solid product with optimized
properties, closer to those of coal, suitable for energetic use. Some condensable coproducts are
released in torrefaction, which can present a high-added value as “green” chemicals.
The objective of this study is firstly to identify a reduced number of representative biomasses with
high occurrence in forest fires in the region of study and susceptible to be recovered through mobile
conversion units. Secondly the suitability of the selected biomasses in torrefaction is assessed.
The selected area of study was Chandrexa de Queixa (Galicia, Spain), because of the high occurrence
of forest fires in the last years [1]. Accordingly, five shrub species (white broom, yellow broom,
heather, fern and gorse) and a highly available deciduous wood (oak) were included in this study.
Torrefaction experiments were carried out in a thermogravimetric analyser (TGA) coupled with a gas
chromatography mass spectrometer device (GC/MS) through a heated storage loop system. Spanish
biomasses were torrefied under these conditions and compared to 14 biomasses representative of
the European diversity (hardwood, softwood, agricultural by-products and herbaceous crops). A
simultaneous study on solid degradation and volatile species release in non-isothermal torrefaction
(200 to 300°C) was carried out for each biomass, in conditions guaranteeing chemical regime [2].
The results showed similarities between the behaviour in torrefaction of the selected raw materials,
which makes possible their simultaneous in-situ valorisation through mobile units. Torrefied solid
has shown a higher carbon content and calorific value, which makes it interesting for energetic
purposes. The composition of the volatile mixture released suggests a direct valorisation by
enhancing the production of the major components (such as acetic acid) through suitable operating
conditions.
References
[1] Centro de Coordinación de la Información Nacional sobre Incendios Forestales, Avance informativo de los incendios
forestales del 1 de enero al 31 de diciembre de 2017, 2017. http://www.mapama.gob.es.
[2] González Martínez M., Dupont C., Thiéry, S., Meyer X., Gourdon C., 2016. Chem. Eng. Tr. 50, 61–66.)
948
MODELLING OF BIOELECTROCHEMICAL REACTORS TO DESIGN SCALED-UP SYSTEMS
R. LACROIX 1, E. ROUBAUD2, A. BERGEL2, R. BASSEGUY2, B. ERABLE2, S. DA SILVA1

1 6T-MIC Ingénieries, Castanet Tolosan, France.
2 Laboratoire de Génie Chimique, Toulouse, France.
Abstract
The WE-MET project, funded under the EU-FP7 ERANETMED scheme, will devise the use of Microbial
Electrochemical Technologies (MET), possibly integrated with other technologies, as a
groundbreaking approach to recover energy trapped in wastewater while simultaneously cleaning up
the wastewater.
Two partners of the project (Laboratoire de Génie Chimique, CNRS, Université de Toulouse and 6T-
MIC Ingénieries) are collaborating to develop a new design of reactor to produce hydrogen at the
cathode and to oxidize organic wastes from water at the anode.
The performance of microbial electrolyser is generally limited by the low conductivity of the
electrolyte, the kinetic of reactions catalyzed by electrochemical biofilms and matter transport. An
extensive modelling study using Comsol Multiphysics® was performed using Michaelis Menten
kinetics at the anode and Butler-Volmer kinetics at the cathode. The model consists in calculating
simultaneously potential and current distribution, velocity and pressure drop for the fluid flow
(continuous supply of wastewater) as well as organic matter transport and consumption. Various
geometries have been considered (fig. 1).
Fig. 1: Potential distribution in the electrolyte for two different anodic geometries
The design of the 3D structure for the anodes was performed by taking into account the impact of
the geometry on the fluid flow, mass transfer and potential/current distribution. The strategic
positioning of the anodes can avoid the formation of preferential path for the liquid flow, and thus
allow optimal consumption of organic matter. The use of 3D anodes instead of 2D plates could
potentially increase the current by 167 mA (from 321 to 488 mA) for a 10 L pilot. The model was
used to design a stack type reactor, consisting in alternating cathodic and anodic compartments. The
model was also used to define proper operational conditions, in order to maximize waste removal
and hydrogen production.
References
[1] Lacroix, R.: Modelling potential/current distribution in microbial electrochemical systems shows how the optimal
bioanode architecture depends on electrolyte conductivity. Phys. Chem. Chem. Phys 16, 22892-902 (2014)
[2] Roubaud, E.: Catalysis of he hydrogen evolution reaction by hydrogen carbonate to decrease the voltage of microbial
electrolysis cell fed with domestic wastewater. Electrochim. Acta 275, 32-39 (2018)
REGENERATION PERFORMANCES OF ACTIVATED COKE AND CARBON CONSUMPTION

IN DIFFERENT REGENERATION ATMOSPHERES
M. YE1,2, Y.R. LI2, F. QI2, S. DING2, T.Y. ZHU2, G.Y. CHEN1

1
School of Environmental Science and Engineering, Tianjin University, Tianjin, China.
2
Beijing Engineering Research Center of Process Pollution Control, National Engineering Laboratory
for Hydrometallurgical Cleaner Production Technology, Institute of Process Engineering, Chinese
Academy of Sciences, Beijing, China.
Keywords：regeneration, activated coke, carbon consumption
Abstract
In the present regeneration technology, for the high regeneration temperature, the thermal energy
and the carbon consumption of the side reactions were very high. Therefore, in order to looking for
better heating regeneration technology, the effects of the heating rate, the regeneration
temperature, the concentration of NH3 and H2O as well as the regeneration time on the regeneration
performance of the regenerated activated coke, in different regeneration atmospheres, were
investigate in this study. The active coke already applied in the practical engineering was selected as
the carbonaceous adsorbent and the adsorption-regeneration performance evaluation experiment of
the regenerated active coke was carried out on the self-built experimental device. When NH3 was
added in the atmosphere, the desulfurization performance and the denitration performance of the
regenerated activated coke could be improved, but the carbon consumption and SO 2 recovery were
decreased. When H2O was added in the atmosphere, the carbon consumption were increased, but
effects on the desulfurization performance and the denitration performance of the regenerated
activated coke could be neglected. For the desulfurization performance and the denitration
performance of the regenerated activated coke as well as SO2 recovery, among all the regeneration
conditions, the regeneration temperature is the most important, and the followed are the heating
rate and the regeneration time. with the increase of the regeneration temperature, the
desulfurization performance of the regenerated activated coke and SO 2 recovery were increased.
949
1 INTRODUCTION
The desulfurization and denitration technology of carbon which did not need water participation and
did not cause secondary pollution, as well as could remove multiple contaminants and recover
sulfur, now, is applied to the govern of multiple industrial smoke [1-3]. That technology mainly uses
the carbonaceous adsorbent to remove SO2 and NOx in the flue gas, and involves adsorption process,
desorption process and sulfur recovery process. During the adsorption process, lots of Sulfuric acid
and ammonium sulphate deposited on the surface of the carbonaceous adsorbent, and thus leading
to the performance of the desulfurization and denitration of the adsorbent decreasing. In order to
increase the utilization rate of the adsorbent, the heating regeneration technology was adopted to
regenerate the adsorbent. The heating regeneration technology is that the saturated carbonaceous
adsorbent was heated to a certain temperature, and compounds adsorbed on the surface of the
adsorbent through the desorption or decomposition reactions released the gaseous product and
meanwhile the activity of the adsorbent was recovered. At present, the engineering application of
the heating regeneration technology mainly employed high temperature nitrogen or steam as the
medium, and the regeneration temperature is 400-450℃. Because of the high regeneration
temperature, during the thermal regeneration process, the thermal energy and the carbon
consumption of the side reactions were increased, but the utilization of the carbonaceous adsorbent
was decreased [4,5]. In order to looking for the better heating regeneration technology, researchers
[6-8] studied the heating regeneration process of the carbonaceous adsorbent. In this research,
when the carbonaceous adsorbent after taking part in the desulfurization and the denitrification
reactions was heated and regenerated in N2, NH3 and H2O atmospheres, the effects of the heating
rate, the regeneration temperature, the concentration and the regeneration time for the
regeneration performance of the regenerated activated coke were studied to provide a certain
theoretical basis for seeking better thermal regeneration conditions.
2 MATERIALS AND METHODS

2.1 Experimental method
The active coke (20-60 mesh, China shanxi xinhua activated carbon factory co. LTD) already applied in
the practical engineering was selected as the carbonaceous adsorbent. Considering the complexity of
the chemical structure and constituent of coal active coke, the influencing factor experiments
contained adsorption process, regeneration process, readsorption process.
The adsorption-regeneration performance evaluation experiment of the active coke was carried out
on the self-built experimental device. The experimental device is consist of : (1) valve system,
including mass flowmeter, flowmeter controller and mixing tank, which could realize the flow control
of SO2, NH3, NO, N2 and O2, and thus configured the experimental needed gas atmosphere. The error
of the flowmeter is 0.2% F.S (Full Scale, F.S); (2) reactor system includes openable type resistance
furnace, temperature controller and quartz reaction tube (diameter: 20 mm, length: 520 mm). A
quartz sieve plate is fixed at the middle of the quartz reaction tube to support the adsorbent, and the
temperature of the tube was provided by the resistance furnace; (3) detecting system includes
heatable gas cell(optical distance is 2.4 m) and FTIR spectrometer. During the adsorption and
regeneration process, the concentration of every constituent gas is measured by FTIR spectrometer;
(4) off-gas treatment system installed active carbon, which can adsorbed SO2, NO and NH3 in the off-
gas avoiding the the toxic and harmful compounds released in the atmosphere.
During the experiment process, the total gas flow rate is 300 ml/min, the quality of the active coke is
950
1.5 g, the air speed is 5700 h-1, the reaction temperature is 150 ℃, the adsorption time is 90 min, and
the composition of the mixture showed in Table 1. During the heat regeneration process, the total
gas flow rate is 180 ml/min, the air speed is 9500 h-1. The concentration and strength of the
composition in the mixture is calibrated by the infrared absorption method.
Table 1: The composition of the mixed gas.
SO2 / ppm NO / ppm NH3 / ppm O2 / % N2

Concentration 1000 500 500 5 balance
2.2 Experimental repeatability verification

The adsorption experiment and the regeneration experiment were both repeated 3 times and the
results were shown in Fig. 1. It can be seen, when the adsorption- regeneration evaluation device
was used for the experiment, the results of the adsorption and regeneration experiments of the
carbonaceous adsorbent have good repeatability.
Fig. 1: Adsorption and regeneration curve. a: adsorption curve; b: generation curve.
3 RESULTS AND DISCUSSION

3.1 Regeneration in the nitrogen atmosphere
Nitrogen could worked as the heat-carrying agent to heat and regenerate the carbonaceous
adsorbent after taking part in the desulfurization and the denitrification reactions, and at the same
time it could avoid excessive carbon consumption during the regeneration process, and thus in favor
of reducing the heating regeneration cost. Therefore, when the activated coke was heated and
regenerated in N2 atmosphere, the effects of the heating rate, the regeneration temperature and the
regeneration time for the regeneration performance of the regenerated activated coke were studied
in this study.
The effects of the heating rates on the denitration performance, the desulfurization performance
and the SO2 recovery rate of the regenerated activated coke and the carbon consumption during the
thermal regeneration process were shown in Fig. 2. The heating rates had significant influence on
the denitration performance of the regeneration activated coke with the maximum denitration
performance at 10 ℃/min, but the effects on the carbon consumption and the desulfurization
performance of the regeneration activated coke were almost negligible. As shown in Fig. 2, SO2
recovery rates gradually increased with the increasing heating rates, and that was probably because
the larger heating rates led to the thermal decomposition reactions of the active functional groups
with strong reducibility, and thus that reduced the reaction rates between the active functional
groups and sulfuric acid, e.g. the reaction between H2SO4 and C(O) on the surface of the absorbent.
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In addition, with the increase of the heating rates, C/SO2 increased gradually, indicating that the
amount of the side effects during the reaction increased.
Fig. 2: The effect of the heating rate (Experimental parameters: the regeneration temperature was 400°C, the regeneration time was
120 min). a: Denitrification efficiency; b: Desulfurization efficiency; c: Carbon consumption; d: C / SO2 and SO2 recovery.
The effects of the regeneration temperature on the denitration performance, the desulfurization
performance and the SO2 recovery rate of the regenerated activated coke and the carbon
consumption during the thermal regeneration process were shown in Fig. 3. The increase of the
regeneration temperature was beneficial for the denitration performance and the SO 2 recovery rate
of the regenerated activated coke, as well as the increase of the carbon consumption, but the
obvious regularity influence of that on the denitration performance of the regenerated activated
coke was not found. With the increase of the regeneration temperature, C/SO2 gradually increased,
indicated that the amount of the side reactions was increased, e.g., the amount of the thermal
decomposition reaction of carboxyl, lactonic group and other oxygen-containing functional group
were increased, and that might be the main reason for the increase of the carbon consumption
during the thermal regeneration process.
Fig. 3: The effect of the regeneration temperature (Experimental parameters: the heating rate was 10°C / min, the regeneration time
was 120 min). a: Denitrification efficiency; b: Desulfurization efficiency; c: carbon consumption; d: / SO2 and SO2 recovery.
952
The effects of the regeneration time on the denitration performance, the desulfurization
consumption during the thermal regeneration process were shown in Fig. 4. The regeneration time
had a certain impact on the denitration performance of the regenerated activated coke, but no
obvious regularity was found. Moreover, the effects of the regeneration time on the desulfurization
performance and the SO2 recovery rate of the regenerated activated coke could be neglected. With
the increase of the regeneration time, the carbon consumption during the thermal regeneration
process firstly increased to a maximum, and then almost remained at that constant after all. That
was probably because, under that regeneration experimental conditions, when the regeneration
time was over 90 minutes, the reactive functional groups on the surface of the active coke with low
thermal stability were already decomposed, considering the varying pattern of C/SO2.
Fig. 4: The effect of the regeneration time (Experimental parameters: the heating rate was 10℃/ min, the regeneration temperature
was 350°C). a: nitrification efficiency; b: sulfurization efficiency; c: Carbon consumption; d: C / SO2 and SO2 recovery.
3.2 Regeneration in the atmosphere with NH3

NH3 was added in the N2 atmosphere, and then the carbonaceous adsorbent after taking part in the
desulfurization and the denitrification reactions was heated and regenerated. During the heating
regeneration process, NH3 with strong reducibility, reacted with active coke, and therefore N in NH3
was fixed on the surface of the active coke and the alkaline functional groups of regenerated active
coke were increased, leading to the increase of the desulfurization and the denitrification
performance of active coke [9-11].
When the activated coke was heated and regenerated in NH3 atmosphere, the effects of the heating
rate, the regeneration temperature, the concentration of NH3 and the regeneration time for the
regeneration performance of the regenerated activated coke were studied.
thermal regeneration process were shown in Fig. 5. The heating rates had great influence on the SO2
recovery rate and C/SO2 of the regenerated activated coke as well as the carbon consumption during
the thermal regeneration process, but the effects of that on the desulfurization performance of the
regenerated activated coke could be neglected. With the increase of the heating rates, the carbon
consumption during the thermal regeneration process firstly increased to a maximum, and then
953
almost remained at that constant after all. In addition, with the increase of the heating rates, C/SO2
and SO2 exhibited changes of a fluctuating, that was probably because the larger heating rates might
have influence on the distribution of NH3.
Fig. 5: The effect of the heating rate (Experimental parameters: the regeneration temperature was 400°C, the NH3 concentration was
3%, the regeneration temperature was 120 min). a: Denitrification efficiency; b: Desulfurization efficiency; c: Carbon consumption; d: C
/ SO2 and SO2 recovery.
Fig. 6: The effect of the regeneration temperature (Experimental parameters: the heating rate was 10 ℃/min, the NH3 concentration
was 3%, the regeneration time was 120 min). a: Denitrification efficiency; b: Desulfurization efficiency; c: Carbon consumption; d: C /
SO2 and SO2 recovery.
The effects of the regeneration temperature on the denitration performance, the desulfurization
consumption during the thermal regeneration process were shown in Fig. 6. With the increase of the
regeneration temperature, the denitration performance, the desulfurization performance and the
SO2 recovery rate of the regenerated activated coke as well as the carbon consumption during the
thermal regeneration process both increased gradually. High regeneration temperature was in favor
of the sulfur-ammonium salt decomposition reaction, sulfate reduction reaction and the reaction of
the activated coke and NH3, and that led to producing more active functional groups, e.g. pyridine-N
954
and pyrrole-N, which might be the reason for the improvement of the denitration performance and
the desulfurization performance of the regenerated activated coke [12,4,11,13-15]. Besides,
according to the variation of C/SO2, improving the regeneration temperature might be more
conductive to the thermal decomposition reaction of the oxygen containing function groups,
comparing to the sulfate reduction reaction.
The effects of the concentration of NH3 on the denitration performance, the desulfurization
consumption during the thermal regeneration process were shown in Fig. 7. The addition of NH3 in
the atmosphere was in favor of the promotion of the denitration performance and the
desulfurization performance of the regenerated activated coke, e.g. the denitration performance of
the regenerated activated coke gradually increased with the increase of the concentrations of NH3
and reached a maximal at the concentration of 3%, and then decreased. However, the increase of the
desulfurization performance had nothing to do with the concentration of NH3. With the increase of
the concentration of NH3, the SO2 recovery rate of the regenerated activated coke was gradually
decreased, and that was probably because NH3 in the atmosphere hindered the sulfate reduction
reaction. Besides, the addition of NH3 in the regenerated atmosphere promoted the carbon
consumption during the thermal regeneration process, and when the concentrations of NH3 were 3%
and 5%, the increase of the carbon consumption was the least. The concentration of NH3 had a
certain impact on C/SO2, but no obvious regularity was found. The value of C/SO2 was the minimum
as the concentration of NH3 was 1% and the addition of NH3 in the atmosphere reduced the side
reactions in the thermal regeneration process, at that time, except that, the addition of NH3
increased the side reactions in the thermal regeneration process.
Fig. 7: The effect of NH3 concentration (Experimental parameters: the heating rate was 10℃/min, the regeneration temperature was
350℃, the regeneration time was 120 min). a: Denitrification efficiency; b: Desulfurization efficiency; c: Carbon consumption; d: C / SO2
and SO2 recovery.
consumption during the thermal regeneration process were shown in Fig. 8. With the increase of the
regeneration time, the denitration performance, the desulfurization performance and the SO 2
recovery rate of the regenerated activated coke both increased gradually, and the carbon
consumption during the thermal regeneration process firstly decreased to a minimum, and then
955
almost remained at that constant after all. The long regeneration time was in favor of the reactions
of NH3 and active coke proceeding to completion in the regeneration atmosphere, and thus more
active functional groups (pyridine-N and pyrrole-N), which were beneficial to improve the denitration
performance and the desulfurization performance, were produced. With the increase of the
regeneration time, the decrease of C/SO2 indicated that regeneration in the atmosphere with NH3
could effectively inhibited the thermal decomposition reactions of the oxygen containing functional
groups, and that was in agreement with the results of [16].
Fig. 8: The effect of the regeneration time (Experimental parameters: the heating rate was 10℃/min, the regeneration temperature
was 350℃, the NH3 concentration was 3%). a: Denitrification efficiency; b: Desulfurization efficiency; c: Carbon consumption; d: C / SO2
and SO2 recovery.
3.3 Regeneration in the atmosphere with H2O

H2O was added in the N2 atmosphere, and then the active coke after taking part in the
desulfurization and the denitrification reactions was heated and regenerated. During the
regeneration process, because of the high regeneration temperature, the active coke could react
with water in the gas phase. The chemical reactions are as follows.
C+2H2 O→CO2 +2H2 (1)
C+H2 O→H2 +CO (2)
The occurrence of such reactions above leaded to the increase of carbon consumption during the
regeneration process, but on the other hand, they also could increase the number of the active
functional groups and micropores on the surface of the active coke, which are beneficial to the
desulphurization and denitrification reactions of the active coke.
Therefore, when the activated coke was heated and regenerated in H 2O atmosphere, the effects of
the heating rate, the regeneration temperature and the regeneration time for the regeneration
performance of the regenerated activated coke were studied in this study.
thermal regeneration process were shown in Fig. 9. The heating rates had great influence on the
desulfurization performance and the SO2 recovery rate of the regenerated activated coke, but the
effects of that on the denitration performance of the regenerated activated coke and the carbon
consumption during the thermal regeneration process could be neglected. With the increase of the
956
heating rates, the SO2 recovery rate of the regenerated activated coke decreased gradually, but
C/SO2 increased gradually, indicating that the increase of the heating rates contributed to the
increase of the amount of the side reaction in the heating regeneration process.
Fig. 9: The effect of the heating rate (Experiment parameters: the regeneration temperature is 400 ℃, the water vapor concentration is
5%, the regeneration time is 120 min). a: Denitrification efficiency; b: Desulfurization efficiency; c: Carbon consumption; d: C / SO2 and
SO2 recovery.
thermal regeneration process were shown in Fig. 10. With the increase of the regeneration time, the
desulfurization performance and the SO2 recovery rate of the regenerated activated coke, the
carbon consumption during the thermal regeneration process as well as C/SO2 both increased
gradually. Thereinto, the main reason for the increase of the carbon consumption might be that the
high regeneration temperature promoted the increase of the amount of the side reactions. The
regeneration temperature had a certain impact on the denitration performance of the regenerated
activated coke, but no obvious regularity was found.
Fig. 10: The effect of the regeneration temperature (Experiment parameters: the heating rate is 10 ℃/min, the concentration of water
vapor is 5%, the regeneration time is 120 min). a: Denitrification efficiency;b: Desulfurization efficiency; c: Carbon consumption; d: C /
957
The effects of the concentration of water vapor on the denitration performance, the desulfurization
consumption during the thermal regeneration process were shown in Fig. 11. In the regeneration
atmosphere, the concentration of water vapor had great influence on the carbon consumption
during the thermal regeneration process, but the impacts of that on the denitration performance,
the desulfurization performance and the SO2 recovery rate of the regenerated activated coke could
be neglected. With the increase of the concentration of water vapor, the carbon consumption during
the thermal regeneration process firstly increased to a maximum, and then almost remained at that
constant after all. That was probably because the chemical reactions between the activated coke and
the water vapor increased with the increase of the concentrations of the water vapor, but for the
activated coke having limited reaction interfaces, the carbon consumption remained almost at a
constant after the water vapor reach a certain concentration.
Fig. 11: The effect of water vapor concentration (Experiment parameters: the heating rate is 10 ℃/min, the regeneration temperature
is 350 ℃, the regeneration time is 120 min). a: Denitrification efficiency; b: Desulfurization efficiency; c: Carbon consumption; d: C / SO2
and SO2 recovery.
consumption during the thermal regeneration process were shown in Fig. 12. The effects of the
regeneration time on the desulfurization performance of the regenerated activated coke could be
neglected, but with the increase of the regeneration time, the SO 2 recovery rate of the regenerated
activated coke, the carbon consumption during the thermal regeneration process and C/SO2 both
increased. Therefore, it could be concluded that, compared to the reduction reaction of H 2SO4, the
thermal decomposition reactions of the active functional groups were more likely to happen.
958
Fig. 12: The effect of the regeneration time (Experiment parameters: the heating rate is 10 ℃/min, the regeneration temperature is
350 ℃, the concentration of water vapor is 5%). a: Denitrification efficiency; b: Desulfurization efficiency; c: Carbon consumption; d: C /
4 CONCLUSIONS
In order to investigate the influence of the heating rate, the regeneration temperature, the
concentration and the regeneration time on the desulphurization and denitrification performance of
the regenerated active coke, the carbon consumption during the heating regeneration process and
the recovery rate of SO2, the self-built experimental device was selected and the regenerated
activated coke was heated in N2, NH3 and H2O atmosphere, respectively. It was found that whether
the active coke heated and regenerated in N2 or NH3 atmosphere, the regeneration temperature had
the greatest effect on the desulphurization and denitrification performance of active coke, the
carbon consumption during the heating regeneration process and the recovery rate of SO 2; the
regeneration time only had effect on the denitrification performance of active coke, the carbon
consumption during the heating regeneration process and the recovery rate of SO 2; the heating rate
had great effect on the carbon consumption during the heating regeneration process and the
recovery rate of SO2. When active coke heated and regenerated in NH3 atmosphere, the
desulphurization and denitrification performance of active coke was increased, but the recovery rate
of SO2 was decreased. When active coke heated and regenerated in H2O atmosphere, the
desulphurization and denitrification performance of active coke was essentially unchanged, but the
carbon consumption during the regeneration was improved. When recovery sulfur is the main
purpose, it is suitable for active coke to heat and regenerate in N2 atmosphere. However, when
restoring the desulfurization and denitrification performance of active coke is the main purpose, it is
suitable for active coke to heat and regenerate in NH3 atmosphere. The above conclusion could
provide a certain theoretical basis for seeking better thermal regeneration conditions.
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960
Proceedings - WasteEng2018 Conference - Prague - July 2-5,2018
ECO SUSTAINABLE RAIL: PRODUCTION OF SUSTAINABLE RAILWAY SLEEPERS FROM

MIXED PLASTICS WASTE
B. P. SILVA1*, J. P. NUNES,1,2 M. C. PAIVA,1,2, J. GONÇALVES,1 A. VILELA,1 A. MARQUES1, S. CASTRO3, R.

RODRIGUES3, J. AMARO3, S. SANTOS4, P. GAIATO4
1 PIEP, Innovation in Polymer Engineering, Campus de Azurém, 4800-058 Guimarães, Portugal
2 Institute for Polymers and Composites, Minho University, Campus de Azurém, 4800-058 Guimarães,
Portugal
3 Extruplás, Rua dos Serralheiros, Estrada do Marco do Grilo, 6, Paio Pires, 2840 Seixal
4 IP, Infraestruturas de Portugal, Campus do Pragal, Praça da Portagem, 2809-013 Almada
Abstract
Plastic materials production and consumption had an exponential growth due to their unique
properties, becoming one of the most used materials in the last century. As a consequence large
volumes of plastic waste is produced, part of which can be separated and recycled. A large fraction
of the plastic waste does not find recycling solutions (Mixed Plastics Waste, MPW) being frequently
landfilled at End-of-Life (EoL). It is imperative to find new solutions for MPW valorization into added-
value products. An interesting application is the manufacture of Plastic Lumber (PL) to produce
plastic posts for non-demanding applications. Our objective is to improve the properties of PL
produced from MPW to provide it with the required characteristics for railway sleeper applications.
Currently, there is a request for viable solutions for the replacement of wood railway sleepers, for
application where concrete sleepers cannot be used [1].
The ECO SUSTAINABLE RAIL project focuses the preparation and characterization a new composite
materials based on MPW/glass fibres obtained by extrusion compounding. Prototype eco-friendly
railroad plastic-sleepers will be produced by intrusion and will be characterized and tested in
simulated operating conditions on a test track. MPW-based materials present low mechanical
properties; within the project the properties of the composites were increased to reach a tensile
modulus of 4,6 GPa. Other relevant properties such as electrical, thermal and flammability
properties, dimensional stability are being adjusted to the necessary performance to meet the
requirements of ISO/DIS 12856, the International Standard for Plastic Railway Sleepers.
The project ECO SUSTAINABLE RAIL aims at contributing with a technical solution with a positive
impact on the EoL problem of MPW, aligned with the principles of circular economy.
References
[1] European Parliament and European Union Council, Directive 2008/98/CE from 19 November 2008, J. of the
European Union, vol. 321, pp. 3-30,2008
961
Authors Index
A.C.MATOS, L. 833 AMARO, J. 962
A.MOLINARES, M. 833 AMAYA, L. 656
A.R.MAIA, G. 833 AMUTIO, M. 925, 926
ABAKR, Y. 670 ANDRE, L. 631
ABANADES, S. 704 ANDREOLA, F. 99
ABD RAHMAN, N.J. 683 ANDRES, A. 515, 850
ABDULKADIR, B. A. 847 ANDRES, Y. 142, 493
ADELARD, L. 145 ANGELIDAKI, I. 297
ADELODUN, A. 804 ANTELO, L.T. 398
ADISTY, D. 164 ANTELO, LUIS. 863
AFFES, R. 590, 633 ANTHEAUME, N. 284
AGAR, D.A. 391, 392, 488, 489 ANTOLINI, D. 196, 267, 308, 510, 550, 867
AGOUDJIL, B. 326, 924 ANTONOPOULOU, G. 254, 634, 845
AGUIAR, M. 723 AOUN, M. 498
AGUILAR LASSERRE, A. 427 ARANCIBIA-MIRANDA, N. 608
AGUILAR USCANGA, M.G. 874 ARCE, C. 669
AGUILAR-USCANGA, M.G. 887 ARENA, U. 35, 60
AHO, A. 298 AREVALO-PEREZ, V.K. 185
AHOU, S. 142 ARLABOSSE, P. 323, 594
AHRENFELDT, J. 49 ARPIAINEN, V. 931
AIL, S. 510 ARREGI, A. 926, 927
ALAMI, D.E. 195 ARROYO CAIRE, J. 645, 685, 741
ALAROTU, M. 523, 931 ARTETXE, M. 926, 927
ALBET, J. 654 ARTOLA, A. 299
AL-DHAFEERI, A. 272 ARVANITIS, T. 932
ALEXANDROPOULOU, M. 254, 634 ASCENSÃO, G. 173
ALIOUA, T. 924 ASIMAKOPOULOS, K. 264
ALMQVIST, J. 490 ASSAOUI, J. 721
AL-NASSER, A. 272 ASTUTININGSIH, S. 164, 242
ALONSO, J. 680 ATHANASOPOULOU, S. 517
AL-SALEM, S. 272 ATONG, D. 610, 921
ALSAYED MAHMOUD, K. 497, 498 AVELLA-FERNANDEZ, E.I. 362
ALVARENGA, N. 465 AWAD, S. 592, 607
ALVAREZ, J. 925, 926 AWE, O.W. 495
ALVAREZ-MURILLO, A. 112 AZUMA, D. 520
AL-WADI, M. 272 AZZARO-PANTEL, C. 427
962
BA, M.S. 650 BEZIAN, J.J. 244
BABA-MOUSSA, L.S. 142 BHUJADE, R. 630
BACQUET, M. 706 BIANCHI, D. 703
BADOS, R. 688 BILLEN, P. 114
BAHILLO, A. 347 BIOTEAU, T. 67
BAJÓN FERNÁNDEZ, Y. 144 BIZZO, W.A. 835
BALME, Q. 270 BLANC, D. 377, 869
BAQUERO, M. 850 BLOCK, C. 183, 509
BARAKAT, A. 195 BOUDENNE, A. 326, 924
BARATIERI, M. 110, 196, 267, 372, 399, 510, 514, 550, 567, 597, BOUDHAN, R. 240, 591
783, 866, 867, ZWART, R. 416
BARBARIAS, I. 926, 927 BOURAS, F. 326
BARBIERI, L. 99 BOURTSALAS, A. 343, 511
BARBOSA, B. 68 BOUTOUIL, M. 691
BAREHA, Y. 108 BOUYSSET, J-P. 389
BARNA, R. 649, 859, 908 BOUZIDI, Y. 284
BARREIROS, A. 704 BOVIATSI, E. 700
BARRENA, R. 945 BOWDEN, N. 596
BARRETO ROCHA, T. 116 BRAS, T. 534, 929
BARRO, R. 688 BRIGHENTI, M. 308
BASILE, F. 703 BRILMAN, W. 660
BASSEGUY, R. 949 BROSSE, J. 344
BASSET, E. 106 BRUINS, M. 596, 611
BASSO, D. 510, 514, 597 BUCKLEY, C.A. 573
BASTIDE, A. 145 BUEKENS, A. 652
BAUTISTA ANGELI, J-R. 493 BUN, K. 87
BAYARD, R. 106 BUN, P. 87
BAYONA, A. 243 BURONFOSSE, M. 284
BELGIORNO, V. 418 BUSSEMAKER, M. 307
BELINE, F. 105, 193 BUTLER, S. 410
BELLO BUGALLO, P. 126, 348, 477, 742, 773, 934 BYSTEDT, A. 524
BELO, A. 929 CABALLERO IGLESIAS, B. 680
BELON, C. 543 CABALLERO-JAIMES, J. 692
BELTRÁN-ARREDONDO, L. 874, 887 CAETANO, A. 704, 909
BEN ATITALLAH, I. 254, 634 CAETANO, N. 854
BENBELKACEM, H. 321 CAILLET, H. 145
BENEDETTI, V. 372, 510, 567, 783 CALDEIRA, C. 612, 653
BENZARTI, K. 924 CALIGIURI, C. 267, 867
BENZERTI, K. 326 CAMPARGUE, M. 391, 392, 424, 489, 492
BERDUGO, A. 849 CÁRDENAS AGUIAR, E. 160, 397
BERGE, N. 112 CARHUARICRA, Y. 687
BERGEL, A. 949 CARRERE, H. 195
BERMUDEZ, A. 325 CARVALHEIRAS, J. 728
BERTAU, M. 586, 702 CARVALHEIRO, F. 345
BETTUCCI, L. 162 CASINI, D. 162, 597
BEZERGIANNI, S. 603 CASLAVSKY, J. 333
963
CASTALDI, M. 110 COUVERT, A. 605
CASTANÓN, S. 582 COZ, A. 669
CASTLEMAN, B. 436 CRESPO, J.P. 534
CASTRO MARTÍNEZ, C. 874 CREST, M. 158, 601
CASTRO, P. 854 CRISTOBAL, J. 612
CASTRO, R. 806 CRNKOVIC, P.M. 755
CASTRO, S. 962 CRUZ, G. 755
CASTRO-MARTINEZ, C. 887 CULOTTE, F. 348
CASTRO-OCHOA, LELIE. 887 CUTARD, T. 587
CAVANI, F. 703 CYR, M. 87
CERDA, A. 945 DA LUZ PEREIRA RODRIGUES, A. 807
CERMÁKOVÁ, A. 144, 464 DA SILVA PEREZ, D. 392, 393, 948
CESARO, A. 418 DA SILVA, J.A. 700
CHANG, Z. 358, 522, 868, 871 DA SILVA, S. 649, 908, 949
CHAPRON, M. 543 DABERT, P. 141, 193
CHARVIN, P. 270 DAILIANIS, S. 845
CHATAIN, V. 106 DALMO, F. 499
CHATROUX, A. 525, 526 DAS, S. 518, 519
CHAUCHERIE, X. 706 DAUMOIN, M. 605
CHEN, D. 324 DE ALMEIDA FELIPE, M.d.G. 803
CHEN, G. 324, 950 DE BRAUER, C. 377, 869
CHEN, J. 944 DE GUARDIA, A. 605
CHEN, W-H. 102, 682 DE MARCO, I. 680
CHENNA, N. 669 DEFOORT, F. 492
CHENNOUF, N. 326, 924 DEGUEURCE, A. 694
CHENZHEN, Y. 793 DEL CASTILLO LLAMOSA, A. 477, 773
CHI, Y. 159, 217, 323, 343, 462, 467, 569, 589, 681 DELALONDE, M. 543
CHIABERGE, S. 703 DELL'ORCO, S. 162
CHIARAMONTI, D. 162, 510, 597 DELVASTO, P. 692
CHO, S. 283 DENG, Y. 531
CHOJNACKA, K. 513 DETLINGER, P. 833
CHORAZY, T. 333, 379 DHIBA, D. 195
CHUNG, J-D. 740 DI CIOCCO, M. 395
CIFRIAN, E. 515, 850 DI STASI, C. 568
CIUTA, S. 110 DIAZ-CHAVEZ, R. 603
CIVILYTE, A. 693 DIGAN, L. 329
CLAUWAERT, P. 660 DIMITRIOU, T. 618
COBO, S. 658 DING, S. 950
COLIN, B. 320 DOMINIGUEZ-RAMOS, A. 658
CONRAD, S. 163, 603 DONG, J. 217, 650, 681
CONTRERAS ANDRADE, I. 874 DOOLEY, S. 332, 602
CORDIOLI, E. 372, 510, 783, 866 DOUCET, F. 436, 437
CORRADO, S. 612, 653 DRAKOPOULOS, V. 845
CORTAZAR, M. 925, 927 DU, C. 920
COSTA, B. 116 DU, W. 657
COSTA, J. 68, 662 DUARTE, F. 465, 534, 929
964
DUARTE, L.C. 345 FREIRE, D. 700
DUBA, K. 865 FREIRE, M.S. 475
DUBOS, S. 329 FUENTES CANO, D. 60, 741, 849
DUCOM, G. 560 GAIATO, P. 962
DUEÑAS, P. 41 GALERA-MARTINEZ, M. 106
DUMAS, C. 265, 329, 361 GALIER, S. 361
DUPONT, C. 393, 394, 424, 489, 491, 492, 526, 948 GANE, J. 369, 613
DURECU, S. 240, 591 GARCÍA HARO, P. 685
DURET, X. 344 GARCÍA RELLÁN, A. 126, 934
DUSSAN, K. 332, 512, 602 GARCIA-DEPRAECT, O. 185
DUTOUQUET, C. 240, 591 GARCIA-ESTRADA, R. 362
DUTTA, A. 373, 529 GARCIA-PEREZ, M. 698, 872
EIBES, G. 834 GARCÍA-SANTIAGO, X. 863
EL HASSOUNI, F. 869 GASCO, G. 160, 397
ELHAMI, O-H. 49 GAUTHIER, D. 911
ENGLUND, F. 524 GAUTIER, M. 560
EPHRAIM, A. 461 GAVALA, H. 184, 264, 328
ERABLE, B. 949 GAZTELU, N. 680
ERÄNEN, K. 298 GCOBO, B. 824
ERNST, B. 265 GEA LEIVA, T. 945, 946
ESCUDERO-SANZ, F.J. 899 GEORGIOU, P. 898
ESPINOSA MODOLO, R.C. 173, 218, 880 GERENTE, C. 58
ESTEBAN, L. 688 GERMAIN, P. 321
FACHE, A. 566 GHANIM, B. 861
FALCOZ, Q. 140, 172, 244 GIRAULT, R. 108, 590, 633
FASQUELLE, T. 244 GIRODS, P. 320
FEIJOO, G. 584, 863 GLAUBER CRUZ, G. 807
FELSBERGER, W. 550 GOELLES, M. 550
FERNANDES, M.d.C. 345 GOETZ, V. 140, 172
FERNANDEZ, E. 925, 926 GOLLAKOTA, A. 533
FERNANDEZ, M. 848 GOMES, S. 465
FERNANDO, A.L. 68, 662 GÓMEZ-BAREA, A. 512, 645, 685, 741, 849
FERREIRA DE ALMEIDA, V. 645, 685, 741 GONÇALVES, J. 962
FERREIRA, B. 739 GONÇALVES, M. 574
FERREIRA, K. 723 GONZALES, E. 687, 862
FERREIRA, V.M. 173 GONZÁLEZ DURÁN, F. 934
FIANI, E. 240, 591 GONZALEZ RODRIGUEZ, M. 427
FIORI, L. 161, 570, 604, 865 GONZALEZ RUIZ, A. 595, 608
FISGATIVA, H. 105, 141 GONZALEZ, B. 568
FLAMANT, G. 244, 911 GONZÁLEZ-ÁLVAREZ, J. 475
FLORIANI ANDERSEN, S.L. 784 GONZALEZ-GARCIA, S. 426, 584
FONT SEGURA, X. 946 GONZALEZ-MARTINEZ, M. 393, 526, 948
FONT, X. 299 GONZÁLEZ-RODRÍGUEZ, J. 475
FONTAINE, P. 859 GOSSET, T. 706
FONTSERE OBIS, M. 321 GOURDON, C. 393, 948
FRANCO-URÍA, A. 398, 863 GOURDON, R. 560
965
GRACHEV, A. 163 HIPPMANN, S. 586
GRATEAU, M. 948 HIRAI, H. 864
GREGOR, J. 870 HLAVINEK, P. 333, 379
GRIGIANTE, M. 196, 308 HOFFMANN, J-F. 140, 172
GRIMALT-ALEMANY, A. 328 HOLLENSTEIN, C. 550
GRONIER, T. 742 HOLMBERG, H. 524
GRONNOW, M. 410 HORCKMANS, L. 521
GROOTJES, S. 416 HORNUNG, A. 686
GROUSET, D. 375, 899 HORVAT, A. 197
GRZELAK, J. 583 HSIAO, K-J. 920
GU, J-H. 269 HU, Y. 113, 323, 600, 920, 928
GUALDRON, A. 325 HUACCACHI, W. 687
GUDKA, B. 410, 613 HUANG, Q. 343, 569, 589
GUÉ, É. 543 HUNG, W-C. 947
GUERRE, V. 566 HURON, M. 526, 707
GUILAYN, F. 158, 601 HURST, P. 410
GULLON, B. 834 HWANG, O. 283
GULLÓN, B. 426, 584 HWANG, S-K. 920
GULLÓN, P. 426, 584, 834 HWANG, Y. 729
HAARLEMMER, G. 524 HYUN, J. 729
HAGNER, M. 421 HYVALUOMA, J. 423
HAJJAJI, W. 689 IAKOVLEVA, A. 163
HAMMOUD, O. 869 IDIR, R. 87
HAN, D.W. 283 IKHU-OMOREGBE, D. 42, 644, 824
HANNULA, M. 423 INGA, A. 687, 862
HARIZAJ, F. 845 IRABIEN, A. 658
HARO, P. 512, 645, 741, 849 IZAGUIRRE CAMPOVERDE, J.K. 582
HASHIM, H. 594 IZYDORCZYK, G. 513
HASOLLI, N. 737, 740 JANNOT, Y. 320
HASSAINE, O. 497 JANOSTAK, F. 870
HAWANGCHU, Y. 922 JANTOVA-PATEL, J. 144
HE, P. 705 JANZON, R. 599
HE, X. 324 JAUDOIN, C. 105
HEBERLEIN, M. 686 JEFFERSON, B. 464
HEIKKINEN, J. 423 JEFFREY, P. 464
HÉLIAS, E. 899 JENSEN, K.N. 97
HENRIKSEN, U.B. 49 JEON, S-M. 737, 740
HERLOEV, M.E. 97 JEONG, D.W. 804
HERNANDEZ, D. 738 JIANG, J. 533
HERNÁNDEZ-LEYVA, S. 887 JIANG, X. 229, 467
HERNÁNDEZ-PEREZ, A. 803 JIMENEZ, J. 158, 601
HERNANDEZ-SANCHEZ, P. 873 JIN, Y. 229
HERSKOWITZ, M. 632 JING, H. 920
HERVY, M. 206 JIROUT, T. 322
HIETALA, D. 533 JO, Y.M. 804, 805
HILIGSMANN, S. 497, 498 JONES, J. 410, 613
966
JORGE, V. 574 KRZYSTEK, L. 583, 710
JOUBERT, A. 240, 591 KUBICKA, D. 603
JUE, Z-F. 920 KUCERIK, J. 379
JULIO, R. 654 KUKURUGYA, F. 521
JUMBRI, K. 683 KULJU, S. 423
JUNG, C.G. 389 KUMAR, N. 298, 374
JUNG, D. 604 KUO, Y-T. 459
KADI, M.E.A. 592 KUTSAY, A. 322
KAHINE, K. 607 KWAPINSKA, M. 197, 309
KALARIKKAL, N. 708 KYRIAKOU, M. 700
KALÉN, G. 391 KYZAS, G. 855
KÄLLI, A. 421, 423, 527 LABIDI, J. 426, 584, 834
KANG, C. 593 LABRINCHA, J. 173, 689, 690, 728
KANHAR, A.H. 435 LACROIX, R. 949
KANO, J. 331 LADAKIS, D. 701
KAPPLER, G. 218 LAKEL, A. 493
KAR, S. 114 LANCELLOTTI, I. 99
KARAM, H. 272 LANDAU, M. 632
KARAM, N-E. 497 LÄNGAUER, D. 682, 858
KARL, J. 138 LANGE, C. 138
KASSARGY, C. 607 LANZERSTORFER, C. 430
KATZ, B. 114 LARGEAU, J-F. 823
KAUR, G. 359 LARSSON, S. 930
KAWAMOTO, H. 370 LARSSON, S.H. 391, 392, 424, 488, 489
KAWI, S. 528 LAVENAN, K. 193
KAZI, F. 670 LAVERGNE, S. 424
KEILANY, M.A. 244 LAVOIE, J-M. 59, 344
KHERIBECH, A. 721 LAZE, P. 845
KHOLKINA, E. 374 LE BIHAN, O. 240, 591
KIM, A. 805 LE COQ, L. 240, 591
KIM, H. 910 LE FLOC'H, T. 493
KIM, J. 729 LE ROUX, S. 605
KIM, J.H. 805 LEAHY, J.J. 197, 309
KIM, K-D. 737, 740 LEA-LANGTON, A. 613
KIM, S.B. 804, 805 LEANG, S. 284
KIRKELUND, G.M. 97 LEBRIHI, A. 195
KIRKMAN, R. 613 LEDAKOWICZ, S. 583, 710
KOLIOS, A. 573 LEE, J. 307
KONECNÁ, E. 709 LEE, J-R. 737, 740
KORKOLIS, A. 897 LEE, K-S. 737, 740
KORNAROS, M. 517 LEE, S.R. 283
KÖRNER, I. 417 LEGRAND, J. 180
KOUTINAS, A. 700, 701 LEHTONEN, J. 374
KRAFT, M. 702 LEKKAS, D.F. 932
KRATKY, L. 322 LEMONT, F. 270, 684
KRUSE, A. 604 LENDORMI, T. 193
967
LEÓN-BECERRIL, E. 185, 535 LYBERATOS, G. 254, 516, 618, 634, 845, 897, 898
LEPEZ, O. 526, 707 LYCZKO, N. 648
LESTANDER, T.A. 488 LYMPERATOU, A. 184
LEU, S-Y. 920 LYTRAS, C. 618
LEVACHER, D. 691 LYTRAS, G.M. 516, 618
LI, B.G. 657 MA, W. 324
LI, C. 581 MABBETT, I. 573
LI, H. 600 MABROUK, M. 684
LI, Q. 696 MAGÁN, A. 475
LI, R. 911 MAGANA, G. 656
LI, W. 522 MAGNIN, R. 684
LI, X. 522, 581, 920 MÄKI-ARVELA, P. 298
LI, Y. 705, 950 MALDINA, M. 308
LI, Z. 600 MANCIO, M. 880
LIBRA, J. 112 MANYA, J. 568
LIETO, A. 395 MANYUCHI, M. 42
LIM, J.W. 847 MARCHAND, M. 424, 492, 525, 526, 526, 684
LIN, B-J. 682 MARCILHAC, C. 105
LIN, C.S.K. 359, 581, 920 MARIA, M. 807
LINDFORS, C. 374 MARIAS, F. 270, 566, 860
LINDQVIST, I. 421 MARIN GALLEGO, M. 476
LIU, C.-F. 947 MARKSTRÖM, E. 524
LIU, H. 923 MAROÑO, M. 848
LIU, J. 429 MARQUES, A. 854
LIU, M. 545 MARQUES, Â. 962
LLANO, T. 515, 669 MARTIN, M. 603
LOIZIDOU, M. 76, 182 MARTINI, S. 550
LOMBARDI, F. 395 MARTINS, A. 465
LONGHURST, P. 420 MARTINS, G. 499
LÓPEZ BARREIRO, D. 660 MARTINS, P. 345
LOPEZ GONZALEZ, P.L. 241 MARUM, L. 929
LOPEZ, D.P. 738 MARX, S. 609
LOPEZ, G. 925, 926, 927 MARZI, T. 428
LOPEZ-FERBER, N. 140, 172 MÁSA, V. 709
LOPEZ-URIONABARRENEC, A. 680 MATAYEVA, A. 703
LOTTI, G. 597 MATEJ, B. 271
LOUBAR, K. 592 MATHIOUDAKIS, D. 618
ZWART, R. 416 MATYKA, M. 710
LU, P. 343 MAUVIEL, G. 206
LU, S. 467, 651, 652 MAZZA, G. 911
LU, Y. 113 MECHICHI, T. 254, 634
LUCIAN, M. 161, 570, 604 MEDEIROS CARDOZO, N.S. 243, 325
LUCKE, S.A. 285, 286 MEDEIROS, C.M.d. 784
LUPSEA-TOADER, M. 377, 869 MEDHIOUB, M. 689
LUTHER, A. 660 MEDINA, A.C. 449, 499
LV, G. 229 MEFFRE, A. 140, 172
968
MEJIAS TORRENT, L. 945 MULIAWAN, J. 242
MEJRI, E. 498 MÜLLER, D. 138
MELIN, K. 490, 523, 524 MUNIRATHINAM, R. 588
MELKIOR, T. 424, 489, 525, 526 MURZIN, D.Y. 298, 374
MELO LIMA GOMES, B.F. 784 MUSSATTO, S. 806
MENDES MORAES, C.A. 880 NAHIL, M.A. 369
MENDES, B. 574 NAIDOO, D. 573
MENDEZ, A. 160, 397 NASRI, M. 254, 634
MENGELLE, E. 329 NATARAJAN, G. 519
METCALF, P. 410 NDIAYE, L-G. 650
METIVIER-PIGNON, H. 106 NEBRA, S. 449, 499
MEYER, X-M. 393, 948 NEUBAUER, Y. 49
MICHALAKIDI, S. 516 NEVES, L. 534
MICHALOPOULOS, I. 516, 618 NEWMAN, D. 101
MIGUEZ RODRIGUEZ, L. 948 NGOIE, W.I. 644
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PROCEEDINGS

7th International Conference

July 2-5, 2018

INSTITUT MINES-TELECOM ÉQUIVALENCE QUADRICHROMIE

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This work is licensed under the Creative Commons

Organising Committee Members

H1 - High temperature energy storage

Tuesday - July 3, 2018

A2 - Biorefinery, phytochemical extraction

Wednesday - July 4, 2018

Thursday - July 5, 2018

Lignocellulosic by-products from Brazilian sugarcane agroindustry for biotechnological

Regeneration performances of activated coke and carbon consumption in different

CIRCULAR ECONOMY: A COLLABORATIVE APPROACH TO WASTE MANAGEMENT

CO-GASIFICATION AS A POSSIBLE ALTERNATIVE FOR AN EFFICIENT

SIMULATION OF BIOGAS PRODUCTION FROM SLAUGHTERHOUSE WASTEWATER IN

ANAEROBIC CODIGESTION OF TANNERY AND SLAUGHTERHOUSE SLUDGE

A.B. MPOFU1, P.J. WELZ1, O.O. OYEKOLA1

The innovative incorporation of slaughterhouses and tanneries nowadays as a way of vertically

Table 1: BMP and Biodegradability results

Composition Biogas yield %VS %TS %COD

Please provide a structured one page abstract describing:

Figures, Tables and equations can be included.

SUSTAINABILITY ANALYSIS OF BIOREFINING SCHEMES FOR REVALORIZATION OF

A. SANCHEZ1, S. SANCHEZ1, P. DUEÑAS1

POTENTIAL FOR TREATING DAIRY INDUSTRY WASTEWATER COGENERATING BIOGAS

M. M. MANYUCHI1,2, R. JAMAKAMGA2, D.I.O. IKHU-OMOREGBE1, O.O. OYEKOLA1,2

Keywords: Hycura, bio-catalysis, biogas, integrated waste water management.

2.2.2 Methodology for microfiltration

2.2.3 Methodology for nanofiltration

2.2.4 Biogas production

3. RESULTS AND DISCUSSION

Oil and grease

Total suspended solids

0 200 400 600 800 1000 1200 1400 1600

3.2 Biogas generation

Figure 2: Biogas production temperature profile from the dairy effluent

Methane Carbon dioxide Nitrogen Vapour Trace elements

Figure 3: Composition of biogas from dairy waste water

4. DESCRIPTION OF THE PROPOSED PROCESS

4.2 Flow equalization

4.3 Membrane bioreactor system

4.4 Nano filtration

4.5 Fixed film bio digester

E-22 E-19 Equipment List

Figure 4: Process flow diagram

COMPARISON OF WOOD CHARS FROM GASIFICATION AND PYROLYSIS FOR

G. RAVENNI1, O.H. ELHAMI2, Y. NEUBAUER2, J. AHRENFELDT1, U.B. HENRIKSEN1

2- MATERIALS AND METHODS

Figure 1: Experimental setup diagram

3- RESULTS AND DISCUSSION

Char BET surface area DFT pore volume Density C H N S

Figure 3: Naphthalene breakthrough curves obtained at 250˚C

When experiments were performed at higher temperature (800˚C), the concentration of

Figure 4: Naphthalene breakthrough curves obtained at 800˚C

Figure 5: Toluene breakthrough curves obtained at 800˚C

A similar trend was observed for toluene (Figure 5) at 800˚C.

Char BET surface area DFT pore volume C H N S

VALORIZATION OF MILLET AND BUCKWHEAT HUSKS CHARS IN A FIXED BED AS LOW-

J.PEÑA1,2, A. VILLOT 1, C.GERENTE 1

UTILIZATION OF RESIDUAL CARBON AND MINERAL CONTENT FROM GASIFICATION

G. PALLA ASSIMA1, J.-M. LAVOIE1

COMPARISON BEHAVIOUR OF COMMERCIAL ACTIVATED CARBON AND COAL-