Advances in Environmental Biology, 8(14) Special 2014, Pages: 24-29

AENSI Journals

Advances in Environmental Biology

ISSN-1995-0756 EISSN-1998-1066

Journal home page: http://www.aensiweb.com/AEB/

Chemical Composition of Bio-Oil Obtained from Biomass via Thermal Controlled

inside The Continuous Pyrolysis Reactor
1,2Kittiphop Promdee, 2Ornrumpha Soubsawwong, 2Chintana Sanvong, 1,3 Tharapong Vitidsant
1
Center of Fuels and Energy from Biomass, Chulalongkorn University, Saraburi 18110, Thailand,
2
Department of Environmental Science, Academic Division, Chulachomklao Royal Military Academy, Nakorn Nayork, 26001, Thailand,
3
Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Bangkok 10330, Thailand

ARTICLE INFO ABSTRACT

Article history: Background: This study examines the thermal pyrolysis of biomass [Cogongrass] for
Received 25 June 2014 synthesis of bio-oil. The thermal pyrolysis was conducted at three different
Received in revised form temperatures, 400, 450 and 500°C and the bio-oil obtained from Cogongrass was
8 July 2014 analysed for its chemical composition. Cogongrass can be categorized as providing
Accepted 14 September 2014 moderate bio-oil yields, between 30-40%, composed of hydrocarbon compounds in the
Available online 27 September 2014 hydroxyl and carboxyl groups, especially; phenols [23.56%], Phenol, 2,6-
dimethoxy[15.62%], Phenol, 2-methoxy-[3.67%], Phenol, 3-methyl-[4.52%], Phenol, 2-
Keywords: methyl-[4.02%],Benzene,1-ethyl-4-methoxy-[2.75%], alcohols and ketones. In the
Pyrolysis Bio-oil present work, which was concerns the feeding rate, the temperatures in reactor and the
Cogongrass Product yields metal ball heat contact reaction for the hi quality of bio-oil with Cogongrass.
Chemical compositions
© 2014 AENSI Publisher All rights reserved.
To Cite This Article: Kittiphop Promdee, Ornrumpha Soubsawwong, Chintana Sanvong, Tharapong Vitidsant., Chemical Composition of
Bio-Oil Obtained from Biomass via Thermal Controlled inside The Continuous Pyrolysis Reactor. Adv. Environ. Biol., 8(14), 24-29, 2014

INTRODUCTION

Bio-Oil is now known for having the potential to provide the projected renewable energy provisions of the
future as biofuels in form of gas, liquid and solid and heat emission in the our of reactor system [1-5].
Biomass can be treated in numerous ways to produce liquids, solids and gases, but one of the technologies that
have the best industrial perspectives is pyrolysis, with challenges in the efficient conversion of biomass to fuels
compatible with internal engines or reactor [6-8]. Pyrolysis process becomes an option for the thermo chemical
conversion of cellulose, hemicelluloses and lignin of biomass into liquid fuels because this process can increase yield
of condensable liquid oil quality.
Natural tissue [Biomass] from photosynthesis is converted to bio-oil and hydrocarbon by pyrolysis showed
in following equations [9,10]:
nCO2  mH2O 
sunlight
 Cn (H2O)m  nO2
H  470 KJ / mol
H
Biomass 
Phrolysis
 Char + Pyrolytic oil high and moderate molecule weight organic liquid [+ other
H
condensable in oxygenate organic + CO2+CO+H2+CH4+H2O+other organic liquid   Aromatic
organic+low molecule weight organic liquid + Char + CO2+CO+H2+CH4+H2O+other.
This research was conducted using Cogongrass transformed to bio-oil by continuous pyrolysis reactor on
standard criteria and analysis the properties of material and products. At present, the fuel is becoming a
concerned in every country [11]. Now we are looking at the fuel which synthesized from natural matters,
especially; weeds biomass [12,13], such as Cogongrass, using the pyrolysis method combined with the control
of the temperature balance in the continuous pyrolysis reactor. The fuels from natural matters have a good
solved product and can reduce a waste in widespread areas of central part of Thailand.
Continuous pyrolysis reactor is one of excellent technologies for synthesized bio-oil [14]. In this case we
want to produce bio-oil in high potential performance of yield and properties by applying the heat transfer
model for control criteria of reactor to generate the alternative energy source [15]. The efficiency of this
research depended on the rounded rocks and twin screw feeder in continuous pyrolysis reactor for
generated bio-oil from Cogongrass.

MATERIALS AND METHODS

Corresponding Author: Kittiphop Promdee. Center of Fuels and Energy from Biomass, Chulalongkorn University,
Saraburi 18110, Thailand,
25 Kittiphop Promdee et al, 2014
Advances in Environmental Biology, 8(14) Special 2014, Pages: 24-29

Feedstock and Experimental Set-up:

The Cogongrass sample is chopped and crushed before being placed in an oven at 100°C for approximately
2 h until the moisture content is below 5%. The sample is then passed through a sieve to obtain particle sizes of
approximately 0.1-1 mm. It is then fed into continuous reactor [Fig. 1], for pyrolysis at the following operating
conditions: Operating temperature 400-500°C, The bio-oil product was analysed by Ultimate analyser and Proximate
analyser for characteristics and elemental composition before calculating the received oil yields. Further analysis of
the chemical compounds found in the bio-oil product was carried out using Gas Chromatography with Mass
Spectrometer.
The received oil yield can be calculated by following formula:

W 
%Liquid yield  100  Liq 
 Wini 
W 
%Solid yield  100  R 
 Wini 

% Gas yield = 100-% Liquid yield-% Solid yield

Wini = Initial weight

WR = Residual solid weight
WLiq = Liquid product weight

The received oil yield of solid phase implies the amount of solid left after pyrolysis and was determined
gravimetrically, the gas phase was calculated as remaining after quantification of the solids and liquids phase.

Chemical Analysis:
Gas Chromatography with Mass Spectrometer, GC-MS was used to analyze the light components in bio-oil
and investigating the molecular compositions qualitatively [15,16]. The analyses detect and identify organic
compounds both aliphatic hydrocarbon and aromatic hydrocarbon of bio-oil from Cogongrass. The pyrolysis
product was directly injected into Gas Chromatograph [GC] system through the pyrolysis interface line. The GC
was equipped with a thermal conductivity detector and Mass Spectrometer [MS] detector [16]. The injection
temperature was 300°C and a split ratio of 50:1 was used. Pyrolysis vapors comprising condensable gases i.e.
bio-oil, acetic acid and water were classified as liquid [15,16]. A total of over 100 compounds were detected.

Fig. 1: Schematic diagram of pyrolysis reactor setup: [1] Continuous pyrolysis reactor [2] Hopper; 2.2 Biomass
Hopper 2.2 Rounded rocks Hopper [3] Charcoal tank [4] Condenser [1 5] Condenser [2 6] Gases
storage [7] Cooling tower [8] Bio-Oil stock [9] Bio-Oil and Gasses Recovering in the system [10]
Cooling pump
RESULTS AND DISCUSSION

Compositions of Cogongrass:
Preliminary investigation of tissue components of Cogongrass, shown in Table 1., reveals it to be mainly
composed of Holocellulose and lignin at 59.38 and 39.45 wt%, respectively. The Holocellulose can be further
separated into 2 categories; 27.96 wt% Alfa-Cellulose and 31.42 wt% Hemicellulose. Results from proximate
analysis and ultimate analysis can be seen in Table 2. Proximate analysis shows low moisture content, low
amount of ash, moderate amount of fixed carbon and high amount of volatiles. This hints at the potential of
Cogongrass as a raw material for high efficiency bio-oil synthesis.

Table 1: The tissue components of cogongrass.

26 Kittiphop Promdee et al, 2014
Advances in Environmental Biology, 8(14) Special 2014, Pages: 24-29

Tissue components [wt%]

Holocellulose 59.38
Alfa-Cellulose 27.96
Hemicellulose 31.42
Lignin 39.45

Table 2: Proximate analysis and ultimate analysis of cogongrass.

Proximate Ultimate
analysis [wt.%] analysis [wt.%]
Moisture 5.2 C 43.87
Ash 10.3 H 8.20
Volatiles 63.3 N 4.60
Fixed carbon 21.2 O 37.92
S 2.19
Trace elements 3.22

The thermal control of experiment was founded that the high temperature in central of the reactor. Thus; the
thermal control and operation in continuous pyrolysis reactor showed that the trend of thermal in Fig. 2. T2
founded that thermal was slightly increasing between 100 to 700°C in 15 to 60 min, difference from T1 and T3
showed that thermal were low slightly increasing between 100 to 500°C in 15 to 60 min and low temperature
than that T2.
Results from proximate analysis and ultimate analysis can be seen in Table 2. Proximate analysis
shows low amount of ash, moderate amount of fixed carbon and high amount of volatiles. This hints at the
potential of Cogongrass as a raw material for high efficiency bio -oil synthesis.

Fig. 2: The thermal controlled and operated in continuous pyrolysis reactor.

The ultimate analysis of Cogongrass determined the proportion of the elements as following; carbon,
hydrogen, nitrogen and oxygen were 43.87, 8.2, 4.6 and 37.92 wt%, respectively [Table 2]. This proportion is similar
to the results from hazelnut cupulae with carbon, hydrogen, nitrogen and oxygen of 51.15, 5.89, 2.12 and 40.84 wt%
respectively [17] and indicates that the obtained pyrolytic oil from Cogongrass may be used as a renewable fuel and
chemical feed stock.
Chemical compound of bio-oil by continuous pyrolysis process
The compounds detected in bio-oil from Cogongrass showed that the hydrocarbon compounds composed of
hydroxyl and carboxyl groups, including; phenols [23.56%], Phenol, 2,6-dimethoxy[15.62%], Phenol, 2-
methoxy-[3.67%], Phenol, 3-methyl-[4.52%], Phenol, 2-methyl-[4.02%], Benzene, 1-ethyl-4-methoxy-[2.75%],
alcohols and ketones.
These chemical compounds showed in investigating the molecular compositions in Fig. 3, detecting
compounds of bio-oil from several biomass [18,19]. However; the compounds detected in bio-oil from
Cogongrass as similar results were reported by the topics; Formation of aromatic structures during the
pyrolysis of bio-oil [18] and Selective production of light oil by biomass pyrolysis with feedstock -
mediated recycling of heavy oil [19,20]. These results show agreement between proposed model and
experimental data of the several biomass [plant matters] lead to pyrolysis process.
All of compounds can be detected in bio-oil obtained from Cogongrass showed the main groups of
hydrocarbon compounds, there are composed of hydroxyl and carboxyl groups. These compounds showed that
the investigating molecular compositions.
It’s have been detected compounds of bio-oil from several biomass [21,22], the results shown a good
samples of molecular compositions detected [Table 3.].
27 Kittiphop Promdee et al, 2014
Advances in Environmental Biology, 8(14) Special 2014, Pages: 24-29

Fig. 3: The amount of some molecule compounds bio-oil obtained from Cogongrass.

Table 3: Compounds detected in bio-oil obtained from Cogongrass

Compound Formula MW Detection
Benzene, 1-ethyl-4-methoxy- C9H12O 136.00 *
1,2-Cyclopentanedione, 3-methyl- C6H8O2 112.12 ×
2-Cyclopenten-1-one, 2,3-dimethyl- C7H10O 110.00 ×
Phenol C6H6O 94.11 ×
Phenol, 2,3-dimethyl- C8H10O 122.16 ×
Phenol, 2,4-dimethyl- C8H10O 122.16 ×
Phenol, 2,5-dimethyl- C8H10O 122.16 ×
Phenol, 2,6-dimethoxy- C8H10O 122.16 ×
Phenol, 2,6-dimethyl- C8H10O 122.16 ×
Phenol, 2-ethyl- C8H10O 122.16 ×
Phenol, 2-methoxy- C7H8O2 124.00 ×
Phenol,2-methoxy-4-[1-propenyl]-, [E]- C10H12O2 164.19 ×
Phenol, 2-methoxy-4-methyl- C10H12O2 164.19 ×
Phenol, 2-methoxy-4-propyl- C10H12O2 164.19 ×
Phenol, 2-methyl- C7H8O 108.13 ×
Phenol, 3,4-dimethyl- C8H10O 122.16 ×
Phenol, 3-methyl- C7H8O 108.13 ×
Phenol, 4-ethyl- C8H10O 122.16 ×
Phenol, 4-ethyl-2-methoxy- C9H12O2 152.18 ×
Butanoic acid, 4 – hydroxyl- C4H8O3 104.00 *
Butyrolactone C4H6O2 86.00 *
2- Cyclopenten-1- one, 2-Methyl C6H8O 96.00 ×
2- Cyclopenten-1- one, 3-Methyl C6H8O 96.00 ×
3-Methyl- Cyclopentenone C6H8O 96.00 ×
3-Methyl-2- Cyclo C6H8O 96.00 *
2,4- Dimethylfuran C6H8O 96.00 *
3,4- Dimethyl C7H10O 110.00 ×
Phosphonic acid C6H7O4P 174.00 ×
4- Hydroxybenzenephosphonic acid C6H7O4P 174.00 *
2,3- Dimethyl-2-Cyclopenten-1-one C7H10O 110.00 *
2,3- Dimethyl C7H10O 110.00 ×
Mequinol C7H8O2 124.00 *
*can not determined × determined
28 Kittiphop Promdee et al, 2014
Advances in Environmental Biology, 8(14) Special 2014, Pages: 24-29

Conculsion:
The continuous pyrolysis reactor for produce bio-oil from Cogongrass showed that the high thermal in
central of the reactor and thermal controlled between 0-500°C within 60 min. The compounds detected in bio-
oil from Cogongrass showed that the hydrocarbon compounds that were composed of hydroxyl and carboxyl
groups, especially; phenols, Phenol, 2,6-dimethoxy, Phenol, 2-methoxy-, Phenol, 2-methyl-, Benzene, 1-ethyl-4-
methoxy-, alcohols and ketones. Thus, in this research, the process of continuous pyrolysis depended on the
mechanism of heat transfer with the shape of coil screw and rounded rocks and concern that the overall
performance system of the continuous pyrolysis reactor for produce bio-oil.

ACKNOWLEDGMENT

This work was supported by the Higher Education Research Promotion and National Research University
Project of Thailand, Office of the Higher Education Commission [EN 272 A], Ratchadaphiseksomphot
Endowment Fund [CU-CLUSTER-FUND], the Thai Government Stimulus Package 2 [TKK2555] under the
Project for Promotion of bio and biomass utilization potential for fuel production and exporting technology, and
Chulalongkorn University and Research Program on Materials for Future Energy, Center of Excellence on
Petrochemical and Materials Technology.
REFERENCES

[1] Chen, H., B. Dou, Y. Song, Y. Xu and Y. Zhang, 2012. Pyrolysis characteristics of sucrose biomass in a
tubular reactor and a thermogravimetric analysis. Fuel, 95: 425-430.
[2] Conesa, J.A. and A. Domene, 2011. Biomasses pyrolysis and combustion kinetics through η-th order
parallel reactions. Thermochimica Acta, 523: 176-181.
[3] Duan, P. and P.E. Savage, 2011. Upgrading of crude algal bio-oil in supercritical water. Bioresou. Technol.,
102: 1899-1906. [5] Duman, G., C. Okutucu, S. Ucar, R. Stahl and J. Anik, 2011. The slow and fast
pyrolysis of cherry seed. Bioresource Technol., 102: 1869-1878.
[4] Garcia-Perez, M., J. Shen, X.S., Wang and C.Z. Li, 2010. Production and fuel properties of fast pyrolysis
oil/bio-diesel blends. Fuel Proc. Technol., 91: 296-305.
[5] Huang, Y., S. Kudo, K. Norinaga, M. Amaike and J.I. Hayashi, 2012. Selective production of light oil by
biomass pyrolysis with feedstock-mediated recycling of heavy oil. Energy Fuels, 26: 256-264.
[6] Huminic, G., A. Huminic, I. Morjan and F. Dumitrache, 2011. Experimental study of the thermal
performance of thermosyphon heat pipe using iron oxide nanoparticles. Int. J. Heat Mass Transfer, 54: 656-
661.
[7] Ioannidou, O., C.G. Jung and A. Zabaniotou, 2011. A thermogravimetric model to predict yield product
distribution in pyrolysis of agricultural biomass. Catalysis Today, 167: 129-134.
[8] Promdee, K, and T. Vitidsant, 2013a. Preparation of Biofuel by Pyrolysis of Plant Matter in a Continuous
Reactor. Theoretical and Experimental Chemistry, 49: 126 – 129.
[9] LaMarca, C., B.M. Moreno and M.T. Klein, 2012. Characteristics of optimal chain transfer solvents for
pyrolysis kinetics. Energy & Fuels, 26: 55-57.
[10] Li, H., Q. Xu, H. Xue and Y. Yan, 2009. Catalytic reforming of the aqueous phase derived from fast-
pyrolysis of biomass. Renewable Energy, 34: 2872-2877.
[11] Lu, Q., W.Z. Li and X.F. Zhu, 2009. Overview of fuel properties of biomass fast pyrolysis oils. Energy
Conversion Manag., 50: 1376-1383. [16] Ma, Z., E. Troussard and J. Van Bokhoven, 2012. Controlling the
selectivity to chemicals from lignin via catalytic fast pyrolysis. Applied Catalysis A: General, pp: 130-136.
[12] Mei-Kuei, L., T. Wem-Tien, S. Yi-lin and L. Sheau-Horng, 2010. Pyrolysis of napier grass in an induction-
heating reactor. Analytical Applied Pyrol., 88: 110-116.
[13] Mortensen, P.M., J.D. Grunwaldt, P.A. Jensen, K.G. Knudsen and A.D. Jensen, 2011. A review of catalytic
upgrading of bio-oil to engine fuels. Applied Catalysis A: General, 407: 1-19.
[14] Razuan, R., Q. Chen, N.K. Finney, V.N. Russell and N.V. Sharifi et al., 2011. Combustion of oil palm
stone in a pilot-scle fluidsed bed reactor. Fuel Proc. Technol., 92: 2219-2225.
[15] Wang, Y., X. Li, D. Mourant, R. Gunawan and S. Zhang et al., 2012. Formation of aromatic structures
during the pyrolysis of bio-oil. Energy & Fuels, 26: 241-247.
[16] Robbins, M.P., G. Evans, J. Valentine, I.S. Donnison and G.G. Allison, 2012. New opportunities for the
exploitation of energy crops by thermochemical conversion in Northern Europe and the UK. Progress
Energy Combustion Sci., 38: 138-155.
[17] Bilgen, S., S. Keles and K. Kaygusuz, 2012. Calculation of higher and lower heating values and chemical
exergy values of liquid products obtained from pyrolysis of hazelnut cupulae. Energy, 41: 380-385.
[18] Skoulou, V. and A. Zabaniotou, 2012. Fe catalysis for lignocellulosic biomass conversion to fuels and
materials via thermochemical processes. Catalysis Today, pp: 231-242.
29 Kittiphop Promdee et al, 2014
Advances in Environmental Biology, 8(14) Special 2014, Pages: 24-29

[19] [Promdee, K, and T. Vitidsant, 2013b. Bio-oil synthesis by pyrolysis of Cogongrass [Imperata Cylindrica.].
Chemistry and Technology of Fuels and Oils. 49: 287 – 292.
[20] Ying, X., W. Tiejun, M. Longlong and C. Guanyi, 2012. Upgrading of fast pyrolysis liquid fuel from
biomass over Ru/γ-Al2O3 catalyst. Energy Conversion Manag., 2012: 172-177.
[21] Heo, H.S., H.J. Park, J.H. Yim, J.M. Sohn and J.H. Park et al., 2010. Influence of operation variables on
fast pyrolysis of Miscanthus sinensis var. purpurascens. Bioresou. Technol., 101: 3672-3677.