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Energy
EnergyProcedia 158
Procedia 00(2019)
(2017)2070–2076
000–000
www.elsevier.com/locate/procedia
10th International Conference on Applied Energy (ICAE2018), 22-25 August 2018, Hong Kong,
10th International Conference on Applied Energy (ICAE2018), 22-25 August 2018, Hong Kong,
China
China

Transesterification of waste
The 15th International cooking
Symposium oil: Quality
on District assessment
Heating and Cooling via
Transesterification of waste cooking oil: Quality assessment via
thermogravimetric analysis
thermogravimetric
Assessing the feasibility of using the analysis
heat demand-outdoor
temperature function
Manar for aaa, Sherien
Almazrouei long-term district
Elagroudy b
b
heat
, Isam demand
Janajreh a,*
a,*
forecast
Manar Almazrouei , Sherien Elagroudy , Isam Janajreh
Mechanical Engineering Department, Khalifa University of Science and Technology, Masdar Institute, Abu Dhabi, UAE, P.O.BOX 54224
a
b
Mechanical Engineering
a Egypt Solid Waste
Department,
a,b,c Management
a UniversityCenter
Khalifa a of Excellence,
of Science Ain Shams
and Technology, University,
b Masdar Cairo.
Institute, cEgypt UAE, P.O.BOXc54224
Abu Dhabi,
I. Andrić *, A. Pina , P. Ferrão , J. Fournier ., B. Lacarrière , O. Le Corre
b
Egypt Solid Waste Management Center of Excellence, Ain Shams University, Cairo. Egypt
a
IN+ Center for Innovation, Technology and Policy Research - Instituto Superior Técnico, Av. Rovisco Pais 1, 1049-001 Lisbon, Portugal
Abstract b
Veolia Recherche & Innovation, 291 Avenue Dreyfous Daniel, 78520 Limay, France
Abstract c
Département Systèmes Énergétiques et Environnement - IMT Atlantique, 4 rue Alfred Kastler, 44300 Nantes, France
Biodiesel is a good substitute for petrol-diesel at lower greenhouse emissions footprint. Biodiesel is commonly generated through
Biodiesel is a goodofsubstitute
transesterification lipid, animalfor petrol-diesel
fat and waste at lower
cookinggreenhouse
oil (WCO) emissions footprint.
with alcohol in theBiodiesel
presenceisofcommonly generated through
catalyst. Assessment of the
transesterification of lipid, animal
product quality of biodiesel and thefat and waste
byproduct forcooking oil (WCO)can
further utilization with
be alcohol
done usingin the presence of catalyst.
Thermogravimetric Assessment
analysis of the
(TGA) instead
product
of more quality
Abstractinvolved ofand
biodiesel and the
specialized byproduct
technique foras
such further
GC/MS utilization
and HLPC. can be
TGAdoneofusing Thermogravimetric
biodiesel analysis (TGA)
and the crude byproduct glycerolinstead
were
of more involved
investigated in thisand specialized
work following technique such as GC/MS
transesterification essay and
under HLPC. TGA
different of biodiesel
reactants and catalysis
ratio and the crudeconcentrations.
byproduct glycerol were
Biodiesel
investigated
TA in
thermographs this work
was following
characterized transesterification
by four events andessay
with under
two different
distinct reactants
peaks shown ratio
in and
the catalysis
derivative
District heating networks are commonly addressed in the literature as one of the most effective solutions for decreasing the concentrations.
of TGA curve. Biodiesel
The crude
TA thermographs
glycerol showed
greenhouse was characterized
three
gas emissions pronounced by
from thepeaks. fourThe
building events
bestand
sector. withsystems
conversion
These two of
distinct
WCO peaks
requiretohighshown
biodiesel in thedetermined
was
investments derivative
which areof TGAoncurve.
based
returned Thethe
the fraction
through crude
of
heat
glycerol
biodiesel showed
or the
sales. Due three
to 2the
nd TGA pronounced
event.climate
changed Highestpeaks. The best
conversion
conditions conversion
was
and of 12:1
WCO
obtainedrenovation
building at topolicies,
biodieselheat
Methanol:WCO was determined
molar ratio in93%
demand based
the on the
compared
future to fraction
could 65%, 77%of
decrease,
biodiesel
and 89% or
prolongingat the
the
nd TGA event. Highest conversion was obtained at 12:1 Methanol:WCO molar ratio 93% compared to 65%, 77%
3:1,2investment
6:1, 9:1 ratio,
returnrespectively.
period. The influence of the catalyst is observed at lower molar ratio by advancing the
and
The89%
mainatscope
conversion 3:1, 65%
from 6:1,this
of 9:1 ratio,is
topaper
77% andrespectively.
to 79%
assesstothe
93% Theat influence
3:1 and
feasibility 6:1of Methanol:WCO
of using the
thecatalyst is observed
heat demand ratio, at lower
respectively.
– outdoor molar
temperatureHigher ratio by for
glycerol
function advancing
quality the
was
heat demand
conversion
obtained fromdistrict
forecast.atThe
lower 65% toof77%
catalyst and 79%
concentration.
Alvalade, to 93%
located in at 3:1 and
Lisbon 6:1 Methanol:WCO
(Portugal), was used asratio,
a caserespectively.
study. TheHigherdistrictglycerol qualityofwas
is consisted 665
obtained
buildingsat that
lowervarycatalyst
in bothconcentration.
construction period and typology. Three weather scenarios (low, medium, high) and three district
Copyright © scenarios
2018 ElsevierwereLtd. All rights reserved.intermediate, deep). To estimate the error, obtained heat demand values were
©renovation
2019 The
Copyright Authors.
©with
2018 Published
Elsevier
developed
Ltd. by
All rights
(shallow,
Elsevier Ltd.
reserved.
Selection
compared and peer-review
results under
from a responsibility
dynamic heat of the scientific
demand model, committee
previously of the 10and
developed
th International Conference on Applied Energy
validated by the authors.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
Selection
(ICAE2018). and peer-review
The results under
showed under
that when only responsibility
weather of the
change scientific committee
is considered, of
the margin the 10 th International Conference on Applied Energy
Peer-review responsibility of the scientific committee of ICAE2018 – The of error
10th could be acceptable
International Conferencefor onsome
Applied applications
Energy.
(ICAE2018).
(the error in annual demand was lower than 20% for all weather scenarios considered). However, after introducing renovation
Keywords:
scenarios,Transesterification; biodiesel; crude
the error value increased up toglycerol;
59.5% thermogravimetric
(depending on the analysis (TGA)
weather and renovation scenarios combination considered).
Keywords: Transesterification; biodiesel; crude glycerol; thermogravimetric analysis (TGA)
The value of slope coefficient increased on average within the range of 3.8% up to 8% per decade, that corresponds to the
decrease in the number of heating hours of 22-139h during the heating season (depending on the combination of weather and
renovation scenarios considered). On the other hand, function intercept increased for 7.8-12.7% per decade (depending on the
coupled scenarios). The values suggested could be used to modify the function parameters for the scenarios considered, and
improve the accuracy of heat demand estimations.

© 2017 The Authors. Published by Elsevier Ltd.

Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and
* Cooling.
Corresponding author. Tel.: +971-2-810-9130; fax: +971-2-810-9109.
*E-mail address:author.
isam.janajreh@ku.ac.ae
Corresponding Tel.: +971-2-810-9130; fax: +971-2-810-9109.
Keywords:
E-mail Heatisam.janajreh@ku.ac.ae
address: demand; Forecast; Climate change
1876-6102 Copyright © 2018 Elsevier Ltd. All rights reserved.
1876-6102 Copyright
Selection and © 2018
peer-review underElsevier Ltd. All of
responsibility rights reserved. committee of the 10th International Conference on Applied Energy (ICAE2018).
the scientific
Selection and peer-review under responsibility of the scientific committee of the 10th International Conference on Applied Energy (ICAE2018).
1876-6102 © 2017 The Authors. Published by Elsevier Ltd.
Peer-review under responsibility of the Scientific Committee of The 15th International Symposium on District Heating and Cooling.
1876-6102 © 2019 The Authors. Published by Elsevier Ltd.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
Peer-review under responsibility of the scientific committee of ICAE2018 – The 10th International Conference on Applied Energy.
10.1016/j.egypro.2019.01.478
 Manar Almazrouei et al. / Energy Procedia 158 (2019) 2070–2076 2071
2 Almazrouei et al. / Energy Procedia 00 (2018) 000–000

1. Introduction

The biodiesel (fatty acid alkyl ester) is more comonly produced by the transesterification process of oil (vegetable
oil, animal fat or waste cooking oil (WCO)) with alcohol in the presence of the catalyst [1]. It is clean, biodegradable,
and characterized with lower emissions compared to the petro-diesel [2, 3]. Other less common biodiesel production
includes direct blending [5], micro-emulsions [6], and thermal cracking [7]. Crude glycerol is the by-product of the
transesterification process. The stochiometric transesterification of one mole of the triglyceride with three moles of
alcohol is presented per Eq. 1 [4]:

𝐶𝐶54 𝐻𝐻104 𝑂𝑂6 (𝑉𝑉𝑉𝑉𝑉𝑉.𝑂𝑂𝑂𝑂𝑂𝑂) + 3 𝐶𝐶𝐻𝐻4 𝑂𝑂(𝑀𝑀𝑀𝑀𝑀𝑀ℎ𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎) ⇌ 3 𝐶𝐶18 𝐻𝐻36 𝑂𝑂2 (𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹) + 𝐶𝐶3 𝐻𝐻8 𝑂𝑂3 (𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺𝐺) (1)

Thermal degradation of the fuel is used to evaluate the needed thermochemical properies of the fuel and their
compositional fraction. It provides information on the thermal, physical and chemical properties of the material
including the decomposition, combustion characteristics, and kinetic as well as thermodynamic parameters. Although
literature is more inclined using GC/MS for monitoring biodiesel qualities, TGA is emerging as direct and simpler
approach for gross analysis [9,10]. Soto, et al. [5] studied the thermal degradation of biodiesel under air atmosphere
and reported three stages of mass loss. Arruda, et al. [6] investigated the combustion behavior of moringa biodiesel
and showed single mass loss event corresponding to the esters combustion. Li, et al. [7] observed a single mass loss
evnet of the devolatalization of peanut oil ester and palm oil methyl ester under N2 atmosphere. Rodríguez, et al. [8]
investigated the thermal behavior of the soy bean biodiesel produced by the transesterification of soybean oil, and
higuereta oil. The experiment conducted in an air atmosphere and the TG curves showed single mass loss step for all
the studied samples which is associated with the ethyle ester decomposition. Bartocciet, al el. [9] investigated the
TGA of sawdust (90%) and glycerol (10%) blend under N2 atmosphere. The onset of glycerol mass loss marked at
150 ̊C and ended at 303 ̊ C peaking at 241 ̊C. Yuan, al el. [11] studied the blending of glycerol and diesel under N2
atmosphere and marked weight loss proportional to glycerol fraction. Crnkovic, et al. [12] reported three phases of
mass loss on the TG curve for glycerol air combustion. Dou, et al. [13] studied the thermal decomposition of crude
and pure glycerol under N2 atmosphere. The results showed four distinct phases of the crude glycerol where the
presence of water and methanol is responsible for the first phase. The pure glycerol, on the other hand, showed single
phase accounted for 95% of the mass loss and spanned in the range of 503-556K. In the above cited work there were
no attempt to assess the purity or the conversion to biodiesel or glycerol using TGA under different transesterification
conditions. It is the main objective of this work to stud the influence of the reactants ratio and catalyst amount on the
generated biodiesel and crude glycerol using TGA thermal signature.

2. Materials and Methods

2.1. Transesterification

The WCO used in the transesterification process was collected from restaurants and residential areas near
Masdar City in Abu Dhabi, UAE. The solid and floating impurities were removed from the samples via 40 µm filtering
papers with the help of low grade heating reaching 50oC. The filtered samples were then heated up to 120 ̊C for several
hours to remove any moister contents. The methoxide was prepared using Sigma-Aldrich methanol of purity ≥ 99.7%
and potassium hydroxide (KOH) of ≥85% KOH concentration at 1% and 0.5% (KOH wt.% of oil/TG). The methoxide
was then mixed with filtered and moisture free WCO and the transesterification process was performed in a multiple
unit batch reactor (Modified VK 7010 Dissolution Apparatus of 8 units). The separation process of the process product
and by-product took place using separatory funnel. Different methanol: oil ratios of 3:1, 6:1, 9:1 and 12:1 and catalyst
ratio of 0.5% and 1% catalyst concentration were used to assess the effect of methanol amount and catalyst
concentration on the products. The amount of waste cooking oil used were fixed to 300 ml for all the performed
experiments. The transesterification process carried out at 40 ̊C temperature and stirring rate of 250 rpm for two hours
processing time.
2072 Manar Almazrouei et al. / Energy Procedia 158 (2019) 2070–2076
Almazrouei at al./ Energy Procedia 00 (2018) 000–000 3

2.2. Thermogravimetric analysis

The DSC/TGA Q600 thermal analyzer used to perform the TGA and derivative thermogravimetric (DTG)
analyses. The experiments were performed under pyrolysis using N2 atmosphere at 100ml/min flow rate and for two
sets of samples, i.e. the biodiesel and the crude glycerol. The samples were placed on the TGA balance arm and
equilibrates at 50 °C for 2 minutes, then is ramped to 700 ̊C at a fixed heating rate of 10 ̊C/min. It is finished
isothermally for 5 minutes and before is left to cool down. All used TGA samples were kept in the range of 27.0±2
mg to eliminate any weight/size degradation dependency. The TGA is subjected to regular calibration, notably the
melting and heat flow of the known pure aluminum which marked near 660.04 oC and 400.7 J g-1. Large deviation, i.e.
|error| ≥ 2%, from the standard values (for aluminum 660.3 oC and 400.1 J g-1) essentially requires further calibration
and adjustment.

3. Results and Discussion

Fig.1 shows the amount of biodiesel and crude glycerol obtained at four different methanol: oil molar ratio
and the two values of catalyst concentration. The obtained fraction of unwashed biodiesel from the experiments
showed an increasing production trend with increase in methanol ratio. The values varied between 295 to 361 ml at
1% catalyst and from 317 to 350ml at 0.5% catalyst. The crude glycerol, also showed an increasing trend as well from
44 to 92 ml at 1% catalyst and from 21 to 102 ml at 0.5% catalyst concentration. Excess methanol found to be more
presence in the crude glycerol fraction than biodiesel due to its glycerol solubility. This will be revealed latter in the
glycerol thermographs.

Fig. 1. The biodiesel yield (left) and the byproduct crude glycerol (right) obtained at different molar ratio and catalyst concentration

Fig.2 shows the thermographs and its derivatives (DTG) curves of biodiesel evaluated at the stipulated
heating rate (10°C/min) in N2 atmospheres. The TGA curves show four stages (I through IV) that can be distinguished
with two pronounced peaks appears in the associated DTG thermograph. Table 1 shows the breakdown of these stages
and their temperature range, weight loss %, and the temperature at the maximum weight loss rate (DTGmax). The first
mass drop (stage I) represents the evaporation of excess methanol and any traces of residual moisture from the
feedstock (WCO). The second stage (II) is the devolatilization of the fatty acid methyl esters (FAME/biodiesel) which
characterized with the largest mass loss. The third stage (III) corresponds to the thermal degradation and
devolatilization of other impurities in the biodiesel sample including the unconverted glyceride (WCO) and
intermediates. The last stage (IV) is the slow degradation of minerals that brought by the catalyst itself. It should be
emphasized that there are distinct differences between biodiesel and petro-diesel thermographs as seen in Fig.2. For
example, biodiesel main degradation occurs in the range of 170 to 492 ̊C whereas the petro-diesel depicts only single
mass loss occurs in the range of 103.34 to 318.54 and peaks at 200 ̊C. The conversion ratio was calculated using Eq.
2 [14], where Wo is the initial weight and Wt is the weight at a given processing time t.

𝑤𝑤0 −𝑤𝑤𝑤𝑤
𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶𝐶% = × 100 (2)
𝑤𝑤0
 biodiesel 12:1, 1%

TG Weight F
60 Diesel

50

40

30

20

4 Manar Almazrouei
Almazrouei et al. Procedia
et al. / Energy / Energy Procedia
00 (2018)158 (2019) 2070–2076
000–000 10
2073
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700
Tempreture ̊C

100 2.3
biodiesel 3:1, 0.5% biodiesel 3:1, 0.5%
2.2
biodiesel 3:1, 1% (b) biodiesel 3:1, 1%
2.1
90 (a) biodiesel 6:1, 0.5% biodiesel 6:1, 0.5%
2

TG Weight Fraction (W/W0)%

TG Weight Fraction (W/W0)%

biodiesel 6:1, 1% biodiesel 6:1, 1%

1.9
80 biodiesel 9:1, 0.5% biodiesel 9:1, 0.5%
1.8
biodiesel 9:1, 1% 1.7 biodiesel 9:1, 1%

70 biodiesel 12:1, 0.5% 1.6 biodiesel 12:1, 0.5%

biodiesel 12:1, 1% 1.5 biodiesel 12:1, 1%
Diesel 1.4 Diesel
60
1.3
1.2
50
1.1 Stage-I Stage-III Stage-IV
1
40 0.9
0.8
30 0.7
0.6
0.5
20
0.4
0.3 Stage-II
10 0.2
0.1
0 0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 50 100 150 200 250 300 350 400 450 500 550 600 650 700
Tempreture ̊C Tempreture ̊C

2.3
2.2
(b)
Fig. 2. (a) TGA (b) DTG of biodiesel at 10 C
biodiesel 3:1, 0.5%
biodiesel 3:1, 1%
̊ /min
2.1
biodiesel 6:1, 0.5%
2
TG Weight Fraction (W/W0)%

biodiesel 6:1, 1%
1.9
biodiesel 9:1, 0.5%

Table 1. Temperature range, mass loss, and DTGmax of the different stages of WCO biodiesel
1.8
1.7 biodiesel 9:1, 1%

1.6 biodiesel 12:1, 0.5%

1.5 biodiesel 12:1, 1%

1.4 Stages TGA characteristics Diesel 3:1, 0.5% 6:1,0.5% 9:1, 0.5% 12:1,0.5%
1.3
1.2 Stage-I Temperature range ̊C 49.958-176.678 49.838-173.477 49.598-171.596 49.943 -170.036
Stage-I Stage-III Stage-IV
1.1
1
Mass% 1.188 1.322 1.634 1.571
0.9
0.8
Temperature range ̊C 176.678-325.874 173.477-320.140 171.596-310.452 170.036-309.502
0.7
0.6
Stage-II Mass% 65.432 79.484 88.727 93.407
0.5 Tmax ̊C 265.025 278.877 276.861 278.337
0.4
0.3 Stage-II DTGmax %/ ̊C 1.220 1.479 2.106 2.210
0.2
0.1 Temperature range ̊C 325.874-492.362 320.140-489.627 310.452-482.328 309.502-474.606
0
50 100 150 Stage-III
200 250 300 350 400 Mass%
450 500 550 600 650 31.324
700 17.742 8.215 4.390
Tempreture ̊C
Tmax ̊C 414.280 401.837 383.077 361.899
DTGmax %/ ̊C 0.541 0.231 0.087 0.048
Stage-IV Temperature range ̊C 492.362-696.026 489.627-696.405 482.328-696.102 474.606-697.355
Mass% 2.056 1.451 1.425 0.632
Stages TGA characteristics 3:1, 1% 6:1,1% 9:1, 1% 12:1,1%
Temperature range ̊C 49.805-175.314 49.602-172.583 49.982-171.282 49.942-171.134
Stage-I Mass% 1.295 1.418 1.480 1.560
Temperature range ̊C 175.314-324.712 172.583-317.192 171.282-314.683 171.134-314.320
Stage-II Mass% 77.170 94.568 93.761 92.566
Tmax ̊C 280.469 281.491 281.755 280.720
DTGmax %/ ̊C 1.316 2.183 2.189 2.077
Temperature range ̊C 324.712-487.666 317.192-471.325 314.683-475.965 314.320-481.136
Stage-III Mass% 20.645 3.432 4.137 5.627
Tmax ̊C 409.740 359.048 360.777 370.697
DTGmax %/ ̊C 0.281 0.041 0.047 0.059
Stage-IV Temperature range ̊C 487.666-696.271 471.325-697.312 475.965-698.214 481.136-698.113
Mass% 0.890 0.581 0.622 0.247

3.1. Biodiesel TGA analysis

In the biodiesel thermographs, the higher the devolatilization (Stage II) mass reduction and the lower impurity
(Stage III) as well as residual mass (Stage IV) presense signify a higher conversion of WCO to biodiesel. At 0.5%
catalyst concentration the evaporation (of alcohol and traces of moisture) in stage I is located in the temperature range
{50, 176.678}, {50,173.477}, {50, 171.596} and {50, 170.036} ̊C and are correspond to mass reduction of 1.188%,
1.322%,1.634% and 1.571% for the 3:1, 6:1, 9:1 and 12:1 methanol: oil ratio, respectively. The biodiesel
devolatilization (stage II) is located in the temperature range of {176.678, 325.874}, {173.477-320.140}, {171.596-
310.452} and {170.036-309.502} ̊C and are corresponding, respectively to mass reduction of 65.432%, 79.484%,
88.727% and 93.407%. The attained conversion was 66.620%, 80.806%, 90.360% and 94.978% that correspond to
3:1, 6:1, 9:1 and 12:1 methanol: oil ratio, respectively. Stage III, or reduction stage, was located in the range of
{325.874-492.362}, {320.140-489.627}, {310.452-482.328} and {309.502-474.606} ̊C that corresponds to mass loss
of 31.324%, 17.742%, 8.215% and 4.390% and conversion values of 97.944%, 98.549%, 98.575% and 99.368% for
the 3:1, 6:1, 9:1 and 12:1 methanol: oil ratio, respectively. The remaining residual mass varies between 0.632 and
2.056% and stays in the temperature range of {474.61- 700} C ̊ . At 1% catalyst concentration, the conversion showed
an increasing trend at higher methanol: oil molar ration. Evaporation stage (I) is in the range of {49.805-175.314},
{49.602-172.583}, {49.982-171.282} and {49.942-171.134} ̊Cat mass loss of 1.295%, 1.418%, 1.480% and 1.560%
for the methanol: oil molar ratio of 3:1, 6:1, 9:1 and 12:1, respectively. Slightly higher moisture content found at
higher methanol: oil ratio. Stage II mass reduction was located in the range of {175.314-324.712}, {172.583 317.192},
{171.282-314.683} and {171.134-314.320} °C at weight loss of 77.170%, 94.568%, 93.761% and 92.566% for the
3:1, 6:1, 9:1 and 12:1 methanol: oil molar ratio, and with apparent and corresponding conversion of 78.465%,
95.986%, 95.241% and 94.126%, respectively. Stage III was located in the range of {324.712-487.666}, {317.192-
 2074 Manar Almazrouei et al. / Energy Procedia 158 (2019) 2070–2076
Almazrouei at al./ Energy Procedia 00 (2018) 000–000 5

471.325}, {314.683-475.965} and {314.320-481.136} ̊C with mass reduction of 20.645%, 3.432%,4.137% and
5.627% and with conversion of 99.110%, 99.419%,99.378% and 99.753% for the 3:1, 6:1, 9:1 and 12:1 methanol: oil
ratio, respectively. The remaining residue mass fraction were in the range of {0.247- 0.890} % at temperature range
of {471.325-700.00} ̊C and are inferior to those obtained at 0.5% catalyst experiments. Accordingly, the updated
actual conversion for biodiesel is depicted in Fig. 3 and is at much lower values that those were reported previously.
It shows the increasing trend with the increasing molar ratio and highlights the higher yield at the 1% in comparison
to 0.5% catalyst particularly at lower methanol:oil ratio. This information, however, was deceiving should one based
the conversion on the basis of the total glycerol generation.

400 1% KOH 0.5% KOH

1% KOH Actual 0.5% KOH Actual
300
Biodisel amount (ml)

200 100 crude glycerol 3:1, 0.5%

90 crude glycerol 3:1, 1%

(a) crude glycerol 6:1, 0.5%
80
crude glycerol 6:1, 1%
100 TG Weight Fraction (W/W0)% 70 Pure glycerol

60

50

0 40

3 30 6 9 12
Methanol/Oil
20
ratio
Fig. 3. Total unwashed and actual biodiesel
10 yield based on the TGA analysis
0
50 100 150 200 250 300 350 400 450 500 550 600 650 700
Tempreture ̊C

100 crude glycerol 3:1, 0.5% 2.6 crude glycerol 3:1, 0.5%
crude glycerol 3:1, 1% 2.4 (b) crude glycerol 3:1, 1%
90
(a) crude glycerol 6:1, 0.5% 2.2
crude glycerol 6:1, 0.5%
80 crude glycerol 6:1, 1%
crude glycerol 6:1, 1% 2
TG Weight Fraction (W/W0)%

Pure glycerol
DTG Derive.Weight %/̊C

70 Pure glycerol 1.8

60 1.6
1.4
50
1.2 Stage-I Stage-II Stage-III Stage-IV
40 1

30 0.8
0.6
20
0.4
10
0.2
0 0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 50 100 150 200 250 300 350 400 450 500 550 600 650 700
Tempreture ̊C Tempreture ̊C

2.6
2.4 (b) Fig. 4. (a) TGA (b) DTG of pure glycerol and crude glycerol at 10 ̊C/min
crude glycerol 3:1, 0.5%
crude glycerol 3:1, 1%
crude glycerol 6:1, 0.5%
2.2
crude glycerol 6:1, 1%
2
Table 2. Temperature range, mass% and DTGmax%/
Pure glycerol ̊C of the different stages of the different crude glycerol samples.
DTG Derive.Weight %/̊C

1.8
1.6 Stages TGA characteristics 3:1, 0.5% 3:1, 1% 6:1,0.5% 6:1,1%
1.4 Temperature range ̊C 49.602 -145.789 49.727-154.033 49.188-146.514 48.977-153.465
1.2 Stage-I Stage-I
Stage-II Stage-III Mass% Stage-IV 8.561 6.647 13.982 14.116
1
Tmax ̊C 122.776 133.114 100.849 106.171
0.8
0.6
DTGmax %/ ̊C 0.156 0.136 0.157 0.127
0.4 Temperature range ̊C 145.789-379 154.033-400.586 146.514 -358.031 153.465-355.480
0.2 Stage-II Mass% 70.774 62.400 73.366 65.782
0 T ̊C 239.373 235.524 238.709 238.583
50 100 150 200 250 300 350 400 450 max 500 550 600 650 700
Tempreture ̊C DTGmax %/ ̊C 0.950 0.654 1.031 0.726
Temperature range ̊C 379-506.392 400.586-511.054 358.031-502.741 355.480-508.584
Stage-III Mass% 13.132 21.616 7.264 11.052
Tmax ̊C 475.474 479.548 474.525 477.030
DTGmax %/ ̊C 0.261 0.431 0.117 0.155
Stage-IV Temperature range ̊C 506.392-695.471 511.054-695.732 502.741-695.546 508.584-695.386
Mass% 7.533 9.337 5.389 9.050
6 Almazrouei et al. / Energy Procedia 00 (2018) 000–000
Manar Almazrouei et al. / Energy Procedia 158 (2019) 2070–2076 2075

3.2. Glycerol TGA analysis

Fig. 4 shows four stages of crude glycerol with three significant DTG peaks compared to a single peak for
the pure glycerol thermograph. Table 2 shows the temperature range, weight loss and the temperature at the maximum
weight loss rate DTGmax for the crude glycerol at 3:1 and 6:1 methanol:oil ratio with 0.5% and 1% catalyst
concentration. Higher methanol:oil ratio failed to stabilize during the TGA analysis due to the rapid and natural
evaporation of the methanol from the open TGA crucible. Stage I shows the degradation or mass loss of the methanol
content within the sample and with higher methanol:oil ratio, more mass reduction incurred. Stage II represents the
glycerol content, while stage III represents the unconverted glycerides. Stage IV represents the remaining residue in
the form of asymptotically degrading catalyst/minerals. For the crude glycerol at 0.5% catalyst concentration, stage I
is located in the temperature range of {49.602 -145.789} and {49.188-146.514} ̊C with mass content of 8.561% and
14.116% for the 3:1 and 6:1 methanol:oil molar ratio, respectively. Stage II is located in the range of {145.789-379}
and {146.514 -358.031} ̊C with mass content of 70.774% and 73.366% and conversion percentage of 79.335 and
87.348 for the 3:1 and 6:1 methanol:oil molar ratio, respectively. The pure glycerol, however, has a single mass drop
located in the temperature range of {139.3454 - 259.9092} C ̊ and with mass fraction of 96.650%. Stage III is the
unconverted glycerides and is located in the temperature range of {379-506.392} and {358.031-502.741} ̊C at mass
fraction of 13.132% and 7.264% and with conversion of 92.467% and 94.611% for the 3:1 and 6:1, respectively.
Lower remaining residue mass of 5.389% in the temperature range of {502.741-695.546} ̊C found for the 6:1 ratio
compared to the 3:1 that contains the remaining residue of 7.533 % in the range {506.392-695.471} ̊C.
Comparing the crude glycerol produced at 1.0% and 0.5% catalyst concentrations, higher vapor and glycerol
contents while lower fraction of unconverted triglyceride found in higher methanol:oil ratio was found in the 1%
catalyst concentration samples. Stage I of the 1% catalyst concentration crude glycerol was located in the temperature
range of {49.727-154.033} and {48.977-153.465} ̊C with mass fraction of 6.647% and 14.116% for the 3:1 and 6:1
methanol:oil molar ratio, respectively. Stage II was located in the temperature range of {154.033-400.586} and
{153.465-355.480} ̊C with a mass fraction of 62.400 and 65.782 and at conversion of 69.048% and 79.898% for the
3:1 and 6:1 methanol:oil molar ratio, respectively. Stage III was located in the range of {400.586-511.054} and
{355.480-508.584} ̊C at mass fraction of 21.616% and 11.052% and with conversion of 90.663% and 90.950% for
the 3:1 and 6:1 ratio, respectively. The remaining mass fractions was 9.337% and 9.050% for the 3:1 and 6:1 located
in the temperature range of {511.054-695.732} and {508.584-695.386}
100 ̊C, respectively. Pure glycerol
Fig. 4 compares the thermal degradation of biodiesel 90 and crude glycerol with the WCO and pure
(a)
glycerol.
Waste cooking oil
TG Weight Fraction (W/W0)%

biodiesel 3:1, 1%
The pure glycerol is located in the same temperature range of80 the stage II of crude glycerol. The waste cooking oil is
Crude glycerol 3:1, 1%
70
locating in the temperature range of the stage III of the crude 60glycerol and biodiesel. The results are an indication that
stage II of the crude glycerol is the glycerol content in the sample,
50 and the stage III of both biodiesel and crude glycerol
is the un-converted WCO. These data suggest the potential of 40
total degradation of each of the waste oil and to some
30
extent the biodiesel, but not the crude glycerol as shown in Fig. 20
5. This is because of the presence of the catalyst in
the byproduct crude glycerol. This necessities crude glycerol 10 pretreatment (washing/adsorption) prior being
introduced to any thermochemical conversion process to 0 50avoid 100
corrosion
150 200 250
and
300
potential
350 400 450
refractory
500 550
deposition
600 650 700
mimicking calcination. Tempreture ̊C

100 3
Pure glycerol Pure glycerol
2.75 (b) Waste cooking oil
90 Waste cooking oil
(a) 2.5 biodiesel 3:1, 1%
TG Weight Fraction (W/W0)%

80 biodiesel 3:1, 1%
DTG Derive.Weight %/̊C

2.25 Crude glycerol 3:1, 1%

Crude glycerol 3:1, 1%
70 2
60 1.75
50 1.5
1.25
40
1
30
0.75
20 0.5
10 0.25
0 0
50 100 150 200 250 300 350 400 450 500 550 600 650 700 50 100 150 200 250 300 350 400 450 500 550 600 650 700
Tempreture ̊C Tempreture ̊C

3
2.75 (b)
Fig. 5 (a) TGA (b) DTG of pure glycerol,
Pure glycerolwaste cooking oil, biodiesel and crude glycerol at 10 ̊C/min
Waste cooking oil
2.5 biodiesel 3:1, 1%
DTG Derive.Weight %/̊C

2.25 Crude glycerol 3:1, 1%

2
1.75
1.5
1.25
1
0.75
0.5
0.25
2076 Manar Almazrouei et al. / Energy Procedia 158 (2019) 2070–2076
Almazrouei at al./ Energy Procedia 00 (2018) 000–000 7

4. Conclusion

The transesterification of waste cooking oil (WCO) was performed under different methanol:oil ratio and catalyst
concentration to obtain different quality of the biodiesel yield and crude glycerol byproduct and to assess them using
TGA analysis. TGA was successfully used to analyze the produced biodiesel and crude glycerol on their composition
and thermal degradation. The biodiesel thermographs showed four stages with two significant DTG peaks. Stage I is
the evaporation of soluble alcohol and traces of moister. Stage II is the devolatilization of the fatty acid methyl ester
(Biodiesel) while stage III represents the unconverted glycerides. Stage IV represents a small content of the suspended
catalyst. The crude glycerol thermographs showed also four stages and with three distinct DTG peaks. Stage I
comprises the residual or unconverted alcohol. Stage II consists of the devolatilization of pure glycerol and stage III
accounts for the release of the unconverted glycerides. The last stage, stage IV consists of the remaining mineral in
the form of slowly degrading catalyst that more present in the crude glycerol than the unwashed biodiesel. The best
biodiesel conversion was obtained at 12:1 methanol: oil ratio and TGA reveals the importance of the catalyst at lower
molar ratio. Higher glycerol content in the crude glycerol sample with lower impurities is an indicative of the glycerol
quality which favors lower catalyst concentration. Results also showed that while pure glycerol, biodiesel, and WCO
can be all devolatilized, the crud glycerol does not as it holds the transesterification catalyst. Therefore, curd glycerol
pretreatment is necessary prior its usage, particularly thermochemically to avoid chemical corrosion and wear.

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