th
V International Symposium on “Fusion of Science & Technology”,
New Delhi, India, January 18-22, 2016
ID: 2016-ISFT- 355
Tetrahydrofuran-Assisted Transesterification
Biodiesel from Waste Cooking Oil
AprajitaChauhan1, V.K. Singh2, Y. Kwatra3
1,2,3
Department of Chemistry, Sri Aurobindo College (University of Delhi), Malviya Nagar, New Dehi-110017, India
1
[email protected]
Abstract: Base-catalyzed transesterification of waste Co-solvent transesterification of various edible and non-
cooking oil for the production of biodiesel was assisted by edible vegetable oils as well as animal fats has been
the addition of cosolventTetrahydrofuran (THF). In addition investigated .Biodiesel production from Waste Cooking
to lowering of reaction temperature and reduction in Oil(WCO) with this co-solvent has also attracted attention
reaction time for transesterification, THF facilitated in the recent past as this feedstock has enormous potential in
production of methyl ester in a single phase. THF-assisted future[1]. THF-assisted biodiesel production has shown
base-catalyzed reaction was optimized for various promising results with reference to improvement in
parameters. Maximum biodiesel production( 92.8%) was transesterification efficiency [10-13].
obtained with 4% THF; 0.6% sodium methoxide (catalyst),
6:1 methanol to oil ratio, 45 min reaction time, 500C There is a difference in the physicochemical properties of
reaction temperature. Added to this, maximum glycerol refined vegetable oils and the waste cooking oils. Moreover
recovery (18.62%) was obtained at 500C using lower WCOs from different regions also differ in their viscosity,
concentrations of THF(2%). Use of THF highlights even density and saponification values and free fatty acid
more economically viable and greener potential for composition[14].Keeping this variation in mind, present
biodiesel production as this co-solvent is non-toxic, un- investigations were carried out on waste cooking oil
reactive and of biomass origin. samples collected from restaurants in South Delhi, with an
objective to ascertain optimal reaction conditions for THF-
Keywords: Biodiesel, waste cooking oil, transesterification, assisted methyl ester production.
tetrahydrofuran, optimization
2. MATERIALAND METHODS
1. INTRODUCTION Waste cooking oil (WCO) was procured from the
There are some inherent problems associated with the use of restaurants and eateries in South Delhi. The oil was
basic catalysts in transesterification of oils and fats in subjected to experimental analysis for various
biodiesel production [3].These include additional inputs in physicochemical properties already outlined by Chauhan et
terms of soap removal solvents, and energy inputs in terms al [1]. Since the free fatty acid content of this feedstock was
of higher temperatures. Some of these steps may also not be < 0.2, no acid catalyst was required. The base-
environment-friendly. Although, use of heterogeneous catalyzedtransesterification reaction was carried out in a
catalysts may have some advantages [4-5], their round-bottomed flask fitted with a magnetic stirrer. The
disadvantages are also many, like high alcohol to oil molar reactor comprised pre-heated waste cooking oil, methanol,
ratio (12-30), high temperature (120-2000C) and a very long sodium methoxide catalyst and THF as a co-solvent. The
reaction time of 3-8 hours [6]. Addition of co-solvents in the process variables were optimized as a) Catalyst
reaction medium is also an alternative approach which has concentration, b) alcohol to oil molar ratio, c) THF
been shown to enhance the reaction rates, as well as concentration, d) Reaction time, e) Reaction temperature,
increasing the solubily and mass transfer between oil and and f) Glycerol recovery.
methanol [7-8].
The Gas Chromatographic analysis of WCO-biodiesel was
Tetrahydrofuran (THF) was chosen as a co-solvent as it conducted to identify and quantify the FAME composition
possesses several advantages. THF has the ability to as per the already standardizedprotocol[2].
dissolve organic compounds at the hydrophobic side as well
3. RESULTSANDDISCUSSION
as bind water and alcohol on the hydrophilic side[9]. It is a
non-hazardous and unreactive chemical with a low boiling The physico-chemical properties of waste-cooking oil were
point (670C). Further, THF is cheap and can also be co- investigatedby us earlier (Chauhan et al 2014). Due to its
distilled and recycled at the end of the reaction process. low free fatty acid value, this oil requires only one stage
ISBN: 978-93-84935-64-1 ♦ 472 ♦
Tetrahydrofuran-Assisted Transesterification Biodiesel from Waste Cooking Oil
catalytic process. The fatty acid methyl ester (FAME) resulted in a slight reduction in the oleic acid methyl ester
constituted more than half (51.88%) by weight of the content (46.75%). Table 1 illustrates the fatty acid
monounsaturated methyl ester, viz., oleic acid methyl ester composition profile of biodiesel produced from present
(Methyl[12E] octadecenoate), making this fuel suitable for WCO samples.
high temperatures[1]. In the present study, addition of THF
TABLE 1: Fatty acids composition of waste cooking oil biodiesel
FAME Molecular Formula Retention time % peak area
Myristic Acid C14:0 8.40 0.108
Palmitic Acid Methyl Ester C17:0 12.34 13.318
Stearic Acid C18:0 17.28 31.95
Oleic Acid C18:1 18.57 46.750
Linolenic Acid C18:2 19.36 6.423
Arachidic Acid C20:0 20.39 0.393
Behinic Acid C22:0 23.09 0.393
Overall total 98.703
3.1 EFFECT OF CATALYST CONCENTRATION ON methyl ester (92.8%) were recorded. Increasing the catalyst
BIODIESEL YIELD concentration resulted in a gradual decline in both
conversion as well as recovery (Table 2). This decline could
The catalyst (sodium methoxide) concentration was varied be attributed to an increase in viscosity and soap formation
from 0.5 to 0.9% (w/v of oil) keeping the other variables which causes difficulty in separation of biodiesel from
constant. Best catalytic concentration was found to be 0.6% glycerol [15].
where maximum recovery (62.5%) and conversion of oil to
100
90
80
70
60
50
40
% Yield
30
20
10
0
1 2 3 4 5
Catalyst Concentration (%) 0.5 0.6 0.7 0.8 0.9
Recovery (%) 51.76 62.5 60.8 58.65 57.4
Conversion(%) 83.25 92.8 91 90.15 89.88
THF to Oil Ratio-4%, Reaction Temperature-500 C, Methanol to oil molar ratio-6:1
Fig. 1. Effect of catalyst concentration on biodiesel yield
3.2 EFFECT OFMETHANOLTO OIL MOLAR RATIO methanol to oil molar ratio (Table 3). Values of both these
sub-parameters declined as the methanol to oil ratio was
Effect of this important parameter was studied by using increased beyond 6:1, which inhibited the catalyst active
different methanol to oil molar ratios ranging between 5:1 center. Since transesterification is an equilibrium-limited
and 9:1. Best results for recovery (68.3%) and conversion of
WCO into its methyl ester (92.8%) were obtained at 6:1
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V International Symposium on “Fusion of Science & Technology”, New Delhi, India, January 18-22, 2016 ♦ 473 ♦
Tetrahydrofuran-Assisted Transesterification Biodiesel from Waste Cooking Oil
reaction, the composition of the reaction mixture will decide
the direction of the reaction.
100
90
80
70
60
50
% Yield
40
30
20
10
0
5:1 6:1 7:1 8:1 9:1
Recovery(%) 59.1 68.3 65.8 64.5 63.2
Conversion (%) 84 92.8 90.3 88.7 87.2
THF to Oil Ratio-4%, Reaction Temperature-500C, Catalyst concentration-0.6%
Fig. 2. Effect of methanol to oil molar ratio on biodiesel yield
3.3 EFFECT OF THF, REACTION TIME AND TEMPERATURE ON YIELD
Effect of THF concentration on biodiesel production at varying temperature revealed maximum yield at 500C using 4% co-
solvent (Table 4). Higher reaction temperature range was required (650C) for a similar catalytic conversion without THF.
Also, a much longer time period (3h) was needed to convert the waste oil stock feed to biodiesel [1].
6% 100
90
5%
80
70
4%
THF conc. (%)
60
Yield (%)
3% 50
40
2%
30
20
1%
10
0% 0
110 100 60 45 30
Decreasing time (min)
THF Temp= 50 Temp=60
Fig. 3.Effect of THF concentration, reaction time and temperature on biodiesel yield
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V International Symposium on “Fusion of Science & Technology”, New Delhi, India, January 18-22, 2016 ♦ 474 ♦
Tetrahydrofuran-Assisted Transesterification Biodiesel from Waste Cooking Oil
3.4EFFECT OF THF AND TEMPERATURE ON GLYCEROL RECOVERY
Glycerol recovery(measured in terms of weight) at different temperature regimes was studied with respect to THF. Maximum
recovery of glycerol(18.62%) was recorded at 500C using 2% co-solvent. Increasing the concentration of THF to 4% and
temperature to 600C resulted in a decline in glycerol yield (Table 5).
6% 20
18
5%
16
14
4%
Glycerol yield (%)
THF conc. (%)
12
3% 10
8
2%
6
4
1%
2
0% 0
110 100 60 45 30
Decreasing time (min)
THF Temp= 50 Temp=60
Fig. 4. Effect of THF concentration and temperature on glycerol recovery
4. CONCLUSIONS oil. Napier Indian Advanced Research Journal of
Science 2015, 17, 31-34.
These results indicate that THF accelerates the [3] Meher, L.C.; Sagar, D.V.; Naik, S.N. Technical
transesterification reaction and augments the conversion of aspects of biodiesel production by
triglycerides at lower temperature, requiring lesser transesterification—a review. Renewable Sustainable
concentration of catalyst. Similar results have been obtained Energy Reviews 2006, 10, 248-268.
in cottonseed oil[16], colza oil[17],rice bran oil[18] and
[4] Helwani, Z.; Othman, M.R.; Aziz, N.; Fernando,
chicken fat [19]. This makes THF as one of the most
W.J.N.; Kim, J. Technologies for production of
preferred green, clean and cheap adjunct for the biodiesel
biodiesel focusing on green catalytic techniques: A
industry.
review. Fuel Processing Technology 2009, 90, 1502-
ACKNOWLEDGEMENT 1514.
[5] Melero, J.A.; Iglesias, J.; Morales, G. Heterogeneous
We gratefully acknowledge the award of DU Innovation acid catalysts for biodiesel production: current status
Project 2013-2014 (SAC-203) by the University of Delhi. and future challenges. Green Chemistry 2009, 11,
Our special thanks to Prof. Naveen Kumar (DTU) for his 1285-1308.
mentorship and providing facilities. Thanks are also due to [6] Jothiramalingam, R; Wang, M.K. Review of recent
Dr. YahayaAlhassan (DTU) for valuable discussions. development in solid, acid, base and enzyme
catalysts (heterogeneous) for biodiesel production.
REFERENCES
Indian Engineering Chemical Research 2009, 48,
[1] Chauhan, A.; Singh, V.K.; Verma, S.; Lahiri, S. Acid 6162-6172.
and base catalysedtransesterification of used [7] Lam, M.K.; Lee, K.T. Accelerating
vegetable (gutter) oil and non-edible oils to fatty acid transesterification reaction with biodiesel as co-
methyl esters. Journal of Biofuels 2014, 5(2), 68-75. solvent: A case study for solid sulfated tin oxide
[2] Chauhan, A. Fatty acid methyl ester (FAME) profile catalyst. Fuel 2012, 89, 3866-3870.
and characterization of biodiesel from waste cooking
th
V International Symposium on “Fusion of Science & Technology”, New Delhi, India, January 18-22, 2016 ♦ 475 ♦
Tetrahydrofuran-Assisted Transesterification Biodiesel from Waste Cooking Oil
[8] Boocock, D.G.B.; Konar, S.K.; Mao, V.; Sidi, H. Journal of Biofuels 2014, 5(2), 83-95.
Fast one-phase oil-rich processes for the preparation [15] Encinar, J.M.; Gonzalez, J.F.; Pardal, A.; Martinez,
of vegetable oil methyl esters. Biomass and G.Transesterification of rapeseed oil with methanol
Bioenergy 1996, 11, 43-50. in the presence of various cosolvents, Proceedings of
[9] Muyassaroh, E.D.D.; Hudha, M.I. Biodiesel Third International Symposium on Energy from
dariMinyakJarakPagardengamVariasiPenambahan Biomass and Waste, Venice, Italy. 8-11 Nov. 2010,
Co-solvendanWaktuReaksi. JurnalTeknikKimia 1-17.
2012, 7, 8-11. [16] Jinsi, C.; Xiangyang, W.; Enzhu, H.; Yufu, X.
[10] Lin, C.-C.; Hsiao, M.-C. Optimization of biodiesel Xianguo, H.; Lijun, P.; Shaotong, J. Biodiesel
production from waste vegetable oil assisted by co- production by transesterification cottonseed oil with
solvent and microwave using a two-step process. ethanol using tetrahydrofuran as cosolvent. IEEE,
Journal of Sustainable Bioenergy Systems 2013, 3, 2011.
1-6. [17] Caglar, E. Biodiesel production using co-solvent.
[11] Zhang, Y.; Dube, M.A.; McLean, D.D.; Kates, M. European Congress of Chemical Engineering
Biodiesel production from waste cooking oil: 1. (ECCE-6) Copenhagen, 16-20 September,
Process design and technological assessment. 2007(Book of Abstracts).
Bioresource Technology 2003, 89, 1-16. [18] Taggar, M.S.; Soni, R.; Singh, S.K.; i, S.S.; Sangha,
[12] Elkady, M.F.; Zaatout, A.; Balbaa, O. Production of M.K. Tetrahydrofuran-assisted base
biodiesel from waste vegetable oil via KM catalysedtransesterification of rice bran oil for
Micromixer. Journal of Chemistry 2015,2015, 1-9. biodiesel production. Journal of Biofuels , 2014, 5,
[13] Math, M.C.; Kumar, S.P.; Chetty, S.V. Technologies 62-67.
for biodiesel production from used cooking oil—a [19] Fransiska, F.; Felicia; Si, Taslim, M. Biodiesel
review. Energy for Sustainable Development 2010, production from chicken fat using tetrafuran as co-
14, 339-245. solvent. Proceedings of the 5thSriwijaya International
[14] PavalavanaPandian, J.; Prabu, B.; Pugazhvadivu, M. Seminar on Energy and Environmental Science &
Indian waste frying oils: Influence of fatty acid Technology, Palembang, Indonesia. Sept. 10-11,
composition on their physic-chemical properties. 2014, 27-31.
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V International Symposium on “Fusion of Science & Technology”, New Delhi, India, January 18-22, 2016 ♦ 476 ♦
