Fast, Easy Preparation of Biodiesel Using Microwave Heating

Nicholas E. Leadbeater* and Lauren M. Stencel

Department of Chemistry and UCONN Biofuels Consortium, UniVersity of Connecticut,
55 North EagleVille Road, Storrs, Connecticut 06269-3060

ReceiVed April 19, 2006. ReVised Manuscript ReceiVed July 6, 2006

The preparation of biodiesel using a scientific microwave apparatus offers a fast, easy route to this valuable
biofuel with advantages of a short reaction time, a low oil/methanol ratio, and an ease of operation. The
methodology allows for the reaction to be run under atmospheric conditions; it is complete in a matter of a
few minutes and can be performed on batch scales up to 3 kg of oil at a time. It can be utilized with new or
used vegetable oil and with methanol or ethanol with a 1:6 ratio of oil/alcohol.

Introduction Scheme 1

At the start of this new millennium, energy demands are ever

increasing but fossil fuels are becoming limited. As a result,
there is increasing interest in developing alternative energy
resources. These include hydrogen cells,1 solar energy,2 and
wind power;3 however, these technologies are still at the
developing stage, and the costs of applying them are high. An
immediately applicable option is replacement of diesel fuel by which also have numerous applications; for example, in the food,
biodiesel, which consists of the simple alkyl esters of fatty cosmetic, and pharmaceutical sectors.11 The most commonly
acids.4 Biofuels represent abundant carbon-neutral renewable used catalysts in transesterification reactions are NaOH, KOH,
resources for the production of bioenergy.5 With little modifica- and H2SO4. The starting oil and methanol are generally heated
tion, diesel engine vehicles can use biodiesel fuels. They can and stirred with the catalyst, or else, in the case of the basic
also be used as heating oils. Biodiesels are biodegradable and catalysts, the base is first dissolved in the methanol prior to
nontoxic and have lower CO and hydrocarbon emissions than addition. Both batch and continuous-flow technologies have
petroleum-based diesel when burned.6,7 Conversely, they do been used to scale-up the reaction.12 An area of recent research
present other technical challenges such as low cloud points and has been the development of solid-acid catalysts for the
elevated NOx emissions.8 reaction.13 Alongside the advances in chemistry, there have been
Biodiesel is generally made from vegetable oils or animal assessments of the economics of biodiesel production.14
fats by transesterification with methanol using an acid or base An area of research of interest to us is the use of controlled
catalyst (Scheme 1).9,10 The products of the reaction are fatty microwave heating for accelerating synthetic organic transfor-
acid methyl esters (FAME), which are the biodiesel and glycerin, mations.15,16 Using a scientific microwave apparatus, it is
possible to perform reactions quickly, efficiently, and safely.17,18
* To whom correspondence should be addressed. E-mail: While many of the publications in the literature focus on the
[Link]@[Link].
(1) (a) Penner, S. S. Energy 2006, 31, 33. (b) Armor, J. N. Catal. Lett.
use of sealed vessels for performing chemistry using microwave
2005, 101, 131. (c) Rowsell J. L. C.; Yaghi, O. M. Angew. Chem., Int. Ed.
2005, 44, 4670. (10) For recent examples of acid-catalysed biodiesel preparation, see (a)
(2) (a) Jacoby, M. Chem. Eng. News 2005, 83, 35. (b) Kruse, O.; di Serio, M.; Tesser, R.; Dimiccoli, M.; Cammarota, F.; Nastasi, M.;
Rupprecht, J.; Mussgnug, J. R.; Dismukes, G. C.; Hankamer, B. Photochem. Santacesaria, E. G. J. Mol. Catal. A: Chem. 2005, 239, 111. (b) Zullaikah,
Photobiol. Sci. 2005, 4, 957. S.; Lai; C. C.; Vali, S. R. Bioresour. Technol. 2005, 96, 1889. (c) Lotero,
(3) (a) Blackler, T.; Iqbal, M. T. Renewable Energy 2006, 31, 489. (b) E.; Liu, Y. J.; Lopez, D. E.; Suwannakarn, K.; Bruce, D. A.; Goodwin, J.
Gjengedal, T. Wind Energy 2005, 8, 361. G. Ind. Eng. Chem. Res. 2005, 44, 5353.
(4) For an introduction to biodiesel, see (a) Pahl, G. Biodiesel: Growing (11) Vicente, G.; Martinez, M.; Aracil, J. Bioresour. Technol. 2004, 92,
A New Energy Economy, Chelsea Green: White River Junction, VT, 2005. 297.
(b) Knothe, G.; Gerpen; J. V.; Krahl, J. The Biodiesel Handbook; The (12) (a) Bouaid, A.; Diaz, Y.; Martinez, M.; Aracil, J. Catal. Today 2005,
American Oil Chemists’ Society: Champaign, IL, 2005. 106, 193. (b) Harvey, A. P.; Mackley, M. R.; Seliger, T. J. Chem. Technol.
(5) For perspectives on biofuels and biomaterials, see (a) Koonin, S. E. Biotechnol. 2003, 78, 338. (c) Haupt, J.; Dimmig, T.; Dittmar, T.;
Science 2006, 311, 435. (b) Ragauskas, A. J.; Williams, C. K.; Davison, B. Ondruschka, B.; Heyn, B.; Lauterbach, M. Chem. Ing. Tech. 2003, 75, 787.
H.; Britovsek, G.; Cairney, J.; Eckert, C. A.; Frederick, W. J.; Hallet, J. P.; (d) Haupt, J.; Dimmig, T.; Dittmar, T.; Ondruschka, B.; Heyn, B.;
Leak, D. J.; Liotta, C. L.; Mielenz, J. R.; Murphy, R.; Templer R.; Lauterbach, M. Chem. Ing. Tech. 2003, 75, 601.
Tschaplinski, T. Science 2006, 311, 484. (13) For recent examples of solid acid-catalysed biodiesel preparation,
(6) Boehman, A. L. Fuel Process. Technol. 2005, 86, 1057. see (a) Kiss, A. A.; Dimian, A. C.; Rothenberg, G. AdV. Synth. Catal. 2006,
(7) Knothe, G.; Sharp, C. A.; Ryan, T. W. Energy Fuels 2006, 20, 403. 348, 75. (b) Xie, W.; Peng, H.; Chen, L. Appl. Catal., A 2006, 300, 67. (c)
(8) Szybist, J. P.; Kirby, S. R. Boehman, A. L. Energy Fuels 2005, 19, Toda, M.; Takagaki, A.; Okamura, M.; Kondo, J. N.; Hayashi, S.; Domen,
1484. K.; Hara, M. Nature 2005, 438, 178. (d) Lopez, D. E.; Bruce, K. D. A.;
(9) For recent examples of base-catalysed biodiesel preparation, see (a) Goodwin, J. G.; Lotero, E. Appl. Catal., A 2005, 295, 97.
Vicente, G.; Martinez, M.; Aracil, J. J. Am. Oil Chem. Soc. 2005, 86, 1057. (14) Haas, M. J.; McAloon, A. J.; Yee, W. C.; Foglia, T. A. Bioresour.
(b) EÅ erèe, T.; Peter, S. Weidner, E. Ind. Eng. Chem. Res. 2005, 44, 9535. Technol. 2006, 97, 671. (b) Haas, M. J. Fuel Process. Technol. 2005, 86,
(c) Meher, L. C.; Naik, S. N.; Das, L. M. J. Sci. Ind. Res. 2004, 63, 913. 1087.

10.1021/ef060163u CCC: $33.50 © xxxx American Chemical Society

Published on Web 08/01/2006 PAGE EST: 2.8
B Energy & Fuels Leadbeater and Stencel

heating, it is also possible to use an open-vessel (reflux) Table 1. Screening Reactions Using Triolein and Methanola
apparatus. Because the preparation of FAME from oil and triolein/methanol KOH time conversion
methanol is a simple transesterification,19 we wanted to see entry ratio (wt %) (min) percentage
whether, using a commercially available scientific microwave 1 1:9 10 10 96
apparatus, it was possible to prepare biodiesel rapidly and in 2 1:9 5 10 97
good conversions. Microwave heating is more efficient than 3 1:9 1 10 13
conventional convection heating and thus would offer a 4 1:9 5 5 96
5 1:9 5 1 95
resourceful way to prepare biodiesel. In addition, it may be 6 1:6 5 1 98
possible to take advantage of the great rate accelerations seen 7b 1:6 5 1 98
in microwave-promoted chemistry to reduce the time for the a Reaction mixtures were heated to 50 °C using an initial microwave
biodiesel production process. Our initial results, focused on power of 25 W and then held at this temperature for the allocated time.
batch-type biodiesel preparation, are presented here. b Using NaOH in place of KOH.

Experimental Section
flask and a glass connector (linking the flask inside the cavity with
General Procedures. All reactions were performed under a reflux condenser outside the cavity) into the other. A fiber-optic
atmospheric pressure in the presence of air. 1H nuclear magnetic probe was placed into the immersion well. The reaction mixture
resonance (NMR) spectra were recorded at 293 K on a 300 or 400 was heated from room temperature to 50 °C using an initial
MHz spectrometer, with chemical shifts being referenced to the microwave power of 600 W and then held at this temperature for
residual peaks of CHCl3 in CDCl3 (in parts per million). Laboratory- 1 min. Upon cooling to room temperature, the reaction vessel was
grade methanol, ethanol, and potassium hydroxide were used as removed from the microwave cavity and the contents were decanted
purchased without any further purification. Soybean oil was into a settling vessel. The extent of the transesterification of soybean
purchased from a local grocery store. Small-scale open-vessel oil was determined by solution 1H NMR spectroscopy. The relevant
microwave reactions were conducted using a commercially available signals chosen for integration were those of methoxy groups in the
monomode microwave unit (CEM Discover). The machine consists FAME (3.66 ppm, singlet) and those of the R-methylene protons
of a continuous focused microwave power delivery system with present in all triglyceride derivatives (2.3 ppm, triplet) of the
an operator selectable power output from 0 to 300 W. Reactions soybean oil.20 The conversion was calculated directly from the
were performed in a 100 mL round-bottom flask. The temperature integrated areas of these signals. The FAME was also analyzed
of the contents of the vessel was monitored using an IR sensor using gas chromatography using the American Society for Testing
located underneath the reaction vessel. The contents of the vessel and Materials (ASTM)21 test method for determination of free and
are stirred by means of a rotating magnetic plate located below the total glycerin.22
floor of the microwave cavity and a Teflon-coated magnetic stir
bar in the vessel. Temperature, pressure, and power profiles were Results and Discussion
monitored using commercially available software provided by the
microwave manufacturer. For the large-scale reactions, a com- Our investigations started by using 9-octadecenoic acid (Z)
mercially available multimode microwave apparatus was used 1,2,3-propanetriyl ester (triolein) as a substrate because this is
(CEM MARS). The machine consists of a continuous microwave a good single-component model for vegetable oil. Using
power delivery system with an operator selectable power output potassium hydroxide as a base, we wanted to look at the effects
from 0 to 1200 W. Reactions were performed in either a 1, 3, or 5 of the methanol/triolein ratio, catalyst loading, and reaction
L round-bottom flask. The temperature of the contents of the vessel temperature and time on the transesterification of triolein with
was monitored using a fiber-optic probe inserted directly into the
methanol to yield methyl oleate. Initial screening reactions were
reaction mixture by means of a glass thermowell. The contents of
the vessel were stirred either by means of a rotating magnetic plate performed using a monomode microwave apparatus in sealed
located below the floor of the microwave cavity and a Teflon-coated tubes at 50 °C using 1 mL of triolein. Our results are shown in
magnetic stir bar in the vessel or else using an overhead paddle Table 1. Reactions were monitored using NMR spectroscopy.
stirrer. Optimal reaction conditions involved using a 1:6 triolein/
Typical Reaction Procedure. To a 5 L two-neck round- methanol ratio (1:2 stoichiometric ratio), 5 wt % KOH, heating
bottomed flask equipped with a stirring bar were added soybean the reaction mixture to 50 °C, and holding at this temperature
oil (3 kg) and a solution of potassium hydroxide (30 g) in methanol for 1 min (entry 6 in Table 1). This gave a 98% conversion of
(810 mL). The reaction mixture was placed into the microwave the triolein to methyl oleate. An increased triolein/methanol ratio
cavity, with an immersion well placed into one of the necks of the (entry 5 in Table 1), reaction time (entries 3 and 4 in Table 1),
and reaction temperature or KOH loading were not necessary.
(15) Other transesterifications using microwave heating have been
reported previously. See for example (a) Bezdushna, E.; Ritter, H.; Troev, Reduction of the KOH loading from 5 to 1 wt % had a negative
K. P. Macromol. Rapid Commun. 2005, 26, 471. (b) Karmee; S. K. Chadha, effect on conversion (entry 3 in Table 1). Changing the base
A. Synth. Commun. 2005, 35, 1151. (c) Roy, I.; Gupta, M. N. Tetrahedron from potassium hydroxide to sodium hydroxide had no signifi-
2003, 59, 5431. cant effect on product conversion (entry 7 in Table 1 ).
(16) For a review, see Leadbeater, N. E. Chem. Commun. 2005, 2881.
(17) (a) Arvela, R. K.; Leadbeater, N. E.; Mack; T. M.; Kormos, C. M. We next performed the reaction in an open vessel using the
Tetrahedron Lett. 2006, 47, 217. (b) Arvela, R. K.; Leadbeater, N. E. Org. monomode microwave apparatus. For ease of operation, we
Lett. 2005, 7, 2101. (c) Arvela, R. K.; Leadbeater, N. E. J. Org. Chem. predissolved the KOH in methanol prior to the reaction. It was
2005, 70, 1786. (d) Arvela, R. K.; Leadbeater, N. E.; Sangi, M. S.; Williams,
V. A.; Granados, P.; Singer, R. D. J. Org. Chem. 2005, 70, 161. possible to scale-up the reaction 10 times (10 mL of triolein)
(18) For books on microwave heating in synthesis, see (a) Kappe, O.; with no negative effect. We then moved to using vegetable oil
Stadler, A. MicrowaVes in Organic and Medicinal Chemistry; Wiley- as a substrate. Because the oil is a mixture of triglycerides, we
VCH: Weinhiem, Germany, 2005. (b) Tierney, J. P., Lidström, P., Eds.;
MicrowaVe Assisted Organic Synthesis; Blackwell: Oxford, U.K., 2005. used literature data in determining the volume of methanol
(c) Loupy, A., Ed.; MicrowaVes in Organic Synthesis; Wiley-VCH:
Wenheim, Germany, 2002. (d) Hayes, B. L. MicrowaVe Synthesis: Chemistry (20) Sercheli, R.; Vargas, R. M.; Schuchardt, U. J. Am. Oil Chem. Soc.
at the Speed of Light; CEM Publishing: Matthews, NC, 2002. 1999, 76, 1207.
(19) For recent reviews on the area, see (a) Roberts, B. A.; Strauss, C. (21) American Society for Testing and Materials (ASTM). http://
R. Acc. Chem. Res. 2005, 38, 653. (b) Kappe, C. O. Angew. Chem., Int. [Link].
Ed. 2004, 43, 6250. (22) ASTM method D 6584-00.
MicrowaVe-Promoted Preparation of Biodiesel PAGE EST: 2.8 Energy & Fuels C

be transesterified in the 5 L vessel was 3 kg (∼3.8 L). Running

the reaction using our optimal conditions (1 wt % KOH, heating
to 50 °C using 600 W of microwave power, and holding for 1
min) resulted in a quantitative conversion to the transesterified
products. The reaction mixture was agitated using an overhead
paddle stirrer.
While using new oil for our screening reactions, we were
also keen to see if the used oil could also be a feedstock for
microwave-promoted biodiesel manufacture. Used frying oils
required to maintain our 1:6 substrate/methanol ratio and used have properties different from those of new oils. The high
0.27 mL of methanol/1 g of oil. Performing the reaction using temperatures of typical cooking processes and the water from
our optimum reaction conditions with 10 mL of oil gave a the foods have effects on the composition and stability of the
quantitative conversion to biodiesel by NMR.23 The biodiesel oil.24 We decided to test used oil in our methodology and,
was also assayed by gas chromatography (GC) using the ASTM working on the 3 kg scale, found it was possible to obtain
test method for determination of free and total glycerin.21,22 quantitive conversion to biodiesel using exactly the same
To increase the scale of the reaction, we moved to a conditions as with new oil.
multimode microwave apparatus equipped with a magnetic Although methanol is the most commonly used alcohol in
stirrer and with the capability to run open-vessel reactions. The the transesterification of vegetable oil to biodiesel, if it could
reaction vessel is placed into the microwave cavity and, using be replaced by ethanol, then it would be possible to obtain both
a glass connector, can be attached to a reflux condenser located starting materials from bioresources. Ethanol is most commonly
outside the microwave cavity. A temperature measurement is made from corn but can also be produced from other feedstocks
possible using a fiber-optic probe inserted directly into the such as grain sorghum, wheat, barley, or potatoes. We screened
reaction mixture by way of a glass immersion tube. We initially ethanol as a substrate in the transesterification of new vegetable
performed the reaction in a 3 L reaction vessel using 2 kg (∼2.3 oil and found that the same conditions as used for methanol
L) of vegetable oil. Working with a 1:6 oil/methanol ratio and worked well, with a quantitative conversion being obtained after
5 wt % KOH, the reaction mixture was heated to 50 °C using 1 min at 50 °C. Again, the KOH was predissolved in the alcohol
a microwave power of 600 W. This took approximately 3.5 min. starting material prior to the reaction.
The mixture was then held at 50 °C for 1 min before being There has been a report of the use of a domestic microwave
allowed to cool to room temperature. A quantitative conversion for the reaction between methanol and seed oils.25 This is,
of the oil to biodiesel was obtained. The mixture was stirred however, limited because of the scale possible and the inherent
continuously during the course of the reaction. This did not reproducibility and safety issues concerned with using a home
totally mix the methanol and oil (which are essentially im- microwave apparatus for synthesis. The only report of a
miscible), but the agitation was sufficient. We were keen to scientific microwave apparatus for transesterification of trig-
re-optimize the reaction conditions and found that, on this large lycerides to fatty acid methyl esters involves use of 10 wt % of
scale, it was possible to decrease the KOH loading to 1 wt % a zeolite catalyst, heating to 170 °C for 2 h in a sealed vessel,
with no noticeable effect on conversion. Using NaOH in place and only moderate conversions are obtained.26 There are two
of KOH gives the same results. patent applications on the use of microwave heating in biofuel
The microwave apparatus has a cavity capable of accom- manufacture.27,28 Our methodology allows for the reaction to
modating a 5 L reaction vessel. We therefore decided to scale- be run under atmospheric conditions; it is complete in a matter
up the reaction further. The maximum quantity of oil that could of a few minutes and can be performed on batch scales up to 3
kg of oil at a time. It can be utilized with new or used vegetable
(23) NMR spectroscopy has been shown to be a valuable tool for oil and with methanol or ethanol. The 1:6 ratio of oil/methanol
monitoring biodiesel preparation. See for example (a) Gelbard, G.; Bres,
O.; Vargas, R. M.; Vielfaure, F.; Schuhardt, U. F. J. Am. Oil Chem. Soc. is lower than many reports when using conventional heating
1995, 72, 1239. (b) Knothe, G. J. Am. Oil Chem. Soc. 2001, 70, 1025. (c) where a ratio of 1:9 up to 1:30 is more commonly seen. Work
Haupt, J.; Dimmig, T.; Dittmar, T.; Ondruschka, B.; Heyn, B.; Lauterbach, is currently underway to translate the methodology from batch
M. Chem. Ing. Tech. 2003, 75, 595.
(24) Tomasevic, A. V.; Siler-Marinkovic, S. S. Fuel Process. Technol.
to a continuous-flow technology as well as developing new
2003, 81, 1. catalysts for improving the composition of the biodiesel product.
(25) Breccia, A.; Esposito, G.; Breccia Fratadocchi, G. B.; Fini, A. J.
MicrowaVe Power Electromag. Energy 1999, 34, 3.
(26) Mazzocchia, C.; Modica, G.; Kaddouri, A.; Nannicini, R. C. R. Acknowledgment. We thank the University of Connecticut for
Chem. 2004, 7, 601. funding and members of the UCONN Biofuels Consortium (J.
(27) Breccia Fratadocchi, A. WO Patent 03/014272 A2, 2003. Stuart) for GC analysis.
(28) Portnoff, M. A.; Purta, D. A.; Nasta, M. A.; Zhang, J.; Pourarian,
F. U.S. Patent 2005/0274065 A1, 2005. EF060163U