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Short communication

Transesterification of castor oil assisted by microwave irradiation

G. Perin a,*, G. Álvaro a, E. Westphal a, L.H. Viana b, R.G. Jacob a,
E.J. Lenardão a, M.G.M. D’Oca c
a
Instituto de Quı́mica e Geociências, Universidade Federal de Pelotas, UFPel, P.O. Box 354, 96010-900 Pelotas, RS, Brazil
b
Departamento de Farmácia-Bioquı́mica e Quı́mica, Universidade Federal do Mato Grosso do Sul, Campo Grande, MS, Brazil
c
Departamento de Quı́mica, Fundacßão Universidade Federal do Rio Grande, FURG, Rio Grande, RS, Brazil

Received 19 September 2007; received in revised form 18 January 2008; accepted 25 January 2008
Available online 20 February 2008

Abstract

Microwave assisted transesterification of castor bean oil was carried out in the presence of methanol or ethanol, using a molar ratio
alcohol/castor bean oil of 6:1, and 10% w/w of acidic silica gel or basic alumina (in relation to the oil mass) as catalyst. Under acid catal-
ysis, the reaction occurred with satisfactory yields using H2SO4 immobilized in SiO2, methanol under conventional conditions (60 °C for
3 h) as well as using microwave irradiation for 30 min. The best results were obtained under basic conditions (Al2O3/50% KOH) using
methanol and conventional (60 °C, stirring, 1 h) or microwave conditions (5 min). In comparison with conventional heating, the cata-
lyzed alcoholysis assisted by microwaves is much faster and leads to higher yields of the desired fatty esters.
Ó 2008 Elsevier Ltd. All rights reserved.

Keywords: Castor oil transesterification; Acidic and basic solids; Microwave irradiation

1. Introduction ported catalyst under solvent-free conditions [10] using

The main component of castor bean oil is besides small
amounts of oleic and linoleic acids (5–7%), ricinoleic acid
(90%), which peculiar chemical properties, turn it attractive
as raw material for the preparation of several compounds
for the fine chemicals industry [1].
The demand of renewable combustible derived from
vegetable oils increased in the last years [2], and has led
to the development of a number of processes for transeste-
rification of oils with methanol or ethanol, involving acidic
[3,4] or basic catalysis [5,6]. Recently, some papers showing
the advantages of microwave irradiated transesterification
methods have been published in the literature [7–9]. How-
ever, to the best of our knowledge, microwave irradiation
to perform the transesterification of castor bean oil with
methanol or ethanol has not yet described.
Looking for cleaner alternatives to classical syntheses,
we have developed several protocols involving solid sup-
*
Corresponding author. Tel./fax: +55 53 32757354.
E-mail address: gelson_perin@ufpel.edu.br (G. Perin).
microwave irradiation [11]. More recently, several solid
acid catalysts, including H2SO4/SiO2 employed in organic
synthesis are found as efficient and reusable catalysts [12].
As a continuation of our studies using SiO2 or Al2O3 as
solid support for basic and acidic catalysts, we describe
here the transesterification of castor bean oil with methanol
or ethanol to afford the respective fatty acid methyl and
ethyl esters (Scheme 1).
2. Experimental
2.1. Chemicals and NMR characteristics
Methanol (99.8%) and ethanol (99.5%) as well as the
other chemicals (analytical grade) were used as purchased
without any further purification. The castor bean oil was
obtained from EMBRAPA-CPACT (Pelotas, RS, Brazil).
The 1H NMR spectra of the fatty esters in CDCl3 were
recorded with a 200 MHz (Bruker DPX 200) spectrometer.
Chemical shifts are expressed as parts per million (ppm)
downfield from tetramethylsilane as an internal standard.

0016-2361/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.01.018

Please cite this article in press as: Perin G et al., Transesterification of castor oil assisted by microwave irradiation, Fuel (2008),
doi:10.1016/j.fuel.2008.01.018
 ARTICLE IN PRESS

2 G. Perin et al. / Fuel xxx (2008) xxx–xxx

O
R O
O
O R acid SiO2 or basic Al2O3 HO
O + 3 R1OH 3 R OR1 + OH
O MW (548W), r.t or heating HO
R OH
O
1
R= R = CH3 or CH3CH2

Scheme 1.

2.2. Catalysts preparation 540 W) under the conditions indicated in Table 1. The reac-
tion was monitored by TLC, performed on glass plates
The supported catalysts were prepared through the fol- coated with silica gel G (Merck) using ethyl acetate and hex-
lowing procedures: ane (30:70 v/v) as mobile phase. After the conclusion of the
(a) SiO2/50% H2SO4 catalyst: 10.0 g of silica (silica gel reaction (see Table 1), the crude mixture was cooled and
60, 230–240 mesh, Merck) and 100 mL of aqueous separated from the catalyst by filtration. Subsequently, it
H2SO4 (50%) were mixed in a beaker and the suspension was transferred to a separatory funnel and glycerol sepa-
stirred at room temperature for 30 min. The resulting solid rated by gravity for 12 h. The alcohol was removed by dis-
was filtered under reduced pressure, dried at 150 °C for tillation and residual catalyst, glycerol and alcohol by
15 h in an oven and cooled to room temperature in a washing the ester with water (2  50 mL). The same proto-
desiccator. col was used for Al2O3/50% KOH.
(b) Al2O3/50% H2SO4: Prepared by the same way using
10.0 g of Al2O3 90 (0.063–0.200 mm, Merck) instead of sil-
ica gel. 2.4. Transesterification assisted by conventional heating
(c) Al2O3/KOH (50%): 5.0 g of alumina (Al2O3 90,
0.063–0.200 mm, Merck), 5.0 g of KOH and 3.0 mL of 2.4.1. Method B
water were mixed in a 100 mL beaker. The suspension To 5.0 g of SiO2/50% H2SO4 and 50.0 g of castor bean
was stirred for 15 min at room temperature, dried in an oil in a 250 mL reaction flask equipped with a reflux con-
oven at 80 °C for 3 h, followed by 15 h at 150 °C and finally denser, 14 mL of methanol (99.8%) or 20.5 mL of ethanol
cooled to room temperature in a desiccator. (99.5%), molar ratio alcohol/castor bean oil = 6:1, was
added at room temperature under stirring and subse-
quently heated to 60 °C. The reaction progress was fol-
2.3. Transesterification assisted by microwave heating lowed by TLC. After completion of the reaction (see
Table 1) the product was separated and purified as
2.3.1. Method A described for Method A. The same protocol was used for
To 5.0 g of the acid catalyst (SiO2/50% H2SO4) and Al2O3/50% KOH.
50.0 g of castor bean oil in a 250 mL reaction flask equipped
with a septum port and 14 mL of methanol (99.8%) or
20.5 mL of ethanol (99.5%), giving a molar ratio: alcohol/ 2.4.2. Method C
castor bean oil = 6:1, was added at room temperature. A mixture of 5.0 g of Al2O3/50% KOH, 50.0 g of castor
The mixture was then irradiated in a common household bean oil and 14 mL of methanol (99.8%), molar ratio alco-
MW oven (Panasonic model Pı́ccolo NN-S42BK, working hol/castor bean oil = 6:1, was stirred at room temperature
at 2.45 MHz, with a programmable power from 40 to for 1.5 h. Subsequently, the product was separated and
Table 1
Preparation of ethyl and methyl esters from castor bean oil
Entry Method Solid supported catalyst Alcohol Experimental conditions Reaction time Conversion (%)
1 C SiO2/50% H2SO4 Methanol Stirring at r.t. 48 h 78
2 B SiO2/30% H2SO4 Methanol Stirring at 60 °C 5h 95
3 B SiO2/40% H2SO4 Methanol Stirring at 60 °C 4h >95
4 B SiO2/50% H2SO4 Methanol Stirring at 60 °C 3h >95
5 A SiO2/50% H2SO4 Methanol MW irradiation (40 W) 30 min 95
6 B SiO2/50% H2SO4 Ethanol Stirring at 60 °C 6h 95
7 A SiO2/50% H2SO4 Ethanol MW irradiation (220 W) 20 min >95
8 A SiO2/30% H2SO4 Ethanol MW irradiation (220 W) 25 min 95
9 C Al2O3/50% KOH Methanol Stirring at r.t. 1.5 h >95
10 B Al2O3/50% KOH Methanol Stirring at 60 °C 1h >95
11 A Al2O3/50% KOH Methanol MW irradiation (40 W) 5 min 95

Please cite this article in press as: Perin G et al., Transesterification of castor oil assisted by microwave irradiation, Fuel (2008),
doi:10.1016/j.fuel.2008.01.018
 ARTICLE IN PRESS
G. Perin et al. / Fuel xxx (2008) xxx–xxx
purified as described for Method A. The same protocol was
used for SiO2/50% H2SO4.
3. Results and discussion
Table 1 summarizes the catalytic activities for the
transesterification of castor bean oil observed under differ-
ent conditions for sulfuric acid immobilized SiO2 as well as
for KOH immobilized on Al2O3.
It was found that using SiO2/30% H2SO4, at room tem-
perature, the reaction is slow and a conversion rate below
60% is observed, even after stirring for 24 h. Using higher
concentrations of acid (40% and 50%), the conversion to
the methyl ester was also incomplete, even after 48 h (entry
1, Table 1). However, when the same reaction was per-
formed at 60 °C, the conversion was already complete after
5 h even with the SiO2/30% H2SO4 catalyst (entry 2, Table
1). The use of higher H2SO4 concentrations (40% and 50%)
with SiO2 reduced the reaction time to 4 and 3 h, respec-
tively (entries 3 and 4, Table 1). Aiming to reduce still more
the reaction time, the mixture was irradiated (40 W) with
microwaves [13]. We observed the complete consume of
the starting oil after 30 min, and the methyl fatty esters
were obtained with comparable conversion rate (entry 5,
Table 1). When the same protocol was performed at higher
MW power (200 W), we observed incomplete consume of
the oil after 30 min, and the reaction mixture turned black.
The use of acidic Al2O3 for the reaction was also stud-
ied. However, the reaction was incomplete under conven-
tional condition as well as under microwave irradiation.
Using acidic conditions for the ethanolysis of castor oil
the best results were achieved under conventional condi-
tions with SiO2/50% H2SO4 stirred at 60 °C for 6 h (entry
6, Table 1). When this mixture was irradiated with micro-
waves (220 W) for 20 min we observed complete conver-
sion of the oil to the respective ethyl esters (entry 7,
Table 1). In comparison with the methanolysis, irradiation
at a higher microwave power was necessary (compare with
entry 5, Table 1).
To verify the intervention of microwave specific effects it
is necessary to perform a study with controlled temperature
of the system, what is not possible with a common domes-
tic oven [14]. Microwave specific effects can be expected
when the polarity of the system is altered during the pro-
gress of the reaction [15]. As the transesterification reaction
involves an increase of the polarity of the system during the
course of the reaction, we believe that a combination of
thermal and MW specific effects (non purely thermal) are
involved here. Although the energy transfer and distribu-
tion in a domestic microwave oven is not controlled, we
found that the microwave-assisted reactions are more effi-
cient, convenient and cleaner.
In the methanolysis using basic alumina as catalyst, we
observed the complete conversion of castor bean oil to its
methyl esters after stirring for 1.5 h, even at room temper-
ature (entry 9, Table 1). The reaction time decreased to 1 h
when the mixture was heated to 60 °C and to 5 min when
Please cite this article in press as: Perin G et al., Transesterification of castor oil assisted by microwave irradiation, Fuel (2008),
doi:10.1016/j.fuel.2008.01.018
3
Table 2
1
H NMR spectral data of fatty acid methyl and ethyl esters
Fatty acid ester Chemical shift (200 MHz, CDCl3; d, ppm)
Methyl 0.90 (t, J 6.8 Hz, 3H); 1.30–1.71 (m, 21H); 2.03–2.11
ricinoleic (m, 2H); 2.21 (t, J 7.2 Hz, 2H); 2.30 (t, J 7.4 Hz, 2H);
acid 3.61–3.72 (m, 1H); 3.66 (s, 3H); 5.32–5.65 (m, 2H).
Ethyl ricinoleic 0.86 (t, J 6.9 Hz, 3H); 1.23–1.60 (m, 21H); 1.57–1.59
acid (m, 2H); 1.99–2.17 (m, 2H); 2.20 (t, J 6.5 Hz, 3H); 2.26
(t, J 7.3 Hz, 2H); 3.55–3.64 (m, 1H); 4.11 (q, J 6.5 Hz,
2H); 5.31–5.46 (m, 2H).
irradiated with microwaves at 40 W (entries 10 and 11,
respectively).
However, reusing the Al2O3/50% KOH catalyst for
additional 2 cycles its activity dropped down and complete
conversion was only observed at room temperature after 3
and 18 h, in the second and third reaction cycle, respec-
tively. Reusing the acid catalyst SiO2/50% H2SO4 at
60 °C the transesterification with methanol was completed
after stirring for 7 h. On the other hand, both solid sup-
ports can be recycled by simple filtration followed by new
acid or alkaline treatment.
The conversion to fatty ester was determined by 1H
NMR analysis (Table 2) based on the signal at the methoxy
(3.66 ppm; s, OCH3) and of the ethoxy groups (4.11 ppm;
q, J 6.5 Hz, OCH2) for the methyl and the ethyl esters,
respectively, in comparison with the signal of the a-methy-
lene hydrogens (4.10–4.40 ppm) present in castor bean oil
[8,16,17].
4. Conclusions
In conclusion, we presented here a methodology for the
transesterification of castor bean oil by microwave irradia-
tion using methanol or ethanol. It was observed that SiO2
is the best support for the acidic alcoholysis, while Al2O3
showed the best results for the basic alcoholysis of castor
oil. Furthermore, the catalytic systems SiO2/50% H2SO4
and Al2O3/50% KOH can be re-used for several cycles
and the reaction time can be reduced from many hours
to a few minutes using MW irradiation.
Acknowledgments
This project was funded by FINEP, FAPERGS and
CNPq. Professor M. Wallau (UFPel) is acknowledged for
the available discussions.
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