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Transesterication of castor oil assisted by microwave irradiation

G. Perin a,*, G. Alvaro a, E. Westphal a, L.H. Viana b, R.G. Jacob a, E.J. Lenardao a, M.G.M. DOca c
a b

Instituto de Qumica e Geociencias, Universidade Federal de Pelotas, UFPel, P.O. Box 354, 96010-900 Pelotas, RS, Brazil Departamento de Farmacia-Bioqumica e Qumica, Universidade Federal do Mato Grosso do Sul, Campo Grande, MS, Brazil c Departamento de Qumica, Fundacao 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 transesterication 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 catalysis, 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 catalyzed alcoholysis assisted by microwaves is much faster and leads to higher yields of the desired fatty esters. 2008 Elsevier Ltd. All rights reserved.
Keywords: Castor oil transesterication; Acidic and basic solids; Microwave irradiation

1. Introduction The main component of castor bean oil is besides small amounts of oleic and linoleic acids (57%), ricinoleic acid (90%), which peculiar chemical properties, turn it attractive as raw material for the preparation of several compounds for the ne 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 transesterication of oils with methanol or ethanol, involving acidic [3,4] or basic catalysis [5,6]. Recently, some papers showing the advantages of microwave irradiated transesterication methods have been published in the literature [79]. However, to the best of our knowledge, microwave irradiation to perform the transesterication 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*

ported catalyst under solvent-free conditions [10] using microwave irradiation [11]. More recently, several solid acid catalysts, including H2SO4/SiO2 employed in organic synthesis are found as ecient 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 transesterication of castor bean oil with methanol or ethanol to aord 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 purication. 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) downeld from tetramethylsilane as an internal standard.

Corresponding author. Tel./fax: +55 53 32757354. E-mail address: gelson_perin@ufpel.edu.br (G. Perin).

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

G. Perin et al. / Fuel 87 (2008) 28382841

O R O O O R O R= R = CH3 or CH3CH2
1

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O R + 3 R1OH acid SiO2 or basic Al2O3 MW (548W), r.t or heating OH 3 R

O OR1 +

HO OH HO

Scheme 1.

2.2. Catalysts preparation The supported catalysts were prepared through the following procedures: (a) SiO2/50% H2SO4 catalyst: 10.0 g of silica (silica gel 60, 230240 mesh, Merck) and 100 mL of aqueous H2SO4 (50%) were mixed in a beaker and the suspension stirred at room temperature for 30 min. The resulting solid was ltered under reduced pressure, dried at 150 C for 15 h in an oven and cooled to room temperature in a desiccator. (b) Al2O3/50% H2SO4: Prepared by the same way using 10.0 g of Al2O3 90 (0.0630.200 mm, Merck) instead of silica gel. (c) Al2O3/KOH (50%): 5.0 g of alumina (Al2O3 90, 0.0630.200 mm, Merck), 5.0 g of KOH and 3.0 mL of water were mixed in a 100 mL beaker. The suspension was stirred for 15 min at room temperature, dried in an oven at 80 C for 3 h, followed by 15 h at 150 C and nally cooled to room temperature in a desiccator. 2.3. Transesterication assisted by microwave heating 2.3.1. Method A To 5.0 g of the acid catalyst (SiO2/50% H2SO4) and 50.0 g of castor bean oil in a 250 mL reaction ask 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/ castor bean oil = 6:1, was added at room temperature. The mixture was then irradiated in a common household MW oven (Panasonic model Pccolo NN-S42BK, working at 2.45 MHz, with a programmable power from 40 to
Table 1 Preparation of ethyl and methyl esters from castor bean oil Entry 1 2 3 4 5 6 7 8 9 10 11 Method C B B B A B A A C B A Solid supported catalyst SiO2/50% H2SO4 SiO2/30% H2SO4 SiO2/40% H2SO4 SiO2/50% H2SO4 SiO2/50% H2SO4 SiO2/50% H2SO4 SiO2/50% H2SO4 SiO2/30% H2SO4 Al2O3/50% KOH Al2O3/50% KOH Al2O3/50% KOH Alcohol Methanol Methanol Methanol Methanol Methanol Ethanol Ethanol Ethanol Methanol Methanol Methanol

540 W) under the conditions indicated in Table 1. The reaction was monitored by TLC, performed on glass plates coated with silica gel G (Merck) using ethyl acetate and hexane (30:70 v/v) as mobile phase. After the conclusion of the reaction (see Table 1), the crude mixture was cooled and separated from the catalyst by ltration. Subsequently, it was transferred to a separatory funnel and glycerol separated by gravity for 12 h. The alcohol was removed by distillation and residual catalyst, glycerol and alcohol by washing the ester with water (2 50 mL). The same protocol was used for Al2O3/50% KOH. 2.4. Transesterication assisted by conventional heating 2.4.1. Method B To 5.0 g of SiO2/50% H2SO4 and 50.0 g of castor bean oil in a 250 mL reaction ask equipped with a reux condenser, 14 mL of methanol (99.8%) or 20.5 mL of ethanol (99.5%), molar ratio alcohol/castor bean oil = 6:1, was added at room temperature under stirring and subsequently heated to 60 C. The reaction progress was followed by TLC. After completion of the reaction (see Table 1) the product was separated and puried as described for Method A. The same protocol was used for Al2O3/50% KOH. 2.4.2. Method C A mixture of 5.0 g of Al2O3/50% KOH, 50.0 g of castor bean oil and 14 mL of methanol (99.8%), molar ratio alcohol/castor bean oil = 6:1, was stirred at room temperature for 1.5 h. Subsequently, the product was separated and

Experimental conditions Stirring at r.t. Stirring at 60 C Stirring at 60 C Stirring at 60 C MW irradiation (40 W) Stirring at 60 C MW irradiation (220 W) MW irradiation (220 W) Stirring at r.t. Stirring at 60 C MW irradiation (40 W)

Reaction time 48 h 5h 4h 3h 30 min 6h 20 min 25 min 1.5 h 1h 5 min

Conversion (%) 78 95 >95 >95 95 95 >95 95 >95 >95 95

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G. Perin et al. / Fuel 87 (2008) 28382841 Table 2 1 H NMR spectral data of fatty acid methyl and ethyl esters Fatty acid ester Chemical shift (200 MHz, CDCl3; d, ppm) 0.90 (t, J 6.8 Hz, 3H); 1.301.71 (m, 21H); 2.032.11 (m, 2H); 2.21 (t, J 7.2 Hz, 2H); 2.30 (t, J 7.4 Hz, 2H); 3.613.72 (m, 1H); 3.66 (s, 3H); 5.325.65 (m, 2H). 0.86 (t, J 6.9 Hz, 3H); 1.231.60 (m, 21H); 1.571.59 (m, 2H); 1.992.17 (m, 2H); 2.20 (t, J 6.5 Hz, 3H); 2.26 (t, J 7.3 Hz, 2H); 3.553.64 (m, 1H); 4.11 (q, J 6.5 Hz, 2H); 5.315.46 (m, 2H).

puried 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 transesterication of castor bean oil observed under dierent conditions for sulfuric acid immobilized SiO2 as well as for KOH immobilized on Al2O3. It was found that using SiO2/30% H2SO4, at room temperature, 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 performed 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, respectively (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 studied. However, the reaction was incomplete under conventional condition as well as under microwave irradiation. Using acidic conditions for the ethanolysis of castor oil the best results were achieved under conventional conditions with SiO2/50% H2SO4 stirred at 60 C for 6 h (entry 6, Table 1). When this mixture was irradiated with microwaves (220 W) for 20 min we observed complete conversion 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 specic eects it is necessary to perform a study with controlled temperature of the system, what is not possible with a common domestic oven [14]. Microwave specic eects can be expected when the polarity of the system is altered during the progress of the reaction [15]. As the transesterication 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 specic eects (non purely thermal) are involved here. Although the energy transfer and distribution in a domestic microwave oven is not controlled, we found that the microwave-assisted reactions are more ecient, 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 temperature (entry 9, Table 1). The reaction time decreased to 1 h when the mixture was heated to 60 C and to 5 min when

Methyl ricinoleic acid Ethyl ricinoleic acid

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, respectively. Reusing the acid catalyst SiO2/50% H2SO4 at 60 C the transesterication with methanol was completed after stirring for 7 h. On the other hand, both solid supports can be recycled by simple ltration 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-methylene hydrogens (4.104.40 ppm) present in castor bean oil [8,16,17]. 4. Conclusions In conclusion, we presented here a methodology for the transesterication of castor bean oil by microwave irradiation 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. References
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