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Bioresource Technology 99 (2008) 32443250

Coee oil as a potential feedstock for biodiesel production

Leandro S. Oliveira
a

a,*

, Adriana S. Franca a, Rodrigo R.S. Camargos a, Vany P. Ferraz

Nucleo de Pesquisa e Desenvolvimento em Cafe, DEQ/UFMG, R. Esprito Santo, 6o andar, 30160-030 Belo Horizonte, MG, Brazil b Departamento de Qumica/UFMG, Av. Antonio Carlos, 6627, 31270-901 Belo Horizonte, MG, Brazil Received 15 May 2007; received in revised form 15 May 2007; accepted 15 May 2007 Available online 13 August 2007

Abstract A preliminary evaluation of the feasibility of producing biodiesel using oil extracted from defective coee beans was conducted as an alternative means of utilizing these beans instead of roasting for consumption of beverage with depreciated quality. Direct transesterications of triglycerides from rened soybean oil (reference) and from oils extracted from healthy and defective coee beans were performed. Type of alcohol employed and time were the reaction parameters studied. Sodium methoxide was used as alkaline catalyst. There was optimal phase separation after reactions using both soybean and healthy coee beans oils when methanol was used. This was not observed when using the oil from defective beans which required further processing to obtain puried alkyl esters. Nevertheless, coee oil was demonstrated to be a potential feedstock for biodiesel production, both from healthy and defective beans, since the corresponding oils were successfully converted to fatty acid methyl and ethyl esters. 2007 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Defective coee beans

1. Introduction Brazil is the largest coee producer in the world (MAPA, 2006). Approximately 20% of its production consists of defective beans, which upon roasting decrease beverage quality (Oliveira et al., 2006). Regardless of growth, harvest and processing conditions, some defects are intrinsic in nature and will always be present. The ones that aect beverage quality the most are black, brown and immature beans. These defective beans are physically separated from the non defective beans prior to commercialization in international markets. However, since to coee producers they represent an investment in growing, harvesting, and handling, these defective beans are commercialized in the internal market in Brazil, where the roasting industry uses them in blends with non defective beans. Thus, the quality of the roasted coee consumed in Brazil is depreciated since, after separation from the exportable portion, defective beans may be representing
*

Corresponding author. Tel.: +55 31 32381777; fax: +55 31 32381789. E-mail address: leandro@deq.ufmg.br (L.S. Oliveira).

more than 50% of the coee consumed in Brazil (Oliveira et al., 2006). In view of this situation, several studies are currently under development in order to nd an alternative use for defective coee beans. One of the alternatives being considered is biodiesel production. Biodiesel is a name applied to fuels manufactured by the esterication of renewable oils, fats and fatty acids. Biodiesel can be employed as a fuel for unmodied diesel engines (Graboski and McCormick, 1998). This type of fuel has been commercially produced in Europe since the early 1990s (Barnwal and Sharma, 2005). Research studies indicate that, when used as a diesel fuel substitute, biodiesel can replace diesel fuel without causing harmful eects to an unmodied diesel engine, while simultaneously reducing harmful exhaust emissions. In addition, biodiesel is completely miscible with petroleum diesel fuel and can be employed as a blend. However, biodiesel is still not economically feasible in comparison to petroleum diesel. Grain (soybean, rapeseed, sunower seed) production costs are responsible for approximately 70% of total fuel production costs (Lotero et al., 2005). Such drawbacks could be minimized by the use of a less valuable feedstock, such

0960-8524/$ - see front matter 2007 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2007.05.074

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as the oil of rejected defective beans, with the advantage of allowing coee producers to produce and use their own fuel. Therefore, the present study aimed at an evaluation of the potential of using oil of defective coee beans as a feedstock for biodiesel production. 2. Methods 2.1. Materials The coee beans used in the present work, both healthy and defective, were acquired from Santo Antonio Estate Coee, an association of coee producers in Minas Gerais State, Brazil. The reference rened soybean oil (Liza, Brazil) was acquired from a local market. The reagents employed (methanol, ethanol, sodium methoxide) were acquired from Synth (Sao Paulo, Brazil). Sodium methox ide was purchased as a 30% solution in methanol. Methanol and ethanol presented 0.02% and 0.2% water contents, respectively. Standards of fatty acids were purchased from SigmaAldrich (Sao Paulo, Brazil). 2.2. Oil extraction Coee beans were ground in a Rotatec grinder (Belo Horizonte, Brazil) prior to oil extraction. The oils of the ground healthy and defective coee beans were obtained by solvent (hexane) extraction in an industrial Soxhlet apparatus (Sociedade Fabbe Ltda, Sao Paulo, Brazil), with an extraction capacity of 25 kg of beans per batch. The oils were extracted in batches for 16 h of duration. After extraction, the solvent was removed in a rotary evaporator (Fisatom, mod. 5502, Sao Paulo, Brazil) at 70 C, under moderate vacuum, until no traces of hexane were detected by gas chromatography. 2.3. Transesterication reactions The direct transesterication of vegetable oils triglycerides was performed with the aim of producing alkyl esters of long chain fatty acids. The reactions were carried out with rened soybean oil and coee oils from defective and healthy beans. The transesterication reactions were performed in a 500 mL cylindrical three-necked reactor, mechanically stirred and heated by a hot water jacket. The temperature of the water in the jacket was controlled by a thermostatic water bath (Nova Etica, Sao Paulo, Bra zil) and it was set to keep the reacting medium at the desired temperature (55 C when using methanol and 60 C for ethanol). Eighty grams of oil were used in the transesterication experiments. Sodium methoxide (nal concentration of 1% w/w based on the mass of oil) was used as an alkaline catalyst for both the soybean and healthy beans coee oil. For the defective coee beans oil, the amount of catalyst used was calculated as the minimum necessary for the transesterication of the triglyceride fraction plus that for

the neutralization of the titrated free fatty acids. Methanol and ethanol were employed in a 6:1 alcohol-to-oil molar ratio. The reactions were carried out at ambient temperature (25 C) and at 55 C and 60 C for methanol and ethanol, respectively. Stirring was kept at 600 rpm (Vicente et al., 2005). After completion of reaction, the pour-o time was 24 h, a time long enough to allow for the complete separation of an upper ester layer and a lower glycerol layer. The upper layer was collected and submitted to a rotary evaporation at 70 C, under moderate vacuum, for the removal of alcohol. After alcohol removal, the ester phase was analyzed by gas chromatography (Varian 3380 Gas Chromatograph, Middelburg, The Netherlands) to determine the yield of fatty acid alkyl esters. The parameters used in the transesterication tests are presented in Table 1. All transesterication tests were conducted in duplicates. 2.4. Analyses of oils and alkyl esters of fatty acids Oil acidity was determined by AOCS method Cd 3d-63 (AOCS, 1998). Moisture content determination was based on mass dierence by oven drying at 105 C for 2 h (Pregnolatto and Pregnolatto, 1985). The samples taken after transesterication of the oils were analyzed by gas chromatography. Twenty-ve microliters of the samples were dried in a nitrogen stream for the removal of the excess solvent and subsequently weighed and diluted in 1 mL methanol. The fatty acid methyl and ethyl esters were injected in a Varian 3380 gas chromatograph, equipped with a ame ionization detector (Middelburg, The Netherlands). The analytic conditions employed were: initial temperature of 200 C, followed by a temperature increase at a rate of 10 C per min up to 240 C. The duration of the analysis was 10 min. A Carbowax 20 M column (Supelco, Bellefonte, PA, USA) was employed. Peak identication was carried out by comparison of the retention times with those for the respective fatty acid methyl esters standards (FAMEs), which were prepared by esterication of fatty acids standards with BF3 in methanol solution according to AOAC method 996.06 (AOAC, 1995). The ester conversions were calculated from the contents of alkyl esters in the ester phase as analyzed by GC and the
Table 1 Parameters employed in the transesterication reactions Oil Soybean Soybean Soybean Soybean Coee healthy Coee healthy Coee healthy Coee healthy Coee defective Coee defective Coee defective Coee defective Temperature (C) 25 25 55 55 25 25 55 55 25 25 55 55 Reaction time (h) 1.0 2.0 0.5 1.0 1.0 2.0 0.5 1.0 1.0 2.0 0.5 1.0

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material balance, as described by Alcantara et al. (2000). Viscosity determinations for fatty acid alkyl esters were based on ASTM method D445-06 (Knothe et al., 2005). 2.5. Statistical analyses All determinations were performed randomly in a total of two replicates. The obtained data were submitted to analysis of variance and the mean values were compared by the Duncan test at 5% probability. 3. Results and discussion The yield of coee beans oil ranged from 10 to 12% on a dry weight basis. The titrated acidities of the reference rened soybean oil and of the oils of healthy and defective coee beans were 0.36 0.08, 2.62 0.29 and 10.04 0.03% (w/w), respectively. It should be noted that the contribution of the defective beans to the acidity of the oil is fairly high, since these beans are partially comprised of fermented beans (black and brown). The triglyceride composition of the coee oils, from both healthy and defective beans, were determined by a thermogravimetric procedure adapted from that proposed by Goodrum and Geller (2002). Coee oil from healthy beans was determined to be comprised of 81% (w/w) triglycerides and the oil from defective beans presented a 76% (w/w) triglyceride fraction, both values falling within the range previously published in the literature (Speer and Kolling-Speer, 2001; Oliveira et al., 2006). The oils were subjected to transesterication reactions without any renement, i.e., with a 19% and 24% fraction of unsaponiable matter for the oils of healthy and defective beans, respectively. The moisture contents of the oils were determined as 0.28 and 0.11 kgwater/kgoil for the oils of healthy and defective beans, respectively. The rened soybean oil presented a negligible amount of water. The fatty acid compositions of the coee oils were determined in a previous study (Oliveira et al., 2006) and the major constituents are linoleic and palmitic acids (44% and 34%, respectively), followed by oleic (9%) and stearic (7%) acids. 3.1. Transesterication of oils Preliminary tests were performed for the transesterication of the soybean and coee oils, using either sodium methoxide or sulfuric acid, to determine the type of catalyst to be used in the experiments. Transesterication and separation of phases were successfully accomplished with both basic and acid catalysts for the soybean oil, and only with the basic catalyst for the coee oil of healthy beans. The transesterication of coee oils using sulfuric acid as a catalyst produced a black gelatinous product that occupied most of the reactor volume with a thin black liquid layer on top of it. Thus, sulfuric acid was not further used as a catalyst in this study. The reaction with the oil of defective coee beans, using sodium methoxide as a catalyst, did not

result in phase separation, although some degree of transesterication was achieved. Emulsion and gel formation were observed in this case. 3.2. Optimization of reaction conditions Reaction time and temperature were the two parameters chosen for the optimization of the transesterication reactions conditions. Reaction time was varied from 0.5 to 2 h and the selected temperature values were 25 C, for both methanol and ethanol as esterifying agents, and 55 C for methanol and 60 C for ethanol. In the case of rened soybean oil, all the reaction products presented optimal separation of phases after 1 h of pour-o time. After 24 h, the ester-rich phases of all samples were crystal clear. The ester-rich phase was collected and the excess solvent (alcohol) was removed in a rotary evaporator. After removal of solvent, the ester phase was kept at rest for another 24 h and a new separation of phases occurred. In the solvent removal procedure, it was observed that the ester phase contained smaller amounts of methanol (2030%) than those products obtained with ethanol (4050%). For recovery of alcohol, losses ranged from 1% to 8% and could be attributed to dierences in the samples handling during reaction and separation, and in the solvent removal procedures. Average values of the ester yields for all reactions with soybean oil are presented in Table 2. Standard deviation values ranged from 0.5% to 1.3% points. It is clear that the ester conversion does not vary signicantly with an increase in reaction time, for a constant temperature. Reactions carried out at room temperature (25 C) presented ester yields approximately 15% points higher than those at 55 C, irrespective of reaction time. There was a 3% point increase in ester conversion with an increase in reaction time for the transesterications carried out with ethanol. An increase in reaction temperature from 25 to 60 C did not cause a signicant increase (approximately 1%) in ester conversion. The reactions with methanol presented higher ester yields at room temperature than any other conditions. However, when using ethanol at 60 C, the ester yields were 2% and 5% points higher than those obtained with methanol at 55 C for reaction times of 30 min and
Table 2 Ester yields for the reactions with rened soybean oil Reaction conditions MetOH 25 C 1 h MetOH 25 C 2 h MetOH 55 C 0.5 h MetOH 55 C 1 h EtOH 25 C 1 h EtOH 25 C 2 h EtOH 60 C 0.5 h EtOH 60 C 1 h Ester yield (%) 96.1 1.2a 95.7 1.0a 81.2 0.8d 80.4 1.3d 84.0 0.5c 87.2 0.7b 82.7 0.5d 85.2 0.7c

Average value Standard deviation; values followed by the same letter in the same column do not dier signicantly by the Duncan test at 5% probability.

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1 h, respectively. Overall, the results indicated that reactions carried out at room temperature lead to higher ester conversions than at higher temperatures, regardless of reaction time and type of alcohol employed. Furthermore, separation of phases after completion of reactions was easier to accomplish with methanol rather than with ethanol, thus, corroborating information previously reported in the literature (Schuchardt et al., 1998; Lotero et al., 2005). Negligible amounts of emulsied and gelatinous matter were observed in the products of reactions carried out at higher temperatures. The characteristics observed for the transesterication reactions with oils from healthy coee beans are summaTable 3 Characteristics observed for the transesterication reactions with oils from healthy coee beans Reaction conditions MetOH 25 C 1h MetOH 25 C 2h MetOH 55 C 0.5 h MetOH 55 C 1h EtOH 25 C 1 h EtOH 25 C 2 h EtOH 60 C 0.5 h EtOH 60 C 1 h Aspects of phase separation Well-dened phase separation with presence of small amounts of emulsied matter in the upper layer Well-dened phase separation with presence of small amounts of emulsied matter in the upper layer Well-dened phase separation with presence of small amounts of emulsied matter in the upper layer Well-dened phase separation with presence of small amounts of emulsied matter in the upper layer No phase separation with presence of emulsied matter Partial phase separation with presence of emulsied matter No phase separation with presence of emulsion and gelatinous matter No phase separation with presence of emulsion

rized in Table 3. The oil samples reacted with methanol yielded optimal separation of phases during pour-o time, with negligible amounts of emulsied and gelatinous matter being observed in the products. When using ethanol, a partial separation of phases was observed only for the reaction carried out at room temperature for 2 h. The other reaction conditions did not lead to separation of phases during pour-o time. All the samples reacted with ethanol presented signicant amounts of gelatinous matter in the reaction products. In order to evaluate whether ester conversion occurred or not, the reactions products that did not separate into two phases were diluted in alcohol and submitted to an acid treatment for neutralization of unreacted catalyst and to facilitate separation of phases. The non-soluble gel was separated by centrifugation, and the upper layer was removed and resubmitted to an evaporation procedure for alcohol removal. After solvent removal, a new separation of phases occurred and formation of gel was not observed. The ester layers were analyzed by GC. The chromatogram for the products obtained in the reaction with ethanol at 55 C, for 1 h, is presented in Fig. 1. Peaks related to both ethyl and methyl esters are clearly noticeable. The methyl esters peaks are due to the presence of methanol in the solution in which the catalyst is commercially available (30% CH3ONa in methanol). All the other chromatograms presented similar ester proles. The average ester conversion results for the reactions with healthy coee oil are presented in Table 4. Standard deviation values ranged from 0.4% to 1.7% points. The conversions obtained for the coee oil were lower than those for the rened soybean oil. These lower conversions

Fig. 1. Chromatogram for biodiesel from coee oil (healthy beans) after 1 h transesterication with ethanol at 55 C.

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Table 4 Ester yields for the reactions with oil from healthy coee beans Reaction conditions MetOH 25 C 1 h MetOH 25 C 2 h MetOH 55 C 0.5 h MetOH 55 C 1 h EtOH 25 C 1 h EtOH 25 C 2 h EtOH 60 C 0.5 h EtOH 60 C 1 h Ester yield (%) 70.1 0.5a 68.4 1.7a 62.3 1.2b 60.4 1.5b 35.0 0.7d 45.2 1.0c 63.9 0.7b 64.2 0.5b

Average value Standard deviation; values followed by the same letter in the same column do not dier signicantly by the Duncan test at 5% probability.

may be attributed to the fact that part of the catalyst was consumed for the production of soap, since there was no addition of catalyst to compensate for the higher free fatty acid content of the healthy coee oil (2.6%). In addition, the presence of unsaponiable matter (19%) may have hindered the interactions between the reactants (triglycerides and alcohol). Likewise, the presence of emulsion in the products (Table 3) increased the solubility of alkyl esters in the glycerol-rich phase (Vicente et al., 2004), which was separated by centrifugation prior to the collection of samples for the analysis, and part of the produced ester may have been removed in that phase. When methanol was employed, there were no signicant dierences in ester conversion with an increase in reaction time. The reactions with ethanol presented lower conversions than those with methanol. In addition, regarding the reactions with ethanol, an increase in reaction time promoted higher ester conversions when the reaction was carried out at room

temperature, and did not aect the conversion for the reaction at 60 C. Although ethanol is expected to lead to higher conversions in shorter reaction times, due to its higher miscibility with the oil, it is also known to hinder phase separation (Table 3). Thus, it makes the determination of the true ester yields dicult, as the reaction products should undergo further processing (acid treatment or addition of glycerine) to allow for good separation of phases. The oil of defective coee beans was subjected to transesterication reactions employing the same conditions as for the oil of healthy beans with the exception that the amount of catalyst was recalculated to account for its higher free fatty acid content (10%). Saponication of the free fatty acids was observed instantaneously as the mixture of alcohol and catalyst was added to the reactor, causing an increase in the viscosity of the reactants mixture. As the alkyl esters began to form, the viscosity of the reacting medium decreased again. After completion of the reaction, the product was set to rest, not separating into phases and acquiring a paste-like texture as it cooled down. After alcohol removal (evaporation), the mixture acquired a solidlike texture. It was subsequently submitted to an acidied alcohol treatment as suggested in the literature (Encinar et al., 2005) and centrifuged afterwards. Following centrifugation, optimal separation of phases was attained. The ester layer was sampled and analyzed by GC. The chromatogram for the reaction with methanol at room temperature is presented in Fig. 2. All the other chromatograms presented similar ester proles. The average ester yields for all the reactions carried out with defective beans oil are presented in Table 5. Standard

Fig. 2. Chromatogram for biodiesel from coee oil (defective beans) after 1 h transesterication with methanol at 25 C.

L.S. Oliveira et al. / Bioresource Technology 99 (2008) 32443250 Table 5 Ester yields for the reactions with oil from defective coee beans Reaction conditions MetOH 25 C 1 h MetOH 25 C 2 h MetOH 55 C 0,5 h MetOH 55 C 1 h EtOH 25 C 1 h EtOH 25 C 2 h EtOH 60 C 0,5 h EtOH 60 C 1 h Ester yield (%) 73.8 1.8a 71.3 1.6a 68.4 1.8a 71.0 1.5a 72.2 1.2a 73.0 0.5a 55.2 1.2b 71.1 1.3a

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Average value Standard deviation; values followed by the same letter in the same column do not dier signicantly by the Duncan test at 5% probability.

deviation values ranged from 0.5% to 1.8% points. The ester yields in this case were higher than those obtained for the oil of healthy coee beans. This can be attributed to the fact that the amount of catalyst used for the oil of defective beans was increased to compensate for a higher amount of free fatty acids. A higher amount of catalyst will allow for reactions with free fatty acids to produce soap and assure that the remaining amount of catalyst is enough to promote transesterication of the entire triglyceride fraction. Again, when compared to the results for the rened soybean oil, the ester yields were lower. It should be noted that the oil of defective coee beans presented a 24% fraction of unsaponiable matter that may have hindered interactions between reactants, thus contributing to the lower yields. The unsaponiable fraction is responsible for imparting a higher viscosity to the oil. In this study, the viscosity of coee oils was determined to be about four times higher than the viscosity of the rened soybean oil (170 mPa s against 43 mPa s). An increase in reaction time did not signicantly aect conversions to esters, except for the reactions with ethanol at 60 C. A major dierence in ester yields was observed for the reactions with ethanol at 60 C, when an increase of 30 min in reaction time caused an increase of 16% points in ester yield. In the case of ethanol, it is known from literature (Lotero et al., 2005) that the transesterication reaction is kinetically controlled, since the reactants (ethanol and oil) are completely miscible (no mass transfer resisTable 6 European biodiesela and diesel No. 2b specications Property Unit Lower limita Upper limita Tobacco seed oil biodiesel b

tance) and, also, the reaction rates are more dependent on temperature than when using methanol. Thus, at higher temperatures (60 C), this dependence on temperature is evidenced and it is further supported by the fact that an increase in time did not favor the ester yield at 25 C. Physical properties for the biodiesel produced from coffee oils are presented in Table 6, together with European specications for commercial biodiesel and Diesel No. 2. All the physical properties for the coee oil biodiesel were within the limits specied by European standards. Concerning the amount of free glycerol in the ester-rich phase, after one acidic methanol washing step (Tomasevic and Siler-Marinkovic, 2003) and a few water washing steps, it was determined to be in the range of 123141 mg/kg. The method employed for the free glycerol determination was that proposed by Bondioli and Bella (2005). 4. Conclusion Oils extracted from healthy and defective coee beans were successfully converted to alkyl esters of fatty acids by transesterication with both methanol and ethanol in the presence of sodium methoxide as an alkaline catalyst. The yields for the reactions with the oil of healthy coee beans were lower than those for the oil of defective beans, indicating the need for correction of the amount of catalyst to be used due to the content of free fatty acids of the oil. Further studies regarding the identication of the factors aecting conversion are needed in order to optimize the production of alkyl esters using the oil from defective coee beans. Removal of unsaponiable matter prior to transesterication is envisaged to be a suitable processing step for improving the ester yield and reducing viscosity of the alkyl esters produced. Regardless of the ester yields obtained, coee oil demonstrated potential as a candidate for feedstock in biodiesel production. Acknowledgements The authors acknowledge nancial support from the following Brazilian Government Agencies: CAPES, CNPq and FAPEMIG.

Coee oil fatty acid methyl estersc Defective Healthy 892.5 3.1**; 3.4* 38498

Soybean oil biodieselc

Diesel No. 2b

Density Viscosity HHVd

* ** a b c

Kg/m3 mm2/s kJ/kg

860 3.5** 35000

900 5**

886.8 3.5**; 6* 39811

894.1 4.9**; 8.9* 38414

876.7 5.7* 39100

841.5 2.9** 44631

Value at 25 C. Value at 40 C. Knothe et al. (2005). Usta (2005). This study, reactions with methanol at 25 C.

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L.S. Oliveira et al. / Bioresource Technology 99 (2008) 32443250 Lotero, E., Liu, Y., Lopez, D.E., Suwannakarn, K., Bruce, D.A., Goodwin Jr., J.G., 2005. Synthesis of biodiesel via acid catalysis. Ind. Eng. Chem. Res. 44, 53535363. Oliveira, L.S., Franca, A.S., Mendonca, J.C.F., Barros-Junior, M.C., 2006. Proximate composition and fatty acids prole of green and roasted defective coee beans. Lebensm. Wiss. Technol. 39, 235 239. MAPA (Ministerio da Agricultura, Pecuaria e Abastecimento) 2006. Coee Statistics, Report 17272006, December 2006, Brazil (in Portuguese). Pregnolatto, W., Pregnolatto, N.P., 1985. Normas Analticas do Instituto Adolfo Lutz, third ed. IAL, Sao Paulo, Brazil (in Portuguese). Schuchardt, U., Sercheli, R., Vargas, R.M., 1998. Transesterication of vegetable oils: a review. J. Braz. Chem. Soc. 9, 199210. Speer, K., Kolling-Speer, I., 2001. Lipids. In: Clarke, R.J., Vitzthum, O.G. (Eds.), Coee. Recent Developments. Blackwell Science Ltd., London, pp. 3349. Tomasevic, A.V., Siler-Marinkovic, S.S., 2003. Methanolysis of used frying oil. Fuel Processing Technology 81, 16. Usta, N., 2005. Use of tobacco seed oil methyl ester in a turbocharged indirect injection diesel engine. Biomass Bioenerg. 28, 7786. Vicente, G., Martnez, M., Aracil, J., 2004. Integrated biodiesel production: a comparison of dierent homogeneous catalysts systems. Bioresource Technol. 92, 297305. Vicente, G., Martnez, M., Aracil, J., Esteban, A., 2005. Kinetics of sunower oil methanolysis. Ind. Eng. Chem. Res. 44, 54475454.

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