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© 1998 Soc. Bras. Química 0103 -- 5053 $6.00 + 0.00
Transesterification of Vegetable Oils: a Review
Ulf Schuchardta, Ricardo Serchelia, and Rogério Matheus Vargas*b
Instituto de Química, Universidade Estadual de Campinas, C.P. 6154, 13083-970 Campinas - SP, Brazil
Instituto de Química, Universidade Federal da Bahia, Campus de Ondina, 40170-290 Salvador - BA, Brazil
Received: May 9, 1997
A transesterificação de óleos vegetais com metanol, bem como as principais aplicações de ésteres metílicos de ácidos graxos, são revisadas. São descritos os aspectos gerais desse processo e a aplicabilidade de diferentes tipos de catalisadores (ácidos, hidróxidos, alcóxidos e carbonatos de metais alcalinos, enzimas e bases não-iônicas, como aminas, amidinas, guanidinas e triamino(imino)fosforanos). Enfoque especial é dado às guanidinas, que podem ser facilmente heterogeneizadas em polímeros orgânicos. No entanto, as bases ancoradas lixiviam dos polímeros. Novas estratégias para a obtenção de guanidinas heterogeneizadas mais resistentes à lixiviação são propostas. Finalmente, são descritas várias aplicações para ésteres de ácidos graxos, obtidos por transesterificação de óleos vegetais. The transesterification of vegetable oils with methanol as well as the main uses of the fatty acid methyl esters are reviewed. The general aspects of this process and the applicability of different types of catalysts (acids, alkaline metal hydroxides, alkoxides and carbonates, enzymes and non-ionic bases, such as amines, amidines, guanidines and triamino(imino)phosphoranes) are described. Special attention is given to guanidines, which can be easily heterogenized on organic polymers. However, the anchored catalysts show leaching problems. New strategies to obtain non-leaching guanidine-containing catalysts are proposed. Finally, several applications of fatty acid esters, obtained by transesterification of vegetable oils, are described.
Keywords: transesterification, fatty acid methyl esters, non-ionic bases, heterogenization
General Aspects of Transesterification
Transesterification is the general term used to describe the important class of organic reactions where an ester is transformed into another through interchange of the alkoxy moiety. When the original ester is reacted with an alcohol, the transesterification process is called alcoholysis (Scheme 1)1. In this review, the term transesterification will be used as synonymous for alcoholysis of carboxylic esters, in agreement with most publications in this field. The transesterification is an equilibrium reaction and the transformation occurs essentially by mixing the reactants. However, the presence of a catalyst (typically a strong acid or
catalyst RCOOR' + R"OH RCOOR" + R'OH
Scheme 1. General equation for a transesterification reaction.
base) accelerates considerably the adjustment of the equilibrium. In order to achieve a high yield of the ester, the alcohol has to be used in excess. The applicability of transesterification is not restricted to laboratory scale. Several relevant industrial processes use this reaction to produce different types of compounds1. An example is the production of PET (polyethylene terephthalate), which involves a step where dimethylterephthalate is transesterified with ethylene glycol in the presence of zinc acetate as catalyst (Scheme 2)2. Furthermore, a large number of acrylic acid derivatives is produced by transesterification of methyl acrylate with different alcohols, in the presence of acid catalysts3-6. If the alcohol and the ester groups are present in the same molecule simple lactones7,8 or macrocycles9-10 are formed by an intramolecular transesterification, as shown
other hand. while the butanolysis (at 117 °C) and ethanolysis (at 78 °C). The protonation of the carbonyl group of the ester leads to the carbocation II which.30. requiring. The overall process is a sequence of three consecutive and reversible reactions. Chem. with an alcohol/oil molar ratio of 30:1 at 65 °C. Due ROCOR' + ROCOR" + ROCOR"' mixture of alkyl esters H2C OH + HC OH H2C OH glycerol catalyst alcohol . Examples of intramolecular transesterification reactions. including the type of catalyst (alkaline or acid).200 Schuchard et al. Transesterification of dimethylterephthalate with ethylene glycol. This suggests that an acid-catalyzed transesterification should be carried out in the absence of water. and to regenerate the catalyst H+. respectively. in Scheme 3. purity of the reactants (mainly water content) and free fatty acid content have an influence on the course of the transesterification and will be discussed below. H OH OH O O p-toluene sulfonic acid H H O Transesterification of Vegetable Oils In the transesterification of vegetable oils. J. However. takes 50 h to reach complete conversion of the vegetable oil (> 99%).24 are applied as catalysts.29. O O O + 2 O HO . in the presence of 1 mol% of H2SO4.26 showed that the methanolysis of soybean oil. O O Acid-Catalyzed Processes The transesterification process is catalyzed by BrØnsted acids. Base-Catalyzed Processes The base-catalyzed transesterification of vegetable oils proceeds faster than the acid-catalyzed reaction26.26 (Scheme 4). which eliminates glycerol to form the new ester IV.and triglycerides31. tipically. These catalysts give very high yields in alkyl esters. so that the ideal alcohol/oil ratio has to be established empirically. Further transesterification reactions can be found in the literature. The alcohol/vegetable oil molar ratio is one of the main factors that influences the transesterification. An excess of the alcohol favors the formation of the products. Soc.2 CH3OH OH HO O O O OH O Scheme 2. alcohol/vegetable oil molar ratio. using the same quantities of catalyst and alcohol. a triglyceride reacts with an alcohol in the presence of a strong acid or base. The stoichiometric reaction requires 1 mol of a triglyceride and 3 mol of the alcohol. temperature. but the reactions are slow. The mechanism of the acid-catalyzed transesterification of vegetable oils is shown in Scheme 5. in order to avoid the competitive formation of carboxylic acids which reduce the yields of alkyl esters. aluminum isopropoxide17-19.28. forming lactones or macrocycles. producing a mixture of fatty acids alkyl esters and glycerol25. Transesterification of vegetable oils. Several aspects. after a nucleophilic attack of the alcohol. However. According to this mechanism. based on the type of catalyst used. preferably by sulfonic27 and sulfuric acids26. an excess of the alcohol is used to increase the yields of the alkyl esters and to allow its phase separation from the glycerol formed. in which metal alkoxides11-16. Pryde et al. HO O p-toluene sulfonic acid OH OR O Scheme 3. On the H2C OCOR' HC OCOR" + 3 ROH H2C OCOR"' triglyceride Scheme 4. an excessive amount of alcohol makes the recovery of the glycerol difficult. tetraalkoxytitanium compounds20-22 and organotin alkoxides23. produces the tetrahedral intermediate III. for a monoglyceride. in which diand monoglycerides are formed as intermediates26. Braz. take 3 and 18 h. considering each individual process. carboxylic acids can be formed by reaction of the carbocation II with water present in the reaction mixture. temperatures above 100 °C and more than 3 h to reach complete conversion30. it can be extended to di.
glyceride R' = carbon chain of the fatty acid R = alkyl group of the alcohol Scheme 5. starting another catalytic cycle. 1. such as alkaline metal alkoxides26. The nucleophilic attack of the alkoxide at the carbonyl group of the triglyceride generates a tetrahedral intermediate (Eq. even if a water-free alcohol/oil mixture is used. Alkaline metal hydroxides (KOH and NaOH) are cheaper than metal alkoxides.Vol. thus regenerating the active species (Eq. Mechanism of the acid-catalyzed transesterification of vegetable oils. The first step (Eq. However. they are a good alternative since they can give the same high conversions of vegetable oils just by increasing the catalyst concentration to 1 or 2 mol%. The latter deprotonates the catalyst. 1) is the reaction of the base with the alcohol. 3). to this reason. 1998 Transesterification of Vegetable Oils 201 O R' OR'' + H + OH I OR'' R' OH + R' II OR'' OH + R' + R O H O R' OR'' + H O OR'' R III OH + . Mechanism of the base-catalyzed transesterification of vegetable oils. but less active.32 and hydroxides29.30. since they give very high yields (> 98%) in short reaction times (30 min) even if they are applied at low molar concentrations (0. Diglycerides and monoglycerides are converted by the same mechanism to a mixture of alkyl esters and glycerol. Nevertheless. The mechanism of the base-catalyzed transesterification of vegetable oils is shown in Scheme 6. 2)11.40.33-36 as well as sodium or potassium carbonates37-39. together with the fact that the alkaline catalysts are less corrosives than acidic compounds. industrial processes usually favor base catalysts. some water is pro- . 9. producing an alkoxide and the protonated catalyst. Alkaline metal alkoxides (as CH3ONa for the methanolysis) are the most active catalysts.H / R''OH O R' IV OR R'' = ' OH OH .5 mol%). No. However. 4). ROH + B RO - + BH+ (1) R'COO CH2 R"COO CH H2 C OCR"' O + - R'COO CH2 R"COO CH OR R"' - OR (2) H2C O C O R'COO CH2 R"COO CH H2C OR O C O - R'COO CH2 R"COO CH R"' H2C O - + ROOCR"' (3) R'COO CH2 R"COO CH H2 C O - R'COO CH2 + BH + R"COO CH H2 C OH + B (4) Scheme 6. from which the alkyl ester and the corresponding anion of the diglyceride are formed (Eq. which is now able to react with a second molecule of the alcohol. they require the absence of water which makes them inappropriate for typical industrial processes30.
3triphenylguanidine60. 2.4 0. In a first series of studies.54 (TBD).51. pyridine49. type of microorganism which generates the enzyme. Lipase-Catalyzed Processes Due to their ready availability and the ease with which they can be handled.5 mmol) of methanol. duced in the system by the reaction of the hydroxide with the alcohol. a great number of organic bases has been developed and used as catalyst or reactant for organic syntheses.30 23. the catalytic activity of some guanidines was compared to that observed using other bases such as the amidines DBU and DBN.95 1 pKa (CH3CN)49 25.7-triazabicyclo[4.3-diphenylguanidine59. 2. and often tolerate organic solvents.4. with consequent soap formation (Scheme 7). Their potential for regioselective and especially for enantioselective synthesis makes them valuable tools41. This undesirable saponification reaction reduces the ester yields and considerably difficults the recovery of the glycerol due to the formation of emulsions30. etc) in order to establish suitable characteristics for an industrial application. hydrolytic enzymes have been widely applied in organic synthesis.6-pentamethylpiO + R' O + R' OH NaOH R' ONa OR H2O R' O + H2O O OH + ROH peridine49. when compared to BEMP and Me7P.3. Saponification reaction of the produced fatty acid alkyl esters. which does not hydrolyse the esters.0]undec-7-ene1. amines such as triethylamine49. temperature. 1.52 25. guanidines such as 1. it seems that the good performance of TBD.9 not available 27. the reaction yields as well as the reaction times are still unfavorable compared to the base-catalyzed reaction systems. This can be explained by the formation of bicarbonate instead of water (Scheme 8). new results have been reported in recent articles and patents42-48.61 and amino.50. Potassium carbonate.diazaphosphorane51 (BEMP) and tris(dimethylamino)methyliminophosphorane51 (Me7P).202 Schuchard et al. The presence of water gives rise to hydrolysis of some of the produced ester. The catalytic site (unshared electron pair of the sp2 N) of TBD is practically unhindered (Scheme 10). is related to its kinetic activity. They do not require any coenzymes. and the triamino(imino)phosphoranes BEMP and Me7P63.8-diazabicyclo[5.2 mmol) of rapeseed oil.57 (TMG).56. a: conditions: 8. It was observed that TBD.3-dimethyl-perhydro-1. However. are reasonably stable. followed by TBD.0]dec-5-ene50. piperidine49. Although the enzyme-catalyzed transesterification processes are not yet commercially developed.2. Using the other bases. Comparison of the catalytic activity of some guanidines.0]non-5-ene49. Among these bases.51 (DBU) and 1.2. 70 °C. Braz.1.5 R' = carbon chain of the fatty acid R = alkyl group of the alcohol Scheme 7. under the same experimental conditions.53 (DBN). The activity and efficiency of such non-ionic bases as catalysts for the transesterification of vegetable oils were studied. The order of the catalytic activity is not directly related to the relative basicity of these compounds. the yields were not higher than 66% (Table 1). Non-Ionic Base-Catalyzed Processes In order to obtain milder reaction conditions and to simplify manipulations. . However.and nitroguanidines62.4.79 Yield (%) after 1 h a 91 66 63 47 32 18 4. Soc. The common aspects of these studies consist in optimizing the reaction conditions (solvent.5-diazabicyclo[4. even if applied at only 1 mol%. allowing an easy access of the methanol for proton transfer.3. are frequently used in organic synthesis.2.00 g (27. the guanidines are more active catalysts and the activity follows their relative basicity. According to the observed results and to the mechanism of the base-catalyzed transesterification (Scheme 6).43 24. since BEMP and Me7P should be the more efficient catalysts.49.3-pentabutylguanidine58 (PBG). used in a concentration of 2 or 3 mol% gives high yields of fatty acid alkyl esters and reduces the soap formation38. produces more than 90% of methyl esters after 1 h.2. Catalyst TBD BEMP Me7P MTBD DBU TMG Relative basicity51 150 6873 4762 43. pH. 1 mol% of catalyst. 1. amidines and triamino(imimo)phosphoranes in the transesterification of rapeseed oil with methanol. 1.50. 1.2.65 3. triamino(imino)phosphoranes such as tert-butylimino-2diethylamino-1.52 (DMAP). shown in Scheme 9. Reaction of potassium carbonate with the alcohol.51 and 4-dimethyl-aminopyridine1. amidines such as 1. 1.6-di-tert-butylpyridine18.104.22.168. while the steric Table 1. J.51.5.6. K2CO3 + ROH R = alkyl group of the alcohol ROK + KHCO3 DBN Scheme 8.3-tetramethylguanidine55.32 23.00 g (62.3. Chem.51.
Although TBD is less active than sodium methoxide (at only 0. When compared to potassium carbonate.Vol. Other bases such as DMAP. Steric hindrance of TBD. Table 2. pyridine and triethylamine were also tested.0 91. as well as extremely resistant to react with thionyl chloride and thiophosgene51. the catalytic activity of other alkylguanidines was also investigated.0 a: 8. 2. Comparison between TBD and the conventional inorganic catalysts. 1 h. these amines did not give satisfactory yields. The results of this study63 are shown in Table 2.3 92.4 93. Catalyst NaOH (1 mol%) K2CO3 (1 mol%) K2CO3 (2 mol%) K2CO3 (3 mol%) TBD (1 mol%) TBD (2 mol%) TBD (3 mol%) Yield (%) after 1 ha 98. Molecular structures of some non-ionic organic bases.g. such as isopropyl bromide. In a third series of studies. NaOH and K2CO3)37-39.00 g (62. 70 °C. in order to establish and understand all factors that may affect their catalytic properties. the catalytic . However. No.0 90.4 89. 1998 Transesterification of Vegetable Oils 203 N N N H TBD N N N N N N P N N DBU DBN BEMP N N P N N N N N CH3 H17C8 H N N N H H N N N H Me7P MTBD DCOG TCG Scheme 9.00 g (27.2 mmol) of rapeseed oil. In a second series of studies. H H H H N N : H H N H H N P N N N : H H H H N H H P N N N Me7P : TBD Scheme 10.5 mmol) of methanol. Due to the excellent performance of TBD in the transesterification of vegetable oils.5%. 1. 9. even at low molar concentrations. the catalytic activity of TBD was compared to that observed for typical industrial catalysts (e. BEMP hindrance shown by the triamino(imino)phosphoranes is so significant that they are practically inert to alkylating agents. DMAP was the most active within this series. its use does not require any special condition. producing only 20% of methyl esters after 1 h. The reaction yields obtained with TBD were close to those observed with NaOH and no undesirable by-products such as soaps (easily formed when alkaline metal hydroxides are used) were observed. CH3ONa produces more than 98% of methyl esters after 30 min). BEMP and Me7P. even at 5 mol%. TBD was always more active.7 84.
2 mmol) of rapeseed oil. J.7-triazabicyclo[4. 7-methyl-1.3. Results obtained in the transesterification of soybean oil with methanol show that 1. H O HO CH2OH H H H O O OH H . giving a conversion of 30% after 1 h. Schuchardt et al. The heterogenization of unsubstituted guanidines can be achieved by their reaction with microcrystalline cellulose activated by cyanuric chloride at the C-6 position (Scheme 11). biguanidine (PCBG) is even more active than TCG. 2.3pentamethylguanidine (PMG). tested principally cellulose and poly(styrene/divinylbenzene). An alcohol/oil mixture of 2:1 was pumped at 60 °C with a rate of 0.2. however. the guanidine-containing cellulose shows a slightly reduced activity.3.4. After deprotonation of the guanidinium salt formed.4. when used at 5 mol%68. Heterogeneously Catalyzed Processes The advantage of using guanidines in the transesterification of vegetable oils is the possibility to heterogenize them on organic polymers. Soc. no definite reason can be given at this point. the reaction was incomplete and the phase separation difficult.2.2.204 Schuchard et al.3-tricyclohexylguanidine (TCG). as observed earlier for the symmetric 1. 70 °C. as a 82% yield of methyl esters is obtained with PCBG after 1 h. The excellent performance of DCOG and TCG is also assigned to the high symmetry of their guanidinium cations.2. This could be due either to leaching of the catalyst or to its irreversible protonation. .5-pentacyclohexylTable 3.00 g (27.5 mmol) of methanol.0]dec-5-ene (MTBD) and 1.00 g (62.48 L/h. also showed a good catalytic performance64. Heterogenization of guanidine on activated microcrystalline cellulose. As no leaching tests were performed. Transesterification of rapeseed oil with methanol using the most active alkylguanidines as catalysts. In the first hour the methyl esters were obtained with high yields and the phase separation was quick69. Cl Yields (%) after 1 ha Catalyst TBD DCOG TCG MTBD PMG 1 mol% 90 74 64 47 49 2 mol% 91 80 91 74 67 3 mol% 93 92 92 90 a: conditions: 8. Braz. activity of several alkylguanidines was compared64.1.3-dicyclohexyl-2-n-octylguanidine (DCOG). The activity order of the catalysts TBD > TCG > DCOG > MTBD > PMG (Table 3) corresponds to their relative base strength. compared to 69% with TCG under the same conditions66. but also polyuretanes and other organic polymers allow the suitable incorporation of guanidines. Chem. This guanidine-containing cellulose was used in a continuous reactor containing 100 g of the catalyst. TBD was always the most active.5. After this. compared to guanidine in homogeneous phase. 1. which is increased by structural factors such as number and type of substituents (cyclic or acyclic chain) 51. however. 1 mol% of catalyst.3trimethylguanidine 65. 1. The heterogenization of guanidines on organic polymers and their use in the transesterification of vegetable oils were described in a patent67.HCl Cl + N N N Cl Cl N H O HO H CH2O H H O O OH H H N N H Cl N Cl H2N N NH2 O HO H N N N H ClC NH2 + NH2 CH2O H H O O OH H Scheme 11.
5 mol% of base. The guanidine-containing polymers (Scheme 12) were used in the transesterification of soybean oil with methanol in several consecutive catalytic cycles. they slowly leached from the polymers. allowing only nine catalytic cycles. which is symmetrically substituted showed an activity as high as polymer I.9 eq. The guanidines heterogenized on linear polystyrene with the use of a ‘spacer-arm’ (polymers III. However. 1. polymer IV showed the same activity as P CH2 N N N I N(CH3)2 P CH2 N N(CH3)2 II polymer II and polymer III was even less active than polymer I70. 70 °C. of methanol. When another methyl group was introduced (polymer VI) its activity was slightly reduced.Vol. VI . a loss of activity was observed. c: turnover frequency: turnover number/ reaction time. b: conditions: 1 eq. at prolonged reaction times. as mentioned above. However. of soybean oil. mainly due to leaching of the anchored base from the polymers. Total turnover numbers and turnover frequencies (after 1 h) observed with guanidine-containing polymers in the transesterification of soybean oil with methanol. 6. IV).b (number of cycles) 124 (9) 118 (9) 36 (5) 30 (4) 84 (6) 42 (7) 15 12 13 12 15 14 I II III IV V VI a: turnover number: mol of products/ mol of catalyst. The use of a ‘spacer-arm’ (polymers III-VI) was expected to improve the performance of the heterogenized catalyst. However. N(CH3)2 P (CH2)5CH2 N N(CH3)2 IV N P (CH2)5CH2 N H V N H N P (CH2)5CH2 N N N P (CH2)5CH2 N CH3 N H III P = polymer chain Scheme 12. Catalyst turnover frequency total turnover (h-1)c numbera. Molecular structures of some guanidine-containing polystyrenes. A summary of the catalytic performance of these polymers is shown in Table 4. Furthermore. No. However. The lower activity of the guanidine-containing polymers I and II. 9. were less active. Despite less active than their homogeneous analogues. 1998 Transesterification of Vegetable Oils 205 The catalytic performance of some alkylguanidines heterogenized on different substituted polystyrenes was investigated70. all polymers with a ‘spacer-arm’ suffered substitution reactions during the recycling experiments to form inactive hexasubstituted guanidinium compounds. the electrophilic character of the methylene group is inTable 4. Polymer V. Polymers I and II have the guanidine moiety bound to the benzylic CH2 group of the polystyrene. the efficiency of the anchored catalysts is practically the same. when compared to their homogeneous analogues. After the protonation of the base. is probably due to the hydrophobicity of the polymer chain which reduces the concentration of the methanol at the active sites. all polymer-containing guanidines could be reused in several consecutive reaction cycles70. The guanidines heterogenized on gel-type poly(styrene/divinylbenzene) with 1 meq Cl/g (polymers I and II) showed a slightly lower activity than their homogeneous analogues but allowed the same high conversions after prolonged reaction times.
emulsifying. thus becoming more susceptible to nucleophilic attack by methoxide ions present in the reaction medium. J. 78-80. etc73. However. as well as lubricants and plastifying agents (C6-C12). The fatty acid methyl esters are further used in the manufacture of carbohydrate fatty acid esters (sucrose polyesters). its activity in the transesterification of vegetable oils is low (14% conversion after 5 h72). and can be used as an alternative fuel substitute for diesel engines (biodiesel)28-30. The alkanolamides. Chem. they can not be produced in a convenient way by esterification of fatty acids. The glycerol also has important applications. CH3OH CH2 N + N(CH3)2 N(CH3)2 H3C N H3C Scheme 13. have a direct application as non-ionic surfactants. The leaching of the guanidines from the other polymers follows a similar mechanism. Schuchardt et al. producing inactive hexasubstituted guanidinium compounds64. Reaction of the heterogenized guanidines III-VI with unreacted 6-bromohexyl substituents. which should give doubly anchored active guanidines whose leaching is less probable. whose production consumes the major part of the methyl esters produced in the world. creased. it is possible to deprotonate these hexasubstituted guanidinium compounds. toothpastes. CH2 OCH3 + NH N CH3 CH3 Br BrR N N R H R N R R N N N R H Scheme 14. This attack results in the removal of the guanidine moiety from the polymer as shown in Scheme 13. thickening and plastifying agents. plastics. However. and raw materials for further synthesis73. there is an additional factor that accelerates the deactivation of the supported catalysts. in cosmetics. Soc. as an azeotrope formed by water and isopropanol avoids the recycling of the alcohol. as the diffusion of the triglycerides through the channels of the Y zeolite is slow due to steric hindrance. food. These two applications will be discussed separately. which can be applied as non-ionic surfactants or edible non-calorific oils74-77. . Braz. The encapsulated guanidine showed a good catalytic activity in the addition reaction of benzaldehyde to acetone71. Leaching of the guanidine moiety from the polymers. as shown in Scheme 15. In order to circumvent the leaching of the guanidines from the polymers. lacquers. depending on the length of their carbon chain. However. Fatty Acid Alkyl Esters as Feedstocks for Industry Fatty acid methyl esters can be transformed into a lot of useful chemicals. encapsulate TCG by the reaction of dicyclohexylcarbodiimide and cyclohexylamine in the supercages of a hydrophobic Y zeolite. The isopropyl esters are also applied as plastifying agents and emollients. as shown in Scheme 14.206 Schuchard et al. For the polymers containing a ‘spacer-arm’. The fatty alcohols are applied as pharmaceutical and cosmetics additives (C16-C18)73. The anchored bases can react with electrophilic functional groups which are further away on the polymer chain. pharmaceuticals.
79. cycloalkanes and alkylbenzenes84. Due to their high viscosity (about 11 to 17 times higher than diesel fuel) and low volatility. • thermal decomposition. 1998 Transesterification of Vegetable Oils 207 alkanolamides RC(O)N(CH2CH2OH)2 isopropylic esters RCO(O)CH(CH3)2 HN(CH2CH2OH)2 HOCH(CH3)2 RCOOCH3 fatty acid methyl esters H2 /CuCr2O4 sucrose RCH2OH fatty alcohols sucrose polyesters RO RO OR O OR biodiesel RO O OR OR O OR R = carbon chain of the fatty acid Scheme 15. there are no technical restrictions to the use of other types of vegetable oils.38. which produces alkanes. the transesterification seems to be the best choice. However. looking for alternative sources of energy is of vital importance. • microemulsions with short chain alcohols (e. Considering the type of the alcohol. 9.80. Several types of vegetable oils. and • transesterification with ethanol or methanol88. the methyl or ethyl esters of fatty acids can be burned directly in unmodified diesel engines. rapeseed38. cellulose processing. the direct use of vegetable oils in fuel engines is problematic. charcoal and natural gas. In the following decades. 83-87. as the physical characteristics of fatty acid esters (biodiesel) are very close to those of diesel fuel32 and the process is relatively simple. these sources are limited. sunflower28 and palm29.Vol. nowadays. alkyl resins. Furthermore. they do not burn completely and form deposits in the fuel injector of diesel engines. The same reaction using ethanol is . it is believed that Rudolf Diesel himself82 started research with respect to the use of vegetable oils as fuel for diesel engines. the studies became more systematic and.30. No. tobacco. Different ways have been considered to reduce the high viscosity of vegetable oils: • dilution of 25 parts of vegetable oil with 75 parts of diesel fuel32. Soybean26. the use of methanol is advantageous as it allows the simultaneous separation of glycerol.82.89. ethanol or methanol)32. Historically. acrolein (a highly toxic substance) is formed through thermal decomposition of glycerol32. the major part of all energy consumed worldwide comes from petroleum. much is known about its use as fuel. • catalytic cracking. However. Some fatty acid methyl esters applications. 1.g. carboxylic acids and aromatic compounds87.37 oils are the most studied. which produces alkanes. and will be exhausted by the end of the next century33.32. with a diversified composition in fatty acids.78. Despite energetically favorable. Vegetable oils are a renewable and potentially inexhaustible source of energy with an energetic content close to diesel fuel82. Fatty Acid Alkyl Esters as Biodiesel With exception of hydroelectricity and nuclear energy. can be used for the preparation of biodiesel. explosives.84. with very low deposit formation37. Thus. Furthermore. alkenes. etc81. Among all these alternatives.79.
J. known as ‘‘olestra’’. R.-J. Part of our work has been developed with financial support from the Commission of the European Communities. 89.E. de Rossi. One possibility would be the use of zeolites with strong basic sites98.S.K. this process still shows some inconveniences such as the need for high temperatures (150 °C). 5. methanol is used as it is the cheapest alcohol in most countries. 6. Acknowledgments The authors acknowledge financial support from FAPESP and fellowships from FAPESP and CNPq. Rehberg. 1947. Vatlas.. H. J. Appl. 9. F.. Chem. R. Normally. D. Arpe. or as substitutes of vegetable oils for noncalorific diets75-77.P. Chem.A. 168. Rev. as well as an oil with a low water content.L. I. Despite the very good reaction yields (about 90%). 17. 4605. J. Am. Shibuya. 72.H.R. Rehberg.L. The guanidines described here have been shown to be efficient catalysts for the transesterification of vegetable oils with commercial anhydrous ethanol69. Rossi. Rehberg. B. 226. Newman. using sodium methoxide as catalyst91-95. 1955. Conclusions and Perspectives The industrial homogeneous catalysts will have to be substituted in the near future by heterogeneous catalysts due to environmental reasons. 66. Fisher. J. 16.. Ayyangar. Wulfman. 2058.5 h) are lower when compared to the previous work. 8. Haken. Chem. Otera. 14. K. J. Davis. Synth. Chem.. Tetrahedron Lett. 39. Drake.H. 1449. Chavan. 4589. which furnished good preliminary results97. T..E. C.. The Y zeolite is not appropriate for this purpose as the rather small diameter of its pore system slows down the diffusion of the fatty acid triglycerides. Mukaiyama. Tökés. 11.. Zubaidha. Chem. Shishido. C. hepta.H. 1993..T. Another possibility would be the encapsulation of guanidines in an appropriate inorganic matrix.H. Chem. Synthesis 1972. p 396. W. Am. 3.. has been studied for more than 20 years75. The temperature (110 °C) and reaction time (2. 1993. 959.. N. 1944. Fatty Acid Esters of Carbohydrates The fatty acid esters of carbohydrates can be obtained by esterification of fatty acids. 7.E. Chem. the catalyst requires a water-free system in order to avoid its deactivation.g..R.S. 1203. more complicated as it requires a water-free alcohol. however. 12. Tetrahedron Lett. 33.S. I. III. or by transesterification of their correspondent alkyl esters with carbohydrates (or other polyols) and constitute an important class of synthetic organic products. using Na as catalyst. 93. Haken. Chem..D. some of these methods require very high temperatures (above 100 °C) and toxic low-volatile solvents (e. 33. J. 69.W. Rizzi and Taylor91. Jr. C. J.. C. which depend on the number and type of the esterified fatty acid. it should be doubly anchored to the polymers. 49. 1950. McGiboney. 1944. 4. in which the SPE are synthesized by transesterification. 10. 2. Soc. 1992. Chem... However. J. 66. developed a two-stage solvent-free process. DMF and DMSO). 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