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Available online at www.sciencedirect.com Energy Conversion and Management 49 (2008) 125–130

Available online at www.sciencedirect.com

Available online at www.sciencedirect.com Energy Conversion and Management 49 (2008) 125–130

Energy Conversion and Management 49 (2008) 125–130

Energy Conversion and Management 49 (2008) 125–130 www.elsevier.com/locate/enconman Comparison of

www.elsevier.com/locate/enconman

Comparison of transesterification methods for production of biodiesel from vegetable oils and fats

Ayhan Demirbas *

Sila Science, Trabzon, Turkey

Received 1 October 2006; accepted 9 May 2007 Available online 18 June 2007

Abstract

Comparative studies on transesterification methods were presented in this work. Biodiesel is obtained from a chemical reaction called transesterification (ester exchange). The reaction converts esters from long chain fatty acids into mono alkyl esters. Chemically, biodiesel commonly is a fatty acid methyl ester. Vegetable oils can be transesterified by heating them with a large excess of anhydrous methanol and an acidic or basic reagent as catalyst. A catalyst is usually used to improve the reaction rate and yield. In a transesterification reac- tion, a larger amount of methanol was used to shift the reaction equilibrium to the right side and produce more methyl esters as the proposed product. Several aspects including the type of catalyst (alkaline, acid or enzyme), alcohol/vegetable oil molar ratio, tempera- ture, purity of the reactants (mainly water content) and free fatty acid content have an influence on the course of the transesterification. A non-catalytic biodiesel production route with supercritical methanol has been developed that allows a simple process and high yield because of the simultaneous transesterification of triglycerides and methyl esterification of fatty acids. In the catalytic supercritical meth- anol transesterification method, the yield of conversion rises to 60–90% for the first 1 min. 2007 Elsevier Ltd. All rights reserved.

Keywords: Biodiesel; Transesterification; Vegetable oil; Methanol; Catalyst

1. Introduction

The possibility of using vegetable oils as fuel has been recognized since the beginning of Diesel engines. Vegetable oil has too high a viscosity for use in most existing Diesel engines as a straight replacement fuel oil. There are a num- ber of ways to reduce the viscosity of the vegetable oil. Dilution, micro-emulsification, pyrolysis and transesterifi- cation are the four techniques applied to solve the prob- lems encountered with the high fuel viscosity. One of the most common methods used to reduce oil viscosity in the biodiesel industry is called transesterification. Chemical conversion of the oil to its corresponding fatty ester is called transesterification [1] . Fig. 1 shows the transesterifi- cation reaction of triglicerides.

* Tel.: +90 462 230 7831; fax: +90 462 248 8508. E-mail address: ayhandemirbas@hotmail.com

0196-8904/$ - see front matter 2007 Elsevier Ltd. All rights reserved.

doi:10.1016/j.enconman.2007.05.002

The biodiesel reaction requires a catalyst such as sodium hydroxide to split the oil molecules and an alcohol (meth- anol or ethanol) to combine with the separated esters. The main byproduct is glycerin. The process reduces the viscos- ity of the end product. Transesterification is widely used to reduce vegetable oil viscosity [2] . Biodiesel is a renewable fuel source. It can be produced from oil from plants or from animal fats that are byproducts in meat processing. One popular process for producing biodiesel from the fats/oils is transesterification of triglyceride by methanol (methanolysis) to make methyl esters of the straight chain fatty acid. The purpose of the transesterification process is to lower the viscosity of the oil. The transesterification reaction proceeds well in the presence of some homoge- neous catalysts such as potassium hydroxide (KOH)/ sodium hydroxide (NaOH) and sulfuric acid, or heteroge- neous catalysts such as metal oxides or carbonates. Sodium hydroxide is very well accepted and widely used because of its low cost and high product yield [3] .

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A. Demirbas / Energy Conversion and Management 49 (2008) 125–130

/ Energy Conversion and Management 49 (2008) 125–130 Fig. 1. Transesterification reaction of triglicerides.

Fig. 1. Transesterification reaction of triglicerides.

Transesterification is the process of exchanging the alk- oxy group of an ester compound by another alcohol. These reactions are often catalyzed by the addition of a base and acid. Bases can catalyze the reaction by removing a proton from the alcohol, thus making it more reactive, while acids can catalyze the reaction by donating a proton to the car- bonyl group, thus making it more reactive [4] . One of the first uses of transesterified vegetable oil (bio- diesel) was powering heavy duty vehicles in South Africa before World War II. The name ‘‘biodiesel’’ has been given to transesterified vegetable oil to describe its use as a Diesel fuel [5] . Biodiesel has significant potential for use as an alterna- tive fuel in compression–ignition engines [3,6] . Biofuels are non-toxic, biodegradable and free of sulfur and carcino- genic compounds [7] , as they are obtained from renewable sources. Biodiesel is a plant derived product, and it con- tains oxygen in its molecule, making it a cleaner burning fuel than petrol and Diesel [8] .

2. Experimental

Vegetable oils can be transesterified by heating them with a large excess of anhydrous methanol and a catalyst. The transesterification reaction can be catalyzed by alkalis [9,10] , acids [11] , or enzymes [12–16].

2.1. Acid catalysed transesterification methods

2.1.1. Methanolic hydrogen chloride

The transesterification is performed with the acidic reagent, which is 5% (w/v) anhydrous hydrogen chloride in methanol. It is most often prepared by bubbling hydrogen chloride gas into dry methanol. The hydrogen chloride gas is commercially available in cylinders or can be prepared by dropping concentrated sulfuric acid slowly onto fused ammonium chloride or into concentrated hydrochloric acid. This method is best suited to bulk preparation of the reagent. The hydrogen chloride gas can be obtained by adding acetyl chloride (5 mL) slowly to cooled dry methanol (50 mL).

2.1.2. Methanolic sulfuric acid

Vegetable oils are transesterified very rapidly by heating in 10% sulfuric acid in methanol until the reflux tempera-

ture is reached. A solution of 1–2% concentrated sulfuric acid in methanol has almost identical properties to 5% methanolic hydrogen chloride and is very easy to prepare.

2.1.3. Boron trifluoride-methanol

Boron trifluoride catalysed transesterification of vegeta- ble oils is one of the most popular methods. For transeste- rification of vegetable oils, boron trifluoride (BF3) in methanol (15–20% w/v) is used.

2.2. Alkali catalytic transesterification methods

In the alkali catalytic methanol transesterification method, the catalyst (KOH or NaOH) is dissolved in methanol by vigorous stirring in a small reactor. The oil is transferred into the biodiesel reactor, and then, the catalyst/alcohol mixture is pumped into the oil. The final mixture is stirred vigorously for 2 h at 340 K in ambient pressure. A successful transesterification reaction produces two liquid phases: ester and crude glycerin. Crude glycerin, the heavier liquid, will collect at the bot- tom after several hours of settling. Phase separation can be observed within 10 min and can be complete within 2 h of settling. Complete settling can take as long as 20 h. After settling is complete, water is added at the rate of 5.5% by volume of the methyl ester of oil and then stirred for 5 min, and the glycerin is allowed to settle again. Washing the ester is a two step process, which is performed with extreme care. A water wash solution at the rate of 28% by volume of oil and 1 g of tannic acid per liter of water is added to the ester and gently agi- tated. Air is carefully introduced into the aqueous layer while simultaneously stirring very gently. This process is continued until the ester layer becomes clear. After set- tling, the aqueous solution is drained, and water alone is added at 28% by volume of oil for the final washing [3,5,17] .

2.2.1. Sodium methoxide catalyzed transesterification

For sodium methoxide catalyzed transesterification, 100 g of vegetable oil is transesterified in toluene (80 mL)

and methanol (200 mL) containing fresh sodium (0.8 g) in 10 min at reflux, and a related procedure has been used to transesterify liter quantities of oils.

2.3. Methylation of free fatty acids with diazomethane

(CH 2 N 2 )

CH 2 N 2 reacts rapidly with free fatty acids to give methyl esters. The CH 2 N 2 is generally prepared in ethereal solu- tion by the action of alkali (a 30% solution of KOH) on

A. Demirbas / Energy Conversion and Management 49 (2008) 125–130

127

a nitrosamide, e.g. N-methyl- N -nitroso- p -toluene-sulfon- amide or nitroso-methyl-urea [18,19] .

2.4. Supercritical alcohol transesterification

In general, methyl and ethyl alcohols are used in super- critical alcohol transesterification.

2.4.1. The non-catalytic supercritical methanol transesterification The non-catalytic supercritical methanol transesterifica- tion is performed in a stainless steel cylindrical reactor (autoclave) at 520 K [5] . In a typical run, the autoclave is charged with a given amount of vegetable oil and liquid methanol with changed molar ratios. After each run, the gas is vented, and the autoclave content is poured into a collecting vessel. All the rest of the contents are removed from the autoclave by washing with methanol. The most important variables affecting the methyl ester yield during the transesterification reaction are the molar ratio of alcohol to vegetable oil and the reaction temperature. Viscosities of the methyl esters from vegeta- ble oils were slightly higher than that of No. 2 Diesel fuel. In the transesterification process, the vegetable oil should have an acid value less than 1, and all materials should be substantially anhydrous. If the acid value were greater than 1, more NaOH or KOH would be spent to neutralize the free fatty acids. Water also causes soap for- mation and frothing. The stoichiometric ratio for the transesterification reaction requires three moles of alcohol and one mole of triglyceride to yield three moles of fatty acid ester and one mole of glycerol. Higher molar ratios result in greater ester production in a shorter time. The vegetable oils were transesterified 1:6–1:40 vegetable oil-alcohol molar ratios in catalytic and supercritical alcohol condi- tions [5] .

2.5. Catalytic supercritical methanol transesterification

Catalytic supercritical methanol transesterification is performed in the autoclave in the presence of 1–5% NaOH

as catalyst at 520 K. In the catalytic supercritical methanol

transesterification method, the yield of conversion rises to 60–90% for the first 1 min.

2.6. Biocatalytic transesterification methods

Biodiesel can be obtained from biocatalytic transesterifi- cation methods [12–16] . Methyl acetate, a novel acyl accep- tor for biodiesel production has been developed, and a comparative study on Novozym 435 catalyzed transesteri- fication of soybean oil for biodiesel production with differ- ent acyl acceptors was studied [16] .

3. Results and discussion

The physical properties of the primary chemical prod- ucts of transesterification are given in Table 1 . The high viscosity of the vegetable oils was the cause of severe oper- ational problems, such as engine deposits. This is a major reason why neat vegetable oils largely have been aban- doned as alternative Diesel fuels in favor of mono–alkyl esters such as methyl esters. The comparisons of various methanolic transesterification methods are tabulated in Table 2 .

3.1. General reaction mechanism of transesterification

The triacylglycerols (vegetable oils and fats) are esters of long chain carboxylic acids combined with glycerol. Car- boxylic acids R–C @ (O)–O–H can be converted to methyl esters R–C @ (O)–O–CH 3 by the action of a transesterifica- tion agent. The parameters affecting the methyl esters for- mation are reaction temperature, pressure, molar ratio, water content and free fatty acid content. It was observed that increasing the reaction temperature had a favorable influence on the yield of ester conversion. The yield of alkyl ester increased with increasing the molar ratio of oil to alcohol [5] . Transesterification consists of a number of con- secutive, reversible reactions [20,21] . The triglyceride is converted stepwise to diglyceride, monoglyceride and finally glycerol Eqs. (1)–(4) in which 1 mol of alkyl esters is removed in each step.

Table 1 Physical properties of chemicals related to transesterification

Name

Specific

Melting

Boiling

Solubility

gravity

point (K)

point (K)

< 10%

(g/mL)

Methylmrystate 0.875

291.0

– Benzene, EtOH, Et 2 O Et 2 O, chloroform EtOH, Et 2 O H 2 O, ether, EtOH H 2 O, ether H 2 O, ether

Methyl

0.825

303.8

469.2

palmitate Methyl stearete 0.850

311.2

488.2

Methyl oleate

0.875

253.4

463.2

Methanol

0.792

176.2

337.9

Ethanol

0.789

161.2

351.6

Glycerol

1.260

255.3

563.2

Source: Ramadhas et al. 2004 [24] ; Bala, 2005 [1].

Table 2 Comparisons of various methanolic transesterification methods

Method

Reaction

Reaction time

temperature (K)

(min)

Acid or alkali catalytic process 303–338 Boron trifluoride-methanol 360–390 Sodium methoxide-catalysed 293–298

60–360

20–50

4–6

Non-catalytic supercritical methanol Catalytic supercritical methanol

523–573

6–12

523–573

0.5–1.5

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A. Demirbas / Energy Conversion and Management 49 (2008) 125–130

Fatty acid (R 1 COOH) + Alcohol (ROH)

Ester (R 1 COOR) + Water (H 2 O)

ð1 Þ

Triglyceride + ROH Diglyceride + RCOOR 1 ð2 Þ

Diglyceride + ROH Monoglyceride + RCOOR 2 ð3 Þ

Monoglyceride + ROH Glycerol + RCOOR 3 ð4 Þ

The formation of alkyl esters from monoglycerides is be- lieved to be a step that determines the reaction rate, since monoglycerides are the most stable intermediate com- pound [17] . Several aspects, including the type of catalyst (alkaline, acid or enzyme), alcohol/vegetable oil molar ratio, temper- ature, purity of the reactants (mainly water content) and free fatty acid content have an influence on the course of the transesterification. In the conventional transesterifica- tion of fats and vegetable oils for biodiesel production, free fatty acid and water always produce negative effects, since the presence of free fatty acids and water causes soap for- mation, consumes catalyst and reduces catalyst effective- ness, all of which result in a low conversion [22] . 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 alk- oxy moiety. When the original ester is reacted with an alco- hol, the transesterification process is called alcoholysis [4] . The transesterification is an equilibrium reaction, and the transformation occurs essentially by mixing the reactants. In the transesterification of vegetable oils, a triglyceride reacts with an alcohol in the presence of a strong acid or base, producing a mixture of fatty acids alkyl esters and glycerol. The stoichiometric reaction requires 1 mol of a triglyceride and 3 mol of the alcohol. However, 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.

3.2. Acid catalyzed transesterification

The transesterification process is catalyzed by BrØnsted acids, preferably by sulfon and sulfuric acids. These cata- lysts give very high yields in alkyl esters, but the reactions are slow. The alcohol/vegetable oil molar ratio is one of the main factors that influence the transesterification. An excess of the alcohol favors the formation of the products. On the other hand, an excessive amount of alcohol makes the recovery of the glycerol difficult, so the ideal alcohol/oil ratio has to be established empirically, considering each individual process. Fig. 2 shows the mechanism of acid cat- alyzed esterification of fatty acids. The initial step is pro- tonation of the acid to give an oxonium ion (1), which can undergo an exchange reaction with an alcohol to give the intermediate (2), and this, in turn, can lose a proton to become an ester (3). Each step in the process is revers- ible, but in the presence of a large excess of the alcohol, the equilibrium point of the reaction is displaced so that

the equilibrium point of the reaction is displaced so that Fig. 2. Mechanism of acid catalyzed

Fig. 2. Mechanism of acid catalyzed esterification of fatty acids.

esterification proceeds virtually to completion. Fig. 3 shows the mechanism of acid catalyzed transesterification of veg- etable oils [23] . The transesterification occurs under similar conditions ( Fig. 3 ). In this instance, initial protonation of the ester is followed by addition of the exchanging alcohol to give the intermediate (4), which can be dissociated via the transitions state (5) to give the ester (6).

3.3. Base catalysed transesterification

Esters, in the presence of a base such as an alcoholate anion, form an anionic intermediate that can dissociate back to the original ester or form the new ester. Transeste- rification can, therefore, occur by this mechanism with basic catalysis but esterification cannot. The base catalyzed transesterification of vegetable oils proceeds faster than the acid catalyzed reaction. The first step is the reaction of the base with the alcohol, producing an alkoxide and the protonated catalyst. The nucleophilic attack of the alkoxide at the carbonyl group of the triglyc- eride generates a tetrahedral intermediate from which the alkyl ester and the corresponding anion of the diglyceride are formed. The latter deprotonates the catalyst, thus regenerating the active species, which is now able to react with a second molecule of the alcohol start another cata- lytic cycle. Diglycerides and monoglycerides are converted by the same mechanism to a mixture of alkyl esters and glycerol. Alkaline metal alkoxides (as CH 3 ONa for the methanolysis) are the most active catalysts, since they give very high yields (>98%) in short reaction times (30 min) even if they are applied at low molar concentrations (0.5 mol%). However, they require the absence of water,

(0.5 mol%). However, they require the absence of water, Fig. 3. Mechanism of acid catalyzed transesterification

Fig. 3. Mechanism of acid catalyzed transesterification of vegetable oils.

A. Demirbas / Energy Conversion and Management 49 (2008) 125–130

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which makes them inappropriate for typical industrial pro- cesses [4] .

3.4. Sodium methoxide catalyzed transesterification

There have been given a number of detailed recipes for sodium methoxide catalyzed transesterification [23] . The methodology can be used on quite a large scale if need be. The reaction between sodium methoxide in methanol and a vegetable oil is very rapid. It has been shown that tri- glycerides can be completely transesterified in 2–5 min at room temperature. The methoxide anion are prepared by dissolving the clean metals in anhydrous methanol. Sodium methoxide (0.5–2 M) in methanol effects transesterification of triglycerides much more rapidly than other transesterifi- cation agents. At equivalent molar concentrations with the same triglyceride samples, potassium methoxide effects complete esterification more quickly than does sodium methoxide. Because of the dangers inherent in handling metallic potassium, which has a very high heat of reaction with methanol, it is preferred to use sodium methoxide in methanol. The reaction is generally slower with alcohols of higher molecular weight. As with acidic catalysis, inert solvents must be added to dissolve the simple lipids before methanolysis will proceed [23] .

3.5. Boron trifluoride catalyzed transesterification

The Lewis acid, boron trifluoride, in the form of its coordination complex with methanol is a powerful acidic catalyst for esterification of fatty acids. One of the most popular of all transesterification catalysts is boron trifluo- ride in methanol (12–14% w/v), and in particular, it is often utilized as a rapid means of esterifying free fatty acids. When it is compared critically with some of the other acidic catalysts under similar conditions, it does not even appear to be any more rapid in its reaction.

3.6. Esterification fatty acids with diazomethane

Diazomethane (CH 2 N 2 ) reacts rapidly with free fatty acids to give methyl esters but does not affect transesterifi- cation of other lipids. The reaction is not instantaneous, however, as has sometimes been assumed, unless a little methanol is present as a catalyst [19] . Carboxylic acids {R–C(@ O)–O–H} can be converted to methyl esters {R– C( @ O)–O–CH 3 } by the action of CH 2 N 2 .

R C(=O) O H + CH 2 N 2 ! R C(=O) OCH 2 H+N 2

ð 5 Þ

Notice that the diazomethane appears to insert itself be- tween the O and the H of the O–H bond Eq. (5) . The high reactivity of diazomethane arises from the fact that it pos- sesses an exceedingly reactive leaving group, the nitrogen molecule N 2 . A nucleophilic substitution reaction on the protonated diazomethane molecule transfers a methyl group to the oxygen atom of the carboxylic acid while lib- erating a very stable product (N 2 gas). This process is very favorable energetically owing to the great stability of N 2 .

3.7. Non-catalytic supercritical alcohol transesterification

Biodiesel, an alternative Diesel fuel, is made from renewable biological sources such as vegetable oils and ani- mal fats by non-catalytic supercritical alcohol transesterifi- cation methods [3] . A non-catalytic biodiesel production route with supercritical methanol has been developed that allows a simple process and high yield because of simulta- neous transesterification of triglycerides and methyl esteri- fication of fatty acids [5] . The parameters affecting the methyl esters formation are reaction temperature, pressure, molar ratio, water content and free fatty acid content. It is evident that at a subcritical state of alcohol, the reaction rate is very low and gradually increases as either pressure or temperature rises. It was observed that increasing the reaction temperature, espe- cially to supercritical conditions, had a favorable influence on the yield of ester conversion. The yield of alkyl ester increased with increasing molar ratio of oil to alcohol [5] . In the supercritical alcohol transesterification method, the yield of conversion rises to 50–95% for the first 10 min. Water content is an important factor in conventional catalytic transesterification of vegetable oil. In the conven- tional transesterification of fats and vegetable oils for bio- diesel production, free fatty acids and water always produce negative effects, since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst effectiveness. In catalyzed methods, the presence of water has negative effects on the yields of methyl esters. However, the presence of water affected pos- itively the formation of methyl esters in our supercritical methanol method. In the supercritical alcohol transesterification method, the yield of conversion rises to 50–95% for the first 8 min. In the catalytic supercritical methanol transesterifi-

min. In the catalytic supercritical methanol transesterifi- Fig. 4. Biodiesel production by enzymatic

Fig. 4. Biodiesel production by enzymatic transesterification with methyl acetate.

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A. Demirbas / Energy Conversion and Management 49 (2008) 125–130

cation method, the yield of conversion rises to 60–90% for the first 1 min.

3.8. Enzyme catalyzed processes

Although, the enzyme catalyzed transesterification pro- cesses are not yet commercially developed, new results have been reported in recent articles and patents. The common aspects of these studies consist in optimizing the reaction conditions (solvent, temperature, pH, type of microorgan- ism that generates the enzyme etc.) in order to establish suitable characteristics for an industrial application. How- ever, the reaction yields, as well as the reaction times, are still unfavorable compared to the base catalyzed reaction systems [4] . Methyl acetate, a novel acyl acceptor for biodiesel pro- duction has been developed, and a comparative study on Novozym 435 catalyzed transesterification of soybean oil for biodiesel production with different acyl acceptors was studied [16] . Fig. 4 shows biodiesel production by enzy- matic transesterification with methyl acetate in the presence the lipase enzyme as catalyst.

4. Conclusion

Various vegetable oil transesterification methods are currently used in the production of biodiesel fuel. As an alternative fuel, vegetable oil is one of the renewable fuels. Chemically, biodiesel is a fatty acid (m)ethyl ester. Bio- diesel plays an important role in meeting future fuel requirements in view of its ability to reduce emissions from Diesel engines for many air pollutant precursors, and the lower toxicity of the Diesel particulate matter emissions have an edge over conventional Diesel as they are obtained from renewable sources. In the supercritical alcohol transe- sterification method, the yield of conversion rises to 50– 95% for the first 8 min. In the catalytic supercritical meth- anol transesterification method, the yield of conversion rises to 60–90% for the first 1 min. The reaction between sodium methoxide in methanol and a vegetable oil is very rapid; for example, completely transesterified in 4–6 min at room temperature. The parameters affecting the methyl esters formation are reaction temperature, pressure, molar ratio, water content and free fatty acid content. It is evident that at a subcritical state of alcohol, the reaction rate is very low and gradually increases as either the pressure or temperature rises. It was observed that increasing the reaction temperature, espe- cially to supercritical conditions, had a favorable influence on the yield of ester conversion. The yield of alkyl ester increased with increasing molar ratio of oil to alcohol.

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