Fuel 90 (2011) 31413155

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Review article

The production of biodiesel from vegetable oils by ethanolysis: Current state and perspectives
kovic , Ana V. Velic , Vlada B. Veljkovic Olivera S. Stamenkovic
Faculty of Technology, University of Ni, 16000 Leskovac, Bulevar Oslobodjenja 124, Serbia

a r t i c l e

i n f o

a b s t r a c t
At present, the homogeneous base-catalyzed methanolysis reaction of vegetable oils is a most often used process for the industrial biodiesel production. The toxicity of methanol, the risk of the methanol vapor explosion and the possibility of the ethanol production from biorenewable resources have contributed to the development of a vegetable oil ethanolysis process for the biodiesel production. In the reaction of vegetable oils and ethanol in the presence of a catalyst, completely agricultural fuels consisted of fatty acid ethyl esters (FAEE) are obtained having physico-chemical properties similar to those of the appropriate methyl esters and diesel fuel. The ethanolysis reaction of various oily feedstocks has been widely studied to optimize the reaction conditions and to develop new catalytic systems and processes based on chemical and biological catalysts, as well as the development of non-catalytic processes. Most researches investigate the application of homogeneous base catalysts. This paper studies the review of vegetable oil ethanolysis investigations for the biodiesel production done so far. The goals of the paper are to present the development of FAEE synthesis by catalytic and non-catalytic processes, their advantages and disadvantages, the inuence of some operating and reaction conditions on the process rate and ethyl esters yield, the kinetics models describing the ethanolysis process rate, the process optimization and the possibilities for improving the FAEE synthesis process. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 30 November 2010 Received in revised form 10 June 2011 Accepted 13 June 2011 Available online 14 July 2011 Keywords: Biodiesel Catalyst Ethanolysis Transesterication

Contents 1. 2. 3. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Vegetable oil ethanolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Chemically catalyzed vegetable oil ethanolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Homogeneously catalyzed vegetable oil ethanolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.2. Heterogeneously catalyzed vegetable oil ethanolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Enzyme-catalyzed vegetable oil ethanolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Non-catalyzed vegetable oil ethanolysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The optimization of vegetable oil ethanolysis reaction conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Kinetics of vegetable oil ethanolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . The possibilities for improving the ethanolysis reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3141 3142 3143 3143 3146 3147 3149 3150 3150 3151 3153 3153 3153

4. 5. 6. 7. 8. 9.

1. Introduction A decrease in the world oil supplies and the instability of great exporting regions caused the increase of the price for both fossil

Corresponding author. Tel.: +381 16 247 203; fax: +381 16 242 859.
). E-mail address: veljkovicvb@yahoo.com (V.B. Veljkovic 0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2011.06.049

fuel and its derivates. Apart from that, high quantities of CO2, which is the basic cause of global warming, are emitted by fossil fuel combustion. For ecological and economic reasons, the obtaining of biofuels from biomass is seriously considered with the possibility to integrate these technologies into the existing industrial plants. EU strategy is that each Member State ensures the share of energy from renewable sources in all forms of transport, which

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et al. / Fuel 90 (2011) 31413155 O.S. Stamenkovic

should be at least 10% of the nal consumption of energy in transport in that Member State in 2020 [1]. One of biofuels used worldwide is biodiesel. Based on European Biodiesel Board data the production of biodiesel in Europe in 2009 was 9 million tons, which is 16.6% more comparing to the year 2008 [2]. The greatest biodiesel producers are Germany (28% total production), France (22%), Spain (9.5%) and Italy (8%). Many countries outside of Europe are also important biodiesel producers, like the USA, Brazil, Argentina, Thailand, and so on [3]. Biodiesel is the mixture of alkyl esters of low aliphatic alcohols and high fatty acids obtained by the alcoholysis process of biological feedstocks rich in triacylglycerols (TAG) fullling the biodiesel quality standard [4]. In combustion engines biodiesel can be used as clean or as a mixture with conventional diesel fuel, which is stable and compatible in all ratios. The use of biodiesel instead of conventional fuel does not require any large-scale technical interventions on the engine. Biodiesel is biodegradable, less toxic and with lower exhaust emission of smoke, dust, COx (x = 1 or 2) and hydrocarbon comparing to fossil diesel which makes it an environmentally friendly fuel [5,6]. The biodiesel production is based on a chemical reaction between TAG and alcohols, well-known in literature as alcoholysis or transesterication, the product of which is the mixture of fatty acid alkyl esters. Commercial processes, as well as most researches, use edible vegetable oils and methanol for biodiesel production and the reaction is carried out in the presence of a homogeneous base catalyst. Recent researches study the use of other oily feedstocks and acyl acceptors, as well as the development and improvement of catalytic and reactor systems. The use of ethanol in the biodiesel synthesis process is very up-to-date due to the possibility of its production from biorenewable sources, so a completely agricultural fuel is obtained by ethanolysis [7]. In this paper previous investigations of the processes used for the biodiesel production by oily feedstocks ethanolysis are analyzed. The aim is to present the advantage of using ethanol as an acyl acceptor, different catalysts in the catalytic process development, the development of non-catalytic processes for fatty acid ethyl esters (FAEE) synthesis, their advantages and disadvantages, the inuence of some operating and reaction conditions on the process rate and ethyl esters yield, the kinetics models describing the ethanolysis process, the process optimization and the possibilities for improving the FAEE synthesis process.

2. Vegetable oil ethanolysis The mixture of FAEE is obtained by the ethanolysis reaction between TAG and ethanol. The main feedstocks TAG source for FAEE production are vegetable oils. The choice of vegetable oils depends on specic conditions in countries in question (climate, agricultural potentials, economic development of the country, population habits regarding secondary raw material collection, etc.). In current technologies, biodiesel production feedstocks were generally edible vegetable oils such as rapeseed and sunower seed oil in Europe, soybean oil in USA and palm oil in tropical countries [4]. Edible oils have a signicant application in food industry, and their prices are relatively high. On the other hand, even if all currently available amounts of edible oils are used for biodiesel production, the obtained quantities of fuel would not satisfy the needs for diesel fuel [8]. In order to fulll the range of oily feedstock, the biodiesel production process development is targeted at the usage of used oils and fats, waste fats, side-stream products of rened edible oil production, non-edible oils and algae oils. The amounts of these feedstock are not high so new kinds of oil-plants, which meet most of the following criteria are being developed: high oil content, low agricultural inputs, compatibility with exist-

ing farm equipment and infrastructure, production in off-season from conventional commodity crops or in agriculturally undesirable lands and favorable free fatty acid (FFA) cotent in the oil [8]. For that purpose different vegetable oils were investigated depending on the geographic position and climate conditions: Jatropha curcas and Balanites aegyptiaca (in Africa and South Asia), Pongamia glabra, Pongamia pinnata, Mesua ferrea, Moringa oleifera, Madhuca indica and microalgae (in Asia), castor (in South America), Thlaspi arvense (in North America), tobacco, tomato and pumpkin oils (in the Balkans). Methanol, ethanol, propanol, buthanol and amyl alcohol were used in the biodiesel production. Higher and secondary alcohols are suitable for the biodiesel production due to good pouring characteristics of their fatty esters at low temperatures. However, high price and complex and expensive alcoholysis conditions make them unsuitable for practical use [9]. Methanol is the most used alcohol in the biodiesel production due to its suitable physicochemical properties, low cost, mild reaction conditions and easy phase separation. But, due to its low boiling point, there is a large explosion risk associated with methanol vapors, and both methanol and methoxide are extremely hazardous materials that should be handled carefully [10]. Besides methanol, ethanol is more frequently used in the biodiesel synthesis, especially in the last decade. Although ethanol is currently more expensive, its advantages are a much superior dissolving power in vegetable oils and low toxicity compared to methanol. The greatest number of vegetable oil ethanolysis researches was done in the South America countries, especially in Brazil, which is one of the greatest producers of ethanol from biomass in the world [3]. As methanolysis, the ethanolysis reaction is reversible and consecutive, where one ethanol mol reacts and one ester mol is formed at every step. An excess of alcohol in relation to the stoichiometric amount needed is usually used to shift the reaction equilibrium farther towards the formation of esters. At low and mild temperatures, the ethanolysis reaction occurs in the presence of a catalyst while a non-catalytic reaction occurs at high temperatures and pressures, most frequently above critical ethanol parameters. The reaction rate and ester yield depend on the quality of the TAG source as well as the presence and type of catalysts and reaction conditions applied. Vegetable oil ethanolysis can be chemically or enzyme catalyzed. Chemical catalysts of alcoholysis (base and acid) can be homogeneous or heterogeneous depending on their dissolving ability in the reaction mixture. Enzymatic alcoholysis using lipase looks attractive and encouraging due to the absence of side reactions, easy product separation, the need for a minimal wastewater treatment and easy glycerol recovery, but the reaction is very slow and the cost of the enzyme is high. Non-catalytic ethanolysis occurring at high temperatures and pressures still does not have any practical application. Vegetable oil ethanolysis demands more energy consumption than methanolysis [11]. FAEE yield depends signicantly on the presence of water in the reaction mixture [12,13]. Stable emulsions are formed during vegetable oil ethanolysis, which makes the separation of ethyl esters from ethanol-glycerol phase more difcult [1417]. The presence of mono- and diacylglycerols (MAG and DAG, respectively) as well as soaps formed by saponication of FFA in vegetable oils, complicates the separation and the purication of esters [16,18]. After the reaction completion excess ethanol is usually recovered by evaporation under reduced pressure [15,16,1923] or distillation [17,24] and glycerol is gravity separated. In some cases, the addition of glycerol [17,25,26] or water [15] in ester phase makes the glycerol separation easier. The use of methanol/ethanol mixture in vegetable oil alcoholysis simplies the reaction product separation [27]. Physico-chemical properties of FAEE primarily depend on oily feedstock [28]. Comparing to fatty acid methyl esters (FAME), FAEE

 et al. / Fuel 90 (2011) 31413155 O.S. Stamenkovic Table 1 Fuel characteristics of FAEE and FAME produced from different vegetable oils. TAG source Alkyl esters FAME FAEE FAME FAEE FAME FAEE FAME FAEE Cloud point (C) +2 0 Pour point (C) 0 2 Cold lter plugging point (C) 3 5 0 0 +1 1 6 to +5 Kinematic viscosity at 40 C (mm2/s) 4.12 4.60 13.34 13.87 4.81 5.04 3.36 3.67 3.55.0 Iodine value (gI2/100 g) 136 130 84.5 67.5 72.8 64.5 6120 Acid value (mg KOH/g) 0.01 0.07 0.08 0.1 0.07 0.12 60.5 Lubricity at 60 C (lm) 198 150 227 203 326 363 6460 Oxidative stability at 110 C (h) 5.0 6.5 15.7 19.4 6.4 7.5 P6 Cetane number 43.9 43.8 67.6 69 55 59 P51

3143

Reference

Soybean oil Castor oil Sunower oil Linseed oil Standard EN14214

[29] [28]

[32] [4]

have higher oxidative stability, lower iodine value [28,29] and better lubricity properties [2830]. In addition, FAEE have a lower cloud point and pour point, which improves the engine start at low temperatures [29] and the extra carbon atom brought by the ethanol molecule slightly increases the heat content and the cetane number [7]. Both viscosity and acid value of FAEE are higher compared to corresponding methyl esters [28,29]. The evaluation of exhaust gas emissions (including nitrogen oxides, CO2 and smoke density) shows that FAEE has a less negative environmental effect in comparison with that caused by the use of FAME [31]. Comparative review of fuel characteristics of some ethyl esters and respective methyl esters produced from different vegetable oils is given in Table 1.

3. Chemically catalyzed vegetable oil ethanolysis 3.1. Homogeneously catalyzed vegetable oil ethanolysis Homogeneously catalyzed vegetable oil ethanolysis is the subject of most FAEE synthesis researches. Most of them are related to the application of homogeneous base catalysts, whereas acid catalysts are rarely investigated. The reasons are a higher activity of base catalysts in mild reaction conditions and a high TAG conversion degree obtained in a short reaction time. Base catalysts used most frequently are sodium and potassium hydroxides and alkoxides. Alkoxides are more expensive and also more difcult to manipulate but their use decreases the amount of water released in the ethanolysis reaction and soap formation which increases the process efciency [33,34]. The use of base catalysts is strictly limited to oils with the low content of FFA and water. Acid catalysts are more corrosive, less efcient and less demanding to regard feedstock quality than base catalysts. Most frequently used acid catalysts are sulfur and hydrochloric acids, as well as Keggin heteropolyacids. The ethanolysis reaction rate and FAEE yield depend on the initial ethanol:oil molar ratio, the catalyst type and loading, the reaction temperature and the agitation intensity. In order to design a reactor or to develop an industrial process it is very important to know what the inuence of operation and reaction conditions on FAEE yield and reaction rate is. However, the researchers do not have the same conclusions on the inuence of certain factors on the ethanolysis reaction rate and ester yield. The review of applied reaction conditions of homogeneously catalyzed ethanolysis for different oils is given in Table 2. The initial ethanol:oil molar ratio signicantly inuences the FAEE yield. Since the reaction is reversible, the increase of the ethanol:oil molar ratio shifts the reaction equilibrium towards FAEE formation. The lower ethanol:oil molar ratio combined with low catalyst loading makes the reaction mixture non separable [23]. Researchers generally agree that the increase of the initial ethanol:oil molar ratio increases the FAEE yield [12,16,1921,39,51].

On the other hand, at higher molar ratios (above 12:1) the glycerol separation was difcult because the ethanol excess hinders the gravity decantation so part of glycerol remains in the ester phase [17,46]. Therefore, the initial ethanol:oil molar ratio is a variable that must always be optimized. The optimal molar ratio depends on the reaction temperature, the kind of the oil used and the catalyst type and loading. At higher reaction temperatures, the highest FAEE yields are obtained at the ethanol:oil molar ratio of 9:1 for Cynara cardunculus oil [7], at the molar ratio of 12:1 for Raphanus sativus [16], soybean [23], sunower [39] oil and the mixture of used olive and sunower oils [46] and at the molar ratio of 18.8:1 for the mixture of castor and soybean oils [52]. For the ethanolysis performed at lower temperatures researchers recommend lower ethanol:oil molar ratio: 5:1 for high oleic sunower and high and low erucic Brassica carinata oils [42] and 6:1 for Raphanus sativus oil [34]. High castor oil FAEE yield is obtained at higher ethanol:oil molar ratios and lower sodium ethoxide loadings or at lower ethanol:oil molar ratios and higher catalyst loadings, independently of the reaction temperature [19,20]. The type of the catalyst applied depends on the content of FFA and water in the reaction mixture. FFA (directly in the reaction with the base catalyst) and water (indirectly via ester hydrolysis) cause the saponication reaction and soap formation [53], thus decreasing both the base catalyst amount in the reaction mixture and the ester yield. The acid catalysts are more suitable for ethanolysis of oils or fats with high FFA. However, the acid-catalyzed ethanolysis reaction is slow and the ester yield obtained is signicantly lower comparing to the base-catalyzed reaction [24]. Acid catalysts are important when waste and used oils and fats are used as feedstocks for the biodiesel production in the two-step process consisting of FFA acid-catalyzed esterication and TAG base-catalyzed ethanolysis [27]. The loading of base catalyst (sodium and potassium hydroxide, methoxide and ethoxide) inuences the TAG conversion degree in vegetable oil ethanolysis. According to some researchers, this is the most important factor inuencing FAEE yield [19,20,42]. The researchers have reported different optimal catalyst loadings. Generally, FAEE yield increases with the increase of the catalyst loading to some values [7,16,17,19,20,23,39,42,46,51]. However, at higher base-catalyst loadings the saponication reaction is favorable, which decreases FAEE yield and creates difculties in the phase separation [7,17,21,23,46]. Optimal catalyst loading is the agreement of these opposite impacts and depends on the kind of oil and base catalysts type. The inuence of the reaction temperature on both the ethanolysis reaction rate and FAEE yield depends on the kind of feedstock, the catalyst type and other reaction conditions. According to a number of studies, the reaction temperature does not signicantly inuence FAEE yield [7,16,19,20,23]. In the initial period, the reaction rate increases with the increase of the temperature but after 2030 min of the reaction its effect becomes unimportant

Table 2 The review on the homogeneous catalyzed ethanolysis of different feedstocks. Feedstock Type, volume of reactor (cm3)/type of agitator, agitation intensity (rpm) Ethanol:oil molar ratio (mol/mol) Catalyst/loading (wt.% to the ol) Temperature(C) Optimal reaction conditions Reaction conditions Yield (conversion) (%)/Time(min) 97.2/60 91.8/30 97/30 98.9/90 (60)/300 [23] [35] [36] [18] [37] Reference

3144

Soybean oil Soybean oil Soybean oil Rapeseed oil Rapeseed oil

Flask, 500/mechanical, 600 Batch reactor, 250/ultrasound (indirect sonication) 4870 W/m2, 40 kHz Erlenmeyer ask, 25/shaker, 450 Batch reactor, 2000/disc stirrer, 10,00020,000 Flask, 100/magnetic, 500

6:1 and 12:1 1.8:110.2:1 10:1 6:17.5:1 1.2:1 and 6:1a

NaOH and KOH/0.3 and 1.0 NaOH/0.140.56 NaOCH3, NaOCH2CH3/0.3 and 0.6 KOH/0.891.33 H3PW12O40, H3PMo12O40, H4SiW12O40, H4SiMo12O40, H2SO4, H3PO4/17b NaOH, KOH, NaOCH3, KOCH3, H2SO4, HCl/0.2c NaOCH2CH3/0.51.5 NaOH and NaOCH2CH3/0.51.5

30 and 70 29 65 2565 60 and 85

70 C; 12:1; 0.3% NaOH 10.2:1; 0.35 0.6% NaOCH2CH3 25 C; 7.5:1; 1.33%; 10 000 min1 85 C; 3.0 mol% H3PW12O40; 6:1 NaOCH3 30 C; 16:1; 1.0% 30 C; 16:1; 1.0% NaOCH2CH3; mechanical stirrer 11:1; 1.75% Amplitude 60%; Pulse 0.3 s/s; 6:1; 0.75% 9:1; 2% water 2.0%

Castor oil Castor oil Castor oil

Batch reactor, 250/magnetic Flask, 250/magnetic, 600 Flask, 250/magnetic, 400 Batch reactor, 1000/ mechanical, 400 Mechanical shaker Erlenmeyer ask, 50/ultrasound (direct sonication) 24 kHz, 200 W, amplitude 20100%, pulse mode 0.1 1 s/s Flask, 500/mechanical Batch reactor, 500/mechanical, 600 Batch reactor, 500/ultrasound (indirect sonication) 24 kHz, 200 W Batch reactor, 500/mechanical Flask, 500/mechanical, 600 Kettle reactor, 1000/mechanical, 5003200 Flask, 250/mechanical, 600 Batch reactor, 500/mechanical, 600 Batch reactor, 500/ultrasound (indirect sonication) 24 kHz, 200 W Erlenmeyer ask

6:1 12:120:1 6:139:1

80 3080 3080

80/360 93.1/30 99/30

[24] [19] [20] et al. / Fuel 90 (2011) 31413155 O.S. Stamenkovic

Castor oil Coconut oil

9.65:112.35:1 4:16:1

KOH/1.332.17 KOH/0.51.25

30 Ambient

80/90 (>98)/7

[25] [22]

Cottonseed oil Cottonseed oil

4:19:1d 7:1

KOH/1 NaOH/1.02.0

78 80

(75)/30 86/60 [78/240]e 90/60 [98/40]e 94.5/10 (%100)/60 97.9/70 98.5/5 88/60 [90/240]e 90/60 [98/40]e 98.7/240 100/240 70/80 95.6/60 (HOSO) 91.3/60 (HEBO) 99.5/60 92/300 (98)/30 (92)/10 81.4/150 81.4/150 82.6/150 75/150 %95/120 70/120 90/120g 72.5/30

[12] [38]

Cynara cardunculus oil Raphanus sativus oil Raphanus sativus oil Sunower oil Sunower oil

3:115:1 6:1 and 12:1 6:114:1 6:112:1 7:1

NaOH and KOH/0.251.5 NaOH/0.4 and 0.8 NaOCH2CH3/0.91.5 NaOH/0.751.25 NaOH/1.02.0

2575 45 i 65 3660 2575 80

75 C; 9:1; 1.0% NaOH 65 C; 12:1; 0.4% 30 C; 6:1; 1.3%; 500 rpm 50 C; 12:1; 0.75% 2.0%

[7] [16] [34] [39] [40]

Sunower oil Soybean oil Forage turnip oil Sunower (HOSO) and Brassica carinata oil (HEBO and LEBO)f

6:1

KOH/0.52.0

Ambient and 50

50 C; 1.0%

[41]

Batch reactor, 500/mechanical, 600

5:17:1

KOH/0.51.5

2032

32 C; 5:1; 1.5% for HOSO and HEBO 20 C; 6:1; 1.5% for LEBO 9:1; 6.0% 60 C; 1% KOH 60 C; 0.8% NaOC2H5 80 C; 12:1; 1%

[42]

Madhuca indica oil Fish oil Sunower oil Rapeseed oil Olive oil Used cooking oil Canola oil Used cooking oil Mixtures of canola and used cooking oil Mixture of used olive and sunower oil

Flask, 500 Flask, 250/ultrasound (indirect sonication) 35 kHz, Flask/ultrasound (direct sonication) 20 kHz Batch reactor, 500/mechanical

4.5:19:1 6:1 6:114:1

H2SO4/1.07.0 KOH/0.51.0 NaOC2H5/0.8 NaOH/0.251.5

78.5 20 and 60 3590

[43] [44] [17]

Batch Parr reactor/600

6:1

KOH/1

50

[45]

Batch reactor, 1000/mechanical

6:115:1

NaOH, KOH, NaOCH3, KOCH3/0.1 1.5

3578

60 C; 12:1; 1.0% KOH

[46]

Waste frying palm oil Palm kernel oil Palm (tucum) oil Triolein

Esteried crude palm oil

Mixture of castor and soybean oil

a b c d e f g h j k

Teon tube (0.9 cm ID 260 cm), Microwave: 2.45 kHz, 800 W Blender Flask, 250/magnetic Erlenmeyer ask, 100/ultrasound (indirect sonication) 40 kHz, 1200 W Erlenmeyer ask, 100/mechanical, 1800 Flask, 250, microwave: 2.45 GHz, 800 W Flask, 250 (conventional heating) Batch reactor, 50/magnetic

12:1 2:15:1 7.5:1 3:19:1

NaOH/3 KOH/1.0 NaOH/1.0 NaOH and KOH/0.53.0 60 60 350 4:1 25 C; 6:1; 1.0% KOH and NaOH

(97)/0.5 96/120 (90)/30 98/20 90/25

[47] [48] [49] [50]

4.5:110.5:1 8.5:1 5.7:1 and 18.8:1

KOH/0.02.0 KOH/1.5 KOH/0.17c

70

8.5:1; 1.5% KOH; 70 W

85j/5 85 /60 97/240

j

[26]

78

18.8:1; 75/25k

[52]

The molar ratio ethanol:ester functions (3xTAG). Mole precent of active sites (H+ or OH) based on the quantity of ester functions (3xmolTAG). Molar ratio catalyst:oil. 0.612.5% Water content in ethanol. In situ ethanolysis. High oleic sunower oil (HOSO), high and low erucic Brassica carinata oils (HEBO and LEBO). Mixture used cooking oil: canola oil with weight ratio of 40:60. The product from the esterication process (ethanol:oil molar ratios 6:1, 1% H2SO4, MW power 70 W and the reaction time of 60 min) of crude palm oil. Ester content 98.1%. Castor/soybean oil wt.%.

et al. / Fuel 90 (2011) 31413155 O.S. Stamenkovic 3145

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et al. / Fuel 90 (2011) 31413155 O.S. Stamenkovic

[19,20,42,51]. The high reaction temperature is unsuitable because of forming soaps which decrease FAEE yield [21,34,54]. Researchers have different views on the optimal temperature of homogeneous base-catalyzed reaction. According to some of them, low temperatures are more suitable [1821,34,42] while the others recommend reaction temperatures in the range between 60 and 80 C [7,12,16,17,23,46]. The solubility of ethanol in vegetable oils is higher than that of methanol [7] and at 25 C it is from 13.16% to 16.41%, depending on the type of vegetable oil [55]. The agitation intensity is of a particular importance because it enables the formation of a stable emulsion of small drops and the increase of the TAG mass transfer from the oil phase towards the interfacial area [5658]. Researches considering the effect of mixing intensity on biodiesel synthesis are commonly focused on the vegetable oil methanolysis [5662]. In the previous studies, vegetable oil ethanolysis has been performed at the agitation intensity in the range from 200 to 600 rpm, using a mechanical or magnetic stirrer (Table 2). Exceptionally, Valle et al. [34] investigated the inuence of the agitation speed in the range from 500 to 3200 rpm on FAEE yield of Raphanus sativus oil. According to them, a high stirring speed (over 500 rpm) was disadvantageous to the efciency of the reaction and the optimal stirring speed was 500 rpm. 3.2. Heterogeneously catalyzed vegetable oil ethanolysis The use of heterogeneous catalysts improves vegetable oil ethanolysis for several reasons. These catalysts can be separated more eas-

ily from the reaction mixture and reused with or without regeneration while the purication of the products is simple and does not require a large amount of water, which makes the process environmentally and economically advantageous [63]. A disadvantage of using heterogeneous catalysts is the formation of three phases leading to diffusion limitations, thus lowering the reaction rate [64]. According to the best authors knowledge, there is no industrial biodiesel production by the heterogeneously catalyzed ethanolysis process. Nowadays, only one industrial biodiesel production process (Esterp-H) developed by the French Institute of Petroleum (IFP) is based on the use of heterogeneous catalysts (mixed oxide of zinc and aluminum) in the vegetable oil methanolysis [65]. The reaction is performed at higher temperature and pressure in two xed bed reactors fed with vegetable oil and methanol at a given ratio. The excess of methanol is removed after each reactor by partial evaporation. Then, esters and glycerol are separated in a settler. The Esterp-H process does not require biodiesel washing steps, making the purication steps of the products much more simpler, and very high yields of methyl esters close to theoretical values are obtained [65]. The possibility of reusing heterogeneous catalysts is one of its advantages but so far only a few catalysts could be reused without a loss in activity. Sreeprasanth et al. [66] reported that K4Zn4[Fe(CN)6]6H2O2(tert-BuOH) could be recycled many times without any signicant loss in activity. An effective ethanolysis catalyst is Mg2CoAl, which was used in seven cycles of canola oil ethanolysis with quite similar FAEE yield of 95 5% in all the cycles, indicating its relatively high stability [67]. CaO was used as

Table 3 The review of the catalyst type and reaction conditions applied in heterogeneously catalyzed ethanolysis. Feedstock Type, volume of reactor (cm3)/type of agitator, agitation intensity (rpm) Batch reactor Parr 4565, 300/ mechanical Batch reactor, 100/mechanical, 800 Erlenmeyer ask, 25/shaker, 450 Erlenmeyer ask, 25/shaker, 450 Flask, 250/mechanical Flask, Microwave (220 W), 250 Teon-lined steel autoclave, 100/ rotating, 50 Mini bench reactor Parr 4560, 300 Ethanol:oil molar ratio (mol/ mol) 20:1 12:1 10:1 10:1 6:1 6:1 6:115:1 Catalyst/loading (wt.% to the oil) SO4/ZrO2/5 Ca(OCH2CH3)/3 Anion exchanged resin (Marathon MSA)/36 CaOLa2O3/8 SiO2/50% H2SO4/10 SiO2/50% H2SO4/10 K4Zn4[Fe(CN)6]6H2O2(tertBuOH)/03 MgO/SBA-15/2 Temperature (C) Yield (conversion) (%)/Time(h) 92/1 91.8 /3 >90/6 71.6/6 %100/6c (95)/6 (>95)/0.33 (90d)/8 (98 )/8 (96)/5
d b

Reference

Soybean oil Soybean oil Soybean oil Soybean oil Castor oil Rubber seed oil Margarine oil Commercial-ediblegrade blended vegetable oil

120a 6575 54 65 60 80170a

[69] [73] [36] [74] [75] [66]

6:1

220a

[76]

Rapeseed oil

Batch reactor (under Ar atmosphere.), 50/magnetic, 500

6:1

MgO/KIT-6/2 MgO/MCM-41/2 H3PW12O40/1.7e H3PW12O40/SiO2/0.6 Cs2HPW12O40/0.5 Mg2CoAl/2 Ion-exchange resin/2040g Comercial resin Dowex monosphere 550A/2.2 CaO/520 CaO/1

80

(80)/5 (67)/5 (27)/3 (14.5)/3 (5.2)/3 %100/5f (%100)/1.5h (>90)/210j %100/6k %90/2

[77]

Canola oil Triolein Sunower oili Sunower oil Graundnut crude oil
a b c d e f g h i j k

Mini bench reactor Parr 4560 Batch reactor Batch reactor, 500/200 Batch reactor, 250/mechanical, 900 Batch reactor, 15/1000

7:116:1 3:110:1 4.2:16.1:1 6:130:1 9:1

140200a 50 3055 75 78

[67] [71] [78] [79] [80]

Under high pressure. At temperature 75 C. With equimolecular etanol-metanol mixture (5:5 mol/mol). At optimal reaction conditions: 15:1, 3% and 170 C. Mole percent of active sites (H+) based on the quantity of ester functions (3xmol TAG). At optimal reaction conditions: 11:1 and 200 C. Weight percent on the total reaction mixture. At optimal reaction conditions: anion porous resin PA306S, 40% and 10:1. In a mixture with oleic acid. At optimal reaction conditions: 19.5% oleic acid; 6.1:1 and 45 C. At optimal reaction conditions:18:1 and 20%.

 et al. / Fuel 90 (2011) 31413155 O.S. Stamenkovic

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a catalyst in ve cycles of sunower ethanolysis and the FAEE yield obtained at the end of each cycle was >97% [68]. However, in most cases multiple uses of heterogeneous catalysts reduce its catalyst activity [6971]. The deactivation of heterogeneous catalyst can be caused by blocking of catalyst active sites with adsorbed molecules of the reaction intermediates or products, the transformation of the catalyst active surface and the catalyst leaching [72]. In order to enable the repeated use of heterogeneous catalysts, there are different techniques for recovering its catalytic activity. For instance, a three-step regeneration method was successfully used for recovering the catalytic activity of anionexchange resin PA306s for the batch ethanolysis process [71]. To utilize numerous advantages of the heterogeneously catalyzed reaction in a continuous process, active and stable catalytic systems should be developed, and reaction conditions are to be optimized. Different compounds were used as a solid catalyst for vegetable oil ethanolysis. A review of the catalyst type and reaction conditions applied in heterogeneously catalyzed ethanolysis is given in Table 3. The catalytic activity of a heterogeneous catalyst has the greatest inuence on the efciency of the heterogeneously catalyzed process. Effective factors on catalyst activity are its nature, preparation and activation, as well as specic surface area, pore size and volume and active site concentration [72,81]. A high FAEE yield can be obtained by using heterogeneous catalysts but the reaction time is longer and the reaction temperature, the catalyst loading and the initial ethanol:oil molar ratio are higher comparing to the homogeneously catalyzed reaction. The aim of the previous researches of heterogeneously catalyzed ethanolysis was mostly to develop a catalyst with a high catalytic activity. The inuence of the reaction conditions on FAEE yield is the subject of up-to-date researches while optimal conditions providing the highest FAEE yield are experimentally determined in every single case. A commercial effect of using heterogeneous catalysts can be enhanced by using waste oily feedstocks usually containing a high FFA amount. The efcient catalysts for the ethanolysis of oils with high FFA content are commercial resin Dowex monosphere 550A [70,78], SO4/ZrO2 [69], WO3/ZrO2 [82] and Fe-Zn cyanide complexes [66]. CaO/MgO [83], anionexchange resin (PA306s) [71] and cation(PK208LH) and anion(PA306s) exchange resins [84] were used in continuous processes of heterogeneously catalyzed ethanolysis. CaO/MgO stones packed in two separate columns were used for FAEE synthesis in a two-step process at 60 C. The rst step involved TAG hydrolysis to FFA and glycerol, which were gravity separated. In the second one FFA were ethanol esteried at the initial ethanol:FFA molar ratio 2:1. This process, known as DUOBIO process, gave a high FAEE yield [83]. Triolein ethanolysis was performed in a continuous expanded bed reactor packed with the heterogeneous anionexchange resin PA306s [71]. A complete triolein conversion was obtained at 50 C, the initial ethanol:triolein molar ratio 10:1 and the residence time of 1 h. A two-step process involving two expanded bed reactors individually packed with the heterogeneous cation-exchange resin (PK208LH) and the anion-exchange resin (PA306s) has been recently developed [84]. For the esterication of FFA, the reaction mixture consisting of crude rice bran oil and ethanol was introduced into the rst reactor and then into the second one, where the ethanolysis of TAG occurred. At ethanol:total fatty acid residue in the crude oil molar ratio of 3.6:1 and at 50 C, the FFA conversion degree obtained in the rst column was 91%, and the nal FAEE yield was 98.6%.

4. Enzyme-catalyzed vegetable oil ethanolysis The use of lipases (EC 3.1.1.3) in the FAEE synthesis has been greatly studied during the last decade. The advantages of this pro-

cess are simpler separation and purication of the reaction products and a minimal quantity of wastewater [85]. Besides these, lipases simultaneously catalyze TAG alcoholysis and FFA esterication [86,87]. The disadvantages are the enzyme high price, slow reaction rate and the necessity to control the reaction parameters carefully [88]. Based on environmental benets, the enzyme-catalyzed process (called green process) is used for biodiesel synthesis and is expected to be widely used in the future. The enzymatic production of FAME was established in Lvming Co. Ltd. and Hainabaichuan Co. Ltd. in China, where immobilized lipases Candida sp. 99125 and Novozyme 435 are used as catalysts, respectively [89]. In the former case, waste cooking oil was used as raw material, the process was conducted in a stirred tank reactor and FAME yields achieved 90% under the optimal conditions. Vegetable oil ethanolysis was investigated in the presence of lipases of different origins. A signicant FAEE yield was achieved by using lipases from Candida antractica [90,91], Chromobacterium viscosum [92], Mucor miehei [90,93], Pseudomonas cepacia [9497], Pseudomonas uorescens [98,99], Porcine pancreatic [100], Rhizomucor miehei [101] and Thermomyces lanuginosus [102,103]. Lipases from Rhizopus delemar [93], Candida rugosa [92,97] and Mucor javanicus [95,97] have low catalytic activity in the ethanolysis process. Generally, enzyme-catalyzed ethanolysis is performed with a high lipase amount (530%). Lipases are usually immobilized, which improves their stability, minimizes downstream operations and allows catalyst reusing. The review on the reaction conditions of the lipase-catalyzed ethanolysis which provide a signicant FAEE yield is given in Table 4. Ester yield depends on the lipase origin, a carrier type, the immobilization technique and applied reaction conditions, the inuence of which all is mostly combined [89,109,110]. Due to the inhibitory effect of ethanol on lipase, the enzyme-catalyzed vegetable oil ethanolysis is generally performed at low ethanol:oil molar ratios. The lipase deactivation degree by ethanol is lower than that by methanol [111]. As in the case of methanolysis this problem can be solved by the ethanol stepwise addition [101,103]. The achieved FAEE yield from soybean oil in the presence of Rhizomucor miehei lipase at the three-step ethanol addition was signicantly higher (60%) than that observed when ethanol was added in a single step at the beginning of the reaction (16.9%) [101]. In order to minimize the inhibitory effect of ethanol, a pretreatment of the immobilized enzyme [111] and the use of solvent [93,99,103] are recommended. In addition, the use of solvents ensures a homogeneous reaction mixture and reduces the reaction mixture viscosity, which decreases the problems associated with mass transfer limitation and signicantly increases the reaction rate [112]. On the other hand, the presence of the solvent increases the energy requirements due to its separation after the reaction completion [99]. Temperature is a very important factor in the enzyme-catalyzed process. The optimal temperature is between 30 and 40 C, which depends on the lipase origin and the immobilization technique applied. Exceptionally, de Oliveira et al. [90] recommend a high reaction temperature (65 C). Water has a strong inuence on the lipase catalytic activity and stability [113] and increases FAEE yield [92,93,97]. However, the excess of water might lead to some sidereactions such as hydrolysis of esters. According to de Oliveira et al. [90], a high FAEE yield is achieved without the addition of water in the reaction mixture. The optimal water content is a compromise between a maximizing enzyme activity for the alcoholysis and the minimizing hydrolysis reaction [96] and depends on the oily feedstock, the lipase origin, the immobilization technique and the organic solvent employed [85]. A reduction of diffusion limitation and the increase of enzymecatalyzed ethanolysis reaction rate can be achieved by performing

3148

Table 4 The review on the reaction conditions of the lipase-catalyzed ethanolysis providing signicant FAEE yield. Lipase source (enzyme commercial name) Carrier Lipase loading (wt.% to the oil) 20 3 30 30 Feedstock Ethanol:oil molar ratio (mol/mol) 10:1 2:1a,b 5:1 5:1 Temperature (C) Solvent Water (wt.% to the oil) Yield (conversion) (%) /Time (h) (81.4)/6 (83.5)/1.5 (27)/12 (75)/10 (75)/10 (50)/10 (55)/10 (37)/12 92/8 98.3/5 68.0/5 97.4/5 98.2/5 (98)/6 82/5 (72)/8 (35)/8 65d/1 (98)/8 (99)/2.5 (92)/2.5 (96)/6 (98)/24 (%70)/80 99/5 (80)/7 55/4 96/7 (%100)/10 (%100)/10 (%100)/10 100/48 89.7/48 Reference

Candida antarctica (Novozym 435) Candida antarctica (Novozym 435) Candida antarctica (Novozym 435) Candida antarctica (Novozym 435)

Macroporous acrylic resin Macroporous acrylic resin Macroporous acrylic resin Macroporous acrylic resin

Castor oil Soybean oil deodorizer distillate Sunower oil Palm oil Groundnut oil Pongamia piata oil Jatropha curcas oil Castor oil Jatropha curcas oil Tallow Soybean oil Rapeseed oil Castor oil Sunower oil Palm kernel oil Coconut oil Soybean oil Jatropha curcas oil Madhuca indica oil

65 50 45 45

Supercritical CO2 Supercritical CO2

[90] [91] [104] [105]

Candida antarctica (Novozym 435) Chromobacterium viscosum Mucor miehei (Lipozyme IM60)

Macroporous acrylic resin Celite-545 Macroporous anion excange resin

20 10 10

5:1 4:1 3:1

45 40 45

Supercritical CO2 Hexane

Mucor miehei (Lipozyme IM) Mucor miehei (Lipozyme) Pseudomonas cepacia (PS 30) Pseudomonas cepacia Pseudomonas cepacia Pseudomonas cepacia

Macroporous anion excange resin Macroporous anion excange resin TMOSe and iso-BTMSf polymer Celite K2SO4 microcrystals Glutaraldehyde Polypropylene Polysiloxanepolyvinyl alcohol hybrid composite Kaolinite Macroporous anion exchange resin Macroporous anion exchange resin Aldehyde-Lewatit VP OC1600 Granulated silica Polysiloxan-polyvinyl alcohol hibrid composite

20 20 10 5 10 10

3:1 11:1 4:1 15.2:1 4:1 4:1

65 45 40 35 50 40

Petroleum ether

0.5c 6d 3 45

[106] [92] [93]

et al. / Fuel 90 (2011) 31413155 O.S. Stamenkovic

[90] [107] [94] [96] [97] [95]

Pseudomonas uorescens (Lipase AK) Pseudomonas uorescens (Lipase AK) Pseudomonas uorescens Porcine pancreatic Rhizomucor miehei (Lipozyme RM IM) Thermomyces lanuginosus (Lipolase 100L) Thermomyces lanuginosus Thermomyces lanuginosus (Lipozyme TL-IM) Burholderia cepacias (Lipase PS)

20g %10 20 10 7 15 15 15 20g

Palm oil Triolein Sunower oil Sunower oil Soybean oil Soybean oil Soybean oil Soybean oil Babbasu oil Beef tallow

18:1 3:1 11:1 3:1 3:1h 7.5:1 7.5:1 3:1h 3:1h 12:1

40 50 45 45 50 31.5 30 30 50

1,4-dioxane Petroleum ether Hexane

4 4 4

[98] [99] [107] [100] [101] [102] [103]

[108]

At optimal reaction conditions:18:1 and 20% a Molar ratio FFA:ethanol. b Two-step ethanol addition. C Percent m/v. d Mole percent. e Tetramethoxysilane. f Iso-butyltrimethoxysilane. G Weight percent on the total reaction mixture. h Three-step ethanol addition.

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Yield (conversion) (%)/Time (ow rate)

Optimal reaction conditions

5. Non-catalyzed vegetable oil ethanolysis Vegetable oil ethanolysis can be performed without a catalyst under high pressure and temperature, most often beyond the critical point of ethanol (243 C and 6.4 MPa). Under supercritical conditions the reaction mixture becomes a single homogeneous phase, which accelerates the reaction rate due to the absence of the interphase mass transfer limitation [114] and alcohol is both a reactant and an acid catalyst [115]. The advantages of non-catalyzed ethanolysis are high reaction rate, simple separation and purication of the reaction products, no waste generation from catalyst separation from the nal product, making this process environmentally friendly. Ethanolysis of TAG and esterication of FFA occur simultaneously, thus enabling the use of waste and crude oils [116]. Due to high capital costs for the reactor and great energy consumption, the non-catalytic process still does not have industrial application. However, an economic study showed that the total investment and operation costs under supercritical conditions [117] are less than those of the conventional method with chemical catalysts [118]. The presence of FFA and water in the feedstock poses no problem in the non-catalytic supercritical process. The conversion tends to increase with the increase of FFA content [115]. Water in the feedstock can hydrolyze the oil and form FFA the esterication of which proceeds faster than the alcoholysis reaction. This difference is the result of at least two possible reasons: the rst is that FFA, particularly unsaturated FFA, are more soluble in alcohol than TAG and the second is probably related to their reaction mechanism, which is more complex in case of the alcoholysis reaction [119,120]. Finally, water contributes to an easier separation at the end of the supercritical process. A great number of non-catalytic process studies deal with vegetable oil methanolysis while the use of ethanol has been recently started. Non-catalytic ethanolysis of different vegetable oils has been studied in batch and continuous reactors under different reaction conditions. The review of the conditions applied in noncatalytic ethanolysis is given in Table 5. Both non-catalytic ethanolysis and methanolysis occur at high alcohol:oil molar ratio. Silva et al. [121] reported that the initial ethanol:oil molar ratio had no signicant inuence on the initial reaction rate, while the reaction conversion was improved at a higher ethanol:oil molar ratio. FAEE yield was increased with the increase of the initial ethanol:oil molar ratio up to 40:1 due to a great ethanol:oli interphase area which allowed more efcient TAG conversion [121]. The system homogeneity was not changed at higher molar ratio so the FAEE yield remained the same [106,124]. According to most results published, the optimal molar ratio is about 40:1 (Table 5). Non-catalytic ethanolysis reaction rate and FAEE yield are increased with the increase of the reaction temperature. The FAEE yield increase of about 20% [32,123] or 10% [104] was observed when the reaction temperature changed from subcritical to super-

Reaction conditions

40:1; 350 C; 20 MPa

350 C; 25 MPa 40 MPa 250 C 250 C 40:1; 325 C

400 40:1; 350 C 200400 200350 40:1 10:170:1 Stainless steel batch reactor, 8 Batch reactor of stainless steel 316L, 11 20 20

Pressure (MPa)

720 20 15, 25 1040 20

Temperature (C)

200375 350 300, 350 300 230, 250 230, 250 275350

Ethanol:oil molar ratio (mol/mol)

10:1100:1 40:1 42:1 42:1 41:1 41:1 30:180:1

Table 5 The review of reaction conditions of non-catalytic vegetable oils ethanolysis.

Tubular reactor of stainless steel 316L, 24 and 42 Tubular reactor composed by two coils of stainless steel 316L, 42 Batch reactor of Inconel-625, 5 Tubular reactor of stainless steel HC276, 95 Stainless-steel cylindrical autoclave Stainless-steel cylindrical autoclave Stainless steel batch reactor, 10

Reactor type, volume (cm3)

Feedstock

Soybean oil Soybean oil Rapeseed oil Rapeseed oil Cottonseed oil Linseed oil Sesame oil Mustard oil Sunower oil Castor oil Linseed oil Palm oil Groundnut oil Pongamia pinata oil Jatropha curcas oil

Batch reactor of stainless steel 316L, 11

10:170:1

200400

20

50:1; 400 C

(80)/15 min 77.5/(1.5 cm3/min) %100/12 min 80/20 min 85/8 min >85/8 min (%100)/40 min (%100)/25 min (%100)/40 min (%100)/30 min (%100)/40 min (95)/30 min (95)/30 min (90)/30 min (90)/30 min

the process in supercritical uids. Supercritical carbon dioxide, considered as a green solvent, is a promising alternative to conventional solvents because it is non-toxic and non-ammable, available in great amounts, inexpensive and has moderate critical temperature and pressure values (31.1 C and 7.38 MPa). The alcoholysis products do not dissolve in carbon dioxide at room conditions, so the separation can easily be achieved by reducing the pressure [105]. However, a few studies deal with enzyme-catalyzed ethanolysis of vegetable oil in supercritical carbon dioxide [104106]. In these researches Novozyme 435 is used as a catalyst and optimal reaction conditions were: ethanol:oil molar ratio 5:1; temperature 45 C and lipase loading 20% or 30%, based on the oil weight (Table 4).

Reference

[121] [122] [119]

[123] [32] [124]

[104] [106]

[105]

3150

et al. / Fuel 90 (2011) 31413155 O.S. Stamenkovic

critical. Under supercritical conditions, the reaction time for the complete conversion is signicantly shortened with the increase of the reaction temperature [106,119,124,125]. On the other hand, high temperature can favor a backward reaction of glycerol with ethyl esters and may cause the product degradation (especially ethyl esters of unsaturated fatty acids), thus decreasing the FAEE yield [121,122,125]. Imahara et al. [126] reported that degradation products compromised the thermal stability of biodiesel. Therefore, a non-catalytic ethanolysis reaction performed at temperatures up to 350 C [121] or 400 C [105] is recommended. Few researchers studied the effect of the reaction pressure on non-catalytic vegetable oil ethanolysis. Their results show that the pressure ranging from 7 to 20 MPa [121] or from 10 to 40 MPa [119] does not signicantly inuence FAEE yield. Capital cost which is lower at low pressures makes these results important for practical use of a non-catalytic process.

6. The optimization of vegetable oil ethanolysis reaction conditions The inuence of the reaction conditions on both FAEE yield and ethanolysis reaction rate cannot be generalized. The determination of optimal operating and reaction conditions is particularly important for increasing the efciency and reducing the process cost. Generally, statistical techniques are used in the optimization of the process. The following statistical techniques have been used in recent researches related to the biodiesel production from different raw materials: full and fractional factorial design, leastsquares ttings and response surface methodology, each of them having advantages and disadvantages. According to Montgomery [127], factorial design can be very effective in optimizing the process if the purpose of planning the experiments is determining the effects of the process factors and their interactions on the system response. The initial ethanol:oil molar ratio, the catalyst loading and the reaction temperature are the most examined factors in biodiesel synthesis optimization while the agitation intensity and reaction time are rarely studied. The optimization of ethanolysis reaction conditions refers mostly to the homogeneous base-catalyzed process, where the following methods have been applied: 23 factorial design [20,23], response surface methodology combined with 23 factorial design [16,42] or with the central composite rotatable design [19,25], multi-linear regression [21] and the combination of fractional factorial and Doehlert experimental designs [34]. These optimization studies are primarily related to the ethanolysis of castor oil [19,20,25] or Raphanus sativus oil [16,34] catalyzed with sodium hydroxide or ethoxide. However, a few studies dealt with the optimization of potassium hydroxide catalyzed ethanolysis of rapeseed [21], soybean [23], sunower and Brassicca carinata [42] oil, where the factorial design with three or more variables at two levels is used. According to most studies, both the catalyst loading and the ethanol:oil molar ratio have the greatest positive impact on FAEE yield while the reaction temperature has no statistically signicant effect [16,19,20,23]. The statistical signicance of the binary interaction between molar ratio and catalyst loading shows that these variables are closely related and actually explained why a molar ratio had a huge effect only when the catalyst loading was low. In addition, neither of the binary and ternary interactions involving the temperature was of statistical signicance. However, Bouaid et al. [42] reported that the inuence of process variables on ethyl ester yield depends on the kind of vegetable oil. The potassium hydroxide catalyst loading had a positive effect on esters yield independently of the oil used. The temperature inuence was signicant and positive on the process of sunower oil ethanolysis

but negative in the case of low and high erucic Brassicca carinata oil. The inuence of ethanol:oil molar ratio positively affected only the ethanolysis process of low erucic Brassicca carinata oil [42]. On the contrary, for the production of FAEE from castor oil, the catalyst loading was the variable that inuenced the ester yield most negatively, while the ethanol:oil ratio had a positive effect on the process [25]. The most adequate conditions to maximize the ester yield were obtained by using the response surface methodology [16,19,25,42]. Exceptionally, Valle et al. [34] studied the inuence of ve variables (ethanol:oil molar ratio, the catalyst loading, reaction temperature, agitation intensity and reaction time) on FAEE yield in the sodium ethoxide catalyzed ethanolysis of Raphanus sativus L. oil. The agitation intensity had the greatest negative effect, while the ethanol:oil molar ratio effect was not signicant. In order to establish the optimal conditions the temperature, reaction time and catalyst loading were studied using the Doehlert design. The optimal conditions were found to be as follows: reaction time of 70 min, temperature of 30 C, sodium ethoxide catalyst loading of 1.3%, ethanol:oil molar ratio of 6:1 and stirrer speed of 500 rpm. Under these conditions, the obtained ethyl ester yield was 97.9%. Optimizing each factor individually, i.e. changing one factor at a time while others are kept unchanged, is a most often used method for the optimization of lipase- and heterogeneously catalyzed, as well as non-catalyzed ethanolysis. So far, statistical methods have not been employed for determining the inuence of the reaction conditions on FAEE yield in heterogeneously catalyzed and noncatalyzed ethanolysis reactions. Instead, the optimal reaction conditions ensuring the highest FAEE yield are established experimentally. Statistical optimization methods are frequently applied in the lipase-catalyzed methanolysis [128130]. Rodrigues et al. [102] optimized the production of FAEE from soybean oil catalyzed by Thermomyces lanuginosus lipase using a central composite design and the response surface methodology. The most important factors affecting the FAEE yield were enzyme loading and water content while the effect of temperature was the lowest compared to other reaction parameters. The ethanol:oil molar ratio had a negative effect on the ester yield which was attributed to the enzyme inhibition and a decrease of its catalytic activity at higher ethanol concentrations [102].

7. Kinetics of vegetable oil ethanolysis Although the reaction kinetics of ethanolysis is fundamental to the reactor design, process analysis, simulation and control, the operation and scale-up, it has been rarely studied. According to most researchers, the homogeneously catalyzed ethanolysis reaction is slower compared to methanolysis [24,27,29,54,131]. This can be explained by the fact that the reactivity of methoxide radicals is higher than that of ethoxide radicals. As the length of the carbon chain increases, nucleophilicity of the alkoxide anion decreases leading to a decrease in the alkoxide anion reactivity [132]. On the other hand, Kim et al. [36] reported that there was no essential difference in conversion rates between methanolysis and ethanolysis in homogeneously (CH3ONa) catalyzed reactions. The reaction mixture can be considered as a pseudo-homogeneous system, where there is no mass transfer limitation, so the overall process kinetics is chemically controlled [51]. The homogeneous base-catalyzed ethanolysis is very fast in the initial reaction period, and it is getting slower as approaching equilibrium. The conversion curves have an asymptotic tendency with time and the nal ethyl ester concentration is reached in 1030 min, dependently of oily feedstocks [7,46]. The kinetics of cottonseed oil ethanolysis in the presence of a different water amount was described by a three reversible consecutive reaction model [12]. The overall

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reaction of castor oil ethanolysis in the kinetically controlled region follows the irreversible rst-order kinetic model with respect to acylglycerols and its activation energy is 70.6 kJ/mol [20]. Georgogianni et al. [38,40] established the rst and second-order reaction with respect to TAG for the base-catalyzed ethanolysis of sunower and cottonseed oils using both mechanical agitation and low-frequency ultrasonication, but they indicated that a better t was obtained for the rst-order reaction kinetics. A simple kinetic model consisting of the irreversible second-order reaction followed by the reversible second-order reaction close to the completion of the ethanolysis reaction was used for the simulation of the TAG conversion and the FAEE formation. The calculated activation energies are in the range 3.443.9 kJ/mol in the temperature interval from 25 to 75 C [51]. In the case of a heterogeneously catalyzed reaction signicant differences in the conversion rates between these processes were observed depending on the type of catalyst. The reaction rate of ethanolysis over a strong base CaOLa2O3 catalyst was lower than that of methanolysis at the same reaction conditions, which was attributed to the higher steric hindrance for carbonyl group of the TAG to approach ethoxide bonded on the catalyst surface [74]. On the contrary, with the hydrophobic resin catalyst (Marathon MSA) the ethanolysis reaction was faster than the methanolysis reaction as a result of a higher afnity of ethanol to the hydrophobic catalyst surface and consequently, easier adsorption of ethoxide on the anion sites of the catalyst [74]. Several kinetic models have been reported for the heterogeneously catalyzed methanolysis reaction. The rst-order model with respect to TAG was most frequently used to describe the methanolysis reaction kinetics [73,133135]. In order to explain et al. [133] and Veljkthe sigmoidal process kinetics, Stamenkovic et al. [134] included TAG mass transfer limitation in the initial ovic reaction period. Kouzu et al. [136] reported that with the methanolysis reaction progress the kinetic model changed from zero to one with respect to TAG. The kinetics of metal oxide catalyzed soybean oil methanolysis was described by the rst-order model with respect to methanol [137]. The kinetics of heterogeneously catalyzed ethanolysis has hardly been studied. The overall reaction rate of canola oil ethanolysis catalyzed by Mg2CoAl follows the rst-order kinetics with respect to all acylglycerols with the activation energy of 60.5 kJ/mol in the temperature range of 140200 C [67]. Only a limited number of kinetic studies of enzyme-catalyzed ethanolysis are found in the literature. A model based on the Ping Pong BiBi mechanism with competitive inhibition is usually applied to describe the kinetics of the ethanolysis of sunower, soybean [138] and castor [106] oil catalyzed by Novozym 435. Models derived from a generalized MichaelisMenten mechanism are used to describe the kinetics of the ethyl esters formation from the fatty acids present in the precursor oil [139,140]. The most appropriate model for ethanolysis of a rafnate product obtained after distillation of olive oil catalyzed by Candida antarctica lipase includes only
Table 6 Activation energies of non-catalytic vegetable oil ethanolysis. Feedstock Sunower oil Soybean oil Palm oil Groundnut oil Pongamia pinata oil Jatropha curcas oil Castor oil Linseed oil
a b

the forward reaction, while in the case of Rhizomucor miehei and Thermomyces lanuginose-lipase catalyzed reaction the kinetic model involves both the forward and reverse reactions [140]. The reverse reaction kinetic model is also applied for simulating Pseudomanas cepacia-lipase catalyzed menhaden oil ethanolysis while the kinetics of tuna oil ethanolysis is described by a more complex model which, besides the forward and reverse reactions, includes the inhibition effects and enzyme deactivation [139]. Contradictory results have been reported about the reaction rate of non-catalytic methanolysis and ethanolysis. According to some researchers, a non-catalytic methanolysis reaction is faster comparing to ethanolysis as a consequence of higher acidity of methanol and the possibility for the simultaneous attack of methanol on all three chains of TAG [32,119,123]. The solubility parameter of ethanol, which is close to the solubility parameter of an oil, is lower than that of methanol, which causes that ethanolysis is faster than methanolysis under non-catalytic reaction conditions [104,105,124]. So far, the kinetics analyses of non-catalytic ethanolysis reaction have been based on the overall reaction and the model of rst-order reaction with respect to TAG [104106,121]. The activation energy values of non-catalytic ethanolysis reaction are shown in Table 6. There is no obvious discontinuity in the Arrhenius dependence around the critical temperature. The results showed that the activation energy is inuenced by the type of vegetable oil. The reaction rate constant of non-catalytic ethanolysis is strongly inuenced by the composition of the vegetable oil [105,106]. The ethanolysis reaction rate is highest for the TAG of saturated fatty acid followed by the TAG of unsaturated acids. Also, the reaction becomes slower with an increasing number of double bonds in the unsaturated acids of TAG. Castor oil contains a uniquely high level of hydroxy fatty acid (ricinoleic acid) and is very different from other oil compositions. Thus, the castor oil ethanolysis reaction rate cannot be compared to other vegetable oils [106].

8. The possibilities for improving the ethanolysis reaction The improvement of the ethanolysis reaction includes all activities leading to increase the FAEE yield and shortening the reaction time. Achieving a high FAEE content in the ester phase is important to meet the quality standard for FAEE as a fuel, which strictly limits the presence of MAG, DAG and TAG. The yield of ethyl esters significantly depends on the separation of ester from the alcohol phase which can be difcult. The use of ultrasound enhances the reaction rate of homogeneously catalyzed ethanolysis, which results in higher FAEE yields in a shorter reaction time [22,35,44,50,141]. Ultrasound-assisted base catalyzed ethanolysis of triolein under optimal reaction conditions gives 98% FAEE yield in less than 20 min, while in the case of mechanical agitation only 90% FAEE yield is obtained in 25 min [50]. Ultrasound is also effective in increasing the FAEE yield in the shorter reaction time in the in situ production of biodiesel from cottonseed [38] and sunower seed [40]. The in situ biodiesel production is a novel method for producing biodiesel from oil-bearing materials in which the extraction and alcoholysis proceed in one step, i.e. the alcohol acted as both an extracting solvent and an esterication reagent. The base-catalyzed in situ ethanolysis requires only 40 min for complete conversion using ultrasonication, while for the conventional in situ base-catalyzed ethanolysis the reaction is not completed even after 4 h [38,40]. The use of ultrasound is economically more benecial than the conventional mechanical stirring method due to less energy consumption. In addition, ultrasonication reduces the separation time so this meth-

Temperature range (C) 200400 200375 200400

Activation energy (kJ/mol) 3 92.9a 78.7b 915

Reference [104] [121] [105]

200350

55 70

[106]

Ethanol:oil molar ratio 20:1. Ethanol:oil molar ratio 40:1.

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od could be effectively used for the continuous biodiesel production [22]. The use of microwave has a similar effect on the ethanolysis reaction rate. Microwave irradiation delivers energy directly to the reactants and a heat transfer is more effective than conventional heat so ethanolysis with microwave radiation can be completed in a much shorter time [26,47]. Suppalakpanya et al. [26] compared the base-catalyzed ethanolysis of esteried crude palm oil under microwave irradiation and conventional heating at 70 C. The high FAEE yield was produced by microwave heating in a 5 min reaction time, while conventional heating would require 1 h to achieve the same ester yield. Continuous ethanolysis of waste frying palm oil gave a conversion over 97% in a 30 s residence time [47]. The reaction time of microwave-assisted heterogeneously catalyzed ethanolysis of castor oil is 18 times less compared to that for a conventional heating method under stirring [75]. The reaction rate of homogeneously catalyzed ethanolysis is increased by the addition of an inert cosolvent, such as tetrahydrofuran, because it can produce a single phase between reactants and eliminates the mass transfer limitation [142]. Mass transfer limitations for heterogeneous catalysts in liquid phase reactions can be minimized by using catalysts impregnated on the supports which not only provide a higher catalytic active surface area through the existence of pores but also enhance the catalyst activity [81]. According to the results of some researchers, FAEE yield increases by performing the ethanolysis process in two stages [16,17,23,46]. After the completion of the rst ethanolysis stage, ethanol and glycerol are separated to yield a crude ester phase which contains unreacted acylglycerols. This phase is subjected to the second ethanolysis reaction carried out at lower ethanol:oil molar ratio and catalyst loading. The two-stage ethanolysis process improves FAEE yield by 16% [17] and 30% [46], compared to the one-stage process. Performing the alcoholysis reaction with the methanol/ethanol mixture can improve the fuel properties of biodiesel [29] and increases the reaction rate [74,131]. This process takes advantage of better solvent properties of ethanol in vegetable oils and easier ester separation using methanol. The FAME formation is faster in comparison to the formation of FAEE, as evidenced by a higher molar ratio of methyl to ethyl esters in the case of equimolar methanolethanol mixture due to higher reactivity of intermediate methoxide anion [27,29,130]. Kim et al. [74] explain a signicant improvement in the alcoholysis rate by combined structures of methoxideethanol or ethoxidemethanol, which generates two reactive sites per alkoxide molecule when the reaction mixture is basic enough to form ethoxide. This combined structure can accelerate the reaction rate and can increase the ester yield when using the alcohol mixture and either homogeneous or heterogeneous catalysts. The resultant FAME/FAEE mixtures exhibit enhanced low temperature properties and oxidative stability, as well as superior lubricity in comparison to neat FAME and also satisfy the biodiesel standard with respect to kinematic viscosity and acid value [29]. The development of commercial enzyme-catalyzed processes is also based on the development of catalytic stable enzymes, which retain their activity in a multiple use. When used as ethanolysis biocatalysts, extracellular lipases should be isolated, puried and immobilized, which is not so easy, especially in industrial conditions. These problems can be overcome by using intracellular lipase, i.e. whole microbial cells spontaneously immobilized on porous particles during batch cultivation. Koda et al. [143] reported the ethanolysis of rapeseed oil using lipase-producing lamentous fungi immobilized on biomass support particles as a whole-cell biocatalyst. Recombinant Aspergillus oryzae expressing Fusarium heterosporum lipase (r-FHL) completely converts rapeseed oil to ethyl ester without producing MAG and DAG. On the other hand,

r-FHL is recycled retaining FAEE yield over 85% by the fth cycle. Protein-coated microcrystals (PCMCs) prepared from a recombinant Aspergillus strain expressing Thermomyces lanuginosus lipase were used for biodiesel synthesis from rened and crude palm oil as well as from palm fatty acid distillate [144]. The highest FAEE yield was obtained in the system containing tert-butanol in molar ratio TAG:tert-BuOH 1:1. PCMC-lipase, after being treated with tert-butanol, was used in eight consecutive batch cycles under optimal reaction conditions with a slight decrease in FAEE yield [144]. FAME yield may be increased by using a mixture of two lipases with different substrate specicities such as in the case of soybean oil methanolysis with a mixture of lipase from Rhizopus oryzae and Candida rugosa. Using this mixture, a conversion greater than 99% was obtained and biodiesel conversion was maintained at over 80% of its original conversion after 10 cycles [145]. Alternatively, using a mixture of lipases, one of which has high activity on FFA (e.g. Candida antarctica B-lipase) and the other on TAG (e.g. Thermomyces lanuginosus lipase), would allow the use of oil with a high FFA content [146]. A possible strategy for the reduction of enzymatic catalyzed process cost is the development of a continuous process. Salum et al. [147] used lipase from Burkholderia cepacia, produced by solid-state fermentation, in ethanolysis of soybean oil in a xed bed reactor with the continuously circulating reaction mixture. The best conversion (95%) was obtained after 46 h at 50 C, with an ethanol:oil molar ratio of 3:1 and with the addition of 1% of water to the reaction medium. Besides the already well known positive effect of water on the non-catalytic ethanolysis, recent studies show that water can further improve ethyl esters synthesis due to its possible catalytic role for the ethanolysis process and reduction of fatty acid degradation [125]. Another alternative method for the biodiesel fuel production which interferes with the formation of undesirable degradation products is a two-step process consisting of hydrolysis of TAG in subcritical water and subsequent FFA esterication by supercritical alcohol [148]. The two-step process provided signicantly higher FAME yields at the same reaction time comparing to a one-step treatment. Mild reaction conditions for hydrolysis and esterication were employed, which avoided the formation of undesirable degradation products and reduced the energy requirements making this process suitable for industrial application. Commercially, biodiesel is mainly made by vegetable oils alcoholysis in stirred tank reactors in the presence of base or acids catalysts. Conventional technologies have a lot of disadvantages related to the long reaction time, high operating cost and energy consumption and tedious downstream processing. Therefore, some process intensication technologies have been developed to improve the process of FAEE synthesis. These technologies utilize novel reactor types such as static mixers, micro-channel reactors, oscillatory ow reactors, cavitational and microwave reactors and rotating/spinning tube reactors. The reaction rate in these reactors is greatly enhanced due to the increased efciency of the heat and mass transfer and interfacial area between the reactants [149]. In reaction/separation coupled processes, the chemical reaction and products separation occur simultaneously, thus shortening the overall reaction time, reducing the initial alcohol:oil molar ratio and requiring fewer downstream processing steps [149]. The use of membrane reactors is particularly suitable for the enzyme-catalyzed process because the ester yield is increased by glycerol separation from the reaction mixture [150]. The improvement of the ethanolysis process also includes ethyl ester phase purication. Instead of water washing, some researchers recommend an adsorptive post-treatment with 2 wt.% Magnesol at 65 C for 20 min with continuous stirring following the completion of the phase separation [16,23]. Magnesol is a commercial adsorbent primarily composed of a synthetic amorphous

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magnesium silicate, which efciently removes water, soap, free glycerol and unreacted acylglycerols from biodiesel [151].

9. Conclusions Methanolysis of vegetable oils in the presence of a homogeneous base catalyst is still the most dominant process for the industrial biodiesel production. The possibility of the ethanol production from biorenewable sources and a number of FAEE advantages as a fuel have directed investigations towards the ethanolysis process development. Most of these studies refer to a homogeneous base-catalyzed ethanolysis of oily feedstocks. Oil quality requirements limiting the application of many cheap oily feedstocks and huge wastewater generated in the ester phase purication, both typical for the use of homogeneous catalysts, are the main reasons for the improvement of the existing and the development of the new production processes. The development of a FAEE production process is focused on simple, cost-effective and environmentallyfriendly processes with high ester yields in a short reaction time. Such a heterogeneously catalyzed process has already been applied for the industrial FAME production. Therefore, the number of studies in the eld of heterogeneously-catalyzed ethanolysis reactions, which are generally slow, has been increased. Different catalysts have been used in these studies in order to develop new, efcient and reusable catalytic systems. Recycling of heterogeneous catalysts without decreasing their catalytic activity provides the basis for the development of continuous FAEE syntheses. A heterogeneous catalyst integrated with continuous processing technologies is expected to get a wider application in the future industrial biodiesel production. Immobilized lipase-catalyzed FAEE synthesis has been a very interesting topic in recent years as it allows the use of mild reaction conditions that are consistent with green process requirements and offers many advantages. Lipases could have signicant importance for the industrial application if its production cost would be reduced. Although non-catalytic ethanolysis possesses some advantages such as high ethyl ester yield in a short reaction time and no pretreatment of the feedstock, there are still some disadvantages. The extreme reaction conditions require more energy, a well-engineered process and higher capital costs. The improvement of the efciency of the non-catalytic ethanolysis process is an essential precondition for its commercialization.

Acknowledgments This work has been funded by the Ministry of Education and Science of the Republic of Serbia (Project No. III 45001).

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