Bioresource Technology 70 (1999) 1±15

Biodiesel production: a review1
Fangrui Maa, Milford A. Hannab,*
b a Department of Food Science and Technology, University of Nebraska, Lincoln, NE, USA Industrial Agricultural Products Center, University of Nebraska, 211 L.W. Chase Hall, Lincoln, NE 68583-0730, USA

Received 24 March 1998; revised 16 December 1998; accepted 2 February 1999

Abstract Biodiesel has become more attractive recently because of its environmental bene®ts and the fact that it is made from renewable resources. The cost of biodiesel, however, is the main hurdle to commercialization of the product. The used cooking oils are used as raw material, adaption of continuous transesteri®cation process and recovery of high quality glycerol from biodiesel by-product (glycerol) are primary options to be considered to lower the cost of biodiesel. There are four primary ways to make biodiesel, direct use and blending, microemulsions, thermal cracking (pyrolysis) and transesteri®cation. The most commonly used method is transesteri®cation of vegetable oils and animal fats. The transesteri®cation reaction is a€ected by molar ratio of glycerides to alcohol, catalysts, reaction temperature, reaction time and free fatty acids and water content of oils or fats. The mechanism and kinetics of the transesteri®cation show how the reaction occurs and progresses. The processes of transesteri®cation and its downstream operations are also addressed. Ó 1999 Published by Elsevier Science B.V. All rights reserved.
Keywords: Biodiesel; Transesteri®cation; Blending; Microemulsion; Thermal cracking

1. Introduction Biodiesel, an alternative diesel fuel, is made from renewable biological sources such as vegetable oils and animal fats. It is biodegradable and nontoxic, has low emission pro®les and so is environmentally bene®cial (Krawczyk, 1996). One hundred years ago, Rudolf Diesel tested vegetable oil as fuel for his engine (Shay, 1993). With the advent of cheap petroleum, appropriate crude oil fractions were re®ned to serve as fuel and diesel fuels and diesel engines evolved together. In the 1930s and 1940s vegetable oils were used as diesel fuels from time to time, but usually only in emergency situations. Recently, because of increases in crude oil prices, limited resources of fossil oil and environmental concerns there has been a renewed focus on vegetable oils and animal fats to make biodiesel fuels. Continued and increasing use of petroleum will intensify local air pollution and magnify the global warming problems caused by CO2 (Shay, 1993). In a particular case, such as the emission of pollutants in
* Corresponding author. Fax: +1-402-472-6338; e-mail: mhanna@unl.edu 1 Journal Series #12109, Agricultural Research Division, Institute of Agriculture and Natural Resources, University of Nebraska±Lincoln.

the closed environments of underground mines, biodiesel fuel has the potential to reduce the level of pollutants and the level of potential or probable carcinogens (Krawczyk, 1996). Fats and oils are primarily water-insoluble, hydrophobic substances in the plant and animal kingdom that are made up of one mole of glycerol and three moles of fatty acids and are commonly referred to as triglycerides (Sonntag, 1979a). Fatty acids vary in carbon chain length and in the number of unsaturated bonds (double bonds). The fatty acids found in vegetable oils are summarized in Table 1. Table 2 shows typical fatty acid compositions of common oil sources. Table 3 gives the compositions of crude tallow. In beef tallow the saturated fatty acid component accounts for almost 50% of the total fatty acids. The higher stearic and palmitic acid contents give beef tallow the unique properties of high melting point and high viscosity. Natural vegetable oils and animal fats are extracted or pressed to obtain crude oil or fat. These usually contain free fatty acids, phospholipids, sterols, water, odorants and other impurities. Even re®ned oils and fats contain small amounts of free fatty acids and water. The free fatty acid and water contents have signi®cant e€ects on the transesteri®cation of glycerides with alcohols

0960-8524/99/$ ± see front matter Ó 1999 Published by Elsevier Science B.V. All rights reserved. PII: S 0 9 6 0 - 8 5 2 4 ( 9 9 ) 0 0 0 2 5 - 5

Their direct uses as biodiesel fuel is precluded by high viscosities.7 20.0 6. engine durability and lubricating oil contamination.1 0.7 8. Considerable research has been done on vegetable oils as diesel fuel. Direct use and blending Beginning in 1980. Ma.5 10.00 0.1 10.00 0. however.49 11. Because of the problems.51 9. Some natural glycerides contain higher levels of unsaturated fatty acids. They are solid at room temperature and cannot be used as fuel in a diesel engine in their original form.5 40. soybean oil. mole% Total GS3 Total GS2 U Total GSU2 Total GU3 35±48 193±202 40±46 47±50 2±8 24±37 14±29 40±50 1±5 examined as a source of methyl ester diesel fuel (Nagel and Lemke.4 Tallow 0.00 0.53 73. % by weight 16:0 11. wt.28 64. coconut oil. Hanna / Bioresource Technology 70 (1999) 1±15 Table 1 Chemical properties of vegetable oil (Goering et al.12 1.5 19.6 Cottonseed 0.00 0.1 0.8 26.23 6.26 16.75 6. have not been studied to the same extent as vegetable oils.00 1. C Fatty acid composition. Animal fats. such as carbon deposits in the engine.51 0.00 24:0 0.9 Coconut 46.2 9.2 F.00 58.52 0.00 18:1 25.5 82.23 0.00 0.67 28.00 18:2 60.1 0.00 0.26 20:0 0.85 0.85 3. Oil from algae.89 0.20 1.20 0. 1982a) Vegetable oil Corn Cottonseed Crambe Peanut Rapeseed Soybean Sun¯ower a b c Fatty acid composition.00 12.00 2. there was considerable discussion regarding use of vegetable oil as a fuel.8 23. bacteria and fungi also have been investigated.93 8. 1990).1 2.2 0.31 0.4 23.9 0.4 42.86 48.24 0.0 42. continuing with microemulsion and pyrolysis and ®nishing with an emphasis on the current process of choice.00 Acid a value 0.00 0.6 14. M.2 44.5 10.2 55.00 32. Bartholomew (1981) addressed the concept of using food for fuel. sun¯ower oil.2 10. This paper reviews the technologies starting with the direct use or blending of oils. Fats.36 0.00 0. 1993)..00 22:0 0.6 Palm 0. although mentioned frequently.00 15.85 0.8 4.00 0.93 22:1 0. Peroxide values are milliquivalents of peroxide per 1000 g of oil sample. Microalgae have been Table 3 Properties and composition of crude beef tallow (Sonntag. Phosphatide (gum) content varies in direct proportion to phosphorus value. (Shay.2 Lard 0. The production of biodiesel 2.1.00 6.73 18:3 0.27 18.1 1. That research included palm oil.% Myristic Palmitic Stearic Oleic Linoleic Glyceride composition.8 53.15 Phos ppm b Peroxide value 18.38 3.8 3.A.3 19. C Wiley melting point.15 3. 1985) Fatty acid Lauric Myristic Palmitic Stearic Oleic Linoleic Linolenic Soybean 0. 1985). Some methods applicable to vegetable oils are not applicable to animal fats because of natural property di€erences.0 using alkaline or acid catalysts.33 2. indicating that petroleum should be the ``alternative'' fuel 15±28 46±52 20±37 0±2 . Four primary production methodologies for producing biodiesel have been studied extensively.00 31.9 2.95 22.60 57.7 0.00 0. associated with the use of oils and fats as diesel fuels.39 0.00 18. 1979c) Characteristics Iodine number Saponi®cation number Titer.4 2.07 11.11 0.40 23.30 55.2 3.4 64. Terpenes and latexes also were studied as diesel fuels (Calvin.70 2.00 Acid values are milligrams of KOH necessary to neutralize the FFA in 1 g of oil sample.2 44.00 8.08 18:0 1.09 1.7 22.80 2. transesteri®cation.7 c 7.1 1.00 0. They also interfere with the separation of fatty acid esters and glycerol.07 0. Table 2 Typical fatty acid composition-common oil source (Kincs.1 2. 2.00 0.14 0. They are liquids at room temperature. contain more saturated fatty acids.6 19.48 0. rapeseed oil and tung oil. which oxidize potassium iodide under conditions of the test.00 9. they must be derivatized to be compatible with existing engines.32 0.2 0.7 30.16 13.00 0.

1983). direct-injection. 6. 2 diesel. The gum did not combust completely. The ¯ow rate of canola was lower than diesel at the same pressure and it dropped to almost zero at À4°C. Mixtures of degummed soybean oil and No. degummed and degummed-dewaxed sun¯ower oils. crude-degummed soybean oil and soybean ethyl ester as complete substitutes for No.F. 2 diesel fuel in the ratios of 1:2 and 1:1 were tested for engine performance and crankcase lubricant viscosity in a John Deere 6-cylinder. Blending or preheating was used as needed to compensate for cooler ambient temperatures.. even though they performed satisfactorily for a short time. The rate of gum formation of winter rapeseed oil was ®ve times slower than that of high linoleic (75±85%) oil. Viscosity can be lowered by blending with pure ethanol. 1983). Ma. especially with direct-injection engines. The viscosity of a 25/75 high sa‚ower oil and diesel blend was 4. but a blend of 20% vegetable oil and 80% diesel fuel was successful. 25 parts of sun¯ower oil and 75 parts of diesel were blended as diesel fuel (Ziejewski et al. The problems include (1) coking and trumpet formation on the injectors to such an extent that fuel atomization does not occur properly or is even prevented as a result of plugged ori®ces. Some short-term experiments used up to a 50/50 ratio.6 L displacement. The ®rst International Conference on Plant and Vegetable Oils as fuels was held in Fargo. (3) ready availability and (4) renewability..7%) erucic acid content of the oil (Peterson et al. 1983). resulting in carbon deposits and lubricating oil thickening.. in 1980. The disadvantages are (1) higher viscosity. Winter rapeseed oil as a diesel fuel was studied because of the high yield and oil content (45%) of winter rapeseed and the high (46. Polyunsaturated fatty acids were very susceptible to polymerization and gum formation caused by oxidation during storage or by complex oxidative and thermal polymerization at the higher temperature and pressure of combustion. (3) oil ring sticking and (4) thickening and gelling of the lubricating oil as a result of contamination by the vegetable oils. while that of straight canola oil was 37. At that point. The advantages of vegetable oils as diesel fuel are (1) liquid nature-portability. The key was suggested to be ®ltering and the only problem reported was lubricating oil contamination (viscosity increase due to polymerization of polyunsaturated vegetable oils). The most advanced work with sun¯ower oil occurred in South Africa because of the oil embargo.0 cSt at 40°C. Short term performance tests were conducted to evaluate crude soybean oil. M. It was considered not suitable for long term use in a direct-injection engine. The lubricating oil thickening and potential gelling existed with the 1:1 blend. The results indicated that 1:2 blend should be suitable as a fuel for agricultural equipment during periods of diesel fuel shortages or allocations. There were no coking and carbon build-up problems. the e€ects of vegetable oil fuels on engine performance and durability and fuel preparation. the viscosity of canola oil and 10% ethanol was 21. The lubricating oil had to be changed every 4.500 miles. Problems appear only after the engine has been operating on vegetable oils for longer periods of time. Oil production. 1983). The viscosities of 50/50 and 70/30 blends of winter rapeseed oil and diesel and whole winter rape oil were much higher (6±18 times) than No. At 37°C. it was not practical to substitute 100% vegetable oil for diesel fuel. Canola oil is much more viscous than the other more commonly tested vegetable oils and. North Dakota in August 1982. (2) heat content (80% of diesel fuel). 1 diesel was used successfully to power a small single-cylinder diesel engine for 850 h. speci®cations and additives. A diesel ¯eet was powered with ®ltered. the viscosity is temperature-dependent. Crude. used frying oil (Anon. The primary concerns discussed were the cost of the fuel. were tested using a single-cylinder precombustion chamber engine (Engler et al.12 cSt at 38°C (Goering. Two severe problems associated with the use of vegetable oils as fuels were oil deterioration and incomplete combustion (Peterson et al. 2 diesel fuel in a 2. 1984b). 1983). as with all ¯uids.59 L. The oils were not suitable because of carbon deposits and lubricating oil fouling. 1983). The results were negative.88 cSt at 40°C. oilseed processing and extraction also were considered in this meeting (ASAE. a 50/50 blend was 19 cSt. while the maximum speci®ed ASTM value is 4. and the viscosity of diesel fuel was 4 cSt (Strayer et al.. A blend of 70/30 winter rapeseed oil and No.000±4. 1982). a 75/25 blend of canola oil and diesel fuel was 40 cSt.82 cSt.. The processed oils which were slightly better than crude oils were not suitable for use as alternative fuels. A mixture of 50/50 soybean oil and Stoddard solvent (48% parans and 52% naphthenes) from Union Oil Co. degummed and alkali re®ned cottonseed oils. Caterpillar Brazil. had a viscosity of 5. but it did not occur with the 1:2 blend.92 cSt at 40°C.15 cSt. The viscosity was 4. turbocharged engine for a total of 600 h (Adams et al.. used pre-combustion chamber engines with a mixture of 10% vegetable oil to maintain total power without any alterations or adjustments to the engine. No adverse wear and no e€ects on lubricating oil or power output were noted. Used cooking oil and a blend of 95% used cooking oil and 5% diesel fuel were used. At 10°C the viscosity of canola oil was 100 cSt. (2) carbon deposits. (2) lower volatility and (3) the reactivity of unsaturated hydrocarbon chains (Pryde.A. 3 cylinder 2600 series Ford . Both blends of saf¯ower and soybean oil passed the 200 h EMA (Engine Manufacturers' Association) test. as well as crude. 1986). Hanna / Bioresource Technology 70 (1999) 1±15 3 rather than vegetable oil and alcohol being the alternatives and some form of renewable energy must begin to take the place of the nonrenewable resources. 1982).

The power remained constant throughout 200 h of operation. Severe injector coking led to decreases in power output and thermal eciency. Chemically alter the vegetable oil to an ester. 3. Short term performances of both ionic and non-ionic microemulsions of aqueous ethanol in soybean oil were nearly as good as that of No. Improper injection timing. 13. Poor combustion at part load with vegetable oils High viscosity of vegetable oil. 1983).. Failure of engine lubricating oil due to polymerization High viscosity of vegetable oil. M.A. low cetane.59 L.. Switch engine to diesel fuel when operation at part load. Chemically alter the vegetable oil to an ester Heat fuel prior to injection. a cetane number of 25 and an ash content of less than 0. A long-term performance test was conducted using a fuel blend of 75% unre®ned mechanically expelled soybean oil and 25% diesel fuel (Schlautman et al. Switch engine to diesel fuel when operation at part load. (1984) prepared an emulsion of 53% (vol) alkali-re®ned and winterized sun¯ower oil. at least in this engine and under the speci®ed EMA operating conditions. Increase motor oil changes. lines and injectors 3. They can improve spray characteristics by explosive vaporization of the low boiling constituents in the micelles (Pryde. acid composition. carbon deposits and lubricating oil thickening are obvious problems. Use higher compression engines. microemulsions with solvents such as methanol. 1987). The durabilities were not determined. 3 cylinder 2600 series Ford diesel engine operating on mechanically expelled-unre®ned soybean oil and sun¯ower oil blended with number 2 diesel fuel on a 25:75 v/v basis. incomplete combustion of fuel. In a Table 4 Known problems. incomplete combustion of fuel. Schlick et al. Hanna / Bioresource Technology 70 (1999) 1±15 diesel engine (Pryor et al. Dilution of engine lubricating oil due to blow-by of vegetable oil Collection of polyunsaturated vegetable oil blow-by in crankcase to the point where polymerization occurs Heat fuel prior to injection. Chemically alter the vegetable oil to an ester..31 cSt at 40°C. (1988) evaluated the performance of a direct injection 2. Plugging and gumming of ®lters. Poor combustion at part load with vegetable oils High viscosity of vegetable oil.4% (vol) 1-butanol. 1986). Chemically alter fuel to an ester Long-term 4. Ma. 1984) Problem Short-term 1. 2 diesel. Ziejewski et al. Switch engine to diesel fuel when operation at part load. This nonionic emulsion had a viscosity of 6. Increase motor oil changes. Chemically alter fuel to an ester Partially re®ne the oil to remove gums. Switch engine to diesel fuel when operation at part load. Engine knocking Probable cause High viscosity.. 1984). Motor oil additives to inhibit oxidation Heat fuel prior to injection.01%. Coking of injectors on piston and head of engine 5. Possibly free fatty acids in vegetable oil. . probable cause and potential solutions for using straight vegetable oil in diesels (Harwood. The fuel blend was burned in a direct injection diesel engine for 159 h before the test was terminated because a constant load could not be held on the engine. Filter to 4-microns Adjust injection timing. in spite of the lower cetane number and energy content (Goering et al. Microemulsions To solve the problem of the high viscosity of vegetable oils.3% (vol) 190-proof ethanol and 33. Lower viscosities and better spray patterns (more even) were observed with an increase of 1-butanol. Potential solution Preheat fuel prior to injection. Chemically alter the vegetable oil to an ester Heat fuel prior to injection. A microemulsion is de®ned as a colloidal equilibrium dispersion of optically isotropic ¯uid microstructures with dimensions generally in the 1±150 nm range formed spontaneously from two normally immiscible liquids and one or more ionic or non-ionic amphiphiles (Schwab et al. and low ¯ash point of vegetable oils Natural gums (phosphatides) in vegetable oil. Direct use of vegetable oils and/or the use of blends of the oils has generally been considered to be not satisfactory and impractical for both direct and indirect diesel engines. ethanol and 1-butanol have been studied. The high viscosity. Excessive carbon deposits on all combustion chamber parts precludes the use of these fuel blends. The probable reasons for the problems and the potential solutions are shown in Table 4. Poor combustion at part load with vegetable oils. Cold weather starting 2. Carbon deposits on piston and head of engine 6. Motor oil additives to inhibit oxidation. Excessive engine wear 7. A longer term evaluation of the engine when using 100% crude soybean oil was prematurely terminated. incomplete combustion of fuel. Other ash Very low cetane of some oils. 1982b). Preheat fuel prior to injection.4 F. as well as gum formation due to oxidation and polymerization during storage and combustion. free fatty acid content. A test failure occurred after 90 h into the screening test due to a 670% increase in the lubricating oil viscosity.

1. 68 kgs of the soap from the saponi®cation of tung oil produced 50 L of crude oil. Thermal cracking (pyrolysis) Pyrolysis. The pyrolyzed material can be vegetable oils. Carboxylic acids accounted for another 9.1 28. to obtain parans and ole®ns similar to those present in petroleum sources. h Higher heating value. 1979). Schwab et al. especially in Table 5 Properties of shipp nonionic fuel (Goering and Fry. 1986. Compositions were determined by GC-MS. All microemulsions with butanol.9 1.9 24.3:1. Schwab et al. M. (1988) used sa‚ower oil as a high oleic oil control.3 9. animal fats.A. The engine performances were the same for a microemulsion of 53% sun¯ower oil and the 25% blend of sun¯ower oil in diesel (Ziejewski et al.. (1987) used the ternary phase equilibrium diagram and the plot of viscosity versus solvent fraction to determine the emulsi®ed fuel formulations.4 2. 1988). The ®rst pyrolysis of vegetable oil was conducted in an attempt to synthesize petroleum from vegetable oil.2 8. The fuel passed the 200 h EMA test. 2 diesel fuel. Grossley et al.1 12. Hanna / Bioresource Technology 70 (1999) 1±15 5 200 h laboratory screening endurance test.. which was re®ned to produce diesel fuel and small amounts of gasoline and kerosene.. Value 4. % of whole sample Cetane No. 25% degummed and alkali-re®ned soybean oil. The total identi®ed hydrocarbons obtained from the distillation of soybean and high oleic sa‚ower oils were 73±77 and 80±88% respectively.9 Air 29.6 .3:33. Schwab et al. The fuel properties are compared in Table 7. 2 diesel.7 Air 40. Schwab et al.F. 1983). 1983. mm2 /s Stability at 5°C.1 16. many investigators have studied the pyrolysis of vegetable oils to obtain products suitable for fuel. 1979b).6±16. The pyrolysis of fats has been investigated for more than 100 years. Copra oil and palm oil stearin were cracked over a standard petroleum catalyst SiO2 /Al2 O3 at 450°C to produce gases.03 >24 41263 13. 2-octanol and cetane improver in the ratio of 52.. The condensed organic phase was fractionated to produce biogasoline and biodiesel fuels. 1984b). (1962) studied the temperature e€ect on the type of products obtained from heated glycerides. 1988). Methanol was often used due to its economic advantage over ethanol. 1988) Percent by weight High oleic sa‚ower N2 sparge Alkanes Alkenes Alkadienes Aromatics Unresolved unsaturates Carboxylic acids Unidenti®ed 37...2 10. A microemulsion prepared by blending soybean oil. It involves heating in the absence of air or oxygen (Sonntag.3 0. a large scale of thermal cracking of tung oil calcium soaps was reported (Chang and Wan.7 Soybean N2 sparge 31. liquids and solids with lower molecular weights.3 9. is the conversion of one substance into another by means of heat or by heat with the aid of a catalyst (Sonntag.1 2. natural fatty acids and methyl esters of fatty acids. in-take valves and tops of the cylinder liners were major problems. 1993). methanol. Catalytic cracking of vegetable oils to produce biofuels has been studied (Pioch et al.2 10.5 12.14 34.9 10. The fuel properties are summarized in Table 5. Catalysts have been used in many studies.7:13. 1979b) and cleavage of chemical bonds to yield small molecules (Weisz et al.1%. kJ/kg Stoichiometric air-fuel ratio Flash point. Soybean oil was thermally decomposed and distilled in air and nitrogen sparged with a standard ASTM distillation apparatus (Niehaus et al. 1947). Tung oil was ®rst saponi®ed with lime and then thermally cracked to yield a crude oil.0 also passed the 200 h EMA test (Goering. Since World War I. 5% 190-proof ethanol and 20% 1-butanol was evaluated in the 200 h EMA screening test (Goering and Fry.6 12. incomplete combustion and an increase of lubricating oil viscosity were reported. 1983.. but irregular injector needle sticking. largely metallic salts. strictly de®ned. 1984a) Property Viscosity at 38°C. but carbon and lacquer deposits on the injector tips. C Ramsbottom carbon residue. Schwab et al.1 9.. which accounted for approximately 60% of the total weight. The compositions of pyrolyzed oils are listed in Table 6 (Alencar et al.5 22.7 those areas of the world that lack deposits of petroleum (Sonntag. no signi®cant deteriorations in performance were observed.. hexanol and octanol met the maximum viscosity requirement for No.0 13. The 2-octanol was an e€ective amphiphile in the micellar solubilization of methanol in triolein and soybean oil. 1979b).0 2.3 5. Shipp nonionic (SNI) fuel containing 50% No. The SNI fuel performed better than a 25% blend of sun¯ower oil in diesel oil.9 5.9 22. 3. heavy carbon deposits. 1984a).7 11.5 8. 1. The main components were alkanes and alkenes. The chemical compositions (heavy hydrocarbons) of the diesel fractions were similar to Table 6 Compositional data of pyrolysis of oils (Alencar et al. In 1947. The mechanisms for the thermal decomposition of a triacylglyceride are given in Fig. Pyrolytic chemistry is dicult to characterize because of the variety of reaction paths and the variety of reaction products that may be obtained from the reactions that occur. Ma.1 28.

3 2.9 .0 36.6 3. fossil fuels. the selectivities of the products (hydrocarbons. The process was simple and e€ective compared with other cracking processes according to the paper.6 4..2 2. Table 7 Fuel properties of thermally cracked soybean oil Soybean oil a Cetane number Higher heating value.5 2.0 0.1 25.0 0.7 max 2. The equipment for thermal cracking and pyrolysis is expensive for modest throughputs.1 4.2 8.7 3. CO2 and H2 ) obtained between 550±850°C with a constant residence time of 320 min and a constant dilution rate of 13 moles of nitrogen/mole of feedstock are provided in Table 8.6 F. (1986).0 3.1 4.0 45.2 1. A ¯ow chart of the micropilot pyrolysis plant for methyl esters from rapeseed oil and a design of the pyrolysis reactor were outlined.A.1 Selectivity (molar % of hydrogen atoms cracked) H2 0. cSt at 37. 1995).9 39.0 0. Ma.6 a 43.1 3. The principal products were linear 1-ole®ns. MJ/kg Pour point C Viscosity.2 32. In addition.9 0.3 2.74 b 43.1 3.6 19.6 1. Data from Schwab et al.9 0. 1995) Selectivity (molar % of carbon atoms cracked) 550°C C1 ±C4 cut C5 ±C9 cut C10 ±C14 cut C15 ±C18 cut Aromatics C3:1 ±C8:1 esters C9:1 ±C16:1 esters Saturated esters CO CO2 Coke Other products 10.2 600°C 18.4 1.6 4.7 1.6 0.6 Data from Niehaus et al.0 16.1 0. To illustrate the distribution of cracking products as a function of pyrolysis temperature.0 40.7 20.3 0.9 5. Hanna / Bioresource Technology 70 (1999) 1±15 Fig.7 max 1.5 3.3 8.9 3.7 13..6 3.3 6.9 7.2 11.6 3.3 2.1 38. CO.6 3.5 2. n-parans and unsaturated methyl esters. There was no waste water or air pollution.0 650°C 28.1 3.3 7.0 39.2 10.5 5.7 2.7 1.1 13.2 21.2 Diesel fuel a 51.7 10.3 850°C 66.8 1. while the products are chemically similar to petroleum-derived Table 8 Selectivities of cracking products as a function of pyrolysis temperature (Billaud et al.6 À6.2 0.2 5.2 1.3 3.7 2.3 À12.0 45.3 2.1 12.5 0.7 2.3 800°C 45. The conversion of methyl colzate increased with an increase of the temperature of pyrolysis.6 À12.3 1.5 0.2 32.5 0. 1988)..4 2.9 1. The mechanism of thermal decomposition of triglycerides (Schwab et al.3 7.1 17.82 b 40.6 4.2 25.3 2.6 5.0 40.6 4.4 7. 1.8 29.5 À6.2 17. High temperatures gave high yields of light hydrocarbons (66% molar ratio at 850°C).6 1.3 700°C 38. Rapeseed oil was pyrolyzed to produce a mixture of methyl esters in a tubular reactor between 500 and 850°C and in nitrogen (Billaud et al.6 3.3 0.9±4.8°C a b Cracked soybean oil b 37.5 1. M.2 2. (1988).9 0.7 0.3 0.6 5.4 750°C 35.

catalyst and tri-. di.and monoglycerides due to the polarity of the molecules and hydrogen bonding. the glycerides and alcohol must be substantially anhydrous (Wright et al. Transesteri®cation of triglycerides with alcohol. sometimes. Obtaining pure esters was not easy. carbonates and corresponding sodium and potassium alkoxides such as sodium methoxide. The impurities raised the cloud and pour points. di. Table 9 Physical properties of chemicals related to transesteri®cation (Zhang.875 (75) 0. 2. It can quickly react with triglycerides and NaOH is easily dissolved in it.792 0. g/ml (°C) 0. The soap lowers the yield of esters and renders the separation of ester and glycerol and the water washing dicult. chloroform EtOH. On the other hand. a 3:1 molar ratio of alcohol to triglycerides is needed. Methanol and ethanol are used most frequently. sodium propoxide and sodium butoxide.875 0. EtOH . However. benzene. acids. which produces soap.850 0. 1945). 3.9 Boiling point (°C) À 196. sodium ethoxide. especially for transesteri®cation of animal fats such as beef tallow. EtOH H2 O(I). ether. The boiling points and melting points of the fatty acids. The triglycerides can be puri®ed by saponi®cation (known as alkali treating) and then transesteri®ed using an alkali catalyst. 1944) because water makes the reaction partially change to saponi®cation. 1994) Name Methyl Myristate Methyl Palmitate Methyl Stearate Methyl Oleate Methanol Ethanol Glycerol Speci®c gravity.and triglycerides increase as the number of carbon atoms in the carbon chain increase. It produced some low value materials and. butanol and amyl alcohol. the saturated components Melting point (°C) 18. 2. To complete a transesteri®cation stoichiometrically. In practice.0 215. glycerol. ether (I) H2 O. The reaction can be catalyzed by alkalis..0 Solubility (>10%) À Acids. ethanol. Hanna / Bioresource Technology 70 (1999) 1±15 7 Fig. Transesteri®cation (Alcoholysis) Transesteri®cation (also called alcoholysis) is the reaction of a fat or oil with an alcohol to form esters and glycerol.0 17.F. Et2 O Et2 O. such as di.A. the removal of oxygen during the thermal processing also removes any environmental bene®ts of using an oxygenated fuel. the products are a mixture of esters.0 À19.2. more gasoline than diesel fuel. the ratio needs to be higher to drive the equilibrium to a maximum ester yield. gasoline and diesel fuel. Because the reaction is reversible. Alcohols are primary and secondary monohydric aliphatic alcohols having 1±8 carbon atoms (Sprules and Price.and monoglycerides (Ma. After transesteri®cation of triglycerides.and monoglycerides. di. since there were impurities in the esters. but decrease with increases in the number of double bonds. Low free fatty acid content in triglycerides is required for alkali-catalyzed transesteri®cation.789 1. Sulfuric acid.7 78.260 For an alkali-catalyzed transesteri®cation. The physical properties of the primary chemical products of transesteri®cation are summarized in Tables 9 and 10. acidcatalyzed transesteri®cation can be used (Keim.8 À97. EtOH. excess alcohol is used to shift the equilibrium to the products side. especially methanol because of its low cost and its physical and chemical advantages (polar and shortest chain alcohol). Lipases also can be used as biocatalysts. Among the alcohols that can be used in the transesteri®cation process are methanol. Alkali-catalyzed transesteri®cation is much faster than acid-catalyzed transesteri®cation and is most often used commercially. KOH. The reaction is shown in Fig. methyl esters. propanol. M.0 À112.4 290. The melting points increase in the order of tri-.8 30. there is a large proportion of saturated fatty acid esters in beef tallow esters (almost 50% w/w). or enzymes. alcohol. sulfonic acids and hydrochloric acid are usually used as acid catalysts.825 (75) 0. Et2 O H2 O. The monoglycerides caused turbidity (crystals) in the mixture of esters. 1950). A catalyst is usually used to improve the reaction rate and yield.0 64.6 38. This portion makes the cloud and pour points higher than that of vegetable oil esters. The alkalis include NaOH. This problem was very obvious. Ma.0 190. 1998). If more water and free fatty acids are in the triglycerides. mono-.

1% H2 SO4 and 77±117°C at 10°C intervals indicated that the reaction began at a slowrate. Rate constants increased with an increase in the amount of catalyst used. Schwab et al.A. K2 CO3 or other similar catalysts were mixed with alcohol.. 1995.3 79. 1987. The ®rst step is an attack on the carbonyl carbon atom of the triglyceride molecule by the anion of the alcohol (methoxide ion) to form a tetrahedral intermediate. In the second step.. 1986).2.. the actual catalyst.5 77. 3.1 5. The reaction rate constants for the alkali-catalyzed reaction were much higher than those for the acid-catalyzed reactions. Fig.1 Melting point (°C) Carbons 14 16 18 18:1 18:2 Acid 54. 1986). Trent. 4 summarizes the mechanism of alkali-catalyzed transesteri®cation. Hanna / Bioresource Technology 70 (1999) 1±15 a Table 10 Melting points of fatty acids.5 Methyl 18. The reaction of methanol with SBO at 6:1 molar ratio with 0. The co-product.. Allen et al. the tetrahedral intermediate reacts with an alcohol (methanol) to regenerate the an- ion of the alcohol (methoxide ion).1 À19. 1944. 1981. most stable polymorphic form. proceeded at a faster rate and then slowed again as the reaction neared completion. . Ma et al. Glycerol is separated by gravitational settling or centrifuging.. 3).. KOH. The activation energies ranged from 8 to 20 kcal/mol. It also is used to make methyl esters for detergents and cosmetics..0 81. with alkali catalysis the forward reaction followed consecutive. needs to be recovered because of its value as an industrial chemical such as CP glycerol... 1979) 1-Monoglyceride 70.0 Melting point of highest melting. although the equilibrium lies towards the production of fatty acid esters and glycerol. The S-shaped curves of the effects of time and temperature on ester formation for a 30:1 ratio of butanol and soybean oil (SBO). The transesteri®cation reactions of vegetable oil with alcohol to esters and glycerol (Freedman et al. Freedman et al. (1986) studied the transesteri®cation kinetics of soybean oil.5 À2.2 12. A mole of ester is liberated at each step.6 Triglyceride 57. Freedman et al. have other value-added applications in foods.6 16. Freedman et al. 1999). Ali. Tanaka et al. second-order kinetics for butanol:SBO ˆ 6:1. 1974). 1987.5 35. 1956). The mechanism and kinetics Transesteri®cation consists of a number of consecutive. In the last step. Fig. reversible reactions (Schwab et al. A small amount of water.3 À6. di-. rearrangement of the tetrahedral intermediate results in the formation of a fatty acid ester and a diglyceride. Ma et al. However. and triglyceridea Fatty acid Name Myristic Palmitic Stearic Oleic Linoleic a (Formo. With acid or alkali catalysis. M.8 À35. Ma.8 F.4 62. When NaOH. 1984. generated in the reaction. 1998b. 1998a. Transesteri®cation is the process used to make biodiesel fuel as it is de®ned in Europe and in the USA. alkoxide group is formed (Sridharan and Mathai. Wimmer. Ea for the shunt reaction triglyceride-glycerol was 20 kcal/mol. may cause soap formation during transesteri®cation. the forward reaction followed pseudo-®rst-order kinetics for butanol:SBO ˆ 30:1. USP glycerol and dynamite glycerol.4 21. Ma et al. The triglyceride is converted stepwise to diglyceride. The reactions are reversible.9 69.5 À13. Freedman et al. detergents and cosmetics. glycerol.8 30.5% sodium methoxide at 20±60°C was a combination of secondorder consecutive and fourth-order shunt reactions. 3. The reaction mechanism for alkali-catalyzed transesteri®cation was formulated as three steps (Eckey.. monoglyceride and ®nally glycerol (Fig. 1986.3-Diglyceride 66.3 1.1. 1992b. 1945. 1945..0 63. methyl esters and mono-.8 76.6 39.5 73. There are numerous transesteri®cation citations in the scienti®c and patent literature (Bradshaw and Meuly.

A. The e€ects of free fatty acids and water on transesteri®cation of beef tallow with methanol were investigated (Ma et al. 1986).. The molar ratio is associated with the type of catalyst used. Transesteri®cation does not require a nitrogen environment. Hanna / Bioresource Technology 70 (1999) 1±15 9 Fig. Bradshaw and Meuly (1944) and Feuge and Grose (1949) also stressed the importance of oils being dry and free (`0. An acid catalyzed reaction needed a 30:1 ratio of BuOH to soybean oil.2. 1974.3 to 5. The ratio of 4. 1956).5%) of free fatty acids. In the ethanolysis of peanut oil. alcohol vapour facilitated this process. (1984) stated that ester yields were signi®cantly reduced if the reactants did not meet these requirements. The reactor was open to the atmosphere via a condenser. If a three step transesteri®cation process was used. 3. Water content was a more critical variable in the transesteri®cation process than were free fatty acids. with a yield of 97±98%. The mechanism of alkali-catalyzed transesteri®cation of triglycerides with alcohol (Sridharan and Mathai. formation of gels and made the separation of glycerol dicult. despite the statements of Feuge and Grose (1949) and Gauglitz and Lehman (1963).8:1 was used in some examples. Methanol present in amounts of above 1.06% w/w and free fatty acid content of beef tallow should be kept below 0.3. the ratio was reduced to 3. Eckey.3:1. The e€ects of moisture and free fatty acids Wright et al. which consumed the catalyst and reduced catalyst eciency.F. Freedman et al. M. The stoichiometric ratio for transesteri®cation requires three moles of alcohol and one mole of glyceride to yield three moles of fatty acid ester and one mole of glycerol.2. thus adding more cost to the process. which diminished their e€ectiveness. The resulting soaps caused an increase in viscosity. If the acid value was greater than 1. Sodium hydroxide or sodium methoxide reacted with moisture and carbon dioxide in the air. The results showed that the water content of beef tallow should be kept below 0. Higher molar ratios result in greater ester conversion in a shorter time. w/w in order to get the best conversion. 1998a). while a alkali-catalyzed reaction required only a 6:1 ratio to achieve the same ester yield for a given reaction time (Freedman et al.2. more NaOH was required to neutralize the free fatty acids. Water also caused soap formation.. In addition. The e€ect of molar ratio One of the most important variables a€ecting the yield of ester is the molar ratio of alcohol to triglyceride. 4.5%. Bradshaw and Meuly (1944) stated that the practical range of molar ratio was from 3. 3. depending upon the quality of the oils.75 equivalents tended to prevent the gravity separation of the glycerol. a 6:1 . The glyceride should have an acid value less than 1 and all materials should be substantially anhydrous. The maximum content of free fatty acids con®rmed the research results of Bradshaw and Meuly (1944) and Feuge and Grose (1949). (1944) noted that the starting materials used for alkali-catalyzed transesteri®cation of glycerides must meet certain speci®cations. Oxygen dissolved in the oil escaped to the atmosphere when the reactant was heated. Ma.25:1 methanol to vegetable oil.

1983). hydrochloric acid or organic sulfonic acid. 87 and 64% for 60.and monoglycerides increased at the beginning and then decreased.1±0. potassium methoxide. 3.5% sodium methoxide catalyst and 60°C. 1995. The reaction mixture was neutralized with a mild acid to stop the reaction.2.5%. used 6:1±30:1 molar ratios with alkalicatalysis to achieve a conversion of 99. potassium amide and potassium hydride. 1950). free fatty acids mucilaginous matter. 1984). The amount of alcohol needed was reduced substantially by working in steps. NaOH and NaOCH3 reached their maximum activities at 0. M. 1950). Hanna / Bioresource Technology 70 (1999) 1±15 molar ratio liberated signi®cantly more glycerine than did a 3:1 molar ratio (Feuge and Grose. sun¯ower. Although the author did not mention the contents of other impurities after re®ning. (1984) studied the e€ect of molar ratio (from 1:1 to 6:1) on ester conversion with vegetable oils. In methanolysis of castor oil to methyl ricinoleate.3 and 0. the normal re®ning process met the requirements of the transesteri®cation process. The process of transesteri®cation and downstream operations Bradshaw and Meuly (1944) patented a process for making soap from natural oils or fats. Soybean. 1950. This two step process included making fatty acid esters from oils.1 h. 3. The production of beef tallow slowed down and reached the maximum value at about 15 min. 3. peanut and cotton seed oils behaved similarly and achieved highest conversions (93±98%) at a 6:1 molar ratio. Ester conversions at the 6:1 ratio for 1% NaOH and 0... sodium amide. An approximate yield of 80% was observed after 1 min for soybean and sun¯ower oils.5% w/w of beef tallow. At the end. was unsatisfactory when the molar ratios were 6:1 and 20:1 (Freedman et al. coconut oil and palm oil. (1981). (Sprules and Price. 45 and 32°C. Hartman. sodium hydride. however. Rapeseed oil was methanolyzed using 1% NaOH or KOH (Nye and Southwell. The oils were transesteri®ed at the conditions of 25±100°C. the reaction proceeded most satisfactorily at 20±35°C with a molar ratio of 6:1± 12:1 and 0. respectively. Zhang reported 80% by tallow weight of esters was recovered in the laboratory. 1984).5% catalyst by weight of oil.10 F.4.. After 0. From one to ®ve min.They found that the molar ratio of 6:1 of methanol to oil gave the best conversion. After 1 h. Sodium methoxide was more e€ective than sodium hydroxide (Freedman et al. ester formation was identical for the 60 and 45°C runs and only slightly lower for the 32°C run.2. acid-catalyzed transesteri®cation is suitable (Sprules and Price.35% (by weight of oil) of NaOH catalyst (Smith. 1949). (1984) transesteri®ed peanut.75 alcohol equivalents. cottonseed. 1984). sodium methoxide. Alkalis include sodium hydroxide. The acids could be sulfuric acid..A. or enzyme. an immobilized lipase was employed to catalyze the methanolysis of corn oil in ¯owing supercritical carbon dioxide with an ester conversion of >98% (Jackson and King. A 30:1 ratio resulted in a high conversion to methyl ester. The crude oil was ®rst re®ned to remove a certain amount of water. 3. Ma et al.2. Ma. The opposite result was observed by Ma et al. acid. 1984). (1998a) studied the e€ect of reaction time on transesteri®cation of beef tallow with methanol..005±0.5. the amount of monoglycerides was higher than that of diglycerides. Zhang 1994). A molar ratio of 6:1 was used for beef tallow transesteri®cation with methanol (Ali. 0.6. the reaction proceeded very fast. the conversions were almost the same for all four oils (93±98%). depending on the oil used. is cheaper and is used widely in large-scale processing. ethanol and butanol. When a large amount of free fatty acids was present in the oil.7. sun¯ower and soybean oils under the condition of methanol to oil ratio of 6:1. For the transesteri®cation of re®ned soybean oil with methanol (6:1) using 1% NaOH. 1996). Sodium hydroxide was also chosen to catalyze the transesteri®cations because it is cheaper. Upon standing. 1984). The e€ect of reaction temperature Transesteri®cation can occur at di€erent temperatures. using 1% concentrated sulfuric acid. potassium hydroxide. Tanaka et al. The temperature and consequently the speed of the reaction could be increased if a closed system or re¯ux was used. 0. then producing soap from the esters. Temperature clearly in¯uenced the reaction rate and yield of esters. Sodium hydroxide. protein.2.10±1. (1998a). More recently. The water content was less than 1% after re®ning. coloring matter and sugars. in his novel two-step transesteri®cation of oils and fats such as tallow. Freedman et al. three di€erent temperatures were used (Freedman et al. 1949). the glycerol and esters . phosphoric acid. Freedman et al. After 1 h. The transesteri®cation of soybean oil with methanol. The di. The e€ect of catalyst Catalysts are classi®ed as alkali. 1984. Alkali-catalyzed transesteri®cation is much faster than acid-catalyzed (Freedman et al. The apparent yield of beef tallow methyl esters surged from 1 to 38. However if a glyceride has a higher free fatty acid content and more water.5% NaOCH3 were almost the same after 60 min (Freedman et al. The reaction was very slow during the ®rst minute due to the mixing and dispersion of methanol into beef tallow. 1956) because of the assumption that a small amount of water was produced upon mixing NaOH and MeOH. respectively. The e€ect of reaction time The conversion rate increases with reaction time. 1. a molar ratio as high as 15:1 was needed under acid catalysis (Sprules and Price. ester yields were 94.. Freedman et al.

After the glycerine was separated. Ma. The ®rst alcoholysis reaction was conducted at or near the boiling temperature of the lower alcohol for 0. C8 and then C10 methyl esters were obtained. i. Emulsion formation during water washing could be problematic. The crude ester layer was then subjected to a second alcoholysis of 8±20% alcohol and 0. the ester layer was transesteri®ed again using 0. methyl.75% of NaOH catalyst were homogenized and then pumped through a reaction coil for about 10 min at 100°C. such as longer separation time and losses of esters and glycerol.2±0.g.5% alkali catalyst for 5±60 min. (1945) patented a continuous process whereby 224 part/min of re®ned coconut oil and 96 part/ min of ethanol containing 0. In this process no methanol recovery was mentioned. the esters were washed with warm water and distilled under vacuum of 133 Pa.A. The process patented by Smith (1949) was almost the same as the process described by Bradshaw and Meuly (1944). then kept at 60°C. (1981) provided a novel method for preparation of lower alkyl. The mixture passed through a preheater to bring the temperature to 110°C followed by loading into a packed column for separation of the ethanol vapour. C16 and saturated and unsaturated C18 fatty acid methyl esters were drawn o€ or were further separated by distillation. The glycerol was separated by setting the mixture for 1±15 min at 40±70°C. 5). The ester layer was fractionally distilled at atmospheric pressure or under reduced pressure (e. Transesteri®cation was conducted using 6:1 molar ratio of methanol/tallow. The glycerol was separated out in a lower layer. esters of fatty acids by the alcoholysis reaction of fatty acid glycerides. The mixture was washed with distilled water until the wash water was clear. The molar ratio increased to 6:1±12:1 and the reaction temperature range was 20±35°C. The second reaction mixture thus admixed with a certain amount of water was left to settle at 40±70°C for 15 min or centrifuged. An overall conversion of 98% or more of the starting fatty glycerides was achieved. The transesteri®cation reaction took place when the reactants were heated to the reaction temperature while passing through the heater. The mixture was then transesteri®ed for 3±4 h to make esters from the free fatty acids. naturally occurring oils or fats. release the free fatty acids from the soap formed and acidify the system. crystallization or other processes.5±2 h. with a lower alcohol in a two-step process. acted methanol. speci®c gravity at 15°C and the Gardner±Holdt viscosity.2% NaOH and 20% methanol at 60°C for about 1 h. the esters were washed countercurrently and dried. The mixture was neutralized with an alkali salt such as calcium carbonate. 5% by oil weight of sulfuric acid was added to neutralize the alkali catalyst. 399 Pa) and with 110 kPa of steam in the heating coils. The reaction was monitored by the refractive index at 25°C. The ester layer was washed and dried under vacuum.e. 5.g. Trent (1945) patented a continuous transesteri®cation process. C14. Impurities such as color compounds were in the aqueous phase and were removed with the water. The reaction ®nished before the reactants and products mixture left the heater. M. The unreacted alcohol vapor was taken out and the products were neutralized before getting into the lower chamber of the reactor where the esters and glycerol were continuously separated (Fig. A continuous transesteri®cation reactor (Trent. The free fatty acids were neutralized with alkali to form soap during the reaction. After the glycerol was removed.F. Reactants were fed into a reactor through a steam heated coil in the upper part of the reactor. For high acid value oils. Zhang (1994) transesteri®ed edible beef tallow with a free fatty acid content of 0. alkali. Hanna / Bioresource Technology 70 (1999) 1±15 11 separated into two layers and the lower layer of glycerol was removed. After the triglycerides were converted to esters. After separation of glycerol. e. The puri®ed ester was heated again to 70°C under vacuum to remove . 1950).27%. The tallow was heated to remove moisture under vacuum. ®ltered and freed of methanol by distillation. 1% (by the weight of tallow) NaOH dissolved in the methanol and 60°C for about 30 min. Allen et al.and then acid-catalyzed transesteri®cations were used (Sprules and Price. Tanaka et al. The residue of C12. 1945). The mixture was distilled subsequently to remove the unre- Fig.

The ester obtained from the ``starting oil plus glyceride'' had a density of 880 kg/m3 . drying the oil phase over anhydrous magnesium sulfate and ®ltering and removing solvent by evaporation (Freedman et al. Kildiran et al.5% mg KOH/g and a methyl ester content >98%. The laboratory scale process yielded 400 g of tallow ester from 500 g of beef tallow. (1998b. After the reaction was ®nished.5% remaining glycerides and 0. Harrington and Catherine (1985) compared the conventional and in-situ processes and found the acid catalyzed in-situ process for sun¯ower seed oil was better than that from the more conventional process. . Hanna / Bioresource Technology 70 (1999) 1±15 residual moisture. After transesteri®cation. but no data were given. 1996). 1999) studied the transesteri®cation process of beef tallow with methanol. Unreacted methanol in the ester layer was removed by distillation or evaporation. The core of his method was to recover free fatty acids in the oil by transesteri®ng them with glycerol to form glycerides. separation of ester and glycerol phases and then puri®cation of beef tallow methyl esters. then neutralized with acid. adding water before removing glycerol could form an emulsion. Corn oil was pumped in a carbon dioxide stream at a rate of 4 ll/min and methanol at 5 ll/min to yield >98% fatty acid methyl esters. Because the solubility of methanol in beef tallow was 19% w/w at 100°C (Ma et al. in high yields. the stirring time was insigni®cant (Ma et al. Wimmer. resulting in losses of esters and glycerol. A continuous process may be possible (Ooi et al. The separated free fatty acids reacted with the non-neutralized glycerol phase at about 200°C. 1996). After the reaction was ®nished.. respectively. 3. by in-situ alcoholysis of soybean oil (Kildiran et al. Stern et al. 1996). They also pointed out that once the two phases were mixed and the reaction was started.. The crystallization onset temperatures (TCO ) of isopropyl esters of lard and tallow were similar to that of methyl esters of soybean oil.. The esters were further puri®ed by dissolving in petroleum ether. M. Muniyappa (1995) suggested the utilization of a higher shear mixing device for making esters from animal fat. Glycerolysis was investigated using a high shearing mixing device.9 g of KOH and 60 L of methanol were added. The author thought this process could lower the production cost of biodiesel fuel. Usually. The optimum operation sequence was to recover the unreacted methanol using vacuum distillation after transesteri®cation. In-situ transesteri®cation of oils was investigated (Harrington and Catherine. When the sodium hydroxide and methanol solution were added to the melted beef tallow in the reactor while stirring.. in both processes (Wimmer. Wimmer (1992b) prepared methyl esters on a relatively small industrial scale by transesteri®ng glycerides with C1 ± 5 alkanols or C2 ± 5 alkoxyalkanols in the presence of basic catalysts.8. several patents were awarded on transesteri®cation of natural oils and fats to make biodiesel fuel.5±10% water or acid was added to neutralize the catalyst. a ¯ow point of À12°C. This process combined the extraction and transesteri®cation of the oil.8 g of KOH.. mixing was essential to disperse the methanol in beef tallow in order to start the reaction. 1992a. An additional 3 h was required for the completion of the reaction. Ma et al. 6. a purer product was obtained. such as isopropyl or 2-butyl (1:66) to reduce the crystallization temperature of biodiesel. (1995) transesteri®ed oils and fats using branched-chain alcohols.2. propyl and butyl esters of soybean fatty acids were obtained directly. Then. The distribution of unreacted methanol between the beef tallow ester phase and the glycerol phase was studied to determine a ecient way of downstream operation (Ma et al. a ¯ash point of 185°C. The triglycerides (acidity of 3. Jackson and King (1996) reported a direct methanolysis of triglycerides using an immobilized lipase in ¯owing supercritical carbon dioxide. a neutralization number of 0. 1999). 1985.A. Other types of transesteri®cations Lee et al. stirring was no longer needed. transesteri®cation reaction mixtures were allowed to cool to room temperature and the esters were separated with a separatory funnel. a large portion of the glycerol was mixed with the ester wash water. 240 L of methanol and 1618 kg of unre®ned rape oil and stirred it for 20 min. The salt was ®ltered and the alcohol evaporated.2%) from the reaction were added to the next alcoholysis step. 80 kg of water were added and the mixture was allowed to stand overnight at room temperature. which are valuable chemical intermediates for detergents and emulsi®ers. Distillation of the ester phase after treatment with Fuller's earth or silica gel was optional. Wimmer (1992a) blended 27. 0. 1998b). adding glacial acetic acid or phosphoric acid to adjust the pH to 7. 1992b).. The rape seed oil methyl esters (`1..12 F.and diglycerides. Ma. The separated glycerol reacted with triglycerides to produce mono. The glycerol was separated from the esters. there was 60% w/w of unreacted methanol in the beef tallow ester phase and 40% w/w in the glycerol phase. The crystal temperatures of isopropyl and 2-butyl esters of soybean oil were 7±11 and 12±14°C lower than that of soybean oil methyl esters. 1998b). a ®lterable limit temperature (FLT) of À18°C. (1995) patented a method to make fatty acid esters from acid oil. Reaction time was the controlling factor in determining the yield of beef tallow esters. Ethyl. By increasing reaction temperature and time and by decreasing the particle size of the soybeans and the water content of ethanol.008% ash) were used without further puri®cation. Finally. washing three times with water. More recently. 1984). It was suggested that it could be used as a substitute for gas oil. However.

A. Johnson. The foundations of this process are a shorter reaction time and greater production capacity. there also are two aspects. V. VII. The purpose of the process is to lower the viscosity of the oil or fat.C. 31. Chem. 1984). The diglycerides are subsequently reduced to monoglycerides. Base catalyzed transesteri®cations are basically ®nished within one hour.F. JAOCS 72. 575±579. the quality of used cooking oils can be bad (Murayama. C. 147±160. Although blending of oils and other solvents and microemulsions of vegetable oils lowers the viscosity..W. The use of used cooking oil can lower the cost signi®cantly. 1994).C.. Craveiro. Alves. Leslie Backers. J. Higher reaction temperatures speed up the reaction and shorten the reaction time. Physical properties of fats and fatty acids.D. Lepori. editor. 1982. Vegetable oil prices are relatively high there. The problem already exists in Asia. catalysts. ®rst removing free fatty acids from used cooking oil before transesteri®cation. E€ects of processing and chemical characteristics of plant oils on performance of an indirect-injection diesel engine. 1996). still exist.. The recommended amount of base used to use is between 0. US Patent 2... Busson. 1945. M. R. Beef tallow as a biodiesel fuel. Rock. the process also is simpler than soap glycerol recovery since there is a negligible amount of soap in biodiesel glycerol. 1543±1548. Modi®cation of vegetable oils. the biodiesel glycerol is more concentrated. Ann. 1268±1270. JAOCS 60. 1949. 1985. Billaud.A. Y. Engler. The monoglycerides are ®nally reduced to fatty acid esters. The cost of raw materials accounts for 60 to 75% of the total cost of biodiesel fuel (Krawczyk. J. There are several choices.W.A. 286A±288A. P. 1982. Conclusions Of the several methods available for producing biodiesel. Biodiesel has become more attractive recently because of its environmental bene®ts and the fact that it is made from renewable resources. Bartholomew. 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