This action might not be possible to undo. Are you sure you want to continue?
Contents lists available at ScienceDirect
journal homepage: www.elsevier.com/locate/apenergy
A review on biodiesel production using catalyzed transesteriﬁcation
Dennis Y.C. Leung *, Xuan Wu, M.K.H. Leung
Department of Mechanical Engineering, The University of Hong Kong, Pokfulam Road, Hong Kong, China
a r t i c l e
i n f o
a b s t r a c t
Biodiesel is a low-emissions diesel substitute fuel made from renewable resources and waste lipid. The most common way to produce biodiesel is through transesteriﬁcation, especially alkali-catalyzed transesteriﬁcation. When the raw materials (oils or fats) have a high percentage of free fatty acids or water, the alkali catalyst will react with the free fatty acids to form soaps. The water can hydrolyze the triglycerides into diglycerides and form more free fatty acids. Both of the above reactions are undesirable and reduce the yield of the biodiesel product. In this situation, the acidic materials should be pre-treated to inhibit the saponiﬁcation reaction. This paper reviews the different approaches of reducing free fatty acids in the raw oil and reﬁnement of crude biodiesel that are adopted in the industry. The main factors affecting the yield of biodiesel, i.e. alcohol quantity, reaction time, reaction temperature and catalyst concentration, are discussed. This paper also described other new processes of biodiesel production. For instance, the Biox co-solvent process converts triglycerides to esters through the selection of inert co-solvents that generates a one-phase oil-rich system. The non-catalytic supercritical methanol process is advantageous in terms of shorter reaction time and lesser puriﬁcation steps but requires high temperature and pressure. For the in situ biodiesel process, the oilseeds are treated directly with methanol in which the catalyst has been preciously dissolved at ambient temperatures and pressure to perform the transesteriﬁcation of oils in the oilseeds. This process, however, cannot handle waste cooking oils and animal fats. Ó 2009 Elsevier Ltd. All rights reserved.
Article history: Received 17 June 2009 Received in revised form 6 October 2009 Accepted 7 October 2009 Available online 7 November 2009 Keywords: Biodiesel Alkali-catalyzed transesteriﬁcation Feedstock Puriﬁcation Mass transfer
Contents 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Biodiesel production with catalyzed transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.1. Basic chemical reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2. Biodiesel production processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.1. Process flow chart . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.2. Raw materials treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.3. Pretreatment of acidic feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.4. Catalyst and alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.5. Mixing and neutralization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.6. Transesterification and separation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.7. Refining crude glycerol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.8. Purification of crude biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.2.9. Quality control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3. Storage of biodiesel product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4. Main factors affecting the yield of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.1. Alcohol quantity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.2. Reaction time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.3. Reaction temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.4. Catalyst concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Other processes of biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.1. Biox co-solvent process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084 1085 1085 1086 1086 1086 1087 1087 1088 1088 1088 1089 1089 1090 1091 1091 1091 1091 1091 1091 1091
* Corresponding author. Tel.: +00 852 2859 7911; fax: +00 852 2858 5415. E-mail address: email@example.com (D.Y.C. Leung). 0306-2619/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.apenergy.2009.10.006
. . . C18:1. it may cause some problems such as the competition with the edible oil market. including diesel and gasoline fuels. .91 0. . . . . . . . . .9. . .5 Heating value (MJ/kg) 39.18] [15. In order to overcome these disadvantages. . .90 205 – 221 – – – – 27. . . . .C. However. . . . . C18:2. the yield and properties of biodiesel products produced from different feedstocks would be quite different from each other. . . . . . . . . . . . . . . . . . . In situ biodiesel process . .2 35. C18:3 Depends on fresh cooking oil 0. . . . . C18:3 C16:0.Y.2 18.13. . . . . . . . . the quality of UFO may cause concern because its physical and chemical properties depend on the contents of fresh cooking oil and UFO may contain lots of undesired impurity. . .11. . C18:0. . C18:0. . . . . . .92 0. . . . . . .5 34 40. . . .76 0. C18:0. .28. Vegetable oils include edible and non-edible oils. C18:1. . . . C18:0. . . C16:0. . .%) C16:0.91 0. .4 0. . UFO is not suitable for human consumption but is a feedstock for biodiesel production. .25–28. C18:1. . . . C18:0. . . C18:1. . .6 29. . .6a 22. . . . . . . there is a great demand for alternative sources of petroleum-based fuel. . . . . C18:1. . . . C18:3 C18:2 C20:3 C18:2. . . . . .9a – 38.92 – 0. C18:1. . . . . .9 35.81 – 2. . C16:0. . . . .7 5. . . .92 234 >230 225 C16:0. . Moreover. . . . . . . .18]  [4. .17. C18:0. . . . . Conclusions. . . C18:1. . .92 0. . . biodiesel is a mixture of methyl esters with long-chain fatty acids and is typically made from nontoxic. Animal fats contain higher saturated fatty acids and normally exist in solid form at room temperature that may cause problems in the production process. . . . . . . Also. C18:0. . . . .90 0. . . .18. . C20:1.1084 D. . . .5 39 38. C20:0. . . . animal fats [16. . . . . .22. . . . . C18:1. .12] Nonedible oil 0. . .3. Supercritical alcohol process . Introduction Due to the depletion of the world’s petroleum reserves and the increasing environmental concerns.29]. . C18:1.2. . . . . . . .18. . . Table 1 shows some feedstocks of biodiesel and their physicochemical properties. . However. . . . . . . More than 95% of biodiesel production feedstocks comes from edible oils since they are mainly produced in many regions and the properties of biodiesel produced from these oils are much suitable to be used as diesel fuel substitute .24 44 – 2. . . .26]. . . . . free fatty acids [18. . . . . .91 Flash point (°C) 254 246 274 267 271 277 – Kinematic viscosity (cst. . choosing a right feedstock is very important [18. . . . . . . C16:0.6 39. C18:2.18. . . . . . . C16:0.19] [3. . many researchers are interested in non-edible oils which are not suitable for human consumption because of the presence of some toxic components in the oils. most non-edible oils contain high free fatty acids.26. . and can be produced on a large scale and environmentally friendly . . . . .10] [17. . . . C18:0. C16:0. . . . .92 0.92 0. . . nonedible oil crops can be grown in waste lands that are not suitable for food crops and the cost of cultivation is much lower because these crops can still sustain reasonably high yield without intensive care [12. . .8.26]. . . . . . C16:1. . .1 3 – 0.20. . . .21] [8. . . at 40 °C) 32. .92 0. .23. . Furthermore. C22:6.24]. . . C22:0 C16:0. .4 –    [17. C20:5. . . which will increase the production cost.24]  Used cooking oil Kinematic viscosity at 38 °C. . . . C18:1. . . C16:0.30–38]. . . . . . . . .0 – 32. . .86 39. and may lower the ester yield of biodiesel below the standards [14. . . C18:0. . . . . . . . . . Acknowledgement .20] [17. . . . .8 29. . . . . . . . Its usage signiﬁcantly reduces the cost of biodiesel production. .18] [5.6 39.18. Type of oil Species Main chemical composition (fatty acid composition wt.05 – 39.25. C18:2 C14:0. . C18:0.5 42. . . . . . C18:3. it will cause deforestation in some countries because more and more forests have been felled for plantation purposes. . C18:2 C18:1. . Density (g/cm3) 0. . . . . . . . . . . C16:1. . C18:0. . . . C18:1. . 1091 1091 1092 1092 1092 1. C18:1. . . . C17:0. . 3.7 39. . . . . . . . . . C18:3 C18:2 C18:2 C18:1. . . . .91 0. .91 0. .1 32. mm2/s. .20] [2. . Biodiesel. . . C18:2. mm2/s. . . .11. . C18:0. .1b – 44. . . . C18:1. . . . C16:0. . . . .2 References Vegetable oil Edible oil Soybean Rapessed Sunﬂower Palm Peanut Corn Camelina Canola Cotton Pumpkin Jatropha curcas Pongamina pinnata Sea mango Palanga Tallow Nile tilapia Poultry Others a b C18:2 C18:2 C18:2 C18:2. . . However. . C20:0. . Chemically. . . biological resources such as vegetable oils [2–24]. .15. . . . C18:2 C16:0. . . . . / Applied Energy 87 (2010) 1083–1095 4. . .8 39. . . . C16:0. . . . . . . other acids C16:0. . . . C18:0. .25 40. . . . . . Table 2 shows some physicochemical properties of biodiesel from different feedstocks and their yields under different production conditions [7. . .16. . . . . . Vegetable oils are promising feedstocks for biodiesel production since they are renewable in nature. . . .90 0. . C18:2 [6. . . . .06 0. . Kinematic viscosity at 37 °C. . C16:1. . Its cost is also higher than vegetable oils . . . . . .55 28 39.27]. C18:1.6 – 39. 3. . C18:0. .2 2. .72 34. . has recently been considered as the best candidate for a diesel fuel substitution because it can be used in any compression ignition engine without the need for modiﬁcation . . . . .15. . . or even used cooking oils (UFO) . . . . . . C18:2 C16:0. a clean renewable fuel. .91 0. . .6 72. .90 0. . . . . . . which increases both the cost of edible oils and biodiesel . . . . References .7. . . . . Thus they may require multiple chemical steps or alternate approaches to produce biodiesel. .14.4 Acid value (mg KOH/g) 0. . Leung et al. . . . . C18:0. . . . . . . . . Since the cost of raw materials accounts about 60–80% of the total cost of biodiesel production. . . C16:0. .23]  [23. . .91 0. . . . . . . C16:0. such as water. . Although at present biodiesel Table 1 Feedstocks for biodiesel production and their physicochemical properties. . . . . C18:1. . . . .18] [9. .
9 0.6     T = reaction temperature (°C). methanol is the preferred alcohol for producing biodiesel because of its low cost. it binds with the catalyst meaning that more catalyst will be needed and hence the process will involve a higher Table 2 Physicochemical properties of biodiesel from different oil source and the yields under the production conditions.1 130 – 0. linoleic. such as monoxide. the alkali catalyst that is used will react with the FFA to form soap.7 115 108. there are several distinct advantages of biodiesel over diesel fuel. cetane number than diesel fuel .888 0. Basic chemical reactions Common vegetable oils or animal fats are esters of saturated and unsaturated monocarboxylic acids with the trihydric alcohol glyceride.20. These esters are called triglycerides.9 97.45 49–50 0.C.856 – 0. forming soap and water.8 – 3. at 40 °C) 4. thermal cracking [55–60]. In addition.12–7a 3. R3 are long-chain hydrocarbons.9 4.43]. The objective of this paper is to give an overview on the technological advancement of producing biodiesel through transesteriﬁcation.3 34 40.885 0.24 0.1 [20.03% H2O in methanol) KOH|1 NaOH|1 KF/ZnO|5. Biodiesel has lower sulfur and aromatic content than diesel fuel and that means it will not emit lots of toxic gas [42. The simpliﬁed form of its chemical reaction is presented in equation CH2-O-CO-R1 | CH-O-CO-R2 | CH2-O-CO-R3 (Triglyceride) (Alcohol) + 3ROH (Catalyst) CH2-OH | CH-OH | CH2-OH (Glycerol) R-O-CO-R 3 (Mixture of fatty acid esters) R-O-CO-R 2 R-O-CO-R 1 ð1Þ where R1.52 – – 0.882– 0.3 152– 157 103. which forms the basis of the present paper.867 – 244. Volumetric ratio of oil/methanol.25 NaOH|1. micro-emulsions .23 [18.20. The main factors affecting the yield of biodiesel and other types of transesteriﬁcation will also be discussed.42 4. oleic.8 104.65 1.08 – – 49 62 54 58–59 CaO|8 (2. R1 —COOH þ ðFFAÞ sodium hydroxide NaOH ! R1 COONa þ H2 O ðsoapÞ ðwaterÞ ð2Þ This reaction is undesirable because the soap lowers the yield of the biodiesel and inhibits the separation of the esters from the glycerol. P = transesteriﬁcation reaction period (min).1.08 4. sometimes called fatty acid chains. Usually.8636 0. Normally.37] [20. a process known as transesteriﬁcation. .53 4.D. unburned hydrocarbons. R2.16 0.35] 95–  96 97.28 98.08–0. A number of methods are currently available and have been adopted for the production of biodiesel fuel. and ﬁnally to glycerol.25–26.39 6. KOH|9 (three step) H2SO4|2. Biodiesel has higher combustion efﬁciency.88– 0.20. which can react with alcohol in the presence of a catalyst.3–5.22] [7.18.88– 0.25] [14.42 3.89 0.7 60.86– 0.888 0. Leung et al.9 80– 95 96.72 94.883 0.8837 0.15 59 51 61 – – – – – 60 30 50 60 1440 90 1440 20 1:30 1:9 1:30 1:7 98.23 – 126 88. The most commonly used method for converting oils to biodiesel is through the transesteriﬁcation of animal fats or vegetable oils. H2SO4|6. Kinematic viscosity at 20 °C. There are four primary ways to produce biodiesel (Table 3): direct use and blending of raw oils [49–53]. (2) shows the saponiﬁcation reaction of the catalyst (sodium hydroxide) and the FFA. it reduces most exhaust emissions except NOx.875 0.8 85 [9.%) Yield (%) References Soybean Rapeseed Sunﬂower Palm Peanut Corn Camelina Canola Cotton Pumpkin Jatropha curcas Pongamina pinnata Sea mango Palanga 0.20] [20. It is biodegradable and more than 90% biodiesel can be biodegraded within 21 days [40. For an alkali-catalyzed transesteriﬁcation.33.45 120.41].5 KOH|1 NaOH|0.75 NaOH|1 NaOH|1 KOH|1 Sulfated zirconiz alumina|6 C6H5CH3 + H3PO4|5 + 5. monoglyceride.25–0.38] 89. / Applied Energy 87 (2010) 1083–1095 1085 cannot entirely replace petroleum-based diesel fuel.4 – – – 0.7 – 142.15 52 40 45 45. 2.5 KOH|2 KOH|1. Vegetable oils and fats may contain small amounts of water and free fatty acids (FFA).5 98 97– 98 83. Eq.%). stearic.5 – 251.4 0. C = amount of catalyst (wt. 1 mol of fatty ester is liberated at each step .9 0.869 201 – 200 207 200 202 – 182 204 202 202 – – – 138.25]  [20.Y.5 KOH|2 (ultrasound) H2SO4|1.25] [20.1 45 – 45 45 38 40–42 42 – 41 Production conditions1 T (°C) P M (min) 65 65 60 Room 60 80 Room 60 65 65 60 65 180 66 90 120 120 584 120 60 60 60 90 60 120 180 180 4 1:12 1:6 1:6 1:11 1:6 1:9 1:6 1:9 1:6 1:6 1:06 1:6 1:8 1:12 b C (wt.88– 0.496 0. and linolenic.34]   0.62 – – 56 54 – 61–63 60–61 – – Tallow Nile tilapia Poultry Used cooking oil 1 a b – – – 4 0.5.27.48 0. When the triglyceride is converted stepwise to diglyceride.78 4. M = molecular ratio of oil/methanol.83 4.07 4.52 NaOH|0. there are ﬁve main types of chains in vegetable oils and animal oils: palmitic. and particulate matter [44–48].883 – 0.99 Density Saponiﬁcation Iodine Acid Cetane Heating (g/cm3) number value value number value (mg KOH/ (MJ/kg) g) 0.88 0.32] 89 85– 96 97. Moreover.2 99. Feedstock Kinematic viscosity (cst. Biodiesel production with catalyzed transesteriﬁcation 2.1 >95 [18.07 67.41 4.25 0. and transesteriﬁcation .
a commercial emulsiﬁer . lower emissions.%. supercritical extraction. which can be vegetable oils. hydration. Process ﬂow chart Today. the FFA can react with alcohol to form ester (biodiesel) by an acid-catalyzed esteriﬁcation reaction. feedstocks with high free fatty acid will react undesirably with the alkali catalyst thereby forming soap. Liu et al. The maximum amount of free fatty acids acceptable in an alkali-catalyzed system is below 2. the catalyst for this reaction is concentrated sulphuric acid.5 wt. Although degumming method can solve the problem. Some crude vegetable oils contain phospholipids that need to be removed in a degumming step.5wt% Catalyst Mixing Alcohol Neutralized oil Pretreatment > FFA>2. free fatty acids.C. acid-catalyzed esteriﬁcation has not gained as much attention as the alkali-catalyzed transesteriﬁcation . retards the transesteriﬁcation reaction through the hydrolysis reaction. acid micelles degumming. 2.2. (3).1086 Table 3 Different methods of biodiesel production. animal fats. The typical hydrolysis reaction is shown in Eq. The characteristics of the raw oils should be investigated before choosing the suitable degumming method because different degumming methods have their advantages and disadvantages . The oil can be separated through membrane ﬁltration according to the average molecular weight or the particle size of phospholipids. used in the production of biodiesel contain tri- Re-neutralization Crude Biodiesel Alcohol Recovery Purification Crude Glycerol Quality Control Biodiesel Fig. Phospholipids can produce lecithin. and other contaminants in various proportions. etc. water. If the oil or fat feedstock has a FFA content over 2. most of the biodiesel is produced by the alkali-catalyzed process. originated either from the oils and fats or formed during the saponiﬁcation reaction. Due to the slow reaction rate and the high methanol to oil molar ratio that is required.2. Methods Direct use and blending Deﬁnition D. . incomplete combustion Heavy carbon deposits. Leung et al.2. a pretreatment step is necessary before the transesteriﬁcation process  (see Section 2. as shown in the equation below: Oils or Fats FFA _ 2. 2. renewability Disadvantage Higher viscosity Lower volatility Reactivity of unsaturated hydrocarbon chains Lower cetane number Problems of using in engines Coking and trumpet formation Carbon deposits Oil ring sticking. CH2-O-CO-R1 | CH-O-CO-R2 | CH2-O-CO-R 3 (Triglyceride) (Water) + H2O CH2-OH | CH-O-CO-R 2 | CH2-O-CO-R3 (Diglyceride) (FFA) + R1-COOH glycerides. Fig.5 wt. / Applied Energy 87 (2010) 1083–1095 Advantage Liquid nature-portability Heat content ($80% of diesel fuel) Readily available. Biodiesel production processes Transesterification Phase separation 2.21] Lower energy content Chemically similar to petroleumderived gasoline and diesel fuel Renewability.1. increase lubrication oil viscosity – References [9–13] Direct use as diesel fuel or blend with diesel fuel Micro-emulsions Thermal cracking (pyrolysis) Transesteriﬁcation A colloidal equilibrium dispersion of optically isotropic ﬂuid microstructures with dimensions generally in the 1–150 nm range formed spontaneously from two immiscible liquids and one or more ionic or non-ionic amphiphiles The conversion of long-chain and saturated substance (biomass basis) to biodiesel by means of heat The reaction of a fat or oil with an alcohol in the presence of catalyst to form esters and glycerol Better spray patterns during combustion Lower fuel viscosities [14. higher cetane number. It can hydrolyze the triglycerides to diglycerides and forms more FFA. This reaction is very useful for handling oils or fats with high FFA. Simpliﬁed process ﬂow chart of alkali-catalyzed biodiesel production.5wt% R1 —COOH þ ROH ! R—O—CO—R1 þ H2 O ðFFAÞ ðalcoholÞ ðfatty acid esterÞ ðwaterÞ Hþ ð4Þ Normally. Water. thickening and gelling of the lubricating oil Irregular injector needle sticking.Y. ð3Þ However.% FFA.2. As described earlier.2. 1. compared the different degumming methods. 1 shows a simpliﬁed ﬂow chart of the alkali-catalyst process. such as membrane ﬁltration. higher combustion efﬁciency Energy intensive and hence higher cost Disposal of byproduct (glycerol and waste water) [15–20] – [21–23] cost . Raw materials treatment The raw materials. or recycled greases.3).
94–99]. The advantage of this approach is that no alcohol is needed during the pretreatment and the water formed from the reaction can be immediately vaporized and vented from the mixture. However. As described earlier. there is a large explosion risk associated with methanol vapors which are colorless and odorless. by reﬁning with supercritical CO2 extraction. propanol. but the reaction rate is slower . An obvious advantage of this approach is that the catalyst (iodine) can be recycled after the esteriﬁcation reaction.2. the high pressure required in this process will be the biggest challenge in its industrial application [71.72]. Li et al. aldehydes. The alcohol materials that can be used in the transesteriﬁcation process include methanol. ethanol.38.3 wt. the drawbacks of this method are its high temperature requirement and relatively slow reaction rate . Due to the low cost of raw materials. this is called the special micelles degumming method. The free fatty acids are removed in a reﬁning step and excess free fatty acids can be removed as soaps in a later pretreatment step. and esteriﬁcation by acidcatalysis . toxicity. easy operation. due to diffusion reasons.3. it can effectively remove the free fatty acids and the peroxidation products that are in the crude oil. The catalysts can be homogeneous acid-catalysts or solid acid-catalysts . one-step esteriﬁcation pretreatment may not reduce the FFA efﬁciently because of the high content of water produced during the reaction. sodium hydroxide and potassium hydroxide are usually used as alkali homogeneous catalysts and alkali-catalyzed transesteriﬁcation is most commonly used commercially [36. Pan et al. Moreover. Leung et al. and the conversion rate is high with no intermediate steps. These materials are the most economic because the alkali-catalyzed transesteriﬁcation process is carried out under a low temperature and pressure environment. Another new method of pretreatment is to add glycerol into the acidic feedstock and heat it to a high temperature of about 200 °C. 2. Moreover. and enzymes [87–89]. They also form water when dissolved in the alcohol reactant and affect the yield . corrosion.68]. Compared with the two former methods. all of which cause undesirable odors and ﬂavors in the oil . steam. However. due to its low boiling point. critic acid or phosphoric acid can be added into the oil which is heated to 70 °C. Therefore. if the percentage of FFA is over 2. However. so it could be separated from the oil by natural settlement. . Next.D. Among these alcohols. Table 4 classiﬁes the three categories of catalysts with their advantages and disadvantages [27. It should be ensured that one is not exposed to these chemicals during biodiesel production.e. reaction temperature: 80 °C. normally with a catalyst such as zinc chloride.101]. If the acid value of the oils or fats is very high. which. and environmental problems. steam distillation for reducing high free fatty acids requires a high temperature and has low efﬁciency. but non-hydratable phospholipids cannot be removed by this method. as reported by Verleyen et al. followed by neutralization through dilute lye. On the other hand. titration is performed. the alkali homogeneous catalysts are highly hygroscopic and absorb water from air during storage. Therefore.5 wt.C. The alkali and acid catalysts include homogeneous and heterogeneous catalysts.82. some heterogeneous catalysts are solid and it could be rapidly separated from the product by ﬁltration.102–109]. inhibits the reaction [33. pretreatment is necessary to reduce the content of FFA. under the optimal conditions (i. because of phospholipids hydrophilicity. solid heterogeneous catalysts can stimulatingly catalyze the transesteriﬁcation and esteriﬁcation reaction that can avoid the pre-esteriﬁcation step. To reduce the cost. they should be properly handled. During this step. including steam distillation . they are less often used commercially because of the longer reaction times and higher cost. The supercritical extraction method is employed to separate the phospholipids. In this case. is injected into the oil at 490–550 K in order to eliminate free fatty acids. the alkali and acid catalysts are more commonly used in biodiesel production . This step also determines the amount of caustic soda required in the neutralization step. free fatty acids will be converted to biodiesel by direct acid esteriﬁcation and the water needs to be removed. An example is so called whole cell biocatalysts which are immobilized within biomass support particles. The common pretreatment is esteriﬁcation of the FFA with methanol in the presence of acidic catalysts (usually sulphuric acid). Methanol is especially used because of its lower cost and its physical and chemical advantages. esteriﬁcation by acid-catalysis makes the best use of the free fatty acids in the oil and transforms it into biodiesel [75. Strong commercial acidic ion exchange resins can be used for the esteriﬁcation of FFA in waste cooking oils but the loss of the catalytic activity maybe a problem [80–84]. The hydration method features a simple process. reaction time: 3 h) that the FFA content can be reduced to <2% . extraction by alcohol method needs a large amount of solvent and the process is complicated.% of oils. deodorization is another important step in the raw material treatment.%. The glycerol will react with the FFA to form monoglycerides and diglycerides. / Applied Energy 87 (2010) 1083–1095 1087 its process involves two steps with the use of an organic solvent. . Because of the limited solubility of free fatty acids in alcohol. 2. However. which reduces the washing requirement. a mixture of alcohol and sulphuric acid can be added into the oils or fats three times (three-step pre-esteriﬁcation). An alternative approach to reduce the FFA is to use iodine as a catalyst to convert free fatty acids into biodiesel. hot water can be added into the oil with stirring. However. ratio of methanol to oils: 1.4. Enzyme catalysts have become more attractive recently since it can avoid soap formation and the puriﬁcation process is simple to accomplish. In addition. However. and high yields reﬁning. butanol. Compare with enzyme catalysts. The phospholipids solubility will be signiﬁcantly reduced. acids.  found through orthogonal tests. and ketones. As described above. In the hydration process. An advantage is that no puriﬁcation is necessary for using these biocatalysts [90–93].  found that the reaction time for this method is about 5 min. thus these catalysts are particularly useful for those feedstocks with high free fatty acid content . solid acid-catalysts offer some advantages for eliminating separation. However. Pretreatment of acidic feedstocks Many pretreatment methods have been proposed for reducing the high free fatty acid content of the oils.33. the reaction proceeds at a slower rate because the reaction mixture constitutes a three-phase system. For removing non-hydratable phospholipids. Catalyst and alcohol In general. in order to determine the percentage of FFA in the oils or fats.75:1.Y.77]. some researchers developed new biocatalysts in recent years. iodine amount: 1. there are three categories of catalysts used for biodiesel production: alkalis.2. methanol and ethanol are used most frequently. Both methanol and methoxide are extremely hazardous materials that should be handled carefully. In addition. using a solid catalyst. unsaturated hydrocarbons. The time required for this process is about 2 h and water must be removed by a separation funnel before adding the mixture into the oils or fats for esteriﬁcation again . this method has no superiority on cost because of its complicated processing [67. some researchers reduce the percent of FFA by using acidic ion exchange resins in a packed bed. Compared with the former one. and amyl alcohol. at 1–6 mm Hg pressure. Then the FFA level will become low and biodiesel can be produced using the traditional alkali-catalyzed transesteriﬁcation method. extraction by alcohol . Ma and Hanna  reported that methanol can react with triglycerides quickly and the alkali catalyst is easily dissolved in it.
The glycerol phase is much denser than the biodiesel phase and settles at the bottom of the reaction vessel. Vanadyl phosphate.6. KOH Advantages High catalytic activity. it may cause problems downstream with the saponiﬁcation and the separation of the glycerol by-product.Y.99– 101. a centrifuge may be used to separate the two phases .103. Al2O3/KI. easily separation. NaOH. Micro jets.  produced biodiesel from vegetable oils assisted by ultrasound which is a useful tool for strengthening the mass transfer of immiscible liquids.101–104] Heterogeneous CaO. the amount of water and free fatty acids in the feedstock oil should be monitored during the reaction. lead to intensive mixing of the system near the phase boundary. and excess alcohol is used to ensure total conversion of the oil to its esters. long reaction times. With the use of ultrasound biodiesel can be produced without heating because the cavitation may lead to a localized increase in temperature at the phase boundary and enhance the reaction [110–112]. Type Alkali Homogeneous Example NaOH. sulphated zirconia. allowing it to be separated from the biodiesel phase. TiO2 =SO2À . ZrO2 =SO2À . Maeda et al. in order to speed up the reaction. and oil during the transesteriﬁcation step. KOH/NaY. Soap that may be generated during the process also contaminates the biodiesel and glycerol phase. . if the free fatty acid level or water level is too high. typically produced glycerol is about 50% glycerol or less in composition and mainly contains water. high molar ratio of alcohol to oil requirement.2. it is best to start agitating the methanol in a mixer and add the catalyst slowly and carefully . the reﬁning of glycerol is also important due to its numerous applications in different industrial products such as moisturizers. 64.  and Thanh et al. CaTiO3. mixing brings the oil. more catalyst needs to be added to complete the reaction. Moreover. Once the methoxide is added into the oil. Most of the catalysts (e. cosmetics. two major products exist: esters (biodiesel) and glycerol. Wen et al. Phase separation can be observed within 10 min and can be completed within several hours of settling.C. CaO–CeO2. Mixing and neutralization The purpose of mixing methanol with the catalyst is to produce methoxide which reacts with the base oils. Recently. and oil are mixed and agitated in a reaction vessel. Normally. 2. alumina/silica supported K2CO3 [33. diffusion limitations. disposable Low FFA requirement.2. saponiﬁcation. environmentally benign. Ultrasonic irradiation causes cavitation of bubbles near the phase boundary between immiscible liquid phases. fewer disposal problems. Once the catalyst completely dissolves in the methanol. It is one of the few products that has a good reactivity on sump oil.104] Acid Homogeneous Concentrated sulphuric acid Catalyze esteriﬁcation and transesteriﬁcation simultaneously. carbon-based 4 4 solid acid catalyst.103. eco-friendly [97. a signiﬁcant amount of contaminants is also present in the biodiesel. more wastewater from puriﬁcation. The unused alkali catalyst is usually neutralized by an acid. the latter can be . a transesteriﬁcation reaction will start. longer catalyst lifetimes Disadvantages Low FFA requirement. the methoxide is ready to be added to the oil. Rhizomucor mieher lipase [82. more wastewater from puriﬁcation. Some alkali catalysts will react with rudimental acids during the pretreatment step or will react with the free fatty acids from the oil. low microporosity. CaMnO3.g. modest operation conditions Noncorrosive.5. high cost References [97. ETS-10 zeolite. and the alcohol into intimate contact while the temperature is kept just below the boiling point of the alcohol (i.1088 D. which means more biofuel can be produced.104] Avoid soap formation. Ca2Fe2O5. more waste from neutralization. low cost. anhydrous conditions. hydrochloric or sulphuric acids are added into the glycerol phase during the re-neutralization step and produce salts such as sodium chloride or potassium sulphate. high reaction temperature and pressure. favorable kinetics. Once the transesteriﬁcation reaction is completed. avoid soap formation Catalyze esteriﬁcation and transesteriﬁcation simultaneously.7. During this step. Leung and Guo  studied the effect of operating conditions on the product yield and pointed out that heating the oil prior to the mixing can increase the reaction rate and hence shorten the reaction time. medicines.98. 2. NaﬁonNR50 Candida antarctica fraction B lipase. and unused catalyst. denaturation [27. KOH) are in solid form and do not readily dissolve into methanol.2. and is extremely effective for washing shearing shed ﬂoor.103] Heterogeneous Enzymes ZnO/I2. CaZrO3.e. unreacted alcohol. carbohydrate-derived catalyst.82.5 °C for methanol). Transesteriﬁcation and separation When the catalyst. As previously mentioned. salts. According to the statements of Van Gerpen et al. / Applied Energy 87 (2010) 1083–1095 Table 4 Advantages and disadvantages at different types of catalysts used in the biodiesel production. diffusion limitations. formed by impinging one liquid to another. nonpolluting. Whittington  reported that glycerol can even be fermented to produce ethanol. Therefore.102. The asymmetric collapse of the cavitation bubbles disrupts the phase boundary and starts emulsiﬁcation instantly. emulsion formation. a neutralization reaction will immediately start. KOH/Al2O3. the reaction pressure is close to the atmospheric pressure to prevent the loss of alcohol. alcohol. recyclable.  fabricated a new reaction vessel – Zigzag micro-channel reactor in recent years and found that less energy consumption for biodiesel synthesis can be achieved by using this reactor. high cost Equipment corrosion. alcohol. Leung et al. In some cases. crude biodiesel needs to be puriﬁed before use. easier puriﬁcation Expensive. Therefore. higher reaction temperature. Reﬁning crude glycerol Although biodiesel is the desired product from the reactions. Therefore. Schumacher  suggested that although the glycerol phase tends to contain a higher percentage of contaminants than the biodiesel. the catalyst.104] 2. difﬁcult to recycle. A stirred reactor is usually used as the reaction vessel for continuous alkali-catalyzed biodiesel production. so it can be used as a heavy duty detergent and degreaser. In some cases. higher selectivity. The reaction mixture is allowed to settle in the reaction vessel in order to allow the initial separation of biodiesel and glycerol. and other glycerol products [115–117]. Amberlyst-15. or the mixture is pumped into a settling vessel. recyclable. anhydrous conditions. there is an increased interest in new technologies related to mass transfer enhancement. niobic acid. weak catalytic activity Low acid site concentrations. soaps. Both the biodiesel and glycerol are contaminated with an unreacted catalyst.
emulsions formation [46. water.2.9. Generally.2. salts. Very effective in removing contaminants Increased cost and production time.2. molecular sieves and silica gels. and free glycerol from the crude biodiesel. After washing several times. the biodiesel and water phases are separated by a separation funnel or centrifuge .76] Membrane extraction Remove the contaminants – Avoids the emulsion formation and decreases the reﬁning loss Probably high cost and low throughput due to contaminants existed [70. soaps.8. because of the immiscibility of water and biodiesel. residual alcohol.. Dry washing. The primary material for water washing is distilled warm water or softened water (slightly acidic) [72. Puriﬁcation of crude biodiesel After separation from the glycerol phase.8. 2.2. there are many disadvantages to this method. operating pressure: 0. In more sophisticated operations. Softened water (slightly acidic) eliminates calcium and magnesium contamination and neutralizes any remaining alkali catalysts .  used dry washing by replacing the water with an ion exchange resin or a magnesium silicate powder in order to remove impurities. emulsions can form when washing the biodiesel made from waste cooking oils or acidic feedstocks because of the soap formation . forms an azeotrope with the water. a hollow ﬁber membrane (1 m long. The alcohol recovery step is more difﬁcult when the alcohol that is used. The crude biodiesel is pumped into the hollow ﬁber membrane (ﬂow rate: 0. 2. water and alcohol are removed to produce 80–88% pure glycerol that can be sold as crude glycerol. In some cases. such as polysulfone. Quality control For commercial fuel. including an increased cost and production time. the glycerol is distilled to 99% or higher purity and sold in different markets . and membrane extraction [123. three main approaches are adopted for purifying biodiesel: water washing. Although the magnesol process has a better effect on the removal of methanol than the ion resins. Both the ion exchange process and the magnesol process have the advantage of being waterless and thus eliminate many of the problems outlined above. Warm water prevents the precipitation of saturated fatty acid esters and retards the formation of emulsions with the use of a gentle washing action. The purity of the biodiesel obtained is about 90% and the other properties conform to the ASTM standards .2. acid is added to crude biodiesel to neutralize any remaining catalyst and to split any soap. In this method. the alcohol vapor is condensed back into liquid and reused in the process. 2. the alcohol may contain water that should be removed in a distillation column before the alcohol is returned to the process. can also be used to remove water from the biodiesel . etc.72–74] – Waterless Overruns the limit in the EN Standard [69. Following this step.8. Normally. Approaches Primary material used Distilled warm water Function Phases separation Advantage Disadvantage References Water washing Softened water Dry washing Ion exchange resin Magnesium silicate powder Polysulfone Prevents precipitation of saturated fatty acid esters Retards the emulsion formation Eliminates calcium and magnesium contamination Brings the free glycerol level down and removing soaps Separation funnel. Water washing.C. Gabelman and Hwang  proved that the contaminants can be removed by using a hollow ﬁber membrane extraction. These two dry washing methods can bring the free glycerol level down and is reasonably effective for removing soaps. liquid efﬂuent. crude biodiesel enters a neutralization step and then passes through an alcohol stripper before the washing step.1 MPa). This approach effectively avoids emulsiﬁcation during the washing step and decreases the loss during the reﬁning process. The remaining water can be removed from the biodiesel by passing the product over heated Na2SO4 (25 wt. Gerpen  stated that neutralization before the washing step reduces the materials required for the washing step and minimizes the potential for emulsions being formed during the washing step. centrifuge.D.71] . free glycerol. 1 mm diameter) ﬁlled with distilled water is immersed into the reactor (20 °C). It also can remove any residual sodium salts and soaps. unreacted alcohol.% of the amount of the ester product) overnight and then be removed by ﬁltration .3. These approaches are brieﬂy shown in Table 5 and discussed in detail as follows. meaning that the contaminants have been completely removed. the alcohol in the glycerol phase can be removed through a vacuum ﬂash process or by other types of evaporators. product loss.1. It is a very promising method for purifying biodiesel. such as ethanol or isopropanol. Leung et al. Cooke et al. Gerpen  proposed the use of a molecular sieve to remove the water generated. Usually. dry washing . and soaps that were generated during the transesteriﬁcation reaction . biodiesel is passed over heated Na2SO4 and then ﬁltered to remove any remaining water . Generally. the ﬁnished biodiesel must be analyzed using sophisticated analytical equipment to ensure it meets inter- Table 5 Different approaches for purifying crude biodiesel. etc. However. 2.124].5 ml/min. none of the products from this process fulﬁll the limits speciﬁed in the EN Standard [128. However. Since both glycerol and alcohol are highly soluble in water.Y. the water phase becomes clear. The primary purpose of this step is to wash out the remnants of the catalyst.2. product loss.75. etc.73]. crude biodiesel is mainly contaminated with residual catalyst. After the re-neutralization step. silica gels. Moreover. Soaps react with the acid to form water soluble salts and free fatty acids.129]. Moreover. water washing is very effective for removing both contaminants. Then. molecular sieves. / Applied Energy 87 (2010) 1083–1095 1089 recovered for use as a fertilizer . 2. Unreacted alcohol should be removed with distillation equipment before the washing step to prevent excess alcohol from entering the wastewater efﬂuent . Membrane extraction. polluting liquid efﬂuent.8.
the storage temperature of most pure biodiesel is generally kept between 7 and 10 °C. in some cases. because water contamination will lead to biological growth in the fuel.130]. Because the European speciﬁcation for sulfur content (i.2 max 0. is used to produce a colorless biodiesel . it should be treated with an antioxidant additive .132]. Bondioli et al.020 max No.2 max 0.5 max 0.42.130]. underground storage of pure biodiesel usually provides the storage temperature necessary for preventing crystal formation . Poor stability can lead to an increased acid value and fuel viscosity and to the formation of gums and sediments. the removal of the free glycerol.05 max – 0.129. the ASTM standard requires the total glycerol to be <0. As mentioned before. Table 6 Speciﬁcations and test methods of ASTM D6751 and EN 14214 standards [129. Biodiesel storage tanks made of aluminum. even as little as 1%. the EN 14214 standard limits the amount of alcohol to a very low level [86. it is limited by the speciﬁcation on levels of sulfated ash. On the other hand. each of these compounds contains a glycerol molecule. Therefore.129]. since residual methanol. including exposure temperature. Even in blends with conventional diesel fuel.134].3. which may lead to engine deposits and high abrasive wear levels [42.0015 max 0.2 max 5 max Test method ASTM D6751 D93 D445 D613 D874 D130 D664 D6584 D6584 D4951 D4530 – D2500 – D1160 D5453 D5453 – D2709 – – – – – – – – – – – – EN 14214 ISO CD3679e EN ISO 3104 EN ISO 5165 ISO 3987 EN ISO 2160 pr EN 14104 pr EN 14105m pr EN 14106 pr EN 14105m pr EN 141101 – EN ISO 10370 – EN SIO 3675 EN SIO 12185 – – – – – EN ISO 12937 EN 12662 pr EN 14112 pr EN 14111 pr EN 14103d pr EN 14103 pr EN 14103d pr EN 141101 pr EN 14105m pr EN 14105m pr EN 14105m pr EN 14108 pr EN 14109 . fuel solvency. Storage of biodiesel product Biodiesel is safe to store and the properties of biodiesel should conform to respective standards after it has been stored for a long time. Table 6 shows the ATSM D 6751 and EN 14214 standards. 3 max 0.41. and the absence of free fatty acids [39.3 max – 860–900 – – – 10 max – 500 max 24 max 6 min 120 max 12 max 1 max 96. if the duration of storing biodiesel or biodiesel blends is more than 6 months. yellow greases. and brown greases leave an objectionable color in the biodiesel.050 max – Report customer – 360 max 0. EN 14214) is much tighter than the US requirement. the most important aspects of the biodiesel product are the completion of the reaction. Property Unit Limits ASTM D6751 Flash point Kinematic viscosity at 40 °C Cetane number Sulphated ash content Copper strip corrosion Acid value Free glycerol Total glycerol Phosphorous content Carbon residue ASTM D6751 (100% sample) EN 14214 (10% bottoms) Cloud point Density at 15 °C Distillation T90 AET Sulfur (S 15 Grade) Sulfur (S 500 Grade) Sulfur content Water and sediment Water content Total contamination Oxidation stability at 110 °C Iodine value Linolenic acid methyl ester Polyunsaturated (P4 double bonds) methyl esters Ester content Methanol content Monoglyceride content Diglyceride content Triglyceride content Alkaline metals (Na + K) °C mm2/s – % (m/m) – mg KOH/g % (m/m) % (m/m) % (m/m) % (m/m) °C kg/m3 °C ppm ppm mg/kg %vol.  stated that the temperature of stored biodiesel should be controlled so as to avoid the formation of crystals which can plug fuel lines and fuel ﬁlters. Even in extremely cold climates. Ali et al. Although there is no color speciﬁcation in the ASTM standard.e.001 max 0. Finally. can reﬂect the properties of the chemical compounds that make up the biodiesel.C. if the transesteriﬁcation reaction is not complete then triglycerides. Some properties in the standard.020 max 0. and other properties provide an indication of the quality of the production process . For this reason.240 max 0. it should be minimized in the stored fuel by using biocides.Y.5 min 0. and ﬂuorinated polyethylene or polypropylene should be selected.0 47 min 0. Lee et al.8 max 0. although a speciﬁc value for the residual catalyst is not included in the ASTM standard.80 max 0. such as the cetane number or density. Mittelbach  stated that most people in the industry expect the biodiesel blending stock to meet the relevant standard before being blended. To ensure safe operation in diesel engines.25 max 0.01 max – 0.0 51 min Class 1 0. steel. Leung et al. residual catalyst and alcohol. biodiesel standards identify the parameters that pure biodiesel must meet before being used as a pure fuel or being blended with distillate fuels [120.1090 D. Chemically. Fuel with excessive free glycerol may plug the fuel ﬁlters and cause combustion problems in the diesel engine. In addition. and material compatibility [40.24% of the ﬁnal biodiesel product [54. / Applied Energy 87 (2010) 1083–1095 national standards.5–5.130]. oxidative stability. which is an effective method for the removal of excessive color. Moreover.0 min 3.0 min 1. an activated carbon bed. A few speciﬁcations have been set but the ASTM D 6751 and EN 14214 standards are the most commonly used standards. or monoglycerides may be left in the ﬁnal product. Teﬂon.130]. Generally. can lower the ﬂashpoint of the ﬁnal biodiesel product from 170 °C to <40 °C.  noted that the stability of biodiesel is an important property when it is to be stored for a prolonged period. There are several key factors that need to be considered for the storage of biodiesel. 2. mg/kg mg/kg h – % (m/m) % (m/m) % (m/m) % (m/m) % (m/m) % (m/m) % (m/m) mg/kg 130. Therefore.9–6.050 max – – – – – – – – – – – – EN 14214 101. diglycerides.  reported that a number of producers in Europe are resorting to the use of vacuum distillation for the removal of sulfur compounds from the ﬁnal biodiesel product. some vegetable oils.
A higher reaction temperature can decrease the viscosities of oils and result in an increased reaction rate. a distinct liquid and vapor phase no longer exist. After the completion of the reaction.143]. An excess of alcohol is used in biodiesel production to ensure that the oils or fats will be completely converted to esters and a higher alcohol triglyceride ratio can result in a greater ester conversion in a shorter time. After the reaction is complete.4. in 1996 . Other processes of biodiesel production 3. triglycerides are converted to esters through the selection of inert co-solvents that generate a onephase oil-rich system [86.Y.1. In situ biodiesel process The in situ biodiesel production is a novel approach for converting oil to biodiesel which was developed by Harrington and D’ArcyEvans in 1985 .139.133. 2. In this process. Reaction time Freedman et al. the most commonly used catalyst for the reaction is sodium hydroxide. and the reaction is completed in a very short time .  found.1.151]. resulting in a loss of esters as well as causing more fatty acids to form soaps [143. Reaction temperature Temperature clearly inﬂuences the reaction and yield of the biodiesel product. However. Supercritical alcohol process As is known.138]. Freedman et al. As mentioned before.47. Leung and Guo  and Eevera et al. Alcohol quantity Many researchers recognized that one of the main factors affecting the yield of biodiesel is the molar ratio of alcohol to triglyceride [28. Usually. This is the reason why the catalyst should be added into the methanol ﬁrst and then mixed with the oil. the molar ratio is associated with the type of catalyst used and the molar ratio of alcohol to triglycerides in most investigations is 6:1. reclaimable co-solvents in a single-pass reaction that takes only seconds at ambient temperature and pressure.61. Demirbas  uses tetrahydrofuran (THF) as a co-solvent to make the methanol soluble. 2. Therefore. During the whole process. This process can handle not only grainbased feedstocks but also waste cooking oils and animal fats. Biox co-solvent process The Biox co-solvent process was developed by Boocock et al. and a shortened reaction time. After a while. Normally. The unique advantage of the Biox co-solvent process is that it uses inert. when a ﬂuid or gas is subjected to temperatures and pressures in excess of its critical point.2.3.% and then decreases a little with a further increase in catalyst concentration. because of the possible hazard and toxicity of the co-solvents.D. however. In contrast to the common alkali-catalyzed method. Further increasing the alcohol amount beyond the optimal ratio will not increase the yield but will increase cost for alcohol recovery . which will affect the product yield because of the hydrolysis reaction .142]. Depending on the oil used. 2. the gas is vented and the product in the reactor is poured into a collecting vessel. Reaction occurs during the heating period.148].94. the optimal temperature ranges from 50 °C to 60 °C [28. In addition. At the beginning.2.5 wt.4. they must be completely removed from the glycerol phase as well as the biodiesel phase and the ﬁnal products should be water-free . such as in the case of waste cooking oil.140].  found that sodium methoxide was more effective than sodium hydroxide because upon mixing sodium hydroxide with methanol a small amount of water will be produced. Leung et al. 3. a number of unusual properties are exhibited. and no catalyst residues appear in either the biodiesel phase or the glycerol phase . the reaction proceeds very fast.3. this approach is believed to be able to solve the problems associated with the two-phase nature of normal methanol/triglyceride mixtures by forming a single phase. a single ﬂuid phase is formed . Van Gerpen et al. the reaction is slow due to the mixing and dispersion of alcohol into the oil.145].138]. Instead. a molar ratio as high as 15:1 is needed when using acid-catalyzed transesteriﬁcation [28. to achieve transesteriﬁcation . with heat supplied from an external heater. 3.147. the ratio for transesteriﬁcation reaction requires 3 mol of alcohol for 1 mol of triglyceride to produce 3 mol of fatty acid ester and 1 mol of glycerol.C. Under such conditions.61.  found that when the reaction temperature increases beyond the optimal level.141]. reaction pressure and temperature) affect the yield of the biodiesel product and the highest yield can be obtained under the optimal conditions. / Applied Energy 87 (2010) 1083–1095 1091 The tanks should minimize the possibility of water contamination and should be cleaned prior to use for biodiesel storage . 3. However. the yield reaches an optimal value when the catalyst (NaOH) concentration reaches 1.148]. 2. that the recovery of excess alcohol is difﬁcult when using this process because the boiling point of the THF co-solvent is very close to that of methanol. and then remains relatively constant with a further increase in the reaction time [28. However.e.144]. The reduction of the yield of the biodiesel is due to the addition of excessive alkali catalyst causing more triglycerides to react with the alkali catalyst and form more soap [28. Supercritical transesteriﬁcation is carried out in a high pressure reactor.4. Moreover.4.146]. Catalyst concentration Catalyst concentration can affect the yield of the biodiesel product. Theoretically. a process for biodiesel production has been developed by a non-catalytic supercritical methanol method [147. Main factors affecting the yield of biodiesel 2. Co-solvent options are available to overcome slow reaction times caused by the extremely low solubility of the alcohol in the triglyceride phase. This is because an insufﬁcient amount of catalysts result in an incomplete conversion of the triglycerides into the fatty acid esters [28. When the percentage of free fatty acids in the oils or fats is high. the biodiesel–glycerol phase separation is clean and both the excess alcohol and the tetrahydrofuran co-solvent can be recovered in a single step .4. several variables (i. the yield of the biodiesel product decreases because a higher reaction temperature accelerates the saponiﬁcation reaction of triglycerides.  found that the conversion rate of fatty acid esters increases with reaction time. the yield reaches a maximum at a reaction time of <90 min. this process has advantages in terms of reaction time and puriﬁcation but requires a high temperature and pressure. excess reaction time will lead to a reduction in the product yield due to the backward reaction of transesteriﬁcation. In this method. The reaction temperature must be less than the boiling point of alcohol in order to ensure that the alcohol will not leak out through vaporization. with the use of an alkali catalyst [47. As the catalyst concentration increases the conversion of triglyceride and the yield of biodiesel increase.4. Because of the lower value of the dielectric constant of methanol in the supercritical state. The yield of biodiesel is increased when the alcohol triglyceride ratio is raised beyond 3 and reaches a maximum. The remaining contents are removed from the reactor by washing it with methanol [150. hence requiring a high amount of energy [94.
Kumar A. Renewable and Sustainable Energy Reviews 2009. Process optimization for biodiesel production from Jatropha. the alkali catalyst will react with the free fatty acids to form soaps and the water can hydrolyze the triglycerides into diglycerides and form more free fatty acids.  Srivastava A. A very promising method for washing biodiesel is the hollow ﬁber membrane extraction.  San Jose Alonso J. Mori T. Hirata S. is washed with water to remove the contaminants until the washing solution is neutral. sunﬂower and rapeseed vegetable oils in a light boiler. Ryan J. including the crude biodiesel. The investigation of blending properties of biodiesel and No. Triglycerides-based diesel fuels. using iodine as a catalyst. the acidic feedstocks should be pre-treated to inhibit the saponiﬁcation reaction. toxicity. corrosion. Lopez Sastre JA. Raheman H. Methyl ester of peanut (Arachis hypogea L. Camelina oil as a fuel for diesel transport engines. Kwon JH. the oilseed lipid. Prasad R. Haas and Scott  found that the ﬁnal biodiesel product can conform to the ASTM standard and the conversion of the oilseed is very high (about 98%). Akba O. the product should ﬁrst be neutralized and then put through an alcohol stripper before cleaning by either one of the following approaches: water washing.  Issariyakul T. Karanja and Polanga oils. Hamú EH. Transesteriﬁcation is basically a sequential reaction. the molar ratio of alcohol to triglycerides should be increased to 6:1 with the use of an alkali catalyst.  Abreu FR.14:200–16.% for NaOH which is the most commonly used catalyst. Wu GY. Bhatia S. These are undesirable reactions which reduce the yield of the biodiesel product.Y. Saydut A.17:191–7. Xie S. et al. The most commonly used alcohol is methanol while sodium hydroxide and potassium hydroxide are the most commonly used catalysts. membrane extraction. After the washing step. Lee KT.  Kaya C. As a commercial fuel. Chem Eng J 2008. which can reduce the cost of feedstock [156.99:1716–21. Xu J.9:13–8.1092 D. and the residual product is biodiesel . and environmental problems. Fuel 2008. Conclusions Biodiesel is a clean-burning diesel fuel with a chemical structure of fatty acid alkyl esters. Biodiesel production from jatropha oil (Jatropha curcas) with high free fatty acids: an optimized process.157]. Xiang B. Rice B. Erdogan S. after reﬁning the raw materials. seed oil with a high content of free fatty acids.  Santos FFP.87:1781–8.2009. Microwave assisted transesteriﬁcation of rapeseed oil.85:360–4. . Nichol R.4:111–33. Energy Sustain Dev 2005.e. O’Connell A. J Jiangsu Polytech Univ 2003. This will trigger the development of more sophisticated methods of biodiesel production and reﬁning to cope with the increasing market demand.15:16–8. Quantitative and qualitative determination of acid value of peanut oil using near-infrared spectrometry. Inﬂuence of feedstock and process chemistry on biodiesel quality. Renew Energy 2009. Energy Convers Manage 2003. The upper layer. reaction temperature. Suarez PAZ. Bioresour Technol 2008. the oilseeds need to be dried before the reaction takes place . Wolf C. Romero-Avila C. glycerol will be produced as a by-product. Fuel 2009. degumming. However. Danisman A. Kulkarni MG.  Demirbas A. a higher molar ratio is needed for acid-catalyzed transesteriﬁcation. The optimal temperature ranged between 50 °C and 60 °C. The lower layer is the alcohol phase and can be recovered. reaction time.209:29–33. Dalai AK. Sampathrajan A. Biodiesel production through the use of different sources and characterization of oils and their esters as the substitute of diesel: a review.  Bernardo A. / Applied Energy 87 (2010) 1083–1095 of its acyglycerols.140:77–85.doi:10. then ﬁltered.  Azcan N. and dry washing.88:1148–50. Fernandes FAN. To ensure a complete transesteriﬁcation reaction. Radiat Phys Chem 1995. Because the conversion rate of fatty acid esters increases with reaction time but the yield of the biodiesel product reaches a maximum at an optimal reaction time.31:569–75. Optimisation of experimental conditions for biodiesel production from alkali-catalysed transesteriﬁcation of Jatropha curcus oil. J Food Eng 2009. J Mol Catal A Chem 2004. reduce the long size of the production system associated with the pre-extraction. Meher LC. and maximize the yield of the biodiesel production. 0 diesel fuel. Of the various methods available for producing biodiesel. Howard-Hildige R. Baysal A. Lima DG.5 wt.fuel. this process cannot handle waste cooking oils and animal fats. Hamamci C. the oilseeds are directly treated at ambient temperature and pressure with a methanol solution in which the catalyst has been previously dissolved. That means that the oil in the oilseeds is not isolated prior to transesteriﬁcation to fatty acid esters [152–154]. Thomas B.  Saraf S. The transesteriﬁcation reaction requires an alcohol as a reactant and a catalyst. when the raw materials (oils or fats) contain a high percentage of free fatty acids or water. Acknowledgement The authors would like to acknowledge the support of the ICEE and the University Development Fund of the University of Hong Kong. Higher reaction temperature can decrease the viscosity of oils. in the presence of acidic catalysts.  Byun MW. which effectively avoids emulsiﬁcation during the washing step and decreases the reﬁning loss. alcohol quantity.44:2093–109. but the reaction rate is slower while the advantage of the last approach is that no alcohol is needed and the water (formed from the reaction) can be immediately vaporized and vented from the mixture. and possibly for the reﬁning of. Malveira JQ. Cerbera odollam (sea mango) oil as a promising non-edible feedstock for biodiesel production. Physicochemical properties of soybean oil extracted from [gamma]-irradiated soybeans.030. However. The ﬁrst approach can eliminate the separation. Zhou X. i. Two layers are formed around the time of the completion of the reaction. enhancing the reaction rate.  Singh SP.  Rao Y. Wang Z.  Chitra P. To reduce the alcohol requirement for high efﬁciency during in situ transesteriﬁcation. With increasing concern over global warming. Kang IJ. There are three primary approaches for reducing the amount of free fatty acids: esteriﬁcation of free fatty acids with methanol. the process could reduce biodiesel production costs. Since this method eliminates the need for the isolation of.34:1257–60. the alkali-catalyzed transesteriﬁcation of vegetable oils and animal fats is currently the most commonly adopted method.  Xu G. Utilization of metal complexes as catalysts in the transesteriﬁcation of Brazilian vegetable oils with different alcohols.88:1588–94. Fuel 2009. Fuel 2009. For reﬁning the crude biodiesel produced. Singh D. Renew Sustain Energy Rev 2000. Lopez E.  Sahoo PK. Because of its numerous industrial applications. Milled oilseeds are mixed with alcohol in which the catalyst had been dissolved and the mixture is heated under reﬂux for 1–5 h. the upper layer is dried over anhydrous sodium sulfate. References 4. Hayashi Y. adding glycerol into the acidic feedstock with a catalyst like zinc chloride and heated to a high temperature.  Kansedo J. Das LM. There are four primary factors affecting the yield of biodiesel. Leung et al. Cruz MGA. For used cooking oils or for oils with a high percentage of free fatty acids. the crude glycerol should be reﬁned with purity higher than 99% to make it usable.46:659–62. Production of biodiesel by ultrasound assisted esteriﬁcation of Oreochromis niloticus oil. During the reaction.32:880–6. Venkatachalam P. Biomass Bioenergy 2008. Bakhshi NN. A note on the combustion of blends of diesel and soya.  Berchmans HJ. Biodiesel fuels from vegetable oils via catalytic and non-catalytic supercritical alcohol transesteriﬁcations and other methods: a survey.C. Ind Crops Prod 2003.) seed oil as a potential feedstock for biodiesel production. The optimal condition of catalyst concentration is about 1.05. the ﬁnished biodiesel must be analyzed using sophisticated analytical equipment to ensure that it meets international standards even if it has been stored for a long time. Biomass Bioenergy 2007. depending on the oil used. Biodiesel production from mixtures of canola oil and used cooking oil. Biodiesel production from crude Jatropha curcas L. Therefore.93:249–52.  Kumar Tiwari A. it is foreseeable that biodiesel usage would continue to grow at a fast pace. Process Saf Environ Prot 2007. and catalyst concentration.1016/j.
 Van Gerpen JH. Method for the preparation of fatty acid alkyl esters. Blake J. Freedman B.C. Hudson B.freepatentsonline. Canola and high erucic rapeseed oil as substitutes for diesel fuel: preliminary tests.html.86:681–8. J Am Oil Chem Soc 1983. Appl Biochem Biotechnol 2000. Ashraf S. Draft Technical Report. Cheng J.  Di Serio M. Davaris C. Dong FM.  Goodrum JW. Bhatia S. Deng S. Venditti R.90:1157–63.  Meher LC. J Yangtze Univ (Nat Sci Ed) 2007. Kaewpiboon C. Lu XH. Savage Jr LD.99:8752–8.98:416–21. Johnson L. Esteriﬁcation of free fatty acids in waste cooking oils (WCO): role of ion-exchange resins. Improving the economics of biodiesel production through the use of low value lipids as feedstocks: vegetable oil soapstock. J Am Oil Chem Soc 2008. He SL. Spill Sci Technol Bull 1999. Ind Crops Prod 1997. J Am Oil Chem Soc 2002.87:2961–6.79:947–53. Fuel 2008.88:560–5. Energy Fuels 2006. URL:http://www. Ziemke M. Fuel Process Technol 2009. Reactions of fats and fatty acids. Appl Catal A: Gen 2008.  Knothe G.  Speidel HK.  Jeromin L.Y.) seed oil as an alternative feedstock for the production of biodiesel in Greece.77:1117–20. Substitutable biodiesel feedstocks for the UK: a review of sustainability issues with reference to the UK RTFO. Inﬂuence of the vegetable oil reﬁning process on free and esteriﬁed sterols. Inﬂuence of the operating conditions on acid degumming process in sunﬂower seed oil. The effect of phosphorus level on the total glycerol and reaction yield of biodiesel bioenergy 2002. Biodiesel production technology. Evaluation of biodiesel obtained from cottonseed oil. Michele CR.  Lin L. da Silva TD. Meirelles A. Huang YQ. Biodiesel production using anionic ion-exchange resin as heterogeneous catalyst.  Haas MJ.  Anon.  de Souza MP. et al. J Am Oil Chem Soc 2001. Lee KT.  Van Gerpen J. Anwar F. Sosinska U. and alkanes in a new technology engine. Muraleedharan C. Biodiesel production from high FFA rubber seed oil. J Mol Catal A: Chem 2005. Science 1979. Qasim M.  Liu GR. Viotto LA.  Soriano Jr NU. Lozano P. Guangzhou.  Li C. Transesteriﬁcation of neat and used frying oil: optimization for biodiesel production. editor. 1093  Chang C. editor. Cao GM. Fuel 1998. Study on extraction and deacidiﬁcation of oils and fats of natural plants by supercritical carbon dioxide. Biomass 1986. Ind Eng Chem 1947.59:780A–1A. Soybeans crude oil miscella degumming utilizing ceramic membranes: transmembrane pressure and velocity effects.349:198–203.97:1392–7. Fuel Process Technol 2009. Deacidiﬁcation of corn oil by solvent extraction in a perforated rotating disc column. Ji JB. Hanif MA. Biodiesel production from crude rice bran oil and properties as fuel. editor. Moser BR. Dewettinck K. Nastasi M. Ataur R. Guaraldo Gonçalves LA.  Rashid U.html.39:1543–8. Appl Energy 2009. de Souza MP. Rasoanantoandro MC.60:1579–87. 619–26]. Aparicio F. Fernanda MBC.  Strayer R. Fuel properties and calculation of higher heating values of vegetable oils. J Cleaner Prod 2009. Oktar N. Toda T. Tomei J. Piriyakananon K. biodiesel and natural gas refuse trucks of the City of Madrid. Biodiesel synthesis via homogeneous Lewis acid-catalyzed transesteriﬁcation. Lai LF. Bioresour Technol 2003.87:216–21. Utilization & Environmental Effects.86:610–5. Koncar M. Santacesaria E. Biomass Bioenergy 2009. Clements D. Single-stage liquid–liquid extraction of miscella with ethyl alcohol. International conference on biomass energy technologies. Argyropoulos DS. Economic assessment and sensitivity analysis. International conference on biomass energy technologies.86:1087–96. Thakernkarnkit W. Barrera M. Adams TT. Potential plant oil feedstock for lipase-catalyzed biodiesel production in Thailand. Lepori W. Craig W.  Sheng M. 2006 [p. Hanna MA. Elizabeth RL. Biofuels from catalytic cracking of tropical vegetable oils. Evaluation of Camelina sativa oil as a feedstock for biodiesel production. Geneste P. China.  Eisenmenger M. The effect of heat on pure triglycerides. Wang Y.32:1202–5. Preparation and properties of diesel fuels from vegetable oils. Peters J.  Canakci M. Study on the degumming process of acidic oil. Production of biodiesel from palm oil (Elaeis guineensis) using heterogeneous catalyst: an optimized process.68:83–6. New York: John Wiley & Sons.  Ma F.  Schinas P. New options for conversion of vegetable oils to alternative fuels.  Leung DYC. I.66:1372–8. Study on the coupling process of catalytic esteriﬁcation and extraction of high acid value waste oil with methanol. Wan S. Fuel 2009. Fuel 2008. Biodiesel production technology: August 2002–January 2004. Javier Sanchez F. Auld D. China’s motor fuels from tung oil. Gomez A. Stimulating the biodegradation of crude oil with biodiesel preliminary results. Fuel Process Technol 2006.  ISTC.  Pina C. Verhe R. 1979. CO: National Renewable Energy Laboratory.48:289–91. Transesteriﬁcation of soybean oil to biodiesel using CaO as a solid base catalyst. Dvorak B. Guo Y. 2008.60:1587–92. Pruszko R. Body composition. Aquaculture 2004.87:265–73. Ruan RS. USEPA. China. Fuel 1987.  Rashid U. Civelekoglu H. Ind Crops Prod 2005.  Niehaus RA.85:55–61.  Ramadhas AS. Biodiesel production: a review. Leung et al.6:113–9. Paulo LSJ. Knothe G. Kuribayashi H. J Am Oil Chem Soc 1991. J Am Oil Chem Soc 1983.D.  Liu X. Hardy RW.  Ozbay N. Winter rape oil fuel for diesel engines: recovery and utilization. Korus R. Cereals Oils Process 2008.33:1646–53. Geller DP. Production of biodiesel fuel from wast edible oil. Chulalaksananukul W.1990. Pereira G.87:1789–98.90:606–10. 2004. Other information: .  Zhang Y.  Turkay S. Shanks B.com/ 5849939.  Gui MM.  Frohlich A. Marcelli GR.  de Carvalho CC. Liu YH. Energy 2008. neat methyl esters. Yu YL. Bioresour Technol 2006. Bagby MO. Pruszko R. Clements D. Zong M. Optimization of alkali-catalyzed transesteriﬁcation of Pongamia pinnata oil for production of biodiesel.  Pan L. Efﬁcient production of biodiesel from high free fatty acid-containing waste oils using various carbohydrate-derived solid acid catalysts.  Demirbas A. Rand M.70:1–15. Filtered used frying fat powers diesel ﬂeet. Zhu S. Yonemoto T. URL:http://www. Heyes TD.77:553–9. Kommanditgesellschaft Auf Aktien. editor.  Schwab AW. Dunford N. Kates M. Fuel 2008. Bioactive components of commercial and supercritical carbon dioxide processed wheat germ oil.86:557–64. China Academic J 2008:26. 2006.  Rashid U. Oleagineux 1993. Sharp CA.84–86:879–97. Energy Sources Part A: Recovery. Trans Am Soc Agric Eng 1986.com/EP0192035B1.freepatentsonline.60: 1574–9.239:111–5. petrodiesel. Bioresour Technol 2008. Noli A. / Applied Energy 87 (2010) 1083–1095  Winayanuwattikun P. Tantong S. J Am Oil Chem Soc 1983. Lightner RL. Fuel 2005. Transesteriﬁcation of vegetable oils promoted by poly(styrenedivinylbenzene) and poly(divinylbenzene). or menhaden oil. In: The 10th Biennial Bioenergy Conference. Biomass Bioenergy 2008. McLean DD. Boise. J Am Oil Chem Soc 1962. et al. Liu CM. Desalination 2006. Waste Management and Research Center. Cunha Petrus JC.  Upham P. Vittayapadung S. Fuel Process Technol 2005. Erdil A. J Food Eng 2008.  Mittelbach M. Feasibility of edible oil vs. Anwar F. Tesser R. He H. In: Swern D. Duan Z. Graille J.87:883–90.  Adams C. Bailey’s industrial oil and fat products. Fuel 2009. J Am Oil Chem Soc 1982. Barrows FT.20:403–8. Process for the pre-esteriﬁcation of free fatty acids in raw fats and/or oils. Synthesis of biodiesel via homogeneous Lewis acid catalyst.  Zubr J. Wollmann G. Biodiesel production from waste cooking oil: 2.17:S37–45. waste edible oil as biodiesel feedstock. Ioannidou S. Piao X. Catalytic production of high-grade fuel (gasoline) from biomass compounds by shape-delective catalysis. Gonçalves LAG. Jayaraj S. In: Zhuang X.  Van Gerpen J. Knothe G. Appl Energy 2006. Exhaust emissions of biodiesel. 1617 Cole Boulevard. 2002.83:594–605. Karavalakis G. Fuel 2008.29:683–9. Thornley P. New two-step method of producing biodiesel from waster cooking oil. Kara H.  Engler C. Knothe G. In: Zhuang X. Chin LH. A comprehensive analysis of biodiesel impacts on exhaust emissions. Biomass Bioenergy 2003. et al.  Harrington KJ. Karonis D. Yarbrough C.  Verleyen T.  Shibasaki-Kitakawa N.238:309–28. Rodeweld PG.88:1302–6. Dube MA.  Crossley A. Sorenson SC.  Patil PD. Bioresour Technol 2007. Guangzhou. Ahmed I.  Liu KKM.78:553–4.90:229–40.  Chen YC. Ying D. Oil-seed crop: Camelina sativa. Production of biodiesel through optimized alkalinecatalyzed transesteriﬁcation of rapeseed oil. Haag WO.  Sonntag A.32:1279–86. Taylor & Francis Ltd. Luo AX. Schroer B. non-edible oil vs.21:25–31. Rice B. Anastopoulos G.  Demirbas A. Cammarota F.  Bhatti HN. Anwar F. Comparison of GHG emissions from diesel. Huyghebaert A. Golden.  Pioch D. 2002. Investigation of soybean oil as a diesel fuel extender: endurance tests. Dimiccoli M.9:1–17. soybean/corn lecithin.5:353–5.4:45–7. Naik SN. Fukumura T. small scale biodiesel production.  Lou W.  Simone MR. Feasibility report. Effects of processing and chemical characteristics of plant oils on performance of an indirect-injection diesel engine. J Am Oil Chem Soc 1983. Bioresour Technol 1999. Dharmagadda VSS.  Hameed BH.  Mudge SM. Optimization of biodiesel production from edible and nonedible vegetable oils. Henkel. Chemical and physical properties of vegetable oil esters and their effect on diesel fuel performance. Viotto LA. Performance and exhaust emissions of a biodiesel engine. Ryan TW. Honda H. Pumpkin (Cucurbita pepo L. Peukert E. Arcaklioglu E. Zannikos F. Anon M. Campana A.33:44–9.  Zhang Y. Chaitep S. Tian DL. Biomass Bioenergy 2008. Biodiesel production from waste tallow. Shanks B.60:1592–6. In: Center IST. growth performance. Rheological characterization of animal fats and their mixtures with #2 fuel oil. J Am Oil Chem Soc 2000. Deacidiﬁcation of sulfur olive oil.  USEPA.39:9–14. Appl Energy 2009.  Weisz PB.84:335–40.  Peterson C.24: 249–56. United States Patent 5849939. 2008. Tomas M. Production of sunﬂower oil methyl esters by optimized alkali-catalyzed methanolysis. Biodegradability of new engineered fuels compared to conventional petroleum fuels and alternative fuels in current use.200:543–5. Boucher P. Chen GY. Guida A. Degumming of corn oil/hexane miscella using a ceramic membrane.206:57–8. and product quality of rainbow trout (Oncorhynchus mykiss) fed diets containing poultry fat. Cracked soybean oil as fuel for a diesel engine. Tapan NA.  Lopez JM. Goering CE.
Kusdiana D. Glycerol: a promising and abundant carbon source for industrial microbiology. Tu S-T. 2007. Price D.57:515–20. Fuel Process Technol 2009. J Am Oil Chem Soc 1996. Luengnaruemitchai A. Viruthagiri T. Danisman A. PhD dissertation. J Am Oil Chem Soc 1999.100:1983–91. Sala M. Butterﬁeld RO. Appl Catal A: Gen 2007.  Mittelbach M.  NBB. Akintola TA. Cost of biodiesel production. Ultrasound-assisted production of biodiesel fuel from vegetable oils in a small scale circulation process. Jai-In S. dos Santos Jr JR. Department of Mechanical Engineering. Kulkarni MG. Zhuge J. Acceleration of catalytic activity of calcium oxide for biodiesel production. Zhang JC. Agricultural Marketing Policy. Transesteriﬁcation in situ of sunﬂower seed oil. soybean. J Mol Catal B: Enzym 2002. Kaieda M.  EN.  Mittelbach M.  Saka S. de Oliveira Lima JR. Fuel 2008. Noda H. Afr J Biotechnol 2007. Fernandes FAN. Current technologies in biodiesel production. Enzymatic production of biodiesel from canola oil using immobilized lipase. Okitsu K. et al.320: 1–7. Crystallization characteristics and fuel properties of tallow methyl esters. 2005. Fuel 2001. Energy Efﬁciency Conserv Auth 2003.44:1429–36. Master thesis. Use of branched-chain esters to reduce the crystallization temperature of biodiesel.27:30–9. Sakai T. Watanabe Y. Sugihara A. Johnson LA.72:1557–64. Optimal transesteriﬁcation duration for biodiesel production from nigerian palm kernel oil.63:1375–80. Biodiesel production from oils and fats with high free fatty acids. Biodiesel fuel production by transesteriﬁcation of oils. Tesser R. da Silva RB. Process Biochem 2005. Meher LC. J Am Oil Chem Soc 1986. Activity of solid catalysts for biodiesel production: a review. free fatty acids. Hollow ﬁber membrane contactors. Tominaga Y. Cigizoglu KB. Small Scale Biodiesel Production: An Overview. Chaves MH.  Zheng M. Matsumoto T. Koo BCP. Van Gerpen J. Wang MP. D’Arcy-Evans C. Sadanaga Y. Xu YP. Bayramoglu M.72:1155–60. Energy Fuels 1996. Biotechnol Adv 2009. Production of fatty esters.  Bondioli P. Dizge N. Bioresour Technol 2009. Sugumar N. Nelson L. Preparation of biodiesel from soybean oil using supercritical methanol and CO2 as co-solvent. Bioresour Technol 2009. 184. Appl Microbiol Biotechnol 2001. Skala D. Bioresour Technol 2008. Bioresour Technol 2009. Production of biodiesel by a twostep supercritical reaction process with adsorption reﬁning.  Ma F. Biomass Bioenergy 1996. Samukawa T. Yeast whole-cell biocatalyst constructed by intracellular overproduction of Rhizopus oryzae lipase is applicable to biodiesel fuel production. Skelton RL.  Karaosmanoglu F. Biomass Bioenergy 2008. Wang D. and USDA/NCAUR. Bonelli B. Cozzolino M. Wen Z. et al. Pryde EH.                              . Optimization of the production of biodiesel from soybean oil by ultrasound assisted methanolysis. Jovanovic D. URL:http://www.  da Silva GP. J Am Oil Chem Soc 1995.34:1145–50.  Predojevic ZJ. Foglia T.com/2494366. United States: NOPCO CHEM CO. Abrams C. Hong Kong. In: Zhuang X. p.73:1191–5. China.86:2639–44. Food Science And Technology.43:2349–56. 4th Mercosur congress on process systems engineering. Bioresour Technol 2006. Storage stability of biodiesel.86:1097–107. Fang H. Kawashima A. Thanh LT. Ind Eng Chem Prod Res Dev 1985.  Bunyakiat K. Fukuda H. Maeda Y. Azcan N. Ultrason Sonochem 2005. Energy Fuels 2006. Aydiner C. Biodiesel production from sunﬂower.78:573–7. Almeida MF. Degradation of biodiesel under different storage conditions. Cao WL. Lukic I. Nawaz Z. Ting DSK. 2003. D’Ippolito SA. Transesteriﬁcation of jatropha oil using immobilized pseudomonas ﬂuorescens.76:789–93. Clements LD.72:699–702.  Alamu OJ. and water on transesteriﬁcation of beef tallow. Renew Energy 2009. Zhu S. Mao V. Long storage stability of biodiesel made from rapeseed and used frying oil. Tanriseven A. Lanzani A. Tjong J.40: 3148–51.34:762–5. Canakci M.ampc.  Freedman B. Fuel Process Technol 2009. USA: University of Nebraska–Lincoln. Sawangkeaw R. Jekayinfa SO. The effects of catalyst.92:405–16. Alumina/silica supported K2CO3 as a catalyst for biodiesel synthesis from sunﬂower oil. Schumacher J. Reader GT. J Am Oil Chem Soc 1984.12:367–72.  Vera CR. Trans Am Soc Agric Eng 2001. Int J Hydrogen Energy 2008. Kawashima A. related information: work performed by Iowa State University.6:2497–501.  Harrington KJ. Soares dos Santos LS. Fukuda H.33:6657–66.  Cooke BS. Keskinler B. / Applied Energy 87 (2010) 1083–1095 PBD: 1 July 2004.  ASTM. Gangl S. Wan Daud WMA. Fuel Process Technol 2005. Kondo A. Rodrigues S. Contiero J. Fatty acids methyl esters from vegetable oil by means of ultrasonic energy. Wen GD. Honda K. Biodiesel processing and production. Renewable Products Development Laboratory. Leung et al. 2007.87:3572–8.101:639–45. 2006.  Ali Y. Ertekin S. Kondo A. Fuel 2008. Hammond EG. p. Wang J. Zhang Q.  Boocock DGB. Mulenga MC.144:459–65. 2008. 161–73. Size: 110 p. Patrono P. Continuous production of biodiesel via transesteriﬁcation from vegetable oils in supercritical methanol. Dalai AK. Puriﬁcation of biodiesel with adsorbent materials 2005. Cuppett S. Lu XP. and waste cooking oils by transesteriﬁcation using lipase immobilized onto a novel microporous polymer. Di Serio M. Lipase-catalyzed production of biodiesel.  Sprules FJ. In: 2nd Mercosur congress on chemical engineering. Makmee S. the University of Hong Kong.41:1261–4. Pryde EH. Biodiesel from vegetable oils via transesteriﬁcation in supercritical methanol.  Demirbas A. URL: http://www. et al. Xu G. Diesel fuel derived from vegetable oils.32:1274–8. Shimada Y. Konar SK. Fuel 2008. Dizge N.87:3522–8. J Membr Sci 1999. Devanesan MG. Tuter M. Demirbas A. Bioresour Technol 2009. Kaieda M.88:627–31. Lima Neto AF. Bandow H. 2004.99:6793–8.  Wang Z. Alvim-Ferraz MCM.61: 1638–43.pdf.100:696–700. J Am Oil Chem Soc 2001. 1950. Vinatoru M.80:225–31.html. Krstic J. Chem Eng J 2008. Fuel properties of tallow and soybean oil esters. Energy Convers Manage 2002.10:890–5. Glycerol production by microbial fermentation: a review. Xu ZS. Intarapong P. Santos FFP. USA: National Biodiesel Board. Dahlquist E. Noiroj K. Parera JM. Alkali catalyzed transesteriﬁcation of cottonseed oil by microwave irradiation. Prior BA.  Berrios M. Veronese S. Guo X. Gasparoli A. J Am Oil Chem Soc 2006. Marmer W. J Am Oil Chem Soc 1995. 2008. Sugihara A. Watanabe Y. Zabeti M. Tian ZJ.17:133–42. Keskinler B.  Lee I. Takenaka N. Hanna MA.100:4690–6.19:201–23.  Duncan J. Fuel 2007.Y. Ngamprasertsith S.  Whittington T.  Leung DYC. J Am Oil Chem Soc 1995. Stavarache C. Fast one-phase oil-rich processes for the preparation of vegetable oil methyl esters.97:250–6.159:61–106. The production of biodiesel from waste frying oils: a comparison of different puriﬁcation steps. Trans Am Soc Agric Eng 1998.11: 43–50. Solid acid catalyzed biodiesel production by simultaneous esteriﬁcation and transesteriﬁcation. Green Chem 2006. Nishimura R. Matsubara K.  Freedman B.24:314–8. Sidi H. editor. Biotechnol Adv 2001. Rajendran K.100:3268–76. Shimada Y.90:770–7. Pieck CL. 1994. Enzymatic alcoholysis for biodiesel fuel production and application of the reaction to oil processing.8:1056–62.  Zhang D. Imer DY. Investigation of the reﬁning step of biodiesel production.C.83:457–60. Biodiesel production via acid catalysis. Alkaline-catalyzed production of biodiesel fuel from virgin canola oil and recycled waste oils. Shu Q.  Han HW. Ban K.90:312–6. Van Gerpen J. ASTM D6751-biodiesel blend stock speciﬁcation (B100).montana. Dias JM.56:7–11. Hanna M. Fuel fact sheets. Yan J. Synthesis of biodiesel from cottonseed oil and methanol using a carbon-based solid acid catalyst. Comparison of puriﬁcation methods for biodiesel.90:1002–8.42:1203–10. Matsumoto T.  Canakci M. Trans Am Soc Agric Eng 1999. Comparison of membrane extraction with traditional extraction methods for biodiesel production.  Gabelman A. Catalysts of Cu(II) and Co(II) ions adsorbed in chitosan used in transesteriﬁcation of soy bean and babassu oils – A new route for biodiesel syntheses. Agric Eng Int: CIGR Ejournal 2007. International conference on biomass energy technologies. Pinzari F. Noda H. J Biosci Bioeng 2001. Comparison of the performance of different homogeneous alkali catalysts during transesteriﬁcation of waste and virgin oils and evaluation of biodiesel quality. Gopinath R. Hwang S. Fuel Process Technol 2009. Transesteriﬁcation kinetics of soybean oil. Takahashi S.  Guo Y. Yang L. Guo Y. Koshikawa T. Guangzhou.20:812–7. Biodiesel production and use by farmers: is it worth considering? Western Australia: Department of Agriculture and Food. Maeda Y.freepatentsonline. Biodiesel production process optimization and characterization to assess the suitability of the product for varied environmental conditions.edu/policypaper/ policy22. Bioresour Technol 1996.87:714–22. Mack M. VI: speciﬁcations and quality control of biodiesel. Mounts TL. Qian WW.  Eevera T. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol. Bertram B. Economic assessment of batch biodiesel production processes using homogeneous and heterogeneous alkali catalysts. The EN 14214 standard-speciﬁcations and test methods. Production of hydrogen by aqueousphase reforming of glycerol. A comparative study of KOH/Al2O3 and KOH/NaY catalysts for biodiesel production via transesteriﬁcation from palm oil. et al. Shimada Y. Yu X. IX. Preparation of biodiesel catalyzed by KF/CaO with ultrasonic. Fedeli E. 2005. J Biosci Bioeng 1999. Aroua MK. Bioresour Technol 2009. Biodiesel production and quality. Bioresour Technol 2009. In: Biodiesel. Vanadyl phosphate catalysts in biodiesel production. Samukawa T.  Gerpen JV. Variables affecting the yields of fatty esters from transesteriﬁed vegetable oils. Renew Energy 2009.100: 3054–60. Saradha S. Biodiesel fuel production from plant oil catalyzed by Rhizopus oryzae lipase in a water-containing system without an organic solvent.1094 D. Intensiﬁcation of biodiesel synthesis using zigzag micro-channel reactors. Biodiesel engine performance and emissions in low temperature combustion. Conversion of vegetable oil to biodiesel using immobilized Candida antarctica lipase. Ma HJ.  He H. Waheed MA.
/ Applied Energy 87 (2010) 1083–1095  Haas M. In situ alkaline transesteriﬁcation: an effective method for the production of fatty acid esters from vegetable oils. French T.C. Bioresour Technol 2009.100:1203–10. Yun Z. Liu S.81:83–9. 1095  Qian JF. Scott K.Y. Toghiani H. Transesteriﬁcation of sunﬂower oil in situ. Scott K. In situ alkaline transesteriﬁcation of cottonseed oil for production of biodiesel and nontoxic cottonseed meal. Foglia T.99:9009–12. Moisture removal substantially improves the efﬁciency of in situ biodiesel production from soybeans.D. Liang K. Tomasevic A.77:1389–91. Wang F. Fuel 1998.84: 197–204.  Siler-Marinkovic S. Leung et al. Marmer W. Hernandez R.  Haas M.  Mondala A. . Biodiesel production by in situ transesteriﬁcation of municipal primary and secondary sludges. J Am Oil Chem Soc 2007. Bioresour Technol 2008. J Am Oil Chem Soc 2004.
This action might not be possible to undo. Are you sure you want to continue?
We've moved you to where you read on your other device.
Get the full title to continue reading from where you left off, or restart the preview.