Applied Energy 87 (2010) 10831095

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

A review on biodiesel production using catalyzed transesterication

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 transesterication, especially alkali-catalyzed transesterication. 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 saponication reaction. This paper reviews the different approaches of reducing free fatty acids in the raw oil and renement 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 purication 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 transesterication of oils in the oilseeds. This process, however, cannot handle waste cooking oils and animal fats. 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 transesterication Feedstock Purication 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

3.

* Corresponding author. Tel.: +00 852 2859 7911; fax: +00 852 2858 5415. E-mail address: ycleung@hku.hk (D.Y.C. Leung). 0306-2619/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.apenergy.2009.10.006

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3.2. Supercritical alcohol process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3. In situ biodiesel process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1091 1091 1092 1092 1092

1. Introduction Due to the depletion of the worlds petroleum reserves and the increasing environmental concerns, there is a great demand for alternative sources of petroleum-based fuel, including diesel and gasoline fuels. Biodiesel, a clean renewable fuel, 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 modication [1]. Chemically, biodiesel is a mixture of methyl esters with long-chain fatty acids and is typically made from nontoxic, biological resources such as vegetable oils [224], animal fats [16,17,23,24], or even used cooking oils (UFO) [10]. Table 1 shows some feedstocks of biodiesel and their physicochemical properties. Vegetable oils are promising feedstocks for biodiesel production since they are renewable in nature, and can be produced on a large scale and environmentally friendly [25]. Vegetable oils include edible and non-edible oils. 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 [26]. However, it may cause some problems such as the competition with the edible oil market, which increases both the cost of edible oils and biodiesel [11]. Moreover, it will cause deforestation in some countries because more and more forests have been felled for plantation purposes. In order to overcome these disadvantages, 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. Furthermore, 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 [12,26]. However, most non-edible oils contain high free fatty acids. Thus they may require multiple chemical steps or alternate approaches to produce biodiesel, which will increase the production cost, and may lower the ester yield of biodiesel below the standards [14,25,27]. Animal fats contain higher saturated fatty acids and normally exist in solid form at room temperature that may cause problems in the production process. Its cost is also higher than vegetable oils [18]. UFO is not suitable for human consumption but is a feedstock for biodiesel production. Its usage signicantly reduces the cost of biodiesel production. However, 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, such as water, free fatty acids [18,26,28,29]. Since the cost of raw materials accounts about 6080% of the total cost of biodiesel production, choosing a right feedstock is very important [18,26]. Also, the yield and properties of biodiesel products produced from different feedstocks would be quite different from each other. Table 2 shows some physicochemical properties of biodiesel from different feedstocks and their yields under different production conditions [7,9,11,14,16,18,20,22,2528,3038]. Although at present biodiesel

Table 1 Feedstocks for biodiesel production and their physicochemical properties. Type of oil Species Main chemical composition (fatty acid composition wt.%) C16:0, C16:0, C16:0, C16:0, C16:0, C22:0 C16:0, C16:0, C18:3, C16:0, C16:0, C16:0, C16:0, C18:1, C18:0, C18:0, C18:0, C18:0, C18:0, C18:0, C20:0, C18:0, C18:0, C18:0, C16:1, C18:2 C18:1, C18:1, C18:1, C18:1, C18:1, C18:1, C20:1, C18:1, C18:1, C18:1, C18:0, Density (g/cm3) 0.91 0.91 0.92 0.92 0.90 0.91 0.91 Flash point (C) 254 246 274 267 271 277 Kinematic viscosity (cst, at 40 C) 32.9 35.1 32.6 39.6a 22.72 34.9a 38.2 18.2 35.6 29.4 Acid value (mg KOH/g) 0.2 2.92 0.1 3 0.76 0.4 0.55 28 39.5 39 38.5 Heating value (MJ/kg) 39.6 39.7 39.6 39.8 39.5 42.2 References

Vegetable oil Edible oil Soybean Rapessed Sunower 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, C20:0, C18:2, C18:3 C18:2 C20:3 C18:2, C18:3 C18:2 C18:2 C18:1, C18:2

[6,15,18,19] [3,8,15,18] [15,18,20] [2,11,18] [9,13,18,20] [17,18] [5,21] [8,10] [17,18] [22] [4,7,12]

Nonedible oil

0.91 0.92 0.92

234 >230 225

C16:0, C18:0, C18:1, C18:2, C18:3 C16:0, C18:0, C18:1, C18:2 C16:0, C18:0, C18:1, C18:2 C14:0, C16:0, C16:1, C17:0, C18:0, C18:1, C18:2 C16:0, C18:1, C20:5, C22:6, other acids C16:0, C16:1, C18:0, C18:1, C18:2, C18:3 Depends on fresh cooking oil

0.91 0.92 0.90 0.92 0.91 0.90 0.90

205 221

27.8 29.6 72.0 32.1b 44.7

5.06 0.24 44 2.81 2.5

34 40.86 39.25 40.05 39.4

[14] [11] [14] [17,23] [16] [23,24] [10]

Used cooking oil

Kinematic viscosity at 38 C, mm2/s. Kinematic viscosity at 37 C, mm2/s.

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cannot entirely replace petroleum-based diesel fuel, there are several distinct advantages of biodiesel over diesel fuel. Biodiesel has higher combustion efciency, cetane number than diesel fuel [39]. It is biodegradable and more than 90% biodiesel can be biodegraded within 21 days [40,41]. Biodiesel has lower sulfur and aromatic content than diesel fuel and that means it will not emit lots of toxic gas [42,43]. Moreover, it reduces most exhaust emissions except NOx, such as monoxide, unburned hydrocarbons, and particulate matter [4448]. A number of methods are currently available and have been adopted for the production of biodiesel fuel. There are four primary ways to produce biodiesel (Table 3): direct use and blending of raw oils [4953], micro-emulsions [54], thermal cracking [5560], and transesterication [61]. The most commonly used method for converting oils to biodiesel is through the transesterication of animal fats or vegetable oils, which forms the basis of the present paper. The objective of this paper is to give an overview on the technological advancement of producing biodiesel through transesterication. The main factors affecting the yield of biodiesel and other types of transesterication will also be discussed. 2. Biodiesel production with catalyzed transesterication 2.1. Basic chemical reactions Common vegetable oils or animal fats are esters of saturated and unsaturated monocarboxylic acids with the trihydric alcohol glyceride. These esters are called triglycerides, which can react with alcohol in the presence of a catalyst, a process known as

transesterication. The simplied 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

1
where R1, R2, R3 are long-chain hydrocarbons, sometimes called fatty acid chains. Normally, there are ve main types of chains in vegetable oils and animal oils: palmitic, stearic, oleic, linoleic, and linolenic. When the triglyceride is converted stepwise to diglyceride, monoglyceride, and nally to glycerol, 1 mol of fatty ester is liberated at each step [61]. Usually, methanol is the preferred alcohol for producing biodiesel because of its low cost. Vegetable oils and fats may contain small amounts of water and free fatty acids (FFA). For an alkali-catalyzed transesterication, the alkali catalyst that is used will react with the FFA to form soap. Eq. (2) shows the saponication reaction of the catalyst (sodium hydroxide) and the FFA, forming soap and water.

R1 COOH
FFA

sodium hydroxide

NaOH

! R1 COONa H2 O
soap water

This reaction is undesirable because the soap lowers the yield of the biodiesel and inhibits the separation of the esters from the glycerol. In addition, 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. Feedstock Kinematic viscosity (cst, at 40 C) 4.08 4.35.83 4.9 4.42 4.42 3.39 6.127a 3.53 4.07 4.41 4.78 4.8 3.99 Density Saponication Iodine Acid Cetane Heating (g/cm3) number value value number value (mg KOH/ (MJ/kg) g) 0.885 0.88 0.888 0.88 0.86 0.9 0.883 0.88 0.89 0.882 0.888 0.88 0.9 0.875 0.8837 0.8636 0.883 0.869 201 200 207 200 202 182 204 202 202 138.7 142.7 60.07 67.45 120.3 152 157 103.8 104.7 115 108.4 0.15 52 40 45 45.3 34 40.1 45 45 45 38 4042 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.%)

Yield (%)

References

Soybean Rapeseed Sunower Palm Peanut Corn Camelina Canola Cotton Pumpkin Jatropha curcas Pongamina pinnata Sea mango Palanga

0.250.45 4950 0.24 0.08 49 62 54 5859

CaO|8 (2.03% H2O in methanol) KOH|1 NaOH|1 KF/ZnO|5.52 NaOH|0.5 KOH|2 KOH|1.5 KOH|1 NaOH|0.75 NaOH|1 NaOH|1 KOH|1 Sulfated zirconiz alumina|6 C6H5CH3 + H3PO4|5 + 5, H2SO4|6.5; KOH|9 (three step) H2SO4|2.5 KOH|2 (ultrasound) H2SO4|1.25 NaOH|1.1

>95

[18,20,27,33,35]

95 [36] 96 97.1 [20,38] 89.23 [18,20,32] 89 85 96 97.9 80 95 96.9 97.5 98 97 98 83.8 85 [9,18,20] [20,25] [31] [20,25] [20,37] [20,22] [7,20,25] [14,2526,34] [11] [14]

0.080.52 0.16 0.48 0.496 0.62 56 54 6163 6061

Tallow Nile tilapia Poultry Used cooking oil

1 a b

0.856 0.867

244.5 251.23

126 88.1 130

0.65 1.4 0.25 0.15

59 51 61

60 30 50 60

1440 90 1440 20

1:30 1:9 1:30 1:7

98.28 98.2 99.72 94.6

[30] [16] [30] [28]

T = reaction temperature (C); P = transesterication reaction period (min); M = molecular ratio of oil/methanol; C = amount of catalyst (wt.%). Kinematic viscosity at 20 C. Volumetric ratio of oil/methanol.

1086 Table 3 Different methods of biodiesel production. Methods Direct use and blending Denition

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Advantage Liquid nature-portability Heat content ($80% of diesel fuel) Readily available; 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; thickening and gelling of the lubricating oil Irregular injector needle sticking; incomplete combustion Heavy carbon deposits; increase lubrication oil viscosity

References [913]

Direct use as diesel fuel or blend with diesel fuel

Micro-emulsions

Thermal cracking (pyrolysis) Transesterication

A colloidal equilibrium dispersion of optically isotropic uid microstructures with dimensions generally in the 1150 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

[14,21]

Lower energy content

Chemically similar to petroleumderived gasoline and diesel fuel Renewability; higher cetane number; lower emissions; higher combustion efciency

Energy intensive and hence higher cost Disposal of byproduct (glycerol and waste water)

[1520]

[2123]

cost [62]. Water, originated either from the oils and fats or formed during the saponication reaction, retards the transesterication reaction through the hydrolysis reaction. It can hydrolyze the triglycerides to diglycerides and forms more FFA. The typical hydrolysis reaction is shown in Eq. (3).
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, free fatty acids, water, and other contaminants in various proportions. Some crude vegetable oils contain phospholipids that need to be removed in a degumming step. Phospholipids can produce lecithin, a commercial emulsier [65]. Liu et al. compared the different degumming methods, such as membrane ltration, hydration, acid micelles degumming, supercritical extraction, etc. The characteristics of the raw oils should be investigated before choosing the suitable degumming method because different degumming methods have their advantages and disadvantages [66]. The oil can be separated through membrane ltration according to the average molecular weight or the particle size of phospholipids. Although degumming method can solve the problem,

3
However, the FFA can react with alcohol to form ester (biodiesel) by an acid-catalyzed esterication reaction. This reaction is very useful for handling oils or fats with high FFA, as shown in the equation below:

Oils or Fats FFA _ 2.5wt% Catalyst Mixing Alcohol Neutralized oil Pretreatment > FFA>2.5wt%

R1 COOH ROH ! ROCOR1 H2 O

FFA alcohol fatty acid ester water

Normally, the catalyst for this reaction is concentrated sulphuric acid. Due to the slow reaction rate and the high methanol to oil molar ratio that is required, acid-catalyzed esterication has not gained as much attention as the alkali-catalyzed transesterication [63]. 2.2. Biodiesel production processes

Transesterification

Phase separation
2.2.1. Process ow chart Today, most of the biodiesel is produced by the alkali-catalyzed process. Fig. 1 shows a simplied ow chart of the alkali-catalyst process. As described earlier, feedstocks with high free fatty acid will react undesirably with the alkali catalyst thereby forming soap. The maximum amount of free fatty acids acceptable in an alkali-catalyzed system is below 2.5 wt.% FFA. If the oil or fat feedstock has a FFA content over 2.5 wt.%, a pretreatment step is necessary before the transesterication process [64] (see Section 2.2.3). 2.2.2. Raw materials treatment The raw materials, which can be vegetable oils, animal fats, or recycled greases, used in the production of biodiesel contain tri-

Re-neutralization Crude Biodiesel

Alcohol Recovery

Purification

Crude Glycerol

Quality Control

Biodiesel
Fig. 1. Simplied process ow chart of alkali-catalyzed biodiesel production.

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its process involves two steps with the use of an organic solvent. Therefore, this method has no superiority on cost because of its complicated processing [67,68]. In the hydration process, because of phospholipids hydrophilicity, hot water can be added into the oil with stirring. The phospholipids solubility will be signicantly reduced, so it could be separated from the oil by natural settlement. The hydration method features a simple process, easy operation, and high yields rening, but non-hydratable phospholipids cannot be removed by this method, as reported by Verleyen et al. [69]. For removing non-hydratable phospholipids, critic acid or phosphoric acid can be added into the oil which is heated to 70 C, this is called the special micelles degumming method. Pan et al. [70] found that the reaction time for this method is about 5 min, followed by neutralization through dilute lye. The supercritical extraction method is employed to separate the phospholipids. Moreover, by rening with supercritical CO2 extraction, it can effectively remove the free fatty acids and the peroxidation products that are in the crude oil. However, the high pressure required in this process will be the biggest challenge in its industrial application [71,72]. The free fatty acids are removed in a rening step and excess free fatty acids can be removed as soaps in a later pretreatment step. In addition, deodorization is another important step in the raw material treatment. During this step, steam, at 16 mm Hg pressure, is injected into the oil at 490550 K in order to eliminate free fatty acids, aldehydes, unsaturated hydrocarbons, and ketones, all of which cause undesirable odors and avors in the oil [73]. Next, in order to determine the percentage of FFA in the oils or fats, titration is performed. As described above, if the percentage of FFA is over 2.5 wt.%, pretreatment is necessary to reduce the content of FFA. This step also determines the amount of caustic soda required in the neutralization step. 2.2.3. Pretreatment of acidic feedstocks Many pretreatment methods have been proposed for reducing the high free fatty acid content of the oils, including steam distillation [74], extraction by alcohol [75], and esterication by acidcatalysis [76]. However, steam distillation for reducing high free fatty acids requires a high temperature and has low efciency. Because of the limited solubility of free fatty acids in alcohol, extraction by alcohol method needs a large amount of solvent and the process is complicated. Compared with the two former methods, esterication by acid-catalysis makes the best use of the free fatty acids in the oil and transforms it into biodiesel [75,77]. The common pretreatment is esterication of the FFA with methanol in the presence of acidic catalysts (usually sulphuric acid). The catalysts can be homogeneous acid-catalysts or solid acid-catalysts [78]. Compared with the former one, solid acid-catalysts offer some advantages for eliminating separation, corrosion, toxicity, and environmental problems, but the reaction rate is slower [76]. As described earlier, free fatty acids will be converted to biodiesel by direct acid esterication and the water needs to be removed. If the acid value of the oils or fats is very high, one-step esterication pretreatment may not reduce the FFA efciently because of the high content of water produced during the reaction. In this case, a mixture of alcohol and sulphuric acid can be added into the oils or fats three times (three-step pre-esterication). 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 esterication again [79]. Moreover, some researchers reduce the percent of FFA by using acidic ion exchange resins in a packed bed. Strong commercial acidic ion exchange resins can be used for the esterication of FFA in waste cooking oils but the loss of the catalytic activity maybe a problem [8084]. An alternative approach to reduce the FFA is to use iodine as a catalyst to convert free fatty acids into biodiesel. An obvious

advantage of this approach is that the catalyst (iodine) can be recycled after the esterication reaction. Li et al. [85] found through orthogonal tests, under the optimal conditions (i.e. iodine amount: 1.3 wt.% of oils; reaction temperature: 80 C; ratio of methanol to oils: 1.75:1; reaction time: 3 h) that the FFA content can be reduced to <2% [85]. Another new method of pretreatment is to add glycerol into the acidic feedstock and heat it to a high temperature of about 200 C, normally with a catalyst such as zinc chloride. The glycerol will react with the FFA to form monoglycerides and diglycerides. Then the FFA level will become low and biodiesel can be produced using the traditional alkali-catalyzed transesterication method. 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, the drawbacks of this method are its high temperature requirement and relatively slow reaction rate [86]. 2.2.4. Catalyst and alcohol In general, there are three categories of catalysts used for biodiesel production: alkalis, acids, and enzymes [8789]. Enzyme catalysts have become more attractive recently since it can avoid soap formation and the purication process is simple to accomplish. However, they are less often used commercially because of the longer reaction times and higher cost. To reduce the cost, some researchers developed new biocatalysts in recent years. An example is so called whole cell biocatalysts which are immobilized within biomass support particles. An advantage is that no purication is necessary for using these biocatalysts [9093]. Compare with enzyme catalysts, the alkali and acid catalysts are more commonly used in biodiesel production [61]. The alkali and acid catalysts include homogeneous and heterogeneous catalysts. Due to the low cost of raw materials, sodium hydroxide and potassium hydroxide are usually used as alkali homogeneous catalysts and alkali-catalyzed transesterication is most commonly used commercially [36,38,9499]. These materials are the most economic because the alkali-catalyzed transesterication process is carried out under a low temperature and pressure environment, and the conversion rate is high with no intermediate steps. However, the alkali homogeneous catalysts are highly hygroscopic and absorb water from air during storage. They also form water when dissolved in the alcohol reactant and affect the yield [28]. Therefore, they should be properly handled. On the other hand, some heterogeneous catalysts are solid and it could be rapidly separated from the product by ltration, which reduces the washing requirement. In addition, solid heterogeneous catalysts can stimulatingly catalyze the transesterication and esterication reaction that can avoid the pre-esterication step, thus these catalysts are particularly useful for those feedstocks with high free fatty acid content [100]. However, using a solid catalyst, the reaction proceeds at a slower rate because the reaction mixture constitutes a three-phase system, which, due to diffusion reasons, inhibits the reaction [33,101]. Table 4 classies the three categories of catalysts with their advantages and disadvantages [27,33,82,102109]. The alcohol materials that can be used in the transesterication process include methanol, ethanol, propanol, butanol, and amyl alcohol. Among these alcohols, methanol and ethanol are used most frequently. Methanol is especially used because of its lower cost and its physical and chemical advantages. Ma and Hanna [61] reported that methanol can react with triglycerides quickly and the alkali catalyst is easily dissolved in it. However, due to its low boiling point, there is a large explosion risk associated with methanol vapors which are colorless and odorless. Both methanol and methoxide are extremely hazardous materials that should be handled carefully. It should be ensured that one is not exposed to these chemicals during biodiesel production.

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Table 4 Advantages and disadvantages at different types of catalysts used in the biodiesel production. Type Alkali Homogeneous Example NaOH, KOH Advantages High catalytic activity, low cost, favorable kinetics, modest operation conditions Noncorrosive, environmentally benign, recyclable, fewer disposal problems, easily separation, higher selectivity, longer catalyst lifetimes Disadvantages Low FFA requirement, anhydrous conditions, saponication, emulsion formation, more wastewater from purication, disposable Low FFA requirement, anhydrous conditions, more wastewater from purication, high molar ratio of alcohol to oil requirement, high reaction temperature and pressure, diffusion limitations, high cost Equipment corrosion, more waste from neutralization, difcult to recycle, higher reaction temperature, long reaction times, weak catalytic activity Low acid site concentrations, low microporosity, diffusion limitations, high cost References [97,101104]

Heterogeneous

CaO, CaTiO3, CaZrO3, CaOCeO2, CaMnO3, Ca2Fe2O5, KOH/Al2O3, KOH/NaY, Al2O3/KI, ETS-10 zeolite, alumina/silica supported K2CO3

[33,99 101,103,104]

Acid Homogeneous

Concentrated sulphuric acid

Catalyze esterication and transesterication simultaneously, avoid soap formation Catalyze esterication and transesterication simultaneously, recyclable, eco-friendly

[97,102,103]

Heterogeneous

Enzymes

ZnO/I2, ZrO2 =SO2 , TiO2 =SO2 , carbon-based 4 4 solid acid catalyst, carbohydrate-derived catalyst, Vanadyl phosphate, niobic acid, sulphated zirconia, Amberlyst-15, NaonNR50 Candida antarctica fraction B lipase, Rhizomucor mieher lipase

[82,98,103,104]

Avoid soap formation, nonpolluting, easier purication

Expensive, denaturation

[27,82,104]

2.2.5. Mixing and neutralization The purpose of mixing methanol with the catalyst is to produce methoxide which reacts with the base oils. Most of the catalysts (e.g. NaOH, KOH) are in solid form and do not readily dissolve into methanol, it is best to start agitating the methanol in a mixer and add the catalyst slowly and carefully [64]. Once the catalyst completely dissolves in the methanol, the methoxide is ready to be added to the oil. Once the methoxide is added into the oil, a neutralization reaction will immediately start. Some alkali catalysts will react with rudimental acids during the pretreatment step or will react with the free fatty acids from the oil. Therefore, more catalyst needs to be added to complete the reaction. 2.2.6. Transesterication and separation When the catalyst, alcohol, and oil are mixed and agitated in a reaction vessel, a transesterication reaction will start. A stirred reactor is usually used as the reaction vessel for continuous alkali-catalyzed biodiesel production. Recently, there is an increased interest in new technologies related to mass transfer enhancement. Maeda et al. [110] and Thanh et al. [111] produced biodiesel from vegetable oils assisted by ultrasound which is a useful tool for strengthening the mass transfer of immiscible liquids. Ultrasonic irradiation causes cavitation of bubbles near the phase boundary between immiscible liquid phases. The asymmetric collapse of the cavitation bubbles disrupts the phase boundary and starts emulsication instantly. Micro jets, formed by impinging one liquid to another, lead to intensive mixing of the system near the phase boundary. 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 [110112]. Moreover, Wen et al. [113] 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. Leung and Guo [28] 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. During this step, in order to speed up the reaction, mixing brings the oil, the catalyst, and the alcohol into intimate contact while the temperature is kept just below the boiling point of the alcohol (i.e. 64.5 C for methanol). Normally, the reaction pressure is close to the atmospheric pressure to prevent the loss

of alcohol, and excess alcohol is used to ensure total conversion of the oil to its esters. As previously mentioned, if the free fatty acid level or water level is too high, it may cause problems downstream with the saponication and the separation of the glycerol by-product. Therefore, the amount of water and free fatty acids in the feedstock oil should be monitored during the reaction. Once the transesterication reaction is completed, two major products exist: esters (biodiesel) and glycerol. The glycerol phase is much denser than the biodiesel phase and settles at the bottom of the reaction vessel, allowing it to be separated from the biodiesel phase. Phase separation can be observed within 10 min and can be completed within several hours of settling. The reaction mixture is allowed to settle in the reaction vessel in order to allow the initial separation of biodiesel and glycerol, or the mixture is pumped into a settling vessel. In some cases, a centrifuge may be used to separate the two phases [86]. Both the biodiesel and glycerol are contaminated with an unreacted catalyst, alcohol, and oil during the transesterication step. Soap that may be generated during the process also contaminates the biodiesel and glycerol phase. Schumacher [114] suggested that although the glycerol phase tends to contain a higher percentage of contaminants than the biodiesel, a signicant amount of contaminants is also present in the biodiesel. Therefore, crude biodiesel needs to be puried before use. 2.2.7. Rening crude glycerol Although biodiesel is the desired product from the reactions, the rening of glycerol is also important due to its numerous applications in different industrial products such as moisturizers, soaps, cosmetics, medicines, and other glycerol products [115117]. It is one of the few products that has a good reactivity on sump oil, and is extremely effective for washing shearing shed oor, so it can be used as a heavy duty detergent and degreaser. Whittington [118] reported that glycerol can even be fermented to produce ethanol, which means more biofuel can be produced. According to the statements of Van Gerpen et al. [86], typically produced glycerol is about 50% glycerol or less in composition and mainly contains water, salts, unreacted alcohol, and unused catalyst. The unused alkali catalyst is usually neutralized by an acid. In some cases, 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, the latter can be

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recovered for use as a fertilizer [119]. Generally, water and alcohol are removed to produce 8088% pure glycerol that can be sold as crude glycerol. In more sophisticated operations, the glycerol is distilled to 99% or higher purity and sold in different markets [120]. After the re-neutralization step, the alcohol in the glycerol phase can be removed through a vacuum ash process or by other types of evaporators. Usually, the alcohol vapor is condensed back into liquid and reused in the process. However, the alcohol may contain water that should be removed in a distillation column before the alcohol is returned to the process. The alcohol recovery step is more difcult when the alcohol that is used, such as ethanol or isopropanol, forms an azeotrope with the water. Gerpen [121] proposed the use of a molecular sieve to remove the water generated. 2.2.8. Purication of crude biodiesel After separation from the glycerol phase, crude biodiesel is mainly contaminated with residual catalyst, water, unreacted alcohol, free glycerol, and soaps that were generated during the transesterication reaction [114]. Normally, crude biodiesel enters a neutralization step and then passes through an alcohol stripper before the washing step. In some cases, acid is added to crude biodiesel to neutralize any remaining catalyst and to split any soap. Soaps react with the acid to form water soluble salts and free fatty acids. Gerpen [121] 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. Unreacted alcohol should be removed with distillation equipment before the washing step to prevent excess alcohol from entering the wastewater efuent [86]. The primary purpose of this step is to wash out the remnants of the catalyst, soaps, salts, residual alcohol, and free glycerol from the crude biodiesel. Generally, three main approaches are adopted for purifying biodiesel: water washing, dry washing [122], and membrane extraction [123,124]. These approaches are briey shown in Table 5 and discussed in detail as follows. 2.2.8.1. Water washing. Since both glycerol and alcohol are highly soluble in water, water washing is very effective for removing both contaminants. It also can remove any residual sodium salts and soaps. The primary material for water washing is distilled warm water or softened water (slightly acidic) [72,73]. Warm water prevents the precipitation of saturated fatty acid esters and retards the formation of emulsions with the use of a gentle washing action. Softened water (slightly acidic) eliminates calcium and magnesium

contamination and neutralizes any remaining alkali catalysts [86]. After washing several times, the water phase becomes clear, meaning that the contaminants have been completely removed. Then, the biodiesel and water phases are separated by a separation funnel or centrifuge [125]. Moreover, because of the immiscibility of water and biodiesel, molecular sieves and silica gels, etc., can also be used to remove water from the biodiesel [86]. The remaining water can be removed from the biodiesel by passing the product over heated Na2SO4 (25 wt.% of the amount of the ester product) overnight and then be removed by ltration [126]. However, there are many disadvantages to this method, including an increased cost and production time, polluting liquid efuent, product loss, etc. Moreover, emulsions can form when washing the biodiesel made from waste cooking oils or acidic feedstocks because of the soap formation [127]. 2.2.8.2. Dry washing. Cooke et al. [122] used dry washing by replacing the water with an ion exchange resin or a magnesium silicate powder in order to remove impurities. These two dry washing methods can bring the free glycerol level down and is reasonably effective for removing soaps. Both the ion exchange process and the magnesol process have the advantage of being waterless and thus eliminate many of the problems outlined above. Although the magnesol process has a better effect on the removal of methanol than the ion resins, none of the products from this process fulll the limits specied in the EN Standard [128,129]. 2.2.8.3. Membrane extraction. Gabelman and Hwang [123] proved that the contaminants can be removed by using a hollow ber membrane extraction, such as polysulfone. In this method, a hollow ber membrane (1 m long, 1 mm diameter) lled with distilled water is immersed into the reactor (20 C). The crude biodiesel is pumped into the hollow ber membrane (ow rate: 0.5 ml/min; operating pressure: 0.1 MPa). Following this step, biodiesel is passed over heated Na2SO4 and then ltered to remove any remaining water [124]. This approach effectively avoids emulsication during the washing step and decreases the loss during the rening process. The purity of the biodiesel obtained is about 90% and the other properties conform to the ASTM standards [130]. It is a very promising method for purifying biodiesel. 2.2.9. Quality control For commercial fuel, the nished biodiesel must be analyzed using sophisticated analytical equipment to ensure it meets inter-

Table 5 Different approaches for purifying crude biodiesel. 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, centrifuge, molecular sieves, silica gels, etc.

Very effective in removing contaminants

Increased cost and production time, liquid efuent, product loss, emulsions formation

[46,7274]

Waterless

Overruns the limit in the EN Standard

[69,75,76]

Membrane extraction

Remove the contaminants

Avoids the emulsion formation and decreases the rening loss

Probably high cost and low throughput due to contaminants existed

[70,71]

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national standards. A few specications have been set but the ASTM D 6751 and EN 14214 standards are the most commonly used standards. Even in blends with conventional diesel fuel, Mittelbach [131] stated that most people in the industry expect the biodiesel blending stock to meet the relevant standard before being blended. Some properties in the standard, such as the cetane number or density, can reect the properties of the chemical compounds that make up the biodiesel, and other properties provide an indication of the quality of the production process [54]. Generally, biodiesel standards identify the parameters that pure biodiesel must meet before being used as a pure fuel or being blended with distillate fuels [120,129,130]. To ensure safe operation in diesel engines, the most important aspects of the biodiesel product are the completion of the reaction, the removal of the free glycerol, residual catalyst and alcohol, and the absence of free fatty acids [39,41,42,132]. As mentioned before, if the transesterication reaction is not complete then triglycerides, diglycerides, or monoglycerides may be left in the nal product. Chemically, each of these compounds contains a glycerol molecule. Fuel with excessive free glycerol may plug the fuel lters and cause combustion problems in the diesel engine. Therefore, the ASTM standard requires the total glycerol to be <0.24% of the nal biodiesel product [54,130]. On the other hand, since residual methanol, even as little as 1%, can lower the ashpoint of the nal biodiesel product from 170 C to <40 C, the EN 14214 standard limits the amount of alcohol to a very low level [86,129]. Finally, although a specic value for the residual catalyst is not included in the ASTM standard, it is limited by the specication on levels of sulfated ash, which may lead to engine deposits and high abrasive wear levels [42,130]. Because the European specication for sulfur content (i.e. EN 14214) is much tighter than the US requirement, Ali et al. [133] reported that a number of producers in Europe are resorting to the

use of vacuum distillation for the removal of sulfur compounds from the nal biodiesel product. In addition, some vegetable oils, yellow greases, and brown greases leave an objectionable color in the biodiesel. Although there is no color specication in the ASTM standard, in some cases, an activated carbon bed, which is an effective method for the removal of excessive color, is used to produce a colorless biodiesel [120]. 2.3. 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. There are several key factors that need to be considered for the storage of biodiesel, including exposure temperature, oxidative stability, fuel solvency, and material compatibility [40,134]. Lee et al. [135] 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 lters. For this reason, the storage temperature of most pure biodiesel is generally kept between 7 and 10 C. Even in extremely cold climates, underground storage of pure biodiesel usually provides the storage temperature necessary for preventing crystal formation [86]. Bondioli et al. [136] noted that the stability of biodiesel is an important property when it is to be stored for a prolonged period. Poor stability can lead to an increased acid value and fuel viscosity and to the formation of gums and sediments. Therefore, if the duration of storing biodiesel or biodiesel blends is more than 6 months, it should be treated with an antioxidant additive [86]. Moreover, because water contamination will lead to biological growth in the fuel, it should be minimized in the stored fuel by using biocides. Biodiesel storage tanks made of aluminum, steel, Teon, and uorinated polyethylene or polypropylene should be selected.

Table 6 Specications and test methods of ASTM D6751 and EN 14214 standards [129,130]. 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. mg/kg mg/kg h % (m/m) % (m/m) % (m/m) % (m/m) % (m/m) % (m/m) % (m/m) mg/kg 130.0 min 1.96.0 47 min 0.020 max No. 3 max 0.80 max 0.020 max 0.240 max 0.001 max 0.050 max Report customer 360 max 0.0015 max 0.05 max 0.050 max EN 14214 101.0 min 3.55.0 51 min Class 1 0.5 max 0.25 max 0.01 max 0.3 max 860900 10 max 500 max 24 max 6 min 120 max 12 max 1 max 96.5 min 0.2 max 0.8 max 0.2 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

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The tanks should minimize the possibility of water contamination and should be cleaned prior to use for biodiesel storage [137]. 2.4. Main factors affecting the yield of biodiesel 2.4.1. Alcohol quantity Many researchers recognized that one of the main factors affecting the yield of biodiesel is the molar ratio of alcohol to triglyceride [28,47,61,138]. Theoretically, the ratio for transesterication reaction requires 3 mol of alcohol for 1 mol of triglyceride to produce 3 mol of fatty acid ester and 1 mol of glycerol. 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. The yield of biodiesel is increased when the alcohol triglyceride ratio is raised beyond 3 and reaches a maximum. Further increasing the alcohol amount beyond the optimal ratio will not increase the yield but will increase cost for alcohol recovery [28]. In addition, 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, with the use of an alkali catalyst [47,138]. When the percentage of free fatty acids in the oils or fats is high, such as in the case of waste cooking oil, a molar ratio as high as 15:1 is needed when using acid-catalyzed transesterication [28,133,139,140]. 2.4.2. Reaction time Freedman et al. [141] found that the conversion rate of fatty acid esters increases with reaction time. At the beginning, the reaction is slow due to the mixing and dispersion of alcohol into the oil. After a while, the reaction proceeds very fast. Normally, the yield reaches a maximum at a reaction time of <90 min, and then remains relatively constant with a further increase in the reaction time [28,142]. Moreover, excess reaction time will lead to a reduction in the product yield due to the backward reaction of transesterication, resulting in a loss of esters as well as causing more fatty acids to form soaps [143,144]. 2.4.3. Reaction temperature Temperature clearly inuences the reaction and yield of the biodiesel product. A higher reaction temperature can decrease the viscosities of oils and result in an increased reaction rate, and a shortened reaction time. However, Leung and Guo [28] and Eevera et al. [143] found that when the reaction temperature increases beyond the optimal level, the yield of the biodiesel product decreases because a higher reaction temperature accelerates the saponication reaction of triglycerides. 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. Depending on the oil used, the optimal temperature ranges from 50 C to 60 C [28,61,141]. 2.4.4. Catalyst concentration Catalyst concentration can affect the yield of the biodiesel product. As mentioned before, the most commonly used catalyst for the reaction is sodium hydroxide. However, Freedman et al. [141] 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, which will affect the product yield because of the hydrolysis reaction [145]. This is the reason why the catalyst should be added into the methanol rst and then mixed with the oil. As the catalyst concentration increases the conversion of triglyceride and the yield of biodiesel increase. This is because an insufcient amount of catalysts result in an incomplete conversion of the triglycerides into the fatty acid esters [28,145]. Usually, the yield reaches an optimal value when the

catalyst (NaOH) concentration reaches 1.5 wt.% and then decreases a little with a further increase in catalyst concentration. 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 [28,143]. 3. Other processes of biodiesel production 3.1. Biox co-solvent process The Biox co-solvent process was developed by Boocock et al. in 1996 [146]. In this process, triglycerides are converted to esters through the selection of inert co-solvents that generate a onephase oil-rich system [86,94,146]. Co-solvent options are available to overcome slow reaction times caused by the extremely low solubility of the alcohol in the triglyceride phase. Demirbas [94] uses tetrahydrofuran (THF) as a co-solvent to make the methanol soluble. After the completion of the reaction, the biodieselglycerol phase separation is clean and both the excess alcohol and the tetrahydrofuran co-solvent can be recovered in a single step [94]. However, because of the possible hazard and toxicity of the co-solvents, they must be completely removed from the glycerol phase as well as the biodiesel phase and the nal products should be water-free [146]. The unique advantage of the Biox co-solvent process is that it uses inert, reclaimable co-solvents in a single-pass reaction that takes only seconds at ambient temperature and pressure, and no catalyst residues appear in either the biodiesel phase or the glycerol phase [86]. This process can handle not only grainbased feedstocks but also waste cooking oils and animal fats. Van Gerpen et al. [62] found, however, that the recovery of excess alcohol is difcult when using this process because the boiling point of the THF co-solvent is very close to that of methanol. 3.2. Supercritical alcohol process As is known, when a uid or gas is subjected to temperatures and pressures in excess of its critical point, a number of unusual properties are exhibited. Under such conditions, a distinct liquid and vapor phase no longer exist. Instead, a single uid phase is formed [86]. Therefore, a process for biodiesel production has been developed by a non-catalytic supercritical methanol method [147,148]. Because of the lower value of the dielectric constant of methanol in the supercritical state, 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, and the reaction is completed in a very short time [149]. Supercritical transesterication is carried out in a high pressure reactor, with heat supplied from an external heater. Reaction occurs during the heating period. After the reaction is complete, the gas is vented and the product in the reactor is poured into a collecting vessel. The remaining contents are removed from the reactor by washing it with methanol [150,151]. During the whole process, several variables (i.e. reaction pressure and temperature) affect the yield of the biodiesel product and the highest yield can be obtained under the optimal conditions. In contrast to the common alkali-catalyzed method, this process has advantages in terms of reaction time and purication but requires a high temperature and pressure, hence requiring a high amount of energy [94,147,148]. 3.3. In situ biodiesel process The in situ biodiesel production is a novel approach for converting oil to biodiesel which was developed by Harrington and DArcyEvans in 1985 [152]. In this method, to achieve transesterication

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of its acyglycerols, 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 transesterication to fatty acid esters [152154]. To reduce the alcohol requirement for high efciency during in situ transesterication, the oilseeds need to be dried before the reaction takes place [155]. Milled oilseeds are mixed with alcohol in which the catalyst had been dissolved and the mixture is heated under reux for 15 h. Two layers are formed around the time of the completion of the reaction. The lower layer is the alcohol phase and can be recovered. The upper layer, including the crude biodiesel, is washed with water to remove the contaminants until the washing solution is neutral. After the washing step, the upper layer is dried over anhydrous sodium sulfate, then ltered, and the residual product is biodiesel [156]. Haas and Scott [155] found that the nal biodiesel product can conform to the ASTM standard and the conversion of the oilseed is very high (about 98%). Since this method eliminates the need for the isolation of, and possibly for the rening of, the oilseed lipid, the process could reduce biodiesel production costs, reduce the long size of the production system associated with the pre-extraction, degumming, and maximize the yield of the biodiesel production. However, this process cannot handle waste cooking oils and animal fats, which can reduce the cost of feedstock [156,157].

There are four primary factors affecting the yield of biodiesel, i.e. alcohol quantity, reaction time, reaction temperature, and catalyst concentration. To ensure a complete transesterication reaction, the molar ratio of alcohol to triglycerides should be increased to 6:1 with the use of an alkali catalyst. For used cooking oils or for oils with a high percentage of free fatty acids, a higher molar ratio is needed for acid-catalyzed transesterication. 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. Higher reaction temperature can decrease the viscosity of oils, enhancing the reaction rate. The optimal temperature ranged between 50 C and 60 C, depending on the oil used. The optimal condition of catalyst concentration is about 1.5 wt.% for NaOH which is the most commonly used catalyst. With increasing concern over global warming, it is foreseeable that biodiesel usage would continue to grow at a fast pace. This will trigger the development of more sophisticated methods of biodiesel production and rening to cope with the increasing market demand. Acknowledgement The authors would like to acknowledge the support of the ICEE and the University Development Fund of the University of Hong Kong. References

4. Conclusions Biodiesel is a clean-burning diesel fuel with a chemical structure of fatty acid alkyl esters. Of the various methods available for producing biodiesel, the alkali-catalyzed transesterication of vegetable oils and animal fats is currently the most commonly adopted method. Transesterication is basically a sequential reaction. However, when the raw materials (oils or fats) contain a high percentage of free fatty acids or water, 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. These are undesirable reactions which reduce the yield of the biodiesel product. Therefore, after rening the raw materials, the acidic feedstocks should be pre-treated to inhibit the saponication reaction. There are three primary approaches for reducing the amount of free fatty acids: esterication of free fatty acids with methanol, in the presence of acidic catalysts; using iodine as a catalyst; adding glycerol into the acidic feedstock with a catalyst like zinc chloride and heated to a high temperature. The rst approach can eliminate the separation, corrosion, toxicity, and environmental problems, 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. The transesterication reaction requires an alcohol as a reactant and a catalyst. The most commonly used alcohol is methanol while sodium hydroxide and potassium hydroxide are the most commonly used catalysts. During the reaction, glycerol will be produced as a by-product. Because of its numerous industrial applications, the crude glycerol should be rened with purity higher than 99% to make it usable. For rening the crude biodiesel produced, the product should rst be neutralized and then put through an alcohol stripper before cleaning by either one of the following approaches: water washing, membrane extraction, and dry washing. A very promising method for washing biodiesel is the hollow ber membrane extraction, which effectively avoids emulsication during the washing step and decreases the rening loss. As a commercial fuel, the nished 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.
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