Applied Energy 87 (2010) 1083–1095

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Applied Energy
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

Article history: Biodiesel is a low-emissions diesel substitute fuel made from renewable resources and waste lipid. The
Received 17 June 2009 most common way to produce biodiesel is through transesterification, especially alkali-catalyzed transe-
Received in revised form 6 October 2009 sterification. When the raw materials (oils or fats) have a high percentage of free fatty acids or water, the
Accepted 7 October 2009
alkali catalyst will react with the free fatty acids to form soaps. The water can hydrolyze the triglycerides
Available online 7 November 2009
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
Keywords:
the saponification reaction. This paper reviews the different approaches of reducing free fatty acids in the
Biodiesel
Alkali-catalyzed transesterification
raw oil and refinement of crude biodiesel that are adopted in the industry. The main factors affecting the
Feedstock yield of biodiesel, i.e. alcohol quantity, reaction time, reaction temperature and catalyst concentration,
Purification are discussed. This paper also described other new processes of biodiesel production. For instance, the
Mass transfer 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 pres-
sure. For the in situ biodiesel process, the oilseeds are treated directly with methanol in which the cat-
alyst 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.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1084
2. Biodiesel production with catalyzed transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1085
2.1. Basic chemical reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1085
2.2. Biodiesel production processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1086
2.2.1. Process flow chart . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1086
2.2.2. Raw materials treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1086
2.2.3. Pretreatment of acidic feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1087
2.2.4. Catalyst and alcohol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1087
2.2.5. Mixing and neutralization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1088
2.2.6. Transesterification and separation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1088
2.2.7. Refining crude glycerol. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1088
2.2.8. Purification of crude biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1089
2.2.9. Quality control . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1089
2.3. Storage of biodiesel product . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1090
2.4. Main factors affecting the yield of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
2.4.1. Alcohol quantity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
2.4.2. Reaction time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
2.4.3. Reaction temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
2.4.4. Catalyst concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
3. Other processes of biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
3.1. Biox co-solvent process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091

* 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 Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.apenergy.2009.10.006
1084 D.Y.C. Leung et al. / Applied Energy 87 (2010) 1083–1095

3.2. Supercritical alcohol process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091

3.3. In situ biodiesel process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
4. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092

1. Introduction
Due to the depletion of the world’s 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 be-
cause it can be used in any compression ignition engine without
the need for modification [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 [2–24],
animal fats [16,17,23,24], or even used cooking oils (UFO) [10]. Ta-
ble 1 shows some feedstocks of biodiesel and their physicochemi-
cal properties. Vegetable oils are promising feedstocks for biodiesel
production since they are renewable in nature, and can be pro-
duced on a large scale and environmentally friendly [25]. Vegeta-
ble 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 biodie-
sel 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, non-
edible 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 inten-
sive care [12,26]. However, most non-edible oils contain high free
fatty acids. Thus they may require multiple chemical steps or alter-
nate approaches to produce biodiesel, which will increase the pro-
duction 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 high-
er than vegetable oils [18]. UFO is not suitable for human con-
sumption but is a feedstock for biodiesel production. Its usage
significantly 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 ac-
counts about 60–80% 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 feed-
stocks would be quite different from each other. Table 2 shows
some physicochemical properties of biodiesel from different feed-
stocks and their yields under different production conditions
[7,9,11,14,16,18,20,22,25–28,30–38]. Although at present biodiesel

Table 1
Feedstocks for biodiesel production and their physicochemical properties.

Type of Species Main chemical composition (fatty Density Flash Kinematic viscosity Acid value Heating value References
oil acid composition wt.%) (g/cm3) point (°C) (cst, at 40 °C) (mg KOH/g) (MJ/kg)
Vegetable oil
Edible oil Soybean C16:0, C18:1, C18:2 0.91 254 32.9 0.2 39.6 [6,15,18,19]
Rapessed C16:0, C18:0, C18:1, C18:2 0.91 246 35.1 2.92 39.7 [3,8,15,18]
Sunflower C16:0, C18:0, C18:1, C18:2 0.92 274 32.6 – 39.6 [15,18,20]
Palm C16:0, C18:0, C18:1, C18:2 0.92 267 39.6a 0.1 – [2,11,18]
Peanut C16:0, C18:0, C18:1, C18:2, C20:0, 0.90 271 22.72 3 39.8 [9,13,18,20]
C22:0
Corn C16:0, C18:0, C18:1, C18:2, C18:3 0.91 277 34.9a – 39.5 [17,18]
Camelina C16:0, C18:0, C18:1, C18:2 0.91 – – 0.76 42.2 [5,21]
C18:3, C20:0, C20:1, C20:3
Canola C16:0, C18:0, C18:1, C18:2, C18:3 38.2 0.4 [8,10]
Cotton C16:0, C18:0, C18:1, C18:2 0.91 234 18.2 39.5 [17,18]
Pumpkin C16:0, C18:0, C18:1, C18:2 0.92 >230 35.6 0.55 39 [22]
Non- Jatropha C16:0, C16:1, C18:0, C18:1, C18:2 0.92 225 29.4 28 38.5 [4,7,12]
edible curcas
oil
Pongamina C16:0, C18:0, C18:1, C18:2, C18:3 0.91 205 27.8 5.06 34 [14]
pinnata
Sea mango C16:0, C18:0, C18:1, C18:2 0.92 – 29.6 0.24 40.86 [11]
Palanga C16:0, C18:0, C18:1, C18:2 0.90 221 72.0 44 39.25 [14]
Tallow C14:0, C16:0, C16:1, C17:0, C18:0, 0.92 – – – 40.05 [17,23]
C18:1, C18:2
Nile tilapia C16:0, C18:1, C20:5, C22:6, other 0.91 – 32.1b 2.81 – [16]
acids
Poultry C16:0, C16:1, C18:0, C18:1, C18:2, 0.90 – – – 39.4 [23,24]
C18:3
Others Used Depends on fresh cooking oil 0.90 – 44.7 2.5 – [10]
cooking oil
a
Kinematic viscosity at 38 °C, mm2/s.
b
Kinematic viscosity at 37 °C, mm2/s.
 D.Y.C. Leung et al. / Applied Energy 87 (2010) 1083–1095 1085

cannot entirely replace petroleum-based diesel fuel, there are sev- transesterification. The simplified form of its chemical reaction is
eral distinct advantages of biodiesel over diesel fuel. Biodiesel has presented in equation
higher combustion efficiency, cetane number than diesel fuel [39].
CH2-O-CO-R1 CH2-OH R-O-CO-R 1
It is biodegradable and more than 90% biodiesel can be biodegrad-
| (Catalyst) |
ed 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 CH-O-CO-R2 + 3ROH CH-OH R-O-CO-R 2

gas [42,43]. Moreover, it reduces most exhaust emissions except | |

NOx, such as monoxide, unburned hydrocarbons, and particulate
matter [44–48].
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 [49–53], micro-emulsions [54], thermal cracking [55–60], and
transesterification [61]. The most commonly used method for con-
verting oils to biodiesel is through the transesterification 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 technolog-
ical advancement of producing biodiesel through transesterifica-
tion. The main factors affecting the yield of biodiesel and other
types of transesterification will also be discussed.
2. Biodiesel production with catalyzed transesterification
CH2-O-CO-R3 CH2-OH R-O-CO-R 3
(Triglyceride) (Alcohol) (Glycerol) (Mixture of fatty acid esters)
ð1Þ
where R1, R2, R3 are long-chain hydrocarbons, sometimes called
fatty acid chains. Normally, there are five main types of chains in
vegetable oils and animal oils: palmitic, stearic, oleic, linoleic, and
linolenic. When the triglyceride is converted stepwise to diglycer-
ide, monoglyceride, and finally to glycerol, 1 mol of fatty ester is lib-
erated 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 transesterification,
the alkali catalyst that is used will react with the FFA to form soap.
Eq. (2) shows the saponification reaction of the catalyst (sodium
hydroxide) and the FFA, forming soap and water.

2.1. Basic chemical reactions R1 —COOH þ NaOH ! R1 COONa þ H2 O ð2Þ

ðFFAÞ sodium hydroxide ðsoapÞ ðwaterÞ

Common vegetable oils or animal fats are esters of saturated This reaction is undesirable because the soap lowers the yield of
and unsaturated monocarboxylic acids with the trihydric alcohol the biodiesel and inhibits the separation of the esters from the
glyceride. These esters are called triglycerides, which can react glycerol. In addition, it binds with the catalyst meaning that more
with alcohol in the presence of a catalyst, a process known as 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 Density Saponification Iodine Acid Cetane Heating Production conditions1 Yield References
viscosity (cst, (g/cm3) number value value number value (%)
T (°C) P M C (wt.%)
at 40 °C) (mg KOH/ (MJ/kg)
(min)
g)
Soybean 4.08 0.885 201 138.7 0.15 52 40 65 90 1:12 CaO|8 (2.03% H2O in >95 [18,20,27,33,35]
methanol)
Rapeseed 4.3–5.83 0.88– – – 0.25–0.45 49–50 45 65 120 1:6 KOH|1 95– [36]
0.888 96
Sunflower 4.9 0.88 200 142.7 0.24 49 45.3 60 120 1:6 NaOH|1 97.1 [20,38]
Palm 4.42 0.86– 207 60.07 0.08 62 34 Room 584 1:11 KF/ZnO|5.52 89.23 [18,20,32]
0.9
Peanut 4.42 0.883 200 67.45 – 54 40.1 60 120 1:6 NaOH|0.5 89 [9,18,20]
Corn 3.39 0.88– 202 120.3 – 58–59 45 80 60 1:9 KOH|2 85– [20,25]
0.89 96
Camelina 6.12–7a 0.882– – 152– 0.08–0.52 – – Room 60 1:6 KOH|1.5 97.9 [31]
0.888 157
Canola 3.53 0.88– 182 103.8 – 56 45 60 60 1:9 KOH|1 80– [20,25]
0.9 95
Cotton 4.07 0.875 204 104.7 0.16 54 45 65 90 1:6 NaOH|0.75 96.9 [20,37]
Pumpkin 4.41 0.8837 202 115 0.48 – 38 65 60 1:6 NaOH|1 97.5 [20,22]
Jatropha 4.78 0.8636 202 108.4 0.496 61–63 40–42 60 120 1:06 NaOH|1 98 [7,20,25]
curcas
Pongamina 4.8 0.883 – – 0.62 60–61 42 65 180 1:6 KOH|1 97– [14,25–26,34]
pinnata 98
Sea mango – – – – – – – 180 180 1:8 Sulfated zirconiz 83.8 [11]
alumina|6
b
Palanga 3.99 0.869 – – – – 41 66 4 1:12 C6H5CH3 + H3PO4|5 + 5, 85 [14]
H2SO4|6.5; KOH|9
(three step)
Tallow – 0.856 244.5 126 0.65 59 – 60 1440 1:30 H2SO4|2.5 98.28 [30]
Nile tilapia – – – 88.1 1.4 51 – 30 90 1:9 KOH|2 (ultrasound) 98.2 [16]
Poultry – 0.867 251.23 130 0.25 61 – 50 1440 1:30 H2SO4|1.25 99.72 [30]
Used 4 – – – 0.15 – – 60 20 1:7 NaOH|1.1 94.6 [28]
cooking
oil
1
T = reaction temperature (°C); P = transesterification reaction period (min); M = molecular ratio of oil/methanol; C = amount of catalyst (wt.%).
a
Kinematic viscosity at 20 °C.
b
Volumetric ratio of oil/methanol.
1086 D.Y.C. Leung et al. / Applied Energy 87 (2010) 1083–1095

Table 3
Different methods of biodiesel production.

Methods Definition Advantage Disadvantage Problems of using in References

engines
Direct use and Direct use as diesel fuel or blend with Liquid nature-portability Higher viscosity Coking and trumpet [9–13]
blending diesel fuel formation
Heat content (80% of diesel fuel) Lower volatility Carbon deposits
Readily available; renewability Reactivity of Oil ring sticking;
unsaturated thickening and gelling of
hydrocarbon chains the lubricating oil
Micro-emulsions A colloidal equilibrium dispersion of Better spray patterns during Lower cetane number Irregular injector needle [14,21]
optically isotropic fluid combustion sticking; incomplete
microstructures with dimensions combustion
generally in the 1–150 nm range Lower fuel viscosities Lower energy content Heavy carbon deposits;
formed spontaneously from two increase lubrication oil
immiscible liquids and one or more viscosity
ionic or non-ionic amphiphiles
Thermal cracking The conversion of long-chain and Chemically similar to petroleum- Energy intensive and – [15–20]
(pyrolysis) saturated substance (biomass basis) derived gasoline and diesel fuel hence higher cost
to biodiesel by means of heat
Transesterification The reaction of a fat or oil with an Renewability; higher cetane Disposal of by- – [21–23]
alcohol in the presence of catalyst to number; lower emissions; higher product (glycerol and
form esters and glycerol combustion efficiency waste water)

cost [62]. Water, originated either from the oils and fats or formed glycerides, free fatty acids, water, and other contaminants in vari-
during the saponification reaction, retards the transesterification ous proportions. Some crude vegetable oils contain phospholipids
reaction through the hydrolysis reaction. It can hydrolyze the tri- that need to be removed in a degumming step. Phospholipids can
glycerides to diglycerides and forms more FFA. The typical hydro- produce lecithin, a commercial emulsifier [65]. Liu et al. compared
lysis reaction is shown in Eq. (3). the different degumming methods, such as membrane filtration,
hydration, acid micelles degumming, supercritical extraction, etc.
CH2-O-CO-R1 CH2-OH
The characteristics of the raw oils should be investigated before
| | choosing the suitable degumming method because different
CH-O-CO-R2 + H2O CH-O-CO-R 2 + R1-COOH degumming methods have their advantages and disadvantages
| | [66]. The oil can be separated through membrane filtration accord-
ing to the average molecular weight or the particle size of phos-
CH2-O-CO-R 3 CH2-O-CO-R3
pholipids. Although degumming method can solve the problem,
(Triglyceride) (Water) (Diglyceride) (FFA)
ð3Þ
However, the FFA can react with alcohol to form ester (biodie- Oils or Fats
sel) by an acid-catalyzed esterification reaction. This reaction is
very useful for handling oils or fats with high FFA, as shown in >
FFA _ 2.5wt% FFA>2.5wt%
the equation below:
Catalyst
Hþ
R1 —COOH þ ROH ! R—O—CO—R1 þ H2 O ð4Þ Pretreatment
ðFFAÞ ðalcoholÞ ðfatty acid esterÞ ðwaterÞ
Mixing
Normally, the catalyst for this reaction is concentrated sulphu-
ric acid. Due to the slow reaction rate and the high methanol to oil Alcohol Neutralized oil
molar ratio that is required, acid-catalyzed esterification has not
gained as much attention as the alkali-catalyzed transesterification
[63]. Transesterification

2.2. Biodiesel production processes

Phase separation
2.2.1. Process flow chart
Today, most of the biodiesel is produced by the alkali-catalyzed Re-neutralization
process. Fig. 1 shows a simplified flow chart of the alkali-catalyst Crude Biodiesel
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 al- Alcohol Recovery Purification
kali-catalyzed system is below 2.5 wt.% FFA. If the oil or fat feed-
stock has a FFA content over 2.5 wt.%, a pretreatment step is
necessary before the transesterification process [64] (see Section Quality Control
Crude Glycerol
2.2.3).

2.2.2. Raw materials treatment Biodiesel

The raw materials, which can be vegetable oils, animal fats, or
recycled greases, used in the production of biodiesel contain tri- Fig. 1. Simplified process flow chart of alkali-catalyzed biodiesel production.
 D.Y.C. Leung et al. / Applied Energy 87 (2010) 1083–1095
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 significantly
reduced, so it could be separated from the oil by natural settle-
ment. The hydration method features a simple process, easy oper-
ation, and high yields refining, 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 supercrit-
ical extraction method is employed to separate the phospholipids.
Moreover, by refining with supercritical CO2 extraction, it can
effectively remove the free fatty acids and the peroxidation prod-
ucts that are in the crude oil. However, the high pressure required
in this process will be the biggest challenge in its industrial appli-
cation [71,72].
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. In addition, deodorization is another important step in the
raw material treatment. During this step, steam, at 1–6 mm Hg
pressure, is injected into the oil at 490–550 K in order to eliminate
free fatty acids, aldehydes, unsaturated hydrocarbons, and ketones,
all of which cause undesirable odors and flavors 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 distilla-
tion [74], extraction by alcohol [75], and esterification by acid-
catalysis [76]. However, steam distillation for reducing high free
fatty acids requires a high temperature and has low efficiency. Be-
cause of the limited solubility of free fatty acids in alcohol, extrac-
tion by alcohol method needs a large amount of solvent and the
process is complicated. Compared with the two former methods,
esterification by acid-catalysis makes the best use of the free fatty
acids in the oil and transforms it into biodiesel [75,77]. The com-
mon pretreatment is esterification of the FFA with methanol in
the presence of acidic catalysts (usually sulphuric acid). The cata-
lysts 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 esterification and the water needs to be removed. If
the acid value of the oils or fats is very high, one-step esterification
pretreatment may not reduce the FFA efficiently 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-esterification). The time re-
quired 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 [79]. Moreover, some researchers re-
duce 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 esterification of FFA in waste cooking oils but the loss
of the catalytic activity maybe a problem [80–84].
An alternative approach to reduce the FFA is to use iodine as a
catalyst to convert free fatty acids into biodiesel. An obvious
1087
advantage of this approach is that the catalyst (iodine) can be recy-
cled after the esterification 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 re-
duced 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 re-
act 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 transesterification 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 require-
ment and relatively slow reaction rate [86].
2.2.4. Catalyst and alcohol
In general, there are three categories of catalysts used for bio-
diesel production: alkalis, acids, and enzymes [87–89]. Enzyme
catalysts have become more attractive recently since it can avoid
soap formation and the purification process is simple to accom-
plish. 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 exam-
ple is so called whole cell biocatalysts which are immobilized
within biomass support particles. An advantage is that no purifica-
tion is necessary for using these biocatalysts [90–93]. Compare
with enzyme catalysts, the alkali and acid catalysts are more com-
monly used in biodiesel production [61]. The alkali and acid cata-
lysts 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 al-
kali-catalyzed transesterification is most commonly used commer-
cially [36,38,94–99]. These materials are the most economic
because the alkali-catalyzed transesterification 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 dis-
solved in the alcohol reactant and affect the yield [28]. Therefore,
they should be properly handled. On the other hand, some hetero-
geneous catalysts are solid and it could be rapidly separated from
the product by filtration, which reduces the washing requirement.
In addition, solid heterogeneous catalysts can stimulatingly cata-
lyze the transesterification and esterification reaction that can
avoid the pre-esterification step, thus these catalysts are particu-
larly 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 classifies the three categories of catalysts with
their advantages and disadvantages [27,33,82,102–109].
The alcohol materials that can be used in the transesterification
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.
1088 D.Y.C. Leung et al. / Applied Energy 87 (2010) 1083–1095
Table 4
Advantages and disadvantages at different types of catalysts used in the biodiesel production.
Type Example
Alkali
Homogeneous NaOH, KOH
Heterogeneous CaO, CaTiO3, CaZrO3, CaO–CeO2, CaMnO3,
Ca2Fe2O5, KOH/Al2O3, KOH/NaY, Al2O3/KI,
ETS-10 zeolite, alumina/silica supported
K2CO3
Acid
Homogeneous Concentrated sulphuric acid
Heterogeneous ZnO/I2, ZrO2 =SO2 2
4 , TiO2 =SO4 , carbon-based
solid acid catalyst, carbohydrate-derived
catalyst, Vanadyl phosphate, niobic acid,
sulphated zirconia, Amberlyst-15, Nafion-
NR50
Enzymes Candida antarctica fraction B lipase,
Rhizomucor mieher lipase
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 com-
pletely dissolves in the methanol, the methoxide is ready to be
added to the oil. Once the methoxide is added into the oil, a neu-
tralization 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 cat-
alyst needs to be added to complete the reaction.
2.2.6. Transesterification and separation
When the catalyst, alcohol, and oil are mixed and agitated in a
reaction vessel, a transesterification reaction will start. A stirred
reactor is usually used as the reaction vessel for continuous alka-
li-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
emulsification instantly. Micro jets, formed by impinging one li-
quid to another, lead to intensive mixing of the system near the
phase boundary. With the use of ultrasound biodiesel can be pro-
duced without heating because the cavitation may lead to a local-
ized increase in temperature at the phase boundary and enhance
the reaction [110–112]. 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
Advantages Disadvantages References
High catalytic activity, low cost, Low FFA requirement, anhydrous conditions, [97,101–104]
favorable kinetics, modest saponification, emulsion formation, more
operation conditions wastewater from purification, disposable
Noncorrosive, environmentally Low FFA requirement, anhydrous conditions, [33,99–
benign, recyclable, fewer disposal more wastewater from purification, high 101,103,104]
problems, easily separation, higher molar ratio of alcohol to oil requirement,
selectivity, longer catalyst lifetimes high reaction temperature and pressure,
diffusion limitations, high cost
Catalyze esterification and Equipment corrosion, more waste from [97,102,103]
transesterification simultaneously, neutralization, difficult to recycle, higher
avoid soap formation reaction temperature, long reaction times,
weak catalytic activity
Catalyze esterification and Low acid site concentrations, low [82,98,103,104]
transesterification simultaneously, microporosity, diffusion limitations, high
recyclable, eco-friendly cost
Avoid soap formation, nonpolluting, Expensive, denaturation [27,82,104]
easier purification
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 saponification and the separation of the glycerol by-prod-
uct. Therefore, the amount of water and free fatty acids in the feed-
stock oil should be monitored during the reaction.
Once the transesterification 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 biodie-
sel 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 ini-
tial 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 unre-
acted catalyst, alcohol, and oil during the transesterification 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 significant amount of contami-
nants is also present in the biodiesel. Therefore, crude biodiesel
needs to be purified before use.
2.2.7. Refining crude glycerol
Although biodiesel is the desired product from the reactions,
the refining of glycerol is also important due to its numerous appli-
cations in different industrial products such as moisturizers, soaps,
cosmetics, medicines, and other glycerol products [115–117]. It is
one of the few products that has a good reactivity on sump oil,
and is extremely effective for washing shearing shed floor, so it
can be used as a heavy duty detergent and degreaser. Whittington
[118] reported that glycerol can even be fermented to produce eth-
anol, 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 cata-
lyst. 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
 D.Y.C. Leung et al. / Applied Energy 87 (2010) 1083–1095 1089

recovered for use as a fertilizer [119]. Generally, water and alcohol
are removed to produce 80–88% 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 flash process or by other types of
evaporators. Usually, the alcohol vapor is condensed back into li-
quid 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
difficult when the alcohol that is used, such as ethanol or isopropa-
nol, forms an azeotrope with the water. Gerpen [121] proposed the
use of a molecular sieve to remove the water generated.
2.2.8. Purification of crude biodiesel
After separation from the glycerol phase, crude biodiesel is
mainly contaminated with residual catalyst, water, unreacted alco-
hol, free glycerol, and soaps that were generated during the transe-
sterification reaction [114]. Normally, crude biodiesel enters a
neutralization step and then passes through an alcohol stripper be-
fore the washing step. In some cases, acid is added to crude biodiesel
to neutralize any remaining catalyst and to split any soap. Soaps re-
act with the acid to form water soluble salts and free fatty acids. Ger-
pen [121] stated that neutralization before the washing step reduces
the materials required for the washing step and minimizes the po-
tential for emulsions being formed during the washing step. Unre-
acted alcohol should be removed with distillation equipment
before the washing step to prevent excess alcohol from entering
the wastewater effluent [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 ap-
proaches are adopted for purifying biodiesel: water washing, dry
washing [122], and membrane extraction [123,124]. These ap-
proaches are briefly 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 pre-
vents 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, mean-
ing that the contaminants have been completely removed. Then,
the biodiesel and water phases are separated by a separation fun-
nel 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 filtration [126]. However, there
are many disadvantages to this method, including an increased
cost and production time, polluting liquid effluent, 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 replac-
ing 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 metha-
nol than the ion resins, none of the products from this process ful-
fill the limits specified 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 fiber
membrane extraction, such as polysulfone. In this method, a hol-
low fiber membrane (1 m long, 1 mm diameter) filled with distilled
water is immersed into the reactor (20 °C). The crude biodiesel is
pumped into the hollow fiber membrane (flow rate: 0.5 ml/min;
operating pressure: 0.1 MPa). Following this step, biodiesel is
passed over heated Na2SO4 and then filtered to remove any
remaining water [124]. This approach effectively avoids emulsifi-
cation during the washing step and decreases the loss during the
refining 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 finished biodiesel must be analyzed
using sophisticated analytical equipment to ensure it meets inter-

Table 5
Different approaches for purifying crude biodiesel.

Approaches Primary Function Phases separation Advantage Disadvantage References

material
used
Water washing Distilled Prevents precipitation Separation funnel, Very effective in Increased cost and production [46,72–74]
warm of saturated fatty acid centrifuge, molecular removing contaminants time, liquid effluent, product loss,
water esters sieves, silica gels, etc. emulsions formation
Retards the emulsion
formation
Softened Eliminates calcium
water and magnesium
contamination
Dry washing Ion Brings the free – Waterless Overruns the limit in the EN [69,75,76]
exchange glycerol level down Standard
resin and removing soaps
Magnesium
silicate
powder
Membrane Polysulfone Remove the – Avoids the emulsion Probably high cost and low [70,71]
extraction contaminants formation and decreases throughput due to contaminants
the refining loss existed
1090 D.Y.C. Leung et al. / Applied Energy 87 (2010) 1083–1095

national standards. A few specifications 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, Mit-
telbach [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 reflect the properties of the chemical com-
pounds 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 transesterification reaction is not complete then triglycer-
ides, diglycerides, or monoglycerides may be left in the final prod-
uct. Chemically, each of these compounds contains a glycerol
molecule. Fuel with excessive free glycerol may plug the fuel filters
and cause combustion problems in the diesel engine. Therefore, the
ASTM standard requires the total glycerol to be <0.24% of the final
biodiesel product [54,130]. On the other hand, since residual meth-
anol, even as little as 1%, can lower the flashpoint of the final bio-
diesel 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 specific value for the residual catalyst is not included
in the ASTM standard, it is limited by the specification on levels
of sulfated ash, which may lead to engine deposits and high abra-
sive wear levels [42,130].
Because the European specification for sulfur content (i.e. EN
14214) is much tighter than the US requirement, Ali et al. [133] re-
ported 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. In addition, some vegetable oils,
yellow greases, and brown greases leave an objectionable color
in the biodiesel. Although there is no color specification 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 filters. For this reason, the storage temper-
ature of most pure biodiesel is generally kept between 7 and 10 °C.
Even in extremely cold climates, underground storage of pure bio-
diesel usually provides the storage temperature necessary for pre-
venting 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 dura-
tion 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 bio-
cides. Biodiesel storage tanks made of aluminum, steel, Teflon,
and fluorinated polyethylene or polypropylene should be selected.

Table 6
Specifications and test methods of ASTM D6751 and EN 14214 standards [129,130].

Property Unit Limits Test method

ASTM D6751 EN 14214 ASTM D6751 EN 14214
Flash point °C 130.0 min 101.0 min D93 ISO CD3679e
Kinematic viscosity at 40 °C mm2/s 1.9–6.0 3.5–5.0 D445 EN ISO 3104
Cetane number – 47 min 51 min D613 EN ISO 5165
Sulphated ash content % (m/m) 0.020 max D874 ISO 3987
Copper strip corrosion – No. 3 max Class 1 D130 EN ISO 2160
Acid value mg KOH/g 0.80 max 0.5 max D664 pr EN 14104
Free glycerol % (m/m) 0.020 max D6584 pr EN 14105m pr EN 14106
Total glycerol % (m/m) 0.240 max 0.25 max D6584 pr EN 14105m
Phosphorous content % (m/m) 0.001 max 0.01 max D4951 pr EN 141101
Carbon residue
ASTM D6751 (100% sample) % (m/m) 0.050 max – D4530 –
EN 14214 (10% bottoms) – 0.3 max – EN ISO 10370
Cloud point °C Report customer – D2500 –
Density at 15 °C kg/m3 – 860–900 – EN SIO 3675 EN SIO 12185
Distillation T90 AET °C 360 max – D1160 –
Sulfur (S 15 Grade) ppm 0.0015 max – D5453 –
Sulfur (S 500 Grade) ppm 0.05 max – D5453 –
Sulfur content mg/kg – 10 max – –
Water and sediment %vol. 0.050 max – D2709 –
Water content mg/kg – 500 max – EN ISO 12937
Total contamination mg/kg – 24 max – EN 12662
Oxidation stability at 110 °C h – 6 min – pr EN 14112
Iodine value – – 120 max – pr EN 14111
Linolenic acid methyl ester % (m/m) – 12 max – pr EN 14103d
Polyunsaturated (P4 double bonds) methyl esters % (m/m) – 1 max – pr EN 14103
Ester content % (m/m) – 96.5 min – pr EN 14103d
Methanol content % (m/m) – 0.2 max – pr EN 141101
Monoglyceride content % (m/m) – 0.8 max – pr EN 14105m
Diglyceride content % (m/m) – 0.2 max – pr EN 14105m
Triglyceride content % (m/m) – 0.2 max – pr EN 14105m
Alkaline metals (Na + K) mg/kg – 5 max – pr EN 14108 pr EN 14109
 D.Y.C. Leung et al. / Applied Energy 87 (2010) 1083–1095
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 tri-
glyceride [28,47,61,138]. Theoretically, the ratio for transesterifica-
tion 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 short-
er time. The yield of biodiesel is increased when the alcohol triglyc-
eride ratio is raised beyond 3 and reaches a maximum. Further
increasing the alcohol amount beyond the optimal ratio will not in-
crease 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 inves-
tigations 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 transesterification
[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 reac-
tion 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 re-
mains relatively constant with a further increase in the reaction
time [28,142]. Moreover, excess reaction time will lead to a reduc-
tion in the product yield due to the backward reaction of transeste-
rification, 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 influences the reaction and yield of the bio-
diesel product. A higher reaction temperature can decrease the vis-
cosities 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 be-
yond the optimal level, the yield of the biodiesel product decreases
because a higher reaction temperature accelerates the saponifica-
tion 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 prod-
uct. 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 first
and then mixed with the oil. As the catalyst concentration in-
creases the conversion of triglyceride and the yield of biodiesel in-
crease. This is because an insufficient amount of catalysts result in
an incomplete conversion of the triglycerides into the fatty acid es-
ters [28,145]. Usually, the yield reaches an optimal value when the
1091
catalyst (NaOH) concentration reaches 1.5 wt.% and then decreases
a little with a further increase in catalyst concentration. The reduc-
tion 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 one-
phase oil-rich system [86,94,146]. Co-solvent options are available
to overcome slow reaction times caused by the extremely low sol-
ubility of the alcohol in the triglyceride phase. Demirbas [94] uses
tetrahydrofuran (THF) as a co-solvent to make the methanol solu-
ble. After the completion of the reaction, the biodiesel–glycerol
phase separation is clean and both the excess alcohol and the tet-
rahydrofuran co-solvent can be recovered in a single step [94].
However, because of the possible hazard and toxicity of the co-sol-
vents, they must be completely removed from the glycerol phase
as well as the biodiesel phase and the final products should be
water-free [146]. The unique advantage of the Biox co-solvent pro-
cess is that it uses inert, reclaimable co-solvents in a single-pass
reaction that takes only seconds at ambient temperature and pres-
sure, and no catalyst residues appear in either the biodiesel phase
or the glycerol phase [86]. This process can handle not only grain-
based feedstocks but also waste cooking oils and animal fats. Van
Gerpen et al. [62] found, however, that the recovery of excess alco-
hol is difficult 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 fluid 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 fluid 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 nat-
ure of normal methanol/triglyceride mixtures by forming a single
phase, and the reaction is completed in a very short time [149].
Supercritical transesterification is carried out in a high pressure
reactor, with heat supplied from an external heater. Reaction oc-
curs 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 com-
mon alkali-catalyzed method, this process has advantages in terms
of reaction time and purification 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 convert-
ing oil to biodiesel which was developed by Harrington and D’Arcy-
Evans in 1985 [152]. In this method, to achieve transesterification
1092 D.Y.C. Leung et al. / Applied Energy 87 (2010) 1083–1095
of its acyglycerols, the oilseeds are directly treated at ambient tem-
perature and pressure with a methanol solution in which the cata-
lyst has been previously dissolved. That means that the oil in the
oilseeds is not isolated prior to transesterification to fatty acid es-
ters [152–154]. To reduce the alcohol requirement for high effi-
ciency during in situ transesterification, 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 reflux for 1–5 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 contami-
nants until the washing solution is neutral. After the washing step,
the upper layer is dried over anhydrous sodium sulfate, then fil-
tered, and the residual product is biodiesel [156]. Haas and Scott
[155] found that the final 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 refining of, the oilseed lipid, the process could re-
duce biodiesel production costs, reduce the long size of the produc-
tion system associated with the pre-extraction, degumming, and
maximize the yield of the biodiesel production. However, this pro-
cess cannot handle waste cooking oils and animal fats, which can
reduce the cost of feedstock [156,157].
4. Conclusions
Biodiesel is a clean-burning diesel fuel with a chemical struc-
ture of fatty acid alkyl esters. Of the various methods available
for producing biodiesel, the alkali-catalyzed transesterification of
vegetable oils and animal fats is currently the most commonly
adopted method. Transesterification is basically a sequential reac-
tion. 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 bio-
diesel product. Therefore, after refining the raw materials, the
acidic feedstocks should be pre-treated to inhibit the saponifica-
tion reaction. There are three primary approaches for reducing
the amount of free fatty acids: esterification of free fatty acids with
methanol, in the presence of acidic catalysts; using iodine as a cat-
alyst; adding glycerol into the acidic feedstock with a catalyst like
zinc chloride and heated to a high temperature. The first approach
can eliminate the separation, corrosion, toxicity, and environmen-
tal 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 transesterification 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 reac-
tion, glycerol will be produced as a by-product. Because of its
numerous industrial applications, the crude glycerol should be re-
fined with purity higher than 99% to make it usable. For refining
the crude biodiesel produced, the product should first be neutral-
ized 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 fiber membrane extraction, which effec-
tively avoids emulsification during the washing step and decreases
the refining loss. As a commercial fuel, 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.
There are four primary factors affecting the yield of biodiesel,
i.e. alcohol quantity, reaction time, reaction temperature, and cat-
alyst concentration. To ensure a complete transesterification reac-
tion, 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 transesterification. Because the con-
version rate of fatty acid esters increases with reaction time but
the yield of the biodiesel product reaches a maximum at an opti-
mal reaction time. Higher reaction temperature can decrease the
viscosity of oils, enhancing the reaction rate. The optimal temper-
ature 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 increas-
ing 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 produc-
tion and refining 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.
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