Applied Energy 87 (2010) 10831095

Contents lists available at ScienceDirect

Applied Energy
j o u r n a l h o m e p a g e : w w w . e l s e v ie r . c o m / l o c a te / a p e n e r g y

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

article info abstract

Article history:
Received 17 June 2009
Received in revised form 6 October 2009 Accepted 7 October
2009
Available online 7 November 2009
Keywords:
Biodiesel
Alkali-catalyzed transesterification Feedstock
Purification Mass transfer

Contents

Biodiesel is a
low-emissions
diesel
substitute fuel
made
from
renewable
resources and
waste
lipid.
The
most
common way
to
produce
biodiesel
is
through
transesterifica
tion,
especially
alkalicatalyzed
transesterification.
When the raw
materials (oils
or fats) have a
high
percentage of
free
fatty
acids
or
water,
the
alkali catalyst
will react with
the free fatty
acids to form
d

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 pretreated to inhibit the saponification reaction.
This paper reviews the different approaches of
reducing free fatty acids in the raw oil and
refinement of crude biodiesel that are adopted
in the industry. The main factors affecting the
yield of biodiesel, i.e. alcohol quantity, reaction
time, reaction temperature and catalyst
concentration, are discussed. This paper also
described other new processes of biodiesel
production. For instance, the Biox co-solvent
process converts triglycerides to esters through
the selection of inert co-solvents that generates
a one-phase oil-rich system. The non-catalytic
supercritical methanol process is advantageous
in terms of shorter reaction time and lesser
purification steps but requires high temperature
and 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.

2009 Elsevier Ltd. All

rights reserved.
0

1. Introduction . .
. . . . . . . . . . . . . . . . . . . . . . . . . . . . .i . . . . . . . . . . . . . . . . . . . . . . .0. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
n
3. Other processes
2. Biodiesel production with catalyzed transesterification
. . . of
. . biodiesel
. . . . . . . .production.
. . . . . . . . . .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. .. . . . . . . . . . . . . . . . . . . . . . . . . . .
g
8
2.1.
Basic chemical reactions . . . . .3.1.
....................................................................................
5
2.2.
Biodiesel production processes. . . . . . . . . . . a. . . . . . . . . . . . . . . . . . . . . . . 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.1.
Process flow chart . . . . . . . . . . . . . .u. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.2.
Raw materials treatment . . . . . . . . . t. . . . . . . . . . . . . . . . . . . . . . . 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.3. Pretreatment of acidic feedstocks . . . h. . . . . . . . . . . . . . . . . . . . . . . 8
................................................
2.2.4.
Catalyst and alcohol . . . . . . . . . . . . o. . . . . . . . . . . . . . . . . . . . . . . 5. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2.5.
Mixing and neutralization . . . . . . . . .r . . . . . . . . . . . . . . . . . . . . . . .9. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
C
2.2.6.
Transesterification and separation. ... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
o
2.2.7.
Refining crude glycerol.
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .7. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
r
T
9
2.2.8. Purification of crude
biodiesel
.............................................................................
r
e
1
2.2.9.
Quality control . e. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
l
1
2.3. Storage of biodiesel product s. . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . ;. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4. Main factors affecting the yield
p of biodiesel . . . . .: . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.1.
Alcohol quantityo. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .f . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.2.
Reaction time . .n. . . . . . . . . . . . . . . .+. . . . . . . . . . . . . . . . . . . . . . .a. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

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1084

D.Y.C. Leung et al. / Applied Energy 87 (2010) 10831095

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

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

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1091
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1092

oils which are not suitable

for human consumption
because of the presence of
Due to the depletion of the worlds petroleum reservessome toxic components in
and the increasing environmental concerns, there is a greatthe oils. Furthermore, nondemand for alternative sources of petroleum-based fuel, edible oil crops can be
including diesel and gasoline fuels. Biodiesel, a clean grown in waste lands that
renewable fuel, has recently been considered as the bestare not suitable for food
candidate for a diesel fuel substitution be-cause it can becrops and the cost of
used in any compression ignition engine without the need cultivation is much lower
for modification [1]. Chemically, biodiesel is a mixture ofbecause these crops can
methyl esters with long-chain fatty acids and is typically still sustain reasonably
made from nontoxic, biological resources such as vegetable high yield without intenoils [224], animal fats [16,17,23,24], or even used cookingsive care [12,26]. However,
most
non-edible
oils
oils (UFO) [10]. Ta-ble 1 shows some feedstocks of
contain high free fatty
biodiesel and their physicochemi-cal properties. Vegetable
acids. Thus they may
oils are promising feedstocks for biodiesel production since
require multiple chemical
they are renewable in nature, and can be pro-duced on a
steps
or
alter-nate
large scale and environmentally friendly [25]. Vegeta-ble oils
approaches to produce
include edible and non-edible oils. More than 95% of
biodiesel,
which
will
biodiesel production feedstocks comes from edible oils
increase the pro-duction
since they are mainly produced in many regions and the
cost, and may lower the
properties of biodie-sel produced from these oils are much
ester yield of biodiesel
suitable to be used as diesel fuel substitute [26]. However, it
below
the
standards
may cause some problems such as the competition with the
[14,25,27]. Animal fats
edible oil market, which increases both the cost of edible
contain higher saturated
oils and biodiesel [11]. Moreover, it will cause deforestation
fatty acids and normally
in some countries because more and more forests have
exist in solid form at room
been felled for plantation purposes. In order to overcome
temperature
that
may
these disadvantages, many researchers are interested in
cause problems in the
non-edible
production process. Its cost
is
also
high-er
than
vegetable oils [18]. UFO is
Table 1
Feedstocks for biodiesel production and their physicochemical properties. not suitable for human con1. Introduction

Type of

Species

oil

acid composition wt.%)

Vegetable oil
Edible oil
Soybean
Rapessed
Sunflower
Palm
Peanut

Tallow
Nile tilapia

Canola
Cotton
Pumpkin
Jatropha
curcas

Poultry
C16:0, C18:1, C18:2
C16:0, C18:0, C18:1, C18:2
Used
C16:0, C18:0, C18:1,Others
C18:2
cooking oil
C16:0, C18:0, C18:1, C18:2
C16:0, C18:0, C18:1, C18:2, C20:0,
a
C22:0
C16:0, C18:0, C18:1,
K C18:2, C18:3
C16:0, C18:0, C18:1,
i C18:2
n C20:3
C18:3, C20:0, C20:1,
e C18:2, C18:3
C16:0, C18:0, C18:1,
m
C16:0, C18:0, C18:1,
a C18:2
C16:0, C18:0, C18:1,
t C18:2
i C18:1, C18:2
C16:0, C16:1, C18:0,
c

Pongamina
pinnata
Sea mango
Palanga

v
i C18:2, C18:3
C16:0, C18:0, C18:1,
s
c
C16:0, C18:0, C18:1,
o C18:2
C16:0, C18:0, C18:1,
s C18:2

Corn
Camelina

Nonedible
oil

Main chemical composition (fatty

i
t
y

t
i
c

a
t

L
C
,

v
i
s
c
o
s
i
t
y

m
m

a
t

/
s
.

3
7

3
8

K
i
n
e
m
a

L
C
,
m
m
2

/
s
.

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 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
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
28,3038]. Although at
present biodiesel

D.Y.C. Leung et al. / Applied Energy 87 (2010) 10831095

transesterification. The simplified

cannot entirely replace petroleum-based diesel form of its chemical reaction is
fuel, there are sev-eral distinct advantages of presented in equation
biodiesel over diesel fuel. Biodiesel has higher
CH
combustion efficiency, cetane number thanCH2OCOR1
(Catalyst)|
diesel fuel [39]. It is biodegradable and more |
CHOH
than 90% biodiesel can be biodegrad-ed withinCHOCOR2 +3ROH
21 days [40,41]. Biodiesel has lower sulfur and |
aromatic content than diesel fuel and thatCH2OCOR3
CH
means it will not emit lots of toxic gas [42,43].(Triglyceride)
(Alcohol)
(Glycerol)
Moreover, it reduces most exhaust emissions
except NOx, such as monoxide, unburned
hydrocarbons, and particulate matter [4448].
where R1, R2, R3 are long-chain
A number of methods are currently available hydrocarbons, sometimes called
and have been adopted for the production offatty acid chains. Normally, there
biodiesel fuel. There are four primary ways toare five main types of chains in
produce biodiesel (Table 3): direct use andvegetable oils and animal oils:
blending of raw oils [4953], micro-emulsionspalmitic, stearic, oleic, linoleic,
[54],
thermal
cracking
[5560],
andand
linolenic.
When
the
transesterification [61]. The most commonlytriglyceride is converted stepwise
used method for con-verting oils to biodiesel isto diglycer-ide, monoglyceride,
through the transesterification of animal fats orand finally to glycerol, 1 mol of
vegetable oils, which forms the basis of the fatty ester is lib-erated at each
present paper. The objective of this paper is to step [61]. Usually, methanol is the
give an overview on the technolog-ical preferred alcohol for producing
advancement of producing biodiesel through biodiesel because of its low cost.
transesterifica-tion. The main factors affecting Vegetable oils and fats may
the yield of biodiesel and other types of contain small amounts of water
transesterification will also be discussed.
and free fatty acids (FFA). For an
alkali-catalyzed
transesterification,
the
alkali
2. Biodiesel production with catalyzed
catalyst that is used will react
transesterification
with the FFA to form soap. Eq. (2)
shows the saponification reaction
2.1. Basic chemical reactions
of the catalyst (sodium hydroxide)
and the FFA, forming soap and
water.

1085

R1COOH
FFA

NaOH

sodium hydroxide

! R1COONa H2O
soap

Common vegetable oils ortriglycerides, which

animal fats are esters ofcan
react
with
saturated and unsaturatedalcohol
in
the
monocarboxylic acids withpresence
of
a
the trihydric alcohol glyceride.catalyst, a process
These esters are calledknown as
Table 2
Physicochemical

water

properties of
biodiesel from

This reaction isseparation of the

undesirable
esters from the
because the soapglycerol. In addition,
lowers the yield ofit binds with the
the biodiesel andcatalyst
meaning
inhibits
thethat more catalyst
different oil
source and the

yields under the conditions.

production

will be needed and

hence the process
will involve a higher

Feedstock

Kinematic
viscosity (cst,
at 40 LC)

Density
3
(g/cm )

Saponification
number

Iodine
value

Acid
Cetane
value
number
(mg KOH/

Heating
value
(MJ/kg)

Production conditions

40

65

g)

T (LC) P
(min)

C (wt.%)

Soybean

4.08

0.885

201

138.7

0.15

Rapeseed

4.35.83

0.250.45 4950

45

65

120 1:6

Sunflower
Palm

4.9
4.42

200
207

142.7
60.07

0.24
0.08

49
62

45.3
34

60
Room

120 1:6
584 1:11

NaOH|1
KF/ZnO|5.52

Peanut
Corn

4.42
3.39

200
202

67.45
120.3

54
5859

40.1
45

60
80

120 1:6
60 1:9

NaOH|0.5
KOH|2

Camelina

6.127

Room

60 1:6

KOH|1.5

3.53

182

152
157
103.8

0.080.52

Canola

56

45

60

60 1:9

KOH|1

Cotton
Pumpkin
Jatropha
curcas
Pongamina
pinnata
Sea mango

4.07
4.41
4.78

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

CaO|8 (2.03% H2O in

methanol)
KOH|1

204
202
202

104.7
115
108.4

0.16
0.48
0.496

54

6163

45
38
4042

65
65
60

90 1:6
60 1:6
120 1:06

NaOH|0.75
NaOH|1
NaOH|1

4.8

0.883

0.62

6061

42

65

180 1:6

KOH|1

180

180 1:8

52

Palanga

3.99

0.869

41

66

Tallow
Nile tilapia
Poultry
Used
cooking
oil

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

90 1:12

4 1:12

1440
90
1440
20

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

Yield
(%)

References

>95

[18,20,27,33,35]

95
[36]
96
97.1 [20,38]
89.23 [18,20,32]
89
85
96
97.9

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

[20,25]

97
98
83.8

[14,2526,34]

85

[14]

98.28
98.2
99.72
94.6

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

T = reaction temperature (LC); P = transesterification reaction period (min); M = molecular ratio of oil/methanol; C = amount of catalyst (wt.%).
Kinematic viscosity at 20 LC.
b Volumetric ratio of oil/methanol.
D.Y.C.
Leung et
al. /
Applied
Energy 87
(2010)
1083
1086
1095
a

Table 3
Different methods of
biodiesel production.
Definition

Advantage

Disadvantage

Problems of using in

References

engines
Direct use and
blending

Micro-emulsions

Thermal cracking
(pyrolysis)

Transesterification

Direct use as diesel fuel

or blend with
diesel fuel

A colloidal equilibrium
dispersion of
optically isotropic fluid
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 longchain 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

Liquid nature-portability

Lower volatility

Coking and trumpet

formation
Carbon deposits

Reactivity of
unsaturated
hydrocarbon chains

Oil ring sticking;

thickening and gelling of
the lubricating oil

Better spray patterns

during
combustion

Lower cetane number

Irregular injector needle

sticking; incomplete

Lower fuel viscosities

Lower energy content

Heat content (80% of

diesel fuel)
Readily available;
renewability

Higher viscosity

[913]

[14,21]

combustion
Heavy carbon deposits;
increase lubrication oil
viscosity
Chemically similar to
petroleumderived gasoline and
diesel fuel
Renewability; higher
cetane
number; lower emissions;
higher
combustion efficiency

Energy intensive and

[1520]

[2123]

hence higher cost

Disposal of byproduct (glycerol and

waste water)

[31]

80
95
96.9
97.5
98

Methods

[9,18,20]
[20,25]

[20,37]
[20,22]
[7,20,25]

[11]

glycerides, free fatty acids,

water,
and
other
contaminants in vari-ous
proportions. Some crude
vegetable
oils
contain
phospholipids that need to
be
removed
in
a
degumming
step.
CH2OCOR1
CH2OH
Phospholipids can produce
|
|
lecithin,
a
commercial
emulsifier [65]. Liu et al.
CHOCOR2
+H2O
CHOCOR2+
compared
the
different
|
|
degumming methods, such
CH2OCOR3
CH2OCOR3
as membrane filtration,
(Triglyceride)
(Water)
(Diglyceride) hydration, acid micelles
degumming,
supercritical
extraction,
etc.
The
characteristics of the raw
However, the FFA can react with alcohol to form ester oils should be investigated
(biodie-sel) by an acid-catalyzed esterification reaction. before
choosing
the
This reaction is very useful for handling oils or fats with suitable
degumming
high FFA, as shown in the equation below:
method because different
degumming methods have
their
advantages
and
ROH H
disadvantages [66]. The oil
R1COOH alcohol ! ROCOR1 H2O
can be separated through

Normally, the catalyst for this reaction is concentrated membrane filtration accordsulphu-ric acid. Due to the slow reaction rate and the high ing
to
the
average
methanol to oil molar ratio that is required, acid-catalyzed molecular weight or the
esterification has not gained as much attention as the particle size of phosalkali-catalyzed transesterification [63].
pholipids.
Although
degumming method can
solve the problem,
2.2. Biodiesel production processes
cost [62]. Water, originated either from the oils and fats or
formed during the saponification reaction, retards the
transesterification reaction through the hydrolysis reaction.
It can hydrolyze the tri-glycerides to diglycerides and forms
more FFA. The typical hydro-lysis reaction is shown in Eq.
(3).

FFA

fatty acid ester

Fig. 1. Simplified process flow

chart of alkali-catalyzed
biodiesel production.

water

2.2.1. Process flow chart

Today, most of the biodiesel is produced by the alkalicatalyzed process. Fig. 1 shows a simplified flow 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 al-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
2.2.3).

Catalyst

Mixing
Alcohol

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 triReneutralization

AlcoholRecovery

Crude
Glycerol

Quality
Control

Biodiesel

D.Y.C. Leung et al. / Applied Energy 87 (2010) 10831095

acid-catalysts or solid acidits process involves two steps with the use of catalysts [78]. Compared with the
an organic solvent. Therefore, this method has former one, solid acid-catalysts
no superiority on cost because of itsoffer some advantages for
complicated processing [67,68]. In theeliminating separation, corrosion,
and
environmental
hydration process, because of phospholipidstoxicity,
hydrophilicity, hot water can be added into the problems, but the reaction rate is
oil with stirring. The phospholipids solubility willslower [76]. As described earlier,
be significantly reduced, so it could befree fatty acids will be converted
separated from the oil by natural settle-ment. to biodiesel by direct acid
The hydration method features a simpleesterification and the water needs
process, easy oper-ation, and high yieldsto be removed. If the acid value
refining, but non-hydratable phospholipidsof the oils or fats is very high,
esterification
cannot be removed by this method, as reportedone-step
by Verleyen et al. [69]. For removing non-pretreatment may not reduce the
hydratable phospholipids, critic acid orFFA efficiently because of the
phosphoric acid can be added into the oil whichhigh content of water produced
is heated to 70 LC, this is called the special during the reaction. In this case,
micelles degumming method. Pan et al. [70]a mixture of alcohol and sulphuric
found that the reaction time for this method isacid can be added into the oils or
about 5 min, followed by neutralization through fats three times (three-step predilute lye. The supercrit-ical extraction methodesterification). The time re-quired
is employed to separate the phospholipids.for this process is about 2 h and
Moreover, by refining with supercritical CO 2water must be removed by a
extraction, it can effectively remove the freeseparation funnel before adding
fatty acids and the peroxidation prod-ucts thatthe mixture into the oils or fats for
again
[79].
are in the crude oil. However, the high pressure esterification
required in this process will be the biggest Moreover, some researchers rechallenge in its industrial appli-cation [71,72]. duce the percent of FFA by using
acidic ion exchange resins in a
The free fatty acids are removed in a packed bed. Strong commercial
refining step and excess free fatty acids can be acidic ion exchange resins can
removed as soaps in a later pretreatment step.be used for the esterification of
In addition, deodorization is another important FFA in waste cooking oils but the
step in the raw material treatment. During thisloss of the catalytic activity
step, steam, at 16 mm Hg pressure, is injected maybe a problem [8084].
into the oil at 490550 K in order to eliminate
free fatty acids, aldehydes, unsaturated An alternative approach to
hydrocarbons, and ketones, all of which causereduce the FFA is to use iodine
undesirable odors and flavors in the oil [73].as a catalyst to convert free fatty
Next, in order to determine the percentage of acids into biodiesel. An obvious
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 acidcatalysis 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

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 LC; 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 LC, 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 [8789].
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 [9093]. Compare
with enzyme catalysts, the alkali
and acid catalysts are more commonly
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-kalicatalyzed transesterification is most commonly

used commer-cially [36,38,9499]. 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 catalyze 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
[27,33,82,102109].
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) 10831095

Table 4
Advantages and disadvantages at different types of catalysts used in the biodiesel production.
Type

Example

Advantages

Disadvantages

References

Alkali
Homogeneous

NaOH, KOH

High catalytic activity, low cost,

favorable kinetics, modest
operation conditions
Noncorrosive, environmentally
benign, recyclable, fewer disposal
problems, easily separation, higher
selectivity, longer catalyst lifetimes

Low FFA requirement, anhydrous conditions,

saponification, emulsion formation, more
wastewater from purification, disposable
Low FFA requirement, anhydrous conditions,
more wastewater from purification, high
molar ratio of alcohol to oil requirement,
high reaction temperature and pressure,
diffusion limitations, high cost

[97,101104]

Catalyze esterification and

transesterification simultaneously,
avoid soap formation

Equipment corrosion, more waste from

neutralization, difficult to recycle, higher
reaction temperature, long reaction times,
weak catalytic activity

[97,102,103]

Catalyze esterification and

transesterification simultaneously,
recyclable, eco-friendly

Low acid site concentrations, low

microporosity, diffusion limitations, high
cost

[82,98,103,104]

Avoid soap formation, nonpolluting,

easier purification

Expensive, denaturation

[27,82,104]

Heterogeneous

Acid
Homogeneous

Heterogeneous

Enzymes

CaO, CaTiO3, CaZrO3, CaOCeO2, CaMnO3,

Ca2Fe2O5, KOH/Al2O3, KOH/NaY, Al2O3/KI,
ETS-10 zeolite, alumina/silica supported
K2CO3

Concentrated sulphuric acid

ZnO/I2, ZrO2=SO4 , TiO2 =SO4 , carbon-based

solid acid catalyst, carbohydrate-derived
catalyst, Vanadyl phosphate, niobic acid,
sulphated zirconia, Amberlyst-15, NafionNR50
Candida antarctica fraction B lipase,
Rhizomucor mieher lipase

hence shorten the reaction

time. During this step, in
order to speed up the
2.2.5. Mixing and neutralization
The purpose of mixing methanol with the catalyst is toreaction, mixing brings the
produce methoxide which reacts with the base oils. Most of oil, the catalyst, and the
into
intimate
the catalysts (e.g. NaOH, KOH) are in solid form and do not alcohol
contact
while
the
readily dissolve into methanol, it is best to start agitating the
temperature
is
kept
just
methanol in a mixer and add the catalyst slowly and
carefully [64]. Once the catalyst com-pletely dissolves in the below the boiling point of
methanol, the methoxide is ready to be added to the oil.the alcohol (i.e. 64.5 LC for
Once the methoxide is added into the oil, a neu-tralization methanol). Normally, the
reaction will immediately start. Some alkali catalysts will reaction pressure is close
the
atmospheric
react with rudimental acids during the pretreatment step orto
will react with the free fatty acids from the oil. Therefore, pressure to prevent the
more cat-alyst needs to be added to complete the reaction. loss
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 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

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 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 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,

[33,99
101,103,104]

alcohol, and oil during the transesterification step. Soap that effective
for
washing
may be generated during the process also contaminates the shearing shed floor, so it
biodiesel and glycerol phase. Schumacher [114] suggestedcan be used as a heavy
detergent
and
that although the glycerol phase tends to contain a higherduty
Whittington
percentage of contaminants than the biodiesel, a significantdegreaser.
amount of contami-nants is also present in the biodiesel. [118] reported that glycerol
Therefore, crude biodiesel needs to be purified before use. can even be fermented to
produce eth-anol, which
means more biofuel can be
2.2.7. Refining crude glycerol
produced.
Although biodiesel is the desired product from the
According
to
the
reactions, the refining of glycerol is also important due to its
statements of Van Gerpen
numerous appli-cations in different industrial products such
et
al.
[86],
typically
as moisturizers, soaps, cosmetics, medicines, and other
produced glycerol is about
glycerol products [115117]. It is one of the few products
50% glycerol or less in
that has a good reactivity on sump oil, and is extremely

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) 10831095

1089
Table 5
Different approaches for purifying crude

recovered for use as a fertilizer [119]. Generally,biodiesel.

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 approaches are adopted for purifying biodiesel:
water washing, dry washing [122], and
membrane extraction [123,124]. These approaches 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
LC). The crude biodiesel is

pumped into the hollow fiber membrane (flow decreases the loss during the
refining process. The purity of the
rate: 0.5 ml/min;
operating pressure: 0.1 MPa). Following this biodiesel obtained is about 90%
step, biodiesel is passed over heated Na2SO4 and the other properties conform
to the ASTM standards [130]. It is
and then filtered to remove any remaining
a very promising method for
water [124]. This approach effectively avoids
purifying biodiesel.
emulsifi-cation during the washing step and
Approaches

Water washing

Primary
material
used
Distilled
warm
water

Softened
water
Dry washing

Membrane
extraction

Ion
exchange
resin
Magnesium
silicate
powder
Polysulfone

2.2.9. Quality control

For commercial fuel, the
finished biodiesel must be
analyzed using sophisticated
analytical equipment to ensure it
meets inter-

Function

Phases separation

Advantage

Disadvantage

References

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 effluent, product loss,
emulsions formation

[46,7274]

Waterless

Overruns the limit in the EN

Standard

[69,75,76]

Remove the
contaminants

Avoids the emulsion

formation and decreases
the refining loss

Probably high cost and low

throughput due to contaminants
existed

[70,71]

1090

D.Y.C. Leung et al. / Applied Energy 87 (2010) 10831095

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 LC to
<40 LC, 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

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

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 LC.
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 treatedminimized in the stored

with an antioxidant additive [86].fuel by using bio-cides.
Moreover,
because
waterBiodiesel storage tanks
contamination will lead to biologicalmade of aluminum, steel,
growth in the fuel, it should beTeflon, and fluorinated
Property
Flash point
Kinematic viscosity at 40 LC
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 LC
Distillation T90 AET
Sulfur (S 15 Grade)
Sulfur (S 500 Grade)
Sulfur content
Water and sediment
Water content
Total contamination
Oxidation stability at 110 LC
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)

Unit

polyethylene
or
polypropylene should be
selected.

Limits

Test method

ASTM D6751

EN 14214

ASTM D6751

EN 14214

LC
2
mm /s

% (m/m)

mg KOH/g
% (m/m)
% (m/m)
% (m/m)

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

101.0 min
3.55.0
51 min

0.25 max
0.01 max

D93
D445
D613
D874
D130
D664
D6584
D6584
D4951

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

% (m/m)

0.050 max

Report customer

360 max
0.0015 max
0.05 max

0.050 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

D4530

D2500

D1160
D5453
D5453

D2709

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

LC
3
kg/m
LC
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

Class 1
0.5 max

D.Y.C. Leung et al. / Applied Energy 87 (2010) 10831095

ratio is associated with the

The tanks should minimize the type of catalyst used and
possibility of water contamination andthe molar ratio of alcohol
should be cleaned prior to use forto triglycerides in most
inves-tigations is 6:1, with
biodiesel storage [137].
the use of an alkali
2.4. Main factors affecting the yield of catalyst [47,138]. When
the percentage of free
biodiesel
fatty acids in the oils or
fats is high, such as in the
2.4.1. Alcohol quantity
Many researchers recognized thatcase of waste cooking oil,
one of the main factors affecting the a molar ratio as high as
yield of biodiesel is the molar ratio of 15:1 is needed when
acid-catalyzed
alcohol to tri-glyceride [28,47,61,138].using
Theoretically,
the
ratio
fortransesterification
transesterifica-tion reaction requires 3[28,133,139,140].
mol of alcohol for 1 mol of triglyceride
to produce 3 mol of fatty acid ester
and 1 mol of glycerol. An excess of2.4.2. Reaction time
alcohol is used in biodiesel production Freedman et al. [141]
to ensure that the oils or fats will be found that the conversion
completely converted to esters and arate of fatty acid esters
higher alcohol triglyceride ratio canincreases with reaction
result in a greater ester conversion in time. At the beginning, the
a short-er time. The yield of biodiesel reac-tion is slow due to
is increased when the alcohol triglyc-the mixing and dispersion
eride ratio is raised beyond 3 andof alcohol into the oil. After
reaches
a
maximum.
Furthera while, the reaction
very
fast.
increasing the alcohol amount beyondproceeds
the
yield
the optimal ratio will not in-crease theNormally,
yield but will increase cost for alcohol reaches a maximum at a
recovery [28]. In addition, the molarreaction time of <90 min,

1091

and
then
re-mains
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 transesterification, 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 reactioncatalyst

(NaOH)
temperature
accelerates
theconcentration reaches 1.5
saponifica-tion
reaction
ofwt.% and then decreases
triglycerides.
The
reactiona little with a further
temperature must be less than theincrease
in
catalyst
boiling point of alcohol in order toconcentration. The reducensure that the alcohol will not leaktion of the yield of the
out through vaporization. Dependingbiodiesel is due to the
on the oil used, the optimaladdition
of
excessive
temperature ranges from 50 LC to 60alkali catalyst causing
LC [28,61,141].
more triglycerides to react
with the alkali catalyst and
form more soap [28,143].
2.4.4. Catalyst concentration
Catalyst concentration can affect
3. Other processes of
the yield of the biodiesel prod-uct. As
biodiesel production
mentioned
before,
the
most
commonly used catalyst for the
3.1. Biox co-solvent
reaction
is
sodium
hydroxide.process
However, Freedman et al. [141] found
that sodium methoxide was more The Biox co-solvent
effective than sodium hydroxideprocess was developed
because
upon
mixing
sodiumby Boocock et al. in 1996
hydroxide with methanol a small[146]. In this process,
amount of water will be produced,triglycerides are converted
which will affect the product yield to esters through the
because of the hydrolysis reactionselection of inert co[145]. This is the reason why thesolvents that generate a
catalyst should be added into theone-phase oil-rich system
methanol first and then mixed with the[86,94,146].
Co-solvent
oil. As the catalyst concentration in-options are available to
creases the conversion of triglyceride overcome slow reaction
and the yield of biodiesel in-crease.times caused by the
This is because an insufficient amountextremely low sol-ubility of
of catalysts result in an incompletethe
alcohol
in
the
conversion of the triglycerides into thetriglyceride
phase.
fatty acid es-ters [28,145]. Usually, theDemirbas
[94]
uses
yield reaches an optimal value whentetrahydrofuran (THF) as
the
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
cosolvent 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 final products
should
be
water-free
[146].
The
unique
advantage of the Biox cosolvent pro-cess is that it
uses inert, reclaimable cosolvents 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
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 noncatalytic
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 twophase 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[94,147,148].

obtained under the optimal conditions.
In contrast to the com-mon alkalicatalyzed method, this process has
advantages in terms of reaction time3.3. In situ biodiesel
and purification but requires a highprocess
temperature and pressure, hence
requiring a high amount of energy

The in situ biodiesel

production is a novel
approach for convert-ing
oil to biodiesel which was
developed by Harrington
and DArcy-Evans in 1985
[152]. In this method, to
achieve transesterification

1092

D.Y.C. Leung et al. / Applied Energy 87 (2010) 10831095

There are four primary

of its acyglycerols, the oilseeds arefactors affecting the yield
directly treated at ambient tem-of biodiesel, i.e. alcohol
perature and pressure with aquantity, reaction time,
methanol solution in which the cata-reaction temperature, and
lyst has been previously dissolved.cat-alyst concentration. To
a
complete
That means that the oil in the oilseeds ensure
reacis
not
isolated
prior
totransesterification
transesterification to fatty acid es-terstion, the molar ratio of
[152154]. To reduce the alcoholalcohol to triglycerides
requirement for high effi-ciency duringshould be increased to 6:1
in situ transesterification, the oilseedswith the use of an alkali
need to be dried before the reactioncatalyst. For used cooking
takes place [155]. Milled oilseeds areoils or for oils with a high
mixed with alcohol in which thepercentage of free fatty
catalyst had been dissolved and theacids, a higher molar ratio
mixture is heated under reflux for 15is needed for acidh. Two layers are formed around the catalyzed
time of the completion of the reaction.transesterification.
The lower layer is the alcohol phaseBecause the con-version
and can be recovered. The upperrate of fatty acid esters
layer, including the crude biodiesel, is increases with reaction
washed with water to remove the time but the yield of the
contami-nants until the washingbiodiesel product reaches
solution is neutral. After the washinga maximum at an opti-mal
time.
Higher
step, the upper layer is dried overreaction
anhydrous sodium sulfate, then fil- reaction temperature can
tered, and the residual product isdecrease the viscosity of
enhancing
the
biodiesel [156]. Haas and Scott [155]oils,
found that the final biodiesel productreaction rate. The optimal
ranged
can conform to the ASTM standardtemper-ature
and the conversion of the oilseed is between 50 LC and 60
very high (about 98%). Since thisLC, depending on the oil
The
optimal
method eliminates the need for the used.
of
catalyst
isolation of, and possibly for thecondition
refining of, the oilseed lipid, the concentration is about 1.5
process could re-duce biodieselwt.% for NaOH which is
production costs, reduce the long sizethe most commonly used
of the produc-tion system associatedcatalyst. With increas-ing
over
global
with the pre-extraction, degumming,concern
warming,
it
is
foreseeable
and maximize the yield of the
biodiesel production. However, thisthat biodiesel usage would
pro-cess cannot handle waste cookingcontinue to grow at a fast
oils and animal fats, which can reducepace. This will trigger the
development of more
the cost of feedstock [156,157].
sophisticated methods of
biodiesel produc-tion and
refining to cope with the
increasing
market
4. Conclusions
demand.
(oils or fats)
Biodiesel is a clean-contain a high
burning diesel fuel withpercentage of
a chemical struc-ture offree fatty acids
fatty acid alkyl esters.or water, the
Of the various methodsalkali catalyst
available for producingwill react with
biodiesel, the alkali-the free fatty
acids to form
catalyzed
transesterification
ofsoaps and the
can
vegetable
oils
andwater
animal fats is currentlyhydrolyze the
the most commonlytriglycerides
adopted
method.into
Transesterification
isdiglycerides
basically a sequentialand form more
reac-tion.
However,free fatty acids.
are
when the raw materialsThese

Acknowledgement
The authors would like
to
acknowledge
the
support of the ICEE and
the
University
Development Fund of the
University of Hong Kong.

References

undesirable
reducing
the
reactions whichamount of free
reduce
thefatty
acids:
yield of the bio-esterification of
diesel product.free fatty acids
Therefore, afterwith methanol,
refining the rawin
the
materials, thepresence
of
acidic
acidic
feedstocks
catalysts;
should be pre-using iodine as
treated
toa
cat-alyst;
inhibit
theadding glycerol
saponifica-tion into the acidic
reaction. Therefeedstock with
are
threea catalyst like
primary
zinc
chloride
approaches forand heated to

a
high
temperature.
The
first
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separation,
corrosion,
toxicity,
and
environmen-tal
problems, but
the
reaction
rate is slower
while
the
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the
last
approach
is
that no alcohol
is needed and

the water (formed from

the reaction) can be
immediately vaporized
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The
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most commonly used
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while sodium hydroxide
and
potassium
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used
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be produced as a byproduct. Because of its
numerous
industrial
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biodiesel
produced, the product
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finished
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that
it
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