Fuel 89 (2010) 19

Contents lists available at ScienceDirect

Fuel
journal homepage: www.elsevier.com/locate/fuel

Review article

A review on FAME production processes

Amish P. Vyas *, Jaswant L. Verma, N. Subrahmanyam
Chemical Engineering Department, Nirma University, Ahmedabad 382481, India

a r t i c l e

i n f o

Article history:
Received 5 June 2009
Received in revised form 6 August 2009
Accepted 6 August 2009
Available online 27 August 2009
Keywords:
Bio-diesel
Transesterication
Ultrasound
Microwave
Algae

a b s t r a c t
Among the options explored for alternative energy sources, bio-diesel is one of the most attractive. This
paper discussed about the various production processes, few of which are applied at industrial level also,
to produce basically FAME (later can be utilized as bio-diesel after purication) and will be termed as biodiesel in this paper. Transesterication of vegetable oils/fats and extraction from algae are the leading
process options for bio-diesel production on large scale. This paper reviews briey the literature on
transesterication reaction using homogeneous, heterogeneous and enzyme catalysts. Employing also
ultrasound, microwave and supercritical alcohol techniques and also algae based bio-diesel.
2009 Elsevier Ltd. All rights reserved.

Contents
1.
2.
3.

4.
5.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Vegetable oil as diesel fuel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bio-diesel production via transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1.
Homogeneous alkali (base) catalyzed transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2.
Homogeneous acid-catalyzed transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.
Heterogeneous acid and base-catalyzed transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.4.
Enzymatic transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5.
Supercritical and subcritical alcohol transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.6.
Microwave assisted transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.7.
Ultrasound assisted transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Bio-diesel from algae oil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
Renewable energy sources are developed worldwide, owing to
high oil prices and to limit greenhouse gas emissions. Petroleum
is the largest single source of energy consumed by the worlds population, exceeding coal, natural gas, nuclear, hydro, and renewable.
Limited crude petroleum reserves and other sources are on the
verge of reaching their peak production. The depletion of known

* Corresponding author. Tel.: +91 2717 241911; fax: +91 2717 241917.
E-mail address: apvyas@nirmauni.ac.in (A.P. Vyas).
0016-2361/$ - see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2009.08.014

1
2
2
2
2
2
3
4
4
6
7
7
8

petroleum reserves will make renewable energy sources more

attractive. Bio-diesel is a renewable fuel that is produced mainly
from vegetable oils and animal fats. Named by the National Soy
Diesel Development Board (presently National Bio-diesel Board)
which has pioneered the commercialization of bio-diesel in the
US during 1992 [1]. Stringent environmental regulations created
huge interest in bio-diesel as an alternative fuel aiming major
reduction of vehicular emissions. Bio-diesel is safe, renewable,
non-toxic, and biodegradable in water (98% biodegrades in just a
few weeks), contains less sulfur compounds and has a high ash
point (>130 C). Table 1 shows the average bio-diesel emissions
compared to conventional diesel [2].

A.P. Vyas et al. / Fuel 89 (2010) 19

Table 1
Average bio-diesel emissions compared to conventional diesel [6].
Emission type

B20 (%)

B100 (%)

Total unburned hydrocarbons

CO
CO2
Particulate matter
NOx
SOx
Polycyclic aromatic hydrocarbons (PAHs)
Nitrated PAHs

20
12
16
12
+2
20
13
50

67
48
79
47
+10
100
80
90

2. Vegetable oil as diesel fuel

It is generally known that vegetable oils and animal fats were
investigated as diesel fuels well before the energy crises of the
1970s and the early 1980s sparked renewed interest in alternative
fuels. It is also known that Rudolf Diesel (18581913), the inventor
of the engine that bears his name, had used peanut oil as fuel in his
invention [3]. High fuel viscosity in compression ignition is the major problem associated in use of vegetable oils as a fuel. Viscosities
of vegetable oil are ranging 1020 times greater than diesel fuel
[4,5].
Four major techniques (dilution, microemulsion, pyrolysis, and
transesterication modication techniques) as well as the direct
use of the oil are used for viscosity reduction. Microemulsions with
alcohols have been prepared to overcome the problem of high viscosity of vegetable oils. Pyrolysis/cracking, dened as the cleavage
to smaller molecules by thermal energy, of vegetable oils over catalysts has been investigated [5,6]. Transesterication process has
been widely used to reduce the high viscosity of triglycerides [7].
Esterication is the sub category of transesterication. This requires two reactants, carboxylic acids (fatty acids) and alcohols.
Esterication reactions are acid-catalyzed and proceed slowly in
the absence of strong acids such as sulfuric acid, phosphoric acid,
organic sulfonic acids and hydrochloric acid [8].
Transesterication (also called alcoholysis) is the reaction of a
fat or oil with an alcohol (with or without catalyst) to form esters
and glycerol. Because the reaction is reversible, excess alcohol is
used to shift the equilibrium to the products side [9]. Under
Transesterication reaction with alcohol the rst step is the conversion of triglycerides to diglycerides, which is followed by the
subsequent conversion of higher glycerides to lower glycerides
and then to glycerol, yielding one methyl ester molecule from each
glyceride at each step [10].
3. Bio-diesel production via transesterication
3.1. Homogeneous alkali (base) catalyzed transesterication
Transesterication reaction can be catalyzed by both homogeneous (alkalies and acids) and heterogeneous catalysts. The most
commonly used alkali catalysts are NaOH, CH3ONa, and KOH
[11]. The reaction mechanism for alkali-catalyzed transesterication was formulated as three steps. The alkali-catalyzed transesterication of vegetable oils proceeds faster than the acid-catalyzed
reaction. The mechanism of the base-catalyzed transesterication
of vegetable oils was discussed by Demirbas [12].
In the alkali catalytic methanol transesterication method, the
catalyst is dissolved into methanol by vigorous stirring in a small
reactor. The oil is transferred into a bio-diesel reactor and then
the catalyst/alcohol mixture is pumped into the oil. The nal mixture is stirred vigorously for 2 h at 340 K at ambient pressure. A
successful transesterication reaction produces two liquid phases:
ester and crude glycerol [13].

Gemma et al. [11] selected four different alkaline catalysts i.e.

NaOH, KOH, CH3ONa, CH3OK for alkali-catalyzed transesterication of Sunower oil. The bio-diesel purity was near 100 wt.% for
all catalysts. High bio-diesel yields were obtained by using the sodium or potassium methoxide (99.33 wt.% and 98.46 wt.%, respectively), because they only contain the hydroxide group, necessary
for saponication, as a low proportion impurity. However, when
sodium or potassium hydroxides were utilized as catalysts, biodiesel yields decreased to 86.71 wt.% and 91.67 wt.%, respectively.
This is due to the presence of the hydroxide group that originated
soaps by triglyceride saponication. Owing to their polarity, the
soaps dissolved into the glycerol phase during the separation stage
after the reaction. In addition, the dissolved soaps increased the
methyl ester solubility in the glycerol, an additional cause of yield
loss [11]. Joana et al. reported higher yields (reaching 97%) using
virgin oils as compared to waste frying oils (reaching 92%) [14].
The base-catalyzed reaction is reported to be very sensitive to
the purity of the reactant. Free fatty acid (FFA) content should
not exceed beyond a certain limit. If FFA content in the oil were
about 3%. It has been found that the alkaline-catalyzed transesterication process is not suitable to produce esters from unrened
oils [15]. In order to prevent saponication during the reaction,
FFA and water content of the feed must be below 0.5 wt.% and
0.05 wt.%, respectively. Because of these limitations, only pure vegetable oil feeds are appropriate for alkali-catalyzed Transesterication without extensive pre-treatment [16].
3.2. Homogeneous acid-catalyzed transesterication
The liquid acid-catalyzed transesterication process is not
much popular as the base-catalyzed process. Homogeneous acidcatalyzed reaction is about 4000 times slower than the homogeneous base-catalyzed reaction. However, the performance of the
acid catalyst is not strongly affected by the presence of FFAs in
the feedstock. In fact, acid catalysts can simultaneously catalyze
both esterication and transesterication. Thus, a great advantage
with acid catalysts is that they can directly produce bio-diesel from
low-cost lipid feedstocks, generally associated with high FFA concentrations (low-cost feedstocks, such as used cooking oil and
greases, commonly have FFAs levels of >6%) [17]. The mechanism
of the acid-catalyzed transesterication of vegetable oils was discussed in detailed by Ulf et al. [18]. For acid-catalyzed systems, sulfuric acid [19,20,16,21], HCl, BF3, H3PO4, and organic sulfonic acids,
have been used by different researchers [17].
Freedman et al. [16] compared the transesterication of soybean oil with methanol, ethanol and butanol using 1% concentrated
sulfuric acid based on the weight of oil. In preliminary experiments
with 6:1 M and 20:1 M ratios at 3 h and 18 h, respectively, conversions to ester were unsatisfactory. A molar ratio of 30:1, however,
resulted in a high conversion to the methyl ester. Each alcoholysis
was conducted near the boiling point of the alcohol. The number of
hours needed to obtain high conversions to the ester were 3, 22,
and 69, respectively, for the butyl, ethyl, and methyl esters [16].
Mohamad et al. reported H2SO4 as superior to HCl commonly used
as acid catalyst for transesterication of used vegetable oils [19].
Table 2 shows the work carried out for bio-diesel production from
various feedstocks under different conditions using homogenous
acid and base catalyst.
3.3. Heterogeneous acid and base-catalyzed transesterication
Homogeneous catalysts showed greater performance toward
transesterication to obtain bio-diesel. The problems associated
with the homogeneous catalysts are the high consumption of energy, form unwanted soap byproduct by reaction of the FFA, expensive separation of the homogeneous catalyst from the reaction

A.P. Vyas et al. / Fuel 89 (2010) 19

Table 2
Homogeneous acid and base-catalyzed transesterication.
Oil

Catalyst

Catalyst amount
(%)

Alcohol wt.%
oil

Oil to alcohol molar

ratio

Reaction
conditions

Ester yield
(%)

Ester conversion
(%)

Ref.

Waste cooking oil

(WCO)
Karanja oil

H2SO4

Methanol

1:20

95 C, 10 h

P90

[21]

KOH

Methanol

1:6

98

Pongamia pinnata
Rapeseed oil

KOH
KOH

1
1

Methanol
Methanol

1:10
1:6

Sunower oil

NaOH

Methanol

1:6

Used frying oil (UFO)

1.1
1.5
1.3
3
1

Methanol

1:7.5

Soybean oil
Soybean oil

NaOH
KOH
CH3ONa
H2SO4
H2SO4

65 C, 2 h,
360 rpm
60 C, 1.5 h
65 C, 2 h,
600 rpm
60 C, 2 h,
600 rpm
70 C, 30 min

1:6
1:30

Soybean oil

H2SO4

0.5

n-Butanol
Methanol
Ethanol
Butanol
Methanol

120 C, 60 min
65 C, 50 h
78 C, 18 h
117 C, 3 h
100 C,
3.5 bar,8 h

1:9

mixture [30] and generation large amount of wastewater during

separation and cleaning of the catalyst and the products [31].
The use of heterogeneous catalysts could be an attractive solution.
Heterogeneous catalysts can be separated more easily from reaction products [32]. Undesired saponication reactions can be
avoided by using heterogeneous acid catalysts. They enable the
transesterication of vegetable oils or animal fats with high contents of FFAs, such as deep-frying oils from restaurants and food
processing [33]. Bio-diesel synthesis using solid catalysts could
potentially lead to cheaper production costs because of reuse of
the catalyst and the possibility for carrying out both transesterication and esterication simultaneously [34].
Satoshi et al. carried out the transesterication of soybean oil
with methanol to fatty acid ester over the solid super acid catalysts
of WZA (tungstated zirconiaalumina), SZA (sulfated zirconiaalumina), and STO (sulfated tin oxide) at 200 C300 C in xed bed
reactor under atmospheric pressure and reported WZA as a promising solid acid catalyst for the production of bio-diesel from soybean oil (conversion over 90%) [35]. Table 3 shows the work
carried out for bio-diesel production from various feedstocks under
different conditions using heterogeneous acid and base catalyst.

[22]

96

92

[23]
[24]

97.1

[25]

85.3
86.0
89.0

[26]

>95
>99
>99
>99
99

[27]
[28,16]

[29]

3.4. Enzymatic transesterication

Enzymatic transesterication using lipase looks attractive and
encouraging for reasons of easy product separation, minimal
wastewater treatment needs, easy glycerol recovery and the
absence of side reactions [48]. Practical use of lipase in pseudohomogenous reaction systems presents several technical difculties such as contamination of the product with residual enzymatic
activity and economic cost. In order to overcome this problem, the
enzyme is usually used in immobilized form so that it can be reused several times to reduce the cost and also to improve the quality of the product [49]. When free enzymes are used in a bio-diesel
process, the enzymatic activity can be partially recovered in the
glycerol phase. However, the build-up of glycerol limits the possible number of reuses [50].
Several studies of lipase-mediated transesterication for biodiesel production in solvent-free system were proposed [51,52].
In such systems, methanol has poor solubility in oil feedstocks,
and too much methanol existing as drops in a system would have
some negative effect on lipase activity [51,53]. To overcome this
problem Yuji et al. recommended the stepwise addition of metha-

Table 3
Transesterication of vegetable oil by using various heterogeneous catalysts.
Catalyst

Catalyst amount wt.% of

oil (%)

Oil

Alcohol

Molar
ratio

Optimum reaction
condition

Ester
conversion (%)

Ester yield
(%)

Ref.

Mg/La (magnesiumlanthanummixed oxide)

Mg/La (magnesiumlanthanummixed oxide)
SZrO2 sulfated zirconia
(Calcium ethoxide) Ca(OCH2CH3)2
(Calcium ethoxide) Ca(OCH2CH3)2
Li/CaO
KF/Al2O3
KNO3/Al2O3
KNO3/Al2O3
KF/Eu2O3
Eu2O3/Al2O3
KI/Al2O3

Sunower

Methanol

53:1

65 C, 30 min

100

[30]

Sunower

Methanol

53:1

100

[30]

5
3
2
4
6.5
6.0
3
10
2.5
3

Soybean
Soybean
Soybean
Karanja
Palm
Soybean
Jatropha
Rapeseed
Soybean
Soybean
Waste oil

Methanol
Methanol
Ethanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol
Methanol

20:1
12:1
12:1
12:1
12:1
15:1
12:1
12:1
6:1
15:1
9:1

Room temperature,
2.2 h
120 C, 1 h
65 C, 1.5 h
75 C, 3 h
65 C, 8 h
65 C, 3 h
65 C, 7 h
70 C, 6 h
65 C, 1 h
70 C, 8 h
65 C, 8 h
200 C, 5 h

87
84
92.5
63.0
96.0
92.0

98.6
95.0
91.8
94.8
90.0

[33]
[36]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[31]
[43]

7.5
3

Soybean
WCO

Methanol
Methanol

15:1
18:1

65 C, 9 h
200 C, 10 h

67.0

98.0

[44]
[45]

3
8

Soybean
Soybean

Methanol
Methanol

10:1
12:1

65 C, 8 h
65 C, 3 h

85.6

95

[46]
[47]

SO24 /TiO2SiO2
MgAl hydrotalcites
(ZS/Si) zinc stearate immobilized on
silica gel
KOH/NaX zeolite
CaO

A.P. Vyas et al. / Fuel 89 (2010) 19

nol, since the solubility of methanol in the alkyl esters is greater

than in the oil, and consequently limits enzyme deactivation
[54]. In addition, the liberated glycerol can also inhibit the reaction
by limiting substrate and product diffusion, due to its insolubility
in oil or organic solvent [55]. The enzymatic alcoholysis of triglyceride was studied in petroleum ether, hexane and gasoline solutions. However, the solubility of methanol and glycerol in these
solvents is low and the above problems probably persisted [56].
To solve this problem, tert-butanol was used as an ideal solvent.
With a certain amount of tert-butanol as the reaction medium,
both methanol and byproduct glycerol are soluble, so the negative
effect caused by methanol and glycerol on lipase catalytic activity
could be totally eliminated [56,57].
Different acyl acceptors have been studied for enzymatic catalyzed bio-diesel production. Alcohol has been chosen as the acyl
acceptors by the majority of the researchers. Several alcohols like
methanol [5759] ethanol [6062], 2-propanol [63] and 2-butanol
[64] have chosen as acyl acceptors for lipase-catalyzed transesterication. Apart from alcohols methyl acetate [65,66] and ethyl acetate [67] were also used as acyl acceptors. Jech et al. used different
types of alcohols to test the deactivation effect on the enzyme.
Both linear alcohols such as methanol, ethanol, propanol and butanol and branched alcohols such as isopropanol, 2-butanol and isobutanol. Jech et al. reported that all of the linear alcohols were
toxic to the immobilized enzyme. The degree of deactivation was
found to be inversely proportional to the number of carbon atoms
in the linear lower alcohols. In case of branched alcohols the degree
of deactivation was to be lower than that by the linear alcohols
[68].
The effect of water content on the production of bio-diesel from
soybean oil using lipases from R. oryzae, C. rugosa and P. uorescens,
Novozym 435 and B. cepacia have all shown that enzyme activity
was low in the absence of water, which supports the fact that a
minimum amount of water is required to activate the enzyme.
With increased addition of water there was a considerable increase
in ester production, showing the enhancement in the activity of the
enzyme [49]. On the other hand Yuji et al. has reported that with
the addition of water that ester production decreased [51]. The
amount of water to be maintained in bio-diesel production using
immobilized lipase depends on the feedstock (the water content
of feedstock differs for waste oil to that of rened oil), source of lipase (some commercial lipases are in a powder form which must
be dissolved in coupling media before immobilization process),
immobilization technique (some immobilization techniques involves the use of water) and the type of acyl acceptor (analytical
grade or reagent grade). Thus, it was recommended to optimize
the water content depending on the reaction system used [48].
Compared to chemical approach enzymatic approach for biodiesel production offers more advantages but cost of lipase is the
major issue for the industrialization of lipase-mediated bio-diesel
production. Du et al. reported that there are two ways to reduce
the lipase cost. One is to reduce the production cost of the lipase,
which can be realized through new lipase development, fermentation optimization, and downstream processing improvement. Another way is to improve/extend the operational life of the lipase,
and this can be achieved through enzyme immobilization, alcoholysis reaction optimization, etc. [53]. Table 4 shows the comparison
of various lipase-mediated bio-diesel production.
3.5. Supercritical and subcritical alcohol transesterication
Transesterication of vegetable oil with non-catalytic supercritical methanol provides a new way of producing bio-diesel. Transesterication reaction in supercritical conditions was completed in
minutes, while the conventional catalytic transesterication takes
several hours [72]. Transesterication of triglycerides (non-polar

molecules) with an alcohol (polar molecule) is usually a heterogeneous (two liquid phases) reaction at conventional processing temperatures because of the incomplete miscibility of the non-polar
and polar components. Under supercritical conditions, however,
the mixture becomes a single homogeneous phase, which will
accelerate the reaction because there is no interphase mass transfer to limit the reaction rate. Another positive effect of using supercritical conditions is that the alcohol is not only a reactant but also
an acid catalyst [73,74].
A reaction mechanism of vegetable oil in supercritical methanol
is presented by Kusdiana and Saka [74]. It is assumed that an alcohol molecule directly attacks the carbonyl atom of the triglyceride
because of the high pressure. In the supercritical state, depending
on pressure and temperature, hydrogen bonding would be signicantly decreased, which would allow methanol to be a free monomer. The transesterication is completed via a methoxide transfer,
whereby the fatty acid methyl ester and diglycerides are formed. In
a similar way, diglyceride is transesteried to form methyl ester
and monoglycerides which is converted further to methyl ester
and glycerol in the last step. The presence of water in the reaction
system does not affect the yield of methyl esters under supercritical alcohol transesterication [74].
Methanol, ethanol, 1-propanol, 1-butanol, or 1-octanol were
used to study the transesterication of rapeseed oil at temperatures of 350 C (rapeseed oil to alcohol molar ratio 42:1) and reported >90% yield of methyl esters was achieved [75,76]. On the
other hand, it took 8 min for ethanol, 1-propanol, and 1-butanol
to obtain the same yield of the corresponding alkyl esters, and even
longer for 1-octanol. In the case of ethanol, 1-propanol, and 1-butanol about 814 min of supercritical treatment was necessary to
achieve almost complete conversions of triglycerides to fatty acid
alkyl esters, while for 1-octanol, 20 min was required to obtain
the same yield.
Synthesis of bio-diesel by supercritical methanol has a drawback with the high cost of apparatus due to the high temperature
and pressure, which are not viable in the large scale practice in
industry [77]. So, researches have focused on how to decrease
the severity of the reaction conditions. Co-solvents, such as carbon
dioxide [75,76,79], hexane [77,78], propane [80] and calcium oxide
[81] and subcritical alcohol [79,82] with small amount of catalyst,
added into the reaction mixture can decrease the operating temperature, pressure and the amount of alcohol. The supercritical
methanol method with co-solvents like hexane and condensed
CO2 can improve the product yield [77]. A 98% yield of methyl esters was observed in 20 min at the subcritical condition (160 C)
with 0.1 wt.% potassium hydroxide and methanol to oil ratio of
24 [78]. Table 5 shows the work carried out for bio-diesel production from various feedstocks under different conditions using
supercritical alcohol.
3.6. Microwave assisted transesterication
The use of microwave heating as a tool for preparative chemistry is continuing to grow. By using microwave irradiation it is often
possible to reduce reaction times signicantly as well as improve
product yields. An alternative energy stimulant, microwave irradiation can be used for the production of the alternative energy
source, bio-diesel [90]. Microwave irradiation activates the smallest degree of variance of polar molecules and ions such as alcohol
with the continuously changing magnetic eld. The changing electrical eld, which interacts with the molecular dipoles and charged
ion, causes these molecules or ions to have a rapid rotation and
heat, is generated due to molecular friction [90]. The preparation
of bio-diesel using microwave offers a fast, easy route to this valuable biofuel with advantages of a short reaction time, a low oil/
methanol ratio, an ease of operation a drastic reduction in the

A.P. Vyas et al. / Fuel 89 (2010) 19

Table 4
Comparison of various lipase-mediated bio-diesel production.
Carrier used

Source of enzyme

a
(%)

Oil

Solvent

Conversion
(%)

Yield
(%)

Ref.

Candida antarctica

1.6
4

Methanol
Methanol

t-Butanol
t-butanol

4:1
4:1

50 C, 24 h
40 C, 12 h

95

88

[56]
[57]

Polypropylene
ep100
-

10

Methanol

Hexane

4.5:1

40 C, 48 h

91

[59]

15

Soybean

Ethanol

7.5:1

96

[60]

10

Jatropha

Ethanol

4:1

31.5 C,
7h
40 C, 10 h

92

[61]

20

Palm

Ethanol

18:1

[62]

10

Propan-2-ol

4:1

Acrylic resin

Candida antarctica

30

Jatropha
Karanja
Sunower
Soybean

58 C,
<24 h
50 C, 8 h

98

Acrylic resin

Pseudomonas
uorescens
Thermomyces
lanuginosus
Chromobactrium
viscosum
Pseudomonas
uorescens
Candida antarctica

Cotton seed
Waste cooking palm
oil
Sunower oil

12:1

40 C, 10 h

92

[63]
[66]

MacroporousAcrylic resin

Toyonite-200 M

Candida antarctica

10

Jatropha

Methyl
acetate
Ethyl acetate

92.8
91.7
93.4
-

11:1

40 C,12 h

91.3

[67]

Candida antarctica
Pseudomonas
uorescens
Candida antarctica

3
9.4

Rapeseed
Sunower

Methanol
1-Propanol

t-Butanol

4:1
3:1

35 C, 12 h
60 C, 20 h

95
91

[69]
[70]

Soybean

Methanol

[Emim][TfO]

4:1

50 C,12 h

80

[71]

Celite-545
POS-PVA

Acrylic resin

Amount of enzyme used (wt.% of oil): a, acyl acceptors: b, alcohol to oil molar ratio: c, optimum reaction conditions: d.

Table 5
Supercritical alcohol transesterication reaction conditions.
Vegetable oil

Molar
ratio

Alcohol

Temperature and
pressure

Reaction
time

Reactor type

Conversion
(%)

Yield
(%)

Ref.

Sunower oil
Rapeseed oil
Hazelnut kernel oil

40:1
42:1
41:1

Methanol
Methanol
Methanol

350 C, 200 bar

350 C, 45 MPa
350 C, NA

40 min
240 s
300 s

96
95
95

[6]
[83]
[84]

Jatropha oil
Soyabean oil
Coconut oil, palm
kernel oil
Cottonseed oil

40:1
40:1
42:1

Methanol
Methanol
Methanol

350 C, 200 bar

310 C, 35 MPa
350 C, 19.0 MPa

40 min
25 min
400 s

8 mL SS reactor
5 ml reaction vessel made of Inconel-625
100 ml cylindrical autoclave made of 316
stainless steel
11 mL reactor of SS 316
75 ml tube reactor
Tubular ow reactor

>90

9596

96

[85]
[86]
[87]

41:1

Methanol

230 C, NA

8 min

Autoclave

[88]

300 C, NA

60 min

8.8 ml SS reactor

98
(Methanol)
75
(Ethanol)
60.30

[89]

Ethanol
Palm oil

45:1

Methanol

NA: not available.

quantity of by-products, and all with reduced energy consumption.

Table 6 shows the comparison of energy consumption for the preparation of bio-diesel using conventional and microwave heating.
Several examples of microwave irradiated transesterication
methods have been reported using homogenous alkali catalyst
[92,93,90], acid catalyst [91] and heterogeneous catalyst [94,95].
Nezihe et al. [92] reported 93.7% (for 1.0% (w/w) KOH) and 92.2%
(for 1.0% (w/w) NaOH) yield of bio-diesel at 313 K temperature
within 1 min under microwave heating. Michael et al. [96] used
continuous-ow microwave methodology for the transesterication and reported continuous-ow microwave methodology for
the transesterication reaction is more energy-efcient than using
a conventional heated apparatus. Microwave assisted transesterication of castor bean oil was carried out in the presence of methanol or ethanol, using a molar ratio alcohol/castor bean oil of 6:1,
and 10% w/w basic alumina (in relation to the oil mass) as catalyst.
A 95% conversion were obtained under basic conditions (Al2O3/50%
KOH) using methanol at conventional (60 C, stirring, 1 h) or
microwave conditions (5 min) [95].
Aside from the great advantages of microwave-assisted reactions, there are also a few drawbacks. Microwave synthesis is not

easily scalable from laboratory small-scale synthesis to industrial

multi kilogram production. The most signicant limitation of the

Table 6
Comparison of energy consumption for the preparation of bio-diesel using conventional and microwave heating [96].

Reaction conditions

Energy consumption
(kJ/L)a

Conventional heatingb
Microwave, continuous-ow at a 7.2 L/min
feedstock ow
Microwave, continuous-ow at a 2 L/min feedstock
owc
Microwave heating, 4.6 L batch reactione

94.3
26.0
60.3 (92.3)d
90.1

Normalized for energy consumed per liter of bio-diesel prepared.

On the basis of values from the joint US Department of Agriculture and US
Department of Energy 1998 study into the life cycle inventory of bio-diesel and
petroleum diesel for use in an urban bus.
c
Assuming a power consumption of 1700 W and a microwave input of 1045 W.
d
Assuming a power consumption of 2600 W and a microwave input of 1600 W.
e
Assuming a power consumption of 1300 W, a microwave input of 800 W, a time
to reach 50 C of 3.5 min, and a hold time at 50 C of 1 min.
b

A.P. Vyas et al. / Fuel 89 (2010) 19

Table 7
Microwave assisted transesterication.
Oil/triolein

Catalyst

a (%)

Alcohol

Microwave conditions

Reaction conditions

c (%)

d (%)

Ref.

Cottonseed oil

KOH

1.5

Methanol

1:6

7 min, 333 K

92.4

[90]

Rapeseed oil

KOH

Methanol

1:6

Reaction mixture irradiated using

21% of an exit power of 1200 W
Reaction mixture irradiated using
67% of an exit power of 1200 W

5 min, 323 K

93.7

[92]

1
1
1
5

Methanol
Ethanol
Methanol
Methanol

1:6
1:6
1:6
1:6

40 W
220 W
40 W
25 W

3 min, 313 K
30 min
25 min
05 min
1 min, 323 K

93.7

[95]

Methanol

1:12

200 W

60 min, 338 K

94

95
95
95
98
98

NaOH
SiO2/50% H2SO4
SiO2/30% H2SO4
Al2O3/50% KOH
KOH
NaOH
H2SO4/C

Castor oil

Triolein
Castor oil

[97]
[98]

Catalyst amount (wt.% of oil): a, oil to alcohol molar ratio: b, ester yield: c, ester conversion: d.

scale up of this technology is the penetration depth of microwave

radiation into the absorbing materials, which is only a few centimeters, depending on their dielectric properties. The safety aspect
is another reason for rejecting microwave reactors in industry [91].
Table 7 shows the work carried out for bio-diesel production from
various feedstocks under different conditions using microwave
irradiation.

3.7. Ultrasound assisted transesterication

Ultrasound has proven to be a very useful tool in enhancing the
reaction rates in a variety of reacting systems. It has successfully
increased the conversion, improved the yield, changed the reaction
pathway, and/or initiated the reaction in biological, chemical, and
electrochemical systems [99]. Ultrasound is dened as sound of a
frequency beyond that to which the human ear can respond. The
normal range of hearing is between 16 Hz and about 18 kHz and
ultrasound is generally considered to lie between 20 kHz to beyond
100 MHz [100] like any sound wave, ultrasound alternately compresses and stretches the molecular spacing of the medium
through which it passes, causing a series of compression and rarefaction cycles. If a large negative pressure gradient is applied to the
liquid so that the distance between the molecules exceeds the critical molecular distance necessary to hold the liquid intact, the liquid will break down and voids (cavities) will be created, i.e.,
cavitation bubbles will form. At high ultrasonic intensities, a small
cavity may grow rapidly through inertial effects. As a result, some
bubbles undergo sudden expansion to an unstable size and collapse violently, generating energy for chemical and mechanical effects [101]. The collapse of the cavitation bubbles disrupts the
phase boundary and causes emulsication, by ultrasonic jets that
impinge one liquid to another [102].

A low frequency ultrasonic irradiation could be useful for

transesterication of triglyceride with alcohol. Ultrasonication provides the mechanical energy for mixing and the required activation
energy for initiating the transesterication reaction [103]. Ultrasonication increases the chemical reaction speed and yield of the
transesterication of vegetable oils and animal fats into bio-diesel
[104]. Ultrasonic assisted transesterication method presents
advantages such as shorter reaction time and less energy consumption than the conventional mechanical stirring method
[105], efcient molar ratio of methanol to TG, and simplicity
[106]. For the transesterication of 1 kg soybean oil conventional
mechanical stirring method and ultrasonic cavitation method
consume 500 and 250 W/kg of energy, respectively [105]. Carmen
et al. [102,107] reported that conversion of vegetable oil (no further information on the nature of the oil was provided) to methyl
esters was the highest for a 1.0% (w/w) NaOH concentration (i.e.,
95% after 10 min at room temperature using Ultrasonication
(28 kHz).
Hoang et al. [108] studied effects of molar ratio, catalyst concentration and temperature on transesterication of triolein with
ethanol under ultrasonic irradiation and reported optimum conditions for the formation of ethyl ester under ultrasonic irradiation at
25 C were E/T (ethanol to triolein) molar ratio of 6:1, base catalyst
(NaOH or KOH) concentration of 1 wt.%, and reaction time of less
than 20 min. Lifka and Ondruschka [109] studied the effect of
ultrasonication versus mechanical stirring on the alkaline transesterication of rapeseed oil using NaOH at a concentration of
0.5% w/w at 45 C. A conversion of 8085% was obtained for both
ultrasonicated and mechanically stirred reactions after 30 min.
Carmen et al. (2007) [110] used ultrasonically driven continuous
process for palm oil transesterication and reported >90% conversion at 20 min residence time in reactor with 6:1 methanol to oil

Table 8
Ultrasound assisted transesterication.
Oil/
triolein

Catalyst

Catalyst
wt.% of oil

Alcohol

Oil to alcohol
molar ratio

Ultrasonic
frequency (kHz)

Source of
ultrasound

Reaction conditions

Ester
yield (%)

Ester
conversion (%)

Ref.

Na

NaoH

0.5

n-Propanol

1:6

28

Ultrasonic cleaner
(1200 W)

25 C, 20 min

92

[102]

Triolein

NaOH

Ethanol

1:6

40
40

25 C, 20 min
25 C,<20 min

88

98

[108]

Triolein

KOH

Methanol

1:6

40

25 C, 10 min

>90

[111]

Soybean

NaOH

1.5

Methanol

NA

24

60 C, 20 min

97

[112]

Frying oil
Fish oil

C2H5ONa

0.8

Ethanol

1:6

20

60 C, 60 min

98.2

[113]

NA: not available.

Ultrasonic cleaner
(1200 W)
Ultrasonic cleaner
(1200 W)
Ultrasonicator
(200 W)
Ultrasonic probe

A.P. Vyas et al. / Fuel 89 (2010) 19

molar ratio. Table 8 shows the work carried out for bio-diesel production from various feedstocks under different conditions using
ultrasound irradiation.

4. Bio-diesel from algae oil

Algae are another source of triglycerides. Microalgae are photosynthetic microorganisms that convert sunlight, water and carbon
dioxide to algal biomass. Algae are more productive than corn or
soybeans, as every cell are a factory. Unlike corn, algae need not
be grown on arable soil and also it can be grows in water bodies
like ponds, lakes and even seas and oceans. Therefore, there are
no food related issues with algae. Algae not only reduce a plants
global warming gases, but also consume other pollutants [114].
Microalgae are producing 15300 times more oil for bio-diesel production than traditional crops on an area basis. Furthermore compared with conventional crop plants which are usually harvested
once or twice a year, microalgae have a very short harvesting cycle
(110 days depending on the process), allowing multiple or con-

Table 9
Comparison of some sources of bio-diesel and oil content of some microalgae [116].

a
b

Crop

Oil yield (L/ha)

Corn
Soybean
Canola
Jatropha
Coconut
Oil palm
Microalgaea
Microalgaeb
-Botryococcus braunil
-Chlorella sp.
-Crypthecodinium cohnii
-Cylindrotheca sp.
-Dunaliella primolecta
-Isochrysis sp.
-Monallanthus salina
-Nannochloris sp.
-Nannochloropsis sp.
-Neochloris oleoabundans
-Nitzschia sp.
-Phaeodactylum tricornutum
-Schizochytrium sp.
-Tetraselmis sueica

172
446
1190
1892
2689
5950
136,900
58,700

tinuous harvests with signicantly increased yields (Table 9).

Greater light capture and conversion efciencies ultimately lead
to reduced fertilizer and nutrient inputs and so resulted in less
waste and pollution [115].
Advantages, other than mentioned above, of deriving bio-diesel
from algae include biofuel contains no sulfur, is non-toxic, and is
highly biodegradable. Depending on species, microalgae produce
many different kinds of lipids, hydrocarbons and other complex
oils. Not all algal oils are satisfactory for making bio-diesel, but
suitable oils occur commonly [116]. Table 9 shows the oil content
of some microalgae.
Harvesting algae and extracting oil present technical and cost
hurdles. The dominant algal species found in a pond could range
from small unicellular to large colonial or lamentous species. Harvesting of the algae for biomass conversion would require a universally applicable harvesting technology, such as centrifugation or
chemical occulation, to enable the recovery of any algal type.
However, these processes are very expensive. Both methods are
expensive when applied in large scale commercial production.
Researchers are seeking the best of a variety of approaches.
Table 10 shows that some companies have just nished R&D on
expansion of production areas through location of new farming
sites [117].

Oil content (dry wt.%)

5. Conclusions

2575
2832
20
1637
23
2533
>20
2035
3168
3554
4547
2030
5077
1523

70% oil (by wt.) in biomass.

30% oil (by wt.) in biomass.

Due to the concern on the availability of recoverable fossil fuel

reserves and the environmental problems caused by the use those
fossil fuels, considerable attention has been given to bio-diesel production as an alternative to petro diesel. Bio-diesel fuel comes from
renewable sources as it is plant- not petroleum-derived and as
such it is biodegradable and less toxic. In addition, relative to conventional diesel, its combustion products have reduced levels of
particulates, carbon oxides, sulfur oxides and, under some conditions, nitrogen oxides. Bio-diesel is made by transesterication
reaction, transesterication is a chemical reaction between triglyceride and alcohol in the presence of catalyst or without catalyst
which gives bio-diesel and by product glycerol. Transesterication
can be carried by using homogeneous (sulfuric acid, sodium
hydroxide, and potassium hydroxide) catalyst, heterogeneous catalyst (sulfated zirconia, MgO, CaO, etc.), enzymatic (lipase) catalyst
and non-catalytic supercritical alcohol. Apart from conventional
techniques for bio-diesel production, application of microwave
and ultrasound are explored for better results compared to conventional methods.

Table 10
Leading the algae-based fuel industry, laboratories, and universities in the US [117].
Company

Research afliation

Status

Funding

Bioreactor

Ohio State University Pilot Project

Bioreactor

Massachusetts Institute of
Technology

Finished R&D, nalizing specs

PetroAlgae (www.petroalgae.com)
Solix Biofuels
(www.solixbiofuels.com)
LiveFuel (www.livefuels.com)

Bioreactor
Bioreactor

Arizona State University

University of Colorado

Pond

Innifuel (www.innifuel.com)

Pond

Algae Biofuels
(www.petrosuninc.com)
Energy Farms (www.tgoiltech.com)

Pond

NREL, Sandia National

Laboratory
University of Nevada at Reno
and the Desert Research
Institute
Undisclosed

R&D
R&D, looking into FischerTropes
processing
R&D

Subsidiary of Green Shift Corp. and

Veridium Corp., Public company
$22 million in venture capital from
Draper Fisher Jurvetson, Polaris, Axis
Partner
Subsidiary of XL Tech Group Inc.
$500,000 University of Colorado

Pond

Nanoforce Technologies

GS Clean Tech (www.gscleantech.com)

GreenFuel Technologies
(www.greenfuelonline.com)

Bioreactor
or pond?

R&D; nal construction phase of

geothermal bio-diesel processing
plant
Final stage of eld testing
R&D

Private funded by Morgenthaler family

Private investors

Subsidiary of PeteroSun Drilling Inc.,

Public Company
Subsidiary of TransGlobal Oil Corp.,
Public Company

A.P. Vyas et al. / Fuel 89 (2010) 19

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