Talha Dan Sulaiman 2016

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VOL. 11, NO.

1, JANUARY 2016

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences


2006-2016 Asian Research Publishing Network (ARPN). All rights reserved.

www.arpnjournals.com

OVERVIEW OF CATALYSTS IN BIODIESEL PRODUCTION


Nur Syakirah Talha and Sarina Sulaiman
Department of Biotechnology Engineering, International Islamic University Malaysia, Kuala Lumpur, Malaysia
E-Mail: [email protected]

ABSTRACT
Transesterification is one of the methods for biodiesel production in which oil or fat is reacted with alcohol, such
as methanol or ethanol, in the presence of a catalyst to form alkyl ester and glycerol. The cost of biodiesel production is
mainly affected by the system used and cost of feedstock. Currently, waste oil or fat is used in the production of biodiesel
as 70 to 90% of the production cost is attributed to raw materials. Alternatively, overall cost of production can also be
reduced by optimizing the efficiency of catalyst used. Therefore, this review paper is aimed to give an overview on the
recent trends of catalyzed transesterification and the advantages and disadvantages of heterogeneous acid/base,
homogeneous acid/base, and enzymatic transesterification. Heterogeneous base catalyst is commonly used because of its
reusability, easier to separate from product, higher reaction rate, lower cost, and require less energy as compared to acidcatalyzed transesterification. However, heterogeneous base catalyst still suffers with the limitations of diffusion, possibility
of saponification to occur, sensitive to FFA content and produce more wastewater. With intense research focus and
development, an ideal catalyst can indeed be develop for optimum production of biodiesel that economically feasible and
environmentally benign for a better future.
Keywords: transesterification, biodiesel, homogeneous catalyst, heterogeneous catalyst, and enzyme catalyst.

INTRODUCTION
The dwindling reserve of conventional energy
resources and their associated environmental problems
have increased the awareness to seek for alternative
renewable and sustainable resources for fuel production.
The production of biofuel is now escalating as a
replacement of fossil fuel.
Biodiesel has become beguiling nowadays for its
environmental benefits and it seems an apposite alternative
fuels for future. It is made from renewable biological
sources such as vegetable oils and animal fats. It is
biodegradable and nontoxic, has low emission profiles and
also environmentally beneficial [1]. The name of Biodiesel
was introduced in the United States in 1992 by the
National Soy diesel Development Board (presently
National bio Diesel Board) which has pioneered the
commercialization of biodiesel in United States [2].
Biodiesel is registered with the US
Environmental Protection Agency as a pure fuel or as a
fuel additive and is a legal fuel for commerce. Biodiesel is
an alternative fuel which can be used in neat form or
blended with petroleum diesel for use in compression
ignition (diesel) engines. The specification for biodiesel is
approved by the American Standards for Testing and
Materials (ASTM) under code 6751 [3].
BIODIESEL PRODUCTION
Imperative efforts have been made to develop
vegetable oil derivatives that have the properties and
performance of hydrocarbons-based diesel fuel,
thereabouts. Singh & Singh (2010) mentioned that
substitutes of triglycerides for diesel fuel are often
associated with the problem of high viscosity, low vitality
and polyunsaturated characters. The problem of high

viscosity of vegetable oils has been approached in several


ways such as preheating the oils, blending or dilution with
other
fuels,
transesterification
and
thermal
cracking/pyrolysis [4].
Demirbas (2009) agreed that transesterification
method is the most viable process adopted known so far
for the lowering of viscosity. Transesterification is defined
as the reaction of a fat or oil with an alcohol in the
presence of catalyst to form esters and glycerol. The
byproduct, which is glycerol, has also commercial value.
The physical characteristics of fatty acid methyl/ethyl ester
are very close to those of petro-diesel fuel and the process
is relatively simple.
CATALYST
In general, there are three categories of catalysts
used for biodiesel production known as alkalis, acids and
enzymes [5][7]. As compare to enzyme catalysts, alkali
and acid catalysts are more commonly used in biodiesel
production [1]. They were then categorized into
homogeneous and heterogeneous catalysts. However,
enzyme catalysts have become more attractive recently
since it can avoid soap formation and the purification
process is simple to accomplish. Nonetheless, Leung et al.
(2010) stated that they are not commercially used because
of the longer reaction times and higher cost. To reduce the
cost, some researchers developed new biocatalysts in
recent years. An advantage is that no purification is
necessary for using these biocatalysts [8][10].
Homogeneous base-catalyzed transesterification
Homogeneous alkaline catalysts are more
preferable and commonly used since transesterification
reaction using its acid counterpart has slower rate [11].

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VOL. 11, NO. 1, JANUARY 2016

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences


2006-2016 Asian Research Publishing Network (ARPN). All rights reserved.

www.arpnjournals.com
The most common basic catalysts are potassium hydroxide
(KOH), potassium methoxide (KOCH3), sodium
hydroxide (NaOH), sodium methoxide (NaOCH3), and
sodium ethoxide (NaOCH2CH3) [12] [13], [14]. These
catalysts are commonly used because of several
advantages such as able to catalyze reaction at low
reaction temperature and atmospheric pressure, high
conversion in shorter time, and economically available
[12]. Sodium methoxide (NaOCH3) and potassium
methoxide (KOCH3) are better catalyst than sodium
hydroxide (NaOH) and potassium hydroxide (KOH) due
to the ability to dissociate into CH3O- and Na+ and CH3Oand K+ respectively when comparing on biodiesel yield
[14]. Alkaline catalyst is more commonly used in
commercial biodiesel production because it do not form
water during transesterification reaction [15].
NaOH and KOH are the most common
homogeneous base catalyst in biodiesel production. Table
1 listed reports that used NaOH and KOH in their works.
The highest biodiesel yield produced by Calophyllum
inophyllum was reported by Silitonga et al. (2014) with
98.53% by using 1 wt% KOH and 9:1 methanol to oil
ratio. Silva, Camargo, and Ferreira (2011) reported 95% of
biodiesel yield from soybean oil by using NaOH with 1.3
wt% catalyst loading and ethanol to oil ratio of 9:1.
Homogeneous acid-catalyzed transesterification
Waste oils contain free fatty acids which cannot
be converted to biodiesel using an alkaline catalyst. These
FFAs will produce soap that inhibit the separation of the
ester, glycerin, and wash water when react with an alkaline
catalyst
[5].
Hence,
liquid
acid-catalyzed
transesterification is proposed in order to overcome lots of
conundrum caused by liquid base catalysts. Sulfuric acid,
sulfonic acid, hydrochloric acid, organic sulfonic acid, and
ferric sulphate are most commonly acids used as catalysts
in transesterification [14]. In the production of biodiesel,
hydrochloric acid and sulfuric acid are favoured as catalyst
[12]. Despite of its insensitivity to FFA in the feedstock
and can catalyzes esterification and transesterification
simultaneously, acid catalyst has been less popular in
transesterification reaction because it has relatively slower
reaction rate [16, 17, 18]. Thus, alcohol to oil molar ratio
is the main factor influencing the reaction. Addition of
excess alcohol can speeds up the reaction and favours the
formation biodiesel product. The steps involve during
acid-catalyzed transesterification are initial protonation of
the acid to give an oxonium ion followed by the oxonium
ion and an alcohol undergo exchange reaction to give the
intermediate which later loses a proton to become an ester
[14].
In a study of acid-catalyzed transesterification of
sunflower oil using HCl as listed in Table 1, Sagiroglu et
al. (2011) reported 95.2% of biodiesel yield with 100C
reaction temperature and 1.85 wt% catalyst loading. Cao
et al. (2013) used H2SO4 in the acid-catalyzed
transesterification with 0.5 wt% catalyst loading reported
92.5% biodiesel yield from Chlorella pyrenoidosa.

Heterogeneous base-catalyzed transesterification


Numbers of research have been conducted on
heterogeneous catalysts to overcome the problems caused
by homogeneous catalyst in biodiesel production. Most of
the heterogeneous catalysts developed for production of
biodiesel are either alkaline oxide or alkaline earth metal
oxide supported over large surface area (Helwani, et al.,
2009). Heterogeneous basic catalysts are more active than
heterogeneous acid catalyst, similar to their homogeneous
counterparts [17]. In addition, solid alkaline catalysts, for
instance, calcium oxide (CaO) provide many advantages
such as higher activity, long catalyst life times, and could
run in moderate reaction condition [18]. Nonetheless, CaO
as catalyst can also slow down the reaction rate of
biodiesel production [19]. Notwithstanding, reaction of
CaO with glycerol can leach out calcium diglyceroxide
during transesterification which result in necessity of an
extra purification step such as ion exchange resin to
remove the soluble content in the biodiesel (Gryglewicz,
1999; Kouzu et al., 2008; Kouzu et al., 2009). Table 1 lists
some of the reaction conditions for various types of
heterogeneous base catalysts in transesterification of lipid.
The highest biodiesel yield was reported by Nakatani et al.
(2009) with 96.5% obtained from soybean oil by using
oyster shells as catalyst. The transesterification was done
in 65C using methanol as alcohol with ratio of 6:1 and 25
wt% catalysts loading for 5 hours reaction. Viriya-empikul
et al. (2012) and Wei et al. (2009) both reported
transesterification by using eggshells as catalyst which is
the closest comparison to this study. Viriya-empikul et al.
(2012) obtained 94.1% biodiesel yield from palm olein oil
when the transesterification was done in 60C for 2 hours
with methanol to oil ratio of 15:1 and 10 wt% catalysts
loading. Whilst Wei et al. (2009) reported 95% biodiesel
yield on soybean oil. The reaction was conducted in 65C
for 3 hours and the methanol to oil ratio was 9:1 with 3
wt% catalysts loading.
Most of the literature reported on heterogeneous
base catalyst used lower reaction temperature (<65C). As
a matter of fact, temperature above 70C will resulted in
lower yield as methanol evaporates at 65C [22].
Furthermore, base-catalyzed transesterification was proved
to have higher reaction rate as compared to acid-catalyzed
transesterification which need more vigorous reaction
condition
including
higher
temperature
during
transesterification [12].
Heterogeneous acid-catalyzed transesterification
Despite of the effectiveness of homogeneous acid
catalyst, it can lead to absolute contamination problems
which require good separation and product purification
processes [11]. This will be resulted in higher production
cost. It is believed that heterogeneous acid catalysts have
the potential as alternative to homogeneous acid catalysts.
Some of advantages of heterogeneous acid catalyst are
insensitive to FFA content, can simultaneously conduct
esterification and transesterification, eliminate the washing
step of biodiesel, simpler separation process of catalyst

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VOL. 11, NO. 1, JANUARY 2016

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences


2006-2016 Asian Research Publishing Network (ARPN). All rights reserved.

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from product, regenerating and reusing the catalyst is
possible and also reduce the corrosion problems [12], [23],
[16], [24], [25]. In addition, solid acid catalysts are
preferred over liquid acid catalysts due the fact that they
contain a multiple sites with different strength of Bronsted
or Lewis acidity [14], [26]. Bronsted acid catalysts have
the advantage of promoting simultaneous esterification
and transesterification with the use of cheaper feedstock
containing high concentration of free fatty acids [27]. A
Lewis acid site is more active as compared to Bronsted but
is at risk to poisoning from water and/or free fatty acids.
Generally said, the low activity of acid catalysts relative to
the counterpart basic ones is due to different reaction
mechanism. However, efforts to utilizing heterogeneous
acid catalyst for transesterification of triglycerides are
limited due to daunting point of view for its low reaction
rates and possible adverse side reaction [26].
Consequently, the mechanisms and factors influence the
reactivity of the solid acid catalysts have not fully
understood.
Not many works were reported on heterogeneous
acid catalyst as compared to heterogeneous base catalyst.
Types of solid acid catalysts that were commonly used in
esterification and transesterification reaction works
include tungsten oxides, sulphonated zirconia (SZ),
sulphonated
saccharides,
Nafionl
resins,
and
organosulphoric functionalized mesoporous silicas [28].
Some of the reaction conditions using heterogeneous acid
catalyzed transesterification are listed in Table 1. Muthu et
al. (2010) reported 95% biodiesel yield from Neem oil by
using sulphated zirconia as solid acid catalyst and
methanol to oil ratio of 9:1. Comparing to Shu et al.
(2010), biodiesel yield from waste vegetable oil was
reported 94.8% by using carbon-based solid acid as
catalyst and methanol for alcohol. Brucato et al. (2010)
used titanium-doped amorphous zirconia as heterogeneous
acid catalyst and obtained 65% biodiesel yield from
rapeseed with higher methanol to oil ratio (40:1).
Enzyme (Biocatalyst) catalyzed transesterification
Enzymatic
transesterification
has
drawn
researchers attention due to the downstream processing
problem posed by chemical transesterification. Huge
amount of wastewater generation and difficulty in glycerol
recovery are some of the problems that eventually increase
the overall production cost of biodiesel and being not
environmental benign. In contrast, enzyme catalysis
occurs without the generation of by-products, easy
recovery product, mild reaction condition, insensitive to
high FFA oil and catalyst can be reuse [23]. Thus, enzyme
catalyzed biodiesel production has proven to have high
potential to be an eco-friendly process and a promising
alternative to the chemical process. However, enzyme
catalyzed biodiesel production has some limitations
especially when implemented in industrial scale because
of high cost of enzyme, slow reaction rate and enzyme
deactivation [29].

Lipase is often used in enzymatic catalyzed


transesterification. Table-1 listed some of works reported
on lipase as biocatalyst in transesterification of biodiesel.
Simes et al. (2015) reported the highest yield of biodiesel
by using babassu oil with 96.0%. The transesterification
reaction was done by immobilized lipase on SiO2. Lipase
can also be immobilized on crystalline PVA as reported by
Bergamasco et al. (2013). Bergamasco et al. (2013)
reported 66.3% of biodiesel by using soybean oil and
ethanol as alcohol with ratio 6:1. In comparison, work
done by Chen et al. (2011) used methanol with the ratio to
oil of 4:1 reported higher biodiesel yield compared to
Bergamasco et al. (2013) with 83.31% FAME by using
also soybean oil.
Waste-derived heterogeneous catalyst
The use of heterogeneous catalyst is promising to
reduce the present high production cost of biodiesel
making it competitive with petro-diesel fuels. Therefore,
research is being directed towards the development of
environmental friendly and cost-effective heterogeneous
catalyst for biodiesel production. In order to make the
biodiesel production more sustainable, the utilization of
waste heterogeneous catalysts has become recent interest.
The alkaline earth metal oxides such as MgO,
CaO, and SrO have the high activity for using in the
typical process which at low temperature and under
atmospheric pressure condition. Among the alkaline earth
metal oxides, CaO is close on the environmental material.
Generally, Ca(NO3)2, CaCO3, or Ca(OH)2 is the raw
material to produce CaO catalysts (Cho et al., 2009). As
alternative way to synthesize CaO catalyst, there are
several natural calcium sources from wastes, such as
eggshell, mollusk shell, and bone. Not only eliminating a
waste management cost, but also the catalysts with high
cost effectiveness can be simultaneously achieved for
biodiesel industry.
The shells of oysters and chicken eggs have been
evaluated as effective catalysts to convert vegetable oil to
methyl ester [31]. Nakatani et al. (2009) showed that by
using 25 wt% of thermally activated (at 700C) oyster
shell at 6:1 methanol:oil molar ratio, the yield of biodiesel
production is over 70% and purity of 98.4% was achieved
in a 5h reaction time. The conversion at a moderate 6:1
(methanol:oil) ratio was achievable at the expense of a
higher catalyst and longer reaction time. Soybean oil was
transesterified with 3 wt% of calcined egg shell at 1000C
to obtain over 95% yield in 3h reaction time with the
conditions of 9:1 methanol:oil molar ratio and a 65C
reaction temperature [33]. In addition, Wei et al. (2009)
found that the waste catalyst is capable of being reused up
to 13 times without much loss in the activity.
High active, reusable solid catalyst was obtained
by calcining eggshell. Calcined eggshell exhibited high
activity towards the transesterification of vegetable oil
with methanol to produce biodiesel. The method of
reusing eggshell waste to prepare catalyst could recycle
the waste, minimizing contaminants, reducing the cost of

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VOL. 11, NO. 1, JANUARY 2016

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences


2006-2016 Asian Research Publishing Network (ARPN). All rights reserved.

www.arpnjournals.com
catalyst, and making the catalyst environmental friendly.
In fact, this high efficient and low-cost eggshell catalyst
could make the process of biodiesel production economic
and fully ecologically friendly. The ecologically friendly
and economic process could effectively reduce the
processing cost of biodiesel, making it competitive with
petroleum diesel [33]. Low-cost catalyst could be used in a
large-scale industrial process of biodiesel, making the
process cheap and ecologically benign. In addition to
biodiesel production, such environmentally benign
eggshell-derived catalysts should find application in a
wide range of other base-catalyzed important organic
reactions.

These catalysts have very high commercial


prospects, especially in biodiesel industries, as they can be
equipped at nominal cost from the waste materials
reducing the biodiesel production cost and making it
competitive with petroleum diesel. Sanjay (2013)
mentioned that easy availability, biodegradability and
environmental acceptability are three factors in favor of
the catalysts as their large scale use will cause no disposal
problem as of the fact they are reusable for several
reaction cycles. These catalysts are considered as greencatalyst which is derived from renewable biomasses and
the biodiesel production is also a promising green
technology.

Table-1. Comparisons of reactions conditions for various types of catalysts.


Reaction conditions
Catalyst

Temp,
C

Type of
alcohol
(alcohol to
oil molar
ratio)

Catalyst
loading,
wt %

Reaction
time, h

Mixing,
rpm

Biodiesel yield

Remarks

Reference

Homogeneous base catalyst


Sodium
hydroxide
(NaOH)

40

Ethanol (9:1)

1.3

1.33

Soybean oil, 95%

Batch
reactor

[35]

Sodium
hydroxide
(NaOH)

55

Methanol
(3:1)

0.5

250

Waste soybean
cooking oil, 68.5%

Shake flask

[36]

Sodium
hydroxide
(NaOH)

60

Methanol
(475:1)

0.1

Rapeseed, 88.8%

Soxhlet

[37]

Potassium
hydroxide
(KOH)

60

Methanol
(4:1)

0.1

550

Pongamia pinnata
seeds, 98.5%

[38]

[39]

Potassium
hydroxide
(KOH)

50

Methanol
(6:1)

0.075

800

Jatropha seed, 87%

Threenecked
round
bottom flask
equipped
with reflux
system

Potassium
hydroxide
(KOH)

55

Methanol
(9:1)

Calophyllum
inophyllum,
98.53%

[40]

Sodium
methoxide
(NaOCH3)

50

Methanol
(6:1)

0.75

0.5

Sesamum indicum
L. seed oil, 87.8%

Batch
reactor

[41]

Heterogeneous base catalyst


Bone

60

Methanol
(20:1)

18

600

Rapeseed oil, 96%


Peanut oil, 94%

Batch
reactor

[29]

Rice Husk

65

Methanol
(24:1)

300

Soybean oil, 99.5%

Shake flask

[42]

Snail shells

60

Methanol
(6.03:1)

Waste frying oil,


99.58%

[43]

- Eggshells
- Snail shells

60

Methanol
(15:1)

10

Palm olein oil,


94.1%
Palm olein oil,

[44]

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VOL. 11, NO. 1, JANUARY 2016

ISSN 1819-6608

ARPN Journal of Engineering and Applied Sciences


2006-2016 Asian Research Publishing Network (ARPN). All rights reserved.

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- Venus shells

93.2%
Palm olein oil,
92.3%

Vegetable oil
asphalt

220

Methanol
(16.8:1)

0.2

4.5

Vegetable oil,
94.8%

[45]

Oyster shells

65

Methanol
(6:1)

25

Soybean oil, 96.5%

Magnetic
stirrer

[32]

Eggshells

65

Methanol
(9:1)

Soybean oil, 95%

[46]

Homogeneous acid catalyst


Hydrochloric
acid (HCl)

100

Methanol

1.85

Sunflower oil,
95.2%

[47]

Sulfuric acid
(H2SO4)

120

Methanol
(40:1)

0.5

Chlorella
pyrenoidosa,
92.5%

[48]

Sulfuric acid
(H2SO4)

50

Methanol
(6:1)

Vegetable oil by
product, >90%

Reflux
condenser
reactor

[49]

Heterogeneous acid catalyst


Titanium-doped
amorphous
zirconia

245

Methanol
(40:1)

11

Rapeseed oil, 65%

[50]

Sulfated
zirconia

65

Methanol
(9:1)

Neem oil, 95%

[51]

Carbon-based
solid acid
catalyst

220

Methanol
(16.8:1)

0.2

4.5

Waste vegetable
oil, 94.8%

[45]

Enzyme catalyst
Lipase

52.1

Methanol
(4:1)

Soybean oil,
83.31%

Continuous
packed bed
reactor

[52]

Immobilized
lipase on SiO2

50

Ethanol
(12:1)

11

Babassu oil, 96.0%

Continuous
packed bed
reactor

[53]

Immobilized
lipase on
crystalline PVA

37

Ethanol (6:1)

72

Soybean oil, 66.3%

[54]

ADVANTAGES AND DISADVANTAGES OF


HOMOGENEOUS AND HETEROGENEOUS
CATALYST
The
advantages
and
disadvantages
of
homogeneous and heterogeneous catalyst are discussed in
Table-2. In general, there are three types of catalyzed
transesterification namely alkali-catalyzed, acid-catalyzed,
and enzymatic transesterification. Enzyme catalysts are
more attractive recently for its simpler purification process
and it can avoid saponification. However, the drawbacks
are high in cost and longer reaction time required.
On the other point, alkali and acid catalysts are
more commonly used in transesterification because of
their availability. Alkali and acid catalysts consist of
homogeneous and heterogeneous types. Sodium hydroxide
and potassium hydroxide are two most popular
homogeneous base catalysts used in transesterification due
to low cost and widely available [37-42]. Alkali-catalyzed

transesterification is considered as economical because the


process can be carried out in low temperature and pressure
environment with high yield. On the other hand,
heterogeneous alkali catalysts are preferable for easier
separation process. Nonetheless, acid catalysts are used
because they can avoid saponification and their
performance is insensitive to FFA content [11].
Homogeneous acid catalysts that are commonly used
include hydrochloric acid and sulphuric acid [49-51]. Even
though homogeneous acid catalysts transesterification is
effective, it leads to serious contamination problems which
require good separation and purification process of the
product. To overcome the limitation, heterogeneous acid
catalyst is used. The appropriate heterogeneous catalysts
can be applied in the transesterification system to simplify
the product separation and purification consequently
reducing waste generation.

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ARPN Journal of Engineering and Applied Sciences


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Table-2. Advantages and disadvantages of different types of catalyst used in transesterification.
Type of catalyst
Homogeneous base catalyst

Heterogeneous base catalyst

Homogeneous acid catalyst

Advantages
Do not form water during
transesterification reaction [14]
4000 times faster reaction rate than acidcatalyzed transesterification [12], [14]
Two-step alkaline-catalyzed
transesterification from used vegetable oil
is an economic method for biodiesel
production [13]
Reaction can occur at mild reaction
condition and thus less energy required
[12], [14]
NaOH and KOH are economically feasible
and widely available [12]
Reusable [47]
Easy to separate from product [47]
Relatively faster reaction rate than acidcatalyzed transesterification [12]
Reaction can occur at mild reaction
condition and relatively lower energy [12]
Long catalyst life times [14]

Heterogeneous acid catalyst

Enzyme catalyst

Disadvantages

Insensitive to FFA and water content in the


oil [11]
Preferred-method if low-grade oil is used
[12]
Esterification and transesterification occur
simultaneously [12]
Saponification can be avoided [55]
Produce high yield of biodiesel [14]
Insensitive to FFA and water content in the
oil [11]
Preferred-method if low-grade oil is used
[12]
Esterification and transesterification occur
simultaneously [12]
Easy separation of catalyst from product
[12]
High possibility to reuse and regenerate the
catalyst [12], [13]
Recyclable [55]
Prevent saponification [55]
Only simple purification step is required
[23], [55]
Environmental friendly and nonpolluting
[14]

CONCLUSIONS
Biodiesel
is
a
non-toxic,
renewable,
biodegradable, and more environmental friendly fuel
which appears to be an alternative fuel to petro-diesel

Sensitive to FFA content in the oil [12]


Saponification can occur if the FFA
content in the oil is more than 2 wt.% [12]
Saponification will decrease the biodiesel
yield and cause problem during product
purification [12], [14]
Produce more wastewater from purification
[55]

Poisoning of the catalyst when exposed to


ambient air [12]
Sensitive to FFA content in the oil due to its
basicity property [12]
Saponification can occur if the FFA content
in the oil is more than 2 wt.% [12]
Saponification will decrease the biodiesel
yield and cause problem during product
purification [12], [14]
Higher molar ratio of alcohol to oil [55]
Produce more wastewater from purification
[55]
Diffusion limitation [55]

Low reaction rate [12], [14], [55]


Can lead to equipment corrosion [12], [55]
Harder separation of catalyst from product
[12]

Low reaction rates [12], [14], [55]


Unfavourable side reaction
Higher cost [55]
High reaction conditions and longer
reaction times [14], [55]
More energy requirement [12]
Leaching of catalyst active sites may result
to product contamination [12]
-

Very slow reaction rate [12]


High cost [12], [55]
Sensitive to alcohol, typically methanol that
can deactivate the enzyme [29]
Inactivation and denaturation of enzyme
can lead to decreasing yield of biodiesel
[16], [55]

counterpart [12], [56]. Biodiesel has become increasingly


attractive for its environmental benefits and the fact that it
is made from renewable sources. Currently, esterification
and transesterification is the most commonly applied

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2006-2016 Asian Research Publishing Network (ARPN). All rights reserved.

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method to synthesize biodiesel [12], [56]. Edible and nonedible vegetable oils or animal fats are generally used in
transesterification to react with alcohols in the presence of
catalyst. However, the prices of these oils and fats are high
which make the overall production cost increased. As an
alternative, many studies were done to develop low cost
catalysts to reduce the production cost. Several catalysts
such as homogeneous/heterogeneous acid catalysts,
homogeneous/heterogeneous
base
catalysts
and
biocatalysts (enzymes) have been studied and applied in
the
synthesis
of
biodiesel.
Base-catalyzed
transesterification is commonly used in commercial
production because of high FAME yield in short reaction
time and the reaction can be done in mild conditions as
compared to acid-catalyzed transesterification [12], [14],
[56]. It was reported that acid-catalyzed transesterification
needs higher alcohol to oil molar ratios despite of it is the
preferable method when low-grade oil is used [12].
Transesterification using heterogeneous base
catalysts are found to be cost effective because of its
reusability, widely available, easy to separate from product
and longer life time [12], [14], [47]. However, the use of
solid alkaline catalysts needs to be thoroughly explored
and developed to reduce saponification and overcome the
diffusion limitations consequently produce better yield.
Development of enzyme catalysts is necessary to
have a more environmental friendly process and fulfil the
environmental needs. The process has potential to
produce high quality product which can compete with
petro-diesel fuel [14]. The concern of global warming
inaugurated the demand of biodiesel over petro-diesel fuel.
It is foreseeable that biodiesel usage would develop at a
fast pace and thus trigger the need to find more
sophisticated methods with both economical and
environmental friendly to produce biodiesel.
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