Talha Dan Sulaiman 2016
Talha Dan Sulaiman 2016
Talha Dan Sulaiman 2016
1, JANUARY 2016
ISSN 1819-6608
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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
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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.
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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].
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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.
Temp,
C
Type of
alcohol
(alcohol to
oil molar
ratio)
Catalyst
loading,
wt %
Reaction
time, h
Mixing,
rpm
Biodiesel yield
Remarks
Reference
40
Ethanol (9:1)
1.3
1.33
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
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]
60
Methanol
(20:1)
18
600
Batch
reactor
[29]
Rice Husk
65
Methanol
(24:1)
300
Shake flask
[42]
Snail shells
60
Methanol
(6.03:1)
[43]
- Eggshells
- Snail shells
60
Methanol
(15:1)
10
[44]
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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
Magnetic
stirrer
[32]
Eggshells
65
Methanol
(9:1)
[46]
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]
245
Methanol
(40:1)
11
[50]
Sulfated
zirconia
65
Methanol
(9:1)
[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
Continuous
packed bed
reactor
[53]
Immobilized
lipase on
crystalline PVA
37
Ethanol (6:1)
72
[54]
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Table-2. Advantages and disadvantages of different types of catalyst used in transesterification.
Type of catalyst
Homogeneous base 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]
Enzyme catalyst
Disadvantages
CONCLUSIONS
Biodiesel
is
a
non-toxic,
renewable,
biodegradable, and more environmental friendly fuel
which appears to be an alternative fuel to petro-diesel
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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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