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Renewable and Sustainable Energy Reviews 57 (2016) 496504

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Renewable and Sustainable Energy Reviews


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Trends in catalytic production of biodiesel from various feedstocks


G. Baskar n, R. Aiswarya
Department of Biotechnology, St. Joseph's College of Engineering, Chennai 600 119, India

art ic l e i nf o

a b s t r a c t

Article history:
Received 7 May 2015
Received in revised form
6 October 2015
Accepted 17 December 2015
Available online 5 January 2016

Biodiesel offers to be one of the renewable fuel that is in great demand due to hike in price and
exploitation of various conventional resources. Biodiesel has gained wide attention as it emits less carbon
monoxide and other pollutants. Biodiesel is known as mono-alkyl esters of long fatty acid, produced by
transesterication in the presence of triglycerides and alcohol. The choice of catalyst and feedstock are
the most important criteria for effective production of biodiesel. Catalyst and raw material selection play
a signicant role in the cost of biodiesel production. The heterogeneous catalyst offers a wide option for
the catalytic selection because of its high selectivity and reusability characteristics. Recent advances in
the eld of catalytic technology for biodiesel production using nanosized catalyst is because of high
stability over the repeated use. Nanocatalyst solves various bottleneck problem associated in the production of biodiesel. The present review is focused on various technologies and challenges linked to the
production process, including some important aspects of feedstock selection. Thus the present review is
maily focused on various catalytic technology used for biodiesel production using different production
methods and potential feedstocks.
& 2015 Elsevier Ltd. All rights reserved.

Keywords:
Biodiesel
Renewable energy
Heterogeneous catalyst
Nanocatalysis

Contents
1.
2.
3.

4.

5.

6.
7.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
Strategies of transesterication reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
Potential feedstock's for biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 497
3.1.
Biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
3.2.
Role of algae in biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
Biodiesel production processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
4.1.
Conventional process. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
4.2.
Other production processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
4.2.1.
Ultrasound assisted transesterication process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
4.2.2.
In-situ transesterication process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 498
4.2.3.
Reactive distillation process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
Catalytic transesterication process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
5.1.
Homogeneous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
5.1.1.
Alkali based catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 499
5.1.2.
Acid catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 500
5.1.3.
Two step transesterication reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 500
5.2.
Heterogeneous catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 500
5.2.1.
Solid acid catalysts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
5.2.2.
Solid base catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
5.3.
Enzyme catalyzed transesterication reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
5.4.
Nanocatalytic technology for biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 501
Supercritical technology/Non-catalytic transesterication reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
Characterization of produced biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502

Corresponding author.
E-mail address: basg2004@gmail.com (G. Baskar).

http://dx.doi.org/10.1016/j.rser.2015.12.101
1364-0321/& 2015 Elsevier Ltd. All rights reserved.

G. Baskar, R. Aiswarya / Renewable and Sustainable Energy Reviews 57 (2016) 496504

497

8. Economic viability of biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502


9. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 502
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 503

1. Introduction
Due to the depletion of conventional resources for fuels,
researchers started to explore alternative sources to meet the energy
demand for present and future. The impending challenges and the
environmental implications has created a wide attention to nd
notable alternative fuels [1]. The crucial energy demand has
accounted as a result of the rapid industrial establishment around
the 19th century. It was reported that the transport sector occupies
second position on high-energy consumption. The usage of oil in
transportation sectors accounts to be 97.6% indicating the importance
of oil resource for the production of energy. Although conventional
sources of oil recorded to be the main source of energy consumption,
it is expected to decline to 30% by 2035 [2]. Energy is reported to be
inevitable for the existence of human life on earth. The main reason
for nding an alternative source of energy is due to uctuations over
the price of crude oil and limited resources around the countries [3].
Biodiesel is one of the fuel that showed an appreciable result in the
reduction of greenhouse gas and noted as a blended component in
the transportation sector [4]. The establishment of liquid biofuel
industries has increased in developed countries to reduce its
dependence over the foreign oil resources [5].
Biodiesel has remained as a good substitute for automobile
engines and recognized as global fuel in recent days. The physical
and chemical properties of biodiesel are similar to the conventional
diesel as it has a higher ash point and lubricating efciency. These
properties paved way for the commercialization of biodiesel with
traces of sulfur and aromatic contents. Biodiesel is considered as
safe for the environment as it showed insignicant contribution of
carbon dioxide and other particulate emissions [6]. Chemically
biodiesel is known as mixture of fatty acid methyl esters derived
from either edible or non-edible oils. Production of biodiesel offers
to be a great challenge to researchers, as the main criteria lies in
minimizing the production cost. Selection of the feedstocks and
catalyst plays an important role as these requires 75% of the total
investment. It has been reported that biodiesel production is mostly
from non-edible and waste oils, which eliminates the competition
over food consumption. Various sources like algal oil, microalgae,
jatropha and grease were reported to reduce the cost by 6090% [7].
The new generation biodiesel intends to utilize raw materials from
renewable feedstocks, providing sustainability and maintaining the
availability of biodiesel at timely needs [8]. Evaluation of the feedstock
with respect to life cycle analysis is important in the production of
biodiesel as percentage of oil and yield are essential criteria in quality
of biodiesel [9]. The different sources for the production of biodiesel
and their respective oil percentage are given in Table 1. The Table 1
shows that the algal biomass possess high oil content when compared to the non-edible seeds. Irrespective to feedstock used, the
presence of a catalyst is essential for the reaction to be completed
[10]. Transesterication of triglyceride is conventionally carried out by
acid and base catalyzed reaction. Though, the reaction time is shorter
in homogeneous catalysts they possess certain constraints which are
rectied by the use of heterogeneous catalysts.
Heterogeneous catalyst has several advantages over the traditional
homogeneous catalyst such that they can be easily recovered and
reused for next successive cycles [11]. The other catalyst reported for
the production of biodiesel are biocatalyst and nanocatalyst. In the
case of enzymatic transesterication, thermal stability and activation
of catalyst makes it effective, whereas the cost of enzyme make it to

be inefcient [12]. Recent advances in the eld of nanocatalyst shows


improvement in the surface area for its effective binding of the
reactant. Also the lifetime of the nanocatalyst used in the reaction
increases with respect to their surface binding efciency [13]. This
review summarizes the outline of different raw materials and the
catalyst used for the biodiesel production and scale-up. Notably,
importance of algal biomass and the blooming nanosized catalyst are
indexed in this review. As transesterication is greatly affected by
various parameters, knowledge on parameters optimization is
necessary. The effect of catalyst concentration, oil to methanol ratio,
temperature and time plays a crucial role in the biodiesel production
process. The major objective of the present review is to consolidate
the trends in development of various catalyst for biodiesel production.

2. Strategies of transesterication reaction


Transesterication is one of the commercial method to produce
biodiesel with the help of alcohol having 18 carbon atoms. The
transesterication reaction is facilitated by the presence of the catalyst [3,14]. Methanol is most widely used owing to its low price and
availability [15]. During the transestercation of triglycerides to fatty
acid alkyl esters, three reversible reactions take place consecutively in
which diglycerides and monoglycerides are the major intermediate
products [16]. The stoichiometric molar ratio of alcohol to oil is three
moles of alcohol and one mole of oil indicating that excess alcohol is
required to shift the equilibrium favoring the formation of methyl
esters [17]. Production of biodiesel has been reported with batch and
continuous reactors with a drawback of batch operations [18].

3. Potential feedstock's for biodiesel production


The barrier in commercialization of biodiesel production is the
cost of feedstock. The use of edible oils sparks with the issue of
energy security while non-edible oils require additional pretreatment steps. In concern to these matters, exploration of waste or
used oils has gained attention due to the effective elimination of
disposal oils [19]. The utilization of waste or non-edible oils has
several advantages such that, they are inexpensive and does not
posses any threat to the environment. It was reported that million
Table 1
Main feedstock used for biodiesel production with their respective oil % [9498].
Type of oil

Feedstock

Oil content % (w/w)

Edible

Soybean
Rapeseed
Sunower
Peanut oil
Coconut
Palm
Jatrropha seed
Pongamia pinnata
Neem oil
Castor
Rubber seed
Sea mango
Cotton seed
Microalagae

1520
3846
2535
4555
6365
3060
3540
2739
2030
53
4050
54
1825
3070

Non-Edible

Other sources

498

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for algal species with high lipid content [2528]. Thus algae seems
to be more preferable feedstock for biodiesel production where
the main difculty lies in the extraction of oil. The extraction of oil
from algae could be efcient by the use of combined solvents.

Table 2
Fatty acid distribution of different feedstock [99106].
6].Source

Fatty acid composition in % (w/w)


C14.0

C16.0

C16.1

C18.1

C18.2

C18.3

Rapeseed
Sunower
Palm
Safower
Soybean
Jatropha curcas
Pongamia
Sea mango
Chicken fat
Tallow
Yellow grease
Porklard
Cottonseed

42.8

11
14.115.3
11.65

3.10
2.43
1.33

0.10

3.06
4.70
3.79
2.60
0.8-0.9

64.4
18.3
40.5
1213.6
22.52
34.345.8
51.5
3.8
37.62
47.20
44.32
41.70
13.2718.3

22.3
72.90
10.1

54
14.115.3
11.65
36.3

3.10
2.43
1.33

8.23

0.2

8.19
0-0.3

30.3
1.45

0.80
0.67
0.2

Neem oil

3.49
5.40

7.07.3
10.58
013

19.82
23.80
23.24
23.50
22.96
28.33
13.616.2

49.161.9

tonnes of waste oil has been generated in recent days as reusing of


oils for human consumption is not preferred due to health problems [20]. Many studies have investigated for the use of waste
cooking oil, greases, animal fats, tallow and spent bleaching for the
biodiesel production.
The cost of waste cooking oils and animal fats was reported to
be three times less than the available virgin oils. The major
drawback in using waste cooking oils and animal fats is that they
contain high fatty acid and moisture content which minimizes the
yield of the product [21]. The feedstock with fatty acid and
moisture content of 2.5% and 0.5% repectively were subjected to
physical and chemical treatment [22]. The other route to reduce
the high fatty acid content into biodiesel is to follow esterication
prior to the transesterication. The fatty acids are converted to
esters by acid pretreatment during esterication [23]. The waste
from oil reneries is also used for the prodduction of fuels, as the
bleaching clay from oil reneries contains 2050% of oil [24].
Selection of feedstock lies with respect to their fatty acid composition. The the fatty acid composition of various feedstock is listed
in Table 2. Novel processes are being designed for the reduction of
time, amount of alcohol and reaction temperature.
3.1. Biodiesel production
Production of biodiesel has been reported under various generations. First generation includes production of biodiesel from
edible oils including sunower, soybean, palm, etc. Literature
supports the information in which 95% of biodiesel productions
are from USA and Europe. The non-edible oils are categorized
under second generation fuels, where jatropha is highly used for
the production. Third generation fuels (algae) are the recent
exploration in research communities, including both micro and
macro species. Algal species solves major issues favoring the efcient process for biodiesel production be [5].
3.2. Role of algae in biodiesel production
Algae seems to be the most promising feedstock for biodiesel
production as the oil content seems to be 100 times more than the
other available sources. Due to this reason, the market size of algae
started to increase twice than expected [9]. It was cited that algal
yields were 5000 gallons per acre, whereas the vegetable oils
accounted with less than 1000 gallons per acre [6]. The main
advantage of using algal biomass is they have high photosynthetic
efciency and better productivity. Recent studies revealed the use
of bioengineering technology tends to reduce the growth period

4. Biodiesel production processes


The vegetable oils can not be used in engines due to their highly
viscosity, low volatility and polyunsaturated characters due to oxidation. In order to overcome these problems various production
methodologies were designed for the production of biodiesel. Pyrolysis, microemulsion, hydrocarbon blending and transesterication
are various methods available for the production of biodiesel [29
32]. Transesterication is the common method for the conversion of
triglycerides to methyl esters as the conversion efciency seems to
be higher when compared to the other methods [33]. Researchers
have reported that the transesterication is highly suitable for the
production with low investment [34].
4.1. Conventional process
Thermal cracking or pyrolysis is the process involving thermal
decomposition for the conversion of organic materials to fuels taking
place in the absence of oxygen. Various investigators reported that
fuel obtained by this method tends to have a high cetane number,
low viscosity and acceptable amount of sulfur [35]. Microemulsion is
the process of using isotropic uid to form a colloidal dispersion of
dimensions from 1150 nm. The maximum viscosity requirement is
met by this method involving both ionic and non-ionic aqueous
solution, which is demonstrated with ethanol in soybean oil [36,37].
Alcoholysis or transesterication is regarded as best the method as
they are simple to produce high quality of biodiesel [38].
4.2. Other production processes
The various other methods for the production of biodiesel are
mainly through transesterication that proceeds with ultrasonication and reactive distillation technology. In-situ transesterication is the other possible method, which resulted in considerable yield of the product.
4.2.1. Ultrasound assisted transesterication process
Ultrasound assisted transesterifcation creates cavitation between
oil and alcohol phases and makes the mixing is efcient. This process
uses less energy consumption when compared to other conventional
mechanical stirring process. It is reported that the cavitation of
bubbles due to ultrasonication enhances the mass transfer rates with
the recordof high yield [39,40]. The ultrasonic wave provides high
temperature and pressure such that it increases the catalytic surface
area with low frequency modes [41,42]. Solid catalyst was reported
to be efcient for ultrasonic assisted transesterication, as the wave
energy breaks the catalyst into ne small particles [4345]. The literature supports the use of ultrasound assisted transesterication
using sunower as major feedstock. The 95% biodiesel yield was
reported at 60 C in 20 min. The frequency maintained throughout
the process was 24 kHz with molar ratio of 7:1 [46]. The ultrasound
assisted transesterication was reported to be highly suitable as
stability of the catalyst were expected to have a longer lifetime.
4.2.2. In-situ transesterication process
In-situ is the process of converting oil seeds directly to biodiesel
where methanol is mixed with the catalyst for transesterication of
triglycerides [47]. The oilseeds were dried for the direct conversion
instead of extracting oil. Thus the amount of alcohol needed for the
reaction can be reduced. In-situ transesterication tends to have

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499

Fig. 1. Catalytic trends in biodiesel production.

high yield (98%) and the cost of both the extraction and degumming
were reduced [48,49]. In-situ transesterication is otherwise known
as reactive extraction where the extraction oil takes place along
with the transesterication of oil into biodiesel [46]. In-situ process
eliminates the expensive cost that are employed for the extraction
oil. In-situ transesterication can be used for any kind of oilseeds/
feedstock [50,51]. In-situ transesterication was investigated in low
quality rice bran with 1523% of triglycerides. The biodiesel yield of
95% was reported using 0.75 g of sulfuric acid and 0.71 g of sodium
hydroxide as catalyst and 150 ml of petroleum of as co-solvent [50].
4.2.3. Reactive distillation process
Reactive distillation is a multifunctional reactor where chemical reaction and distillation occur in single equipment. The main
advantage is easy recycling of product and by-product. Both catalytic and non-catalytic reactions are possible under this category.
The distillation of methyl acetate was reported with reduction of
10% in energy consumption and 50% increase in the production
rate [52]. The presence of ash evaporator, decanter, and distillation column ensures the purity of the nal product. Production of
biodiesel using reactive distillation was investigated using soybean
oil with the yield of 94.54% biodieel under optimum conditions of
6 min reaction time, 6:1 M ratio of ethanol to oil and 1.5% (w/w) of
sodium hydroxide as catalyst [53]. The use of reactive distillation
for the production of biodiesel reduces the amount of alcohol and
reported to be economically acceptable with high selectivity [54].

5. Catalytic transesterication process


Presence of catalyst increases the rate of the reaction consequently
yield of the product also increases. The catalysts used for the transesterication reaction are grouped into three categories as homogeneous, heterogeneous and enzymes as catalyst. Various catalytic
trends in biodiesel production is described in Fig. 1. Transesterication
can also be carried by non-catalytic mechanism under super critical

conditions. The overview of various catalysts for the production of


biodiesel have been discussed the following chapters in detail and
summaried their merits and demerits as listed in Table 3.
5.1. Homogeneous catalysts
The most preferred catalyst used for the production of biodiesel
is homogeneous catalyst as they are simple to use and requires less
time for the completion of the reaction. Both acids and bases such
as H2SO4, NaOH, KOH comes under this category. The mechanism of
catalysts is based on the nucleophillic attack on the carbonyl group
[55]. The main advantage of homogeneous catalyst is, it requires
mild operating conditions for the reaction to take place [10,30]. In
large production of biodiesel, homogeneous catalyst tends to consume the catalyst involving a number of washing and purication
steps. The main disadvantage of homogeneous catalyst is, it generates large amounts of wastewater [4]. The investigation has been
made to develop new technologies for reducing these issues.
5.1.1. Alkali based catalysts
Alkaline catalysts have found to be 4000 times faster than the
acid catalyst. This catalyst is most preferred for the commercial
preparations of biodiesel. It was investigated with alkaline catalysts
such as NaOH and KOH for the reaction at 65 C, methanol to oil
ratio of 6:1 with catalyst loading of 1%. The biodiesel yield obtained
were 85.9% and 91.67% respectively [56]. In order to improve the
production process, microwave irradiation was performed to study
the effect of the parameters with the same alkaline catalyst. The
reaction was carried out at 500 W of power maintained at reux
conditions also the mixture was irradiated at different interval of
time with the yield of 100% [57]. Alkaline metal alkoxides were
reported to be an active catalyst with a yield greater than 98%. The
use of alkaline catalyst tends to complete the reaction in lesser time
also with less molar concentration. On using base catalyst the free
fatty acid content of the feedstock should be low to avoid saponication which decreases the yield of biodiesel [58].

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Table 3
List of homogeneous catalyst used for transesterication reaction [107109].
9].Catalyst

Source

Reaction conditions

Yield % (w/w)

NaOH
CH3ONa
KOH
H2S04

WCO
Soybean
Pongamia pinnata
Jatropha

M/O ratio-6:1, 0.7% catalyst concentration, 50 C reaction temperature, 90 min of reaction time.
M/O ratio-10:1, catalyst concentration-0.5%, reaction temperature-75 C, reaction time-30 mins,
M/Oratio-10:1, catalyst concentration-1%, temperature-105 C, reaction time-90 min,
M/O-0.28 v/v, catalyst concentration-1.4 v/v, temperature-60 C, reaction time-88 min

86
94
92
99

Table 4
List of heterogeneous catalyst commonly used for biodiesel production [110122].
2].Catalyst

Source

KI/Mg-Al-mixed metal oxides


CaO/Al2O3

T-70 C, t-8h, M/O- 20:1, catalyst amount-5 wt%


T 64.29 C, t-5 h, M/O ratio-12.14:1,catalyst amount5.97 wt%
Sunower oil
T-75 C, t-45 min, M/O ratio-4:1, catalyst amount-1.3 wt%
Jatropha
T-45 C, t-1.5 h, M/O ratio-4:1, catalyst amount-1 wt%
Soybean
T-70 C, t-2 h, M/O ratio-6:1, catalyst concentration-0.7wt
Sunower
T-65 C, t-50 min, M/O ratio-53:1, catalyst amount-0.1wt
Sunower
T-170 C, t-8 h, M/O rati-15:1, catalyst concentration-3 wt%
Canola oil
T-50 C, t-4 h, catalyst loading-2 wt%,
Jatropha
T-90 C, t-3 h, M/O- 20:1, catalyst concentration-4 wt%
Sunower oil
Catalyst concentration-3%, t-5 h, T-200 C, M/O-20:1
Waste cooking oil Catalyst concentration-3%, t-10 h, T-200 C, M/O-18:1
Soybean
T-150 C, t-1 h, M/O-1:1, catalyst concentration-0.2 wt%
Soybean
T-250 C, M/O- 40:1
Soybean
T-65 C, t- 9 h, catalyst loading-3%, M/O-3:1
Soybean
T-65 C, t-1 h, catalyst concentration-6%, M/O-12:1
Soybean
T-75 C, t-20 h, M/O-20:1, catalyst content-10%

CaO
Mg-Al hydrotalcite
K2CO3 supported MgO
Mg/Zr
Fe-Zn Double metal cyanide (DMC) complex
Na/BaO
SO42  /TiO2
WO3/ZrO2
ZS/Si
Vanadium phosphate solid
Al2O3/ ZrO2/WO3
Zno/KF
Zno/Ba
SBA-15-SO3H-P123 Solphonic acid supported
on mesoporous silica

Reaction conditions

Soybean
Palm oil

5.1.2. Acid catalysts


Acid catalyzed transesterication reaction requires high of
amounts of alcohol for high yield of esters. The advantage of acid
catalyst is that they are performed at low temperature and pressure.
Bronsted acids such sulfuric and sulfonic acids are used for transesterication reaction yielding high biodiesel. On protonation of ion
the methyl/ ethyl ester are obtained with the displacement of
alcohol. The use of sulfuric acid for the completion of a transesterication reaction was achieved in single step acid catalysis
reaction with high FFA content [59]. The effect of canola oil conversion to biodiesel under various operating conditions was studied. The AlCl3 and ZnCl2 were used as catalyst and compared. The
catalytic activity of AlCl3 was found to be more active than ZnCl2
[60]. Water content seems to great challenge for the acid catalyzed
reaction as the presence of water content deactivates the catalyst.
This issue arises due to polar carboxylic group present in the
feedstock [22]. The other noted disadvantage with acid catalysis is
that they lead to corrosion and decreasing the yield of the product.
List of homogeneous catalyst frequently used for the production of
biodiesel are NaOH, KOH, H2SO4 and CH3Na. The optimial conditions for biodiesel production using various homogeneous catalyst
are listed in Table 4.
5.1.3. Two step transesterication reactions
Two step transesterication are employed for feedstock with
high FFA content of 0.53%. This process is carried by carrying acid
treatment followed by alkali treatment [61]. Researchers have
reported that two-step process eliminates the problems associated
with single step such as separation of the product from glycerol
and slow reaction. Investigations on two step transesterication
reaction using ferric sulfate followed by alkali treatment reported
97.22% yield under optimal conditions of 10:1 methanol to oil
ratio, 4 h of reaction time and temperature of 95 C. The limitations of this two-step process on the removal of catalyst can be
rectied by the neutralization of the catalysts [62].

Yield % (w/w)
490
98.64
80
95.2
99.5
98
98.3
97.5
97
97
98
80
90
87
95
85

5.2. Heterogeneous catalysts


Heterogeneous catalysts are known to be a solid catalyst
showing an effective and convenient catalyst for the commercial
production of biodiesel at industrial scale. These are used for biodiesel production from different feedstocks as reported by scientic
communities. Heterogeneous catalysts are tolerant with high fatty
acid and water content. Heterogeneous catalysts can be easily
separated and reused. Heterogeneous catalysts are grouped into
acid and base catalysts [32]. Acid catalyst has the advantage that
they can be used for both simultaneous esterication and transesterication process. Base catalyst requires lesser amount of the
catalyst for the transesterication reaction to proceed. The main
disadvantages reported for heterogeneous catalysts is, they tend to
form three phases with oil and alcohol leading to mass transfer
limitations with decreasesed rate of reaction. These limitations can
be solved by using co-solvent such as n-hexane, tetrahydrofuran
and ethanol, which increases the miscibility of oil and solvent. The
use of heterogeneous catalyst posses large surface area with pores
for the active interaction of reactant and oil [63,15].
Heterogeneous catalysts are derived even from waste resources
[19]. Heterogeneous catalyst is also derived from renewable biomass or natural resources such as mollusc shells, egg shell, ashes
and rocks etc. [64]. Adsorption of reactant and desorption of products takes place on the surface of the solid catalyst for the reaction
to take place with increased reaction rate. Heterogeneous catalyst
usually requires less unit operations as it posses bifuctional property. The mass transfer problems associated with heterogeneous
can be solved by using structure promoters or catalyst supports
which provide more specic area and pore for active species which
can act with large triglyceride molecules [8]. The use of solid catalyst requires the basic understanding of the interaction between
acid and base strength where the surface of the catalyst exists a
hydrophobic nature for the adsorption of triglycerides to yield

G. Baskar, R. Aiswarya / Renewable and Sustainable Energy Reviews 57 (2016) 496504

501

Table 5
Merits and demerits of various catalyst [73,81,123128].
8].Type of catalyst

Merits

Homogeneous catalyst

Demerits

Reaction tends to be faster Reaction occurs at mild condition. Insensitive


to fatty acid and water content. On using acid catalyst simultaneous
esterication and transesterication are possible. Base catalysis highly
favors kinetics.
Heterogeneous catalyst Easy separation. High possibility of reusing and regenerating the catalyst. Longer lifetime of catalyst. Fewer disposal problem. Non corrosive.
Higher selectivity in case of alkaline catalyst.
Enzyme
Carried at low temperature. Requires less purication step.

methyl esters. Hence, heterogeneous catalysts have commercially


gained its signicance due to their surface and other properties.
5.2.1. Solid acid catalysts
Exploration of heterogeneous catalyst is vigorous due to various
constrains during the production of biodiesel from homogeneous
catalysts. Heteropoly acids and their derivatives were reported to be
efcient heterogeneous catalyst for the transesterication reaction
as they are tolerant to water [6]. Heterogeneous catalysts are
reported to be useful as they contain different strengths of lewis
acidity. Heterogeneous acid catalyst such as sulphated zirconia and
tungstated zirconica are reported for the conversion of triglycerides
to fatty acid methyl esters for better yield than homogeneous catalyst [65]. Biodiesel yield by homogeneous catalyst was compared
with heterogeneous catalyst such as WOX/Al2O3(WAL), WOX/SiO2/
ZnO and WOx/SnO2. The activity showed to better with SiO2 followed by ZnO with the yield of 98% under optimum conditions of
0.3%(w/w) methanol to oil, 10 g of catalyst, reaction temperature of
110 C and 2 h of reaction time. Thus the mass transfer limitations
in the liquid phase reactions can be solved by using catalyst support
such as zinc, zirconium and silica [66].
5.2.2. Solid base catalysts
Solid base catalyst is widely preferred on account of its activity
and strong basic sites. Base solid catalysts such as single metal, mixed
metal, doped metal oxides, alkali earth metals and transition metal
oxides are widely used. The basic sites of metal oxides are generated
from metal ion which contains Lewis acid and the bronsted base site
from anion. The MgO, CaO, SrO, BaO are the various single metal
oxides cited for base catalyzed transesterication reaction [67]. The
strength of MgO as base solid catalyst is weak and less soluble in
alcohol. The strength of MgO catalyst increases with increasing the
calcinating temperature to 873 K [68]. The solid catalyst Zno-La2O3 is
utilized for the production of biodiesel with a yield of 92.3% under
batch reactors. This catalyst showed better activity to 17 times
through recycling nature [69]. The CaO is reported to be more active
than MgO due to their strong basic site of catalyst. Alkaline earth
metal oxides are proved to effective for low fatty acids at mild
operating conditions. In order to increase the stability and activity,
researchers focused on the doped metal oxides as solid catalyst.
Doping of alkali tends to improve the surface area, strength and pore
size of the synthesized material. The activity of Li-doped was
reported to be effective with 23%(w/w) of doping with CaO. The yield
was found to be nearer to 100% with 20 min of reaction time [70].
Various solid catalyst, including both acid and base catalyst predominantly used for the transesterication reaction along with the
optimal conditions are detailed in Table 5.

It lead to soap formation where they decrease the yield on other


hand generates large amount of water. In case of acid catalyst
reaction is little slow and sometimes it leads to corrosiveness.
Separation of catalyst from the product seems to be difcult
Leaching of catalyst Requires high temperature and oil methanol
ratio. Diffusion limitation.
Slow reaction rate. Deactivation of enzyme on exposure to alcohol.
Expensive.

Though enzyme technology was widely used for biodiesel production, it is still in the stage of extensive research to for commercialization [71]. In case of enzymatic transesterication, lipase is the
rst choice of enzyme for researchers. The lipase used for transesterication can be of intracellular or extracellular in nature [72].
Lipase has gained attention due to various constrains with other
catalysts like separation of glycerol during the process. Use of lipase
as catalyst makes it efcient for transesterication process, because
they requires mild conditions, can be easily separated and reused
for several cycles without loss in activity [73]. The enzymatic
transesterication can efcienly utilize high free fatty acid feedstocks with less energy input [74]. Enzymes have good tolerance
over the free fatty acid level, but it is unable to provide the complete
reaction under the standard specication. Lipase can be operated at
lower reaction temperature than the chemical catalyst, thus the
lipase is extensively studied for the biocatalytic transesterication
reaction. However, the cost of the enzyme and deactivation of the
enzyme at higher operating conditions makes it unattractive. Various microbial species are reported for enzymatic transestercation.
Candida antarctica was used for the conversion of vegetable oil to
biodiesel and was found that it can be effectively used with secondary alcohol giving branched alkyl esters [75].
Candida antaractia lipase were reported for 97% biodiesel yield
with intended increase over the activity [76]. Lipase used for the
transesterication reaction should be nonsterospecic for the conversion of methyl esters. The enzyme used should exhibit low
product inhibition and alcohol resistance for the complete synthesis
of biodiesel. Immobilization technique plays a key role in reducing
the cost by reusing the enzyme for several cycle. Immobilization of
enzyme over the support tends to increase the stability and
resuablity of the enzyme. The mass transport phenomenon plays a
vital role with respect to the pore size of the carrier and reactants
used over the reaction [77]. Regiospecic lipases act at a position of
1,3 triglyceride molecules where the activity was maintained
because of the presence of acyl migration [78]. The stability and
conversion of regiospecic lipases were maintained by immobilization over polar support or by silica gel [79]. Lipase reaction was
reported to be complex as the lipolytic reaction depends upon the
interfacial area and also it activates the enzyme with the access of
the substrate [80]. One problem identied for the use of biocatalyst
is deactivation of the enzyme by the solvent. Investigations reported the stepwise addition of methanol can prevent the inactivation
of enzyme and overcome the problem associated with the use of
lipase as biocatalyst. The use of immobilized lipase reported to
produce 90% biodiesel yield from waste cooking oil and can be
recycled up to 50 times without loss in activity [81].
5.4. Nanocatalytic technology for biodiesel production

5.3. Enzyme catalyzed transesterication reaction


Enzymatic approaches were justied for the use in the production of biodiesel due to its advantages over the chemical catalyst.

Nanocatalyst plays a crucial role in the eld of energy and


environment. The specic area of the nanocatalyst solves various
bottleneck problems associated with transesterication reaction for

502

G. Baskar, R. Aiswarya / Renewable and Sustainable Energy Reviews 57 (2016) 496504

the production of biodiesel using other catalyst. Increased stability,


activity and reusability are important characteristics of nanocatalyst. Nanocatalyst has high selectivity due to nano-dimensional
pores on the surface [82]. The nanoparticle tends to reduce the
diffusion limitations and provides an efcient surface to volume
ratio for enzyme loading. Nanocomposites has gained attention as
they possess a large surface area with enhanced interaction
between the reactant and catalyst. Sodium titanate nanotubes was
used as catalyst for the production of biodiesel. The surface area of
the catalyst was found to have 200 m2/g with a pore volume of
0.61 cm3/g. The yield was around 98% with 1% catalyst loading and
20:1 of methanol to oil ratio[83]. The KF/-Al2O3 was reported as
nano-solid base catalyst for the production of biodiesel. The reaction was performed in the sonication mode of 45 W and the yield
was reported as 95% [84].
Hybrid nanospheres with lipase was reported to be used for the
transesterication reaction along with methanol for biodiesel production. The activity of catalyst after was found unchanged even after
second cycle. Metallic nanoparticles were conjugated with proteins
and enzymes. Magnetic nanoparticles along with lipase were used
for the production of biodiesel and reported to have intense activity.
High activity depends on the structure of nanobiocatalyst and the
type of immobilization used. Besides, surface modication of the
nanoparticles through immobilization provides bifunctional characteristics for the production of biodiesel. The reaction was found to
be efcient because of the stability of the nanobiocatalyst [85]. Lipase
coated magnetic nanoparticle was reported for the production of
FAME from soybean and olive oil. The enzyme from species Candida
rugosa on magnetic nanoparticle was reported with maximum yield
of 94% [86]. Immobilization of enzyme over the support is not sufcient for the high yield of methyl esters. Selection of a reactor is also
important in applying to industrial level. Scale-up of the transesterication reaction was achieved by using the packed bed reactors for
the efcient synthesis of biodiesel using nanobiocomposite [87].
Magnetic nanocarriers were found to be efcient. But the availability
of enzyme and binding capacity in terms of stabilization creates
termination at industrial scale [88,89].

6. Supercritical technology/Non-catalytic transesterication


reaction
Supercritical processes do not require a catalyst for the reaction
to initiate. Supercritical method has a greater advantage than
transesterication reaction using the catalysts. The nal purication of the product is not required because the supercritical process does not involve the use of catalyst. This method can be used
for the feedstock which has high-water content, as the presence of
water does not inuence the reactions at supercritical condtion.
The reaction time for the supercritical process is 24 min [90].
Production of biodiesel from palm oil under supercritical method
along with monitoring of different variables was reported. The
major drawback in using supercritical process for commercial
biodiesel production is the high operting temperature and pressure with a high ratio of oil to methanol [91].

7. Characterization of produced biodiesel


Major characterization of biodiesel has been done through
chromatographic and spectroscopic studies. TLC was the rst
technique, in which glycerides was analyzed qualitatively. The other
methods paved way for the analysis of biodiesel conversion rate are
GCMS and HPLC. The most preferred technique for the quantication of the components in biodiesel is GCMS due to its icreased
accuracy. HPLC has an advantage that it cna be used for different

feedstocks. Spectroscopic techniques used for characterization are


NMR and IR. NMR is most commonly applied for the determination
of blend level. Particularly 1H-NMR was reported to monitor the
yield of transesterication where the conversion is calculated from
the peaks corresponding to the different ppm range. The other
analytical method is IR spectroscopic techniques, which gives
details about the estimation of both FAME and triglycerides
simultaneously. The quality of the biodiesel is assessed from the
physio-chemical data analysis, such as kinematic viscosity, density,
cloud point and pour point in accordance with ASTM [5].

8. Economic viability of biodiesel production


The major cost of biodiesel production lies on raw material and
catalyst used for the reaction. The estimated cost of raw material and
catalyst in large facilities was found to be 10% and 4060% in small
scale. Research has been broadened, including lipid and algae for the
selection of raw materials. Small-scale production units are likely to
follow batch process, whereas medium to large scale units follows
continuous mode of operation [92]. In order to minimize the cost, the
integrated supercritical condition is recommended to reduce the
investment in production processes [93]. The other factor that contributes towards the cost of biodiesel production is net energy storage of the fuel. For the production of biodiesel, continuous transesterication plays a signicant role. In accordance with the International Energy Agency, cost of biodiesel production is expensive
than gasoline and conventional diesel. The survey shows the evidence that biodiesel cost over 0.5 US$/liter when compared to normal diesel rate of 0.35/liter. In addition, the cost seems to be three
times higher in developing countries. Hence, enormous research and
development is required along with governed policies from the
government to make biodiesel economically feasible [1,2].

9. Conclusions
The growing interest in the eld of renewable energy has
attracted researchers around the world in exploring various sources
for biodieel production with the advent of catalytic technology.
Selection of catalyst in terms of reducing time and cost plays a key
role in creating a dynamic energy market. The energy demand
resulted in search of sustainable oil resources such as algal species
for the production of biodiesel. Algal biomass have started gaining
attention due to their massied oil content. Though microalgal
species have greater signicance, use of macro algae received
positive effect in terms of growth, management and utilization. The
type and concentration of catalyst are key factors which directly
relates to the conversion rate. Base catalyst has been reported frequently with edible oil of low fatty acid contents. The conversion
rate is directly proportional to the catalyst concentration and temperature, which reduces the biodiesel yield as a result of saponication. The acid and the base catalyzed process have greater reaction rate, however it is remain undesired due its non-recoverability.
The bifunctional solid nanocatalyst shows a new method of biodiesel production by catalyzing both esterication and transesterication at same the time. Novel catalyst with crucial modications
by creating a synergy between emerging technologies helps in
obtaining maximum biodiesel yield. Utilization of enzymatic catalyst showed better results, but not widely considered due to cost of
the enzyme despite various immobilization techniques avaialable.
Apart from the development of suitable catalyst, one major drawback still exists is commercialization of biodiesel from laboratory to
industrial level. The major constraints for scale-up process is heat
and mass transfer problems. The recent developments such as
ultrasonication technology, microwave irradiation and various ow

G. Baskar, R. Aiswarya / Renewable and Sustainable Energy Reviews 57 (2016) 496504

reactors tends to overcome major limitations. Hence, nding an


alternative commercial technology to facilitate the transesterication is more prominent with respect to heat, mass, mixing intensity
over the reaction. Materialization of the mentioned technologies
with certain coupling innovation requires extensive research for its
vital establishment. Supporting policies are required for promoting
the biofuel production along with the other conventional energy
sources. Thus, biodiesel acts as signicant fuel for the next generation by creating an eco friendly environment.

References
[1] Aransiola EF, Ojumu TV, Oyekola OO, Madzimbamuto TF, Ikhu-Omoregbe
DIO. Review of current technology for biodiesel production. State Art Biomass Bioenerg 2014;61:27697.
[2] Atabani AE, Silitonga AS, Badruddin IA, Mahlia TMI, Masjuki HH, Mekhilef S.
A comprehensive review on biodiesel as an alternative energy resource and
its characteristics. Renew Sustain Energy Rev 2012;16:207093.
[3] Talebian-Kiakalaieh A, Saidina Amin NA, Mazaheri H. A review on novel
processes of biodiesel production from waste cooking oil. Appl Energ
2013;104:683710.
[4] Semwal S, Arora AK, Badoni RP, Tuli DK. Biodiesel production using heterogeneous catalysts. Bioresour Technol 2011;102:215161.
[5] Tariq M, Ali S, Khalid N. Activity of homogeneous and heterogeneous catalysts, spectroscopic and chromatographic characterization of biodiesel: A
review. Renew Sust Energ Rev 2012;16:630316.
[6] Ahmad G, Oki M. Biodiesel production from algae by using heterogeneous
catalysts: a critical review. Energy 2014;78:7283.
[7] Kiss AA. Novel process for biodiesel by reactive absorption. Sep Purif Technol
2009;69(3):2807.
[8] Borges ME, Diaz L. Recent development on heterogeneous catalysts for biodiesel production by oil esterication and transesterication reactions: A
review. Renew Sust Energ Rev 2012;18:283949.
[9] Ahmad AL, Mat Yasin NH, Derek CJC, Lim JK. Microalgae as a sustainable
energy source for biodiesel production: A review. Renew Sust Energ Rev
2011;15(1):58493.
[10] Sharma Yogesh C, Singh Bhaskar, Korstad. A test developments on application of heterogenous basic catalysts for an efcient and eco friendly synthesis of biodiesel: A review. Fuel 2011;90:130924.
[11] Yu X, Wen Z, Li H, Tu ST, Yan J. Transesterication of Pistacia chinensis oil for
biodiesel catalyzed by CaOCeO2 mixed oxides. Fuel 2011;80:186874.
[12] Marchetti JM, Miguel VU, Errazu AF. Possible methods for biodiesel production. Renew Sust Energ Rev 2007;11:130011.
[13] Kim J, Jia H, Wang P. Challenges in biocatalyis for enzyme-based biofuel cells.
Biotechnol Adv 2006;24:296308.
[14] Demirbas A. Biodiesel production from vegetable oils via catalytic and noncatalytic supercritical methanol transesterication methods. Prog Energy
Combust Sci 2005;31:46687.
[15] Zabeti M, Daud WMAW, Aroua MK. Activity of solid catalysts for biodiesel
production: a review. Fuel Process Technol 2009;90:7707.
[16] Eckey EW. Esterication and interesterication. J Am Oil Chem Soc
1956;33:5759.
[17] Sunita G, Devassy BM, Vinu A, Sawant DP, Balasubramanian VV, Halli-gudi
SB. Synthesis of biodiesel over zirconia-supported isopoly and heteropoly
tungstate catalyst. Catal Commun 2008;9:696702.
[18] Darnoko D, Cheryan M. Continuous production of palm methyl esters. J Am
Oil Chem Soc 2000;77:126972.
[19] Nurtri I, Maniam GP, Hindryawati N, Yusoff MM, Ganesan S. Potential of
feedstock and catalysts from waste in biodiesel preparation: A review. Energ
Convers Manage 2013;74:395402.
[20] See SW, Karthikeyan S, Balasubramanian R. Health risk assessment of
occupational exposure to particulate-phase polycyclic aromatic hydrocarbons associated with Chinese, Malay and Indian cooking. J Environ Monit
2006;8:36976.
[21] Jacobson K, Gopinath R, Meher LC, Dalai AK. Solid acid catalyzed biodiesel
production from waste cooking oil. Appl Catal B-Environ 2008;85:8691.
[22] Canakci M, Van Gerpen J. Biodiesel production via acid catalysis. Trans ASABE
1999;42(5):120310.
[23] Alptekin E, Canakci M. Optimization of pretreatment reaction for methyl
ester production from chicken fat. Fuel 2010;89:40359.
[24] Ong JTL. Oil recovery from spent bleaching earth and disposal of the
extracted material. J Am Oil Chem Soc 1983;60:3145.
[25] Janaun J, Ellis N. Perspectives on biodiesel as a sustainable fuel. Renew Sust
Energ Rev 2010;14(4):131220.
[26] Mata TM, Martins AA, Caetano NS. Microalgae for biodiesel production and
other applications: A review. Renew Sust Energ Rev 2010;14:21732.
[27] Demirbas A, Demirbas MF. Importance of algae oil as a source of biodiesel.
Energ Convers Manage 2011;52:16370.
[28] Singh J, Gu S. Biomass conversion to energy in India-a critique. Renew Sust
Energ Rev 2010;14:136778.

503

[29] Ma F, Hanna MA. Biodiesel production: a review. Bioresour Technol 1999;70


(1):115.
[30] Meher LC, Sagar DV, Naik SN. Technical aspects of biodiesel production by
transesterication-A review. Renew Sust Energ Rev 2006;10:24868.
[31] Lian S, Li H, Tang J, Tong D, Hu C. Integration of extraction and transesterication of lipid from Jatropha seeds for the production of biodiesel. Appl
Energ 2012;98:5407.
[32] Helwani Z, Othman MR, Aziz N, Kim J, Fernando WJN. Solid catalysis for
transesterication of triglycerides with methanol. Appl Catal A-Gen
2009;363:110.
[33] Juan JC, Kartika DA, Wu TY, Hin TYY. Biodiesel production from jatropha oil
by catalytic and non-catalytic approaches: A overview. Bioresour Technol
2011;102:45260.
[34] Lin L, Cunshan Z, Vittayapadung S, Xiangqian S, Mingdong D. Opportunities
and challenges for biodiesel fuel. Appl Energ 2011;88(4):102031.
[35] Sharma YC, Singh B, Upadhyay SN. Advancements in development and
characterization of biodiesel: A review. Fuel 2008;87(12):235573.
[36] Balat M, Balat H. Progress in biodiesel processing. Appl Energ 2010;87
(6):181535.
[37] Agarwal AK. Biofuels (alcohols and biodiesel) applications as fuels for
internal combustion engines. Prog Energy Combust Sci 2007;33(3):23371.
[38] Vyas AP, Verma JL, Subrahmanyam N. A review on FAME production process.
Fuel 2010;89:19.
[39] Fan X, Wang X, Chen F. Ultrasonically assisted production of biodiesel from
crude cottonseed oil. Int J Green Energy 2010;7:11727.
[40] Koh MY, Ghazi TI Mohd. A review of biodiesel production from Jatropha
curcas oil. Renew Sust Energ Rev 2011;15:224051.
[41] Yu D, Tian L, Wu H, Wang S, Wang Y, Na D. Ultrasonic irradiation with
vibration for biodiesel production from soybean oil by Novozym 435. Process
Biochem 2010;45:51925.
[42] Ji J, Wang J, Li Y, Yu Y, Xu Z. Preparation of biodiesel with the help of
ultrasonic and hydrodynamic cavitation. Ultrasonics 2006;44:4114.
[43] Mikkola JP, Salmi T. Three-phase catalytic hydrogenation of xylose to xylitolprolonging the catalyst activity by means of on-line ultrasonic treatment.
Catal Today 2001;64:2717.
[44] Mootabadi H, Salamatinia B, Bhatia S, Abdullah AZ. Ultrasonic-assisted biodiesel production process from palm oil using alkaline earth metal oxides as
the heterogeneous catalysts. Fuel 2010;89:181825.
[45] Stavarache C, Vinatoru M, Maeda Y. Ultrasonic versus silent methylation of
vegetable oils. Ultrason Sonochem 2006;13:4017.
[46] Georgogianni KG, Kontominas MG, Pomomis PJ, Avlonitis D, Gergis V. Conventional and insitu transesterication of sunower seed oil for the production of biodiesel. Fuel Process Technol 2008;89:5039.
[47] Harrington KJ, DArcy-Evans C. Transesterication in situ of sunower seed
oil. Ind Eng Chem Prod Res Dev 1985;24:3148.
[48] Haas MJ, Scott KM, Foglia TA, Marmer WN. The general applicability of in situ
transesterication for the production of fatty acid esters from a variety of
feedstocks. J Am Oil Chem Soc 2007;84:96370.
[49] Qian J, Wang F, Liu S, Yun Z. In situ alkaline transesterication of cottonseed
oil for production of biodiesel and nontoxic cottonseed meal. Bioresour
Technol 2008;99:900912.
[50] Lei H, Ding X, Zhang H, Chen X, Li Y, Zhang H. In situ production of fatty acid
methyl ester from low quality rice bran: an economical route for biodiesel
production. Fuel 2010;89:14759.
[51] Haas MJ, Scott KM. Moisture removal substantially improves the efciency of
in situ biodiesel production from soybeans. J Am Oil Chem Soc 2007;84:197204.
[52] Wang J, Ge X, Wang Z, Jin Y. Experimental studies on the catalytic distillation
for hydrolysis of methyl acetate. Chem Eng Technol 2001;24(2):1559.
[53] Da Silva ND, Santander CMG, Batistella CB, Filho RM, Maciel. iodiesel production from integration between reaction and separation system: reactive
distillation process. Appl Biochem Biotechnol 2010;161:24554.
[54] Lee JS, Saka S. Biodiesel production by heterogeneous catalysts and supercritical technologies. Bioresour Technol 2010;101:7191200.
[55] Endalew AK, Yohannes K, Rolando Z. Inorganic heterogeneous catalysts for biodiesel production from vegetable oils. Biomass Bioenerg 2011;35:3787809.
[56] Vicente G, Martinez M, Aracil J. Integrated biodiesel production: a comparison of different homogenous systems. Bioresour Technol 2004;92:297305.
[57] Refaat AA, El Sheltawy ST, Sadek KU. Optimum reaction time, performance
and exhaust emission of biodiesel produced by microwave irradiation. Int J
Environ Sci Technol 2008;5:31522.
[58] Kondamudi N, Mohapatra SK, Misra M. Quintinite as a bifunctional heterogeneous catalyst for biodiesel synthesis. Appl Catal A-Chem 2011;393(1):3643.
[59] Palligarnai TV, Briggs M. Biodiesel production current state of the art and
challenges. J Ind Microbiol Biot 2008;35:42130.
[60] Soriano NU, Venditti R, Argyropoulos DS. Biodiesel synthesis via homogeneous lewis acid-catalyzed transesterication. Fuel 2009;88:5605.
[61] Atadashi IM, Aroua MK, Abdul Aziz AR, Sulaiman NMN. Production of biodiesel using high free fatty acid feedstocks. Renew Sust Energy Rev 2012;16
(5):327585.
[62] Wang Y, Ou S, Liu P, Xue F, Tang S. Comparison of two different processes to
synthesize biodiesel by waste cooking oil. Mol Catal A-Chem 2006;252:10712.
[63] Furuta S, Matsuhashi H, Arata K. Biodiesel fuel production with solid
amorphous-zirconia catalysis in xed bed reactor. Biomass Bioenerg
2006;30:8703.

504

G. Baskar, R. Aiswarya / Renewable and Sustainable Energy Reviews 57 (2016) 496504

[64] Chakraborty R, Bepari S, Banerjee A. Application of calcined waste sh (Labeo


rohita) scale as low-cost heterogeneous catalyst for biodiesel synthesis.
Bioresour Technol 2011;102:36108.
[65] Park YM, Lee DW, Kim DK, Lee JS, Lee KY. The heterogeneous catalyst system
for the continuous conversion of free fatty acids in used vegetable oils for the
production of biodiesel. Catal Today 2008;131:23843.
[66] Komintarachat C, Chuepeng S. Solid acid catalyst for biodiesel production
from waste used cooking oils. Am Chem Soc 2009;48:93503.
[67] Mo X, Lotero E, Lu C, Liu Y, Goodwin Jr JG. A novel sulfonated carbon composite solid acid catalyst for biodiesel synthesis. Catal Lett 2008;123:16.
[68] Yacob AR, MKAA Mustajab, Samadi NS. Calcination temperature of nano MgO
effect on base transesterication of palm oil. World Acad Sci Eng Technol
2009;56:40812.
[69] Yan S, Salley SO, Ng KYS. Simultaneous transesterication and esterication
of unrened or waste oils over ZnOLa2O3 catalyst. Appl Cat A-Gen
2009;353:20312.
[70] Watkins RS, Lee AF, Wilson K. Li-CaO catalysed triglyceride transesterication for biodiesel applications. Green Chem 2006;6:33540.
[71] Sivasamy A, Cheah KY, Fornasiero P, Kemausuor F, Zinoviev S, Miertus S.
Catalytic applications in the production of Biodiesel from vegetable oils.
Chem Sus Chem 2009;2:278300.
[72] Fukuda H, Kondo A, Noda H. Biodiesel fuel production by transesterication
of oils. J Biosci Eng 2001;92:40516.
[73] Lam MK, Lee KT, Mohamed AR. Homogeneous, heterogeneous and enzymatic catalysis for transesterication of high free fatty acid oil waste cooking
oil to biodiesel: A review. Biotechnol Adv 2010;28:50018.
[74] Kuan IC, Lee CC, Tsai BH, Lee SL, Lee WT, Yu CY. Optimizing the production of
biodiesel using lipase entrapped in biomimetic silica. Energies 2013;6:205264.
[75] Noureddini H, Gao X, Philkana RS. Immobilized Pseudomonas cepacia lipase
for biodiesel fuel production from soyabean oil. Bioresour Technol
2005;96:76977.
[76] Zeng J, Du W, Liu X, Liu D, Dai L. Study on the effect of cultivation parameters
and pretreatment on Rhizopus oryzae cell-catalyzed transesterication of
vegetable oils for biodiesel production. J Mol Catal B-Enzym 2006;43:158.
[77] Fjerback L, Christensen KV, Norddahal B. A Review of the Current State of
Biodiesel Production Using Enzymatic Transesterication. Biotechnol Bioeng
2009;102:1298315.
[78] Li W, Li RW, Li Q, Du W, Liu D. Acyl migration and kinetic study of 1
(3) positional specic lipase of Rhizopus oryzae catalyzed methanolysis of
triglyceride for biodiesel production. Process Biochem 2010;45:188893.
[79] Szczsna Antczak M, Kubiak A, Antczak T, Bielecki S. Enzymatic biodiesel
synthesis -key factors affecting efciency of the process. Renew Energ
2009;34:118594.
[80] Kumar S, Kikon K, Upadhyay A, Kanwar SS, Gupta R. Production, purication,
and characterization of lipase from thermophilic and alkaliphilic Bacillus
coagulans BTS-3. Protein Expres Purif 2005;41:3844.
[81] Shimada Y, Watanabe Y, Sugihara A, Tominaga Y. Enzymatic alcoholysis for
biodiesel fuel production and application of the reaction to oil processing. J
Mol Catal B-Enzym 2002;17:13342.
[82] Baskar G, Aiswarya R. Nanocatalyst for transesterication of fatty acids into
biodiesel. Int J Nanobiotechnol 2015;1:14.
[83] Hernandez-Hipolito P, Garcia-Castillejos M, Martinez-Klimova E, JuarezFlores N, Gomez-Cortes A, Klimova TK. Biodiesel production with nanotubular sodium titanate as a catalyst. Catal Today 2014;220222:411.
[84] Shahraki H, Entezari MH, Goharshadi EK. Sono-synthesis of biodiesel from
soybean oil by KF/-Al2O3 as a nano-solid-base catalyst. Ultrason Sonochem
2015;23:26674.
[85] Macario A, Verri F, Diaz U, Corma A, Giordano G. Pure silica nanoparticles for
liposome/lipase system encapsulation: Application in biodiesel production.
Catalysis Today 2013;204:14855.
[86] Xie T, Wang A, Huang L, Li H, Chen Z, Wang Q. Recent advances in the
support and technology used in enzyme immobilization. Afr J Biotechnol
2009;8:472433.
[87] Wang X, Liu X, Zhao C, Ding Y, Xu P. Biodiesel production in packed-bed
reactors using lipasenanoparticle biocomposite. Bioresour Technol
2011;102:63525.
[88] Ngo TPN, Li A, Tiew KW, Li Z. Efcient transformation of grease to biodiesel
using highly active and easily recyclable magnetic nanobiocatalyst aggregates. Bioresour Technol 2013;145:2339.
[89] Schuler C, Caruso F. Preparation of enzyme multilayers on colloids for biocatalysis. Macromol Rapid Commun 2000;21:7503.
[90] Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in supercritical methanol. Fuel 2001;80:22531.
[91] Tan KT, Lee KT, Mohamed AR. Effects of free fatty acids, water content and
co-solvent on biodiesel production by supercritical methanol reaction. J
Supercrit Fluids 2010;53:8891.
[92] Skarlis S, Kondili E, Kaldellis J. Small-scale biodiesel production economics: a
case study focus on Crete Island. J Clean Prod 2012;20(1):206.
[93] Pinzi S, Lopez-Gimenez F, Ruiz J, Dorado M. Response surface modeling to
predict biodiesel yield in a multi-feedstock biodiesel production plant.
Bioresour Technol 2010;101(24):958793.
[94] Karmakar A, Karmakar S, Mukherjee S. Properties of various plants and animals
feedstocks for biodiesel production. Bioresour Technol 2010;101:720110.
[95] Kibazohi O, Sangwan RS. Vegetable oil production potential from Jatropha
curcas, Croton megalocarpus, Aleurites moluccana, Moringa oleifera and

Pachira glabra: assessment of renewable energy resources for bio-energy


production in Africa. Biomass Bioenergy 2011;35:13526.
[96] Hathurusingha S, Ashwath N, Midmore D. Provenance variations in seedrelated characters and oil content of Calophyllum inophyllum in northern
Australia and Sri Lanka. New Forests 2011;41:8994.
[97] Yusuf NNAN Kamarudin SK, Yaakub Z. Overview on the current trends in
biodiesel production. Energy Convers Manage 2011;52:274151.
[98] Gui MM, Lee KT, Bhatia S. Feasibility of edible oil vs. non-edible oil vs. waste
edible oil as biodiesel feedstock. Energy 2008;33:164653.
[99] Vicente G, Martinez M, Aracil J. ptimization of integrated biodiesel production part 1. A study of biodiesel purity and yield. Bioresour Technol
2007;98:172433.
[100] Giannelos PN, Zannikos F, Stournas S, Lois E, Anastopoulos G. Tobacco seed
oil as an alternative diesel fuel: physical and chemical properties. Ind Crop
Prod 2002;16:19.
[101] Rezanka T, Rezankova H. Characterization of fatty acids and triacylglycerols in
vegetable oils by gas chromatography and statistical analysis. Anal Chim Acta
1999;398:25361.
[102] Naik M, Meher LC, Naik SN, Das LM. Production of biodiesel from high free
fatty acid Karanja (Pongamia pinnata) oil. Biomass Bioenerg 2008;32:3547.
[103] Kansedo J, Lee KT, Bhatia S. Cerbera odollam (sea mango) oil as a promising
non-edible feedstock for biodiesel production. Fuel 2009;88:114850.
[104] Guinda A, Dobarganes MC, Ruiz-Mendez MV, Mancha M. Chemical and
physical properties of a sunower oil with high levels of oleic and palmitic
acids. Eur J Lipid Sci Technol 2003;105:1307.
[105] Leung DYC, Wu X, Leung MKH. A review on biodiesel production using catalyzed transesterication. Appl Energ 2010;87:108395.
[106] Wyatt VT, Hess MA, Dunn RO, Foglia TA, Haas MJ, Marmer WN. Fuel properties and nitrogen oxide emission levels of biodiesel produced from animal
fats. J Am Chem Soc 2005;82:58591.
[107] Karmee SK, Chadha A. Preparation of biodiesel from crude oil of Pongamia
pinnata. Bioresour Technol 2005;96:14259.
[108] Liu X, He H, Wang Y, Zhu S. Transesterication of soybean oil to biodiesel
using CaO as a solid base catalyst. Fuel 2008;87:21621.
[109] Meng X, Chen G, Wang Y. Biodiesel production from waste cooking oil via
alkali catalyst and its engine test. Fuel Process Technol 2008;89:8517.
[110] Xie W, Huang X. Synthesis of biodiesel from soybean oil using heterogeneous
KF/ZnO catalyst. Catalysis Lett 2006;107:539.
[111] Lu H, Liu Y, Zhou H, Yang Y, Chen M, Liang B. Production of biodiesel from
Jatropha curcas oil. Comput Chem Eng 2009;33:10916.
[112] DCruz A, Kulkarni MG, Meher LC, Dalai AK. Synthesis of biodiesel from
canola oil using heterogeneous base catalyst. J Am Oil Chem Soc
2007;84:93743.
[113] Sreeprasanth PS, Srivastava R, Srinivas D, Ratnasamy P. Hydrophobic, solid
acid catalysts for production of biofuels and lubricants. Appl Catal A-Gen
2006;314:14859.
[114] Sree R, Babu NS, Prasad PSS, Lingaiah N. Transesterication of edible and nonedible oils over basic solid Mg/Zr catalysts. Fuel Process Technol
2009;90:1527.
[115] Liang X, Gao S, Wu H, Yang J. Highly efcient procedure for the synthesis of
biodiesel from soybean oil. Fuel Process Technol 2009;90:7014.
[116] Zabeti M, WMAW Daud, Aroua MK. Biodiesel production using aluminasupported calcium oxide: an optimization study. Fuel Process Technol
2010;91:2438.
[117] Tantirungrotechai J, Chotmongkoolsap P, Pohmakotr M. Synthesis, characterization, and activity in transesterication of mesoporous MgAl mixedmetal oxides. Micropor Mesopor Mat 2010;128:417.
[118] Jacobson K, Rajesh G, Lekha CM, Ajay KD. Solid acid catalyzed biodiesel
production from waste cooking oil. Appl Catal B-Environ 2008;85:8691.
[119] Di Serio M, Cozzolino M, Tesser R, Patrono P, Pinzari F, Bonelli B, Santacesaria
E. Vanadyl phosphate catalysts in biodiesel production. Appl Catal A-Gen
2007;320:17.
[120] Lin VSY, Radu DR. Use of functionalized mesoporous silicates to esterify fatty
acids and transesterify oils. United State Patent 2006;7(122) 688 B2.
[121] Albuquerque MCG, Jimenez-Urbistondo I, Santamaria-Gonzalez J, Merida
Robles JM, Moreno-Tost R, Rodriguez-Castellon E, Jimenez-Lopez A, MairelesTorres P. CaO supported on mesoporous silicas as base catalysts for transesterication reactions. Appl Catal A-Gen 2008;334:3543.
[122] Xie W, Yang Z. Ba-ZnO catalysts for soybean oil transesterication. Catal Lett
2007;117:15965.
[123] Dizge N, Keskinler B. Enzymatic production of biodiesel from canola oil using
immobilized lipase. Biomass Bioenerg 2008;32:12748.
[124] Kawashima A, Matsubara K, Honda K. Acceleration of catalytic activity of calcium
oxide for biodiesel production. Bioresour Technol 2009;100:696700.
[125] Leung DYC, Koo BCP, Guo Y. Degradation of biodiesel under different storage
conditions. Bioresour Technol 2006;97:2506.
[126] Bajaj A, Lohan P, Jha PN, Mehrotra R. Biodiesel production through lipase catalyzed transesterication: An overview. J Mol Catal B-Enzym 2010;62:914.
[127] Dias JM, Alvim-Ferraz MCM, Almeida MF. Comparison of the performance of
different homogeneous alkali catalysts during transesterication of waste
and virgin oils and evaluation of biodiesel quality. Fuel 2008;87:35728.
[128] Da Silva RB, Lima AFN, Soares DL, Santos S, De Oliveira JRL, Chaves MH, Dos
Santos Jr JR, De Lima GM, De Moura EM, De Moura CV. Catalysts of Cu (II) and
Co (II) ions adsorbed in chitosan used in transesterication of soybean and
babassu oilsa new route for biodiesel syntheses. Bioresour Technol
2008;99:67938.