Professional Documents
Culture Documents
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.
497
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
Feedstock
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
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
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
499
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].
500
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
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
Yield % (w/w)
490
98.64
80
95.2
99.5
98
98.3
97.5
97
97
98
80
90
87
95
85
501
Table 5
Merits and demerits of various catalyst [73,81,123128].
8].Type of catalyst
Merits
Homogeneous catalyst
Demerits
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
502
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
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
504