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Advancements in Development and Characterization of Biodiesel: A Review
Advancements in Development and Characterization of Biodiesel: A Review
com
Review article
Environmental Engineering and Research Laboratories, Department of Applied Chemistry, Institute of Technology, Banaras Hindu University,
Varanasi, UP 221 005, India
b
Department of Chemical Engineering and Technology, Institute of Technology, Banaras Hindu University, Varanasi, UP 221 005, India
Received 7 November 2007; received in revised form 21 January 2008; accepted 22 January 2008
Available online 20 February 2008
Abstract
An ever increasing demand of fuels has been a challenge for todays scientic workers. The fossil fuel resources are dwindling day by
day. Biodiesel seems to be a solution for future. Biodiesel is an environmentally viable fuel. Out of the four ways viz. direct use and blending, micro-emulsions, thermal cracking and transesterication, most commonly used method is transesterication of vegetable oils, fats,
waste oils, etc. Latest aspects of development of biodiesel have been discussed in this work. Yield of biodiesel is aected by molar ratio,
moisture and water content, reaction temperature, stirring, specic gravity, etc. Biodegradability, kinetics involved in the process of biodiesel production, and its stability have been critically reviewed. Emissions and performance of biodiesel has also been reported.
2008 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Transesterication; Catalyst; Stability; Biodegradation
Contents
1.
2.
3.
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6.
7.
8.
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1. Various raw materials used as feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Production of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Acid esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Alkaline transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
A special reference to karanja . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Effect of different parameters on production of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1. Effect of molar ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2. Effect of moisture and water content on the yield of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.3. Effect of free fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.4. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.5. Effect of stirring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.6. Effect of specific gravity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Biodegradability of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Stability of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Kinetics of the reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Diesel engine emissions and performance of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Corresponding author. Tel.: +91 542 2307025 (O), +91 9935616119 (M); fax: +91 542 2316428.
E-mail address: y_sharma_2002@redimail.com (Y.C. Sharma).
0016-2361/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.01.014
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9.
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12.
Indian scenario . . . . . . . . . . . . . . . . . . . . . . . .
Cost of biodiesel . . . . . . . . . . . . . . . . . . . . . . .
Instrumentation involved in biodiesel production
Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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1. Introduction
Whenever I think of fuel, a picture of villages of developing nations eclipsed in darkness, full of poverty, no
planned mechanization, agriculture depending on rain
God for irrigation comes before my eyes. Be it lighting
the house, agriculture, or cooking, each process requires
energy. Energy, most countries do not have energy even
to light the cities! Superconductivity and hydrogen energy
reected some promise but these were completely shortlived. Biodiesel, yes, probably biodiesel is the FUEL of
future.
Biodiesel is derived from vegetable oils and hence is a
renewable fuel. Gasoline and diesel come in the category
of non-renewable fuel and will last for a limited period of
time. These non-renewable fuels also emit pollutants in
the form of oxides of nitrogen, oxides of sulphur, carbon
dioxide, carbon monoxide, lead, hydrocarbons, etc. during
their processing and use. A renewable fuel such as biodiesel, with lesser exhaust emissions, is the need of the day.
Hence, researchers and scientic community worldwide
have focused on development of biodiesel and the optimization of the processes to meet the standards and specications needed for the fuel to be used commercially without
compromising on the durability of engine parts. The interest in the use of renewable fuel started with the direct use of
vegetable oils as a substitute for diesel. However, their
direct use in compression ignition engines was restricted
due to high viscosity which resulted in poor fuel atomization, incomplete combustion and carbon deposition on
the injector and the valve seats causing serious engine fouling [1]. Other constraints of the direct application of vegetable oil were its low volatility and polyunsaturated
character. To overcome these constraints, the processes like
pyrolysis, micro-emulsication, transesterication, etc.
were especially developed. Pyrolysis of the vegetable oil
resulted in products with low viscosity, high cetane number, accepted amounts of sulphur, water and sediments,
accepted copper corrosion values but were unacceptable
in the terms of their ash contents, carbon residues, and
pour points. Similarly, micro-emulsion of vegetable oil
lowered the viscosity of the oil but resulted in irregular
injector needle sticking, heavy carbon deposits and incomplete combustion during 200 h laboratory screening endurance test [2]. Transesterication is a chemical reaction
between triglyceride and alcohol in the presence of a catalyst. It consists of a sequence of three consecutive reversible
reactions where triglycerides are converted to diglycerides,
diglycerides are converted to monoglycerides followed by
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Table 1
Values of initial FFA content of dierent feedstock
Feedstock
Reference
Rubber oil
Karanja oil
Tobacco oil
Polanga oil
Jatropha oil
Mahua oil
Karanja oil
17.0
2.53
35.0
22.0
14.0
19.0
2.53
37.96 0.018
40.0
<2.0
0.95
<2.0
<2.0
<1.0
<1.0
0.3
1.05 0.018
<1.0
0.5, H2SO4
0.5, H2SO4
1.0/2.0, H2SO4
0.65, H2SO4
1.43, H2SO4
1.0, H2SO4
KOH (appropriate amount)
2.0 Fe2SO4
[1]
[3]
[7]
[8]
[9]
[10]
[11]
[16]
[18]
Table 2
Yield of biodiesel with dierent feedstock
Oil taken for study
Yield
(%)
Conversion
(%)
Reference
89.5
91
99
98
9798
97.02
90.04
87.5
[3]
[7]
[8]
[9]
[10]
[11]
[14]
[15]
[16]
[19]
[19]
[20]
Chlorella protothecoides
Chlorella protothecoides
56
85
92/95
98.4
98
94
Nearly
complete
>80
[21]
[22]
protothecoides to 99% from Jatropha curcas. The conversion of biodiesel ranged from more than 80% from
C. prothecoides to 98.4% from soybean oil.
Various oils have been in use in dierent countries as
raw materials for biodiesel production owing to its availability. Soybean oil is commonly used in United States
and rapeseed oil is used in many European countries for
biodiesel production, whereas, coconut oil and palm oils
are used in Malaysia for biodiesel production [1013].
Transesterication of edible oils has also been carried out
from the oil of canola and sunower. Other edible and
non-edible oils, animal fats, algae and waste cooking oils
have also been investigated by researchers for the development of biodiesel [1431]. Table 3 depicts the work carried
out for biodiesel production from various feedstocks under
dierent conditions. Type and amount of variables such as
feedstock, alcohol, molar ratio, catalyst, reaction temperature, time duration, rate and mode of stirring aects the
yield and conversion of biodiesel.
2358
Table 3
Biodiesel production from dierent feedstock
Feedstock
Transesterication
stages
Alcohol
Molar
ratio
(methanol
to oil)
Catalyst
Reaction
temperature
(K)
Duration
Stirring
Conversion/yield
Reference
2004
Sunower oil
Single step
Supercritical
methanol
Supercritical
ethanol
Methanol
Ethanol
40:1
No catalyst
473673
(pressure
200 bar)
10
40 min
[20]
5:1
Supercritical
CO2 + lipase (Novozym
435) 30 wt% of oil
KOH (1% by wt)
ZnO
Hb-Zeolite
Montmorillonite
1% v/v H2SO4
318
6h
7896%
conversion with
increase in
temperature
23% conversion
27% conversion
378
1.5 h
[14]
393
24 h
333
1h
92%
83%
59%
47%
98%
1h
20
30 min
30 min
Magnetic stirrer
[1]
[22]
Ester content
98 wt%
Ester content
94.6 wt%
Yield 91% in
30 min
[19]
2005
Pongamia pinnata
Single step
Methanol
2005
Madhuca indica
Two step
Methanol
2005
Two step
2006
Chlorella
protothecoides
Chlorella
protothecoides
Neat canola oil
2006
2006
Single step
Methanol
0.300.35
v/v
0.25 v/v
6:1
318 5
Methanol
9:1
56:1
318 5
303
Methanol
56:1
303
4h
Methanol
6:1
318
15 min
7:1
333
20 min
18:1
333.0 0.1
25 min
Nicotiana
tabacum L.
(tobacco)
Two step
10:1
Methanol
6:1
30 min
conversion
conversion
conversion
conversion
yield
[10]
[21]
[7]
Year
Ref
2006
Pongamia pinnata
2006
Soybean oil
2006
Monosodium
glutamate
wastewater
Soybean oil
2006
2007
2007
Methanol
Methanol
6:1
12:1
4.5:1
338
448
2h
1h
2h
Yield 9798%
[11]
Conversion over
95%
Conversion 100%
Yield
92.54 2.00%
[23]
333
353
10 min
5 min
Yield 100%
[25]
[12]
85% yield in
90 min
Complete in 4 h
reaction
>99% yield
[8]
[9]
Two step
Methanol
0.5 M
12.5%, v/v
Methanol
6:1
NaOH
318
10
20 min
Single step
Methanol
3:1
NaOH/KOH (1 wt% of
oil)
24 h
Methanol
6:1
Anhydrous H2SO4
(98.4%) 0.65% by volume
338
2h
Methanol
9:1
0.28 v/v
333
4h
4h
88 min
0.16 v/v
10:1
323
24 min
60 min
98.8% purity
[26]
333
368
338
318 2
100 min
4h
1h
30 min
97.02% conversion
[27]
[16]
[3]
2007
Jatropha curcas
2007
Triolein
Alkali catalysed
Single step
Ethanol
2007
2007
Sunower oil
Waste cooking oil
Single step
Two step
Methanol
Methanol
2007
Karanja
Two step
Methanol
13:1
10:1
6:1
8:1
9:1
NaOH/KOH
30 min
[24]
Jatropha,
pongamia,
sunower,
soybean, palm
Calophyllum
inophyllum
Single step
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FFA. The FFA level of fresh soybean oil has been reported
to change from 0.04% to 1.51% after 70 h of frying at
463 K [41]. Hence, due to higher FFA, direct conversion
of waste restaurant oil and animal fats to biodiesel via
alkaline catalyst is not possible. The level of FFA, therefore, is reduced by an acid catalyst.
Following this advantage, researchers have advocated
the use of rendered animal fats and restaurant waste oils
as biodiesel feedstocks [18,4247]. A major limiting factor
of biodiesel is its inverse relationship between its oxidation
stability and its cold ow properties. Saturated compounds
have good oxidation stability but poor cold temperature
properties. Unsaturated compounds have better low temperature properties but fail in oxidation stability [12,17].
Here, the waste oil product can be of advantage over the
neat vegetable oil as they have a higher proportion of saturated fatty acids [17] and hence can provide better oxidative stability. Wang et al. [16] have achieved 97.02% yield of
biodiesel from waste cooking oil of high acid value i.e.
75.92 0.036 mg KOH/g, by a two step catalysis process.
A novel method has been developed by Xue et al. [24]
for the production of biodiesel from monosodium glutamate wastewater having COD of 10,000 mg/L. After treatment the COD removal was 85% with 10% formation of
crude lipid. The crude lipid was biosynthesized by rhodotorula glutinis by transesterication reaction with methyl
ester yield of 92.54 2.0%. Biodiesel has also been synthesized using triolein as a feedstock [26]. Fig. 1 depicts the
basic scheme for biodiesel production [48].
2. Production of biodiesel
2.1. Acid esterication
The acid value is a measure of the number of acidic
functional groups in a sample and is measured in terms
of the quantity of potassium hydroxide required to neutralize the sample. Acid value of the feedstock for alkaline
transesterication has to be reduced to less than 2.0 mg
KOH/g [15,4951]. However, other authors advocate it to
be less than 4.0 mg KOH/g [1,3]. The commonly used catalyst during acid esterication of neat oil is sulphuric acid
(H2SO4) [1,3,710]. Nevertheless, this process too has a
drawback as water is produced along with ester from the
reaction of FFA with alcohol which inhibits the transesterication of glycerides [17]. For waste cooking oil too the
acid employed is sulphuric acid [2931]. But in this case,
the conversion reported is low (82%) and the alcohol
required for the reaction is high (200% excess of ethanol)
[16]. Wang et al. [16] have, therefore, tried a new catalyst
Fe2(SO4)3 (ferric sulphate) as an alternate to sulphuric acid
and have reported much better conversion (97.02%). As,
ferric sulphate is insoluble in oil, it was centrifuged from
the liquid after acid esterication and reused for the next
batch. High temperature and high concentration of
H2SO4 as catalyst could burn some of the oil which will
then cause low yield of biodiesel product.
2.2. Alkaline transesterication
For oil samples with FFA below 2.0%, alkaline transesterication is preferred over the acid catalyzed transesterication as the former is reported to proceed about 4000
times faster than the latter [2]. The common catalyst
employed during alkaline transesterication at industrial
level application includes the homogeneous catalysts
sodium hydroxide, potassium hydroxide, etc.
The use of homogeneous catalyst such as sodium
hydroxide and potassium hydroxide has been successful
at industrial level for production of biodiesel. However,
the biodiesel and glycerin produced have to be puried to
remove the basic catalyst and need its separation by washing with hot distilled water twice or thrice. Thus, heterogeneous catalyst has also been tried by researchers to
overcome this drawback of time consumption and colossal
consumption of water. The heterogeneous catalyst can be
separated from the nal product by ltration which checks
time consumption and prevents the consumption of large
volume of water. The ltered solid then can be reused.
The application of a heterogeneous catalyst, CaO has been
tested by Grandos et al. for its feasibility [27]. The experiments conrmed that CaO could be used as a catalyat for
the transesterication reaction without signicant deactivation up to eight runs with signicant amount of CaO.
Leung and Guo [19] tried three dierent homogeneous
catalysts i.e. sodium hydroxide (NaOH), potassium
hydroxide (KOH), and sodium methoxide (CH3ONa).
The optimum requirement of the catalyst were 1.1, 1.3
and 1.5 wt% for NaOH, CH3ONa, and KOH respectively
for the maximum ester content. The amount of NaOH
required was less than the amounts of both the CH3ONa
or KOH for the same conversion of fatty acid methyl ester
as NaOH has lower molar mass (40 g/mol), compared to
CH3ONa (54 g/mol) and KOH (56 g/mol).
However, in terms of yield, CH3ONa proved to be a better catalyst than NaOH and KOH because CH3ONa dissociates into CH3 O and Na+ and does not form any water
as side product. On the other hand, NaOH and KOH
forms sodium (or potassium) methoxide when dissolved
in methanol and produces water. This water then reacts
with Na+ (or K+) to form sodium (or potassium) soaps.
Potassium methoxide (KOCH3) has also been used as an
alkali catalyst by dissolving potassium hydroxide in methanol [52]. Sharma and Singh [3] reported better yield with
NaOH as a catalyst over KOH while using magnetic stirrer. Whereas, when mechanical stirrer was adopted the
yield was same with equal amount of NaOH and KOH
(0.5 wt%). However, during the separation of the nal
products from glycerol, KOH was more convenient. Potassium soaps being softer than sodium soaps did not block
the bottom of separating funnel unlike latter and were
removed easily. Hence, KOH as catalyst is preferred over
NaOH at industrial level application [3,19].
The base catalyzed reaction is reported to be very sensitive to the purity of the reactant. FFA content should not
exceed beyond a certain limit. The eciency of the reaction
was aected to some extent when FFA content exceeded
0.5 wt% [28]. However, when the feedstock is waste cooking oil, the limit of FFA is a bit relaxed and FFA content
a little beyond 1.0 wt% did not have any eect on the
methyl ester conversion [16,53]. The amount of catalyst
(KOH) required was 1.0 wt% to reach 97.02% conversion
of biodiesel.
Ramadhas et al. [1] have reduced the acid value to less
than 2.0% through acid catalyst followed by alkaline
transesterication. The amount of catalyst used for alkaline transesterication ranged between 0.3% and 1.0%.
The maximum conversion eciency was reported at 0.5%
of NaOH during alkaline transesterication. Excess
amount of catalyst gave rise to formation of an emulsion.
This increased the viscosity and led to the formation of
gels. Conversion eciency decreased to 60% when the catalyst amount was increased to 0.8% (wt of NaOH/wt of
oil). However, esterication also did not take place without
sucient amount of the catalyst.
Srivastava and Verma [54] used sodium methoxide solution prepared by dissolving NaOH (28.5 g) and methanol
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2362
hydrotalcites, MgO and CaO [27,5762]. In addition, reactor heating was not needed when MgO was used as a catalyst in batch process [57].
Another method where neither acid nor base catalyst is
required is non-catalytic transesterication where supercritical methanol is used instead of methanol and nearly
complete conversion is achieved. The reason is that, the
oil and supercritical methanol exist in the single phase
[20,6367]. The advantage with supercritical methanol is
that the conversion gets 95% complete in 10 min. But at
the same time, higher molar ratio (40:1) is employed. The
supercritical condition is based on the eect of relationship
between pressure and temperature upon the thermophysical properties of the solvent, such as dielectric constant,
viscosity, specic weight and polarity. There is a decrease
in the dielectric constant of methanol in supercritical state.
Fig. 2 depicts the inuence of temperature and alcohol used
in the synthesis of biodiesel. In methanol, conversion
increased from 78% to 96% with increase in temperature.
The conversion was even higher with supercritical ethanol
as the solubility parameter of ethanol is closer to the solubility parameter of the oil. But, high temperature and high
pressure conditions i.e. 573 K and 20 MPa are needed for
the reaction to proceed and complete. [13,20]. Another
added advantage with heterogeneous based catalyst is the
lesser consumption of catalyst. As per the study by Zhang
et al. [29] annually 88 tonnes of sodium hydroxide is
needed for 8000 tonnes of biodiesel production. While as
per the simulation study by Dossin et al. [57] the requirement of MgO will be only 5.7 tonnes for 100,000 tonnes
production of biodiesel.
3. A special reference to karanja
Among the several indigenous plant species, karanja is
one of the medium sized plants found in several parts of
India. The plant is also said to be highly tolerant to salinity
and is reported to be grown in various soil textures viz.
stony, sandy and clayey. Karanja can grow in humid as
well as subtropical environments with annual rainfall ranging between 500 and 2500 mm. This is one of the reasons
for wide availability of this plant species. The constituents
of karanja oil viz. furanoavones, furanoavonols, chromenoavones, avones and furanodiketones make the oil
non-edible and hence the oil is underutilized. The presence
of these constituents, however, gives the oil antifungal
characteristics and enhances its application in medicinal
ointments. The woody part of the tree is still in use by tribal people where the plant is locally available such as
brushing of teeth. The oil expelled from the seeds is also
burned during the festival of lighting to purify the environment. All these applications are at local or regional level
and 94% of the oil from plant is still underutilized. The
present production of karanja oil approximately is 200 million tons per annum [11]. However, its production potential is much more i.e. 135,000 million tones per annum
[8]. The time needed by the tree to mature ranges from 4
to 7 years and depending on the size of the tree the yield
of kernels per tree is between 8 and 24 kg. The oil content
extracted by various authors ranges between 30.0 to 33%
[3,14]. The oil is used by common people due to its low cost
and easy availability. The fatty acid composition of karanja
oil has been reported in Table 4. Karanja oil comprises of
Table 4
Dierent fatty acids present in karanja oil [107]
Fatty acid
(common
name)
Systematic name
Formula
Structure
wt%
Palmitic
Stearic
Oleic
Linoleic
Arachidic
Gadoleic
Behenic
Lignoceric
Hexadecanoic
Octadecanoic
cis-9-octadecenoic
cis-9, cis-12-octadecadienoic
Eicosanoic
11-eicosenoic
Docosanoic
Tetracosanoic
C16H32O2
C18H36O2
C18H34O2
C18H32O2
C20H40O2
C20H38O2
C22H44O2
C24H48O2
16:0
18:0
18:1
18:2
20:0
20:1
22:0
24:0
10.6
6.8
49.4
19.0
4.1
2.4
5.3
2.4
2363
Table 5
Test method and limits of biodiesel along with its comparison with karanja oil methyl ester [12]
Property (units)
IS 15607 limits
D-93
D-445
D-874
D-5453
D-2500
D-130
D-613
D-2709
D-4530
D-664
D-6584
D-6584
D-4951
D-1160
NA
Min. 130
1.96.0
Max. 0.02
Max. 0.05
NA
Max. 3
Min. 47
Max. 0.05
Max. 0.05
Max. 0.80
Max. 0.02
Max. 0.24
Max. 0.001
90% at 360 C
NA
IS 1448 P:21
IS 1448 P:25
IS 1448 P:4
ASTM D 5453
IS 1448 P:10
IS 1448 P:15
IS 1448 P:9
D-2709
D-4530
IS 1448 P:1/Sec. 1
D-6584
D-6584
D-4951
Not under spec.
EN 14112
Min. 120
2.56.0
Max. 0.02
Max. 0.005
NA
Max. 1
Min. 51
Max. 0.05
Max. 0.05
Max. 0.50
Max. 0.02
Max. 0.25
Max. 0.001
Min. 6 h
141
4.16
0.002
0.003
4
1
55.1
0.03
<0.01
0.10
0.01
0.01
<0.001
90%
2.35
2364
Fig. 4. Eect of FFA on the yield of methyl ester during alkali catalyzed
transesterication.
Fig. 5. The variation of product specic gravity with reaction time under
dierent molar ratio of methanol to oil. Reaction conditions: 303 K,
160 rpm, 100% catalyst quantity based on oil weight.
2365
Table 6
Comparison of dierent technologies to produce biodiesel
Variable
Alkali catalysis
Lipase catalysis
Supercritical alcohol
Acid catalysis
333343
Sapanoed products
Interference with reaction
Normal
Dicult
Repeated washing
Cheap
303313
Methyl esters
No inuence
Higher
Easy
None
Relatively expensive
512658
Esters
Good
Medium
328353
Esters
Interference with reaction
Normal
Dicult
Repeated washing
Cheap
and 600 rpm. Sharma and Singh [3] reported that mode of
stirring too plays a vital role in the transesterication reaction. The yield of biodiesel increased from 85% to 89.5%
when magnetic stirrer (1000 rpm) was replaced with
mechanical stirrer (1100 rpm). A plausible explanation
may be a thorough mixing of the reactants by mechanical
stirrer.
4.6. Eect of specic gravity
Lower value of the specic gravity of the nal product is
an indication of completion of reaction and removal of
heavy glycerine. The inuence of molar ratio, temperature
and catalyst quantity on the specic gravity of the biodiesel
was studied by Miao and Wu [21]. The specic gravity of
the product decreased sharply up to 2 h of reaction time
using 30:1 molar ratio and up to 4 h of reaction time using
45:1 and 56:1 molar ratio after which it was almost constant. The best process combination reduced the product
specic gravity from 0.912 to 0.864 with 100% catalyst,
56:1 molar ratio at 303 K in 4 h of reaction time. Fig. 5
depicts the change in specic gravity with reaction time
under dierent molar ratio of methanol to oil. A comparison of dierent technologies to produce biodiesel is shown
in Table 6 [48].
5. Biodegradability of biodiesel
Biodiesel is reported to be highly biodegradable in freshwater as well as soil environments. 9098% of biodiesel is
mineralized in 2128 days under aerobic as well as anaerobic conditions [7375]. Biodiesel has been reported to
remove twice the amount of crude oil from sand as conventional shoreline cleaners [76]. Biodiesel increases the biodegradability of crude oil by means of cometabolism. More
Table 7
Biodegradability of fossil diesel
%
degradation
No. of
days
Reference
67
81
9095
42
18
109
310
365
30
50
[77]
[78]
[79]
[80]
[80]
2366
through this route leads to obligomerization even at ambient temperature. As the deterioration of biodiesel is attributed to the formation of peroxide in the initial step, the
remedy suggested is to prevent peroxide formation during
the stages of biodiesel manufacture and throughout its distribution chain [12,81]. As biodiesels are primarily made
from vegetable oils which do contain naturally occurring
antioxidants such as tocopherols, sterols and tocotrienols
and these remain in the biodiesel during the process of
manufacture. However, the distillation and purication
step destroys these natural antioxidants and hence becomes
prone to oxidation. Synthetic antioxidants such as phenolic
types or aminic types have to be added to make it stable
and hence acceptable in market [12,81,8385]. Sarin et al.
[12] suggested blending jatropha biodiesel with palm biodiesel to reduce the antioxidant dosage by 8090% to maintain good oxidation stability.
TG M $ DG FAME
K4
K2
DG M $ MG FAME
K5
K3
MG M $ G FAME
K6
2
3
4
where, TG, triglycerides; DG, diglycerides; MG, monoglycerides; M, methanol and FAME, fatty acid methyl
esters.
The values of rate constants for forward reactions, K1,
K2 and K3, are found to be 5.00, 4.93 and 29.67 dm3 mol1
min1 and the values of the rate constants of backward
reactions involved in the kinetics of biodiesel development,
K4, K5, and K6 are reported to be 3.54, 2.99 and
0.79 dm3 mol1 min1. A software MATLAB 6.1 was used
to generate concentration prole of glycerol, tri-,di-, and
monoglycerides and fatty acid methyl ester. Fig. 6 shows
the concentration proles of all components in which a plateau is reached at equilibrium [52].
+2.0
10.1
21.1
11.0
ers. This reduces the iodine value. Boehman et al. [99] and
Kegl [100] recommended to retard the injection timing
which could lead to decrease in NOx emission. Nabi
et al. [101] advocated for the exhaust gas recirculation to
reduce the NOx emission.
Kegl [102] stressed on the importance of fuel injection
system to reduce the engine emissions as well as fuel consumption. Author suggests that pressure squareness (ratio
of mean to maximum injection pressure) should be at maximum and fuelling in the rst part of injection has to be less
to reduce NOx emission. Simultaneously, the fuelling in the
last part of injection should be less to reduce the smoke
emissions. Shahid and Jamal [103] reported that blend of
biodiesel till B20 (20% biodiesel and 80% diesel) would
2367
Table 9
List of 26 indigenous plant meeting US, Germany and European standards (a oil from kernel, b oil from seeds, osa: other saturated acids, uk: unknown) [107]
Sources
Oil
SN
IV
CN
39.5a
42.0b
41.6b
204.0
203.6
201.1
92.6
87.2
76.0
52.22
53.47
56.33
67.0a
201.5
84.0
57.48
36.9b
73.0a
52.0a
202.9
204.6
236.6
85.3
77.3
77.5
54.00
55.58
51.9
14:0 (0.4); 16:0 (19.7); 16:1 (0.4); 18:0 (6.5); 18:1 (50.3); 18:2 (21.6); 18:3 (0.4); 20:4 (0.7)
16:0 (29.0); 18:0 (9.7); 18:1 (38.3); 18:2 (21.8); 18:3 (1.2)
1:0 (2.0); 2:0 (1.7); 16:0 (25.1); 18:0 (6.7); 18:1 (46.1); 18:2 (15.4); 18:3 (3.0)
40.0b
38.0a
57.5a
40.0b
41.8a
47.5a
198.8
205.2
200.5
202.6
199.6
200.4
77.8
68.5
84.51
93.0
82.9
97.6
56.24
57.51
54.50
52.31
54.99
51.57
16:0
14:0
14:0
14:0
16:0
16:0
65.0a
201.4
71.5
57.3
16:0 (17.9); 16:1 (2.5); 18:0 (18.5); 18:1 (42.7); 18:2 (13.7); 18:3 (2.1); 24:0 (2.6)
68.5a
44.5a
35.5b
201.0
201.1
199.7
81.3
69.3
76.0
55.10
57.83
56.32
14:0 (0.9); 16:0 (10.8); 18:0 (12.4); 18:1 (60.0); 18:2 (15.0); 20:0 (0.9)
16:0 (14.9); 18:0 (14.4); 18:1 (61.9); 18:2 (7.5); 20:0 (1.3)
16:0 (9.7); 18:0 (2.4); 18:1 (83.8); 18:2 (0.8); 20:0 (3.3)
35.0a
33.0b
33.0b
45.5a
40.0b
40.0b
47.0a
199.7
196.7
198.6
195.0
193.0
202.1
202.0
75.4
80.9
81.8
64.5
57.9
74.2
62.2
56.66
55.84
55.37
59.77
61.55
56.61
59.32
16:0 (9.1); 16:1 (2.1); 18:0 (2.7); 18:1 (79.4); 18:2 (0.7); 18:3 (0.2); 20:0 (5.8)
16:0 (10.6); 18:0 (6.8); 18:1 (49.4); 18:2 (19.0); 20:0 (4.1); 20:1 (2.4); 22:0 (5.3); 24:0 (2.4)
16:0 (10.4); 18:0 (5.5); 18:1 (64.4); 18:2 (12.4); 20:0 (1.8); 20:1 (2.6); 22:0 (1.2); 22:1 (1.7)
16:0 (5.4); 18:0 (8.5); 18:1 (55.1); 18:2 (8.2); 20:0 (20.7); 22:0 (2.1)
16:0 (1.6); 16:1 (3.1); 18:0 (10.1); 18:1 (52.5); 20:0 (19.7); 22:0 (4.0); 22:1 (0.9); gadolic acid (8.4)
14:0 (1.0); 16:0 (17.8); 18:0 (14.0); 18:1 (46.3); 18:2 (17.9); 20:0 (3.0)
16:0 (19.0); 18:0 (14.0); 18:1 (63.0); 18:2 (3.0); 20:0 (1.0)
35.0b
37.4b
202.6
208.7
98.4
49.9
51.09
61.22
2368
Table 10
List of 11 species meeting the US biodiesel standards on the basis of fatty acid composition, SN, IV and CN (a oil from kernel, b oil from seeds, osa: other
saturated acids, uk: unknown) [107]
Sources
Oil
SN
IV
CN
Vallaris solanacea
Kuntze
Balanites roxburghii
Planch
Croton tiglium Linn
Hydnocarpus wightiana
Blume
Mappia foetida Milers
Perilla frutescens
Britton
Aphanamixis
polystachya Park
Princeptia utilis Royle
Meyna laxiora Robyns
Aegle marmelos correa
Roxb
Tectona grandis Linn
33.0b
198.3
104.7
50.26
16:0 (7.2); 18:0 (14.4); 18:1 (35.3); 18:2 (40.4); 20:0 (1.8); 22:0 (0.4); 24:0 (0.5)
43.0a
188.9
109.9
50.46
16:0 (17.0); 16:1 (4.3); 18:0 (7.8); 18:1 (32.4); 18:2 (31.3); 18:3 (7.2)
45.0b
63.0a
203.9
210.5
102.9
102.1
49.9
49.25
48.0b
40.5b
200.7
199.0
101.3
193.9
50.70
30.09
14:0 (11.0); 16:0 (1.2); 18:0 (0.5); 18:1 (56.0); 18:2 (29.0); 20:0 (2.3)
16:0 (1.8); 18:1 (6.9); hydnocarpic acid (48.7); gorlic acid (12.2); chaulmoogric acid (27.0);
chaulmoogtic homolog (3.4)
16:0 (7.1); 18:0 (17.7); 18:1 (38.4); 18:3 (36.8)
18:1 (9.8); 18:2 (47.5); 18:3 (36.2); osa (6.5)
35.0a
203.8
109.1
48.52
16:0 (23.1); 18:0 (12.8); 18:1 (21.5); 18:2 (29.0); 18:3 (13.6)
37.2a
38.5b
34.0b
201.9
202.8
202.5
108.4
101.3
114.9
48.94
50.42
48.30
14:0 (1.8); 16:0 (15.2); 18:0 (4.5); 18:1 (32.6); 18:2 (43.6); 24:0 (0.9) uk (1.4)
16:0 (18.8); 18:0 (9.0); 18:1 (32.5); 18:2 (39.7)
16:0 (16.6); 18:0 (8.8); 18:1 (30.5); 18:2 (36.0); 18:3 (8.1)
44.5a
200.9
111.3
48.31
14:0 (0.2); 16:0 (11.0); 18:0 (10.2); 18:1 (29.5); 18:2 (46.4); 18:3 (0.4); 20:0 (2.3)
2369
Table 11
Instrumentation involved in characterization of biodiesel
Feedstock
Reference
Tobacco
Polanga seed oil
Pongamia pinnata
[7]
[8]
[11]
[26]
[27]
Biopiles
Canola, corn, peanut, olive, waste
vegetable
Castor oil
[12]
[14]
[16]
[19]
[20]
[21]
[22]
[23]
[24]
[79]
[85]
[104]
2370
2371
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