Advancements in Development and Characterization of Biodiesel

Review article
Advancements in development and characterization

of biodiesel: A review
Y.C. Sharma
a,
*
, B. Singh
a
, S.N. Upadhyay
b
a
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 blend-
ing, 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 bio-
diesel 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. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2356
1.1. Various raw materials used as feedstock . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2357
2. Production of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2360
2.1. Acid esterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2360
2.2. Alkaline transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2360
3. A special reference to karanja . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2362
4. Effect of different parameters on production of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2363
4.1. Effect of molar ratio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2363
4.2. Effect of moisture and water content on the yield of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2363
4.3. Effect of free fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2364
4.4. Effect of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2364
4.5. Effect of stirring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2364
4.6. Effect of specific gravity. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2365
5. Biodegradability of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2365
6. Stability of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2365
7. Kinetics of the reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2366
8. Diesel engine emissions and performance of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2366
0016-2361/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2008.01.014
*
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).
www.fuelrst.com
Available online at www.sciencedirect.com
Fuel 87 (2008) 23552373
9. Indian scenario . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2368
10. Cost of biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2368
11. Instrumentation involved in biodiesel production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
12. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2370
1. Introduction
Whenever I think of fuel, a picture of villages of devel-
oping 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 short-
lived. 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 biodie-
sel, with lesser exhaust emissions, is the need of the day.
Hence, researchers and scientic community worldwide
have focused on development of biodiesel and the optimi-
zation of the processes to meet the standards and specica-
tions needed for the fuel to be used commercially without
compromising on the durability of engine parts. The inter-
est 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 atomiza-
tion, incomplete combustion and carbon deposition on
the injector and the valve seats causing serious engine foul-
ing [1]. Other constraints of the direct application of vege-
table 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 num-
ber, 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 incom-
plete combustion during 200 h laboratory screening endur-
ance test [2]. Transesterication is a chemical reaction
between triglyceride and alcohol in the presence of a cata-
lyst. It consists of a sequence of three consecutive reversible
reactions where triglycerides are converted to diglycerides,
diglycerides are converted to monoglycerides followed by
the conversion of monoglycerides to glycerol. In each step
an ester is produced and thus three ester molecules are pro-
duced from one molecule of triglyceride [3]. Out of these
three methods, transesterication is the most viable process
adopted known so far for the lowering of viscosity. It also
gives glycerol as a by-product which has a commercial
value.
Stoichiometrically, three moles of alcohol are required
for each mole of triglyceride, but in general, a higher molar
ratio is often employed for maximum ester production
depending upon the type of feedstock, amount of catalyst,
temperature, etc. Commonly used alcohols include metha-
nol, ethanol, propanol and butanol. However, the yield of
biodiesel is independent of the type of the alcohol used and
the selection of one of these depends on cost and perfor-
mance. Methanol is preferred over others due to its low
cost [1]. The conventional catalysts used are acid and alkali
catalysts depending upon the nature of the oil used for bio-
diesel production. Another catalyst being studied is lipase.
Lipase has advantage over acid and alkali catalysts but its
cost is a limiting factor for its use in large scale production
of biodiesel. Choice of acid and alkali catalysts depends on
the free fatty acids (FFA) content in the raw oil. FFA
should not exceed a certain amount for transesterication
to occur by an alkali catalyst. Invariably, on all aspects
of development of biodiesel, Ma and Hanna [4] have done
signicant work. Canakci and Van Gerpan [5,6] reported
that transesterication was not feasible if FFA content in
the oil was about 3%. Ramadhas et al. [1] and Veljkovic
et al. [7] used rubber seed oil and tobacco seed oil, respec-
tively, with higher free fatty acid content (17%). The
authors reduced the FFA value to more than 2.0%, which
corresponds to 4.0 mg KOH/g, by acid esterication using
H
2
SO
4
as a catalyst. Sahoo et al. [8] used zero catalyzed
transesterication (using toluene) and acid esterication
(using H
2
SO
4
) prior to alkaline esterication to reduce
the acid value from 22.0% to 2.0%. Sharma and Singh [3]
also favored acid esterication prior to alkaline transesteri-
cation with karanja oil as feedstock having FFA of 2.53%
(5.06 mg KOH/g) using H
2
SO
4
. In the same manner, the
acid value of jatropha which corresponds to 14% FFA
was reduced to less than 1% by using H
2
SO
4
[9]. Table 1
depicts the values of initial FFA of the feedstock, the level
reached after acid esterication and the amount of H
2
SO
4
used. After treatment with acid catalyst, H
2
SO
4
, the free
fatty acid (FFA) value is reduced to less than 2.0% to make
transesterication reaction feasible. Table 2 depicts the
yield/conversion of biodiesel with dierent oils taken.
The yield of biodiesel ranged from 56% from Chlorella
2356 Y.C. Sharma et al. / Fuel 87 (2008) 23552373
protothecoides to 99% from Jatropha curcas. The conver-
sion 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 avail-
ability. 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 develop-
ment 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 tempera-
ture, time duration, rate and mode of stirring aects the
yield and conversion of biodiesel.
1.1. Various raw materials used as feedstock
Leung and Guo [19] compared the transesterication
reaction conditions of neat canola oil with used frying oil
(UFO). A comparatively higher temperature (333 K),
higher molar ratio (7:1, methanol/UFO), and more amount
of catalyst (1.1 wt% NaOH) was needed when compared to
edible canola oil where optimal conditions were 315
318 K, 6:1 methanol/oil molar ratio and 1.0 wt% NaOH.
However, comparatively a less time (20 min) was needed
in UFO for completion of reaction in comparison to canola
oil where reaction time took 60 min. Non-edible oils used
for transesterication mostly are the oils with higher free
fatty acids such as rubber (Ficus elastica), jatropha (J. cur-
cas), karanja (Pongamia pinnata), mahua (Madhuca indica),
polanga (Calophyllum inophyllum), tobacco (Nicotina taba-
cum), etc. In an attempt to reduce the cost of biodiesel, mic-
roalgal oils have also been tried by researchers as a source
of feedstock for the production of biodiesel due to their
higher photosynthetic eciency, higher biomass produc-
tion and faster growth as compared to other energy crops
[3235]. Miao and Wu [21] reported production of biodie-
sel from microalga C. protothecoides using 100% catalyst
quantity (based on oil weight) with 56:1 molar ratio of
methanol to oil at temperature of 303 K in 4 h of reaction
time. The specic gravity of biodiesel produced reduced
from initial value of 0.91 to a nal value of 0.86. Xu
et al. [22] obtained high quality and low cost biodiesel from
microalgae C. protothecoides of heating value 41 MJ kg
1
,
density 0.864 kg L
1
and viscosity 5.2 10
4
Pa S at
313 K. C. protothecoides have earlier been reported as a
feedstock for aquaculture feeds, human food supplements
and pharmaceuticals [3639].
Attributing to its low cost, waste cooking oil has also
been tried by researchers to develop biodiesel. The idea
comes from the fact that triglycerides comprise of greases
and oil. Oils are generally in liquid state at room tempera-
ture, whereas greases and fats are in solid state at room
temperature. Recycled grease is termed as waste grease
and is classied as yellow and brown grease depending
on free fatty acid composition [17]. The price of yellow
grease (FFA < 15%) ranges from $0.04 to $0.09 kg
1
while
the price of brown grease (FFA > 15%) ranges between
0.004 and $0.014 kg
1
[40]. Biodiesel development from
grease can reduce its production cost. In United States,
an estimate reveals that biodiesel production from 5.2 bil-
lion kg/year of greases and animal fats could replace 1.5
million gallons of diesel fuel. The major constraint of direct
application of waste frying oil lies in its higher amount of
Table 2
Yield of biodiesel with dierent feedstock
Oil taken for study Yield
(%)
Conversion
(%)
Reference
Karanja (Pongamia pinnata) 89.5 [3]
Tobacco (Nicotina tabacum) 91 [7]
Polanga (Calophyllum inophyllum) 85 [8]
Jatropha (Jatropha curcas) 99 [9]
Mahua (Madhuca indica) 98 [10]
Karanja (Pongamia pinnata) 9798 [11]
Karanja (Pongamia pinnata) 92/95 [14]
Soybean (Glycine max) 98.4 [15]
Waste cooking oil 97.02 [16]
Canola oil (Brassica napus) 90.04 98 [19]
Used frying oil 87.5 94 [19]
Sunower oil (Helianthus annuus) Nearly
complete
[20]
Chlorella protothecoides 56 [21]
Chlorella protothecoides >80 [22]
Table 1
Values of initial FFA content of dierent feedstock
Feedstock Initial FFA (%) FFA after treatment (%) Amount (%) and catalyst used Reference
Rubber oil 17.0 <2.0 0.5, H
2
SO
4
[1]
Karanja oil 2.53 0.95 0.5, H
2
SO
4
[3]
Tobacco oil 35.0 <2.0 1.0/2.0, H
2
SO
4
[7]
Polanga oil 22.0 <2.0 0.65, H
2
SO
4
[8]
Jatropha oil 14.0 <1.0 1.43, H
2
SO
4
[9]
Mahua oil 19.0 <1.0 1.0, H
2
SO
4
[10]
Karanja oil 2.53 0.3 KOH (appropriate amount) [11]
37.96 0.018 1.05 0.018 2.0 Fe
2
SO
4
[16]
40.0 <1.0 [18]
Y.C. Sharma et al. / Fuel 87 (2008) 23552373 2357
Table 3
Biodiesel production from dierent feedstock
Year
Ref
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
40:1 No catalyst 473673
(pressure
200 bar)
10
40 min
7896%
conversion with
increase in
temperature
[20]
Supercritical
ethanol
Methanol 5:1 Supercritical
CO
2
+ lipase (Novozym
435) 30 wt% of oil
318 6 h 23% conversion
Ethanol 27% conversion
2005 Pongamia pinnata Single step Methanol 10:1 KOH (1% by wt) 378 1.5 h 92% conversion [14]
ZnO 83% conversion
Hb-Zeolite 393 24 h 59% conversion
Montmorillonite 47% conversion
2005 Madhuca indica Two step Methanol 0.300.35
v/v
1% v/v H
2
SO
4
333 1 h 98% yield [10]
0.25 v/v 0.7% w/v KOH 1 h
2005 Rubber seed oil Two step Methanol 6:1 H
2
SO
4
0.5% by volume 318 5 20
30 min
Magnetic stirrer [1]
9:1 NaOH 0.5% by volume 318 5 30 min
2006 Chlorella
protothecoides
Methanol 56:1 Acid catalyst 303 More than 80%
conversion
[22]
2006 Chlorella
protothecoides
Methanol 56:1 H
2
SO
4
(100%) on the
basis of oil weight
303 4 h 63% yield [21]
2006 Neat canola oil Single step Methanol 6:1 NaOH 1.0 wt% 318 15 min Magnetic stirring 1100 rpm in
the rst stage (10 min) and
600 rpm in second stage
Ester content
98 wt%
[19]
Used frying oil 7:1 NaOH 1.1 wt% 333 20 min Ester content
94.6 wt%
2006 Nicotiana
tabacum L.
(tobacco)
Two step Methanol 18:1 H
2
SO
4
(1% with lower
molar ratio) (2% with
higher molar ratio)
333.0 0.1 25 min Magnetic stirrer 400 rpm Yield 91% in
30 min
[7]
6:1 KOH (1% based on the
oil wt.)
30 min
2
3
5
8
Y
.
C
.
S
h
a
r
m
a
e
t
a
l
.
/
F
u
e
l
8
7
(
2
0
0
8
)
2
3
5
5
2
3
7
3
2006 Pongamia pinnata Single step Methanol 6:1 KOH (1% by weight) 338 2 h Mechanical stirrer 360 rpnm Yield 9798% [11]
12:1 1 h
2006 Soybean oil Methanol 4.5:1 TiO
2
/ZrO
2
(11 wt% Ti) 448 2 h Conversion over
95%
[23]
Al
2
O
3
/ZrO
2
(2.6 wt% Al)
K
2
O/ZrO
2
(3.3 wt% K) Conversion 100%
2006 Monosodium
glutamate
wastewater
Two step Methanol 0.5 M 1 ml KOH (0.5 M) 333 10 min Yield
92.54 2.00%
[24]
12.5%, v/v 1 ml BF
3
(12.5%, v/v) 353 5 min
2006 Soybean oil Single step alkali
catalyzed
Methanol 6:1 NaOH 318 10
20 min
Mechanical stirrer 900 rpm Yield 100% [25]
Power ultrasonic (frequency
19.7 KHz, power 150 W)
Hydrodynamic cavitation
(operation pressure 0.7 MPa)
2007 Jatropha,
pongamia,
sunower,
soybean, palm
Single step Methanol 3:1 NaOH/KOH (1 wt% of
oil)
24 h Stirring [12]
2007 Calophyllum
inophyllum
Three step zero
catalysed
Methanol 6:1 Anhydrous H
2
SO
4
(98.4%) 0.65% by volume
338 2 h Mechanical stirring 450 rpm 85% yield in
90 min
[8]
Acid catalysed 4 h Complete in 4 h
reaction Alkali catalysed 9:1 KOH 1.5% by weight 4 h
2007 Jatropha curcas Two step acid
catalysed
Methanol 0.28 v/v H
2
SO
4
1.43% v/v
(3.5 + acid value, w/v
KOH)
333 88 min >99% yield [9]
Alkali catalysed 0.16 v/v 24 min
2007 Triolein Single step Ethanol 10:1 Anion exchange resin 323 60 min 98.8% purity [26]
Cation exchange resin
(heterogeneous catalyst)
2007 Sunower oil Single step Methanol 13:1 Activated CaO (1 wt%) 333 100 min Helix stirrer 1000 rpm [27]
2007 Waste cooking oil Two step Methanol 10:1 Fe
2
SO
4
368 4 h No stirring because boiling was
sucient
97.02% conversion [16]
6:1 KOH 338 1 h
2007 Karanja Two step Methanol 8:1 H
2
SO
4
318 2 30 min Magnetic/mechanical 89.5% yield with
mechanical
[3]
9:1 NaOH/KOH 30 min 85% yield with
magnetic
Y
.
C
.
S
h
a
r
m
a
e
t
a
l
.
/
F
u
e
l
8
7
(
2
0
0
8
)
2
3
5
5
2
3
7
3
2
3
5
9
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, there-
fore, 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 tem-
perature 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 sat-
urated fatty acids [17] and hence can provide better oxida-
tive 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 gluta-
mate wastewater having COD of 10,000 mg/L. After treat-
ment the COD removal was 85% with 10% formation of
crude lipid. The crude lipid was biosynthesized by rhodo-
torula glutinis by transesterication reaction with methyl
ester yield of 92.54 2.0%. Biodiesel has also been synthe-
sized 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 neutral-
ize 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 cat-
alyst during acid esterication of neat oil is sulphuric acid
(H
2
SO
4
) [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 transeste-
rication 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
Fe
2
(SO
4
)
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
H
2
SO
4
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 transe-
sterication is preferred over the acid catalyzed transesteri-
cation 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 wash-
ing with hot distilled water twice or thrice. Thus, heteroge-
neous 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
Fig. 1. Basic scheme for biodiesel production.
tested by Grandos et al. for its feasibility [27]. The experi-
ments conrmed that CaO could be used as a catalyat for
the transesterication reaction without signicant deactiva-
tion 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 (CH
3
ONa).
The optimum requirement of the catalyst were 1.1, 1.3
and 1.5 wt% for NaOH, CH
3
ONa, and KOH respectively
for the maximum ester content. The amount of NaOH
required was less than the amounts of both the CH
3
ONa
or KOH for the same conversion of fatty acid methyl ester
as NaOH has lower molar mass (40 g/mol), compared to
CH
3
ONa (54 g/mol) and KOH (56 g/mol).
However, in terms of yield, CH
3
ONa proved to be a bet-
ter catalyst than NaOH and KOH because CH
3
ONa disso-
ciates into CH
3
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 (KOCH
3
) has also been used as an
alkali catalyst by dissolving potassium hydroxide in meth-
anol [52]. Sharma and Singh [3] reported better yield with
NaOH as a catalyst over KOH while using magnetic stir-
rer. 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. Potas-
sium 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 sensi-
tive 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 cook-
ing 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 alka-
line 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 cat-
alyst 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 solu-
tion prepared by dissolving NaOH (28.5 g) and methanol
(2.0 kg) as an alkaline catalyst for transesterication.
Sahoo et al. [8] used alkaline transesterication after reduc-
ing the free fatty acid value from 44 mg KOH/g (i.e. 22%)
to less than 4 mg KOH/g (i.e. <2%) through zero catalyzed
and acid catalyzed transesterication. 1.5% by weight of
potassium hydroxide was found sucient for the maximum
yield of ester. Sarin et al. [12] prepared a series of biodiesel
from the edible oils such as sunower, soybean, palm and
non-edible oils such as jatropha and karanja. The catalyst
used was either NaOH or KOH with 1 wt % of oil.
The amount of alkali catalyst was calculated on the
basis of the amount needed to neutralize the unreacted
acids plus 0.35% for virgin oil which came out to be
0.55% w/v KOH [9]. 1.0% KOH was reported as the opti-
mal amount for alkaline transesterication reaction of
karanja oil by Meher et al. [11] and Karmee and Chadha
[14]. Karmee and Chadha also tried Hb-Zeolite, montmo-
rillonite K-10 and ZnO but the conversion of fatty acid
methyl ester was less. Around 83% conversion with ZnO
was possible only with a longer reaction time of 24 h. Even
lesser conversions of 59% and 47% were achieved with Hb-
Zeolite and montmorillonite K-10, respectively, in compar-
ison to 92% achieved by KOH.
While using the rened karanja oil, the conversion
reached to 99% with 0.5% of NaOH or CH
3
ONa [14].
1% KOH was optimum amount of catalyst even with used
frying oil reported by Marinkovic and Tomasevic [55].
Ghadge and Raheman [10] calculated the amount of cata-
lyst to be 0.7% w/v KOH as the cumulative sum of 0.5% for
catalyst plus the amount needed to neutralize the unreacted
acids (2 mg KOH/g) i.e. 0.2%. NaOH was used as a cata-
lyst by Ji et al. [25] with power ultrasonic and hydrody-
namic cavitation methods and found the methods
superior as compared to mechanical stirring. The amount
of KOH used for the transesterication of tobacco (Nicoti-
ana tabacum) oil after acid esterication as reported by Vel-
jkovic et al. [7] is 1.0% (based on oil weight) with a yield of
91%. Using the same oil Usta got a yield of 86%. Hence,
the two step process of acid and alkaline esterication
can be expected to yield a better result when compared to
one step base catalyzed transesterication [56]. In an
attempt to nd a new catalyst, Furuta et al. [23] tested
amorphous zirconia solid catalysts, TiO
2
/ZrO
2
(11 wt%
Ti) and Al
2
O
3
/ZrO
2
(2.6 wt% of Al) and reported more
than 95% conversion. The reason for this is the amphoteric
nature of zirconia. However, the temperature required was
quite high i.e. 448473 K.
The homogeneous catalysts require neutralization and
separation steps from the reaction mixture. To accomplish
this, water, solvents and energy are needed. To overcome
these, heterogeneous based catalysts have been tested by
researchers, where separation is possible without using
solvent and shows easy regeneration. The nature of the
nal product has been less corrosive in character and the
whole process is termed safer, cheaper and more environ-
ment friendly [57]. The heterogeneous catalyst being used
by researchers include alkalineearth oxides, zeolites,
hydrotalcites, MgO and CaO [27,5762]. In addition, reac-
tor heating was not needed when MgO was used as a cat-
alyst in batch process [57].
Another method where neither acid nor base catalyst is
required is non-catalytic transesterication where super-
critical 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 thermophysi-
cal 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 solu-
bility 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 require-
ment 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 rang-
ing 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, chro-
menoavones, 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 tri-
bal 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 environ-
ment. 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 mil-
lion tons per annum [11]. However, its production poten-
tial 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
Fig. 2. Synthesis of biodiesel at various temperatures in supercritical (a)
methanol, (b) ethanol (j) 473 K, () 523 K, (N) 573 K, (.) 623 K, ()
673 K.
Table 4
Dierent fatty acids present in karanja oil [107]
Fatty acid
(common
name)
Systematic name Formula Structure wt%
Palmitic Hexadecanoic C
16
H
32
O
2
16:0 10.6
Stearic Octadecanoic C
18
H
36
O
2
18:0 6.8
Oleic cis-9-octadecenoic C
18
H
34
O
2
18:1 49.4
Linoleic cis-9, cis-12-octadecadienoic C
18
H
32
O
2
18:2 19.0
Arachidic Eicosanoic C
20
H
40
O
2
20:0 4.1
Gadoleic 11-eicosenoic C
20
H
38
O
2
20:1 2.4
Behenic Docosanoic C
22
H
44
O
2
22:0 5.3
Lignoceric Tetracosanoic C
24
H
48
O
2
24:0 2.4
29.2% saturated fatty acids and 70.8% unsaturated fatty
acids. The maximum proportion comprises of oleic acid
(cis-9-octadecenoic) i.e. 49.4%, whereas, gadoleic acid
(11-eicosenoic, 2.4%) and linoceric acid (tetracosanoic,
2.4%) are in traces. Table 5 depicts the ASTM 6751 and
IS 15607 test methods and limits for biodiesel. In respect
of karanja, it is observed that it meets all the specication
of American Society for Testing and Materials (ASTM)
and Indian Standards but fails in oxidation stability test.
Hence, appropriate methods have to be devised to make
the karanja oil methyl ester t for commercialization.
For the transesterication reaction, Sharma and Singh
[3] advocated for 8:1 molar ratio during acidic esterication
so as to reduce the acid value below 2 mg KOH/g i.e. 1.0%
FFA. For the alkaline transesterication reaction, the
authors advocate 9:1 molar ratio for the completion of
the reaction. Mechanical stirrer produced better results
than magnetic stirrer and resulted in higher yield (89.5%)
in 1 h with 0.5% H
2
SO
4
and 0.5% NaOH at 318 2 K.
Meher et al. [11] have neutralized the oil by using potas-
sium hydroxide to reduce the acid value of the oil from
5.06 mg KOH/g to 0.6 mg KOH/g. The yield of 97.0
98.0% was achieved in 2 h with 6:1 molar ratio (metha-
nol:oil); and in 1 h with 12:1 molar ratio. The optimum
temperature was 338 K with the rate of stirring 360 rpm
and 1% KOH as catalyst. Karmee and Chadha [14] have
reported 92% conversion with karanja oil using 10:1
molar ratio (methanol:oil) at 333 K with 1.0% KOH by
weight.
4. Eect of dierent parameters on production of biodiesel
4.1. Eect of molar ratio
Ramadhas et al. [1] and Sahoo et al. [8] reported 6:1
molar ratio during acid esterication and 9:1 molar ratio
(alcohol:oil) during alkaline esterication to be the opti-
mum amount for biodiesel production from high FFA rub-
ber seed oil and polanga seed oil respectively. Sharma and
Singh [3] used similar two step transesterication and took
8:1 molar ratio for acid esterication and 9:1 molar ratio
for alkaline esterication for optimum yield of biodiesel
production from karanja oil. Veljkovic et al. [7] used 18:1
molar ratio during acid esterication and 6:1 molar ratio
during alkaline esterication. Meher et al. [11] carried out
investigation with 6:1 molar ratio during acid esterication
and 12:1 molar ratio during alkaline esterication. Instead
of taking molar ratio, Tiwary et al.[9] and Ghadge and
Raheman [10] used volume as a measure of ratio. While
Tiwary et al. used 0.28 v/v (methanol/oil) during acid
esterication and 0.16 v/v (methanol/oil) during alkaline
esterication, Ghadge and Raheman used 0.300.35 v/v
(methanol/oil) during acid esterication and 0.25 v/v
(methanol/oil) during alkaline esterication. Karmee and
Chadha [14] used a single step transesterication and
have achieved 92% conversion by taking 10:1 molar
ratio.
Presence of sucient amount of methanol during the
transesterication reaction is essential to break the glycer-
ine-fatty acid linkages [68]. But excess of methanol should
be avoided. Increasing the molar ratio of methanol/oil
beyond 6:1 neither increases the product yield nor the ester
content, but rather makes the ester recovery process com-
plicated and raised its cost. Leung and Guo [19] suggested
that methanol has polar hydroxyl group which can act as
an emulsier causing emulsication. Thus separation of
the ester layer from the water layer becomes dicult. Miao
and Wu [21] have reported that addition of large quantity
of methanol, i.e. 70:1 and 84:1 molar ratio slowed down the
separation of the ester and glycerol phases during the pro-
duction of biodiesel. 56:1 molar ratio was reported to be
optimum for transesterication of microalgal oil.
4.2. Eect of moisture and water content on the yield of
biodiesel
Kusdiana and Saka [69] observed that water could
pose a greater negative eect than presence of free fatty
Table 5
Test method and limits of biodiesel along with its comparison with karanja oil methyl ester [12]
Property (units) ASTM 6751 test method ASTM 6751 limits IS 15607 test method IS 15607 limits Karanja oil methyl ester
Flash point (C) D-93 Min. 130 IS 1448 P:21 Min. 120 141
Viscosity at 40 C (cSt) D-445 1.96.0 IS 1448 P:25 2.56.0 4.16
Sulphated ash (mass%) D-874 Max. 0.02 IS 1448 P:4 Max. 0.02 0.002
Sulphur (mass%) D-5453 Max. 0.05 ASTM D 5453 Max. 0.005 0.003
Cloud point (C) D-2500 NA IS 1448 P:10 NA 4
Copper corrosion D-130 Max. 3 IS 1448 P:15 Max. 1 1
Cetane number D-613 Min. 47 IS 1448 P:9 Min. 51 55.1
Water and sediment (vol. %) D-2709 Max. 0.05 D-2709 Max. 0.05 0.03
CCR 100% (mass%) D-4530 Max. 0.05 D-4530 Max. 0.05 <0.01
Neutralization value (mg, KOH/gm) D-664 Max. 0.80 IS 1448 P:1/Sec. 1 Max. 0.50 0.10
Free glycerin (mass%) D-6584 Max. 0.02 D-6584 Max. 0.02 0.01
Total glycerin (mass%) D-6584 Max. 0.24 D-6584 Max. 0.25 0.01
Phosphorus (mass%) D-4951 Max. 0.001 D-4951 Max. 0.001 <0.001
Distillation temperature D-1160 90% at 360 C Not under spec. 90%
Oxidation stability, h NA NA EN 14112 Min. 6 h 2.35
acids and hence the feedstock should be water free.
Romano [70] and Canakci and Van Gerpen [5] insisted
that even a small amount of water (0.1%) in the transeste-
rication reaction would decrease the ester conversion
from vegetable oil. Demirbas [13] too reported a decrease
in yield of the alkyl ester due to presence of water and
FFA as they cause soap formation, consume catalyst
and reduce the eectiveness of catalyst. Srivastava and
Verma [54] removed the moisture content from the vege-
table oil by heating in oven for 1 h at 383 K. Meher et al.
[11] too reported a precautionary step to prevent moisture
absorbance and maintenance of catalytic activity by pre-
paring the fresh solution of potassium hydroxide and
methanol. Ellis et al. [52] found that even a small amount
of water in the feedstock or from esterication reaction
producing water from FFA might cause reduction in con-
version of fatty acid methyl ester and formation of soap
instead. At the same time the presence of water had a
positive eect in the yield of methyl esters when methanol
at room temperature was substituted by supercritical
methanol. However, no explanation for this has been pro-
vided. [13]. Fig. 3 depicts the inuence of water content
on yield of methyl esters. It is observed that acid catalyst
is most prone to presence of water followed by alkaline
catalyst. No eect on ester content was observed when
supercritical methanol was used. The presence of water
had negligible eect on the conversion while using lipase
as a catalyst [20,71].
4.3. Eect of free fatty acids
Free fatty acids (FFAs) content after acid esterication
should be minimal or otherwise less than 2% FFAs. These
FFAs react with the alkaline catalyst to produce soaps
instead of esters. Fig. 4 depicts the eect of FFAs on the
yield of methyl ester during alkali catalysed transesterica-
tion. There is a signicant drop in the ester conversion
when the free fatty acids are beyond 2% [72].
4.4. Eect of temperature
The temperature maintained by the researchers during
dierent steps range between 318 and 338 K. The boiling
point of methanol is 333.7 K. Temperature higher than this
will burn the alcohol and will result in much lesser yield. A
study by Leung and Guo [19] showed that temperature
higher than 323 K had a negative impact on the product
yield for neat oil, but had a positive eect for waste oil with
higher viscosities.
4.5. Eect of stirring
Stirring can play an important role in the yield of biodie-
sel production. Meher et al. [11] conducted the transesteri-
cation reaction with 180, 360 and 600 revolutions per
minute (rpm) and reported incomplete reaction with
180 rpm. The yield of methyl ester was same with 360
Fig. 3. Plots for yields of methyl esters as a function of water content in
transesterication of triglycerides.
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.
and 600 rpm. Sharma and Singh [3] reported that mode of
stirring too plays a vital role in the transesterication reac-
tion. 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 con-
stant. 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 compari-
son of dierent technologies to produce biodiesel is shown
in Table 6 [48].
5. Biodegradability of biodiesel
Biodiesel is reported to be highly biodegradable in fresh-
water as well as soil environments. 9098% of biodiesel is
mineralized in 2128 days under aerobic as well as anaero-
bic conditions [7375]. Biodiesel has been reported to
remove twice the amount of crude oil from sand as conven-
tional shoreline cleaners [76]. Biodiesel increases the biode-
gradability of crude oil by means of cometabolism. More
than 98% degradation of pure biodiesel after 28 days is
reported by Pasqualino et al. [73] in comparison to 50%
and 56% by diesel fuel and gasoline respectively. Also,
the time taken to reach 50% biodegradation reduced from
28 to 22 days in 5% biodiesel mixture and from 28 to 16
days in case of 20% biodiesel mixture at room temperature.
The biodegradability of the mixture was reported to
increase with addition of biodiesel. Table 7 depicts the bio-
degradability of fossil diesel under dierent conditions [77
80].
6. Stability of biodiesel
Biodiesel, chemically is fatty acid methyl ester if alcohol
used during transesterication is methanol or fatty acid
ethyl ester in case of ethanol. This ester molecule will get
hydrolyzed to alcohol and acid in the presence of air. Con-
version of ester into alcohol will lead to reduction in ash
point whereas conversion of ester into acid will increase the
total acid number. This makes the biodiesel unstable on
storage [12]. The stability of biodiesel also depends on
the feedstock used for the biodiesel production. The feed-
stock with larger proportion of saturated fatty acids will
be more stable than those having larger proportion of
unsaturated fatty acids. But again, higher portion of satu-
rated fatty acid lowers the low temperature properties such
as cloud and pour points. Hence, a major drawback of bio-
diesel lies in its tradeo between the level of saturation of
biodiesel and its cold ow properties [12,17]. The oxidation
stability of biodiesel is not dependent on the total number
of double bonds but on the total number of bis-allylic sites
(the methylene CH directly adjacent to the two double
bonds). These esters undergo auto-oxidation which is
dependent on the number and position of the double bonds
and forms by-product such as acids, esters, aldehydes,
ketones, lactones, etc. [12,8183].
Fatty acid methyl esters form a radical next to the dou-
ble bond during the oxidation process. This radical binds
with the oxygen in air, which is a biradical to form peroxide
radical. A new radical is created from the fatty acid methyl
ester by this peroxide radical which binds with oxygen in
air. This augments the auto-oxidation cycle at an exponen-
tial rapid rate whereby 100 new radicals are created quickly
from one single radical resulting in the formation of a series
of by-products. The fuel thus gets deteriorated as there is
formation of sediment and gum. Peroxide formation
Table 6
Comparison of dierent technologies to produce biodiesel
Variable Alkali catalysis Lipase catalysis Supercritical alcohol Acid catalysis
Reaction temperature (K) 333343 303313 512658 328353
Free fatty acid in raw materials Sapanoed products Methyl esters Esters Esters
Water in raw materials Interference with reaction No inuence Interference with reaction
Yield of methyl esters Normal Higher Good Normal
Recovery of glycerol Dicult Easy Dicult
Purication of methyl esters Repeated washing None Repeated washing
Production cost of catalyst Cheap Relatively expensive Medium Cheap
Table 7
Biodegradability of fossil diesel
%
degradation
No. of
days
Reference
Articially contaminated soils 67 109 [77]
Using soil columns 81 310 [78]
Fuel contaminated soil in the arctic 9095 365 [79]
Under aerobic conditions 42 30 [80]
Under anaerobic conditions 18 50 [80]
through this route leads to obligomerization even at ambi-
ent temperature. As the deterioration of biodiesel is attrib-
uted 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 dis-
tribution 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 bio-
diesel to reduce the antioxidant dosage by 8090% to main-
tain good oxidation stability.
7. Kinetics of the reaction
Transesterication reaction consists of a sequence of
reversible reactions [52].
In the rst step, triglycerides are converted to diglycerides
which get converted to monoglycerides in the next
step. In the third and last step, monoglycerides are
converted to glycerol. In each of the steps an ester is
formed. Thus three esters are obtained from one triglycer-
ides molecule.
TGM$
K
1
K
4
DGFAME 2
DGM$
K
2
K
5
MGFAME 3
MGM$
K
3
K
6
GFAME 4
where, TG, triglycerides; DG, diglycerides; MG, mono-
glycerides; M, methanol and FAME, fatty acid methyl
esters.
The values of rate constants for forward reactions, K
1
,
K
2
and K
3
, are found to be 5.00, 4.93 and 29.67 dm
3
mol
1
min
1
and the values of the rate constants of backward
reactions involved in the kinetics of biodiesel development,
K
4
, K
5
, and K
6
are reported to be 3.54, 2.99 and
0.79 dm
3
mol
1
min
1
. 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 pla-
teau is reached at equilibrium [52].
8. Diesel engine emissions and performance of biodiesel
Researchers worldwide are on a consensus that biodie-
sel, irrespective of the feedstock used results in a decrease
in the emissions of hydrocarbons (HC), carbon monoxide
(CO), particulate matter (PM) emissions and sulphur diox-
ide (SO
2
). Only oxides of nitrogen (NO
x
) are reported to
increase which is due to oxygen content in the biodiesel
[8694]. It is also said to be carbon neutral as it contributes
no net carbon dioxide to the atmosphere [9597]. However,
in a study conducted by Sahoo et al. [8] the NO
x
emission
from 100% biodiesel lowered to 4% for polanga seed oil.
This is attributed by the authors to dierence in engine
geometry, compression ratio, less reaction time and tem-
perature. A remarkable decrease in the emission of unburnt
hydrocarbon was observed. 40% reduction of CO
2
emis-
sions was observed for B20 and B100 biodiesel. Thermal
eciency of the engine also improved by 0.1%. Smoke
emissions reduced by 35% in the case of B60 biodiesel.
The results were obtained without any engine hardware
modications. Other authors have suggested various strat-
egies to eliminate the NO
x
emission. Szybist et al. [98] sug-
gested to change the chemical composition of feedstock by
increasing the methyl oleate and addition of cetane improv-
1
Fig. 6. Simulated concentration prole of glycerol (G), tri-glyceride (TG),
di-glyceride (DG), mono-glyceride (MG) and fatty acid methyl ester
(FAME) during transesterication.
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 NO
x
emission. Nabi
et al. [101] advocated for the exhaust gas recirculation to
reduce the NO
x
emission.
Kegl [102] stressed on the importance of fuel injection
system to reduce the engine emissions as well as fuel con-
sumption. Author suggests that pressure squareness (ratio
of mean to maximum injection pressure) should be at max-
imum and fuelling in the rst part of injection has to be less
to reduce NO
x
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
be safe above which it would cause maintenance problem
and might damage the engine. A study on comparison of
carbonyls emissions from diesel and biodiesel blend was
carried by Correa and Arbilla [104]. Higher emission of
formaldehyde, acetaldehyde, acrolein, acetone, propional-
dehyde, and butyraldehyde was observed from B2, B5,
B10 and B20 blends than neat diesel. However, signicant
reduction in emission in terms of benzaldehyde was
observed from biodiesel blends.
Srivastava and Verma [54] have reported the HC, CO
and NO emissions from karanja oil methyl ester to be
slightly higher as compared with petrodiesel. HC emission
of diesel at maximum load was 85 ppm, while that of bio-
diesel was 120 ppm due to poor mixing with air. CO emis-
sion of diesel at maximum load was reported to be 0.18%
as compared to 0.21% of biodiesel and NO emission was
reported to be 12% higher than that of biodiesel. Maximum
thermal eciency of methyl ester and brake specic fuel
consumption of the biodiesel were quite close to that of die-
sel and hence the authors were of the view that karanja oil
methyl ester can replace diesel as an alternative fuel. Table
8 depicts emission impact of 20 vol% for soybean based
biodiesel. It can be seen that there is a signicant reduction
Table 8
Emission impact of 20 vol% biodiesel for soybean based biodiesel added to
an average base diesel fuel
Percent change in emissions
NO
x
(nitrogen oxides) +2.0
PM (particulate matter) 10.1
HC (hydrocarbons) 21.1
CO (carbon monoxides) 11.0
Table 9
List of 26 indigenous plant meeting US, Germany and European standards (
a
oil fromkernel,
b
oil fromseeds, osa: other saturated acids, uk: unknown) [107]
Sources Oil SN IV CN Fatty acid composition (%)
Rhus succedanea Linn 39.5
a
204.0 92.6 52.22 16:0 (25.4); 18:1 (46.8); 18:2 (27.8)
Annona reticulate Linn 42.0
b
203.6 87.2 53.47 14:0 (1.0); 16:0 (17.2); 16:1 (4.2); 18:0 (7.5); 18:1 (48.4); 18:2 (21.7)
Ervatamia coronaria
Stapf
41.6
b
201.1 76.0 56.33 16:0 (24.4); 16:1 (0.2); 18:0 (7.2); 18:1 (50.5); 18:2 (15.8); 18:3 (0.6); 20:0 (0.7); 20:1 (0.2); 22:0
(0.2); uk (0.2)
Thevetia peruviana
Merrill
67.0
a
201.5 84.0 57.48 16:0 (15.6); 18:0 (10.5); 8:1 (60.9); 18:2 (5.2); 18:3 (7.4); 20:0 (0.3); 22:0 (0.1)
Basella rubra Linn 36.9
b
202.9 85.3 54.00 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)
Canarium commune Linn 73.0
a
204.6 77.3 55.58 16:0 (29.0); 18:0 (9.7); 18:1 (38.3); 18:2 (21.8); 18:3 (1.2)
Celastrus paniculatus
Linn
52.0
a
236.6 77.5 51.9 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)
Terminalia bellirica Roxb 40.0
b
198.8 77.8 56.24 16:0 (35.0); 18:1 (24.0); 18:2 (31.0); osa (10.0)
Vernonia cinerea Less 38.0
a
205.2 68.5 57.51 14:0 (8.0); 16:0 (23.0); 18:0 (8.0); 18:1 (32.0); 18:2 (22.0); 20:0 (3.0); 22:0 (4.0)
Corylus avellana 57.5
a
200.5 84.51 54.50 14:0 (3.2); 16:0 (3.1); 18:0 (2.6); 18:1 (88.0); 18:2 (2.9); uk (0.2)
Jatropa curcas Linn 40.0
b
202.6 93.0 52.31 14:0 (1.4); 16:0 (15.6); 18:0 (9.7); 18:1 (40.8); 18:2 (32.1); 20:0 (0.4)
Putranjiva roxburghii 41.8
a
199.6 82.9 54.99 16:0 (8.0); 18:0 (15.0); 18:1 (56.0); 18:2 (18.0); 20:0 (3.0)
Calophyllum apetalum
Wild
47.5
a
200.4 97.6 51.57 16:0 (8.0); 18:0 (14.0); 18:1 (48.0); 18:2 (30.0)
Calophyllum inophyllum
Linn
65.0
a
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)
Mesua ferrea Linn 68.5
a
201.0 81.3 55.10 14:0 (0.9); 16:0 (10.8); 18:0 (12.4); 18:1 (60.0); 18:2 (15.0); 20:0 (0.9)
Azadirachta indica 44.5
a
201.1 69.3 57.83 16:0 (14.9); 18:0 (14.4); 18:1 (61.9); 18:2 (7.5); 20:0 (1.3)
Moringa concanensis
Nimmo
35.5
b
199.7 76.0 56.32 16:0 (9.7); 18:0 (2.4); 18:1 (83.8); 18:2 (0.8); 20:0 (3.3)
Moringa oleifera Lam 35.0
a
199.7 75.4 56.66 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)
Pongamia pinnata Pierre 33.0
b
196.7 80.9 55.84 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)
Ziziphus mauritiana Lam 33.0
b
198.6 81.8 55.37 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)
Sapindus trifoliatus Linn 45.5
a
195.0 64.5 59.77 16:0 (5.4); 18:0 (8.5); 18:1 (55.1); 18:2 (8.2); 20:0 (20.7); 22:0 (2.1)
Schleichera oleosa Oken 40.0
b
193.0 57.9 61.55 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)
Madhuca indica JF Gmel 40.0
b
202.1 74.2 56.61 14:0 (1.0); 16:0 (17.8); 18:0 (14.0); 18:1 (46.3); 18:2 (17.9); 20:0 (3.0)
Mimusops hexendra
Robx
47.0
a
202.0 62.2 59.32 16:0 (19.0); 18:0 (14.0); 18:1 (63.0); 18:2 (3.0); 20:0 (1.0)
Pterygota alata Rbr 35.0
b
202.6 98.4 51.09 16:0 (14.5); 18:0 (8.5); 18:1 (44.0); 18:2 (32.4); uk (1.0)
Holoptelia integrifolia 37.4
b
208.7 49.9 61.22 14:0 (3.5); 16:0 (35.1); 16:1 (1.9); 18:0 (4.5); 18:1 (53.3); 20:0 (1.1); uk (1.4)
in HC (21%), CO (10%), PM (11%) and 2.0% increase in
NO
x
emission [105].
9. Indian scenario
India imports more than 40% of its edible oil require-
ment and hence non-edible oils are used for the develop-
ment of biodiesel. India is a agrarian nation and has rich
plant biodiversity which can support the development of
biodiesel. India also has a vast geographical area with agri-
cultural lands as well as wastelands on which oil bearing
plants can be planted. Common non-edible oil bearing
plants and trees include neem, karanja, mahua, jatropha,
etc. The oil yields from these species at present are insu-
cient to meet the demand for raw material on large scale
production of biodiesel. Hence, there has been government
initiatives and interest from few private rms to enhance
the production and distribution facilities of biodiesel
throughout the country. The Petroleum Ministry has set
a target for biodiesel to meet 20% of Indias diesel demand.
Governments initiative has resulted in large scale planta-
tion of J. curcas in the state Andhra Pradesh. Oil and Nat-
ural Gas Corporation (ONGC) has planned to build an
export oriented renery at kakinada in Andhra Pradesh
which will have a annual production capacity of 5.57.5
million tonnes [106].
Azam et al. [107] have studied the prole of 75 indige-
nous plant species of India containing 30% or more oil in
their seed, fruit or nut. Out of these plants, based on sapon-
ication number, iodine value, cetane number and fatty
acid composition, 26 species were found to be most suitable
for use as biodiesel and they met the biodiesel standards of
USA (ASTM D 6751-02, ASTM PS 121-99), Germany
(DIN V 51606) and European Standard Organization
(EN 14214). Another 11 plant species met the specications
of US biodiesel standards. Authors predicts that cultiva-
tion of Azardirachta indica or P. pinnata on 40.09 million
and 19.9 million ha, respectively, will meet the target of
100% replacement of imported biodiesel which amounted
to 87.5 million tons in 20032004. These 37 species are
listed in Tables 9 and 10. Among these species, jatropha
(Jatropha curcas), karanja (P. pinnata), neem (A. indica),
mahua (Madhuca indica) and polanga (Calophyllum
inophyllum) have catched the attention of researchers and
biodiesel manufacturer in India and feasibility of rest of
the plant species still remains unexplored.
10. Cost of biodiesel
Various factors contributing to the cost of biodiesel
include raw material, other reactants, nature of purica-
tion, its storage, etc. However, the major factor which con-
tributes the cost of biodiesel production is the feedstock,
which is about 80% of the total operating cost [108]. Cost
of biodiesel reported by Zhang et al. [29] is US $0.5 l
1
as compared to US $0.35 for normal diesel. Bender in his
review has reported the cost of biodiesel to be US
$0.30 l
1
and US $0.69 l
1
when the fuel was produced
from soybean and rapeseed respectively. The intact oilseed
was taken as starting material while calculating the cost.
Canakci and Van Gerpen while using a small pilot scale
plant in a batch process estimated the cost to be US
$0.42 l
1
while using rened, bleached and deodorized soy-
bean oil. The prots from glycerol and capital cost for
operation was not included [109,110].
Haas et al. [111] in a study of review on biodiesel pro-
duction cost found the feedstock to contribute a substantial
portion in production cost. A process model was prepared
by the author to estimate biodiesel production costs. Tak-
ing all the factors into account viz. raw material (vegetable
oil, methanol, catalysts), utilities (electricity, etc.), labour,
supplies, general works and depreciation, the cost of bio-
diesel was estimated to be US $0.561 l
1
. The coproduct
glycerol as 80% w/w aqueous solution was valued to be
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 Fatty acid composition (%)
Vallaris solanacea
Kuntze
33.0
b
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)
Balanites roxburghii
Planch
43.0
a
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)
Croton tiglium Linn 45.0
b
203.9 102.9 49.9 14:0 (11.0); 16:0 (1.2); 18:0 (0.5); 18:1 (56.0); 18:2 (29.0); 20:0 (2.3)
Hydnocarpus wightiana
Blume
63.0
a
210.5 102.1 49.25 16:0 (1.8); 18:1 (6.9); hydnocarpic acid (48.7); gorlic acid (12.2); chaulmoogric acid (27.0);
chaulmoogtic homolog (3.4)
Mappia foetida Milers 48.0
b
200.7 101.3 50.70 16:0 (7.1); 18:0 (17.7); 18:1 (38.4); 18:3 (36.8)
Perilla frutescens
Britton
40.5
b
199.0 193.9 30.09 18:1 (9.8); 18:2 (47.5); 18:3 (36.2); osa (6.5)
Aphanamixis
polystachya Park
35.0
a
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)
Princeptia utilis Royle 37.2
a
201.9 108.4 48.94 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)
Meyna laxiora Robyns 38.5
b
202.8 101.3 50.42 16:0 (18.8); 18:0 (9.0); 18:1 (32.5); 18:2 (39.7)
Aegle marmelos correa
Roxb
34.0
b
202.5 114.9 48.30 16:0 (16.6); 18:0 (8.8); 18:1 (30.5); 18:2 (36.0); 18:3 (8.1)
Tectona grandis Linn 44.5
a
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)
US $0.034 l
1
and reduced the production cost of biodiesel
by 6% on deduction of this value from original cost. Hence,
the gross operating cost of biodiesel was estimated to be
US $0.527 l
1
, of which the feedstock comprised 87.36%
of the overall cost of biodiesel production.
Nas and Berktay [112] too concluded that feedstock cost
is the major component contributing to the cost of biodie-
sel production. In a comparison of feedstock viz. soybean
oil and yellow grease (recycled cooking oil from restau-
rants), it was estimated that yellow grease is quite less
expensive that soybean oil. On the contrary, the supply
of yellow grease is limited and has other applications and
hence it cannot be used on a large scale production. An
eight year comprehensive study (from 20042005 to
20122013), on the price rise of petroleum diesel, yellow
grease and soybean oil is reported. Cost of petroleum has
been estimated to rise from 0.67 to 0.75 (i.e. 11.94%
increase). Biodiesel fuel obtained from yellow grease is esti-
mated to rise from 1.41 to 1.55 (i.e. 9.93% increase). Biodie-
sel fuel from soybean oil will rise from 2.54 to 2.80 (i.e.
10.24% increase). Author is of opinion that biodiesel will
not be produced at a cost comparable with that of petro-
diesel unless the soybean oil price decline.
Biodiesel comprises of 11% oxygen by weight which
improve the combustion process and hence has reduced
emissions in terms of hydrocarbon, carbon monoxide and
particulate emissions but increases nitrogen oxide emis-
sions. Nitrogen oxide emissions from biodiesel can be
reduced by adding cetane enhancers that are di-tert-butyl
peroxide at 1% or 2-ethylhexyl nitrate at 0.5%. However,
addition of these enhancers will increase the cost of biodiesel
production. Nevertheless, reduction in emission of oxides of
nitrogen is desired as they are ozone precursors and after
reaching stratosphere it will result in ozone layer depletion.
In Indian context, the government has xed the price of
biodiesel delivered at reneries to be Rs. 26.50 l
1
. This
rate of biodiesel has been xed after the Indian government
has provided subsidies in order to encourage its application
[113].
The cost of biodiesel after blending with petrodiesel will
reduce as the cost of biodiesel becomes less signicant in
blended form. At present, biodiesel can be blended with
80% petrodiesel (B20) without any engine modication. B
100 (100% biodiesel) costed US $3.76 per gallon of biodie-
sel in USA in June 2006, whereas, B 20 (20% biodiesel and
80% petrodiesel) costed US $2.98 per gallon of biodiesel.
Table 11
Instrumentation involved in characterization of biodiesel
Feedstock Instrument involved for characterization Reference
Tobacco High performance liquid chromatograph [7]
Polanga seed oil High performance liquid chromatograph [8]
Pongamia pinnata (i) HPLC (Perkin-Elmer series 200) equipped with refractive index detector (shodex RI 71)
(ii) H NMR Bruker DPX 300 spectrometer (Bruker, Rheinstetten, Germany)
(iii) Gas chromatograph (for analysis of fatty acid composition of karanja oil)
[11]
Jatropha, Pongamia, sunower,
soybean, palm
(i) GC (Model HR/GC/5300) [for fatty acid composition of vegetable oils)
(ii) Thin layer chromatography (TLC)
[12]
Pongamia pinnata Gas chromatography (Nucon, India) equipped with a FID detector [14]
Waste cooking oil Gas chromatography (GC) equipped with a capillary column (SPBTM-5, 30 m 0.32 mm 0.25
lm) and a FID
[16]
Neat and used frying oil (i) HP 6890 series II Gas Chromatograph with a 3365/II GC-chemstation and a FID
(ii) Thin layer chromatography (TLC)
[19]
Sunower oil (i) Gel permeation chromatograph (GPC)
(ii) Gas chromatograph (GC), Nucon 5765, India
[20]
Microalgal oil CE-440 elemental analyzer (for determining elemental composition of biodiesel) [21]
Microalga chlorella protothecoides Gas Chromatographymass spectrometric analysis [22]
Soybean oil (i) X-ray diractometer
(ii) GPC with an RI (refractive index) detector, (carrier: THF)
(iii) Gas chromatographymass spectrometer
[23]
Lipid extracted from the cell of R.
glutinis
Gas chromatograph [24]
Triolein HPLC system (Hitachi, Ltd, Tokyo, Japan, D-7000 interface, L-7100 [26]
Sunower oil For FAME determination Agilent 6890 GC with a HP INNOwax capillary column [27]
For catalyst characterization
(i) Balzer Prisma quadrupole mass spectrometer (QMS 200)
(ii) Seifert 3000 XRD diractometer (equipped with a PW gonimeter)
(iii) VG Escalab 200 R spectrometer (equipped with a hemispherical electron analyzer)
(iv) Nicolet 5700 Fourier transform spectrophotometer (equipped with an Hg-col-Te
cryodetector)
Biopiles Gas chromatographymass spectrometer [79]
Canola, corn, peanut, olive, waste
vegetable
Gas chromatography [85]
Castor oil (i) Size exclusion chromatography (SEC)
(ii) Fourier-transformed infrared spectroscopy
[104]
11. Instrumentation involved in biodiesel production
For production of biodiesel, there are some primary
steps. If kernel or seeds are taken as starting materials, in
rst step the raw oil is to be expelled from the kernel by
mechanical crusher. This raw oil is in fact feedstock for
development of biodiesel. After feedstock is obtained,
beakers, measuring asks, test tubes, separating funnels,
etc. are needed up to development of biodiesel. Practically
no instruments are needed till its development. Most of the
instruments are used for characterization of the biodiesel
product. Further, the instruments used for characterization
can be divided into the categories of minor and major
equipments. Viscometer, cetane number analyzer, etc. are
minor equipments. Flash point, cloud point, pour point,
etc. are also determined by minor instruments. Major
instruments are however, needed for chemical characteriza-
tion of biodiesel product. Gas chromatograph, gas chro-
matographmass spectrometer, high performance liquid
chromatograph, fourier transformed infrared spectrome-
ter, elemental analyzer etc. are the major instruments used
for chemical characterization of the product. The major
instruments are listed in Table 11.
12. Conclusions
Biodiesel is derived from a varied range of vegetable oil
(edible and non-edible), animal fats, used frying oil, waste
cooking oil and wastewater. The edible oil in use at present
is soybean, sunower, canola, palm. The non-edible oil used
as feedstock for biodiesel production includes J. curcas, P.
pinnata, M. indica, F. elastica, A. indica, C. inophyllum,
etc. The main advantage in its usage is attributed to lesser
exhaust emissions in terms of carbon monoxide, hydrocar-
bons, particulate matter, polycyclic aromatic hydrocarbon
compounds and nitrited polycyclic aromatic hydrocarbon
compounds. Biodiesel is said to be carbon neutral as more
of carbon dioxide is absorbed by the biodiesel yielding
plants than what is added to the atmosphere when used as
fuel. Exhaust emissions of NO
x
can be controlled by adopt-
ing certain strategies such as change in composition of feed-
stock, addition of cetane improvers, retardation of injection
timing, exhaust gas recirculation, etc.
Transesterication is the process successfully employed
at present to reduce the viscosity of biodiesel and improve
other characteristics. Methanol being cheaper is the com-
monly used alcohol during transesterication reaction.
Among the catalysts, homogeneous catalysts such as sul-
phuric acid, sodium hydroxide, potassium hydroxide are
commonly used at industrial level production of biodiesel.
Heterogeneous catalysts such as calcium oxide, magnesium
oxide and others are also being tried to decrease the cata-
lyst amount and production cost of biodiesel. Transesteri-
cation reaction can be completed even without catalyst
by using supercritical methanol but it will increase the pro-
duction cost of biodiesel as it is energy intensive. The molar
ratio of alcohol to oil required is 3:1 by stoichiometry, but
excess molar ratio has been used for biodiesel production
for better yield in lesser time. The molar ratio employed
during acid esterication is between 6:1 and 18:1 whereas
the molar ratio used alkaline transesterication ranges
between 5:1 and 12:1 after reducing the acid value to less
than 2.0% approximately. The temperature ranges between
318 and 338 K as the boiling point of methanol is 337.7 K
and heating beyond this temperature would burn metha-
nol. However, higher temperature is employed while using
supercritical methanol (473573 K). Depending on the
feedstock taken; amount and type of alcohol and catalyst;
temperature employed; mode and rate of stirring; there is
dierence in the yield of biodiesel which varied from 80
to 100%. The percent conversion of biodiesel also ranged
between 80% and 100%.
Another added advantage of biodiesel is that it is biode-
gradable in nature. When used as blend along with diesel
fuel, it shows positive synergic eect of biodegradation by
means of cometabolism. Major disadvantage of biodiesel
is the inverse relationship of oxidation stability of biodiesel
with its low temperature properties which includes cloud
point and pour point. Higher composition of saturated fatty
acids in feedstock will increase the oxidation stability of bio-
diesel but will lower its cloud and pour points. Whereas,
higher composition of unsaturated fatty acids will enhance
the cloud point and pour point of biodiesel but will have a
poor oxidation stability. Hence, a balance has to be main-
tained between the ratio of saturates and unsaturates for
the oil to be used as a feedstock for biodiesel production.
Edible oils are in use in developed nations such as USA
and European nations but developing nations are not self
sucient in the production of edible oils and hence have
emphasized in the application of a number of non-edible
oils. In a country like India, which is rich in plant biodiver-
sity, there are many plant species whose seeds remain
unutilized and underutilized have been tried for biodiesel
production. These species have shown promises and fullls
various biodiesel standards. However, there still is paucity
in terms of all the standards which should be fullled for
the large commercial application and its acceptance from
public and governing bodies.
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