A Critical Review of Bio-Diesel As A Vehicular Fuel

A critical review of bio-diesel as a vehicular fuel
Mustafa Balat
*
, Havva Balat
Sila Science and Energy Unlimited Company, University Mahallesi, Trabzon, Turkey
a r t i c l e i n f o
Article history:
Received 16 August 2007
Accepted 24 March 2008
Available online 2 May 2008
Keywords:
Vegetable oil
Bio-diesel
Fuel properties
Transesterication
Market development
Economy
a b s t r a c t
The use of vegetable oils as alternative fuels has been around for one hundred years when the inventor of
the diesel engine Rudolph Diesel rst tested peanut oil, in his compression-ignition engine. In 1970, sci-
entists discovered that the viscosity of vegetable oils could be reduced by a simple chemical process and
that it could perform as diesel fuel in modern engine. Considerable efforts have been made to develop
vegetable oil derivatives that approximate the properties and performance of the hydrocarbon-based die-
sel fuels. Bio-diesel is an alternative to petroleum-based fuels derived from vegetable oils, animal fats,
and used waste cooking oil including triglycerides. Bio-diesel production is a very modern and technolog-
ical area for researchers due to the relevance that it is winning everyday because of the increase in the
petroleum price and the environmental advantages. Transesterication is the most common method
and leads to monoalkyl esters of vegetable oils and fats, now called bio-diesel when used for fuel
purposes.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
Bio-diesel is an alternative to petroleum-based fuels derived
from vegetable oils, animal fats, and used waste cooking oil
including triglycerides. Since the petroleum crises in 1970s, the
rapidly increasing prices and uncertainties concerning petroleum
availability, a growing concern of the environment and the effect
of greenhouse gases during the last decades, has revived more
and more interests in the use of vegetable oils as a substitute
of fossil fuel [1]. Vegetable oils are widely available from various
sources, and the glycerides present in the oils can be considered
as a viable alternative for diesel fuel [2]. Vegetable oils have good
heating power and provide exhaust gas with almost no sulfur and
aromatic polycyclic compounds. Due to the fact that vegetable
oils are produced from plants, their burning leads to a complete
recyclable carbon dioxide (CO
2
) [3]. Vegetable oils can be used
as fuels for diesel engines, but their viscosities are much higher
than usual diesel fuel and require modications of the engines
[4].
2. Bio-diesel production from vegetable oils
2.1. Literature review
The use of vegetable oils as alternative fuels has been around
for one hundred years when the inventor of the diesel engine Ru-
dolph Diesel rst tested peanut oil, in his compression-ignition
engine [5]. In the 1930s and 1940s vegetable oils were used as
diesel fuels from time to time, but usually only in emergency sit-
uations [6]. In 1940 rst trials with vegetable oil methyl and ethyl
esters were carried out in France and, at the same time, scientists
in Belgium were using palm oil ethyl ester as a fuel for buses. Not
much was done until the late 1970s and early 1980s, when con-
cerns about high petroleum prices motivated extensive experi-
mentation with fats and oils as alternative fuels [7]. Bio-diesel
(mono alkyl esters) started to be widely produced in the early
1990s and since then production has been increasing steadily. In
the European Union (EU), bio-diesel began to be promoted in
the 1980s as a means to prevent the decline of rural areas while
responding to increasing levels of energy demand. However, it
only began to be widely developed in the second half of the
1990s [8].
Bio-diesel production is a very modern and technological area
for researchers due to the relevance that it is winning everyday be-
cause of the increase in the petroleum price and the environmental
advantages [9]. The most common way of producing bio-diesel is
the transesterication of vegetable oils and animal fats. Transeste-
rication is not a new process. It was conducted as early as 1853 by
two scientists E. Duffy and J. Patrick. Since that time several studies
have been carried out using different oils such as cotton seed [10],
soybean [11,12], waste cooking [13], rapeseed [1416], sunower
seed [17], winter rape [18], frying [19,20], different alcohols such
as methanol [21], ethanol [22], buthanol [23] as well as different
catalysts, homogeneous ones such as sodium hydroxide [22,24],
potassium hydroxide [22,25], sulfuric acid [26], and supercritical
uids or enzymes such as lipases [2729].
0196-8904/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2008.03.016
* Corresponding author. Tel.: +90 462 871 3025; fax: +90 462 871 3110.
E-mail address: mustafabalat@yahoo.com (M. Balat).
Energy Conversion and Management 49 (2008) 27272741
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2.2. Vegetable oils as diesel fuels
Vegetable oils, also known as triglycerides, have the chemical
structure given in Fig. 1 comprise of 98% triglycerides and small
amounts of mono- and diglycerides [32]. Triglycerides are esters
of three fatty acids and one glycerol. These contain substantial
amounts of oxygen in its structure [33]. The fatty acids vary in their
carbon chain length and in the number of double bonds [34]. Dif-
ferent types of vegetable oils have different types of fatty acids. Ta-
ble 1 shows the empirical formula and structure of various fatty
acids present in vegetable oils.
The disadvantages of vegetable oils as diesel fuel are [35]: higher
viscosity, lower volatility and the reactivity of unsaturated hydro-
carbon chains. Vegetable oils have their own advantages [1]: rst
of all, they are available everywhere in the world. Secondly, they
are renewable as the vegetables which produce oil seeds can be
planted year after year. Thirdly, they are greener to the environ-
ment, as they seldom contain sulfur element in them.
In 1970, scientists discovered that the viscosity of vegetable oils
could be reduced by a simple chemical process and that it could
perform as diesel fuel in modern engine. Fundamentally, high vis-
cosity appears to be a property at the root of many problems asso-
ciated with direct use of vegetable oils as engine fuel [36]. The
vegetable oils, as alternative engine fuels, are all extremely viscous
with viscosities ranging from 10 to 20 times greater than that of
petroleum-derived diesel fuel [37]. Viscosity of No. 2 diesel fuel
is 2.7 mm
2
/s at 38 C [34]. Viscosities of vegetable oils and their
methyl esters are given in Fig. 2. The injection and atomization
characteristics of the vegetable oils are signicantly different than
those of petroleum-derived diesel fuels, mainly as the result of
their high viscosities [38]. Modern diesel engines have fuel-injec-
tion systems that are sensitive to viscosity changes. A way to avoid
these problems is to reduce the viscosity of vegetable oil in order to
improve its performance [1]. Known problems, probable cause and
potential solutions for using straight vegetable oil in diesels are
shown in Table 2.
Several experimental studies showed that vegetable oils can be
used as alternative fuel for diesel engines. Some of these vegetable
oils are as follows: hazelnut [39], sunower [40], rapeseed [41,42],
cottonseed [43,44], frying [45], jojoba [46], and Jatropha curcas
[47].
The effect of temperature on viscosities of Jatropha oil and var-
ious blends in the range 2575 C has been investigated by Prama-
nik [47]. Results of this study are shown in Fig. 3. The results show
that the viscosity of Jatropha oil is higher than diesel oil at any
temperature.
2.3. Derivatives of vegetable oils as diesel fuels
Considerable efforts have been made to develop vegetable oil
derivatives that approximate the properties and performance of
the hydrocarbon-based diesel fuels. The problems with substitut-
ing triglycerides for diesel fuels are mostly associated with their
high viscosities, low volatilities and polyunsaturated character
[31]. The viscosity of vegetable oils, when used as diesel fuel, can
be reduced in at least four different ways: (1) dilution with hydro-
carbons (blending), (2) emulsication, (3) pyrolysis (thermal crack-
ing), and (4) transesterication (alcoholysis). Transesterication is
the most common method and leads to monoalkyl esters of vege-
table oils and fats, now called bio-diesel when used for fuel pur-
poses. Pyrolysis, cracking, or other methods of decomposition of
vegetable oils to yield fuels of varying nature is an approach that
accounts for a signicant amount of the literature in historic
times [46].
2.3.1. Dilution
Vegetable oils may be used with dilution modication tech-
nique as an alternative diesel fuel [47]. Dilution is an additional
possible solution to the viscosity problem of vegetable oils as dis-
cussed above [48]. Viscosity of vegetable oil can be lowered by
blending with pure ethanol. 25% of sunower oil and 75% of diesel
were blending as diesel fuel. The viscosity was 4.88 cSt at 40 C,
while the maximum specied ASTM value is 4.0 cSt at 38 C. This
mixture was not suitable for long-term use in a direct injection en-
gine [35,49]. A study was carried out by using the dilution tech-
nique on the same frying oil [50].
Results with this technology have been mixed and engine prob-
lems similar to those found with neat vegetable oils as fuels were
observed here also. A model on vegetable oil atomization showed
Fig. 1. Structure of a typical triglyceride molecule (source: Ref. [30]).
Table 1
Chemical structure of common fatty acids
Name of fatty
acid
Chemical name of fatty acids Structure
(xx:y)
Formula
Lauric Dodecanoic 12:0 C
12
H
24
O
2
Myristic Tetradecanoic 14:0 C
14
H
28
O
2
Palmitic Hexadecanoic 16:0 C
16
H
32
O
2
Stearic Octadecanoic 18:0 C
18
H
36
O
2
Arachidic Eicosanoic 20:0 C
20
H
40
O
2
Behenic Docosanoic 22:0 C
22
H
44
O
2
Lignoceric Tetracosanoic 24:0 C
24
H
48
O
2
Oleic cis-9-Octadecenoic 18:1 C
18
H
34
O
2
Linoleic cis-9,cis-12-Octadecadienoic 18:2 C
18
H
32
O
2
Linolenic cis-9,cis-l2,cis-15-
Octadecatrienoic
18:3 C
18
H
30
O
2
Erucle cis-13-Docosenoic 22:1 C
32
H
42
O
2
Source: Ref. [30].
Fig. 2. Viscosities of vegetable oils and their methyl esters (mm
2
/s) at 38 C (source:
Ref. [32]).
2728 M. Balat, H. Balat / Energy Conversion and Management 49 (2008) 27272741
that blends of No. 2 Diesel fuel with vegetable oil should contain
from 0% to 34% vegetable oil if proper atomization was to be
achieved [48].
2.3.2. Microemulsion
Various derivatives such as microemulsions or blends of various
vegetable oils with conventional fuel have been proposed as alter-
native fuels for diesel engines [3]. Microemulsions are isotropic,
clear, or translucent thermodynamically stable dispersions of oil,
water, surfactant, and often a small amphiphilic molecule, called
co-surfactant [31,5153]. The formation of microemulsions (co-
solvency) is one of the four potential solutions for solving the prob-
lem of vegetable oil viscosity. Microemulsions are dened as trans-
parent, thermodynamically stable colloidal dispersions in which
the diameter of the dispersed-phase particles is less than one-
fourth the wavelength of visible light. Microemulsion-based fuels
are sometimes also termed hybrid fuels, although blends of con-
ventional diesel fuel with vegetable oils have also been called hy-
brid fuels [48].
Some of these fuels in diesel engines were tested by the Engine
Manufacturers Association (EMA). Shipp non-ionic (SNI) fuel con-
taining 50% No. 2 Diesel fuel, 25% degummed and alkali-rened
soybean oil, 5% 190-proof ethanol and 20% 1-butanol was evalu-
ated in the 200 h EMA screening test. The fuel passed the 200 h
EMA test, but carbon and lacquer deposits on the injector tips,
in-take valves and tops of the cylinder liners were major problems.
The SNI fuel performed better than a 25% blend of sunower oil in
diesel oil. The engine performances were the same for a micro-
emulsion of 53% sunower oil and the 25% blend of sunower oil
in diesel [6]. A microemulsion fuel containing soybean oil,
methanol, 2-octanol, and a cetane enhancer was the cheapest veg-
etable oil-based alternative diesel fuel ever to pass the EMA test
[48].
2.3.3. Pyrolysis (thermal cracking)
The pyrolysis refers to chemical change caused by the applica-
tion of thermal energy in the presence of an air or nitrogen sparge
[51]. The pyrolysis of fats has been investigated for more than 100
years, especially in those areas of the world that lack deposits of
petroleum [6]. The pyrolysis of different triglycerides was used
for fuel supply in different countries during the First and Second
World Wars. For instance, a tung oil pyrolysis batch system was
used in China as a hydrocarbon supply during World War II. These
hydrocarbons were used as raw materials for gasoline and diesel-
like fuel production in a cracking system similar to the petroleum
process now used [54].
Thermal decomposition of triglycerides produces the com-
pounds of classes including alkanes, alkenes, alkadienes, aromatics
and carboxylic acids. Different types of vegetable oils produce large
differences in the composition of the thermally decomposed oil.
Fig. 4 outlines a schematic that accounts for the formation of al-
kanes, alkenes, alkadienes, aromatics and carboxylic acids from
pyrolysis of triglycerides [31]. The main components are alkanes
and alkanes, which accounted for approximately 60% of the total
feeder weight. Carboxylic acids accounted for another 9.616.1%.
It is believed that as the reaction progresses the residue becomes
less reactive and forms stable chemical structures, and conse-
quently the activation energy increases as the decomposition level
of vegetable oil residue increases [55]. The yields of pyrolysis of
vegetable oils are given in Table 3.
Soybean oil pyrolyzed distillate, which consisted mainly of al-
kanes, alkenes, and carboxylic acids had a cetane number of 43,
exceeding that of soybean oil (37.9) and the ASTM minimum value
Table 2
Known problems, probable cause and potential solutions for using straight vegetable oil in diesels
Problem Probable cause Potential solution
Short term
1. Cold weather starting High viscosity, low cetane, and low ash point of vegetable oils Pre-heat fuel prior to injection. Chemically alter fuel to an ester.
Partially rene the oil to remove gums. Filter to 4 lm 2. Plugging and gumming
of lters, lines and
injectors
Natural gums (phosphatides) in vegetable oil. Other ash
3. Engine knocking Very low cetane of some oils. Improper injection timing Adjust injection timing. Use higher compression engines. Pre-heat fuel
prior to injection. Chemically alter fuel to an ester
Long term
4. Coking of injectors on
piston and head of
engine
High viscosity of vegetable oil, incomplete combustion of fuel. Poor
combustion at part load with vegetable oils
Heat fuel prior to injection. Switch engine to diesel fuel when
operation at part load. Chemically alter the vegetable oil to an ester
5. Carbon deposits on
piston and head of
engine
High viscosity of vegetable oil, incomplete combustion of fuel. Poor
combustion at part load with vegetable oils
operation at part load. Chemically alter the vegetable oil to an ester
6. Excessive engine wear High viscosity of vegetable oil, incomplete combustion of fuel. Poor
combustion at part load with vegetable oils. Possibly free fatty acids in
vegetable oil. Dilution of engine lubricating oil due to blow-by of
vegetable oil
operation at part load. Chemically alter the vegetable oil to an ester.
Increase motor oil changes. Motor oil additives to inhibit oxidation
7. Failure of engine
lubricating oil due to
polymerization
Collection of polyunsaturated vegetable oil blow-by in crankcase to
the point where polymerization occurs
operation at part load. Chemically alter the vegetable oil to an ester.
Increase motor oil changes. Motor oil additives to inhibit oxidation
Source: Ref. [6].
Fig. 3. Effect of temperature on viscosity of Jatropha oil and various blends (J:
Jatropha oil; D: Diesel fuel; source: Ref. [45]).
M. Balat, H. Balat / Energy Conversion and Management 49 (2008) 27272741 2729
of 40. The viscosity of the distillate was 10.2 cSt at 38 C, which is
higher than the ASTM specication for Diesel fuel No. 2 (1.9
4.1 cSt) but considerably below that of soybean oil (32.6 cSt).
Short-term engine tests were carried out on this fuel. Used cotton-
seed oil from the frying process was decomposed with Na
2
CO
3
as
catalyst at 450 C to give a pyrolyzate containing mainly C
820
al-
kanes (70%) besides alkenes and aromatics [48].
Many kinds of vegetable oil species have been subjected to
pyrolysis conditions. Some of these vegetable oils are as follows:
soybean [54,56,57], rapeseed [58], palm tree [54,59], castor [54],
safower [58], olive husk [60], and tung [61].
Recently, the yields of decarboxylation products by pyrolysis
from vegetable oil soaps have been investigated by Demirbas and
Kara [32]. The maximum decarboxylation products of pyrolyses
were 96.8%, 97.1%, 97.5%, and 97.8%, respectively, from sunower
oil, corn oil, cottonseed oil, and soybean oil at 610 K (337 C),
respectively. Oxidative pyrolysis of Na-soaps is given as following
reaction [32,33,49]:
4RCOONa O
2
!2R-R 2Na
2
CO
3
2CO
2
1
The soaps obtained from the vegetable oils can be pyrolyzed into
hydrocarbon-rich products according to Eq. (1) with higher yields
at lower temperatures.
2.3.4. Transesterication (alcoholysis)
Transesterication is the reaction of vegetable oil or animal fat
with an alcohol, in most cases methanol, to form esters and glyc-
erol. The transesterication reaction is affected by alcohol type,
molar ratio of glycerides to alcohol, type and amount of catalyst,
reaction temperature, reaction time and free fatty acids and water
content of vegetable oils or animal fats. The transesterication
reaction proceeds with or without a catalyst by using primary or
secondary monohydric aliphatic alcohols having 18 carbon atoms
as follows [21,35,48]:
Triglycerides Monohydric alcohol
!Glycerin Mono-alkyl esters 2

Generally, the reaction temperature near the boiling point of
the alcohol is recommended. Nevertheless, the reaction may be
carried out at room temperature [62]. The reactions take place at
low temperatures (65 C) and at modest pressures (2 atm,
1 atm = 101.325 kPa). Bio-diesel is further puried by washing
and evaporation to remove any remaining methanol. The oil
(87%), alcohol (9%), and catalyst (1%) are the inputs in the produc-
tion of bio-diesel (86%), the main output [63]. Pre-treatment is not
required if the reaction is carried out under high pressure
(9000 kPa) and high temperature (240 C), where simultaneous
esterication and transesterication take place with maximum
yield obtained at temperatures ranging from 60 to 80 C at a molar
ratio of 6:1 [30]. The alcohols employed in the transesterication
are generally short chain alcohols such as methanol, ethanol, pro-
panol, and butanol. It was reported that when transesterication of
soybean oil using methanol, ethanol and butanol was performed,
9698% of ester could be obtained after 1 h of reaction [2].
2.3.4.1. Catalytic transesterication. Catalysts used for the transe-
sterication of triglycerides are classied as alkali, acid, enzyme
or heterogeneous catalysts, among which alkali catalysts like so-
dium hydroxide, sodium methoxide, potassium hydroxide, potas-
sium methoxide are more effective [5]. Sulfuric acid, hydrochloric
acid and sulfonic acid are usually preferred as acid catalysts. The
heterogeneous catalysts include enzymes, titanium-silicates,
Fig. 4. The mechanism of thermal decomposition of triglycerides (source: Ref. [31]).
Table 3
Yields of pyrolysis of vegetable oils (percent by weight)
High oleic acid safower Soybean oil
N
2
sparge Air N
2
sparge Air
Alkanes 37.5 40.9 31.1 29.9
Alkanes 22.2 22.0 28.3 24.9
Alkadienes 8.1 13.0 9.4 10.9
Carboxylic acids 11.5 176.1 12.2 9.6
Unresolved unsaturates 9.7 10.1 5.5 5.1
Aromatics 2.3 2.2 2.3 1.9
Unidentied 8.7 12.7 10.9 12.6
Source: Refs. [6,33,49].
alkaline-earth metal compounds, anion exchange resins and guan-
adines heterogenized on organic polymers [64]. The catalytic
transesterication of vegetable oils with methanol is an important
industrial method used in bio-diesel synthesis. Also known as
methanolysis, this reaction is well studied and established using
acids or alkalis, such as sulfuric acid or sodium hydroxide as cata-
lysts. However, these catalytic systems are less active or com-
pletely inactive for long chain alcohols. Usually, industries use
sodium or potassium hydroxide or sodium or potassium methox-
ide as catalyst, since they are relatively cheap and quite active
for this reaction [65]. Fig. 5 shows the catalytic bio-diesel produc-
tion diagram.
2.3.4.1.1. Alkali-catalyzed transesterication. The transesterica-
tion process is catalyzed by alkaline metal alkoxides [53,66], and
hydroxides [2,3,6770], as well as sodium or potassium carbonates
[71,72]. A simplied block ow diagram for a typical base-cata-
lyzed process for the production of bio-diesel is shown in Fig. 6
[73]. The alkaline catalysts show high performance for obtaining
vegetable oils with high quality, but a question often arises; that
is, the oils contain signicant amounts of free fatty acids which
cannot be converted into bio-diesels but to a lot of soap [74]. These
free fatty acids react with the alkaline catalyst to produce soaps
that inhibit the separation of the bio-diesel, glycerin, and wash
water [75]. Triglycerides are readily transesteried batchwise in
the presence of alkaline catalyst at atmospheric pressure and at a
temperature of approximately 6070 C with an excess of metha-
nol [31]. It often takes at least several hours to ensure the alkali
(NaOH or KOH) catalytic transesterication reaction is complete.
Moreover, removal of these catalysts is technically difcult and
brings extra cost to the nal product [49,76].
Alkaline metal alkoxides (as CH
3
ONa for the methanolysis) are
the most active catalysts, since they give very high yields (>98%)
in short reaction times (30 min) even if they are applied at low mo-
lar concentrations (0.5 mol%). Alkaline metal hydroxides (KOH and
NaOH) are cheaper than metal alkoxides, but less active. Neverthe-
less, they are a good alternative since they can give the same high
conversions of vegetable oils just by increasing the catalyst con-
centration to 1 or 2 mol% [77].
The great thing about this transesterication process is that
some of the methanol can be recovered and that glycerin (that is
used in pharmaceuticals and other applications) is also a by-prod-
uct. In this process, the glycerin needs to be removed to assure that
it does not get converted to formaldehyde or acetaldehyde when
burned; both of which would pose a health hazard. It is particularly
interesting that the oil to be used is typically derived from the soy-
bean, a high protein legume of which 80% is animal feed and the
remaining 20% will serve as the oil in the bio-diesel synthesis [78].
2.3.4.1.2. Acid catalyzed transesterication. The transesterication
process is catalyzed by sulfuric [7981], hydrochloric [79,82], and
organic sulfonic acids [83]. A simplied block ow diagram of the
acid-catalyzed process is shown in Fig. 7. In general, acid catalyzed
reactions are performed at high alcohol-to-oil molar ratios, low-to-
moderate temperatures and pressures, and high acid catalyst
concentrations. Acid-catalyzed reactions require the use of high
alcohol-to-oil molar ratios in order to obtain good product yields
in practical reaction times. However, ester yields do not propor-
tionally increase with molar ratio. For instance, for soybean meth-
anolysis using sulfuric acid, ester formation sharply improved from
77% using a methanol-to-oil ratio of 3.3:1 to 87.8% with a ratio of
6:1. Higher molar ratios showed only moderate improvement until
reaching a maximum value at a 30:1 ratio (98.4%) [73]. Despite its
insensitivity to free fatty acids in the feedstock, acid-catalyzed
transesterication has been largely ignored mainly because of its
relatively slower reaction rate [84].
2.3.4.1.3. Enzyme catalyzed transesterication. The transesterica-
tion process is catalyzed by lipases such as Candida antarctica
Fig. 5. Catalytic bio-diesel production diagram.
Fig. 6. A simplied block ow diagram for a typical base-catalyzed process for the production of bio-diesel (source: Ref. [73]).
[10,11,28,85], Candida rugasa [86], Pseudomonas cepacia [87,88],
immobilized lipase (Lipozyme RMIM) [89,90], Pseudomonas sp. [91],
and Rhizomucor miehei [91,92].
The enzymatic alcoholysis of soybean oil with methanol and
ethanol was investigated using a commercial, immobilized lipase
(Lipozyme RMIM) [90]. In that study, the best conditions were ob-
tained in a solvent-free system with ethanol/oil molar ratio of
3.0, temperature of 50 C, and enzyme concentration of 7.0% (w/
w). They obtained yield 60% after 1 h of reaction. In another study,
Shah and Gupta [88] obtained a high yield (98%) by using P. cepacia
lipase immobilized on celite at 50 C in the presence of 45% (w/w)
water in 8 h.
As for the enzyme-catalyzed system, it requires a much longer
reaction time than the other two systems [84]. Both extracellular
and intracellular lipases are also able to effectively catalyze the
transesterication of triglycerides in either aqueous or non-aque-
ous systems, and as shown in Table 4, enzymatic transesterica-
tion methods can overcome the problems mentioned above [51].
The advantages of lipase-catalyzed transesterication, com-
pared to the chemically-catalyzed reaction, are emphasized [93].
The main problem of the lipase-catalyzed process is the high cost
of the lipases used as catalyst [10]. The enzyme reactions are
highly specic and chemically clean. Because the alcohol can be
inhibitory to the enzyme, a typical strategy is to feed the alcohol
into the reactor in three steps of 1:1 mole ratio each. The reactions
are very slow, with a three step sequence requiring from 4 to 40 h,
or more. The reaction conditions are modest, from 35 to 45 C [94].
2.3.4.2. Non-catalytic supercritical methanol transesterication. The
transestercation of triglycerides by supercritical methanol
(SCM), ethanol, propanol and butanol has proved to be the most
promising process [35]. Fig. 8 shows supercritical ethanol transe-
sterication system. The critical temperatures and critical pres-
sures of the various alcohols are shown in Table 5. Recently, Saka
and Kusdiana [95] have developed a catalyst-free method for bio-
diesel fuel production by employing supercritical methanol. The
supercritical treatment at 350 C, 43 MPa and 240 s with a molar
Table 4
Comparison between alkali-catalysis and lipase-catalysis methods for bio-diesel fuel
production
Alkali-catalysis process Lipase-catalysis
process
Reaction temperature (C) 6070 3040
Free fatty acids in raw
materials
Saponied products Methyl esters
Water in raw materials Interference with the
reaction
No inuence
Yield of methyl esters Normal Higher
Recovery of glycerol Difcult Easy
Purication of methyl esters Repeated washing None
Production of catalyst Cheap Relatively expensive
Source: Ref. [51].
Fig. 7. A simplied block ow diagram of the acid-catalyzed process for the production of bio-diesel (source: Ref. [73]).
Fig. 8. Supercritical ethanol transesterication system. 1. Autoclave, 2. Electrical
furnace, 3. Temperature control monitor, 4. Pressure control monitor, 5. Product
exit valve, 6. Condenser, 7. Product collecting vessel (source: Ref. [97]).
Table 5
Critical temperatures and critical pressures of various alcohols
Alcohol Critical temperature (C) Critical pressure (MPa)
Methanol 239.2 8.1
Ethanol 243.2 6.4
1-Propanol 264.2 5.1
1-Butanol 287.2 4.9
Source: Ref. [35].
ratio of 42 in methanol is the optimum condition for transesteri-
cation of rapeseed oil to bio-diesel fuel [96]. Results of this study
are given Table 6.
Demirbas [76] investigated the changes in yield percentage of
methyl esters with supercritical methanol method with a molar ra-
tio of 41. The critical temperature and the critical pressure of meth-
anol were 512.4 K and 8.0 MPa, respectively. In that study, it was
concluded that increasing reaction temperature, especially super-
critical temperatures had a favorable inuence on ester conversion.
The yields of ethyl esters from vegetable oils via transesterica-
tion in supercritical ethanol were investigated [97]. Fig. 9 shows
the changes in yield percentage of ethyl esters as treated with
sub- and supercritical ethanol at different temperatures as a func-
tion of reaction time. The critical temperature and the critical pres-
sure of ethanol were 516.2 K and 6.4 MPa, respectively.
The non-catalyst options are designed to overcome the reaction
initiation lag time caused by the extremely low solubility of the
alcohol in the TG phase. One approach that is nearing commercial-
ization is the use of a co-solvent, tetrahydrofuran (THF), to solubi-
lize the methanol. The result is a fast reaction, on the order of 5
10 min, and no catalyst residues in either the ester or the glycerol
phase. The THF co-solvent is chosen, in part, because it has a boil-
ing point very close to that of methanol. This system requires a
rather low operating temperature, 30 C. Another non-catalytic ap-
proach is the use of a high (42:1) alcohol to oil ratio. Under super-
critical conditions (350400 C and >80 atm or 1200 psi). The
reaction is complete in about 4 min [94].
Reaction by supercritical methanol has some advantages [98]:
(1) glycerides and free fatty acids are reacted with equivalent rates,
(2) the homogeneous phase eliminates diffusive problems, (3) the
process tolerates great percentages of water in the feedstock cata-
lytic process require the periodical renoval of water in the feed-
stock or in intermediate stage to prevent catalyst deactivation,
(4) the catalyst renoval step is eliminated, and (5) if high metha-
nol:oil ratios are used, total conversion of the oil can be achieved
in a few minutes. Some disadvantages of the one-stage supercriti-
cal method are clear: (1) it operates at very high pressures (25
40 MPa), (2) the high temperatures bring along proportionally high
heating and cooling costs, (3) high methanol:oil ratios (usually set
at 42) involve high costs for the evaporation of the unreacted
methanol, and (4) the process as posed to date does not explain
how to reduce free glycerol to less than 0.02% as established in
the ASTM D6584 or other equivalent international standards.
2.3.4.3. Effect of reaction parameters on conversion yield of
transesterication.
2.3.4.3.1. Effect of free fatty acid and moisture. The free fatty acid
(FFA) and moisture content are key parameters for determining
the viability of the vegetable oil transesterication process [5]. In
the transesterication, FFAs and water always produce negative ef-
fects, since the presence of FFAs and water causes soap formation,
consumes catalyst and reduces catalyst effectiveness, all of which
result in a low conversion [99]. In catalyzed methods, the presence
of water has negative effects on the yields of methyl esters [35]. In
acid catalyzed transesterication, fatty acids can be formed by the
reaction of carbocation II with the water in the reaction mixture
[100]. These free fatty acids react with the alkaline catalyst to pro-
duce soaps that inhibit the separation of the bio-diesel, glycerin,
and wash water [75]. To carry the base catalyzed reaction to com-
pletion; a free fatty acid value lower than 3% is needed [5]. Figs. 10
and 11 show a direct comparison of the yield of methyl esters from
various preparation methods as triglycerides with various water
and FFA contents are treated [35,101,102].
The presence of water has a greater negative effect on transeste-
rication than that of the FFAs. Ma et al. [103] investigated the
transesterication of beef tallow catalyzed by sodium hydroxide
(NaOH) in presence of FFAs and water. These authors reported that
water and free fatty acid contents of beef tallow had to be main-
tained below 0.06 wt% and 0.5 wt%, respectively. Using NaOH cat-
alyzed transesterication, methyl esters can generally be prepared
in high yields for low FFA oils, being nearly quantitative for the
palm oils containing <1% FFA. For example, the yield of methyl
esters from RBD (rened, bleached and deodorized) palm oil with
about 0.05% FFA was 98% [100].
2.3.4.3.2. The effect of molar ratio and alcohol type. One of the most
important factors that affect the yield of ester is the molar ratio of
alcohol to triglyceride. Although the stoichiometric molar ratio of
methanol to triglyceride for transesterication is 3:1, higher molar
ratios are used to enhance the solubility and to increase the contact
between the triglyceride and alcohol molecules [104]. Higher mo-
lar ratios result in greater ester conversion in a shorter time. In the
Table 6
Comparison of the yields in alkaline-catalyzed, acid-catalyzed and supercritical methanol
Raw material Free fatty acid content (wt%) Water content (wt%) Yields of methyl esters (wt%)
Alkaline-catalyzed Acid-catalyzed Supercritical methanol
Rapeseed oil 2.0 0.02 97.0 98.4 98.5
Palm oil 5.3 2.1 94.4 97.8 98.9
Frying oil 5.6 0.2 94.1 97.8 96.9
Waste palm oil >20.0 >61.0 95.8
Source: Ref. [96].
Fig. 9. Changes in yield percentage of ethyl esters as treated with sub- and
supercritical ethanol at different temperatures as a function of reaction time. Molar
ratio of vegetable oil-to-ethyl alcohol: 1:40 (source: Ref. [97]).
transesterication of peanut oil with ethanol, a 6:1 molar ratio
liberated signicantly more glycerine than a ratio of 3:1 [105].
Freedman et al. [106] investigated the effect of molar ratio on
the transesterication of sunower oil with methanol. They ob-
tained the results for transesterication of sunower oil, in which
the molar ratio varied from 6:1 to 1:1 and concluded that 98% con-
version to ester was obtained at a molar ratio of 6.1. The transeste-
rication of Rice Bran oil with methanol was studied at molar
ratios of 4:1, 5:1, and 6:1 [107]. At molar ratios of 4:1 and 5:1,
there was signicant increase in yield when the reaction time
was increased from 4 to 6 h. Among the three molar ratios studied,
ratio 6:1 gave the best results. Results obtained are summarized in
Table 7. In the previously mentioned work of Noureddini et al.
[104], the authors showed that at all mixing levels the molar ratio
of 8:l results in signicantly higher conversions than 6:1. Tomas-
evic and Siler-Marinkovic [20] observed that the molar ratio is
much more effective than catalyst on the transesterication
reaction.
The molar ratio is associated with the type of catalyst used.
Acid-catalyzed reactions require the use of high alcohol-to-oil mo-
lar ratios in order to obtain good product yields in practical reac-
tion times. However, ester yields do not proportionally increase
with molar ratio. For instance, for soybean methanolysis using sul-
furic acid, ester formation sharply improved from 77% using a
methanol-to-oil ratio of 3.3:1 to 87.8% with a ratio of 6:1. Higher
molar ratios showed only moderate improvement until reaching
a maximum value at a 30:1 ratio (98.4%) [73].
The effect of molar ratio of dibutyltin oxide to dimethyl carbon-
ate (DMC) on the transesterication of DMC with phenol was stud-
ied in the presence of triic acid (Bu
2
SnO/CF
3
SO
3
H = 1/1) at 180 C.
The yields of methyl phenyl carbonate (MPC) and diphenyl carbon-
ate (DPC) increased rapidly with increasing molar ratio of dibutyl-
tin oxide/DMC = 0.02. Above 0.02, however, the yields of MPC and
DPC remained unchanged. Results of this study are shown in
Fig. 12 [108].
Another important variable affecting the yield of methyl ester is
the type of alcohol to triglyceride. In general, short chain alcohols
such as methanol, ethanol, propanol, and butanol can be used in
the transesterication reaction to obtain high methyl ester yields.
Canakci and Van Gerpen [109] investigated the effect of different
alcohol types on acid-catalyzed transesterication of pure soybean
oil. They obtained yields from 87.8% to 95.8% after 48 and 96 h of
reaction. Results obtained are summarized in Table 8.
2.3.4.3.3. The effect of catalyst. Catalysts used for the transesteri-
cation of triglycerides are classied as alkali, acid, enzyme. Alkali-
catalyzed transesterication is much faster than acid-catalyzed
transesterication and is most often used commercially [6]. May
[100] studied the effect of different catalysts types on methanolysis
of RBD palm oil with a low FFA content of <0.1%. In that study, it
was concluded that Na, NaOH and KOH are effective catalysts. Re-
sults of this study are shown in Table 9.
In the previously mentioned work of Stavarache et al. [3], the
authors investigated the effect of different catalyst concentrations
on base-catalyzed transesterication during bio-diesel production
from vegetable oil by means of ultrasonic energy. The best yields
were obtained when the catalyst was used in small concentration,
i.e., 0.5% wt/wt of oil. Meneghetti et al. [110] investigated the effect
of different catalyst types at different temperatures during the pro-
duction of free and bound ethyl ester (FAEE) from castor oil. Re-
sults from that study showed that hydrochloric acid is much
more effective than sodium hydroxide at higher reaction tempera-
tures (Fig. 13).
2.3.4.3.4. The effect of reaction temperature and time. Transesteri-
cation can occur in different temperatures depending on the type
Fig. 10. Yields of methyl esters as a function of water content in transesterication
of triglycerides (source: Refs. [35,101,102]).
Fig. 11. Yields of methyl esters as a function of free fatty acid content in transes-
terication of triglycerides (source: Refs. [35,101,102]).
Table 7
Effect of reaction time and methanol-to-oil molar ratio
Serial no. Reaction time (min) Percent conversion at molar ratio Percent yield at molar ratio
4:1 5:1 6:1 4:1 5:1 6:1
1 15 85 89 93 45 46 62
2 30 86 89 94 53 54 66
3 45 88 91 94 57 59 72
4 60 90 92 94 61 67 77
5 120 91 93 94 66 67 72
6 240 92 94 95 66 67 82
7 360 92 95 97 83 82 83
Source: Ref. [107].
of oil employed [5,6,111]. A few works reported the reaction at
room temperature [22,112114]. Encinar et al. [22] studied the
transesterication reaction, with ethanol, of Cynara cardunculus L.
oils using sodium and potassium hydroxides as catalysts and re-
ported 91.6% conversion at room temperature. For the transesteri-
cation of palm oil with methanol (6:1) and 1% KOH, the reaction
was studied at different temperatures [115]. After 4 min, ester
yields were 73% and 82% for 50 and 65 C, respectively. The effect
of reaction temperature on production of propyl oleate was exam-
ined at the temperature range from 40 C to 70 C with free immo-
bilized P. uorescens lipase [116]. The conversion ratio to propyl
oleate was observed highest at 60 C, whereas the activity highly
decreased at 70 C. Demirbas [21] investigated the effect of reac-
tion temperature on methyl ester yield of non-catalytic transeste-
rication in sub- and supercritical methanol from sunower oil. In
that study, it was concluded that increasing the reaction tempera-
ture had a favorable inuence on the yield of methyl ester (Fig. 14).
The conversion rate increases with reaction time. Kim et al. [24]
studied the transesterication reaction, with methanol (6:1), of
vegetable oils using NaOH and Na/NaOH/c-Al
2
O
3
as catalysts at
60 C. They reached the maximum bio-diesel yield within 1 h both
for the case of homogeneous and heterogeneous catalyst system.
For the homogeneous catalyst system, the maximum bio-diesel
production yield was higher by 20% than that of the heterogeneous
catalyst system [24]. Results of this study are shown in Fig. 15.
3. Source for bio-diesel production
Bio-diesel can be produced from any material that contains
fatty acids, be they linked to other molecules or present as free
fatty acids. Thus various vegetable fats and oils, animal fats, waste
greases, and edible oil processing wastes can be used as feedstocks
for bio-diesel production [117]. There are more than 350 oil-bear-
ing crops identied, among which only sunower, safower, soy-
bean, cottonseed, rapeseed, and peanut oils are considered as
potential alternative fuels for diesel engines [32,35,97,118,119].
However, in recent years, animal fats and especially recycled
greases and used vegetable oils have found increasing attention
Fig. 12. Effect of molar ratio on the transesterication of DMC with phenol. Dim-
ethyl carbonate (40 mmol), phenol (200 mmol), benzene (40 ml), molecular sieves
(30 g), Bu
2
SnO/CF
3
SO
3
H = 1/1, 180 C, 3 h (source: Ref. [108]).
Table 8
The effect of alcohol type on conversion and specic gravity of ester
Alcohol type Boiling
point
(C)
Reaction
temperature
(C)
Ester
conversion
(C)
Specic gravity of
bio-diesel
Methanol 65 60 87.8 0.8876
2-Propanol 82.4 75 92.9 0.8786
1-Butanol 117 110 92.1 0.8782
Ethanol 78.5 75 95.8 0.8814
Source: Ref. [109].
Table 9
Effect of different catalysts on transesterication of palm oil
a
Catalyst Amount
(wt% based on oil)
Reaction
time (min)
Remarks
Na 0.1 1632 99% yield
NaOH 0.2 1632 98% yield
KOH 1 1632 98% yield
H
2
SO
4
(conc.) 1 >300 50% yield
HCl (conc.) 1 >300 30% yield
Ion exchange resin (H+) 2 >300 Too slow
Dowex 50 (Na+) 1 >300 Too slow
Acid treated orisil 2 >300 Too slow
Activated silica gel 1 >300 Not suitable
a
The following conditions were used: type of oil = RBD palm oil (FFA = 0.05%);
ratio of oil-to-solvent (methanol) = 1:15.6; temperature = reux temperature.
(Source: Ref. [100].)
Fig. 13. The effect of different catalyst types at different temperatures during the
production of FAEE from castor oil (percentage yield) (source: Ref. [110]).
Fig. 14. Effect of temperature on methyl ester yield of non-catalytic transesteri-
cation in sub- and supercritical methanol from sunower oil (source: Ref. [21]).
as sources of bio-diesel, the latter primarily as inexpensive feed-
stocks [120]. Rapeseed and soybeans are the two most commonly
used feedstocks for bio-diesel today. Rapeseed has a higher oil con-
tent than soybeans. They both have alternative markets as cooking
oil and food, pushing up their prices. Rapeseed produces about
435 l of bio-diesel per acre, but high-yield rapeseed can produce
as much as 550 l. Soybeans produce about 160 l per acre. Sunow-
ers can produce 280 l of bio-diesel per acre, palm oil as much as
975 l [121].
Any fatty acid source may be used to prepare bio-diesel, but
most scientic articles take soybean as a bio-diesel source
(Fig. 16) [111]. In the EU bio-diesel is predominantly produced
from vegetable oils and especially from rapeseed and sunower.
The majority of bio-diesel in the United States is made from soy-
bean oil (estimated at over 90%), but a few producers use other oil-
seed crops, palm oil, animal fats and recycled oils to make bio-
diesel [122].
Different types of oils have different types of fatty acids
(Table 1). The fatty acids are different in relation to the chain
length, degree of unsaturation or presence of other chemical func-
tions (Table 10) [111].
4. Bio-diesel market development
The global bio-diesel industry is among the fastest-growing
markets the chemical industry has ever seen [123]. Bio-diesel pro-
duction is highest in the EU, where more bio-diesel is produced
than ethanol, but total production of both fuels is fairly small com-
pared to production of bio-ethanol in Brazil and the United States
[124]. Two factors have contributed to the EUs becoming the
world leader in bio-diesel production. One is the reform of the
Common Agricultural Policy (CAP), a supranational and domesti-
cally oriented farm policy for EU member countries, adopted in
1992 and implemented in 19931994. The 1992 reform addressed
agricultural surpluses through supply control in the form of a man-
datory, paid, set-aside program. The second factor is high fuel
taxes, which have enabled indirect subsidies for bio-fuel produc-
tion through partial or full exemption of the fuel excise tax. Taxes
normally constitute 50% or more of the retail price of diesel in EU
member states. In February 1994, the European Parliament
adopted a 90% tax exemption for bio-diesel [121].
The EU is the world leader in the production and consumption
of bio-diesel. According to the European Bio-diesel Boards 2007
gures [125], the EU produced 4.98 million tons (approx. 1.5 bil-
lion gallons) of bio-diesel in 2006, up from 3.18 million tons (ap-
prox. 961 million gallons) in 2005. The EU accounted for 77% of
global bio-diesel production in 2006. Bio-diesel accounted for
nearly 80% of EU bio-fuel production [126]. Table 11 shows the
EUs bio-diesel production during 20042006 [125,127]. The EU
is expected to continue to be the main market and producer of
bio-diesel, followed by the United States and Brazil [8]. The EC
Bio-fuels Directive of 2003 required a voluntary market share of
5.75% bio-fuels for each member state by 2010. Other countries
(including Netherlands, India, China, Thailand and New Zealand)
and individual states in the United States and Canada have since
established mandatory bio-fuels targets and yet others have re-
moved excise taxes. Such policies should see additional capacity
for bio-ethanol and bio-diesel production developed [128]. The po-
tential market for bio-diesel is estimated to be in the order of 20 EJ
Fig. 15. Effect of reaction time on the bio-diesel production yield. Methanol/VO
molar ratio 6:1, reaction temperature 60 C, stirring speed 300 rpm, without co-
solvent (source: Ref. [24]).
Fig. 16. Leading bio-diesel sources cited in scientic articles (source: Ref. [111]).
Table 10
Fatty acid composition of some vegetable oils (%)
Vegetable oil Palmitic 16:0 Stearic 18:0 Palmitoleic 16:1 Oleic 18:1 Linoleic 18:2 Ricinic 12-OH-oleic Other acids
Tallow 29.0 24.5 44.5
Coconut oil 5.0 3.0 6.0 65.0
Olive oil 14.6 75.4 10.0
Groundnut oil 8.5 6.0 51.6 26.0
Cotton oil 28.6 0.9 0.1 13.0 57.2 0.2
Corn oil 6.0 2.0 44.0 48.0
Soybean oil 11.0 2.0 20.0 64.0 3.0
Hazelnut kernel 4.9 2.6 0.2 81.4 10.5 0.3
Poppy seed 12.6 4.0 0.1 22.3 60.2 0.8
Rapeseed 3.5 0.9 0.1 54.1 22.3 9.1
Safower seed 7.3 1.9 0.1 13.5 77.0 0.2
Sunower seed 6.4 2.9 0.1 17.7 72.8 0.1
Castor oil 3.0 3.0 3.0 1.2 89.5 0.3
Source: Ref. [111].
by 2050, assuming development of synthetic bio-fuel production
technologies [129].
Bio-diesel output in Germany where the biggest in the EU
industry was hit by taxes last year jumped to 2.66 million tons
in 2006 from 1.67 million tons in 2005 (Table 11). Looking at world
bio-diesel production, 42% of the world total in 2006 was ac-
counted for by Germany, where market conditions were highly
favorable (Fig. 17). Other countries with signicant bio-diesel mar-
kets in 2006 included France, the United States, Italy and the Uni-
ted Kingdom.
The United States was the worlds second-largest producer of
bio-diesel, behind the EU. The United States bio-diesel production
remained very small and at until the United States Department of
Agriculture (USDA) created the Bioenergy Program in Fiscal Year
(FY) 2000 that encouraged bio-diesel production through cash
payments to producers [122]. Mostly as a result of this program,
bio-diesel production reached from 1 million gallons (approx.
3300 tons) in 1999 [126] to 250 million gallons (approx.
836,000 tons) in 2006 [125]. By 2010, the United States is expected
to become the largest single bio-diesel market, accounting for
roughly 18% of world bio-diesel consumption [123]. Experts pre-
dict that, in the best case scenario, in the next 20 years bio-diesel
could take care of 25% of the United States diesel needs [8].
5. Bio-diesel as a vehicular fuel
Bio-diesel is a cleaner-burning diesel replacement fuel made
from natural, renewable sources such as new and used vegetable
oils and animal fats. Just like petroleum diesel, bio-diesel operates
in compression-ignition engines or Diesel engines. Bio-diesel has
physical properties very similar to conventional diesel [76]. The
bio-diesel was characterized by determining its density, viscosity,
high heating value, cetane index, cloud and pour points, character-
istics of distillation, and ash and combustion points according to
ISO norms [22,130]. Selected properties of diesel and bio-diesel
fuels are given in Table 12 [131].
Viscosity is the most important property of bio-diesel since it
affects the operation of the fuel injection equipment, particularly
at low temperatures when the increase in viscosity affects the u-
idity of the fuel. Bio-diesel has a viscosity close to that of diesel
fuels [21,35]. The higher viscosity range of bio-diesel helps to re-
duce barrel/plunger leakage and increase injector efciency in en-
gines [121]. Viscosity measurements have been made over the
temperature range 20100 C for blends of different bio-diesel
with No. 2 diesel fuel [131]. The viscosity of the distillate was
10.2 mm
2
/s at 38 C, which is higher than the ASTM specication
for No. 2 Diesel fuel (1.94.1 mm
2
/s) but considerably below that
of soybean oil (32.6 mm
2
/s) [101].
Bio-diesel offers safety benets over petroleum diesel because it
is much less combustible, with a ash point greater than 150 C,
compared to 77 C for petroleum diesel [132]. The cetane number
of bio-diesel is generally higher than conventional diesel. The ce-
tane number of bio-diesel is around 50. Bio-diesel has lower volu-
metric heating values (about 12%) than diesel fuels but has a high
cetane number and ash point [31].
Density is another important property of bio-diesel. It is the
weight of a unit volume of uid. Specic gravity is the ratio of
the density of a liquid to the density of water. Specic gravity of
bio-diesels ranges between 0.87 and 0.89. Fuel injection equip-
ment operates on a volume metering system, hence a higher den-
sity for bio-diesel results in the delivery of a slightly greater mass
of fuel [35,133].
Two important parameters for low temperature applications of
a fuel are Cloud Point (CP) and Pour Point (PP). The CP is the tem-
perature at which wax rst becomes visible when the fuel is
cooled. The PP is the temperature at which the amount of wax
out of solution is sufcient to gel the fuel, thus it is the lowest tem-
perature at which the fuel can ow. Bio-diesel has higher CP and PP
compared to conventional diesel [35,134]. The esters have CP and
PP that are 1525 C higher than those of diesel fuels [31].
Methyl esters of vegetable oils have several outstanding advan-
tages among other new-renewable and clean engine fuel alterna-
tives [21,102,135]. A number of technical advantages of bio-
diesel fuel [130,136]: (1) it prolongs engine life and reduces the
need for maintenance (bio-diesel has better lubricating qualities
than fossil diesel); (2) it is safer to handle, being less toxic, more
biodegradable, and having a higher ash point; (3) it reduces some
exhaust emissions (although it may, in some circumstances, raise
Table 11
The EUs bio-diesel production by country (1000 tons)
Country 2004 2005 2006
Germany 1035 1669 2662
France 348 492 743
Italy 320 396 447
UK 9 51 192
Austria 57 85 123
Poland 0 100 116
Czech Rep. 60 133 107
Spain 13 73 99
Portugal 0 1 91
Slovakia 15 78 82
Denmark 70 71 80
Others 6 35 148
Total EU 1933 3184 4890
Source: Refs. [125,127].
Fig. 17. The top ve bio-diesel producers in 2006.
Table 12
Specications of diesel and bio-diesel fuels
Fuel property Diesel Bio-diesel
Fuel standard ASTM D975 ASTM PS 121
Fuel composition C10C21 HC C12C22 FAME
Lower heating value (MJ/m
3
) 36.6 10
3
32.6 10
3
Kinematic viscosity at 40 C (mm
2
/s) 1.34.1 1.96.0
Specic gravity at 15.5 C 0.85 0.88
Density at 15 C (kg/m
3
) 848 878
Water (ppm by wt.) 161 0.05% max
Carbon (wt%) 87 77
Hydrogen (wt%) 13 12
Oxygen (by diff.) (wt%) 0 11
Sulfur (wt%) 0.05 max 0.00.0024
Boiling point (C) 188343 182338
Flash point (C) 6080 100170
Cloud point (C) 15 to 5 3 to 12
Pour point (C) 35 to 15 15 to 10
Cetane number 4055 4865
Stoichiometric air/fuel ratio (wt./wt.) 15 13.8
Source: Ref. [131].
others). Bio-diesel fuels have many advantages over petroleum
diesel fuel: produce less smoke and particles, have higher cetane
number, produce lower carbon monoxide and hydrocarbon emis-
sions, are renewable, biodegradable and non-toxic. When ethyl es-
ters are used as fuel the advantage of totally recyclable carbon
dioxide cycle is obtained since ethyl alcohol could be of vegetal ori-
gin [3].
The technical disadvantages of bio-diesel/fossil diesel blends in-
clude problems with fuel freezing in cold weather, reduced energy
density, and degradation of fuel under storage for prolonged peri-
ods. One additional problem is encountered when blends are rst
introduced into equipment that has a long history of pure hydro-
carbon usage. Hydrocarbon fuels typically form a layer of deposits
on the inside of tanks, hoses, etc. Bio-diesel blends loosen these
deposits, causing them to block fuel lters. However, this is a min-
or problem, easily remedied by proper lter maintenance during
the period following introduction of the bio-diesel blend [136].
Bio-diesel can be blended at any level with petroleum diesel to
create a bio-diesel blend. It can be used in compression-ignition
(diesel) engines with little or no modications [24]. Several studies
show bio-diesel can run in a conventional diesel engine for an ex-
tended time. Researchers in several states including Missouri and
Idaho, have run diesel engines in pickups, city buses, large trucks
and tractors on various mixes of bio-diesel/diesel fuel. These mix-
tures have ranged from 2/98% (B2), 20/80% (B20) up to 100% (B100)
[33,130,137].
Bio-diesel is often used as a blend B20 (20 vol.% bio-diesel and
80 vol.% conventional diesel) rather than using B100 (100 vol.%
bio-diesel). It is asserted that 90% of air toxics can be eliminated
by using B100 whereas 2040% are reduced using B20. A further
assertion is that the risk of illness and life threatening diseases
can be reduced using bio-diesel blends [131]. Bio-diesel blends of
up to 20% reduce the emissions of HC, CO, SO
2
, and particulates,
as well as improve the engine performance [138,139]. Table 13
shows a summary of engine tests completed at the University of
Idaho. These tests were performed with a 100% and a 20% mix of
ethyl and methyl ester of rapeseed oil [137].
6. Bio-diesel economy
In previous economic studies of bio-diesel production, the main
economic criteria were capital cost, manufacturing cost and bio-
diesel break-even price. The economic performance of a bio-diesel
plant (e.g., xed capital cost, total manufacturing cost, and the
break-even price of bio-diesel) can be determined once certain fac-
tors are identied, such as plant capacity, process technology, raw
material cost and chemical costs [13]. At present, the high cost of
bio-diesel is the major obstacle to its commercialization. Bio-diesel
usually costs over US$0.5/l, compared to US$0.35/l for petroleum-
based diesel [84].
The major economic factor to consider for input costs of bio-
diesel production is the feedstock, which is about 80% of the total
operating cost. Other important costs are labor, methanol and cat-
alyst, which must be added to the feedstock [35]. Using an esti-
mated process cost, exclusive of feedstock cost, of US$0.158/l
($0.60/gal) for bio-diesel production, and estimating a feedstock
cost of US$0.539/l ($2.04/gal) for rened soy oil, an overall cost
of US$0.70/l ($2.64/gal) for the production of soy-based bio-diesel
was estimated [117]. Palm oil is the main option that is traded
internationally, and with potential for import in the short term
[140]. Costs for production from palm oil are estimated; the results
are shown in Table 14.
Bio-diesel from animal fat is currently the cheapest option
($0.4$0.5/l) while traditional transesterication of vegetable oil
is at present around $0.6$0.8/l. Cost reductions of $0.1$0.3/l
are expected from economies of scale for new processes. The cost
of BTL diesel from ligno-cellulose is more than $0.9/l (feedstock
$3.6/GJ), with a potential reduction to $0.7$0.8/l [129].
With pre-tax diesel priced at US$0.18/l in the United States and
US$0.200.24/l in some European countries, bio-diesel is thus cur-
rently not economically feasible, and more research and technolog-
ical development will be needed [33,35,49,130,141,142]. The cost
of bio-diesel production results in a generally accepted view of
the industry in Europe that bio-diesel production is not protable
without scal support [142144].
The cost of bio-diesel for IC engine is slightly greater than that
of diesel oil (approximate difference of 0.06 4/l). The specic fuel
consumption, a function of the engine speed, is higher in bio-diesel
than in diesel oil. Bench-test results previously reported showed
that the average value of SFC for bio-diesel is 17% greater that that
of diesel oil. Other tests on different engines show that the increase
ranges from 5% to 20%. Under these conditions the specic cost in
4/kWh shows an increase by about 2.1%. If the cost of the two fuels
is the same, the specic cost for the engine running on bio-diesel is
9.8% higher [145].
Table 13
Engine emission results from the University of Idaho
Emission 100% Ester fuel (B100) (%) 20/80 Mix (B20) (%)
Hydrocarbons 52.4 19.0
Carbon monoxide 47.6 26.1
Nitrous oxides 10.0 3.7
Carbon dioxide 0.9 0.7
Particulates 9.9 2.8
Source: Ref. [137].
Table 14
Costs of bio-diesel production
Plant size Capital costs Feedstock Methanol Other Total Glycerol credit Net Distribution and blending Total
ktpa Million liters
Tallow-based ($/l)
5 6 0.33 0.40 0.05 0.11 0.89 0.12 0.77 0.08 0.85
20 23 0.15 0.40 0.05 0.10 0.70 0.12 0.58 0.08 0.66
40 46 0.11 0.40 0.05 0.09 0.64 0.12 0.52 0.09 0.61
60 69 0.08 0.40 0.05 0.08 0.61 0.12 0.49 0.15 0.64
120 137 0.06 0.40 0.05 0.06 0.56 0.12 0.44 0.15 0.60
Palm oil ($/l)
50 60 0.09 0.73 0.05 0.08 0.95 0.12 0.83 0.04 0.88
60 71 0.08 0.73 0.05 0.08 0.94 0.12 0.82 0.04 0.86
120 143 0.06 0.73 0.05 0.06 0.89 0.12 0.78 0.04 0.82
Source: Ref. [140].
7. Conclusion
The problems with substituting triglycerides for diesel fuels are
mostly associated with their high viscosities, low volatilities and
polyunsaturated character. The viscosity of vegetable oils, when
used as diesel fuel, can be reduced in at least four different ways:
(1) dilution with hydrocarbons (blending), (2) emulsication, (3)
pyrolysis (thermal cracking), and (4) transesterication (alcoholy-
sis). Transesterication is the most common method and leads to
monoalkyl esters of vegetable oils and fats, now called bio-diesel
when used for fuel purposes. The main factors affecting transeste-
rication are molar ratio of glycerides to alcohol, catalyst, reaction
temperature and pressure, reaction time and the contents of free
fatty acids and water in oils. The commonly accepted molar ratios
of alcohol to glycerides are 6:130:1.
Bio-diesel is a cleaner-burning diesel replacement fuel made
from natural, renewable sources such as new and used vegetable
oils and animal fats. Just like petroleum diesel, bio-diesel operates
in compression-ignition engines or Diesel engines. The bio-diesel
was characterized by determining its density, viscosity, high heat-
ing value, cetane index, cloud and pour points, characteristics of
distillation, and ash and combustion points according to ISO
norms. Viscosity is the most important property of bio-diesel since
it affects the operation of the fuel injection equipment, particularly
at low temperatures when the increase in viscosity affects the u-
idity of the fuel.
The major economic factor to consider for input costs of bio-
diesel production is the feedstock, which is about 80% of the total
operating cost. Other important costs are labor, methanol and cat-
alyst, which must be added to the feedstock. Using an estimated
process cost, exclusive of feedstock cost, of US$0.158/l ($0.60/gal)
for bio-diesel production, and estimating a feedstock cost of
US$0.539/l ($2.04/gal) for rened soy oil, an overall cost of
US$0.70/l ($2.64/gal) for the production of soy-based bio-diesel
was estimated.
Acknowledgement
The authors gratefully acknowledges the support provided by
Sila Science and expresses his gratitude to its manager.
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A Critical Review of Bio-Diesel As A Vehicular Fuel

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