Energy Conversion and Management 47 (2006) 22712282

www.elsevier.com/locate/enconman

Biodiesel production via non-catalytic SCF method

and biodiesel fuel characteristics
Ayhan Demirbas

Department of Chemical Engineering, Selcuk University, Campus, 42031 Konya, Turkey

Received 15 June 2005; accepted 28 November 2005
Available online 9 January 2006

Abstract
Vegetable oil (m)ethyl esters, commonly referred to as biodiesel, are prominent candidates as alternative Diesel fuels.
Biodiesel is technically competitive with or oers technical advantages compared to conventional petroleum Diesel fuel.
The vegetable oils, as alternative engine fuels, are all extremely viscous with viscosities ranging from 10 to 20 times greater
than that of petroleum Diesel fuel. The purpose of the transesterication process is to lower the viscosity of the oil. Transesterications of vegetable oils in supercritical methanol are performed without using any catalyst. The most important variables aecting the methyl ester yield during the transesterication reaction are the molar ratio of alcohol to vegetable oil
and the reaction temperature. Biodiesel has become more attractive recently because of its environmental benets. The cost
of biodiesel, however, is the main obstacle to commercialization of the product. With cooking oils used as raw material, the
viability of a continuous transesterication process and recovery of high quality glycerol as a biodiesel by product are
primary options to be considered to lower the cost of biodiesel. Supercritical methanol has a high potential for both transesterication of triglycerides and methyl esterication of free fatty acids to methyl esters for a Diesel fuel substitute. In
the supercritical methanol transesterication method, the yield of conversion increases to 95% in 10 min. The viscosity
values of vegetable oils are between 27.2 and 53.6 mm2/s, whereas those of vegetable oil methyl esters are between 3.59
and 4.63 mm2/s. The ash point values of vegetable oil methyl esters are much lower than those of vegetable oils. An
increase in density from 860 to 885 kg/m3 for vegetable oil methyl esters or biodiesels increases the viscosity from 3.59
to 4.63 mm2/s. Biodiesel is an environmentally friendly fuel that can be used in any Diesel engine without modication.
2005 Elsevier Ltd. All rights reserved.
Keywords: Vegetable oil; Biodiesel; Supercritical (m)ethanol; Fuel properties; Viscosity

1. Introduction
A sustainable biofuel has two favorable properties which are its availability from renewable raw material
and its lower negative environmental impact than that of fossil fuels. Various vegetable oil extraction and
transesterication technologies are currently used in the production of biodiesel fuel. As an alternative fuel,
*

Tel.: +90 462 230 7831; fax: +90 462 248 8508.
E-mail address: ayhandemirbas@hotmail.com

0196-8904/$ - see front matter 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2005.11.019

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vegetable oil is one of the renewable fuels. Vegetable oil is a potentially inexhaustible source of energy with an
energetic content close to that of Diesel fuel. The vegetable oil fuels have not been acceptable because they
were more expensive than petroleum fuels. The major problem associated with the use of pure vegetable oils
as fuels, for Diesel engines, is caused by the high fuel viscosity in compression ignition. There are more than
350 oil bearing crops identied, among which only sunower, saower, soybean, cottonseed, rapeseed and
peanut oils are considered as potential alternative fuels for Diesel engines.
The direct use of vegetable oils as fuel for engines is problematic. Because of their high viscosity (about 10
20 times higher than that of Diesel fuel) and low volatility, they do not burn completely and form deposits in
the fuel injectors of Diesel engines. Dierent ways have been considered to reduce the high viscosity of vegetable oils: (a) dilution, (b) microemulsions, (c) pyrolysis, (d) catalytic cracking and (e) transesterication.
Among all these alternatives, transesterication seems to be the best choice, as the physical characteristics
of fatty acid esters (biodiesels) are very close to those of Diesel fuel and the process is relatively simple. Furthermore, the methyl or ethyl esters of fatty acids can be burned directly in unmodied Diesel engines with
very low deposit formation.
Vegetable oil and animal fat (m)ethyl esters, commonly referred to as biodiesel, are prominent candidates
as alternative Diesel fuels [1]. Biodiesel can be processed from any type of vegetable oils and animal fats: (1)
food grade vegetable oils, such as soybean, canola, palm, sunower and peanut; (2) animal fats, such as lard,
tallow, chicken fat and sh oils and (3) used cooking oils from restaurants. Biodiesel is technically competitive
with or oers technical advantages compared to conventional petroleum Diesel fuel. Besides being a renewable
and domestic resource, biodiesel reduces most emissions while engine performance and fuel economy are
nearly identical to those of conventional fuels. Alternative fuels and propulsion systems have the potential
to solve many of the current social problems and concerns, from air pollution and global warming to other
environmental improvements and sustainability issues [2,3].
While soybean oil is of primary interest as a biodiesel source in the United States, many European countries
are concerned with rapeseed oil, and countries with tropical climates prefer to utilize coconut oil or palm oil.
Other vegetable oils, including sunower, saower, etc., have also been investigated. Furthermore, other
sources of biodiesel studied include animal fats and used or waste cooking oils. Sources of biodiesel with some
emphasis on developing countries have been discussed [4].
2. Transesterication
The transesterication reaction proceeds with or without any catalyst by using primary or secondary monohydric aliphatic alcohols having 18 carbon atoms as follows:
Triglycerides Monohydric  Glycerin Monoalkylesters

Transesterication means taking a triglyceride molecule or a complex fatty acid, neutralizing the free fatty
acids, removing the glycerin and creating an alcohol ester. The reaction is shown in Eq. (1). A catalyst is usually used to improve the reaction rate and yield. Theoretically, the transesterication reaction is an equilibrium
reaction. In this reaction, however, a larger amount of methanol was used to shift the reaction equilibrium to
the right side and produce more methyl esters as the proposed product.
2.1. Catalytic transesterication
The transesterication reaction can be catalyzed by both homogeneous and heterogeneous catalysts. In
turn, the homogeneous catalysts include alkalis and acids. The most commonly used alkali catalysts are
sodium hydroxide, sodium methoxide and potassium hydroxide. In this sense, numerous references can be
found in the background literature. Sulfuric acid, hydrochloric acid and sulfonic acid are usually preferred
as acid catalysts. Finally, the heterogeneous catalysts include enzymes, titanium silicates, alkaline earth metal
compounds, anion exchange resins and guanadines heterogenized on organic polymers [1]. The transesterication reaction can be catalyzed by alkalis [5], acids [6], or enzymes [711].
The catalyst is dissolved into the methanol by vigorous stirring in a small reactor. The oil is transferred into
the biodiesel reactor, and then the catalyst/alcohol mixture is pumped into the oil. The nal mixture is stirred

A. Demirbas / Energy Conversion and Management 47 (2006) 22712282

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vigorously for 2 h at 340 K in ambient pressure. A successful transesterication reaction produces two liquid
phases: ester and crude glycerin. Crude glycerin, the heavier liquid, will collect at the bottom after several
hours of settling. Phase separation can be observed within 10 min and can be complete within 2 h of settling.
Complete settling can take as long as 20 h. After settling is complete, water is added at the rate of 5.5% by
volume of the methyl ester of oil and then stirred for 5 min, and the glycerin is allowed to settle again. Washing the ester is a two-step process, which is carried out with extreme care. A water wash solution at the rate of
28% by volume of oil and 1 g of tannic acid per liter of water is added to the ester and gently agitated. Air is
carefully introduced into the aqueous layer while simultaneously stirring very gently. This process is continued
until the ester layer becomes clear. After settling, the aqueous solution is drained, and water alone is added at
28% by volume of oil for the nal washing [1214].
2.2. Non-catalytic transesterication in supercritical conditions
The transestercation of triglycerides by supercritical methanol (SCM), ethanol, propanol and butanol has
proved to be the most promising process. Table 1 shows the critical temperatures and critical pressures of the
various alcohols. A non-catalytic biodiesel production route with supercritical methanol has been developed
that allows a simple process and high yield because of simultaneous transesterication of triglycerides and
methyl esterication of fatty acids [15]. Because of having similar properties to petrodiesel, biodiesel, a transesteried product of vegetable oil, is considered as the most promising one for a Diesel fuel substitute. A reaction mechanism of vegetable oil in SCM was proposed based on the mechanism developed by Krammer and
Vogel [16] for the hydrolysis of esters in sub/supercritical water. The basic idea of supercritical treatment is
based on the eect of the relationship between pressure and temperature upon the thermophysical properties
of the solvent, such as dielectric constant, viscosity, specic weight and polarity [17]. The transesterication of
sunower oil was investigated in SCM and supercritical ethanol at various temperatures (475675 K) [18].
The most important variables aecting the methyl ester yield during the transesterication reaction are the
molar ratio of alcohol to vegetable oil and the reaction temperature. The viscosities of the methyl esters from
vegetable oils were slightly higher than that of No. 2 Diesel fuel. The variables aecting the ester yield during
the transesterication reaction are the molar ratio of alcohol to vegetable oil, reaction temperature, reaction
time, water content and catalyst. It was observed that increasing the reaction temperature, especially to supercritical temperatures, had a favorable inuence on ester conversion [13].
The stoichiometric ratio for the transesterication reaction requires three moles of alcohol and one mole of
triglyceride to yield three moles of fatty acid ester and one mole of glycerol. Higher molar ratios result in
greater ester production in a shorter time. The vegetable oils were transesteried with 1:61:40 vegetable
oilalcohol molar ratios in catalytic and supercritical alcohol conditions [13].
In the supercritical alcohol transesterication method, the yield of conversion increases to 5095% in the
rst 10 min. Fig. 1 shows the plots for the changes in the fatty acids alkyl esters conversion from triglycerides
as treated in supercritical alcohols at 575 K [19].
Water content is an important factor in the conventional catalytic transesterication of vegetable oil. In the
conventional transesterication of fats and vegetable oils for biodiesel production, free fatty acids and water
always produce negative eects, since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst eectiveness. In catalyzed methods, the presence of water has negative
eects on the yields of methyl esters. However, the presence of water aected positively the formation of
methyl esters in our supercritical methanol method. Fig. 2 shows the plots for the yields of methyl esters as

Table 1
Critical temperatures and critical pressures of various alcohols
Alcohol

Critical temperature (K)

Critical pressure (MPa)

Methanol
Ethanol
1-Propanol
1-Butanol

512.2
516.2
537.2
560.2

8.1
6.4
5.1
4.9

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A. Demirbas / Energy Conversion and Management 47 (2006) 22712282

Fatty acid alkyl ester, %

100
80

60
Methanol
Ethanol

40

1-Propanol
1-Butanol

20

1-Octanol

10

20

30

40

50

Reaction time, min

Fig. 1. Plots for changes in fatty acids alkyl esters conversion from triglycerides as treated in supercritical alcohol at 575 K (Source: Ref.
[19]).

Supercritical methanol
Acid catalyst

Alkaline catalyst

Methyl ester, %

100
80
60
40
20
0
0

Water content, %
Fig. 2. Plots for yields of methyl esters as a function of water content in transesterication of triglycerides (Source: Ref. [21]).

Supercritical methanol

alkaline catalyst

Acid catalyst

Methyl ester, %

100
80
60
40
20
0

10

20

30

Free fatty acid content, %

Fig. 3. Plots for yields of methyl esters as a function of free fatty acid content (Source: Ref. [21]).

a function of water content in transesterication of triglycerides. Fig. 3 shows the plots for the yields of methyl
esters as a function of free fatty acid content in biodiesel production [20,21]. Comparisons between the catalytic commercial methanol process and the SCM method for biodiesel from vegetable oils by transesterication are given in Table 2.

A. Demirbas / Energy Conversion and Management 47 (2006) 22712282

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Table 2
Comparisons between catalytic methanol (MeOH) process and supercritical methanol (SCM) method for biodiesel from vegetable oils by
transesterication

Methylating agent
Catalyst
Reaction temperature (K)
Reaction pressure (MPa)
Reaction time (min)
Methyl ester yield (wt%)
Removal for purication
Free fatty acids
Continuity easiness

Catalytic MeOH process

SCM method

Methanol
Alkali
303338
0.1
60360
96
Methanol, catalyst, glycerol, soaps
Saponied products
Discontinue

Methanol
None
523573
1025
715
98
Methanol
Methyl esters, water
Easy continuity

3. Biodiesel economy
The advantages of biodiesel can be listed as follows: it reduces greenhouse gas emissions; it helps to reduce a
countrys reliance on crude oil imports and supports agriculture by providing a new labor and market opportunities for domestic crops; it enhances the lubricating property; and it is widely accepted by vehicle manufacturers [22,23].
The major economic factor to consider for input costs of biodiesel production is the feedstock, which is
about 80% of the total operating cost. Other important costs are labor, methanol and catalyst, which must
be added to the feedstock.
The cost of biodiesel fuels varies depending on the base stock, geographic area, variability in crop production from season to season, the price of crude petroleum and other factors. Biodiesel can be over double the
price of petroleum Diesel. The high price of biodiesel is in large part due to the high price of the feedstock.
However, biodiesel can be made from other feedstocks, including beef tallow, pork lard and yellow grease.
Biodiesel has become more attractive recently because of its environmental benets. With cooking oils used
as raw material, the viability of a continuous transesterication process and recovery of high quality glycerol
as a biodiesel by product are primary options to be considered to lower the cost of biodiesel [12,24]. With
recent increases in petroleum prices and uncertainties concerning petroleum availability, there is renewed
interest in vegetable oil fuels for Diesel engines.
Most of the biodiesel that is currently made uses soybean oil, methanol and an alkaline catalyst. The high
value of soybean oil as a food product makes production of a cost eective fuel very challenging. However,
there are large amounts of low cost oils and fats such as restaurant wastes and animal fats that could be converted to biodiesel. The problem with processing these low cost oils and fats is that they often contain large
amounts of free fatty acids (FFA) that cannot be converted to biodiesel using an alkaline catalyst [14,25].
A review of 12 economic feasibility studies shows that the projected costs for biodiesel (BD) from oilseed or
animal fats have a range US$0.300.69/l, including meal and glycerin credits and the assumption of reduced
capital investment costs by having the crushing and/or esterication facility added onto an existing grain or
tallow facility. Rough projections of the cost of BD from vegetable oil and waste grease are, respectively,
US$0.540.62/l and US$0.340.42/l. With pre-tax Diesel priced at US$0.18/l in the US and US$0.200.24/l
in some European countries, BD is, thus, currently not economically feasible, and more research and technological development will be needed [14,26].
4. Fuel properties of vegetable oils and biodiesels
Vegetable oils can be used as fuel for combustion engines, but its viscosity is much higher than that of the
usual Diesel fuel and requires modications of the engines. The major problem associated with the use of pure
vegetable oils as fuels, for Diesel engines, is caused by its high fuel viscosity in compression ignition. Therefore,
vegetable oils are converted into their (m)ethyl esters (biodiesels) by transesterication.

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Several types of vegetable oils, with a diversied composition in fatty acids, can be used for the preparation
of biodiesel. Soybean, rapeseed, sunower and palm oils are the most studied. However, there are no technical
restrictions to the use of other types of vegetable oils. Considering the type of alcohol, the use of methanol is
advantageous as it allows simultaneous separation of the glycerol. The same reaction using ethanol is more
complicated as it requires a water free alcohol, as well as oil with low water content in order to obtain glycerol
separation [27].
The use of vegetable oils as alternative renewable fuel competing with petroleum was proposed in the beginning of the 1980s. The advantages of vegetable oils as Diesel fuel are liquid nature-portability, ready availability, renewability, higher heat content (about 88% of Diesel No. 2 fuel), lower sulfur content, lower aromatic
content and biodegradability.
The disadvantages of vegetable oils as Diesel fuel are higher viscosity, lower volatility and the reactivity of
unsaturated hydrocarbon chains.
Short-term tests using neat vegetable oil showed promising results. Problems appear only after the engine
has been operating on vegetable oil for longer periods of time. The problems met in long-term engine tests
according to results obtained by earlier researchers may be classied as follows: injector coking and trumpet
formation on the injectors, more carbon deposits, oil ring sticking and thickening and gelling of the engine
lubricant oil [14]. The biodiesel esters were characterized for their physical and fuel properties including density, viscosity, iodine value, acid value, cloud point, pure point, gross heat of combustion and volatility.
Methyl and ethyl esters prepared from a particular vegetable oil had similar viscosities, cloud points and pour
points, whereas methyl, ethyl, 2-propyl and butyl esters derived from a particular vegetable oil had similar
gross heating values. However, their densities, which were 27% higher than those of Diesel fuels, statistically
decreased in the order of methyl similar to 2-propyl > ethyl > butyl esters. The higher heating values of the
biodiesel fuels, on a mass basis, are 913% lower than Diesel No. 2 (D2). The viscosities of biodiesel fuels
are twice that of D2. The cloud and pour points of D2 are signicantly lower than those of the biodiesel fuels.
The biodiesel fuels produced slightly lower power and torque and higher fuel consumption than D2.
The properties of biodiesel are close to those of Diesel fuels. The biodiesel was characterized by determining
its viscosity, density, cetane number, cloud and pour points, characteristics of distillation, ash and combustion points and higher heating value (HHV) according to ISO norms. Some fuel properties of methyl ester
biodiesel are presented in Table 3.
Biodiesel is an ecient, clean, 100% natural energy alternative to petroleum fuels. The many advantages of
biodiesel fuel include the following: safe for use in all conventional Diesel engines, oers the same performance
and engine durability as petroleum Diesel fuel, non-ammable and non-toxic and reduces tailpipe emissions,
visible smoke and noxious fumes and odors. Biodiesel is better than Diesel fuel in terms of sulfur content, ash
point, aromatic content and biodegradability [14].
4.1. Viscosity
Viscosity is a measure of the internal friction or resistance of an oil to ow. As the temperature of oil is
increased, its viscosity decreases, and it is, therefore, able to ow more readily. Viscosity is measured on several dierent scales, including Redwood No. 1 at 100 F, Engler Degrees, Saybolt Seconds, etc., the number of
seconds required for 50 ml. of an oil to ow out of a standard Redwood viscosimeter at a denite temperature.

Table 3
Fuel properties of methyl ester biodiesels
Source

Viscosity, cSt, at 313.2 K

Density, g/ml, at 288.7 K

Cetane number

Reference

Sunower
Soybean
Palm
Peanut
Babassu
Tallow

4.6
4.1
5.7
4.9
3.6
4.1

0.880
0.884
0.880
0.876

0.877

49
46
62
54
63
58

[33]
[34]
[33]
[35]
[35]
[20]

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2277

Viscosity is the most important property of biodiesel since it aects the operation of the fuel injection equipment, particularly at low temperatures when the increase in viscosity aects the uidity of the fuel. Biodiesel
has a viscosity close to that of Diesel fuels. High viscosity leads to poorer atomization of the fuel spray and less
accurate operation of the fuel injectors. A novel process of BD fuel production has been developed by a noncatalytic supercritical methanol method.
The viscosity of the distillate was 10.2 mm2/s at 311 K, which is higher than the ASTM specication for No.
2 Diesel fuel (1.94.1 mm2/s) but considerably below that of soybean oil (32.6 mm2/s). Used cottonseed oil
from the cooking process was decomposed with Na2CO3 as catalyst at 725 K to give a pyrolyzate containing
mainly C820 alkanes (69.6%) besides alkenes and aromatics. The pyrolyzate had lower viscosity, pour point,
and ash point than No. 2 Diesel fuel and equivalent heating values. The cetane number of the pyrolyzate was
lower than that of No. 2 Diesel fuel [21].
The vegetable oils were all extremely viscous, with viscosities ranging 1020 times greater than that of No. 2
Diesel fuel. Castor oil is in a class by itself with a viscosity more than 100 times that of No. 2 Diesel fuel [14].
The viscosity of oil can be lowered by blending with pure ethanol. 25 parts of sunower oil and 75 parts of
Diesel were blending as Diesel fuel. The viscosity was 4.88 cSt at 313 K, while the maximum specied ASTM
value is 4.0 cSt at 313 K. This mixture was not suitable for long-term use in a direct injection engine.
To reduce the high viscosity of vegetable oils, microemulsions with immiscible liquids, such as methanol,
ethanol and ionic or non-ionic amphiphiles have been studied [3,28]. Short engine performances of both
ionic and non-ionic microemulsions of ethanol in soybean oil were nearly as good as those of D2 fuel. All
microemulsions with butanol, hexanol and octanol met the maximum viscosity requirement for D2 fuel.
The 2-octanol was found to be an eective amphiphile in the micellar solubilization of methanol in triolein
and soybean oil.
4.2. Density
Density is another important property of biodiesel. 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. The specic gravity of biodiesels ranges between
0.87 and 0.89 (Table 3). Fuel injection equipment operates on a volume metering system, hence a higher density for biodiesel results in the delivery of a slightly greater mass of fuel.
4.3. Cetane number
Cetane number (CN) is based on two compounds, namely hexadecane with a cetane number of 100 and
heptamethylnonane with a cetane number of 15. The CN scale also shows that straight chain, saturated hydrocarbons have higher CN compared to branched chain or aromatic compounds of similar molecular weight and
number of carbon atoms. The CN of biodiesel is generally higher than that of conventional Diesel. The CN is
one of the prime indicators of the quality of Diesel fuel. It relates to the ignition delay time of a fuel upon
injection into the combustion chamber. The CN is a measure of the ignition quality of Diesel fuels, and high
CN implies short ignition delay. The longer the fatty acid carbon chains and the more saturated the molecules,
the higher the CN will be. The CN of biodiesel from animal fats is higher than those from vegetable oils.
4.4. Cloud point and pour point
Two important parameters for low temperature applications of a fuel are cloud point (CP) and pour point
(PP). The CP is the temperature 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 sucient to gel the fuel, thus it is the lowest temperature at which the fuel can ow. Biodiesel has higher CP and PP compared to conventional Diesel [29].
4.5. Emission impacts for biodiesel fuels
Biodiesel fuels have generally been found to be non-toxic and are biodegradable, which may promote
their use in applications where biodegradability is desired. Neat biodiesel and biodiesel blends used in an

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A. Demirbas / Energy Conversion and Management 47 (2006) 22712282

unmodied Diesel engine reduce particulate matter (PM), hydrocarbons (HC) and carbon monoxide (CO)
emissions and increase nitrogen oxides (NOx) emissions compared with petroleum based Diesel fuel [30].
The emission impacts of 20 vol% biodiesel for soybean-based biodiesel added to an average base Diesel fuel
are given in Table 4.
4.6. Comparison of fuel properties and combustion characteristics of methyl and ethyl alcohols and their esters
In general, the physical and chemical properties and the performance of ethyl esters are comparable to
those of methyl esters. Methyl and ethyl esters have almost the same heat content. The viscosities of the ethyl
esters are slightly higher, and the cloud and pour points are slightly lower than those of methyl esters. Engine
tests demonstrated that methyl esters produce slightly higher power and torque than ethyl esters [31]. Some
desirable attributes of the ethyl esters over methyl esters are signicantly lower smoke opacity, lower exhaust
temperatures and lower pour point. The ethyl esters tended to have more injector coking than the methyl
esters. Some properties of fuels are given in Table 5.
Ethanol is produced as a more environmentally benign fuel. The systemic eect of ethyl alcohol diers from
that of methyl alcohol. Ethyl alcohol is rapidly oxidized in the body to carbon dioxide and water, and in contrast to methyl alcohol, no cumulative eect occurs. Ethanol is also a preferred alcohol in the transesterication process compared to methanol because it is derived from agricultural products and is renewable and
biologically less objectionable in the environment.
Methanol use in current technology vehicles has some distinct advantages and disadvantages. On the plus
side, methanol has a higher octane rating than gasoline. Methanol has high heat of vaporization that results in
lower peak ame temperatures than gasoline and lower nitrogen oxide emissions. Its greater tolerance to lean
combustion higher air to fuel equivalence ratios results in generally lower overall emissions and higher energy
eciency. However, several disadvantages must be studied and overcome before neat methanol is considered a
viable alternative to gasoline. The energy density of methanol is about half that of gasoline, reducing the range
a vehicle can travel on an equivalent tank of fuel.
There are some important dierences in the combustion characteristics of alcohols and hydrocarbons.
Alcohols have higher ame speeds and extended ammability limits. Pure methanol is very ammable, and
its ame is colorless when ignited. The alcohols mix in all proportions with water due to the polar nature
of the OH group. Low volatility is indicated by high boiling point and high ash point. Combustion of alcohol
in the presence of air can be initiated by an intensive source of localized energy, such as a ame or a spark, and
also, the mixture can be ignited by application of energy by means of heat and pressure, such as happens in the
compression stroke of a piston engine. The high latent heat of vaporization of alcohols cools the air entering

Table 4
Emission impacts of 20 vol% biodiesel for soybean-based biodiesel added to an average base Diesel fuel
Percent change in emissions
Nitrogen oxides (NOx)
Particular matter (PM)
Hydrocarbons (HC)
Carbon monoxide (CO)

+2.0
10.1
21.1
11.0

Source: Ref. [30].

Table 5
Some properties of fuels
Fuel property

Gasoline

Diesel No. 2

Iso-octane

Methanol

Ethanol

Cetane number
Octane number
Auto-ignition temperature (K)
Latent heat of vaporization (MJ/kg)
Lower heating value (MJ/kg)

96
644
0.35
44.0

50

588
0.22
42.6

100
530
0.26
45.0

5
112
737
1.18
19.9

8
107
606
0.91
26.7

A. Demirbas / Energy Conversion and Management 47 (2006) 22712282

2279

the combustion chamber of the engine, thereby increasing the air density and mass ow. This leads to
increased volumetric eciency and reduced compression temperatures. The oxygen contents of alcohols
depress the heating value of the fuel in comparison with that of hydrocarbon fuels. The heat of combustion
per unit volume of alcohol is approximately half that of iso-octane.
Methanol is not miscible with hydrocarbons, and separation ensues readily in the presence of small quantities of water, particularly with a reduction in temperature. On the other hand, anhydrous ethanol is completely miscible in all proportions with gasoline, although separation may be eected by water addition or
by cooling. If water is already present, the water tolerance is higher for ethanol than for methanol and can
be improved by the addition of higher alcohols, such as butanol. Also, benzene or acetone can be used.
The wear problem is believed to be caused by formic acid attack, when methanol is used or acetic acid attack
when ethanol is used.
Dry methanol is very corrosive to some aluminum alloys, but additional water at 1% almost completely
inhibits corrosion. It must be noted that methanol with additional water at more than 2% becomes corrosive
again. Ethanol always contains some acetic acid and is particularly corrosive to aluminum alloys.
Since alcohols, especially methanol, can be readily ignited by hot surfaces, pre-ignition can occur. It must
be emphasized here that pre-ignition and knocking in an alcohol engine is a much more dangerous condition
than in gasoline engines. Other properties, however, are favorable to the increase of power and reduction of
fuel consumption. Such properties are as follows: (1) number of molecules or products is more than that of
reactants; (2) extended limits of ammability; (3) high octane number; (4) high latent heat of vaporization;
(5) constant boiling temperature; and (6) high density.
When Diesel engines are converted to alcohols, some properties of gasoline, Diesel and alcohol should be
concerned. Table 5 shows the properties of the fuels. There are several methods for converting a Diesel engine
to alcohol to discuss.
5. Engine performance tests
The methyl ester of vegetable oil was evaluated as a fuel in compression ignition engines (CIE) by researchers [17,32]. They concluded that the performance of the esters of vegetable oil did not dier greatly from that
of Diesel fuel. The brake power was nearly the same as with Diesel fuel, while the specic fuel consumption
was higher than that of Diesel fuel. Based on crankcase oil analysis, engine wear rates were low, but some oil
dilution did occur. Carbon deposits inside the engine were normal with the exception of intake valve deposits.
The results showed the transesterication treatment decreased the injector coking to a level signicantly lower
than that observed with D2. Although most researchers agree that vegetable oil ester fuels are suitable for use
in CIE, a few contrary results have also been obtained. The results of these studies point out that most vegetable oil esters are suitable as Diesel substitutes, but that more long-term studies are necessary for commercial
utilization to become practical.
5.1. Alcoholdiesel emulsions
Because alcohols have limited solubility in Diesel, a stable emulsion must be formed that will allow it to be
injected before separation occurs. A hydro-shear emulsication unit can be used to produce emulsions of
Dieselalcohol. However, the emulsion can only remain stable for 45 s. In addition, 12% alcohol (energy basis)
is the maximum percentage. This kind of method has several problems, which are as follows: (a) specic fuel
consumption at low speed increases, (b) high cost and (c) instability. Therefore, other methods are developed.
5.2. Fumigation
Fumigation is a process of introducing alcohol into the Diesel engine (up to 50%) by means of a carburetor
in the inlet manifold. At the same time, the Diesel pump operates at a reduced ow. In this process, the Diesel
fuel is used for generating a pilot ame.
Alcohol is used as a fumigation fuel. At low loads, the quantity of alcohol must be reduced to prevent misre. On the other hand, at high loads, the quantity of alcohol must also be reduced to prevent pre-ignition.

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5.3. Dual injection

In dual injection systems, a small amount of Diesel is injected as a pilot fuel for the ignition source, and a
large amount of alcohol is injected as the main fuel. It must be noted that the pilot fuel must be injected prior
to injection of the alcohol. Some ideal results can be achieved when this method is used. The thermal eciency
is better. At the same time, the NOx emission is lower. Moreover, the CO emissions and HC emissions are the
same. However, the system requires two fuel pumps, thus, leading to a high cost. Meanwhile, alcohol needs
additives for lubricity.
5.4. Injector coking
A visual inspection of the injector types would indicate no dierence between the biodiesel fuels as compared with injectors tested on Diesel No. 2 fuel. The overall injector coking is considerably low. Linear regression is used to compare injector coking, viscosity, percent of esteried oil, total glycerol and heat of
combustion data with the others.
5.5. Heated surfaces
Alcohol can ignite with hot surfaces. For this reason, glow plugs can be utilized as a source of ignition for
alcohol. In this system, the specic fuel consumption depends on the glow plug positions and temperatures. It
must be noted that the temperature of the glow plugs must vary with load. However, the glow plug becomes
inecient at a high load. In addition, the specic fuel consumption is higher than that of Diesel.
5.6. Torque tests
The peak torque is less for the ester fuels than Diesel but occurs at lower engine speed, and generally, the
torque curves are atter. Testing includes the power and torque of the methyl esters and Diesel fuel and ethyl
esters versus Diesel fuel. The biodiesel fuels, on the average, decrease power by 5% compared to that of Diesel
fuel at rated load.
5.7. Spark ignition
When a spark plug is used, a Diesel engine can be converted to an Otto cycle engine. In this case, the compression ratio should be reduced, from 16:1 to 10.5:1. There are two types of such conversions. They are as
follows: (a) The original fuel injection system is maintained. Alcohol needs an additive for lubricity. Besides,
both a distributor and spark plugs need to be installed, thus leading to a high cost of conversion. It is critical
to adjust an ideal injection and spark timing for this kind of conversion. (b) The original fuel injection is eliminated, but a carburetor, spark plugs and a distributor need to be installed, which increases the cost of conversion. In this conversion, spark timing is critical.
6. Conclusion
Hundreds of scientic articles and various other reports from around the world dealing with biodiesel fuels
have appeared in print. They have advanced from being purely experimental fuels to the initial stages of commercialization. Nevertheless, various technical and economic aspects require further improvement of these
fuels.
A sustainable biofuel has two favorable properties, which are availability from renewable raw material and
its lower negative environmental impact than that of fossil fuels. Various vegetable oil extraction and transesterication technologies are currently used in the production of biodiesel fuel. As an alternative fuel, vegetable oil is one of the renewable fuels.
The parameters aecting the methyl esters formation are reaction temperature, pressure, molar ratio, water
content and free fatty acid content. It is evident that at a subcritical state of alcohol, the reaction rate is so low

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and gradually increases as either pressure or temperature rises. It was observed that increasing the reaction
temperature, especially to supercritical conditions, had a favorable inuence on the yield of ester conversion.
The yield of the alkyl ester increased with increasing the molar ratio of oil to alcohol. In the supercritical alcohol transesterication method, the yield of conversion increases to 5095% in the rst 10 min.
Water content is an important factor in the conventional catalytic transesterication of vegetable oil. In the
conventional transesterication of fats and vegetable oils for biodiesel production, free fatty acids and water
always produce negative eects since the presence of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst eectiveness. In catalyzed methods, the presence of water has negative
eects on the yields of methyl esters. However, the presence of water aected positively the formation of
methyl esters in our supercritical methanol method.
Viscosity is the most important property of biodiesel since it aects the operation of fuel injection equipment, particularly at low temperatures when the increase in viscosity aects the uidity of the fuel. Biodiesel
has a viscosity close to that of Diesel fuels. High viscosity leads to poorer atomization of the fuel spray and less
accurate operation of the fuel injectors. A novel process of biodiesel fuel production has been developed by a
non-catalytic supercritical methanol method.
The ash point values of vegetable oil methyl esters are much lower than those of vegetable oils. An
increase in density from 860 to 885 kg/m3 for vegetable oil methyl esters or biodiesels increases the viscosity
from 3.59 to 4.63 mm2/s, and the increases are highly regular.
Acknowledgment
This study was nancially supported by the Scientic Research Project (BAP in Turkish initials) of Selcuk
University.
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