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New Options for Conversion of Vegetable Oils to

Alternative Fuels
a a
Ayhan Demirbaş & Huseyin Kara
a
Department of Chemical Engineering , Selcuk University , Konya, Turkey
Published online: 16 Aug 2006.

To cite this article: Ayhan Demirbaş & Huseyin Kara (2006) New Options for Conversion of Vegetable Oils to Alternative Fuels,
Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 28:7, 619-626, DOI: 10.1080/009083190951357

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 Energy Sources, Part A, 28:619–626, 2006
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/009083190951357

New Options for Conversion of Vegetable Oils to

Alternative Fuels

AYHAN DEMIRBAŞ
HUSEYIN KARA
Department of Chemical Engineering
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Selcuk University
Konya, Turkey

Biodiesel from transesterification of vegetable oils is an excellent alternative fuel.

There is, however, a need to develop a direct process for conversion of vegetable
oils into gasoline-competitive biodiesel and other petroleum products. Methyl esters
of vegetable oils have several outstanding advantages among other new-renewable
and clean engine fuel alternatives. The purpose of the transesterification process is to
lower the viscosity of vegetable oil. Compared to No. 2 diesel fuel, all of the vegetable
oils are much more viscous, whereas methyl esters of vegetable oils are slightly more
viscous. The methyl esters are more volatile than those of the vegetable oils. Con-
version of vegetable oils to useful fuels involves the pyrolysis and catalytic cracking
of the oils into lower molecular products. Pyrolysis produces more biogasoline than
biodiesel fuel. Soap pyrolysis products of vegetable oils can be used as alternative
diesel engine fuel. The soaps obtained from the vegetable oils can be pyrolyzed into
hydrocarbon-rich products. Zinc chloride catalyst contributed greatly to high amounts
of hydrocarbons in the liquid product. The yield of ZnCl2 catalytic conversion of the
soybean oil reached the maximum 79.9% at 660 K.
Keywords vegetable oil, biodiesel, biogasoline, pyrolysis, catalytic conversion

Vegetable oils contain up to three fatty acids and are linked to a glycerin molecule
with ester linkages called a triglyceride. The fatty acids are similar in their carbon chain
length and in numbers of double bonds. There was little difference between the gross heat
content of any of the vegetable oils (Demirbaş, 1998). Heat contents were approximately
88% of that of No. 2 diesel.
Vegetable oils can be used as fuels for diesel engines, but their viscosities are much
higher than usual diesel fuel and require modifications of the engines (Kerschbaum and
Rinke, 2004). Therefore, vegetable oils are converted into biodiesel by transesterification.
Technical aspects of biodiesel are approached, such as physical and chemical characteris-
tics of methyl esters, related to its performance in compression ignition engines (Saucedo,
2001).
Biodiesel, defined as the monoalkyl esters of fatty acids derived from vegetable
oil or animal fat, in application as an extender for combustion in compression ignition
(diesel) engines (CIEs) has demonstrated a number of promising characteristics, including

This study has been supported by Scientific Research Project (BAP in Turkish initials) of
Selcuk University.
Address correspondence to Prof. Ayhan Demirbaş, Selcuk University, Department of Chemical
Engineering, 42031 Konya, Turkey. E-mail: ayhandemirbas@hotmail.com

619
 620 A. Demirbaş and H. Kara

reduction of exhaust emissions (Dunn, 2001). Transesterified, renewable oils have proven
to be a viable alternative diesel engine fuel with characteristics similar to those of diesel
fuel. Biodiesel fuels have become more attractive recently because of their environmental
benefits and the fact that they are made from renewable resources (Ma and Hanna, 1999).
Diesel boiling range material is of particular interest because it has been shown to reduce
particulate emissions significantly relative to petroleum diesel (Giannelos et al., 2002).
They are biodegradable, nontoxic, and show low emission during combustion. There
are, however, some disadvantages. Biodiesel fuels are not petroleum-competitive fuels,
because they are more expensive than normal diesel fuel and are often only competitive
because they are tax-favored.
There are more than 350 oil-bearing crops identified, among which only sunflower,
safflower, soybean, cottonseed, rapeseed, and peanut oils are considered as potential alter-
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native fuels for diesel engines (Goering et al., 1982; Pryor et al., 1982). The advantages
of vegetable oils as diesel fuel are liquid nature-portability, ready availability, renewabil-
ity, biodegradability, higher heat content (about 88% of D2 fuel), lower sulfur content,
and lower aromatic content. The disadvantages of vegetable oils as diesel fuel are higher
viscosity, lower volatility, and the reactivity of unsaturated hydrocarbon chains.

Oil Refining Processes

Crude oils obtained by oil seed processes have to be refined to remove undesirable ac-
companying substances. The typical oil refining process includes degumming, chemical
or physical refining, bleaching, vinterization, and deodorization. Deodorization is an im-
portant step in the oil refining process. During this step, steam at 1–6 mm Hg pressure
is injected into the oil at 490–550 K in order to eliminate free fatty acids, aldehydes,
unsaturated hydrocarbons, and ketones, which cause undesirable odors and flavors in
the oil.
The traditional alkaline refining is often replaced by physical refining in which
the use of chemicals is reduced. The most widely used method is steam refining. The
crude oil quality is very important to obtain high quality refined oil. Furthermore, the
oil should be efficiently degummed to remove phospholipids as well as heavy metals
and bleached to remove pigments and metals. Degumming provides the advantages of
producing lecithin and reducing the phosphatide, and decreasing load in caustic refining.
If physical refining is subsequently employed, it is essential to degum oils which have
high phosphatide content for both economic and product quality purposes.
The purpose of caustic refining is to remove free fatty acids, phosphatides, and other
materials, including protein meal, glycerol, carbohydrates, resins and metals. In addition,
some color reduction (pigment removal) is also achieved.
Degummed crude oil is fed to the refining process. Caustic soda (sodium hydroxide)
is fed in the proper strength and quantity to react with the free fatty acids and phosphatides
to form soap stock and is effective in removing some of the other impurities from the
oil stream. Soap stock and other impurities are separated from the oil by centrifuges.
Caustic soda is not completely selective in reacting with the targets of free fatty acid and
phosphatides, therefore, some triglycerides are hydrolyzed and saponified (broken down
and converted to soap).

Experimental
The vegetable oils from sunflower seed, corn, cottonseed, and soybean used in this study
were supplied from different Turkish vegetal sources.
 Conversion of Vegetable Oils to Alternative Fuels 621

Biodiesels are obtained from vegetable oils by alkali catalytic and supercritical
methanol transesterification processes (Demirbaş, 2002, 2003). Biodiesel was synthe-
sized in supercritical methanol. Refined edible vegetable oils were used for the reactions
(Madras et al., 2004). The supercritical methanol transesterification was carried out in an
autoclave in which the pressure and temperature were monitored in real time, covering
up 100 MPa and 850 K, respectively. In a typical run, the autoclave was charged with a
given amount of vegetable oil and liquid methanol with changed molar ratios.
Pyrolysis of the vegetable oils and their soaps were performed in an apparatus de-
signed for this purpose. The main element of this device was a tubular reactor of height
95.1 mm, ID 17.0 mm, and OD 19.0 mm, inserted vertically into an electrically heated
tubular furnace. A similar pyrolysis apparatus was illustrated in the earlier study (Akdeniz
et al., 1998).
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Biodiesel from transesterification of vegetable oils is an excellent alternative fuel,

yet biodiesel fuels were not acceptable because they were more expensive than petroleum
fuels. There is a need to develop a direct process for conversion of vegetable oil into
gasoline-competitive biodiesel and other petroleum products. Catalytic conversion of the
vegetable oil samples were carried out at 610–690 K. Zinc chloride was used as catalyst
in catalytic cracking experiments.

Results and Discussion

Table 1 indicates the fatty acid compositions of the vegetable oils. Palmitic (16:0) and
stearic (18:0) were the most common saturated fatty acids, with every vegetable oil
containing at least a small amount of each one. Similarly, oleic (18:1) was the most
common monounsaturated fatty acid. All of the vegetable oils contained highly linoleic
acid (18:2).
Figure 1 shows the distillation curves for sunflower oil, corn oil, cottonseed oil, and
soybean oil. The yield of distillation from the oil sample reached the maximum 77.8% for
sunflower oil and 83.4% for soybean oil at 630 K. Preliminary data indicate a complex
mixture of products including alkanes, alkenes, and carboxylic compounds (Goering
et al., 1982). Typically, it was not possible to distill all of the vegetable oil and some
brownish residue remained in the distillation flask. The value for the induction period
of the distilled product was very low. The induction period values for the undistilled
samples decreased very rapidly during storage, especially with exposure to light and air
(Mittelbach and Gangl, 2001).
Figure 2 shows the distillation curves of vegetable oil methyl esters. The yield of
distillation from the methyl sample reached the maximum 96.8% for sunflower oil and
97.9% for soybean oil at 640 K.

Table 1
Fatty acid compositions of vegetable oil samples

Oil sample 16:0 16:1 18:0 18:1 18:2 18:3 Others

Cottonseed 28.7 0 0.9 13.0 57.4 0 0

Sunflower seed 6.4 0.1 2.9 17.7 72.9 0 0
Corn 11.8 0 2.0 24.8 61.3 0 0.3
Soybean 13.9 0.3 2.1 23.2 56.2 4.3 0
Source: Demirbaş, 1998.
 622 A. Demirbaş and H. Kara
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Figure 1. Distillation curves for vegetable oils.

Viscosities of vegetable oils and their methyl esters are given in Figure 3. Viscosity
of No. 2 diesel fuel is 2.7 mm2 /s at 311 K. The vegetable oils were all extremely viscous
with viscosities ranging 10 to 20 times greater than No. 2 diesel fuel. The major problem
associated with the use of pure vegetable oils as fuels diesel engines is caused by high
fuel viscosity in compression ignition.
The yields of decarboxylation products by pyrolysis from vegetable oil soaps are
given in Figure 4. In 1947, a large scale of thermal cracking of tung oil calcium soap was
reported (Chand and Wan, 1947). Tung oil was saponified with lime and then thermally
cracked to yield a crude oil, which was refined to produce diesel fuel and small amounts
of gasoline and kerosene. Sixty-eight kg of the tung oil soap produced 50 L of crude oil.
The maximum decarboxylation products of pyrolyses were 96.8, 97.1, 97.5, and 97.8%,

Figure 2. Distillation curves of vegetable oil methyl esters.

 Conversion of Vegetable Oils to Alternative Fuels 623
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Figure 3. Viscosities of vegetable oils and their methyl esters (mm2 /s) at 311 K.

respectively, from sunflower oil, corn oil, cottonseed oil, and soybean oil at 610 K,
respectively. Oxidative pyrolysis of Na-soaps is given as following reaction:

4RCOONa + O2 → 2R-R + 2Na2 CO3 + 2CO2 . (1)

The soaps obtained from the vegetable oils can be pyrolyzed into hydrocarbon-rich prod-
ucts according to Eq. (1) with higher yields at lower temperatures. These findings are in
general agreement with results given in the literature (Barsic and Humke, 1981).
The yields of liquid products from the conversion of vegetable oils over ZnCl2
catalyst are given in Figure 5. As can be seen in Figure 5, the conversion yields of the
oils increased with increase in reaction temperature up to 660 K. The yield of conversion
of the soybean oil reached the maximum 79.9% at 660 K. The decrease in yield of

Figure 4. Yields of decarboxylation products by pyrolysis from vegetable oil soaps.

 624 A. Demirbaş and H. Kara
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Figure 5. Yields of liquid products from the conversion of vegetable oils over ZnCl2 catalyst.

conversion could probably be due to the coke and gas formation at the higher reaction
temperatures. As more coke was deposited on the catalyst’s surface, the effect of cracking
reduced. Formation gasoline range hydrocarbons reached a maximum, 35.8% of converted
material, at 660 K. Formation of aromatic and gas oil-range hydrocarbons showed a
similar trend (Demirbaş, 2003).
The yields of pyrolysis products of soybean oil are given in Table 2. The pyrolysis
of aliphatic long chain compounds, particularly when petroleum is concerned, is known
as cracking. In thermal cracking alkanes are simply passed through a chamber heated to
a high temperature. Large alkanes are converted into smaller alkanes, alkenes, and some
hydrogen.

Table 2
Yields of pyrolysis products of soybean oil
(percent by weight)

N2 sparge Air

Alkanes 31.1 29.9

Alkenes 28.3 24.9
Alkadienes 9.4 10.9
Carboxylic acids 12.2 9.6
Unresolved unsaturates 5.5 5.1
Aromatics 2.3 1.9
Unidentified 10.9 12.6
Sources: Ma and Hanna, 1999; Scwab et al., 1988;
Alencar et al., 1983.
 Conversion of Vegetable Oils to Alternative Fuels 625

Table 3
Yields of liquid products from the conversion of sunflower oil over ZnCl2 catalyst

Temperature (K) 610 630 650 660 670 690

Conversion, wt% of SFO 35.6 60.7 71.5 78.3 74.9 68.4

Gaseous product, wt% 3.4 5.1 6.4 7.0 8.9 10.6
Aromatic content, wt% 8.5 9.3 9.0 9.6 8.2 8.8
Gasoline content, wt% 28.6 30.4 29.4 35.8 32.7 29.3
Gas oil content, wt% 6.6 7.3 8.4 10.7 8.6 7.9
Coke residue, wt% 0.2 0.3 0.4 0.5 2.4 6.8
Water formation, wt% 3.4 3.7 4.1 4.5 4.1 3.8
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Unidentified, wt% 49.3 43.9 42.3 31.9 35.1 32.8

Source: Demirbaş, 2003.

The yields of liquid products from the conversion of sunflower oil over ZnCl2 catalyst
are given in Table 3. Conversion of vegetable oils to useful fuels involves the cracking
of the oils into lower molecular products. For this purpose different catalysts like silica-
alumina and zeolite were used (Pioch et al., 1993). It was found that conversion of
palm and copra oil was 84 wt% and 74 wt%, respectively; however, the production
of gaseous product was high, in the range of 33 to 35 wt%. Silica-alumina catalyst was
highly selective for obtaining aliphatic hydrocarbons, mainly in the kerosene boiling point
range (Katikaneni et al., 1995). The organic liquid product obtained with silica-alumina
contained between 4 to 31 wt% aliphatic hydrocarbons and 14 to 58 wt% aromatic
hydrocarbons. The conversion was high and ranged between 81 and 99 wt%. Silica-
alumina catalysts are suitable for converting vegetable oils to aliphatic hydrocarbons.
The catalyst acidity and pore size affect the formation of aromatic and aliphatic
hydrocarbons. Hydrogen transfer reactions, which are essential for hydrocarbon forma-
tion, are known to increase with catalyst acidity. High acid density of ZnCl2 , as a Lewis
acid, catalyst contributed greatly to high amounts of hydrocarbons in the liquid product.
The hydrocarbon formation can be identified as deoxygenation, cracking, and aromatiza-
tion with H-transfer. Deoxygenation can take place via decarboxylation and dehydration
(Chang and Silvestri, 1977).
The vegetable oil was converted to hydrocarbons using a shape-selective zeolite
catalyst (Leng et al., 1999). The oil can be converted to aromatics and hydrocarbons
in the gasoline, diesel, and kerosene range, light gases, coke, and water with a yield
of 70 wt%. The maximum yield of gasoline-range hydrocarbons was 40 wt% of total
product.

Conclusion
Vegetable oils can be converted to a maximum of liquid and gaseous hydrocarbons by
transesterification, decarboxylation, deoxygenation, and catalytic cracking processes.
Vegetable oils can be used as fuels for diesel engines, but their viscosities are much
higher than usual diesel fuel and require modifications of the engines. The vegetable
oil fuels have not been acceptable because they were more expensive than petroleum
fuels. With recent increases in petroleum prices and uncertainties concerning petroleum
availability, there is renewed interest in vegetable oil fuels for diesel engines. Methyl
 626 A. Demirbaş and H. Kara

esters (biodiesel) of vegetable oils have several outstanding advantages among other
new-renewable, efficient, clean and 100% natural energy alternatives to petroleum fuels.
Pyrolysis produces more biogasoline than biodiesel fuel. Soap pyrolysis (decarboxy-
lation) products of vegetable oils can be used as alternative diesel engine fuel. The
maximum decarboxylation products of pyrolyses were 96.8, 97.1, 97.5, and 97.8% from
sunflower oil, corn oil, cottonseed oil and soybean oil at 610 K, respectively.
The conversion of vegetable oils can be carried out over ZnCl2 catalyst, and the
conversion yields of the oils increased with increase in reaction temperature up to 660 K.
The yield of conversion of the soybean oil reached the maximum 79.9% at 660 K.

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