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ENERGY EXPLORATION & EXPLOITATION Volume 25 Number 1 2007 pp. 6370 63

Thermal Degradation of Fatty Acids in Biodiesel

Production by Supercritical Methanol

Ayhan Demirbas
Sila Science, P. K. 216, TR-61035 Trabzon, Turkey

ABSTRACT
In this study, thermal degradation of the fatty acids of sunflower seed oil during
biodiesel production by supercritical methanol method was investigated. The
term biodiesel means the monoalkyl esters of long chain fatty acids made from
biolipids such as vegetable oils, animal fats, tall oil or algae oils. The oils and
fats contain polyunsaturated fatty acid chains that their double bonds have
highly chemical reactivity. The thermal degradation occurs on the double bonds
of unsaturated aliphatic carbons chains in fatty acids. Oxidation of biodiesel is
results in the formation of hydroperoxides. The formation of the hydroperoxide
follows a well known peroxidation chain mechanism. The olefinic unsaturated
fatty acid oxidation is a multi-step reaction process where primary products
decompose and chemically interact with each other to form numerous secondary
oxidation products. The content of linoleic acid in the sunflower seed oil is
72.4%, while the linoleic acid account for 62.5% of the total fatty acids in the
biodiesel. The proportion of the linoleic acid is lower in the biodiesel obtained
by supercritical methanol transesterfication method. The viscosity of biodiesel
increases with increasing of thermal degradation degree due to the trans isomer
formation on double bonds. The decomposition of biodiesel and its
corresponding fatty acids linearly increases from 293 K to 625 K. The densities
of biodiesel fuels decreased linearly with temperature from 293 K to 575 K. The
combustion heat of biodiesel partially decreases with increasing of thermal
degradation degree.

Keywords: Biodiesel, thermal degradation, oxidation, fatty acids

I. INTRODUCTION
Biodiesel is monoalkyl esters of long chain fatty acids made from biolipids such as
vegetable oils, animal fats or algae and can be used in Diesel engines.

Address correspondence to Professor Ayhan Demirbas, P. K. 216, TR 61035 Trabzon, Turkey.

E-mail: ayhandemirbas@hotmail.com
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64 Thermal Degradation of Fatty Acids in Biodiesel Production by Supercritical Methanol

Biodiesel is an alternative fuel from renewable sources and reduces the emission of
some pollutants. Biodiesel is an efficient, clean, 100 per cent natural energy alternative
to petroleum fuels. Among the many advantages of biodiesel fuel include the
following: safe for use in all conventional diesel engines, offers the same performance
and engine durability as petroleum diesel fuel, non-flammable and non-toxic, reduces
tailpipe emissions, visible smoke and noxious fumes and odors. Biodiesel is better than
diesel fuel in terms of sulfur content, flash point, aromatic content and biodegradability
[1].
The properties of biodiesel are close to diesel fuels. The biodiesel was characterised
by determining its viscosity, density, cetane number, cloud and pour points,
characteristics of distillation, flash and combustion points and higher heating value
(HHV). One of the most important characteristics of diesel fuel is its ability to
autoignite, a characteristic that is quantified by a fuels cetane number or cetane index,
where a higher cetane number or index means that the fuel ignites more quickly. Some
fuel properties of methyl ester biodiesls are presented in Table 1.

Table 1. Fuel properties of methyl ester biodiesels

Source Viscosity Density Cetane Reference

cSt at 313.2 K g/mL at 288.7 K Number number
Sunflower 4.6 0.880 49 [11]
Soybean 4.1 0.884 46 [12]
Palm 5.7 0.880 62 [11]
Peanut 4.9 0.876 54 [13]
Babassu 3.6 - 63 [13]
Tallow 4.1 0.877 58 [14]

Viscosity is the most important property of biodiesel since it affects the operation of
fuel injection equipment, particularly at low temperatures when the increase in
viscosity affects the fluidity of the fuel. Biodiesel has viscosity close to diesel fuels.
High viscosity leads to poorer atomization of the fuel spray and less accurate operation
of the fuel injectors. The viscosities of biodiesel fuels are twice that of No. 2 Diesel
fuel.
Density is another important property of biodiesel. It is the weight of a unit volume
of fluid. Specific gravity is the ratio of the density of a liquid to the density of water.
Specific gravity of biodiesels ranges between 0.87 and 0.89 (Table 1).
Cetane number (CN) is based on two compounds, namely hexadecane with a Cetane
of 100 and heptamethylnonane with a Cetane 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 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 ignition
quality of diesel fuels and high CN implies short ignition delay.
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ENERGY EXPLORATION & EXPLOITATION Volume 25 Number 1 2007 65

Two important parameters for low temperature applications of a fuel are Cloud
Point (CP) and Pour Point (PP). The "cloud point" is the temperature at which a sample
of the fuel starts to appear cloudy, indicating that wax crystals have begun to form. At
even lower temperatures, diesel fuel becomes a gel that cannot be pumped. The "pour
point" is the temperature below which the fuel will not flow. The cloud and pour points
for biodiesel are higher than those for petroleum diesel. The CP is the temperature at
which wax first becomes visible when the fuel is cooled. The PP is the temperature at
which the amount of wax out of solution is sufficient to gel the fuel, thus it is the lowest
temperature at which the fuel can flow. Biodiesel has higher CP and PP compared to
conventional diesel [2].
The higher heating values of the biodiesel fuels, on a mass basis, are 9% to 13%
lower than D2. Table 2 shows the comparisons of properties of vegetable oils and their
esters with diesel fuel [3].

Table 2. Comparisons of properties of vegetable oils and their esters with diesel
fuel

Fuel type Caloricfic value Density Viscosity at 300 K Cetane

(MJ/kg) (kg/m3) (mm2 /s) number
Diesel fuel 43.4 815 4.3 47.0
Sunflower oil 39.5 918 58.5 37.1
Sunflower methyl ester 40.6 878 10.3 45.5
Cotton seed oil 39.6 912 50.1 48.1
Cotton seed methyl ester 40.6 874 11.1 45.5
Soybean oil 39.6 914 65.4 38.0
Soybean methyl ester 39.8 872 11.1 37.0
Corn oil 37.8 915 46.3 37.6
Opium poppy oil 38.9 921 56.1
Rapeseed oil 37.6 914 39.2 37.6
Source: Ref. [3].

Biodiesel fuels have generally been found to be nontoxic and are biodegradable, which
may promote their use in applications where biodegradability is desired. Neat biodiesel
and biodiesel blends reduce particulate matter (PM), hydrocarbons (HC) and carbon
monoxide (CO) emissions and increase nitrogen oxides (NOx) emissions compared
with petroleum-based diesel fuel used in an unmodified diesel engine (EPA, 2002).
The emission impacts of 20 vol% biodiesel for soybean-based biodiesel added to an
average base diesel fuel are given in Table 3.
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66 Thermal Degradation of Fatty Acids in Biodiesel Production by Supercritical Methanol

Table 3. Emission impacts of 20 vol% biodiesel for soybeanbased biodiesel

added to an average base diesel fuel

Emissions Percent change in emissions

NOx (nitrogen oxides) +2.0
PM (particular matter) 10.1
HC (hydrocarbons) 21.1
CO (carbon monoxide) 11.0
Source: Ref. [15].

II. EXPERIMENTAL
Sunflower seed oil samples used in this study were supplied from Turkish vegetable
sources. Methanol was purchased from Merck and purified prior to use. The pure fatty
acid (palmitic, stearic, palmitoleic, oleic and linoleic) samples were supplied from
Merck and Fluka.
The supercitical methanol (SC MeOH) transesrterification system employed in this
work is shown in Fig. 1. All the runs of SFE were performed in a 100-mL cylindrical
autoclave made of 316 stainless steel in which the pressure and temperature was
monitored in a real time, covering up 100 MPa and 850 K, respectively. The sample
was loaded from the bolt hole into the autoclave, and the hole was plugged with a
screw bolt after each run. In a typical run, the autoclave was charged with a given
amount of vegetable oil (20-30 g) and liquid methanol (30-50 g) with changed molar
ratios [4].

Figure 1. Supercritical methanol transesterification system. 1. Autoclave, 2. Electrical

furnace, 3. Temperature control monitor, 4. Pressure control monitor, 5. Product exit
valve, 6. Condenser, 7. Product collecting vessel.
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ENERGY EXPLORATION & EXPLOITATION Volume 25 Number 1 2007 67

The autoclave was supplied with heat from an external heater, and power was
adjusted to give an approximate heating time of 20 min. The temperature of the
reaction vessel was measured with an iron-constantan thermocouple. After each run,
the gas was vented, and the autoclave was poured into a collecting vessel. All the rest
of the contents were removed from the autoclave by washing with methanol.
The methyl esters of the fatty acids were analyzed by GC (Hewlett-Packard 5790)
on a 12 m 0.2 mm capillary column coated with Carbowax PEG 20.

III. RESULTS AND DISCUSSION

The chemical compositions of fatty acids of sunflower seed oil and biodiesel are
presented in Table 4. The content of linoleic acid in the sunflower seed oil is 72.4%,
while the linoleic acid account for 62.5% of the total fatty acids in the biodiesel. The
proportion of the linoleic acid is lower in the biodiesel obtained by supercritical
methanol transesterfication method. Partial degradation of the linoleic acid may be
occurred in the supercritical methanol transesterification due to high temperature
(<513 K). The high temperature had a much greater effect on the linoleic acid, as a
polyunsaturated fatty acid, than saturated and mono saturated fatty acids.

Table 4. Chemical compositions of fatty acids in sunflower seed oil and biodiesel
by supercritical methanol method

Fatty acid, as methyl ester Vegetable oil Biodiesel

Myristic (14:0) 0.1 0.1
Palmitic (16:0) 6.7 8.1
Stearic (18:0) 2.9 3.7
Oleic (9c18:1) 17.7 25.4
Linoleic (9c, 12c18:2) 72.4 62.5
Others 0.2 0.2

Many of the vegetable oils contain polyunsaturated fatty acid chains that are
methylene-interrupted rather than conjugated. The double bond of unsaturated fatty
acids restricts rotation of the hydrogen atoms attached to them. Therefore an
unsaturated fatty acid with a double bond can exist in two forms. The cis form in which
the two hydrogens are on the same "side" and the trans form in which the hydrogen
atoms are on the opposite sides.
Trans unsaturated fatty acids, or trans fats, are solid fats produced artificially by
heating liquid vegetable oils in the presence of metal catalysts and hydrogen. This
process, partial hydrogenation, causes carbon atoms to bond in a straight configuration
and remain in a solid state at room temperature [5].
Viscosity is one of the most important fuel properties. The effects of viscosity can
be seen in the quality of atomization and combustion as well as engine wear. The
quality of fuel atomization is significantly affected by viscosity [6]. The viscosity of
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68 Thermal Degradation of Fatty Acids in Biodiesel Production by Supercritical Methanol

biodiesel increases with increasing of thermal degradation degree due to the trans
isomer formation on double bonds. The decomposition of biodiesel and its
corresponding fatty acids linearly increases from 293 K to 625 K. The densities of
biodiesel fuels decreased linearly with temperature from 293 K to 575 K [7]. The
combustion heat of biodiesel decreases with increasing of thermal degradation degree
[8].
Physical properties that are sensitive to the effects of fatty oil oxidation include
viscosity, refractive index, and di-electric constant. Fig. 2 show the mechanism of
peroxy radical formation on methylene group. In oxidative instability, the methylene
group (- CH2-) carbons between the olefinic carbons are the sites of first attack [9].

Figure 2. Mechanism of peroxy radical formation on methylene group.

Oxidation of biodiesel is results in the formation of hydroperoxides. The formation of

the hydroperoxide follows a well known peroxidation chain mechanism. Oxidative
lipid modifications occur through lipid peroxidation mechanisms in which free radicals
and reactive oxygen species abstract a methylene hydrogen atom from polyunsaturated
fatty acids, producing a carbon-centered lipid radical. Spontaneous rearrangement of
the 1,4-pentadiene yields a conjugated diene, which reacts with molecular oxygen to
form a lipid peroxyl radical. Abstraction of a proton from neighboring polyunsaturated
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ENERGY EXPLORATION & EXPLOITATION Volume 25 Number 1 2007 69

fatty acids produces a lipid hydroperoxide (LOOH) and regeneration of a carbon-

centered lipid radical, thereby propagating the radical reaction [10]. After hydrogen is
removed from such carbons oxygen rapidly attacks and a LOOH is ultimately formed
where the polyunsaturation has been isomerized to include a conjugated diene. This
reaction is a chain mechanism that can proceed rapidly once an initial induction period
has occurred. The greater the level of unsaturation in a fatty oil or ester, the more
susceptible it will be to oxidation. Once the LOOHs have formed, they decompose and
inter-react to form numerous secondary oxidation products including higher molecular
weight oligomers often called polymers.

IV. CONCLUSION
Thermal degradation of the fatty acids of sunflower seed oil during biodiesel
production by supercritical methanol method was investigated in this work.
The thermal degradation occurs on the double bonds of unsaturated aliphatic
carbons chains in biolipids. Oxidation of biodiesel is results in the formation of
hydroperoxides. Many of the biolipids contain polyunsaturated fatty acid chains that
their double bonds have highly chemical reactivity.
The viscosity of biodiesel increases with increasing of thermal degradation degree
due to the trans isomer formation on double bonds. The decomposition of biodiesel
linearly increases with increasing of temperature. The densities of biodiesel fuels
decreased linearly with increasing of temperature. The combustion heat of biodiesel
decreases with increasing of thermal degradation degree.

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