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Energy Sources, Part A: Recovery, Utilization, and

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Biodiesel Production Facilities from Vegetable Oils and

Animal Fats
a b
A. Demirbas & S. Karslioglu
a
Department of Chemical Engineering, Selcuk University, Konya, Turkey
b
Department of Chemistry, Karadeniz Technical University, Trabzon, Turkey
Published online: 23 Feb 2007.

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 Energy Sources, Part A, 29:133–141, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1556-7036 print/1556-7230 online
DOI: 10.1080/009083190951320

Biodiesel Production Facilities from

Vegetable Oils and Animal Fats

A. DEMIRBAS
Department of Chemical Engineering
Selcuk University
Konya, Turkey
Downloaded by [Florida State University] at 12:32 13 May 2013

S. KARSLIOGLU
Department of Chemistry
Karadeniz Technical University
Trabzon, Turkey

Abstract Biodiesel is a renewable fuel that can be produced from vegetable oils,
animal fats, and used cooking oil including triglycerides. Biodiesel, an alternative
biodegradable diesel fuel, is derived from triglycerides by transesterification with
methanol and ethanol. Concerns about the depletion of diesel fuel reserves and the
pollution caused by continuously increasing energy demands make biodiesel an attrac-
tive alternative motor fuel for compression ignition engines. There are four different
ways of modifying vegetable oils and fats to use them as diesel fuel, such as pyrolysis
(thermal cracking), dilution with hydrocarbons (blending), emulsification and trans-
esterification. The most commonly used process is transesterification of vegetable oils
and animal fats. The transesterification reaction is affected by molar ratio of glyc-
erides to alcohol, catalysts, reaction temperature, reaction time and free fatty acids
and water content of oils or fats. In the transesterification, free fatty acids and wa-
ter always produce negative effects, since the presence of free fatty acids and water
causes soap formation, consumes catalyst and reduces catalyst effectiveness, all of
which result in a low conversion. Biodiesel has over double the price of diesel. The
high price of biodiesel is in large part due to the high price of the feedstock.

Keywords biodiesel, fat, supercritical alcohol, transesterification, vegetable oil

Introduction
Biodiesel has been defined as the monoalkyl esters of long-chain fatty acids derived
from renewable feedstocks, such as vegetable oils or animal fats, for use in compression-
ignition (diesel) engines (Krawczyk, 1996). Recently, biodiesel has become more attrac-
tive because of its environmental benefits and the fact that it is made from renewable
resources (Ma and Hanna, 1999). Different ways of modifying vegetable oils and fats
to use them as diesel fuel, such as direct use, pyrolysis, dilution with hydrocarbons and
emulsification, have been considered. Direct use of vegetable oils and the use of blends

Address correspondence to Professor Ayhan Demirbas, Selcuk University, Muh. Mim. Faculty,
Department of Chemical Engineering, Campus, 42031 Konya, Turkey. E-mail: ayhandemirbas@
hotmail.com

133
 134 A. Demirbas and S. Karslioglu

of oils have several problems (Demirbas, 2003). Pyrolysis, defined as the cleavage to
smaller molecules by thermal energy, of vegetable oils over petroleum catalysts, has
been investigated (Ziejewski et al., 1983; Bhatia, 2004). Emulsification with alcohols
has been prepared to overcome the problem of high viscosity of vegetable oils (Madras
et al., 2004). The transesterfication of triglycerides by methanol, ethanol, propanol and
butanol has proved to be the most promising process (Gryglewicz, 1999). Table 1 shows
critical temperatures and critical pressures of various alcohols. Biodiesel, an alternative
diesel fuel, is made from renewable biological sources such as vegetable oils and ani-
mal fats by catalytic and non-catalytic supercritical alcohol transesterification methods
(Demirbas, 2002a, 2003). A non-catalytic biodiesel production route with supercritical
methanol has been developed that allows a simple process and high yield because of
simultaneous transesterification of triglycerides and methyl esterification of fatty acids
(Demirbas, 2002b). Because of having similar properties to petroleum based diesel fuel,
biodiesel, a transesterified product of vegetable oil, is considered as the most promising
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for diesel fuel substitute.

Several common vegetable oils, such as sunflower, palm, rapeseed, soybean, cotton-
seed and corn oils, and their fatty acids can be used as the sample of vegetable oil.
Biodiesel is easier to produce and cleaner with equivalent amounts of processing when
starting with clean vegetable oil. The tallow, lard and yellow grease biodiesels need
additional processing at the end of transesterification due to including high free fatty
acid. Diesel derived from rapeseed oil is the most common biodiesel available in Europe,
while soybean biodiesel is dominant in the United States. Table 2 shows the global
production of vegetable oils.
Biodiesel is generally made of methyl esters of fatty acids produced by the trans-
esterification reaction of triglycerides with methanol with the help of a catalyst (Clark
et al., 1984). Methanol is a relatively inexpensive alcohol and it has small molecular
mass. A reaction mechanism of vegetable oil in supercritical methanol was proposed
based on the mechanism developed by Krammer and Vogel (2000) for the hydrolysis of
esters in sub/supercritical water. The basic idea of supercritical treatment is a relationship
between pressure and temperature upon thermophysical properties of the solvent such as
dielectric constant, viscosity, specific weight, and polarity (Kusdiana and Saka, 2001).
In the conventional transesterification of animal fats and vegetable oils for biodiesel
production, free fatty acids and water always produced negative effects since the presence
of free fatty acids and water causes soap formation, consumes catalyst and reduces catalyst
effectiveness, all of which result in a low conversion (Komers et al., 2001).

Table 1
Critical temperatures and critical
pressures of various alcohols

Critical Critical
temperature pressure
Alcohol (K) (MPa)

Methanol 512.2 8.1

Ethanol 516.2 6.4
1-Propanol 537.2 5.1
1-Butanol 560.2 4.9
 Biodiesel from Vegetable Oils 135

Table 2
Global production of
vegetable oils

Vegetable Production in
oil million tons

Soybean 12.0
Palm 10.0
Rapeseed 8.5
Sunflower 7.0
Cottonseed 5.0
Peanut 3.5
Coconut 2.6
Olive 1.6
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Linseed 0.5
Other 10.9
Total 61.6
Source: Prakash, 1998.

Mechanism of Transesterification
Transesterification consists of a number of consecutive, reversible reactions (Schwab
et al., 1987; Freedman et al., 1986). The triglyceride is converted stepwise to diglyceride,
monoglyceride and finally glycerol (Eqs. (2)–(4)), in which 1 mol of alkyl esters is
removed in each step. The reaction mechanism for alkali-catalyzed transesterification
was formulated as three steps (Eckey, 1956; Sridharan and Mathai, 1974). The formation
of alkyl esters from monoglycerides is believed as a step that determines the reaction
rate, since monoglycerides are the most stable intermediate compound (Ma and Hanna,
1999).

Fatty acid (R1 COOH) + Alcohol (ROH)
Ester (R1 COOR) + Water (H2 O) (1)

Triglyceride + ROH
Diglyceride + RCOOR1 (2)

Diglyceride + ROH
Monoglyceride + RCOOR2 (3)

Monoglyceride + ROH
Glycerol + RCOOR3 (4)

Fuel Properties of Biodiesels

The properties of biodiesel are close to diesel fuels. The biodiesel was characterized by
determining its viscosity, density, cetane number, cloud and pour points, characteristics
of distillation, flash and combustion points, and higher heating value (HHV) according
to ISO norms (Encinar et al., 2002). Some fuel properties of methyl ester biodiesls are
presented in Table 3.
Viscosity is the most important property of biodiesel since it affects the opera-
tion 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.
 136 A. Demirbas and S. Karslioglu

Table 3
Fuel properties of methyl ester biodiesels

Viscosity Density Cetane

Source (g/mL at 288.7 K) (cSt at 313.2 K) number Reference

Sunflower 4.6 0.880 49 Pischinger et al., 1982

Soybean 4.1 0.884 46 Schwab et al., 1987
Palm 5.7 0.880 62 Pischinger et al., 1982
Peanut 4.9 0.876 54 Srivastava and Prasad, 2000
Babassu 3.6 — 63 Srivastava and Prasad, 2000
Tallow 4.1 0.877 58 Ali et al., 1985

High viscosity leads to poorer atomization of the fuel spray and less accurate operation
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of the fuel injectors. A novel process of biodiesel fuel production has been developed
by a non-catalytic supercritical methanol method. Table 4 summarizes the superiority
of supercritical methanol process over the commercial catalyzed method. The supercrit-
ical methanol process is non-catalytic, has simpler purification, lower reaction time, and
lower energy use. Therefore, the supercritical methanol method would be more effective
and efficient than the common commercial process (Kusdiana and Saka, 2001; Saka and
Kusdiana, 2001). The conversion of triglycerides into methyl or ethyl esters through the
transesterification process reduces the molecular weight to one-third that of the triglyc-
eride reduces the viscosity by a factor of about eight. Viscosities show the same trends
as temperatures, with the lard and tallow biodiesels higher than the soybean and rapeseed
biodiesels.
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 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.

Table 4
Comparisons between catalytic commercial methanol (MeOH) process and supercritical
methanol (MeOH) method for biodiesel from vegetable oils by transesterification

Catalytic Supercritical
MeOH process MeOH method

Methylating agent Methanol Methanol

Catalyst Acid or alkali None
Reaction temperature (K) 303–338 523–573
Reaction pressure (MPa) 0.1 10–25
Reaction time (min) 60–360 6–15
Methyl ester yield (wt%) 97 98
Removal for purification Methanol, catalyst, saponified Methanol
products
Free fatty acids Saponified products Methyl esters, water
Process Complicated Simple
 Biodiesel from Vegetable Oils 137

Table 5
Emission impacts of 20 vol% biodiesel for
soybean–based biodiesel added to an
average base diesel fuel

Percent change
in emissions

NOx (nitrogen oxides) +2.0

PM (particular matter) −10.1
HC (hydrocarbons) −21.1
CO (carbon monoxide) −11.0
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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. The longer the fatty acid carbon chains and
the more saturated the molecules, the higher the CN. The CN of biodiesel from animal
fats is higher than those of vegetable oils.
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 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 (Prakash, 1998).
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 com-
pared 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 5.

Effect of Reaction Parameters on Conversion Yield of Transesterification

The parameters affecting 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, reaction rate is so low and gradually increased as either pressure or
temperature rises. It was observed that increasing the reaction temperature, especially
to supercritical conditions, had a favorable influence on the yield of ester conversion.
The yield of alkyl ester increased with increasing the molar ratio of oil to alcohol
(Demirbas, 2002a). In the supercritical alcohol transesterification method, the yield of
conversion raises 50–95% for first 10 min. Figure 1 shows the plots for changes in
fatty acids alkyl esters conversion from triglycerides as treated in supercritical alcohols
at 575 K.
 138 A. Demirbas and S. Karslioglu
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Figure 1. Plots for changes in fatty acids alkyl esters conversion from triglycerides as treated in
supercritical alcohol at 575 K.

Figure 2. Plots for yields of methyl esters as a function of water content in transesterification of
triglycerides.
 Biodiesel from Vegetable Oils 139
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Figure 3. Plots for yields of methyl esters as a function of free fatty acid content in biodiesel
production.

Water content is an important factor in the conventional catalytic transesterification

of vegetable oil. In the conventional transesterification of fats and vegetable oils for
biodiesel production, free fatty acids and water always produce negative effects since
the presence of free fatty acids and water causes soap formation, consumes catalyst and
reduces catalyst effectiveness. In catalyzed methods, the presence of water has negative
effects on the yields of methyl esters. However, the presence of water positively affected
the formation of methyl esters in our supercritical methanol method. Figure 2 shows the
plots for yields of methyl esters as a function of water content in transesterification of
triglycerides. Figure 3 shows the plots for yields of methyl esters as a function of free
fatty acid content in biodiesel production (Kusdiana and Saka, 2004).

Biodiesel Economy
The cost of biodiesel fuels varies depending on the base stock, geographic area, variability
in crop production from season to season, the price of the crude petroleum and other
factors. Biodiesel has over double the price of 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
Fatty acid methyl ester could be produced from tall oil, a by-product in the manu-
facture of pulp by the Kraft process. Tall oil consists of free C18 unsaturated fatty acids,
resin acids and relatively small amounts of unsaponifiables. The fatty acid fraction of tall
oil contains mainly oleic acid, linoleic acid and its isomers. Tall oil fatty acids are easily
converted into their methyl esters by reaction with methanol, whereas the resin acids are
virtually unesterified due to hindered effect (Demirbas, 1991).
Biodiesel has become more attractive recently because of its environmental benefits.
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 transesterification
process and recovery of high quality glycerol as a biodiesel by-product are primary
options to be considered to lower the cost of biodiesel (Ma and Hanna, 1999).
 140 A. Demirbas and S. Karslioglu

Conclusion
Compared to diesel fuel, biodiesel is chemically simple since it contains only six or seven
fatty acid esters. Generally speaking, biodiesels have higher CN, higher viscosity, and
higher cloud and pour points compared to conventional diesel. Biodiesel has a higher CN
with other characteristics similar to diesel fuel. Thus, it can be used in diesel engines
without any modifications. Biodiesel is mixed with diesel to bring much of the beneficial
characteristics to diesel equipment, while reducing the overall cost of the fuel.
Biodiesel, due to its biodegradable nature, and essentially no sulfur and aromatic
contents, offers promise to reduce particulate and toxic emissions, and is considered to
be an attractive transportation fuel for use in environmentally sensitive applications. It is
also reported that adding small amounts of biodiesel to conventional diesel can improve
fuel lubricity, extend engine life, and increase fuel efficiency (Prakash, 1998).
The biodiesels have high boiling points, flash points, and extremely low vapor pres-
sure, as well as an inability to smoke under the smoke point test. These results indicate
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a high level of safety for handling biodiesels.

Supercritical methanol has a high potential for both transesterification of triglycerides
and methyl esterification of free fatty acids to methyl esters for diesel fuel substitute. In
the supercritical methanol transesterification method, the yield of conversion raises 95%
for 10 minutes.

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