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Biodiesel From Animal Fat and Oil
Biodiesel From Animal Fat and Oil
To cite this article: A. Demirbas & S. Karslioglu (2007): Biodiesel Production Facilities from Vegetable Oils and Animal Fats,
Energy Sources, Part A: Recovery, Utilization, and Environmental Effects, 29:2, 133-141
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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
A. DEMIRBAS
Department of Chemical Engineering
Selcuk University
Konya, Turkey
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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.
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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Table 1
Critical temperatures and critical
pressures of various alcohols
Critical Critical
temperature pressure
Alcohol (K) (MPa)
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)
Table 3
Fuel properties of methyl ester biodiesels
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
Table 5
Emission impacts of 20 vol% biodiesel for
soybean–based biodiesel added to an
average base diesel fuel
Percent change
in emissions
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.
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.
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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