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S. Yan
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Tian C. Zhang
6.1 INTRODUCTION
123
Biodiesel Production
124 BIODIESEL PRODUCTION
crops by production industry. In Korea, fats from cows and swine are the major
resources for animal fat biodiesel production (Kim et al. 2012); in Brazil, biodiesel
from fats are being produced from chicken fats, tallow, and lard.
Recently, utilization of animal fat as animal feed has been decreased because
animal fat possibly transmits various animal diseases. Compared with biodiesel
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from vegetable oil, biodiesel from animal fat has advantages because of its higher
calorific value and cetane number (CN). However, animal fat biodiesel is less
stable to oxidation, because of the absence of natural antioxidants and has a major
cold filter plugging point because of a diverse amount of saturated fatty acids.
When additions of other raw materials are obtained, the fuel characteristics may
be improved (Dias et al. 2012). Without any transformation, animal fat has been
used to improve the rheological properties of fuel oil. The utilization of waste
animal fat to produce biodiesel opens a door to recycle the waste that otherwise
would have been washed down the drain or as a feedstock for the soap industry.
Many animal fats are low-quality feedstock compared with vegetable oil because of
the huge quantity of free fatty acids (FFAs) in animal fats. Using animal fat to
produce biodiesel can be considered as a reasonable way to minimize the cost of
biodiesel production. Other factors determining the feasibility of using animal fats
to produce biodiesel are the engine performance and harmful components derived
after using biodiesel produced from animal fats. Another factor is safe utilization
of animal fat biodiesel because animal fats are usually contaminated with prions
(Canoira et al. 2008).
Until now, it has been estimated that the total US biodiesel production is
more than 3.79 billion L) in 2012, of which, production of biodiesel from animal
fat accounts for nearly half. This chapter is designed to cover all possible aspects of
animal fat biodiesel. The chapter provides the sources of animal fats and the
factors affecting rendering techniques and other chemical parameters. It also
introduces comparative studies of the FFAs from various animal fat sources to get
an estimation of maximum saturated and unsaturated fatty acid production. The
presence of various metals in animal fat and the techniques for using natural
resources to convert biodiesel are described. Finally, the economic impacts as well
as the pros and cons of using animal fats for biodiesel production are discussed.
The use of animal wastes as raw materials for biodiesel production has three major
advantages: (1) does not compete with the food market; (2) recycles waste; and
(3) reduces production costs. Concerns exist for the utilization of low-cost waste
sources for biodiesel production, which otherwise cannot be used as human food,
such as waste animal fats, which are either from meat, chicken, or fish processing
industries. Biodiesel production from animal fats are usually environmentally
friendly and are a lower-cost alternative. Waste animal fats of tallow, lard, and
poultry fat are usually collected from slaughterhouses and meat processing
Biodiesel Production
ANIMAL FAT BIODIESEL 125
industries. At the laboratory scale, these are melted and filtered for removal of gums,
residues of protein, and other suspended particles (Mata et al. 2010). Other resources
are the aquatic resources (e.g., fish oil) for producing biodiesel. The conversion
process of biodiesel from fish oil is simple. After the fish oil has been produced from
the leftover waste of the fishing industry, the oil is cleaned with the addition of
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caustic soda and then purified with methanol for production of biodiesel. An
estimate shows 1 kg of fish waste can produce up to 1.3 L of biodiesel (Piccolo 2009).
In general, all biodiesels produced from animal fats have lower iodine values
when compared with the value fixed by European standard EN 14214. Animal fats
are usually incorporated with vegetable oils to achieve a product with an iodine
value according to the specifications (Encinar et al. 2011). Animal fats are usually
classified as tallow, lard, chicken fats, and various mixed animal fats. Tallow,
which is extracted from residues of bovine slaughter, can be filtered and contains
90% of total fatty acids with unsaponifiable impurities up to 1.5%. It does not
contain any FFA. Lard is extracted from swine slaughterhouses, and the specifi-
cation of lard is the same as that of tallow. Chicken fats are extracted from broiler
slaughterhouses, again containing 90% of total fatty acids and nearly 3% of
unsaponifiable impurities without any FFA. Animal fat mixtures are extracted
from slaughter residues of mammals and birds with 2% unsaponifiable impurities
(Feddern et al. 2011).
Biodiesel Production
126 BIODIESEL PRODUCTION
2000). In the European Union (EU), pressure cooking is one of the efficient
methods. However, in North America, it is not considered as an effective method.
In the fat melting method, only discrete adipose tissues are used, and it produces a
high-end product, which is too fine to justify its use for biodiesel production
because very clean fats are never considered for biodiesel production (Baribeau
et al. 2007). Both biodiesel and direct firing of the tallow has been proposed as low-
risk end uses for tallow from livestock (Nelson 2006). In a rendering method
developed by Ejikeme et al. (2013), the thick piece of lard or tallow was obtained
by cutting the lard or tallow into small pieces and then melting it at 40 °C. NaOH
and methanol were added to it and heated at 40 °C again for 90 min. It was then
immersed in cold water, and then its lower layer was washed consecutively four
times to remove the unreacted catalyst. Furthermore, properties like flash point,
heating temperature, and pH values were determined.
Rendering products leave the slaughtering process and are considered as a
waste stream. These rendered products are then processed in the rendering units
to yield meat, bone meal and tallow. Furthermore, this tallow is then transported
to the biodiesel plant for transesterification prior to production of biodiesel
(Niederl and Narodoslawsky 2004). Certain rendering types include dry and wet
rendering, but for most tallow-based products, dry rendering is the suitably
preferred approach. The difference lies in the rendering methods in which the
system uses either wet or dry rendering principles. The system, where low
temperature is maintained for rendering, is called wet rendering, and this process
is usually continuous, whereas the system for which high temperature is main-
tained for rendering is called dry rendering and these processes are often
continuous or in batch. The rendering products are beef and sheep tallow, meat,
and bone meal because they are meant for biodiesel production. People involved
with rendering must be aware that the final usage affects the required product
quality and specific requirements to produce the end product. Significant para-
meters for the usage of tallow in biodiesel are plastics, moisture, impurities, and
unsaponifiables (Meat and Livestock Australia 2009).
Biodiesel Production
ANIMAL FAT BIODIESEL 127
composition. The viscosity and density of biodiesel fuels are important parameters
because they influence the key properties in any diesel engine. Different blends of
biodiesel fuels were prepared to check the fuel characteristics. It was observed that
viscosities of the animal fat–derived fatty acid methyl esters are higher than that of
the esters based on soy (Altun et al. 2010).
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Oner and Altun (2009) prepared different blends of biodiesel directly from
Blend 100 to Blend 50, and Blend 20 and Blend 5, and injected the different grades
of biodiesel into the combustion chamber of the engine. The higher density of the
biodiesel along with its viscosity leads to the utilization of a larger volume of
biodiesel and poor atomization of the fuel (Xue et al. 2011). Biodiesel prepared
from animal tallow or fat, although an inexpensive and cheap source, leads to
highly viscous biodiesel and a high content of saturated fatty acids. When density
and viscosity of the biodiesel and diesel fuel were compared, it was observed that
diesel fuel has 3.6663 mm2/s of viscosity at 40 °C, whereas biodiesel has viscosity of
5.072 mm2/s, and density of diesel fuel is 843.51 kg/m3. Nearly 1.8 billion lbs
(3.53 billion kg) of animal fats are produced annually in the United States.
Experimental investigations have proved that beef tallow can be easily esterified to
components with properties similar to that of the esters from vegetable oil. Beef
tallow’s transesterification leads to the formation of a gel-like material with a high
concentration of saturated fatty acids components in beef tallow or cow tallow
because of poor agitation and low conversion of triglycerides, which leads to
incomplete reactions (Muniyappa et al. 1996, Ghazavi et al. 2012).
Biodiesel Production
128 BIODIESEL PRODUCTION
of ethanol because ethanol has a very low CN (approximately 5 to 8). The CNs of
biodiesel from animal tallow and diesel are 56 to 58.8 for biodiesel, whereas CN is
47 for diesel (Altun et al. 2011, Darunde and Deshmukh 2012).
Pig fat, either in rendered or unrendered form, is called lard. The qualities of lard
vary somewhat, depending on the part of the pig from which the fat is taken and
how the lard is processed. Lard can be obtained from any part of the pig if there is a
high concentration of fatty tissue. Lard may be rendered by either of two
processes: wet or dry. In wet rendering, pig fat is boiled in water or steamed
at a high temperature, and the lard, which is insoluble in water, is skimmed off the
surface of the mixture or it is separated in an industrial centrifuge. In dry
rendering, the fat is exposed to high heat in a pan or oven without the presence
of water (a process similar to frying bacon). The two processes yield somewhat
differing products. Wet rendered lard has a more neutral flavor, a lighter color,
and a high smoke point. Dry rendered lard is equivalent to brown in color and
flavor and has a lower smoke point. The highest grade of lard, known as leaf lard,
is obtained from the fat deposit surrounding the kidneys. Leaf lard has little pork
flavor, making it ideal for use in baked goods, where it is valued for its ability to
produce flaky, moist pie crusts. The next highest grade of lard is obtained from
fatback, the hard fat between the back skin and muscle of the pig. The lowest grade
(for purposes of rendering into lard) is obtained from the soft fat surrounding
digestive organs, making it an efficient resource for biodiesel production. Pig lard
has similar composition as that of tallow; however, they have different fatty acid
content and iodine value (Gatlin et al. 2002).
The waste frying oils are known to be scarce, but waste animal fats such as pig
lard are more abundant in the environment. These pig lards had a common
application as human feeds, but over the years, certain practices of using pig lard
simultaneously decreased as the possibility of severe animal disease and the
consequent obligation to effectively discard or recycle the waste fats in the
environment increased. Also, animal fats have a significant content of saturated
fatty acids, and the fuel produced has a higher cold filter plugging point compared
with biodiesel from vegetable oils. Therefore, it might not be appropriate to use it
purely (100%) in vehicles during cold weather. It has been observed that biodiesel
production from waste lard by acid catalysis might have higher yields than basic
catalysis; however, greater amounts of sulfuric acid (25% to 50% of fat weight), a
higher molar ratio of methanol to fat (30:1), and much longer reaction time (24 h)
were used compared with basic transesterification. Pork wastes (mainly consisting
of fat and residual skin and meat) were collected at a local butchery, and the fat
extraction was made by heating until the fat was melted and separated from the
solid remaining residue. This product was finally filtered at reduced pressure.
The extracted fat was kept in a freezer at 4 °C during the experimental period. The
waste lard had an acid value of 14.57 mg KOH/g. Basic transesterification of lard at
65 °C, 1.0% [weight by weight (w/w)] NaOH, and a 6:1 molar ratio of methanol
resulted in immediate soap production (Singh et al. 2006).
Biodiesel Production
ANIMAL FAT BIODIESEL 129
A mixture of the waste lard with soybean oil was also studied as possible raw
material for biodiesel production. Biodiesel production from acid lard was
effectively enabled by a two-step synthesis. The influence of the pre-esterification
conditions in biodiesel quality was studied, and two predictive models were
further obtained. The catalyst amount and temperature mostly affected biodiesel
quality. The selected conditions, which led to a product viscosity of 4.81 mm2/s
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and a purity of 99.6% by weight were 65 °C, 2.0% by weight H2SO4, and 5 h.
A mixture of waste lard and soybean oil was used to produce biodiesel using a one-
step synthesis, and the good results obtained indicated that blending might be an
interesting alternative to recycle wastes and even improve some product proper-
ties. Due to the existence of C17:0, in some animal fats, a correction should be
performed to the method proposed by EN 14214 for biodiesel purity determina-
tion (Dias et al. 2009).
Lee et al. (2002) fractionated lard with acetone to reduce the saturated fatty
acid content in the recovered fractions that were further used for cold tempera-
ture–resistant biodiesel production. However, by dry-fractionation, the unsatu-
rated fatty acid content increased only 1.9% to 4.6% from that of neat lard. Alkyl
ester as biodiesel needs stable performance at cold temperatures. Thus, solvent
fractionation was conducted to reduce the content of saturated fatty acid from lard
owing to their relatively high melting point.
In a pretreatment of pork lard as the raw material, the pork lard was first
heated at 100 ºC to eliminate residual water and then cooled to near the reaction
temperature (60 ºC). Synthesis of biodiesel was made by transesterification. The
mixtures of waste frying oil and lard were prepared considering the increase in the
fat fraction of the mixture (Buzetzki et al. 2010), varying from 0−1 (w/w), in
0.2 intervals. The fat was weighed and added to the reactor, which already
contained the necessary amount of oil. A defined amount of methanol (6:1 molar
ratio to oil) premixed with NaOH (0.8% by weight) was added to the reactor,
which already had 100 g of the raw material mixture, preheated at the reaction
temperature. At the point the reaction started, the reactor consisted of a 1 L flat
bottom flask immersed in a temperature controlling bath, equipped with a water-
cooled condenser and a magnetic stirrer. The biodiesel quality was obtained when
the minimum purity (96.5% by weight) was closely obtained only when waste
frying oil was used alone and when 0.2% of lard was incorporated in the raw
material (96.3% by weight); however, it ranged from 93.9 to 96.3 (% by weight)
being always close to the limit. Concerning the influence of raw material
composition in biodiesel quality, it was postulated that the parameter of the
biodiesel obtained from the mixture corresponded to the weighted average of the
parameter of biodiesel resulting from each component. The equation was reported
in the literature (Dias et al. 2008a).
Biodiesel Production
130 BIODIESEL PRODUCTION
in the fat. High iodine value indicates a higher potential for biodiesel degradation,
either through thermal oxidation or free radical attack. The traditional method for
the determination of iodine value uses the methodology described by Johnston
and Li (2011) and adopted by American Oil Chemist Society (AOCS). The
polyunsaturated fatty acids (PUFAs) to saturated fatty acids (SFAs) ratio is
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commonly referred to as the iodine value (IV), which is based on the laboratory
procedure using iodine to measure the number of double bonds (degree of
unsaturation) in fats and oils (Jordahl 2012). Raw material (pork lard) was
previously heated to melt. The reaction was carried out under constant stirring
for 40 min. The reaction mixture was heated up to 80 °C for 15 min until complete
ethanol evaporation. Hexane was added to extract the biodiesel phase. Then, the
hexane was evaporated, and the biodiesel recovered was dried in anhydrous
sodium sulfate and characterized.
The IV of the biodiesel samples was calculated by means of the equation in
which area of one hydrogen and the molecular weight is needed. It has been
suggested that 1H nuclear magnetic resonance (NMR) method is a reliable
alternative for the determination of the iodine value for ethylic biodiesel samples.
Based on the formula, pig lard was calculated as 70.6 using 1H NMR method and
71.0 using the AOCS method, which is far lesser than the IV of canola, corn, or
soybean samples (Reda et al. 2007). Although at certain places, the IV of pork lard
was calculated as 67 g I2/100 g (Sathiyagnanam et al. 2012), whereas the IV of
waste frying oil (waste cooking oil) was 117 g I2/100 g (Dias et al. 2008a).
Biodiesel Production
ANIMAL FAT BIODIESEL 131
depending on the kind of feathers used (Alptekin and Canakci 2011). Chicken
feather contains nearly 11% of fat, whereas duck and turkey feathers contain 6.7%
of fat (Lopes 2011).
Optimization of the transesterification reaction was investigated with different
methanol:oil ratios, reaction temperature, reaction time, and the catalyst amount.
The obtained ester was characterized by determining its fuel properties according to
standard test methods. The solid chicken fat was melted at around 65 °C, filtered,
centrifuged, and decanted to remove other suspended particles. The processed fat
was homogeneous in nature and was stored in airtight opaque plastic jars to prevent
oxidation. The percentages of yield of methyl esters are presented as graphs for
different conditions (Panneerselvam et al. 2011, Fadhil et al. 2012). High ester yields
up to 99% were obtained from chicken fat after 24 h in the presence of sulfuric acid
(Alptekin et al. 2011). The percentage of yield of methyl esters is calculated by the
equation in which methyl esters are divided by the melted chicken fat. Henceforth,
the biodiesel yield is calculated similarly, that is, mass of biodiesel divided by the
mass of the raw material (Phalakornkule et al. 2009).
The study on the biodiesel production process and optimization of chicken fat
showed that the quantity of catalyst, amount of methanol, reaction temperature,
and reaction time are the main factors affecting the production of methyl esters.
The optimal reaction conditions for production of methyl esters from chicken and
mutton fat were established as follows: the reaction time of 90 min at 60 °C; the
6:1 molar ratio of methanol to oil; and 0.38 g of KOH/g of oil for chicken fat for
50 mL of chicken fat. The use of chicken fat is very suitable as low-cost feedstocks
for biodiesel production (Panneerselvam et al. 2011). Chicken fat density variation
was experimentally measured in the temperature range from 25 °C to 100 °C; it is
said that chicken fat is thermally stable up to ∼350 °C. Given the negligible
volatility of chicken fat, a linear variation was obtained and then extrapolated to
account for densities at reaction temperatures.
It has also been reported that a preheating step of chicken fat feedstock of up to
350 °C can be used without a significant thermal decomposition (Marulanda et al.
2010), and the associated chicken fat has an acid number of 26.89 (Alptekin et al.
2011). The yield of fat extraction from poultry wastes was 40 % by weight. The
characterization of the fat showed an AV of 0.92 mg KOH/g and an iodine number
of 80 g of I2/100 g. The AV of the raw material has a good alkaline transesterification
due to reduced risk of catalyst consumption by FFAs (Moreira et al. 2010).
Biodiesel Production
132 BIODIESEL PRODUCTION
technology, but the adaptability of this technology to aquatic resources has only
recently attracted public interest. The process is relatively simple. The production
of biodiesel starts with crushing the fish waste. This allows the oil to be extracted,
which is mixed with methanol (roughly 9%) and caustic soda (to separate the
glycerin from the biodiesel). Aquafinca, which specializes in processing of tilapia
fish, is estimated to be producing more than 15,000 L of biodiesel from tilapia fish
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oil a day. The biodiesel is then used to produce electricity at its production facility
as well as running its vehicles. Aquafinca operates a tilapia farming facility in the
El Cajon dam as well as at Yojoa Lake. Andersen and Weinbach (2010) reported
that 623 kt by-products from fish are the theoretical maximum available amounts
that could be utilized for biodiesel production. However, 166 kt of the byproduct is
being dumped, of which 48 kt are dumped on shore. Biodiesel from fish residue/
waste could also promote more efficient use of aquatic living resources and
generate additional income for fishing and fish farming communities.
Fish oil biodiesel indicates significant sensitivity to oxygen exposure, leading
to the formation of varnish on the surfaces of the fuel handling system (Witmer
2010). According to Taku Renewable Resources (2010), salmon oil has a rapid
oxidative rate and a high free fatty acid content, which necessitates the addition of
antioxidants (such as citric acid or phosphoric acid) to the oil prior to transester-
ification and in relatively high quantities if the oil is going to be stored even for just
a few days prior to biodiesel production (Taku Renewable Resources 2010). In a
study by El-Mashad et al. (2006), salmon oil extracted from acidified waste and
salmon oil extracted from rendered waste were used as feedstock. The researchers
found virtually no difference between the two feedstocks. Both salmon oils
required a sulfuric acid pretreatment to bring down the high AV of the oil, and
both oils yielded approximately the same amount of biodiesel for the same cost.
Based on the weight of the salmon oils prior to transesterification, a maximum
99% biodiesel yield was achieved. However, the researchers calculated that up to
15% of the esters were lost during the final washing and drying steps due to the
formation of emulsion in the biofuel. Finally, a preliminary economic analysis
revealed that the cost of salmon oil biodiesel production was almost twice the cost
of soybean oil biodiesel production (El-Mashad et al. 2006). Salmon oil and
salmon oil biodiesel have similar characteristics of corn biodiesel from corn oil.
Unisea, based in Dutch Harbor, has been processing and burning fish oil as
waste in its boilers for decades, along with other Pacific Rim seafood processors.
According to Steigers (2002), since 2001, Unisea has also used burned fish oil as
petrol-diesel blends in their electrical generators. In addition, as part of the Alaska
Biodiesel Demonstration Project, Unisea shipped more than 18,000 gal. (68,137 L)
of walleye pollock oil to Hawaii in 2005, and Pacific Biodiesel processed this fish
oil into biodiesel before it was shipped back to Alaska for testing (Witmer and
Schmid 2008). This project established fish oil–based biodiesel as a viable engine
product for engine operability in Alaska, but also identified critical storage and
handling problems with the fish oil–based biodiesel. Aquafinca is a tilapia farm,
rendering plant, and biodiesel production facility located approximately 125 miles
(201.0 kms) from San Pedro Sula, the administrative capital of Honduras.
Biodiesel Production
ANIMAL FAT BIODIESEL 133
The farm currently harvests roughly 200,000 lbs (90,718 kg) of tilapia a day, of
which approximately 54% [(108,000 lbs) (48,987 kg)] is waste including viscera,
heads, frames, and skins. The skins are immediately separated from the rest of the
byproducts, dried, and sold to China to produce gelatin. Viscera, heads, and
frames are ground and rendered at high heat to approximately 16,000 lbs
(7,257 kg) of fish oil (8% yield) and 22,000 lbs (9,979 kg) of fishmeal
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(11% yield). Of the 16,000 lbs (7,257 kg) of fish oil, approximately 10,000 to
12,000 lbs (4,536 to 5,443 kg) or 1,200 to 1,500 gal. (4,542 to 5,678 L) are converted
to biodiesel daily. It has been demonstrated that 3,000 gal. (11,356 L) of biodiesel
was produced in a day from the catfish byproducts, which are nearly 110,000 lbs
(49,895 kg) per day and salmon byproducts produced each day are 50,000 lbs
(22,679 kg). The oil content of the biodiesel feedstock is high, ranging from
8% (farmed tilapia) to 30% (farmed Atlantic salmon) (Taku Renewable Resources
2010).
Some fish oils contain essential fatty acids like omega-3, which is a highly
valued commodity especially in the pharmaceutical industry. Therefore, care must
be taken on which types of fish are used when producing the fish oil. According to
Piccolo (2009), one of the lowest in the omega-3 content but high in oil is catfish,
with an omega-3 content of 0.18 g/100 g of fish. Another note of care is the acid
content of the oil extracted. For example, salmon oil is high in acid, and this acid
needs to be removed. Therefore, an additional step in removing this acid is
required. Sulfuric acid is added to reduce the AV of the oil. Once this has been
done, the process of transesterification can begin. In 2007, the National Techno-
logical Centre for the Canning of Fish Products in Spain was looking for ways to
produce biodiesel with fish fat available in wastewater generated by the canning
industry (Piccolo 2009). Any marine fish oil methyl ester must have density of
0.860 g/cm3 and viscosity of 7.20 at 40 °C with a CN of 50.9, which are much less
than the CN of waste oil methyl ester (Fok et al. 2012).
Different feedstock oils are used to produce biodiesel. The effect of various
operating and processing parameters on transesterification depends on quality
and source of the feedstock oil. According to FFA content, different technological
approaches can be used. One approach is the alkali-catalyzed process because the
FFA content in collected frying oil was less than 1%; , but however, when FFA
content is a higher value, like on bovine tallow, it is a significant step to do a two-
step process, which are esterification and transesterification (Ribeiro et al. 2011).
To produce biodiesel, low-cost animal wastes with relatively high FFA are used,
after reduction of FFA by 1% in the pretreatment reaction. Chicken fat is a low-
cost feedstock for biodiesel production compared to high-grade vegetable oils. Fat
is usually extracted from feather meal, which is prepared from chicken wastes,
including chicken feathers, blood, offal, and trims after the rendering process.
Biodiesel Production
134 BIODIESEL PRODUCTION
Feather meal contains a significant amount of chicken fat. The fat content of the
feather meal varies from 2% to 12%, depending on the kind of feathers used.
However, they often contain significant amounts of FFA. The fats with high FFA
cannot be converted to biodiesel using alkaline catalysts. Mostly, sulfuric acid is
considered as the best catalyst for reducing the FFA level. Another method is the
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removal by KOH in the form of soap (Alptekin et al. 2011). The FFA reacts with
alcohol to form ester of biodiesel through
Hþ
..
.
R1 -COOH þ ROH → R-O-CO-R1 þ H2 O
FFA Alcohol Fatty acid ester water (6-1)
The water content of the fats is relatively low; however, conversion can be
affected. For the alkaline-catalyzed method, the conversion was slightly reduced
when more water was added. However, in the acid-catalyzed method, only as little
as 0.1% of added water would lead to some reduction of the yield of methyl esters.
Most properties of biodiesel depend on the feedstock used. It has been reported by
Knothe (2006) that biodiesel viscosity and density can be predicted based on
feedstock fatty acid profile. High viscosity is expected because the main fatty acids
have a long chain of carbon and a low degree of unsaturation, and thus, no high
density is expected for the same reasons. Density increases with a decrease in chain
length and an increase in the number of double bonds (Encinar et al. 2011). The
production of poultry meat has increased significantly in recent years, and the
recycling of fatty wastes resulting from its slaughter has been the subject of study
since their incorporation in animal diets was restricted. Consequently, poultry fat
is currently considered a potentially good low-cost raw material for biodiesel
production. Biodiesel composition, which relates to the composition of the waste
poultry fat used, was determined by gas chromatography. The methyl esters
contained in the biodiesel were identified by comparing retention times with those
of chromatographic standards. Water content was always higher than the maxi-
mum set by EN 14214, independent of the transesterification conditions used.
This fact showed that the drying method selected should be improved or replaced
by others of greater effectiveness, such as evaporation under reduced pressure
(Moreira et al. 2010).
The fatty acid methyl ester content, or ester content, is an indicator of the
purity of biodiesel, and EN 14214 indicates a minimum of 96.5% by weight to
ensure quality. This parameter is very important to prevent an illegal mixture of
other substances. Biodiesel production from recycled wastes represents lower
yields than when virgin oils are used. Accordingly, when using poultry fat as raw
material, the yields were not very high, that is, from 73 to 86% by weight. However,
such disadvantages can be compensated by the value added to the wastes through
Biodiesel Production
ANIMAL FAT BIODIESEL 135
their recycling, the cost reduction on waste treatment, and the reduction of
greenhouse gases emissions (Chhetri et al. 2008, Moreira et al. 2010). Fish oil is
composed mainly of unsaturated fatty acids (USFAs) and is particularly rich in
PUFAs; thus, it can be used as raw oil for biodiesel production to improve fuel flow
fluidity at low operating temperatures. In general, biodiesel fuels produced from
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raw oil with longer chain fatty acids have a higher CN and thus superior
compression ignition characteristics. The deterioration rate of a lipid or oil is
significantly influenced by the amount and composition of unsaturated fatty acids
and by the number and location of the double bonds in the chemical compounds.
The oxidation instability starts with the methyl group (-CH2-) carbons attacking
the olefinic carbons as part of the peroxidation chain mechanism. The USFA
content may be converted to form primary oxidation products such as hydro-
peroxides and conjugated dienes, which may be either isolated or accumulated at
an accelerated rate. The marine fish oil biodiesel contained 37.06% by weight of
saturated fatty acids and 37.3% by weight of long carbon chain (in the range of
C20−C22) fatty acids and is likely to have a greater kinematic viscosity than
biodiesel made from general vegetable oils (Lin and Lee 2010).
Clifford et al. (2008) compared the chemistry of diesel fuel with that of biodiesel
and found that biodiesel typically has different fats and oils; biodiesel contains
common types of fatty acids, ranging from 12 to 22 carbon atoms, with 16 to
18 carbons being the most common. Some of the chains are saturated; others are
monosaturated; the rest are polyunsaturated. Within the limits of specifications, the
differing levels of saturation can affect biodiesel fuel properties. Beef tallow can
undergo oxidation reactions in the presence of oxygen, high temperatures, and light
because of the presence of USFAs. This decreases the biodiesel stability, because the
ester derivative of oleic acid is monounsaturated and may suffer reactions from
photo-oxidation and autoxidation. The boiling point is a significant aspect of the
biodiesel, and it relates to the quality of the biodiesel. In beef tallow, decomposition
occurs at higher temperatures, because of high predominance of the fatty acids with
higher molecular weight (usually they are the ones with C18:0). Among beef tallow,
low thermal stability has been observed, as 70.60% of saturated esters are present.
Eventually, cetane numbers, heat of combustion, melting point, and viscosity of
neat fatty acids increase with increasing chain length and decrease with increasing
unsaturation (Araujo et al. 2010).
Table 6-1 lists FFAs available in various animal and fish fat wastes. Crude
lipids have impurities such as phospholipids, FFAs, aldehydes, ketones, and
pigments. For improving stability and quality, numerous degrees of purifications
were implemented. Common methods are (1) bleaching to remove pigments,
minerals, FFAs, aldehydes, and ketones; (2) degumming to remove phospholipids;
(3) deodorizing to remove FFAs; and (4) neutralization to remove water. For the
palatability of the lipids, winterizing is a common technique to improve trans-
parency, which later impacts the brightness. Triglycerides consist of a glycerol
backbone esterified to three fatty acids, which are either essential or nonessential.
The energy liberated depends on the carbon chain length and the degree of
unsaturation of the fatty acids. Longer chains yield more energy than shorter
Biodiesel Production
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Table 6-1. Composition of FFAs from Different Sources of Animal, Poultry, and Fish Wastes.
136
FAME
composition C10:0 C12:0 C14:0 C16:0 C16:1 C17:0 C18:0 C18:1 C18:2 C18:3 C19:0 C20:1 C20:4 C20:5 C22:6 References
Inedible/edible — 13.147 18.48 23.57 — — 28.175 27.471 27.108 — — 30.05 — — — Trushenski and
tallow Lochmann (2009),
Araujo et al. (2010),
Bayraktar and Bayir
(2012)
Lard — — 1.3 20.66 1.98 0.48 10.91 39.13 19.55 1.21 — 0.91 — 0.12 0.2 Robles et al. (2003),
Rohman et al.
(2012), Tang et al.
BIODIESEL PRODUCTION
(2008)
Poultry fat — — 1.5 27.6 4.5 — 12.1 42.8 10.5 0.7 — — 0.37 — — Marulanda et al.
(2010), Alptekin
and Canakci
(2011), Alptekin
et al. (2011),
Encinar et al.
Biodiesel Production
(2011)
Fish fat — — — 19.61 5.16 — 5.24 20.94 — — — — — 3.7 15.91 Lin and Lee (2010)
Other fat waste 3.1 35.6 7.6 14.8 3.8 — 3.6 23.6 5.8 — 1.4 — — — — Li et al. (2011)
Biodiesel — — 0.6 2.4 5.8 — 5.5 41 21 1.4 — 0.4 — — — Moreira et al. (2010),
Panneerselvam
et al. (2011)
EN 14103 — — — — — — — — — Maximum — — — — — Lin and Lee (2010)
12.0
ANIMAL FAT BIODIESEL 137
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Figure 6-1. % of unsaturated fatty acids and saturated fatty acids in different
animal fats, poultry fats and fish wastes: (a) USFAs; and (b) SFAs.
chains, and saturated chains (with no double bonds) yield more energy than
unsaturated chains (Trushenski and Lochmann 2009).
The presence of more SFAs crystallizes easily for the biodiesel fuel, which
further causes fuel filter plugging and other performance hazards (Gerpen 2005).
FFAs have double bonds and are unsaturated FFAs. These double bonds are
unstable and can eventually break in the presence of water and heat; therefore,
USFAs tend to spoil faster than SFAs (Popescu and Ionel 2011). Often, biodiesel
produced with such oils tends to break down quickly, and biodiesel made from
such USFAs tends to degrade overnight. Figure 6-1 shows the results of a
comparative study on various percentages of USFAs and SFAs. Tallow has the
lowest number of USFAs, whereas lard, poultry fat, and fish fat have the highest
(Cunha et al. 2012).
Biodiesel Production
138 BIODIESEL PRODUCTION
respectively; whereas animal fats have much higher sulfur levels, usually more
than 15 ppm. Feedstocks, which are usually higher at FFA, are treated with sulfuric
acid for the reduction of FFA prior to transesterification. In that case, phase
separation is a must for the removal of sulfur from the fuel layer (He et al. 2009).
The sulfur from the animal fat usually originates from sulfur-containing amino
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acids, which are associated with proteins and carried off from the rendering
process. The sulfur contents in tallow, fish, and poultry are the maximum; whereas
sulfur content in lard is a minimum by 1 ppm as shown in Figure 6-2 (Choi et al.
2012, Janchiv et al. 2012).
Phosphorus does damage to catalytic converters that are being used in
emission control systems. Therefore, to produce biodiesel, low phosphorus must
be maintained. At a study done by Ostrovsky et al. (2006), the European Union
leads the way to environmental protection and implementation of the production
of biodiesel. At a tolerance level of 10 ppm, the Inductively coupled plasma mass
spectrometry (ICP) system is ensured to reliably meet the anticipated lower levels
per regulations now. A low amount of phosphorus is present in lard, compared
with the rest of the animal wastes. In biodiesel (according to ASTM D6751),
phosphorus limitation is just 10 ppm (Moser et al. 2013), whereas the combined
amount of magnesium and calcium must be less than 5 ppm according to the test
method by EN 14538. Accordingly, one must even measure calcium, magnesium,
sodium, and potassium in the biodiesel to avoid any issues about ionization
interferences among the alkali metals. Tallow and poultry fat have the highest
phosphorus and even higher calcium (Atabani et al. 2012), whereas calcium in lard
is the lowest (0.1 ppm), and phosphorus in fish fat is 49 ppm (Sugiura 2009).
Biodiesel Production
ANIMAL FAT BIODIESEL 139
toward forming deposits in the equipment, and hence catalyze undesired reactions
and simultaneously poison the control equipment. Therefore, to avoid that,
combinations of metals are made in a category in which Na + K are considered
and Ca + Mg are considered and quantified (US Department of Energy 2009).
If poultry fat methyl ester has a high CN, its disadvantages include high freezing
point and viscosity even if the poultry fat methyl ester is noncorrosive, clean, and
renewable. These disadvantages limit the usage of biodiesel fuels in diesel engines.
To improve the biodiesel, magnesium-based additives of a 16 mmol/L concen-
tration were added to the poultry fat methyl ester to lower the freezing point and
viscosity. These additions support the idea of the catalytic cracking effect of the
additives, which are with smaller chains of hydrocarbons (Guru et al. 2010).
Sodium and potassium may be present in biodiesel as abrasive solids or
soluble metallic soaps. Sodium and potassium are usually added as catalysts in the
form of sodium and potassium hydroxide for transesterification as they have
excellent stability and activity (Ali et al. 2012). However, the drawbacks of such
catalysts are that they are insoluble and corrode the apparatus. As a solid catalyst,
it can decrease the cost of biodiesel and even the steps of purification (Jiang et al.
2010). However, sodium and potassium do not directly come from the animal
waste. Another supported catalyst used is potassium carbonate. After transester-
ification is complete, potassium carbonate can be extracted easily from the leftover
biomass with the help of inexpensive classical extraction technology (Baroi et al.
2009). Singh et al. (2006) showed that the potassium-based catalyst gave better
yields than the sodium-based catalyst. Usage of sodium and potassium hydroxide
flakes are common because they are inexpensive. The residual catalyst of sodium
and potassium hydroxide should be removed from the biodiesel through succes-
sive washes with water, after which quantification of metals must be done to
ensure the quality of the biodiesel product (Jesus et al. 2008). Increasing usage
of biodiesel worldwide implies the necessity for controlling the quality of
the biodiesel to avoid any undesirable mechanical and environmental effects
(Demirbas 2009, Caland et al. 2012).
Biodiesel Production
140 BIODIESEL PRODUCTION
enhanced in the presence of CO2 as the reaction medium and bond disassociation,
which is accelerated at temperatures greater than 550 °C in the presence of CO2.
Biodiesel Production
ANIMAL FAT BIODIESEL 141
(45.35, 109, and 96.16 million kg) by poultry fat and 170, 431, and 371 million lbs
(77.11, 195.4, and 168.283 million kg) by tallow, respectively (US Energy Informa-
tion Administration 2012). For a long time, the European Union was the world’s
largest biodiesel producer, representing nearly 70% of the entire biofuel market in
the transport industry. For 2010, 2011, and 2012, the total animal fat contribution to
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produce biodiesel was 390, 420, and 335 million tons (Table 6-2) for the grand total
of biodiesel production of 9.4, 9.4, and 9.65 million tons, respectively (Peters et al.
2011, Flach et al. 2012). For 2013, the animal fat contribution was estimated to be
340 million tons to produce 10.1 million tons biodiesel (Flach et al. 2012). To
understand the economic impact of the usage mandatory of various blends of
biodiesel produced in Canada to date, Stiefelmeyer et al. (2006) did a study by
focusing on the oilseed sector and the rendered animal fats industry, which were
supposed to be the major feedstocks for the biodiesel production. Certain para-
meters were estimated with respect to the nature of the markets of the feedstocks.
Other estimations were the economic effects of 2% and 5% biodiesel blend with
fossil fuel diesel. As shown in Table 6-2, for 2010, 2011, and 2012, total biodiesel
production by Canada only was 139, 158, and 284 million L, of which one of the
feedstock animal fat contributed at 95, 105, and 84 million tons, respectively. For
2013, of the estimated 538 million L, 135 million tons were contributed by animal fat
for biodiesel production (Brent Evans and Dessureault 2012).
Despite the wide variety of feedstocks that are potentially useful to produce
biodiesel, soybeans have nearly 77% of total biodiesel feedstock, followed by animal
fat, which accounts for 16% (Barros 2012). In 2012 and 2013, total biodiesel
production in Brazil was 2.7 and 2.760 (forecasted) billion L. Brazilian National
Agency for Petroleum, Natural Gas and Biofuels (ANP) has even estimated that 1 kg
of animal fat is equivalent to 1.064 L of biodiesel. Australia has biodiesel industries
also, and the main source is from animal fat and waste cooking oil. For 2010, the
total biodiesel produced was approximately 180 million tons. After 2010, many
Australia-based biodiesel manufacturers were shut down because the economic
viability of the operations in the industries decreased (Department of Resources,
Energy and Tourism Australia 2011). However, earlier in 2004 and 2005, total
production of biodiesel was approximately 1 and 4 million L (Paech 2006). Biodiesel
Biodiesel Production
142 BIODIESEL PRODUCTION
units are set in even smaller countries like Turkey, which has many small biodiesel
manufacturing facilities to meet the needs of the local population. Very large
biodiesel facilities in order to meet the needs of industries are very few, but it is a
promising business for the European Union, who promote biodiesel facilities in the
nation and in the worldwide arena. Along with favoring economics and increasing
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demand, smaller nations are coming up for the production of biodiesel (Kleindorfer
and Öktem 2007).
Like any biofuel counterpart, biodiesel has its own pros and cons, depending on
the type of feedstock used for the preparation of biodiesel. The universal benefit
would be the reduction of the reliance of fossil fuels and henceforth, simultaneous
reduction of the amount of emissions of greenhouse gases. One concern may be
the interference of biodiesel and its feedstock with the human food chain or factors
like deforestation. The significant advantage is the reduction of CO2 in the
environment. However, a gradual increase in the production of nitrogen oxide
(NOx) has been reported (Colomar et al. 2000, Chapman et al. 2003). Other
factors that affect the pros and cons of biodiesel include the following:
• Physical and chemical characteristics of animal fats: The properties of various
animal fats (tallow, lard, poultry fat, and fish fat) affect the resulting biodiesel
product properties. Certain standards were set for biodiesel that are desig-
nated under ASTM D6751; biodiesel from animal fats must meet those
specifications (Groschen 2002). Temperature is an importance characteristic
of the biodiesel property and the commodity from which biodiesel was
prepared. Biodiesel has the tendency to solidify in cold weather. For instance,
if it is made from animal fats, the biodiesel will primarily be in the solid phase
at room temperature, and the final product has the potential to further solidify
at relatively cold temperature. For instance, tallow (rendered form of beef)
processed from suet is always solid at room temperature. In fact, tallow can be
kept for an extended period without refrigeration to avoid decomposition, but
it is supposed to be kept in an airtight container for oxidation prevention
(Meat and Livestock Australia Limited 2011). This factor is dependent on the
presence of SFAs (Fontana 2009).
• Price rate of animal fats in various market places: Considering that animal fats
can be used in biodiesel production, the availability of animal fats as tallow,
lard, poultry fat, or fish fat will have an impact on the price of the raw
materials. Depending on the region, the prices may vary compared with the
other feedstock such as sunflower, canola, and soybean. According to
Minnesota’s biodiesel law, diesel fuel sold in the United States must contain
approximately 2% of biodiesel (Groschen 2002).
• Tax regulations: The United States and the European Union have benefited from
biodiesel consumption subsidies. The subsidies vary from United States and
Biodiesel Production
ANIMAL FAT BIODIESEL 143
European Union. In the European Union, the tax exemption is at the retail fuel
pump; however, in the United States, the tax credit is at price/3,785 L of biodiesel
fuel, which has since been discontinued. Any policy being released has impacts
on the market. Because the EU tax exemption is much higher than the US tax
credits, the worldwide biodiesel market prices are set on the EU parameters. The
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prices must tally with the world oil prices (de Gorter et al. 2010).
6.8 SUMMARY
Biodiesel Production
144 BIODIESEL PRODUCTION
6.9 ACKNOWLEDGMENTS
The authors sincerely thank the Natural Sciences and Engineering Research
Council of Canada (Grant A4984, RDCPJ 379601, Canada Research Chair) for
financial support. The views and opinions expressed in this chapter are strictly
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