CHAPTER 2

LITERATURE REVIEW

2.1 Biodiesel

The history of biodiesel started in the mid 1800's. In those days the process of
transesterfication was used to separate glycerine from oil. Rudolf Diesel (1858-1913)
developed the first engine to run on peanut oil. When Rudolf Diesel demonstrated his diesel
engine at the Paris Show in 1900, he ran it on straight peanut oil. Dating from early 1920s,
many vegetable oils were investigated, including palm oil, soybean oil, cottonseed oil, and
castor oil. These early studies showed satisfactory performance of vegetable oil as fuel for
diesel engines (Knothe G, 2005). However, there were concerns that their higher costs as
compared to petroleum fuel would prevent their prevalent uses. In spite of their performance
in diesel engine, vegetable oils create engine problems when used as diesel fuel in both
indirect and direct-injection engines. The major drawback of vegetable oils is their high
viscosity which causes coking, varnishing and trumpet formation on the injectors that results
in poor atomization and ultimately leads to operational problems such as engine deposits (Ma
F, 1999). Possible solutions to reduce the viscosity of vegetable oil include heating,
transesterification, pyrolysis, dilution with petroleum-based fuels, and emulsification
(Schawab A, 1987).

Transesterification is the most common method which yields mono alkyl esters of long chain
fatty acids or fatty acid alkyl ester (FAAE). This idea originated in 1938 when it was noted
that glycerine has a low calorific value and is likely to cause excess carbon deposit in the
engine and, therefore, should be eliminated from glyceride oils used as diesel fuel. During that
period, it was proposed that the engine should run on what was referred to as residue fatty
acid (Walton J, 1938). This residue fatty acid is known today as biodiesel, although ester
was not yet mentioned. In fact, the high molecular weight of the triglyceride molecule is
responsible for much of the viscosity of vegetable oil, whereas the fatty acids are typically ten
(10) times less viscous than their parent vegetable oil at room temperature. During the
summer of 1938, an urban bus running between Brussels and Louvain was operated on ethyl
ester produced from palm oil. The engine performance was satisfactory and it was noted that
the viscosity of ethyl ester was less than that of palm oil. The term biodiesel made its first
appearance in a paper published in 1988 and this term was used exponentially thereafter
(Wang R, 1989).
Biodiesel is often defined as the mono alkyl esters of long chain fatty acids. Such esters may
be prepared from acyl-glycerides (usually triglyceride) in vegetable oils via transesterification
with short chain alcohols. Biodiesel production is a very modern and technological area for
researchers due to the relevance that it is winning everyday because of the increase in the
petroleum price and the environmental advantages (Mustafa, 2011). It is an alternatives fuel
for diesel engines that is produced by chemical reaction of a vegetable oils or animal fats with
an alcohol such as methanol. The product is called as methyl ester or biodiesel, which is
receiving high attention as an alternative, nontoxic, biodegradable and renewable diesel fuels
(Ma and Hanna, 1999). The use of biodiesel reduces global warming gas emission such as
carbon dioxide. Biodiesel has no aromatics, almost no sulphur and contains 11% oxygen by
weight. These characteristics of biodiesel reduce the emissions of carbon monoxide,
hydrocarbon and particulate matter in the exhaust gas compared to petroleum-based diesel
fuels (Graboski and McCormick, 1998). Therefore, biodiesel has become one of the most
common bio-fuels in the world (Lin et al., 2011). Biodiesel is miscible in all portions with
petroleum based diesel and, thus, can be effectively used as a neat biodiesel or blended with
petroleum based diesel fuel (Knothe G, 2005). The blends of biodiesel and petro-diesel are
often coded to represent the percent volume of the blend. B20, for example, indicates the
blend of 20 vol.% biodiesel and 80 vol.% petro-diesel.
2.1.1 Advantages of The Use Of Biodisel
Some of the advantages of using biodiesel as a replacement for diesel fuel are:
Renewable fuel, obtained from vegetable oils or animal fats.
Low toxicity, in comparison with diesel fuel. Degrades more rapidly than diesel fuel,
minimizing the environmental consequences of biofuel spills.
Lower emissions of contaminants: carbon monoxide, particulate matter, polycyclic
aromatic hydrocarbons, aldehydes.
Lower health risk, due to reduced emissions of carcinogenic substances.
No sulfur dioxide (SO2) emissions.
Higher flash point (100_C minimum).
May be blended with diesel fuel at any proportion; both fuels may be mixed during
the fuel supply to vehicles.
Excellent properties as a lubricant.
It is the only alternative fuel that can be used in a conventional diesel engine,
without modifications.
Used cooking oils and fat residues from meat processing may be used as raw
materials.

2.1.2 Disadvantages of the Use of Biodiesel

There are certain disadvantages of using biodiesel as a replacement for diesel fuel
that must be taken into consideration:
Slightly higher fuel consumption due to the lower calorific value of biodiesel.
Slightly higher nitrous oxide (NOx) emissions than diesel fuel.
Higher freezing point than diesel fuel. This may be inconvenient in cold
climates.
It is less stable than diesel fuel, and therefore long-term storage (more than six
months) of biodiesel is not recommended.
May degrade plastic and natural rubber gaskets and hoses when used in pure
form, in which case replacement with Teflon_ components is recommended.
It dissolves the deposits of sediments and other contaminants from diesel fuel in
storage tanks and fuel lines, which then are flushed away by the biofuel into the
engine, where they can cause problems in the valves and injection systems. In
consequence, the cleaning of tanks prior to filling with biodiesel is recommended.
It must be noted that these disadvantages are significantly reduced when biodiesel is used in
blends with diesel fuel.
2.1.3 Biodiesel Specifications
The American Society for Testing and Materials International (ASTM) specification for
biodiesel (B100) is ASTM D6751-02. It is summarized in Table 2.1 Some of the test methods
listed in it performs more than one role. These methods ensure that the fuel performs same as
intended in CI engines and as tests to ensure that the manufacturer produced a high quality
B100. Each of these properties and the test method used to measure it are briefly described
below. Detail explanations about its property requirements and specific methods can be found
in literature (Tyson k, 2009).

Table 2.1 Specification for Biodiesel

Property Unit ASTM D-6751 EN 14214

Limits Test Limit Test

methods s methods
 0 3
Density(15 C) kg/m N/S N/S 860- ENISO
Ester content mass % N/S N/S 900
96.5 3675
EN 14103
Cetane number - 47 min D 613 min
51 min ENISO
Flash point o
C 130 D 93 120 5165
ISO/CD
Water content volume min
0.050 D2709 min
500 3679
ENISO
Sulphated ash %
mass % max
0.020 D874 max
0.02 12937
ISO 3987
Copper Corrosion Grade max
No.3 D130 max
No.1 ENISO
Acid number mgKO max.
0.80 D 664 0.5 2160
EN 14104
Free glycerol H/g
mass % max
0.02 D 6584 max
0.02 EN 14105
Total glycerol mass % max
0.240 D 6584 max
0.25 EN 14105
Phosphorous content mass % max
0.001 D 4951 max
10 EN 14107
Iodine number - max
N/S N/S max
120 EN 14111
Oxidative H N/S N/S max
6 min EN 14112
0
stability(110
Mono-glycerols C) mass % N/S N/S 0.8 EN 14105
Di-glycerols mass % N/S N/S max
0.2 EN 14105
Tri-glycerols mass % N/S N/S max
0.2 EN 14105
Methanol mass % N/S N/S max
0.2 EN 14110
High calorific value MJ/kg N/S N/S max
N/S N/S
Low calorific value MJ/kg N/S N/S N/S N/S
Oxygen Content % N/S N/S N/S N/S
Source: National Renewable Energy Laboratory Subcontractor Report 2004

Flash point: it is defined as the lowest temperature corrected to a barometric pressure of

101.3 Kpa (760 mmHg), at which application of an ignition source causes the vapours of a
specimen to ignite under specified conditions of test. For biodiesel, this test is a measure of
residual alcohol and determinant for flammability classification of materials.
Water and Sediment: It is a test that determines the volume of free water and sediment in
middle distillate fuels having viscosities at 40 C in the range 1.0 to 4.1 mm 2/s and densities
in the range of 700 to 900 kg/m 3. This test is a measure of cleanliness of fuel. For biodiesel,
this test is determinant of presence of free water droplets and sediment particles.
Kinematic Viscosity: It is defined as the resistance to flow of a fluid under gravity. It is a
basic design specification for fuel injectors used in diesel engines. For biodiesel it is quick
and easy method for estimating the degree of completion of batch reaction.
Sulfated Ash: It is the residue remaining after a fuel sample has been carbonized, and the
residue subsequently treated with sulphuric acid and heated to a constant weight. This test
monitors the mineral ash residual when fuel is burned. For biodiesel, this test is an important
indicator of the quantity of residual metals in the fuel that came from the catalyst used in the
esterification process.
Sulfur: This method covers the determination of total sulphur in liquid hydrocarbons, boiling
in the range from approximately 25 to 400 C, with viscosities between approximately 0.2 and
20 cSt (mm2/s) at room temperature. Biodiesel feedstock typically have very little sulphur,
but this test is an indicator of contamination of protein material and/or carryover catalyst
material or neutralization material from the production process.
Copper Strip Corrosion: The copper strip corrosion is used for detection of the
corrosiveness to copper of fuels and solvents. This test monitors the presence of acids in the
fuel. For B100, the most likely source of a test failure would be excessive free fatty acids,
which are determined in accordance with an additional specification.
Cetane Number: The cetane number is a measure of the ignition performance of a diesel fuel
obtained by comparing it to reference fuels in a standardized engine test. This test is a
measure of how easily the fuel will ignite in the engine. For biodiesel, the cetane number is
seldom an issue because all of the common fatty acid esters have cetane numbers near or
above 47.
Cloud Point: The cloud point is the temperature at which a cloud of wax crystals first appears
in a liquid when it is cooled down under specific conditions. The cloud point is a critical
factor in cold weather performance for all diesel fuels. For biodiesel, cloud point is typically
higher than the cloud point of conventional diesel. It can then be modified in following ways
to get the lower cloud point.
- The use of additives that retard the formation of solid crystals in the B100 by various
mechanisms.
- The blending feedstock that is relatively high in saturated fatty acids with feedstock that
have lower saturated fatty acid content.

Carbon Residue: In petroleum products, the part remaining after a sample has been subjected
to thermal decomposition, is the carbon residue. The carbon residue is a measure of how
much residual carbon remains after combustion. The test basically involves heating the fuel to
a high temperature in the absence of oxygen. The most common cause of excess carbon
residues in biodiesel is an excessive level of total glycerin.
Acid Number: The acid number is the quantity of base, expressed as milligrams of potassium
hydroxide per gram of sample, required to titrate a sample to a specified end point. The acid
number is a direct measure of free fatty acids in B100. The free fatty acids can lead to
corrosion and may be a symptom of water in the fuel.
Free Glycerin: Free glycerol is the glycerol present as molecular glycerol in the fuel. It
results from incomplete separation of the ester and glycerol products after the
transesterification reaction. This can be a result of imperfect water washing or other
approaches that do not effectively separate the glycerol from the biodiesel.
Total Glycerin: Total glycerol is the sum of free and bonded glycerol. Bonded glycerol is
the glycerol portion of the mono-, di-, and triglyceride molecules. High values of total
glycerin are indicators of incomplete esterification reactions and predictors of excessive
carbon deposits in the engine.
Phosphorous: This test covers the quantitative determination of barium, calcium, copper,
magnesium, phosphorus, sulphur, and zinc in unused lubricating oils and additive packages.
In the case of B100, phosphorus can come from incomplete refining of the phospholipids (or
gums) from the vegetable oil and from bone and proteins encountered in the rendering
process.
Vacuum Distillation end point: The vacuum distillation end point test covers the
determination, at reduced pressures, of the range of boiling points for petroleum products that
can be partially or completely vaporized at a maximum liquid temperature of 400C.
Petroleum fractions have tens to hundreds of individual compounds mixed together. In B100
there are, at most, ten different esters present, and they can be identified using gas or liquid
chromatography and Nuclear magnetic Resonance chromatography .
2.1.4 Environmental Impacts of Biodiesel
As an alternative fuel, biodiesel is becoming increasingly important due to diminishing
petroleum reserves and adverse environmental consequences of exhaust gases from
petroleum-fuelled engines (Karmarkar S, Karmakar A and Mukhejee, 2010). In contrast to
conventional petrodiesel, it is environmental friendly and creates substantial reduction in
emission, hence, these properties make Biodiesel a good alternative fuel to petroleum-based
diesel oil (Khan S, etal 2009).
Biodiesel has many other environmental benefits, such as it is biodegradable, non-toxic, and
has low emission profile (including potential carcinogens) [20, 21]. It can be used in todays
vehicle fleets worldwide and may also offer a viable path to sustainable transportation fuel
[22]. Moreover, it does not contribute to global warming due to its closed carbon cycle
because the primary feedstock for biodiesel is a biologically-based material that can be grown
season after season. And, since the carbon in the fuel was 9
originally removed from the air by plants, there is no net increase in carbon dioxide levels
[23].
Biodiesel is safer fuel as it has high flash point temperature of 154 oC [24]. It is regarded as
clean fuel since it does not contain carcinogenic substances and its sulphur content level is
also lower than its content in petrodiesel [25].
It is well known that biodiesel is non-toxic, contains no aromatics and is less pollutant to both
water and soil. It is the most suitable fuel in environmentally sensitive areas (national parks,
lakes, rivers) or in confined areas where environmental conditions and worker protection must
meet high standards (underground mines, quarries) [26]. Moreover, it contains about 10%
built in oxygen, which helps it to burn fully and also expected to reduce exhaust emissions. Its
higher cetane number (CN) improves the ignition quality even when blended with petroleum
diesel [27].
Nevertheless, diesel engines emit particulate matter, nitrogen oxides, greenhouse gases, and
air toxics [28]. Hence, the important property of Biodiesel is, then, its ability to reduce such
pollutants as carbon monoxide, unburned hydrocarbons and particulate emission from engines
[23]. Studies also showed significantly lower levels of emissions of specific toxic compounds
for Biodiesel and Biodiesel blends, including aldehydes, polyaromatic hydrocarbons (PAH),
and nitro-polyaromatic hydrocarbons (nPAH) [29]. 10
2 Modern Processes of Biodiesel Production
2.1 The Basic Concept
Biodiesel is defined as the mono-alkyl esters of long chain fatty acids (derived from vegetable
oils or animal fats). It is the product of the reaction of a straight chain alcohol, such as
methanol or ethanol (in the presence of catalyst NaOH, KOH or CH3ONa) with a fat or oil
(triglycerides) to form the mixture of fatty esters of long chain fatty acids (Biodiesel) and
glycerol (glycerin) [30, 31]. Biodiesel represents a suitable renewable substitute for petroleum
based diesel and is accepted as an alternative diesel fuel in a steadily growing number of
countries around the world. Fatty acid methyl esters or ethyl esters (FAME/EE), from
vegetable oils, have shown promise as Biodiesel, as the result of improved viscosity, volatility
and combustion behavior relative to raw triglycerides, while maintaining their cetane number
(around 50) [32].
2.2 Technological Platforms
Vegetable oils are produced from numerous oil seed crops with varying fatty acid
composition. While all vegetable oils have high-energy content, most require some processing
to assure safe fuel use in internal combustion engines [26].
Various methods were used to produce fuels from vegetable oils or fats including; direct use
of vegetable oils & fats and/or blending at different proportions with diesel, microemulsions
with simple alcohols, thermal cracking (pyrolysis) to alkanes, alkenes, alkadienes etc., batch
wise transesterification (alcoholysis) (figure 2.1) and the continuous base-catalyzed process
(Appendix 1) [33, 34]. More literature related to advantages and disadvantages of different
methods of biodiesel production can be studied in the review on biodiesel production [56].
The continuous
2.2 Raw Material for Biodiesel Production
There are several types of raw materials for biodiesel production. The most common
feedstock comes from vegetable oil. There are two types of vegetable oils that are edible and
non-edible oils. More than 95% of biodiesel production feedstock come from edible oils since
they are mainly produced in many regions and the properties of biodiesel produced from these
oils are much suitable to be used as diesel fuel substitute.
By converting edible oils into biodiesel, food resources are actually being converted into
automotive fuels. It is believed that large-scale production of biodiesel from edible oils may
bring global imbalance to the food supply and demand market, therefore emphasis is placed
on non edible oil for biodiesel production (Gui et al., 2008).
2.2.1 Commonly used edible oil
2.2.1.1 Soy beans oil
Soybean oil is used as a major source of edible oil throughout the world. With about 222
million tonnes, soybean is the most important oil bearing plant cultivated world-wide and its
production is seeing a further expansion, particularly in the USA, Brazil and Argentina
(Bockey, 2006). According to the National Board of Biodiesel (USA), soybean oil is the
primary source for biodiesel production in US and an estimated 75 million gallons of
biodiesel were to be produced in 2005. Soybeans can be produced without or nearly zero
nitrogen. This makes soybeans advantageous for the production of biodiesel as nitrogen
fertilizer is one of the most energy costly inputs in crop production. (Pimental and Patzek,
2005) studied the energy estimation for producing soybean biodiesel. They reported that 5546
kg of soybeans were required for producing 1000 kg of oil and biodiesel production using
soybean required 27% more fossil energy than the biodiesel fuel produced.
2.2.1.2 Sunflower oil
Sunflower with high oil content is one of the more prominent oilseed crops for biodiesel
production. At one point, it was considered to be the second primary source of edible oil next
to soybean. Sunflower can grow in a variety of climatic conditions but it is considered to be
an inefficient user of nutrients. Average yield is approximately reported to be lower than
soybean yields, and necessary inputs are greater (Pimental and Patzek, 2005).

2.2.1.3 Palm oil

Oil is derived from both the flesh and the seed of the palm fruit. The fruit consists of an outer
pulp, which is the source of crude palm oil and two or three kernels, which are the source of
another oil type palm kernel oil. Crude palm oil is semisolid at room temperature. Palm
kernel oil is rich in lauric and myristic fatty acid with an excellent oxidative stability and
sharp melting. Malaysia is the worlds largest palm growing country and palm plantation
covers two-third of its agricultural lands. Palm oil has been proved to be an efficient biodiesel
source. The average yield of approximately 6000 l of palm oil/ha can produce 4800 l of
biodiesel. It has been stated that palm oil can have high levels of fatty acids, which require
extra methanol transesterification before it can be used as biodiesel, thus increasing the cost of
production somewhat (Crabbe et al., 2001). Farmers in Ghana are producing biodiesel from
palm kernel oil for powering their farm vehicles and generators.
2.4.1.4 Peanut oil
The peanut or groundnut is native to South America, Mexico and Central America. Rudolf
Diesel, the inventor of compression-ignition engines, used first time peanut oil in 1900. The
physico-chemical characteristics of peanut oil biodiesel (POB) closely resemble to those of
diesel fuel (Mittelbach and Tritthart, 1988). Peanut oil produces approximately 1170 l
biodiesel/ha, compared to 475 l for soybean oil (Mittelbach and Tritthart, 1988). But the
production of biodiesel from peanut oil is not economically viable as peanut oil is more
valuable than soy oil in the world market. Studies are going on at the University of Georgia to
develop non-edible peanut varieties which are high in oil, but will not compete with peanuts
grown for food or cooking oil purposes.

2.2.2 Commonly used non edible oil

2.2.2.1 Jatropha
Recently Jatropha is being considered as one of the most promising potential oil source to
produce biodiesel in Asia, Europe and Africa. Jatropha can grow under a wide variety of
climatic conditions like severe heat, low rainfall, high rainfall and frost. Jatropha is grown in
marginal and waste lands with no possibility of land use competing with food production.
Jatropha oil content varies depending on the types of species, climatic conditions and mainly
on the altitude where it is grown. Various parts of the plant have medicinal values. Apart from
supplying oils for diesel replacement, the growing of the tree itself effectively reduces CO2
concentrations in the atmosphere. In developing countries like India it has been identified as
the major source of biodiesel (Aninidita et al., 2012).
2.2.2.2 Pongamia oil
It is a hardy tree of 1215 m height, branches spread into hemispherical crown of dense green
leaves and native to the Asian sub-continent. Pongamia can survive in adverse conditions like
draught, heat, frost, salinity etc. Most of the physical and chemical properties of the directly
extracted oil are almost similar to those of the diesel, though conardson carbon residue is
higher in case of it and due to high viscosity preheating is necessary to start a diesel engine
(Shrinivasa, 2001). The toxic substances present in the oil limits its use as cooking oil. The
seedcake after oil extraction can be utilized as nematicide.
2.2.2.3 Neem oil
Neem oil is light to dark brown in colour and bitter in taste. The Neem tree is native to India
and Burma and almost the whole tree is usable for various purposes such as medicines,
pesticides and organic fertilizer. Neem can be grown on very marginal soils that may be very
rocky, shallow, dry, or pan-forming. Neem tree can tolerate some extreme conditions like
temperature of 45 C and rainfall less than 35 cm per year. Azadirachtin is the main
constituent of Neem seed oil which varies from 300 to 2500 ppm depending on the extraction
technology and quality of the Neem seeds crushed. The oil contains sulphurous compounds
which gives it a pungent odor and a less-clean burn than other vegetable oils
(Aninidita et al., 2012).

2.2.3 Potential edible oil

2.2.3.1 Moringa oleifera oil
The Moringa or Ben-oil tree is believed to be native to India, Arabia, and possibly even across
Africa and the Caribbean. It thrives in subtropical to tropical dry to moist climates, tolerating
rainfall from 25 to 300 plus cm annually with temperatures ranging from 19 to 28C. It is a
fast growing tree and can tolerate draught, sandy soil, bacteria and fungi. In addition to its
nutritional value, M. oleifera has got many useful medicinal uses. Ben-oil trees are capable of
producing seed pods within the first year after planting. Full fruit bearing can be expected by
the second full year. The trees can continue producing pods for several years. Oil qualities are
similar to that of olive oil, and the degummed oil has favorable characteristics for use as a
replacement for petroleum diesel ( Tsaknis et al., 1999).
There has been strong international interest in Moringa with claims that it can annually
produce 10002000 l of biodiesel from one hectare. Biodiesel produced from Moringa oil
exhibit a high cetane number of approximately 67, one of the highest found for a biodiesel
fuel, enhanced oxidative stability and high cloud point ( Umer et al.,2008).
2.2.3.2 Coconut oil
Coconut is widely harvested in tropical coastal areas. Coconut oil accounts for nearly 20% of
the vegetable oil produced in the world. Coconut oil is extracted from the copra, the dried
flesh of the nut. Coconut oil remains solid at relatively high temperature than most of other
vegetable oils. In liquid form, Coconut oil burns very neatly in diesel engines. Coconut oil has
the potential to yield 50% motor fuel as diesel fuel. The main drawback of using coconut oil
in engines is that it starts solidifying at a temperature below 22 C and by 14 C it
does not flow at all (Aninidita et al., 2012).
2.4.3.3 Corn oil
Corn is a starch crop. It is mainly sown in USA for its starch and protein content. It is not
practically viable to grow this crop specifically for biodiesel production as the extraction
process cannot produce a grade of oil which is suitable enough for production of biodiesel.
But when the crop is turned into ethanol after fermentation, the oil can easily be separated and
viably used for biodiesel production. In the USA, interest has grown up to use corn oil as
source material for biodiesel production (Aninidita et al., 2010).

2.2.4 Potential non edible oil

2.2.4.1 Algae oil
It was reported that algae (micro and macro) were one of the best sources of biodiesel;
microalgae have much more oil than macroalgae and it is much easier and faster to grow
(Shay, 1993). The best algae for biodiesel would be microalgae and are the highest yielding
feedstock for biodiesel and it can produce up to 250 times the amount of oil per acre as
soybeans (Hossain et al., 2008). Microalgae may be the potential and economical source of
biodiesel because of its high yield and non-requirement of farmland or fresh water. Oil
content in microalgae can exceed 80% by weight of dry biomass (Spolaore et al., 2006).
Microalgal oils differ from most vegetable oils in being quite rich in polyunsaturated fatty
acids with four or more double bonds (Belarbi et al., 2000). Studies show that biodiesel can be
produced from macro algae also even though the lipid content (1.37.8%, dry weight) of
macro algae is less than micro algae (Hossain et al.,2008). Yusuf (2007) reported that
microalgae appear to be the only source of renewable biodiesel that is capable of meeting the
global demand for transport fuels. Oil productivity of many microalgae greatly exceeds the oil
productivity of the best producing oil crops.
2.2.4.2 Castor oil
Castor oil has been identified as a potential raw material for the production of biodiesel in
Brazil. Castor oil is comprised almost entirely (ca. 90%) of triglycerides of ricinoleic acid
(12-hydroxy-cisoctadec-9-enoic acid) in which the presence of a hydroxyl group at C-12
imparts several unique chemical and physical properties and thus, castor oil and its derivatives
are completely soluble in alcohols and exhibit viscosities that are up to sevenfold higher than
those of other vegetable oils (Kulkarni and Sawant, 2003). Although castor has potential for
very high oil yield, the fact that it is considered a weed by many agricultural producers
certainly limits its viability as an option to produce significant amounts of biodiesel. In spite
of the fact that transesterification reduces the viscosity significantly, the biodiesel capacity of
the castor oil is still being researched to find out whether the final viscosity of castor oil
biodiesel is within acceptable range for use in the diesel engines.
2.2.5. Used Cooking Oil
The properties of used cooking oil depend highly on the origin and history of the oil. The
origin of used cooking oil determines its fatty acid compositions. The history or duration that
the oil is exposed to water, heat, food, micro-organisms and oxygen during cooking
determines its physical and chemical properties such as viscosity, water content, free fatty
acid content, and the presence of polymerized and oxidized compounds.
Oil degradation during cooking occurs through three main reactions: thermolytic, oxidative,
and hydrolytic reactions. Thermolytic reactions occur in the absence of oxygen and saturated
fatty acids, forming alkanes, fatty acids, ketones, esters, and diacylglycerides that are
decomposed at high temperatures. In addition, dimeric compounds are major products of
thermolytic reactions of unsaturated fatty acids. Dimerization and polymerization of
unsaturated fatty acids take place via Diels-Alder reactions. For example, a reaction between
conjugated diene from linoleate and oleate can take place to produce a tetra-substituted
cyclohexene (Nawar w, 1984). In the presence of oxygen, oxidative and nonoxidative
reactions will occur simultaneously. Oxidative reactions occur in a series of initiation,
propagation, and termination steps as shown in Figure 2.1. The initial step involves
abstraction of hydrogen from unsaturated fatty acid to form a free radical (R) followed by a
reaction of the radical with molecular oxygen to form peroxide radicals (ROO). The
propagation phase involves intermolecular interactions, whereby the peroxide radical
abstracts hydrogen from an adjacent molecule, which gives rise to hydroperoxides (ROOH)
and a new free radical.

Figure 2.1 Approximate Oil Yield for Different Crops

2.3 Synthesis Routes
Nowadays, there are numerous synthesis routes in the production of biodiesel which using
different alcohols and catalysts. Four of the biodiesel synthesis routes are direct use and
blending of raw oils, micro-emulsions, thermal cracking (pyrolysis) and transesterification
with process descriptions shown in Table 2.1, 2.2, 2.3 and 2.4 respectively. In this paper,
transesterification was chosen to be the method to produce biodiesel because through this
process, biodiesel will have a higher cetane number, lower emissions, higher combustion
efficiency and renewable.
Table 2.1: Direct use and blending of raw oils process description
Process Direct use and blending
Definition Direct use as diesel fuel or blend with diesel fuel

Advantage Liquid nature-portability

Heat content (80% of diesel fuel)
Readily available and renewability
Disadvantage Higher viscosity
Lower volatility
 Reactivity of unsaturated hydrocarbon chain

Table 2.2: Micro-emulsions process description

Process Micro-emulsions
Definition Direct use as diesel fuel or blend with diesel fuel
Advantage Liquid nature-portability
Heat content (80% of diesel fuel)
Readily available and renewability
Disadvantage Higher viscosity
Lower volatility
Reactivity of unsaturated hydrocarbon chains
Problems of using in Coking and trumpet formation
Engines Carbon deposits
Oil ring sticking
Thickening and gelling of the lubricating oil
Source: Alonso et al (2008)

Table 2.3: Thermal cracking (pyrolysis) process description

Process Thermal cracking (pyrolysis
Definition The conversion of long-chain and saturated
substance (biomass basis) to biodiesel by
means of heat
Advantage Chemically similar to petroleum-derived
gasoline and diesel fuel
Disadvantage Energy intensive and hence higher cost
Source : Alonso et al (2008)

Table 2.4: Transesterification process description

Process Transesterification
Definition The reaction of a fat or oil with an alcohol in the
presence of catalyst to form esters and glycerol
Advantages Renewability
Higher cetane number
Lower emissions
Higher combustion efficiency
Disadvantage Disposal of by-product (glycerol and waste water)
Source: Schinas et al (2009)
2.4 Basic chemical reactions
The figure below depict the simplified form of chemical reaction which is presented in
equation.
Vegetable oils or animal fats are esters of saturated and unsaturated monocarboxylic acids
with the trihydric alcohol glyceride. These esters are called triglycerides, which can react with
alcohol in the presence of a catalyst, a process known as transesterification. R1, R2 and R3 in
below figure are long-chain hydrocarbons, sometimes called fatty acid chains. Normally, there
are five main types of chains in vegetable oils and animal oils: palmitic, stearic, oleic, linoleic,
and linolenic. 1 mol of fatty ester is liberated at each step of the conversion process of
triglyceride into diglyceride, monoglyceride, and finally to glycerol (Dennis et al, 2010).

Figure 2.2: Basic chemical reaction

2.7 Catalyst
Normally, there are three type of catalysts being used in transesterification which are alkalis,
acids, and enzymes. All three catalysts including their advantages, disadvantages and example
of catalyst are shown in Tables 2.5, 2.6, 2.7and 2.8 respectively. In this research,
potassium hydroxide was chosen as a catalyst to be used transesterification because it is
cheaper and most commercially use in small and large scale biodiesel production compare to
acid and enzyme catalyst (Umer and Anwar, 2008) The cost of transesterification process
which use alkali catalyst especially potassium hydroxide is cheap because the process is
carried out at low temperature of around 60oC. Moreover, it require no intermediate step and
high conversion rate.
Table 2.5: Alkali homogeneous catalyst
Type Homogeneous
Advantages High catalytic activity
Low cost
Favourable kinetics
modest operation conditions
Disadvantages Low FFA requirement
Anhydrous conditions
Saponification
Emulsion formation
More waste water from purification
Disposable
Example NaOH
KOH
Source: Dizge et al (2009)

Table 2.6: Alkali heterogeneous catalyst

Type Heterogeneous
Advantages Noncorrosive,
Environmentally benign
Recyclable
Fewer disposal problems
Easily separation
Higher selectivity
Longer catalyst lifetimes
Disadvantages Low FFA requirement
Anhydrous conditions
More wastewater from purification
High molar ratio of alcohol to oil requirement
High reaction temperature and pressure
Diffusion limitations
Example CaO
CaTiO3
CaZrO3
CaOCeO2
CaMnO3
Ca2Fe2O5
KOH/Al2O3
Source: Liu et al (2008)

Table 2.7: Acid homogeneous catalyst

Type Homogeneous
Advantages Catalyse esterification and transesterification simultaneously
Avoid soap formation
Disadvantages Equipment corrosion
More waste from neutralization
Difficult to recycle
Higher reaction temperature
Long reaction times
Weak catalytic activity
Example Concentrated sulphuric acid
Source: Dizge et al (2009)

Table 2.8: Acid heterogeneous catalyst

Type Heterogeneous
Advantages Catalyze esterification and transesterification simultaneously,
recyclable
Eco-friendly
Disadvantages Low acid site concentrations
Low microporosity
Diffusion limitations
High cost
Example Carbon-based solid acid catalyst
Carbohydrate-derived catalyst
Vanadyl phosphate
Niobic acid
Sulphated zirconia
Amberlyst-15
Nafion-NR50
Source: Lou et al (2008)

2.7 Alcohol
There are several types of alcohol that can be used in transesterification process such as
methanol, ethanol, propanol, iso-propanol, butanol and amyl-alcohol (Encinar et al., 2007)

Among aforementioned alcohols, methanol is the most extensively used in the production of
biodiesel (Chang and Liu, 2009). . Moreover, methanol can react with vegetable oils or
animal fats in a short period of time and potassium hydroxide is easily dissolved in it.