Biodiesel is a liquid biofuel obtained by chemical processes from vegetable

oils or animal fats and an alcohol that can be used in diesel engines, alone or
blended with diesel oil.

Biodiesel production is a very modern and technological area for researchers due to the relevance that it
is winning every day because of the increase in the petroleum price and the environmental advantages.
Different studies have been carried out using different oils as raw material, different alcohol (methanol,
ethanol, butane) as well as different catalysts, homogeneous ones such as sodium hydroxide, potassium
hydroxide, sulphuric acid and supercritical fluids, and heterogeneous ones such as lipases. One of the
advantages of this fuel is that the raw materials used to produce it are natural and renewable. All these
types of oils come from vegetables or animal fat, making it biodegradable and nontoxic. Conventionally,
biodiesel is produced either in single-stage or double-stage batch process or by continuous flow-type
trans esterification process. A number of methods are currently available and have been adopted for the
production of biodiesel fuel. There are four primary ways to produce biodiesel 1. Direct use and blending
of raw oils. 2. Micro-emulsions. 3. Thermal cracking. 4. Trans esterification.

2.2 Raw Materials for Biodiesel Production

The raw materials for biodiesel production are vegetable oils, animal fats and short
chain alcohols. The oils most used for worldwide biodiesel production are rapeseed (mainly
in the European Union countries), soybean (Argentina and the United
States of America), palm (Asian and Central American countries) and sunflower,
although other oils are also used, including peanut, linseed, safflower, used vegetable oils,
and also animal fats. Methanol is the most frequently used alcohol
although ethanol can also be used.
Since cost is the main concern in biodiesel production and trading (mainly due
to oil prices), the use of non-edible vegetable oils has been studied for several
years with good results.
8 2 Introduction to Biodiesel Production
Besides its lower cost, another undeniable advantage of non-edible oils for
biodiesel production lies in the fact that no foodstuffs are spent to produce fuel [4].
These and other reasons have led to medium- and large-scale biodiesel production
trials in several countries, using non-edible oils such as castor oil, tung, cotton,
jojoba and jatropha. Animal fats are also an interesting option, especially in
countries with plenty of livestock resources, although it is necessary to carry out
preliminary treatment since they are solid; furthermore, highly acidic grease from
cattle, pork, poultry, and fish can be used.
Microalgae appear to be a very important alternative for future biodiesel production due to
their very high oil yield; however, it must be taken into account that
only some species are useful for biofuel production.
Although the properties of oils and fats used as raw materials may differ, the
properties of biodiesel must be the same, complying with the requirements set by
international standards.

2.2.1 Typical Oil Crops Useful for Biodiesel Production

The main characteristics of typical oil crops that have been found useful for
biodiesel production are summarized in the following paragraphs [6–10].
2.2.1.1 Rapeseed and Canola
Rapeseed adapts well to low fertility soils, but with high sulfur content. With a
high oil yield (40–50%), it may be grown as a winter-cover crop, allows double
cultivation and crop rotation.
It is the most important raw material for biodiesel production in the European
Community. However, there were technological limitations for sowing and harvesting in
some Central and South American countries, mainly due to the lack of
adequate information about fertilization, seed handling, and storage (the seeds are
very small and require specialized agricultural machinery). Moreover, low prices
in comparison to wheat (its main competitor for crop rotation) and low production
per unit area have limited its use.
Rapeseed flour has high nutritional value, in comparison to soybean; it is used
as a protein supplement in cattle rations.
Sometimes canola and rapeseed are considered to be synonymous; canola
(Canadian oil low acid) is the result of the genetic modification of rapeseed in the
past 40 years, in Canada, to reduce the content of erucic acid and glucosinolates in
rapeseed oil, which causes inconvenience when used in animal and human
consumption.
Canola oil is highly appreciated due to its high quality, and with olive oil, it is
considered as one of the best for cooking as it helps to reduce blood cholesterol
levels.
2.2 Raw Materials for Biodiesel Production 9
2.2.1.2 Soybean
It is a legume originating in East Asia. Depending on environmental conditions
and genetic varieties, the plants show wide variations in height. Leading soybean
producing countries are the United States, Brazil, Argentina, China, and India.
Biodiesel production form soybean yields other valuable sub-products in
addition to glycerin: soybean meal and pellets (used as food for livestock) and
flour (which have a high content of lecithin, a protein). Grain yield varies between
2,000 and 4,000 kg/hectare. Since the seeds are very rich in protein, oil content is
around 18%.
2.2.1.3 Oil Palm
Oil palm [11] is a tropical plant that reaches a height of 20–25 m with a life cycle
of about 25 years. Full production is reached 8 years after planting.
Two kinds of oil are obtained from the fruit: palm oil proper, from the pulp, and
palm kernel oil, from the nut of the fruit (after oil extraction, palm kernel cake is
used as livestock food). Several high oil-yield varieties have been developed.
Indonesia and Malaysia are the leading producers.
International demand for palm oil has increased steadily during the past years,
the oil being used for cooking, and as a raw material for margarine production and
as an additive for butter and bakery products.
It is important to remark that pure palm oil is semisolid at room temperature
(20–22 C), and in many applications is mixed with other vegetable oils, sometimes
partially hydrogenated.
2.2.1.4 Sunflower
Sunflower ‘‘seeds’’ are really a fruit, the inedible wall (husk) surrounding the seed
that is in the kernel.
The great importance of sunflower lies in the excellent quality of the edible oil
extracted from its seeds. It is highly regarded from the point of view of nutritional
quality, taste and flavor. Moreover, after oil extraction, the remaining cake is used
as a livestock feed. It must be noted that sunflower oil has a very low content of
linoleic acid, and therefore it may be stored for long periods.
Sunflower adapts well to adverse environmental conditions and does not require
specialized agricultural equipment and can be used for crop rotation with soybean
and corn. Oil yield of current hybrids is in the range 48–52%.
2.2.1.5 Peanut
The quality of peanut is strongly affected by weather conditions during the harvest.
Peanuts are mainly used for human consumption, in the manufacture of peanut
10 2 Introduction to Biodiesel Production
butter, and as an ingredient for confectionery and other processed foods. Peanuts
of lower quality (including the rejects from the confectionery industry) are used for
oil production, which has a steady demand in the international market. Peanut oil
is used in blends for cooking and as a flavoring agent in the confectionery industry.
The flour left over, following oil extraction, is of high quality with high protein
content; in pellet form, it is used as a livestock feed.
2.2.1.6 Flax
Flax [12] is a plant of temperate climates, with blue flowers. Linen is made with
the threads from the stem of the plant and the oil from the seeds is called linseed
oil, used in paint manufacture. Flax seeds have nutritional value for human consumption
since they are a source of polyunsaturated fatty acids necessary for
human health. Moreover, the cake left over, following oil extraction, is used as a
livestock feed.
The plant adapts well to a wide range of temperature and humidity; however,
high temperatures and plentiful rain do not favor high yields of seed and fiber.
Flax seeds contain between 30 and 48% of oil, and protein content is between
20 and 30%. It is important to remark that linseed oil is rich in polyunsaturated
fatty acids, linolenic acid being from 40 to 68% of the total.
2.2.1.7 Safflower
Safflower adapts well to dry environments. Although the grain yield per hectare is
low, the oil content of the seed is high, from 30 to 40%. Therefore, it has economic
potential for arid regions. Currently, safflower is used in oil and flour production
and as bird feed.
There are two varieties, one rich in mono-unsaturated fatty acids (oleic acid)
and the other with a high percentage of polyunsaturated fatty acids (linoleic acid).
Both varieties have a low content of saturated fatty acids.
The oil from safflower is of high quality and low in cholesterol content. Other
than being used for human consumption, it is used in the manufacture of paints and
other coating compounds, lacquers and soaps.
It is important to note that safflower oil is extracted by means of hydraulic
presses, without the use of solvents, and refined by conventional methods, without
anti-oxidant additives.
The flour from safflower is rich in fiber and contains about 24% proteins. It is
used as a protein supplement for livestock feed.
2.2.1.8 Castor Seed
The castor oil plant grows in tropical climates, with temperatures in the range
20–30 C; it cannot endure frost. It is important to note that once the seeds start
2.2 Raw Materials for Biodiesel Production 11
germinating, the temperature must not fall below 12 C. The plant needs a warm
and humid period in its vegetative phase and a dry season for ripening and harvesting. It
requires plenty of sunlight and adapts well to several varieties of soils.
The total rainfall during the growth cycle must be in the range 700–1,400 mm;
although it is resistant to drought, the castor oil plant needs at least 5 months of
rain during the year.
Castor oil is a triglyceride, ricinolenic acid being the main constituent (about
90%). The oil is non-edible and toxic owing to the presence of 1–5% of ricin, a
toxic protein that can be removed by cold pressing and filtering. The presence of
hydroxyl groups in its molecules makes it unusually polar as compared to other
vegetable oils.
2.2.1.9 Tung
Tung [12] is a tree that adapts well to tropical and sub-tropical climates.
The optimum temperature for tung is between 18 and 26 C, with low yearly
rainfall.
During the harvest season, the dry nuts fall off from the tung tree and are
collected from the ground. Nut production starts 3 years after the planting.
The oil from tung nuts is non-edible and used in the manufacture of paints and
varnishes, especially for marine use.
2.2.1.10 Cotton
Among non-foodstuffs, cotton is the most widely traded commodity. It is produced
in more than 80 countries and distributed worldwide. After the harvest, it may be
traded as raw cotton, fiber or seeds. In cotton mills, fiber and seeds are separated
from raw cotton.
Cotton fiber is processed to produce fabric and thread, for use in the textile
industry. In addition, cotton oil and flour are obtained from the seed; the latter is
rich in protein and is used in livestock feed and after further processing, for human
consumption.
2.2.1.11 Jojoba
Although jojoba can survive extreme drought, it requires irrigation to achieve an
economically viable yield.
Jojoba needs a warm climate, but a cold spell is necessary for the flowers to
mature. Rainfall must be very low during the harvest season (summer). The plant
reaches its full productivity 10 years after planting.
The oil from jojoba is mainly used in the cosmetics industry; therefore, its
market is quickly saturated.
12 2 Introduction to Biodiesel Production
2.2.1.12 Jatropha
Jatropha is a shrub that adapts well to arid environments. Jatropha curcas is the
most known variety; it requires little water or additional care; therefore, it is
adequate for warm regions with little fertility. Productivity may be reduced by
irregular rainfall or strong winds during the flowering season. Yield depends on
climate, soil, rainfall and treatment during sowing and harvesting. Jatropha plants
become productive after 3 or 4 years, and their lifespan is about 50 years.
Oil yield depends on the method of extraction; it is 28–32% using presses and
up to 52% by solvent extraction. Since the seeds are toxic, jatropha oil is nonedible. The
toxicity is due to the presence of curcasin (a globulin) and jatrophic
acid (as toxic as ricin).
2.2.1.13 Avocado
Avocado is a tree between 5 and 15 m in height. The weight of the fruit is between
120 and 2.5 kg and the harvesting period varies from 5 to 15 months. The avocado
fruit matures after picking and not on the tree.
Oil may be obtained from the fruit pulp and pit. It has a high nutritional value,
since it contains essential fatty acids, minerals, protein and vitamins A, B6, C, D,
and E. The content of saturated fatty acids in the pulp of the fruit and in the oil is
low; on the contrary, it is very high in mono-unsaturated fatty acids (about 96%
being oleic acid). The oil content of the fruit is in the range 12–30%.
2.2.1.14 Microalgae
Microalgae have great potential for biodiesel production, since the oil yield (in
liters per hectare) could be one to two orders of magnitude higher than that of other
raw materials. Oil content is usually from 20 to 50%, although in some species it
can be higher than 70% [13]. However, it is important to note that not all microalgae are
adequate for biodiesel production.
High levels of CO2, water, light, nutrients and mineral salts are necessary for
the growth of microalgae. Production processes take place in raceway ponds and
photobiological reactors [13]

2.3 Biodiesel Production Process

Biodiesel is produced from vegetable oils or animal fats and an alcohol, through a
transesterification reaction [1, 2, 4, 5]. This chemical reaction converts an ester
(vegetable oil or animal fat) into a mixture of esters of the fatty acids that makes
up the oil (or fat). Biodiesel is obtained from the purification of the mixture of fatty
acid methyl esters (FAME). A catalyst is used to accelerate the reaction (Fig. 2.5).
According to the catalyst used, transesterification can be basic, acidic or enzymatic, the
former being the most frequently used, as indicated in Box 2.3.
A generic transesterification reaction is presented in Eq. (2.1); RCOOR 0 indicates an ester, R
00OH an alcohol, R 0OH another alcohol (glycerol), RCOOR 00 an
ester mixture and cat a catalyst:
RCOOR 0 þ R00OH ,cat R0OH þ RCOOR00 ð2 :1Þ
When methanol is the alcohol used in the transesterification process, the
product of the reaction is a mixture of methyl esters; similarly, if ethanol were
Box 2.2 Most Important Alcohols Used in Biodiesel
Production
Methanol. Most widely used, in spite of its toxicity. It is a substance of
petrochemical origin.
Ethanol. Less used, requires more complex production technology and the
reaction speeds are lower. It can be produced from biomass.
23233
2332
21231
3
H C OCOR H C OH CH OCOR
HC OCOR CH OH HC OH CH OCOR
H C OCOR H C OH CH OCOR
NaOH
−−−
−−

used, the reaction product would be a mixture of ethyl esters. In both cases,
glycerin will be the co-product of the reaction. This is shown schematically in
Figs. 2.5 and 2.6.
Although transesterification is the most important step in biodiesel production
(since it originates the mixture of esters), additional steps are necessary to obtain a
product that complies with international standards [4, 17], as shown in Box 2.4. In
consequence, once the chemical reaction is completed and the two phases (mix of
esters and glycerin) are separated, the mix of methyl esters must be purified to
reduce the concentration of contaminants to acceptable levels. These include
remnants of catalyst, water and methanol; the latter is usually mixed in excess
proportion with the raw materials in order to achieve higher conversion efficiency
in the transesterification reaction. In the following sections the steps of the purification
process will be described in detail

Environmental Benefits of Biodiesel

5.1 Emissions Biodiesel is the only alternative fuel to voluntarily perform EPA Tier I and Tier II testing to
quantify emission characteristics and health effects. That study found that B20 (20% biodiesel blended
with 80% conventional diesel fuel) reduced total hydrocarbons by up to 30%, Carbon Monoxide up to
20%, and total particulate matter up to 15%. Typically, emissions of nitrogen oxides are either slightly
reduced or slightly increased depending on the duty cycle of the engine and testing methods used.
Increases in NOx can be effectively eliminated with the use of normal mechanical remediation
techniques (e.g. catalysts or timing changes). Research also documents the fact that the ozone forming
potential of the hydrocarbon emissions of pure biodiesel is nearly 50% less than that of petroleum fuel.
Pure biodiesel does not contain sulphur and therefore reduces sulphur dioxide exhaust from diesel
engines to virtually zero.Figure 2.shows Bus run by pure Biodiesel. Biodiesel can also help meet national
goals for the net reduction of atmospheric carbon. As a renewable fuel derived from organic materials,
biodiesel and blends of biodiesel reduce the net amount of carbon dioxide in the biosphere. A study by
the US Department of Energy has found that biodiesel production and use, in comparison to petroleum
diesel, produces 78.5% less CO2 emissions. Carbon dioxide is “taken up” by the annual production of
crops such as soybeans and then released when vegetable oil based biodiesel is combusted. This makes
biodiesel the best technology currently available for heavy-duty diesel applications to reduce
atmospheric carbon. Biodieselreduces GHGs by 41% compared with diesel, reduces several major air
pollutants, and has minimal impact on human and environmental health through N, P, and pesticide
release.

5.2 Health Effects Biodiesel is safer for people to breathe. Research conducted in the US shows biodiesel
emissions have decreased levels of all target polycyclic aromatic hydrocarbons (PAH) and nitrited PAH
compounds, as compared to petroleum diesel exhaust. PAH and nPAH compounds have been identified
as potential cancer causing compounds. Targeted PAH compounds were reduced by 75 to 85 percent,
with the exception of benzo(a) anthracene, which was reduced by roughly 50 percent. Target nPAH
compounds were also reduced dramatically with biodiesel fuel, with 2-nitrofluorene and 1-nitropyrene
reduced by 90 percent, and the rest of the nPAH compounds reduced to only trace levels. All of these
reductions are due to the fact the biodiesel fuel contains no aromatic compounds.
5.3 Energy Balance Biodiesel helps preserve and protect natural resources. For every one unit of energy
needed to produce biodiesel, 5.5 units of energy are gained. Because of this high energy balance and
since it is domestically produced, biodiesel use can greatly contribute to domestic energy
security.Among current food-based biofuels, soybean biodiesel has major advantages over corn grain
ethanol. Biodiesel provides 93% more usable energy than the fossil energy needed for its production.
5.4 Biodegradability and Toxicity Biodiesel is nontoxic and biodegradable. Tests sponsored by the United
States Department of Agriculture confirm that biodiesel is ten times less toxic than table salt and
biodegrades as fast as dextrose (a test sugar).

Pollution
In the United States, biodiesel is the only alternative fuel to have successfully completed the
Health Effects Testing requirements (Tier I and Tier II) of the Clean Air Act (1990).

Biodiesel can reduce the direct tailpipe-emission of particulates, small particles of solid
combustion products, on vehicles with particulate filters by as much as 20 percent compared
with low-sulfur (< 50 ppm) diesel. Particulate emissions as the result of production are reduced
by around 50 percent compared with fossil-sourced diesel. (Beer et al., 2004). Biodiesel has a
higher cetane rating than petrodiesel, which can improve performance and clean up emissions
compared to crude petro-diesel (with cetane lower than 40). Biodiesel contains fewer aromatic
hydrocarbons: benzofluoranthene: 56% reduction; Benzopyrenes: 71% reduction

Carbonyl Emissions
When considering the emissions from fossil fuel and biofuel use, research typically focuses on
major pollutants such as hydrocarbons. It is generally recognized that using biodiesel in place of
diesel results in a substantial reduction in regulated gas emissions, but there has been a lack of
information in research literature about the non-regulated compounds which also play a role in
air pollution.[13] One study focused on the emissions of non-criteria carbonyl compounds from
the burning of pure diesel and biodiesel blends in heavy-duty diesel engines. The results found
that carbonyl emissions of formaldehyde, acetaldehyde, acrolein, acetone, propionaldehyde and
butyraldehyde, were higher in biodiesel mixtures than emissions from pure diesel. Biodiesel use
results in higher carbonyl emissions but lower total hydrocarbon emissions, which may be better
as an alternative fuel source. Other studies have been done which conflict with these results, but
comparisons are difficult to make due to various factors that differ between studies (such as types
of fuel and engines used). In a paper which compared 12 research articles on carbonyl emissions
from biodiesel fuel use, it found that 8 of the papers reported increased carbonyl compound
emissions while 4 showed the opposite.[13] This is evidence that there is still much research
required on these compounds.