Lecture #: Biodiesel Production

Wasi ur Rahman

Guest Teacher
Industrial Chemistry Section
Department of Chemistry
Aligarh Muslim University

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 1. INTRODUCTION

The energy demand of the world is increasing fast mainly because of the rapid growth experienced by fast
developing economies. Most energy resources, such as petroleum, coal, and natural gas, are non- renewable
sources that are limited because supplies are running out. As well as the increase in energy demand,
increases in prices and environmental problems created by fossil fuels are creating opportunities to explore
alternative energy sources. Common types of alternative energy sources are, Biofuels (biodiesel), Solar
energy, Wind energy, Geothermal energy etc.

1.1 BIODIESEEL

Biodiesel is an alternative fuel for diesel engines that is produced by chemically reacting a vegetable oil
or animal fat with an alcohol such as methanol. The reaction requires a catalyst, usually a strong base,
such as sodium or potassium hydroxide, and produces new chemical compounds called methyl esters. It is
these esters that have come to be known as biodiesel. Because its primary feedstock is a vegetable oil or
animal fat, biodiesel is generally considered to be renewable. Biodiesel is considered to contribute much
less to global warming than fossil fuels. Diesel engines operated on biodiesel have lower emissions of
carbon monoxide, unburned hydrocarbons, particulate matter, and air toxics than when operated on
petroleum-based diesel fuel.

Fig – 1.1 Samples of biodiesel

With less than a decade of commercial-scale production, the industry is proud of its careful approach to
growth and strong focus on sustainability. Production has increased from about 25 million gallons in the
early 2000s to almost 1.1 billion gallons in 2012. This represents a small but growing component of the
annual U.S. on-road diesel market of about 35 billion to 40 billion gallons. Consistent with projected
feedstock availability, the industry has established a goal of producing about 10 percent of the diesel
transportation market by 2022.

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Reaching that goal would significantly lessen U.S. dependence on imported oil, bolstering national
security and reducing our trade deficit. At the same time, biodiesel‟s growth would boost the U.S.
economy, not just by creating jobs but also by reducing our dependence on global oil markets and
vulnerability to price spikes. There are currently about 200 biodiesel plants across the country – from
Washington State to Iowa to North Carolina – with registered capacity to produce some 3 billion gallons
of fuel. The industry is supporting more than 62,000 jobs, generating billions of dollars in GDP,
household income and tax revenues. The industry‟s economic impact is poised to grow significantly with
continued production increases. The industry supports jobs in a variety of sectors, from manufacturing to
transportation, agriculture and service.
The EPA has recognized biodiesel‟s environmental benefits by classifying it as an Advanced Biofuel,
making biodiesel the only commercial-scale U.S. fuel produced nationwide to meet the agency‟s
advanced criteria. According to the EPA, biodiesel reduces greenhouse gas emissions by at least 57
percent and up to 86 percent when compared to petroleum diesel – making it one of the most practical and
cost-effective ways to immediately address climate change. In addition, biodiesel sharply reduces major
tailpipe pollutants from petroleum diesel, particularly from older diesel vehicles. This is important
because the EPA has consistently cited diesel exhaust – primarily from older trucks, buses and other
vehicles – as one of the nation's most dangerous pollutants.

1.1.1 Why Biodiesel Is Important?

The diesel engines that power most trucks and buses are not only highly efficient power plants, they are
also very versatile in the fuels they can use. Rudolf Diesel first conceived of the engine that now bears his
name as running on powdered coal. A ruinous engine explosion taught him to value liquid fuels. He
subsequently hit on the idea of using vegetable oil. The engine that he demonstrated at the World
Exhibition in Paris in 1900 ran on oil extracted from peanuts.
Nearly a century of reliance on dwindling petroleum reserves has taught us the wisdom of looking to
Nature‟s bounty for our fuels, as Rudolf Diesel once did. Biofuels, such as biodiesel and bioethanol, are
good for the environment because they add fewer emissions to the atmosphere than petroleum- based
fuels. Biofuels are also made from plant materials, which are available in inexhaustible supply. Biodiesel
is a biodegradable and nontoxic diesel fuel substitute that can be used in late-model (after 1992) diesel
engines without any need to modify the engines beforehand. Biodiesel is actually good for diesel engines.
It lubricates better than petroleum- based diesel fuel and has excellent solvent properties. Conventional
diesel fuel can leave deposits inside fuel lines, storage tanks, and fuel delivery systems over time.
Biodiesel dissolves this sediment while adding no deposits of its own, resulting in cleaner, more trouble-

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free fuel handling systems once fuel filters clogged with diesel sediments have been replaced after the
switch to biodiesel has been made. Use of 100% biodiesel fuel does reduce the fuel economy and power
of diesel engines by 10%. This means that 1.1 gallons of biodiesel are equivalent to one gallon of
conventional diesel fuel. Although both biodiesel and conventional diesel fuel tend to gel or freeze in cold
weather, biodiesel switches from the liquid state at higher temperatures than petroleum based diesel fuel..
Biodiesel is safe to handle and transport because it is as biodegradable as sugar, ten times less toxic than
table salt, and burns at a relatively high temperature. Biodiesel actually degrades about four times faster
than petroleum-based diesel fuel when accidentally released into the environment .Because it is physically
similar to petroleum-based diesel fuel, biodiesel can be blended with diesel fuel in any proportion. Many
federal and state fleet vehicles now use biodiesel blends in their diesel engines. The most common blend
is a mixture consisting of 20% biodiesel and 80% petroleum diesel, called B20 [5]. The motive for
blending the fuels is to gain some of the advantages of biodiesel while avoiding higher costs. Biodiesel is
currently higher in price than conventional diesel fuel costs.

1.1.2 Biodiesel History

The concept of using vegetable oil as an engine fuel likely dates when Rudolf Diesel (1858-1913)
developed the first engine to run on peanut oil, and demonstrated at the World Exhibition in Paris in
1900. Unfortunately, R. Diesel died in 1913 before his vision of a vegetable oil powered engine was fully
realized. Rudolf Diesel firmly believed the utilization of a biomass fuel to be the real future of his engine.
"The use of vegetable oils for engine fuels may seem insignificant today. But such oils may become in the
course of time as important as the petroleum and coal tar products of the present time”. He wanted to
provide farmers the opportunity to produce their own fuel. In 1911, he said "The diesel engine can be fed
with vegetable oils and would help considerably in the development of agriculture of the countries which
use it".

After R. Diesel death, the petroleum industry was rapidly developing and produced a cheap by-product
"diesel fuel" powering a modified "diesel-engine". Thus, clean vegetable oil was forgotten as a renewable
source of power. Modern diesels are now designed to run on a less viscous fuel than vegetable oil but, in
times of fuel shortages, cars and trucks were successfully run on preheated peanut oil and animal fat. It
seems that the upper rate for inclusion of rapeseed oil with diesel fuel is about 25% but crude vegetal oil
as a diesel fuel extender induces poorer cold-starting performance compared with diesel fuel or biodiesel
made with fatty esters.

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Today's diesel engines require a clean-burning, stable fuel operating under a variety of conditions. In the
mid-1970s, fuel shortages spurred interest in diversifying fuel resources, and thus biodiesel as fatty esters
was developed as an alternative to petroleum diesel. Later, in the 1990s, interest was raising due to the
large pollution reduction benefits coming from the use of biodiesel. The use of biodiesel is affected by
legislation and regulations in all countries. On February 9, 2004, the Government of the Philippines
directed all of its departments to incorporate one percent by volume coconut biodiesel in diesel fuel for
use in government vehicles. The EU Council of Ministers adopted new pan-EU rules for the detaxation of
biodiesel and bio fuel on October 27, 2003.Large-volume production occurs mainly in Europe, with
production there now exceeding 1.4 million tons per year. Western European biodiesel production
capacity was estimated at about 2 million metric tons per year largely produced through the
transesterification process, about one-half thereof in Germany (440,000 and 350,000 MT in France and
Italy, respectively). In the United States, by 1995, 10 percent of all federal vehicles were to be using
alternative fuels to set an example for the private automotive and fuel industries. Several studies are now
funded to promote the use of blends of biodiesel and heating oil in USA. In USA soybean oil is the
principal oil being utilized for biodiesel (about 80,000 tons in 2003).

1.1.3 Biodiesel as an Alternative Fuel

The use of biodiesel leads to the substantial reduction in PM, HC and CO emissions accompanying with
the imperceptible power loss, the increase in fuel consumption and the increase in NOx emission on
conventional diesel engines with no or fewer modification. And it favours to reduce carbon deposit and
wear of the key engine parts. Therefore, the blends of biodiesel with small content in place of petroleum
diesel can help in controlling air pollution and easing the pressure on scarce resources without
significantly sacrificing engine power and economy. Currently, BD is more expensive to produce than
PD, which appears to be the primary factor keeping it from being in more widespread use. Current
worldwide production of vegetable oil and animal fat is not enough to replace liquid fossil fuel use
(maximum replacement percentage: w20–25%).Methyl esters of vegetable oils (BDs) have several
outstanding advantages among other new-renewable and clean engine fuel alternatives. BD is easier to
produce and cleaner with equivalent amounts of processing when starting with clean vegetable oil.

1.1.4 Advantages

Biodiesel is an ecological fuel which has the following characteristics:

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  It is obtained from renewable raw materials. Biodiesel can be produced from vegetal, animal and
recycled oils. Among vegetables, although there are more than three hundred types of oil, the
most common one in biodiesel production is soybean, rape, sunflower and palm. The recycled
oils come from the collection of sectors such as restaurants, nourishing, domestic kitchens, etc.
 During its combustion it costs smaller amount of CO2 than the one absorbed on their growth, so
that the final balance of CO2 emissions is positive. In fact, it is considered as a CO2 neutral
emissary. Therefore, the combustion of biodiesel does not contribute to the greenhouse effect, it is
neutral and it aids to fulfill the protocol of Kyoto.
 Do contain neither benzene nor other carcinogenic aromatic substances, such as aromatic
hydrocarbons.
 It is easily biodegradable, and in case of spill and/or accident, it do not put in danger neither the
ground nor underground waters. Biodiesel is biodegradable in approximately 21 days.
 Is not dangerous merchandise, the flash point is over 110ºC . Biodiesel flash point is over 110ºC,
for that reason it is not classified like dangerous merchandise, which helps on safe storage and
safe manipulation.
 The higher cetane number of biodiesel compared to petro-diesel indicates potential for higher
engine performance. Tests have shown that biodiesel has similar or better fuel consumption,
horsepower and torque than conventional diesel.
 Production of 1t/ha/year of high protein seed cake (60% crude protein) that can be potentially
used as animal and fish feed and organic matter that could be used as organic fertilizer
particularly in remote areas.
 Localized production and availability of quality fuel.
 Restoration of degraded land over a period of time.
 Generation of rural employment.

1.1.5 Disadvantages

 At low temperatures, it can begin to solidify and to form crystals that can obstruct the conducts of
the fuel. Due to its solvent properties, it can soften and degrade certain materials, such as natural
rubber and polyurethane foam.
 Production costs still can be higher than the cost of diesel itself. It all basically depends on the oil
source which has been used.

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  Biodiesel performance per liter is about 10% less in terms of energy than the performance of
petroleum diesel fuel. That is because 41.92 MJ/Kg diesels is compared to 37.55 MJ/Kg biodiesel
energy contents according to figures from IEA, 2004.

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 2. BIODIESEL FEEDSTOCKS
The main feedstocks for biodiesel production are oils(vegetable oil,animal oils, waste cooking oils etc) ,
alcohols, and catalyst. The feedstock can be classified as below:
i. Oil
a. Plant based
b. Animal based
c. Waste oil
d. Microbial based
ii. Catalyst
a. Acidic
b. Alkaline
c. Enzymatic
iii. Alcohol
a. Methanol
b. Ethanol
c. Butanol
2.1 OIL

2.1.1 Plant Derived

Plant derived feedstock has gained importance because of their origination from a renewable source.
Biodiesel prepared from plant derived feed has the potential to replace the petro diesel fuel as it has
properties similar to petroleum diesel and causes fewer emissions. Also the production of plant derived
feedstock requires lesser energy input and also they have higher energy content. The feedstock is pure oils
which are derived from various crops and plants such as soyabean, canola (rapeseed), corn, cottonseed,
flax, sunflower, peanut, and palm.
CH2O–OCHCH2CH2. ....... CH2CH3
CHO–OCHCH2CH2. ........ CH2CH3
CH2O–OCHCH2CH2. ....... CH2CH3
Molecular Structure Triglycerides

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 2.1.2 EDIBLE OIL

A. Palm Oil
The world's largest palm oil biodiesel plant is the Finnish operated Nested oil biodiesel plant in
Singapore, which opened in 2011.Palm oil can be used to produce biodiesel, which is also known as palm
oil methyl ester. Palm oil methyl ester is created through a process called transesterification. Palm oil
biodiesel is often blended with other fuels to create palm oil biodiesel blends. Palm oil biodiesel meets the
European EN14214 standard for biodiesels. According to a 2008 report published in the
Renewable and Sustainable Energy Reviews palm oil was determined to be a sustainable source of both
food and biofuel. The production of palm oil biodiesel does not pose a threat to edible palm oil supplies.

B. Soyabean Oil

Soyabean oil is the primary feedstock used for biodiesel production in the U.S. Soybean biodiesel
production is divided into five distinct processes. Soyabean biodiesel was a net energy generator based on
a greater than unity NER. They included the energy use in growing and harvesting the crop, extracting the
oil, and trans-esterifying the oil based on three different scenarios. The first scenario used U.S. national
average energy use data for soyabean farming, oil extraction, refining, and transesterification. The second
scenario represented the existing best‐case energy efficiency capability for soyabean cultivation, oil
extraction, refining, and esterification in the U.S. The third scenario was developed to represent future
industry potential based on state‐of‐the‐art agricultural practices integrated with the latest technological
advances in the extraction and esterification of soyabean oil.

C. Rapeseed

Rapeseed is a bright yellow flowering member of the family Brassicaceae (mustard or cabbage family).
Rapeseed oil is used as diesel fuel, either as biodiesel straight in heated fuel systems, or blended with
petroleum distillates for powering motor vehicles Owing to the costs of growing, crushing, and refining
rapeseed biodiesel, rapeseed-derived biodiesel from new oil costs more to produce than standard diesel
fuel, so diesel fuels are commonly made from the used oil. Rapeseed oil is the preferred oil stock for
biodiesel production in most of Europe, accounting for about 80% of the feedstock, partly because
rapeseed produces more oil per unit of land area compared to other oil sources, such as soybeans, but
primarily because canola oil has a significantly lower gel point than most other vegetable oils.

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2.1.2 Non Edible Oil

A. Karanja

Non-edible oil contains several non-saponifiable and toxic components, which make them unsuitable for
human consumption. Karanja (Pongamiapinnata) is an underutilized plant which is grown in many parts
of India. Sometimes the oil is contaminated with high free fatty acids (FFA) depending upon the moisture
content in the seed during collection as well as oil expression. The production of biodiesel from high
FFA Karanja oil because the conventional alkali-catalysed route is not the feasible route. The first step is
acid-catalysed esterification by using 0.5% H2SO4, alcohol 6:1 molar ratio with respect to the high FFA
Karanja oil to produce methyl ester by lowering the acid value, and the next step is alkali- catalyzed
transesterification . The yield of biodiesel from high FFA Karanja oil by dual step process has been
observed to be 96.6–97%.

B. Jatropha

For the reason of the demand for edible oil being higher than its domestic production, there is no
possibility of diverting this oil for production of bio-diesel. Fortunately there is a large area of degraded
forest land and unutilized public land, field boundaries and fallow lands of farmers where non-edible oil
can be grown . There are many tree species which bear seeds rich in oil. Of these some promising tree
species have been evaluated and it has been found that there are a number of them such as
PongamiaPinnata(„Honge‟ or „Karanja‟) and Jatropha curcas which would be very suitable in our
conditions. However, Jatropha curcas has been found to be the most suitable species for the purpose on
many grounds that are discussed below:
 It can be grown as a quick yielding plant even in adverse land situations viz. degraded and barren
lands under forest and non-forest use, dry and drought prone areas, marginal lands and as agro
forestry crop. It can be planted on fallow lands and along farmers field boundaries as hedge because it
does not grow too tall as well as on vacant lands alongside railways, highways, irrigation canals and
unused lands in townships etc. under Public/Private Sector Undertakings.
 The seeds of Jatropha are available during the non-rainy season, which facilitates better collection and
processing.
 Raising Jatropha plant and its maintenance creates jobs for the rural poor, particularly the landless, in
plantation and primary processing through expellers.

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 It has multiple uses and after the extraction of oil from the seeds, the oil cake left behind is excellent
organic manure, the bio mass of Jatropha curcas enriches the soil and it can also be put to other uses .

Table 2.1: Properties of Jatropha Oil [46]

Flash point 240/110 °C

Carbon residue 0.64
Cetane value 51.0
Distillation point (°C) 295 °C
Kinematics Viscosity 50.73 cs
Sulphur % 0.13 %
Calorific value 9 470 kcal/kg
Pour point 8 °C
Viscosity (cp) (30 °C) 52.6 (5.51)2
Specific gravity (15 °C/4 °C) 0.917/ 0.923(0.881)

C. Mahua

The two major species of genus Mahua found in India are M.Indica and Mahuacalongifolia. M.Indica is
one of the forest based tree-borne non edible oils with large production potential of about 60 million tons
per annum in India. The Mahua oil generally contains of about 20% FFAs and a procedure for converting
this Mahua oil to biodiesel is very much required

2.1.3 Microbial Derived

Algae are organisms that grow in aquatic environments and use light and carbon dioxide (CO 2) to create
biomass. There are two classifications of algae: Macro-algae and Microalgae. Macro algae are the large
(measured in inches), multi-cellular algae often seen growing in ponds. These larger algae can grow in a
variety of ways. The largest multi-cellular algae are called seaweed; an example is the giant kelp plant
which can be more than 100 feet long.

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2.1.4 Animal Derived: Fats and Oil

Choice of the fats or oils to be used in producing biodiesel is both a process chemistry decision and an
economic decision. With respect to process chemistry, the greatest difference among the choices of fats
and oils is the amount of free fatty acids that are associated with the triglycerides. Most vegetable oils
have a low percentage of associated free fatty acids.

2.2 ALCOHOL

The most commonly used primary alcohol used in biodiesel production is methanol, although other
alcohols, such as ethanol, iso-propanol, and butyl, can be used. A key quality factor for the primary
alcohol is the water content. Water interferes with transesterification reactions and can result in poor
yields and high levels of soap, free fatty acids, and triglycerides in the final fuel. Unfortunately, all the
lower alcohols are hygroscopic and are capable of absorbing water from the air. Many alcohols have been
used to make biodiesel. As long as the product esters meet ASTM 6751, it does not make any chemical
difference which alcohol is used in the process. Other issues such as cost of the alcohol, the amount of
alcohol needed for the reaction, the ease of recovering and recycling the alcohol, fuel tax credits, and
global warming issues influence the choice of alcohol.
In addition, a base catalyzed process typically uses an operating mole ratio of 6:1 mole of alcohol rather
than the 3:1 ratio required by the reaction. The reason for using extra alcohol is that it “drives” the
reaction closer to the 99 % yield we need to meet the total glycerol standard for fuel grade biodiesel. The
unused alcohol must be recovered and recycled back into the process to minimize operating costs and
environmental impacts. Methanol is considerably easier to recover than the ethanol. Ethanol forms an
azeotrope with water so it is expensive to purify the ethanol during recovery. If the water is not removed
it will interfere with the reactions. Methanol recycles easier because it doesn‟t form an azeotrope. These
two factors are the reason that even though methanol is more toxic, it is the preferred alcohol for
producing biodiesel. Methanol has a flash point of 10 °C, while the flash point of ethanol is 8°C, so both
are considered highly flammable.

2.3 CATALYST

Biodiesel is produced by the transestrification reaction using alcohol with the presence of catalyst.
Transestrification is a reversible reaction of fat or oil, with a primary alcohol to form esters and glycerol

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and esters. A catalyst is usually used to improve the reaction rate & yield. No catalyst are used in the case
of the supercritical methanol method. Where methanol & oil mixture is superheated to more than 35
degree centigrade and the reaction completes in 3-5 minutes to form esters & glycerol. In general, there
are three categories used for biodiesel production.
1) Acid catalyst
2) Alkali catalyst
3) Enzymes catalyst

2.3.1 Acid Catalyst

Acid catalyst generally used are sulfonic acid and Sulphuric acid. These acids give very high yields in
alkyl esters but these reactions are slow, requiring high temp. and more than 3 hr. to complete the
conversion.

Homogeneous

An acid-catalyst, usually a strong acid such as sulphuric, hydrochloric or phosphoric acid, is more
favourable than base-catalyst because the reaction does not form soap. However, the acid-catalyst is very
sensitive to the water content of the raw materials. Disadvantages of the acid-catalyst are that they require
higher temperature and longer reaction time, in addition to causing undesired corrosion of the equipment .

Heterogeneous

Heterogeneous acid catalysts performed less activity, but they are favorable for low-qualified oil
feedstocks with high FFAs. Now, synthetic solid acids have already amounted to hundreds of species,
most of them can be used in esterification and transesterification reactions. Solid acids keep stable activity
in conversion of low-qualified oils or fats to biodiesel. Currently developed solid catalysts are; cation
exchange resin (i.e. Amberlyst-15 and NR50), mineral salts (i.e. ferric sulfate, zirconium sulfate, and
alum phosphate and zirconium tungsten), and supported solid acid and heteropolyacid catalysts.

2.3.2 Alkali Catalyst

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Most commonly used alkali for the production of biodiesel is KOH, & NaOH & sodium methoxide. For
an alkali catalyst transestrification, the glycerides & alcohol must be anhydrous became water makes the
reaction partially changed to saponification, which produces soap. This soap lowers the yield of esters and
makes the separation of biodiesel and glycerin complicated

Homogeneous Catalyst

The alkali homogeneous catalyst are highly hygroscopic and absorb water from air during storage. They
also form water when dissolved in the alcohol reactant and affect the yield. Therefore they should be
properly handled.

Heterogeneous Catalyst

Some of these catalysts are solid and it could be rapidly separated from the product by filtration which
reduces the washing requirement. In addition solid heterogeneous catalyst can stimulating catalyse the
transestrification and esterification reaction that can avoid the pre esterification step . Thus these catalysts
are particularly useful for the feed stock with high free fatty acid content. However, using a solid catalyst,
the reaction proceeds at a slower rate because the reaction mixture constitutes a three phase system which
due to diffusion.

2.3.4 Enzyme Catalyst

Enzyme catalyst has become more important recently since it can avoid soap formation and the
purification process is simple to accomplish. Enzyme catalyst are used less because of the lower reaction
time & higher cost. To reduce the cost, some researchers developed new biocatalyst in recent years.
Advantages is that no purification is necessary for using these biocatalyst

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PRODUCTION METHODS OF BIODIESEL

There are various methods of production of biodiesel and they can be classified as follows:
 Pyrolysis
 Micro emulsification
 Dilution
 Transesterification.
i. Co-solvent Method
ii. Supercritical Method
iii. Ultrasonic method
iv. Microwave method

3.1 Pyrolysis

Pyrolysis is the process in which chemical change occurs by the application of thermal energy in the
absence of air or nitrogen. The liquid fractions of the thermally decomposed vegetable oils are likely to
approach diesel fuels. The pyrolyzate or product had lower viscosity, flash point, and pour point then
diesel fuel and equivalent calorific values. The cetane number of the pyrolyzate was lower. The pyrolyzed
vegetable oils contain acceptable amounts of sulphur, water and sediments and give acceptable copper
corrosion values but unacceptable ash, carbon residual and pour point. Depending on the operating
conditions, the Pyrolysis process can be divided into three subclasses: conventional Pyrolysis, fast
Pyrolysis and flash Pyrolysis.

3.2 Micro Emulsification

The formation of micro emulsion is potential solutions for solving the problem of vegetable oil viscosity.
Micro emulsions are described as transparent, thermodynamically stable colloidal dispersion. The droplet
diameters in micro emulsions ranges from 100 to 1000 Å. Micro emulsion can be formed by vegetable
oils with an ester and dispersant (co solvent), or of vegetable oils, and alcohol and a surfactant and a
cetane improver, with or without diesel fuels. All micro emulsions with Butanol, Hexanol and Octanol
approach the maximum viscosity requirement for diesel fuel.

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3.3 Dilution

The dilution of vegetable oils can be completed with such material as diesel fuels, solvent or ethanol.
Dilution reduces the viscosity and density of vegetable oils. The addition of 4% ethanol to diesel fuel
increases the brake thermal efficiency, brake torque and brake power, while decreasing the brake specific
fuel consumption. Since the boiling point of ethanol is less than that of diesel fuel, it could assist the
development of the combustion process through an unburned blend spray.

3.4 Transesterification

Transesterification (also called alcoholysis) is the reaction of a fat or oil with an alcohol to form esters
and glycerol. The reaction is shown in Fig. 3.1. A catalyst is usually improved the reaction rate and yield.
Because the reaction is reversible, excess alcohol is used to shift the equilibrium to the products side.
Methanol, ethanol, Propanol, Butanol and amyl alcohol can be used in transesterification. Methanol and
ethanol are used most frequently especially methanol because of its low cost and its physical and
chemical advantages because it is polar and shortest chain alcohol. Methanol can quickly react with
triglycerides and NaOH is easily dissolved in it. To complete a transesterifications toichiometrically, a 3:1
molar ratio of alcohol to triglycerides is needed. In practice, the ratio needs to be higher to drive the
equilibrium to a maximum ester yield. The reaction can be catalysed by alkalis, acids, or enzymes. The
alkalis containing NaOH, KOH, carbonates and corresponding sodium and potassium alkoxides such as
sodium methoxide, sodium ethoxide, sodium prop-oxide and sodium butoxide. Sulphuric acid, sulfonic
acids and hydrochloric acid are usually used as acid catalysts. Alkali-catalysedtransesterification is much
faster than acid-catalysedtransesterification and is most often used commercially. For an alkali-
catalysedtransesterification, the glyceride and alcohol must be substantially anhydrous because water
makes the reaction partially change to saponification, which produces soap. The soap lowers the yield of
esters and renders the separation of ester and glycerol and the water washing difficult. Low free fatty acid
content in triglycerides is required for alkali-catalysedTransesterification. If more water and free fatty
acids are in the triglycerides, acid catalyzed Transesterification can be used. The triglycerides can be
purified by saponification (known as alkali treating) and then transesterified using an alkali catalyst .

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 Fig 3.1: Transesterification Reaction

(Where R1, R2, and R3 are long chains of carbons and hydrogen atoms, sometimes called fatty acid
chains.)

3.4.1 Co-Solvent Method

The main problem for the lower rate of transesterification is that the reaction mixture is not homogeneous
because the oils and alcohols are not miscible each other because of their chemical structures. Oil
disperses in the methanol medium, so the probability and the rate of collision of the glyceride and the
methoxide (the mixture of methanol and the alkaline catalyst – KOH orNaOH) molecules becomes lower.
This lowers the rate of collisions of molecules and so the rate of reaction causes longer reaction times,
higher operating expenses and labour. To overcome this difficulty of the heterogeneous mixing of the
reactants, a single phase reaction has been proposed. The proposed model includes a cyclic solvent
introduced into the reaction mixture which makes both the oil and methanol miscible. This solvent can be
a numerous of different solvents with the boiling point up to 100°C.

3.4.2 Supercritical Method

Supercritical method also called Saka method was first introduced in 2001 for biodiesel production.
Supercritical method was developed to avoid using of catalyst and reducing the time for
transesterification. When transesterification occurs without co-solvent, and catalysed by acid and alkali
catalyst, reaction is usually two phase heterogeneous reaction, reaction rate between oil and alcohol
highly controlled by mass transfer . On the other hand under supercritical method triglycerides can be
well dissolved in methanol because of having high miscibility in the molecular level between the two.

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Therefore the mixture of oil and alcohol becomes a single phase. This would accelerate the rate of
reaction because there is no obstacle between reactants.

3.4.3 Ultrasonic Method

To shorten the reaction time, ultrasonic wave is one technique providing excellent mixing between the
two phases. It will break down the liquid and form the cavitations bubbles resulting in the rising of mass
transfer rate and acoustic streaming mixing. Ultrasonic system which increases the mixing rate of
Jatropha oil and methanol for both homogeneous and heterogeneous transesterification. The system is
equipped with convertor, horn and reactor. The ultrasonic wave generated from transducer in the
convertor part and transmitted to the horn tip to cause the cavitation in the mixture of oil and methanol.
Ultrasonic power and frequency applied at 1500W and 20 kHz.

3.5 Factors affecting the Production of Biodiesel

Factors that affect the production of Biodiesel are:

i. Moisture content
ii. FFA
iii. Molar ratio of Alcohol
iv. Catalyst
v. Temperature
vi. Time
vii. Stirring Speed

3.5.1 Moisture Content

Presence of moisture in feed has negative effect on the production of Biodiesel as it leads to the formation
of soap. Also if moisture is present then oil will require more amount of catalyst.

3.5.2 FFA

Free fatty acid content also affects the yield of Biodiesel production. Free fatty acid content must be less
than1 for base catalysed reaction. If FFA content is greater than 1 than acid catalysed reaction is used.

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3.5.3 Molar Ratio of Alcohol

Molar ratio of alcohol plays an important role in the production of Biodiesel. For transesterification
reaction one mole of oil/fat require 3 moles of alcohol usually. If excess of alcohol is used the yield of
Biodiesel is increased. However after a certain concentration there is no effect on the yield of Biodiesel.
Also use of excess alcohol results in an increase in the cost of alcohol recovery. .The molar ratio of
alcohol varies with the type of catalyst and the type of feed. When alkali catalysed reaction is used then
molar ratio of alcohol that is used normally is 6:1. If the feed possess high FFA content than alkali
catalyst will not be effective, than acid catalyst is used. For this more amount of alcohol is required. For
e.g. Waste cooking oil having FFA content 15, requires 18:1 molar ratio of methanol.

3.5.4 Catalyst

Catalyst is another important parameter that effects the production of Biodiesel. Most commonly used
catalyst for the production of Biodiesel is KOH and NaOH. However it was observed that sodium
methoxide as catalyst would be more effective. Reason for this is that when NaOH is used as catalyst, it
reacts with alcohol (methanol) to produce sodium methoxide and water. This water though less in amount
can affect the yield of Biodiesel. Therefore it is better to used sodium methoxide as catalyst. If catalyst is
used in insufficient amount this will lead to incomplete conversion of oil/fat into Biodiesel. Also if more
amount of catalyst is used it will lead to the formation of soap. If FFA content of oil/fat is high than acid
catalyst is used.

3.5.5 Temperature

Temperature is another important factor that affects the yield of Biodiesel. Temperature is usually kept
below the boiling point of alcohol so that alcohol does not evaporate. When methanol is used than
temperature is kept below 60oC, when ethanol is used temperature is kept less than 75oC. If temperature is
increased beyond the optimum temperature range, it results in a decrease in the yield of Biodiesel.
Because the higher temperature leads to saponification reaction.

3.5.6 Time

It was observed that time also affects the yield of Biodiesel production. The reaction is slow at the
beginning due to mixing of alcohol and catalyst. After that the reaction proceeds fast. If the

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reaction is allowed to proceed for a longer time the yield of Biodiesel is increased. However if time is
increases beyond the optimum limit, it will result in the decrease in yield of Biodiesel as reverse reaction
takes place leading to the formation of soap.

3.6.7 Stirring Speed

Stirring is done to mix the catalyst mixture and oil/fat leading to the formation of Biodiesel. This
parameter plays important role in the formation of Biodiesel. If stirring speed is slow it results in lower
product yield, if speed is high it will result in reverse reaction leading to the formation of soap.

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