biod report pdf

A REPORT SEMINAR ON PRODUCTION OF BIODISEL FROM COTTONSEED OIL
Dr.Babasaheb Ambedkar Technological University Page 1
A
SEMINAR ON
BIO-DIESEL
Submitted by
SWAPNIL SUNIL NADE
(2151460)
Under the guidance of
Prof. S. S. PATIL
DEPARTMENT OF CHEMICAL ENGINEERING
INSTITUTE OF CHEMICAL ENGINEERING
DR.BABASAHEB AMBEDKAR TECHNOLOGICAL
UNIVERSITY,LONERE(RAIGAD)-402103
2017-2018

DR.BABASAHEB AMBEDKAR TECHNOLOGICALUNIVERSITY
LONERE-402103,TAL–MANGAON,DIST.-RAIGAD.
DEPARTMENT OF CHEMICAL ENGINEERING
==========================================================================
CERTIFICATE
This is to certify that the seminar report entitled BIO-DIESEL is a bonafide work carried
out by Mr.Swapnil Sunil Nade of third year chemical Engineering.
It is approved for partial requirement for diploma in chemical Engineering of Dr.
Babasaheb Ambedkar Technological University, Lonere, Raigad–402103.
PROF. SAGAR PATIL Prof. R.S.KULKARNI
(GUIDE) Head
Department of Chemial Engineering
Examiner:
1.Prof. Y.Y.Karkare
2.
Place:
Date:

ACKNOWLEDGEMENT
I am indebted to our pro-active Guide Prof. Sagar Patil without whose able guidance this
work would have not been a success. His constructive criticism and useful timely suggestions
and encouragement in every step immensely helped me to carry out the project work. His
invaluable presence was a great boost for us in achieving our goal.
I would like to thank our Head of Department Prof. R. S. Kulkarni & all the staff of
Chemical Engineering Department. I am also thankful to the librarian of Dr. Babasaheb
Ambedkar Technological University, Lonere..
Last but certainly not the least, I would like to thank our friends for their inspiration and
also those who helped me directly and indirectly in my seminar work.
Thank you.
Swapnil Sunil Nade
(2151460)

ABSTRACT
The world is getting modernized and industrialized day by day. As a
result vehicles an engines are increasing. But energy sources used in these engines are limited
and decreasing gradually. This situation leads to seek an alternative fuel for diesel engine.
Biodiesel is an alternative fuel for diesel engine. The esters of vegetables oil animal fats are
known as Biodiesel. This paper investigates the prospect of making of biodiesel from cottonseed
oil.Cottonseed is a renewable non-edible plant. Cottonseed is widely growing hardy plant in arid
and semi-arid regions of the country on degraded soils having low fertility and moisture. The
seeds of Cottonseed contain 50-60% oil. In this study the oil has been converted to biodiesel by
the well-known transesterification process and used it to diesel engine for performance
evaluation.

INDEX
Sr No. Topics Page No.
1 Introduction 1
2 History 5
3 Materials 8
4 Methods of production 10
5 Transesterification 12
6 Advantages & Disadvantages of Biodiesel Fuel 23
7 Conclusion 25
8 References 26

LIST OF DIAGRAMS
Sr.no. No. Of Diagrams Title
1. Fig.5.1 Trans esterification reaction
2. Fig .5.1.1 Separation of Biodiesel
3. Fig .5.2.1 Biodiesel washing
4. Fig .5.3.1 Drying of Biodiesel
5. Fig. 5.4.4.1 The effect of temperature on yield of biodiesel

CHAPTER 1
INTRODUCTION
The depletion of world petroleum reserves and the increased environmental concerns have
stimulated the search for alternative sources for petroleum-based fuel, including diesel fuels.
Because of the closer properties biodiesel fuel (fatty acid methyl ester) from vegetable oil is
considered as the best candidate for diesel fuel substitute in diesel engines. With increasing
demand on the use of fossil fuels, stronger threat to clean environment is being posed as burning
of fossil fuels is associated with emissions like CO2, CO, SOx, NOx and particulate matter and
are currently the dominant global source of emissions. The harmful exhaust emissions from the
engines, rapid increase in the prices of petroleum products and uncertainties of their supply have
Jointly created renewed interest among the researchers to search for suitable alternative fuels.
Compressed natural gas, propane, hydrogen, and alcohol-based substances (ethanol, methanol,
and other neat alcohol) all have their proponent. The prices of fuel are going up day after day in
the world. So, ways and means have been sought for many years to be able to produce oil
substitute fuel. Biodiesel extracted from vegetable oil is one such renewable alternative under
consideration. The production of biodiesel would be cheap as it could be extracted from non
edible oil sources.
Biodiesel is derived from vegetable oils or animal fats through transesterification.
Transesterification is also called alcoholysis, which uses alcohols in the presence of catalyst that
chemically breaks the molecules of triglycerides into alkyl esters as biodiesel fuels and glycerol
as a by-product. The commonly used alcohols for the transesterification include methanol,
ethanol, propanol, butanol, and amyl alcohol. Methanol and ethanol are adopted most frequently,
particularly the former due to its low cost. The three basic methods of ester production from
oil/fat are the base-catalyzed transesterification, the acid catalyzed transesterification and
enzymatic catalysis. Alkali catalyzed transesterification process is the common process for
production, because it can achieve high purity and high yield of biodiesel in short time.
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. Cottonseed oil
is obtained from the seed of cotton plant. The cotton plant is grown for its fibre. The oil is a by-
product with about 12 per cent of the gross value of the total product. Cottonseed oil was once

the major vegetable oil competing with the more widely-used animal fats. Today, it occupies
ninth place in production tables after five vegetable oils (soybean, palm, rape/canola, sunflower
and groundnut) and three land animal fats (tallow, lard and butter). Cottonseed oil is unusual
among commodity vegetable oils in that it contains a relatively high level of palmitic acid
(typically 23%) along with oleic acid (17%) and linoleic acid (56%). Cottonseed oil is cooking
oil extracted from the delinted and decorticated cottonseed. The cleaned seed meats are first
passed through a series of pressure rolls to produce thin flakes, after which the flakes are cooked
under steam pressure, which ruptures the oil cells. Subsequently, the flakes are either pressed in
hydraulic presses or processed in continuous screw-type expellers which remove the oil under
high pressure. There are various methods of extracting oil from oil producing seeds and these to
a large extent determine the quality of the oil. The various methods include; mechanical
extraction, traditional extraction, steam and high pressure method and solvent extraction. The
solvent extraction method is gaining acceptance, although not to as great an extent as in
soyabean oil production. Average yield of oil is about 16 - 17 percent of the cottonseed.
Treatment of the crude oil to produce refined grades is similar to that used for soyabean; it
involves alkali refining to remove impurities, bleaching with activated clays and finally,
steaming under vacuum conditions to remove traces of odour.
The advantages of biodiesel as perfect alternative energy sources, emission of NOx is one of the
setbacks of biodiesel. The temperature within the cylinders of a vehicle fuelled with Biodiesel
would increase due to the enhanced combustion as a result of high oxygen content of biodiesel.
This increase in temperature stimulates the production of NOx from the reaction with nitrogen in
the air, which results in a small increase in NOx emission compared to those produced from
conventional diesel fuel. Aside from the formation of NOx by the engine powered with biodiesel,
the chemical contents of biodiesel is also a fatty acid methyl ester when the alcohol used during
transesterification is methanol or fatty acid ethyl ester in case of ethanol. These ester molecules
are susceptible to hydrolytic and oxidization reactions resulting in the formation of polymers.
This makes the biodiesel unstable on storage and hence cannot sit on the shelf for long time as it
develops mould when it gets old. Exploring the means of producing biodiesel that will compete
well with the existing petroleum diesel is of much interest in the recent biodiesel research,
especially for those methods concentrating on minimizing the raw material cost. Biodiesel as
alternative energy source can be produced from different sources [1].

Biodiesel is an alternative to petroleum based fuels derived from vegetable oils, animal
fats, and used cooking oil including triglycerides. Vegetable oils widely available from various
sources and the glycerides present in the oils can be considered as a viable alternative for diesel
fuel. They have good heating power and provide exhaust gas with almost no sulphur and
aromatic polycyclic compounds. Vegetable oils are produced from plants, their burning leads to
complete recyclable carbon dioxide (CO2).One of the main problems of vegetable oil use in
engine is their higher kinematic viscosity because of heavier triglycerides and phospholipids.
Vegetable oils are not suitable as fuels for diesel engines, since they have to be modified to bring
their combustion related properties closer to mineral diesel. This fuel modification is mainly
aimed at reducing the viscosity in order to get rid of flow or atomization related problems.
Biodiesel has become more attractive recently because of its environmental benefits and the fact
that it is made from renewable resources [1].The world energy crisis is a result of population
growth and increasing consumption of energy in both developed countries and emerging
economies. The greater demand for petroleum products as a result of an enormous increase in the
number of automobiles serves the growing problem of the developing countries. With crude oil
reserves estimated to last only for a few decades, therefore efforts are on way to find out new
alternatives to diesel. Depletion of crude oil would cause a major impact on the transportation
sector. Of the various alternate fuels under consideration, biodiesel derived from vegetable oils,
appears to be the most promising alternative fuel to diesel. More than 95% of the world’s
biodiesel is produced from edible vegetable oils, thereby increasing demand throughout the
worldwide for vegetable oil production. The most commonly used oils for the production of
biodiesel are Soybean, Sunflower, Palm, Rapeseed, Canola, Cottonseed [8], and Jatropha. Since
the prices of edible vegetable oils are higher than that of diesel fuel, therefore waste vegetable
oils and non-edible crude vegetable oils are preferred as potential low priced biodiesel sources.
The contribution of non-edible plant oils as new sources for biodiesel production have the
advantage of not competing with edible oils produced from crop plants. A lot of research work
has already been carried out to use vegetable oil both in its pure form and also in modified form.
Studies have shown that the usage of vegetable oils in pure form is possible but not preferable.
Biodiesel can be used in pure form (100%) or blended with the conventional diesel fuel up to
20% to create a biodiesel blended fuel for its use in the compression ignition engines. It can be

used as a standalone fuel or blended with petroleum diesel in diesel engines. Biodiesel can be
used neat (B100) or at various blend ratios with
diesel fuel. A blend of 5% biodiesel (B5) can already be included within existing diesel fuel
supplies without identification. Currently, there is resistance from engine manufacturers to
warrant engines above 5% biodiesel blends. Biodiesel has attracted considerable interest as a
substitute or blend component for conventional petroleum diesel fuel (petro diesel).
Biodiesel, defined as simple mono alkyl esters of long chain fatty acids prepared from
vegetable oils or animal fats, possesses a number of technical advantages over petro diesel, such
as derivation from renewable and domestic feed stocks, displacement of imported petroleum,
inherent lubricant, essentially no sulphurcontent, superior flash point and biodegradability,
reduced toxicity, as well as reduction in most regulated exhaust emissions.
The Cotton plant is one of the most important raw materials of textile industry for fibers
and food industry due to its 17-24% oil and 40-43% protein contents. Turkey has about
760000ha (6)

CHAPTER 2
HISTORY
The use of vegetable oils as alternative fuels has been studied at the beginning of
twentieth century when the inventor of the diesel engine Rudolf Diesel first tested peanut oil in
compression ignition engine (Diesel, 1912)[7]. He said the use of vegetable oils for the engine
fuels may seem insignificant today, but such oils may in course of time be as important as
petroleum and the coal tar products of the present time. The potential of vegetable oil to serve as
alternative fuel was considered during the oil crisis in 1970s (Knothe, 2001)[2]. Vegetable oils
occupy a prominent position in the development of alternative fuels although, there have been
many problems associated with using it directly in diesel engine. These include, coking and
trumpet formation on the injectors to such an extent that fuel atomization does not occur properly
or even prevented as a result of plugged orifices. Carbon depositions on the pistons, oil ring
sticking, thickening or gelling of the lubricating oil is a result of contamination by vegetable oils
and lubricating problems. The plant oils usually contain free fatty acids, phospholipids, sterols,
water, odorants and other impurities, because of these, the oil cannot be used as fuel directly. To
overcome these problems the oil requires chemical modification to bring their combustion
related properties closer to mineral oil. The biodiesel is a perfect substitute for diesel oil, with
environmental externalities (positive energy balance, low emissions of pollutants) and social
(space for inclusion of family farming) positive. The use of diesel fuel is predominant in buses
and trucks. In some countries, such as Europe, the diesel reaches also be used by light
vehicles.The market for biodiesel has grown so exponentially in recent years. World production
in liters, increased from 1.4 billion in 2003 to just over 8 billion in 2006. The current targets for
mandatory addition were imposed by the countries that should increase the demand to almost 90
billion liters. However, the installed capacity in the world won’t be able to meet this demand.
Adding up all existing production units to those in construction, the worldwide capacity of
biodiesel production reaches about only 35 billion liters.The present review aims to study the
prospects and opportunities of introducing vegetable oils and their derivatives as fuel in diesel
engines. Some fuel properties are always available in vegetable oils. In this investigation
Cottonseed oil is chosen for producing biodiesel as an alternative fuel for diesel engine.Fuel-
related properties of these oils are reviewed and compared with those of conventional diesel
fuel.[4]

Biodiesel is produced by transesterifying the oil with an alcohol such as methanol under
mild conditions in the presence of a base catalyst. Satisfactory amount of biodiesel is produced
from Cottonseed oil at 3:1M ratio of methanol and oil. Biodiesel from cottonseed oil has various
fuel properties which are similar to diesel. The petroleum fuels play a very important role in the
development of industries, transportation, and agricultural sector and to meet many other basic
human needs. However, these fuels are limited and depleting day by day as the consumption is
increasing very rapidly. Moreover, their use is increasing pollution at an alarming rate. India is
importing more than 80% of its fuel demand. It is becoming an increasingly popular alternative
fuel for diesel engines. Biodiesel is a clean renewable fuel, and hence has recently been
considered as the best substitute for a diesel fuel because it can be used in any compression
ignition engine without the need for modification. Chemically, biodiesel is a mixture of methyl
esters with long chain fatty acids. It is produced from renewable biological sources such as
vegetable oils and animal fat by simple transesterification reaction. More than 95% of biodiesel
production feed stocks come from edible oils. However, it may cause some problems such as the
competition with the edible oil market, which increases both the cost of edible oils and biodiesel.
In order to overcome these disadvantages, many researchers are interested in non-edible oils
which are not suitable for human consumption because of the presence of some toxic
components in the oils. Since the cost of raw materials accounts about 60–80% of the total cost
of biodiesel production, choosing a right feedstock is very important. The technique and
technology of production also plays very important role in its production as the yield varies from
process to process. A number of methods are currently available and have been adopted for the
production of biodiesel fuel. The most commonly used method for converting oils to biodiesel is
through the transesterification of animal fats or vegetable oils. of cotton harvesting area, 882 000
tons of cotton fiber production per annum with a yield of 1160 kg/ha of lint cotton and therefore
is one of the foremost cotton producing countries of the world. The residue oil cake is also used
as a bio fertilizer and cattle feed supplement. The fatty acid composition of the CSO is palmitic,
stearic, oleic and linoleic acids.
However, positive impacts on biodiversity may be realized as a result of ameliorating the
rate of change of atmospheric composition and global climate and if bioenergy crops and
cropping systems can help to reduce Green House Gases emissions. The development and
deployment of dedicated bioenergy crops have been proposed as a strategy to produce energy

without impacting food security, or the environment. The dedicated bioenergy crops are mainly
perennial herbaceous and woody plant species. Genetic resources for the development of
dedicated energy crops with low requirements for biological, chemical or physical pre-treatment
are more eco-friendly and will contribute more to Global climate change mitigation. Due to the
perennial nature of most Second Generation Energy crops, field resistance against diseases and
pests should be mutagenic.
Pure biodiesel (B100) can be used in any petroleum diesel engine, though it is more commonly
used in lower concentrations. Since biodiesel is more often used in a blend with petroleum
diesel, there are fewer formal studies about the effects on pure biodiesel in unmodified engines
and vehicles in day-to-day use. Fuel which meets the standards and engine parts that can
withstand the greater solvent properties of biodiesel are expected to and in reported cases does
run without any additional problems than the use of compared to
petroleum diesel.

CHAPTER 3
MATERIALS
Biodiesel is made from natural Resources. It is made from vegetable oils or animal fats. The
raw materials that are used to extract oil in order to produce biodiesel are cottonseed , Jatropha,
palm, soya bean, peanut, coconut. These crops can be grown for the production of biodiesel. [1]
01. Cottonseed oil
Molecular formula:
Molecular Weight (MW) =201.2072 g/mol
Density (𝜌)= 0.930 g/ml
Purity = 99 %
02. Ethanol
Molecular formula = C2H5OH
Molecular Weight = 46.068 g/mol
Density (𝜌) = 0.789 g/ml
Purity = 99.9 %
Boiling point = 78.37°c
Melting point = -114°c
Vapour pressure = 5.95 kpa

03. Methanol
Molecular formula = CH3 OH
Density (𝜌) = 0.792 g/ml
Purity = 99 %
Boiling point = 64°c
Melting point = -97.7°c
CAS NO = 67-56-1
04. Potassium hydroxide
Molecular formula = KOH
Density (𝜌) = 2.12 g/m

CHAPTER 4
METHODS OF PRODUCTION
There are three methods to make biodiesel.
4.1 Micro emulsions
Microemulsion is defined as transparent or clear equilibrium thermodynamically stable colloidal
dispersion of microstructure with the diameter ranging from 100-1000Å formed spontaneously
from two normally immisicibleliquids and one or more ionic or non-ionic amphiphiles. To solve
the problem of the high viscosity of oils, microemulsion with solvents such as methanol, ethanol
and 1-butanol are used. The spray characteristics by explosive vaporization of the low boiling
constitute in the micelles can be improved. An emulsion of alkali-refined and winterized
cottonseed oil (53 % V/V), ethanol (13% V/V) and 1- butanol (33% V/V) was prepared which
showed viscosity of 6.31cSt at 40°C, a cetane number of 25.
4.2.Thermal cracking or pyrolysis
Pyrolysis also known as thermal cracking is the thermal conversion of the organic matter
in the absence of oxygen with the help of a catalyst. Many investigators have studied the
pyrolysis of triglycerides with the aim of obtaining product suitable for diesel engine. The
pyrolysis of oils and their cakes of many non-edible species such as Pongamia, Jatropha, Mahua,
Tung tree, castor oil have been studied by the investigators to obtain suitable alternative for
combustion engines. The large scale thermal cracking of Tung oil calcium soap was reported,
where the Tung oil was saponified with lime and then thermally cracked to yield crude oil, which
was refined to produce diesel fuel and small amount of gasoline and Kerosene. Sixty eight kgs of
soap from the saponification of Tung oil produced fifty litres of crude oil. Soyabean oil was
thermally decomposed and distilled in air and nitrogen sparged with standard ASTM distillation
apparatus. Schwab, et al., used safflower oil for pyrolysis because of high oleic content. Copra
oil and palm oil were cracked over a standard petroleum catalyst SiO2 or Al2O3 at 450°C to
produce gases, liquids and solids with lower molecular weights. Here the condensed organic
phase was fractioned to produce bio-gasoline and biodiesel fuels. The chemical compositions of
diesel fractions were found similar to fossil fuels. The thermal decomposition of the triglycerides
produces alkanes, alkenes, alkamides, aromatics and carboxyl acids. The pyrolyzate had lower
viscosity, flash point and equivalent calorific values and lower cetane number compared to the

diesel fuel. However the pyrolysed vegetable oil posses acceptable amount of sulphur, water and
sediment and gave acceptable copper corrosion values, they are unaccepted in terms of ash,
carbon residues and pour point and cetane number. The removal of oxygen during the thermal
processing also eliminated environmental benefits of using oxygenated fuels. It also produced
some low level materials and sometimes more gasoline than diesel fuel and most importantly the
equipment used for pyrolysis is expensive for modest throughputs.
4..3Transesterification.
Of these transesterification is seems to promising, hence described in detail in this paper.
The transesterification reaction is affected by the molar ratio of raw materials used, catalyst
concentration, reaction temperature, reaction time and free fatty acids, water content of oils or
fats.

CHAPTER 5
TRANSESTERIFICATION
The transesterification process an alcohol (like methanol) reacts with the triglyceride oils
contained in vegetable oils, animal fats, or recycled greases, forming fatty acid alkys
esters(biodiesel) and glycerine. The reaction requires heat and a strong base catalyst, such as
sodium hydroxide or potassium hydroxide. The simplified transesterification reaction is shown
below.
Triglycerides + Free Fatty Acids (<4%) + Alcohol ————> Alkyl esters + glycerine
To make a biodiesel molecule, oil must undergo transesterification enabling a fatty acid to
undergo esterification. Transesterification and esterification of oils and fatty acids can be
accomplished in the presence of an alcohol and a catalyst. The overall stoichiometric view of this
process is shown in the reaction below. Common alcohols used in this process are short chain
alcohols, most notably methanol and ethanol. The catalysts commonly used for this process are
chemical catalysts, biocatalysts, and non-enzymatic heterogeneous catalysts.
The transesterification reaction was carried out at 60°C where, 1 % (w/w) catalyst (KOH) to oil
was used and 6:1 molar ratio of the methanol to Cottonseed oil was taken in the three neck flask
that was kept on the magnetic stirrer set at 600 rpm. The methoxide was prepared by adding
required amount of KOH to the methanol and the mixture was stirred well. When the
temperature of the raw oil in the three necked round bottom flask reached 60°C, the methoxide
mixture was slowly added. The temperature was kept just below the boiling point of the
methanol (64.5 °C). In order to speed up the reaction in this process, mixing was done which
brings the oil, the catalyst and the alcohol into intimate contact. Transparent chillired colour fluid
was observed in the reaction vessel after half an hour. The reaction process was run for one and
half hour (as shown in fig.3). Some amount of sample was drained and observed for separation
of ester and glyce1rol into two distinct layers.

Fig.5.1.Transesterification Reaction
5.1 Separation of the by-products
Biodiesel and glycerol are the two major products that existed once the transesterification
reaction is completed. The reaction mixture is transferred to the separation funnel. The glycerol
phase which is much denser than the biodiesel phase settles at the bottom of the reaction vessels
allowing it to separate from the biodiesel phase. Phase separation was completed within several
hours of settling in the separating funnel . The glycerine layer was drained out from the
separating funnel and stored.

Fig.5.1.1.Separation Of By-Product
5.2 Methanol recovery
The biodiesel obtained by the transesterification was transferred to the three necked flask. The
distillation setup was arranged along with the recovery flask. The recovering process of methanol
was carried out at 70oC (temperature higher than the boiling point of methanol) at slow rotation
on the stirrer (100 rpm). The condensed methanol was collected and stored.
• Methanol recovery:- The methanol is typically removed after the biodiesel and glycerine have
been separated, to prevent the reaction from reversing itself and so the methanol is cleaned and
recycled back. condensed methanol was collected and stored.
5.3 Purification of the biodiesel
5.3.1 Washing of the biodiesel
The crude biodiesel is transferred to the washing funnel. Warm water heated to about 50°C was
poured slowly on to the biodiesel in the washing funnel and allowed to settle for one hour. Water
being denser than the biodiesel dissolves the impurities (potassium hydroxide, methanol and
small amount of glycerol) forms the layer and settles at the bottom. The bottom layer was

drained slowly. Washing step was repeated till the drained soap water shows pH equals to the
normal water that was used for washing .
.
Fig.5.2.1. Biodiesel Washing
5.3.2. Drying of the biodiesel
The biodiesel after washing was transferred to a beaker and heated to 110°C. The water
content in the biodiesel evaporates, thus the moisture is removed (Fig.8). The biodiesel is cooled
and stored in a clean and dry container.

Fig.5.3.1.Drying Of BioDiesel
5.4 Factors affecting the yield of biodiesel
5.4.1 The effect of molar ratio of alcohol to oil
One of the most important factors affecting the yield of biodiesel is the molar ratio of alcohol to
triglycerides. The stoichiometry of the transesterification reaction requires three moles of alcohol
per mole of triglycerides to yield three moles of fatty esters and 1 mole of glycerol. However,
transesterification is an equilibrium reaction which requires large excess of alcohol to drive the
reaction to right. An excess of alcohol is used in biodiesel production for greater conversion of
oils or fats in short time. The molar ratio has no effect on acid value, peroxide, saponification
and iodine value of methyl esters. The increase of alcohol beyond the optimal ratio lowers the
yield and will increase the cost of biodiesel recovery. The high molar ratio of alcohol to
vegetable oil interferes with the separation of glycerine because there will be increase in
solubility. When glycerine remains in solution it derives the equilibrium reaction back to the left,
lowering the yield of the ester. Cottonseed oil showed highest conversion (upto 94 %) at 6:1
molar ratio. The molar ratio of 6:1 is normally used in industrial processes to obtain higher yield
of methyl ester.

5.4.2 The effect of catalyst concentration
Catalyst concentration can affect the yield of biodiesel. As the catalysts concentration increases
the yield of the biodiesel increases. The insufficient amount of catalysts results in an incomplete
conversion of the triglycerides into the fatty acid esters. The yield usually reaches an optimal
value when the catalyst concentration reaches 1.5 wt. % and then decreases a little with further
increase in catalyst concentration, this is reported in case of KOH concentration. The reduction
in the yield of the biodiesel is due to the addition of excessive alkali catalyst causing more
triglycerides to react with the alkali catalyst and form more soap. As a catalyst in the process of
alkaline methanolysis, mostly sodium hydroxide or potassium hydroxide have been used both in
concentration from 0.4 to 2% w/w of oil. Refined and crude oils with 1% of either sodium
hydroxide or potassium hydroxide catalyst resulted successful conversion.
5.4.3 The effect of reaction time
The conversion rate of fatty acid ester increases with reaction time. At the beginning, the
reaction is slow due to mixing and dispersion of alcohol into the oil and it proceeds very fast
after a while. After one hour the conversion was almost the (upto 94%). The yields reached a
maximum at a reaction time of less than 90 minutes and then remain relatively constant with a
further increase in the reaction time. Moreover excess reaction time will lead to reduction in
the product yield due to the backward reaction of the transesterification, thus, resulting in a loss
of esters and causing more fatty acids to form soaps.
5.4.4 The effect of reaction temperature on yield of biodiesel
Temperature has great influence on the reaction and yield of the biodiesel products. A higher
reaction temperature can decrease the viscosities of oils and result in an increased reaction rate
and a shortened reaction time. When the reaction temperature increases beyond the optimal level,
the yield of the biodiesel products decreases because, a higher reaction temperature accelerates
the saponification reaction of triglycerides. The reaction temperature must be less than the
boiling point of the alcohol in order to ensure that alcohol will not leak out through vaporization.
Generally the reaction is carried out close to the boiling point of methanol (60-70°C). For the
transesterification of refined cottonseed oil with methanol (6:1) ratio using 1% KOH, four

different temperatures were studied. It was observed that after one hour, ester yields were 94%,
90%, 87% and 64% for 60°C, 52°C, 45°C and 32°C respectively. After one hour, ester formation
was identical for 60°C, 52°C and 45°C runs and only slightly lower for the 32°C run (as shown
in fig.9)
Fig.5.4.4.1.The Effect Of Reaction Temp. On Yield Of Biodiesel
5.4.5 Mixing intensity
Mixing is very important in the transesterification reaction, as oil is immiscible with potassium
hydroxide methanol solution. Once the two phases are mixed and the reaction is started, stirring
is no longer needed. Initially the effect of mixing on transesterification was studied, no reaction
was observed without mixing, when KOH- MeOH was added to the Cottonseed oil in the beaker
while stirring the reaction speed was insignificant. Thus, reaction time was the controlling factor
in determining the yield of methyl esters. This suggests that stirring speed investigated exceeded
the threshold requirement of the mixing.
5.4.6 Alcohol recovery
Once the methyl ester and glycerine is separated after the transesterification reaction, the excess
alcohol is removed by flash evaporation at 90°C. The alcohol vapours are condensed back into

liquid methanol and is re-used. The alcohol may contain water that has to be removed before its
reuse in the process.
5.4.7 Refining of crude biodiesel
The crude biodiesel obtained from transesterification is mainly contaminated with residual
catalyst, water, unreacted alcohol, free glycerol and soap generated during the alkali catalysed
transesterification reaction.

5.4.7.1 Water washing
Since both glycerol and alcohol are highly soluble in water, water washing is very effective for
removing both contaminants. It can also remove any residual sodium salts and soaps. The
primary material for water washing is distilled warm water or softened water (slightly acidic).
Warm water prevents the precipitation of saturated fatty acid esters and retards the formation of
emulsions with the use of a gentle washing action. Softened water (slightly acidic) eliminates
calcium and magnesia contamination and neutralizes any remaining alkali catalysts. After
washing several times, the water phase becomes clear, indicating that the contaminants have
been completely removed. The biodiesel and water phases are separated by a separation funnel.
Moreover, because of the immiscibility of water and biodiesel, molecular sieves and silica gels
can also be used to remove water from the biodiesel.
5.4.7.2 Dry Washing
In dry washing biodiesel is heated up to 100°c for removal of water content from biodiesel after
water washing.
5.5 Fuel properties
The quality of biodiesel fuel is influenced by various factors which include the quality of
feedstock, fatty acid composition of the feedstock, type of production and refining process
employed and the post production parameters. Therefore it is necessary to install a
standardization of fuel quality. The standardization for biodiesel is utilized to protect both
biodiesel consumers and producers as well as to support the development of biodiesel industries.
Standards for the quality of the biodiesel have been defined in countries like Germany, Italy,
France, The Czech Republic United States, Australia and Europe. Australia was the first country
in the world to define and approve the standards for rapeseed oil methyl esters as biodiesel fuel.
All alternative biodiesel fuels should meet the international standard specification of biodiesel
such as ASTM 6571(America), EN 14214(Europe) and so on. These standards describe the
physical and chemical characterization of variety of biodiesel produced from non-edible and
edible oil sources. Important physical and chemical characteristics of feedstock that influences
the biodiesel production and its qualities are mentioned below,

5.5.1 Determination of Density
Density is the ratio between mass and volume of liquid or solid which is expressed in units of
gram /ml. This physical property gives an indication of the delay between the injection and
combustion of the fuel in a diesel engine and the energy per unit mass. Density influences the
efficiency of fuel atomization for airless combustion system.
DENSITY =MASS / VOLUME
5.5.2 Kinematic viscosity
Viscosity is the resistance of fluid to flow. The kinematic viscosity was determined by Canon-
Fenske method. The Canon- Fenske tube number 100 was filled with oil sample to the bulb
marked at the top and closed at the top. The viscometer tube was held in the thermostat water
bath and heated until it reaches 40 °C. This temperature was maintained for a period of
20-30 minutes. The tube was opened and simultaneously the stop watch was started. Once the oil
flow reached the mark at the bottom on the bulb, the stop watch was stopped. Seconds on the
stop watch were noted and calculated for kinematic viscosity.
Kinematic viscosity = Number of seconds X Calibration factor of the bulb.
5.5.3 Free Fatty Acid (FFA)
The interaction of FFA in the feedstock and sodium methoxide catalyst may form emulsions
which make separation of the biodiesel more difficult, possibly leading to yield loss. Emulsions
can also increase cost by introducing extra cleaning steps and replacement of filters. To
minimize the generation of soaps during the reaction, the target reduction for FFA in the
feedstock is 0.5 wt % or less
5.5.4 Acid Number
The free fatty acid content is known as acid number or acid value. The acid number is the
measure of the amount of carboxylic acid groups in chemical compounds such as a fatty acid, or
in a mixture of compound. A small amount of free fatty acids is usually present in the oils along
with triglycerides. Acid number is expressed as mg KOH required in neutralising per gram of the
fatty acid methyl esters. Acid number also called as neutralization number provides an indication

of the level of lubricant degradation while the fuel is in service. Higher acid content can cause
severe corrosion in fuel supply system and internal combustion engine. The maximum acid value
set by a European standard and ASTM is of 0.5mg KOH/g.
5.5.5 Iodine Number
The iodine value is the measure of the degree of unsaturation in the oil. It is an index of the
number of double bond in the biodiesel which determines the degree of unsaturation of the
biodiesel. This property influences the oxidation stability and polymerization of glycerides.
Higher number of double bonds in the biodiesel has greater potential to polymerize and hence
results in lesser stability. This can lead to the formation of deposits in the diesel engine injectors.
Iodine number is directly correlated to biodiesel viscosity, cetane number and cold
filter plugging point. The iodine value is set to a maximum value of 120 mg I2/g according to
EN 14111.
5.5.6 Saponification Value
Saponification is the process by which the fatty acids in the glycerides of oil are hydrolyzed by
an alkali. Saponification value is the amount (mg) of alkali required to saponify a definite
quantity (gm) of an oil or fat. This value is useful for a comparative study of the fatty acid chain
length in oils. Saponification value is a measure of the average molecular weight or the chain
length of the fatty acids present. As most of the mass of a triglyceride is in the three fatty acids, it
allows for comparison of the average fatty acid chain length.
5.5.7 Flash Point
Flash point of the fuel is the temperature at which it gets ignited when exposed to a flame or air
spark. It varies inversely with the fuels volatility. The flash point is the lowest temperatures at
which biodiesel emits enough vapours to ignite. It is measured according to ASTM D93 and EN
ISO 3679.

CHAPTER 6
Advantages & Disadvantages of biodiesel fuel
Advantages:
1.Biodiesel fuel is a renewable energy source unlike petroleum-based diesel.
2. An excessive production of soybeans in the world makes it an economic way to utilize
this surplus for manufacturing the Biodiesel fuel.
3.One of the main biodiesel fuel advantages is that it is less polluting than petroleum
diesel.
4. The lack of sulphur in 100% biodiesel extends the life of catalytic converters.
5. Another of the advantages of biodiesel fuel is that it can also be blended with other
energy resources and oil.
6. Biodiesel fuel can also be used in existing oil heating systems and diesel engines
without making any alterations.
7. It can also be distributed through existing diesel fuel pumps, which is another
biodiesel fuel advantage over .other alternative fuels.
8. The lubricating property of the biodiesel may lengthen the lifetime of engines.

Disadvantages:
1. At present, Biodiesel fuel is about one and a half times more expensive than petroleum
diesel fuel.
2. It requires energy to produce biodiesel fuel from soy crops, plus there is the energy of
sowing, fertilizing and harvesting.
3. Another biodiesel fuel disadvantage is that it can harm rubber hoses in some engines.
4. As Biodiesel cleans the dirt from the engine, this dirt can then get collected in the fuel
filter, thus clogging it. So, filters have to be changed after the first several hours of
biodiesel use.
5. Biodiesel fuel distribution infrastructure needs improvement, which is another of the
biodiesel fuel disadvantages.

CHAPTER 7
CONCLUSION
Biodiesel is a viable substitute for petroleum-based diesel fuel. Its advantages are
improved lubricity, higher cetane number, cleaner emissions (except for NOx), reduced
global warming, and enhanced rural development. Cottonseed oil has potential as an
alternative energy source. However, this oil alone will not solve our dependence on foreign
oil within any practical time frame. Use of this and other alternative energy sources could
contribute to a more stable supply of energy. Major production centers on the level of
modern petroleum refineries have not been developed. The economics of biodiesel fuels
compared to traditional petroleum resources are marginal; public policy needs to be revised
to encourage development. Increased cottonseed oil production would require a significant
commitment of resources. Land for production would need to be contracted, crushing and
biodiesel production plants need to be built, distribution and storage facilities constructed,
and monitoring of users for detection of problems in large-scale use are all needed to
encourage development of the industry. To meet the challenges of excessive import, we have
to strengthen our oilseed sector and lay special emphasis on harnessing the existing and
augmenting future potential source of green fuel. The organized plantation and systematic
collection of cottonseed oil, being potential bio-diesel substitutes will reduce the import
burden of crude petroleum substantially. The emphasis should be made to invest in
agriculture sector for exploitation of existing potential by establishing model seed
procurement centres, installing reprocessing and processing facilities, oil extraction unit,
trans-esterification units etc. There is also need to augment the future potential by investing
largely on compact organized plantation of Cottonseed on the available wastelands of the
country. This will enable our country to become independent in the fuel sector by promoting
and adopting bio-fuel as an alternative to petroleum fuels. It is evidenced that there are new
work opportunities in cottonseed cultivation and biodiesel production related sectors, and the
industry can be grown in a manner that favours many prosperous independent farmers and
farming communities.

CHAPTER 8
REFERENCES
[1] Duel, H.J. (1951). The Lipids: Their Chemistry and Biochemistry. 1:53-57.
[2] Freedman, B., Pryde, E.H., Mounts, T.L., 1984. Variables affecting the yields of fatty esters
from transesterified vegetable oils. JAOCS 61,1638-1643.
[3] Knothe G, Dunn RO, Bagby MO (1997) Biodiesel: the use of vegetable oils and their
derivatives as alternative diesel fuels. In: Fuels and Chemicals from Biomass, 1st edn. American
Chemical Society, New York.
[4] Noureddini H, Zhu D (1997) Kinetics of transesterification of soybean oil. J Am Oil Chem
Soc 74(11):1457–1463.
[5] Calhoun D.S. and Bowman D.T., in Smith, C.W., and CothrenSS, J. T., eds., (1999). Cotton
Origin, History, Technology and Production. John Wiley & Sons, New York. P 361-414.
[6] Peterson, C.L. 1980. Vegetable oils—Renewable fuels for diesel engines. ASAE Paper No.
PNW 80-105. St. Joseph,Mich.: ASA
[7] based diesel fuels. Chapter 2 in G. Knothe, J. Van Gerpen, and J. Krahl, eds. The Biodiesel
Handbook.

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