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Optimization of Process Parameters for Production of

Biodiesel

CHAPTER 1
INTRODUCTION

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Optimization of Process Parameters for Production of


Biodiesel
1.1 BACKGROUND
Our environment, which is endowed by nature, needs to be protected from ever increasing
Chemical pollution. The energy demand of the world is increasing fast mainly because of the
rapid growth of human population and industrialization by fast developing countries, such as,
China, India. Fortunately, people all over the world are becoming aware of the problem of
consuming too much of energy and are making conscious efforts to conserve it and avoid
pressure on the mother earth. Conservation of energy helps to lower the amount of pollutants
released into the air and protect the environment. The interaction between the natural resources
and the population needs to be balanced in order to ensure the continuity of the human race. So,
energy is essential to life and its conservation has become all more an absolute necessity.
Common sources of energy are petroleum, natural gas and coal from fossil fuels. This growing
consumption of energy has rapidly depleted non-renewable sources of energy. Rising price of
fossil-based fuels and potential shortage in the future have led to a major concern about the
energy security in every country. Moreover, there are many disadvantages of using fossil-based
fuels, such as atmospheric pollution and environmental issues. Fossil fuels emissions are major
contributors of greenhouse gases which may lead to global warming. Combustion from fossil
fuels is major source of air pollutants, which consist of CO, NOx, hydrocarbons and particulates.
The disadvantages and shortages of fossil fuels have motivated many researchers to find an
alternative source of renewable energy.

This is creating an opportunity to explore alternative energy sources.


The key question to address is: What alternatives can be developed & used? In addition, we must
ensure that future generation can also use these new alternatives.
The development of modern technologies related to alternative energy sources, as well as
researches in the field of renewable fuels enable scientist to develop cost effective methods for

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obtaining unconventional fuels Biomass, Bioethanol, Biomethanol, biohydrogen, Biogas,
Biodiesel and others.
The concept dates back to 1885 when Dr. Rudolf Diesel built the first diesel engine with the full
intention of running it on vegetative source. He first displayed his engine at the Paris show of
1900 and astounded everyone when he ran the patented engine on any hydrocarbon fuel available
- which included gasoline and peanut oil. In 1912, he stated that the use of vegetable oils for
engine fuels may seem insignificant today. But such oils may in the course of time become as
important as petroleum and the coal tar products of present time. In 1970, Scientists discovered
that the viscosity of vegetable oils could be reduced in a simple chemical process and that it
could work well as diesel fuel in modern engine. This fuel is called Bio- Diesel.

1.2 BIODIESEL: A FUEL OF FUTURE


Biodiesel is one of the most promising alternative fuels for diesel engines. The demand of
biodiesel has significantly increased from 2005 in all over the world. Biodiesel is defined as a
fuel comprising of monoalkyl esters of long chain fatty acids derived from vegetable oil or
animal fats. The main components of vegetable oils and animal fats are triglycerides or also
known as esters of fatty acids attached to a glycerol. Normally, triglycerides of vegetable oils and
animal fats consist of several different fatty acids. Different fatty acids have different physical
and chemical properties and the composition of these fatty acids will be the most important
parameters influencing the corresponding properties of a vegetable oils and animal fats.
Direct use of vegetable oils and animal fats as combustible fuel is not suitable due to their high
kinematic viscosity and low volatility. Furthermore, its long term use posed serious problems
such as deposition, ring sticking and injector chocking in engine. Therefore, vegetable oils and
animal fats must be subjected to chemical reaction such as transesterification to reduce the
viscosity of oils. In that reaction, triglycerides are converted into fatty acid methyl ester (F
AME), in the presence of short chain alcohol, such as methanol or ethanol, and a catalyst, such
as alkali or acid, with glycerol as a byproduct.

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Optimization of Process Parameters for Production of


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There are several advantages of biodiesel as compared to conventional diesel.


Advantages of biodiesel are:

It helps to reduce carbon dioxide and other pollutants emission from engines.
Engine modification is not needed as it has similar properties to diesel fuel.
It comes from renewable sources whereby people can grow their own fuel.
Diesel engine performs better on biodiesel due to a high cetane number.
High purity ofbiodiesel would eliminate the use of lubricant.
Biodiesel production is more efficient as compared to fossil fuels as there will be no

underwater plantation, drilling and refinery.


Biodiesel would make an area become independent of its need for energy as it can be
produced, pumped, stored and burned just like petroleum diesel fuel and can be used
pure, or in blends with petroleum diesel fuel in any proportion.
Power and Performance - The degree to which fuel provides proper lubrication is its
lubricity. Low lubricity petroleum diesel Emissions and Greenhouse Gas Reduction Biodiesel provides significantly reduced emissions of carbon monoxide, particulate
matter, unburned hydrocarbons and sulfates compared to petroleum diesel fuel.
Additionally, biodiesel reduces emissions of carcinogenic compounds by as much as 85%
compared with petro diesel. When blended with petroleum diesel fuel, these emission
reductions are generally directly proportional to the amount of biodiesel in the blend.
Greenhouse Gases Carbon dioxide released from biodiesel and the combustion does not
contribute any new emissions of CO 2 as it is part of the carbon cycle. Closed carbon
cycle will reduce 80% of CO 2
Example: growing oil feedstock consumes four to six times more CO 2 than biodiesel exhaust.
Smog-Forming Pollutants (Ozone precursors) - Compared to diesel, biodiesel effects on engine
exhaust are furnished and that follows: B100 refers to neat biodiesel; B20 fuel can cause
premature failure of injection system components and decreased performance. Biodiesel

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Optimization of Process Parameters for Production of


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provides excellent lubricity to the fuel injection system. Producing biodiesel fuels can help create
local economic revitalization and local environmental benefits.
Many groups interested in promoting the use of biodiesel already exist at the local, state and
national level. Biodiesel is designed for complete compatibility with petroleum diesel and can be
blended in any ratio, from additive levels to 100 % biodiesel. In the United States today,
biodiesel is typically produced from soyabean or rapeseed oil or can be reprocessed from waste
cooking oils or animal fats, such as, waste fish oil.
Because it is made of these easily obtainable plant- based material Biodiesel can be considered a
new technology, taking into account that all these years consumers have had to settle for
traditional diesel. Biodiesel is not harmful to the environment. A vehicle tends to pollute the
environment and emits harmful gasses, if injected with HSD whereas if the engine is using
biodiesel, it emits no harmful gasses and rather keeps the environment pollution free. Biodiesel
may not require an engine modification. Biodiesel can be blended with diesel so as to improve
the efficiency of the engine without any hassles. Biodiesel is cheap. You can even make biodiesel
in your backyard.
Transesterified vegetable oil (biodiesel) was used to power heavy-duty vehicles in South Africa
before World War II. It was patented in the US in the 1950s by Colgate, though Biolipid
transesterification may have been discovered much earlier.
In the 1940s, researchers were looking for a method to more readily produce glycerol, which was
used to produce explosives for World War II. Many of the methods used today by producers and
home brewers have their origin in the original 1940s research. Biolipid transesterification has
also been recently shown by Japanese researchers to be possible using a super-critical methanol
methodology, whereby high temperature, high-pressure vessels are used to physically catalyze
the biolipid/methanol reaction into fatty-acid methyl esters...
If your engine can work with biodiesel fuel alone, then you really need not go to the gas station
to buy fuel. You can just manufacture some for your own personal use. Any Vehicle using
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Optimization of Process Parameters for Production of


Biodiesel
Biodiesel has very low idle starting noise. It is noted that biodiesel has a Cetane number of over
100. Cetane number is used to measure the quality of the fuels ignition. If the fuel has a high
Cetane number, it can be sure that what one gets is a very easy cold starting coupled with a low
idle noise.

1.3 BIODIESEL ACTIVITIES IN INDIA


NEW DELHI: In one of the biggest initiatives for bio- fuel production in the country, Indian
Railways is poised to set up four bio-diesel plants costing about Rs 120 crore. While two biodiesel esterification plants 22 are going to be commissioned at Raipur and Chennai during the
next two years, the other two units will be set up subsequently, a senior Railway Ministry official
said. Each plant, estimated to cost around Rs 30 crore, will produce 30 tons bio-diesel per day,
which means more than 9,000 tons a year, the official said. Produced from waste oil, fatty acid
and non-edible vegetable
Biodiesel is cost effective because it is produced locally. Biodiesel as a fuel not only helps
reducing the ollution, but also reduces health hazards and gives the society A CLEANER AND
GREENER TOMORROW.

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South Western Railway general manager P.K. Saxena flagging off the train in
Hubballion Thursday.

1.4 OBJECTIVES
To determine the yield of biodiesel from waste oil.
To optimize the process parameters (Methanol to oil ratio, Quantity of catalyst,
Reaction time) for the biodiesel production.
To determine the physicochemical properties of the neem biodiesel using standard
methods, while the fatty acid profile is to be determine using gas chromatography.

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Optimization of Process Parameters for Production of


Biodiesel

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Optimization of Process Parameters for Production of


Biodiesel

CHAPTER 2
LITERATURE REVIEW

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Optimization of Process Parameters for Production of


Biodiesel
2.1 REVIEW OF PAPERS
Optimization of two step transesterification production of biodiesel from neem
(Azadirachta indica) oil.
This work investigated the optimization of biodiesel production from neem (Azadirachta indica)
oil using a two-step transesterification process and determination of the qualities of the neem oil
biodiesel. Biodiesel production was carried out using a two-step transesterification process. The
first step was carried out using 0.60 w/w methanol-to-oil ratio in the presence of 1% w/w H2SO4
as an acid catalyst in 1 h at 50C. The second step was base (NaOH) transesterification of the
product from the first step using conditions specified in the optimization design. The central
composite design optimization conditions for the second step were temperature (45C to 65C),
catalyst amount (0.45% to 1.45% w/w), reaction time (45 to 65 min), and methanol/oil molar
ratio (1.5 to 7.5). The physicochemical properties of the neem biodiesel were carried out using
standard methods, while the fatty acid profile was determined using gas chromatography.
Optimized biodiesel yield of 89.69% was produced at reaction time of 65 min, catalyst amount
of 0.95 g, temperature of 55C, and methanol/oil molar ratio of 4.5:1. The values for the
physicochemical properties are 0.05% moisture content, 0.9 specific gravity at 25C, 5.5 mm2/S
kinematic viscosity, 207 mg KOH/g, 70.7 g I2/100 g iodine value, 55.31 cetane number, 39.85
MJ/Kg calorific value, 4 pour point, 8 cloud point, and 110 flash point. These values conform to
international standards, in particular, American Society Testing Materials (ASTM).
It can be concluded that neem biodiesel showed a general compliance with known standards
judging from its physicochemical properties and the engine test. These, coupled with its high
yield, attested to the production viability and efficiency of neem biodiesel using two-step
transesterification process.

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Optimization of Process Parameters for Production of


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Optimization of Biodiesel Production from Cottonseed Oil by Transesterification


Using NaOH and Methanol
In this study, the transesterification of cottonseed oil with methanol was carried out using NaOH.
The parameters, such as molar methanol:oil ratio, NaOH %,and temperature effecting the yield
and biodiesel quality, were investigated to optimize biodiesel production from cottonseed oil.
Below 50C, transesterification of cottonseed oil was not completed at any molar methanol:oil
ratios and catalyst percentages in 1 h. In 3:1 methanol:oil ratio, full conversion was not observed.
Optimum conversion was obtained at 6:1 methanol:oil ratio and at temperatures between 50 and
60C. Above 60C, some difficulties were encountered in the washing step. Biodiesels that were
produced at different molar methanol:oil ratios, NaOH concentrations, and temperatures were
tested according to accepted standard methods and the results were compared with standard
values.

Optimization of Biodiesel production from mixed oil (Karanja &Dairy waste Scum
oil) using Homogeneous Catalyst.
Here, crude mixed oil was used as feedstock for biodiesel production by Homogeneous Catalyst.
The reaction in the presence of KOH as catalyst was carried out to investigate the optimum
conditions and study the effect of variables on the reaction. The variables included methanol to
oil molar ratios, catalyst concentrations, reaction temperature and reaction times. Gas
chromatography was used to determine the fatty acid composition of mixed oil. The optimum
conditions for mixed oil biodiesel production were a catalyst concentration of 1.0% w/w of oil, a
reaction temperature of 70oC, a reaction time of 30minutes 6:1 methanol to oil molar ratio at
400rpm. The methyl ester content under these optimum conditions was 95.10%, and all the
measured properties of mixed oil biodiesel met the ASTM standards.

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Methanolysis optimization of sesame (Sesamum indicum) oil to biodiesel and fuel


quality characterization
Statistical approach was employed to optimize biodiesel production from sesame oil in this work.
Precisely, response surface methodology was applied, and the effects of four variables, viz.
reaction temperature, catalyst amount, reaction time, and methanol/oil molar ratio, and their
reciprocal interactions were determined. Central composite rotatable design was used to generate
a total of 30 individual experiments, which were designed to study the effects of these variables
during alkali-catalyzed methanolysis of sesame oil. A statistical model predicted the highest
conversion yield of sesame biodiesel to be 99.71% at the following optimized variable
conditions: reaction temperature of 63C, catalyst amount of 1.04 wt. %, and methanol/oil molar
ratio of 6.24, with a reaction time of 51.09 min. Using these variables under experimental
condition in four independent replicates, an actual biodiesel yield of 98.36% was accomplished.
The fuel properties of biodiesel produced were found to be within the ASTM D6751 and DIN
EN 14214 biodiesel specifications.

Synthesis of Biodiesel Synthesis of Biodiesel from neem oil using Sulfated Zirconia
via transesterification
Sulfated zirconia (SZ) is a widely used catalyst, which is synthesized by a solvent free method
and the synthesized catalyst has been characterized. Neem Methyl Ester (Biodiesel) was
prepared by a two-step process of esterification and transesterification from Neem oil with
methanol in the presence of catalyst. Acid catalyst was used for the esterification and alkali
catalyst (KOH) for the transesterification reaction. Optimal Free Fatty Acid (FFA) conversion
was achieved using 1 wt% SZ as an acid catalyst with a methanol-to-oil molar ratio of 9:1,
temperature of 65C and reaction time of 2 h. The acid value was reduced to 94% of the raw oil
(24.76 mg KOH/g), which confirmed the conversion. Consequently, this pretreatment reduces
the overall complexity of the process and a conversion efficiency of 95% is achieved when
pretreated oil reacts with methanol in the presence of KOH.
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Optimization of Process Parameters for Production of


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Calcium oxide from Pomacea sp. shell as a catalyst for biodiesel production
Heterogeneous catalysts are promising catalyst for the transesterification reaction of vegetable
oils to produce biodiesel. In this study, the Pomacea sp. shell was used as the raw material for
CaO catalyst. The calcination of Pomacea sp. shell was conducted at 900C for 2 h. The raw
material and the resulting CaO catalyst were characterized using X-ray diffraction, X-ray
fluorescense spectrometry, and Fourier transform infrared spectroscopy analysis. From the
experimental results, it was found that the maximum yield of fatty acid methyl esters was
95.61% at the following reaction conditions: reaction temperature of 60C, a reaction period of 4
h, a ratio of methanol-oil at 7:1, and amount of catalyst at 4% w/w. The physical and chemical
properties of biodiesel were determined based on ASTM standard, and the values obtained were
confirmed with the Indonesian National Standard (SNI-04-7182-2006) and (B100)-ASTM
D6751-07b.

2.2 TRANSTERIFICATION PROCESS


Many researchers have concluded that vegetable oil and their derivatives hold promise as
alternative fuels for diesel engines that the use of raw vegetables oils for diesel engines can
cause numerous engine related problems due to their high viscosity, low volatility, high cetane
number which can lead to severe engine deposits, injector coking, and piston ring sticking. These
effects can be eliminated or reduced through transesterification of the vegetable oil to form an
alkyl ester.
In organic chemistry, transesterification is the process of exchanging the organic group R of
an ester with the organic group R of an alcoholHeterogeneous catalysts are promising catalyst
for the transesterification reaction of vegetable oils to produce biodiesel. In this study, the
Pomacea sp. shell was used as the raw material for CaO catalyst. The calcination of Pomacea sp.
shell was conducted at 900C for 2 h. The raw material and the resulting CaO catalyst were
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characterized using X-ray diffraction, X-ray fluorescense spectrometry, and Fourier transform
infrared spectroscopy analysis.
From the experimental results, it was found that the maximum yield of fatty acid methyl esters
was 95.61% at the following reaction conditions: reaction temperature of 60C, a reaction period
of 4 h, a ratio of methanol-oil at 7:1, and amount of catalyst at 4% w/w. The physical and
chemical properties of biodiesel were determined based on ASTM standard, and the values
obtained were confirmed with the Indonesian National Standard (SNI-04-7182-2006) and
(B100)-ASTM D6751-07b.
Many researchers have concluded that vegetable oil and their derivatives hold promise as
alternative fuels for diesel .These reactions are often catalyzed by the addition of an acid or base
catalyst. The reaction can also be accomplished with the help of enzymes (biocatalysts)
particularly lipases.

Transesterification: alcohol + ester different alcohol + different ester


Strong acids catalyse the reaction by donating a proton to the carbonyl group, thus making it a
more potent electrophile, whereas bases catalyse the reaction by removing a proton from the
alcohol, thus making it more nucleophilic. Esters with larger alkoxy groups can be made from
methyl or ethyl esters in high purity by heating the mixture of ester, acid/base, and large alcohol
and evaporating the small alcohol to drive equilibrium.

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In the transesterification mechanism, the carbonyl carbon of the starting ester (RCOOR 1)
undergoes nucleophilic attack by the incoming alkoxide (R2O) to give a tetrahedral intermediate,
which either reverts to the starting material, or proceeds to the transesterified product (RCOOR2).

The various species exist in equilibrium, and the product distribution depends on the relative
energies of the reactant and product.

The stoichiometry requires 1 mol of triglyceride and 3 moles of methanol to give 3 moles of fatty
acid methyl esters (FAME, Biodiesel) and 1 mol of glycerol. Diglycerides and monoglycerids are
the intermediates in this process. The glycerol is separated by setteling or centrifugation

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Optimization of Process Parameters for Production of


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CHAPTER 3
MATERIALS
&
METHODOLOGY

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Optimization of Process Parameters for Production of


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3.1 MATERIALS
The material sources were:
1. Waste cooking palm oil: collected from local restaurants with high FFA content and stored at
room temperature. The fatty acid composition was determined by gas chromatography (GC) as
described later.
2. Fresh palm oil: purchased from local oil mill.
3. Catalysts: Calcium Hydroxide (CaOH) of 98.2 % purity,
Sodium Hydroxide (NaOH) pellets of 97 % purity.
Concentrated Sulphuric acid (H2SO4) of 99.8% purity.
4. Methanol (CH3OH) of 98 % purity.
These chemicals were purchased from VISSO CHEMICALS, BELAGAVI.
3.1.1 PALM OIL
Palm oil is an edible vegetable oil derived from the mesocarp (reddish pulp) of the fruit of the
oil palms,Palm oil has an especially high concentration of saturated fat, specifically, of the 16carbon saturated fatty acid palmitic acid, to which it gives its name. Monounsaturated oleic acid
is also a major constituent of palm oil.
3.1.2 CATALYSTS
Catalysts are used to accelerate a chemical reaction by reducing the activation energy, which is
the energy needed to initiate the reaction. There are two kinds of catalysts typical to any
biodiesel process: homogeneous and heterogeneous. Homogeneous catalysts function in the
same phase (liquid, gaseous, etc.) as the reactants. Typically, homogeneous catalysts are
dissolved in a solvent with the substrates. Heterogeneous catalysis is the opposite of
homogeneous catalysis, meaning it occurs in a different phase than the reactants.

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Most heterogeneous catalysts are solids that act on substrates in a liquid or gaseous reaction
mixture. Diverse mechanisms for reactions on surfaces are known, depending on how the
adsorption takes place. The total surface area of solid has an important affect on the reaction rate;
the smaller the catalyst particle size, the larger the surface area for a given mass of particles.
Homogeneous catalysts for biodiesel production have been around for quite some time, but
heterogeneous catalyst is a fairly newer development in the realm of biodiesel production. The
most common alkali catalysts are: Sodium hydroxide (NaOH) Potassium hydroxide (KOH).
SODIUM HYDROXIDE (NaOH)
In our project we first used NaOH which is a homogeneous catalyst. Sodium hydroxide (NaOH),
also known as lye and caustic soda, is an inorganic compound. It is a white solid and highly
caustic metallic base and alkali salt of sodium which is available in pellets, flakes, granules, and
as prepared solutions at a number of different concentrations.
Advantages of NaOH over KOH Cost of catalyst : On an average, KOH costs more than NaOH.
Effects on Glycerin: One of the biggest differences of using NaOH vs. KOH can be seen
in the glycerin layer. Glycerin from NaOH reacted oil tends to be much thicker and can
even solidify into a thick gooey mess. Glycerin from KOH reacted Biodiesel on the other
hand is nice & liquid; even when its allowed to cool down to extremely low
temperatures.
Effects On Methanol at Ambient Temperatures: KOH will cause methanol to boil much
more violently at hotter temperatures than NaOH. Ive seen KOH added to methanol that
was over 100 F and it boiled like crazy (which can be potentially dangerous). However,
NaOH doesnt boil nearly as violently when added to methanol at hot temperatures.
How much more? For 50 gallons of oil with a 5% free fatty acid content, itll likely
require about 2175 grams of NaOH. However, it will take roughly 3030 grams of KOH
for the same oil. Itll dissolve faster, but you use more of it.

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0.1N NaOH solution is prepared by dissolving 4g of NaOH pellets in 1 lt. of distilled water. It is
used in base transesterification process.
CALCIUM OXIDE (CaO)
Secondly we used CaO which is a heterogeneous catalyst. Calcium oxide (CaO), commonly
known as quicklime or burnt lime, is a widely used chemical compound. It is a white, caustic,
alkaline, crystalline solid at room temperature.
The broadly used term "lime" connotes calcium-containing inorganic materials, in which
carbonates, oxides and hydroxides of calcium, silicon, magnesium, aluminium, and iron
predominate. Quicklime is relatively inexpensive. Both it and a chemical derivative (calcium
hydroxide, of which quicklime is the base anhydride) are important commodity chemicals.
Preparation of Calcinated Calcium oxide (CaO) catalyst for Transesterification process
24 grams of calcium oxide was dipped in 200ml of ammonium carbonate solution (12%
by wt.) then the mixture was stirred for 30 minutes at room temperature. After filtration
and drying the precipitate at 110C for about 6 hours, the dried solid was milled and then
calcined at 900C for 1.5 hours in a muffle furnace. After cooling in a dessicator to room
temperature the base calcium oxide (CaO) catalyst is ready to use.
SULPHURIC ACID (H2SO4)
Typically sulfuric acid is used as the homogeneous acid catalyst for the esterification of
FFAs.Sulfuric acid (alternative spelling sulphuric acid) is a highly corrosive strong mineral acid
with the molecular formula H2SO4 and molecular weight 98.079 g/mol. It is a pungent-ethereal,
colorless to slightly yellow viscous liquid that is soluble in water at all concentrations.[6]
Sometimes, it is dyed dark brown during production to alert people to its hazards. [7] The
historical name of this acid is oil of vitriol.

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Sulfuric acid is a diprotic acid and shows different properties depending upon its concentration.
Its corrosiveness on other materials, like metals, living tissues or even stones, can be mainly
ascribed to its strong acidic nature and, if concentrated, strong dehydrating and oxidizing
properties.
3.1.3 METHANOL
Methanol, also known as methyl alcohol, wood alcohol, wood naphtha or wood spirits, is a
chemical with formula CH3OH (often abbreviated MeOH). It is the simplest alcohol, and is a
light, volatile, colorless, flammable, liquid with a distinctive odor that is very similar to but
slightly sweeter than ethanol (drinking alcohol). At room temperature it is a polar liquid. Most
methanol today is produced from the methane found in natural gas, but methanol is also
produced from all types of biomass, coal, waste, and even CO2 pollution from power plants.

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3.2 METHODOLOGY
3.2.1 PREPARATION OF BIODIESEL:
Biodiesel production is carried out using a two step transesterification process
Acid catalyzed transesterification process followed by base catalyzed transesterification process.
This process has been used to convert vegetable oils with free fatty acids value.
1. Cooking oil is collected from restaurants.
2. Transesterification reaction uses H2SO4 (Catalyst) and methanol as reactant.
3. Initially oil is heated strongly around 80 for 30mins using magnetic stirrer to reduce
the viscosity of oil.

a) Acid catalyzed transesterification process


This step is a pretreatment to remove FFA in oil and reduces the FFA.
It is carried out using 50ml of methanol and 0.2 ml conc. H 2SO4 mixed together
inside a 250ml conical flask.
Conical flask is then inserted into a water bath at 50.
This mixture is later added to 200ml of warmed oil (cooking oil) inside a 500ml
conical flask and is placed on a magnetic stirrer with heater.

a) Base catalyzed transesterification process


Product of acid transesterification is used for base transesterification.
Calculated amount of NaOH and ethanol is added to each reaction for the
specified temperature and reaction time.
Optimized conditions for this step areTemperature
: 40C to 60C
Catalyst
: 0.45% to 1.45 % w/w
Reaction time
: 45 to 65 min
Methanol to oil ratio: 1.5 to 7.5
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c) Separation of biodiesel from glycerin


After base transesterification process the biodiesel was allowed to settle for at
least 24 hours inside a separating funnel.
Top layer- biodiesel, bottom layer glycerin.
Glycerin is drained off and biodiesel is collected.
d) Washing and drying of biodiesel
Separated biodiesel is mixed with warm distilled water at 50 and the
mixture is shaken vigorously.
The water is allowed to drain through the bottom of the separating funnel.
It is done 5 times until a clear biodiesel is obtained.

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CHAPTER 4
TESTING AND ANALYSIS

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Optimization of Process Parameters for Production of


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4.1 GAS CHROMATOGRAPHY
Gas chromatography (GC) is a common type of chromatography used in analytical chemistry
for separating and analyzing compounds that can be vaporized without decomposition. Typical
uses of GC include testing the purity of a particular substance, or separating the different
components of a mixture (the relative amounts of such components can also be determined). In
some situations, GC may help in identifying a compound.
In gas chromatography, the mobile phase (or "moving phase") is a carrier gas, usually an inert
gas such as helium or an un reactive gas such as nitrogen. Helium remains the most commonly
used carrier gas in about 90% of instruments although hydrogen is preferred for improved
separations.The stationary phase is a microscopic layer of liquid or polymer on an inert solid
support, inside a piece of glass or metal tubing called a column (an homage to the fractionating
column used in distillation). The instrument used to perform gas chromatography is called a gas
chromatograph

Fig: Equipment of Gas Chromatography

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Optimization of Process Parameters for Production of


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In the case of gas-liquid chromatography, the column is usually packed with solid particles that
are coated with a non-volatile liquid, referred to as the stationary phase. As the sample mixture
moves through the column, sample components that interact strongly with the stationary phase
spend more time in the stationary phase vs. the moving phase and thus require more time to
move through the column. For example, a non-polar molecule such as hexane would interact
strongly with a non-polar stationary phase and would have a large retention time.
Retention time is defined as the time from injection of the sample to the time a specific sample
component is detected and is given the symbol tr. While polarity is usually the major factor
governing separation, the boiling points of components of the sample also play a role in
determining retention time. Components with higher volatility (lower boiling points) tend to
spend more time in the moving gas phase and therefore tend to have shorter retention times.
After exiting the column the separated components are detected and a detector response is
recorded. GC is to separate and detect components of a mixture as efficiently of a given
chromatographic column.
Generally chromatographic data is presented as a graph of detector response (y-axis) against
retention time (x-axis), which is called a chromatogram. This provides a spectrum of peaks for a
sample representing the analytes present in a sample eluting from the column at different times.
Retention time can be used to identify analytes if the method conditions are constant. Also, the
pattern of peaks will be constant for a sample under constant conditions and can identify
complex mixtures of analytes. However, in most modern applications, the GC is connected to a
mass spectrometer or similar detector that is capable of identifying the analytes represented by
the peaks.
The area under a peak is proportional to the amount of analyte present in the chromatogram. By
calculating the area of the peak using the mathematical function of integration, the concentration
of an analyte in the original sample can be determined. Concentration can be calculated using a
calibration curve created by finding the response for a series of concentrations of analyte, or by
determining the relative response factor of an analyte.
If any of the peaks overlap, accurate measurements of these is not possible. If two peaks have the
same retention time, accurate identification is not possible. Thus, it is desirable to have no peak
overlap or co-elution.

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Optimization of Process Parameters for Production of


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4.2 SAPONIFICATION VALUE


Saponification value (or "saponification number"/"Koettstorfer number",also referred to as
"sap" in short) represents the number of milli grams of potassium hydroxide required to saponify
1g of oil under the conditions specified. It is a measure of the average molecular weight (or chain
length) of all the fatty acids present. As most of the mass of a fat/tri-ester is in the 3 fatty acids, it
allows for comparison of the average fatty acid chain length. The long chain fatty acids found in
fats have a low saponification value because they have a relatively fewer number of carboxylic
functional groups per unit mass of the fat as compared to short chain fatty acids. If more moles
of base are required to saponify N grams of fat then there are more moles of the fat and the chain
lengths are relatively small, given the following relation:
Number of moles = mass of oil/relative atomic mass

Procedure:
Materials Required:
Palm oil (used and unused)
Conical Flask

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Optimization of Process Parameters for Production of


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100ml beaker
Weigh Balance
Reflux condenser
Boiling Water bath
pipette (25ml)
Burette

Reagents Required:
Aalcoholic KOH(95% ethanol, v/v)
Potassium hydroxide [0.5N]
Hydrochloric acid[0.5N]
Phenolphthalein indicator

Procedure:
A known weight of the given sample of oil is taken and then transferred into
iodine flask.
Add 25ml of 0.5N alcoholic KOH and 25ml of alcohol into the flask through
pipette and mix well.
Add the same amount of alcohol and 0.5 KOH in another flask for blank
determination.
Fill the flask with water condensers and reflux the contents on a water bath for a
period of 1 hour.

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Optimization of Process Parameters for Production of


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Cool the contents slightly and disconnect the condenser. Rinse the condenser with
a small amount of distilled water into the condenser.
Now add 2-3 drops of phenolphthalein indicator to both the flasks and titrate the
contents of the two flasks with 0.5N HCl until the pink colour disappears .
Note down the endpoint of blank and test .
The difference between the blank and test reading gives the number of millilitres
of 0.5N KOH required to saponify 1g of fat.
Calculate the saponification value using the formula :

Saponification value or number of fat = mg of KOH consumed by 1g of fat.


Weight of KOH = Normality of KOH * Equivalent weight* volume of KOH in litres
Volume of KOH consumed by 1g fat = [Blank tes

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Optimization of Process Parameters for Production of


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4.3 ACID VALUE
In chemistry, acid value (or "neutralization number" or "acid number" or "acidity") is the mass
of potassium hydroxide (KOH) in milligrams that is required to neutralize one gram of the oil.
The acid number is a measure of the amount of carboxylic acid groups in a chemical compound,
such as a fatty acid, or in a mixture of compounds.

Procedure for estimating Free Fatty Acid


1. Take 50 ml of neutralized rectified sprit in a conical flask.
2. Measure 10 ml of filtered oil and add into the above conical flask.
3. Heat the contents to 70 C for fist bubbling.
4. Titrate using N/10 (0.1 N) NaOH using Phenolphthalein indicated for pink or red end
point.

4.4 VISCOSITY
The viscosity of a fluid is a measure of its resistance to gradual deformation by
shear stress or tensile stress. For liquids, it corresponds to the informal concept of
"thickness"; Viscosity is a measure of an oil's resistance to flow. It decreases (thins)
with increasing temperature and increases (or thickens) with decreased
temperature. An oil's viscosity is measured most commonly by kinematic viscosity
and reported in a unit called the centistoke (cSt). Kinematic viscosity is measured in
the time it takes for a specific volume of oil to flow through a special device called a
capillary tube.

The benefits of oils with a higher VI are:


1. A general increase in viscosity at higher temperatures, which results in lower oil
consumption and less wear.
2. A reduced viscosity at lower temperatures, which will improve starting and lower fuel
consumption.

4.5 FLASH POINT

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Optimization of Process Parameters for Production of


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The flash point of a volatile material is the lowest temperature at which vapors of a fluid will
ignite. Measuring a flash point requires an ignition source. At the flash point, the vapor may
cease to burn when the ignition source is removed.
The Cleveland open-cup method is one of three main methods in chemistry for determining the
flash point of a petroleum product using a Cleveland open-cup apparatus, also known as a
Cleveland open-cup tester. First, the test cup of the apparatus (usually brass) is filled to a certain
level with a portion of the biodiesel. Then, the temperature of this chemical is increased rapidly
and then at a slow, constant rate as it approaches the theoretical flash point.
The increase in temperature will cause the chemical to begin to produce flammable vapor in
increasing quantities and density. The lowest temperature at which a small test flame
passing over the surface of the liquid causes the vapor to ignite is considered the
chemical's flash point. This apparatus may also be used to determine the chemical's
fire point which is considered to have been reached when the application of the test
flame produces at least five continuous seconds of ignition.

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Optimization of Process Parameters for Production of


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CHAPTER 5
RESULTS

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Optimization of Process Parameters for Production of


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5.1 TABULATION AND CALCULATIONS

1. CATALYST: Sodium Hydroxide (NaOH)


OIL : Used oil
I. Methanol to Oil ratio - 4:1
Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

II. Methanol to Oil ratio - 6:1


Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

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Optimization of Process Parameters for Production of


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3

III.Methanol to Oil Ratio - 8:1


Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

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Optimization of Process Parameters for Production of


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2. CATALYST: Sodium Hydroxide (NaOH)

OIL: Unused oil


I. Methanol to Oil ratio - 4:1
Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

II. Methanol to Oil ratio - 6:1


Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

III.Methanol to Oil Ratio - 8:1


Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

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Optimization of Process Parameters for Production of


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3. CATALYST: Calcium oxide (CaO)

OIL: Used Oil


I. Methanol to Oil ratio - 4:1
Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

II. Methanol to Oil ratio - 6:1


Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

III.Methanol to Oil Ratio - 8:1


Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

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Optimization of Process Parameters for Production of


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4. CATALYST: Calcium Oxide (CaO)


OIL: Unused Oil
I. Methanol to Oil ratio - 4:1
Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

II. Methanol to Oil ratio - 6:1


Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

III. Methanol to Oil Ratio - 8:1


Sl No.

Time
(Hours)

2.5

Amount of biodiesel obtained


(after distillation)

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Optimization of Process Parameters for Production of


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4.2 GAS CHROMATOGRAPHY

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Optimization of Process Parameters for Production of


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Optimization of Process Parameters for Production of


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5.3 SAPONIFICATION VALUE

1. OBSERVATIONS AND CALCULATIONS


A) Weight of the oil sample taken = g
B) Volume of alcoholic KOH added to the flasks = 25ml
Burette Reading
Final level
Initial level
Vol. of N/2 HCl

Sample tritration (V1)

Blank tritration (V2)

Volume of N/2 HCl used for sample titrations = V1 ml


Volume of N/2 HCl used for blank titrations = V1 ml
Volume of N/2 HCl equivalent to KOH used in saponification g of oil sample = V2 V1
= ml
Mg of KOH present in (V2 V1)ml of N/2 KOH = (V2 V1) * 0.5*56
Saponification value of the sample = (V2 V1)/W *28 =

4.4 ACID VALUE


1. OBSERVATIONS AND CALCULATIONS
Initial weight of beaker, oil and dropper =
Final Weight of the oil sample taken = g
Weight of beaker, oil and dropper =
Volume of N/100 KOH used in the test =

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Optimization of Process Parameters for Production of


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Volume of N/100 KOH used in the blank =Therefore volume of N/100 KOH used
against acid in (W1 W2) g of oil = (A-B) ml
Acid value = (ml of KOH used * Normality * 56) / (weight of sample)

4.5 QUANTITATIVE TESTS VALUES


4.5.1 Flash point and Fire point values
Oil
used
used
used

Catalyst
NaOH
NaOH
NaOH

Methanol : oil
4:1
4:1
6:1

Time (hours)
3
4
4

Flash point
42
42
40

Fire point
46
45
43

4.5.2 Viscosity and Density


Weight of empty flask = 47.6g
Weight of filled flask= 103.08g
Total time taken = 57 sec

Weight of filled flask after stirring = 101.96g


Total time taken = 54 sec
Mass of oil = 103.08 47.6 = 55.48g.

1. Density = mass/60 = 55.48/60 = 0.92 g/cc


2. Kinematic viscosity V = A*t- (B/t)
= 0.0026*57-(1.79/56)
= 0.117exp-4 m2/sec.
3. Absolute viscosity = K*V *Density
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Optimization of Process Parameters for Production of


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= 0.117*0.92
= 0.1076 poise = 107.6exp-3 Nsec/m2

4.6 GAS CHROMATOGRAPHY OF BIODIESEL


4.6.1 Comparison with ASTM Standards
American Society for Testing and Materials (ASTM) is an international standards organization
that develops and publishes voluntary consensus technical standards for a wide range of
materials, products, systems, and services. The obtained fuel properties are compared with
ASTM standards and it is found that all the values are within specified range.
Sl.NO
1
2
3
4

Properties
Flash point (oC)
Viscosity
Specific Gravity
Pour pint

Standard

Range

Obtained

GC/MS analyses of feed oil and the product oil were performed at Shivaji University, Kolhapur.
Gas chromatography analysis of biodiesel prepared from NaOH and CaO is shown in table . The
percentage of unsaturated fatty acid is 80.27 % for NaOH catalyst and 79.01% using CaO
catalyst. Biodiesel fuel with more unsaturated fatty acid composition has more density but has
less viscosity, lower cetane number and heating value. It has lower thermal effiency compared to
high saturated fatty acid composition. It emits lower HC and CO and less smoke compared to
highly saturated biodiesel fuel (Olugbenga Olufemi Awolu).

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4.6.2 Fatty acid profile of fresh oil using CaO

Fatty acid

Percent composition %

Unsaturated fractions
Oleic acid (C18:1)

19.1

Linoleic acid (C18:2)

57.1

Linolenic acid (C18:3)

.11

Hexadecanoic acid

2.7

Saturated fractions
Palmitic acid (C16:0)

11.1

Stearic acid (C18:0)

9.9

Total

100%

Fatty acid

Percent composition %

Unsaturated fractions
Oleic acid (C18:1)

18.1

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