PRODUCTION OF BIODIESEL BY TRANS-ESTERIFICATION USING

USED VEGETABLE OIL (PALM)

A Thesis submitted in partial

Fulfillment of the Requirements for the Award of the Degree of

MASTER OF TECHNOLOGY
IN
CHEMICAL ENGINEERING

By

KHAJA MOYUNUDDIN.MD
(B.Tech Chemical)

Under the Esteemed Guidance of

Prof. Ch. V. Ramachandra Murthy

Principal
Andhra University College of Engineering (A)

DEPARTMENT OF CHEMICAL ENGINEERING

ANDHRA UNIVERSITY COLLEGE OF ENGINEERING
(AUTONOMOUS)
PRODUCTION OF BIODIESEL BY TRANS-ESTERIFICATION USING
USED VEGETABLE OIL

A Thesis submitted in partial

Fulfillment of the Requirements for the Award of the Degree of

MASTER OF TECHNOLOGY
IN
CHEMICAL ENGINEERING

By

KHAJA MOYUNUDDIN.MD
(B.Tech Chemical)

Under the Esteemed Guidance of

Prof. Ch. V. Ramachandra Murthy

Principal
Andhra University College of Engineering (A)

DEPARTMENT OF CHEMICAL ENGINEERING

ANDHRA UNIVERSITY COLLEGE OF ENGINEERING
(AUTONOMOUS)
 ANDHRA UNIVERSITY COLLEGE OF ENGINEERING
(AUTONOMOUS)

CERTIFICATE

This is to certify that the dissertation thesis entitled "Production Of Bio-diesel by trans-
esterification using Used Vegetable oil (palm)" is a bonafide work carried out by Khaja
moyunuddin.Md (311206202009) student of Master of Technology in Chemical Engineering
Department, Andhra University College of Engineering (A), Visakhapatnam. It is the result of
research work carried out by me under the guidance and supervision of Prof. Ch. V.
Ramachandra Murthy for partial fulfillment of the award of degree of Master of Technology in
Chemical Engineering, during the academic year 2012-2013.This work has not been published or
submitted elsewhere for the award of any other degree.

Prof. V. Sujatha Prof. Ch. V. Ramachandra Murthy

Head of the Department Project Guide
Dept. of Chemical Engineering Dept. of Chemical Engineering
AUCE (A) AUCE (A)
 CONTENTS

PAGE NUMBER
DECLARATION i
ACKNOWLEDGEMENT ii
NOMENCLATURE iv
LIST OF TABLES v
LIST OF FIGURES vi

CHAPTER - 1 INTRODUCTION 1
CHAPTER- 2 BIODIESEL PRODUCTION 7
CHAPTER -3 LITERATURE REVIEW 15
CHAPTER -4 EXPERIMENTAL WORK 29
CHAPTER- 5 EXPERIMENTAL PROCEDURE 34
CHAPTER- 6 RESULTS & DISCUSSION 42
CHAPTER - 7 CONCLUSIONS 57
REFERENCES 58
APPENDIX - A SAMPLE CALCULATIONS 63
APPENDIX - B CALCULATED DATA TABLES 69
 DECLARATION

I, (Khaja moyunuddin.Md) do hereby declare that this investigation work

entitled " Production Of Biodiesel by Trans-Esterification using Used Vegetable Oil (palm)
has been originally carried out by me under the guidance of Prof. Ch. V.
Ramachandra Murthy, Chemical Engineering, Andhra University College of
Engineering (A), in the partial fulfillment of the award of the degree of Master of
Technology in Chemical Engineering, Dept. of Chemical Engineering, Andhra
University College of Engineering (A), Visakhapatnam. I also declare that I have not
submitted this dissertation to any other university for the award of any other
degree.

Place: Visakhapatnam Khaja moyunuddin.Md

Date: Reg. No. : 311206202009

i
 ACKNOWLEDGEMENT

I express my deep sense of gratitude to my institution , "Andhra University

College of Engineering (A)", Visakhapatnam, which has provided me an opportunity to

fulfill my long cherished dream.

It is my privilege to express sincere gratitude to Prof. Ch. V. Ramachandra

Murthy, Department of Chemical Engineering, Andhra University College of Engineering (A),
Visakhapatnam, for his valuable guidance, constructive criticism and untiring help, which
enabled me to complete my dissertation work successfully and recommended me to work on
such a prestigious project. .
I would like to express my sincere gratitude and appreciation to Prof.V. Sujatha,
Head of the Department, Department of Chemical Engineering, Andhra University College of
Engineering (A), Visakhapatnam for supporting me for the successful completion of the work.

I also express my sincere thanks to Prof. P. King, Chairman, Board of Studies

in Department of Chemical Engineering and Prof. S. V. Naidu , Faculty Chairman,

Department of Chemical Engineering for their help and suggestions during my work.

I also thank Dr. P.Venkateswara Rao , Asst. prof., Department of Mechanical

Engineering for permitting me to work in the lab.

I express my thanks to Mrs.M.Deepa, Associate professor, Department of Chemical

Engineering for permitting me to work in the lab.

ii
It is pleasure to express my deep sense of gratitude and indebtedness to the entire faculty,
Department of Chemical Engineering, Andhra University College of Engineering (A),
Visakhapatnam, for their valuable guidance, encouragement and support, who have directly or
indirectly had a hand in the successful completion of my project work.

It is pleasure to express my affectionate thanks to my dear friends, Anudeep.G,

N.Vinaya, Ch. V Naga Sowjanya ,VenkataRamachandra.P, Sravan

Kumar.D, Suresh.P for their help, moral support and encouragement throughout the
dissertation work.

Most of all, I would like to thank my father Gouse mohiddin Md, my mother
Gousia Begum,my brothers Zaheer Abbas and Ramizuddin, my uncle Syed

Mastan Ali and all my well-wishers for giving me the most needed moral support for the
successful completion of this project work.

Khaja Moyunuddin Md.

(B.Tech Chemical)

iii
 NOMENCLATURE

UVO : Used vegetable oil

WCO : Waste cooking oil

FFA : Free fatty acid

EPA : Environmental protection agency

WFG : Waste fryer grease

JC : Jatropha curcas

JG : Jatropha gossypiifolia

ME : Methyl ester

FAME : Fatty acid methyl ester

GC_MS : Gas Chromatography_ Mass Spectroscopy

FTIR : Fourier Transform Infrared

SS : Soap Stock

: Density

: Kinematic viscosity

Cst : Centistroke

CFR : Cooperative Fuel Research

iv
 LIST OF TABLES

TABLE-4.1 Fatty acid composition of feed 31

TABLE-4.2 Density, Acid value, molecular weight of oil 32

TABLE-6.1 Comparison of Regular Diesel &obtained Bio-Diesel 56

TABLE-A1 Fatty Acid Composition for palm methyl ester 67

TABLE-B1 Preparation of Methyl Palm Ester with KOH catalyst 69

TABLE-B2 Preparation of Methyl Palm Ester with NaOH catalyst 70

TABLE-B.3 Properties of Methyl Palm Ester, KOH Catalyst 71

TABLE-B.4 Properties of Methyl Palm Ester, NaOH Catalyst 72

TABLE-B.5 Gas Chromatography report for Methyl Palm Ester, KOH Catalyst 73

TABLE-B.6 Gas Chromatography report for Methyl Palm Ester, KOH Catalyst 74

v
 LIST OF FIGURES

Fig No Title Page No

Fig-1.1 World bio-fuel consumption 6

Fig-2.1 Inventor of bio-diesel, Dr. Rudolf Diesel 8

Fig-4.1 Used vegetable oil (Feed) 32

Fig-4.2 Experimental setup for trans-esterification 33

Fig-5.1 pre conditioning of oil 34

Fig-5.2 Layers of ester and glycerin 36

Fig-5.3(a) Water washing of sample for purification 37

(b) Purified bio-diesel 37

(c) Soap water 37

Fig-5.4(a) Glycerin bottles 38

(b) Bio-diesel bottles 38

Fig-5.5 Redwood viscometer 39

Fig-6.1 Effect of mole ratio on yield with KOH as catalyst 43

Fig-6.2 Effect of mole ratio on yield with NaOH as catalyst 44

Fig-6.3 Effect of catalyst concentration (KOH) on yield 45

Fig-6.4 Effect of catalyst concentration (NaOH) on yield 45

Fig-6.5 Effect of catalyst concentration (KOH) on Kinematic viscosity 46

Fig-6.6 Effect of catalyst concentration (NaOH) on Kinematic viscosity 47

Fig-6.7 Effect of mole ratio on Kinematic viscosity with KOH as catalyst 48

Fig-6.8 Effect of mole ratio on Kinematic viscosity with NaOH as catalyst 49

vi
Fig-6.9 Effect of catalyst concentration (KOH) on Flash point 50

Fig-6.10 Effect of catalyst concentration (NaOH) on Flash point 51

Fig-6.11 Effect of mole ratio on Flash point with KOH as catalyst 52

Fig-6.12 Effect of mole ratio on Flash point with NaOH as catalyst 53

Fig-6.13 Effect of catalyst concentration (KOH) on Cetane number 54

Fig-6.14 Effect of catalyst concentration (NaOH) on Cetane number 55

Fig-A.1 Titration to identify acid value 64

vii
 Chapter-1

INTRODUCTION

Several billion gallons of waste vegetable oil is produced every year around the
world, mainly from industrial deep fat fryers found in potato processing plants, factories
manufacturing foods, and restaurants. Some of this wastage is already being re-used by
other industries, such as in animal feed and cosmetics, but the amount that is still being
wasted and ending up in land-fill sites is alarming. Therefore it makes commercial and
environmental sense to re-use this oil for making biodiesel.
Making biodiesel from used vegetable oil (UVO) is much the same as when using
straight vegetable oil, except that the oil will need filtering first to remove debris, and
because it has been used and most likely re-heated several times, more fatty acids will be
present so we need to determine how much more sodium hydroxide (or potassium
hydroxide) to add to neutralize these acids. This is called a titration test. Vegetable Oil is
commonly available everywhere and there at every home and most households dump the
waste oil rather
than utilizing that. Making biodiesel from waste vegetable oil is one of the most
productive ways to utilize waste vegetable oil.
Moreover, day by day fuel is getting expensive and inflation is hitting new highs
across every country across the world. Everyone has started looking for cheap substitutes
for everything in the world. Making Biodiesel from waste vegetable oil is an upcoming
way of preserving energy and meeting our own requirements without depending on
anyone.
Biodiesel is a diesel fuel that is made by reacting vegetable oil (cooking oil) with
other common chemicals that are easily available in the market. Biodiesel may be used in
any diesel automotive engine in its pure form or blended with petroleum-based diesel, so
need not worry about anything. No modifications are required, and the result is a less-
expensive, renewable, clean-burning fuel.
Biodiesel is a product of great interest for its environmental characteristics. It is
biodegradable and it's renewable. It has the advantages of dramatically reduced sulfate
and hydrocarbon emissions and reduces particulate matter. It is nontoxic and does not
damage water quality. Biodiesel is a fuel that can be made from pure or waste vegetable oils
such as soya and rape seed (canola) oil, mixed with methane and a small amount of
lye. It runs a diesel engine just as petroleum-based diesel would.

1
 Chapter-1

Additionally to its environmental characteristics, It is evident, that there is a latent

demand of this product because of the recent rises in the price of oil, and the realization
that fossil fuels will eventually run out, not to mention the damage burning them does to
our planet, this resulted in renewed interest in fuel made from plant oils or biodiesel. That
is why it is necessary to study the potential of biodiesel, as well as to study its feasibility,
if it will be used as a viable alternative fuel in the future.

1.1 IImporrtttance of Biodiesel

mpo anc of mpor
ance
It's Economical
Biodiesel can be produced by individuals on a small scale relatively inexpensively
when compared to Petro diesel. Figures range anywhere from $0.40 a gallon to about $1.25
a gallon depending on the cost of materials required to make it. With prices that low, most
people are able to save hundreds of dollars on their fuel bills. In some cases it even goes
into the thousands of dollars. With savings like that, most people are able to recoup their
initial investment on the equipment needed to make biodiesel within a matter of months.

It's Renewable
Biodiesel has been touted far and wide for its renewable properties. Instead of
making a fuel from a finite resource such as crude oil, Biodiesel can be produced from
renewable resources such as organic oils, fats, and tallow. This means that it can be made
from things that can be re-grown, reproduced, and reused. So, if you need more, you can just
grow another crop of seeds for the oil.

It's Good For the Environment

When Biodiesel is used to power diesel engines, the emissions at the tailpipe are
significantly reduced. Studies by the US National Renewable Energy Lab indicate drops in
several key areas' that help the environment. Carbon Dioxide, Hydrocarbons, and
Particulate Matter (the black smoke from diesels) all are significantly reduced when
Biodiesel is used. When used in older diesel engines such as indirect combustion diesels, the
results are astounding. There was a reduction in the tailpipe emissions of nearly 90%. It also
has a positive energy balance.

2
 Chapter-1

It supports farmers
When Biodiesel is made from organic oils such as Canola, Soy, Peanut, or other
domestically grown seed crops, it helps the farming community out. Because the oil
used to make Biodiesel is "domestically grown", it keeps the money flowing to those
that "grow" the feedstock. This continues to help out the renewable aspect of Biodiesel
because this means more seed crops can be grown by local farmers.

It reduces dependency on Crude Oil

When Biodiesel is used in place of petro-diesel, it reduces the amount of crude oil
used up. This means that it helps to reduce our dependence on a limited resource and
increases our use of renewable resources. We think that's a great step toward reducing our
dependence on a fuel that may not be around forever.

It's enjoyable to make

We think that making Biodiesel is one of the funniest things in the world to do.
With a little practice and know-how it can easily be made and is extremely simple to do.
We've found it to be an incredibly fulfilling experience. There's just something to be said
for being able to make your own fuel and drive past a gas station and wave instead of
pulling up for a fill-up. Words just don't describe the incredible feeling we get each time we
make a batch.

It's good for the engine

Biodiesel, unlike Petro-diesel, has a much higher "lubricity" to it. This means that
it's essentially "slipperier" than normal diesel fuel. With the added "lubricity" of
Biodiesel, engines have been shown to experience less wear and tear when used on a
regular basis. Also, because Biodiesel is less polluting, it means that it's easier on the
engine. US Government Studies have shown that in some cases large fleets using
Biodiesel have been able to go longer between oil changes because the oil stay's cleaner
when Biodiesel is used.

3
 Chapter-1

It's the perfect alternative fuel

When compared to several other Alternative Fuels available, Biodiesel comes
out way ahead. Most alternative fuels require changes to a vehicle to be used. Natural
Gas & Propane require special tanks to be installed and changes to the fuel injection
system must be made as well. Ethanol also requires specialized changes to the fuel
injection system. Electricity requires a completely different engine.
In most cases, once a vehicle undergoes the conversion necessary to run the
alternative fuel, there's no going back. You either run the alternative fuel or you don't
run the vehicle.

1.1.An Overview of Bio-fuel:

Self-sufficiency in energy requirement is critical to the success of any developing

economy. With the depletion of oil resources as well as the negative environmental impact
associated with the use of fossil fuels, there is a renewed interest in alternate
energy sources.
As world reserves of fossil fuels and raw materials are limited, it has stimulated active
research interest in nonpetroleum, renewable, and nonpolluting fuels. Bio-fuels are the only
viable source of energy for the foreseeable future and can still form the base for
sustainable development in terms of socioeconomic and environmental concerns.
Bio-fuels are renewable fuels that are produced predominantly from domestic
biomass feedstock, or as a by-product from the industrial processing of agricultural or
food products, or from the recovery and reprocessing of products such as cooking and
vegetable oil. Bio-ethanol and biodiesel are the most widely recognized bio-fuel sources
for the transport sector and appear to be promising future energy sources.
Bio-fuel does not contain petroleum, but it can be blended in any proportion with
petroleum fuel to create a bio-fuel blend. It can be used in conventional heating
equipment or diesel engines with no major modification. Bio-fuel is in the process of
acquiring a cult status. It does not provide an opportunity to address issues of energy
security and climate change. It is simple to use, biodegradable, nontoxic and essentially free
of sulfur and aromatics. By themselves or as blends, bio-fuels such as bio-ethanol can
help cut substantially both oil imports and carbon emissions. There is a need to evolve the
right bio-fuel model in terms of the feedstock and technology, and a plan of action to ensure
availability over the long term. Efforts to identify the right varieties of feedstock

4
 Chapter-1

and to put in place the research and development, production, and processing facilities on
a national scale have been unreliable.
Bio-fuels are energy carriers that store the energy derived from biomass,
commonly produced from plants, animals and micro-organisms and organic wastes. Bio-
fuels may be solid, liquid or gaseous and include all kinds of biomass and derived
products used for energetic purposes. Bio-fuels are renewable energy sources, meaning
that fresh supplies can be re-grown. They are a possible substitute product for fossil fuels.
Compared with the latter product there are some advantages to subscribe to bio-fuels.
Advantages and benefits of bio-fuels, however, depend on the categorization of the specific
bio-fuel, type of feedstock used and technology applied to produce it.
Biomass energy generates far less air emissions than fossil fuels, reduces the
amount of waste sent to landfills and decreases our reliance on foreign oil. Biomass energy
also creates thousands of jobs and helps revitalize rural communities.CO2 is part of the
Earth's natural carbon cycle, which circulates carbon through the atmosphere, plants,
animals, oceans, soil, and rocks. This cycle maintains a life-sustaining and delicate
natural balance between storing, releasing, and recycling carbon. By using bio-fuels such
as bio-ethanol and biodiesel for transportation, we can help restore the natural balance of
CO2 in the atmosphere. Besides displacing fossil fuels, the feed stocks used to make bio-
fuels require CO2 to grow, and they absorb what they need from the atmosphere. Thus,
much or all of the CO2 released when biomass is converted into a bio-fuel and burned in
automobile engines is recaptured when new biomass is grown to produce more bio fuels.

1.2.1 Bio fuel generation:

Bio-fuels for transport are commonly addressed according to their current or future
availability as first, second or third generation bio-fuels. Second and third generation bio-
fuels are also called "advanced" bio-fuels.
First-generation bio-fuels are commercially produced using conventional
technology. The basic feed stocks are seeds, grains, or whole plants from crops such as
corn, sugar cane, rapeseed, wheat, sunflower seeds or oil palm. These plants were
originally selected as food or fodder and most are still mainly used to feed people. The most
common first-generation bio-fuels are bio-ethanol (currently over 80% of liquid bio-
fuels production by energy content), followed by biodiesel, vegetable oil, and biogas.
Second-generation bio-fuels-can be produced from a variety of non-food sources.
These include waste biomass, the stalks of wheat, corn Stover, wood, and special energy

5
 Chapter-1

or biomass crops (e.g. Miscanthus). Second-generation bio-fuels use biomass to liquid

technology, by thermo chemical conversion (mainly to produce biodiesel) or fermentation
(e.g. to produce cellulosic ethanol).Many second-generation bio-fuels are under
development such as bio-hydrogen, bio-methanol, DMF, Bio-DME, Fischer-Tropsch diesel,
bio-hydrogen diesel, and mixed alcohols.
Third-generation bio-fuel is Algae fuel, also called oilgae, is a bio-fuel from algae
and addressed as a third-generation bio-fuel. Algae are feed-stocks from aquatic
cultivation for production of triglycerides (from algal oil) to produce biodiesel. The
processing technology is basically the same as for biodiesel from second-generation feed
stocks. Other third -generation bio-fuels include alcohols like bio-propanol or bio- butanol,
which due to lack of production experience are usually not considered to be
relevant as fuels on the market before 2050, though increased investment could accelerate
their development. The same feed stocks as for first-generation ethanol can be used, but
using more sophisticated technology. Propanol can be derived from chemical processing
such as dehydration followed by hydrogenation. As a transport fuel, butanol has
properties closer to gasoline than bio ethanol.
Current use of bio-fuels for transport on the global scale is dominated by bio-
ethanol and biodiesel, whereas the use of other bio-fuels for transport like biogas and pure
plant oil seem to be restricted to local and regional pilot cases, and second-generation bio-
fuels are still in the development stage. Commercial investment in advanced (second-
generation) bio-fuel plants is beginning in Canada, Germany, Finland, Japan, the
Netherlands, Sweden, and the United States.

Figure-1.1: World Bio-fuel consumption

6
 Chapter-2

BIODIESEL PRODUCTION

In the most general sense, biodiesel refers to any diesel fuel substitute derived from
renewable biomass. More specifically, biodiesel is defined as an oxygenated, sulfur-free,
biodegradable, non-toxic, and eco-friendly alternative diesel oil. Chemically, it can be
defined as a fuel composed of mono-alkyl esters of long chain fatty acids derived from
renewable sources, such as vegetable oil, animal fat, and used cooking oil designated as
B100, and also it must meet the special requirements such as the ASTM and the European
standards. For these to be considered as viable transportation fuels, they must meet stringent
quality standards. One popular process for producing biodiesel is trans-esterification.
Biodiesel is made from a variety of natural oils such as soybeans, rapeseeds, coconuts, and
even recycled cooking oil. Rapeseed oil dominates the growing biodiesel industry in Europe.
In the United States, biodiesel is made from soybean oil because more soybean oil is
produced in the United States than all other sources of fats and oil combined.
The injection and atomization characteristics of the vegetable oils are significantly
different than those of petroleum derived diesel fuels, mainly as the result of their high
viscosities. Modern diesel engines have fuel-injection system that is sensitive to viscosity
change. One way to avoid these problems is to reduce fuel viscosity of vegetable oil in order
to improve its performance. The conversion of vegetable oils into biodiesel is an effective
way to overcome all the problems associated with the vegetable oils. Dilution, micro
emulsification, pyrolysis, and trans-esterification are the four techniques applied to solve the
problems encountered with the high fuel viscosity.
Trans-esterification is the most common method and leads to mono alkyl esters of
vegetable oils and fats, now called biodiesel when used for fuel purposes. The methyl ester
produced by trans-esterification of vegetable oil has a high cetane number, low viscosity and
improved heating value compared to those of pure vegetable oil which results in shorter
ignition delay and longer combustion duration and hence low particulate emissions.

7
 Chapter-2

2.1 History of Biodiesel

Dr. Rudolf Diesel invented the diesel engine to run on a host of fuels including coal
dust suspended in water, heavy mineral oil, and vegetable oils. Dr. Diesel's first engine
experiments were catastrophic failures, but by the time he showed his engine at the World
Exhibition in Paris in 1900, his engine was running on 100% with peanut oil. Dr. Diesel (Fig.
2.1) was visionary. In 1911 he stated ''the diesel engine can be fed with vegetable oils and
would help considerably in the development of agriculture of the countries, which use it''. In
1912, Diesel said,' the use of vegetable oils for engine fuels may seem insignificant today.
But such oils may become in course of time as important as petroleum and the coal tar
products of the present time''. Since Dr. Diesel's untimely death in 1913, his engine has been
modified to run on the polluting petroleum fuel, now known as ''diesel''. Nevertheless, his
ideas on agriculture and his invention provided the foundation for a society fueled with clean,
renewable, locally grown fuel.
In the 1930s and 1940s, vegetable oils were used as diesel substitutes from time to
time, but usually only in emergency situations. Recently, because of increase in crude oil
prices, limited resources of fossil oil and environmental concerns, there has been a renewed
focus on vegetable oils and animal fats to make biodiesel. Continued and increasing use of
petroleum will intensify local air pollution and magnify the global warming problems caused
by carbon dioxide.
In a particular case, such as the emission of pollutants in the closed environment of
underground mines, biodiesel has the potential to reduce the level of pollutants and the level
of potential for probable carcinogens.

Figure- 2.1: Dr. Rudolf Diesel

8
 Chapter-2

2.2 The advantages of using vegetable oils as fuels

Vegetable oils are liquid fuels from renewable sources; they do not over-burden the
environment with emissions. Vegetable oils have potential for making marginal land
productive by their property of nitrogen fixation in the soil. Their production requires lesser
energy input in production. They have higher energy content than other energy crops like
alcohol. They have 90% of the heat content of diesel and they have a favorable output/input
ratio of about 2-4:1 for un-irrigated crop production. The current prices of vegetable oils in
world are nearly competitive with petroleum fuel price. Vegetable oil combustion has cleaner
emission spectra and simpler processing technology. But these are not economically feasible
yet and need further R&D work for development of on farm processing technology.
Due to the rapid decline in crude oil reserves, the use of vegetable oils as diesel fuels
is again promoted in many countries. Depending up on climate and soil conditions, different
nations are looking into different vegetable oils for diesel fuels.
For example, soybean oil in the USA, rapeseed and sunflower oils in Europe, palm oil
in Southeast Asia(mainly Malaysia and Indonesia), and coconut oil in Philippines are being
considered as substitutes for mineral diesel.
An acceptable alternative fuel for engine has to fulfill the environmental and energy
security needs without sacrificing operating performance. Vegetable oils can be successfully
used in CI engine through engine modifications and fuel modifications because Vegetable oil
in its raw form cannot be used in engines. It has to be converted to a more engine-friendly
fuel called biodiesel. Biodiesel has comparable energy density, cetane number, heat of
vaporization, and stoichiometric air/fuel ratio with mineral diesel. The large molecular size of
the component triglycerides result in the oil having higher viscosity compared with that of
mineral diesel. Viscosity affects the handling of the fuels by pump and injector system, and
the shape of fuel spray.

2.3 Characteristics of oils or fats affecting their suitability for use as biodiesel
Calorific Value, Heat of Combustion- Heating Value or Heat of Combustion, isthe amount of
heating energy released by the combustion of a unit value of fuels. One of the most important
determinants of heating value is moisture content. Air-dried biomass typically has about 15-
20% moisture, whereas the moisture content for oven-dried biomass is negligible. Moisture

9
 Chapter-2

content in coals varies in the range 2-30%. However, the bulk density of most biomass feed
stocks is generally low, even after densification - between about 10 and 40% of the bulk
density of most fossil fuels. Liquid bio-fuels however have bulk densities comparable to
those for fossil fuels.
Melt Point or Pour Point- Melt or pour point refers to the temperature at which the oil in
solid form starts to melt or pour. In cases where the temperatures fall below the melt point,
the entire fuel system including all fuel lines and fuel tank will need to be heated.
Cloud Point- The temperature at which an oil starts to solidify is known as the cloud point.
While operating an engine at temperatures below oil's cloud point, heating will be necessary
in order to avoid waxing of the fuel.
Flash Point- The flash point temperature of a fuel is the minimum temperature at which the
fuel will ignite (flash) on application of an ignition source. Flash point varies inversely with
the fuel's volatility. Minimum flash point temperatures are required for proper safety and
handling of diesel fuel.
Iodine Value- Iodine Value (IV) is a value of the amount of iodine, measured in grams,
absorbed by 100 grams of given oil.

Iodine value (or Iodine number) is commonly used as a measure of the chemical stability
properties of different biodiesel fuels against such oxidation as described above. The Iodine
value is determined by measuring the number of double bonds in the mixture of fatty acid
chains in the fuel by introducing iodine into 100 grams of the sample under test and
measuring how many grams of that iodine are absorbed. Iodine absorption occurs at double
bond positions - thus a higher IV number indicates a higher quantity of double bonds in the
sample, greater potential to polymerize and hence lesser stability.
Viscosity- Viscosity refers to the thickness of the oil, and is determined by measuring the
amount of time taken for a given measure of oil to pass through an orifice of a specified size.
Viscosity affects injector lubrication and fuel atomization. Fuels with low viscosity may not
provide sufficient lubrication for the precision fit of fuel injection pumps, resulting in leakage
or increased wear. Fuel atomization is also affected by fuel viscosity. Diesel fuels with high
viscosity tend to form larger droplets on injection which can cause poor combustion,
increased exhaust smoke and emissions.

10
 Chapter-2

Cetane Number- Is a relative measure of the interval between the beginning of injection and
auto ignition of the fuel. As the cetane number is high, the shorter the delay interval and the
greater its combustibility. Fuels with low Cetane Numbers will result in difficult starting,
noise and exhaust smoke. In general, diesel engines will operate better on fuels with Cetane
Numbers above 50. Cetane tests provide information on the ignition quality of a diesel fuel.
Research using cetane tests will provide information on potential tailoring of vegetable oil-
derived compounds and additives to enhance their fuel properties.
Density- Is the weight per unit volume. Oils that are denser contain more energy. For
example, petrol and diesel fuels give comparable energy by weight, but diesel is denser and
hence gives more energy per liter. The aspects listed above are the key aspects that determine
the efficiency of a fuel for diesel engines. There are other aspects/characteristics which do
not have a direct bearing on the performance, but are important for reasons such as
environmental impact etc. These are:
Ash Percentage - Ash is a measure of the amount of metals contained in the fuel. High
concentrations of these materials can cause injector tip plugging, combustion deposits and
injection system wear. The ash content is important for the heating value, as heating value
decreases with increasing ash content.Ash content for bio-fuels is typically lower than for
most coals, and sulfur content is much lower than for many fossil fuels. Unlike coal ash,
which may contain toxic metals and other trace contaminants, biomass ash may be used as a
soil amendment to help replenish nutrients removed by harvest.
Sulfur Percentage - The percentage by weight, of sulfur in the fuel Sulfur content is limited
by law to very small percentages for diesel fuel used in on-road applications.

2.4 Biodiesel feed stocks:

In general, biodiesel feedstock can be categorized into three groups:
Vegetable oils (edible or non-edible oils)
Animal fats
Used waste cooking oil including triglycerides.
But also a variety of oils can be used to produce biodiesel, algae, which can be grown
using waste materials such as sewage and without displacing land currently used for food
production and oil from halophytes such as salicornia bigelovii, which can be grown using

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 Chapter-2

saltwater in coastal areas where conventional crops cannot be grown, with yields equal to the
yields of soybeans and other oilseeds grown using freshwater irrigation.
Among those feed stocks, vegetable oils have become more attractive recently
because of its environmental benefits and the fact that it is made from renewable resources.
The concept of using vegetable oil as a transportation fuel dates back to 1893 when Dr.
Rudolf Diesel developed the first diesel engine to run on vegetable oil. Vegetable oil is one
of the renewable fuels. Vegetable oils have the potential to substitute a fraction of petroleum
distillates and petroleum-based petro chemicals in the near future. The basic constituent of
vegetable oils is triglyceride. Vegetable oils comprise 90 to 98% triglycerides and small
amounts of mono- and di-glycerides .These usually contain free fatty acids (FFAs), water,
sterols, phospholipids, odorants and other impurities. Different types of vegetable oils have
different types of fatty acids.
The advantages of vegetable oils as diesel fuel are their portability, ready availability,
renewability, higher heat content (about 88% of D2 fuel), lower sulfur content, lower
aromatic content, and biodegradability. The main disadvantages of vegetable oils as diesel
fuel are higher viscosity, lower volatility, and the reactivity of unsaturated hydrocarbon
chains.
The injection and atomization characteristics of the vegetable oils are significantly
different than those of petroleum-derived diesel fuels, mainly as the result of their high
viscosities. The vegetable oils, as alternative engine fuels, are all extremely viscous with
viscosities ranging from 9 to 17 times greater than that of petroleum-derived diesel fuel.
Modern diesel engines have fuel-injection system that is sensitive to viscosity change.
One way to avoid these problems is to reduce fuel viscosity of vegetable oil in order
to improve its performance. The vegetable oils may be blended to reduce the viscosity with
diesel in presence of some additives to improve its properties. Heating and blending of
vegetable oils may reduce the viscosity and improve volatility of vegetable oils but its
molecular structure remains unchanged hence polyunsaturated character remains. Blending
of vegetable oils with diesel, however, reduces the viscosity drastically and the fuel handling
system of the engine can handle vegetable oil-diesel blends without any problems. The
conversion of vegetable oils into FAME is an effective way to overcome all the problems
associated with the vegetable oils.

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 Chapter-2

The most common way of producing biodiesel is the trans-esterification of vegetable

oils. The methyl ester produced by trans-esterification of vegetable oil has a high cetane
number, low viscosity and improved heating value compared to those of pure vegetable oil
which results in shorter ignition delay and longer combustion duration and hence low
particulate emissions. Its use results in the minimization of carbon deposits on injector
nozzles.

2.5 Environmental problems for disposing used cooking oil

Used cooking oil causes severe environmental problems, a liter of oil poured into a
watercourse can pollute up to 1000 tanks of 500 liters". It's feasible to demonstrate the
contamination with the dumping of these oils to the main water sources. The oil which
reaches the water sources increases its organic pollution load, to form layerson the water
surface to prevent the oxygen exchange and alters the ecosystem. The dumping of the oil also
causes problems in the pipes drain obstructing them and creating odors and increasing the
cost of wastewater treatment. For this reason, has been necessary to create a way to recover
this oil and reuse it.
Also due to the wear and tear resulting in sewer pipes may cause overflows of the
system, generating diseases that can cause mild stomach cramps to diseases potentially fatal,
such as cholera, infectious hepatitis and gastroenteritis, due to the sewage contains water
which can transport bacteria, viruses, parasites, intestinal worms and molds. The dangerous
odors generate impact negatively on health, is formed hydrogen sulfide (H2S), which can
cause irritation of the respiratory tract, skin infections, headaches and eye irritation.

2.6 Biodiesel production from used cooking oil:

At present, production of vegetable oil and animal fat worldwide is not sufficient to
replace liquid fossil fuel use. There are a few environmental groups who protest the increased
amount of farming and the subsequent over-fertilization, increased pesticide use, and land
use conversion necessary to produce the additional vegetable oil.
Waste vegetable oil has been proposed by many as the best source of oil to produce
biodiesel. Here too, the available supply is far less than the quantity needed to replace the
amount of petroleum-based fuel that is burned for transportation and home heating in the

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 Chapter-2

world. According to the United States Environmental Protection Agency (EPA), restaurants
in the US produce about 300 million US gallons (1,000,000 m) of waste cooking oil
annually. And in the present work the usage of waste cooking oil reduces the environmental
problems which are formed due to disposal of waste cooking oil.
For a genuinely renewable energy source, plants would have to be considered. Plants
convert solar energy into chemical energy through photosynthesis. Biodiesel ultimately
stores this chemical energy and releases it on combustion. The carbon dioxide and water
produced can participate in the photosynthetic cycle, so that plants can offer a sustainable oil
source for biodiesel production.
The methods used for biodiesel production from used cooking oil are similar to that
of conventional trans-esterification processes. Selection of a particular process depends on
the amount of free fatty acid and water content of the used cooking oil. It is reported that the
feedstock such as refined vegetable oil, crude vegetable oil , used cooking oil ,animal oil and
trap greases generally contain 0.05%, 0.3%- 0.7%, 5%-30% and 40%-100% of free fatty acid
respectively. Most biodiesel production processes can tolerate up to 1% water in the
feedstock, even this small quantity of water will increase soap formation and measurably
affect the trans-esterification process.

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 Chapter - 3

LITERATURE REVIEW

Demirbas [1] investigated on use of used cooking oil as feedstock reduces biodiesel
production cost by about 60- 70% because the feedstock cost constitutes approximately 70-
95% of the overall biodiesel production cost. It is reported that the prices of biodiesel will be
reduced approximately to the half with the use of low cost feedstock. More-over used
cooking oils can be a workable feedstock for biodiesel production as they are easily
available. The use of non-edible plant oils when compared with edible oils is very significant
because of the tremendous demand for edible oils as food, and they are far too expensive to
be used as fuel at present. The land use for growing oilseeds as feedstocks for the biodiesel
production competes with the use of land for food production.
Thirumarimurugan, et al. [2]has studied on the conversion of waste sunflower oil
used for domestic purposes such as cooking oil into biodiesel using an alkali catalyzed trans-
esterification process.Reports experimental data on the production of fatty acid methyl esters
from sunflower oil using sodium hydroxide (NaOH) as alkaline catalyst. The variables
affecting the yield and characteristics of the biodiesel produced from these vegetable oils
were studied.
Deshpande, et al. [3]conducted work to produce methyl ester fuels based on non
edible oils like castor oil by using different catalysts like NaOH and H2SO4. The effect of
various parameters like temp, residence time, and catalyst concentration investigated on yield
of biodiesel and physical properties like Viscosity, Specific gravity, Acid value.
AyhanDemirbas [4]has observed that in the supercritical methanol trans-
esterification method, the yield of conversion increases to 95% in 10 min. Supercritical
methanol has a high potential for both trans-esterification of triglycerides and methyl
esterification of free fatty acids to methyl esters for a Diesel fuel substitute. The viscosity
values of vegetable oils are between 27.2 and 53.6 mm2/s, whereas those of vegetable oil
methyl esters are between 3.59 and 4.63 mm2/s. The flash point values of vegetable oil
methyl esters are much lower than those of vegetable oils. An increase in density for
vegetable oil methyl esters or biodiesels increases the viscosity.

15
 Chapter - 3

TitipongIssariyakul, et al.[5] carried out the trans-esterification of waste fryer

grease (WFG) containing 5-6 wt.% free fatty acid (FFA) with methanol, ethanol, and
mixtures of methanol/ethanol maintaining the oil to alcohol molar ratio of 1:6, and initially
with KOH as a catalyst was investigated by Mixtures of methanol and ethanol were used for
trans-esterification in order to use the better solvent property of ethanol and rapid equilibrium
using methanol. Formation of soap by reaction of FFA present in WFG with KOH instigated
difficulty in the separation of glycerol from biodiesel ester. To untangle this problem, two-
stage (acid and alkali catalyzed) method was used for biodiesel synthesis. More than 90%
ester was obtained when two-stage method was used compared to 50% ester in single stage
alkaline catalyst. In the case of mixed alcohol, a relatively smaller amount of ethyl esters was
formed along with methyl esters. Acid value, viscosity, and cetane number of all the esters
prepared from WFG were within the range of the ASTM standard. Esters obtained from
WFG showed good performance as a lubricity additive.

Bo Liu, et al. [6]investigated on the optimization for tuning operation parameters,

such as methanol dosage, catalyst concentration, reaction temperature and time.Biodiesel is a
renewable fuel conventionally prepared by trans-esterification of pre-extracted vegetable oils
and animal fats of all resources with methanol, catalyzed by strong acids or bases. Reports on
a novel biodiesel production method that features acid-promoted direct methanolysis of
cellular biomass of oleaginous yeasts and filamentous fungi. This integrated method is thus
effective and technically attractive, as dried microbial biomass as feedstocks omits otherwise
tedious and time-consuming oil extraction processes.

Arjun, et al. [7]experimented with waste cooking oils and KOH catalyst to produce
biodiesel. He characterized the biodiesel by its physical and fuel properties including density,
viscosity, acid value, flash point, cloud point, pour point, cetane index, water and sediment
content, total and free glycerin content, di-glycerides and mono-glycerides, phosphorus
content and sulfur content according to ASTM standards.

Anikeev, et al. [8]. Found that the oil type produced insignificant effect on the
product composition (fatty acid esters) and oil conversion value.Biodiesel synthesis from
vegetable oils with supercritical methanol and KOH is experimented by Trans-esterification

16
 Chapter - 3

reactions of sunflower, rapeseed, cottonseed and cameline oils in supercritical methanol were
studied in a flow reactor under equal conditions.

Gerardo, et al. [9]undertaken the manufacture of biodiesel as a case study by to

demonstrate and describe this achievement. Results from this study show the positive
features of this process and identify opportunities for sustainability improvement in the areas
of material and energy use, environmental impacts, and economics during the production of
this important bio-fuel. Therefore, GREENSCOPE is proposed as a fundamental tool for
evaluating and designing more sustainable chemical processes.

Singh, et al. [10]. Biodiesel production through the use of different sources and
characterization of oils and their esters as the substitute of diesel: A review was done by
Several methods available for producing Biodiesel, trans-esterification of natural oils and fats
are currently the method of choice. The purpose of the process is to lower the viscosity of the
oil or fat. Researchers focused mainly the edible oils to produce the Biodiesel because of
easily availability and familiarity. Very few researchers concentrated on Non edible oil for
the same purpose.

Non-edible oils can also be utilized for making Biodiesel fuel. For the production of
Biodiesel fuel, an alkali-catalysis process has been established that gives high conversion
levels of oils to methyl esters. Enzymatic processes using both extra cellular and intracellular
lipases have recently been developed. The cost of lipase production is the main hurdle to
commercialization of the lipase-catalyzed process; several attempts have been made to
develop cost-effective systems. In terms of production cost, there also are two aspects, the
trans-esterification process and byproduct (glycerol) recovery. A continuous trans-
esterification process is one choice to lower the production cost. The foundations of this
process are a shorter reaction time and greater production capacity. The recovery of high
quality glycerol is another way to lower production cost. Land may be a cost increasing
factor for Biodiesel production, because of more and more land required to live the growing
population. To overcome the land problem, the high yielding Biodiesel plants (non edible
producing plants) should be grown in marginal and waste land areas.

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 Chapter - 3

Xiaohu Fan, et al. [11]evaluated the feasibility of using recycled canola oil as raw
material to produce ASTM standard biodiesel by Two-step reaction, acid-catalyzed
esterification followed by alkali-catalyzed trans-esterification. The high level of free fatty
acids ( FFA) in the recycled canola oil was reduced to less than 1% by acid-catalyzed
esterification with 40/1 molar ratio of methanol to FFA in the presence of 5% (v/v, based on
FFA) sulfuric acid. Further alkali-catalyzed trans-esterification was carried out at 6/1 molar
ratio of methanol to oil and 1% (wt%, based on oil weight) potassium hydroxide. The
characterizations of produced biodiesel showed that it met the ASTM D 6751 with respect to
the kinematic viscosity at 40 C, acid number, flash point, water and sediment, cold soak
filtration test, oxidation stability, free and total glycerin etc. At the same time, the properties
of by-product crude glycerol, such as flash point, moisture by Karl Fisher, ash, glycerol
content, were also characterized, which can facilitate further glycerol purification and expand
its applications, thus enhancing the overall profitability of the biodiesel production process.

Jefferson, et al. [12] studied on the two genus of the Jatropha family: the Jatropha
gossypiifolia (JG) and Jatropha curcas L. (JC)in order to delimitate their potential as raw
material for biodiesel production. The oil content in wild seeds and some physical-chemical
properties of the oils and the biodiesel obtained from them were evaluated. The studied
physical-chemical properties of the JC and JG biodiesel are in acceptable range for use as
biodiesel in diesel engines, showing a promising economic exploitation of these raw
materials in semi-arid regions. However, further agronomic studies are needed in order to
improve the seed production and the crude oil properties.

The use of microalgae can be a suitable alternative feedstock for next generation
biofuels because certain species contain high amounts of oil, which could be extracted,
processed and refined into transportation fuels, using currently available technology; they
have fast growth rate, permit the use of non-arable land and non-potable water, use far less
water and do not displace food crops cultures; their production is not seasonal and they can
be harvested daily.

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 Chapter - 3

Gemma Vicente, et al. [13]. has done the comparison study of different
homogeneous catalysts systems for the biodiesel production which is carried out by the most
common catalysts for biodiesel production are homogeneous basic catalysts. In this paper, a
comparison is made of different basic catalysts (sodium meth oxide, potassium methoxide,
sodium hydroxide and potassium hydroxide) for methanolysis of sunflower oil. All the
reactions were carried out under the same experimental conditions in a batch stirred reactor
and the subsequent separation and purification stages in a decanter.

The analytical methods included gas chromatography and the determination of fat and
oil conventional parameters. The biodiesel purity was near 100 wt. % for all catalysts.
However, near 100 wt. % biodiesel yields were only obtained with the methoxide catalysts.
According to the material balance of the process, yield losses were due to triglyceride
saponification and methyl ester dissolution in glycerol. Obtained biodiesel met the measured
specifications, except for the iodine value, according to the German and EU draft standards.
Although all the trans-esterification reactions were quite rapid and the biodiesel layers
achieved nearly 100% methyl ester concentrations, the reactions using sodium hydroxide
turned out the fastest.

Saka, et al. [14] investigated trans-esterification reaction of rapeseed oil in

supercritical methanol without using any catalyst. An experiment has been carried out in the
batch-type reaction vessel preheated at 350 and 400 0C and at a pressure of 4565 MPa, and
with a molar ratio of 1:42 of the rapeseed oil to methanol. It was consequently demonstrated
that, in a preheating temperature of 350 0C, 240 s of supercritical treatment of methanol was
sufficient to convert the rapeseed oil to methyl esters and that, although the prepared methyl
esters were basically the same as those of the common method with a basic catalyst, the yield
of methyl esters by the former was found to be higher than that by the latter. In addition, it
was found that this supercritical methanol process requires the shorter reaction time and
simpler purification procedure because of the unused catalyst.
Canakci, et al. [15] gave some specific results that are based on the process
development portion of biodiesel production from Oils and fats with high free fatty acids.
The acid-catalyzed pretreatment reaction decreased the acid value of the synthetic mixture to
less than 2 mg KOH/g with a 2-step process. Increasing the acid catalyst amount is very

19
 Chapter - 3

effective in decreasing the acid value of the mixture. Ethanol decreased the FFA level of the
synthetic mixture faster than methanol. With KOH as the alkaline catalyst, it was found that
the acid value of the feedstock needed to be reduced to 1 mg KOH/g (0.5% FFA) in order to
get good ester conversion.

The two-step acid catalysis pretreatment process was successful in decreasing the
acid value of yellow and brown grease to less than 2 mg KOH/g but a higher molar ratio and
more time were required than was expected based on the work with the simulated high FFA
feedstock. It was observed that the alkaline catalyst amount and type affect the trans-
esterification reaction completeness and yield. NaOCH3 is more effective than KOH.

Edward Crabbe, et al. [16].Investigated the three principle variables, molar ratio of
methanol to oil, amount of catalyst, and reaction temperature, affecting the yield of acid-
catalyzed production of methyl ester (biodiesel) from crude palm oil. The biodiesel was then
used as an extractant in batch and continuous acetone-butanol-ethanol fermentation, and its
fuel properties and that of the biodiesel-ABE (acetone-butanol-ethanol) product mix
extracted from the batch culture analyzed. The optimized variables, 40:1 methanol/oil
(mol/mol) with 5% H2SO4 (vol. /wt.) reacted at 95C for 9 h, gave a maximum ester yield of
97%. Biodiesel preferentially extracted butanol, and enhanced its production in the batch
culture from 10 to 12 g. l-1. The fuel properties of biodiesel and the biodiesel-ABE mix were
comparable to that of No.2 diesel, but their cetane numbers and the boiling points of the 90%
fractions were higher. Therefore, they could serve as efficient No. 2 diesel substitutes. The
biodiesel-ABE mixture had the highest cetane number.

Yomi Watanabe, et al. [17] Candida antarcticali pase is inactivated in a mixture of

vegetable oil and more than 1:2 molar equivalent of methanol against the total fatty acids.
revealed that the inactivation was eliminated by three successive additions of 1:3 molar
equivalent of methanol and have developed a three-step methanolysis by which over 95% of
the oil triacylglycerol (TAG) were converted to their corresponding methyl esters (ME). In
his study, the lipase was not inactivated even though 2:3 molar equivalent of methanol was
present in a mixture of acylglycerol (AG) and 33% ME (AG/ME33). Then his finding led to
a two-step methanolysis of the oil TAG. When two-step reaction was repeated by transferring

20
 Chapter - 3

the immobilized lipase to a fresh substrate mixture, the enzyme could be used 70 cycles (105
d) without any decrease in the conversion. From the viewpoint of the industrial production of
biodiesel fuel production, the two-step reaction was conducted using a reactor with impeller.
However, the enzyme carrier was easily destroyed, and the lipase could be used only several
times. Thus, they attempted flow reaction using a column packed with immobilized Candida
lipase. Because the lipase packed in the column was drastically inactivated by feeding a
mixture of AG/ME33 and 2:3 molar equivalent of methanol, three-step flow reaction was
performed using three columns packed with 3.0 g immobilized lipase.

Hak-Joo Kim, et al. [18].Performeda study for optimizing the reaction conditions
such as the reaction time, the stirring speed, the use of co-solvent, the oil to methanol ratio,
and the amount of catalyst.An environmentally benign process for the production of biodiesel
from Vegetable Oils using heterogeneous catalyst was developed by Na/NaOH/-Al2O3
heterogeneous base catalyst was firstly adopted for the production of biodiesel. The
Na/NaOH/-Al2O3 heterogeneous base catalyst showed almost the same activity under the
optimized reaction conditions compared to conventional homogeneous NaOH catalyst. The
basic strength of Na/NaOH/ -Al2O3 catalyst was estimated and the correlation with the
activity towards trans-esterification was proposed.

Weiliang Cao, et al. [19].Carried out the trans-esterification of soybean oil in

supercritical methanol in the absence of catalyst by a co-solvent which was added to the
reaction mixture in order to decrease the operating temperature, pressure and molar ratio of
alcohol to vegetable oil. With propane as co-solvent in the reaction system, there was a
significant decrease in the severity of the conditions required for supercritical reaction, which
makes the production of biodiesel using supercritical methanol viable as an industrial
process. A high yield of methyl esters (biodiesel) was observed and the production process is
environmentally friendly. Furthermore the co-solvent can be reused after suitable
pretreatment.

Ramadhas, et al. [20] experimented the biodiesel production from high FFA rubber
seed oil by the difficulty with alkaline-esterification of non-edible type oils and fats oils is
that they often contain large amounts of free fatty acids (FFA). These free fatty acids quickly

21
 Chapter - 3

react with the alkaline catalyst to produce soaps that inhibit the separation of the ester and
glycerin. A two-step trans-esterification process is developed to convert the high FFA oils to
its mono-esters. The first step, acid catalyzed esterification reduces the FFA content of the oil
to less than 2%. The second step, alkaline catalyzed trans-esterification process converts the
products of the first step to its mono-esters and glycerol. The major factors affect the
conversion efficiency of the process such as molar ratio, amount of catalyst, reaction
temperature and reaction duration is analyzed. The two-step esterification procedure converts
rubber seed oil to its methyl esters. The viscosity of biodiesel oil is nearer to that of diesel
and the calorific value is about 14% less than that of diesel. The important properties of
biodiesel such as specific gravity, flash point, cloud point and pour point are found out and
compared with that of diesel. This study supports the production of biodiesel from unrefined
rubber seed oil as a viable alternative to the diesel fuel.

Edgar Lotero, et al. [21] currently, alkaline bases are used to catalyze the reaction.
These catalysts require anhydrous conditions and feedstocks with low levels of free fatty
acids (FFAs). Inexpensive feedstocks containing high levels of FFAs cannot be directly used
with the base catalysts currently employed. Strong liquid acid catalysts are less sensitive to
FFAs and can simultaneously conduct esterification and trans-esterification. However, they
are slower and necessitate higher reaction temperatures. Nonetheless, acid-catalyzed
processes could produce biodiesel from low-cost feedstocks, lowering production costs.
Better yet, if solid acid catalysts could replace liquid acids, the corrosion and environmental
problems associated with them could be avoided and product purification protocols reduced,
significantly simplifying biodiesel production and reducing cost. Research was related to
biodiesel production using acid catalysts, including solid acids.

HosseinNoureddini, et al. [22].Enzymatic trans-esterification of soybean oil with

methanol and ethanol was studied by Lipase PS from Pseudornonascepacia resulted in the
highest yield of alkyl esters. Lipase from Pseudornonascepacia was further investigated in
immobilized from within chemically inert, hydrophobic sol-gel support. The gel-entrapped
lipase was prepared by poly condensation of hydrolyzed tetra-methoxysilane and iso-
butyltrirnethoxysilene.Using the immobilized lipase PS, the effects of water and alcohol

22
 Chapter - 3

concentration, enzyme loading enzyme thermal stability, and temperature in the trans-
esterification reaction were investigated.

Mustafa Canakci [23].The potential of restaurant waste lipids as biodiesel

feedstocks was examined by Waste cooking oils, restaurant grease and animal fats are
potential feedstocks for biodiesel. These inexpensive feedstocks represent one-third of the
US total fats and oil production, but are currently devoted mostly to industrial uses and
animal feed. The characteristics of feedstock are very important during the initial research
and production stage. Free fatty acids and moisture reduce the efficiency of trans-
esterification in converting these feedstocks into biodiesel. Hence, this study was conducted
to determine the level of these contaminants in feedstock samples from a rendering plant.
Levels of free fatty acids varied from 0.7% to 41.8%, and moisture from 0.01% to 55.38%.
These wide ranges indicate that an efficient process for converting waste grease and animal
fats must tolerate a wide range of feedstock properties.

Michael [24] investigated the production of fatty acid methyl esters (FAME;
biodiesel) from soapstock (SS); a byproduct of edible oil refining that is substantially less
expensive than edible-grade refined oils. The most effective method involved the complete
saponification of the soapstock followed by acidulation using methods similar to those
presently employed in industry. This resulted in acid oil with a free fatty acid (FFA) content
greater than 90%. These fatty acids were efficiently converted to methyl esters by acid-
catalyzed esterification. The fatty acid composition of the resulting ester product reflected
that of soy soapstock and was largely similar to that of soybean oil.

Thompson. [25] Characterization of crude glycerol from biodiesel Production from

multiple feedstocks was investigated by Glycerol is the principal by-product of biodiesel
production. For each gallon of biodiesel produced, approximately0.3 kg of crude glycerol
accompanies. Such crude glycerol possesses very low value because of the impurities
contained. As the demand and production of biodiesel grow exponentially, the utilization of
the glycerol becomes an urgent topic. TheMake-up of crude glycerol varies depending on the
parent feedstock and the biodiesel production process. Before the crudeGlycerol could be
considered for possible value-added utilizations, it is necessary to characterize it on its

23
 Chapter - 3

physical, chemical, and nutritional properties. This article reports the characterization of
crude glycerol obtained from different seed oil feedstocks of mustard, rapeseed, canola,
crambe, soybean, and waste cooking oils. Batch processes of biodiesel productionwere used
as the means of crude glycerol preparation using unrefined vegetable oils, methanol, and
sodium methylate as theCatalyst. After separation from biodiesel, the crude glycerol from
each of the oils was analyzed using ASTM and other standard test methods. Elemental
impurities, nutritional value, and other chemical properties were tested.

Masato Kouzu, et al. [26] was experimented with solid base catalyst for biodiesel
production with environmental benignity, trans-esterification of edible soybean oil with
refluxing methanol was carried out in the presence of calcium oxide (CaO), -hydroxide
(Ca(OH)2), or -carbonate (CaCO3). At 1 h of reaction time, yield of FAME was 93% for
CaO, 12% for Ca(OH)2, and 0% for CaCO3. Under the same reacting condition, sodium
hydroxide with the homogeneous catalysis brought about the complete conversion into
FAME. Also, CaO was used for the further tests trans-esterifying waste cooking oil (WCO)
with acid value of 5.1 mg-KOH/g. The yield of FAME was above 99% at 2 h of reaction
time, but a portion of catalyst changed into calcium soap by reacting with free fatty acids
included in WCO at initial stage of the trans-esterification. Owing to the neutralizing reaction
of the catalyst, concentration of calcium in FAME increased from 187 ppm to 3065 ppm. By
processing WCO at reflux of methanol in the presence of cation-exchange resin, only the free
fatty acids could be converted into FAME. The trans-esterification of the processed WCO
with acid value of 0.3 mg-KOH/g resulted in the production of FAME including calcium of
565 ppm.

Xuejun Liu, et al. [27].Calcium ethoxide is proposed as a catalyst for the trans-
esterification of soybean oil to biodiesel with methanol and ethanol by First, calcium
ethoxide was synthesized through a calcium reaction with ethanol. Then, its physical and
chemical characteristics were determined using instrumental methods such as Brunauer-
Emmett-Teller surface area measurements, scanning electron micrographs, and particle size
distribution measurements. The effects of the mass ratio of catalyst to oil, the molar ratio of
methanol to oil, and the reaction temperature were studied to optimize the reaction
conditions. The experimental results showed that the optimum conditions are a 12:1 molar

24
 Chapter - 3

ratio of methanol to oil, the addition of 3% Ca(OCH2CH3)2 catalyst, and a 65 C reaction

temperature. A 95.0% biodiesel yield was obtained within 1.5 h in these conditions, and the
activation energy was 54 149 J/mol. It also indicated that the catalysis performance of
calcium ethoxide is better than that of CaO. Besides, a 91.8% biodiesel yield was obtained
when it catalyzed soybean oil to biodiesel with ethanol.

Sharif Hossain, et al. [28] used common species Oedogoniumand Spirogyra to

compare the amount of biodiesel production. Algal oil and biodiesel (ester) production was
higher in Oedogoniumthan Spirogyra sp. However, biomass (after oil extraction) was higher
in Spirogyra than Oedogoniumsp. Sediments (glycerin, water and pigments) was higher in
Spirogyra than Oedogoniumsp. There was no difference of pH between Spirogyra and
Oedogoniumsp. The results indicate that biodiesel can be produced from both species and
Oedogoniumis better source than Spirogyra sp.

Hiroaki Imahara, et al. [29].Effect of CO2/N2 addition to supercritical methanol on

reactivity's and fuel qualities in biodiesel production is studied by Addition of the third
component to supercritical methanol has been studied in the literature for biodiesel
production in order to reduce reaction temperature without deteriorating the reaction rate.
However, effect of pressure had often been neglected in the discussion. In this paper,
therefore, effect of pressure was examined with hexane, carbon dioxide (CO2) and nitrogen
(N2) as one of the third components, using batch-type and flow-type reactors. As a result, it
was found that an addition of the third component did not contribute to better product yield at
constant reaction pressure. Furthermore, the reaction rate was found to be determined by
pressure and concentration of the reactants involved in trans-esterification, not by the
function of so-called co-solvent. Additionally, N2 addition was found to contribute to
improvement in oxidation stability and reduction of the total glycerol content, thus offering
high-quality biodiesel production.

Luisa Gouveia,et al. [30] experimented with Neochlorisoleabundans and

Nannochloropsissp. and these algae proved to be suitable as raw materials for biofuels
production, due to their high oil content (29.0 and 28.7% respectively). Both microalgae,
when grown under nitrogen deficient culture medium, show a great increase in oil quantity

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 Chapter - 3

(e.g. Neochlorisoleabundanscan reach 56%, results not shown). If the purpose is to produce
biodiesel from one algal species, Scenedesmusobliquuspresents the most adequate fatty acid
profile, namely in terms of linolenic and polyunsaturated fatty acids. However,
Neochlorisoleabundans, Nannochloropsis sp. and Dunaliellatertiolectacan also be used if
associated with other microalgae oils and/or vegetable oils.

Stella Bezergianni, et al. [31] Hydrocracking of vegetable oils is a prominent

technology for the production of bio-fuels. Compares the product yields and quality of
hydrocracking fresh and used cooking oil under nominal operating conditions. Cracking,
heteroatom removal and saturation reaction mechanisms are evaluated for both feedstock
types and for three typical hydrocracking temperatures. The assessment of both feedstocks
indicates that they are both suitable for high diesel yields with smaller kerosene/jet and
gasoline/naphtha yields. As temperature increases, diesel selectivity increases for both
feedstock types. However, the used oil feedstock exhibits higher kerosene/jet and naphtha
selectivity at low temperatures (350 C) and lower at the highest hydrocracking temperature
(390 C).

ShiroSaka, et al. [32].New process for catalyst-free biodiesel production using

subcritical acetic acid and supercritical methanol is investigated by the production of glycerol
as a by-product is unavoidable in the current conventional biodiesel manufacturing processes.
Since biodiesel production is expected to increase in the near future, effective utilization of
glycerol will become an issue of interest. In this study, therefore, a process consisting of
subcritical acetic acid treatment to convert rapeseed oil to fatty acids and tri acetin followed
by conversion of the obtained fatty acids to their fatty acid methyl esters in supercritical
methanol treatment was investigated. The obtained results clearly revealed that this two-step
reaction could proceed effectively at a high reaction rate, and that fatty acid methyl esters and
tri acetin could be obtained under milder reaction condition than the one-step process
utilizing supercritical methyl acetate and supercritical methanol.

Junming Xu, et al. [33]discussedthe production of biodiesel using waste

triglycerides as feedstock offers economic advantages over its production from edible oils.
However, because of its high acidity and chemical complexity, many problems arise in the

26
 Chapter - 3

production of biodiesel. To facilitate the use of waste oils as a feedstock of biofuels, there is
an alternative method to obtain pyrolytic oil by thermal chemical conversion. the
observations on the production of biofuels by a pyrolysis reaction from high-acid-value waste
oil. It was found that the pyrolytic products consisted of hydrocarbon compounds
accompanied by undesired products, such as carboxylic acids. These pyrolytic oils were
further reacted with an alcohol to decrease their acid value. The results showed that the acid
number of the pyrolytic oil decreased dramatically from 28.8 to 2.0 mg of KOH/g after
esterification. The results of gas chromatography mass spectrometry (GC_MS) and Fourier
transform infrared (FTIR) spectroscopy analyses indicated that the pyrolysis of waste oil
generates fuels that have chemical compositions comparable to that of petroleum-based fuel.

Mariano Martin, et al. [34].was simulatedThe optimal production of second-

generation biodiesel using waste cooking oil and algae oil. They consider five different
technologies for the trans-esterification of the oil (homogeneous acid- or alkali-catalyzed,
heterogeneous basic-catalyzed, enzymatic, and supercritical un catalyzed). They formulate
the problem as a mixed-integer nonlinear programming (MINLP) problem where the models
for each of the reactors are based on surface response methodology to capture the effects of
the variables on the yield. The aim is to perform simultaneous optimization and heat
integration for the production of biodiesel from each of the different oil sources in terms of
the technology to use and the operating conditions to apply. Furthermore, a process network
is designed to minimize the freshwater consumption. The optimal conditions in the reactors
differ from those traditionally used because the separation tasks are taken into account in this
work. For algae oil, the optimal process employs alkali as the catalyst and has a production
cost of 0.42$/gal, an energy consumption of 1.94 MJ/gal, and a freshwater consumption of
0.60 gal water/gal ethanol. For cooking oil, the optimal process is the one with the
heterogeneous catalyst and has a production cost and energy and water consumption of
$0.66/gal, 1.94 MJ/gal, and 0.33 gal water/gal ethanol, respectively.

Ali Jazie, et al. [35].was investigated Egg Shell Waste-Catalyzed Trans-esterification

of Mustard Oil: Optimization Using Response Surface Methodology (RSM).The suitability
of mustard oil (low grade edible oil with high production rate in India) forbiodiesel
production using waste of egg shell as a cost-effective and environmental friendly process

27
 Chapter - 3

wasinvestigated. Response Surface Methodology (RSM) in combination with Central

Composite Design (CCD)was used to optimize the biodiesel production parameters. A
quadratic polynomial equation was obtained formustard oil methyl ester yield by multiple
regression analysis. Interactions between the variables werevalidated statistically. The
optimum conditions of the independent variables in the present work were 9:1molar ratio of
methanol to oil, 3 wt% eggshell catalyst (calcined at 900C, 2 hr), 60C reaction
temperaturesat reaction time of 3 hr. The predicted mustard oil methyl ester yield was
94.89% under the optimal conditions.Verification experiment (95%) confirmed the validity
of the predicted model. Reusability and effect ofcalcination temperature on activity of
eggshell catalysts were also investigated. The results indicated that the egg shell can be
repeated use for 14 times with no apparent loss of activity.

Jon Van Gerpen [36]Biodiesel processing and quality are closely related. The
processes used to refine the feedstock and convert it to biodiesel determine whether the fuel
will meet the applicable specifications. Described the processing and production of biodiesel
and how this determines fuel quality. The emphasis will be on processing as it is conducted
in the United States, where most biodiesel is produced by reacting soybean oil or used
cooking oils with methanol and the standard for fuel quality will be ASTM D 6751-02.

28
 Chapter- 4

EXPERIMENTAL WORK

In the present investigation experimental work was carried out in two stages. In the
first stage, process development study using waste frying oil (Palm oil) as feed stock.In the
second stage biodiesel samples obtained in the experimental work were evaluated

The process development studies are divided in to three steps:

Preconditioning of oil.
Effect of catalyst concentration and mole ratio of oil to alcohol in trans-esterification
reaction
Purification of products and quality testing

The following properties were evaluated for the biodiesel samples obtained in the process
development work.
Density
Specific Gravity
Kinematic Viscosity
Flash Point
Fire Point
Acid Value

The trans-esterification of the waste frying oil (Palm) has been carried out using
sodium hydroxide and potassium hydroxide as catalyst.

The experimental studies include the effect of mole ratio (oil to alcohol) in the range
of 1:3 to 1:9 and the effect of concentration in the range of 0.5 to 2 wt%. The physical
properties of the biodiesel sample obtained from 32 experiments have been evaluated for
comparison

29
 Chapter- 4

4.1. Process Development:

Chemicals

Methanol(CH3OH)
Sodium Hydroxide(NaOH)
Potassium Hydroxide(KOH))
Glacial acetic acid(C2H4O2)
Hexane(C6H14)
Diethyl Ether(C4H10O)
Potassium Permanganate(KmNO4)
Ethanol(C2H5OH)
Phenolphthalein indicator(C20H14O)

Apparatus
Three neck round bottom flask
Condenser
Thermometer
Plate heater with a magnetic stirrer
Separating funnels
Beakers
Glass funnel
Stoppers
TLC plate(Thin layer chromatography)

Quality testing equipment

Pensky-Martens open-cup flash-point
Redwood Viscometer
Cloud-Pour point analyzer
GC (Gas chromatography)
Specific gravity bottle

30
 Chapter- 4

Sources of feed stock

In this present experimental work used vegetable oil (Palm oil) is chosen as feed
stock. UVO is collected from hotels and street food stalls

Density, acid value, molecular weight and fatty acid composition for used vegetable
oil are given below. The molecular weight of the oil has been calculated on the basis of fatty
acid composition

TABLE-4.1:Fatty acid composition of feed

S Fatty Acid %
no composition
1 C8:0(Caprilic) 0.024
2 C10:0 (Capric) 0.016
3 C12:0(Lauric) 0.216
4 C14:0 (myristic) 0.794
5 C16:0 (Palmitic) 44.1
6 C16:1(Palmitoleic) 0.208
7 C18:0 (Stearic) 4.121
8 C18:1 (Oleic) 39.0
9 C18:2 (Linoleic) 10.52
10 C18:3 0.132
11 (Linolenic) 0.146
12 C20:0 (Arachidic) 0
13 C20:1 (Gadoleic) 0.060
14 C22:0 (Behinic) 0
15 C22:1 (Erucic) 0.054
16 C24:0 (Lignoceric) 0.61
Others

31
 Chapter- 4

TABLE-4.2: Density, Acid value, molecular weight of oil

Name of the oil Density Acid Value Molecular

Weight
Used vegetable oil 0.918 1.6 846.24
(Palm oil)

Figure 4.1: Used vegetable oil (Feed)

4.2. Experimental setup:

The experimental setup was shown in figure4.2.Three necked flat bottomed glass flask of
2000ml capacity was used for transesterification reaction. A double coiled reflux condenser
was fitted to a neck of the glass flask for condensing methanol (CH3OH) vapours during the
reaction. Cooling water was circulated through coils of the condenser. A thermometer was
fitted to the second neck of the flask. A glass thermometer of 0-2000crange was placed in the
thermometer to measure the temperature of the reaction mixture. A plate heater with a
magnetic stirrer was used for uniform heating of the contents of the flask. Oil, methanol and

32
 Chapter- 4

other chemicals were transferred through the third neck of the flask at the start of each
experimental run using glass funnel and was Stopperd during the reaction. A constant
temperature bath was provided to maintain the temperature of the contents in the flask was
650c.

Figure 4.2: Experimental setup for trans-esterification.

33
 Chapter-5

EXPERIMENTAL PROCEDURE

5.1. Preconditioning of oil

Preconditioning of oil involved the removal of the moisture and neutralization of

free fatty acids (FFA). Usually the present feed (Used vegetable oil) consist less than 5%
of FFA but they need to be neutralized as they result in the formation of soap. For
determination of FFA present in the oil taken, we titrated the oil sample with 0.1N KOH
solution with Phenolphthalein as indicator. Volume in ml of 0.1N KOH required to
neutralize 1gram of oil is called acid value. And with this we determined the amount of
KOH needed to neutralize the FFA's in the oil. Thus by adding calculated amount of
KOH, FFA's are removed in the form of soap.

Removal of moisture involved heating the oil sample up to 105-120oC and

maintaining it there for few minutes so that all moisture gets evaporated. If required
vacuum pump arrangement is used to remove the moisture present.

Figure- 5.1: Pre conditioning of oil (UVO)

34
 Chapter-5

5.2. Trans-esterification reaction

In this step, calculated amount of catalyst (NaOH/KOH) is accurately weighed

and dissolved completely in methanol. Calculated amount of oil sample is taken in three
necked flat bottom round flask as shown in figure 4.2 and it is put over the flat plate
heater and heated. To this methanol taken in 9:1 mole ratio (3:1, 6:1, 7.5:1, 9:1) (alcohol
to oil) is gently added such that no amount of methanol gets evaporated. The condenser is
readily fitted to middle neck of three necked flask. To the other neck, thermometer is
fixed and the third neck is closed with a stopper.

Now the stirrer is put on, and the whole batch of oil and methanol are thoroughly
mixed to attain uniform reaction. The temperature of the bath is maintained in the range
of 650c and the reaction is carried out for 90 minutes.

After the reaction time is over, the batch is withdrawn from the heater and cooled to room
temperature on cooling formation of two layers is observed. The whole batch is poured in
to a separating funnel as in figure 5.1 and allowed for least 5hours to get clear separation
of ester and glycerin. Glycerin formed at the bottom is taken out as a by-product. The
obtained ester is subjected to further purification.

35
Acid treatment carried Settling is carried Base treatment carried
outAcid treatment
approx. 60C. Incarried
this outSettling is carried
in Decanter for outBase treatment
approx. 60C. Incarried
this
out
processapprox. 60C.
100ml In ofthis out in Decanter
approx. 2 Hrs. for process 158ml methanolthis
out approx. 60C. In
process and 100ml
methanol 2-3ml of of approx. 2 Hrs. andprocess
7.3 158ml methanol
grams of
methanol
sulphuric acidand 2-3ml of
is added. KOH/NaOH is added. of
and 7.3 grams
sulphuric acid is added. KOH/NaOH is added.

Settling is carried out

Dehydration is
Separate the in Settling is carriedforout
Decanter
carried at 100C and is
Dehydration
carried isatobtained.
100C and glycerine and oilthe
Separate in
approx. 6Decanter
Hrs (in thisfor
biodiesel glycerine
biodiesel is obtained. wash the oiland
withoil approx.glycerine
process 6 Hrs (in isthis
wash water.
distilled the oil with process
settled at theglycerine
bottom). is
distilled water. settled at the bottom).

Block Diagram for Transesterification Procedure

The process of transesterification consists of four basic steps.

1. Acid treatment followed by settling process

2. Base treatment followed by settling process
3. Water washing
4. Dehydration.

Acid Treatment

For the acid treatment one liter of filtered raw Palm oil is taken into a conical flask
and heated to 35oC to melt the solid fats present in the oil by keeping on an
electric heater which is having a magnetic stirrer for continuous stirring of the oil,
it is shown in the figure 4.3.

Methanol of 99 % pure is added (0.1 liters/liter of oil) to the heated oil. It is stirred
for five to ten minutes.
 One milliliter of 95 % pure sulfuric acid (H2SO4) is added for each liter of oil
using a graduated eye dropper.

The compound is stirred for one hour maintaining the temperature at 35oC to
60oC.

Heating is stopped and the mixture is stirred for another hour.

The mixture is allowed to settle for eight hours in a decanter to remove pulp
portion present in the oil, which is precipitated at the bottom of the decanter.

Second stage (Base catalyzed stage)

6 grams of sodium hydroxide (NaOH) is added to 0.2 liters of methanol and
stirred thoroughly to produce sodium-methoxide.

Half of the prepared sodium-methoxide is poured into the unheated mixture and
the mixture is stirred for five minutes. This will neutralize the sulfuric acid.

The mixture is heated to 55oC and the whole reaction is maintained.

Remaining sodium-methoxide is added to the heated mixture and stirred at a speed

between 500 and 600 rpm, as shown in figure .

After one hour the mixture is poured into a decanter and allowed to settle for 8
hours. As glycerin is heavier than the biodiesel, it will settle at the bottom. The
glycerin is separated from the biodiesel, as shown in figure .
 Chapter-5

Figure- 5.2: Layers of Ester (upper layer) & Glycerin (bottom layer)

5.3. Purification of products

The ester was treated further, to remove the excess methanol and catalyst
(KOH/NaOH) present. For removing the catalyst present in the ester small amount of
glacial acetic acid is added to get a neutral ester and then it is washed with hot distilled
water to remove any traces of catalyst present. Washing is done with distilled water at
500C and 600C to remove any traces of methanol or catalyst. Thus pure ester is heated to
105-1200C for 10 min. to remove any moisture present. Thus obtained ester is almost
pure.

36
 Chapter-5

(a) (b)

(c)

Figure- 5.3: (a): Water washing for purification and (b) purified 100%biodiesel
(c) Soap water

37
 Chapter-5

(a)

38
 Chapter-5

5.4. Yield of esters:

The yields of methyl palm ester at 0.5 ,1 ,1.5 ,2 wt% of potassium hydroxide
(KOH) were shown in table B.1andthe yields of methyl palm ester at 0.25 ,0.5 ,1 ,1.5
wt% of sodium hydroxide (NAOH) were shown in table B.2.

5.5. Evaluation of bio-diesel sample:

The bio diesel samples prepared in the process development studies were
evaluated by determining the physical properties mentioned below:

Density

Density of the sample was calculated by multiplying the specific gravity of the
sample with density of water

Density () = specific gravity of sample*of

water

Specific Gravity

Specific gravity was determined using a 50 ml density bottle

Specific Gravity = of sample/ of

water

Kinematic viscosity

Using redwood viscometer, redwood seconds (t) were determined. The values of
the kinematic viscosity of the samples were calculated using the equation given below:

K.V ( ) =A*
tr-B/tr

A=0.00264, B= 1.9 tr100

A=0.00264, B= 0.5 tr>100
A, B are standard values
tr = Time run down(sec)

Figure- 5.5: Redwood viscometer

39
 Chapter-5

Flash point

The flash point is the temperature at which the oil begins to evolve vapors in
sufficient quantity to form an explosive or inflammable mixture with air.

Fire point

It is defined as the temperature of the vapor at which the flame continuously

burns.

Cloud point

The cloud point of a fluid is the temperature at which dissolved solids are no
longer completely soluble, precipitating as a second phase giving the fluid a cloudy
appearance. This term is relevant to several applications with different consequences. .

Pour point

The pour point of a liquid is the lowest temperature at which it becomes semi
solid and loses its flow characteristics.

Acid value

The number of milligrams of KOH required to neutralize 1gram oil (or) fat

Iodine value

The iodine value is the mass of iodine in grams that is consumed by 100 grams of
a chemical substance. Iodine numbers are often used to determine the amount of
unsaturation in fatty acids. This unsaturation is in the form of double bonds.

Iodine value is the total of

=(C16.1*0.95)+(C18.1*0.86)+(C18.2*1.73)+(C18.3*2.611)+(C20.1*0.785)+(C22.1*0.7
2

40
 Chapter-5

Cetane number

A quantity indicating the ignition properties of fuel relative to cetane as a

standard.

(Cetane index is used as a substitute for the cetane number of fuel).

Cetane number is the total of

=[(C10*47.9)/100]+[(C12*60.8)/100]+[(C14*73.5)/100]+[(C16*74.3)/100]+[(C18*75.7)
/100]+[(C18.4*55)/100]+[(C18.2*42.2)/100]+[(C18.3*22.7)/100]

41
 Chapter-6

RESULTS AND DISCUSSIONS

6.1. Bio-diesel Production process from used vegetable oil (palm oil):

Used vegetable oil (UVO) has properties different from the properties of
refined/crude fresh cooking oil. During frying process; presence of heat and water accelerates
the hydrolysis of triglycerides and increases content of free fatty acids in oil. Oxidation
stability of the oil is disturbed because of the contact of hot oil with food, and peroxide value
of oil increases. Viscosity of oil increases considerably, because of the formation of di-meric
and polymeric acids and glycerides. Correspondingly, molecular mass and iodine value
decreases and saponification value and density increases.

The free fatty acid and moisture content are important process parameter for the
biodiesel production i.e. trans-esterification process. They are the vital key for determining
the viability of the vegetable oil trans-esterification process. Thus the process of biodiesel
production from UVO differs from that of fresh oil. The problem with processing UVO is
that they usually contain large amounts of free fatty acids that cannot be converted to
biodiesel using an alkaline catalyst due to formation of salts (soap) and hence smaller is the
conversion efficiency. The soaps prevent separation of biodiesel from glycerin fraction.

The moisture content in UVO should be removed before starting up the trans-
esterification and excess free fatty acids should be neutralized. In the present experimental
work the free fatty acids were naturalized by using additional catalyst (NaOH) and moisture
was dried out by heating the feed stock to 110oC for a period of 15minutes with continuous
steering. However, to neutralize the free fatty acids accumulated in the UVO, extreme care
has to be taken. This is because, during the neutralizing the free fatty acids, as both excess as
well as insufficient amount of catalyst may cause soap formation.

Hence to determine the correct amount of catalyst required, a titration must be

performed on the oil being transesterified. One simple method is presented below, using a
chemical indicator called phenolphthalein. In the titration, 0.1N of NaOH in distilled water is
titrated against the titration sample which is essentially a solution of 20ml of Ethanol and 6
ml of oil sample with 2-3 drops of indicator. The end point of the titration is marked when

42
 Chapter-6

the titration sample turns pink and stays pink for 10 seconds. The number of milliliters of
0.1% NaOH solution needed is equal to the number of extra grams of pure sodium hydroxide
catalyst needed to produce the proper reaction to make biodiesel from UVO.

6.2. Effect of mole ratio on Bio-diesel yield:

Methyl ester of used vegetable oil (palm oil) has been prepared in this work in thirty
two experimental runs. Trans-esterification reaction was studied for four different mole
ratios. The NaOH/KOH catalyst amount was varied in the range of 0.5% to 2%. These
percentages are based on volume of oil used for the trans-esterification reaction. The catalyst
amount also effects the yield of process is shown in figure 6.1 & 6.2 for KOH & NaOH
respectively.

100 y = -2.83x2 + 0.685x + 93.03

R = 0.999
98
y = -1.59x2 - 2.903x + 101.2
R = 0.978
96

94

92 y = 0.51x2 - 5.213x + 101.6

Yield

R = 1
%

90

88

86 y = -1.06x2 - 1.122x + 100.2

R = 0.999
84

82
0 0.5 1 1.5 2 2.5
Catalyst wt%

3-moles 6-moles 7.5-moles 9-moles

Figure-6.1: %yield vs various catalyst concentrations for various mole ratios of

Methyl palm ester with KOH catalyst

43
 Chapter-6

100 y = 3.884x2 - 22.03x + 97.11 y = -3.957x2 - 8.256x + 96.21

R = 0.989 R = 0.994

95 y = -4.560x2 - 8.687x + 99.73

R = 0.993

y = -0.484x2 - 10.57x + 101.1

90
R = 0.997
Yield

85
%

80

75

70
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Catalyst wt%

3-moles 6-moles 7.5-moles 9-moles

Figure-6.2: %yield vs various catalyst concentrations for various mole ratios of

Methyl palm ester with NaOH catalyst

The alkali-catalyst process attained maximum yield for used vegetable oil at 0.5%
KOH, 0.25% NaOH catalyst concentration .It was observed that the yield started to decline
when the catalyst concentration was increased.

6.3. Effect of catalyst concentration on Bio-diesel yield:

Methanol to oil mole ratio was varied for used cooking oil within the range of 3:1 to 9:1.
The maximum Bio-diesel yield for used vegetable oil was found at the methanol to oil mole
ratio 9:1 in alkali-trans-esterification.the yield remains the moreover same with further
increase in the methanol to oil mole ratio.

44
 Chapter-6

100
y = -0.306x2 + 4.75x + 81.26
98 R = 0.988
96
94
92
%Yiel

90 y = -0.181x2 + 3.355x + 82.40

d

R = 0.993
88
y = -0.078x2 + 2.368x + 81.35
86 R = 0.996
84 y = -0.142x2 + 3.486x + 74.20
R = 0.977
82
2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5
Mole ratio

0.5-cat% 1-cat% 1.5-cat% 2-cat%

6.3. %yield vs mole ratio at various catalyst concentrations for

Methyl palm ester with KOH catalyst

100 y = 0.017x2 + 1.377x + 81.59

y = 0.074x2 + 0.23x + 90.98 R = 0.996
95 R = 0.944
90

85
%Yiel

80
d

y = 0.491x2 - 4.091x + 80.59

75
R = 0.959
70 y = 0.064x2 + 0.998x + 76.17
R = 0.999
65

60
2 3 4 5 6 7 8 9 10
Mole ratio

0.25%cat 0.5%cat 1%cat 1.5%cat

6.4. %yield vs mole ratio at various catalyst concentrations for

Methyl palm ester with NaOH catalyst
45
 Chapter-6

6.4. Effect of catalyst concentration on kinematic viscosity:

By using redwood viscometer the kinematic viscosity was determined for various
samples produced by varying mole ratios from 3:1 to 9:1.The resulted kinematic viscosities
for KOH &NaOH catalyst are given in table B.3 & B.4.From the obtained results it is
observed that increase of methanol to oil mole ratio, decreases the Kinematic viscosity for
both of the catalyst from the figures 6.5 & 6.6.

4.6
y = 0.027x2 - 0.443x + 5.583 y = 0.022x2 - 0.366x + 5.1
R = 0.999 R = 1
4.4 y = 0.017x2 - 0.29x + 4.716
R = 0.999

4.2

4
Kinematic
Viscosity

3.8

3.6

3.4 y = 0.012x2 - 0.213x + 4.332

R = 0.996

3.2
2 3 4 5 6 7 8 9 10
Mole ratio
0.5-cat% 1-cat% 1.5-cat% 2-cat%

Figure6.5. Mole ratio vs Kinematic viscosity at various catalyst concentrations

For methyl palm ester with KOH catalyst

46
 Chapter-6

5 y = 0.010x2 - 0.22x + 5.367 y = 0.007x2 - 0.203x + 5.049

R = 0.998 R = 0.997
4.8
y = -0.007x2 + 0.003x + 4.050
4.6 R = 0.993

4.4

4.2
Kinematic

4
Viscosity

3.8

3.6

3.4
y = 0.007x2 - 0.136x + 4.049
3.2 R = 0.986

3
2 3 4 5 6 7 8 9 10
Mole ratio

0.25%cat 0.5%cat 1%cat 1.5%cat

Figure6.6. Mole ratio vs Kinematic viscosity at various catalyst concentrations

For methyl palm ester with NaOH catalyst

47
 Chapter-6

6.5. Effect of Mole ratio on kinematic viscosity:

From the results given in tables B.3 & B.4, it can be concluded that the lowest values of
kinematic viscosities for palm ester at higher concentrations of the catalyst in the different
mole ratios studied in the present investigation. At the same time, the concentrations does not
show any marked difference in the values of centane index.

The catalyst concentration has a profound effect on the values of both kinematic viscosity
and cetane index for palm ester. The variation in kinematic viscosities with change in catalyst
concentrations are given in figures 6.7 & 6.8. For lower acid value oils, the experiments were
conducted for the mole ratios from 3:1 to 9:1. The values of kinematic viscosities decreased
when the catalyst concentration is raised from 0.5 % to 2 % for KOH and 0.25% to
1.5 % for NaOH. For the same increase of catalyst concentration, the cetane index is
increased. It is clear from these results that the conversion of oil to ester is low even the
concentration is raised.

4.6
y = 0.1x2 - 0.71x + 4.825
4.4 R = 0.998

4.2 y = 0.1x2 - 0.51x + 4.125

R = 0.994
4 y = 0.1x2 - 0.51x + 4.025
R = 0.994
Kinematic
Viscosity

3.8

3.6

3.4
y = -0.2x + 3.7
3.2 R = 1
3
0.25 0.45 0.65 0.85 1.05 1.25 1.45 1.65 1.85 2.05 2.25
Wt %of the catalyst(KOH)

3-Moles 6-Moles 7.5-Moles 9-Moles

Figure-6.7: Mole ratio vs Kinematic viscosity at various catalyst concentrations

For methyl palm ester with KOH catalyst

48
 Chapter-6

5 y = 0.361x2 - 1.517x + 5.160

R = 0.999
4.8 y = 0.229x2 - 1.094x + 4.635
R = 0.992
4.6
y = 0.315x2 - 1.212x + 4.529
4.4 R = 0.957

4.2
y = 0.524x2 - 1.600x + 4.533
Kinematic

4 R = 0.984
Viscosity

3.8

3.6

3.4

3.2

3
0.1 0.3 0.5 0.7 0.9 1.1 1.3 1.5 1.7
Wt% of catalyst(NAOH)

3-Moles 6-Moles 7.5-Moles 9-Moles

Figure-6.8: Mole ratio vs Kinematic viscosity at various catalyst concentrations

For methyl palm ester with NaOH catalyst

49
 Chapter-6

6.6. Effect of catalyst concentration on flash point:

The flash point is the temperature at which the oil begins to evolve vapors in sufficient
quantity to form an explosive or inflammable mixture with air.

The values of flash point of palm methyl ester were obtained by using Pensky-
Martens open-cup flash-point equipment. The variation of flash point with respective mole
ratio is given in the table B.3 & B.4. It was observed that the values of flash points gradually
decreased for palm ester as the mole ratio is increased. From figure 6.9, the flash point varies
from 185oC to 1600c by increasing the methanol to oil mole ratio from 3:1 to 9:1by using
KOH as catalyst.

190 y = 0.121x2 - 3.466x + 194.3 y = -0.151x - 0.366x + 181.4y = -0.121x2 - 0.533x + 177.6 2
R = 0.999 R = 0.999 R = 0.999
185 y = -0.030x2 - 1.833x + 178.8
R = 0.997

180

175
Flash
point

170

165

160
0.5%cat 1%cat 1.5%cat 2%cat
155
2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5
Mole ratio

Figure-6.9: Mole ratio vs Flash point at various catalyst concentrations

For methyl palm ester with KOH catalyst

50
 Chapter-6

From figure 6.10, the flash point varies from 188oC to 174oC by increasing the
methanol to oil mole ratio from 3:1 to 9:1by using NaOH as catalyst.

190 y = -0.030x2 - 1.166x + 191.8 y = -0.090x2 - 0.166x + 185.4y = 0.010x2 - 1.7x + 189.1
R = 0.995 R = 0.937 R = 0.969
188

186 y = -0.060x2 - 0.333x + 181.6

R = 0.96
184
Flash point

182

180
0
c

178

176

174

172
2.5 3.5 4.5 5.5 6.5 7.5 8.5 9.5
Mole ratio

0.25%cat NaOH 0.5%cat NaOH 1%cat NaOH 1.5%cat

Figure-6.10: Mole ratio vs Flash point at various catalyst concentrations

For methyl palm ester with NaOH catalyst

51
 Chapter-6

6.7. Effect of Mole ratio on flash point:

The variation of flash point with respective mole ratio is given in the table B.3 & B.4.
It was observed that the values of flash points gradually increased for palm ester as the mole
ratio is decreased. From figure 6.11, the flash point varies from 173oC to 185oC by increasing
the KOH catalyst concentration from 0.5% to 2 % at 3:1 methanol to oil ratio.

Flash point increases means the volatile nature of a biodiesel decreases, so that it can
be used even at higher temperatures.

190
y = 1x2 + 4.9x + 164.2
y = 4x2 - 2x + 173 R = 0.999 y = 1x2 + 5.3x + 160.2 y = 4x2 - 1.6x + 160
R = 1 R = 0.994 R = 0.991
185

180

175
Flash
point

170

165

160

155
0 0.5 1 1.5 2 2.5
Catalyst wt%

3-Moles 6-Moles 7.5-Moles 9-Moles

Figure 6.11: Catalyst concentration (KOH) vs flash point at

Various mole ratios for methyl palm ester

52
 Chapter-6

From figure 6.12, the flash point varies from 180oC to 188oC by increasing the NaOH
catalyst concentration from 0.5% to 2 % at 3:1 methanol to oil ratio. From the figures 6.9 -
6.12 it is concluded that less mole ratio and high catalyst concentration gives better flash
point.

190
y = -1.527x2 + 7.296x + 176.4 y = -0.100x2 + 5.532x + 172.8
2.191x2 + 2.587x + 179.2 R = 0.992 R = 0.988
188 y =
R = 0.999
186

184

182
Flash
point

180

178
y = 1.527x2 + 0.703x + 174.5
176 R = 0.985

174

172
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Catalyst wt%
3-Moles 6-Moles 7.5-Moles 9-Moles

Figure6.12:Catalyst concentration(NaOH)vs flash point at various

Mole ratios for methyl palm ester

53
 Chapter-6

6.8. Effect of Catalyst concentration on cetane number:

The cetane number test method for diesel fuel was developed in the 1930s by the
Cooperative Fuel Research (CFR) committee and later standardized by ASTM. The method
involves running the fuel in a single cylinder engine with a continuously variable
compression ratio under a fixed set of conditions. Although the method has been updated
over the years, it is still based on the original engine design.

Two specific hydrocarbons were chosen to define the cetane number scale: 1-methyl
naphthalene ( also called - methyl naphthalene), which burns poorly in a diesel engine, was assigned a
cetane number of zero and n- hexadecane (cetane), which burns well, was assigned a cetane
number of 100. There hydrocarbons are the primary reference fuels for the method.

61.8

61.6

61.4

61.2

61 y = 0.002x2 + 0.898x + 59.89

R = 0.996
number
Cetane

60.8

60.6

60.4

60.2
0 0.5 1 1.5 2 2.5
Catalyst wt%(KOH)

9:1 mole ratio

Figure6.13: Catalyst concentration (KOH) vs Cetane number

54
 Chapter-6

The cetane number fuel defined as the volume percent of n-hexadecane in the blend
of n -hexadecane and 1-methyl naphthalene that gives the same ignition delay period as the
test sample. In other words, it is a relative measure of the interval between the beginning of
injection and auto ignition of the fuel. The higher the number, the shorter is the delay
interval.

In the present work, the cetane numbers of the bio-diesel samples were increasing as
KOH/NaOH catalyst concentration increases. The resulted graphs are given in figures 6.13
& 6.14.

61.4

61.2
y = -0.444x2 + 1.566x + 59.95
R = 0.949
61

60.8
number
Cetane

60.6

60.4

60.2

60
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
Catalust wt%(NAOH)

9:1 mole ratio

Figure6.14: Catalyst concentration (NaOH) vs Cetane number

55
 Chapter-6

6.9. Comparison of Regular Diesel &obtained Bio-Diesel:

S Properties (Feed)Used Bio- Biodiesel Regular

.No. Palm Oil diesel standard Diesel
(Palm ASTM/
methyl EN
ester)
1. Density 0.912 0.859 0.860- 0.85
(gm/cm3) 0.900
2. Kinematic 38 3.4 2to6 3
Viscosity
At 40oC (cst)
3. Flash point - 173 >130 70
(oC)
4. Cloud point 13 10.7 -3 to 15 -35 to 5
(oC)
5. Pour point 11 8.7 -5 to 10 -35 to -
(oC) 15
6. Cetane no. - 61.689 48 to 65 48
7. Acid Value 1.6 0.0561 <0.5 -
(mg KOH/ gm)

TABLE-6.1: Comparison of Regular Diesel &obtained Bio-Diesel

56
 Chapter-7

CONCLUSIONS

This study revealed that biodiesel could be produced successfully from the used palm
oil by alkali- catalyzed trans-esterification. The production of biodiesel from used vegetable
oil offers a triple-facet solution: economic, environmental and waste management.

This process technology made it possible to produce biodiesel from recycled frying
oils comparable in quality to that of virgin vegetable oil biodiesel with an added attractive
advantage of being lower in price. Thus, biodiesel produced from recycled frying oils has the
same possibilities to be utilized.

In considering the range of tests performed in this project, the specifications used to
identify acceptable biodiesels do not need any additions. The viscosity of used vegetable
(palm) oil reduces substantially after trans-esterification and is comparable to petro-diesel
and the physical and chemical properties of biodiesel produced conform to EN/ASTM
standards.

Testing indicated there are problems in operating with low temperatures and that the
minimum temperatures at which biodiesels are usable increase with the move from vegetable
to animal sources, probably due to the greater degree of saturation.

The effects of different parameters such as reaction time, temperature, catalyst

concentration and reactant ratio on the biodiesel yield were analyzed.

We can conclude that using water as a washing agent does not affect the reaction
productivity at the same time it increases purity of the product. The unique variables that
affect the biodiesel production are the catalyst concentration and the molar ratio alcohol/oil.
According with the above, the best conditions of operation are:
Molar ratio oil to alcohol: 1:9
Catalyst concentration of: 2% w/w
Reaction temperature: 65 C
Washing agent: water at 40 C

57
 References

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Biomass resource facilities and biomass conversion processing for fuels and chemicals, P.K.
216, TR-61035-Trabzon, Turkey
2. M. Thirumarimurugan, V. M. Sivakumar, A. Merly Xavier, D. Prabhakaran, and T.
Kannadasan
Preparation of Biodiesel from Sunflower Oil by Transesterification 3.
Deshpande D.P.1, Urunkar Y.D. and Thakare P.D.
Production of Biodiesel from Castor Oil using acid and Base catalysts
Research Journal of Chemical Sciences, Vol. 2, 2012
4. Ayhan Demirbas
Biodiesel from waste cooking oil via basecatalytic
5. Titipong Issariyakul, Mangesh G. Kulkarni, Ajay K. Dalai, Narendra N. Bakhshi
Production of biodiesel from waste fryer grease using mixed methanol/ethanol system
6. Bo Liu and Zongbao (Kent) Zhao
Biodiesel production by direct methanolysis of oleaginous microbial biomass
Journal of Chemical Technology and Biotechnology, vol. 82, 2007, PP: 775-780
7. Arjun B. Chhetri , K. Chris Watts and M. Rafiqul Islam
Waste Cooking Oil as an Alternate Feedstock for Biodiesel Production
J. of Energies, vol. 1, 2008, PP: 3-18.
8. Anikeev, E.Yu. Yakovleva
Biodiesel synthesis from vegetable oils with supercritical methanol
9. Gerardo J. Ruiz-Mercado, Michael A. Gonzalez, and Raymond L. Smith
Sustainability Indicators for Chemical Processes: III. Biodiesel Case Study
Ind. Eng. Chem. Res., vol. 52, 2013, PP: 67476760.
10. S.P. Singh, Dipti Singh
Biodiesel production through the use of different sources and characterization of oils and
their esters as the substitute of diesel: A review
J. of Renewable and Sustainable Energy Reviews, Vol. 14, 2010, PP: 200-216.

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11. Xiaohu Fan, Rachel Burton and Greg Austic

Preparation and Characterization of Biodiesel Produced from Recycled Canola Oil
The Open Fuels & Energy Science Journal, Vol.2, 2009, PP: 113-118.
12. Jefferson S. de Oliveira, Polyanna M. Leite, Lincoln B. de Souza, Vincius M. Mello,
Eid C. Silva, Joel C. Rubim, Simoni M.P. Meneghetti, Paulo A.Z. Suarez.
Characteristics and composition of Jatropha gossypiifolia and Jatropha curcas L. oils and
application for biodiesel production
J. of Biomass and bio-energy, Vol. 33, 2009, PP: 449 - 453.
13. Gemma Vicente, Mercedes Mart_nez, Jos_e Aracil
Integrated biodiesel production: a comparison of different homogeneous catalysts systems J.
of Bioresource Technology, Vol. 92, 2004, PP: 297-305.
14. S.Saka, D. Kusdiana
Biodiesel fuel from rapeseed oil as prepared in supercritical methanol J.
Fuel, Vol. 80, 2001, PP: 225-231.
15. M. Canakci, j. Van gerpen
Biodiesel production from Oils and fats with high free fatty acids
Transactions of the ASAE, vol. 44, 2001, pp: 1429-1436.
16. Edward Crabbe, Cirilo Nolasco-Hipolito, Genta Kobayashi, Kenji Sonomoto, Ayaaki
Ishizaki
Biodiesel production from crude palm oil and evaluation of butanol extraction and fuel
properties
J. of Process Biochemistry, Vol. 37, 2001, PP: 65-71.
17. Yomi Watanabe, Yuji Shimada, Akio Sugihara, Hideo Noda, Hideki Fukuda, and Yoshio
Tominaga
Continuous Production of Biodiesel Fuel from Vegetable Oil Using Immobilized Candida
antarctica Lipase
JAOCS, Vol. 77, 2000.
18. Hak-Joo Kim, Bo-Seung Kang, Min-Ju Kim, Young Moo Park, Deog-Keun Kim, Jin-Suk
Lee, Kwan-Young Lee
Transesterification of vegetable oil to biodiesel using heterogeneous base catalyst J.
of Catalysis Today, Vol. 93-95, 2004, PP: 315-320.

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19. Weiliang Cao, Hengwen Han, Jingchang Zhang

Preparation of biodiesel from soybean oil using supercritical methanol and co-solvent J.
Fuel, Vol. 84, 2005, PP: 347-351.
20. A.S. Ramadhas, S. Jayaraj, C. Muraleedharan
Biodiesel production from high FFA rubber seed oil
J. of Fuel, Vol. 84, 2005, PP: 335-340
21. Edgar Lotero, Yijun Liu, Dora E. Lopez, Kaewta Suwannakarn, David A. Bruce, and
James G. Goodwin.
Synthesis of Biodiesel via Acid Catalysis
J. of Ind. Eng. Chem. Res., Vol.44, 2005, PP: 5353-5363.
22. Hossein Noureddini, X Gao, R S. Philkana
Immobilized Pseudornonas cepacia lipase forbiodiesel fuel production from soybean oil
Bioresource Technology, vol. 96, 2005, PP: 769-777.
23. Mustafa Canakci
The potential of restaurant waste lipids as biodiesel feedstocks
J. of Bio-resource Technology, 2005.
24. Michael J. Haas
Improving the economics of biodiesel production through the use of low value lipids as
feedstocks: vegetable oil soapstock
J. of Fuel Processing Technology, Vol. 86, 2005, PP: 1087- 1096.
25. J. C. Thompson, b. B. He
Characterization of crude glycerol from biodiesel production from multiple feedstocks J.
of Applied engineering in agriculture, vol. 22, 2006, PP: 261-265.
26. Masato Kouzu, Takekazu Kasuno, Masahiko Tajika, Yoshikazu Sugimoto, Shinya
Yamanaka, Jusuke Hidaka
Calcium oxide as a solid base catalyst for transesterification of soybean oil and its application
to biodiesel production
J. of Fuel, Vol. 87, 2008, PP: 2798-2806.
27. Xuejun Liu, Xianglan Piao, Yujun Wang and Shenlin Zhu
Calcium Ethoxide as a Solid Base Catalyst for the Transesterification of Soybean Oil to
Biodiesel

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J. of Energy & Fuels, vol. 22, 2008, PP: 1313-1317.

28. A.B.M. Sharif Hossain, Aishah Salleh, Amru Nasrulhaq Boyce, Partha chowdhury and
Mohd Naqiuddin
Biodiesel Fuel Production from Algae as Renewable Energy
American Journal of Biochemistry and Biotechnology, vol. 4, 2008, PP: 250-254.
29. Hiroaki Imahara, Jiayu Xin, Shiro Saka
Effect of CO2/N2 addition to supercritical methanol on reactivities and fuel qualities in
biodiesel production.
30. Luisa Gouveia Ana Cristina Oliveira
Microalgae as a raw material for biofuels production
J. of Ind Microbiol Biotechno, vol.36, 2009, PP: 269-274.
31. Stella Bezergianni, Spyros Voutetakis and Aggeliki Kalogianni
Catalytic Hydrocracking of Fresh and Used Cooking Oil Ind.
Eng. Chem. Res., vol. 48, 2009, PP: 8402-8406. 32. Shiro
Saka , Yohei Isayama, Zul Ilham, Xin Jiayu
New process for catalyst-free biodiesel production using subcritical acetic acid and
33. Junming Xu, Guomin Xiao, Yonghong Zhou, and Jianchun Jiang
Production of Biofuels from High-Acid-Value Waste Oils J. of
Energy Fuels, Vol. 25, 2011, PP: 4638-4642.
34. Mariano Martn and Ignacio E. Grossmann
Simultaneous Optimization and Heat Integration for Biodiesel Production from Cooking Oil
and Algae
Ind. Eng. Chem. Res., vol. 51, 2012, PP: 79988014.
35. Ali A. Jazie, H. Pramanik and A. S. K. Sinha
Egg Shell Waste-Catalyzed Transesterification of Mustard Oil: Optimization Using Response
Surface Methodology (RSM). IPCSIT, Vol. 56, 2012.
36. Jon Van Gerpen
Biodiesel Production and Fuel Quality

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 References

37. http://www.biodieselbooklet.co.uk/biodiesel-wvo.html
38. http://www.tcbiodiesel.com/making-biodiesel-from-waste-vegetable-oil/
39. http://www.marcussharpe.com/biodiesel.shtml
40. http://www.utahbiodieselsupply.com/whybiodiesel.php
41. http://oaithesis.eur.nl

62
 Appendix-A

SAMPLE CALCULATIONS

A.1. Sample calculations for trans- etherification:

Density of feed:

Weight of empty bottle (w1) =38.39gm

Weight of bottle with distill water (w2) =88.12gm

Weight of water = w2-w1 = 88.12-38.39 =49.73

of water at room temperature = 0.994gm\cm3
Volume = wt of water / of water=49.73/0.994=50.03ml

Weight of bottle with oil sample (w3) =84.30gm

Weight of oil =w3-w1=84.30-38.39=45.91gm
of oil sample = M/V=45.91/50.03

=0.918gm\cm3
Specific gravity of feed:
Sp Gr = of sample/ of water

of water = M/V =49.73/50 = 0.994 g/cm3

of sample =0.918 g/cm3
Sp Gr =0.918/0.994 = 0.923
Kinematic viscosity of feed (UVO): at 400c K.V ( ) =A* tr-B/tr

A=0.00264, B= 1.9 tr100

A=0.00264, B= 0.5 tr>100
A, B are standard values
tr = Time run down(sec)
tr= 148sec,A=0.00264, B=0.5
K.V ( ) =0.00264*148-0.5/148
=0.39072-0.003378=0.387342 (38.7cst)

63
 Appendix-A

Acid value of feed:

AV =56.1*0.1N*titer value/ Volume of sample taken

Titer value =1.8 ml, Volume of sample taken = 6 ml

AV =56.1*0.1*1.8/6 = 1.6 mgKOH/g

Figure: A.1- Titration to identify Acid value

A.2. Trans-esterification of used vegetable oil (UVO) of 9:1 mole ratio and 2 wt%
KOH & NAOH catalysts:

Oil

Weight of oil taken = (Volume of oil)*(density of the oil).

Moles of oil = (Weight of oil)/ (Molecular weight of oil).

Methanol

Moles of methanol taken = 9(mole of oil)

Weight of methanol taken = (Moles of methanol)*(Molecular weight of methanol)

Volume of methanol taken = (Weight of methanol)/(density of methanol)

64
 Appendix-A

Catalyst

Catalyst taken = 2 wt% of the oil

Experimental number-16 (Used vegetable oil)

Volume of oil taken = 400 ml

Weight of oil taken = 400*0.918 =367.2 gm

Molecular weight of oil = 846.1

Moles of oil =wt/mol .wt = 367.2/846.1 =0.4339 moles

Moles of methanol taken = 9*0.4339 = 3.90 Moles

Weight of methanol taken = 3.9*32.04 = 125.12

Volume of methanol taken = M/ = 125.12/0.791 = 158 ml

Catalyst taken = 0.02*367.2 = 7.3 grams

A.3. Sample calculation for physical properties of Biodiesel (Methyl Palm Ester)
sample:

Sample calculation is shown below. Physical properties of biodiesel samples are shown in
tables B.1 & B.2

For the palm ester sample of 9:1 mole ratio and 2wt% KOH catalyst

Density:

Density () =M/V
Mass of sample (M) = 42.96 mg
Volume of sample (V) = 50.03 ml

= M/V =42.96/50.03=0.859 g/cm3

65
 Appendix-A

Specific gravity:

Sp. Gr. = of sample/ of water

of water = M/V =49.73/50 = 0.994 g/cm3

of sample =0.859 g/cm3

Sp. Gr. =0.859/0.994 = 0.864

Acid value:

AV =56.1*0.1N*titer value/ Volume of sample taken

Titer value =0.1 ml, Volume of sample taken = 10 ml

AV =56.1*0.1*0.1/10 = 0.0561 mgKOH/g

Kinematic viscosity of Methyl Palm Ester:

K.V ( ) =A* tr-B/tr

A=0.00264, B= 1.9 tr100

A=0.00264, B= 0.5 tr>100
A, B are standard values
tr = Time run down(sec)

tr= 34.15sec,A=0.00264, B=1.9

K.V ( ) =0.00264*34.15-1.9/34.15

= 0.090156-0.0556368=0.0345

K V ( ) = 3.4 (cst)

66
 Appendix-A

TABLE-A1: Fatty Acid Composition for palm methyl ester: From GC

(Gas Chromatography)

Fatty Acid %
Composition

C 8:0 (Caprylic) 0.024

C10:0 (Capric) 0.016

C12:0 (Lauric) 0.216

C14:0 ( Myristic ) 0.954

C16:0 ( Palmitic ) 40.163

C16:1 ( Palmitoleic ) 0.208

C18:0 ( Stearic ) 4.355

C18:1 ( Oleic ) 42.440

C18:2 ( Linoleic ) 10.266

C18:3 ( Linolenic ) 0.162

C20:0 ( Arachidic ) 0.184

C20:1( Gadoleic) 0

C22:0 ( Behenic ) 0.060

C22:1( Erucic) 0

C24:0 ( Lignoceric ) 0.085

Others 0.867

67
 Appendix-A

Iodine value

= (C16.1*0.95)+(C18.1*0.86)+(C18.2*1.73)+(C18.3*2.611)+(C20.1*0.785)+(C22.1*0.723)

= (0.208*0.95)+(42.440*0.86)+(10.266*1.73)+(0.162*2.611)+(0*0.785)+(0*0.723)

= 0.1976+36.4984+17.76018+0.422982+0+0

= 54.87916

Cetane number

= [(C10*47.9)/100]+[(C12*60.8)/100]+[(C14*73.5)/100]+[(C16*74.3)/100]+

[(C18*75.7)/100]+ [(C18.4*55)/100]+[(C18.2*42.2)/100]+[(C18.3*22.7)/100]

= 0.008+0.131+0.701+29.841+3.297+23.342+4.332+0.037

= 61.689

68
 Appendix - B

CALUCULATED DATA
TABLE-B.1: Preparation of Methyl Palm Ester

Catalyst: Potassium hydroxide (KOH), Temperature: 650c, Reaction time: 11/2 hour (90 min)

Oil Alcohol CH3OH catalyst Methyl Glycerin + excess Loss in %Ester S.No
(ml) (ml) mole ratio wt % ester(gm) alcohol(gm) wash(gm) %Yield Content
1 400(367.2) 52(41.71) 1:03 0.5 340.43 58.89 11.48 92.7 -
2 400(367.2) 52(41.71) 1 333.41 69.3 9.98 90.79 -
3 400(367.2) 52(41.71) 1.5 325.86 80.11 8.62 88.79 -
4 400(367.2) 52(41.71) 2 305.67 88.95 7.86 83.05 -
5 400(367.2) 105(83.41) 1:06 0.5 364.1 83.11 5.4 99.1 -
6 400(367.2) 105(83.41) 1 358.26 92.89 3.5 97.49 -
7 400(367.2) 105(83.41) 1.5 340.18 102.9 3.39 92.5 -
8 400(367.2) 105(83.41) 2 328.1 123 3.18 89.3 -
9 400(367.2) 131.8(104.2) 01:07.5 0.5 364.3 104.9 4 99.2 -
10 400(367.2) 131.8(104.2) 1 356.18 116 3 96.99 -
11 400(367.2) 131.8(104.2) 1.5 349.08 125.01 3 95 -
12 400(367.2) 131.8(104.2) 2 342.9 133.12 3.07 93.3 -
13 400(367.2) 158(125) 1:09 0.5 365.16 126 2 99.4 97.4
14 400(367.2) 158(125) 1 360.42 134.4 1.98 98 98.1
15 400(367.2) 158(125) 1.5 353.19 141.81 2.8 96.18 98.8
16 400(367.2) 158(125) 2 344.16 152.84 2.77 93.72 99.1

69
 Appendix - B

TABLE-B.2: Preparation of Methyl Palm Ester

Catalyst: Sodium hydroxide, Temperature: 650c, Reaction time: 11/2 hour

Oil Alcohol CH3OH catlyst Methyl Glycerin +excess Loss in %Ester

S.No (ml) CH3OH(ml) mole ratio wt % ester(gm) alcohol(gm) wash(gm) %Yield content
1 300(275.4) 39.5(31.24) 1:03 0.25 254.65 39.05 12.7 92.46 -
2 300(275.4) 39.5(31.24) 1:03 0.5 236.67 59.64 10.09 85.93 -
3 300(275.4) 39.5(31.24) 1:03 1 219.59 80.35 6.46 79.73 -
4 300(275.4) 39.5(31.24) 1:03 1.5 199.89 102.26 4.25 72.58 -
5 300(275.4) 78.9(62.47) 1:06 0.25 259.85 71.01 7 94.35 -
6 300(275.4) 78.9(62.47) 1:06 0.5 248.58 82.89 6.4 90.26 -
7 300(275.4) 78.9(62.47) 1:06 1 232.9 99.46 5.51 84.56 -8
300(275.4) 78.9(62.47) 1:06 1.5 205.91 127.87 4.09 74.76 -
9 300(275.4) 98.7(78.09) 01:07.5 0.25 269.55 78.84 5.08 97.8 -
10 300(275.4) 98.7(78.09) 01:07.5 0.5 256.86 92.44 4.17 93.26 -
11 300(275.4) 98.7(78.09) 01:07.5 1 240.19 109.47 3.81 87.14 -12
300(275.4) 98.7(78.09) 01:07.5 1.5 209.98 140.09 3.4 76.24 -
13 300(275.4) 118.4(93.71) 1:09 0.25 271.88 93.89 3.33 98.72 96.27
14 300(275.4) 118.4(93.71) 1:09 0.5 262.53 103.9 2.68 95.32 96.6
15 300(275.4) 118.4(93.71) 1:09 1 248.95 118.23 1.92 90.39 97
16 300(275.4) 118.4(93.71) 1:09 1.5 231.68 135.78 1.64 84.12 98.6

70
 Appendix - B

TABLE-B.3: Properties of Methyl Palm Ester, KOH Catalyst

CH3OH catalyst Density acid kinematic cloud pour flash fire

mole wt % () value visc0osity at point point point point
S.No ratio (gm/cc) (mgKOH/g) 40 c (cst) (0c) (0c) (0c) (0c)

1 1:03 0.5 0.87 0.2805 4.5 11.2 9.3 173 180

2 1 0.867 0.168 4.2 11.2 9.2 175 184

3 1.5 0.8652 0.1122 4 11.1 9.2 179 190

4 2 0.8648 0.1122 3.4 11.1 9.1 185 196

5 1:06 0.5 0.869 0.2805 3.8 11 9.1 167 178

6 1 0.868 0.2244 3.7 11 9 170 181

7 1.5 0.8664 0.168 3.5 11 9 174 186

8 2 0.8652 0.168 3.4 10.9 8.9 178 189

9 01:07.5 0.5 0.8656 0.2244 3.8 10.9 8.7 163 168

10 1 0.8644 0.168 3.6 10.9 8.7 167 175

11 1.5 0.8624 0.112 3.5 10.9 8.7 170 178

12 2 0.861 0.112 3.4 10.9 8.8 175 182

13 1:09 0.5 0.8648 0.168 3.8 10.8 8.9 160 167

14 1 0.8629 0.112 3.6 10.8 8.8 163 169

15 1.5 0.86 0.112 3.5 10.7 8.6 166 174

16 2 0.859 0.0561 3.4 10.7 8.7 173 181

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 Appendix - B

TABLE-B.5: Properties of Methyl Palm Ester, NAOH Catalyst

Density acid kinematic cloud poure flash fire

CH3OH catlyst () value visc0osity at point point point point
S.No mole ratio wt % (gm/cc) (mgKOH/g) 40 c (cst) (0c) (0c) (0c) (0c)

1 1:03 0.25 0.8659 0.2244 4.8 11.3 9.2 180 189

2 0.5 0.8632 0.168 4.5 11.3 9.2 184 197

3 1 0.8611 0.1122 4 11.2 9.1 184 198

4 1.5 0.859 0.1122 3.7 11.2 9.1 188 201

5 1:06 0.25 0.865 0.2805 4.4 11.2 9.1 178 190

6 0.5 0.8643 0.2244 4.1 11.1 9.1 180 192

7 1 0.864 0.2244 3.8 11 9 182 197

8 1.5 0.86 0.1122 3.5 11 9 184 199

9 01:07.5 0.25 0.8647 0.2244 4.3 10.9 8.8 175 189

10 0.5 0.8642 0.168 3.9 10.9 8.8 176 193

11 1 0.8637 0.168 3.7 10.9 8.9 178 197

12 1.5 0.8631 0.168 3.4 10.9 8.9 181 199

13 1:09 0.25 0.863 0.168 4.2 10.8 8.8 174 187

14 0.5 0.8628 0.1122 3.8 10.8 8.8 175 186

15 1 0.861 0.1122 3.5 10.8 8.8 177 191

16 1.5 0.86 0.1122 3.4 10.7 8.8 179 194

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 Appendix - B

TABLE-B.4: Gas Chromatography report for Methyl Palm Ester, KOH Catalyst

CH3OH catalyst wt free mono di tri total iodine Cetane S.No

mole ratio % glycerol glycerides glycerides glycerides glycerol value number
1 1:03 0.5 0 0.354 0.092 0.089 0.112317 - -
2 1 0 0.351 0.086 0.076 0.10937 - -
3 1.5 0 0.286 0.071 0.061 0.0891 - -
4 2 0 0.211 0.022 0.04 0.061 - -
5 1:06 0.5 0 0.342 0.086 0.076 0.107078 - -
6 1 0 0.289 0.069 0.06 0.08953 - -
7 1.5 0 0.201 0.044 0.034 0.060917 - -
8 2 0 0.184 0.021 0.029 0.052847 - -
9 01:07.5 0.5 0 0.268 0.061 0.059 0.082957 - -
10 1 0 0.241 0.054 0.041 0.073238 - -
11 1.5 0 0.231 0.027 0.028 0.065569 - -
12 2 0 0.226 0.019 0.02 0.06235 - -
13 1:09 0.5 0 0.286 0.06 0.047 0.086171 54.91 60.359
14 1 0 0.211 0.051 0.029 0.063932 54.819 60.759
15 1.5 0 0.194 0.023 0.021 0.054853 54.684 61.287
16 2 0 0.161 0.012 0.017 0.044486 54.358 61.689

73
 Appendix - B

TABLE-B.6: Gas Chromatography report for Methyl Palm Ester, NAOH Catalyst

CH3OH mole catalyst free mono di tri iodine Cetane

S.No ratio wt % glycerol glycerides glycerides glycerides total glycerol value number
1 1:03 0.25 0.005 0.346 0.098 0.091 0.116323 - -
2 0.5 0.005 0.325 0.084 0.078 0.10766 - -
3 1 0.005 0.264 0.079 0.066 0.090178 - -
4 1.5 0 0.205 0.031 0.042 0.060941 - -
5 1:06 0.25 0.004 0.334 0.081 0.071 0.107823 - -
6 0.5 0.003 0.299 0.064 0.058 0.094179 - -
7 1 0.003 0.2 0.04 0.036 0.063308 - -
8 1.5 0 0.198 0.028 0.024 0.056882 - -
9 01:07.5 0.25 0.002 0.286 0.054 0.048 0.08743 - -
10 0.5 0.002 0.239 0.047 0.037 0.073331 - -
11 1 0 0.232 0.021 0.02 0.06416 - -
12 1.5 0 0.211 0.018 0.019 0.058277 - -13 1:09 0.25
0 0.254 0.056 0.049 0.077657 55.135 60.245 14 0.5 0
0.212 0.044 0.037 0.064031 54.985 60.758 15 1 0 0.196
0.022 0.021 0.055223 54.719 60.985
16 0.15 0 0.177 0.014 0.011 0.048228 54.586 61.328

74