Table of Contents

CHAPTER 1.............................................................................................................3
INTRODUCTION....................................................................................................3
1.1 Overview of Research....................................................................................3
1.2 Problem Statement.........................................................................................5
1.3 Objectives.......................................................................................................5
1.4 Scope Of Study..............................................................................................5
1.5 Rationale and Significance.............................................................................6
1.6 Types of cooking oil.......................................................................................6
1.6.1 Palm oil...................................................................................................6
1.6.2 Rapeseed or canola oil.................................................................................7
1.6.3 Sunflower oil...............................................................................................7
Chapter# 2................................................................................................................8
LITERATURE REVIEW.........................................................................................8
2.1 Historical Background on Biodiesel Production............................................8
2.2 Biodiesel production is a very modern and technological area for
researchers........................................................................................................................9
2.3 The Future Of Biodiesel Fuel.........................................................................9
2.4 Raw Materials..............................................................................................10
2.5 Straight Vegetable oil:.................................................................................10
2.6 Waste Cooking Oils (WCO).........................................................................11
2.7 Solvent..........................................................................................................11
2.8 Catalyst.........................................................................................................11
REFERNCES.........................................................................................................12
01. According to B.K. Barnwaland M.P. Sharma (2006)...................................12
02. According to Utlu.Z (2007).......................................................................12

03. According to Utlu.Z and Kocak MS. (2008)..............................................13

04. According to Ma F,Hanna MA (1999)........................................................13
05. According to Zhang Y, Dube MA, McLean DD, Kates M (2003)..............13
06. According to Nelson, R. G.; Hower, S. A. (1994)........................................13
07 . According to Canakci, M.; Gerpen, J. V. (2001)........................................13
08 . According to ukuda, H.; Kondo, A.; Noda, H (2001)................................13
09 . According to Lang, X.; Dalai, A. K.; Bakhshi, N. N.; Reaney, M. J.; Hertz,
P. B (2002)......................................................................................................................14
10 . According to Encinar JM, Gonzalez JF, Lopez FJ, Mittelbach M. (2005)..14
11. According to (Supes et al., 2004)................................................................14
12. According to Carrraretto C, Macor , Mirandola A, Stoppato A, Tonon S.
(2004).............................................................................................................................14
13. According to Dorado MP, Ballesteros E, Lopez FJ, Mittelbach M. (2004). 14
14. According to Encinar JM, Gonzalez JF, Lopez FJ, Mittelbach M. (2005)...15
CHAPTER 3...........................................................................................................16
METHODOLOGY.................................................................................................16
3.1 Introduction................................................................................................16
3.2 Raw Material................................................................................................16
3.2.1. Chemicals.............................................................................................16
3.2.2. Raw Materials......................................................................................17
3.3 Preparation of Biodiesel by Three-step Method..........................................19
3.3.1. Saponification......................................................................................20
3.3.2. Acidification.........................................................................................20
3.3.3 Trans-esterification of Free fatty acid (FFA).........................................20
3.4 Analysis....................................................................................................22

CHAPTER 1
INTRODUCTION

1.1 Overview of Research

Soaring prices of fossil diesel, the increasing environmental issues and, moreover,
the projected exhaustion of fossil fuels has changed the global energy trends and
prompted the research, considerably, towards the alternative fuel sources. Of the
alternative fuels, bio-diesel has attracted huge attention of the global market because of its
renewability, non-toxicity, better gas emissions and its bio-degradability. The American
Society for Testing and Materials (ASTM) defines bio-diesel fuel as mono-alkyl esters of
long chain fatty acids derived from a renewable lipids feedstock, such as vegetable or
animal fat. As an alternative fuel, bio-diesel is used alone in its neat form. However, it is
also blended with petroleum based diesel.
Biodiesel, derived from vegetable oil or animal fats by trans-esterification
with alcohol like methanol and ethanol, is recommended for use as a substitute for
petroleum based diesel mainly because biodiesel is an oxygenated, renewable,
biodegradable and environmentally friendly biofuel with similar flow and combustion
properties and also low emission profile (Altin and Selim, 2001). It helps to reduces
global warming gas emissions such as carbon dioxide. Biodiesel has no aromatics, almost
no sulfur and contains 11% oxygen by weight. This characteristics of biodiesel reduce the
emissions of carbon- monoxide, hydrocarbon and particulate matter in the exhaust gas
compared to petroleum based diesel fuels (Peterson and Hustrulid, 1998). According to
Utlu and Kocak, there was on average of a decrease of 14% for CO2, 17.1% for CO and
22.5% for smoke density when using biodiesel. No engine modifications are necessary;
Biodiesel can be poured straight into any Diesel fuel tank. It provides lubricating
properties that can reduce engine wear and extend engine life.
Currently, compared to petroleum based diesel, the high cost of biodiesel is a
major barrier to its commercialization. It is reported that approximately 70%-85% of the

total biodiesel production cost arises from the cost of the raw material (Fukuda et al,
2001). Use of low cost feedstock such as waste cooking oil (WCO) should help make
biodiesel competitive in price with petroleum diesel. Everywhere in the world, there is an
enormous amount of waste lipids generated from restaurants, food processing industries
and fast food shops every day (Mittlebach and Gangl, 2001).
Because of the good properties and the environment improvement, many
countries pay much attention to research and development (R&D) of biodiesel industry
and constitute favorable legislation for it. More than 2.7 million tons biodiesel in 2003
was made in Europe, and 8-10 million tons is expected in 2010 (Altin and Selim, 2001).
In Pakistan, waste cooking oil (WCO) is available in large quantities from
restaurants, hotel chains, confectionaries and domestic cooking. Average consumption of
edible oil in Pakistan is 10 liters per month by one family giving rise to an estimated
quantity of 240million liters of WCO in Pakistan every year (assuming that 10% of edible
oil in Pakistan becomes waste). Estimating an 85% yield of Biodiesel from WCO, a
minimum approximate quantity of 155 million liters per year Biodiesel from WCO can
be produced in Pakistan. From the marketing point of view there is a chain of dealers for
collection and further selling of WCO. Price for 1 liter of WCO from these sources may
vary from Rs. 20 45.The cost constraints can be overcome by developing strategies for
coordination between dealers, stakeholders and users of WCO and subsidiary on the
production and sale of Biodiesel.

1.2 Problem Statement

The problem was to determine the extent to which various parameters effect
on batch trans-esterification process i.e. Bio-diesel conversion, where Waste Cooking Oil
and methanol are the starting materials and sodium hydroxide ( NaOH ) is the catalyst.

Heavy reliance on imported petroleum fuels.

Completely open to shocks in oil prices.
Poor waste cooking oil disposal practices.
Failure to embrace technology to foster fuel diversification.

Unrealized potential in fuel production despite available technology.

Poor development of waste re-uses policies.

1.3 Objectives

The objective of this research is to Survey quality and availability of waste

cooking oil from commercial food preparation services and thus, examine the
performance of yield and purity of bio-diesel produced in the trans-esterification process.

1.4 Scope Of Study

Trans-esterification of waste cooking oil.

To investigate the effect of methanol/waste cooking oil ratio, sodium

hydroxide concentration and temperature on the trans-esterification process.

1.5 Rationale and Significance

The rationale of this research is to identify the important variables and to

propose a suitable approach in scaling up the production of biodiesel Waste Cooking oil
using batch trans-esterification process. With the important variables such as catalyst
concentration, reaction time, reaction temperature and ratio of methanol to waste oil used,
we can produce high quality of biodiesel which have a high yield and high purity of
methyl ester content.
The elevating energy demand in the industrial as well as in the domestic
sector and the pollution problems, caused due to the widespread use of fossil fuels have
made it increasingly necessary to develop the renewable energy sources of smaller

environmental impact than the fossil fuels such diesel fuels. The alternative fuel must be
technically feasible, economically competitive, environmentally acceptable and readily
available that is familiar to biodiesel properties. Biodiesel is also biodegradable, nontoxic and has low emission profiles as compare to diesel fuel.

1.6 Types of cooking oil

Among the alternatives as a vegetal raw material to extract the oil are: oil palm,
soybean, sesame, cotton, corn, canola, sunflower and olives.
1.6.1 Palm oil
Palm oil is retrieved from the mesocarp of the Palm fruit, this oil is regarded as
the second most widely produced only surpassed by the soybean oil. The oil palm is a
tropical plant characteristic of warmer climates that grows below 500 meters above sea
level. Hence Colombia is the largest producer of palm oil in Latin America and the fourth
in the world. "The extracted oil from the palm contains a relationship 1:1 between
saturated and unsaturated fatty acids, is also a major source of natural antioxidants as
tocopherols, tocotrienols and carotenes: It has been proven that Palm oil is natural
source vitamin E, in the form of tocopherols and tocotrienols. The tocotrienol act as
protectors against cells aging, arthrosclerosis, cancer and some neurodegenerative
diseases such as Alzheimer's disease. Unrefined palm oil is the richest in beta-carotene
natural source; its consumption has proved to be very useful for preventing and treating
the deficiency of vitamin A in risk population.

1.6.2 Rapeseed or canola oil

Rapeseed is a "special oil seed in the cruciferous family. Many of the species of
this family have been cultivated since long time ago that their roots, stems, flowers and
seeds are edible. I really grow in climates that go from temperate to slightly cold and wet
(minimum of 0 C and maximum of 40 C). When the seeds of rapeseed are crushed we
can obtain oil and a kind of pulp or prized residue from always to feed livestock, since
that gives a 34% protein and 15% crude fiber. The biodegradable properties of rapeseed
or canola oil make it ideal to be used on the basis of paints, herbicides, lubricants, food
etc.

1.6.3 Sunflower oil

The oil extracted from sunflower seeds is considered to be of high quality for a
low percentage of saturated fatty acids and a high percentage of unsaturated fatty acids. It
also contains essential fatty acids and a considerable amount of tocopherols that gives it
stability. The acidic composition of the sunflower depends on the genotype and the
environment. There are currently three groups of genotypes: traditional, oleic medium and
oleic high.

1.6.4 Peanut
The quality of peanut is strongly affected by weather conditions during the
harvest. Peanuts are mainly used for human consumption, in the manufacture of peanut
10 2 Introduction to Biodiesel Production butter, and as an ingredient for confectionery
and other processed foods. Peanuts of lower quality (including the rejects from the
confectionery industry) are used for oil production, which has a steady demand in the
international market. Peanut oil is used in blends for cooking and as a flavoring agent in
the confectionery industry. The flour left over, following oil extraction, is of high quality
with high protein content; in pellet form, it is used as a livestock feed.

Chapter# 2
LITERATURE REVIEW

2.1 Historical Background on Biodiesel Production

In 1900 Rudolf Diesel used 1st time peanut oil(Vegetable oil) as a Liquid fuel in
Internal Combustion Engines. However Petroleum became the dominant energy source
and petroleum diesel was then developed as the primary fuel for diesel engines because of
its low cost and easy availability. So, Vegetable oil-based fuels gained little attention,
except in times of high oil prices and shortages. World War II and the oil crises of the
1970s saw brief interest in using vegetable oils to fuel diesel engines. Unfortunately, the
newer diesel engine designs could not run on traditional vegetable oils, due to the much
higher viscosity of vegetable oil compared to petroleum diesel fuel. A way was needed to
lower the viscosity of vegetable oils to a point where they could be burned properly in the
diesel engine. Many methods have been proposed to perform this task, including
pyrolysis, blending with solvents, and even emulsifying the fuel with water or alcohols,
none of which have provided a suitable solution.
It was a Belgian inventor in 1937 who first proposed using transesterification to
convert vegetable oils into fatty acid alkyl esters and use them as a diesel fuel
replacement. The process of transesterification converts vegetable oil into three smaller
molecules which are much less viscous and easy to burn in a diesel engine. The
transesterification reaction is the basis for the production of modern biodiesel.
At that time the pyrolysis of different triglycerides was also used for liquid fuel
supply in different countries.

For Example:
Hydrocarbons were produced in China by a Tung oil pyrolysis batch system used
as liquid fuels (Chang and Wan, 1947).
Fatty acids ethyl or methyl esters was obtained by trans-esterification or
alcoholysis of vegetable oils or esterification of fatty acids combined with transesterification of triglycerides (Keim, 1945).

2.2 Biodiesel production is a very modern and technological area for

researchers

It is an alternatives fuel for diesel engines that is produced by chemical reaction

of a vegetable oils or animal fats with an alcohol such as methanol. The product is called
as methyl ester or biodiesel, which is receiving high attention as an alternative, nontoxic,
biodegradable and renewable diesel fuels (Ma and Hanna, 1999).

When biodiesel displaces petroleum diesel, it reduces global warming gas

emission such as carbon dioxide. Biodiesel has no aromatics, almost no sulfur and
contains 11% oxygen by weight. These characteristics of biodiesel reduces the emissions
of carbon monoxide, hydrocarbon and particulate matter in the exhaust gas compare
petroleum-based diesel fuels (Peterson and Hustrulid, 1998).

2.3 The Future Of Biodiesel Fuel

Due to its clean emissions profile, ease of use, and many other benefits, biodiesel
is quickly becoming one of the fastest growing alternative fuels in the world. With
minimal subsidy biodiesel is cost competitive with petroleum diesel, and millions of users
have found and enjoyed the benefits of the fuel. The future of biodiesel lies in the worlds
ability to produce renewable feed stocks such as vegetable oils and fats to keep the cost of
biodiesel competitive with petroleum, without supplanting land necessary for food

production, or destroying natural ecosystems in the process. Creating biodiesel in a

sustainable manner will allow this clean, renewable, and cost effective fuel to help ease
the world through increasing shortages of petroleum, while providing economic and
environmental benefits well into the 21st century.

2.4 Raw Materials

There are several sources that can be use as raw material for
biodiesel production, such as non edible oil, animal fats and vegetable oil. However, the
vegetable oils extracted from plant that are composed of triglycerides was used because it
contains similar fuel properties to diesel fuel except the higher viscosity and low
oxidative stability that must be encountered before being converted into biodiesel.
The vegetable oils that mostly used in transesterification reaction include pure
plant oils (PPOs) or straight vegetable oils (SVOs) and waste vegetable oils (WVOs).
(Knothe et al., 2001).

2.5 Straight Vegetable oil:

Pure plant oils (PPO) or commonly known as straight vegetable
oils is not a byproduct of other industries either coming from domestic usage. Actually,
the straight vegetable oils is a highly grade of oil extracted primarily from plant, usually,
seeds of oilseed plants.
(SVOs) are the best starting material compare to waste cooking oils because of the
conversion of triglyceride to fatty acid methyl ester is high and the reaction time is
relatively short. (Encinar et al., 2006).

2.6 Waste Cooking Oils (WCO)

The feedstock coming from waste vegetable oils or commonly known as
waste cooking oils is one of the alternative sources among other higher grade or refine

oils. Waste cooking oil is easy to collect from other industries such as domestic usage and
restaurant and also cheaper than other oils (refine oils). Hence, by using these oils as the
raw material, we can reduce the cost in biodiesel production.
Waste cooking oils is an effective way to reduce the cost of biodiesel production.
(Encinar 2006)

2.7 Solvent
Alcohol is primary and secondary monohydric aliphatic alcohols having one to
eight carbon atoms. In transesterification process, the main solvent use is alcohol. The
examples of alcohol that can be used in the transesterification of triglycerides are
methanol, ethanol, propanol, butanol and amyl alcohol. Methanol is the most widely use
because of its low price and its physical and chemical advantages (polar and shortest
chain alcohol).
It can quickly react with triglycerides and sodium hydroxide and easily dissolved
in it. (Marchetti et al., 2005).

2.8 Catalyst
A catalyst is a substance that accelerates the rate of reaction by lowering its
activation energy. A catalyst recovered unchanged and it does not appear in the product.
Catalyst used in the transesterification of triglycerides can be classified as:
Homogeneous Catalyst
Heterogeneous Catalyst
Enzyme catalyst.

Excess amount of catalyst would lead to the higher amount of production cost and
reduce product yield. Fangrui Ma and Milford A. Hanna (1999)
Many researchers have reported the biodiesel production in several ways:

 The effect of operating parameters

The effect of solvent
The effect of type of catalyst
Heterogeneous catalyst
Homogenous catalyst
Enzyme catalyst

REFERNCES
01. According to B.K. Barnwaland M.P. Sharma (2006)
(Prospects of biodiesel production from vegetable oils)
Biodiesel is renewable and does not contribute to global warming due to its closed
carbon cycle. A life cycle analysis of biodiesel showed that overall CO2 emissions were
reduced by 78% compared with petroleum-based diesel fuel.

02. According to Utlu.Z (2007)

(Evaluation of Biodeisel from waste cooking oil. Energy sources,)
The conversion of this amount of Waste cooking oil into fuel also eliminates the
enviornmental impacts caused by the harmful disposal of these waste oils such as into
drains.

03. According to Utlu.Z and Kocak MS. (2008)

(The effect of biodiesel fuel obtained from waste cooking oil on direct injection
diesel engine perfomances and exhaust emissions)
There was an average of decrease of 14% for CO2 , 17.1% for CO and 22.5% for
smoke density when using biodiesel.

04. According to Ma F,Hanna MA (1999)

The raw material costs and limited availaibilty of vegitable oil feed stocks always
critical issues for biodiesel production. High cost of vegetable oils, which could be upto
75% of the total manufacturing cost, has led to production cost of biodiesel become
approximately 1.5 times higher then that of diesel.

05. According to Zhang Y, Dube MA, McLean DD, Kates M (2003)

(Biodiesel production from waste cooking oil: 2. Economic assessment and sensitivity
analysis) Price of waste cooking oil (WCO) us 2-3 times cheaper then virgin vegetable
oils. Consquently, the total manufacturing cost of biodiesel can be significantly reduced.

06. According to Nelson, R. G.; Hower, S. A. (1994)

The significant factors that affect the cost of biodiesel are feedstock cost, plant
size, and value of the glycerine byproduct

07 . According to Canakci, M.; Gerpen, J. V. (2001)

The water in waste cooking oil also affects the methyl ester yield by favoring
saponification reaction.

08 . According to ukuda, H.; Kondo, A.; Noda, H (2001)

The rate of the alkaline-catalyzed transesterification reaction is fast, compared to that

using acids, and it is reported that the rate could be as high as 4000 times, compared to
that using an acidic catalyst.

09 . According to Lang, X.; Dalai, A. K.; Bakhshi, N. N.; Reaney, M. J.;

Hertz, P. B (2002)

It has been well-reported that biodiesel obtained from canola and soybean oil acts very
well as a diesel fuel substitute.

10 . According to Encinar JM, Gonzalez JF, Lopez FJ, Mittelbach M.

(2005)
(Optimization of alkali catalyzed transesterfication of Brassica Carinata oil for
Biodiesel production)
Alkali catalysts used in transesterfication can be potassium hydroxide, Sodium
Hydroxide or alkali methoxides. However Potassium Hydroxide was considered as a best
catalyst for transesterfication for waste cooking oil.

11. According to (Supes et al., 2004).

The Alkaline earth metal oxides compound is very favorable used in
transesterification process because it is slightly soluble in organic solvents

12. According to Carrraretto C, Macor , Mirandola A, Stoppato A,

Tonon S.(2004)
(Biodiesel as alternative fuel: experimental analysis and energetic evaluations)
Most Viable option for biodiesel is in boilers with minor modifications of nozzles
and gaskets that give a comparable efficiency and less fouling.
However the optimum conditions for Biodiesel production (Methanol/oils ratio
and concentration of catalyst) are inconsistent. They strongly depend upon on the
properties of WCO.

13. According to Dorado MP, Ballesteros E, Lopez FJ, Mittelbach M.

(2004)
(Optimization of alkali catalyzed transesterfication of Brassica Carinata oil for Biodiesel
production)
They found that ester yield reached 90% at the methanol/oil ratio of 3.48:1 and
1.26wt% NaOH.

14. According to Encinar JM, Gonzalez JF, Lopez FJ, Mittelbach M.

(2005)
(Optimization of alkali catalyzed transesterfication of Brassica Carinata oil for Biodiesel
production)
While they revealed that the best results obtained at the molar ratio of 6:1 and 1% NaOH.

15. Centikaya and Karaosmanoglu

CHAPTER 3
METHODOLOGY

3.1 Introduction

The most common way to produce Biodiesel is via Batch Trans-esterification

which refers to a catalyzed chemical reaction involving vegetable oil and an alcohol to
yield fatty acid alkyl esters (i.e., biodiesel) and glycerol.

Trans-esterification of triglyceride with alcohol to form biodiesel.

3.2 Raw Material

The biodiesel production comes mostly from oils extracted oilseed plants
especially sunflower, soy, rapeseed and animal fats. However, any material that contains
triglycerides can be used for the biodiesel production. "In addition to the oil or fat is
needed an alcohol and catalyst to convert oils and fats in alkyl esters.
3.2.1. Chemicals
Methanol (99-100%), ethanol (99-100%), sodium hydroxide pellets (96%), potassium
hydroxide pellets (>84%), phenolphthalein (PH 8.2-9.8), acetone (99%), diethyl ether ,
hydrochloric acid (37%), iodine , sodium iodide, bromine, carbon tetrachloride, glacial
acetic acid, potassium dichromate etc. All the chemicals were used as analytical reagent
grade.

3.2.2. Raw Materials

Waste cook oil (palm oil and soybean oil) was collected from local restaurants and
shops located in Hyderabad city in Pakistan. The waste cooking oil samples so obtained
were different in a way that;
(a) collection after being used several times for frying purposes.

(b) Collection of waste cooking oil, used only once.

The oil was filtered and its properties were measured.
Melting 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 thecloud
point. While operating an engine at temperatures below oils 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 atwhich
the fuel will ignite (flash) on application of an ignition source. Flash point varies
inversely with the fuels 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.
Acid Number- a measure of the amount of free acids (as fatty acids) in a substance (as
an oil or resin) usually expressed as the number of milligrams of potassium hydroxide
required to neutralize one gram of the substance called also acid number.

 Saponification Number- a measure of the total free and combined acids especially
in a fat, wax, or resin expressed as the number of milligrams of potassium hydroxide
required for the complete saponification of one gram of substancecalled
also saponification value.

TABLE 1
Physical properties of Waste Cooking Oil Samples and Diesel.
Property

Unit

Sample 1

Sample 2

Sample 3

Sample 4

Acid Number

mg
NaOH/g

0.67

1.90

2.33

1.76

Saponification
number

mg
NaOH/g

268.22

264.10

272.00

270.4

Iodine number

mg
NaOH/g

9.4

10.77

13.00

12.66

Density

g/cm3

0.90

0.92

0.88

0.91

Flash point

298

308

266

276

Cloud point

26

16

22

14

Pour point

18

13

19

12

Viscosity @
40C

Cs/s

52.24

65.55

38.85

40.33

TABLE 2

Quantitative Analysis: Fatty acids in Waste Cooking Oil

Bio-diesel

180

150

3.3 Preparation of Biodiesel by Three-step Method

Three-step method consists of Saponification followed by acidification to produce
FFA and finally esterification of FFA to produce biodiesel [12].

3.3.1. Saponification
For saponification process required amount of WCO was taken in a three necked
flask and mixed with different stoichiometric amount of aqueous sodium hydroxide
solution. The mixture was heated under reflux with vigorous stirring at temperature of
100C for different time. The reaction was stopped by cooling the reaction volume.
Aqueous sodium hydroxide solution was prepared by dissolving required amount of dry
sodium hydroxide (NaOH) in 60-90ml water. The reaction time and different molar ratio
of oil to sodium hydroxide solution through saponification process were optimized.

3.3.2. Acidification
After saponification, produced sodium soap solution was treated with different
stoichiometric amount of concentrated hydrochloric acid at a temperature of 65-70C
under reflux with vigorous stirring. After dissolving the soap, the fatty acid contents were
separated in separating funnel. After separation, hot water wash was given for removing
mineral acid from the fatty acid. The FFA content was determined by titration method.
The different molar ratio of soap to hydrochloric acid was given and the ratio was
optimized.

3.3.3 Trans-esterification of Free fatty acid (FFA)

When acidification was completed, produced FFA was reacted with different
stoichiometric amount of methanol under reflux with vigorous stirring at different
temperature, catalyst concentration, different molar ratio of methanol to FFA and different

time. All the reaction parameters were optimized. After a certain time, the mixture was
poured into a separating funnel. The ester layer was separated by gravity and located in
the upper layer. The glycerol, extra methanol and undesired products were in the lower
layer were decanted. The ester layer was washed with hot water, several times, until the
washings were neutral. The ester layer ( bio-diesel) was then dried over sodium sulphate
and filtered.
After preparing the biodiesel from WCO various physico-chemical properties
were measured and compared with the standard biodiesel. The yield of biodiesel was
calculated by the following equation:
(1)
Where, W (biodiesel) is the weight of produced biodiesel and W (oil) is weight of
oil.

& methanol
& methanol

Fig:- Mixing of potassium hydroxide pellets

Fig:- Agitation of oil and mixing solution of potassium hydroxide pellets

Fig:- Biodiesel-Glycerin separation

Once separate the glycerin from biodiesel, it is carried out the washing on the
funnels. Separate the glycerin, the biodiesel must be washed because that may contain
residues of catalyst, methanol, soaps and glycerides without reacting. Two types of
washings are established according to the experimental design. In one of the washing,
water at 40 C is used for three washes. Other tests of washing have been conducted with
acetic acid 10% wt, where is used the same amount of used cooking oil; two washes are
carried out with acid solution and the third is done with deionized water.

Fig. First biodiesel wash: (a) Water at 40 C (b) acetic acid solution

The distillation is carried out at 40 C, temperature which is below the boiling

point of methanol. The vacuum pump is used in order to minimize the time of distillation
and vacuum trap is used to prevent waste of alcohol and water to the pump.

Fig. Biodiesel distillation (a) Mounting: i. vacuum pump ii. Vacuum trap iii. Hot
plate iv.Thermometer (b) Distilled biodiesel.
3.4 Analysis
Fatty acids quantity was determined by using Gas Chromatography. The physical
properties of raw material Waste Cooking Oil Samples and Bio-diesel, so formed, were
measured by using ASTM standard methods.

CHAPTER 4
RESULTS AND DISCUSSION

4.2 Effect of Methanol-to-Oil Molar Ratio

The molar ratio of methanol to waste cooking oil is one of the most important
variables which affect the yield of Bio-diesel. Although, three moles of methanol are
required for each mole of triglyceride (3:1), but in common practice, a higher molar ratio
is required in order to drive the reaction towards completion and produce more FAME
(fatty acid methyl esters) as products .The work of Centikaya and Karaosmanoglu [15]