http://gotest.

pk/education/jobs/sindh-police-jobs-for-asi-andconstable-karachi-announced/
http://www.watchonlinemovies.com.pk/

Abstract:
The country of Pakistan has the capability to use biodiesel for their
transportation needs. This would increase their fuel security, economy and
environmental impact. Animal fat oil produces a high yield of biodiesel. This thesis
outlines studies done to find the optimal method for converting animal fat oil to
usable biodiesel. The amount of alkaline catalyst and ratio of methanol to fresh oil
for the greatest conversion of fatty acid methyl esters are reported. In addition, the
optimal reaction was established. Finding the most efficient way to convert animal
fat oil to biodiesel would allow for this biodiesel to be produced as economically
as possible.

Acknowledgements:
This project team would like to thank our super visor
assistant professor DR. Parvez for his continued guidance and support throughout
the entirety of this project. Also, we would like to thank coordinator DR. Zia ullah
shah, for sharing his interest for the topic of this thesis. We would like to give
special thanks to HOD DR. Farrukh Hussain, for answering our questions and
pointing us in the right direction, for trouble shooting our equipment when needed.
Without these teachers we would not be able to participate in this project.

Table of Contents
Abstract:.........................................................................................................................................1
Acknowledgements:.......................................................................................................................2
Introduction:..................................................................................................................................4
What are Biofuels:.........................................................................................................................4
Figure: Sources of main liquid biofuels for automobiles........................................................4
Petroleum Diesel:...........................................................................................................................5
Biodiesel Description:....................................................................................................................6
Crops useful for biodiesel production:.........................................................................................6
Chemistry of biodiesel:..................................................................................................................6
Transesterification Reaction:........................................................................................................7
Types of biodiesel:..........................................................................................................................8
Petroleum Diesel and Biodiesel Comparison:.............................................................................8
Composition Comparison:............................................................................................................9
Viscosity:.........................................................................................................................................9
Cetane Number:.............................................................................................................................9
Flash point:...................................................................................................................................10
Carbon residue:............................................................................................................................10
Lubricity:......................................................................................................................................10
Other Comparisons:....................................................................................................................11
Environmental Comparison:......................................................................................................11
Advantages of biodiesel:..............................................................................................................12
Disadvantages of biodiesel:.........................................................................................................12
Needs for research:......................................................................................................................13
1) Energy security........................................................................................................................13
2) Economic development...........................................................................................................13
3) Mitigation of climate change..................................................................................................14

Situation in world:.......................................................................................................................14
Situation in Pakistan:..................................................................................................................17
Importance of obtaining biodiesel from waste fats collected from leather:...........................19
Biodiesel Economy:......................................................................................................................19
Literature review:........................................................................................................................21
Materials and methods:...............................................................................................................25
Materials:......................................................................................................................................25
Methodology:................................................................................................................................25
Pretreatment:...............................................................................................................................26
Transesterification:......................................................................................................................26
Development of Process Parameters:.........................................................................................27
Separation of Biodiesel:...............................................................................................................27
Purification of Biodiesel:.............................................................................................................28
Methanol Distillation:..................................................................................................................28
Washing Procedure:....................................................................................................................28
Drying:..........................................................................................................................................28
Analysis of Biodiesel:...................................................................................................................29
Results and discussions:..............................................................................................................30
Possible sources of error:............................................................................................................31
Loss of methanol:.........................................................................................................................32
Integrity of catalyst:....................................................................................................................32
Limitations Found During Experiments:..................................................................................33
Table shows the values of the total hydrocarbons of , diesel and biodiesel, it can be noticed
that the biodiesel has the lowest value of hydrocarbons..........................................................33
Table shows the mean values of the resulted emissions for every fuel. For SO2, O2 and CO2
it can be noticed that the values for every fuel are almost similar..........................................34
Figure: B100 emissions compared to petroleum diesel emissions by percentage..................34
Conclusion:...................................................................................................................................35
Recommendations:......................................................................................................................36
References:...................................................................................................................................37

Chapter: 1
Introduction:
What are Biofuels:
Biofuels are energy carriers that store the energy derived
from biomass, commonly produced from plants, animals and micro-organisms and
organic wastes. Biofuels may be solid, liquid or gaseous and include all kinds of
biomass and derived products used for energetic purposes. Biofuels are renewable
energy sources, meaning that fresh supplies can be regrown. They are a possible
substitute product for fossil fuels. Compared with the latter product there are some
advantages to subscribe to biofuels. Advantages and benefits of biofuels, however,
depend on the categorization of the specific biofuel, type of feedstock used and
technology applied to produce it.

Figure: Sources of main liquid biofuels for automobiles

There are a variety of biofuels potentially available, but the main biofuels being
considered globally are biodiesel and bioethanol. Bio-ethanol can be produced
from a number of crops including sugarcane, corn (maze), wheat and sugar beet.
Biodiesel is the fuel that can be produced from straight vegetable oils, edible and
non-edible, recycled waste vegetable oils, and animal fat. The main producing
countries for transport biofuels are the USA, Brazil, and the EU. Production in the
United States was mostly ethanol from corn, in Brazil was ethanol from sugar
cane, and in the European Union was mostly biodiesel from rapeseed.

Petroleum Diesel:
The two most popular types of transportation fuels are
diesel and gasoline. Gasoline uses spark ignition engines that are used by over 90%
of the small car industry in the United States (Kemp, 2006). Petroleum diesel fuels
are used in the compression ignition engine. Diesel engines are quieter and emit
less smoke than they have in the past. For a certain amount of power, diesel
6

engines require 30%-60% less fuel (Kemp, 2006). Since diesel engines require less
fuel, there are less greenhouse emissions contributed to diesel engines per mile
driven. Overall diesel engines produce more power and are longer lasting then
gasoline engines. Petroleum diesel is processed from crude oil through refining
(Sheehan, et al.1998). This process distills crude oil through distillation to separate
hydrocarbons by their boiling points. The largest hydrocarbons that are the bottom
of the distillation column are the least expensive hydrocarbons used. The top of the
column is the more expensive hydrocarbons that have gone through the most
separation and refinement (Kemp, 2006). Liquefied petroleum gas and gasoline are
at the top of the column, diesel fuels are slightly less refined than gasoline (Kemp,
2006). Lower grade hydrocarbons can be processed a second time in a crackling
unit to increase their value and some of those products can be used as diesel fuels.

Biodiesel Description:
Biodiesel is a renewable fuel source that can
replace petroleum diesel in compression ignition engines without any change to the
engine (Kemp, 2006). Rudolf Diesel first used plant oils in his diesel engine in
1900. The low price of petroleum based fuels increased interest in petroleum fuels
over that of biofuels. Due to this, interest and research in biofuels diminished
(Mittelbach & Remshmidt, 2006).

Crops useful for biodiesel production:

Biodiesel can be produced
from a number of different feedstocks such as corn, soy, palm, coconut, or
sunflower oil. Additionally, it can be produced from other oil bearing plants that

are not consumed as a food source such as Jojoba, Karanja, and Jatropha curcas (J.
curcas) oil.

Chemistry of biodiesel:
To change oil to a biodiesel, the process of
transesterification of the feedstock is done. The process of transesterification of
plant oils was done as far back as 1852. It was used in the fat and soap industry in
the 1930s and 1940s (Mittelbach & Remshmidt, 2006). Fatty acid methyl ester
production through transesterification of plant oils became popular in the 1980s
and has increased to be the most common type of biofuel for transportation
(Mittelbach & Remshmidt, 2006). The biodiesel feedstock, a vegetable or plant,
can be chosen based on the availability of the plant and the plant oils ability to
produce esters. In Europe, the majority of biodiesel is produced from rapeseed oil,
while in the United States soybeans are much more abundant so soybean oil is used
more frequently for biodiesel production (Sheehan, et al.1998).

Transesterification Reaction:
To produce biodiesel, raw oils are
processed to create a product that will burn efficiently without byproducts that
harm engine parts. Raw oils have high viscosity and lower volatilities

NOx Nitrogen Oxides

PM Particulate Matter
CO Carbon Dioxide
HC Hydrocarbons

and contain many impurities such as free fatty acids, because of these
characteristics; deposits can form in engines causing mechanical failures. To
8

reduce the high viscosity of triglycerides and free fatty acids in oil,
transesterification is used (Meher, Sagar & Naik, 2004). In this reaction, alcohol is
reacted with the triglycerides that are in fats and oils. Triglycerides are three chains
of fatty acids joined by a glycerin molecule (Mittelbach & Remshmidt, 2006). The
reaction takes place in the presence of a catalyst; the catalyst can either be a base
catalyst or acid catalyst based on the percent of fatty acids in the oil (Meher et al.,
2004). The transesterification process removes the glycerin from the triglycerides
with alcohol, forming fatty acid methyl esters (FAME), the technical name for
biodiesel. Transesterification of triglycerides is a three-step process where alcohol
molecules react with one fatty acid chain at a time (Meher et al., 2004). The first
step is the rate limiting step in which the triglyceride reacts with the alcohol, a
diglyceride and ester is formed. The diglyceride then reacts with another alcohol
molecule to form a monoglyceride and second ester molecule. Finally, a third
molecule of alcohol is reacted with the monoglyceride to form glycerol and a third
ester (Meher et al., 2004).

Types of biodiesel:
Five different grades used by the ASTM:
1.
2.
3.
4.
5.

Grade Low Sulfur No. 1-D,

Grade Low Sulfur No. 2-D,
Grade No. 1-D,
Grade No. 2-D,
Grade No. 3-D.

Grades 2-D and 3-D are the two out of the five that are not used for automobile
applications because they are less refined (Kemp, 2006).

Petroleum Diesel and Biodiesel Comparison:

The switch from
petroleum-based diesel compared to biodiesel has its advantages and
disadvantages. There are changes in energy efficiency based on composition,
changes in environmental impacts, and differences in cost between the two types of
diesel.

Composition Comparison:
Variables measured for diesel fuels that affect
efficiency include viscosity, cetane number, flash point, carbon residue, and
lubricity. by processing fat oil the properties become closer to those of diesel fuels.
This makes the biodiesel much more compatible with diesel engines (Tiwari,
Akhilesh, & Raheman, 2007).

Viscosity:
The viscosity of a fluid can be defined as the measure of how
resistive the fluid is to flow. A very viscous fluid would have a greater resistance to
flow (Motta, 2007). Raw oils can be 20 times higher in viscosity than that of
petroleum fuels. Higher viscosity can lead to incomplete combustion and low fuel
atomization (Kemp, 2006) because the fuel is thicker. A viscometer can be used to
measure the viscosity of a fuel. The main difference between diesel and raw oils is
the viscosity of the oils. Plant oils have a much higher viscosity than diesel (Kumar
et al, 2003).

10

Cetane Number:
The cetane number measures the time delay between the
start of ignition and the start of combustion of the fuel. This measurement is used
for light distillate diesel oils and biodiesels. The normal range is between 45 and
55 cetanes (Kemp, 2006). A minimum number, of 47, is set for fuel quality
(Mittelbach & Remshmidt, 2006). This measurement describes the combustion
quality of diesel fuel in a compression ignition. A higher cetane number correlates
to a short delay between ignition and combustion, which provides for more time
for complete combustion during the combustion process petroleum diesel, can have
higher cetane numbers due to additives in the diesel, such as lubricants and
detergents; this is the difference between regular and premium fuels. Petroleum
diesels range between 38 and 45, biodiesels normally range from 46 to 52 making
biodiesel engines more effect when comparing cetane numbers.

Flash point:
The flash point of oil measures the ability for a heated fuel to
ignite and measures the lowest temperature at which combustion can occur (Kemp,
2006). A higher flashpoint temperature means it is harder for the fuel to ignite. The
lower a flash point temperature is below ambient temperature the more dangerous
the fuel is, because it is more likely to combust at any point. Petroleum diesel has a
much lower flash point than biodiesel, so it will combust much easier, but is also
much more dangerous to transport.

Carbon residue:
The carbon residue of oil will determine the amount of
combustion of a fuel (Kemp, 2006). The closer to complete combustion a fuel has,
11

the fuel will leave fewer deposits meaning it will have a lower carbon residue. The
deposits will decrease the efficiency of an engine. Biodiesel does have a higher
percentage of carbon residue than petroleum diesel, transesterification does
decrease this compared to fresh oils but not as low as petroleum.

Lubricity:
Petroleum diesel requires additives so that the fuel does not cause
engine wear because of its low lubricity properties. The emissions from the
additives contain particulate matter made up of acids (such as nitrates and sulfates),
organic chemicals, metals, soil, and dust particles (Environmental Protection
Agency, 2009) which can cause health and environmental problems. Biodiesel
does not require any additives for lubrication when being used as the main source
of fuel. In addition, biodiesel can be added to petroleum diesel as an additive to
increase its lubricating properties without adding compounds that increase
particulate matter.

Other Comparisons:
Storage can be a problem for fuels. Biodiesel can
absorb water lowering the efficiency (Kemp, 2006). Water can react to create
soaps, which decrease the viscosity of the oil. Biodiesel does not require additives,
is nontoxic to the environment and biodegradable. In addition, biodiesel has a
higher combustion temperature and therefore is less ignitable so it safer to
transport then petroleum diesel fuels (Mittelbach & Remshmidt, 2006).

12

Environmental Comparison:
There are many favorable environmental traits to biodiesel. As stated earlier, the
first trait is the absence of many harmful compounds that are normally found in
petroleum diesel products such as sulfur and aromatics. There is also a reduction of
unburned hydrocarbons, carbon monoxide, and particulate matter that is normal in
a petroleum diesel fuel. Carbon dioxide is a major emission concern because its
effect on climate change and green house gases. A U.S. Department of Energy
(National Biodiesel Board) study in 2009 found that biodiesel emits 78.5% less
carbon dioxide then petroleum diesel. Biodiesel emits less carbon monoxide and
hydrocarbon emissions than petroleum diesel. One of the reasons for this is the
higher amount of oxygen in biodiesel, which increases the amount of complete
combustion of the fuel (Mittelbach & Remshmidt, 2006).

Advantages of biodiesel:
Biodiesel fuel is a renewable energy source unlike petroleum-based diesel.
An excessive production of soybeans in the world makes it an economic way to
utilize

this

surplus

for

manufacturing

the

Biodiesel

fuel.

One of the main biodiesel fuel advantages is that it is less polluting than
petroleum

diesel.

The lack of sulfur in 100% biodiesel extends the life of catalytic converters.
Another of the advantages of biodiesel fuel is that it can also be blended with
other

energy

resources

and

oil.

Biodiesel fuel can also be used in existing oil heating systems and diesel engines
without

making

any

alterations.

It can also be distributed through existing diesel fuel pumps, which is another

13

biodiesel

fuel

advantage

over

other

alternative

fuels.

The lubricating property of the biodiesel may lengthen the lifetime of engines.

Disadvantages of biodiesel:
At present, Biodiesel fuel is bout one and a half times more expensive than
petroleum

diesel

fuel.

It requires energy to produce biodiesel fuel from soy crops, plaus there is the
energy

of

sowing,

fertilizing

and

harvesting.

Another biodiesel fuel disadvantage is that it can harm rubber hoses in some
engines.
As Biodiesel cleans the dirt from the engine, this dirt can then get collected in the
fuel filter, thus clogging it. So, filters have to be changed after the first several
hours

of

biodiesel

use.

Biodiesel fuel distribution infrastructure needs improvement, which is another of

the biodiesel fuel disadvantages.

Needs for research:

1) Energy security
Energy security is the constant availability and supply of
affordable energy for consumers and industry. Risks to energy security include, for
example, disruptions to the supply of imported fossil fuels, limited availability of
fuel, and energy price spikes. The possibility of deriving biofuels from locally
grown sources and using them as alternatives to petrol products is attractive for
many countries, including the UK, that currently depend largely on fossil fuels.

14

2) Economic development
Investment in biofuels could lead to a significant
boost in economic development, including the creation of new jobs and new
sources of income for farmers. This would be of particular benefit to developing
countries in which a large proportion of the population are employed in agriculture.
Global economic growth has contributed to a dramatic rise in world energy
demand. In developing countries, energy consumption is predicted to increase by
84 per cent by 2035, and new sources of energy, such as biofuels, may have a role
to play in meeting this demand.

3) Mitigation of climate change

In the UK, transport accounts for
around a fifth of total greenhouse gas emissions. It is hoped that, with appropriate
production methods, biofuels will produce significantly fewer greenhouse gas
emissions than are currently produced by fossil fuels. The apparent potential of
biofuels to address all three of the above challenges makes them an attractive
option to policy makers.

Situation in world:
Brazil and the US still account for the majority of global
bioethanol production. International trade in ethanol is expected to grow rapidly
over the next decade, mainly with exports from Brazil to the US and EU. However,
growth in international trade in biodiesel is anticipated not to grow significantly
due to technical issues, issues surrounding trade in palm oil, policies such as anti
dumping duties, and increased national production of biodiesel by consuming
countries. Recent statistics on biofuels production and consumption in EU Member
15

States in 2011 are available . This indicates that "between 2010 and 2011 biofuel
consumption increased by 3%, which translates into 13.6 million tonnes of oil
equivalent (toe) used in 2011 compared to 13.2 million toe in 2010. The European
Unions attention has shifted to setting up sustainability systems to verify that the
biofuel used in the various countries complies with the Renewable Energy
Directives sustainability criteria."
In 2010, The European biodiesel board estimated that European Union biodiesel
production totalled 9.6 million metric tons. The EBB estimates the EU is
responsible for over half of the worlds biodiesel output. In 2011, production
decreased by 10% to 8.6 million metric tons.

16

17

18

Situation in Pakistan:
Alternative energy is hot issue in worlds economy.
Pakistan is equipped with many alternative energy options that are expand of
renewable energy (biodiesel scenario in Pakistan). In Pakistan various alternatives
available to oil and hydro sources of energy. But one alternative is most interesting
that is biodiesel production industry. Pakistan is having landscape and agro scene
that is rich of bio fuel resources. There are many seeds which can produce
biodiesel by their oil e.g. brassica, pongamia pinnata, and ricinus communis. The
program is made in Pakistan that is targeting production of biodiesel through
renewable resources such as: vegetable oil, animal fats, specific plant seeds, and
recycled cooking oil (national biodiesel program). On biodiesel technology,
numerous projects have been initiated at different universities and industries in
Pakistan. Unfortunately, all efforts have been conducted individually, and
apparently, there was minimal knowledge sharing between and among institutions.
This work is an effort at assembling all the figures produced by numerous national
organizations and to present it in an articulate form for the assistance of the future.

19

20

Importance of obtaining biodiesel from waste fats collected

from leather:
Our society is highly dependent on petroleum for its activities.
However, petroleum is a finite source and causes several environmental problems
such as rising carbon dioxide levels in the atmosphere. About 90% is used as an
energy source for transportation, heat and electricity generation, being the
remaining sources used as feedstocks in the chemical industry (Carlsson, 2009). As
demands for energy are increasing and fossil fuels are limited, research is directed
towards alternative renewable fuels (Bhatti et al., 2008). High petroleum prices and
the scarcity of known petroleum reserves demand the study of other sources of
energy. In this context, agroindustrial wastes (animal fats, wood, manure) play an
important role as energetic materials. Oils and fats are basically triacylglycerols
(TAG) composed of three long-chain fatty acids. These triacylglycerols have
higher viscosity and therefore cannot be used as fuel in common diesel engines. In
order to reduce viscosity, triacylglycerols are converted into esters by
transesterification reaction. By this means, three smaller molecules of ester and one
molecule of glycerin are obtained from one molecule of fat or oil. Glycerin is
removed as by-product and esters are known as biodiesel (Fazal et al., 2011).

Biodiesel Economy:
The economic benefits of a biodiesel industry would
include value added to the feedstock, an increased number of rural manufacturing
jobs, increased income taxes, increased investments in plant and equipment, an
expanded manufacturing sector, an increased tax base from plant operations and
21

income taxes, improvement in the current account balance, and reductions in health
care costs due to improved air quality and greenhouse gas mitigation. The major
economic factor to consider for input costs of biodiesel production is the feedstock,
which is about 80% of the total operating cost. Other important costs are labor,
methanol and catalyst, which must be added to the feedstock. The cost of biodiesel
fuels varies depending on the base stock, geographic area, variability in crop
production from season to season, the price of crude petroleum and other factors.
However, biodiesel can be made from other feedstocks, including used vegetable
oil, beef tallow, pork lard and yellow grease. Biodiesel has become more attractive
recently because of its environmental benefits. With recent increases in petroleum
prices and uncertainties concerning petroleum availability, there is renewed interest
in vegetable oil fuels for Diesel engines. there are large amounts of low cost oils
and fats such as restaurant wastes and animal fats that could be converted to
biodiesel. biodiesel (BD) from oilseed or animal fats have a range US $0.30
0.69/l, including meal and glycerin credits and the assumption of reduced capital
investment costs by having the crushing and/or esterification facility added onto an
existing grain or tallow facility. Rough projections of the cost of BD from
vegetable oil and waste grease are respectively,US$0.540.62/l and US$0.34
0.42/l. With pre-tax Diesel priced at US$0.18/l in the US and US$0.200.24/l in
some European countries, BD is, thus, currently not economically feasible, and
more research and technological development will be needed.

22

Chapter: 2

Literature review:
The reports of about 130 scientists who published their results between 1980 and
2008. As the fossil fuels are depleting day by day, there is a need to find out an
alternative fuel to fulfill the energy demand of the world (S.A.basha, at el 2009).
Biodiesel is one of the best available sources to fulfill the energy demand of the
world. More than 350 oil-bearing crops identified, among which some only
considered as potential alternative fuels for diesel engines. The scientists and
researchers conducted tests by using different oils and their blends with diesel. ( K.
Raja Gopal 2009)
A vast majority of the scientists reported that short-term engine tests using
vegetable oils as fuels were very promising but the long-term test results showed
higher carbon built up and lubricating oil contamination results in engine failure.
They concluded that vegetable oils, either chemically altered or blended with
diesel to prevent the engine failure. It was reported that the combustion
characteristics of biodiesel are similar as diesel and blends were found shorter
ignition delay, higher ignition temperature, higher ignition pressure and peak heat
release (S. Jebaraj 2009). The engine power output was found to be equivalent to
that of diesel fuel. In addition, it observed that the base catalysts are more effective
than acid catalysts and enzymes.
Biodiesel has become more attractive recently because of its environmental
benefits and the fact that it is made from renewable resources (Fangrui Ma 1999).
23

The cost of biodiesel, however, is the main hurdle to commercialization of the

product. The used cooking oils (Al-Zuhair S, 2005) are used as raw material,
adaption of continuous transesterification process and recovery of high quality
glycerol from biodiesel by-product (glycerol) are primary options to be considered
to lower the cost of biodiesel (Fangrui Ma 1999). There are four primary ways to
make biodiesel, direct use and blending, microemulsions, thermal cracking
(pyrolysis) and transesterification(Fangrui Ma, Milford A Hanna, 1999). The most
commonly used method is transesterification of vegetable oils and animal fats. The
transesterification reaction is affected by molar ratio of glycerides to alcohol,
catalysts, reaction temperature, reaction time and free fatty acids and water content
of oils or fats (Patil and Deng, 2009). The mechanism and kinetics of the
transesterification show how the reaction occurs and progresses.
In 1895, Rudolf Diesel developed a new engine with the intention that it could use
a variety of fuels, including vegetable oil. When he showcased it to the public at
the 1900 Paris Worlds Fair, he had the engine run on peanut oil. As the diesel
engine became more widely adopted in subsequent years, however, petroleumbased diesel fuel proved to be less expensive and became the fuel of choice.
Biodiesel is made up of fourteen different types of fatty acids, which are
transformed into fatty acid methyl esters (FAME) by transesterification. Different
fractions of each type of FAME present in various feedstocks influence some
properties of fuels. Fats and oils are primarily water-insoluble, hydrophobic
substances in the plant and animal kingdom that are made up of one mole of
glycerol and three moles of fatty acids and are commonly referred to as
triglycerides (Sonntag, 1979a). Fatty acids vary in carbon chain length and in the
number of unsaturated bonds (double bonds). The fatty acids found in vegetable
oils are fatty acid compositions of common oil sources. Some natural glycerides
24

contain higher levels of unsaturated fatty acids. They are liquids at room
temperature. Their direct uses as biodiesel fuel is precluded by high viscosities.
Fats, however, contain more saturated fatty acids. They are solid at room
temperature and cannot be used as fuel in a diesel engine in their original form.
Because of the problems, such as carbon deposits in the engine, engine durability
and lubricating oil contamination, associated with the use of oils and fats as diesel
fuels, they must be derivatized to be compatible with existing engines. Four
primary production methodologies for producing biodiesel have been studied
extensively. This paper reviews the technologies starting with the direct use or
blending of oils, continuing with microemulsion and pyrolysis and nishing with an
emphasis on the current process of choice, transesterication. The rst International
Conference on Plant and Vegetable Oils as fuels was held in Fargo, North Dakota
in August 1982. The primary concerns discussed were the cost of the fuel, the
eects of vegetable oil fuels on engine performance and durability and fuel
preparation, specications and additives. Oil production, oilseed processing and
extraction also were considered in this meeting (ASAE, 1982). A diesel eet was
powered with ltered, used frying oil (Anon, 1982). Used cooking oil and a blend of
95% used cooking oil and 5% diesel fuel were used. Blending or preheating was
used as needed to compensate for cooler ambient temperatures. There were no
coking and carbon build-up problems. Canola oil is much more viscous than the
other more commonly tested vegetable oils and, as with all uids, the viscosity is
temperature-dependent. At 10C the viscosity of canola oil was 100 cSt; a 75/25
blend of canola oil and diesel fuel was 40 cSt; a 50/50 blend was 19 cSt; and the
viscosity of diesel fuel was 4 cSt (Strayer et al., 1983). The ow rate of canola was
lower than diesel at the same pressure and it dropped to almost zero at 4C.
Viscosity can be lowered by blending with pure ethanol. At 37C, the viscosity of
canola oil and 10% ethanol was 21.15 cSt, while that of straight canola oil was
25

37.82 cSt. Transesterication (also called alcoholysis) is the reaction of a fat or oil
with an alcohol to form esters and glycerol. Among the alcohols that can be used in
the transesterification process are methanol, ethanol, propanol, butanol and amyl
alcohol. Methanol and ethanol are used most frequently, especially methanol
because of its low cost and its physical and chemical advantages (polar and
shortest chain alcohol). The reaction can be catalyzed by alkalis, acids, or enzymes.
The alkalis include NaOH, KOH, carbonates and corresponding sodium and
potassium alkoxides such as sodium methoxide, sodium ethoxide, sodium
propoxide and sodium butoxide. Sulfuric acid, sulfonic acids and hydrochloric acid
are usually used as acid catalysts. For an alkali-catalyzed transesterification, the
glycerides and alcohol must be substantially anhydrous (Wright et al., 1944)
because water makes the reaction partially change to saponification, which
produces soap. Low free fatty acid content in triglycerides is required for alkalicatalyzed transesterification. If more water and free fatty acids are in the
triglycerides, acidcatalyzed transesterification can be used (Keim, 1945). The
triglycerides can be purifed by saponifcation (known as alkali treating) and then
transesterifed using an alkali catalyst.

Chapter: 3
26

Materials and methods:

Materials:
Animal fat, potassium hydroxide (80%) pure, methanol, Erlenmeyer
flasks were used as laboratory scale reactors for the experimental studies in this
work. Graduated cylinders were also used for measuring liquids. All glassware in
the lab was washed with Alconox and rinsed with acetone prior to use to avoid
contamination. A hot plate with magnetic stirrer arrangement was used for all
heating and mixing needs.

Methodology:
In the method of biodiesel preparation five steps are involved:
1 Pretreatment
2 Trans-esterification Reaction
3 Separation of Biodiesel
4 Purification of Biodiesel
5 Analysis of Biodiesel

Pretreatment:
The first step to producing fat oil is the pretreatment of oil.
Water content and acidity must be tested because both could affect the production
27

of biodiesel. Water can react with free fatty acids to form soap if left in oil so
before any experimentation is done, the oil must be pretreated to remove water. For
this purpose fat is heated to 120oC. A recovery flask was connected to the
condenser and used to recover water. The weight of the oil was recorded before
and after processing in order to determine approximate percentage of water
contained in fresh fat oil. KOH was used for titration because acid values are
measured in amount of KOH and KOH was already acquired for the alkaline
catalyst (Patil & Deng , 2009). To titrate the oil, a base solution was made by
dissolving KOH in distilled water. Methanol must be added so that the oil and base
solution will mix but it has a slight acidity and must be neutralized first. Fat oil is
then added to methanol solution.

Transesterification:
The transesterification reaction was in 500 mL samples
of fat oil that had been pretreated to remove water. Methanol 100 ml and KOH 3.8
g were prepared by measuring the amounts of methanol and catalyst for a reaction.
They were then mixed until they were a homogenous solution. Transesterification
by an alkaline catalyst is a common procedure for the production of biodiesel. For
alkaline catalyzed transesterification, research shows that methanol and KOH are
the best additives to use based on cost and availability. Using known methods for
producing biodiesel from edible and non-edible oils a base procedure of mixing,
amounts of additives and reaction time was decided. With the laboratory
equipment available and known procedures, four reaction vessels of 50 mL
Erlenmeyer flasks were used. The purpose of this project was to determine the
optimal parameters for this experiment.

28

Development of Process Parameters:

The variation of process
parameters was set for the second transesterification step. The experiments had
varying the parameters of the reaction to find the optimal production of biodiesel.
Previous research on transesterification and J. curcas oil was used to outline three
steps: making catalyst mixture, reaction of oil, and separation of products. 25 mL
fresh oil was used for each sample. The parameters to be varied were reaction time,
methanol to oil ratio, and catalyst-to-oil ratio. These parameters are the most
expensive parts of the transesterification reaction and the simplest to control given
the lab set up. Other research has been done to vary temperature of the reaction but
as stated, the hotplate does not control temperature well. For all reactions, the
temperature was set on minimum and stayed around 70C. The first parameter
tested was reaction time, all other variables were kept constant for eight samples
for parameters in this reaction set. The variation in reaction time was for 30, 60,
90, and 120 mins. Methanol variation amounts were 5, 10, 15, and 20 mL, for 25
mL of fresh oil and 0.45 g of KOH for a reaction time of 1 hr.

Separation of Biodiesel:
Manual separation by using a pipette was decided
for separating the glycerin and biodiesel layers. The small separation size made a
separatory funnel not necessary and not as accurate as using a pipette.

Purification of Biodiesel:
The biodiesel layer has traces of excess
methanol and catalyst. There are a few different methods for purification of

29

biodiesel, including washing, heating, and the addition of catalyst. Methanol can be
removed by evaporation and catalyst can be removed by washing.

Methanol Distillation:
The biodiesel product was first distilled to remove
the un-reacted methanol by heating. The biodiesel sample was moved from an
Erlenmeyer flask to a round bottom flask that was connected to a simple
distillation set up with a Liebig condenser (Chromic, 2002). Methanol will
evaporate at 65oC and water will evaporate at 100 oC, so the dram vial was held in a
hot water bath of over 100oC for 20 minutes to evaporate excess methanol and
potential water in the mixture.

Washing Procedure:
Water is a solvent that will dissolve catalyst and
methanol and separate from the oil after being mixed, so it was used as a washing
element. The biodiesel layer was washed three times. This procedure is a common
one used by mixing and then separating the water.

Drying:
The final step was to ensure that the biodiesel was dry. All that is needed
for this is heating to remove water left from the washing.

Analysis of Biodiesel:
To test for the optimal parameters for producing
biodiesel a way of analyzing the samples was created. The weight percent of
biodiesel compared to the whole sample after transesterification was compared.
30

After transesterification, there are two products: the biodiesel and glycerin. The
sample with the highest percent of biodiesel layer would then be the most efficient.

Chapter: 4

Results and discussions:

The first set of batches produced a number of
different results. In some of the experiments two distinct layers formed, the top
31

layer (translucent yellow) and the bottom layer (translucent brown). From the
literature, it was understood that the top layer was a mixture of the fatty acid
methyl esters and bottom layer was glycerin. The biodiesel layer varied in its
lucidity, appearing to be very cloudy in some of the batches and clear in others.
Some of the batches resulted in failure because there was no separation at all; in
later experiments, additional methanol was added to the reaction, because it was
believed that sufficient methanol required for esterification might have been lost
via evaporation to poorly sealed environment. To check the superficial quality of
the biodiesel, a visual analysis was done on the product after the initial
transesterification reaction to see if two distinct layers have formed.

32

The success of the transesterification reaction was determined by the conversion of

the initial reactants to the two different layers that formed as well as the lucidity of
the biodiesel. the layers separate, a significant amount initially separates at 30
minutes of reaction time to approximately 50% and again at 60 minutes to
approximately 70%.

Possible sources of error:

Throughout the laboratory experimentation,
several challenges arose that could have decreased the ability of triglycerides to
convert to fatty acid methyl esters. Methanol and the catalyst (potassium
hydroxide) play critical roles in transesterification; there were challenges with both
reactants. Methanol readily evaporates if left open to the atmosphere. Moreover,
the strength of the stock potassium hydroxide could not be verified.

Loss of methanol:
As the reaction was heated to temperature, the pressure in
the reactor vessel built up until the stopcock was pushed out of the flask. Stopcocks
were replaced immediately and refastened with duct tape. However, there was a
definitely loss of methanol. Sufficient methanol is paramount for the maximum
conversion to fatty acid methyl esters. Additionally, there may have been loss of
methanol to the atmosphere when pouring and mixing methanol with catalyst and
oil. Minimal time was spent with reactants sitting stagnant in open containers to
avoid this loss.

33

Integrity of catalyst:
The potassium hydroxide catalyst was obtained from
the chemistry stockroom in Goddard Hall. The container of catalyst was previously
used by others as well as sitting on the self for an unknown amount of time. The
purity of catalyst was originally 85% potassium hydroxide; yet, its strength at the
time of use could not be verified. Over time, there was the possibility of the
potassium hydroxide absorbing water from the atmosphere affecting its strength.
Water interferes with transesterification and unwanted emulsions can occur. There
was no process done to remove any water from the potassium hydroxide, because
the catalyst would melt when heated to 100oC.

Limitations Found During Experiments:

The experiments required
a set temperature of 60oC. The minimum setting on the hotplate ran at a
temperature of approximately 65C. For all experimentation, the hotplate was set
on the minimum setting but varied between 65oC and 70oC. In the literature, it was
stated that poor regulation of temperatures might result in the creation of additional
free fatty acids.

Fuel type

Cooling water Exhaust

Total

Filter

smoke

temperature

temperature

hydrocarbons

number

(mean

ppm

(mean value)

value)
Diesel

75

273

6.50

5.60

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Biodiesel

77

269

4.57

4.63

Table shows the values of the total hydrocarbons of , diesel and biodiesel, it can be noticed
that the biodiesel has the lowest value of hydrocarbons and this was expected due to
oxygenated nature of biodiesel where more oxygen is available for burning and reducing
hydrocarbon emissions in the exhaust.

SO2

NO

NO2

NOx

CO

O2 Vol.- CO2

ppm

ppm

ppm

ppm

ppm

Vol.-%

(Mean

(Mean

(Mean

(Mean

(Mean

(Mean

(Mean

value)

value)

value)

value)

value

Value)

Value)

Diesel

18,850

541

33,500

574,50

88,650

10,675

7,445

biodiesel

18,225

480

27,980

507,98

281,85

10,800

7,505

Fuel type

Table shows the mean values of the resulted emissions for every fuel. For SO2, O2 and CO2 it can
be noticed that the values for every fuel are almost similar. For NOx, it can be noticed that the
rapeseed oil has the lowest value of NOx, while diesel has the highest value. The higher NOx
emissions may be due to the higher cetane rating and oxygen content of the fuel, so that
atmospheric nitrogen is oxidized more readily. For CO, it is noticed that biodiesel has more value of
CO than diesel and higher CO emission means that the combustion was not done completely.

35

Figure: B100 emissions compared to petroleum diesel emissions by percentage

Conclusion:
During this project, we aimed to provide recommendations to the
scientific community on the parameters required for efficient production of fat oil
biodiesel. The task was to uncover specific methods and scientific procedures to
produce biodiesel from fat oil as well as the feasibility of implementation for largescale production. Experiments were conducted in a laboratory to determine ideal
parameters to be considered in the processing of biodiesel derived from animal fat
oil. The highest conversion of 87% was obtained before washing. Due to rises
prices in petroleum, it is advised that smaller countries start to decrease their
dependence on petroleum oil by converting to biodiesel. By increasing efforts to
find new sustainable methods of development, such as considering the production
of biodiesel from animal fat oil, the government of Pakistan can diminish its
dependency on petroleum products. The change to biodiesel will also increase the
36

self-sufficiency of the economy of Pakistan by subtracting foreign dependency

transportation fuel.

Recommendations:
An increased amount of information on the animal fat oil was desired for this
project. In future studies it is recommended to obtain an information sheet from the
company tabulating how the company had processed the oil and the current state.
In addition, the catalyst used in this project was possibly compromised due to
contact with water vapor in the air. As a result, it is recommended to purchase fresh
catalyst when completing a transesterification reaction.

37

References:
Anderson, D., & Derek Masterson, B. M. (24-28 August 2003). Industrial
Biodiesel Plant Design and Engineering

Barta, P. (2007, August 24). global race for biofuels. Wall Street Journal ,
A1.

Energy Information Administration. (2008, December 8). World Petroleum

Data. Retrieved

38

 Ma, F., & Hanna, M. (1999). Biodiesel production: a review. Bioresource

Technology , 1-15.

Jaffery, R. S. (2009). When oil grows on trees.

Meher, L. C., Sagar, D. V., & Naik, a. S. (2004). Technical aspects of

biodiesel production by transesterification - a review. Renewable &
Sustainable Energy Reviews , 248-268.

National Biodiesel Board. (2009). Benefts of Biodiesel.

Patil, P. D., & Deng, S. (2009). Optimization of biodiesel production from

edible and non-edible vegetable oils. Fuel , 13021306.

Pramanik, K. (2003). Properties and use of Jatropha curcas oil and diesel
fuel blends in
compression ignition engine. Renewable Energy, 28, 239-248.

Schober, S., Seidl, I., & Mittelbach, M. (2006). Ester Content evaluation in
biodiesel from animal fats and lauric oils. Scientific Technology , Volume
108 Page 309-314.
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 Sheehan, J., Camobreco, V., Duffield, J., Graboski, M., & Shapouri, H.
(1998). An Overview of Biodiesel and Petroleum Diesel Life Cycles.
Golden, Colorado.

Tiwari, A., Akhilesh, K., & Raheman, H. (2007). Biodiesel production with
high free fatty acids: An optimized process. Biomass & Bioenergy,569-575.
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