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The Manufacture of Biodiesel from the used vegetable oil

By

Nada E.M. ElSolh

A thesis submitted to the Faculty of Engineering at Kassel and Cairo Universities for the
degree of Master of Science

Departments of Electrical and Mechanical Engineering


Degree Program: Renewable Energy and Energy Efficiency for the Middle East North Africa
Region- Cooperation between Kassel and Cairo Universities

Under the supervision of

Prof. Jrgen Schmid Prof. Fatma Ashour


Electrical Engineering Department Chemical Engineering Dpartment
Faculty of Engineering Faculty of Engineering
Kassel University Cairo University

Kassel, 28 Feb. 2011

i
The Manufacture of Biodiesel from the used vegetable oil

By

Nada E.M. ElSolh

A thesis submitted to the Faculty of Engineering at Kassel and Cairo Universities for the
Degree of Master of Science

Departments of Electrical and Mechanical Engineering


Degree Program: Renewable Energy and Energy Efficiency for the Middle East North Africa
Region- Cooperation between Kassel and Cairo Universities

1st examiner: Prof.-Dr. Fatma Ashour


2nd examiner: Prof.-Dr. Jrgen Schmid
3rd examiner: Prof. Hendawi Salem

Kassel, 28 Feb. 2011

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Abstract
The increasing awareness of the depletion of fossil fuel resources and the environmental
benefits of biodiesel fuel has made it more attractive in recent times. Its primary advantages
deal with it being one of the most renewable fuels currently available and it is also non-toxic
and biodegradable. It can also be used directly in most diesel engines without requiring
extensive engine modifications. However, the cost of biodiesel is the major hurdle to its
commercialization in comparison to petroleum-based diesel fuel. The high cost is primarily
due to the raw material, mostly neat vegetable oil. Used cooking oil is one of the economical
sources for biodiesel production. However, the products formed during frying, can affect the
transesterification reaction and the biodiesel properties.

The production of biodiesel from waste vegetable oil offers a triple-facet solution: economic,
environmental and waste management. The new process technologies developed during the
last years 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. From an economic point of view; the production of biodiesel is very feedstock
sensitive. Many previous reports estimated the cost of biodiesel production based on
assumptions, made by their authors, regarding production volume, feedstock and chemical
technology. From a waste management standpoint, producing biodiesel from used frying oil
is environmentally beneficial, since it provides a cleaner way for disposing these products;
meanwhile, it can yield valuable cuts in CO2 as well as significant tail-pipe pollution gains.

Any fatty acid source may be used to prepare biodiesel. Thus, any animal or plant lipid
should be a ready substrate for the production of biodiesel. The use of edible vegetable oils
and animal fats for biodiesel production has recently been of great concern because they
compete with food materials - the food versus fuel dispute (Pimentel et al., 2009; Srinivasan,
2009). There are concerns that biodiesel feedstock may compete with food supply in the
long-term. Hence, the recent focus is the use of non-edible plant oil source and waste
products of edible oil industry as the feedstock for biodiesel production meeting the
international standards. Quality standards are prerequisites for the commercial use of any
fuel product.

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This Master Thesis is about the manufacturing of biodiesel from the used vegetable oil. This
study aims to define the requirements for biodiesel production by the esterification process,
testing its quality by determining some parameters such as density, kinematics viscosity,
high heating value, cetane number, flash point, cloud pint and pour point and comparing it to
Diesel fuel, testing the engine performance, testing the emissions of biodiesel and comparing
it to diesel emission, and the strategic issues to be considered to assess its feasibility, or
likelihood of succeeding. This analysis is useful either when starting a new business, or
identifying new opportunities for an existing business. Therefore, it will be extremely helpful
for taking rational decisions about the development of a biodiesel production plant.

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Acknowledgements

In the first place I want to thank God for giving me the strength to finish this Master Thesis.
Three semesters passed and I had some good days and other hard ones, and whenever I
was down, God gave me the hope and strength to continue this Master Thesis successfully.
Words cannot express my thanks to my wonderful family for their non stopping support
during the period of my study and for believing in me and in my work.
Special thanks go to Prof. Dahlhaus, the coordinator of the REMENA Master Program,
for being understandable and allowing me to do my defense in Kassel, that was very kind
and generous of him, its known about him that hes very supportive to students.
I would like to thank my supervisors Prof. Fatma Ashour from Cairo University and Prof.
Jrgen Schmid from Kassel University for their supervision, advice and guidance from the
very early stage of my Master thesis as well as providing me great experiences through out
this work. And of course many thanks to all my professors in Cairo and Kassel Universities
for their non stopping support
I also want to thank Prof. Schmid for arranging the practical work of my Master thesis in
the University of Applied Science (HAW) in Amberg, in Germany and giving me this
opportunity to work in the Mechanical Engineering department that will help me out in many
ways in my future education.
Special thanks to Stefanie Reil, Prof. Schmids PhD student, for helping from the first
day I arrived to Amberg, from putting the basics for my Master Thesis until the day of
submitting it, also I will not forget her wonderful team, Sabine Feldmeier for letting me work
with her CHNS device and Suzanna Ritz for helping me in arranging my thesis, and of
course many thanks to the other people who helped me in my thesis. I just cant remember
all the names.
Many many thanks to Raphael Lechner, a PhD student, for helping me in performing all
the experiments needed for my thesis in the lab, also many thanks to him for giving me much
from his time whenever I have questions concerning my thesis and for reviewing all of my
thesis.
This paper would not have been possible without the support of the DAAD, the German
Academic Exchange Service, special thanks to Mr. Heinemann and Mrs. Anke Stahl for
bearing with us and answering all of our questions patiently. Also many thanks to everyone
who made the REMENA Master Program a successful one.
Finally, I would like to thank my colleagues in the REMENA Master Program for their
support and I would like to say that it was a nice opportunity for me to meet these nice
people.

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Contentsts
1 Motivation...........................................................................................1
2 Why Biodiesel?!......................................................................................3

3 Introduction...............................................................................................6

4 An Overview..............................................................................................9
4.1 Bio Energy..................................................................................................9
4.2 Biomass energy........................................................................................10
4.3 The Carbon Cycle.....................................................................................11
4.3.1 Movement of Carbon through the atmosphere..12
4.3.2 The carbon cycle and biofuels..13

5 Biofuels....................................................................................................14
5.1 What are Biofuels.....................................................................................14
5.2 Biofuel generation.....................................................................................19

6 Biodiesel Production..............................................................................22
6.1 What is Biodiesel......................................................................................22
6.2 History of Biodiesel...................................................................................23
6.3 The advantages of using vegetable oils as fuels:....................................24
6.4 Characteristics of oils or fats affecting their suitability for use as
biodiesel....25
6.5 Review of biodiesel feedstock.27
6.6 Vegetable oils as diesel fuels...................................................................28
6.7 Transesterification of vegetable oil:..........................................................29
6.8 Biodiesel production from used cooking oil..............................................31

7 Biodiesel as an engine fuel...................................................................34


7.1 Overview..34
7.2 Technical characteristics of biodiesel as a transportation fuel.................34
7.3 Engine performance characteristics of biodiesel......................................37
7.4 Engine emissions from biodiesel..............................................................38
7.5 Environmental Benefits of Biodiesel Fuel.................................................39
7.6 Environmental benefits in comparison to petroleum based fuels include 41
7.7 Some challenges for using biodiesel fuel.................................................42

8 Biodiesel Economy................................................................................43
8.1 Overview.43

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8.2 Biodiesel production economic balance....45
8.2.1 Feedstock prices.....45
8.2.2 Biodiesel production costs.45
8.2.3 Taxation of energy products..47

9 Experimental Part.....................................................................48
9.1 The production of Biodiesel from rapeseed oil experiment................49
9.1.1 Pressing of Rapeseed oil....49
9.1.2 The determination of free fatty acid...50
9.1.3 Transestrification: .51
9.1.4 Thin layer chromatography.....51
9.2 Fuel analytics..53
9.2.1 Introduction. ..53
9.2.2 Technical Details and Standards of diesel and biodiesel...53
9.2.3 Kinematic Viscosity measurement: The Ubbelohde viscometer...55
9.2.4 Density Measurement: Hydrometer and Pycnometer.57
9.2.4.1 Hydrometer......................57
9.2.4.2 Pycnometer.......58
9.2.5 Heating value Measurement: the Bomb Calorimeter.59
9.2.6 Measuring the oxidation stability....61
9.3 CHNS Elemental Analyzer (EA)..65
9.4 Experimental and Standard results of density, viscosity, heating value and
oxidation stability for rapeseed oil, two types of biodiesel and diesel
fuel...69
9.5 Discussion of results..75
9.6 The Emission testing experiment for rapeseed oil, low sulfur diesel fuel and
biodiesel (from gas station)..79
9.6.1 Equipment used..79
9.6.2 Procedure of the emission testing experiment........83
9.6.3 Tabulated Results of the emission testing experiment.........85
9.6.4 Graphical Results: Comparing the emissions of rapeseed oil, diesel and
biodiesel...88
9.6.5 Discussion of Results: Comparing between the results of the emission
testing experiment of diesel and biodiesel fuels....92

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10 Summary......94
11 Conclusion and Recommendations..97

Bibliography...100
List of Figures..................................................................................................103
List of tables.....................................................................................................105
Appendix A......107
Appendix B..123

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Abbreviations

Symbol Meaning

ASTM American Society for Testing and Materials


Bxx The level of blending biodiesel with petroleum diesel
B2 2% biodiesel and 98% petroleum diesel
B5 5% biodiesel and 95% petroleum diesel
B20 20%biodiesel and 80% petroleum diesel
B100 Pure biodiesel
BD Bio Diesel
Bsfc brake-specific fuel consumption
Btu/lb British thermal unit per pound
CH4 Methane
CI Compression Ignition
CO Carbon monoxide
CO2 Carbon dioxide
D2 Diesel fuel
Derv Diesel engine road vehicle
DI Direct injection
DME Dimethyl ether (CH3OCH3 )
DMF Dimethylfuran ((CH3)2C4H2O)
EEA European Environment Agency
EPA Environmental Protection Agency
EN14214 European standards for biodiesel
EU European Union
FAE Fatty acid esters
FAME Fatty acid methyl ester

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FFAs Free fatty acids
FID Flame ionization detector
H2 Hydrogen
IEA International Energy Agency
KW Kilo watt
LHV Lower heating value
LPG Liquefied petroleum gas
CNG Compressed natural gas
MTBE Methyl tertiary-butyl ether
NDIR Non dispersive infrared sensor
NO Nitric oxide
NOx Nitrogen Oxide
N2O Nitrous oxide
O2 Oxygen
OECD Organization for Economic Co-operation and Development
POME Palm oil methyl esters
PM Particular matter
Pr Rapeseed price
REN21 Renewable Energy Policy Network for the 21st Century
R&D Research & Development
Rpm Revolutions per minute
SME Soya bean oil methyl ester
SO2 Sulfur dioxide
THC Total Hydrocarbon Analyzer
UV Ultra Violet
VIS Visual light spectrometer

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Chapter 1
Motivation

Several billions of gallons of waste vegetable oil are 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 waste
vegetable oil (WVO) 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.(1) 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.(2)
Biodiesel is a product of great interest for its environmental characteristics. It is
biodegradable and its 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. (3)

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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.

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Chapter 2
Why Biodiesel?!

It's Economical
Biodiesel can be produced by individuals on a small scale relatively inexpensively when
compared to Petrodiesel. 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 tallows. This means that it can be made from things
that can be regrown, 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.

3
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 petrodiesel, 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 Petrodiesel, 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.

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

4
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. (4)

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Chapter 3
Introduction

During the last century, the consumption of energy has increased a lot due to the change in
the life style and the significant growth of population. This increase of energy demand has
been supplied by the use of fossil resources, which caused the crises of the fossil fuel
depletion, the increase in its price and the serious environmental impacts as global warming,
acidification, deforestation, ozone depletion, Eutrophication and photochemical smog. As
fossil fuels are limited sources of energy, this increasing demand for energy has led to a
search for alternative sources of energy that would be economically efficient, socially
equitable, and environmentally sound. Two of the main contributors of this increase of energy
demand have been the transportation and the basic industry sectors, being the largest
energy consumers. The transport sector is a major consumer of petroleum fuels such as
diesel, gasoline, liquefied petroleum gas(LPG) and compressed natural gas (CNG)
(Demirbas, 2006). Demand for transport fuels has risen significantly during the past few
decades. (IEA, 2008). The demand for transport fuel has been increasing and expectations
are that this trend will stay unchanged for the coming decades. In fact, with a worldwide
increasing number of vehicles and a rising demand of emerging economies, demand will
probably rise even harder. Transport fuel demand is traditionally satisfied by fossil fuel
demand. However, resources of these fuels are running out, prices of fossil fuels are
expected to rise and the combustion of fossil fuels has detrimental effects on the climate.
The expected scarcity of petroleum supplies and the negative environmental consequences
of fossil fuels have spurred the search for renewable transportation biofuels (Hill, Nelson,
Tilman, Polasky& Tiffany, 2006).

Biofuels appear to be a solution to substitute fossil fuels because, resources for it will not run
out (as fresh supplies can be re grown), they are becoming cost wise competitive with
fossil fuels, they appear to be more environmental friendly and they are rather accessible to
distribute and use as applicable infrastructure and technologies exists and are readily avail-
able. Forecasts are that transport on a global scale will increase demand for conventional
fuels with up to a maximum annual growth of 1.3% up to 2030. This would result in a daily
demand of around 18.4 billion litres (up from around 13.4 billion litres per day in 2005) (The
Royal Society, 2008).

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Conventional fuel, however, are predicted to become scarcely (The Royal Society, 2008) as
petroleum reserves are limited (Demirbas, 2006), for this reason these fuels are set to be-
come increasingly costly in the coming decades. Renewable fuels, made from biomass,
have enormous potential and can meet many times the present world energy demand (IEA,
2008). Biomass can be used for energy in several ways; one of these is the conversion into
liquid or gaseous fuels such as ethanol and bio-diesel for use in mobile source combustion
(Marshall, 2007). In fact global demand for liquid biofuels more than tripled between 2000
and 2007. And future targets and investment plans suggest strong growth will continue in
near future (IEA, 2008). The potential of biofuels appear to be enormous from an
economical, political and environmental perspective. Speaking in terms of advantages, much
heard is that they, as an alternative fuel, could solve several issues as the increasing energy
prices worldwide, the increasing need of energy imports, the negative environmental
consequences of fossil fuel combustion and the security of national energy supply for many
countries.

Biofuels appear to be more environment friendly in comparison to fossil fuels considering the
emission of greenhouse gasses when consumed. Examples of those gasses are carbon
dioxide (CO2), methane (CH4) and nitrous oxide (N2O). Those gasses pose risks as they
tend to warm the earths surface (Randelli, 2007). The energy content of biofuels differs from
conventional fuels. Total energy output per liter of biofuel is determined by the feedstock
used, region where the feedstock is grown and production techniques applied. Randelli
(2007) provides, for example, energy contents of biodiesel and bio ethanol. According to
Randelli, Biodiesel has an energy ratio compared to diesel of about 1.1 to 1, which means
that its energy contents are 87% of those of diesel. Bio ethanol has an energy ratio
compared to gasoline of 1.42 (67% of gasoline).The amount that is similar to the amount of
energy content of one litres gasoline is referred to as gasoline equivalent.

Biodiesel production is a very modern and technological area for researchers as an


alternative fuel for diesel engines because of the increase in the petroleum price, its
renewability and the environmental advantages. Biodiesel can be produced from renewable
sources such as vegetable oil, animal fat and used cooking oil. Currently, the cost of
biodiesel is high as compared to conventional diesel oil because most of the biodiesel is
produced from pure vegetable oil. Extensive use of edible oils may cause other significant
problems such as starvation in developing countries.

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However, the cost of biodiesel can be reduced by using low cost feedstock such as animal
fat and used cooking oil. It is estimated that the cost of biodiesel is approximately 1.5 times
higher than that of diesel fuel due to the use of food grade oil for biodiesel production.

The term waste vegetable oil (WVO) refers to vegetable oil which has been used in food
production and which is no longer viable for its intended use. Waste vegetable oil arises from
many different sources, including domestic, commercial and industrial. Waste vegetable oil is
a potentially problematic waste stream which requires to be properly managed. The disposal
of waste vegetable oil can be problematic when disposed, incorrectly, down kitchen sinks,
where it can quickly cause blockages of sewer pipes when the oil solidifies. Properties of
degraded used frying oil after it gets into sewage system are conductive to corrosion of metal
and concrete elements. It also affects installations in waste water treatment plants. Thus, it
adds to the cost of treating effluent or pollutes waterways.

The use of used cooking oil as feedstock reduces biodiesel production cost by about 60
70% because the feedstock cost constitutes approximately 7095% 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 [Kemp, 2006; Radich, 2006; Anh et al., 2008]. 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. (5)

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Chapter 4
An Overview of Bioenergy, Biomass and the Carbon
Cycle

4.1 Bio Energy


Bioenergy is one of the so-called renewable energies. Its is the energy that is contained in
living or recently living biological organisms. (6)

Bio-energy is obtained from organic matter, either directly from plants or indirectly from
industrial, commercial, domestic or agricultural products and waste. The use of bioenergy is
generally classed as a carbon-neutral process because the carbon dioxide released during
the generation of energy is balanced by that absorbed by plants during their growth. (7)

The term bio-energy really covers two areas: bio-fuel which is the transformation of plant
materials into liquid fuel, and bio-mass, where solid plant materials are burnt in a power plant
and this process creates energy, which can then be for immediate use or stored. (8)

Advanced and efficient conversion technologies now allow the extraction of biofuels besides
the traditional use of bioenergy; Modern bioenergy comprises biofuels for transport, and
processed biomass for heat and electricity production.

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4.2 Biomass Energy
Biomass is the name given to all the earths living matter. It is a general term for material
derived from growing plants or from animal manure (which is effectively a processed form of
plant material). It is a rather simple term for all organic material that stems from plants
(including algae), trees and crops. Biomass energy is derived from plant and animal material,
such as wood from natural forests, waste from agricultural and forestry processes and
industrial, human or animal wastes.

Plants absorb solar energy, using it to drive the process of photosynthesis, which enables
them to live. The energy in biomass from plant matter originally comes from solar energy
through the process known as photosynthesis. The energy, which is stored in plants and
animals (that eat plants or other animals), or in the wastes that they produce, is called
biomass energy. This energy can be recovered by burning biomass as a fuel. During
combustion, biomass releases heat and carbon dioxide that was absorbed while the plant
was growing. Essentially, the use of biomass is the reversal of photosynthesis. Therefore,
the energy obtained from biomass is a form of renewable energy and, in principle,
utilizing this energy does not add carbon dioxide to the environment, in contrast to fossil
fuels. Biomass can be used directly (e.g. burning wood for heating and cooking) or
indirectly by converting it into a liquid or gaseous fuel (e.g. alcohol from sugar crops or
biogas from animal waste).

Biomass is used in a similar way to fossil fuels, by burning it at a constant rate in a boiler
furnace to heat water and produce steam. Liquid biofuels, such as wheat, sugar, root,
rapeseed and sunflower oil, are currently being used in some member states of the
European Union.

Biomass provides a clean, renewable energy source that could dramatically improve our
environment, economy and energy security. 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. (9)

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4.3 The Carbon Cycle
Carbon is an element that is part of oceans, air, rocks, soil and all living things, Carbon
doesnt stay in one place but it is always on the move.

Carbon moves naturally to and from various parts of the Earth. This is called the carbon
cycle. Today, however, scientists have found that more carbon is moving into the
atmosphere from other parts of the Earth when fossil fuels, like coal and oil, are burned.

Carbon dioxide is a greenhouse gas and traps heat in the atmosphere. Without it and other
greenhouse gases, Earth would be a frozen world. But humans have burned so much fuel
that there is about 30% more carbon dioxide in the air today than there was about 150 years
ago. The atmosphere has not held this much carbon for at least 420,000 years according to
data from ice cores. More greenhouse gases such as carbon dioxide in our atmosphere are
causing our planet to become warmer. (10)

Figure 4.3.1: The Carbon Cycle; the movement of Carbon dioxide through the atmosphere.

11
( http://www.windows2universe.org)

11
4.3.1 Movement of Carbon through the atmosphere

- Carbon moves from the atmosphere to plants.

In the atmosphere, carbon is attached to oxygen in a gas called carbon dioxide (CO2). With
the help of the Sun, through the process of photosynthesis, carbon dioxide is pulled from the
air to make plant food from carbon.

- Carbon moves from plants to animals.

Through food chains, the carbon that is in plants moves to the animals that eat them.
Animals that eat other animals get the carbon from their food too.

-Carbon moves from plants and animals to the ground.

When plants and animals die, their bodies, wood and leaves decay bringing the carbon into
the ground. Some becomes buried miles underground and will become fossil fuels in millions
and millions of years.

-Carbon moves from living things to the atmosphere.

Each time you exhale, you are releasing carbon dioxide gas (CO2) into the atmosphere.
Animals and plants get rid of carbon dioxide gas through a process called respiration.

-Carbon moves from fossil fuels to the atmosphere when fuels are burned.

When humans burn fossil fuels to power factories, power plants, cars and trucks, most of the
carbon quickly enters the atmosphere as carbon dioxide gas. Each year, five and a half
billion tons of carbon is released by burning fossil fuels. Thats the weight of 100 million adult
African elephants! Of the huge amount of carbon that is released from fuels, 3.3 billion tons
enters the atmosphere and most of the rest becomes dissolved in seawater.

- Carbon moves from the atmosphere to the oceans.

12
The oceans, and other bodies of water, soak up some carbon from the atmosphere.12

4.3.2 The carbon cycle and biofuels

CO2 is part of the Earths 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
biofuels such as bioethanol and biodiesel for transportation, we can help restore the natural
balance of CO2 in the atmosphere. Besides displacing fossil fuels, the feedstocks used to
make biofuels 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 biofuel and burned
in automobile engines is recaptured when new biomass is grown to produce more biofuels.
(13)

Figure 4.3.2: Biofuels and the carbon cycle

12
( http://www.energyfuturecoalition.org/biofuels)

13
Chapter 5

Biofuels

5.1 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.

Table 5.1: Major benefits of Biofuels


14
( Political, economic and environmental impacts of biofuels: A review Ayhan Demirbas * Sila Science, Trabzon,
Turkey)

14
There are two global liquid transportation biofuels that might replace gasoline and diesel fuel;
these are ethanol and biodiesel, respectively. Transport is one of the main energy consuming
sectors. It is assumed that biodiesel is used as a petroleum diesel replacement and that
ethanol is used as a gasoline replacement. Figure 5.1.1 shows the sources of the main liquid
biofuels for automobiles.

Figure 1.1.1: Sources of main liquid biofuels for automobiles

15
( Biodiesel, a realistic fuel alternative for diesel engines- springer-2008.pdf)

Bioethanol, followed by biodiesel are the most produced types of biofuel. Figure 5.1.2 shows
the worlds top ethanol and biodiesel producers in 2008. The United States (US) and Brazil
are currently the leading ethanol producers and the expectations are that this will at least
until 2018 remain so. The European Union (EU) is the worlds leading producer of biodiesel.

15
Figure 5.1.2: The worlds top ethanol and biodiesel producers in 2008 (REN21, 2009)

Biofuels for transportation primarily driven by government policies, world ethanol production
for transport fuel tripled between 2000 and 2007 from 17 billion to more than 52billion litres,
while biodiesel expanded eleven-fold from less than 1 billion to almost 11 billion litres (Fig.3).
These fuels together provided 1.8% of the worlds transport fuel by energy value (36 Mtoe
out of a total of 2007 Mtoe) (OECD 2008). In Europe there has been a continuing increase in
the use of biofuels in road transport over the past decade from 0.1% in 1997 to 2.6% in 2007
(EEA 2008 a,b).

Figure 5.1.2: Global ethanol and biodiesel production 2000-2008 with projection to 2015

16
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.

Figure 5.1.3: Biodiesel Production Cycle


16
( http://www.window.state.tx.us/specialrpt/energy/renewable/biodiesel.php)

Figure 5.1.4 shows the Biodiesel production Cycle, solar energy and carbon dioxide along
with other inputs are used to grow crops that are in turn harvested and processed. As an
example, soybeans are crushed to produce oil that is the basic material to be turned into
biodiesel. The production process forces the vegetable oil to react with a catalyst to produce
fatty acid esters, the chemical name for biodiesel. The fuel is then used in existing vehicles
which also produce carbon dioxide.

17
Figure 4.1.5: Ethanol Production Cycle
17
( http://www.window.state.tx.us/specialrpt/energy/renewable/ethanol.php)

Figure 5.1.5 shows Ethanol Production Cycle, Ethanol supporters say that its production and
consumption are carbon-neutral. Crops like corn are finely ground and separated into their
component sugars. The sugars are distilled to make ethanol, which can be used as an
alternative fuel, which releases carbon dioxide that is reabsorbed by the original crops.

18
5.2 Biofuel generation
Biofuels for transport are commonly addressed according to their current or future availability
as first, second or third generation biofuels (OECD/ IEA 2008). Second and third generation
biofuels are also called advanced biofuels.

First-generation biofuels are commercially produced using conventional technology. The


basic feedstocks 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
biofuels are bioethanol (currently over 80% of liquid biofuels production by energy content),
followed by biodiesel, vegetable oil, and biogas.

Second-generation biofuels can be produced from a variety of non-food sources. These


include waste biomass, the stalks of wheat, corn stover, wood, and special energy or
biomass crops (e.g. Miscanthus). Second-generation biofuels use biomass to liquid (BtL)
technology, by thermo chemical conversion (mainly to produce biodiesel) or fermentation
(e.g. to produce cellulosic ethanol).Many second-generation biofuels are under development
such as biohydrogen, biomethanol, DMF, Bio-DME, Fischer-Tropsch diesel, biohydrogen
diesel, and mixed alcohols.

Third-generation biofuel: Algae fuel, also called oilgae, is a biofuel from algae and
addressed as a third-generation biofuel (OECD/IEA 2008). Algae are feedstocks 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
feedstocks. Other third -generation biofuels 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 (OECD/IEA 2008), though increased investment could accelerate
their development. The same feedstocks 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 bioethanol.

19
18
Table 5.2: An Overview of the product biofuel, per generation type ( Own elaboration, primarily based on
http://news.mongabay.com)

Current use of biofuels for transport on the global scale is dominated by bioethanol and
biodiesel, whereas the use of other biofuels for transport like biogas and pure plant oil seem
to be restricted to local and regional pilot cases, and second-generation biofuels are still in
the development stage. Commercial investment in advanced (second-generation) biofuel
plants is beginning in Canada, Germany, Finland, Japan, the Netherlands, Sweden, and the
United States (REN21 2008; EEA 2008a,b).

20
Figure 5.2: The Worlds and EUs biofuel consumption

21
Chapter 6

Biodiesel production

6.1 What is Biodiesel


In the most general sense, biodiesel refers to any diesel fuel substitute derived from
renewable biomass. More specifically, biodiesel is dened as an oxygenated, sulfur-free,
biodegradable, non-toxic, and eco-friendly alternative diesel oil. Chemically, it can be
dened 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
transesterification. 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. (19)

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 transesterification are the four techniques applied to solve the problems encountered
with the high fuel viscosity. Transesterification 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 transesterification 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.

22
6.2 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. Diesels 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% peanut oil. Dr. Diesel (Fig. 14)
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. Diesels 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 6.2: Dr. Rudolf Diesel

23
6.2 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 24:1 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.

24
6.3 Characteristics of oils or fats affecting their suitability for use
as biodiesel

Calorific Value, Heat of Combustion Heating Value or Heat of Combustion, is


the 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 content in coals varies in the range 2-30%. However, the
bulk density of most biomass feedstocks is generally low, even after densification
between about 10 and 40% of the bulk density of most fossil fuels. Liquid biofuels 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 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 at
which 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 a 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

25
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.

Cetane Number - Is a relative measure of the interval between the beginning of


injection and auto ignition of the fuel. The higher the cetane number, 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
26
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 sulphur 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.
(20)

6.5 Review of biodiesel feedstocks


In general, biodiesel feedstock can be categorized into three groups: vegetable oils (edible or
non-edible oils), animal fats, and 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
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.

Many advocates suggest that waste vegetable oil is the best source of oil to produce
biodiesel, but since the available supply is drastically less than the amount of petroleum-
based fuel that is burned for transportation and home heating in the world; this local solution
does not scale well. (21)

27
6.6 Vegetable oils as diesel fuels
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 become more attractive recently because of its
environmental benefits and the fact that it is made from renewable resources. 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 diglycerides .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 oildiesel 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.

The most common way of producing biodiesel is the transesterification of vegetable oils. The
methyl ester produced by transesterification of vegetable oil has a high cetane number, low
viscosity and improved heating value compared to those of pure vegetable oil which results

28
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.

6.7 Transesterification of vegetable oil


Transesterification is the process of separating the fatty acids from their glycerol backbone to
form fatty acid esters (FAE) and free glycerol [Meher, et al., 2006; Morrison and Boyd, 2005;
Abhullah, etal., 2007]. Fatty acid esters commonly known as biodiesel can be produced in
batches or continuously by transesterifying triglycerides such as animal fat or vegetable oil
with lower molecular weight alcohols in the presence of a base or an acid catalyst. This
reaction occurs stepwise, with monoglycerides and diglycerides as intermediate products.
The transesterification process of converting vegetable oils to biodiesel is shown in Figure 8.
The "R" groups are the fatty acids, which are usually 12 to 22 carbons in length. The large
vegetable oil molecule is reduced to about 1/3 its original size, lowering the viscosity making
it similar to diesel fuel. The resulting fuel operates similar to diesel fuel in an engine. The
reaction produces three molecules of an ester fuel from one molecule of vegetable oil.

Figure 6.7: The transesterification process of converting vegetable oils to biodiesel

(22)http://www.ag.ndsu.edu/pubs/ageng/machine/ae1240w.htm

29
In such reaction known as transesterification, a triglyceride is allowed to react with a
threefold excess of an alcohol such as ethanol or methanol, and this alcohol takes the place
of the ester linkage to glycerol, yielding three fatty acid esters of the new alcohol and
glycerol. Above the process using methanol is shown in figure 8. Here three molecules of
one alcohol are replacing glycerol, another alcohol, in the triglyceride.

Vegetable oils have to undergo the process of transesterification to be usable in internal


combustion engines. Biodiesel is the product of the process of transesterification. Biodiesel is
biodegradable, non-toxic and essentially free from sulfur; it is renewable and can be
produced from agriculture and plant resources. Biodiesel is an alternative fuel, which has a
correlation with sustainable development, energy conservation, management, efficiency and
environmental preservation. Transesterification is the reaction of a fat or oil with an alcohol to
form esters and glycerol. Alcohol combines with the triglycerides to form glycerol and esters.
A catalyst is usually used to improve their action rate and yield. Since the reaction is
reversible, excess alcohol is required to shift the equilibrium to the product side. Among the
alcohols that can be used in the transesterification process are methanol, ethanol, propanol,
butanol and amyl alcohol.

The process of transesterification brings about drastic change in viscosity of vegetable oil.
The biodiesel thus produced by this process is totally miscible with mineral diesel in any
proportion. Biodiesel viscosity comes very close to that of mineral diesel hence no problems
in the existing fuel handling system. Flash point of the biodiesel gets lowered after
esterification and the cetane number gets improved. Even lower concentrations of biodiesel
act as cetane number improver for biodiesel blend. Calorific value of biodiesel is also found
to be very close to mineral diesel. Some typical observations from the engine tests
suggested that the thermal efficiency of the engine generally improves; cooling losses and
exhaust gas temperature increase, smoke opacity generally gets lower for biodiesel blends.
Possible reason may be additional lubricity properties of the biodiesel; hence reduced
frictional losses (FHP). The energy thus saved increases thermal efficiency, cooling losses
and exhaust losses from the engine. The thermal efficiency starts reducing after a certain
concentration of biodiesel. Flash point, density, pour point, cetane number, calorific value of
biodiesel comes in very close range to that of mineral diesel.

30
6.8 Biodiesel production from used cooking oil
The methods used for biodiesel production from used cooking oil are similar to that of
conventional transesterification 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 [Canakciand Van Gerpen, 2001; Enweremadu and Mbarawa, 2009]. 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 transesterification
process [Canakci and Ozsezen, 2005; Freedman et al., 1984].

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
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.
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 rate of oil production is different for each plant. As a
biofuel, plant oils will always be preferable to animal fats. (23)

31
Table 6.8: Comparison of properties of waste cooking oil, biodiesel from waste cooking oil and commercial diesel
fuel. (24 Source: http://www.sciencedirect.com/.pdf Biodiesel from waste cooking oil via base-catalytic and
supercritical methanol transesterification Ayhan Demirbas * Sila Science, Trabzon 61040, Turkey)

Fuel property Waste Biodiesel Commercial


vegetable oil from waste diesel fuel
vegetable oil

Kinematic 36.4 5.3 1.94.1


viscosity
(mm2/s, at
313 K)

Density (kg/L, 0.924 0.897 0.0750.840


at 288 K)

Flash point 485 469 340358


(K)

Pour point (K) 284 262 254260


Cetane 49 54 4046
number

Ash content 0.006 0.004 0.0080.010


(%)

Sulfur content 0.09 0.06 0.350.55


(%)

Carbon 0.46 0.33 0.350.40


residue (%)

Water content 0.42 0.04 0.020.05


(%)

Higher 41.40 42.65 45.6246.48


heating value
(MJ/kg)

Free fatty acid 1.32 0.10 -


(mg KOH/g
oil)
Iodine value 141.5 - -

32
Table 6.8 shows comparison of properties of waste cooking oil, biodiesel from waste cooking
oil and commercial diesel fuel. The properties of biodiesel and diesel fuels, in general, show
many similarities, and therefore, biodiesel is rated as a realistic fuel as an alternative to
diesel. This is due to the fact that the conversion of waste cooking oil into methyl esters
through the transesterification process approximately reduces the molecular weight to one
third, reduces the viscosity by about one-seventh, reduces the flashpoint slightly and
increases the volatility marginally, and reduces pour point considerably.

33
Chapter 7
Biodiesel as an engine fuel

7.1 Overview
The best way to use vegetable oil as fuel is to convert it in to biodiesel. Biodiesel is the name
of clean burning mono-alkyl ester-based oxygenated fuel made from natural, renewable
sources such as new/used vegetable oils and animal fats. The resulting biodiesel is quite
similar to conventional diesel in its main characteristics. Biodiesel contains no petroleum
products, but it is compatible with conventional diesel and can be blended in any proportion
with mineral diesel to create a stable biodiesel blend. The level of blending with petroleum
diesel is referred as Bxx, where xx indicates the amount of biodiesel in the blend (i.e. B10
blend is10% biodiesel and 90% diesel. It can be used in CI engine with no major modification
in the engine hardware.

7.2 Technical characteristics of biodiesel as a transportation fuel


Biodiesel is a cleaner burning alternative to petroleum-based diesel fuel. Just like petroleum-
based diesel fuel, biodiesel operates in the compression ignition (diesel) engines. The
successful introduction and commercialization of biodiesel in many countries around the
world has been accompanied by the development of standards to ensure high product quality
and user confidence. Some biodiesel standards are ASTM D6751 (ASTM = American
Society for Testing and Materials) and the European standard EN14214. The biodiesel is
characterized by determining its physical and fuel properties including density, viscosity,
iodine value, acid value, cloud point, pure point, gross heat of combustion and volatility. In
general, biodiesel compares well to petroleum-based diesel. The advantages of biodiesel as
diesel fuel are its portability, ready availability, renewability, higher combustion efficiency,
lower sulfur and aromatic content, higher cetane number and higher biodegradability. The
main disadvantages of biodiesel as diesel fuel are its higher viscosity, lower energy content,
higher cloud point and pour point, higher nitrogen oxide emission, lower engine speed and
power, injector coking, engine compatibility, high price, and higher engine wear. Biodiesel
offers safety benefits over diesel fuel because it is much less combustible, with a flash point

34
greater than 423 K compared to 350 K for petroleum-based diesel fuel. Biodiesel has a
higher cetane number (around 50) than diesel fuel, no aromatics, no sulfur, and contains 10
11% oxygen by weight. The cetane number is a commonly used indicator for the
determination of diesel fuel quality, especially the ignition quality. It measures the readiness
of the fuel to auto-ignite when injected into the engine. Ignition quality is one of the properties
of biodiesel that is determined by the structure of the fatty acid methyl ester (FAME)
component. Viscosity is the most important property of biodiesel since it affects the operation
of the fuel injection equipment, particularly at low temperatures when the increase in
viscosity affects the fluidity of the fuel. Biodiesel has a viscosity close to that of diesel fuels.
High viscosity leads to poorer atomization of the fuel spray and less accurate operation of the
fuel injectors. Elemental composition and relative amounts of compounds present in
biodiesel and diesel fuel are given in Tables 2 and 3.Due to presence of electronegative
element oxygen, biodiesel is slightly more polar than diesel fuel as a result viscosity of
biodiesel is higher than diesel fuel. Presence of elemental oxygen lowers the heating value of
biodiesel when compared the diesel fuel.

The lower heating value (LHV) is the most common value used for engine applications. It is
used as an indicator of the energy content of the fuel. Biodiesel generally has a LHV that is
12% less than No. 2 diesel fuel on a weight basis (16,000 Btu/lb compared with18,300
Btu/lb). Since the biodiesel has a higher density, the LHV is only 8% less on a volume basis
(118,170 Btu/gallon for biodiesel compared with 129,050 Btu/gallon for No. 2 diesel
fuel).Biodiesel can be used as pure fuel or blended at any level with petroleum-based diesel
for use by diesel engines. The most common biodiesel blends are B2 (2% biodiesel and 98%
petroleum diesel),B5 (5% biodiesel and 95% petroleum diesel), and B20 (20%biodiesel and
80% petroleum diesel). The technical disadvantages of biodiesel/petroleum diesel blends
include problems with fuel freezing in cold weather, reduced energy density, and degradation
of fuel under storage for prolonged periods. Biodiesel blends up to B20 can be used in nearly
all diesel equipment and are compatible with most storage and distribution equipment. These
low level blends generally do not require any engine modifications. Higher blends and B100
(pure biodiesel) may be used in some engines with little or no modification, although the
transportation and storage of B100 requires special management.

The characteristics of biodiesel are close to mineral diesel, and, therefore, biodiesel
becomes a strong candidate to replace the mineral diesel if the need arises. The conversion
of triglycerides into methyl or ethyl esters through the transesterification process reduces the

35
molecular weight to one-thirds that of the triglycerides, the viscosity by a factor of about eight
and increases the volatility marginally. Biodiesel has viscosity close to mineral diesel. This
vegetable oil esters contain1011% oxygen by weight, which may encourage combustion
than hydrocarbon-based diesel in an engine. The cetane number of biodiesel is around50.
Biodiesel has lower volumetric heating values (about 10%) than mineral diesel but has a high
cetane number and flash point. The esters have cloud point and pour points that are 1525
1C higher than those of mineral diesel.

Table 7.2: Properties of Biodiesel prepared from vegetable oils

36
7.3 Engine performance characteristics of biodiesel

Biodiesel has low heating value, (10% lower than diesel) on weight basis because of
presence of substantial amount of oxygen in the fuel but at the same time biodiesel has a
higher specific gravity (0.88) as compared to mineral diesel (0.85) so overall impact is
approximately 5% lower energy content per unit volume. Thermal efficiency of an engine
operating on biodiesel is generally better than that operating on diesel. Brake-specific energy
consumption (bsec) is a more reliable criterion compared to brake-specific fuel consumption
(bsfc) for comparing fuels having different calorific values and densities. Several
experimental investigations have been carried out by researchers around the world to
evaluate the engine performance of different biodiesel blends. Masjuki et al. investigated
preheated palm oil methyl esters (POME) in the diesel engine. They observed that by
preheating the POME above room temperature, the engine performance, especially the
brake power output and exhaust emission characteristics improved significantly. Scholl and
Sorenson studied the combustion of soya bean oil methyl ester (SME) in a direct injection
diesel engine. They found that most of the relevant combustion parameters for SME such as
ignition delay, peak pressure, and rate of pressure rise were close to those observed for
diesel combustion at the same engine load, speed, timing and nozzle diameter. They also
investigated combustion and emissions characteristics with SME and diesel for different
injector orifice diameter. It was found that ignition delay for the two fuels were comparable in
magnitude, and the ignition delay of SME was found to be more sensitive to nozzle diameter
than diesel. CO emissions from SME were slightly lower, Hydrocarbon emissions reduced
drastically, NOx for two fuels were comparable and smoke numbers for the SME were lower
than that of diesel. Altin et al. investigated the use of sunflower oil, cottonseed oil, soya bean
oil and their methyl esters in a single cylinder, four-stroke direct injection diesel engine. The
variations of maximum engine torque values in relation with the fuel types are shown in Fig.
20. The maximum torque with diesel operation was 43.1Nm at 1300 rpm. For ease of
comparison, this torque was assumed 100% as reference. The observed maximum torque
values of the vegetable oil fuel operations were also at about1300 rpm but less than the
diesel fuel value for each fuel. The maximum power with diesel fuel operation was 7.45kW at
1700 rpm. As before, this power was assumed 100% as reference. Observed maximum
power values of the vegetable oil fuel operations were also at about 1700 rpm but less than
the diesel fuel value for each fuel. These results may also be due to the higher viscosity and

37
lower heating values of vegetable oils. Specific fuel consumption is one of the important
parameters of an engine and is defined as the consumption per unit of power in a unit of
time. Specific fuel consumption values of the methyl esters were generally less than those of
the raw vegetable oils. The higher specific fuel consumption values in the case of vegetable
oils are due to their lower energy content.

7.4 Engine emissions from biodiesel


Since biodiesel is free from sulfur hence less sulfate emissions and particulate reduction is
reported in the exhaust. Due to near absence of sulfur in biodiesel, it helps reduce the
problem of acid rain due to transportation fuels. The lack of aromatic hydrocarbon (benzene,
toluene etc.) in biodiesel reduces unregulated emissions as well like ketone, benzene etc.
Breathing particulate has been found to be hazard for human health, especially in terms of
respiratory system problem. PM consists of elemental carbon (31%), sulfates and
moisture(14%), unburnt fuel (7%), unburnt lubricating oil (40%) and remaining may be
metals and others substances. Smoke opacity is a direct measure of smoke and soot.
Various studies show that smoke opacity for biodiesel is generally lower. Several
experimental investigations are performed on 4-stroke DI diesel engines with vegetable oil
methyl esters and found that hydrocarbon emissions are much lower in case of biodiesel
compared to diesel. This is also due to oxygenated nature of biodiesel where more oxygen is
available for burning and reducing hydrocarbon emissions in the exhaust. CO is a toxic
combustion product resulting from incomplete combustion of hydrocarbons. In presence of
sufficient oxygen, CO is converted intoCO2. Biodiesel is an oxygenated fuel and leads to
more complete combustion; hence CO emissions reduce in the exhaust. Altin et al. reported
that CO emission for biodiesel is marginally higher in comparison to diesel.

38
Figure7.4: B100 emissions compared to petroleum diesel emissions by percentage

(U.S. Department of Energy National Renewable Energy Laboratory, Biodiesel Handling and Use
Guidelines)

7.5 Environmental Benefits of Biodiesel Fuel


The steadily rising price of petroleum products and the environmental impact of procuring,
manufacturing, and using them create the need for alternate energy sources. Biodiesel, fuel
that is chemically prepared from vegetable oil, provides an environmentally friendly substitute
for diesel fuel. It is classified as a biofuel because it originates from a biological source. Its
biological origin makes it biodegradable and nontoxic. Other advantages of biodiesel fuel
over petroleum diesel are the increased oxygen content, no sulfur content, increased
lubricity, and lower emissions of particulate matter upon combustion. The Clean Air Act of
1990 mandates oxygenated additives to be added to gasoline in cities with excessive levels
of ozone and carbon monoxide pollution because they lead to a reduction in carbon
monoxide emissions. Biodiesel contains about 11% oxygen by mass so no additional
oxygenated additives are necessary. A later ruling by the Environmental Protection Agency
in 1994 required that 30% of the oxygenated additives to reformulated gasoline (gasoline
whose composition has been altered to reduce concentrations of undesirable substances) be
from renewable resources, and the most popular additive, methyl tertiary-butyl ether, MTBE,
is made from methanol, a nonrenewable source. This ruling supports the use of ethanol,
which is produced largely from corn, in place of the methanol, but biodiesel is another
renewable source of an oxygenated additive. Absence of sulfur content is desirable because

39
sulfur indirectly increases carbon monoxide emissions by coating the catalytic converter,
reducing its efficiency in catalyzing complete combustion of the gasoline to carbon dioxide.
The increased lubricity provided by biodiesel, even in blends as low as 3%, prolongs engine
life, with less frequent need for engine part replacement. Particulate matter is carbon and
soot, so lowering these emission levels leads to cleaner air also.

One of the most attractive aspects of biodiesel use is that is provides a means of recycling
carbon dioxide, so there is no net increase in global warming. As with any complete
combustion, carbon dioxide and water are the end products, but these will be taken up by the
plant to ultimately lead to production of new biodiesel. Fossil fuels, which took millions of
years to form, are not replenishable in the near future, whereas biofuels can ideally be
replenished in one growing season. Figure 7.5 shows a very simple cycle of carbon of
biodiesel and fossil fuel with different time frames. Although diesel fuel can be written into a
similar cycle, the time frames are entirely different, so that diesel fuel is not renewable in a
reasonable time period. (25)

Figure 7.5: A simple cycle of carbon dioxide of biodiesel and fossil fuel with different time frames

26
( http://www.uic.edu/classes/chem/clandrie/orgolabs/CASPiE/CASPiE_assets/biodiesel1_module.pdf)

40
7.6 Environmental benefits in comparison to petroleum based
fuels include

Biodiesel is the only alternative fuel to have fully completed the health effects testing
requirements of the Clean Air Act. The use of biodiesel in a conventional diesel engine
results in substantial reduction of unburned hydrocarbons, carbon monoxide, and particulate
matter compared to emissions from diesel fuel. In addition, the exhaust emissions of sulfur
oxides and sulfates (major components of acid rain) from biodiesel are essentially eliminated
compared to diesel.

Of the major exhaust pollutants, both unburned hydrocarbons and nitrogen oxides are ozone
or smog forming precursors. The use of biodiesel results in a substantial reduction of
unburned hydrocarbons. Emissions of nitrogen oxides are either slightly reduced or slightly
increased depending on the duty cycle of the engine and testing methods used. Based on
engine testing, using the most stringent emissions testing protocols required by EPA for
certification of fuels or fuel additives in the US, the overall ozone forming potential of the
speciated hydrocarbon emissions from biodiesel was nearly 50 percent less than that
measured for diesel fuel.

Carbon monoxide emissions are reduced around 50% and carbon dioxide by around 78%
overall based on the fact that the carbon comes from carbon already present in the earths
atmosphere, not from its crust, as in petrodiesel.

Fewer aromatic hydrocarbons are present a 56% reduction in

benzofluoranthene and 71% reduction in benzopyrenes.

Particulate emissions are reduced by up to 65%, leading to reduced cancer risks of up to


94% according to tests sponsored by the Department of Energy.

Its higher cetane rating than petrodiesel causes more rapid ignition when injected into the
engine. It also has the highest energy content of any alternative fuel in its pure form (B100).

Biodiesel is biodegradable and non-toxic - tests sponsored by the United States


Department of Agriculture confirm biodiesel is less toxic than table salt and biodegrades as
quickly as sugar.

Pure biodiesel (B100) can be used in any petroleum diesel engine, though it is more
commonly used in lower concentrations. The recent mandates for ultra-low sulfur petrodiesel

41
make it necessary to use additives to increase lubricity and flow properties, so biodiesel is an
obvious choice. Even the 2% formulation (B2) is capable of restoring lubricity to the fuel. B5
is often used in snow removal equipment and other municipal systems.

Biodiesel is less flammable than gasoline or petrodiesel. Its flash point (>150 C) is much
higher than that of petroleum diesel (64 C) or gasoline (45 C). (27)

7.7 Some challenges for using biodiesel fuel


Biodiesel has higher nitrogen oxide NOx emissions than petrodiesel. 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. Catalytic converters and properly tuned
engines can reduce these emissions.

While the flash point of biodiesel is higher than that of gasoline or petrodiesel, its gel point
of varies depending on the ester composition. Most biodiesel has a somewhat higher gel and
cloud point than petrodiesel. This requires the heating of storage tanks, especially in cooler
climates.

Water contamination: Biodiesel is hydrophilic because of its oxygen content that permits
hydrogen bonding of water molecules. Water that is not removed during processing or
present from storage tank condensation causes problems because:

- It reduces the heat of combustion of the fuel, leading to more smoke,

harder starting, and less power.

- It leads to corrosion of vital fuel system components: fuel pumps, injector

pumps, fuel lines, etc.

- It freezes to form ice crystals near 0 C (32 F), which are sites for gel

formation of the fuel, decreasing its flow properties.

The growth of microbe colonies, which can plug up a fuel system, is increased by water
presence. This is an ongoing problem for biodiesel users with heater fuel tanks13. (27)

42
Chapter 8

Biodiesel Economy

8.1 Overview:
The technical and economic advantages of biodiesel are that, it reduces greenhouse gas
emissions because it reduces some exhaust emissions; it helps to reduce a countrys
reliance on crude oil imports and supports agriculture by providing a new labor and market
opportunities for domestic crops; it enhances the lubricating property; it is safer to handle,
being less toxic, more biodegradable and it is widely accepted by vehicle manufacturers.

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 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.
Biodiesel can be over double the price of petroleum Diesel. The high price of biodiesel is in
large part due to the high price of the feedstock. 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 cooking oils
used as raw material, the viability of a continuous transesterification process and recovery of
high quality glycerol as a biodiesel by product are primary options to be considered to lower
the cost of biodiesel. With recent increases in petroleum prices and uncertainties concerning
petroleum availability, there is renewed interest in vegetable oil fuels for Diesel engines. Most
of the biodiesel that is currently made uses soybean oil, methanol and an alkaline catalyst.
The high value of soybean oil as a food product makes production of a cost effective fuel

43
very challenging. However, there are large amounts of low cost oils and fats such as
restaurant wastes and animal fats that could be converted to biodiesel. The problem with
processing these low cost oils and fats is that they often contain large amounts of free fatty
acids (FFA) that cannot be converted to biodiesel using an alkaline catalyst. A review of 12
economic feasibility studies shows that the projected costs for biodiesel (BD) from oilseed or
animal fats have a range US $0.300.69/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$0.340.42/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.

Biodiesel is a technologically feasible alternative to petrodiesel, but nowadays biodiesel costs


1.5 to 3 times more than fossil diesel in developed countries. Biodiesel is more expensive
than petrodiesel, though it is still commonly produced in relatively small quantities (in
comparison to petroleum products and ethanol). The competitiveness of biodiesel to
petrodiesel depends on the fuel taxation rates and policies. Generally, the production costs
of biodiesel remain much higher than those of petrodiesel. Therefore, biodiesel is not
competitive with petrodiesel under current economic conditions. The competitiveness of
biodiesel relies on the price of the biomass feedstock and costs associated with the
conversion technology.

Moreover, Low production costs of crude oil derivatives are another crucial handicap for the
biodiesel marketing. In this sense, the continuous increase of crude oil prices approaches
biodiesel production cost to those ones of fossil diesel, converting this difference from
handicap to a potential opportunity for enhancing the bio-diesel application. Figure 8.1 shows
the evolution of fossil diesel prices in EU. (28)

44
Figure 8.1: Price of fossil diesel (commercial use) Euro/l

(28 http://ftp.jrc.es/EURdoc/eur20279en.pdf)

8.2 Biodiesel production economic balance

Several (non-technological) limiting factors have been stopping until now the development of
the bio-diesel industry. These limiting factors are feedstock prices, bio-diesel production
costs, crude oil prices and taxation of energy products.

8.2.1 Feedstock prices

No matter the technological process adopted for bio-diesel manufacturing, the largest share
of production cost of bio-diesel is the feedstock cost. The feedstock cost is the major
obstacle to the market feasibility of bio-diesel. Rape-seed, used in bio-diesel sector, covers
around half of the non-food area under set-aside scheme.

8.2.2 Biodiesel production costs

The estimated costs for biodiesel can be split up into fixed and variable costs. Fixed costs
come from extracting the vegetable oil from seed and processing this vegetable oil into
biodiesel. These costs include manufacturing, capital, and labor costs. Glycerol and protein
meal for livestock feed are byproducts that might help to offset the cost of biodiesel
production. The sale of these byproducts is considered fixed income.

Rape-seed price (Pr) is considered as variable one. It is also considered that


manufacturing 1 litre of bio-diesel needs 2.23 kg. rapeseed on average basis.

45
Table 8.2.2: Bio-diesel cost production depending on rape-seed price in Euro/l (Sources: ATLAS
Database, US National Renewable Energy Laboratory (NREL), IPTS data gathering & elaboration)

Fixed costs
Manufacturing costs 0.147
Capital costs (annualised) 0.012
Staff and overhead costs 0.005
0.005
Fixed income
By-products income 0.084
TOTAL fixed factors 0.080
Variable costs
1 liter of bio-diesel requires Pr*2.23
2.23 kg of rape-seed
TOTAL PRODUCTION 0.08 + Pr*2.23
COSTS
Remark: (Pr) - rapeseed price

By assuming the reference rape-seed price of 0.214 Euro/kg, a net cost of 0.557 Euro/l
biodiesel is obtained.

Three salient facts have to be underlined with respect to this cost structure:

First of all, the largest share in the final costs belongs to the procurement costs of
bio- mass. In the above case, the share of the rape-seed cost in the final product is
about 70 %. Other reports, quoted by the US NREL, state a raw material cost share
up to 90 % of the total cost. This share mainly depends on the assumptions made
about the prices of raw bio-mass.
The second salient fact is that the sale of by-products is an important source of
income, which rises significantly the competitiveness of the overall process. In the
above scenario, the income from by-products consists of about 15 % of the total
production costs. Other reports state for this figure even 35 % share of the total
production cost.
At the last, but not at the least, when making cost and price comparisons between
bio- diesel and fossil diesel, a parameter, reflecting the fuel consumption substitution
ratio between bio-diesel and fossil diesel, ensuing from their different energy
content, should be applied. (28)

46
8.2.3 Taxation of energy products
There is no harmonized European policy, either for fossil fuels or for bio-fuels. Each
Member State implements own domestic regulations, inside the EU framework for taxation of
energy products. The minimum levels of taxation are modified depending on whether these
motor fuels are used for certain industrial or commercial purposes. The proposal refers to:
agriculture and forestry; stationary motors; plant and machinery, used in construction; civil
engineering and public works; vehicles, intended for use off the public roadway; passenger
transport and captive fleets, which provide services to public bodies. On the other hand,
Member States may apply total or partial tax exemptions or reductions for energy products
used under fiscal control in pilot projects for technological development. Also, such
preferences might be applied for more environmentally-friendly products or in relation to fuels
from renewable sources, e.g. bio-diesel. (28)

47
Chapter 9
Experimental part

- The production of biodiesel from rapeseed oil


experiment...............................................................................................................9.1

- Fuel analytics experiments: Determining some properties of Rapeseed oil, Diesel


and two types of biodiesel one produced in the Lab and the other from the gas
station; density, kinematic viscosity, lower calorific value and oxidation
stability......................................................................................................................9.2

- The Emission testing experiment for rapeseed oil, low sulfur diesel fuel and
biodiesel (from gas station).......................................................................................9.6

Experiments were performed in the lab of the University of Applied Science (HAW), Amberg,
Germany Nov.2010-Feb.2011.

48
9.1 The production of biodiesel from rapeseed oil experiment

Figure 9.1: Biodiesel produced in the Lab.

9.1.1 Pressing of Rapeseed oil.


1.2 Kg of, seven- year- old rapeseed, was pressed which gave 500 ml of Rapeseed oil and
the pressed oil was filtered using filter paper for 24 hours. 50 ml of the filtered oil was used
for the determination of the free fatty acid percentage.

Figure 9.1.1.1: Rapeseed oil press in lab

49
Figure 9.1.1.2: The filtration of 50 ml of rapeseed oil in lab

9.1.2 The determination of free fatty acid


10 grams of the filtered rapeseed oil was put in 250 ml Erlenmeyer flask, and then 50 ml of
diethyl ether and ethanol were added. Stirring was done until the oil was completely
dissolved in the solvent mixture. A burette was filled with about 10-15 ml of ethanolic KOH
solution, 3-4 drops of phenolphthalein (1% in ethanol) and a magnetic stir bar were given to
the solution in the Erlenmeyer flask, and then the KOH solution was added to the mixture
(mixture titration).When the color of the mixture changed, the mixture was left another 30
second to be sure of the new color.

- A formula was used to determine the concentration of free fatty acid in

Rapeseed oil:

% free fatty acid = a * avg.mol.wght. / 10 * E

where:
a: volume [ml] of KOH * 0.1 [mol / ml]

avg.mol.wght.: 314 g / mol


E: initial weight in grams

50
A computer program of Biodiesel, shown in figure 8.2, was used to determine the
amounts of addition of methanol and KOH for esterification

Figure 9.1.2: Biodiesel RME-Rechner

(29 Chemical Engineering department, HAW)

9.1.3 Transestrification:
The rapeseed oil was heated up to 30 oC, and was put on a stir, the KOH was dissolved in
the Methanol and slowly the methanol-KOH was allowed into the oil in drops and the oil was
left to the next day.

9.1.4 Thin layer chromatography:

A good way to check for impurities; how many different compounds are in a sample,
very small quantities of the samples are placed on the special TLC plates. The plate
is put in a container with a solvent or solvent mixture, the solvent runs up the plate
and will separate the different kinds of molecules based on polarity differences and
size differences.

51
There are two phases of Thin layer chromatography a stationary phase (a solid, or a liquid
supported on a solid) and a mobile phase (a liquid or a gas).

The mobile phase flows through the stationary phase and carries the components of the
mixture with it. Different components travel at different rates. The stationary phase in this
case is silica gel coated on a thin piece of rigid plastic. The mobile phase in this case is a
mixture of solvents hexane and ethyl acetate in a specific ratio (v/v). (30)

Figure 9.1.4: Thin layer chromatography device in the Lab.

(31 Thin layer chromatography device in the Lab Lab of chemical engineering department in HAW)

52
9.2 Fuel analytics: Determining some properties of Rapeseed oil,
Diesel and two types of Biodiesel; one produced in the Lab and
the other from the gas station; density, kinematic viscosity,
lower calorific value and oxidation stability

9.2.1 Introduction
A reliable operation of combustion engines is only possible, when important characteristics
and substances of content of the fuel are defined. These properties have to fulfil certain
limiting values, otherwise guaranty and warranty agreement for proper engine operation or
the conformity with relevant emissions regulations cannot be given. Besides that, defined fuel
qualities are essential for the evaluation of operation characteristics and the ongoing
development of engine technique. The specification of fuel quality by the use of consistent
parameters and testing methods also enables fuel improvement, if necessary. Moreover, the
comparison of engines emission behaviour is only possible when certified fuels (reference
fuels) are used. Finally a defined fuel quality is basis for trading fuels. (32)

9.2.2 Technical Details and Standards of diesel and biodiesel

There are three existing specification standards for diesel & Biodiesel fuels (EN590, DIN
51606 & EN14214).

EN590 (actually EN590:2000) describes the physical properties that all diesel fuel must meet
if it is to be sold in the EU, Czech Republic, Iceland, Norway or Switzerland. It allows the
blending of up to 5% Biodiesel with 'normal' DERV - a 95/5 mix.

DIN 51606 is a German standard for Biodiesel, is considered to be the highest standard
currently existing, and is regarded by almost all vehicle manufacturers as evidence of
compliance with the strictest standards for diesel fuels. The vast majority of Biodiesel
produced commercially meets or exceeds this standard.

EN14214 is the standard for biodiesel now having recently been finalized by the European
Standards organisation CEN. It is broadly based on DIN 51606.

53
Table 9.2.2: Some properties of diesel and biodiesel standards
33
( http://www.biodieselfillingstations.co.uk/approvals.htm)

Properties Unit Derv ( EN590) Biodiesel Biodiesel


(DIN51606) (EN14214)

Density @ g/cm 0.82-0.86 0.875-0.9 0.86-0.9


15C

Viscosity @ mm/s 2.0-4.5 3.5-5.0 3.5-5.0


40C

Flashpoint C >55 >110 >101

Sulphur % mass 0.20 <0.01 <0.01

Carbon (% weight) 0.30 <0.03 <0.03


Residue

Total mg/kg Unknown <20 <24


Contamination

Cetane - >45 >49 >51


Number
Derv: diesel oil used in cars and lorries with diesel engines; from d(iesel) e(ngine) r(oad) v(ehicle)

54
9.2.3 Kinematic Viscosity measurement: The Ubbelohde viscometer

Viscosity refers to a fluids resistance to flow at a given temperature. A fuel that is too viscous
can hinder the operation of an engine. Kinematic viscosity measures the ease with which a
fluid will flow under force. It is different from absolute viscosity, also called dynamic viscosity.
Kinematic viscosity is obtained by dividing the dynamic viscosity by the density of the fluid. If
two fluids with the same absolute viscosity are allowed to flow freely on a slope, the fluid with
higher density will flow faster because it is heavier. The density of biodiesel varies depending
on its feedstock. Longer and straighter chains (saturated fats) tend to have higher density
than shorter and unsaturated molecules. Kinematic viscosity allows comparison between the
engine performance of different fuels, independent of the density of the fuels. Two fuels with
the same kinematic viscosity should have the same hydraulic fuel properties, even though
one fuel may be denser than the other. The highest acceptable kinematic viscosity for
biodiesel as specified in D6751 is 6.0. EN 14214, the biodiesel standard for the European
market, specifies a viscosity limit for biodiesel of 3.55.0 mm 2/s. If a batch of biodiesel does
not meet this specification, the viscosity can be corrected by blending it with a fuel that has a
lower or higher viscosity.

The Ubbelohde type viscometer, shown in figure 9.6, is a measuring instrument which uses a
capillary based method of measuring viscosity. The device was invented by the German
chemist Leo Ubbelohde (1877-1964).The Ubbelohde viscometer is a u-shaped piece of
glassware with a reservoir on one side and a measuring bulb with a capillary on the other. A
liquid is introduced into the reservoir then sucked through the capillary and measuring bulb.
The liquid is allowed to travel back through the measuring bulb and the time it takes for the
liquid to pass through two calibrated marks is a measure for viscosity. The Ubbelohde device
has a third arm extending from the end of the capillary and open to the atmosphere. In this
way the pressure head only depends on a fixed height and no longer on the total volume of
liquid. The advantage of this instrument is that the values obtained are independent of the
concentration. (34)

55
Figure9.2.3: The Ubbelohde viscometer

(35 http://www.thefullwiki.org/Viscometer)

Table 9.2.3: Experimental results of kinematic viscosity for rapeseed oil, two types of biodiesel and diesel fuel

Fuel type Kinematic viscosity (mm2/s)

Rapeseed oil 36.22

Biodiesel (lab) 5.706

Biodiesel (gas station) 4.454

Diesel 3.095

Table 9.2.3 shows the experimental results of kinematic viscosity for rapeseed oil, two types
of biodiesel and diesel fuel. It could be noticed from the table that the rapeseed oil has the
highest viscosity among the other fuels because vegetable based oils tend to be fairly
viscous and dont flow too easily. Also, it could be noticed that diesel has lowest viscosity.
Biodiesel of the two types has higher viscosity than diesel specially the one produced in the

56
lab because not all of rapeseed oil was converted completely to biodiesel, it had a little
amount of rapeseed oil and its known that rapeseed oil has high viscosity.

9.2.4 Density Measurement: Hydrometer and Pycnometer

Density is the weight per unit volume. Diesel fuels have higher densities and therefore it
gives more energy than that of the petrol. The densities of the vegetable oils are higher, but
during the transesterification process the density is decreased, however they are denser than
the diesel fuels and thereby they are an efficient alternative. (36)

9.2.4.1 Hydrometer:

A hydrometer is an instrument used to measure the specific gravity (or relative density) of
liquids; that is, the ratio of the density of the liquid to the density of water. A hydrometer is
usually made of glass and consists of a cylindrical stem and a bulb weighted with mercury or
lead shot to make it float upright. The liquid to be tested is poured into a tall container, often
a graduated cylinder, and the hydrometer is gently lowered into the liquid until it floats freely.
The point at which the surface of the liquid touches the stem of the hydrometer is noted.
Hydrometers usually contain a scale inside the stem, so that the specific gravity can be read
directly. A variety of scales exist, and are used depending on the context.

Figure9.2.4.1: Hydrometer (37 http://en.wikipedia.org/wiki/Hydrometer)

57
9.2.4.2 Pycnometer

A pycnometer is a small flask with a glass stopper. A capillary opening which runs along the
length of the stopper makes it possible to fill the pycnometer completely- that is, without
leaving a bubble of air in the flask.

Figure 9.2.4.2: Pycnometer

(38 http://en.wikipedia.org/wiki/File:PycnometerEmpty.jpg)

Table 9.2.4: Experimental results of Density for rapeseed oil, two types of biodiesel and diesel fuel

Fuel type Density g / cm

Hydrometer Pycnometer

Rapeseed oil 0.921 0.922

Biodiesel (lab) 0.880 0.879

Biodiesel (gas - 0.885


station)

Diesel - 0.825

58
Table 9.2.4 shows the experimental results of Density for rapeseed oil, two types of biodiesel
and diesel fuel. It could be noticed for rapeseed oil and biodiesel produced in the lab, density
was measured by hydrometer and pycnometer, it can be noticed that rapeseed oil has the
highest density because vegetable oils are denser in their chemical structure. Also, it could
be noticed that diesel and biodiesel have close densities, with higher density for biodiesel
due to the fact that biodiesel is made out of vegetable oil and that it is not converted to 100%
biodiesel.

9.2.5 Heating value Measurement: the Bomb Calorimeter

Heating value or Heat of combustion is the amount of heating energy released by the
combustion of a unit value of fuels. The most important determinants of the heating value are
the moisture content. It is because of this, that the purified Biodiesel is dried. The moisture
content of the Biodiesel is low and this increases the heating value of the fuel.(39,40)

A bomb calorimeter is a type of constant-volume calorimeter used in measuring the heat of


combustion of a particular reaction. Bomb calorimeters have to withstand the large pressure
within the calorimeter as the reaction is being measured. Electrical energy is used to ignite
the fuel; as the fuel is burning, it will heat up the surrounding air, which expands and escapes
through a tube that leads the air out of the calorimeter. When the air is escaping through the
copper tube it will also heat up the water outside the tube. The temperature of the water
allows for calculating calorie content of the fuel.

The calorimeter gives the value of the high heating value or the GROSS (or higher) calorific
value for a fuel. The net calorific value is then obtained by subtracting the latent heat of the
water present from the gross calorific value. The latent heat of vaporization of water is 2.5
MJ/kg.

59
Figure 9.2.5: Bomb Calorimeter

(41 http://en.wikipedia.org/wiki/Calorimeter)

Table 9.2.5: Experimental results of Lower heating value for rapeseed oil, two types of biodiesel and diesel fuel

Fuel type Lower heating value


(kJ/kg)

Rapeseed oil 36922

Biodiesel (lab) 37510

Biodiesel (gas 38105


station)

Diesel 46221

Table 9.2.5 shows the experimental results of Lower heating value for rapeseed oil, two
types of biodiesel and diesel fuel. It could be noticed that diesel has the highest heating
value, which means that the energy released of diesel combustion is the highest, while
biodiesel comes in the second place of amount of energy released and the last one is the
rapeseed oil.

60
9.2.6 Measuring the oxidation stability:

Because of the chemical structure of fatty acid methyl esters (FAME), they age more quickly
than fossil diesel fuels. Therefore it was considered to include a limit for oxidation stability in
the existing quality standard for biodiesel. Oxidative stability is an important parameter in the
characterization of fats and oils.
Transestrification of vegetable oils with methanol produces the methyl esters of the fatty
acids (together with glycerol as a byproduct). These have only a limited shelf-life as they are
slowly oxidized by atmospheric oxygen. The resulting oxidation products can cause damage
to combustion engines. This is why oxidation stability is an important quality criterion for
biodiesel, which needs to be regularly determined during production. With the Rancimat this
determination can be carried out quickly and simply, and the value is given in hours.
The fuel sample is heated up to 110 C, compressed air is supplied through the fuel into a
flask with distilled water. Conductivity of the distilled water is measured; when it raises the
fuel begins to deteriorate. The point at which the conductivity curve bends as shown in
Figure 9.2.6.1 (the red line) is defined as the oxidation stability.
The oxidation stability of diesel is measured differently from rapeseed oil and biodiesel.
Diesel is heated up to 95C for 16 hours and exposed to 3 liter per hour of pure oxygen
(accelerated aging), because of the aging resin will be formed in the diesel (deterioration of
diesel), the concentration of resin in the diesel is measured and the value is given in gram
per cubic meter.(42)

Figure 9.2.6: The Rancimat device


(43 http://www.springerlink.com/content/g811177h40r6344p/)

61
Table 9.2.6: Experimental results of Oxidation stability for rapeseed oil, two types of biodiesel and diesel fuel

Fuel type Oxidation stability


(hours)

Rapeseed oil 3.03

Biodiesel (lab) 18.78

Biodiesel (gas 7.640


station)

Diesel 16.38

Table 9.2.6 shows the experimental results of Oxidation stability for rapeseed oil, two types
of biodiesel and diesel fuel. It could be noticed from table 9.2.6 that the oxidation stability for
rapeseed oil is 3.03 hours, and in the standard results for rapeeed oil, shown in table 9.4.1,
the minimum is five hours, this due to that the rapeseed oil which was used in the lab was
not a fresh one, it was one year old oil.

For the oxidation stability of biodiesel which was produced in the lab, The value isnt
reasonable (18.78). Theres a very big difference between the standard value (6 h) shown in
table 9.4.3 (6 hours), this could be due to a fault in the experiment e.g. compressed air which
was supplied to the biodiesel could have failed for some hours during the night.

For biodiesel, from gas station, it could be noticed that the oxidation stability result shown in
table 9.2.6 (7.640 hours), is close to the European Standard EN 14214 of biodiesel shown in
table 9.4.3 (6 hours) this is because its commercial biodiesel which is sold in gas stations,
where it should meet the standards of biodiesel.

For diesel fuel the oxidation stability is measured in a different way than that for rapeseed oil
and biodiesel, here the result of oxidation stability for diesel which was got from the lab, was
done by the rancimant method as for rapeseed oil and biodiesel but its not accurate for
diesel. The oxidation stability for diesel according to the standard method couldnt not be
performed in the lab because the experiment needs pure oxygen, which gives a very
flammable mixture together with diesel and the lab is not equipped for that.

62
Figure 9.2.6.1: The oxidation stability graph of rapeseed oil

Figure 9.2.6.2: The oxidation stability graph of biodiesel (from gas station)

63
Figure 9.2.6.3: The oxidation stability graph of biodiesel (produced in lab)

Figure 9.2.6.4: The oxidation stability graph of diesel fuel

Figures from 9.2.6.until 9.2.6.4 show the oxidation stability of rapeseed oil, two types of
biodiesel (from lab and gas station) and diesel fuel respectively. The red line shows the point
at which the conductivity curve bends which is defined as the oxidation stability.

64
9.3 CHNS Elemental Analyzer (EA):

CHNS elemental analyzers provide a means for the rapid determination of carbon, hydrogen,
nitrogen and sulphur in organic matrices and other types of materials. They are capable of
handling a wide variety of sample types, including solids, liquids, volatile and viscous
samples, in the fields of pharmaceuticals, polymers, chemicals, environment, food and
energy. The analyzers are often constructed in modular form such that they can be set up in
a number of different configurations to determine, for example, CHN, CHNS, CNS or N
depending on the application. This adaptability allows not only flexibility of operation but also
the use of a wide range of sample weights from a fraction of a milligram to several grams
(macro-systems.)

Basic principles

In the combustion process (furnace at ca. 1000oC), carbon is converted to carbon dioxide;
hydrogen to water; nitrogen to nitrogen gas/ oxides of nitrogen and sulphur to sulphur
dioxide. If other elements such as chlorine are present, they will also be converted to
combustion products, such as hydrogen chloride. A variety of absorbents are used to remove
these additional combustion products as well as some of the principal elements, sulphur for
example, if no determination of these additional elements is required.

The combustion products are swept out of the combustion chamber by inert carrier gas such
as helium and passed over heated (about 600o C) high purity copper. This copper can be
situated at the base of the combustion chamber or in a separate furnace. The function of this
copper is to remove any oxygen not consumed in the initial combustion and to convert any
oxides of nitrogen to nitrogen gas. The gases are then passed through the absorbent traps in
order to leave only carbon dioxide, water, nitrogen and sulphur dioxide.

Detection of the gases can be carried out in a variety of ways including (i) a GC separation
followed by quantification using thermal conductivity detection (ii) a partial separation by GC
(frontal chromatography) followed by thermal conductivity detection (CHN but not S) (iii) a
series of separate infra-red and thermal conductivity cells for detection of individual

65
compounds. Quantification of the elements requires calibration for each element by using
high purity micro-analytical standard compounds such as acetanilide and benzoic acid.(44)

More specifications about the CHNS Elemental Analyzer are shown in Appendix A, A.9.

Figure 9.3: CHNS-O Elemental Analyzer

(45 http://www.cecri.res.in/CIF/cif.htm)

Table 9.3.1: Elementary analyzer results for biodiesel produced in Lab.

66
Table 9.3.1 shows an example of the results of carbon, hydrogen, nitrogen and sulphur
contents for biodiesel produced in the lab of the elementary analyzer device. Three results of
three samples of biodiesel are shown in the figure. The samples were made and put into the
elementary analyzer, to make sure that the device is working well and that good results are
given and that was shown from the close results that were got for the three samples. Then
these results are entered into the calorimeter device to get the lower heating value of the
biodiesel which is shown in table 9.6 as 37510 kJ/kg.

Table 9.3.2: Elementary analyzer results for diesel fuel and rapeseed oil

67
Table 9.3.2 shows the results of carbon, hydrogen, nitrogen and sulphur contents for diesel
fuel and rapeseed oil of the elementary analyzer device. Three results of three samples of
biodiesel are shown in the table. The samples were made and put into the elementary
analyzer, to make sure that the device is working well and that good results are given and
that was shown from the close results that were got for the three samples.

Table 9.3.3: Elementary analyzer results for biodiesel (gas station)

68
Table 9.3.3 shows the results of carbon, hydrogen, nitrogen and sulphur contents for
biodiesel, which was bought from gas station, of the elementary analyzer device. Three
results of three samples of biodiesel are shown in the table. The samples were made and put
into the elementary analyzer, to make sure that the device is working well and that good
results are given and that was shown from the close results that were got for the three
samples. Then these results are entered into the calorimeter device to get the lower heating
value of this biodiesel

69
9.4 Experimental and Standard results of Density, Kinematic
viscosity, Lower heating value and Oxidation stability for rapeseed
oil, two types of biodiesel and diesel fuel

Table 9.4.1: Characteristic properties for Rapeseed 0il according to DIN 51 605 - German Rapeseed Oil Fuel
Standard (46 http://www.biofuelsb2b.com/useful)

Properties Unit Limiting Value

Min. Max.

Density (15C) kg/m3 900 930

Kinematic mm2/S - 38
Viscosity
(40C)

Calorific kJ/kg 35000 -


Value

Oxidation h 5.0 -
Stability
(110C)

70
Table 9.4.2: Characteristic properties for Rapeseed 0il according to experiments done in the Lab. of the
FachHochSchule, Amberg 2010/2011

Properties Unit Value

Density (15C)
Hydrometer kg/m3 921

Pycnometer 922

Kinematic mm2/s 36.22

Viscosity (40C)

Lower heating value kJ/kg 36922

Oxidation h 3.03

Stability (113C)

Table 9.4 shows the results of the density, the kinematic viscosity, the lower heating value
and the oxidation stability of rapeseed oil, and comparing these results with the standard
results of rapeseed oil according to the DIN 51 605 - German Rapeseed Oil Fuel Standard
which are shown in table 8.3, it can be noticed that the results are so close to each other,
except for the oxidation stability. In the standard results, the min. is five hours and the result
that was got in the Lab. Its three hours and this due to that the rapeseed oil which was used
in the lab was not a fresh one, it was a one year old oil.

71
Table 9.4.3: Characteristic properties for Biodiesel according to European Standard EN 14214.

(47www.biofuels2b2.com)

Properties Unit European


Standard EN
14214

Density g / cm 0.86 - 0.90

( 15C)

Viscosity at
40C , mm/s 3.5
min
5.0
max

Lower kJ/kg 36000


Heating
Value

Oxidation h 6.0

stability
110C

72
Table 9.4.4: Characteristic properties for two types of Biodiesel, one produced in the lab. of the Fachhochschule,
Amberg 2010,/2011 and the other one was bought from the gas station.

Properties Unit Value

Biodiesel (Lab) Biodiesel (gas station)

Density

( 15C) g / cm
Hydrometer 0.880 -

Pycnometer 0.879 0.885

Viscosity at 5.706 4.454


40C , mm/s
min

max

Lower kJ/kg 37510 38105


Heating
Value

Oxidation h 18.78 7.640

stability
110C

Table 9.4.4 shows the results of the density, the kinematic viscosity, the lower heating value
and the oxidation stability of two types of biodiesel, one is produced in the Lab and the other
one was bought from the gas station. It can be noticed that results are close to each other
except for the oxidation stability, which is very high for the biodiesel produced in the lab. This
is due to the fact that the biodiesel which is bought from the gas station has higher quality
than the biodiesel produced in the Lab because once the reaction of the tranesterification is
completed, some additional steps take place other than the separation of biodiesel and

73
glycerin which was done only in the Lab, such as the removal of the excess alcohol in
glycerin and biodiesel phases is removed with a flash evaporation process or by distillation
and Methyl Ester Wash. The biodiesel is sometimes purified by washing gently with warm
water to remove residual catalyst or soaps, dried, and sent to storage, resulting in a clear
amber-yellow liquid with a viscosity similar to petrodiesel.This was seen clearly in the photos
taken for the two types of biodiesel. Comparing these results with the standard results of
biodiesel, shown in table 9.5 according to the European Standard EN 14214, it can be
noticed that the results for the biodiesel bought from the gas station are closer to the
standard ones than the other type of biodiesel produced in the Lab, because the commercial
fuel must meet any required specifications.

Table 9.4.5: Characteristic properties for Diesel according to the DIN EN 590 standards, July1999.

Properties Unit Value

Min. Max.

Density kg / m 820 845

( 15C)

Viscosity at 2.00 4.50


40C , mm/s
min
max

Lower kJ/kg 42500


Heating
Value

Oxidation g/ml 25

stability
110C

74
Table 9.4.6: Characteristic properties for Diesel according to according to experiments done in the Lab. of the
FachHochSchule, Amberg, 2010/2011

Properties Unit Value

Density g / cm 0.825
(pycnometer)
( 15C)

Viscosity at 40C mm/s 3.095

Lower Heating kJ/kg 46221


Value

Oxidation h 16.38
stability
110C

Table 9.4.6 shows the results of the density, the kinematic viscosity, the lower heating value
and the oxidation stability of Diesel fuel, and comparing these results with the standard
results of Diesel fuel according to the DIN EN 590 standards, July1999, which are shown in
table 9.7, it can be noticed that the results are so close to each other, except for the oxidation
stability. In the standard results, its measured in grams per cubic meters and not in hours as
in the standard results for rapeseed oil and biodiesel because the oxidation stability for diesel
is measured differently as was mentioned previously. Here the result of oxidation stability for
diesel which was got from the lab, was done by the rancimant method and its not accurate
for diesel. Unfortunately, the oxidation stability for diesel according to the standard method
couldnt not be performed in the Lab because the experiment needs pure oxygen, which
gives a very flammable mixture together with diesel and the Lab is not equipped for that.

75
9.5 Discussion of results: Comparing between experimental and standard of
the fuel analytics results of rapeseed oil, diesel and biodiesel.

For the biodiesel which was produced from rapeseed oil in the Lab, it could be noticed that
its not of high quality. That could be noticed from the color of the biodiesel compared to the
commercial biodiesel (from the gas station). Also, the oxidation stability experiment (18.78 h)
could show the low quality of biodiesel produced in the lab because comparing it to
commercial biodiesel (7.64 h). That is due to the fact that commercial biodiesel undergoes
additional steps once the transestrification is completed, such as the removal of the excess
alcohol in glycerin and biodiesel phases is removed with a flash evaporation process or by
distillation and Methyl Ester Wash. Also, the biodiesel is sometimes purified by washing
gently with warm water to remove residual catalyst or soaps, dried, and sent to storage,
resulting in a clear amber-yellow liquid with a viscosity similar to petro-diesel, which is the
color of the commercial biodiesel.

Figure 9.5.1: Biodiesel from gas station Figure 9.5.2: Biodiesel produced in the lab

76
For the results of the properties that were determined for rapeseed oil, diesel and two types
of biodiesel (produced in lab and from gas station), which were the density, the kinematic
viscosity, the lower calorific value and the oxidation stability. These results were compared to
the standard values.

For rapeseed oil, it could be noticed that most of the experimental results of the density, the
kinematic viscosity, and the lower calorific value shown in table 9.4, are very close to the
German Rapeseed Oil Fuel Standard DIN 51 605 shown in table 9.3. For the experimental
result of the oxidation stability, it can be noticed that in the standard results, the min. is five
hours and the result that was got in the lab was three hours and this due to that the rapeseed
oil which was used in the lab was not a fresh one, it was one year old oil.

For biodiesel, from gas station, it could be noticed that most of the experimental results of
the density, the kinematic viscosity, the lower calorific value and the oxidation stability shown
in table 9.6, are very close to the European Standard EN 14214 of biodiesel shown in table
9.5. This is because its commercial biodiesel which is sold in gas stations, where it should
meet the standards of biodiesel.

For biodiesel, produced in the lab and as was mentioned before, its not of high quality as
commercial biodiesel. It could be noticed from the experimental results shown in table 9.6, of
the density, and the lower heating value that they are close to the European Standard EN
14214 of biodiesel. But for the kinematic viscosity, it could be noticed that the experimental
result (5.706 mm/s) is a little bit higher than the max. of the standard value (5 mm/s ) and
this because the biodiesel produced in the lab was not converted completely to biodiesel, it
had a little amount of rapeseed oil and its known that rapeseed oil has high viscosity, so
thats why the biodiesel had higher viscosity. For the oxidation stability, theres a very big
difference between the standard value (6 h) and the experimental one (18.78 h). This value
is too high to be reasonable, this could be due to a fault in the experiment e.g. compressed
air which was supplied to the biodiesel could have failed for some hours during the night.

For diesel fuel, it could be noticed that most of the experimental results of the density, the
kinematic viscosity, and the lower calorific value shown in table 9.8, are very close to the DIN
EN 590 standards of diesel shown in table 9.7. This is because its commercial diesel which
is sold in gas stations, where it should meet the standards of diesel fuel. But for the oxidation
stability, in the standard results, its measured in grams per cubic meters and not in hours as
in the standard results for rapeseed oil and biodiesel, this is because the oxidation stability
for diesel is measured in a different way than that for rapeseed oil and biodiesel. Here the

77
result of oxidation stability for diesel which was got from the lab, was done by the rancimant
method as for rapeseed oil and biodiesel but its not accurate. Unfortunately, the oxidation
stability for diesel according to the standard method couldnt not be performed in the lab
because the experiment needs pure oxygen, which gives a very flammable mixture together
with diesel and the lab is not equipped for that.

78
9.6 The Emission testing experiment for rapeseed oil, low sulfur
diesel fuel and biodiesel (from gas station).

9.6.1 Equipment used:

1- Engine used:

Tractor Diesel engine of type Kubota 05 Series D1105-E3B, it is a three cylinder swirl
chamber engine with a total displacement of 1.1 liter.

The engine is used for driving a generator to produce electricity; waste heat of the engine is
used for heating (co-generation unit).

Electric and thermal power of co-generation unit respectively are 5 and 12 Kw, respectively.
(48)

More specifications about engine can be found in Appendix B, B.1

Figure 9.6.1.1: Kubota diesel engine

79
2- MLT 4 Multi-Component Gas Analyzer

MLT 4 Multi-Component Gas Analyzer is a multi-component, multi-method analysis using


infrared, ultraviolet, thermal conductivity, paramagnetic and electrochemical sensor
technologies. Housed in a 19-inch enclosure (thermostatically-controlled option), the MLT 4
Gas Analyzer can measure up to five gas components by combining the different
technologies into one unit. (49)

More specifications about this device can be found in Appendix B, B.2

The version of the MLT 4 gas analyzer which is used at the Fachhochschule, is equipped
with NDIR and UV/ VIS analyzers for O2, CO2, CO, NO, NO2, SO2, H2 AND CH4.
NDIR: Non dispersive infrared sensor

UV: Ultra Violet

VIS: Visual light spectrometer

Figure 9.6.1.2: MLT 4 Gas analyzer

80
3- Total Hydrocarbon Analyzer (THC)

The Total Hydrocarbon Analyzer is designed especially for mobile use at various sites and
operating conditions both for continuous and short monitoring. Features of the total
hydrocarbon analyzer include measuring ranges from 1 ppm to 100,000 ppm, internal air
supply and a patented miniature heated sensor block with a flame ioni- sation detector
controlled up to 240 C, making it possible to measure in steam saturated gases. The
instrument is suitable for compliance to national reference measuring methods and
regulations for emission measuring and for the efficiency control of thermal, catalytic,
biological and activated carbon exhaust air purifying plants and other emission sources,
permitting control of these processes. (50)

More specifications are shown in Appendix B, B.3

The THC analyzer measures according to the hot FID principle.

FID: Flame ionization detector

Figure 9.6.1.3:: Total hydrocarbon analyzer

81
4- BRIGON - Smoke Tester:

The BRIGON-Smoke is a device for determining the smoke number. It is easy to handle,
lightweight and reliable instrument.

The smoke tester forces a gas sample to cross the filter paper and leave a soot spot, which
is then compared with smoke scale to determine smoke number. High smoke number is an
obvious symptom of incomplete combustion and may have various reasons, as well as
serious consequences (air pollution, soot disposition on heat exchange surfaces, fuel waste,
etc.)

The contents of this smoke tester include smoke tester, filter paper, smoke scale and
lubricant oil. (51)

More specifications about this device can be found in AppendixB, B.4.

Figure 9.6.1.4: Smoke tester device

82
9.6.2 Procedure of the emission testing experiment
In this experiment, the emissions of three fuels, were measured and compared in a diesel
engine. Rapeseed oil, diesel fuel and biodiesel fuel from gas station were used in the
experiment. The emissions the gas analyzer measured were: SO2, CO, O2, CO2, and NOx
which was the sum of NO and NO2.Hydrocarbons of fuels were measured alone by the
hydrocarbon analyzer device. The reading of hydrocarbons was changed every five seconds
and three readings were taken in three different times as shown in table 9.9. The mean value
of the three readings was recorded in table 8.10 for total hydrocarbons.

For the soot measurement, it was measured by the smoke tester device, which was
mentioned previously in section 9.3.2 in the used equipment part. Three samples were taken
from the exhaust on a filter paper for every fuel by the smoke tester device. Actually it can be
seen from figure 9.16 that there are four samples on the filter paper, three are numbered and
one is without a number. The one without a number is the first sample taken to clean the
exhaust. After that by using a detecting device, it was possible to determine the soot or
smoke number for every sample and the mean value of the three values was taken.

Figure 9.6.2.1: Smoke / soot samples in lab

83
Figure 9.6.2.2: Densitometer (device for determining the smoke number) and the smoke scale in lab

The diesel engine of type Kubota 05 Series D1105-E3B was turned on, the engines speed
was1500 rpm and the electric load was 5 Kw at full load. The first fuel was used was the
rapeseed oil, the average time for every fuel was 15 minutes in the engine. Measurements of
the emissions were taken after the temperatures of the engines cooling water and exhaust
were stable. Three measurements of hydrocarbons were taken at three different times as
shown in table 8.9. Then three samples of ash or soot were taken on a filter paper and ash or
smoke number was measured by a detecting device. The gas analyzer took measurements
every 5 seconds for 15 minutes and the file of the emission measurements was saved on a
special computer program to calculate the mean values. The same procedure was used for
diesel and biodiesel fuels.

84
9.6.3 Tabulated Results of the emission testing experiment

Table 9.6.3.1: Three different readings for the total hydrocarbons in three different times and three different
readings for ash number for every fuel.

Fuel type Total hydrocarbons Ash number


(ppm) @ different times (samples)

Rapeseed 10 @ 9 @ 9:48 10 @ 9:55 6.7 6.8 6.9


oil 9:43

Diesel 7@ 6.5 @ 10:25 6 @ 10:34 5.0 5.3 6.5

10:17

Biodiesel 4.5 @ 4.6 @ 10:58 4.6 @ 11:03 5.4 5.8 5.7

10:25

Table 9.6.3.1shows three different readings of the total hydrocarbons at three different times
for rapeseed oil, diesel and biodiesel. It can be noticed that there is no big difference in the
readings for every fuel. Also, it can be noticed that the rapeseed oil has the highest readings
of the total hydrocarbons while the biodiesel has the lowest readings which is reasonable.
For the smoke number, it can be noticed that rapeseed oil also has the highest readings,
while diesel and biodiesel readings are close to each other, but the biodiesel smoke number
for biodiesel is a little bit higher than diesel.

85
Table 9.6.3.2: The values of cooling water temperature, the exhaust temperature, the mean values of the total
hydrocarbons and the smoke number for every fuel.

Fuel type Cooling Exhaust Total Filter smoke


water temperature hydrocarbons number
temperature ppm (Mean (Mean
C
C value) value)

Rapeseed 72 277 9.67 6.80


oil

Diesel 75 273 6.50 5.60

Biodiesel 77 269 4.57 5.63

Table 9.6.3.2 shows the values of the total hydrocarbons of the rapeseed oil, 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.

86
Table 9.6.3.3 Mean values of the resulted emissions for every fuel

Fuel type SO2 NO NO2 NOx CO O2 Vol.-% CO2


Vol.-%
ppm ppm ppm ppm ppm (Mean
(Mean (Mean (Mean (Mean (Mean value (Mean
value
value) value) value) value) value

Rapeseed 18,225 480 27,980 507,98 281,85 10,800 7,505


oil

Diesel 18,850 541 33,500 574,50 88,650 10,675 7,445

Biodiesel 18,865 529,5 35,250 564,75 99,950 10,715 7,485

Table 9.6.3.3 shows the mean values of the resulted emissions for every fuel that were
measured by the gas analyzer. 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.

87
9.6.4 Graphical Results: Comparing the emissions of rapeseed oil,
diesel and biodiesel

Figure 9.6.4.1 : Resulted SO2 emissions for rapeseed oil, diesel and biodiesel

Figure 9.6.4.2: Resulted NOx emissions for rapeseed oil, diesel and biodiesel

88
Figure 9.6.4.3: Resulted CO emissions for rapeseed oil, diesel and biodiesel

Figure 9.6.4.4: Resulted O2 emissions for rapeseed oil, diesel and biodiesel

89
Figure 9.6.4.5: Resulted CO2 emissions for rapeseed oil, diesel and biodiesel

Figure 9.6.4.6: Resulted hydrocarbon emissions for rapeseed oil, diesel and biodiesel

90
Figure 9.6.4.7: Resulted filter smoke number for rapeseed oil, diesel and biodiesel

Figures from 9.6.4.1 until 9.6.4.7 show the graphs of the experimental results of SO2, NOx,
CO, O2, CO2, unburned hydrocarbons and the smoke number respectively for rapeseed oil,
biodiesel and diesel fuel.

91
9.6.5 Discussion of Results: Comparing between the results of the
emission testing experiment of diesel and biodiesel fuels

For SO2, and as was mentioned before in section 7.4, biodiesel is free from sulfur hence
produces less sulfate emissions, but according to the experimental results of SO2 emissions
which are shown in table 9.11 and figure 9.18, it can be noticed that the SO2 emission of
biodiesel is too high, actually biodiesel has the highest value of SO2 when compared to
diesel and rapeseed oil in figure 9.18. Well, definitely this was a wrong result because the
SO2 channel of the gas analyzer was not calibrated due to the lack of reference gas for SO2.
Moreover, the diesel which was used is a low-sulfur diesel, which also proves that the results
that were got were wrong ones. For the NOx, which are the sum of NO and NO2 emissions,
and as was mentioned before in section 7.7, biodiesel has higher nitrogen oxide NOx
emissions than petrodiesel. 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.
According to the experimental results of NOx emissions, it can be noticed from table 9.11
and figure 9.19, that the biodiesel has lower NOx emissions than diesel. For CO emissions,
and as was mentioned in section 7.4, CO emissions are reduced in the exhaust when using
biodiesel fuel, because biodiesel contains more oxygen than diesel fuel and this results in
complete combustion. According to the experimental results, it can be noticed from table
9.11 and figure 9.20, that biodiesel has higher CO emissions than diesel, and this means that
the combustion for biodiesel was not a complete one, and hence produced more CO
emissions than diesel fuel. For the CO2, and as was mentioned in section 7.6, that One of
the most attractive aspects of biodiesel use is that it provides a means of recycling carbon
dioxide, so there is no net increase in global warming. As with any complete combustion,
carbon dioxide and water are the end products, but these will be taken up by the plant to
ultimately lead to production of new biodiesel. According to the experimental results, it can
be noticed from table 9.11 and figure 9.22, that biodiesel and diesel have very close values
of CO2 emissions, but the biodiesel is slightly higher, maybe this is due to the fact that
biodiesel has to burn more hydrocarbons, to give the same amount of energy that the diesel
fuel does, because it has less heating value than diesel, and because of that more CO2 is
produced. For the O2, the experimental results for diesel and biodiesel are close to each,
biodiesel has slightly higher value, and this is because of the oxygenated nature of biodiesel
where more oxygen is available for burning. For the hydrocarbon emissions, as was

92
mentioned in section 7.4, hydrocarbon emissions are much lower in case of biodiesel
compared to diesel. This is due to oxygenated nature of biodiesel where more oxygen is
available for burning and reducing hydrocarbon emissions in the exhaust the use of biodiesel
results in a substantial reduction of un-burned hydrocarbons, and according to the
experimental results, it can be noticed from table 9.10 and figure 9.23 that the hydrocarbon
emissions of biodiesel are lower than those for hydrocarbons by almost 30% which means
the hydrocarbons emissions are reduced when using biodiesel fuel compared to diesel fuel

For the Filter smoke number or as was mentioned in section 7.4, the smoke opacity which
is a direct measure of smoke and soot. Various studies show that smoke opacity for biodiesel
is generally lower. According to the experimental results shown in table 9.10 and figure 9.24,
it can be noticed that diesel and biodiesel have almost the same mean value of the smoke
number; maybe this is due to the lack of oxygen in the combustion of diesel and biodiesel
and because both fuels have similarity in characteristics.

93
Chapter 10
Summary

The study of this Master thesis was about the manufacturing of biodiesel from the waste
vegetable oil. This study showed that biodiesel is an environmentally friendly due to its less
polluting and renewable nature compared with conventional petroleum diesel fuel. Moreover,
it could be used in any diesel engine without modification. Biodiesel could be made out of
pure or waste vegetable through a transesterification process in the presence of a catalyst.
The purpose of the transesterification process is to lower the viscosity of the oil, which is
better for the engine performance.

Biodiesel esters are characterized by their physical and fuel properties including density,
viscosity, iodine value, acid value, cloud point, pure point, gross heat of combustion, and
volatility. Biodiesel fuels produce slightly lower power and torque and consume more fuel
than diesel fuel. Biodiesel is better than diesel fuel in terms of sulfur content, flash point,
aromatic content, and biodegradability (Bala, 2005).

The cost of biodiesels varies depending on the base stock, geographic area, variability in
crop production from season to season, the price of crude petroleum, and other factors.
Biodiesel is more than twice as expensive as petroleum diesel. The high price of biodiesel is
in large part due to the high price of the feedstock. However, biodiesel can be made from
other feedstocks of low cost oils and fats such as restaurant waste and animal fats that could
be converted into biodiesel. The problem with processing these low-cost oils and fats is that
they often contain large amounts of free fatty acids (FFA) that cannot be converted into
biodiesel using an alkaline catalyst (Demirbas, 2003; Canakci and Van Gerpen, 2001).If the
biodiesel valorized efficiently at energy purpose, so would be benefit for the environment and
the local population, job creation, provision of modern energy carriers to rural communities.

Many experiments were performed on biodiesel in the lab; the first one was producing the
biodiesel from the rapeseed oil. The biodiesel produced wasnt of high quality as the
commercial biodiesel or biodiesel from the gas station. This is due to the fact that commercial
biodiesel which was produced in the lab didnt undergo under additional steps once the
transestrification is completed as for commercial biodiesel; e.g. the removal of the excess
alcohol in glycerin and biodiesel phases with a flash evaporation process or by distillation

94
and Methyl Ester Wash. Also washing gently with warm water to remove residual catalyst or
soaps, dried, and sent to storage, resulting in a clear amber-yellow liquid with a viscosity
similar to petro-diesel. From figures 10.1 and 10.2, it could be noticed the difference in colors
between the biodiesel from gas station and biodiesel produced in the lab.

Figure 10.1: Biodiesel from gas station Figure 10.2: Biodiesel produced in
the lab

For the fuel analytics, the properties of density, kinematic viscosity, lower calorific value and
oxidation stability for Rapeseed oil, Diesel and two types of Biodiesel were tested and
compared to standard values.

For rapeseed oil, it was noticed that most of the experimental results matched the German
Rapeseed Oil Fuel Standard DIN 51 605 except for the oxidation stability, it can be noticed
that in the standard results, the minimum was five hours and the result that was got in the lab
was three hours and this due to that the rapeseed oil which was used in the lab was not a
fresh one, it was one year old oil. For biodiesel, from gas station, it was noticed that most of
the experimental results matched the European Standard EN 14214 of biodiesel .This was
because its a commercial biodiesel which is sold in gas stations, where it should meet the
standards of biodiesel. For biodiesel, produced in the lab and as was mentioned before that
it wasnt of high quality as commercial biodiesel, the experimental results of the density, and
the lower heating value were very close to the European Standard EN 14214 of biodiesel.
But for the kinematic viscosity, it was noticed that the experimental result (5.706 mm/s) was
a little bit higher than the maximum of the standard value (5 mm/s). That was because the
biodiesel produced in the lab was not converted completely to biodiesel, it had a little amount
of rapeseed oil and its known that rapeseed oil has high viscosity, so thats why the biodiesel
had higher viscosity. For the oxidation stability, there was a very big difference between the
standard value (6 hours) and the experimental one (18.78 hours). This value was too high to
be reasonable, this could be due to a fault in the experiment e.g. compressed air which was

95
supplied to the biodiesel could have failed for some hours during the night. For diesel fuel, it
was noticed that most of the experimental results were very close to the DIN EN 590
standards of diesel that was because its a commercial diesel which is sold in gas stations,
where it should meet the standards of diesel fuel. But for the oxidation stability, it was noticed
that in the standard results it was measured in grams per cubic (g/m3) meters and not in
hours (h) as in the standard results for rapeseed oil and biodiesel, this is due to the fact that
the oxidation stability for diesel is measured in a different way than that for rapeseed oil and
biodiesel. The experimental result of oxidation stability for diesel which was got from the lab
was done by the rancimat method as for rapeseed oil and biodiesel but it was not accurate
for diesel. Unfortunately, the oxidation stability for diesel according to the standard method
couldnt not be performed in the lab because the experiment needs pure oxygen, which gives
a very flammable mixture together with diesel and the lab is not equipped for that.

For the emissions testing experiment, the emissions of SO2, CO, O2, CO2, NO and NO2
were tested using the MTL 4 gas analyzer, also the total hydrocarbons were tested by the
total hydrocarbon analyzer device and the soot or smoke number was tested by the smoke
tester device for rapeseed oil, biodiesel (from gas station) and diesel fuel. The comparison of
the emissions was made between biodiesel and diesel fuels.

It was noticed from emissions testing experiment that the experimental results didnt match
what was said in theory about the emissions of diesel and biodiesel as in section 7.4, 7.5 and
7.6. The only reduction that was noticed was in the unburned hydrocarbons by almost 30%
and the NOx. It was noticed also that emissions of SO2 of biodiesel were too high in spite of
the fact that biodiesel id free from sulfur. This result was a wrong one because the SO2
channel of the gas analyzer was not calibrated due to the lack of reference gas for SO2 in
the gas analyzer. For CO, it was noticed that biodiesel had higher emissions than diesel fuel
and this meant that the combustion for biodiesel was not a complete one because there was
not enough oxygen, and hence produced more CO emissions than diesel fuel. This might be
because the engine that was used in the experiment was not adapted to biodiesel use. Also,
CO2 emissions of biodiesel were close to those of diesel fuel, and according to theory, there
should be reduction in CO2 emissions. Maybe this is due to the fact that biodiesel has to
burn more hydrocarbons, to give the same amount of energy that the diesel fuel does,
because biodiesel has less heating value than diesel, and because of that more CO2 is
produced. The measurement of the smoke number for biodiesel was not accurate, biodiesel
and diesel had very close values of smoke number and according to theory, biodiesel should
have less smoke number. Maybe the changes of the smoke number were too small to be
detected at certain conditions.

96
Chapter 11

Conclusion and Recommendations

In a world where every action must be weighed against its demerits, where everything should
be balanced between power and the environment, in a world like today, where petroleum
reserves are becoming limited and will eventually run out and the critical issue of oil peak
and the environmental concerns, all have prompted deeper research into the area of
alternatives to fossil fuels which are biofuels such as biodiesel and bioethanol. Biodiesel has
become more attractive recently because of its environmental benefits and the fact that it is
made from renewable resources. Biodiesel is briefly defined as the monoalkyl esters of
vegetable oils or animal fats. Biodiesel is the best candidate for diesel fuels in diesel engines.
It burns like petroleum diesel as it involves regulated pollutants. So it necessary to implement
the use of biodiesel over the current petroleum and gasoline because of all the merit and
advantages it brings forth to the table. In comparison to petroleum and gasoline, biodiesel
beats its competitors in all categories of toxic substance emissions and poses close to no
threat to the environment. What's more, instead of increasing the carbon dioxide levels in the
atmosphere, the overall production and use of biodiesel consumes more carbon dioxide than
it emits, thus making it a valuable tool in preventing global warming.

Not only does petroleum diesel harm our environment through emissions of toxic sub-
stances, but it also has negative affects on us physically. Many health problems and
illnesses have been traced back to emissions from petroleum diesel. These emissions have
been related to many cases of cancer, cardiovascular and respiratory disease, asthma and
infections in the lungs. By using biodiesel in the place of petroleum diesel, not only will we be
helping the environment with a much better alternative, but we would be significantly
reducing many health risks.

The fact that most biodiesels are domestically produced means that by using more of it, the
market of biodiesel would actually stimulate the economy, reducing a countrys dependence
on foreign oil imports. Also, the implementation of biodiesel is extremely easy and requires
little or no modifications to the typical diesel engine, making it a very easy and smooth
transition.

97
When we weigh the advantages of biofuel against its disadvantages, it is clear that it brings
more than it takes away because biofuels are easily available from common biomass
sources, carbon dioxide cycle occurs in combustion, they are very environmentally friendly,
and they are biodegradable and contribute to sustainability (Puppan, 2002).

It is true that commercial food are used to make biodiesel but if there is a surplus of it, why
not put the excess to better use. Not only does it match its rivals in energy output, it also
reduces the damage done to the world.

The production of biodiesel from waste vegetable oil offers a triple-facet solution: economic,
environmental and waste management. The new process technologies developed during the
last years 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.

Recommendations:

Further research should be done on the following areas:

- Nowadays bio-diesel cost is 1.5 to 3 times higher than the fossil diesel cost because
the largest share of production cost of bio-diesel is the feedstock cost. Therefore, bio-
diesel is not competitive to fossil diesel under current economic conditions, where the
positive externalities, such as impacts on environment, employment, climate changes
and trade balance are not reflected in the price mechanism. However, biodiesel can
be made from other feedstocks of low cost oils and fats such as restaurant waste and
animal fats that could be converted into biodiesel. The problem with processing
these low-cost oils and fats is that they often contain large amounts of free fatty acids
(FFA) that cannot be converted into biodiesel using an alkaline catalyst (Demirbas,
2003; Canakci and Van Gerpen, 2001).

- Important operating disadvantages of bio-diesel in comparison with fossil diesel are


cold start problems and the lower energy content. This increases fuel consumption
when biodiesel is used (either in pure or in blended form) in comparison with
application of pure fossil diesel, in proportion to the share of the bio-diesel content.
Taking into account the higher production value of bio-diesel as compared to the

98
fossil diesel, this increase in fuel consumption raises in addition the overall cost of
application of bio-diesel as an alternative to fossil diesel.

- The competitiveness of bio-diesel relies on the prices of bio-mass feedstock and


costs, linked to the conversion technology. Depending on the feedstock used, by-
products may have more or less relative importance.

- Further experiments should be done in the lab such as producing the biodiesel from
pure or waste vegetable oil and make it undergo under all the additional steps once
the transestrification is completed as to get a biodiesel of high quality as for
commercial biodiesel. Also, further fuel analytics should be done on biodiesel to get
properties that match the standard values such as density, viscosity, heating value
and oxidation stability. Moreover, further experiments of fuel analytics could be done
to get other fuel properties as flash point, cloud point, cetane number, etc. and last
but not least the further emission testing should be done on different engines using
the biodiesel fuel to get results that show the reduction of emissions when using
biodiesel as it said in theory.

99
Bibliography

(1) http://www.biodieselbooklet.co.uk/biodiesel-wvo.html

(2) http://www.tcbiodiesel.com/making-biodiesel-from-waste-vegetable-oil/

(3) http://www.marcussharpe.com/biodiesel.shtml

(4) http://www.utahbiodieselsupply.com/whybiodiesel.php

(5) http://oaithesis.eur.nl

(6) http://www.bioenergywiki.net/What_is_bioenergy

(7) http://renet-eu-india.com/energybio.php

(8) http://www.sustainablebuild.co.uk/BioEnergy.html

(9) Biomass resource facilities and biomass conversion processing for

fuels and chemicals, AyhanDemirba s * P.K. 216, TR-61035-Trabzon, Turkey

(10) http://www.windows2universe.org/earth/Water/co2_cycle.html

(11) http://www.windows2universe.org

(12) http://www.energyfuturecoalition.org/biofuels

(13) http://www.ppvir.org/pdf

(14) Political, economic and environmental impacts of biofuels: A review Ayhan Demirb

(15) Biodiesel, a realistic fuel alternative for diesel engines- springer-2008.pdf

(16) http://www.window.state.tx.us/specialrpt/energy/renewable/biodiesel.php

(17) http://www.window.state.tx.us/specialrpt/energy/renewable/ethanol.php

(18) http://news.mongabay.com

(19) http://www.nrel.gov

(20) http://www.bdpedia.com/biodiesel/char/char.html

(21) www.wikipedia.org/wiki/Biodiesel#Biodiesel_feedstocks

(22) http://www.ag.ndsu.edu/pubs/ageng/machine/ae1240w.htm

(23) www.wikipedia.org/wiki/Biodiesel

100
(24) http://www.sciencedirect.com/.pdf Biodiesel from waste cooking oil via base-
catalytic and supercritical methanol transesterification Ayhan Demirbas

(25) http://www.uic.edu/ biodiesel1_module.pdf

(26) http://www.biodiesel.org

(27) http://www.biodiesel1_module.com/pdf

(28) http://ftp.jrc.es/EURdoc/eur20279en.pdf

(29) Biodiesel RME-Rechner Chemical Engineering department, HAW

(30) The production of biodiesel from rapeseed oil experiment, Chemical Engineering
department, university of applied science (HAW).

(31) Thin layer chromatography device in the Lab of chemical engineering department in
HAW

(32) www. Berlin072-prestandarddinv51605.com/pdf

(33) http://www.biodieselfillingstations.co.uk/approvals.htm

(34) Kinematic Viscosity experiment, Mechanical Engineering department, University of


Applied Science (HAW), Amberg, German

(35) http://www.thefullwiki.org/Viscometer)

(36) http://classle.net/bookpage/properties-biodiesel

(37) http://en.wikipedia.org/wiki/Hydrometer

(38) http://en.wikipedia.org/wiki/File:PycnometerEmpty.jpg

(39) http://classle.net/bookpage/properties-biodiesel

(40) Heating value experiment, Mechanical Engineering department, University of Applied


Science (HAW), Amberg, Germany

(41) http://en.wikipedia.org/wiki/Calorimeter

(42) http://www.metrohm.com/com/downloads/OMS/oxidation_stability.pdf

(43) http://www.springerlink.com/content

(44) http://www.rsc.org/images

(45) http://www.cecri.res.in/CIF/cif.htm

(46) http://www.biofuelsb2b.com/useful

(47) www.biofuels2b2.com

(48) http://www.kubotaengine.com/products/05/d1105_e3_2.html

101
(49) http://www2.emersonprocess.com

(50) http://www.quantitech.co.uk

(51) http://www.brigon.de/englisch/smoke-tester.html

102
List of Figures
Figure 4.3.1:The Carbon Cycle;The movement of Carbon dioxide through the
atmosphere............................................................................................................................11

Figure 4.3.2: Biofuels and the carbon cycle..........................................................................13

Figure 5.1.1: Sources of main liquid biofuels for automobiles...............................................15

Figure 5.1.2: The worlds top ethanol and biodiesel producers in 2008 (REN21,2009).......16

Figure 5.1.3: Global ethanol and biodiesel production 2000-2008 with projection to 2015..17

Figure 5.1.4: Biodiesel Production Cycle.17

Figure 5.1.5: Ethanol Production Cycle18

Figure 5.2: The Worlds and EUs biofuel consumption..........................................................21

Figure 6.2: Dr. Rudolf Diesel..................................................................................................23

Figure 6.7: Conversion of Vegetable Oil to Biodiesel............................................................29

Figure7.4: B100 emissions compared to petroleum diesel emissions by percentage.........39

Figure 7.5: A simple cycle of carbon dioxide of biodiesel and fossil fuel with different time
frames..................................................................................................................................40

Figure 8.1: Price of fossil diesel (commercial use) Euro/l....................................................45

Figure 9.1: Biodiesel produced in the lab............................................................................49

Figure 6.2.1: Dr. Rudolf Diesel............................................................................................49

Figure 9.1.1.2: The filtration of 50 ml of rapeseed oil..........................................................50

Figure 9.1.2: Biodiesel RME Rechner.................................................................................51

Figure 9.1.4: Thin layer chromatography device in the Lab................................................52

Figure9.2.3: The Ubbelohde viscometer.............................................................................56

Figure9.2.4.1: Hydrometer..................................................................................................57

Figure 9.2.4.2: Pycnometer.................................................................................................58

Figure 9.2.5: Bomb Calorimeter..........................................................................................60

Figure 9.2.6: The Rancimat device......................................................................................61

Figure 9.2.6.1: The oxidation stability graph of rapeseed oil...............................................63

Figure 9.2.6.2: The oxidation stability graph of biodiesel (from gas station).......................63

Figure 9.2.6.3: The oxidation stability graph of biodiesel (produced in lab)........................64

103
Figure 9.2.6.4: The oxidation stability graph of diesel fuel..................................................64

Figure 9.3: CHNS-O Elemental Analyzer............................................................................66

Figure 9.5.1: Biodiesel from gas station..............................................................................76

Figure 9.5.2: Biodiesel produced in the lab.........................................................................76

Figure 9.6.1.1: Kubota diesel engine...................................................................................79

Figure 9.6.1.2: MLT 4 Gas analyzer....................................................................................80

Figure 9.6.1.3: Total hydrocarbon analyzer.........................................................................81

Figure 9.6.1.4: Smoke tester device....................................................................................82

Figure 9.6.2.1: Smoke / soot samples.................................................................................83

Figure 9.6.2.2: Densitometer (device for determining the smoke number).........................84

and the smoke scale

Figure 9.6.4.1 : Resulted SO2 emissions for rapeseed oil, diesel and biodiesel................88

Figure 9.6.4.2: Resulted NOx emissions for rapeseed oil, diesel and biodiesel.................88

Figure 9.6.4.3: Resulted CO emissions for rapeseed oil, diesel and biodiesel...................89

Figure 9.6.4.4: Resulted O2 emissions for rapeseed oil, diesel and biodiesel....................89

Figure 9.6.4.5: Resulted CO2 emissions for rapeseed oil, diesel and biodiesel.................90

Figure 9.6.4.6: Resulted hydrocarbon emissions for rapeseed oil, diesel and biodiesel.....90

Figure 9.6.4.7: Resulted filter smoke number for rapeseed oil, diesel and biodiesel...........91

Figure 10.1: Biodiesel from gas station..................................................................................95

Figure 10.2: Biodiesel produced in the lab.............................................................................95

104
List of Tables
Table 5.1: Major benefits of Biofuels...................................................................................14

Table 5.2: An Overview of the product biofuel, per generation type...................................20

Table 6.8: Comparison of properties of waste cooking oil, biodiesel from waste cooking oil
and commercial diesel fuel..................................................................................................32

Table 7.2: Properties of Biodiesel prepared from vegetable oils.........................................36

Table 8.2.2: Bio-diesel cost production depending on rape-seed price in Euro/l................46

Table 9.2.2: Some properties of diesel and biodiesel standards...54

Table 9.2.3: Experimental results of kinematic viscosity for rapeseed oil, two types of
biodiesel and diesel fuel......................................................................................................56

Table 9.2.4: Experimental results of Density for rapeseed oil, two types of biodiesel and
diesel fuel............................................................................................................................58

Table 9.2.5: Experimental results of Lower heating value for rapeseed oil, two types of
biodiesel and diesel fuel......................................................................................................60

Table 9.2.6: Experimental results of Oxidation stability for rapeseed oil, two types of biodiesel
and diesel fuel.....................................................................................................................62

Table 9.3.1: Elementary analyzer results for biodiesel produced in lab..............................67

Table 9.3.2: Elementary analyzer results for diesel fuel and rapeseed oil..........................68

Table 9.3.3: Elementary analyzer results for biodiesel (gas station)...................................69

Table 9.4.1: Characteristic properties for Rapeseed 0il according to DIN 51 605 - German
Rapeseed Oil Fuel Standard...............................................................................................70

Table 9.4.2: Characteristic properties for Rapeseed 0il according to experiments done in the
Lab. of the FachHochSchule, Amberg 2010/2011..............................................................71

Table 9.4.3: Characteristic properties for Biodiesel according to European

Standard EN 14214.............................................................................................................72

Table 9.4.4: Characteristic properties for two types of Biodiesel, one produced in the lab. of
the Fachhochschule, Amberg 2010,/2011 and the other one was bought from the gas
station..................................................................................................................................73

Table 9.4.5: Characteristic properties for Diesel according to the DIN EN 590 standards,
July1999..............................................................................................................................74

Table 9.4.6: Characteristic properties for Diesel according to according to experiments done
in the Lab. of the FachHochSchule, Amberg, 2010/2011...............................75

105
Table 9.6.3.1: Three different readings for the total hydrocarbons in three different times and
three different readings for ash number for every fuel........................................................85

Table 9.6.3.3 Mean values of the resulted emissions for every fuel...................................86

Table 9.6.3.2: The values of cooling water temperature, the exhaust temperature, the mean
values of the total hydrocarbons and the smoke number for every fuel.87

106
Appendix A: The experiment of biodiesel production from rapeseed oil, the
experiments of Density, Kinematic viscosity, High calorific value and Oxidation stability
experiments for fuel analytics of rapeseed oil. (These experiments were done also on Diesel
and Biodiesel), the DIN 51605 of Rapeseed oil, 2005-06 and the DIN EN 590 for Diesel,
July, 1999.

A.1 The production of biodiesel from rapeseed oil experiment.108

A.2 Density experiment....110

A.3 Temperature corrector for Hydrometers table......111

A.4 Kinematic Viscosity Experiment..112

A.5 High heating value Experiment...114

A.6 The oxidation stability Experiment.....116

A.7 DIN 51605 of Rapeseed oil, 2005-06119

A.8 DIN EN 590 for Diesel..120

A.9 CHNS Elementary Analyzer....121

107
A.1 The production of biodiesel from rapeseed oil experiment

108
109
A.2 Density experiment

110
A.3 Temperature corrector for Hydrometers table

A.4 Kinematic Viscosity Experiment


111
112
113
A.5 High heating value Experiment

114
115
A.6 The oxidation stability Experiment

116
117
118
A.7 DIN 51605 of Rapeseed oil, 2005-06

119
A.8 DIN EN 590 for Diesel

120
A.9 CHNS Elementary Analyzer

121
122
Appendix B :Specifications of equipment used for the emission testing experiment

B.1 Specifications of Engine124

B.2 Specifications of Gas Analyzer126

B.3 Specifications of Hydrocarbon analyzer.130

B.4 Specifications of Brigon smoke tester133

123
B.1 Specifications of Engine

124
125
B.2 Specifications of Gas Analyzer

126
127
128
129
B.3 Specifications of Hydrocarbon analyzer

130
131
132
B.4 Specifications of Brigon smoke tester

133