ABSTRACT

The alternative fuel biodiesel is produced from the transesterification

of vegetable oils and animal fats to fatty acid methyl esters. Engine
and unconventional fuels lab, Centre for energy studies, IIT Delhi has a
biodiesel reactor that can be used to run this reaction and produce
biodiesel. Keeping in mind, the growing energy consumption in the
world and the demand for better and cleaner fuels, biodiesel provides a
very good alternative.
Presently Petroleum constitutes the maximum percentage of meeting
the energy demand. But these are fossil fuels which cannot be
renewed and are going to be exhausted in the near future. Biodiesel
has many important technical advantages over petrodiesel, such as
inherent lubricity, low toxicity, derivation from a renewable and
domestic feedstock, superior flash point and biodegradability,
negligible sulfur content, and lower exhaust emissions and can be used
in diesel engines without significant modifications. Important
disadvantages of biodiesel include high feedstock cost, inferior storage
and oxidative stability, lower volumetric energy content, inferior lowtemperature operability, and in some cases, higher NOx exhaust
emissions.
This report analyses the different methods of preparation of biodiesel,
different types of catalysts that may be used for biodiesel production,
different types of alcohol used for biodiesel production, effect of the
reaction variables in transesterification, kinetics of the
transesterification reaction, different by-products of transesterification
reaction, their treatment and separation.
In this study, the biodiesel produced from Pongamia Pinnata (Karanja)
oil was prepared by a method of alkali-catalysed transesterification.
The effects of biodiesel addition to diesel fuel on the performance and
emissions of a naturally aspirated single cylinder compression ignition

engine were examined. The significant improvement in reduction of

Carbon monoxide were found for biodiesel and its blends at higher
engine loads. Hydrocarbon had no evident variation for all tested fuels.
Nitrogen oxides emissions were slightly higher for biodiesel and its
blends. The use of transesterified Pongamia Pinnata crude oil can be
partially substituted for the diesel fuel at most operating conditions in
terms of the performance parameters and emissions without any
engine modifications.

CONTENTS
Introduction
-Global and Indian scenario in biodiesel production
-Advantages and disadvantages of biodiesel
-Importance of alternative feedstocks for biodiesel
production
-Different methods of production of biodieselPyrolysis
Micro Emulsification
Dilution
Transesterification
Transesterification
Transesterification process variables- Reaction
temperature
- Alcohol to
oil ratio
- Mixing
intensity

- Purity of
reactants
- Effect of
moisture and free fatty acids
- Catalyst
type and concentration
Different catalytic processes employed for
transesterification
- Acid
catalyzed processes
- Base
catalyzed processes
- Lipase
catalyzed processes
- Non-ionic
base catalyzed processes
Heterogenously catalyzed processes
Different types of alcohols employed for
transesterification
Methanolysis
- Ethanolysis
Kinetics of the transesterification reaction
Biodiesel production and characterization-Biodiesel production procedure
-Biodiesel properties
By-products of biodiesel production- Glycerine

- De-oiled
cake
Basic flowchart for biodiesel production
Alternative methods of biodiesel production- Super
critical process
- Ultra and high shear
in-line and batch reactors
- Ultrasonic reactor
method
- Microwave
irradiation technique

Experimental apparatus and test conditions

Results and discussion
Appendix
References

1.INTRODUCTION

Energy is defined as the ability to do work. Energy is found in different forms such
as heat, light, motion and sound. There are many forms of energy, but they can all
be put into two categories: Kinetic and potential. Electric, radiant, thermal and
sound energies are kinetic; chemical, stored mechanical, nuclear and gravitational
energies are potential forms of energy.
Energy sources can be classified into three groups: Fossil, renewable and fissile. The
term fossil refers to an early geological age. Fossil fuels were formed many years
ago and are not renewable. The fossil energy sources are petroleum, coal, natural
gas, bitumen, natural gas, oil shales and tar sands. The main fissile energy sources
are Uranium and thorium. The term fissile refers to materials that are fissionable by
neutrons with zero kinetic energy. In nuclear science, a fissile material is one that is
capable of sustaining a chain reaction of nuclear fission. The principle fissile
materials are uranium-235, plutonium-239 and uranium-233. Figure 1.1 shows the
worldwide energy consumption in the year 2005.

Today, most of the energy we use comes from fossil fuels: Petroleum, coal and
natural gas. While fossil fuels are still being created today by underground heat and
pressure, they are being consumed more rapidly than they are being created. For
that reason, fossil fuels are considered non-renewable(Demirbas A., Biodiesel: A
realistic fuel alternative for diesel engines, 2008).

Source- Demirbas 2006a

Fig 1.2 shows the oil production scenario for the next 75 years.
The renewable energy sources such as biomass, hydro, wind, solar (thermal and
photovoltaic), geothermal, marine and hydrogen will play an important role in the
future. By 2040, approximately half of all the global energy supply will come from
renewable sources, and electricity supply from the renewable sources will be 80% of
the total global renewable energy supply (EWEA 2005, EREC 2006).
The diesel engine is frequently used in transportation, power generation and many
miscellaneous applications including industrial and agricultural. The major
pollutants from diesel engine are smoke, particulate matter(PM), carbon
monoxide(CO), Nitrogen Oxides(NOX) and unburnt hydrocarbons(UBHC). Among
different pollutants, the most significant are smoke and nitrogen oxides. For
achieving this goal, two methods have been followed: adaptation of the engine to
the fuel and adaptation of the fuel to the engine(Mittelbach et al. 1999).
Considering the large number of available engines, the second option seems to be
more viable. Hence, there is a need to explore viable alternative fuels that can be
used in the Compression ignition engines. Any such fuel should not only match the
performance of diesel but should also meet or exceed the current emission norms.
Harvesting renewable energy has also become an important energy source
worldwide. The alternate fuel must be readily available, technically feasible,
economically viable and also meet the pollution norms(Kumar et al. 2012).
One of the possible alternatives to fossil fuel is vegetable oil. The development of
vegetable oil started about a century ago. Also during World War II, vegetable oils
were used as fuels during emergency situations. In principle, any vegetable or seed
oil which essentially consists of triglycerides of long chain saturated and

unsaturated fatty acid can be used in diesel engines. The fuel is biodegradable, non
toxic and above all has an emission profile comparable to fossil diesel. The
characteristics of vegetable oil fall within a fairly narrow band and are quite close to
those of diesel. However, the initial research on the use of vegetable oil as a fuel in
engines has resulted in very negative impacts on the engine. It has been shown in
previous work that utilization of vegetable oil in diesel engine leads to problem in
pumping, atomization, gumming, injector fouling, piston ring sticking and
contamination of lubrication oil in the long run operation. It is due to high viscosity,
density, iodine value and poor non-volatility(Zejeweski et al. 1986) . Hence it is
essential to reduce the viscosity of the vegetable oils for better combustion by
preheating, thermal cracking and transesterification. Transesterification is primarily
used to convert vegetable oil to a form that can be used in diesel engines and is
called biodiesel.
Biodiesel can be defined as mono-alkyl esters of long chain fatty acids derived from
vegetable oils or animal fats which confirm the ASTM(American Society for
Testing and Materials) specifications for use in diesel engine. It is considered a
clean fuel as it has almost no sulphur, no aromatics and has about 10% built-in
oxygen, which helps it to burn completely and also gives it a higher cetane
number(Amigun et al.2008). Biodiesel may be easier to commercialize than other
alternative fuels. Biodiesel has been reported to be made from a number of
feedstocks. In general the feedstocks can be divided into four different categories:

EDIBLE VEGETABLE OIL:- Sunflower, Rapeseed, Rice bran, Soybean,

Coconut, corn, Palm, Oilve, Pistachia Palestine, Sesame seed, peanut, opium
poppy, Safflower oil etc.
NON-EDIBLE VEGETABLE OIL:- Jatropha, Karanja or Pongamia Pinnata,
Neem, Jojoba, Cottonseed, Linseed, Mahua, Deccan Hemp, Kusum, Orange,
Rubberseed, Sea mango, Algae and halophytes.
Waste or recycled oil.
Animal Fats: Tallow, yellow grease, Chicken fat and byproducts from fish oil
etc.

The production and utilization of biodiesel as diesel fuel has been well tested and
evaluated in several countries. Also due to its properties similar to those of diesel, it
can be used as a viable alternative without any significant change in the existing
diesel engine as well as fuel storage and distribution infrastructure. The goal of the
present study is to evaluate the performance and emission of the diesel engine
operating on biodiesel in relation to its different blends.

2. A BRIEF SUMMARY OF THE INDIAN AND

GLOBAL SCENARIO
2.1- Global Scenario

Due to energy crisis of the 1970s, many countries developed different renewable
energy technologies in order to reduce dependence on import of fossil fuels, while
many others have pursued renewable enrgy development to protect the
environment. Energy cost depends upon certain factors such as natural resource
endowments, political and economic systems, and cultural tradition of countries.
The importance of biodiesel can be well visualized from the fact that fossil based oil,
coal and gas reserves will be exhausted in less than another 10 decades. The
estimated production of vegetable oil feedstock worldwide is estimated to be 100
million tonnes. The production of biodiesel has registered commendable increase
during the past ten years (Kumar et al. 2012). The figure is shown in figure 1.

The biodiesel production in the European Union(EU) has increased from 1065
thousand tonnes in 2002 to 10289 tonnes in 2007 due to the initiative of the EU to
promote biodiesel. Two draft directives by the council of Europe and the European
Parliament, concerning the reduction of the GHG( Greenhouse gases) emissions and
energy supply diversification, have contributed a lot towards the development of
biodiesel. In the EU, rapeseed oil, sunflower oil and cottonseed oil are the preferred
feedstock. In the UK, most of the biodiesel is being produced from waste vegetable
oil(WVO) which is the cheapest feedstock. Among the EU countries, France has been
very consistent in implementing policies related to biofuels since last 20 years.
Biofuel was one of the key points of the climate plan introduced by the French
Government. However, Germany has taken lead in the production of vegetable oil
methyl ester (VOME) in the year 2001 with a production of 2,662 thousand tonnes,
followed by France (743 thousand tonnes), whereas Italy (447 thousand tonnes) and
UK (192 thousand tonnes) rank 3rd and 4th, respectively. Spain exempted biodiesel
from fuel excise tax to promote the consumption of biodiesel on 1st January, 2000.
The Greek Government also started its biodiesel program following European
Directive on the promotion of the use of biofuels for transport.Biodiesel in Lithuania
is produced from Rapeseed (Kumar et al. 2012).
In theUSA,therearemorethan170biodieselplantswith soybean as the
mainfeedstockforproductionof biodiesel. A
blendof20%biodieselwith80%diesel(B20)isconsideredtobe the mostsuitable for
transportation sector. InEnergy Policy

Act1992oftheUSA,biodieselhasbeenrecognizedas alternative
fuelforvehicles.EnvironmentalProtectionAgency (EPA)
alsorecognizesbiodieselbecauseofitslessharmfuleffect on human health.
TheBrazilianbiodieselprogramwas created bytheMinistryofScienceandTechnologyin
October 30, 2002. Soybean,sunflower,peanut,cotton,castorbean, rapeseed,
palmandcoconutarethemainoilseedsinBraziland the
governmentauthorizedadditionofbiodiesel(5%)to diesel.
Brazilhas47biodieselplantsauthorizedto operate. The municipal governmentandnongovernmentalorganizations (NGOs)
inJapanareutilizingmainlyrecycledrapeseedoilasthe main
feedstockforproducingbiodiesel.AsofMarch2008,the total
amountofbiodieselproductionwasestimatedat10,000 kiloliter.
Japanhasstartedaroundtwentybiodieselfuel projects since 2007.
Pakistanhasidentified Pongamia pinnata, rape- seed
andcastorbeanaspotentialresourceforproductionof biodiesel (Amigun et al. 2008).

2.2- Indian Scenario

Excessive oil dependence in todays world requires us to look at ways to reduce this
dependence while augmenting the supply of transportation fuels to meet societys
needs and ensure progressive development. While research focusses on alternative
fuels, it is now apparent that liquid hydrocarbon fuels will continue to be important
globally, at least in the near foreseeable future.
The growth of Indian economy in 2009-10 was estimated as 8% by quick estimate
released on 31 January 2011 as per the advance estimates of the central statistics
office (CSO) released on 7 february 2011. Despite a slowing global economy, India
stood as the fourth largest energy consumer in the world after the US, China and
Russia, in the year 2009. The combination of rising oil consumption and relatively
flat production(Fig 2) has left India increasingly dependent on imports to meet its
petroleum demand. India is one of the top 10 oil consuming countries in the world.
The countrys exisiting annual crude oil production is at about 32 million tonnes. In
India, bulk of the freight(over 60%) and passenger traffic(over 80%) is carried by
road., and diesel and petrol contribute to 98% of the energy consumed in the
transport sector (Kumar et al. 2012).

To reduce the dependency on imported oil, production and utilization of biodiesel

may be solution in a developing country like India. In India, the demand for edible
oil is much higher than its domestic production thus the edible oil cannot be
diverted for the production of biodiesel. This fact is well established by the
production and import data of edible oil(Fig 3).

Indias per capita energy consumption rate remains one of the lowest at 512.4 kgoe
(Kilogram of oil equivalent) against the world average of 1674 kgoe (2003). India is
the worlds fifth largest energy consumer. It is projected that it will soon surpass
Russia and Japan to take third place by 2030. The challenge is, therefore, to ensure
development on a sustainable path by creating a domestic policy for the countrys
energy sector. Its capacity to develop relationship with foreign energy sectors also
needs to be enhanced(Adholeya A, TERI, 2005).

Being a tropical country, India has high forest land, having a large range of trees
which yield significant quantity of oil seeds. The main non-edible oils in India are
Neem(Azadirachta Indica), Mahua(Madhuca Indica), Karanja(Pongamia Pinnata),
Sal(Shoria Robusta), Kusum(Schleichera Oleosa) and Ratanjyot(Jatropha Curcas) and
their productions are about 100,000, 180,000, 55,000, 180,000, 25,000 and 15,000t
per annum respectively. The possibility of commercial production of jatropha,
karanja and mahua has been explored for biodiesel. These crops can not only meet
the demand for biofuel production but can also green the wastelands in drought
prone areas without sacrificing the food and fodder security and to improve the
livelihoods of the rural poor.
The government of India plans to achieve a GDP (gross domestic product) growth
rate of 10% in the eleventh Five-year plan and maintain an average growth of about
8% in the next 15 years (Planning Commission 2002).
India ranks sixth in the world in terms of energy demand accounting for 3.5% of
world commercial energy demand in 2001. The energy demand is expected to grow
at 4.8%. A large part of Indias population, mostly in rural areas, do not have access
to it. At 479Kg of oil equivalent to the per capita energy consumption, it is very low.
Hence a programme for the development of energy from raw material which grows
in the rural areas will go a long way in providing energy security to the rural people
(Report of the committee on development of biofuel; Planning Commission, Govt. of
India, 2003).
The rationale of taking up a major programme for the production of bio-diesel in
India for blending with diesel lies in the context of:

Bio-diesel being a superior fuel than HSD from the environmental point of
view.
Use of bio-diesel becomes compelling in view of the tightening of automobile
vehicle emission standards and court interventions.
The need to provide energy security, especially for the rural areas.
The need to create employment.
Providing nutrients to soil, checking soil erosion and land degradation.
Rehabilitating degraded lands through greening.
Addressing global concern relating to containing carbon emissions as
provided in the framework convention on climate change.
Reduce dependence on crude oil imports.

[Report of the committee on development of biofuel; Planning Commission,

Govt. of India, 2003]

ADVANTAGES OF BIODIESEL
(1)Clean Fuel:- Biodiesel is considered as a clean fuel since it has almost no
sulphur(<15ppm), no aromatics and has about 10% built-in oxygen, which helps it
to burn fully.
(2)Inherent lubricity:-Bio-diesel is reported to have a superior lubricity than
petroleum diesel which in turn helps in decreasing the engine wear.

(3)Superior Flash Point:- Flash point of bio-diesel is high(around 130 o C). Its
blending with diesel fuel can be utilized to increase the flash point of diesel
particularly in India where the flash point is 35 o C which is below the world average
of 55o C. This is important from the safety point of view.
(4)Viscosity:- The viscosity of biodiesel is higher(1.9 to 6.0 cSt) and is reported to
result into gum formation in injector, cylinder liner etc if used in neat form. However
blends of upto 20% should not give any problem.
(5)Higher Cetane Number:- Cetane number of biodiesel is in the range of 48-60.
(6)Renewable and domestic feedstock:- The different feedstock used for the
production of biodiesel are renewable and can be produced domestically for the
production of biodiesel. It is a very good option from the environment point of view.
(7)Biodegradability:- Biodiesel is biodegradable and hence does not cause a
major concern for waste materials produced in the environment. It can decompose
as the result of natural agents such as bacteria. According to the EPA, biodiesel
degrades at a rate four times faster than conventional diesel fuel. This way, in the
event of a spill, the cleanup would be easier and the aftermath would not be as
frightening. This would also hold true for biodiesel blends.

(8)Lower particulate emissions:- Sulfur and its related compounds contribute to

the formation of acid rain; carbon monoxide is a widely recognized toxin; and
carbon dioxide contributes to the greenhouse effect. There are also some lesser
known compounds that cause concern, such as polycyclic aromatic hydrocarbons
(PAHs), ring-shaped compounds that have been linked to the formation of certain
types of cancer. Particulate matter (PM) has negative health effects, and unburned
hydrocarbons contribute to the formation of smog and ozone.
[B.R. Moser, U.S Department of Agriculture, 2009; Report of the committee on
development of biofuel, Planning Commission, Govt. of India, 2003]

Studies conducted on biodiesel have shown substantial reduction in particulate

matter (25-50%).Non-regulated emissions like PAH etc were also found to be lower.
Thus, bio-diesel can supplemement the supply of environment friendly fuels in our
country in future. The table given below gives information regarding the percentage
decrease of various particulate matter for different blends of biodiesel.

In addition, B100 can reduce CO2 emissions by 78 percent and lower the
carcinogenic properties of diesel fuel by 94 percent [National Biodiesel Board, U.S.
DOE Office of Transportation Technologies, 2009].

DISADVANTAGES OF BIODIESEL:(1)High feedstock cost:- The different feedstock required for biodiesel production
are expensive and difficult to obtain. Therefore it is costlier than normal diesel
(2)Inferior storage and oxidative stability:-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.
(3)Lower volumetric energy content:- Biodiesel in general has a 10% lower
volumetric energy content than petroleum diesel.

(4)Low-Temperature operability:-There are several major sources of potential low

temperature operability problems with biodiesel:

Formation of waxes in the fuelLong chain methyl esters, especially

saturated ones, can solidify as the fuel temperatures drops. These can plug
filters and cause engines to not start or stall shortly after start-up.

Formation of precipitates from fuel contaminantsSome fuel contaminants

such as saturated monoglycerides, sterol glucosides and soaps can lead to
the formation of filter plugging precipitates at temperatures above the fuels
cloud point.

Fuel system icingAt sub-zero temperatures, water from fuel contamination

can freeze, causing the precipitation of ice particles

(5)Higher NOxemission:- A marginal increase(1-6%) in NOX emission has been

reported in biodiesel. But it can be taken care of either by optimization of engine
parts or by using De-NOX catalyst.
[B.R. Moser, U.S Department of Agriculture,2009; Report of the committee on
development of biofuel, Planning Commission, Govt. of India, 2003]

3.IMPORTANCE OF ALTERNATIVE FEEDSTOCK

SOURCES
A rapid increase in biodiesel production capacity andgovernmental mandates for
alternative fuel usage around the world in the last several years has necessitated
the development of alternative biodiesel feedstock, as it does not appear possible to
meet the increased production capacity and mandated demand with traditional
sources of biodiesel (soybeans, rapeseed/canola, palm, and various
Greases and used cooking oils, for instance) (B.R. Moser, USDA, 2009)
The continueddrive for energy sustainability and independence among energyconsuming countries, governmental mandates for alternative fuel usage and
increased global production capacity contribute to the need for alternative sources
of biodiesel fuel (B.R. Moser, USDA, 2009)
Lastly, the high prices of commodity vegetable oils and animal fats have made the
search for alternative feedstocks very important (B.R. Moser, USDA, 2009)
Desirable characteristics of alternative oilseed feedstocksfor biodiesel production
include adaptability to local growing conditions (rainfall, soil type, latitude, etc.),
regional availability, high oil content, favorable fatty acid composition, compatibility
with existing farm infrastructure, low agricultural inputs (water, fertilizer,
pesticides), definable growth season, uniform seed maturation rates, potential
markets for agricultural by-products, and the ability to grow in agriculturally
undesirable lands and/or in the off season from conventional commodity crops (B.R.
Moser, USDA, 2009)
Biodiesel fuels prepared from feedstocks that meet at least a majority of the above
criteria will hold the most promise as alternatives to petrodiesel. In general, there
are four major biodiesel feedstock categories: algae, oilseeds, animal fats, and
various low-value materials such as used
Cooking oils, greases, and soapstocks (B.R. Moser, USDA, 2009).

4.DIFFERENT METHODS OF PRODUCTION OF

BIODIESEL

The alternative diesel fuels must be technically and environmentally acceptable,

and economically competitive. From the viewpoint of these requirements,
triglycerides(Vegetable oils/animal fats) and their derivatives may be considered as
viable alternatives for diesel fuels.The problems with substituting triglycerides for
diesel fuels are mostly associated with their high viscosities, low volatilities and
polyunsaturated character. The problems have been mitigated by developing
vegetable oil derivatives that approximate the properties and performance and
make them compatible with hydrocarbon based diesel fuels through:

Pyrolysis
Microemulsification
Dilution
Transesterification

(Report of the committee on the development of biofuels, Planning Commission,

Govt of India, 2003)

4.1- Pyrolysis
Pyrolysis refers to a chemical change caused by the application of thermal energy in
the absence of air or nitrogen. The liquid fractions of the thermally decomposed
vegetable oila re likely to approach diesel fuels. The pyrolyzate had lower viscosity,
flash point and pour point than diesel fuel and equivalent calorific values. The
cetane number of the pyrolyzate was lower. The pyrolysed vegetable oils contain
acceptable amounts of sulphur, water and sediment and give acceptable copper
corrosion values but unacceptable ash, carbon residue and pour point. (Report of
the committee on the development of biofuels, Planning Commission, Govt of India,
2003)

4.2-Micro-emulsification
The formation of microemulsions(co-solvency) is one of the potential solutions for
solving the problem of vegetable oil viscosity. Micro-emulsions are defined as
transparent, thermodynamically stable colloidal dispersions. The droplet diameters
in micro-emulsions range from 100 to 1000 . A micro-emulsion can be made of
vegetable oils with an ester and dispersant(co-solvent), or of vegetable oils, an
alcohol and a surfactant and a cetane improver, with or without diesel fuels.
Water(from aqueous ethanol) may also be present in order to use lower-prrof
ethanol, thus increasing water tolerance of the micro-emulsions. (Report of the
committee on the development of biofuels, Planning Commission, Govt of India,
2003)

4.3- Dilution
Dilution of vegetable oils may be accomplished by using materials such as diesel
fuels, solvent and ethanol. (Report of the committee on the development of
biofuels, Planning Commission, Govt of India, 2003)

4.4- Transesterification
This is the most common method of production of biodiesel from vegetable oil and
animal fat feedstock. There are various methods for carrying out this
transesterification reaction including common batch process, ultrasonic method,
supercritical process and microwave method. (B.R. Moser, USDA, 2009)
Transesterification, also called alcoholysis, is the displacement of alcohol from an
ester by another alcohol in a process similar to hydrolysis, except that an alcohol is
used instead of water. This process has been widely used to reduce the viscosity of
triglycerides. (B.R. Moser, USDA, 2009)
A brief outline of the transesterification reaction is given below.

4.4.1.Mechanism of transesterification:- It involves a TAG reaction

with a short chain monohydric alcohol normally in the presence of a catalyst at
elevated temperature to form Fatty Acid Alkyl Esters(FAAE) and glycerol.
The conversion of TAG to biodiesel is a stepwise process whereby the alcohol
initially reacts with the TAG as the alkoxide anion to form FAAE and
Diacylglycerol(DAG) which react further with alcohol to create another molecule of
FAAE and Monoacylglycerol(MAG). Lastly MAG undergoes alcoholysis to produce
another molecule of FAAE and glycerol. The combined FAAE collectively is known as
biodiesel (Knothe et al. 2005)

4.4.2.Transesterification process variables

The most important variables that influence transesterification reaction time and
conversion are reaction temperature, ratio of alcohol to oil, mixing intensity, purity
of reactants, effects of moisture and free fatty acids, and catalyst type and
concentration. (Report of the committee on the development of biofuels, Planning
commission, Govt. of India, 2003)

Reaction Temperature
The rate of reaction is strongly influenced by the reaction temperature. However,
given enough time, the reaction will proceed to near completion even at room
temperature. Generally, the reaction is carried out close to the boiling point of
methanol(60o-70o C) at atmospheric pressure. These mild reaction conditions,
however, require the removal of free fatty acids from the oil using the process of
refining and pre-esterification. Therefore, degummed and deacidified feedstocks are
used under these conditions. Pretreatment is not required if the reaction is carried
out under high pressure(9000 KPa) and high temperature(240 o C). Under these
conditions, simultaneous esterification and transesterification take place. The
maximum yield of esters occurs at temperatures ranging from 60 oC to 80oC at a
molar ratio(alcohol to oil) of 6:1. Further increase in temperature is reported to have

a negative effect on the conversion. (Freedman et al. 1984, Lotero et al. 2005, Naik
et al. 2008)

Alcohol to Oil ratio

Another important variable affecting the yield of ester is the molar ratio of alcohol
to vegetable oil. The stoichiometry of the transesterification requires 3 moles of
alcohol per mole of triglyceride to yield 3 moles of fatty esters and 1 mole of
glycerol. To shift the transesterification reaction to the right, it is necessary to use
either excess of alcohol or remove one of the products from the reaction mixture.
The second option is preferred wherever feasible, since in this way, the reaction can
be driven to completion. When 100% excess methanol is used, the reaction rate is
at its highest. A molar ratio of 6:1 is normally used in industrial processes to obtain
methyl ester yields higher than 98% by weight (Freedman et al. 1984).
Transmethylated palm oil at 70oC, when taken in an organic solvent(toluene) with
sodium methoxide as catalyst, the conversion increases with increase in molar ratio
of methanol to palm oil. However, higher molar ratio of alcohol to vegetable oil
interferes in the separation of glycerol. Thus, it is advisable to use a molar ratio of 46. (Krisnangkura et al. 1992)

Mixing Intensity
In the transesterification reaction, the reactants initially form a two-phase liquid
system. The reaction is diffusion-controlled and poor diffusion between the phases
results in a slow rate. As methyl esters are formed, they act as a mutual solvent for
the reactants and a single-phase system is formed. The mixing effect is most
significant during the slow rate condition of the reaction. As the single phase is
established, mixing becomes insignificant.(Adholeya A., TERI, 2005)

Purity of reactants
Impurities present in the oil also affect conversion levels. Under the same conditions
as described earlier, 67%-84% conversion into esters, using crude vegetable oils,
can be obtained, compared with 94%-97% using refined vegetable oils(Reefat et al.
2009). The free fatty acids in the original oils interfere with the catalyst. However,
under the conditions of high temperature and pressure, this problem can be
overcome (Ngamprasertsith et al. 2002)

Effects of Moisture and Free-Fatty Acids(FFAs)

For alkali-catalysed transesterification, the glycerides and alcohols must be
substantially anhydrous because water causes the reaction to change partially to
saponification, a process that produces soap. The soap consumes the catalyst and
reduces catalytic efficiency. It also causes an increase in viscosity and aids in the

formation of gels, causing difficulty in achieving separation of glycerol (Lotero et al.

2005).
If the feedstock contains a significant percentage of FFA(>3wt%), typical
homogenous base catalysts, such as sodium or potassium hydroxide or methoxide
will not be effective as a result of an unwanted side reaction in which catalyst will
react with FFA to form soap(sodium salt of fatty acid) and water(or methanol in case
of sodium methoxide), thus irreversibly quenching the catalyst and resulting in an
unwanted mixture of FFA, unreacted TAG, soap, DAG, MAG, biodiesel, glycerol, water
and/or methanol. Infact the base-catalysed esterification of the feedstock will be
significantly retarded if the FFA content of the feedstock is 3wt% or greater (Naik et
al. 2005).A further complicating factor of high FFA content is the production of water
upon reaction with homogenous base catalysts. Water is particularly problematic
because, in the presence of any remaining catalyst, it can participate in hydrolysis
with biodiesel to produce additional FFA and methanol (Demirbas A, 2010)

Catalyst type and concentration

Alkali metal alkoxides are the most effective transesterification catalysts compared
to acidic catalysts. Sodium alkoxides are among the most efficient catalysts used for
the purpose, although KOH and NaOH can also be used.
Transmethylations occur approximately 4000 times faster in the presence of an
alkaline catalyst than that in the presence of an acidic catalyst. Also base-catalysed
reactions are performed at generally lower temperature, pressure and reaction
times are less. They are less corrosive to industrial equipments. Fewer capital and
operating costs are required in case of base-catalysed transesterification.The
alkaline catalyst concentration in the range of 0.5%-1% by weight leads to 94%99% conversion of vegetable oils into esters (Lui et al. 2008)
Homogenous acid-catalysed reaction holds an important advantage over basecatalysed reaction in that the performance of catalyst is not adversely influenced in
the presence of FFA (Lotero et al. 2005). Acids can simultaneously catalyse both
esterification and transesterification (Demirbas A, 2004)

It has been shown that lipases are able to catalyse the alcoholysis of triglycerides in
both aqueous and
non-aqueous systems (Narasimhrao et al. 2007)

4.4.3.Different catalytic process employed in

transesterification
Acid-Catalysed Processes
The trans-esterification process is catalyzed by bronsted acids, preferably by
sulphonic and sulphuric acids. These catalysts give very high yields in alkyl esters,
but the reactions are slow, requiring, typically, temperatures above 100 oC. These
reactions take more than 3-hours to reach complete conversion. Pryde(1983)
showed that the methanolysis of soybean oil, in the presence of 1%mol of sulphuric
acid, with alcohol to oil molar ratio of 30:1 at 65 oC, takes 50 hours to effect
complete conversion of the vegetable oil(>99%), while butanolysis(at 117 oC) and
ethanolysis(at 78oC), using the same quantities of catalyst and alcohol, take 3 and
18 hours respectively (Adholeya A, TERI, 2005).
The mechanism of the acid-catalysed transesterification of vegetable-oils is shown
in the figure given below.

The protonation of the carbonyl group of the ester leads to the carbocation II, which,
after a nucleophilic attack of the alcohol, produces the tetrahedral intermediate III,
which eliminates glycerol to form the new ester IV and regenerate the catalyst H +.
According to this mechanism, carboxylic acids can be formed by reaction of the
carbocation II with water present in the reaction mixture. This suggests that an acidcatalysed transesterification should be carried out in the absence of water so as to
avoid the competitive formation of carboxylic acids that reduce the yield of alkyl
esters.
(Adholeya A, TERI, 2005)

Base Catalysed Processes

The base-catalysed transesterification of vegetable oils proceeds faster than acidcatalysed reaction. Due to this reason, coupled with the fact that alkaline catalysts
are less corrosive than acidic compounds, industrial processes usually favour base
catalysts such as alkaline metal alkoxides and hydroxides as well as sodium or
potassium carbonates. The mechanism of base-catalysed transesterification of
vegetable oils is shown in the figure below.

The first step is the reaction of the base with the alcohol, producing an alkoxide and
the protonated catalyst. The nucleophilic attack of the alkoxide ion on the carbonyl
group of the triglyceride generates a tetrahedral intermediate from which the alkyl
ester and the corresponding anion of the diglyceride are formed. The latter
deprotonates the catalyst, thus regenerating the active species, which is now able
to react with a second molecule of the alcohol, starting another catalytic cycle.
Diglycerides and Monoglycerides are converted by the same mechanism to a
mixture of alkyl esters and glycerol. Alkaline metal alkoxides(as CH 3ONa[Sodium
Methylate] for the methanolysis) are the most active catalysts, as they give very

high yield(>98%) in very short reaction times(30 minutes) even if they are applied
at low molar concentrations(0.5mol%). However they require the absence of water,
which makes them inappropriate for typical industrial processes. Alkaline metal
hydroxides (KOH and NaOH) are cheaper than metal alkoxides, but less active.
Nevertheless, they are a good alternative, since they can give the same high
conversionsof vegetable oils just by increasing the catalyst concentration to 1mol%
or 2mol%. However, even if a water-free alcohol/oil mixture is used, some water is
produced in the system by the reaction of the hydroxide with the alcohol. The
presence of the water gives rise to hydrolysis of some of the produced ester, with
consequent soap formation. This undesirable saponification reaction reduces the
ester yield and consequently makes the recovery of the glycerol difficult due to
formation of emulsions. Potassium Carbonate, used in a concentration of 2 mol% or
3mol%, gives high yield of fatty acid alkyl esters and reduces the soap formation.
This can be explained by the formation of bicarbonate instead of water, which does
not hydrolyse the esters (Adholeya A, TERI, 2005)

Lipase-catalysed processes
Due to their ready availability and the ease with which they can be handled,
hydrolytic enzymes have been widely employed in organic synthesis. They do not
require any co-enzymes, are reasonably stable, and often tolerate organic solvents.
Their potential for regioselective, especially for enantioselective synthesis, makes
them valuable tools.
Although the enzyme-catalysed transesterification processes are not commercially
developed as yet, new results have been reported in recent articles and patents.
The common aspects of these studies consist in optimizing the reaction conditions
(solvent, temperature, pH, type of micro-organism that generates the enzyme and
so on) to establish suitable characteristics for an industrial application. However,
the reaction yields as well as the reaction times are still unfavourable compared to
base-catalysed reaction systems.
The kinetics of triglyceride transesterification with methanol, that is, methanolysis,
catalyzed by Ryzopus oryzae lipase appear to be in accordance with a successive
reaction mechanism. That is, triglycerides and partial glycerides are first hydrolysed
by lipase to partial glycerides and free fatty acids, respectively, after which methyl
esters are synthesized from free fatty acids and methanol. This suggests that, unlike
in the case of alkali-catalysed methanolysis, free fatty acids contained in used oils
can be easily converted to methyl esters (Narasimhrao et al. 2007)

Non-Ionic base catalyzed processes

In order to obtain milder reaction conditions and to simplify manipulations, a
number of organic bases have been developed and are used as a catalysts or
reactants for organic synthesis. Among these bases, amines such as triethylamine,
piperidine, 1,2,2,6,6-pentamethylpiperidine, pentamethlypiperidine, pyridine, 2,6-ditert-butylpyridine and DMAP(1,8-diazabicycloundec-7-ene), DBN(1,5-

diazabicyclonon-5-ene), TMG(1,1,3,3-tetramethylguanidine), PBG(1,1,2,3,3pentabutylguanidine), 1,3-diphenylguanidine, 1,2,3-triphenylguanidine,

amonoguanidines and nitroguanidines, triamino(imino)phosphoranes such as
BEMP(tertbutylimino-diethylamino-1,3-dimethyl-perhydro-1,3,2-diazaphosphorane
and Me7P (tris[dimethylamino] methyl iminophosphorane), are frequently used in
organic synthesis. The activity and efficiency of such non-ionic base catalysts for
the transesterification of vegetable oils were studied. In a first series of studies, the
catalytic activity of some guanidines was compared to that observed using other
bases such as the amidines DBU and DBN, and triamino(imino) phosphoranes BEMP
and Me7P6. It was observed that TBD, even if applied at only 1 mol%, produces more
than 90% of methyl esters after one hour. Yields were not higher than 66% when
other bases were used under the same experimental conditions. The order of
catalytic activities is not directly related to the relative basicity of those compounds,
since BEMP and Me7P6 should be the more efficient catalysts, followed by TBD.
However the guanidines are more active catalysts and the activity follows their
relative basicity (Adholeya A, TERI, 2005)
According to the observed results and the mechanism of the base-catalysed
transesterification, it seems that the good performance of TBD, when compared to
BEMP and Me7P6, is related to its kinetic activity. Other bases such as DMAP, pyridine
and triethylamine were also tested. However even at 5 mol%, these amines did not
give satisfactory yields. DMAP was most active within this series, producing only
20% of methyl esters after one hour (Adholeya A, TERI, 2005)
The catalytic activity of TBD was compared to that observed for typical industrial
catalysts (for example, NaOH and Potassium Carbonate). The results of this study
are given in the following table. The reaction yields obtained with TBD were close to
those obtained wth NaOH and no undesirable by-products such as soaps(easily
formed when alkaline metal hydroxides are used) were observed (Lui et al. 2007)
Molecular structure of some non-ionic bases

Comparison of yield of different catalysts

Catalyst Name
Yield(%) after 1 hour
NaOH(1 mol%)
91.17
K2CO3(1 mol%)
84.0
K2CO3(2 mol%)
90.3
TBD(1 mol%)
89.0
TBD(2 mol%)
91.4
TBD(3 mol%)
91.10
(Source:- Production and technology of bio-diesel: Alok Adholeya, Pradeep K
Dadhich, TERI 2008)
When compared to potassium carbonate, TBD was always more active even at
lower concentrations. Although TBD is less active than sodium methoxide (at only
0.5%, CH3ONa produces more than 98% of methyl esters after 30 minutes), its use
does not require any special condition.

Heterogenously Catalysed Processes

The advantage of using guanidines in the transesterification of vegetable oils lies in
the possibility to heterogenise them on organic polymers. Schuardt, Sercheli and
Vargas(1998) tested principally cellulose and poly(styrene/divinylbenzene);
polyurethanes and other organic polymers also allow the suitable incorporation of
guanidines. The heterogenisation of guanidines on organic polymers, and their use
in the transesterification of vegetable oils were described in a patent. The
heterogenisation of unsubstituted guanidines can be achieved by their reaction with
microcrystalline cellulose activated by cyanuric chloride at the C-6 position. After
deprotonation of the guanidinium salt, the guanidine-containing cellulose shows

slightly reduced activity, compared to guanidine in homogenous phase. Giving a

conversion of 30% after one hour, when used at 5 mol%. This guanindine-containing
cellulose was used in a continuous reactor containing 100g of the catalyst. An
alcohol/oil mixture of 2:1 was pumped at 60oC, at a rate of 0.48 litres/hour. In the
first hour, the methyl esters were obtained with high yields and the phase
separation was quick. After this, however, the reaction was incomplete and the
phase separation difficult. This could be due to either leaching of the catalyst or its
irreversible protonation. As no leaching tests were performed, no definite reason
can be given at this point (Adholeya A, TERI, 2005)

4.4.4.Different types of alcohols employed for

transesterifcation
The alcohols used in transesterification are primary or secondary monohydric
aliphatic alcohols having 1-8 carbon atoms.Methanol is the most common alcohol
used in the production of biodiesel. Other alcohols may also be used in the
preparation of biodiesel, such as ethanol, propanol, iso-propanol, and butanol
(Adholeya A, TERI, 2005)

Methanolysis
Advantages of Methanol as alcohol: It is cheap
It is a polar and short chain alcohol
The classic reaction conditions for the methanolysis of vegetable oils or animal fats
are
6:1 molar ratio of methanol to oil
0.5 wt.% alkali catalyst (with respect to TAG)
600+ rpm
60C reaction temperature
1 h reaction time
The transesterification reaction employing methanol commences as two immiscible
phases as a result of the very low solubility of TAG in methanol. Boocock(1996)
proved this fact by showing that only 7.5g of soybean oil is soluble in 1L of
methanol at 30oC.The polar homogenous alkali catalyst is essentially exclusively
dissolved in the polar methanol phase at the beginning of the reaction and does not
come into contact with the TAG phase unless sufficient agitation is introduced.
Stirring of sufficient magnitude causes TAG transport into the methanol phase
where it is rapidly converted into FAME and glycerol. The rate at which FAME are
produced during the transesterification reaction is thus controlled by mass-transfer

limitations, which results in a lag time before conversion to FAME begins. Once DAG
and MAG intermediates are formed in sufficient quantity during the
transesterification reaction, they serve as surfactants that improve mass transfer of
TAG into the methanol phase (Boocock et al. 1996). The reaction eventually
transforms into another biphasic system that consists of ester-rich (FAME) and
glycerol-rich phases. The alkali catalyst is preferentially soluble in the more polar
glycerol-rich phase, which may result in a retardation of the rate of reaction. The
glycerol-rich phase settles to the bottom of the reaction vessel when agitation is
ceased, which facilitatespurification of FAME (Freedman et al. 1984)
As a result of the biphasic nature of the reaction mixture, there is a lag time at the
beginning of the methanolysis reaction before FAME begins to form, after which the
reaction speeds up, but then quickly decelerates. The addition of co-solvents such
as tetrahydrofuran (THF) to the methanolysis reaction significantly accelerates the
production of FAME as a result of the formation of a monophasic as opposed to a
biphasic reaction mixture.However, the molar ratio of methanol to oil must be
increased to at least 25:1, which results in additional solvent that must be removed
and recovered during purification. Other possibilities for accelerating the
methanolysis reaction are microwave or ultrasonic irradiation (Freedman et al.
1984)

A number of recent studies have described optimal reaction conditions for biodiesel
production from various feedstocks using response surface
methodology(RSM).Parameters that are normally optimized to produce the most
biodiesel include catalyst type and amount, reaction time and temperature, amount
of alcohol, and/or agitation intensity.

Ethanolysis
Advantages of Ethanol as alcohol:

It can be derived from agricultural products.

It is renewable and biologically less objectionable.

The classic conditions for ethanolysis of vegetable oils or animal fats are
6:1 molar ratio of ethanol to oil
0.5 wt.% catalyst (with respect to TAG)
600+ rpm
75C reaction temperature
1 h reaction time
(Freedman et al. 1986)
Ethanolysis proceeds at a slower rate than methanolysis because of the higher
reactivity of the methoxide anion in comparison to ethoxide. As the length of the

carbon chain of the alkoxide anion increases, a corresponding decrease in

nucleophilicity occurs, resulting in a reduction in the reactivity of ethoxide in
comparison to methoxide. An example of this phenomenon is the transesterification
(at 25C) of canola oil with a 1:1 mixture of ethanol and methanol (to provide an
overall molar ratio of alcohol to oil of 6:1) that results in 50% more methyl than
ethyl esters.Another example is the transesterification of canola oil at 25C with a
1:1 mixture of ethanol and methanol that results in methyl to ethyl ester ratios of
2.7:1 and at 75C with a 1:1 mixture of ethanol and methanol that results in methyl
to ethyl ester ratios of 1.3:1 (Freedman et al. 1986).These results indicate that
methyl esters are preferentially formed at both ambient and elevated reaction
temperatures,but at elevated temperatures, the preference is diminished. Even
though the formation of ethyl esters is comparatively slow, the overall rate of
formation of esters is faster than with methanol alone due to the better solubility of
TAG in a mixture of methanol and ethanol, which results in a reduction of mass
transfer limitations. For example, ultrasonically assisted transesterification of
Meliaazedarach(syringa) oil with methanol is complete after 40 min and with
ethanol is complete after 20 min, respectively (Adholeya A, TERI, 2005)
The base-catalyzed formation of fatty acid ethyl esters (FAEE) is more complicated
than the production of FAME. Specifically, the formation of stable emulsions during
ethanolysis is problematic during subsequent purification. In the case of
methanolysis, these emulsions quickly and easily separate to form a lower glycerolrich and an upper FAME-rich phase after agitation of the reaction has ceased. In
ethanolysis, these emulsions are much more stable and severely complicate
separation and purification of biodiesel (Boocock et al. 2006). Ethanol is less polar
than methanol, so it is slightlymore miscible with TAG at ambient temperature than
methanol, but mechanical agitation during the transesterification reaction is once
again required to facilitate sufficient mass transfer between phases (Kulkarni et al.
2007).

4.4.5.Kinetics of the transesterification reaction

Freedman, Butterfield and Pryde(1986) studied the trransesterification kinetics of
soybean oil. The S-Shaped curves of the effects of time and temperature on ester
formation for a butanol and soybean oil ratio of 1, 1% H 2SO4 and 77-117oC at 10oC
intervals indicated that the reaction began at a slow rate, proceeded at a faster rate
and then slowed down again as the reaction neared completion. With acid or alkali
catalysts, the forward reaction followed pseudo-first order kinetics when butanol
and soybean oil ratio was 30:1. However, with alkali catalysts, the forward reaction
followed consecutive, second-order kinetics, when butanol and soybean oil ratio was
6:1. The reaction of methanol with soybean oil at 6:1 molar ratio with 0.5% sodium
methoxide at 20-60oC was a combination of second-order consecutive and fourthorder shunt reactions. The reaction rate constant for the alkali catalyzed reaction
were much higher than those for the acid-catalysed reactions. Rate constants
increased with an increase in the amount of catalyst used. E a, the activation energy,

ranged from 8 Kcal/Mole to 20 Kcal/mole. Ea for the shunt reaction triglycerideglycerol was 20 Kcal/mol (Freedman et al. 1986)
Boocock et al. have developed a novel techniquefor accelerating the
transesterification reaction rate. During its early stages, the transesterification rate
is limited by the low solubility of the alcohol, especially methanol, in the oil.
Boocock proposed the addition of a cosolvent to create a single phase, and this
greatly accelerates the reaction so that it reaches substantial completion in a few
minutes. The complexity with this method is the additional complexity of recovering
and recycling the cosolvent although this can be simplified by choosing a cosolvent
with boiling point near that of the alcohol being used.

5.BIODIESEL PRODUCTION AND

CHARACTERIZATION
5.1.Biodiesel Production Procedure
The biodiesel fuel used in this study was produced from the transesterification of
Pongamia Pinnata crude oil with Methanol(CH3OH) catalyzed by Potassium
Hydroxide(KOH). First the crude oil was gently heated at 70 oC to free the oil from
volatile impurities. 500ml of crude was mixed with 300ml methanol and 5ml of
98%sulphuric acid in the first titration step and the reaction was carried out at 65 oC
for 2hours 25 minutes. This was done to make the oil free from the fatty acids as
the free fatty acid concentration in the oil was more than 10%. In the second
titration step, 300ml of methanol was mixed with 5gm of KOH as catalyst and the
same reaction conditions were employed for 2hours 45 minutes. The water wash
process was employed for about 10-12 times by gently agitating the mixture with
warm water in a separating funnel with 50% biodiesel and 50% water. The agitated
mixture was allowed to separate into two layers for 15-20 minutes. After the
mixture had settled, the water was drained out and pure biodiesel was obtained.

2.Physical Properties of biodiesel

The fatty ester composition, along with the presence of contaminants and minor
components, dictates the fuel properties of biodiesel fuel. Because each feedstock
has a unique chemical composition; biodiesel produced from different feedstocks
will in turn have different fuel properties. Important properties of biodiesel that are
directly influenced by fatty ester composition and thepresence of contaminants and
minor components include low-temperature operability, oxidative and storage
stability, kinematic viscosity, exhaust emissions, cetane number, and energy
content. In the context of biodiesel, minor components are defined as naturally
occurring species found in vegetable oils and animal fats and may include
tocopherols, phospholipids, steryl glucosides (also called sterol glucosides, steryl
glycosides, sterol glycosides, or phytosterols), chlorophyll, fat soluble vitamins, and
hydrocarbons (such as alkanes, squalene,carotenes, and polycyclic aromatic

hydrocarbon). Contaminants are defined as incomplete or unwanted reaction

products, such as FFA, soaps, TAG, DAG, MAG, alcohol, catalyst, glycerol, metals,
and water (B.R. Moser, USDA, 2009)
A study conducted by G.B Adebayo(2011) concluded the following physical
properties of biodiesel

Some other physical properties of biodiesel are illustrated below:-

(1)Low-Temperature operability or cold-flow characteristics:- Lowtemperature operability of biodiesel is normally determined by three common
parameters: cloud point (CP; ASTM D2500 or D5773), pour point (PP; ASTM D97 or
D5949), and cold filter plugging point (CFPP; ASTM D6371). The cloud point is
defined as the temperature at which crystal growth is large enough (diameter0.5
m) to be visible to the naked eye. At temperatures below the CP, larger crystals
fuse together and form agglomerations that eventually become extensive enough to
prevent pouring of the fluid. The lowest temperature at which the fluid will pour is
defined as the PP. The CFPP is defined as the lowest temperature at which a given
volume of biodiesel completely flows under vacuum through a wire mesh filter
screen within 60 s. The CFPP is generally considered to be a more reliable indicator
of low-temperature operability than CP or PP, since the fuel will contain solids of
sufficient size to render the engine inoperable due to fuel filter plugging once the
CFPP is reached (Chiu et al 2004, Park et al. 2008). It should be noted that it is
inappropriate to measure CP, PP, and CFPP ofchemically pure compounds (pure
methyl oleate, for instance). Instead, determination of melting point (mp) as a
means to measure low-temperature operability is appropriate for chemically pure
compounds. The CP, PP, CFPP, and LTFT attempt to quantify low-temperature
behavior of complex mixtures (such as biodiesel) that are composed of constituents
that generally exhibit a relatively wide range of mp (or freezing points, fp). For
instance, in the case of CP, it is very likely that initial crystal growth that occurs on
cooling of biodiesel to sub-ambient conditions is primarily a result of higher melting
constituents undergoing crystallization (Moser B.R, USDA, 2009).
The low-temperature behavior of chemical compounds is dictated by their molecular
structure. It mainly depends on chain length, degree of unsaturation, orientation of
the double bond and the type of ester head group. Common traditional diesel have
-16oC and -27oC for the CP and the PP on the other hand, biodiesel produced from
soybean oil typically have 0o C and -2oC of the CP and the PP (Reefat A. 2009).

Molecular interactions have significant effect on crystallization. Saturated

compounds crystallize faster than unsaturated compounds due to double bonds
structures (Lotero et al. 2005). Double bonds provide the spatial geometry which
prevents from packing at lower temperature. Biodiesel derived from beef tallow or
palm oil contains high amount of saturated compounds have much higher CP than
biodiesel derived from canola or linseed oil. It has been reported by Rodrigues et al.
that double bonds located near the ends of carbon chain can pack more efficiently
than double bonds found in middle of carbon chain (Reefat A.2009). Not only double
bonds but also chain lengths affect properties in low temperature (Tang et al.2008).
Other studies showed that branched carbon chains can crystallize slower than linear
carbon chains which have larger van der Waals attractions (Nascimento et al. 2005).
With respect to ester headgroup, the mp of FAEE is generally lower with larger
alkylhead groups up to about eight carbons. For instance,methyl, ethyl, and butyl
stearates have mp of 39C, 32C,and 28C, respectively (Anonymous 2007).
Ways to improve cold-flow properties
The first method is blending biodiesel with traditional diesel (Zakaria et al. 2007).
Since traditional diesel is mainly consisted of hydrocarbon, mixture of biodiesel and
petroleum diesel can reduce crystallization temperature. The second method is
called winterization and this method removes components which have higher
melting point by separation processes. However, this method is highly expensive in
biodiesel production process (Hamada et al. 2010). In addition, removing saturated
compounds results in decreasing the ignition quality and calorific value (Kazankev
et al. 2006). The third method is adding additives in biodiesel. Polymers and
copolymers are commonly used as pour point depressants and wax dispersants
(Nubia et al. 2007). In general, those additives have oil-soluble long chain alkyl
group with polar structure moiety which can interfere the host material in
molecular-level and prevent aggregation process of wax and particles due tothe
polar moiety (Zakaria et al. 2007, Hamada et al. 2010, Song et al. 2005).

(2)Oxidation Stability:-Autoxidation of lipids, including biodiesel, produces free

radicals through hydrogen abstraction in the presence of various initiators such as

light, heat, peroxides, hydroperoxides, and transition metals (Frankel 2005).These
free radicals further react exothermically with molecular oxygen to produce
peroxides, which react with unoxidized lipids to produce additional free radicals.
Generally, the rate limiting step in the autoxidation of lipids is initial hydrogen
abstraction. Accelerated methods to determine oxidative stability of lipids, such as
EN 14112 or AOCS Cd 12b-92, use elevated temperatures to greatly accelerate the
initial hydrogen abstraction step. The EN 14112 method increases the amount of
oxygen available to react with lipid-free radicals by pumping air at a constant rate
through the sample (Frankel 2005). Products that ultimately form through oxidation
of lipids may include aldehydes, shorter-chain fatty acids, other oxygenated species
(such as ketones), and polymers. The rate of autoxidation is dependant on the
number and location of methyleneinterrupted double bonds contained within FAAE
(Frankel 2005). Materials that contain more methylene carbons allylic to sites of
unsaturation (such as polyunsaturated esters) are particularly vulnerable to
autoxidation because there are more carbon-carbon double bonds and fewer

hydrogen molecules on the fatty acid chains. When biodiesel made from
unsaturated oil is exposed to oxygen, the oxygen attaches itself to the bis-allylic
site directly adjacent to the two double bonds, which initiates an autoxidation chain
reaction sequence (Shah et al. 2009). Oxidation stability is not related to the
number of double bonds available but rather the number of bis-allylic sites
(McCormick et al. 2007). The initiation step is the formation of a free radical that
can react directly with oxygen. This leads to the formation of a peroxide or
hydroperoxide molecule. The most reactive site for initial formation is the bis-allylic
position. The radials formed at the bis-allylic sites immediately isomerize to form a
more stable conjugated structure, which reacts directly with oxygen to form
peroxide. The existence of these molecules is an early indication of oxidation taking
place, and it is measured in terms of peroxide value (McCormick et al. 2007). Later,
aldehydes and ketones are formed. Finally, during the polymerization process,
resins are produced making the fuel unusable (Shah et al.2009). The oxidation
products formed in biodiesel affect fuel storage life, contribute to deposit formation
in tanks, and they may cause clogging of fuel filters and injection systems. The
volatile organic acids formed as secondary by products of the oxidative degradation,
may stimulate corrosion in the fuel system.
Due to its chemical structure, oxidation rates of FAME can depend on many
variables such as temperature, light, radiation intensity, presence of naturally
occurring antioxidants and more. The oxidation stability of FAME can be increased
by adding additional natural and synthetic antioxidants. However, naturally
occurring antioxidants in FAME have shown relatively poor efficiency compared with
synthetic antioxidants. The antioxidants work by binding free radicals and stopping
chain reactions. In this way, fatty peroxyradicals are stabilized and the oxidation
chain reaction is broken.
Several approaches for increasing relative resistance to oxidation of fatty
derivatives have been shown to be successful for biodiesel. Storage under an inert
nitrogen atmosphere retarted oxidation of methyl and ethyl esters of sunflower seed
oil for storage at temperatures at upto 50oC (Du Plessis et al.1985). Bondioli et al.
studies the effects of storage container characteristics and reported that aging of
methyl esters of rapeseed oil in glass containers at 40 oC did not significantly affect
fuel quality with respect to viscosity, cetane number, specific gravity, flash point or
cold flow properties.
There are two types of anti-oxidants- Natural anti-axidants and synthetic antioxidants.
Natural anti-oxidants involves -Tocopherol. Synthetic anti-oxidants involves
BHA( Butylated hydroxyanisole), BHT( Butyl-4-hydroxytoluene), TBHQ( tbutylhydroxyquinone), DTBHQ( 2,5-di-tert-butyl-hydoquinone), PG( Propylgallate),
PY( Pyrogallol) and ascorbic palmitate.In general, natural anti-oxidant
concentrations are high in undistilled fuels prepared from fresh vegetable oil
(Mittelbach et al. 2004). Distillation of biodiesel often results in a decrease in the
oxidative stability owing to the removal of natural antioxidants.
The oxidative stability of biodiesels can be enhanced by adding additional natural or
synthetic anti-oxidants. However, naturally occurring anti-oxidants were shown to
provide relatively poor oxidation stabilization of biodiesels compared to synthetic

anti-oxidants(Shah et al. 2009). Anti-oxidants also retard polymerization but do not

inhibit it completely( Shah et. Al 2009).
The oxidative stability of biodiesel is determined by the measuring the induction
period (IP) using the Rancimat test (EN14112). In this test, samples of 3g (B100) or
7.5 g (B20) are held at 110oC with a constant air flow of 10 L/h bubbled through the
fuel and into a water reservoir. The IP is determined by the appearance of a sudden
increase in the conductivity of the water due to the formation of volatile acids. The
American Society for Testing and Materials (ASTM) has set an oxidative stability
standard of 3-h minimum for B100 and 6-h minimum for B20. The European
Committee for standardization adopted a 6 h minimum IP for B100.Biodiesel fuels
with longer OSI times are more stable to oxidation than samples with shorter
values.
Oxidative stability and low-temperature operability are normally inversely related:
structural factors that improve oxidative stability adversely influence lowtemperature operability and vice versa. Ester head group is the only exception to
this relationship, as larger ester head groups tend to improve both low-temperature
performance and oxidative stability.

(3)Kinematic Viscosity:- Kinematic viscosity is the primary reason why

biodiesel is used as an alternative fuel instead of neat vegetable oils or animal fats.
Fuel is sprayed into compressed air and broken down into small droplets forming a
cone shape. So Viscosity is major factor to determine the atomization quality, size of
droplets and spray growth (Anand et al. 2010). High viscosity fuels tend to have a
lower spray cone angle and larger droplet size which requires higher pumping
power (Anand et al. 2010).Also high viscosity increases poor atomization
performance, which leads to operational issues such as breakage of the fuel pumps
and injectors (Alptekin et al. 2008). On the other hand, low viscosity can cause
lubrication issue (Refaat A. 2009). The kinematic viscosity of biodiesel is
approximately an order of magnitude less than typical vegetable oils or animal fats
and is slightly higher than petrodiesel. According to ASTM D6751, the kinematic
viscosity of biodiesel have to meet the requirement of value between 1.9 to 6.0 cSt
at 40oC (Knothe et al. 2007). Several structural features influence the kinematic
viscosities of FAAE, such as chain length, degree of unsaturation, double bond
orientation, and type of ester head group.
Factors such as longer chain length and larger ester head group result in increases
in kinematic viscosity (Refaat A. 2009).Increasing the degree of unsaturation results
in a decrease in kinematic viscosity, as evidenced by comparison of the methyl
esters of stearic (5.85 mm2/s), oleic (4.51 mm2/s), linoleic (3.65 mm2/s), and
linolenic (3.14 mm2/s) acids. One double bond increases viscosity due to stronger
interactions between p electrons of double bonds than no double bond, which has
only van der Waals interaction (Rodrigues et al. 2006). On the other hand, two or
more double bonds have spatial geometry which weakens interactions between p
orbitals and leads to a reduction of viscosity (Refaat A. 2009)

Double bond orientation also impacts kinematic viscosity, as seen by comparison of

methyl elaidate (5.86 mm2/s) and methyl linoelaidate (5.33 mm2/s) to the
corresponding cis isomers (Knothe et al. 2005).
In addition, density is one of the physical properties that affects directly engine
performance characteristics related to other quality measurements such as a
heating value and a combustion quality (Alptekin et al. 2008).Density increases as
the number of double bonds increases and chain length shortens (Refaat A. 2009).
However, low density impurities such as methanol can reduce density (Refaat A.
2009).

(4)Exhaust Emissions:- Exhaust emissions include oxides of nitrogen (NOx), PM

(particulate matter), THC (total hydrocarbons), and carbon monoxide (CO). Neither
ASTM D6751 nor EN 14214 contains specifications relating to exhaust emissions.
Combustionof biodiesel (B100) in diesel engines results in an average increase in
NOx exhaust emissions of 12% and decreases in PM, THC, and CO emissions of
48%, 77%, and 48%, respectively, in comparison to petrodiesel. For B20 blends of
SME (Soy Methyl Ester)in petrodiesel, NOx emissions are increased by 04% versus
neat petrodiesel, but PM, THC, and CO emissions are reduced by 10%, 20%, and
11%, respectively. Another study demonstrated that combustion of B5 and B20
blends of ULSD in a modern diesel engine equipped with Exhaust gas
recirculation(EGR) showed no significant difference in NOx emissions from that of
neat ULSD. The increase in NOx emissions with combustion of biodiesel and in some
cases biodieselpetrodiesel blends is of concern in environmentally sensitive areas
such as national parks and urban centers. Reduction of smog-forming NOx exhaust
emissions to levels equal to or lower than those observed for petrodiesel is essential
for universal acceptance of biodiesel (Report of the committee on the development
of biofuels, Planning commission, Govt. of India, 2003)
Several engine or after-treatment technologies, such as exhaust gas recirculation,
selective catalytic reduction, diesel oxidation catalysts, and NOx or particulate
traps, may reduce NOx exhaust emissions of biodiesel and blends with petrodiesel.
A factor influencing NOx emissions is the chemical nature of FAAE that constitute
biodiesel (McCormick et al. 2003). Specifically, decreasing the chain length and/or
increasing the number of double bonds (i.e. higher iodine value) of FAAE results in
an increase in NOx emissions (Knothe et al. 1997).

Source:-http://www1.eere.energy.gov/vehiclesandfuels/images/facts/fotw449.gif

(5)Cetane Number:-Cetane number or CN is a measure of a fuel's ignition delay,

the time period between the start of injection and the first identifiable pressure
increase during combustion of the fuel. In a particular diesel engine, higher cetane
fuels will have shorter ignition delay periods than lower cetane fuels
(http://en.wikipedia.org/wiki/Cetane_number)
Cetane number (CN) is determined in accordance with ASTM D613. Generally,
shorter ignition delay times result in higher CN and vice versa. Hexadecane, also
known as cetane (trivial name), which gives the cetane scale its name, is the highquality reference standard with a short ignition delay time and an arbitrarily
assigned CN of 100. The compound 2,2,4,4,6,8,8-heptamethylnonane is the lowquality reference standard with a long ignition delay time and an arbitrarily
assigned CN of 15. The end points of the CN scale indicate that branching
negatively impacts CN. Also influencing CN is chain length, which yields higher CN
for longer chain compounds, in the case of the methyl esters of lauric (CN 67),
palmitic (CN 86), and stearic (CN 101) acids. Increasing levels of unsaturation
negatively impact CN, as evidenced by the methyl esters of stearic (101), oleic (59),
linoleic (38), and linolenic (23) acids (Knothe et al. 1997). The effect of ester head
group on CN is not well-defined. Generally, it would be expected that CN would
increase with increasing ester head group size, but this is not necessarily the case
(Knothe et al. 2006). For instance, the CN of methyl, ethyl, propyl, and butyl esters
of oleic acid are 59, 68, 59, and 62. The concomitant influences of chain length and
unsaturation on CN of biodiesel is evident by comparison of PME and SME (Knothe
et al. 2006).

(6)Lubricity:- Lubricity is determined at 60C in accordance to ASTM D6079 using

a high-frequency reciprocating rig instrument. During the course of the experiment,
a ball and disk are submerged in a liquid sample and rubbed at 60C against each

other for 75 min at a rate of 50 Hz to generate a wear scar. At the conclusion of the
experiment, the maximum length of the wear scar is determined, and this value
represents the lubricity of the sample. Shorter wear scar values indicate that the
sample has superior lubricity versus anther sample that resulted in a longer wear
scar. Lubricity is not prescribed in ASTM D6751 or EN 14214. However, the
petrodiesel standards, ASTM D975 and EN 590, contain maximum allowable wear
scar limits of 520 and 460 m, respectively. Biodiesel possesses inherently good
lubricity, especially when compared to petrodiesel. For instance, the lubricity of
ULSD (without lubricity-enhancing additives) is 551 m, whereas SME displays a
substantially lower value of 162 m. In another example, the lubricities of additivefree ULSD and SME were 651 and 129 m, respectively (Knothe et al. 2005). Ascan
be seen from the above two examples, additive-free ULSD fails to satisfy either of
the petrodiesel fuel standards(ASTM D975 and EN 590) with respect to lubricity. The
poor lubricity of petrodiesel requires lubricity-enhancing additives or blending with
another fuel of sufficient lubricity to achieve a satisfactory lubricity value. The
reason for the poor lubricity of ULSD is not exclusively the removal of sulfurcontaining compounds during hydrodesulfurization,but rather that polar compounds
with otherheteroatoms such as oxygen and nitrogen are also removed. As such,
biodiesel serves as an excellent lubricityenhancingadditive for ULSD. For example,
B2 and B20blends of SME in ULSD improve lubricity from 551 to 212and 171 m,
respectively (Moser et al. 2008).Various structural features such as the presence
ofheteroatoms, chain length, and unsaturation influencelubricity of biodiesel.
Biodiesel fuels possess at least twooxygen atoms that in large part explains their
enhancedlubricities over typical hydrocarbon containing petrodiesel fuels. Another
structuralfeature that is known to influence lubricity is chain length (Knothe et al.
2005). As seen in table given below, compounds of increasing chain length
generally display increasingly superior lubricity values(shorter wear scar values),
although the correlation is notPerfect.

(7)Contaminants:- Contaminants in biodiesel may include methanol, water,

catalyst, glycerol, FFA, soaps, metals, MAG, DAG, and TAG. Methanol contamination
in biodiesel is indirectly measured through flash point determination following ASTM
D93. If biodiesel is contaminated with methanol, it will fail to meet the minimum
flash point specified in relevant fuel standards. Methanol contamination normally
results from insufficient purification of biodiesel following the transesterification
reaction (Knothe et al. 2005). Water is a major source of fuel contamination. While
fuel leaving a production facility may be virtually free of water, once it enters the
existing distribution and storage network, it will come into contact with water as a
result of environmental humidity. Water in biodiesel causes three serious problems:
corrosion of engine fuel system components, promotion of microbial growth, and
hydrolysis of FAME (Demirbas A 2003). Glycerol may be present in insufficiently
purified biodiesel, which is determined using ASTM D6584 or EN 14105. Both ASTM
D6751 and EN 14214 contain limits for the maximum allowable levels of glycerol
permitted in biodiesel. Glycerol is suspected of contributing to engine deposit
formation during combustion. Bound glycerol (MAG + DAG + TAG) is limited in ASTM
D6751 by the total glycerol (total glycerol = free + bound glycerol) specification and
in EN 14214 by individual MAG, DAG, and TAG limits, and atotal glycerol
requirement (Knothe et al. 2005)

The structural features of individual fatty esters determine the physical properties of
biodiesel including ignition quality, heat of combustion, exhaust emissions,
oxidative stability, cold flow, viscosity, density and lubricity. The quality
specifications have to fulfill with the European standard specification (EN) 14214 or
American Society for Testing and Materials (ASTM) D6751. Thus, it is critical to
identify the chemical structures of biodiesel in order to understand overall fuel
properties.
Compositions of biodiesel are generally analyzed by instruments such as gas
chromatography-mass spectroscopy (GC/MS), Fourier transform infrared
spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and highperformance liquid chromatography (HPLC).
Melting point, Standard heat of combustion, kinematic viscosity, Oil stability Index,
Cetane number and lubricity of FAAE commonly found in biodiesel

a ME methyl ester, EE ethyl ester, BE butyl ester

bValues are from Anonymous (2007) or Knothe (2008)
cValues from Moser, submitted for publication
dValues from Knothe and Steidley (2005a)
eValues from Knothe (2008) or Moser (2008b)
f Values from Knothe et al. (2003) or Knothe (2008)
gValues from Knothe and Steidley (2005b

BY-PRODUCTS OF TRANSESTERIFICATION

Glycerine
Glycerol from biodiesel contains some peculiar impurities because of which it may
not be suitable to process it using the usual technologies to produce pharmaceutical
or top-grade product. Utilisation of glycerol as a raw material for the production of
other chemicals will increase in the coming years as large quantity (200000
tonnes/year) of glycerol will be available against the present demand for glycerol in
India which is in the tune of 40000 tonnes/year. This even if 5% diesel is to replaced
by biodiesel.
(Adholeya A., TERI, 2005)
In general, glycerol may be used as a chemical feedstock in the production of
polyurethanes, polyesters, polyethers, and other materials. Glycerol may also be
found in lubricants, wrapping and packaging materials, foods, drugs, cosmetics, and
tobacco products. Applications and products that displace existing petroleumderived materials or feedstocks are of particular interest. A recent significant
advance is the development of a synthetic route to propylene glycol (1,2propanediol) from glycerol, which represents a viable alternative to the classic
petrochemical route from propylene (Dasari et al. 2005; Suppes 2006; Feng et al.
2008). Propylene glycol represents a replacement for the common toxic antifreeze
component ethylene glycol.

De-Oiled Cake

The meal cake can be used to generate biogas and thereafter the remaining meal
cake may be used as a fertilizer and also as cattle feed after detoxification. The
kernels may be used as a rodent repellant.
(Adholeya A., TERI, 2005)

BASIC FLOWCHART FOR BIODIESEL PRODUCTION

PURIFICATION OF THE GLYCEROL PHASE AFTER TRANSESTERIFICATION

Due to low solubility and high density of glycerol in the esters, this separation can
be accomplished with either a settling tank or a centrifuge. The excess methanol
tends to act as a solubiliser and can slow the separation. However this excess
methanol is not usually removed from the reaction stream until after the glycerol
and methyl esters are separated due to concern about reversing the
transesterification reaction.
After separation from the glycerol, methyl esters enter a neutralization step and
then pass through a methanol stripper, usually a vacuum flash process or a falling
film evaporator, before water washing. Acid is added to the biodiesel to neutralize
any residual catalyst and to split any soap that may have formed during the
reaction. Soaps will react with the acids to form water soluble salts and free fatty
acids. The salts will be removed during the water washing step, and the free fatty
acids will stay in the biodiesel. The water washing step is intended to remove any
remaining catalyst, soap, salts, methanol, or free glycerol from the biodiesel.
Neutralization before washing reduces the water required and minimizes the
potential for emulsions to form when the wash water is added to the biodiesel.
Following the wash process, any remaining water is removed from the biodiesel by a
vacuum flash process.
The glycerol stream leaving the separator is only about 50% glycerol. It contains
some of the excess methanol and most of the catalyst and soap. In this form, the
glycerol has little value and disposal may be difficult. The methanol content requires
the glycerol to be treated as hazardous waste. The first step in refining the glycerol
is usually to add acid to split the soaps into free fatty acids and salts. The free fatty
acids are not soluble in the glycerol and will rise to the top where they can be
removed and recycled. The salts remain with the glycerol although depending on
the chemical compounds present, some may precipitate out. Mittelbach describes a
process for esterifying these free fatty acids and then returning them to the
transesterification reaction stream. One frequently touted option is to use
potassium hydroxide as the reaction catalyst and phosphoric acid for neutralization
so that the salt formed is potassium phosphate, which can be used for fertilizer.
After acidulation and separation of the free fatty acids, the methanol in the glycerol
is removed by a vacuum flash process or another type of evaporator. At this point,
the glycerol should have a purity of approximately 85% and is typically sold to a
glycerol refiner. The glycerol refining process takes the purity up to 99.5% to 99.7%
using vacuum distillation or ion exchange processes. The methanol that is removed
from the methyl ester and glycerol streams will tend to collect any water that may
have entered the process. This water should be removed in a distillation column
before the methanol is returned to the process. This step is more difficult if an
alcohol such as ethanol or isopropanol is used that forms an azeotrope with water.
Then a molecular sieve is used to remove the water.

ALTERNATIVE PRODUCTION TECHNIQUES OF BIODIESEL

Super Critical Process
An alternative, catalyst-free method for transesterification
uses supercritical methanol at high temperatures and pressures in a continuous
process. In the supercritical state, the oil and methanol are in a single phase, and
reaction occurs spontaneously and rapidly. The process can tolerate water in the
feedstock, free fatty acids are converted to methyl esters instead of soap, so a wide
variety of feedstocks can be used. Also the catalyst removal step is eliminated. High
temperatures and pressures are required, but energy costs of production are similar
or less than catalytic production routes.
A supercritical fluid is any substance whose temperature and pressure are above its
critical point.(Ngamprasertsith et al. 2002)

Ultra and high-shear in-line and batch reactors

Ultra- and High Shear in-line or batch reactors allow production of biodiesel
continuously, semi- continuously, and in batch-mode. This drastically reduces
production time and increases production volume.
The reaction takes place in the high-energetic shear zone of the Ultra- and High
Shear mixer by reducing the droplet size of the immiscible liquids such as oil or fats
and methanol. Therefore, the smaller the droplet size the larger the surface area the
faster the catalyst can react (http://en.wikipedia.org/wiki/Biodiesel)

Ultrasonic Reactor Method

In the ultrasonic reactor method, the ultrasonic waves cause the reaction mixture to
produce and collapse bubbles constantly. This cavitation provides simultaneously
the mixing and heating required to carry out the transesterification process. Thus
using an ultrasonic reactor for biodiesel production drastically reduces the reaction
time, reaction temperatures, and energy input. Hence the process of

transesterification can run inline rather than using the time consuming batch
processing. Industrial scale ultrasonic devices allow for the industrial scale
processing of several thousand barrels per day.
(http://en.wikipedia.org/wiki/Biodiesel)

Microwave irradiation technique

The optimum parametric conditions obtained from the conventional technique were
applied using microwave irradiation in order to compare the systems. The study
showed that the application of radio frequency microwave energy offers a fast, easy
route to this valuable biofuel with the advantages of enhancing the reaction rate
(2 min instead of 150 min) and of improving the separation process. The
methodology allows for the use of high free fatty acid content feedstock, including
Jatropha oil. However, this emerging technology needs to be further investigated for
possible scale-up for industrial application (B.R. Moser, USDA, 2009).

6.EXPERIMENTAL APPARATUS AND TEST

CONDITIONS
6.1.Experimental Apparatus
The engine used was a single cylinder, naturally aspirated, 4-stroke, water cooled,
direct injection diesel engine. The basic data of the engine used is given in the table
below.

Sr.
No
1

Description

Data

Name of the Engine manufacturer

Kirloskar Oil
Engines Ltd.
Vertical, 4-stroke
cycle, singleacting, totally
enclosed, highspeed compression
ignition diesel
engine
1
4.41 KW or 6.0 bhp

Type of engine

3
4

Number of cylinders
IS Rating at 1500 rpm

Direction of rotation

Bore

CW/ACW when
looking at flywheel
end
87.5mm

7
8

Stroke
Cubic Capacity

110mm
0.662 litres

Nominal compression ratios

17.5:1

10
11

Fuel timing by spill(BTDC)

Valve Timing
Inlet valve opens BTDC
Inlet valve closes closes
ABDC
Exhaust valve opens BBDC
Exhaust valve closes ATDC
Valve clearance-in cold condition
Inlet
Exhaust

23 degree

12

4.5 degree
35.5 degree
35.5 degree
4.5 degree

0.18mm
0.20mm

Gaseous emissions were measured by using the AVL Digas 4000 gas analyzer. To
ensure that the accuracy of the measured values was high, the gas analyser was
calibrated before each measurement using reference gases. A Tecktronix TDS 2014
four channel digital storeage oscilloscope attached to AVL Piezo Amplifier A03 was
used to measure the peak pressure of the piston during a cycle with the help of a
piezoelectric sensor.

6.2- Engine test Procedure

The experiments were carried out by using B0 (100% neat diesel), B2(2% biodiesel
and 98% diesel), B5(5% biodiesel and 95% diesel), B10(10% biodiesel and 90%
diesel), B20(20% biodiesel and 80% diesel) and B100(100% neat biodiesel) at
different engine loads. Before running the engine to a new fuel, it was allowed to
run for sufficient time to consume the remaining fuel from the previous experiment.
To evaluate the performance parameters, important operating parameters such as
engine speed, power output, fuel consumption, exhaust emissions and cylinder
pressure were measured.

7. RESULTS AND DISCUSSIONS

7.1-Combustion Characteristics
7.1.1- Peak Pressure
The variations of peak cylinder gas pressure was with brake power for different
blends of biodiesel are given in the figure below.

Peak Cylinder Pressure vs Load

66
64
62
60

Peak Cylinder Pressure (in bar)

58
56
54
52
50

2.5

3.5

Load (in KW)

Diesel

B2

B5

B10

B20

B100

In a CI engine, the peak cylinder pressure depends on the burned fuel fraction
during the premixed burning phase, i.e. the initial phase of combustion. The cylinder
pressure characterizes the ability of the fuel to mix well with the air and burn
(Ganesan V :IC Engines, 2012). Biodiesel and its blends follow the similar cylinder
pressure pattern to that of diesel fuel under both operating conditions. It is clear
that the peak cylinder pressure is higher for biodiesel and its blends at lower
operating loads but they are almost identical at higher operating loads. This may be
because the ignition delay period increases with the decrease in engine load. As the
engine load decreases, the residual gas temperature and the wall temperature
decrease which leads to lower charge temperature at injection and lengthens the
ignition delay period. At low engine loads, because of the larger ignition delay
periods, combustion starts later for diesel fuel than for biodiesel and its blends
(Ganesan V: IC Engines, 2012). As a result, the peak cylinder pressure attains a
lower value as it is further away from the TDC in the expansion stroke at low engine
loads. However as the engine load increases, the ignition delay of diesel fuel
decreases, resulting in initiation of combustion before the TDC and the pressure
rises more quickly because of higher premixed burning.

7.2- Performance Characterisitics

7.2.1- Brake Specific Fuel Consumption
The variation in brake specific fuel consumption (BSFC) against brake power for
different blends of biodiesel in shown in the above figure. BSFC is the ratio between
mass flow of the tested fuel and the effective power (Ganesan V, IC engines, 2012).

Brake Specific Fuel Consumption vs Brake Power

600
550
500
450

BSFC (in g/KW-h)

400
350
300
250

2.5

3.5

Brake Power (in KW)

Diesel

B2

B5

B10

B20

B100

It was found that the BSFC value of the biodiesel and its blends are slightly higher
than those of diesel fuel under all range of engine loads. The BSFC of the diesel
engine depends upon factors such as volumetric fuel injection system, fuel density,
viscosity and lower heating value (Ganesan V, IC engines, 2012). Therefore more
biodiesel and it blends are needed to produce the same amount of energy due to its
lower heating value in comparison with diesel fuel.

7.2.2- Brake Thermal Efficiency

Brake thermal efficiency (BTE) is the ratio between the power output and the energy
introduced through fuel injection, the latter being the product of the injected fuel
mass flow rate and the lower heating value. The figure below shows the variation of
Brake thermal efficiency for different blends of biodiesel under different range of
loads.

Brake Thermal Efficiency vs Brake Power

35
30
25
20

Brake Thermal Efficiency (in %)

15
10
5
0

2.5

3.5

Brake Power (in KW)

Diesel

B2

B5

B10

B20

B100

It can be seen that the BTE of biodiesel and its blends are slightly lower than that of
diesel fuel. The maximum BTE of diesel fuel is 0.3265 and that of biodiesel and its
blends are less than 0.3265. The main reason is that biodiesel has higher viscosity,
density and lower heating value than diesel fuel. The higher viscosity leads to
decreased atomization and fuel vaporization and hence the BTE of biodiesel is less
than that of diesel fuel.

7.3- Emission Characterisitics

7.3.1- NOX Emissions
The Nitrogen oxide emissions are analysed in the figure given below.

NOX Emissions vs Load

1100
1000
900
800
700

NOX Emissions (in PPM)

600
500
400
300
200
100

2.5

3.5

Load (in KW)

Diesel

B2

B5

B10

B20

B100

There are mainly three factors- oxygen concentration, combustion temperature and
time, affecting the NOX emissions. NOX emissions of biodiesel and its blends are
slightly higher than those of diesel fuel. The higher temperature of combustion and
the presence of oxygen in biodiesel cause higher NO X emission, especially at high
engine loads.

7.3.2- CO emissions
The CO emissions for the different blends of biodiesel under different range of load
is given in the figure below.

CO Emissions vs Load

Co Emissions (In % of volume)

0.06
0.05
0.05
0.04
0.04
0.03
0.03
0.02
0.02
0.01
0.01
0

2.5

3.5

Load (in KW)

Diesel

B2

B5

B10

B20

B100

The CO emissions did not follow any particular trend. In general, the CO emissions
for biodiesel and its blends are lower than that for diesel fuel. This is because
biodiesel has more oxygen content than diesel fuel which leads to more efficient
combustion resulting in lower CO emissions.

7.3.3- CO2 emissions

The CO2 emissions of biodiesel and its blends are shown in the figure below.

CO2 Emissions vs Load

CO2 Emissions (in % of vol)

2.5

3.5

Load (in KW)

Diesel

B2

B5

B10

B20

B100

The CO2 emissions of biodiesel showed a random plot. The lower percentage
biodiesel blends(B2, B5 and B10) showed CO 2 emissions similar to petroleum diesel.
But the higher composition blends(B20 and B100) showed higher levels of CO 2

emissions than petroleum diesel. This may be attributed to the increasing content of
O2 in the fuel which leads to the more production of CO 2 which is a product of
combustion.

7.3.4- Unburnt HC(Hydrocarbon) emissions

The figure below shows the variation of unburnt hydrocarbons of different blends of
biodiesel.

HC emissions vs Load
60

50

40

HC Emissions (in PPM) 30

20

10

2.5

3.5

Load (in KW)

Diesel

B2

B5

B10

B20

B100

There is no definite trend for the HC emissions in biodiesel blends. These differences
are insignificant as there levels are in absolute terms small. But the higher biodiesel
blends(B20 and B100) showed larger HC emissions than lower blends of biodiesel
and diesel. This may be due to the high density of biodiesel, leading to poor
atomization and vaporization, in turn leading to a lean mixture, which in turn leads
to low peak temperatures. These low temperatures might be leading to incomplete
burning of fuel, especially near the walls of the combustion chamber, which may be
one of the reasons for higher HC emissions.

8.CONCLUSIONS
The properties, performance, emissions and combustion
characteristics of a direct injection compression ignition engine
fueled with biodiesel and its blends have been analysed and
compared with the diesel fuel. The results of the present work are
summarized as follows: A methyl ester biodiesel is produced from karanja
(pongamia pinnata) oil by a method of alkaline-catalysed
transesterification. The diesel engine can perform
satisfactorily on biodiesel and its blends with diesel fuel
without any significant engine modifications.
The BSFC increases with increase in percentage of biodiesel.
This is because of the lower heating value and high density
and viscosity of biodiesel for which greater amount of fuel is
required for the same energy need.
The oxygen content in biodiesel results in better combustion
chamber temperature, which leads to higher NOX emissions
especially at higher engine loads. HC emissions of low
percentage blends have little difference from diesel fuel but
HC emissions of high percentage blends are more than
diesel because of the biodiesel being a lean mixture.
The combustion starts earlier for biodiesel and its blends.
The peak cylinder pressure of biodiesel and its blends than
for diesel. The peak cylinder pressure for biodiesel and its
blends is higher than that for diesel fuel, and almost
identical at high engine loads.
The study suggests that the oxygen content in biodiesel plays
a key role in engine performance and biodiesel is a very
important fuel of the future which can replace petroleum
diesel.

APPENDIX
ASTM D6751 standards for biodiesel

EN 14214 standards for biodiesel

ASTM D7467 biodiesel-petrodiesel blend B6-B20 fuel standard

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