waste cookin oil

1. RESEARCH ARTICLE
BIO-DIESEL PRODUCTION FROM WASTE COOKING OIL AND
FACTOR AFEECTS TO ITS FORMATION:
Abdul Karim Chaudhary, Shashikant Sharma
akc3582@gmail.com, shashikant.sharma313@gmail.com
Department of mechanical engineering ,SORT Peoples University,Bhopal,India
ABSTRACT
Waste cooking oil which contain large amount of fatty acids are collected by
the environmental protection in many parts of the world. Continuous use of
petroleum sourced fuels is now widely recognized as unsustainable because of
depleting supplies and the contribution of these fuels to the accumulation of carbon
dioxide and carbon monoxide in the environment. Renewable, carbon neutral,
transport fuels are necessary for environmental and economic sustainability. The aim
of work, biodiesel was extracted double stage trans-esterification process from waste
cooking oil and to study the performance and emission characteristics of diesel
engine.
In this study, waste cooking oil was used to extract the bio-diesel. The
extracted bio diesel was blended with sole fuel and B20% blend (20% of bio diesel +
80% of diesel) has been selected. From literature review, it is understood that B20%
blend the engine can run without any modification in the operational parameters and
enhance the performance of the engine with bio-diesel. From the experimental
investigation it was observed that the brake thermal efficiency increased for B20%
blend by 1.5% when compared to that of conventional diesel fuel. The CO, HC,

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Smoke were found to decrease with the B20% blend with slightly increase in NOx
emission compared to that of sole fuel.
Key Words: Bidiesel,waste cooking oil, Pyrolysis,Micro-
emulsification,transesterifacatio
INTRODUCTION
In recent years, biodiesel has gained international attention as a source of alternative
fuel due to characteristics like high degradability, no toxicity, and low emission of carbon
monoxide, particulate matter and unburned hydrocarbons. Biodiesel is a mixture of alkyl
esters and it can be used in conventional compression ignitions engines, which need almost
no modification. As well, biodiesel can be used as heating oil and as fuel. So far, this
alternative fuel has been successfully produced by transesterification of vegetable oils and
animal fats using homogeneous basic catalysts (mainly sodium or potassium hydroxide
dissolved in methanol). Traditional homogeneous catalysts (basic or acid) possess
advantages including high activity (complete conversion within 1 h) and mild reaction
conditions (from 40 to 65 °C and atmospheric pressure). However, the use of homogeneous
catalysts leads to soap production. Besides, in the homogeneous process the catalyst is
consumed thus reducing the catalytic efficiency. This causes an increase in viscosity and the
formation of gels. In addition, the method for the removal of the catalyst after reaction is
technically difficult and a large amount of wastewater is produced in order to separate and
clean the products, which increases the overall cost of the process. Thus, the total cost of the
biodiesel production based on homogeneous catalysis, is not yet sufficiently competitive as
compared to the cost of diesel production from petroleum.
An alternative is the development of heterogeneous catalysts that could eliminate the
additional running costs associated with the aforementioned stages of separation and
purification. In addition, the use of heterogeneous catalysts does not produce soap through

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free fatty acid neutralization and triglyceride saponification. Therefore, development of
efficient heterogeneous catalysts is important since opens up the possibility of another
pathway for biodiesel production. The efficiency of the heterogeneous process depends,
however, on several variables such as type of oil, molar ratio alcohol to oil, temperature and
catalyst type. So, one among alternate production methods of biodiesel is catalytic cracking
to improve quality of oil. This process is selected for production of biodiesel from mango
seed oil.
Environmental pollution is very serious problem for our human beings and flora-
fauna. The environment is polluted day by day from industrial emissions and road vehicles
emissions. Petrol engine and diesel engine produced different types of harmful gases during
combustion like NOx, CO, CO2, HC and some quantity SOx due to incomplete combustion.
These gases are produced by different engine factor such as piston bowl geometry, injection
timing, compression ratio etc. These entire factors also affect the combustion efficiency, fuel
consumption and engine brake power. To reduce the emissions engine manufacturers try to
best design, the combustion chamber and other level. At combustion chamber geometry
design to reduce the NOx many researchers studied the different piston bowl geometry.
Flow phenomena in internal combustion (IC) engines are extremely complex, and
the flow field is further complicated by the presence of swirl, squish, tumble and chemical
reactions. A complete understanding of the physical processes of fluid motion in combustion
chambers is essential in developing efficient engine design and control diagnostics.
Diesel engines have been greatly improved in terms of efficiency and reduced
emission level. However, the combustion process also depends highly on an efficient fuel-air
mixture, particularly in high-speed direct-injection diesel engines. Among these processes,
the flow conditions inside the cylinder at the end of the compression stroke and near the top
dead center are critical for fuel air mixing, wall heat transfer and engine performance
improvement. The mixing process is affected by the intake swirls, fuel injection system and

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combustion chamber configuration. Thus good engine operation requires fuel spray matching
air movement and combustion chamber configuration.
Most of our energy requirements are met by fossil fuels for good technological
reasons. Depletion of the petroleum reserves is a big concern, it is estimated that the world
resources of oil will be exhausted within 50 years. Environmental concern about air pollution
caused by the combustion of fossil fuels has also lead to serious implications. The diesel
engine is main prime movers compare to any other engine in transportations, power
generation and many miscellaneous applications i.e. in industries and agriculture. The major
pollutants from diesel engine are smoke, particulate matter (PM), carbon monoxide (CO),
nitrogen oxides (NOx) and unburnt hydrocarbons (UBHC). Incomplete combustion increases
the pollution level as compared to proper combustion. Due to reliance on transport
consumptions of fossil fuels has increase drastically and the world witness long term damage
to the climate. As transport is one of the few industrial sectors where emissions are still
growing and this fact has made transport a major contributor of green house gases (GHGs).
Generally carbon dioxide, methane, nitrous oxide, ozone etc are known as green house gases.
These gases interact with solar terrestrial radiation and causing imbalance on the Earth’s
climate system and increases earth surface temperature.
The significant effect of global warming has been felt for last two decades. This rise
in earth surface temperature is known as global warming. Reducing the emission of the gases
will lead to the solution to the climate change problem. Different methods of reducing the
climate change problem. Different methods of reducing the climate change problem could be
increasing the use of carbon capture and storage (CCS) techniques, increasing energy
efficiency and promoting the use of renewable energy and carbon free fuels. Different
methods like modifying the engine design, treating the exhaust gas and by fuel modification
exhaust gas emission of an engine can be reduce. To overcome the problems associated with

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the use of petroleum derived fuels, it is urgently needed to develop a renewable energy
source of energy which must be environmentally clean.
Research on the production of biofuel from the fossil fuels are causing the global
climate change due to catalytic cracking of mango seed oil has been well developed. This
method is able to crack complex hydrocarbons to yield less complex structures. With the
help of a catalyst, the reaction may be conducted at a lower temperature and pressure;
moreover the quality and quantity of the products may be enhanced. In the catalytic cracking
of vegetable oil to produce biofuel, the type and products’ compositions are influenced by
several factors, such as time, temperature, flow rate of the raw materials and type of
catalysts. Many types of catalyst have been used in the catalytic cracking to produce biofuel.
The catalysts have been developed to be used in the catalytic cracking of vegetable oil to
produce biofuel.
. Biodiesel
The major components of vegetable oils and animal fats are triacylglycerols (TAG;
often also called triglycerides). Chemically, TAG are esters of fatty acids (FA) with glycerol
(1,2,3-propanetriol; glycerol is often also called glycerine). The TAG of vegetable oils and
animal fats typically contain several different FA. Thus, different FA can be attached to one
glycerol backbone. The different FA that are contained in the TAG comprise the FA profile
(or FA composition) of the vegetable oil or animal fat. Because different FA have different
physical and chemical properties, the FA profile is probably the most important parameter
influencing the corresponding properties of a vegetable oil or animal fat. Biodiesel can be
produced from a great variety of feedstocks. These feedstocks include most common
vegetable oils (e.g., soybean, cottonseed, palm, peanut, rapeseed/canola, sunflower,

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safflower, coconut) and animal fats (usually tallow) as well as waste oils (e.g., used frying
oils). The choice of feedstock depends largely on geography. Depending on the origin and
quality of the feedstock, changes to the production process may be necessary. Biodiesel is
miscible with petrodiesel in all ratios. In many countries, this has led to the use of blends of
biodiesel with petrodiesel instead of neat biodiesel. It is important to note that these blends
with petrodiesel are not biodiesel. Often blends with petrodiesel are denoted by acronyms
such as B20, which indicates a blend of 20% biodiesel with petrodiesel.
History ofBiodiesel
The use of vegetable oils as alternative fuels has been around for one hundred years
when the inventor of the diesel engine Rudolph Diesel first tested peanut oil, in his
compression-ignition engine. In the 1930s and 1940s vegetable oils were used as diesel fuels
from time to time, but usually only in emergency situations. In 1940 first trials with
vegetable oil methyl and ethyl esters were carried out in France and, at the same time,
scientists in Belgium were using palm oil ethyl ester as a fuel for buses. Not much was done
until the late 1970s and early 1980s, when concerns about high petroleum prices motivated
extensive experimentation with fats and oils as alternative fuels. Bio-diesel (mono alkyl
esters) started to be widely produced in the early 1990s and since then production has been
increasing steadily. In the European Union (EU), bio-diesel began to be promoted in the
1980s as a means to prevent the decline of rural areas while 3 responding to increasing levels
of energy demand. However, it only began to be widely developed in the second half of the
1990s.

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Methods
Generally the direct use of vegetable oils in the diesel engine is not preferred due to
their high viscosity. Four methods to reduce the high viscosity of vegetable oils to enable
their use in common diesel engines without operational problems such as engine deposits
have been investigated.
 Pyrolysis;
 Micro-emulsification;
 Dilution; and
 Transesterification.
Phyrolysis
Pyrolysis is the conversion of one substance into another by means of heat or by
heat with the aid of a catalyst. It involves heating in the absence of air or oxygen and
cleavage of chemical bonds to yield small molecules The liquid fractions of the
thermally decomposed vegetable oil are likely to approach diesel fuels. The pyrolyzates
have lower viscosity, flash point, and pour point than diesel fuel and equivalent calorific
values. The cetane number of the pyrolyzate is 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.Micro-
emulsification
The formation of microemulsions (co-solvency) is one of the potential solutions for
solving the problem of vegetable oil viscosity. A microemulsion is defined as a colloidal
equilibrium dispersion of optically isotropic fluid microstructures with dimensions generally
in the 1±150 nm range formed spontaneously from two normally immiscible liquids and one

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or more ionic or non-ionic amphiphiles. 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 4 without diesel fuels. Water (from aqueous ethanol) may also be
present in order to use lower-proof ethanol, thus increasing water tolerance of the micro-
emulsions.
Transesterification Process
Transesterification is also called alcoholysis, is the displacement of alcohol from on
ester by another alcohol in a process similar to hydrolysis.
This process has been widely used to reduce the viscosity of triglycerides. The
transesterification reaction is represented by the general equation
R COOR’ + R” R COOR” + R’ OH
If methanol is used in the above reaction, it is formed as methanolysis. The reaction
of glyceride with methanol is represent by the general equation triglycerides are readily
transesterified in the presence of alkaline catalyst at atmospheric pressure and at a
temperature of approximately go to 70C with an excess of methanol. The mixture at end of
the reaction is allowed to settle. The lower glycerol layer is drawn off while the upper methyl
ester layer is washed to remove entrained glycerol and is then processed further.
The excess methanol is recovered by distillation and sent to rectifying column for
purification and recycled. The transesterification works well when the starting oil is of light
quantity. However, quite often low quality oils are used as raw materials for biodiesel
preparation. In case where the free fatty acid content of the oil is above 4%, difficulty arise
due to formation of soaps which promote emulsification during the water working stage and
at an FFA content above 2% he process becomes unworkable.

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If the free fatty acid content of the oil is below 4% single stage process is adopted. If
the free fatty acid content s greater than 4% double stage process is adopted.
Process variable in transesterification
The most important variable that influence transesterification reaction time and
conversion are;
 Oil temperature
 Reaction temperature
 Ratio of alcohol to oil
 Intensity of mixing
 Purity of reactants
 Catalyst type and concentration
Oil temperature
The temperature to which oil is heated before mixing with catalyst and methanol
affects the reaction. It was observed that increase in oil temperature marginally increase the
percentage oil to biodiesel conversion as well as the biodiesel recovery. However the tests
were conducted upto only 60C as higher temperature may result in methanol less in batch
process.
Reaction temperature
The rate of reaction is strongly influenced by the reaction temperature. Generally the
reaction is conducted close to the boiling point of methanol (60C to 70C) at atmospheric

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pressure. The maximum yield of esters occurs at temperature ranging 60C to 80C at a
molar ratio (alcohol to oil) of 6:1. Further increasing in temperature is reported to have a
negative effect on conversion. Studies have indicated that give enough time,
transesterification can proceed satisfactorily at ambient temperature in concentration of
alkaline catalyst. It was observed that biodiesel recovery was affected at very low
temperature, but conversion was almost unaffected.
Ratio ofalcohol to oil
Another important variable affecting the yield of ester is the molar ratio of alcohol to
vegetable oil. A molar ratio of 6:1 normally used in industrial process to obtain methyl ester
yields higher than 98% by weight. Higher molar ratio of alcohol to vegetable oil interferes in
the separation of glycerol it was observed that lower molar ratio required more reaction time
with higher molar ratios conversation increased but recovery decreases due to poor
separation of glycerol. It was found that the optimum molar ratios depend upon the type and
quality of oil.
Mixing intensity
The mixing effect is more significant during the slow rate region of
transesterification process as the single phase in established mixing becomes in significant.
The understanding of the mixing effects of the kinetics of the transesterification process is a
very tool in the scale up and design. It was observed that adding methanol and catalyst to the
oil, 5-10 minutes string helps in the higher rate of conversion and recovery.

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Purity of the reactants
Alkali metal alkoxides are the most effective transesterification catalyst compared to
the acidic catalyst. Sodium alkoxides are among the most efficient catalysts used for this
purpose, although potassium hydroxide and sodium hydroxide can also be used.
Transesterification occurs many folds faster in the presence of an alkaline catalyst than those
catalysed by the same amount of acidic catalyst. Most commercial trans-esterification are
conducted with alkaline catalysts. The alkaline catalyst concentration in the range of 0.5 to
1% by weight yields 94 to 99% conversion of vegetable oil into esters. Further, increase in
catalyst concentration does not increase the conversion and it adds to extra costs because it is
necessary to remove it from the reaction medium at the end.
It was observed that higher amounts of sodium hydroxide catalyst were required for
higher FFA oil. Otherwise higher amount of sodium hydroxide resulted in reduced recovery
due to more quantity of glycerol being separated from the oil.
Washing and collection
The contents were separated in to two layers. The less density layer of methyl esters
floated upper portion of separating funnel. The colour difference between the two layers
enabled their easy separation.
The traces of soap and glycerine present in the methyl ester layer had to be removed.
Washing the esters with distilled water thrice. Washing was done by adding approximately
15% by volume of distilled water to methyl esters and it is allowed to settle. Since the
methyl esters are less density then water, they float on the top and were removed by
separating funnel. The clean methyl esters are obtained. The methyl esters are heated to
105C to 110C to remove the water content and it is cooled. The pure biodiesel is collected
in the container.

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This procedure is repeated for different catalysts for the production of biodiesel.
Recovery ofmethanol
Depending on the kind of oil used it takes from 110-160 millilitres of methanol per
liter of oil to form the methyl esters molecule and also need to use an excess of methanol to
push the conversion process towards completion. The total used is usually 20% and more of
the volume of oil used, 200ml per liter or more.
Much of the excess methanol can be recovered after the process for reuse, simply by
boiling it off in a closed container with an outlet leading to a simple condenser. Methanol
boils at 64.7C, though of course it starts vaporizing well before it reaches boiling point.
Methanol does not form an azeotrope with water and relatively pure methanol is recovered.
Pure enough to re-use in the next batch.
Methanol can be recovered at the end of the process, or just form the glycerine by-
product layer, since most of the excess methanol collects in the by-product and it’s that much
less material to heat. Start at 65-70C as the proportion of methanol left in the by-product
mixture decreases the boiling point will increase to raise the temperature to keep the
methanol vaporizing, perhaps to as highly 100C or more, though the bulk of it should have
been recovered by then.
Benefits ofbiodiesel
One of the main driving forces for biodiesel widespread use is the limitation of
greenhouse gas emissions (CO2 being the major one) by the Kyoto Protocol. Along 9 with
ethanol and other biomass derived fuels, biodiesel is an important bio-energy. When plants
photosynthesize, they use the sun's energy to pull CO2 out of the atmosphere and incorporate

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it into biomass. Part of the solar energy is locked into the chemical structure within the
biomass. There are a number of thermal, chemical or microbial processes that can be used to
release this energy or convert it into a more convenient form for human use. As a form of
bio-energy, biodiesel is nearly carbon-neutral, i.e., the CO2 it produces on burning will be
absorbed naturally from CO2 in the air and recycled without an overall net increase in the
atmospheric CO2 inventory, thus making an almost zero contribution to global warming
There are many distinct benefits of using biodiesel compare to diesel fuel.
 Considered to be environmental friendly, biodiesel is one of the most renewable
fuels compare to diesel fuel.
 It is biodegradable.
 It is derived from a renewable domestic resource, thus reducing dependence on and
preserving petroleum. It can be domestically produced, offering the possibility of
reducing petroleum imports,
 Reductions of most exhaust emissions relative to conventional diesel fuel, generating
lower emissions of hydrocarbons, particulates and carbon monoxide;
 Biodiesel has a relatively higher flash point, >150 °C, indicating that it presents a
very low fire hazard; leading to safer handling and storage,
 Biodiesel provides greater lubricity than petroleum diesel, thus reducing engine
wear. In fact, biodiesel can be used as a lubricity enhancer for low-sulphur
petroleum diesel formulations,
 Toxicity tests show that biodiesel is considerably less toxic than diesel fuel (Haws,
1997).
 Biodiesel can be used directly in most diesel engines without requiring extensive
engine modifications.

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Waste cooking oil as feedstock biodiesel
The term “waste cooking oil” (WCO) refers to vegetable oil which has been used in
food production and which is no longer viable for its intended use. WCO arises from many
different sources, including domestic, commercial and industrial. WCO is a potentially
problematic waste stream which requires to be properly managed. The disposal of WCO can
be problematic when disposed, incorrectly, down kitchen sinks, where it can quickly cause
blockages of sewer pipes when the oil solidifies. Properties of degraded used frying oil after
it gets into sewage system are conducive to corrosion of metal and concrete elements. It also
affects installations in waste water treatment plants. Thus, it adds to the cost of treating
effluent or pollutes waterways.
Any fatty acid source may be used to prepare biodiesel. Thus, any animal or plant
lipid should be a ready substrate for the production of biodiesel. The use of edible vegetable
oils and animal fats for biodiesel production has recently been of great concern because they
compete with food materials - the food versus fuel dispute. There are concerns that biodiesel
feedstock may compete with food supply in the long-term. From an economic point of view;
the production of biodiesel is very feedstock sensitive. Many previous reports estimated the
cost of biodiesel production based on assumptions, made by their authors, regarding
production volume, feedstock and chemical technology. In all these reports, feedstock cost
comprises a very substantial portion of overall biodiesel cost.
The process of converting waste cooking oil into biodiesel can be broken down into
five primary sequential steps in figure 4.1

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Figure 4.1. Generalized waste cooking oil-to-biodiesel fuel processflowdiagram
1. The first step is the waste oil collection. While each collection technique can be
different, it requires coordination between the collectors and the oil producing facility
(restaurant, community, cafeteria, municipality, etc.).
2. The second step is a pre-treatment process, which is broken into two sub-steps. The
oil is most likely to contain residual water, as well as solid food particles. Therefore, the
first pre-treatment step is to separate out the water and solids. This is crucial to ensure
full conversion of oil to biodiesel, described further below. Once separated, the oil is
then titrated to determine the concentration of free fatty acids (FFA). This determines
the necessary amount of catalyst for the transesterification reaction.
3. Following the pre-treatment process, the waste cooking oil feedstock is ready for the
transesterification reaction. The oil, a triglyceride, reacts with an alcohol, Waste Oil
Collection Pre-treatment Transesterification Biodiesel and Glycerol Separation
Utilization typically methanol, in the presence of a catalyst to produce fatty acid esters
(Figure 2) [13]. The oil is composed of three fatty acid chains with a glycerine “back
bone.” The alcohol breaks off the three fatty acid chains from the glycerine and then
attaches to each of the three free fatty acid chains making a fatty acid ester, or
commonly known as biodiesel. The broken off glycerin is the by-product of this
production process.
4. Once the transesterification reaction is complete, the biodiesel and glycerine will
separate with time, due to their different densities. When the products separate, there
will be two distinct layers with visible color and viscosity differences. The glycerine
will be the bottom layer because it is denser than biodiesel. The glycerine separation
step is simply draining off the bottom layer of glycerine.

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5. Once separated, the biodiesel and glycerin by-product can be utilized in appropriate
applications. Biodiesel can be used as a substitute for petroleum diesel fuels (fuel oil for
heating applications), while glycerin has numerous uses as a food additive, soaps
production, etc.
Bio-diesel production by transesterification method
A laboratory-scale biodiesel production set-up was as shown the figure 4.1. It
consists of a motorized stirrer, straight coil electric heater and stainless steel containers. The
system was designed to produce maximum 5 liter of biodiesel. Temperature of the mixture
of the triglyceride, methanol and catalyst were maintained at about 60C.
The method adopted for preparation of biodiesel from Sapotta seed oil for this work
is, transesterification which is a process of using methanol (CH3OH) in the presence ofa catalyst,
such as potassium hydroxide (KOH),to chemically break the molecule of Sapotta seed oil into an
ester and glycerol. This process is a reaction of the oil with an alcohol to remove the glycerine,
which is a by-product of biodiesel production.

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figure Schematic diagram of Biodiesel Plant (5 lit. Capacity)
The procedure done is given below: 1000ml of waste cooking oil is taken in a
container. 15 grams of Potassium hydroxide alkaline catalyst (KOH) is weighed. 200 ml of
methanol is taken is beaker. KOH is mixed with the alcohol and it is stirred until they are
properly dissolved. Waste cooking oil is taken in a container and is stirred with a mechanical
stirrer and simultaneously heated with the help of a heating coil The speed of the stirrer
should be minimum and when the temperature of the raw oil reaches 62C the KOH-alcohol
solution is poured into the raw oil container and the container is closed with a air tight lid.
Now the solution is stirred at high speeds. Care should be taken that the temperature does not
exceed 62 C as ethanol evaporates at temperatures higher than 60C. Also the KOH-alcohol
solution is mixed with the waste cooking oil only at 62 C because heat is generated when
KOH and alcohol are mixed together and the temperature of the raw oil should be more than

18. 18
this when mixing is done if the reactions have to take place properly. After stirring the
animal oil-KOH-alcohol solution at 62 C for ½ an hour the solution is transferred to a glass
container. Now separation takes place and biodiesel gets collected in the upper portion of the
glass container whereas glycerine gets collected in the bottom portion. This glycerine is
removed from the container. Then the biodiesel is washed with water. Again glycerine gets
separated from the biodiesel and is removed. The biodiesel is washed with water repeatedly
until no glycerine is there in the biodiesel. Now this biodiesel is heated to 100 C to vaporize
the water content in it. The resulting product is the biodiesel which is ready for use.
Physical and chemical properties of waste cooking oil
Property Waste cooking oil
Acidvalue (mgKOH/g) 2.1
Kinematicviscosityat40oC (cSt) 35.3
Fatty acid composition (wt%)
Myristic(C14:0) 0.9
Palmitic(C16:0) 20.4
Palmitoleic(C16:1) 4.6
Stearic(C18:0) 4.8
Oleic(C18:1) 52.9
Linoleic(C18:2) 13.5
Arachidic(C20:0) 0.12
Mean molecularwt(g/mol) 856

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CONCLUSION
Biodiesel is a successful alternating fuel and it can be used directly as a fuel in
diesel engine without any modification of engine.Transesterification method is very
common method to reduce the viscosity while producing biodiesel.The main purpose of
biodiesel is to reduce the exhaust emissions in terms of carbon monoxide
(CO),hydrocarbon(HC) and particulate matter.The blend B20% shows significant reduction
in CO,HC and smoke emission when compared to diesel fuel.The NOx emission for
biodiesel is significantly raised.
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