Project phase 2

A STUDY ON PRODUCTION OF BIO-DIESEL AND GLYCERIN SOAP

2012-2013

CHAPTER 1

INTRODUCTION

1.1 GENERALBiodiesel is becoming prominent among the alternatives to

conventional petro-diesel due to economic, environmental and

social factors. The quality of biodiesel is influenced by the

nature of feedstock and the production processes employed.

High amounts of free fatty acids (FFA) in the feedstock are

known to be detrimental to the quality of biodiesel. Vegetable

oils are among the various sources of energy fuels being

considered as alternatives to fossil fuels. Rapeseed, soybean,

sunflower, coconut and palm oils have been the main raw

materials for biodiesel production. However, these oils are

required in refined forms to obtain quality biodiesel and in

addition they are food stuffs. This makes production of

biodiesel from these sources uneconomical. Non-edible plant

oils such as found in jatropha and castor beans may provide

better alternatives. Plant-derived oils could be used directly

in diesel engines or blended with petro-diesel however, their

high viscosity lead to problems in the engine .

Biodiesel is the name for a variety of Easter-based

fuels generally defined as the mono alkyl esters made from non

edible oils such as Pongamia or Jatropha or Neem or Simaruoba

oil, or sometimes from animal fats through a simple trans-

esterification process. This renewable source is as efficient

Department of Environmental Engineering PESCE, Mandya


2012-2013

as petroleum diesel in powering unmodified diesel engine. The

concept of using vegetable oil as an engine fuel by Rudolf

Diesel(1858-1913) when he developed the first engine to run on

peanut oil, as he demonstrated at the World Exhibition in

Paris in 1900. Unfortunately, Rudolf Diesel died in 1913,

before his vision of a vegetable oil powered engine was

realized. After R. Diesel’s findings the petroleum industry

rapidly developed and produced a cheap by-product “diesel

fuel” powering a modified “diesel-engine”. Thus, clean

vegetable oil was forgotten as a renewable source of power.

From 1990-91 to 2010-11, India’s oil imports increased

dramatically from 21 to 120 million tonnes. Biodiesel could

stimulate agricultural development and create employment and

income for many of the rural poor. At the same time, thereby

satisfy a significant part of the country’s fuel demand,

increasing India’s energy security and saving foreign

exchange. Shifting to biodiesel could also reduce greenhouse

gas emissions and urban air pollution.

The Government of India approved a National

policy on Bio fuels in September 2008, setting an indicative

target to raise blending of biodiesel with diesel to 20% by

2017 and scrapping taxes and duties on biodiesel.

A by-product from making bio-diesel is glycerine. In a

process called transesterification, waste vegetable oil (WVO)

is broken down into esters (bio-diesel) and glycerine. This

glycerine can be filtered to remove any food particles or



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impurities, and used as an industrial degreaser in its raw

form, composted and used as a fertilizer, or made into bar

soap. Bar soap made from our glycerine by-product is excellent

for use in the shop because of its degreasing abilities, but

can also be used as a household soap for everyday use. Adding

fragrances and dyes will make household use. Ingredients used

in making bar soap from glycerine are, glycerine, water and

lye. The amounts of water and lye used will affect the

lathering abilities of the soap, and found that the more water

used, the more lather the soap will produce. And using more

lye will produce a soap which is very strong and cuts grease

well, but also dries out the skin.

Glycerol (also known as glycerine) is a major by-

product in the biodiesel manufacturing process. As the

biodiesel industry is rapidly expanding, a glut of crude

glycerol is being created. Because this glycerol is expensive

to purify for use in the food, pharmaceutical, or cosmetics

industries, biodiesel producers must seek alternative methods

for its disposal. The objective of this project is to provide

a general background in terms of waste glycerol utilization.

1.2 Importance of the study

The scarcity of fossil fuels, growing emissions of

combustion-generated pollutants, and their increasing costs,

have made alternative fuel sources more attractive. Biodiesel

(fatty acid methyl esters) produced by the process of trans



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esterification of vegetable oils or animal fats with methanol

are potential substitutes for petroleum-based diesel fuels.

Compared to conventional diesel, biodiesel has the advantages

of being biodegradable, renewable, non-toxic, and has low

pollutant emissions (especially SOx) . In process of biodiesel

production, a heavier separate liquid phase is formed, termed

the glycerol phase. The glycerol portion represents

approximately 16 to 18% of the weight of the input of the oil

and fat, and its composition is not stabilized.

Today`s world is extremely dependent on hydrocarbons for

its energy requirements. Unfortunately, these resources are

exhaustible and are being used up at a rapid rate. Thus, there

is a need for alternative energy sources. Biodiesel provide an

efficient and inexpensive alternative. Biodiesel is a very

good proposition to replace non-renewable energy sources like

petroleum. There are many benefits of using biodiesel, Firstly

it is a clean fuel. By “clean” we mean it is friendly to the

environment. The second major benefit of biodiesel is that it

is highly biodegradable. Because of its very low

degradability, crude oil is often a big problem in cases like

oil spills.

Biodiesel eliminates this problem. Biodiesel is also

immensely helpful in reducing pollution as it significantly

reduces CO2 emissions compared to the conventional diesel. The

world is getting modernized and industrialized day by day. As

a result vehicles and engines are increasing. But energy

sources used in these engines are limited and decreasing



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gradually. This situation leads to seek an alternative fuel

for diesel engine. Biodiesel is an alternative fuel for diesel

engine. The esters of vegetables oil, animal fats are known as

Biodiesel. Compared to diesel fuel, biodiesel emissions are

substantially better for the environment and, in turn, better

for the health of the environment's inhabitants. Specifically,

the emissions of particulate matter, carbon monoxide and total

unburned hydrocarbons from biodiesel are each much less than

those from petroleum diesel.

Commonly sulphur is added to diesel fuel to increase its

lubrication. Once burned, sulphur dioxide is emitted and acid

rain results. Biodiesel, however, is naturally lubricious and

good for engine parts. Biodiesel contains only trace amounts

of sulphur so its exhaust has considerably less sulphur

dioxide. Biodiesel is miscible in petroleum diesel. This means

that the two can be mixed in any proportion and poured into

the fuel tank. Common language for a biodiesel/diesel mix is

"B" followed by the percent of biodiesel; so 20% biodiesel and

80% diesel is called B20. Pure biodiesel is called B100. That

biodiesel is miscible in petroleum diesel is advantageous when

a user has only limited biodiesel supply, is concerned about

the slightly higher cost of biodiesel or needs a greater

amount of petroleum diesel for cold-weather operability. In

very cold conditions, biodiesel begins to crystallize becomes

thicker and may be unusable on the engine. Some take this as

grounds to criticize biodiesel, but there are simple and

effective ways to use biodiesel throughout the winter.



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One may use additives in the fuel, install any of a

number of heating systems or use the biodiesel in a blend with

petroleum diesel (which crystallizes at a lower

temperature).There are many operating benefits for the user.

As mentioned already, biodiesel provides significantly higher

lubrication for the engine. Biodiesel has been shown to reduce

the need for engine maintenance. When any kind of maintenance

is required for the engine, the mechanic needs no specific

training because biodiesel does not require any sort of engine

modification. The mechanic need not even know that the engine

runs on grease. Additionally, the flash point of biodiesel is

more than 300oF and is safer to handle and store than any

petroleum based fuels.

Bio-fuels are derived from renewable bio-mass resources

and, therefore, provide a strategic advantage to promote

sustainable development and to supplement conventional energy

sources in meeting the rapidly increasing requirements for

transportation fuels associated with high economic growth, as

well as in meeting the energy needs of India’s vast rural

population. Bio fuels can increasingly satisfy these energy

needs in an environmentally benign and cost effective manner

while reducing dependence on import of fossil fuels and

thereby providing a higher degree of National Energy Security.

The growth of bio-fuels around the globe is spurred largely by

energy security and environmental concerns and a wide range



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of market mechanisms, incentives and subsidies have been put

in place to facilitate their growth. Developing countries,

apart from these considerations, also view bio-fuels as a

potential means to stimulate rural development and create

employment opportunities. The Indian approach to bio-fuels,

in particular, is somewhat different to the current

international approaches which could lead to conflict with

food security. It is based solely on non-food feed stocks to

be raised on degraded or wastelands that are not suited to

agriculture, thus avoiding a possible conflict of fuel vs.

food security.

Glycerol is generated as a by-product, not only when

biodiesel fuels are produced chemically, but also when they

are manufactured enzymatically and during the production of

bio-ethanol. The dramatic growth of the biodiesel industry has

created a surplus of glycerol that has resulted in a dramatic

10-fold decrease in crude glycerol prices in recent years and

has generated environmental concerns associated with

contaminated glycerol disposal. Anaerobic digestion is an

attractive waste treatment practice in which both pollution

control and energy recovery can be achieved.

1.3 Scope of the present study

Biodiesel production produces three major biodiesel

waste products: glycerine, methanol, and (sometimes) water.

Untreated biodiesel waste product is toxic - mostly because it



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contains methanol. In a lot of smaller plants biodiesel waste

product is not disposed of properly. This is unfortunate as

biodiesel producers are typically very environmentally aware.

The glycerine that comes out of the biodiesel process is laden

with methanol and caustic chemicals. Glycerine is probably the

worst biodiesel waste product. The real problem with glycerine

is that it is hard to process without investing a lot of money

in expensive equipment. For every 100 litres of biodiesel that

we make we will end up with 20-25 litres of glycerine. This

20-25 litres of glycerine can have up to 25% methanol in it

and should be considered hazardous waste. 50ml of methanol is

a lethal dose so there is a lot of methanol in glycerine.

Glycerine soap is gentler on skin than most soaps, making it a

good choice for people who have particularly dry or sensitive

skin. According to Vermont Soap Organics, glycerine soap also

has a lower pH than other soaps, which helps the skin retain

its natural moisture. Since glycerine is hygroscopic, it may

also help moisturize the skin by attracting water from the

air. Hence glycerine should be used as a by-product for

manufacture of soap. The present scope of the study is to

manufacture of soap using glycerine which is hazardous in

nature.

India is one of the fastest growing economies in the

world. The Development Objectives focus on economic growth,

equity and human wellbeing. Energy is a critical input for

socio-economic development. The energy strategy of a country

aims at efficiency and security and to provide access which



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being environment friendly and achievement of an optimum mix

of primary resources for energy generation. Fossil fuels will

continue to play a dominant role in the energy scenario in our

country in the next few decades. However, conventional or

fossil fuel resources are limited, non-renewable, polluting

and, therefore, need to be used prudently. On the other hand,

renewable energy resources are indigenous, non-polluting and

virtually inexhaustible. India is endowed with abundant

renewable energy resources. Therefore, their use should be

encouraged in every possible way. The crude oil price has

been fluctuating in the world market and has increased

significantly in the recent past, reaching a level of more

than $ 140 per barrel. Such unforeseen escalation of crude oil

prices is severely straining various economies in all over the

world, particularly those of the developing countries.

Petro-based oil meets about 95% of the requirement for

transportation fuels, and the demand has been steadily

rising. Provisional estimates have indicated crude oil

consumption in 2007-08 at about 156 million tonnes. The

domestic crude oil is able to meet only about 23% of the

demand, while the rest is met from imported crude. India’s

energy security would remain vulnerable until alternative

fuels to substitute and supplement petro-based fuels are

developed based on indigenously produced renewable feed

stocks. In bio fuels, the country has a ray of hope in

providing energy security. Bio fuels are environment

friendly fuels and their utilization would address



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global concerns about containment of carbon emissions. The

transportation sector has been identified as a major

polluting sector.

CHAPTER-2



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LITERATURE REVIEW

2.1 GeneralIn this chapter, the available literature in the area of

present investigation has been reviewed and an attempt has

been made to bring out gaps in the knowledge relevant to

present host, different studies on manufacturing process of

bio-diesel and production of glycerine soap have been

reviewed. In addition various report techniques to analyse the

bio-diesel and glycerine soap are also been made.

Kazi mostafijur rahman et.al.(4) has carried out investigation

on “Bio-diesel from jatropha oil as an alternative fuel for

diesel engines.” The world is getting modernized and

industrialized day by day. As a result vehicles and engines

are increasing. But energy sources used in these engines are

limited and decreasing gradually. This situation leads to seek

an alternative fuel for diesel engine. Biodiesel is anBabaganagutti, et.al.(2) has carried out investigation on

“Biodiesel kinematics viscosity analysis.” Biodiesel is a

renewable and promising fuel alternatively ear marked for use

in Compression Ignition (CI) engines. For it to be applicable

in CI engines, there are a number of quality tests required

for its certification. Kinematics viscosity is one of the most

significant test properties. The viscosity difference



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experienced between the oil and the biodiesel produced forms

the basis of an analytical method use to determining the

conversion of vegetable oil to methyl ester. This paper

presents the definitions, test procedure specifications, and

experimental results for the kinematics viscosity of

Balaniteaegyptiaca oil to biodiesel. In addition, the

kinematics viscosity results have been used to extrapolate the

Viscosity Index (VI) values of the produced biodiesel

Aldo okullo et.al.(1) has carried out investigation on

“Physico-chemical properties of biodiesel from jatropha and

caster oils”. Biodiesel is becoming prominent among the

alternatives to conventional petro-diesel due to economic,

environmental and social factors. The quality of biodiesel is

influenced by the nature of feedstock and the production

processes employed. High amounts of free fatty acids (FFA) in

the feedstock are known to be detrimental to the quality of

biodiesel. In addition, oils with compounds containing

hydroxyl groups possess high viscosity due to hydrogen

bonding. American Standards and Testing Materials, (ASTM DMedachandrashekar et.al.(6) has carried out investigation on

“Synthesis of biodiesel.”The Petroleum product resources are

limited and their consumption is increasing very fast with

globalization and high technology development since last

decade.. Since the prices of these products are on the rise at

any given time, there is a need to search for an alternate



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source, which would fuel our vehicles without any major

vehicle modification. The solution to these problems will be

obtained by utilizing the vegetable oils. Especially, some

vegetable oils like Jatropha, Mahua, Neem are chosen because

some of their properties resembled diesel. The test has been

carried out in compression ignition engine.

Diesel is a fossil fuel made from crude oil or petroleum.

It is found in pools or reservoirs in ground. More than a

million year is required to form a single drop of diesel and

it cannot be produced in laboratory. Therefore the supply of

diesel is limited. Today India is mainly dependent on Arab

countries for their fuel supplies. Even the Rajasthan Oil

reservoirs are expected to yield only about 2 to 2.5 million

tonnes annually. The country will thus have to continue

importing oil over 70% of its need until some alternative

fuels are used which makes India self sustainable.

2.2 Biodiesel

Biodiesel is a biodegradable and non-toxic alternative

fuel produced from new or used vegetable oil that is produced

from renewable resources. It can be used in any Diesel engine

without modification. Pure biodiesel has the highest BTU

content of any alternative fuel. It also has the highest

energy balance of any fuel. For every unit of fossil energy

needed to produce biodiesel, more than 3 units of energy are

gained. As for gasoline and diesel, every one unit put in



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yields only about one half unit. Because biodiesel is made

from plant oil or animal fat, it is renewable. Moreover, the

carbon dioxide taken up by plants during photosynthesis helps

to mitigate the carbon dioxide emitted from using biodiesel so

there is no net carbon introduced to the atmosphere. Compared

to diesel fuel, biodiesel emissions are substantially better

for the environment and, in turn, better for the health of the

environment's inhabitants. Specifically, the emissions of

particulate matter, carbon monoxide and total unburned

hydrocarbons from biodiesel are each much less than those from

petroleum diesel. Commonly sulphur is added to diesel fuel to

increase its lubrication. Once burned, sulphur dioxide is

emitted and acid rain results. Biodiesel, however, is

naturally lubricious and good for engine parts. Biodiesel

contains only trace amounts of sulphur so its exhaust has

considerably less sulphur dioxide.(Murugesan, et.al.)

Biodiesel has been shown to reduce the need for engine

maintenance. When any kind of maintenance is required for the

engine, the mechanic needs no specific training because

biodiesel does not require any sort of engine modification.

The mechanic need not even know that the engine runs on

grease. Additionally, the flash point of biodiesel is more

than 300F and is safer to handle and store than any petroleum

based fuels. Biodiesel can be produced from different

varieties of feed stocks. These feed stocks include most

common edible vegetable oils(jatropha, Pongamia....)as well as

waste oils. Biodiesel has several distinct advantages compared



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with petro diesel in addition to being fully competitive with

petro diesel in most technical aspects;

1. Derivation from a renewable domestic resource, thus

reducing dependence on and preserving petroleum.

2. Biodegradability.

3. Reduction of most exhaust emissions.

4. Higher flash point, leading to safer handling and storage

5. Excellent lubrication.

2.3 Why are vegetable oils and animal fats

Transesterified to biodiesel

The major reason that vegetable oils and animal fats are

Transesterified to biodiesel is that the kinematic viscosity

of the biodiesel is much closer to that of petro diesel. The

high viscosity of untransesterified oils and fats leads to

operational problems in diesel engine such as deposits on

various engine parts. Although there are engines and burners

that can use untransesterificated oils, the vast majority of

engines require the lower-viscosity fuel.

2.4 Biodiesel Crops Biodiesel crops are harvested and pressed in oil presses

to extract the vegetable oil (SVO). The oil is then mixed with

a catalyst and methanol. It goes through a process

called transesterification to produce this bio fuel. Biodiesel

can also be made from waste vegetable oil (WVO), and animal

fats. Each source of oil has unique benefits.



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Soybeans. Soybeans are America's primary source of biodiesel

feedstock (90% in 2006). They can produce 48 gallons of oil

per acre. Soy plants grow well in America. Soybeans were one

of the largest crops in 2000.

Palm , which can produce an astounding 635 gallons of oil per

acre, has the highest oil yield of plants currently grown for

biodiesel feedstock. It is mainly grown in Malaysia and

Indonesia. It does pose some environmental concerns though.

Jatropha seeds can contain up to 40% oil, producing an average

of 202 gallons of oil per acre. Another benefit is that this

plant can thrive in marginal lands. Also, the seeds are

poisonous; therefore using this as a biodiesel crop would not

compete with food supply.

Canola is a genetically modified type of rapeseed. It will

produce an average of 100 gallons of oil per acre. In

2008/2009, it was the third most produced vegetable oil in the

world.



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2.5 Some of the Less Common Feedstock Crops:-

• Mustard seed is a type of rapeseed. It contains 25-40% oil.

The meal left over after processing can be used as an organic

pesticide.

• Radish - wild radish can contain up to 48% oil, and is

drought tolerant.

• Sunflower produces an average of 102 gallons of oil per

acre.

• Castor bean averages 151 gallons of oil per acre.

• Coconut produces approximately 287 gallons per acre.

2.6 Ingredients of biodiesel

Biodiesel is an alternative, clean-burning fuel that canbe used in any diesel engine. We can make our own homemade

biodiesel using a few basic ingredients: vegetable oil,

methanol and lye. We should use extreme caution when making

our own biodiesel because there is a potential for chemical

burns and inhalation of toxic fumes. Always use safety

equipment to minimize our risk of these dangers.

A) Vegetable Oil

At the heart of any biodiesel recipe is the actual oil,

and vegetable oil is an economical and plentiful choice



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compared to other types of oils. Vegetable oil is about 20

percent glycerine, which is separated from the vegetable oil

in a process called transesterification. When vegetable oil

is mixed with an alcohol, such as methanol, and then combined

with a catalyst, such as lye, the glycerine is separated from

the vegetable oil. With the glycerine taken out of the

mixture, the result is far less viscous, which will help to

increase engine efficiency.

B) Methanol

Methanol, also known as wood alcohol, is a flammable

alcohol. It is produced using a chemical process that combines

natural gas and a catalyst to produce methanol and water

vapour as a by-product. Using methanol that is 25 percent by

volume will produce the highest quality biodiesel with a

complete reaction of approximately 98 percent, according to

the Rensselaer Polytechnic Institute. Methanol is combined

with the catalyst, usually sodium hydroxide or lye, which is

then added to the vegetable oil. When combining methanol and

lye, be cautious because the fumes released are toxic. Mix

these chemicals in a well-ventilated area, such as outdoors,

to protect our self from the fumes.

C) Sodium Hydroxide



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Sodium hydroxide is also known as lye, and it can be

purchased at most plumbing or home improvement stores. Sodium

hydroxide is used as the catalyst in the biodiesel making

process. Lye is a corrosive substance that can cause skin

burns, so it’s important to wear rubber gloves when handling

it. Steve Howell, the technical director for the National

Biodiesel Board, says that sodium hydroxide is the catalyst of

choice when it comes to making homemade biodiesel because it

is effective and cheap. The disadvantage of using lye is that

when mixed with methanol, it can become extremely explosive if

exposed to a spark of flame.

2.7 Quality standards:

Development of test methods, procedures and

protocols would be taken up on priority along with

introduction of standards and certification for different bio

fuels and end use applications. The Bureau of Indian

Standards (BIS) has already evolved a standard (IS-15607) for

Bio-diesel (B 100), which is the Indian adaptation of the

American Standard ASTM D-6751 and European Standard EN-14214.

BIS has also published IS: 2796: 2008 which covers

specification for motor gasoline blended with 5% ethanol and

motor gasoline blended with 10% ethanol.



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2.8Benefits Substitute or extender for petroleum diesel.

No need of any special pumps or high pressure equipment

for fuelling.

No need to buy special vehicles or engines to run on

bio-diesel.

100 percent bio diesel reduces carbon dioxide emissions

by more than 75 percent compared to petroleum diesel.

Using a blend of 20 percent bio-diesel reduces carbon

dioxide emissions by 15 percent.

Biodiesel is an oxygenated fuel, so it contributes to a

more complete fuel burn and a greatly improved emissions

profile. Biodiesel produces fewer particulate, carbon

monoxide, greenhouse gases and sulphur dioxide emissions,

reducing public health risks.

It will reduce the country's dependence on imported oil.

Its flash point is > 150°C, compared to 77°C for

petroleum diesel. Hence, it is safe to handle, store, and

transport.

Has superior lubrication capabilities and increases

engine life.

2.9Waste produces from bio-diesel and its effect onenvironment

Biodiesel production produces three major biodiesel waste

products: glycerin, methanol, and (sometimes) water...

Untreated biodiesel waste product is toxic - mostly because it



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contains methanol. In a lot of smaller plants biodiesel

waste product is not disposed of properly. This is unfortunate

as biodiesel producers are typically very environmentally

aware. The glycerin that comes out of the biodiesel process

is laden with methanol and caustic chemicals. Glycerin is

probably the worst biodiesel waste product. The real problem

with glycerin is that it is hard to process without investing

a lot of money in expensive equipment. For every 100 litres of

biodiesel that we make we will end up with 20-25 litres of

glycerin. This 20-25 litters of glycerin can have up to 25%

methanol in it and should be considered hazardous waste. 50ml

of methanol is a lethal dose so there is a lot of methanol in

glycerin. It should be treated in the same way as pure

methanol,

In small scale production three things typically happen to theglycerin.

1. It is thrown down the drain

2. It is stored somewhere in containers in the hope that

someday a use will be found for it.

3. It is spread on the ground or thrown into a landfill.

we have seen producers with small plants who have thousands of

litres of glycerin stashed away, this is a bad idea!

2.9.1 Wash Water



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The wash water that is used to clean biodiesel will also be

contaminated with methanol. As a biodiesel waste product this

must be disposed of properly. The water from the first wash

will have a lot of methanol in it. This methanol means that

the water is toxic. It will also contain a lot of soaps and

caustic chemicals. We should check with our local water

treatment plant as to whether this is acceptable to them or

not. Some water treatment plants do not mind some methanol as

the bacteria in the plant thrive on it. However it is always a

matter of degree and we must consult them before doing

anything.

The wash water should never be disposed off into ground

water. Doing so can result in methanol contaminating the water

table which could be a major pollution problem.

2.10 BY-PRODUCT UTILIZATION

Glycerin and Seed cake utilisation

Glycerin is a by-product of making biodiesel.

After the glycerin is filtered to remove any food

particles or impurities, we can make it

into lye bar soap.

Seed cake utilisation

Considering the future scenario of non edible

oil seeds utilization for biodiesel production in the

country from Atrophy and panama pinnata, there is need



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for efficient utilization of their cakes. The direct

utilization of cake is also not recommended for use as

organic manure. The present and forthcoming use of non-

edible oil seeds in India for production of biodiesel is

due to massive plantation of Jatropha and pongamia

pinnata on waste lands.

The utilization of generated cakes in an environment

friendly manner cannot be ignored, because its disposal

as waste would create environmental problems. The

presence of non-edible oil seed cakes in the open

atmosphere would generate following gases due to self

decomposition of biomass over the action of various

microorganism.

Gases from waste sources:CH4, N2O, H2S, NH3, CO2.

The best strategy is to manage and utilize non-

edible cakes as ‘biomass’ resources rather than disposing

them as ‘waste’ so that energy and economic benefits, as

well as environmental benefits, can be realized.

Anaerobic digestion of these cakes could significantly

reduce the gaseous emissions from waste disposal.

Therefore, anaerobic digestion of these cakes would be a

better way of cake utilization for energy generation and

further, effluent as enriched organic manure for organic

farming.



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Mechanical/solvent extraction of oil

oil

Non edible seeds

Anaerobic digestion

Transesterification

Deoiled


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FIG-2.1 Schematic diagram of utilization of non-edible

oil seeds for production of renewable liquid (biodiesel)

and gaseous fuels (biogas).

Source: Karnataka state Biodiesel Development board and

KSCST Bangalore,

2.11 GLYCERINE

Glycerine is a neutral, sweet-tasting,Department of Environmental Engineering PESCE, Mandya

Glycerine

Biodiesel

Methane enrichment and bottling into cylinder(Bio-methane equivalent to CNG)

Application (substitute of CNG)

CNG vehicles for automotive and transport purposes.

Biogas(60-70%CH4

Direct application (cooking,heatin

EnrichedOrganic manure

Slurry

Diesel engine operation (Blending

Industrial applications(soap manufacturin


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2.14 Properties of glycerine

1) Molecular weight = 92.09

2) Specific Gravity (in air) 1.2636 (20°C); 1.2620

(25°C)

3) Melting point =18.17ºC

4) Boiling point(760mm Hg) = 290ºC

5) Density (20ºC) =1.261 g/cm3

6) Vapour pressure = 0.0025 mm Hg at 50ºC

= O.195 mm Hg at 100ºC

= 4.3 mm Hg at 150ºC

= 46 mm Hg at 200ºC

7) Refractive index = 1.474

8) Surface tension = 63.4 dyne/cm at 20ºC(100%

glycerol)

9) Compressibility (28.5ºC) = 2.1×10 MPa

10) Viscosity = 1499 c.p. at 20ºC (100% glycerol)

11) Specific heat = 0.5779 cal/gm at

26ºC(99.94%glycerol)

12) Heat of vaporization = 21060 cal/mole at 55ºC

= 18170 cal/mole at 195ºC



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13) Heat of formation = 159.6 Kcal/gm mole

14) Heat of combustion = 1662 KJ/mole

15) Heat of fusion = 18.3 KJ/mole

16) Thermal conductivity = 0.29 w/ºK

17) Flash point = 177ºC

18) Fire point = 204ºC

Glycerol is completely soluble in water and alcohol. It

is slightly soluble in ether, ethyl acetate, and

dioxane and insoluble in hydrocarbons. Glycerol has

useful solvent properties similar to those of water and

simple aliphatic alcohol's because of its three-

hydroxyl groups. Glycerol is a useful solvent for many

solids, both organic and inorganic which is

particularly important for the preparation of

pharmaceuticals. The solubility of gases in glycerol,

like other liquids is temperature and pressure

dependent.

CHEMICAL PROPERTIES

Glycerol is a reactive molecule that undergoes all the

usual reactions of alcohols. The two terminal primary

hydroxyl groups are more reactive than the internal

secondary hydroxyl group. Under neutral or alkaline

conditions, glycerol can be heated to 250ºC without



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formation of acrolein. Reactions with glycerol are

therefore best carried out under alkaline or neutral

conditions at 180ºC, alkaline glycerol begins to

dehydrate forming ether-linked polyglycerols. At room

temperature glycerol rapidly absorbs water. When dilute

it is attacked by microorganism. On oxidation, glycerol

yields variety of product depending upon the reaction

conditions. By the use of mild oxidizing agent it is

possible to oxidize only one hydroxyl group to yield

Glyceraldehyde. These compounds may be considered very

simple aldose and simplest ketoses respectively and

mixture of two compounds obtained from glycerol as well

as glyceraldehyde has been Called glycerose. Nitric

acid converts glycerol to glyceric acid CH2CHCHOHCOOH

melting at 134-135ºC when pure, but usually obtained as

syrupy. Oily liquid soluble in water and alcohol, but

insoluble in ether.

Some industrially important reaction products of

glycerol include:

1) Mono-,di-,and tri esters of inorganic and organic

acids

2) Mono and diglyceride of fatty acids formed by

transesterification of triglycerides(from fats)

3) Aliphatic and aromatic esters formed by reactions

with alkylating agents respectively



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4) Polyglycerols formed by the intermolecular

alienation of water with alkaline catalyst

5) Cyclic 1,2-or 1,3-acetals or ketals formed by the

reaction with aldehyde or ketons respectively

2.15 Products from glycerine

There are products that can be made out of the glycerine,

most commonly soaps, hand cleaners, floor cleaners etc.

Although it is brown and very unattractive the glycerine makes

a very good soap. It is important that the methanol is removed

before it is converted into another product. Manufacturing

soap out of a biodiesel waste product like glycerine is very

beneficial as it is recycling an already recycled item. The

easiest way to remove the methanol is to distil it out. You do

not need a sophisticated still to remove the methanol, a

relatively simple column still will do just fine.

Once the methanol has been removed the glycerine is a lot

safer to dispose off and this can be done in a number of ways.

It can be composted in a big compost heap. A smaller

compost heap is soon overwhelmed. we should only compost

glycerine made from potassium based catalysts.

It can be neutralized with acid and then disposed of

through regular drains. Check with our water treatment

plant before throwing anything down the drain.


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We can make soaps and cleaning products out of it or use

it as is for a floor cleaner. Feed it into an anaerobic

digester.

Mix it 50% with kerosene, it makes a great engine

cleaner.

Glycerin can be used to produce a hydrogen rich gas for

use in fertilizers, food production and chemical plants.

It can also be taken to a wastewater treatment plant

where it will be added to a methane digester .

2.16 Glycerin Soaps – Benefits and AdvantagesMany of the commercial soaps available today don’t

have glycerine in them. The reason for this is because

glycerine, which is a natural by-product of the soap

production process, has fantastic moisture retention and

softening qualities. These are all the qualities that

manufacturers of lotions and cream are after. Thus,

manufacturers of mass produced commercial soaps extract

the glycerine from the soaps and sell it off to

manufacturers of lotions and creams. There are many

advantages and benefits to using glycerine soap as these

soaps are proven to be more moisturizing. In fact,

glycerine soaps are considered to be some of the most

moisturizing soaps available on the market. Qualities of

these soaps allow the soap to be both moisturizing and

softening and suitable for different type of skins. These

soaps will help our skin to remain moisturized and become


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healthy. There are various other benefits to using

glycerine soap, including the following:

• An all natural soap: One of the main advantages of

using glycerine soap is that if we buy the correct brand, it

can be made from entirely natural ingredients and processes.

These soaps aren’t produced from synthetic ingredients.

However, we will need to keep in mind that

different soap manufacturers make use of different

manufacturing processes. Although most glycerine soaps are

100% natural, certain manufacturers of glycerine soaps might

add some synthetic ingredients to their soaps so it is worth

verifying that the soaps completely natural.

• Sensitive skin: Sensitive skin in particular will

benefit from glycerine soap due to its moisturizing and

softening qualities and natural ingredients. The use of

synthetic ingredients in soap can actually cause severe skin

complications or irritate or exacerbate skin problems. Even

the most sensitive of skin can use glycerine soaps. These

soaps can even be used on skins suffering from problems such

as psoriases and eczema. The skin irritations and negative

reactions produced by regular soap is not a problem for

those who use glycerine soap.

• Skin moisturizing: Glycerin has been proven to act as

humectants, which means that it is able to attract moisture.

Thanks to this inherent quality of glycerine, this soap will



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attract moisture to the skin and also effectively lock it

in. This will provide the skin with a constant source of

hydration, preventing the skin from drying out. This is not

the case with certain other brands of commercial soap with a

low or nonexistent level of glycerine, which dries the skin

out and makes it feel tight and flaky.

• Healthier skin: By using glycerine soap, we will keep

our skin moisturized which will create the great foundation

for a healthy and vibrant, supple skin. This will help us to

even prevent wrinkles, tears in the skin and stretch marks,

among other benefits.



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CHAPTER-3

MATERIALS AND METHODOLOGY

3.1 General

Making biodiesel can be a simple, effective way to

produce liquid transportation fuel that has both financial and

environmental benefits. Another advantage of biodiesel is that

it can be made from waste cooking oil after it has already

been used for cooking foods in the kitchen, cafeteria, or

restaurant. Unfortunately, the chemical process of making

biodiesel, transesterification, results in two products:

biodiesel and glycerine. The biodiesel is the primary product,

but the glycerine is very useful as well. Therefore we refer

to the glycerine produced during the biodiesel reaction as a

“by-product”. By-products retain both financial and

environmental value. Glycerin derived from biodiesel

production is a low quality product because it contains many



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contaminants from the biodiesel reaction. Biodiesel glycerine

is actually a mixture of free fatty acids (FFA) that were

neutralized during transesterification. The only contaminant

that poses a risk is the methanol. The yield of glycerine from

a batch of biodiesel is about 20 percent. When making 100

litres of biodiesel, there will be at least 20 litres of

glycerine as a side product. If you were to turn the whole 20

litres of glycerine into bars of soap you would end up with at

least 100 of them. Seriously though, it does open the

possibility for another source of income, selling hand

cleaners and floor cleaners etc.

3.2 PRODUCTION OF BIODIESEL

3.2.1Materials used

The Materials used for making 100ml of biodiesel are as

follows

100 ml of oil

20 ml of methanol

0.9 grams of KOH.

Erlenmeyer flask

Magnetic stirrer bar

3.2.2 Calculation of Free Fatty Acid (FFA)

Calculation Formula:



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FFA Content= 28.2x(Normality of NaOH) x (Titration value)

(Weight of the oil)

Example: If the weight of oil is 10 grams, the Titration

value is 15 ml (burette reading of ml of NaOH consumed during

titration), and normality of NaOH is 0.1

Then FFA Content = 28.2 X 0.1X 15= 4.23 % FFA

10

3.2.3 Procedure for production of biodiesel

The production of biodiesel is carried out in two methods one

is Single stage method and other is Double stage method,

depending upon the amount of FFA present in the crude oil. If

the percentage of FFA is 5 and above single stage is not

allowed. We should follow the Double stage process.

Single stage process Procedure for making 100 ml of Biodiesel in single stage

process are as follows,

1. Take 100 ml of oil in an Erlenmeyer flask.

2. Place a magnetic stirrer bar into the flask and

start heating upto 55-60oC.

3. In a separate Erlenmeyer flask take 20 ml of

methanol and add 0.9 grams of KOH and stir until

dissolved.

4. Once the methanol and KOH is mixed (called

methoxide), it can be added to the warm oil in three

phases.



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5. In the first phase add 12.0 ml of methoxide and the

oil is stirring.

6. Keep the remaining methoxide covered tightly until

it is needed.

7. Let the oil and methoxide mixture react for 45 to 60

minutes at 55-60oC temperature.

8. After the oil and methoxide mixture reacted, pour

into a seperatoryfunnel and allow the glycerine

waste to settle for about one hour.

9. After settling, drain the glycerine from the bottom

of the funnel and pour the top layer (crude

biodiesel) back into the Erlenmeyer flask.

10. In the second phase add 4 ml of methoxide to

the crude biodiesel and, repeating steps 6-8.

11. In the third phase add the remaining 4 ml of

methoxidean repeat steps 6-8 for a third time.

12. After the third reaction, put the crude

biodiesel into a clean beaker and stir and heat to

about 75oC in order to boil off any remaining

methanol that may present.

Washing of crude biodiesel

The next step is to wash the crude biodiesel that we

produced,

1.Pour the warm methanol-free, crude biodiesel into

a clean separator funnel



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2.Add 75-100 ml of warm tap water to the separator

funnel with the biodiesel and allow to settle for 15

minutes.

3. Let the water settle out of the biodiesel layer

(water is on bottom) and then drain out the water.

4. Repeat the steps 2 and 3 in two times. Check the

pH in between every washing. The desired pH after

washing is completed is 7.

5. Heat the washed biodiesel to 105oC in order to

remove the residual water.

Double stage processProcedure for making one litre of Biodiesel are as follows,

1. Measure the FFA level in the raw oil, take 1

litre of raw oil into

3-Neck flask and put the magnetic pellet and

adjust the RPM to suitable speed.

2. Fix the reflux condenser and keep water

circulation on and maintain temperature at 60oC

3. Add 2.25 grams of methanol and 0.05 grams of

H2SO4 for each percentage of FFA (calculate

properly)

4. Agitate the mixture in the reaction vessel (3-

Neck flask) at 60oC for about 60 to 90 minutes.

5. Transfer the mixture to the separating funnel

and allow settling for at least 2-3 hours.



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6. A dark layer will appear at the top of the oil

is an Acid layer.

7. Drain the bottom layer to 3-Neck flask and

measure the new FFA.

8. If the new FFA is more than 2%, then adjust the

RPM to 200 and set the temperature to 60oC.

Return to step no, 2 and repeat the process

till the FFA level is reduced to less than 2%.

9. In the mean time, take 200ml of methanol per

litre of oil and calculate quantity of NaOH (as

per new FFA) and mix it in a beaker, and add

the same to 3-Neck flask slowly.

10. After the addition of “Methoxide mixture”

into the reaction vessel, agitate the mixture

at a suitable RPM and maintain the temperature

at 63oc for 60 to 90 minutes.

11. Then follow the procedure as per single

stage process.

Note: Methanol should be added first and then H2SO4 should be

added to oil, very slowly and carefully.

3.2.4 Calculation of methanol and H2SO4 in double stage

Density of pongamia oil 0.925

Weight of pongamia 925grams per litre

Methanol standard 2.25/FFA

H2SO4 standard 0.05/FFA

Methanol density 0.794



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Density of H2SO4 1.84

Example:

Qty of raw oil =100 gm

FFA level = 5%

Required Methanol = 2.25 x 5 FFA = 11.25gm/0.794 = 14.168ml

Required H2SO4 = 0.05 x 5 FFA = 0.25gm/1.84 = 0.1356ml


Plantation ofBio-fuel

Harvesting ofseeds

Drying ofthe seeds

Sorting ofseeds and

Expelling ofoil by

Crude oilSeed cake

Settling of heavy particles in the

Application in pharmaceuticals animalfeed pesticide etc,

Filtering of theMethoxide


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Fig 3.1 Schematic Diagram of Biodiesel Production

Source: Karnataka state Biodiesel Development board and KSCST

Bangalore,

3.3 BIODIESEL TESTING


Determination ofFFA

Transesterification

GlycerolBiodiesel /methyl

Recovery ofmethan

Soap producti

Washing of Biodiesel

Drying of Biodiesel at

Biodiesel quality analysis DensityFlash pointCopper strip corrosion test

Ready for blending


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Plate 3.1 Flash Point Test By Pensky Marten’s

PROCEDURE:1. Thoroughly clean and dry all parts of the cup and itsaccessories before starting the test.

2. Fill the cup with the sample of biodiesel to be tested tothe level indicated.

3. Place the lid on the cup and set the heating.(Heat at arate of 5-60C per minute with continuous stirring of biodiesel

4. Dip the test flame into oil vapour when temp is within 100Cof the probable temperature.

5. Check after every 10C rise in temperature.

6. When test flame produces distinct flash, note thetemperature.



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PROCEDURE:

1. Pour measured quantity of biodiesel in the copper

strip corrosion test bomb.

2. Immerse the polished copper strip in the oil in the

test bomb apparatus.

3. Keep the copper strip corrosion test bomb apparatus

with biodiesel in a water bath vertically.

4. Heat the water bath for 3 hours.

5. Maintained the temperature at 50oC± 1oC.

6. After 3 hours remove the copper strip from the

apparatus.

7. Compare with ASTM copper strip corrosion standards.



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Plate 3.3 Density Test By Hydrometer Method

PROCEDURE:

1. Take 500ml of the biodiesel in a clean dry measuring

cylinder.

2. Heat it to a temperature of 15oC.

3. Allow the biodiesel to settle.

4. Gently lower the hydrometer into the biodiesel in the

cylinder unit it floats freely. Note, the point at which

the surface of the biodiesel touches the stem of the

hydrometer. Read the hydrometer level.



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5. The hydrometer reading is the density of the

biodiesel.

Plate 3.4 Kinematic Viscosity Test

PROCEDURE:

1. Fill the biodiesel in the cannon-fenske viscometer

tube no,100 (Direct type).



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2. Hold the viscometer tube in the viscometer-water-

bath apparatus.

3. Heat to 40oC and maintain the temperature for a

period of 20-30 minutes.

4. The above procedure is carried out so that oil

attains the prescribed temperature during test.

5. After 30 minutes open the and simultaneously start

the stop watch.

6. Stop the stop watch once flow reaches the bottom of

mark in a bulb.

7. Note the time in seconds on the stopwatch.

Kinematic viscosity= (no, of seconds) x

(standard factor of the bulb of the

viscometer tube using for testing)

3.4 PRODUCTION OF GLYCERIN BAR SOAP

3.4.1 Removing Methanol

The first step in any of these recipes is to remove the

methanol from the glycerine. If we do not do methanol recovery

in our glycerine it will contain a high percentage of

methanol. This will be dangerous to the health of whoever is

using the products as well as being dangerous to you when you

heat the glycerine. All residual methanol must be removed



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before the glycerine can be used for other purposes. Methanol

will boil off at temperatures above 68°C.The glycerine can be

distilled to capture the methanol or simply heated under a

fume hood to remove methanol. Allow 45 minutes of boiling at

temperature to ensure all methanol is driven off. Once the

methanol is removed, the glycerine is safe to handle and is

suitable for making soap.

3.4.2 Materials:-

The Materials used for making Glycerin bar soap are as follows

Glycerine

Strainer

Measuring containers

Lye

Stainless steel pot

Stainless steel spoon

Plastic storage bin

Knife

Zipper plastic bags

Fragrance oils (optional)



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3.4.3 ProcedureProcedure for making glycerine bar soap are as follows,

1.Place the glycerine in a stainless steel pot and heat it to

150oF to remove any traces of methanol.

2.Strain the glycerine to remove any impurities and then

return it to the pot.

3.Take 1/4 litre of water for every litre of glycerine and

heat the water to 100o F. This works out to a 1-to-4 ratio of

water to glycerine.

4.Stir approximately 38.5 grams per litre of lye in to the

heated water until it is completely dissolved.

5.Add the water and lye mixture to the glycerine.

6.Continue to heat for another 10 minutes, stirring

occasionally.

7.Remove the mixture from the heat and stir for another 10

minutes. we may see it start to foam.

8.Pour the mixture into a shallow container. A plastic storage

bin with a lid works well. The size and number of containers

needed depends on the amount of glycerine we are using and the

desired thickness of the soap.

9.Cover the liquid with a piece of plywood or cardboard to

help hold the heat in so the soap cures properly. Let it cool

and solidify for 24 hours.

10.Run a knife around the edge of the soap to loosen it and

then flip the container over to remove the soap.

11.Cut the soap into 45 bars that measure 3-by-2 inches.



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12.Wait at least 4 more days before using the soap. During

this additional drying time, the soap will turn from a dark

brown to a lighter tan colour.

13.Store the soap in zipper plastic bags with wax paper

between the bars so they don’t stick together.

References

[1] Aldo.okullo et,al.”Physico-chemical properties of

biodiesel from jatropha and caster oils" Department of



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chemical and mining engineering university of Dar es Salaam.

Vol.2, no.1, 2012

[2] Babaganagutti,et.al“Biodiesel kinematics viscosity

analysis.” ARPN Journal of engineering and applied science

vol.7 no:4, 2012

[3] Gonzalez-Pajuelo M, (2005) et,al. Metabolic engineering of clostridium acetobutylicum for the industrial production of1,3-propanediol from glycerol. Metabolic Engineering 7: 329-336.

[4] Kazimostafijurahman,et.al. .“Bio-diesel from jatropha oil

as an alternative fuel for diesel engines.” International

journal of IJMME-IJENS vol,10 no:03

[5] Manual by Karnataka state Biodiesel Development board and

Karnataka state council for science and technology, Indian

Institute of science campus, Bangalore

[6]Meda Chandra sekhar et.al.“Synthesis of

biodiesel.”International journal of engineering science and

technology vol,2(8).2010

[7] Murugesan A., Umarani C., et al., “Production and Analysis

of Biodiesel from non-edible oils”. A Review.Renewable and

Sustainable Energy Reviews, vol. 13, pp. 825-834, 2009.



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[8] Mu Y, Teng H, et,al. (2006) Microbial production of 1,3-propanediol by klebsiella pneumoniae using crude glycerol frombiodiesel preparations. Biotechnology Letters 28: 1755-1759.

[9] Pramanik K, “Properties and use of jatropha curcas oil

and diesel fuel blends in compression ignition engine”.

Renewable Energy, vol. 28, pp. 239-248, 2003.

[10] Schievano, A.and D'Imporzano, G.et,al. Substituting

energy crops with organic wastes and agro-industrial residues

for biogas production. Journal of Environmental Management

90:2537-2541. 2009.

[11] Thompson, J.C., and He. B.B. “ Characterization of crude

glycerol from biodiesel production from multiple feedstocks."

Applied Engineering in Agriculture 22:261-265. 2006.


Project phase 2

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