GREEN

CHEMISTRY-
Biodiesel

Submitted by: D.M.Rohan Thomas

Class: XII-A
Submitted to: Chemistry Department

CONTENTS

 Introduction
 What is Biodiesel?
 Uses of Biodiesel
 Raw materials for Biodiesel Production
 Preparation of Biodiesel
  Reactions involved
 Biodiesel Fuel Features
 Advantages of Biodiesel
 Disadvantages of Biodiesel
 Environmental Effects
 Conclusion

Introduction

Biodiesel is a liquid biofuel obtained by chemical processes from vegetable oils or

animal fats and an alcohol that can be used in diesel engines, alone or blended
with diesel oil.
ASTM International (originally known as the American Society for Testing and
Materials) defines biodiesel as a mixture of long chain monoalkylic esters from
fatty acids obtained from renewable resources, to be used in diesel engines.
Blends with diesel fuel are indicated as ‘‘Bx’’, where ‘‘x’’ is the percentage of
biodiesel in the blend. For instance, ‘B5’ indicates a blend with 5% biodiesel and
95% diesel fuel; in consequence, B100 indicates pure biodiesel.
Biodiesel, a diesel fuel substitute that can be made from a variety of oils, fats, and
greases, is of interest to farmers for a number of reasons: It can provide an
additional market for vegetable oils and animal fats; it can allow farmers to grow
the fuel they need for farm machinery; and it can decrease U.S. dependence on
imported oil since fuel feedstocks can be grown domestically.
Biodiesel is a renewable source of energy that can help reduce greenhouse gas
emissions and minimize the “carbon footprint” of agriculture. It contributes less
to global warming because the carbon in the fuel was removed from the air by
the plant feedstock.
In addition, biodiesel produces less air pollution (exhaust emissions) than diesel
made from fossil fuels. A 1998 study by the USDA and US DOE found that using
pure biodiesel in urban buses “results in substantial reductions in life cycle
emissions of total particulate matter, carbon monoxide and sulfur oxides (32%,
35% and 8% reductions, respectively, relative to petroleum diesel’s life cycle).”
(Sheehan et al., 1998).

WHAT IS BIODIESEL
 Biodiesel refers to a non-petroleum-based diesel fuel consisting of short
chain alkyl (methyl or ethyl) esters, made by transesterification of
vegetable oil or animal fat (tallow), which can be used (alone, or blended
with conventional petrol diesel) in unmodified diesel-engine vehicles.
 Biodiesel is an alternative fuel similar to conventional or ‘fossil’ diesel.
Biodiesel can be produced from straight vegetable oil, animal oil/fats,
tallow and waste cooking oil.
  The process used to convert these oils to Biodiesel is called
transesterification.
This process is described in more detail below:
The largest possible source of suitable oil comes from oil crops such as
rapeseed, palm or soybean. In the UK rapeseed represents the greatest
potential for biodiesel production. Most biodiesel produced at present is
produced from waste vegetable oil sourced from restaurants, chip shops,
industrial food producers such as Birdseye etc. Though oil straight from the
agricultural industry represents the greatest potential source it is not being
produced commercially simply because the raw oil is too expensive. After
the cost of converting, it to biodiesel has been added, it is simply too
expensive to compete with fossil diesel. Waste vegetable oil can often be
sourced for free or sourced already treated for a small price. (The waste oil
must be treated before conversion to biodiesel to remove impurities). The
result is Biodiesel produced from waste vegetable oil can compete with
fossil diesel. More about the cost of biodiesel and how factors such as duty
play an important role can be found here.
 Uses of Biodiesel
1. Transportation

 More than 30% of energy consumed in the United States is used

for vehicle transportation. Across the globe, transport takes
account of 24% of energy and more than 60% of absorbed oil.
This means that over a third of the oil is used to operate vehicles.
 The main problem with alternatives is that solar, wind and other
alternative power is not practical for transportation. Experts
believe that efficient breakthroughs in practical technology
advances are still decades away.
 In short, biofuel can be turned into a hydrogen steam that is
meant to be used in adjoining fuel-cell. More major car brands
have already invested in stations for biofuel-powered vehicles.

2. Energy Generation

 In addition to producing fuel for transportation, fuel cells have a

power-generating application that is available for electricity.
Biofuel can be used to generate power in backup systems were
emission matters most. This includes facilities such as schools,
hospitals and other forms located in residential areas.
 In fact, the largest market for biofuel to turn into energy
generation for over 350,000 homes from landfill gas in the United
Kingdom.

3. Provide Heat
  Bioheat has grown over the past few years. As the primary use of
natural gas that comes from fossil fuel, the heat that comes from
hydraulic fracturing will lead to the production of natural gas.
While natural gas does not need to come from fossil material, it is
also able to originate from the recently grown material.
 A majority of biofuel that is used for heating is substantial. As
wood is the most practical method to heat, houses use wood
burning stoves rather than gas or electricity. A blend of biodiesel
will reduce the emission of both nitrogen and Sulphur dioxide.

4. Charging Electronics

 According to scientists from Saint Luis University, a fuel cell was

developed with cooking oil and sugar to generate electricity;
consumers will be able to use these cells instead of generating
electricity. Consumers may be able to use fuel cells in place of
batteries to charge anything from computers to cell phones. While
they are still in the process of development, cells have the
potential to become a ready source of power.

5. Clean Oil Spills and Grease

 Biofuel is known to be environmentally friendly; biofuel can also

help to clean up oil spills and grease. It has been tested to work as
a potential cleaning agent for areas where crude oil contaminated
the waters.
 The results have also been found to increase the recovery areas
and allow it to be removed from the water. Biofuel can also be
used as an industrial solvent for cleaning metal, which is also
beneficial due to its lack of toxic impact.
6. Cooking

 While kerosene is the most common ingredient to use for stoves

and non-wick lanterns, biodiesel works just as great

7. Lubricate

 Diesel fuel is required to reduce the Sulphur concentration as

Sulphur provides the most lubricity of fuel. This is important when
it comes to keeping the engine properly functioning and avoiding
premature infection failure.

8. Remove paint and adhesive

 Biofuel can replace toxic products that are designed to remove

paint and adhesives. Biofuel is also considered as the best
method for removing non-critical applications.

9. Create energy when fossil fuel runs out

 As the oil supply is starting to run out. This has caused us to

question how fuel can be extracted without destroying the
environment. Biofuel –will help the government create a stable
method of producing energy that is cost-effective.
10. Reduce cost and need for imported oil

 More than 84% of the world’s petroleum is used in the United

States. Despite the increase in fuel demands, the U.S. has recently
started to decrease the need since 2006. This allows biofuels to
become the best factor in energy reduction.
 Analysts say that replacing imported oil with biofuel will help to
stabilize the economy when oil is disrupted. It does not matter
how much the United States spends on oil import but how the
overall economy must be stabilized.
 Would you use biofuel for your needs? What would you use
biofuel for? Comment below and let us know what you think.
 Biodiesel Plant

Raw Materials for Biodiesel

Production

The raw materials for biodiesel production are vegetable oils, animal
fats and short chain alcohols. The oils most used for worldwide
biodiesel production are rapeseed (mainly in the European Union
countries), soybean (Argentina and the United States of America), palm
(Asian and Central American countries) and sunflower, although other
oils are also used, including peanut, linseed, safflower, used vegetable
oils, and also animal fats. Methanol is the most frequently used alcohol
although ethanol can also be used.

Since cost is the main concern in biodiesel production and trading

(mainly due to oil prices), the use of non-edible vegetable oils has been
studied for several years with good results.

Besides its lower cost, another undeniable advantage of non-edible oils

for biodiesel production lies in the fact that no foodstuffs are spent to
produce fuel. These and other reasons have led to medium- and large-
scale biodiesel production trials in several countries, using non-edible
oils such as castor oil, tung, cotton, jojoba and jatropha. Animal fats are
also an interesting option, especially in countries with plenty of
livestock resources, although it is necessary to carry out preliminary
treatment since they are solid; furthermore, highly acidic grease from
cattle, pork, poultry, and fish can be used.
Microalgae appear to be a very important alternative for future
biodiesel production due to their very high oil yield; however, it must be
considered that only some species are useful for biofuel production.

Although the properties of oils and fats used as raw materials may
differ, the properties of biodiesel must be the same, complying with the
requirements set by international standards.
 Preparation of
Biodiesel

As mentioned above biodiesel can be produced from straight vegetable oil,

animal oil/fats, tallow and waste oils. There are three basic routes to biodiesel
production from oils and fats:
 Base catalyzed transesterification of the oil.
 Direct acid catalyzed transesterification of the oil.
 Conversion of the oil to its fatty acids and then to biodiesel.
Almost all biodiesel is produced using base catalyzed transesterification as it is the
most economical process requiring only low temperatures and pressures and
producing a 98% conversion yield. For this reason, only this process will be
described in this report.
The Transesterification process is the reaction of a triglyceride (fat/oil) with an
alcohol to form esters and glycerol. A triglyceride has a glycerin molecule at its
base with three long chain fatty acids attached. The characteristics of the fat are
determined by the nature of the fatty acids attached to the glycerin. The nature of
the fatty acids can in turn affect the characteristics of the biodiesel. During the
esterification process, the triglyceride is reacted with alcohol in the presence of a
catalyst, usually a strong alkaline like sodium hydroxide. The alcohol reacts with
fatty acids to form the mono-alkyl ester, or biodiesel and crude glycerol. In most
production methanol or ethanol is the alcohol used (methanol produces methyl
esters, ethanol produces ethyl esters) and is base catalyzed by either potassium
or sodium hydroxide. Potassium hydroxide has been found to be more suitable
for the ethyl ester biodiesel production, either base can be used for the methyl
ester. A common product of the transesterification process is Rape Methyl Ester
(RME) produced from raw rapeseed oil reacted with methanol.
 Reactions Involved
Transesterification:
 Biodiesel is commonly produced by the transesterification of the vegetable
oil or animal fat feedstock, and other non-edible raw materials such as
frying oil, etc. There are several methods for carrying out this
transesterification reaction including the common batch process,
heterogeneous catalysts, [supercritical processes, ultrasonic methods, and
even microwave methods.
 Chemically, trans esterified biodiesel comprises a mix of mono-alkyl esters
of long chain fatty acids. The most common form uses methanol (converted
to sodium methoxide) to produce methyl esters (commonly referred to as
Fatty Acid Methyl Ester – FAME) as it is the cheapest alcohol available,
though ethanol can be used to produce an ethyl ester (commonly referred
to as Fatty Acid Ethyl Ester – FAEE) biodiesel and higher alcohols such as
isopropanol and butanol have also been used. Using alcohols of higher
molecular weights improves the cold flow properties of the resulting ester,
at the cost of a less efficient transesterification reaction. A lipid
transesterification production process is used to convert the base oil to the
desired esters. Any free fatty acids (FFAs) in the base oil are either
converted to soap and removed from the process, or they are esterified
(yielding more biodiesel) using an acidic catalyst. After this processing,
unlike straight vegetable oil, biodiesel has combustion properties very
similar to those of petroleum diesel and can replace it in most current uses.
 The methanol used in most biodiesel production processes is made using
fossil fuel inputs. However, there are sources of renewable methanol made
using carbon dioxide or biomass as feedstock, making their production
processes free of fossil fuels.

 A by-product of the transesterification process is the production of glycerol.

For every 1 ton of biodiesel that is manufactured, 100 kg of glycerol are
produced. Originally, there was a valuable market for glycerol, which
 assisted the economics of the process as a whole. However, with the
increase in global biodiesel production, the market price for this crude
glycerol (containing 20% water and catalyst residues) has crashed. Research
is being conducted globally to use this glycerol as a chemical building block
(see chemical intermediate under Wikipedia article "Glycerol"). One
initiative in the UK is The Glycerol Challenge.
 Usually, this crude glycerol must be purified, typically by performing
vacuum distillation. This is rather energy intensive. The refined glycerol
(98%+ purity) can then be utilized directly or converted into other products.
The following announcements were made in 2007: A joint venture of
Ashland Inc. and Cargill announced plans to make propylene glycol in
Europe from glycerol and Dow Chemical announced similar plans for North
America. Dow also plans to build a plant in China to make epichlorohydrin
from glycerol. [epichlorohydrin is a raw material for epoxy resins.

Production Process

Mixing of alcohol and catalyst:

The catalyst is typically sodium hydroxide (caustic soda) or potassium
hydroxide (potash). It is dissolved in the alcohol using a standard
agitator or mixer. Reaction. The alcohol/catalyst mix is then charged
into a closed reaction vessel and the oil or fat is added. The system
from here on is totally closed to the atmosphere to prevent the loss of
alcohol. The reaction mix is kept just above the boiling point of the
alcohol (around 160 °F) to speed up the reaction and the reaction
takes place. Recommended reaction time varies from 1 to 8 hours,
 and some systems recommend the reaction take place at room
temperature. Excess alcohol is normally used to ensure total
conversion of the fat or oil to its esters. Care must be taken to monitor
the amount of water and free fatty acids in the incoming oil or fat. If
the free fatty acid level or water level is too high, it may cause
problems with soap formation and the separation of the glycerin by-
product downstream.

Separation:
Once the reaction is complete, two major products exist: glycerin and
biodiesel. Each has a substantial amount of excess methanol that was
used in the reaction. The reacted mixture is sometimes neutralized at this
step if needed. The glycerin phase is much denser than biodiesel phase
and the two can be gravity separated with glycerin simply drawn off the
bottom of the settling vessel. In some cases, a centrifuge is used to
separate the two materials faster.

Alcohol Removal
Once the glycerin and biodiesel phases have been separated, the excess
alcohol in each phase is removed with a flash evaporation process or by
distillation. In other systems, the alcohol is removed, and the mixture
neutralized before the glycerin and esters have been separated. In either
case, the alcohol is recovered using distillation equipment and is re-used.
Care must be taken to ensure no water accumulates in the recovered
alcohol stream.

Glycerin Neutralization
The glycerin by-product contains unused catalyst and soaps that are
neutralized with an acid and sent to storage as crude glycerin. In some
cases, the salt formed during this phase is recovered for use as fertilizer. In
most cases the salt is left in the glycerin. Water and alcohol are removed to
produce 80-88% pure glycerin that is ready to be sold as crude glycerin. In
more sophisticated operations, the glycerin is distilled to 99% or higher
purity and sold into the cosmetic and pharmaceutical markets.
Methyl Ester Wash
Once separated from the glycerin, the biodiesel is sometimes purified by
washing gently with warm water to remove residual catalyst or soaps,
dried, and sent to storage. In some processes this step is unnecessary.
This is normally the end of the production process resulting in a clear
amber-yellow liquid with a viscosity similar to Petro diesel. In some systems
the biodiesel is distilled in an additional step to remove small amounts of
color bodies to produce a colorless biodiesel.

Product Quality
Prior to use as a commercial fuel, the finished biodiesel must be analyzed
using sophisticated analytical equipment to ensure it meets any required
specifications. The most important aspects of biodiesel production to
ensure trouble free operation in diesel engines are:
 Complete Reaction
 Removal of Glycerin
 Removal of Catalyst
 Removal of Alcohol
 Absence of Free Fatty Acids

Biodiesel Fuel Features

 Power:
 One of the major advantages is the fact that it can be used in exiting
engines & fuel injection equipment (no modification required) without
negative impact to operating performance.
Fuel availability/economy:
 Virtually the same MPG rating as petrol-diesel & the only alternative fuel
for heavyweight vehicles requiring no special dispensing & storage
equipment.
Production/Refining:
 Can be done at home (wasted veggie oil) & farms (virgin oils from seeds),
being the only alternative fuel that can boost of a zero total emissions
production facility. By selling the simultaneously produced glycerol, the
cost of BD is basically the same cost of the oil used to make it.
Storage:
 Readily blends & stays blended with petrol-diesel so it can be stored &
dispensed wherever diesel is stored or sold.
Combustibility/Safety:
 Biodiesel has a very high flash point (300⁰F) making it one of the safest of
all alternative fuels.
Lubricity:
 The only alternative fuel that can actually extend engine life because of its
superior lubricating & cleaning properties. The present “low Sulphur” diesel
fuel is badly wearing the injection pumps of not protected diesel engine.
 Advantages of Biodiesel
 As already mentioned in the formation of biodiesel, it is an eco-friendly fuel
and does not produce remarkable waste. Besides this, other advantages of
biodiesel include -
 It is safe to use as it does not create any toxic residue.
 This fuel has a lower emission rate, making it reliable for longer use.
 It also finds use in alteration with petroleum diesel oil.
 This is also used as a heating fuel in specific boilers.
 Other benefits of biodiesel include its user-friendliness. You do not have to
modify the engines for using it.
 You should note that once you have studied so far, you shall be able to jot
down the properties of biodiesel too. All these points discussed above are
based on the features which have facilitated the formation and advantages
of using biodiesel.
 One of the main advantages of using biodiesel is that it can be used in
existing diesel engines with little or no modifications at all and can replace
fossil fuels to become the most preferred primary transport energy source.
Biodiesel can be used in 100% (B100) or blends with petroleum diesel. For
example, B20 variant is a 20% blend of biodiesel with 80% diesel fuel. It
improves engine lubrication and increases engine life since it is virtually
sulfur-free.
 Biofuels are produced locally, and thousands of people are employed in the
biofuel production plant. Since biodiesel is produced from crops, an
increase in demand for biodiesel leads to a corresponding increase in
demand for suitable biofuel crops. Moreover, it creates less emission by
reducing the amount of suspended particles in the air. This reduces the cost
of healthcare products.
 According to the National Laboratory reports, carbon dioxide emissions
reduced by a staggering 74% when we shift from petroleum to biodiesel.
Even the California Air Resources Board has reported quite similar figures.
So, using biodiesel is actually more advantageous than you think! One fuel
solves three glaring problems (pollution, squandering and global warming)
that are linked with the usage of fossil fuels.
 Disadvantages of Biodiesel

 Biodiesel is currently about one and a half times more expensive than
petroleum diesel fuel. Part of this cost is because the most common source
of oil is the soybean, which is only 20% oil. However, the costs of biodiesel
can be reduced by making biodiesel from recycled cooking oils rather than
from new soybeans, or by making it from plant matter with higher oil
content.
 It takes energy to produce biodiesel fuel from soy crops, including the
energy of sowing, fertilizing and harvesting.
 Biodiesel fuel can damage rubber hoses in some engines, particularly in cars
built before 1994. You should check with the manufacturer before using
biodiesel to see if you need to replace any hoses or rubber seals.
 Biodiesel cleans the dirt from the engine. This dirt then collects in the fuel
filter, which can clog it. Clogging occurs most often when biodiesel is first
used after a period of operation with petroleum diesel, so filters should be
changed after the first several hours of biodiesel use.
 It requires a large amount of energy to produce biodiesel fuel from soy
crops as energy is needed for sowing, fertilizing and harvesting crops. Apart
from that, raw material needs to be transported through trucks, which may
consume some additional fuel. Some scientists believe that producing one
gallon of biofuel needs energy equivalent to several gallons of petroleum
fuel.
 Since biofuels are made from animal and vegetable fat, more demand for
these products may raise prices for these products and create a food crisis
in some countries. For example, the production of biodiesel from corn may
raise its demand, and it might become more expensive, which may deprive
poor people of having it.
 Biodiesel is made from a variety of biofuel crops. When the oil is extracted
and converted to fuel using the chemical process, the result can vary in the
ability to produce power. In short, not all biofuel crops are the same as the
amount of vegetable oil may vary.
 Environmental effects
The surge of interest in biodiesel has highlighted several environmental effects
associated with its use. These potentially include reductions in greenhouse gas
emissions, deforestation, pollution and the rate of biodegradation.
According to the Renewable Fuel Standards Program Regulatory Impact Analysis,
released by the Environmental Protection Agency (EPA) of the United States in
February 2010, biodiesel from soy oil results, on average, in a 57% reduction in
greenhouse gases compared to petroleum diesel, and biodiesel produced from
waste grease results in an 86% reduction. See chapter 2.6 of the EPA report for
more detailed information.
However, environmental organizations, for example, Rainforest Rescue and
Greenpeace, criticize the cultivation of plants used for biodiesel production, e.g.,
oil palms, soybeans and sugar cane. The deforestation of rainforests exacerbates
climate change and sensitive ecosystems are destroyed to clear land for oil palm,
soybean and sugar cane plantations. Moreover, biofuels contribute to world
hunger, since arable land is no longer used for growing foods. The Environmental
Protection Agency published data in January 2012, showing that biofuels made
from palm oil will not count towards the renewable fuels mandate of the United
States as they are not climate friendly. Environmentalists welcome the conclusion
because the growth of oil palm plantations has driven tropical deforestation, for
example, in Indonesia and Malaysia.
Indonesia produces biodiesel primarily from palm oil. Since agricultural land is
limited, in order to plant monocultures of oil palms, land used for other
cultivations, or the tropical forest needs to be cleared. A major environmental
threat is then the destruction of rainforests in Indonesia.
Biodiesel's Physical
Characteristics

Specific gravity 0.88

Kinematic viscosity at 40°C 4.0 to 6.0

Cetane number 47 to 65

Higher heating value, Btu/gal ˜127,960

Lower heating value, Btu/gal ˜119,550

Density, lb/gal at 15.5°C 7.3

Carbon, wt% 77

Hydrogen, wt% 12

Oxygen, by dif. wt% 11

Boiling point, °C 315-350

Flash point, °C 100-170

Sulfur, wt% 0.0 to 0.0015

Cloud point, °C -3 to 15

Pour point, °C -5 to 10
 Conclusion
Biodiesel production from oil palm by a process that use ethanol produced
from the solid residues of the same palm instead of methanol, offers high
degree of integration and decrease of environmental impacts compared to
the individual production of biodiesel and bioethanol. This option is very
attractive considering not only the energy consumption, but also the
decrease of the solid wastes generated during the processing of oil palm.
Palm press fiber produced during oil extraction has a high content of
lignocellulosic biomass making them very suitable materials for their
conversion into ethanol.