Biodiesel

Introduction:
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 on 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.

It refers to a vegetable oil - or animal fat-based diesel

fuel consisting of long-chain alkyl (methyl, ethyl, or propyl) esters.
Biodiesel is typically made by chemically reacting lipids (e.g.,
vegetable oil, soybean oil, animal fat with
an alcohol producing fatty acid esters.
Biodiesel is meant to be used in standard diesel engines and is
thus distinct from the vegetable and waste oils used to
fuel converted diesel engines. Biodiesel can be used alone, or
blended with petrodiesel in any proportions. Biodiesel blends can
also be used as heating oil.
The National Biodiesel Board (USA) also has a technical
definition of "biodiesel" as a mono-alkyl ester.

Why Biodiesel?
It's Economical
Biodiesel can be produced by individuals on a small scale
relatively inexpensively when compared to Petrodiesel. Figures
range anywhere from $0.40 a gallon to about $1.25 a gallon
depending on the cost of materials required to make it. With
prices that low, most people are able to save hundreds of dollars
on their fuel bills. In some cases it even goes into the thousands
of dollars. With savings like that, most people are able to recoup
their initial investment on the equipment needed to make
biodiesel within a matter of months.

It's Renewable
Biodiesel has been touted far and wide for its renewable
properties. Instead of making a fuel from a finite resource such as
crude oil, Biodiesel can be produced from renewable resources
such as organic oils, fats, and tallows. This means that it can be
made from things that can be regrown, reproduced, and reused.
So, if you need more, you can just grow another crop of seeds for
the oil.

It's Good For the Environment

When Biodiesel is used to power diesel engines, the emissions at
the tailpipe are significantly reduced. Studies by the US National
Renewable Energy Lab indicate drops in several key areas that
help the environment. Carbon Dioxide, Hydrocarbons, and
Particulate Matter (the black smoke from diesels) all are
significantly reduced when Biodiesel is used. When used in older
diesel engines such as indirect combustion diesels, the results
are astounding. There was a reduction in the tailpipe emissions of
nearly 90%. It also has a positive energy balance.

It supports farmers
When Biodiesel is made from organic oils such as Canola, Soy,
Peanut, or other domestically grown seed crops, it helps the
farming community out. Because the oil used to make Biodiesel is
"domestically grown", it keeps the money flowing to those that
"grow" the feedstock. This continues to help out the renewable
aspect of Biodiesel because this means more seed crops can be
grown by local farmers.

It reduces dependency on Crude Oil

When Biodiesel is used in place of petrodiesel, it reduces the
amount of crude oil used up. This means that it helps to reduce
our dependence on a limited resource and increases our use of
renewable resources. We think that's a great step toward
reducing our dependence on a fuel that may not be around
forever.

It's enjoyable to make

We think that making Biodiesel is one of the funniest things in the
world to do. With a little practice and know-how it can easily be
made and is extremely simple to do. We've found it to be an
incredibly fulfilling experience. There's just something to be said
for being able to make your own fuel and drive past a gas station
and wave instead of pulling up for a fill-up. Words just don't
describe the incredible feeling we get each time we make a batch.

It's good for the engine

Biodiesel, unlike Petrodiesel, has a much higher "lubricity" to it.
This means that it's essentially "slipperier" than normal diesel fuel.
With the added "lubricity" of Biodiesel, engines have been shown
to experience less wear and tear when used on a regular basis.
Also, because Biodiesel is less polluting, it means that it's easier
on the engine. US Government Studies have shown that in some
cases large fleets using Biodiesel have been able to go longer
between oil changes because the oil stay's cleaner when
Biodiesel is used.

It's the perfect alternative fuel

When compared to several other Alternative Fuels available,
Biodiesel comes out way ahead. Most alternative fuels require
changes to a vehicle to be used. Natural Gas & Propane require
special tanks to be installed and changes to the fuel injection
system must be made as well. Ethanol also requires specialized
changes to the fuel injection system. Electricity requires a
completely different engine. In most cases, once a vehicle
undergoes the conversion necessary to run the alternative fuel,
there's no going back. You either run the alternative fuel or you
don't run the vehicle.

Applications
Biodiesel can be used in pure form (B100) or may be blended
with petroleum diesel at any concentration in most injection pump
diesel engines. New extreme high-pressure (29,000 psi) common
rail engines have strict factory limits of B5 or B20, depending on
manufacturer. Biodiesel has different solvent properties than
petrodiesel, and will degrade natural rubber gaskets and hoses in
vehicles (mostly vehicles manufactured before 1992), although
these tend to wear out naturally and most likely will have already
been replaced with FKM, which is nonreactive to biodiesel.
Biodiesel has been known to break down deposits of residue in
the fuel lines where petrodiesel has been used. As a result, fuel
filters may become clogged with particulates if a quick transition
to pure biodiesel is made. Therefore, it is recommended to
change the fuel filters on engines and heaters shortly after first
switching to a biodiesel blend.

Production
Biodiesel is commonly produced by the transesterification of the
vegetable oil or animal fat feedstock. There are several methods
for carrying out this transesterification reaction including the
common batch process, supercritical processes, ultrasonic
methods, and even microwave methods. Biodiesel production is
the process of producing the biofuel, biodiesel, through the
chemical reactions transesterification and esterification. This
involves vegetable or animal fats and oils being reacted with
short-chain alcohols (typically methanol or ethanol). 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.

Chemically, transesterified 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 the 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 has to be purified, typically by

performing vacuum distillation. This is rather energy intensive.
The refined glycerol (98%+ purity) can then be utilised 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 epichlorhydrin from glycerol Epichlorhydrin is a raw material
for epoxy resins.

Process steps involved in

production
The major steps required to synthesize biodiesel are as follows:

Feedstock Pretreatment
Common feedstock used in biodiesel production include yellow
grease (recycled vegetable oil), "virgin" vegetable oil, and tallow.
Recycled oil is processed to remove impurities from cooking,
storage, and handling, such as dirt, charred food, and water.
Virgin oils are refined, but not to a food-grade level. Degumming
to remove phospholipids and other plant matter is common,
though refinement processes vary.

Regardless of the feedstock, water is removed as its presence

during base-catalyzed transesterification causes the triglycerides
to hydrolyze, giving salts of the fatty acids (soaps) instead of
producing biodiesel.
 Determination and treatment of free
fatty acids
A sample of the cleaned feedstock oil is titrated with a
standardized base solution in order to determine the
concentration of free fatty acids (carboxylic acids) present in the
vegetable oil sample. These acids are then either esterified into
biodiesel, esterified into glycerides, or removed, typically through
neutralization.

Reactions
Base-catalyzed transesterification reacts lipids (fats and oils) with
alcohol (typically methanol or ethanol) to produce biodiesel and
an impure coproduct, glycerol. If the feedstock oil is used or has a
high acid content, acid-catalyzed esterification can be used to
react fatty acids with alcohol to produce biodiesel. Other methods,
such as fixed-bed reactors, supercritical reactors, and ultrasonic
reactors, forgo or decrease the use of chemical catalysts.

Product purification
Products of the reaction include not only biodiesel, but also
byproducts, soap, glycerol, excess alcohol, and trace amounts of
water. All of these byproducts must be removed to meet the
standards, but the order of removal is process-dependent.

The density of glycerol is greater than that of biodiesel, and this

property difference is exploited to separate the bulk of the glycerol
coproduct. Residual methanol is typically recovered by distillation
and reused. Soaps can be removed or converted into acids.
Residual water is also removed from the fuel.

Reactions
1-Transesterification
Animal and plant fats and oils are composed of triglycerides,
which are esters formed by the reactions of three free fatty
acids and the trihydric alcohol, glycerol. In the transesterification
process, the added alcohol (commonly, methanol or ethanol)
is deprotonated with a base to make it a stronger nucleophile. As
can be seen, the reaction has no other inputs than the triglyceride
and the alcohol. Under normal conditions, this reaction will
proceed either exceedingly slowly or not at all, so heat, as well as
catalysts (acid and/or base) are used to speed the reaction. It is
important to note that the acid or base are not consumed by the
transesterification reaction, thus they are not reactants, but
catalysts. Common catalysts for transesterification include sodium
hydroxide, potassium hydroxide, and sodium methoxide.

Almost all biodiesel is produced from virgin vegetable oils using

the base-catalyzed technique as it is the most economical
process for treating virgin vegetable oils, requiring only low
temperatures and pressures and producing over 98%
conversion yield (provided the starting oil is low in moisture and
free fatty acids). However, biodiesel produced from other sources
or by other methods may require acid catalysis, which is much
slower. Since it is the predominant method for commercial-scale
production, only the base-catalyzed transesterification process
will be described below.
Triglycerides (1) are reacted with an alcohol such as ethanol (2)
to give ethyl esters of fatty acids (3) and glycerol (4):

R1, R2, R3 : Alkyl group

The alcohol reacts with the fatty acids to form the mono-alkyl
ester (biodiesel) and crude glycerol. The reaction between
the biolipid (fat or oil) and the alcohol is a reversible reaction so
excess alcohol must be added to ensure complete conversion.

2-Base-catalysed transesterification
mechanism
The transesterification reaction is base catalyzed. Any strong
base capable of deprotonating the alcohol will do (e.g. NaOH,
KOH, sodium methoxide, etc.), but the sodium and potassium
hydroxides are often chosen for their cost. The presence of
water causes undesirable base hydrolysis, so the reaction
must be kept dry.

In the transesterification mechanism, the carbonyl carbon of

the starting ester (RCOOR1) undergoes nucleophilic attack by
the incoming alkoxide (R2O) to give a tetrahedral intermediate,
 which either reverts to the starting material, or proceeds to the
transesterified product (RCOOR2). The various species exist in
equilibrium, and the product distribution depends on the
relative energies of the reactant and product.

Production Process
An example of a simple production flow chart is proved below with
a brief explanation of each step.
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 the excess
methanol that was used in the reaction. The reacted mixture is
sometimes neutralized at this step if needed. The glycerin phase
is much more dense 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 others 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 petrodiesel. 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 using a commercial fuel, the finished biodiesel
must be analyzed 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

References
 http://www.esru.strath.ac.uk/EandE/Web_sites/02-
03/biofuels/what_biodiesel.htm
https://en.wikipedia.org/wiki/Biodiesel_production

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Characterization of the Key Fuel Properties of Ethyl Esters" (5
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"Pre-Treatment For Oil Biodiesel Processors & Biodiesel

Equipment by Biodiesel Experts International,
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Dub, Marc A, et al. (2007). "Acid-Catalyzed Transesterification

of Canola Oil to Biodiesel under Single- and Two-Phase
Reaction Conditions". Energy & Fuels 21: 24502459.
American Chemical Society. Retrieved on 2007-11-01.

Bunkyakiat, Kunchana; et al. (2006). "Continuous Production of

Biodiesel via Transesterification from Vegetable Oils in
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Vera, C.R.; S.A. D'Ippolito; C.L. Pieck; J.M.Parera (2005-08-

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