Biodiesel

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 petrodiesel) in unmodified diesel-engine
vehicles.
Biodiesel is distinguished from the straight vegetable oil (SVO) (sometimes referred to as
"waste vegetable oil", "WVO", "used vegetable oil", "UVO", "pure plant oil", "PPO") used
(alone, or blended) as fuels in some converted diesel vehicles.
"Biodiesel" is standardized as mono-alkyl ester and other kinds of diesel-grade fuels of
biological origin are not included.
Blends
Blends of biodiesel and conventional hydrocarbon-based diesel are products most commonly
distributed for use in the retail diesel fuel marketplace.
Much of the world uses a system known as the "B" factor to state the amount of biodiesel in
any fuel mix: fuel containing 20% biodiesel is labeled B20, while pure biodiesel is referred to
as B100.
It is common in the USA to see B99.9 because a federal tax credit is awarded to the first
entity which blends petroleum diesel with pure biodiesel .
Blends of 20 percent biodiesel with 80 percent petroleum diesel (B20) can generally be used
in unmodified diesel engines.
Biodiesel can also be used in its pure form (B100), but may require certain engine
modifications to avoid maintenance and performance problems.
Blending B100 with petro diesel may be accomplished by:
Mixing in tanks at manufacturing point prior to delivery to tanker truck
Splash mixing in the tanker truck (adding specific percentages of Biodiesel and Petro Diesel)
In-line mixing, two components arrive at tanker truck simultaneously.
Origin
On August 31, 1937, G. Chavanne of the University of Brussels (Belgium) was granted a
patent for a 'Procedure for the transformation of vegetable oils for their uses as fuels' (fr.
'Procédé de Transformation d’Huiles Végétales en Vue de Leur Utilisation comme
Carburants') Belgian Patent 422,877.
This patent described the alcoholysis (often referred to as transesterification) of vegetable oils
using ethanol (and mentions methanol) in order to separate the fatty acids from the glycerol
by replacing the glycerol with short linear alcohols.
This appears to be the first account of the production of what is known as 'biodiesel' today.
Applications
Biodiesel can be used in pure form (B100) or may be blended with petroleum diesel at any
concentration in most modern diesel engines.
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.
Distribution

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Since the passage of the Energy Policy Act of 2005 biodiesel use has been increasing in the
United States.
Fueling stations make biodiesel readily available to consumers across Europe, and
increasingly in the USA and Canada.
A growing number of transport fleets use it as an additive in their fuel.
Biodiesel is often more expensive to purchase than petroleum diesel but this is expected to
diminish due to economies of scale and agricultural subsidies versus the rising cost of
petroleum as reserves are depleted.
Vehicular use and manufacturer acceptance
In 2005, Chrysler (then part of DaimlerChrysler) released the Jeep Liberty CRD diesels from
the factory into the American market with 5% biodiesel blends, indicating at least partial
acceptance of biodiesel as an acceptable diesel fuel additive.
In 2007, DaimlerChrysler indicated intention to increase warranty coverage to 20% biodiesel
blends if biofuel quality in the United States can be standardized.
Railroad use
The British businessman Richard Branson's Virgin Voyager train, number 220007 Thames
Voyager, billed as the world's first "biodiesel train" was converted to run on 80% petrodiesel
and only 20% biodiesel, and it is claimed it will save 14% on direct emissions.
Similarly, a train in eastern Washington will be running on a 25% biodiesel 75% petrodiesel
blend during summer, purchasing fuel from a biodiesel producer seated along the railroad
tracks.
The train will be powered by biodiesel made in part from Washington-grown canola.
Aircraft use
Aircraft manufacturers are even more cautious due to the inherent risks of air travel, but a test
flight has been performed by a Czech Aircraft (completely powered on biofuel); testing has
been announced by Rolls Royce plc, Air New Zealand and Boeing (one engine out of four on
a Boeing 747); and commercial passenger jet testing has also been announced by Virgin
Atlantic's Richard Branson.
The world's first biofuel-powered commercial aircraft took off from London's Heathrow
Airport on February 24, 2008 and touched down in Amsterdam on a demonstration flight
hailed as a first step towards "cleaner" flying.
The "BioJet" fuel for this flight was produced by Seattle based Imperium Renewables, Inc.
As a heating oil
Biodiesel can also be used as a heating fuel in domestic and commercial boilers, sometimes
known as bioheat.
Older furnaces may contain rubber parts that would be affected by biodiesel's solvent
properties, but can otherwise burn biodiesel without any conversion required.
Care must be taken at first, however, given that varnishes left behind by petrodiesel will be
released and can clog pipes- fuel filtering and prompt filter replacement is required.
Another approach is to start using biodiesel as blend, and decreasing the petroleum
proportion over time can allow the varnishes to come off more gradually and be less likely to
clog.
Thanks to its strong solvent properties, however, the furnace is cleaned out and generally
becomes more efficient.
A technical research paper describes laboratory research and field trials project using pure
biodiesel and biodiesel blends as a heating fuel in oil fired boilers.
During the Biodiesel Expo 2006 in the UK, Andrew J. Robertson presented his biodiesel
heating oil research from his technical paper and suggested that B20 biodiesel could reduce
UK household CO2 emissions by 1.5 million tons per year.

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Historical background
Transesterification of a vegetable oil was conducted as early as 1853 by scientists E. Duffy
and J. Patrick, many years before the first diesel engine became functional.
Rudolf Diesel's prime model, a single 10 ft (3 m) iron cylinder with a flywheel at its base, ran
on its own power for the first time in Augsburg, Germany, on August 10, 1893.
In remembrance of this event, August 10 has been declared "International Biodiesel Day".
Rudolf Diesel demonstrated a Diesel engine running on peanut oil (at the request of the
French government) built by the French Otto Company at the World Fair in Paris, France in
1900, where it received the Grand Prix (highest prize).
This engine stood as an example of Diesel's vision because it was powered by peanut oil — a
biofuel, though not biodiesel, since it was not transesterified.
He believed that the utilization of biomass fuel was the real future of his engine.
In a 1912 speech Diesel said, "the use of vegetable oils for engine fuels may seem
insignificant today but such oils may become, in the course of time, as important as
petroleum and the coal-tar products of the present time."
During the 1920s, diesel engine manufacturers altered their engines to utilize the lower
viscosity of petrodiesel (a fossil fuel), rather than vegetable oil (a biomass fuel).
The petroleum industries were able to make inroads in fuel markets because their fuel was
much cheaper to produce than the biomass alternatives. The result, for many years, was a
near elimination of the biomass fuel production infrastructure.
Only recently, have environmental impact concerns and a decreasing price differential made
biomass fuels such as biodiesel a growing alternative.
Despite the widespread use of fossil petroleum-derived diesel fuels, interest in vegetable oils
as fuels in internal combustion engines is reported in several countries during the 1920s and
1930's and later during World War II.
Belgium, France, Italy, the United Kingdom, Portugal, Germany, Brazil, Argentina, Japan
and China have been reported to have tested and used vegetable oils as diesel fuels during
this time.
Some operational problems were reported due to the high viscosity of vegetable oils
compared to petroleum diesel fuel, which result in poor atomization of the fuel in the fuel
spray and often leads to deposits and coking of the injectors, combustion chamber and valves.
Attempts to overcome these problems included heating of the vegetable oil, blending it with
petroleum-derived diesel fuel or ethanol, pyrolysis and cracking of the oils.
On August 31, 1937, G. Chavanne of the University of Brussels (Belgium) was granted a
patent for a "Procedure for the transformation of vegetable oils for their uses as fuels" (fr.
'Procédé de Transformation d’Huiles Végétales en Vue de Leur Utilisation comme
Carburants') Belgian Patent 422,877.
This patent described the alcoholysis (often referred to as transesterification) of vegetable oils
using methanol and ethanol in order to separate the fatty acids from the glycerol by replacing
the glycerol by short linear alcohols.
This appears to be the first account of the production of what is known as "biodiesel" today.
Research into the use of transesterified sunflower oil, and refining it to diesel fuel standards,
was initiated in South Africa in 1979.
By 1983, the process for producing fuel-quality, engine-tested biodiesel was completed and
published internationally.
An Austrian company, Gaskoks, obtained the technology from the South African Agricultural
Engineers; the company erected the first biodiesel pilot plant in November 1987, and the first
industrial-scale plant in April 1989 (with a capacity of 30,000 tons of rapeseed per annum).

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Throughout the 1990s, plants were opened in many European countries, including the Czech
Republic, Germany and Sweden. France launched local production of biodiesel fuel (referred
to as diester) from rapeseed oil, which is mixed into regular diesel fuel at a level of 5%, and
into the diesel fuel used by some captive fleets (e.g. public transportation) at a level of 30%.
Renault, Peugeot and other manufacturers have certified truck engines for use with up to that
level of partial biodiesel; experiments with 50% biodiesel are underway.
During the same period, nations in other parts of the world also saw local production of
biodiesel starting up: by 1998, the Austrian Biofuels Institute had identified 21 countries with
commercial biodiesel projects. 100% Biodiesel is now available at many normal service
stations across Europe.
In September 2005 Minnesota became the first U.S. state to mandate that all diesel fuel sold
in the state contain part biodiesel, requiring a content of at least 2% biodiesel.

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 Biodiesel

BIODIESEL

Properties
Biodiesel has better lubricating properties than today's lower viscosity diesel fuels.
Biodiesel addition reduces engine wear increasing the life of the fuel injection equipment that
relies on the fuel for its lubrication, such as high pressure injection pumps, pump injectors
(also called unit injectors) and fuel injectors.
The calorific value of biodiesel is about 37.27 MJ/L. This is 9% lower than regular Number 2
petrodiesel. Variations in biodiesel energy density is more dependent on the feedstock used
than the production process.
Still these variations are less than for petrodiesel.
It has been claimed biodiesel gives better lubricity and more complete combustion thus
increasing the engine energy output and partially compensating for the higher energy density
of petrodiesel.
Biodiesel is a liquid which varies in color — between golden and dark brown — depending
on the production feedstock.
It is immiscible with water, has a high boiling point and low vapor pressure.
The flash point of biodiesel (>130 °C, >266 °F) is significantly higher than that of petroleum
diesel (64 °C, 147 °F) or gasoline (−45 °C, -52 °F). Biodiesel has a density of ~ 0.88 g/cm³,
less than that of water.
Biodiesel has a viscosity similar to petrodiesel, the current industry term for diesel produced
from petroleum.
Biodiesel has high lubricity and virtually no sulfur content, and it is often used as an additive
to Ultra-Low Sulfur Diesel (ULSD) fuel.
Material compatibility
Plastics: High density polyethylene is compatible but PVC is slowly degraded. Polystyrenes
are melted on contact with biodiesel.
Metals: Biodiesel has an effect on copper-based materials (i.e. brass), and it also effects zinc,
tin, lead, and cast iron.
Stainless steels (316 and 304) and aluminum are unaffected.
Rubber: Biodiesel also effects types of natural rubbers found in some older engine
components. Studies have also found that fluorinated elastomers (FKM) cured with peroxide
and base-metal oxides can be degraded when biodiesel loses its stability caused by oxidation.
However testing with FKM- GBL-S and FKM- GF-S where found to be the toughest
elastomer to handle biodiesel in all conditions.
Technical standards
Biodiesel has a number of standards for its quality including the European standard EN
14214 and the ASTM D6751 USA and Canada.

Gelling
The cloud point, or temperature at which pure (B100) biodiesel starts to gel, varies
significantly and depends upon the mix of esters and therefore the feedstock oil used to
produce the biodiesel.
For example, biodiesel produced from low erucic acid varieties of canola seed (RME) starts
to gel at approximately −10 °C (14 °F).
Biodiesel produced from tallow tends to gel at around +16 °C (61 °F).
As of 2006, there are a very limited number of products that will significantly lower the gel
point of straight biodiesel.

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A number of studies have shown that winter operation is possible with biodiesel blended with
other fuel oils including #2 low sulfur diesel fuel and #1 diesel / kerosene.
The exact blend depends on the operating environment: successful operations have run using
a 65% LS #2, 30% K #1, and 5% bio blend.
Other areas have run a 70% Low Sulfur #2, 20% Kerosene #1, and 10% bio blend or an 80%
K#1, and 20% biodiesel blend.

According to the National Biodiesel Board (NBB), B20 (20% biodiesel, 80% petrodiesel)
does not need any treatment in addition to what is already taken with petrodiesel.
To permit the use of biodiesel without mixing and without the possibility of gelling at low
temperatures, some people modify their vehicles with a second fuel tank for biodiesel in
addition to the standard fuel tank.
Alternately, a vehicle with two tanks is chosen. The second fuel tank is insulated and a
heating coil using engine coolant is run through the tank.
When a temperature sensor indicates that the fuel is warm enough to burn, the driver switches
from the petrodiesel tank to the biodiesel tank.
This is similar to the method used for running straight vegetable oil.
Contamination by water
Biodiesel may contain small but problematic quantities of water. Although it is hydrophobic
(non-miscible with water molecules), it is said to be, at the same time, hygroscopic to the
point of attracting water molecules from atmospheric moisture; one of the reasons biodiesel
can absorb water is the persistence of mono and diglycerides left over from an incomplete
reaction.
These molecules can act as an emulsifier, allowing water to mix with the biodiesel.
In addition, there may be water that is residual to processing or resulting from storage tank
condensation.
The presence of water is a problem because:
Water reduces the heat of combustion of the bulk fuel. This means more smoke, harder
starting, less power.
Water causes corrosion of vital fuel system components: fuel pumps, injector pumps, fuel
lines, etc.
Water & microbes cause the paper element filters in the system to fail (rot), which in turn
results in premature failure of the fuel pump due to ingestion of large particles.
Water freezes to form ice crystals near 0 °C (32 °F). These crystals provide sites for
nucleation and accelerate the gelling of the residual fuel.
Water accelerates the growth of microbe colonies, which can plug up a fuel system. Biodiesel
users who have heated fuel tanks therefore face a year-round microbe problem.
Additionally, water can cause pitting in the pistons on a diesel engine.
Previously, the amount of water contaminating biodiesel has been difficult to measure by
taking samples, since water and oil separate. However, it is now possible to measure the
water content using water-in-oil sensors.
Water contamination is also a potential problem when using certain chemical catalysts
involved in the production process, substantially reducing catalytic efficiency of base (high
pH) catalysts such as KOH.
However, the super-critical methanol production methodology, whereby the
transesterification process of oil feedstock and methanol is effectuated under high
temperature and pressure, has been shown to be largely unaffected by the presence of water
contamination during the production phase.
Availability and prices

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In some countries biodiesel is less expensive than conventional diesel.

Global biodiesel production reached 3.8 million tons in 2005. Approximately 85% of
biodiesel production came from the European Union.
In the United States, average retail (at the pump) prices, including Federal and state fuel
taxes, of B2/B5 are lower than petroleum diesel by about 12 cents, and B20 blends are the
same as petrodiesel.
B99 and B100 generally cost more than petrodiesel except where local governments provide
a subsidy.
Biodiesel production
Biodiesel production is the act of producing the biofuel, biodiesel, through either
transesterification or alcoholysis.
The process involves reacting vegetable oils or animal fats catalytically with a short-chain
aliphatic alcohols (typically methanol or ethanol).

Transesterification reaction

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These chains are designated by two numbers separated by a colon.

The first number designates the number of carbon atoms in the chain and the second number
designates the number of double bonds.
Note that the number of carbon atoms includes the carbon that is double bonded to the
oxygen atom at one end of the fatty acid (called the carboxylic carbon).
This is the end that the methanol attaches to when methyl esters are produced.

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Transesterfication of soybean oil

For simplicity, consider an oil such as soybean oil to consist of pure triolein.
Triolein is a triglyceride in which all three fatty acid chains are oleic acid. This
is near the actual number of carbons and hydrogens and gives a molecular
weight that is near the value for soybean oil.
If triolein is reacted with methanol, the reaction will be that shown in Figure 2.
Note that weights for each of the compounds in the reaction are given.
These are based on the fact that one molecule of triolein reacts with 3
molecules of methanol to produce 3 molecules of methyl oleate, the biodiesel
product, and one mole of glycerol.
Glyceride is an ester of glycerol and fatty acids that occurs naturally as fats and fatty oils

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With excess Methanol

We do not actually conduct the reaction this way. We usually add 60% to 100% excess
methanol to ensure that the reaction goes to completion.
In general, reactions can be encouraged to progress by adding an excess of one of the
reactants or by removing one of the products.
The reaction of triolein with 100% excess (XS) methanol is shown in Figure 3.
The reaction also requires about 1% (based on the weight of oil) of sodium hydroxide or a
similar catalyst that mostly ends up in the glycerol.

Product Quality
The standard for biodiesel allows 0.24% total glycerol in the final product.
It is clear that a molecule of a triglyceride can be considered to contain a molecule of
glycerol, sometimes called the glycerol backbone.
In the case of triolein, the mole of glycerol would weigh 92.10 g and the mole of triolein
weighs 885.46 g.
Therefore, triolein can be considered to consist of 92.10/885.46 = 0.104, or 10.4% glycerol.
This glycerol is called bound glycerol because it is chemically bound to the triolein molecule.
Bound glycerol can also be associated with monoglycerides and diglycerides, the partial
reaction products of the conversion of triglycerides to alkyl esters.
The structures of these molecules are shown in Figure 4.

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The alcohol reacts with the fatty acids to form the mono-alkyl ester (or biodiesel) and crude
glycerol.
The reaction between the biolipid (fat or oil) and the alcohol is a reversible reaction so the
alcohol must be added in excess to drive the reaction towards the right and ensure complete
conversion.
The transesterification reaction is base catalyzed. Any strong base capable of deprotonating
the alcohol will do (e.g. NaOH, KOH, Sodium methoxide, etc.).
Commonly the base (KOH, NaOH) is dissolved in the alcohol to make a convenient method
of dispersing the otherwise solid catalyst into the oil. The ROH needs to be very dry.
Any water in the process promotes the saponification reaction, thereby producing salts of
fatty acids (soaps) and consuming the base, and thus inhibits the transesterification reaction.
Once the alcohol mixture is made, it is added to the triglyceride. The reaction that follows
replaces the alkyl group on the triglyceride in a series of steps.
The lower layer of the process is composed primarily of glycerine and other waste products.
The top layer, a mixture of biodiesel and alcohol, is decanted. The excess alcohol can be
distilled off, or it can be extracted with water.
If the latter, the biodiesel should be dried by distillation or with a drying agent.
Vegetable oils and biodiesel
As you know, biodiesel is derived from vegetable oils.
The major components of vegetable oils are triglycerides.
Triglycerides are esters of glycerol (an alcohol with a hydroxy group on each of its three
carbon atoms) with long-chain acids, commonly called fatty acids.
Tables 4 and 5 list the most common fatty acids and their corresponding methyl esters.
Note from the comparison of the rational names of the fatty acids with their structural
formulas how the position of the double bonds is defined by numbers.

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The number of carbon atoms is counted by beginning with the first carbon having the
functional group defining the fatty compound as acid or ester.

As you can see from the former example (for example, 1-propanol and 2-propanol), this way
of counting holds for other functional groups as well.
The trivial names of fatty acids and their esters are far more commonly used than their
rational names.

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