BIOFUELS

(BIODIESEL PRODUCTION)

BY ZAMA DLAMINI
INTRODUCTION TO BIODIESEL PRODUCTION
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 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.
Advantages of the Use of Biodiesel
• Renewable fuel, obtained from vegetable oils or animal fats.
• Low toxicity, in comparison with diesel fuel.
• Lower emissions of contaminants: carbon monoxide, particulate matter,
polycyclic aromatic hydrocarbons, aldehydes (toxic, carcinogenic and
cardiovascular effects).
• Lower health risk, due to reduced emissions of carcinogenic substances.
• No sulfur dioxide (SO2) emissions. – respiratory system
• May be blended with diesel fuel at any proportion; both fuels may be mixed
during the fuel supply to vehicles.
• Excellent properties as a lubricant.
• Used cooking oils and fat residues from meat processing may be used as raw
materials.
Disadvantages of the Use of Biodiesel as a replacement for diesel fuel
• Slightly higher fuel consumption due to the lower calorific value of biodiesel.
• Slightly higher nitrous oxide (NOx) emissions than diesel fuel - (green house gas)
• Higher freezing point than diesel fuel. This may be inconvenient in cold climates.
• It is less stable than diesel fuel, and therefore long-term storage (more than six
months) of biodiesel is not recommended.
• May degrade plastic and natural rubber gaskets and hoses when used in pure
form, in this case, the use of Teflon components is recommended - (chemical
resistance).
• It dissolves the deposits of sediments and other contaminants from diesel fuel in
storage tanks and fuel lines, which then are flushed away by the biofuel into the
engine, where they can cause problems in the valves and injection systems. In
consequence, the cleaning of tanks prior to filling with biodiesel is
recommended.
Raw Materials for Biodiesel Production
• Raw materials for biodiesel production are vegetable oils, animal fats and short
chain alcohols.
• Oils most used for worldwide biodiesel production are rape seed, soybean,
palm 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.
• Another undeniable advantage of non-edible oils for biodiesel production lies in
the fact that no foodstuffs are used to produce fuel.
• 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.
• Microalgae appear to be a very important alternative for future biodiesel
production due to their very high oil yield; however, it must be taken into account
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.
Typical Oil Crops Useful for Biodiesel Production
• The main characteristics of typical oil crops that have been found useful for
biodiesel production are summarized below.
Rapeseed and Canola
• Rapeseed adapts well to low fertility soils, but with high sulfur content. With a
high oil yield (40–50%), it may be grown as a winter-cover crop, allows double
cultivation and crop rotation.
• It is the most important raw material for biodiesel production in the European
Community. However, there were technological limitations for sowing and
harvesting in some countries, mainly due to the lack of adequate information
about fertilization, seed handling, and storage (the seeds are very small and
require specialized agricultural machinery).
Soybean
• It is a legume originating in East Asia.
• Depending on environmental conditions and genetic varieties, the plants show
wide variations in height.
• Biodiesel production form soybean yields other valuable sub-products in addition
to glycerin: soybean meal and pellets (used as food for livestock) and flour (which
have a high content of lecithin, a protein used in industry – food -).
• Grain yield varies between 2,000 and 4,000 kg/hectare. Since the seeds are very
rich in protein, oil content is around 18%.
Oil Palm
• Oil palm is a tropical plant that reaches a height of 20–25 m with a life cycle of
about 25 years. Full production is reached 8 years after planting.
• Two kinds of oil are obtained from the fruit: palm oil proper, from the pulp, and
palm kernel oil, from the nut of the fruit (after oil extraction, palm kernel cake is
used as livestock food).
Sunflower
• Sunflower ‘‘seeds’’ are really a fruit, theres an
inedible wall (husk) surrounding the seed that is in
the kernel.
• After oil extraction, the remaining cake is used as a
livestock feed.
• May be stored for longer periods.
• Sunflower adapts well to adverse environmental
conditions and does not require specialized
agricultural equipment and can be used for crop
rotation with soybean and corn.
• Oil yield of current hybrids is in the range 48–52%.
Peanut
• Peanuts are mainly used for human
consumption, in the manufacture of peanut
butter, and as an ingredient for confectionery
and other processed foods.
• Peanuts of lower quality (including the rejects
from the confectionery industry) are used for
oil production, which has a steady demand in
the international market.
• Peanut oil is used in blends for cooking and as
a flavoring agent in the confectionery
industry. The flour left over, following oil
extraction, is of high quality with high protein
content; in pellet form, it is used as a livestock
feed.
Flax
• Flax is a plant with blue flowers. Linen
is made with the threads from the stem
of the plant and the oil from the seeds
is called linseed oil, used in paint
manufacture.
• The cake left over, following oil
extraction, is used as a livestock feed.
• The plant adapts well to a wide range
of temperature and humidity; however,
high temperatures and plentiful rain do
not favor high yields of seed and fiber.
• Flax seeds contain between 30 and
48% of oil, and protein content is
between 20 and 30%.
Castor Seed
• The plant needs a warm and humid period
in its vegetative phase and a dry season for
ripening and harvesting. It requires plenty
of sunlight and adapts well to several
varieties of soils.
• Castor oil is a triglyceride which could be
used for biodiesel making. The oil is non-
edible and toxic owing to the presence of
1–5% of ricin, a toxic protein that can be
removed by cold pressing and filtering.
Cotton
• Among non-foodstuffs, cotton is the most
widely traded commodity.
• After the harvest, it may be traded as raw
cotton, fiber or seeds.
• In cotton mills, fiber and seeds are separated
from raw cotton. Cotton fiber is processed to
produce fabric and thread, for use in the textile
industry. In addition, cotton oil and flour are
obtained from the seed as it is rich in protein
and is used in livestock feed.
Jatropha
• Jatropha is a shrub that adapts well to arid
environments.
• Yield depends on climate, soil, rainfall and
treatment during sowing and harvesting.
Jatropha plants become productive after 3 or 4
years.
• Oil yield depends on the method of extraction; it
is 28–32% using presses and up to 52% by
solvent extraction. Since the seeds are toxic,
jatropha oil is nonedible. The toxicity is due to
the presence of curcasin (a globulin) and
jatrophic acid (as toxic as ricin).
Avocado
• Avocado is a tree between 5 and 15 m in
height.
• Harvesting period varies from 5 to 15 months.
The avocado fruit matures after picking and not
on the tree.
• Oil may be obtained from the fruit pulp and pit.

• The oil content of the fruit is in the range 12–

30%.
Algae
• Microalgae are cultivated in algaecultures.
• Microalgae are microscopic single-cell aquatic plants with the potential
to produce large quantities of lipids (plant oils) that are well suited for
use in biodiesel production.
• There are two main systems of cultivating algae:
• Algae can be cultured in "open-pond" systems and in closed systems.
In open-pond systems algae are vulnerable of being invaded by other algal
species and bacteria. The number of species that have been successfully
cultivated for oil production in an outdoor system is relatively small. In
open systems there is no control about water temperature and lighting
conditions. The advantages of these systems are the low costs and the
high production capacity.
• The second possibility of cultivating algae is in a closed system, a pond system
which is covered by a greenhouse. Mainly for economic reasons these systems
usually are smaller system, but they have many advantages. These systems
allow the cultivation of more species which are protected from other species
from outside. It also extends the growing season.
• Algae can be also grown in a photobioreactor which incorporates some type of
light source. It is a closed system in which everything that the algae needs to
grow (CO2, nutrients, water, light) must be introduced into the system. Also a
covered pond can be considered a photobioreactor. Different types of
photobioreactors include:
• Tanks provided with a light source
• Polyethylene sleeves or bags
• Glass or plastic tubes
Tubular photobioreacter
• Due to the dense growth of the algae, the mixture of water and algae has to be
stirred to allow that light reaches all algae, as light only penetrates the top 7-11
cm in most cultures.
• **Recently the potential of cultivating algae near power plants has been
recognized as the algae can be fed by CO2 emissions.
• This is possible because carbon dioxide and nitrogen oxides are the primary
nutrients for the growth of microalgae.
• Thus oil-rich microalgae, that feed on the emissions of coal, petroleum, and
natural gas power plants, could be produced by integrated systems.
• Today, the private start-up company, GreenFuel, is working to commercialize this
technology.
 Animal Fats
• Animal fats are co-products mainly from meat and fishery
industries. It can be received from cattle, chicken and fish.
• Tallow derived from infected cattle is also considered as an
interesting feedstock. The problem with all these sources is
the discontinuity of supply.
• It is possible that suddenly a high bulk of material is
available followed by a period with no supply. Naturally, all
animal fat is only a co-product and therefore is often
restricted as it has not been produced primarily for a
biodiesel program.
• Nevertheless all these animal fats are characterized by high
amounts of saturated fatty acids resulting in methyl esters
with poor cold temperature properties. This poses
problems in winter.
Waste Oils
• There is a large variety of waste oils available for biofuel production. In general
these waste oils are inexpensive and offer an additional environmental impact by
using substances which would otherwise have to be disposed. The origin of the
oil can be characterized by three types:
• Waste oil from households and restaurants
• Waste oil from food industry
• Waste oil from non-food industry
• Rape, soybean, palm and coconut oils are the waste oils most frequently used in
biodiesel production. The use of these waste vegetable oils (WVO) requires
additional processing to filter out residues and to handle the acids produced by
high temperatures.
Biodiesel Production Process
• Biodiesel is produced from vegetable oils or animal fats and an alcohol, through a
transesterification reaction.
• This chemical reaction converts an ester (vegetable oil or animal fat) into a
mixture of esters of the fatty acids that makes up the oil (or fat).
• Esters have a general formula R – COO - R’ and are made from bonding an alcohol
with organic acids.
• Biodiesel is obtained from the purification of the mixture of fatty acid methyl
esters (FAME).
• A catalyst is used to accelerate the reaction. According to the catalyst used,
transesterification can be basic, acidic or enzymatic.
Basic transesterification reaction with
methanol
Stages of Biodiesel Production Process
• Feedstock preparation
• Oil extraction
• Alcohol-catalyst mixing
• Chemical reaction
• Separation of the reaction products

FEEDSTOCK PREPARATION
• The preparation of seeds involves removal of outer layers of the fruit to expose the
kernels or seeds, and its drying to reduce moisture content. The seeds are
separated from fruits, and the fruits that do not dehisce are cracked open manually.
• The separated seeds or kernels are sieved, cleaned and stored at room
temperature. Seeds can be either dried in the oven or sun dried to appropriate
moisture. The kernels or seeds have to be prepared in such a way that they contain
optimum moisture content for high oil extraction.
Oil Extraction
• The oil extraction of the feedstock is the first process step of both PPO and
biodiesel processing. Regarding the scale of production and the infrastructure,
there are two fundamental production process types for vegetable oils:
• Industrial: centralized production by refining in large industrial plants
• Small scale pressing: decentralized cold pressing directly on farms or in
cooperatives
• In small scale cold pressing facilities, the cleaned oil seeds are exclusively
mechanically pressed at maximum temperatures of 40 ºC. Suspended solids are
removed by filtration or sedimentation.
• As a co-product, the press cake is left with a remaining oil content of usually over
10 %, which is used as a protein-rich fodder (livestock feed) . Due to higher
production costs, the decentralized oil production by farmers is not widely
applied today, although the chance of additional income for farmers is given.
Furthermore, the co-product could be directly used for feeding the animals.
Small scale oil press
• The common way in oil extraction is the treatment of feedstock in centralized
industrial large scale plants.
• First, the feedstock has to be pre-treated. For better illustration purposes, the
processing of rape oil is used here as an example for oil extraction. Within the
pre-treatment the rape seeds have to be dried first, but only if it will be stored
more for than ten days. In this case, the typical water content of rape seeds,
which is about 15 %, has to be reduced to 9 %. Subsequently, the rape seeds are
cleaned.
• Additionally, other seeds that are larger in size, such as sunflower seeds, have to
be peeled. After this treatment seeds are crushed, and temperature and
moisture content are conditioned. The adjustment of a specific moisture content
is important as too high contents make penetration of the solvent difficult,
whereas too low contents enhances compactness and consequently also make
solvent penetration difficult.
• The conditioning of temperature above 80 °C is necessary to deactivate
microorganisms and to avoid smearing of the press through coagulated proteins.
• Additionally the crushed seeds can be better penetrated by the solvent and the
oil flow is better as it is more liquid. After conditioning, the oil seeds are pressed
at these higher temperatures (80 °C).
• Thereby approximately 75 % of the total rape oil content can be extracted. This
pressed raw oil then is filtered and dehydrated and the final pure oil can be used
for further refining into PPO or for biodiesel production.
• When pressing rape seeds, the press cake is left as co-product. It still contains the
remaining 25 % of the total rape seed oil content and therefore is further treated.
• First, the press cake has to be crushed so that the added solvent, which is usually
hexane, can extract the oil at temperatures of up to 80 ºC. The results of this
process step are a mixture of oil with hexane, also called miscella, and the so
called extraction grist. The solvent is separated from both compounds and
recycled to the process. After these process steps, the oil has more undesired
components as in cold pressing.
• They are removed by refining. The end product is an oil designated as fully
refined in edible oil quality.
• The final end product is always unrefined oil. After refining, which is described
subsequently, the plant oil can be directly used as PPO. For the use as biodiesel it
has to be transesterificated
Transesterification process
• The first step is to mix the alcohol for reaction with the catalyst, typically
a strong base such as NaOH or KOH. The alcohol/catalyst is then reacted
with the fatty acid so that the transesterification reaction takes place.
• The catalyst is prepared by mixing methanol and a strong base such as
sodium hydroxide or potassium hydroxide.
• During the preparation, the NaOH breaks into ions of Na+ and OH-. The
OH- abstracts the hydrogen from methanol to form water and leaves the
CH3O- available for reaction.
• Water will increase the possibility of a side reaction with free fatty acids
(fatty acids that are not triglycerides) to form soap (saponification
reaction), an unwanted reaction.
• The three attached carbons with hydrogen react with OH- ions and form glycerin,
while the CH3 group reacts with the free fatty acid to form the fatty acid methyl
ester.
• The reaction typically takes place at between 40-65°C. As the reaction
temperature goes higher, the rate of reaction will increase, typically 1-2 hours at
60 °C versus 2-4 hours at 40°C. If the reaction is higher than 65°C, a pressure
vessel is required because methanol will boil at 65°C. It also helps to increase the
methanol to oil ratio.
• Water is added to both the biodiesel and glycerol to remove unwanted side
products, particularly glycerol, that may remain in the biodiesel.
• The wash water is separated out similar to solvent extraction (it contains some
glycerol), and the trace water is evaporated out of the biodiesel. Acid is added to
the glycerol in order to provide neutralized glycerol
Separation of the Reaction Products
• Takes place by decantation: the mixture of fatty acids methyl esters (FAME)
separates from glycerin forming two phases, since they have different densities;
the two phases begin to form immediately after the stirring of the mixture is
stopped.
• Due to their different chemical affinities, most of the catalyst and excess alcohol
will concentrate in the lower phase (glycerin), while most of the mono-, di-, and
triglycerides will concentrate in the upper phase (FAME).
• Once the interphase is clearly and completely defined, the two phases may be
physically separated.
• After the separation of glycerin, the FAME mixture contains impurities such as
remnants of alcohol, catalyst and mono-, di-, and triglycerides. These impurities
confer undesirable characteristics to FAME, for instance, increased cloud point
and pour point, lower flash point, etc.
• In consequence a purification process is necessary for the final product to comply
with standards.
Purification of the Reaction Products
• The mixture of fatty acids methyl esters (FAME) obtained from the
transesterification reaction must be purified in order to comply with established
quality standards for biodiesel. Therefore, FAME must be washed, neutralized and
dried.
• Successive washing steps with water remove the remains of methanol, catalyst
and glycerin, since these contaminants are water-soluble.
• Care must be taken to avoid the formation of emulsions during the washing steps,
since they would reduce the efficiency of the process.
• The first washing step is carried out with acidified water, to neutralize the
mixture of esters. Then, two additional washing steps are made with water only.
• Finally the traces of water must be eliminated by a drying step. After drying, the
purified product is ready for characterization as biodiesel according to
international standards.
• Glycerin as obtained from the chemical reaction is not of high quality and has no
commercial value. Therefore, it must be purified after the phase separation. In
addition to the high quality glycerin, part of the methanol is recovered for
reutilization in the transesterification reaction (both from FAME and glycerin),
and thus lowering biodiesel production costs.
Glycerin
• Referred to as glycerol, glycerin or glycyl alcohol. Chemically an alcohol, it is a
liquid of high viscosity at room temperature, odorless, transparent, colorless, of
low toxicity and sweet taste.
• The boiling point of glycerin is high, 290 degrees C , and its viscosity increases
noticeably at low temperature, down to its freezing point, 18 degrees C .
• It is a polar substance that can be mixed with water and alcohols, and is also a
good solvent. Glycerin is hygroscopic (ability to absorb moisture from
surrounding environment) and has humectant properties (retaining / preserving
moisture).
Uses
• As an additive in the manufacture of soaps, to improve their properties
• In the manufacture of nitroglycerin for the production of explosives
• In the food industry, for the manufacture of sweets, soft drinks, and pet foods and
in the conservation of canned fruit
• Due to its moisturizing properties, in the cosmetics industry for the manufacture of
creams and lotions
• In the chemical industry, for the fabrication of urethane foams, alkydic resins (organic
polester) and cellophane (thin, transparent sheet made of regenerated cellulose,useful
for food packaging), among other uses
• In the pharmaceutical industry, for the manufacture of ointments, creams and lotions
• In the manufacture of certain inks
• For the lubrication of molds.