15.

2 PRODUCTION OF FUELS

Objectives

By the end of this sub-topic students should be able to:

 Describe the process of fermentation.

 Outline the fractional distillation of crude oil.
 Describe the destructive distillation of coal and wood.
 Describe the production of biodiesel from Jatropha oil.

Fermentation

 Fermentation is the process of using yeast to convert carbohydrates

into alcohol.

 In the fermentation of ethanol, glucose is converted to ethanol and

carbon dioxide through the action of enzymes (zymase) in the yeast:

Glucose → Carbon dioxide + Ethanol

C6H12O6 → 2CO2 + 2C2H5OH

 Living organisms called yeast provide the enzymes needed to

catalyse the reaction. The conditions needed for fermentation include:
o A moderate temperature of 25°C to 50°C.
o Water (provided by the glucose solution).
o An absence of oxygen (air must be kept out).

 The reaction would not happen fast enough at colder temperatures and
the enzyme would be denatured at higher temperatures.

 It is important that the mixture is kept in anaerobic conditions

(without oxygen) in a sealed container. This is for two reasons:

- Firstly, fermentation is the consequence of the anaerobic

respiration of yeast: if oxygen was present, the yeast would
respire aerobically and no fermentation would take place;

- Secondly, any oxygen present could oxidise the ethanol into

ethanoic acid, a major component of vinegar, which is
undesirable for the drinking purposes of ethanol.
  Fermentation is a slow process and stops when the ethanol
concentration reaches about 15%. The ethanol is separated from the
reaction mixture using fractional distillation.

Fig 15.2.1 Fractional distillation

 The dilute ethanol solution is placed in a flask at the bottom of a

fractionating column attached to a Liebig condenser. The flask is then
heated to over 78oC but less than 100oC, which are the boiling points
of ethanol and water respectively, and the ethanol then rises ahead of
the water solvent, collects in the Liebig condenser and is condensed
into a more concentrated ethanol solution, with a concentration of up
to 95%, which collects in a separate flask beyond the Liebig
condenser.
  Different concentrations of ethanol are present in different alcoholic
drinks:

- Beer typically has a strength of 4%.

- Wine typically has a strength of up to 20%.

- Vodka, gin and most other spirits typically have strengths of

35% to 50%.
 Ethanol made by fermentation is a renewable fuel because plants
provide the glucose needed, absorbing carbon dioxide from the
atmosphere as they grow. When the ethanol is burned, the carbon
dioxide returns to the atmosphere.

Biogas
 Biogas is a biofuel produced from the anaerobic fermentation of
carbohydrates in plant material or waste (e.g. food peelings or
manure) by bacteria.
 Anaerobic fermentation is a biological process in which microorganisms
break down biodegradable material in the absence of oxygen creating
two important products: biogas and digestate.
 Biogas is mainly composed of methane, carbon dioxide and other trace
gases. However, the proportion of methane within the biogas can vary
between 50% and 80%, depending on whether some oxygen is able to
enter at the beginning or during the process.
 If oxygen is present, the bacteria will respire aerobically and will
produce a gas with a higher proportion of carbon dioxide and a lower
proportion of methane.
 Biogas can be produced on a small scale in a biogas
generator/digester, which can be made of simple materials.
 A biogas digester is an airtight chamber that facilitates the
anaerobic degradation of sludge and/or biodegradable waste (e.g.
animal manure, kitchen and garden wastes). It also facilitates the
collection of the biogas, a mixture of methane (CH4) and carbon
dioxide (CO2) produced in the fermentation processes in the digester.
 The carbohydrate-containing materials are fed in, and a range of
bacteria anaerobically ferment the carbohydrate into biogas. The
remaining solids settle to the base of the digester and can be run off to
be used as fertiliser for the land.
  Anaerobic micro-organisms can decompose all kinds of organic
materials. Of these, short chain hydrocarbons, such as sugars, are
easiest to decompose.
 Longer chain hydrocarbons, such as celluloses are more difficult to
decompose and the digestion process will therefore take longer.
 Woody materials that contain long chain hydrocarbons, such as lignin,
are not suitable for decomposition by anaerobic micro-organisms

Fig 15.2.2 Bio-digester

 The gas forms in the slurry and collects at the top of the chamber,
mixing the slurry as it rises. The pressure exerted by the rising gas
 can be used to transport the gas to the collection vessel or directly to
where it is going to be used.
 If a bigger, more sophisticated biogas generator is used, biogas can
also be produced on a large scale.
 Biogas is naturally produced in landfill sites as bacteria anaerobically
break down our rubbish, but normally the methane escapes into the
atmosphere where it contributes to global warming.
 If a pipe network with holes in it can be built into the landfill site - and
the methane is prevented from escaping into the atmosphere by
covering the site - then the methane can be collected via the pipe
network.
 The methane can then be used as a fuel to generate electricity or heat.
This is an example of biogas generation on a commercial scale.

Advantages
 Generation of renewable energy.
 Small land area required (most of the structure can be built
underground).
 Can be built and repaired with locally available materials.
 No electrical energy required.
 Combined treatment of animal, human and solid organic waste.
 Conservation of nutrients.
 Long service life.
 Low to moderate capital costs; low operating costs.
Disadvantages
 Requires expert design and skilled construction.
 Substrates need to contain high amounts of organic matter for biogas
production.
 Incomplete pathogen removal, the digestate might require further
treatment.
 Limited gas production below 15°C.
 Requires seeding (start-up can be long due to the low growth yield of
anaerobic bacteria).
Separating crude oil

 Crude oil is subjected to the process of refining in which it is separated

into fractions by fractional distillation.
 Fractional distillation is a method of separating and purifying liquid
mixtures. It separates liquids with different boiling points.
 The crude oil is heated to about 370°C and the vapours passed into a
fractionating tower which is about 60m high.

Fig 15.2.3 Oil refinery processes

 The column is hotter at the bottom and cooler at the top.

 Fractions that collect at the top have lower boiling points than those at
the bottom.
 As hydrocarbon gas travels up the column, the temperature decreases
and the hydrocarbon will start to turn into liquid. It condenses and can
be tapped off.
  Some hydrocarbon gases have very low boiling points such that they
do not condense in the tower.
 Other large hydrocarbons in the crude oil remain as liquid and are
removed from the bottom of the column as residue.

Uses of fractions

 All hydrocarbons burn in air to form water and carbon dioxide and
releasing a lot of heat.
Primary fractions of crude oil

Fraction Approximate boiling Comments and uses

point and carbon
atoms
Gas fraction Below 40˚C  A mixture of
(refinery gases) C 1 - C7 methane ethane,
propane and butane.
 Further separated
into:
1. Gaseous heating
fuel (as Liquid
Petroleum Gas-
LPG).
2. Unsaturated
hydrocarbons
used to
manufacture
plastics.
3. Solvents
.
Petrol (gasoline) 30˚C - 180˚C  Undergoes the
C6 - C 12 process of
reforming.
 Additives are added.
 Used as fuel for
cars.
 Naphtha 110˚C – 195˚C  Used as a raw
C5 – C16 material for the
chemical industry.
 Used for producing
high octane petrol
(gasoline) through
catalytic reforming.
Kerosene (or 150˚C - 240˚C  Treated to remove
paraffin) C11 - C16 unsaturated
compounds.
 Used as jet fuel, as
domestic heating oil
and as paraffin for
small lamps and
heaters.
Diesel 220 ˚C – 250 ˚C  Used as fuel for
C15 – C25 diesel engines on
buses, Lorries, cars
and railways.
 Some is also
cracked to form
other organic
compounds and to
form petrol.
Fuel (heavy) oil 250 ˚C – 360 ˚C  Used as fuel for
C20 – C70 ships, industrial
furnaces.
 Distilled to produce:
1. Waxes, polishes
and greases.
2. Lubricating oils.
Residues Above 350 ˚C  Used to make
(bitumen) >C70 bitumen, it is a thick
black material mixed
with rock and chips
to make the top
surfaces of roads.

Destructive Distillation of Coal

Coke is a fuel in its own right which can be used in homes and factories. But
it is largely used as a reducing agent in the extraction of metals from their
ores. It is also used in making fuel gases like water gas which is a mixture of
carbon monoxide and hydrogen.

Another by product namely coal tar which is a mixture of different carbon

compounds that can be used to make soap, fats, dyes plastics perfumes,
drugs, pesticides and explosives.

The other by product, ammonia is used for making fertilizers such as

ammonium sulphate, ammonium superphosphate.

The coal gas, also called as a town gas is a mixture of hydrogen, methane
and carbon monoxide which are combustible making the coal gas an
excellent fuel having high calorific values.

 Coke and charcoal are readily prepared by the destructive distillation of

coal and wood, respectively.
 Destructive distillation differs from ordinary distillation in that the
substances first decompose at a high temperature, and part or all of the
decomposition products are then distilled.
 This process of heating coal in the absence of air is called destructive
distillation of coal.
 When coal is heated in the absence of air, complex compounds of carbon
undergo decomposition to form such substances as benzene, toluene,
naphthalene, anthracene, phenol, etc
 These substances pass off as a vapour and are condensed into a liquid
called coal tar by cooling. Because the boiling point of carbon is extremely
high, the carbon that is present in coal is left as a residue. Carbon
prepared in this manner is called coke.
 When wood is heated in the absence of air, the complex carbon
compounds undergo decomposition to form volatile products and a
residue of carbon called charcoal.
 Neither coke nor charcoal is pure carbon. The mineral content originally
present in the coal or wood is still present in the coke or charcoal. The
most important volatile products resulting from the distillation of wood
are methyl alcohol, CH3OH, acetone, (CH3)2CO, and acetic acid, CH3COOH.
 The destructive distillation of coal can be carried out in the laboratory.
 The apparatus is set up as shown in the figure below:
Fig 15.2.4 Destructive distillation

Finely powdered coal taken in a test tube is heated. As the coal breaks down
coke, coal tar, ammonia and coal gas are produced. Coal tar collects at the
bottom of the second test tube with water and coal gas escapes out through
the side tube. The ammonia produced is absorbed in the water forming
ammonia liquor (ammonium hydroxide). The black residue left in the tube
after coal is thermally decomposed is coke.

Procedure: Set-up the apparatus shown above. Fill test tube B about ½
full of water. Water in the test tube cools and condenses the vapours.
Half fill tube “A” with finely powdered coal and heat strongly. From time
to time while heating, test the gas escaping from jet “C” with a burning
splint. Continue heating until no further change occurs. Note the
appearance of the liquid which condenses in the bottle. When test tube
“A” cools, remove the residue and examine it.
 Destructive Distillation of Wood: Remove the coke from test tube “A” and
the liquid from bottle “B”. Repeat the experiment using wood instead of
coal. Do not use new equipment. Check to see if a combustible gas is
evolved. Note the appearance and amount of the liquid which condenses
in bottle “B”. Examine the residue.

Biodiesel
 It 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.

Advantages of the use of Biodiesel

• Renewable fuel, obtained from vegetable oils or animal fats.
• Low toxicity, in comparison with diesel fuel.
• Degrades more rapidly than diesel fuel, minimizing the environmental
consequences of biofuel spills.
• Lower emissions of contaminants: carbon monoxide, particulate
matter, aromatic hydrocarbons and aldehydes.
• Lower health risk, due to reduced emissions of carcinogenic
substances.
• No sulphur dioxide (SO2) emissions which causes respiratory diseases
and acid rains.
• 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.
• It is the only alternative fuel that can be used in a conventional diesel
engine, without modifications.
• Used cooking oils and fat residues from meat processing may be used
as raw materials

Disadvantages of the use of Biodiesel

 • Slightly higher fuel consumption due to the lower calorific value of
biodiesel.
• Slightly higher nitrous oxide (NOx) emissions than diesel fuel.
• 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.
• 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. It must be noted
that these disadvantages are significantly reduced when biodiesel is
used in blends with diesel fuel.

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 soyabean,
palm, sunflower, peanut, used vegetable oils, and Jatropha.
 Methanol is the most frequently used alcohol.

Jatropha
 Jatropha is a shrub that adapts well to arid environments.
 It requires little water or additional care; therefore, it is adequate for
warm regions with little fertility.
 Jatropha plants become productive after 3 or 4 years, and their
lifespan is about 50 years. Oil yield depends on the method of
extraction; it is up to 52% using presses.
 Jatropha seeds are toxic, jatropha oil is non-edible. The toxicity is due
to the presence of curcasin (a globulin) and jatrophic acid (as toxic as
ricin).

Biodiesel Production using Jatropha

 Biodiesel is produced from jatropha (a vegetable oil) and an alcohol,
through a transesterification reaction.
 Fig 15.2.5 Jatropha seed and Jatropha tree

 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).
 Biodiesel is obtained from the purification of the mixture of fatty acid
methyl esters. A catalyst is used to accelerate the reaction.
 According to the catalyst used, transesterification can be basic, acidic
or enzymatic.
 The integrated process to produce bio-diesel from Jatropha has four
main stages:
Fig 15.2.6 Biodiesel Process Flow

1. Extraction
o The most common way of extracting the Jatropha seed oil
is through a mechanical press, either manually or
electrically powered.
o This process is not very efficient, with only about 50-60%
of oil being extracted from the seed, and the rest is left in
the seed residue which can be further extracted using
solvent extraction.
2. Filtration and sedimentation
o After the mechanical pressing, the oil is passed through a
fine wire mesh which traps all solid particle of a
considerable size.
o The wire mesh is continually monitored for the
accumulation of particles.
o Particles trapped by the wire mesh are mainly the remains
of the crushed seeds.
o The oil is then passed on to the sedimentation tanks.
 o In the sedimentation tank, the oil is allowed to settle for
24 hours allowing for the settling of suspended particles
that may have bypassed filtration (e.g. clay particles that
mostly come with seeds)
o The oil is then pumped into the reactors where
transesterification occurs.

3. Transesterification
o Transesterification is the process of chemically reacting a
fat or oil with an alcohol in a presence of a catalyst.
o The alcohol used for this process is usually methanol or
ethanol.
o The catalyst is usually potassium hydroxide.
o The main product of transesterification is biodiesel and the
co-product is glycerin.
o Two types of reactors are used, which are continuously
stirred tank jacketed reactor and non-jacketed pump
agitated reactor.
o The catalyst (KOH) is mixed with methanol to produce
methoxide in a separate reactor.
o Methanol and potassium hydroxide are mixed using the
reaction ratio of 10:1. It is an exothermic reaction.
o The methoxide produced is fed into the reactors together
with the jatropha oil to produce methyl esters (biodiesel).
o The reaction is complete after the formation of two phases,
glycerol at the bottom and biodiesel at the top.
o Glycerin is denser than biodiesel.
o The reaction mechanism for the biodiesel production is
illustrated below:
4. Decanting
o After transesterification, the product is pumped to the
setter tanks.
o The product is allowed to settle under gravity and separate
resulting in two layers of biodiesel and glycerol.
o Glycerin settles at the bottom and the lighter biodiesel
settles on top.
o Glycerol is sucked by means of a centrifugal pump into
storage tanks.
o Biodiesel is also pumped to storage tanks.