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Cost: Coke should be cheap and easily available.

Manufacture of Metallurgical Coke:


(i) Beehive Oven
(ii) Otto Hoffmann oven
(i) Beehive oven: A beehive oven is a fire-brick
chamber having a dome-shaped structure. The
dimensions of a typical oven are 4m and 2.5m high.
The roof is provided with a hole for charging the
coal from the top. Another hole, the discharging
hole is provided in the circumference of the lower
part of the wall. A number of ovens are built in a
row with common walls between neighbouring
ovens.
Fig. 5: Beehive coke oven
Demerits of Beehive ovens: The demerits are
No recovery of byproducts, which are useful
chemicals and are allowed to escape.
Lower coke yield due to partial combustion
Lack of flexibility of operation
(ii) Otto-Hoffmanns oven or By-product Oven: The
beehive ovens have been replaced by chamber ovens
which works on regenerative principle of heat
economy. All the valuable products are recovered
from the outgoing flue gases.
Construction: It consists of no. of narrow rectangular
chambers made of silica bricks.
Fig. 6: A single chamber of Otto Hoffmanns oven
Working: Coal is charged into the chamber.
The coke ovens are heated to 1200
o
C by burning
gaseous fuels.
The process of carbonization takes place layer by
layer in the coal charge.
As the coal adjacent to the oven walls gets heated, a
plastic zone is formed which moves away from the
walls towards the central zone.
As the coal is converted into coke, there is decrease
in volume. This is because of the removal of volatile
matter in the form of tar and gas at about 500
o
C. At
further high temperature, the plastic mass solidifies
into hard and porous mass called coke.
Regenerative principle is employed to achieve as
economical heating as possible.
Regenerators are built underneath the ovens.The flue
gases pass their heat to the checker brick work of
regenerators until the temperature rises to 1000
o
C.
Regenerators work on the principle of alternate
heating and cooling cycles. This is achieved by
periodically changing the direction of flow of gases
through the vertical flues every 30 min or so.
Carbonization of a charge of coal takes about 11-18
hours. After the process is complete, red hot coke is
pushed outside by means of a ram which is electrically
driven. The coke falls into a quenching car. The yield is
75 % of coal.
Fig. 7: Otto Hoffmanns Byproduct coke oven
Recovery of byproducts: The gases and vapours
evolved on carbonization in coke ovens are not
allowed to mix with the combustion and are collected
separately.The coke oven gas is treated separately
for the recovery of the valuable byproducts.
Fig. 8: Coke-Oven gas treatment plant
(i) Recovery of Tar: The gas from the coke ovens is
passed through a tower in which liquor ammonia is
sprayed.Tar and dust get collected in a tank. The
tank is provided with a heating coils to recover
back ammonia.
(ii) Recovery of ammonia: The gases are then
passed through a tower where water is sprayed to
recover ammonia. The ammonia can also be
recovered by dissolving it in H2SO4 to form
(NH4)2SO4, which is then used as a fertilizer.
(iii) Recovery of Naphthalene: The gases are
passed through a cooling tower, where water at a
low temperature is sprayed.The gas is scrubbed
with water until its temp. reduces.
(iv) Recovery of Benzol: The gases are then
introduced into a light oil or benzol scrubber, where
benzene along with its homologue is removed and is
collected at the bottom.
(v) Recovery of H
2
S and other S compounds: are
removed from the coke oven gas after the light oil has
been separated out.



The SO
2
obtained can be used for the manufacturing
of sulphuric acid, which can be used to absorb NH
3

from the coal gas.
O H S Fe S H O Fe
2
3
3 2 2
3
3 2

3 2
2
2
4
2
3 2
2
4
3 2
2
O Fe O FeO
SO FeO O S Fe


Liquid Fuels: The importance of liquid fuels is the
fact that almost all combustion engines run on them.
The largest source of liquid fuels is petroleum. The
calorific value of petroleum is about 40000 kJ/kg.
There are other supplements of liquid fuels such as
coal tar, crude benzol, syntheic liquid fuel made from
coal etc.
Petroleum: The term petroleum means rock oil. It is
also called mineral oil.
Petroleum is a complex mixture of paraffinic, olefinic
and aromatic hydrocarbons with small quantities of
organic compounds containing oxygen, nitrogen and
sulphur.
Composition:

Element Carbon Hydrogen Sulphur Oxygen Nitrogen
Percentage 80-87 11.1-15 0.1-3.5 0.1-0.9 0.4-0.9
The ash of the crude oil is 0.1%.Metals e.g., Silicon,
iron, aluminium, calcium, magnesium, nickel and
sodium.
Crude oil is a mixture of straight chain paraffins and
aromatic hydrocarbons e.g., benzene, toluene,
naphthalenes etc.
Sulphur is present in the form of derivatives of
hydrocarbons such as alkylsulphides, aromatic
sulphides etc. Nitrogen is present in the form of
pyridine, quinoline derivatives, pyrrole etc. Comined
oxygen is present as carboxylic acids, ketones and
phenols.
The objectionable odour of crude petroleum is due to
the presence of sulphur compounds in it.
Classification of Crude Petroleum
Residue obtained
after distillation
Name Contents

Paraffin wax




Asphalt

Paraffin wax and
asphalt
Paraffin
base



Asphaltic
base
Mixed
base
Straight chain
hydrocarbons and
small amounts
naphthenes and
aromatic hydrocarbons
Aromatic and
naphthenic
hydrocarbons
Paraffins, naphthenes
and aromatic
hydrocarbons
Processing of Crude Petroleum:
Petroleum is found deep below the earth crust. The oil
is found floating over salt water or brine. Generally,
accumulation of natural gas occurs above the oil.
Fig. 9: Pumping of oil
Refining of Petroleum
Crude oil reaching the surface, generally consists of a
mixture of solid, liquid and gaseous hydrocarbons
containing sand and water.
After the removal of dirt, water and much of the
associated natural gas, the crude oil is separated into
a no of useful fractions by fractional distillation.
The resultant fractions are then subjected to
purification known as refining of petroleum.
Steps involved in refining of petroleum:
(i) Demulsification: The crude oil coming out from
the well, is in the form of stable emulsion of oil and
salt water, which is yellow to dark brown in colour.
The demulsification is achieved by Cottrells process,
in which the water is removed from the oil by electrical
process. The crude oil is subjected to an electrical
field, when droplets of colloidal water coalesce to form
large drops which separate out from the oil.
(ii) Removal of harmful impurities: Excessive salt
content such as NaCl and MgCl
2
can corrode the
refining equipment. These are removed by washing
with water.
The objectionable sulphur compound are removed by
treating the oil with copper oxide. The copper sulphide
so formed is separated by filtration.
(iii) Fractional Distillation: It is done in tall
fractionating tower or column made up of steel.
In continuous process, the crude oil is preheated to
350-380
o
C in specially designed tubular furnace
known as pipe still.
Fig. 10: Fractional
distillation of crude
petroleum
The hot vapours from the crude are passed through a
tall fractionating column, called bubble tower.
Bubble tower consists of horizontal trays provided with
a no of small chimneys, through which vapours rise.
These chimneys are covered with loose caps, known
as bubble caps. These bubble caps help to provide an
intimate contact between the escaping vapours and
down coming liquid.
The temperature in the fractionating tower decreases
gradually on moving upwards.
As the vapours of the crude oil go up, they become
gradually cooler and fractional condensation takes
place at different heights of column.
The residue from the bottom of the fractionating tower
is vacuum distilled to recover various fractions
Fig. 11: Vacuum distillation of residual oil
There is yet another type of fractional distillation called
Top-flashing.






In top flashing, there is better control of product
composition, but requires more pumps and
instruments and hence is an expensive process.
Fig. 11: Top Flashing
Cracking: Gasoline is the most imp fraction of crude
petroleum. The yield of this fraction is only 20% of the
crude oil. The yield of heavier petroleum fraction is
quite high. Therefore, heavier fractions are converted
into more useful fraction, gasoline.
This is achieved by a technique called cracking.
Cracking is the process by which heavier fractions are
converted into lighter fractions by the application of
heat, with or without catalyst. Cracking involves the
rupture of C-C and C-H bonds in the chains of high
molecular weight hydrocarbons.
e.g:
6
H
3
C
12
H
5
C
Cracking
18
H
8
C
C

36 B.Pt C

174 B.Pt
pentene pentane - n Decane
10
H
5
C
12
H
5
C
Cracking
22
H
10
C



Nearly 50% of todays gasoline is obtained by
cracking. The gasoline obtained by cracking is far
more superior than straight run gasoline.
The process of cracking involves the following
chemical changes:
Higher hydrocarbons are converted to lower
hydrocarbons by C-C cleavage. The product obtained
on cracking have low boiling points than initial
reactant.
Formation of branched chain hydrocarbons takes
place from straight chain alkanes.
Unsaturated hydrocarbons are obtained from
saturated hydrocarbons.
Cyclization may takes place.
Cracking can also be used for the production of olefins
from naphthas, oil gas from kerosene. Cracking can be
carried out by two methods
Thermal Cracking: When it takes place simply by the
application of heat and pressure, the process is called
thermal cracking. The heavy oils are subjected to high
temperature and pressure, when the bigger
hydrocarbons break down to give smaller molecules of
paraffins, olefins etc. The thermal stability among the
constitutents of petroleum fractions increases as
Paraffins < naphthenes < aromatics
(a) Liquid Phase thermal cracking: The charge is
kept in the liquid form by applying high pressures of
the range 30-100 kg/cm
2
at a suitable temperature of
476-530
o
C. The cracked products are separated in a
fractionating column.
The important fractions are: Cracked gasoline (30-
35%), Cracking gases (10-45%); Cracked fuel oil (50-
55%).
(b) Vapour phase thermal cracking: By this method,
only those oils which vapourize at low temperatures
can be cracked. The petroleum fractions of low boiling
range like kerosene oil, are heated at a temp of 670-
720
o
C under low pressure.
Mechanism of thermal cracking: It follows free radical
mechanism.
Initiation

3
CH
2
)
2
(CH
2
H C
2
H C
3
)
2
(CH
3
CH
Heat
3
CH
7
)
2
(CH
3
CH


Propagation
The free radical formed are thermally unstable and
undergo fission at the b-position to yield a new radical
and an olefin.


Catalytic cracking: Cracking is brought about in the
presence of a catalyst at much lower temperatures
and pressures. The catalyst used is mainly a mixture
of silica and alumina. Most recent catalyst used is
zeolite. The quality and yield of gasoline is greatly
improved by this method.
2 2 3 2 2 2 2 3 CH CH CH H C CH CH CH CH

Advantages of catalytic cracking over thermal
cracking:
High temp and pressure are not required in the
presence of a catalyst.
The use of catalyst not only accelerates the cracking
reactions but also introduces new reactions which
considerably modify the yield and the nature of the
products.
The yield of the gasoline is higher.
No external fuel is required for cracking.
The process can be better controlled so desired
products can be obtained.
The product contains a very little amount of
undesirable sulphur because a major portion of it
escapes out as H
2
S gas, during cracking.
It yields less coke, less gas and more liquid products.
The evolution of by-product gas can be further
minimized, thereby increasing t he yield of desired
product.
Catalysts are selective in action and hence cracking
of only high boiling fractions takes place.
Coke forming materials are absorbed by the catalysts
as soon as they are formed.
In an internal combustion engine a mixture of
gasoline vapour and air is used as a fuel.
After the reaction is initiated by a spark, a
flame should spread rapidly and smoothly
through the gas mixture and the expanding
gas drives the piston down the cylinder. In
certain circumstances the rate of oxidation is
so high that the last portion of the mixture
detonates, producing an explosive sound
called knocking
The tendency of fuel constituent to knock is in the
following order
Straight
chain>branched>olefins>cycloparaffins>aromatics
An antiknocking agent is used to increase the
octane number of a fuel.
TEL ( Tetra ethyl lead)
Methyl cyclopentadienyl Manganese tricarbonyl
Ferrocene
Iron pentacarbonyl
Toluene
Iso octane

Octane number: is defined as the percentage of iso
octane present in a mixture of iso-octane and n-
heptane, which has the same knocking characteristics
as that of fuel under examination, under same set of
conditions.
Thus a gasoline with an octane no of 80, would give
the same knocking as a mixture of iso octane and n-
heptane containing 80% of iso octane by volume.
Greater the octane number, greater is the antiknock
property of the fuel.
Cetane Rating: Fuels required for diesel engine are in
contrast to petrol engine fuels, hence a separate scale
is used to grade the diesel oils as they cannot be
graded on octane number scale.
The cetane number of a diesel oil is defined as the
percentage of cetane in a mixture of cetane and a-
methyl naphthalene which will have the same ignition
characteristics as the fuel under test, under same set
of conditions.
Cetane is n-hexadecane
The cetane rating of a fuel depend upon the nature
and composition of hydrocarbon. The straight chain
hydrocarbons ignite quite readily while aromatics do
not ignite easily. Ignition quality order among the
constituents of diesel engine fuels in order of
decreasing cetane no, is as follows:
n-alkanes> naphthenes > alkenes > aromatics
This is an approximate measure of the aromatic
content of a hydrocarbon fuel.
It is defined as the lowest temperature at which a
fuel oil is completely miscible with an equal volume
of aniline.
Aniline is an aromatic compound and aromatics are
more miscible in aniline than are paraffins.
Hence, the lower the aniline point, the higher the
aromatics content in the fuel oil.
The higher the aromatics content, the lower the
cetane number of the fuel.
The aniline point can thus be used to indicate the
probable ignition behavior of a diesel fuel.
The Diesel Index indicates the ignition quality
of the fuel. It is found to correlate,
approximately, to the cetane number of
commercial fuels. It is obtained by the
following equation



Diesel Index and cetane number are usually
about 50. Lower values will result in smoky
exhaust


100
60 int F gravity API Degrees x F po aniline
Index Diesel
o o

Gaseous Fuels
Advantages of gaseous fuels
Least amount of handling
Simplest burners systems
Burner systems require least
maintenance
Environmental benefits: lowest GHG
and other emissions
Gaseous Fuels
Classification of gaseous fuels
(A) Fuels naturally found in nature
-Natural gas
-Methane from coal mines
(B) Fuel gases made from solid fuel
-Gases derived from coal
-Gases derived from waste and biomass
-From other industrial processes
(C) Gases made from petroleum
-Liquefied Petroleum gas (LPG)
-Refinery gases
-Gases from oil gasification
(D) Gases from some fermentation
Gaseous Fuels
Calorific value
Fuel should be compared based on the net
calorific value (NCV), especially natural gas
Typical physical and chemical properties of various gaseous fuels
Fuel
Gas
Relative
Density
Higher Heating
Value kCal/Nm
3

Air/Fuel
ratio m
3
/m
3

Flame
Temp
o
C
Flame
speed m/s
Natural
Gas
0.6 9350 10 1954 0.290
Propane 1.52 22200 25 1967 0.460
Butane 1.96 28500 32 1973 0.870
Type of Fuels
Gaseous Fuels
Natural gas
Methane: 95%
Remaing 5%: ethane, propane, butane, pentane,
nitrogen, hydrogen, CO, carbon dioxide, other
gases
High calorific value fuel
Does not require storage facilities
No sulphur
Mixes readily with air without producing smoke or
soot
Natural gas is finding increasing use as a
domestic, transportation and industrial fuel.
It is used as a raw material for the synthesis
of methanol, formaldehyde and other
chemical compounds.
It is used as a source of H
2
Ammonia used for the process for extracting
nickel from its ore is made by reacting N
2

with natural gas.
Varieties of LPG bought and sold include
mixes that are primarily propane (C
3
H
8
),
primarily butane (C
4
H
10
) and, most
commonly, mixes including both propane and
butane and isobutane depending on the
season in winter more propane, in summer
more butane
[
. Propylene and butylenes are
usually also present in small concentration. A
powerful odorant, ethanethiol, is added so
that leaks can be detected easily
Liquefied petroleum gas (also called LPG, GPL, LP
Gas, or liquid propane gas) is a flammable mixture
of hydrocarbon gases used as a fuel in cooking,
heating appliances and vehicles.
It is used as a feedstock for the manufacture of
various chemicals and olefins by pyrolysis.
Other industrial application includes its use in
portable blow lamps, soldering, welding, annealing
hardening, brazing, steel cutting etc.
It is increasingly used as an aerosol propellant and
a refrigerant, replacing chlorofluorocarbons in an
effort to reduce damage to the ozone layer.
When specifically used as a vehicle fuel it is often
referred to as autogas.
CNG is made by compressing natural gas
(which is mainly composed of methane [CH
4
]),
to less than 1% of the volume it occupies at
standard atmospheric pressure
. It is stored and distributed in hard containers
at a pressure of 200248 bar (29003600
psi), usually in cylindrical or spherical shapes.
Compressed natural gas (CNG) is a fossil fuel
substitute for gasoline (petrol), diesel, or
propane/LPG. Although its combustion does
produce greenhouse gases, it is a more
environmentally clean alternative to those
fuels, and it is much safer than other fuels in
the event of a spill (natural gas is lighter than
air, and disperses quickly when released).
CNG may also be mixed with biogas,
produced from landfills or wastewater, which
doesn't increase the concentration of carbon
in the atmosphere.
Cars and locomotives.

Type of Fuels
Comparing Fuels
Fuel Oil Coal Natural
Gas
Carbon 84 41.11 74
Hydrogen 12 2.76 25
Sulphur 3 0.41 -
Oxygen 1 9.89 Trace
Nitrogen Trace 1.22 0.75
Ash Trace 38.63 -
Water Trace 5.98 -
1. Calculate the weight and volume of air
required for combustion of 3kg of carbon.
2. Calculate the minimum weight of air
required for complete combustion of 1kg of
fuel containing C=90%, H=3.5%, O= 3.0%, S=
0.5%, water=1%, N=0.5% and rest is ash.
3. A gaseous fuel has the following
composition by volume: H=20%, CH4= 5%,
CO= 20%, CO2= 5% and N= 45%
If 50% excess of air is used find the weight of
air acutally supplied per m
3
of this gas
Power Alcohol: Ethyl alcohol is an important liquid
fuel and when it is used in an internal combustion
engines, it is called power alcohol.
Generally gasoline and alcohol are present in the ratio
of 4:1. Its octane no is 90.
Manufacture of Power Alcohol: Ethyl alcohol can be
manufactured from hydrocarbons, carbohydrates,
starches and molasses, waste sulphite liquor from
paper and pulp mills.
Ethyl alcohol is mainly manufactured from molasses.
The formation of alcohol involves the following steps:
(i) Dilution: High concentration of sugars in molasses
(ii) Addition of dilute sulphuric acid: For fermentation
the pH of the solution should be kept between 4 to 5.
(iii) Addition of ammonium salts: When molasses
contain insufficient yeast food, some neutrient
substanceslke ammonium sulphate and ammonium
phosphate are added to overcome the deficiency of
phosphorous and nitrogen.
(iv) Addition of yeast: This is the main step in the
formation of alcohol from mollases. To the solution a
selected strain of yeast is added. The mixture s kept at
a temperature of 30
o
C for 2-3 days.
2
2
5 2
2
6 12 6
6 12 6 6 12 5 2 11 22 12
CO OH H C
Zymase
O H C
O H C O H C
Invertase
O H O H C




(v) Distillation: It is carried out in a specially
designed plant called coffey still.
Distillation of wash/wort
(vi) Azeotropic distillation: The alcohol obtained
after distillation is mixed with benzene or
carbontetrachloride and subjected to distillation.
The benzene or carbontetrachloride distills over
taking away a portion of alcohol and water leaving
behind absolute alcohol.
Advantages of Alcohol blended gasoline:
1. The octane no of alcohol is quite high. Hence on
blending with gasoline, it increases the octane no
of gasoline.
2. There is no decrease in power output or increase in
specific fuel consumption on blending alcohol with
gasoline.
3. The starting difficulties because of high boiling point
of alcohol is overcome, when it is used in blended
form with gasoline.
4. Alcohol-petrol blend has a tendency to absorb any
traces of moisture present.
Disadvantages of Alcohol blended Gasoline:
1. The calorific value of alcohol is low and hence the
alcohol lowers the calorific value of petrol.
2. Since the air required for complete combustion of
blend is less than the air required for petrol.
3. The ratio of flow of blend is to be increased to 1.56
times to that of pure petrol by altering the size of
carburetor jet.