Fuels

Fuel is a combustible substance which during

combustion gives large amount of heat.
There are chemical fuels, nuclear fuels and fossil
fuels.
Classification of Fuels
These can be classified on the basis of their
occurrence and physical state
On the basis of occurrence they are of two types:
Primary Fuels: Fuels which occur in nature as such
are called primary fuels. E.g., wood, peat, coal,
petroleum, and natural gas.
Secondary Fuels: The fuels which are derived from
the primary fuels by further chemical processing are
called secondary fuels. E,g., coke, charcoal,
kerosene, coal gas, producer gas etc.
(ii) On the basis of physical state these may be
classified as:
Solid Fuels
Liquid Fuels
Gaseous Fuels
Calorific value: It is defined as the total quantity of
heat liberated when a unit mass of a fuel is burnt
completely.
Units of Calorific value:

System Solid/Liquid Gaseous

Fuels Fuels
CGS Calories/gm Calories/cm3
MKS k cal/kg k cal/m3
B.T.U BTU/lb BTU/ft3

The quantity of heat can be measured in the

following units:
(i) Calorie: It is defined as the amount of heat
required to raise the temperature of 1gm of water by
1oC 1 calorie = 4.184 Joules
(ii) Kilo Calorie: 1 k cal = 1000 cal
(iii) British thermal unit: (B. T. U.) It is defined as
the amount of heat required to raise the temperature
of 1 pound of water through 1oF.
1 B.T.U. = 252 Cal = 0.252 k cal
(IV) Centigrade heat unit (C.H.U): It is defined as
the amount of heat required to raise the temperature
of 1 pound of water through 1oC.
1k cal = 3.968 B.T.U.
= 2.2 C.H.U. restore
Characteristics of Good Fuel:
(i) Suitability: The fuel selected should be most suitable for
the process. E.g., coke made out of bituminous coal is
most suitable for blast furnace.
(ii) High Calorific value
(iii) Ignition Temperature: A good fuel should have moderate
ignition temperature.
(iv) Moisture content: Should be low
(v) Non combustible matter content
(vi) Velocity of combustion: It should be moderate
(vii) Nature of the products
(viii) Cost of fuel, (ix) Smoke, (x) Control of the process
Gross and net calorific Value
Gross Calorific Value: It is the total amount of heat
generated when a unit quantity of fuel is completely
burnt in oxygen and the products of combustion are
cooled down to the room temperature.
As the products of combustion are cooled down to
room temperature, the steam gets condensed into
water and latent heat is evolved. Thus in the
determination of gross calorific value, the latent heat
also gets included in the measured heat. Therefore,
gross calorific value is also called the higher calorific
value.
The calorific value which is determined by Bomb
calorimeter gives the higher calorific value (HCV)
Net Calorific Value: It is defined as the net heat
produced when a unit quantity of fuel is completely
burnt and the products of combustion are allowed to
escape.
The water vapour do not condense and escape with
hot combustion gases. Hence, lesser amount than
gross calorific value is available. It is also known as
lower calorific value (LCV).
LCV=HCV-Latent heat of water vapours formed
Since 1 part by weight of hydrogen gives nine parts
by weight of water i.e.
H  1O  H O
2 2 2 2
Therefore,
LCV=HCV-weight of hydrogen x 9 x latent heat of
steam
= HCV-weight of hydrogen x 9 x 587
Determination of Calorific value
1. Determination of calorific value of solid and non
volatile liquid fuels: It is determined by bomb
calorimeter.
Principle: A known amount of the fuel is burnt in
excess of oxygen and heat liberated is transferred to
a known amount of water. The calorific value of the
fuel is then determined by applying the principle of
calorimetery i.e. Heat gained = Heat lost
Bomb Calorimeter
Calculations
Let weight of the fuel sample taken = x g
Weight of water in the calorimeter = W g
Water equivalent of the Calorimeter, stirrer, bomb,
thermometer = w g
Initial temperature of water = t1oC
Final temperature of water = t2oC
Higher or gross calorific value = C cal/g
Heat gained by water = W x t x specific heat of water
= W (t2-t1) x 1 cal
Heat gained by Calorimeter = w (t2-t1) cal
Heat liberated by the fuel = x C cal
Heat liberated by the fuel = Heat gained by water and
calorimeter
x C = (W+w) (t2-t1) cal
C=(W+W)(t2-t1) cal/g
x
Net Calorific value:
Let percentage of hydrogen in the fuel = H
Weight of water produced from 1 gm of the fuel =
9H/100 gm
Heat liberated during condensation of steam
= 0.09H  587 cal
Net (Lower calorific value) = GCV-Latent heat of
water formed
= C-0.09H  587 cal/gm
Corrections: For accurate results the following
corrections are also incorporated:
(a) Fuse wire correction: As Mg wire is used for
ignition, the heat generated by burning of Mg wire
is also included in the gross calorific value. Hence
this amount of heat has to be subtracted from the
total value.
(b) Acid Correction: During combustion, sulphur and
nitrogen present in the fuel are oxidized to their
corresponding acids under high pressure and
temperature.
S  O  SO
2 2
2SO  O  2H O  2H SO H = -144,000 Cal
2 2 2 2 4
2 N  5O  2H O  4HNO H = -57,160 Cal
2 2 2 3
The corrections must be made for the heat liberated
in the bomb by the formation of H2SO4 and HNO3.
The amount of H2SO4 and HNO3 is analyzed by
washings of the calorimeter.
For each ml of 0.1 N H2SO4 formed, 3.6 calories
should be subtracted.
For each ml of 0.01 HNO3 formed, 1.43 calories must
be subtracted.

(C) Cooling correction: As the temperature rises

above the room temperature, the loss of heat does
occur due to radiation, and the highest temperature
recorded will be slightly less than that obtained. A
temperature correction is therefore necessary to get
the correct rise in temperature.
If the time taken for the water in the calorimeter to
cool down from the maximum temperature attained, to
the room temperature is x minutes and the rate of
cooling is dt/min, then the cooling correction = x  dt.
This should be added to the observed rise in
temperature.
Therefore, Gross calorific value
C=(W+w)(t2-t1+Cooling correction)-[Acid+ fuse
corrections] / Mass of the fuel.
Theoretical calculation of Calorific value of a Fuel:
The calorific value of a fuel can be calculated if the
percentages of the constituent elements are known.

Substrate Calorific value

Carbon 8080

Hydrogen 34500

Sulphur 2240
If oxygen is also present, it combines with hydrogen to
form H2O. Thus the hydrogen in the combined form is
not available for combustion and is called fixed
hydrogen.
Amount of hydrogen available for combustion = Total
mass of hydrogen-hydrogen combined with oxygen.
1
H 2  O2  H 2O
2
1g 8g 9g
Fixed Hydrogen = Mass of oxygen in the fuel
Therefore, mass of hydrogen available for combustion
= Total mass of hydrogen-1/8 mass of oxygen in fuel
=H-O/8
Dulong’s formula for calculating the calorific value is
given as:
Gross calorific Value (HCV)
1 O
 [8080C  34,500( H  )  2,240 S ]kcal / kg
100 8

Net Calorific value (LCV)

9H
 [ HCV   587]kcal / kg
100
 [ HCV  0.09 H  587]kcal / kg
FUEL
part -2
Solid Fuels: Primary as well as secondary are widely
used in domestic and industrial purposes.
e.g., wood, coal, charcoal and coke.
Wood: Wood has been used as a fuel from ancient
times. Due to large scale deforestation, wood is no
longer used except in forest areas where wood is
available at a low cost.
Wood when freshly cut contains 25-50% moisture.
Normally it is used in air dried condition with 10-15
percent moisture content.
The calorific value of air dried wood is about 3500-
4500 kcal/kg.
When wood burns, the ash content is low but the
oxygen content is very high. This makes even dry
wood a fuel of low calorific value.
Wood charcoal is obtained by destructive distillation of
wood.
The major use of wood charcoal is for producing
activated carbon.
Coal: coal is regarded as a fossil fuel produced from
the vegetable debris under conditions of high
temperature and pressure over million of years.
The transformation of the vegetable debris to coal
takes place in two stages:
(a) Biochemical or peat stage: During this stage, the
plant materials were attacked by various micro
organisms.
(b) Chemical stage or metamorphism: In this stage,
the peat deposit buried under sedimentary deposits
lose moisture and volatile components under the
effect of high temperature and pressure.
The peat gets enriched in carbon whereas its oxygen
content decreases.
The spongy peat transforms into hard brittle coal
gradually. The time required for the formation of
young brown coal is of the order of 107 years.
Classification of Coal: Coals are mainly classified on
the basis of their degree of coalification from the
parent material, wood. When wood is converted into
coal, there is gradual increase in the concentration of
carbon and decrease in the percentage of oxygen and
nitrogen.
Coal is given a ranking depending upon the carbon
content of the coal from wood to anthracite.
Type of Percentage (dry, mineral matter % calorific
coal free basis) moist value
C H O N VM ure

Wood 45-50 5-6 20-40 0-0.5 - 70-90 4000-

4500
Peat 45-60 3.5-6.5 20-45 0.75-3 45-75 70-90 4125-
5280
Brown Coal 60-75 4.5-5.5 17-35 0.75-2 45-60 30-50 6600-
7100
6600-
Bituminous 75-90 4.0-5.5 20-30 0.75-2 11-50 10-20 8800
coal

8470-
Anthracite 90-95 3-4 2-3 0.5-2 3.8-10 1.5-3.5 8800
Analysis of Coal
Coal is analysed in two ways:
1. Proximate analysis

2. Ultimate analysis

The results of analysis are generally reported in the

following ways:
As received basis
Air dried basis
Moisture free basis (oven dried)
Moisture and ash free basis
Proximate Analysis
The data varies with the procedure adopted and
hence it is called proximate analysis.
It gives information about the practical utility of coal.
Proximate analysis of coal determines the moisture,
ash, volatile matter and fixed carbon of coal.
1. Moisture Content: Air dried moisture is
determined by heating a known amount of coal to
105-110 oC in an electric hot air oven for about one
hour. After one hour, it is taken out from the oven
and cooled in a dessicator and weighed.
Percentage of moisture= Loss in weight 100

Weight of coal taken
•Excess of moisture is undesirable in coal.

•Moisture lowers the heating value of coal and takes away

appreciable amount of the liberated heat in the form of latent
heat of vapourisation.
•Excessive surface moisture may cause difficulty in handling
the coal.
•Presence of excessive moisture quenches fire in the furnace.

2. Volatile Matter: consists of a complex mixture of gaseous

and liquid products resulting from the thermal decomposition of
the coal. It consists of mainly combustible gases such as H2,
CO, CH4 and other hydrocarbons
It is determined by heating a known weight of
moisture free coal sample in a covered platinum
crucible at 950  20oC for 7 minutes.
Percentage of volatile matter =
Loss of weight due to removal of volatile matter 100

Weight of coal sample taken

Significance
A high percent of volatile matter indicates that a large
proportion of fuel is burnt as a gas.
The high volatile content gives long flames, high
smoke and relatively low heating values.
For efficient use of fuel, the outgoing combustible
gases has to be burnt by supplying secondary air.
High volatile matter content is desirable in coal gas
manufacture because volatile matter in a coal
denotes the proportion of the coal which will be
converted into gas and tar products by heat.
Ash: Coal contains inorganic mineral substances
which are converted into ash by chemical reactions
during the combustion of coal.
Ash usually consists of silica, alumina, iron oxide and
small quantities of lime, magnesia etc.
Ash content is determined by heating the residue left
after the removal of volatile matter at 700  50oC for
½ an hour without covering
 Weight of the residue left 100

Percentage of ash =
Weight of the coal

Ash can be classified as intrinsic ash and extrinsic

ash.
The mineral matter originally present in vegetable
matter from which the coal was formed is called
intrinsic ash. It consists of oxides of Na, K, Mg, Ca and
Si.
The mineral matter like clay, gypsum, dirt which gets
mixed up during mining and handling of coal constitute
the extrinsic ash which remains as a residue after the
combustion. E.g., CaSO4, CaCO3, Fe2O3 etc.
The high percentage of ash is undesirable. It
reduces the calorific value of coal.
In furnace grate, the ash may restrict the passage of
air and lower the rate of combustion.
High ash leads to large heat losses and leads to
formation of ash lumps.
The composition of ash and fusion range also
influences the efficiency of coal.
When coal is used in boiler, the fusion temperature
of ash is very significant. Ash having fusion
temperature below 1200oC is called fusible ash and
above 1430oC is called refractory ash.
Apart from loss of efficiency of coal, clinker formation
also leads to loss of fuel because some coal particles
also get embedded in the clinkers.
Fixed Carbon: Fixed carbon content increases from
lignite to anthracite. Higher the percentage of fixed
carbon greater is its calorific value and better is the
quality of coal.
The percentage of fixed carbon is given by:
Percentage of fixed carbon = 100-[% of
moisture+volatile matter+ash]
Significance: Higher the percentage of fixed carbon,
greater its calorific value
•The percentage of fixed carbon helps in designing the
furnace and shape of the fire-box because it is the
fixed carbon that burns in the solid state.
Ultimate analysis:
It is carried out to ascertain the composition of coal.
Ultimate analysis includes the estimation of carbon,
hydrogen, sulphur, nitrogen and oxygen.
1. Carbon and Hydrogen: A known amount of coal is
taken in a combustion tube and is burnt in excess of
pure oxygen.
C  O  CO
2 2
H  1O  H O
2 2 2 2
 Fig 3. Estimation of carbon and hydrogen
2KOH  CO  K CO  H O
2 2 3 2
CaCl  7 H O  CaCl .7 H O
2 2 2 2
44 g of CO2 contain = 12 g of carbon
Y g of CO2 contain = 12  y
44
 Percentage of carbon  12  y 100
44 weight of coal taken
18 g of water contain = 2 g of hydrogen
Z g of water contain  2  zg of hydrogen
18
Percentage of hydrogen  2  z 100
18 weight of coal taken

Significance:
Calorific value of a fuel is directly related to its
carbon content.
A higher percentage of carbon reduces the size of
the combustion chamber
High percentage of hydrogen also increases the
calorific value of coal. The content of hydrogen in
coals varies between 4.5 to 6.5 percent from peat to
bituminous stage.
2. Nitrogen: Nitrogen present in coal sample can be
estimated by Kjeldahl’s method.
Nitrogen  H SO Heat
 ( NH ) SO
2 4 42 4
The contents are then transferred to a round bottomed
flask and solution is heated with excess of NaOH.
The ammonia gas thus liberated is absorbed in a
known volume of a standard solution of acid used.
 Fig 4. Estimation of nitrogen by Kjeldahl’s method

The unused acid is then determined by titrating with

NaOH. From the volume of acid used by NH3
liberated, the percentage of nitrogen can be
calculated.
( NH ) SO 2NaOH
   Na SO  2 NH  2H O
42 4 2 4 3 2

NH  H SO  ( NH ) SO
3 2 4 42 4
3. Suphur: A known amount of coal is burnt completely in
bomb calorimeter in presence of oxygen. Ash thus formed
contains sulphur of caol as sulphate, which is extracted with dil
HCl. The acid extract is then treated with BaCl2 solution to
precipitate sulphate as BaSO4.

The precipitate is filtered, washed, dried, and weighed, from which

sulphur in coal cab be computed as:
Carbonization of Coal (Manufacture of Coke)
It is the process of heating the coal in absence of air to
a sufficiently high temperature, so that the coal
undergoes decomposition and yields a residue which
is richer in carbon content than the original fuel.
Caking and coking of coals: some coals have a
tendency to soften and swell at higher temperatures,
to form a solid coherent mass with porous structure.
Such coals are called caking coals. The residue
formed is called coke. If the coke is hard, porous and
strong, than the coal, from which it is formed, it is
called coking coal. All coking coals are caking coals
but all caking coals are not coking coals.
This property is found only in bituminous type of coal.
Coals with a high percentage of volatile matter are not
fit for coking and are used for gas making. The coals
having 20-30 % volatile matter are good coking coals.
Process of carbonization:
First moisture and occluded gases are driven off.
At about 260-270oC carbon, water, H2S, some low
molecular alkenes and alkanes are evolved.
At about 350oC the decomposition of coal is
accompanied by evolution of gases and elimination of
vapours takes place.
At about 400oC, caking coal becomes soft and plastic.
At about 700oC, hydrogen is evolved
Above 800oC, main gaseous products are evolved
Gases evolved from the plastic mass, expand it to give
foam like appearance.
At further high temperatures this foam like mass
solidifies to form a solid mass with porous structure
called coke.
Types of carbonization
(i) Low temperature carbonization

(ii) High temperature carbonization

(i) Low temperature carbonization: When the
destructive distillation of coal is carried out at
temperatures between 500-700oC.
It is practiced for the production of semi coke. Which
is also called soft coke.
The yield of coke is about 75-80 %.
The coke thus produced contains 5 to 15 % volatile
matter.
The various products of low temperature
carbonization are semi coke, low temperature tar,
crude low temperature spirit and gas.
LTC plants normally use low rank coals. These low
rank coals produce excessive smoke on burning.
Semi coke from LTC is highly reactive and can be
easily ignited into a smokeless flame
The gas which is obtained as a byproduct has higher
calorific value of about 6500-9500 kcal/m3.
(ii) High temperature carbonization: It is carried out
at 900-1200oC. HTC is used for the production of pure,
hard, strong and porous metallurgical coke containing
1-3 % volatile matter. The yield of the coke is 65-75%.
The byproducts-gas and tar have greater amounts of
aromatic hydrocarbons. The gas which is obtained has
lower calorific value of about 5000-6000 kcal/m3 than
that produced in LTC; but the yield of the gas is higher.
The coke obtained is very much harder than the coke
obtained from LTC process and hence is called hard
coke.
Metallurgical coke: The properties of coke depend
on porosity, reactivity and the amount of volatile
matter retained by coke during carbonization. Coke
is mainly used as a heat source and reducing
agent in metallurgy. A good coke in metallurgical
process should possess the following
characteristics:
(i) Purity: The metallurgical coke should contain
lower percentage of moisture, ash, sulphur and
phosphorous.
(ii) Porosity: The coke should be porous so as to
provide contact between carbon and oxygen.
(iii) Strength: The coke used in metallurgical process
should have high strength so as to withstand the
weight of the ore, flux etc. in the furnace.
(iv) size: Metallurgical coke should be of medium
size.
(v) Combustibility: Coke should burn easily. The
combustibility of coke depends on the nature of the
coal, carbonization temperature and reaction
temperature.
(vi) Calorific value: It should be high.
(vii) Reactivity: Reactivity of coke is its ability to react
with CO2, steam, air and oxygen. The reactivity should
not be too high. The reactivity toward CO2 represent
the reduction of CO2
CO ( g )  C (s)  2CO( g )
2
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-Hoffmann’s 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 Hoffmann’s oven
Working: Coal is charged into the chamber.
The coke ovens are heated to 1200oC 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 500oC. 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 1000oC.
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.
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 Benzene: The gases are then sprayed with
petroleum, when benzene and its homologues are removed.
(v) Recovery of H2S and other S compounds: are removed
from the coke oven gas after the light oil has been separated
out.

Fe O  3H S  Fe S  3H O
2 3 2 2 3 2
2Fe S 4O  2FeO  3SO
2 3 2 2
4FeO  O  2Fe O
2 2 3
The SO2 obtained can be used for the manufacturing of
sulphuric acid, which can be used to absorb NH3 from the coal
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 Name Contents
after distillation
Paraffin wax Paraffin Straight chain
base oil hydrocarbons and
small amounts
naphthenes and
aromatic hydrocarbons
Aromatic and
Asphalt Asphaltic naphthenic
base oil hydrocarbons
Paraffin wax and Mixed Paraffins, naphthenes
asphalt base oil 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
The demulsification is achieved by Cottrell’s 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 MgCl2 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 heated to about
400 oC 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.

Fig. 11: Top Flashing

In top flashing, there is better control of product

composition, but requires more pumps and
instruments and hence is an expensive process.
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:
 C H Cracking C H
 C H
10 22 5 12 5 10
Decane n - pentane pentene
B.Pt 174ο C B.Pt  36ο C

C H Cracking
  C H C H
8 18 5 12 3 6

Nearly 50% of today’s gasoline is obtained by

cracking. The gasoline obtained by cracking is far
more superior than straight run gasoline.
The process of cracking involves the full 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/cm2 at a suitable temperature of
476-530 oC. 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 oC under low pressure.
Mechanism of thermal cracking: It follows free radical
mechanism.
Initiation
CH (CH ) CH Heat  H C
  CH (CH ) C  H (CH ) CH
3 27 3 3 23 2 2 22 3
Propagation
The free radical formed are thermally unstable and
undergo fission at the b-position to yield a new radical
and an olefin.

CH 3  CH 2CH 2  CH 2  C H 2  CH 3  CH 2  CH 2

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.
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 H2S 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.
 Knocking and Anti-knocking
In a spark-ignition petrol engine, a phenomenon that occurs when
unburned fuel-air mixture explodes in the combustion chamber
before being ignited by the spark. The resulting shock waves
produce a metallic knocking sound. Loss of power occurs, which
can be prevented by reducing the compression ratio, re-designing
the geometry of the combustion chamber, or increasing the octane
number of the petrol.(formerly by the use of tetraethyl lead anti-
knock additives, but now increasingly by MTBE – methyl tertiary
butyl ether in unleaded petrol). An antiknock agent is a gasoline
additive used to reduce engine knocking and increase the fuel's
octane rating.
The typical antiknock agents in use are:
Tetra-ethyl lead (phased out)
Methyl cyclo pentadienyl manganese tricarbonyl (MMT)
Ferrocene, Iron pentacarbonyl, Toluene, Isooctane
Octane rating of a spark ignition engine fuel is a
measure of the resistance to detonation or knocking
compared to a mixture of iso -octane (2,2,4-tri methyl
pentane, an isomer of octane) and n- heptane. It is a
numerical representation of the antiknock properties of
motor fuel, compared with a standard reference fuel,
such as isooctane, which has an octane number of 100.
Octane rating does not relate to the energy content of
the fuel .It is only a measure of the fuel's tendency to
burn in a controlled manner, rather than exploding in an
uncontrolled manner.
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 > branched alkanes
> aromatics
Aniline Point
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.