FUELS

Definition and classification of fuels

A fuel can be defined as any combustible substance which during combustion gives large
amount of industrially and / or domestically useful heat.

Heat evolved by burning of fuels is used mainly for heating purposes; it can also perform
other very important functions like coal in locomotive engines; and petrol, in internal combustion
engines are used for doing mechanical works.

Classifications

Fuels can be classified:

(a) On the basis of their occurrence

(1) Natural or Primary fuels: Fuels which are found in nature as such are called
natural fuels. Example: wood, coal, peat, crude petroleum and natural gas

(2) Artificial or Secondary fuels: Fuels which are prepared artificially generally from
primary fuels are called artificial fuels. Example: coke (obtained from coal), petrol,
diesel, kerosene oil (obtained from crude petroleum by fractional distillation).

(b) On the basis of physical state of aggregation

On this basis, there are three types of fuels viz. Solid, liquid and gaseous.

Table 1. Classification of chemical fuels.

Type of fuel Natural or Primary Artificial or Secondary

Solid Wood, peat, lignite, dung, coal Charcoal, coke etc.

Liquid Crude petroleum oil Petrol, diesel

Gaseous Natural gas Coal gas, oil gas, bio-gas,

water gas etc.

1
Characteristics of good fuel:

1. High calorific value

2. Moderate ignition temperature
3. Low moisture content
4. Low non-combustible matter content
5. Moderate rate of combustion
6. Harmless combustion products
7. Low cost
8. Easy to transport
9. Low storage cost

CALORIFIC VALUE

Calorific of a fuel is the total quantity of heat liberated from the combustion of a unit
mass (or unit volume) of the fuel in air or oxygen.

Units of heat:

1. Calorie: Calorie is the amount of heat required to raise the temperature of one gram of
water through 1 OC (ie. Suppose from 15 OC to 16 OC)
2. Kilocalorie: Kilocalorie is the amount of heat required to raise the temperature of 1
kilogram of water through 1 OC
1kcal = 1000 calorie

Units of calorific value

The calorific value is generally expressed in calorie/gram (cal/g) or kilocalorie/kilogram

(kcal/kg) in case of solid or liquid fuel. In case of gaseous fuels, the unit mainly used is
kilocalorie/cubic metre (kcal/m3).

2
COMPARISON BETWEEN SOLID, LIQUID AND GASEOUS FUEL

Solid fuels

Advantages:
1. They are easy to transport
2. They are convenient to store without any risk of spontaneous explosion
3. Their cost of production is low
4. They possess moderate ignition temperature

Disadvantages:

1. Their ash content is high

2. Their thermal efficiency is low
3. Their handling cost is high
4. Their calorific value is low

Liquid fuels

Advantages:

1. They possess high calorific value per unit mass than solid fuels
2. They burn without forming dust, ash etc.
3. They possess moderate ignition temperature
4. They are easy to transport through pipes
5. They can be stored indefinitely without any loss
6. They are clean in use and economic in labour

Disadvantages:

1. The cost of liquid fuel is relatively much higher as compared to solid fuels
2. Costly special storage tanks are required for storing liquid fuels
3. High risk of fire hazards, particularly in case of a highly inflammable and volatile
liquid fuel
4. For efficient burning, specially constructed burners and spraying apparatus are
required

3
Gaseous fuels

Advantage:

1. They can be easily transported through pipes, thereby reducing the labour cost
2. They have lower ignition temperature as compared to solid and liquid fuels
3. They have high heat content and hence, help us having higher temperatures
4. They are free from solid and liquid impurities
5. They burn without the formation of smoke and ash
6. They have high calorific value

Disadvantages:

1. They need special storage tank

2. They are highly inflammable, so chances of fire hazards are high
3. They are costly as compared to solid and liquid fuels

DETERMINATION OF CALORIFIC VALUE

BOMB CALORIMETER

Principle: A known mass of the fuel is burnt and the quantity of heat produced is absorbed in
water and measured. Then the quantity of heat produced by burning of a unit mass of the fuel is
calculated.

Construction: Bomb calorimeter consists of a strong cylinder stainless steel bomb in which the
combustion of fuel is made to take place. It has a lid, which can be screwed to the body of the
bomb so as to make a perfect gas tight seal. The lid is provided with two stainless steel electrodes
and an oxygen inlet valve. To one of the electrode, a small ring is attached. In this ring, a nickel
or stainless steel crucible can be supported. The bomb is placed in a copper calorimeter, which is
surrounded by an air-jacket and water-jackets to prevent heat losses due to radiation. The
calorimeter is provided with an electrically operated stirrer and Beckmann’s thermometer, which
can read accurately temperature difference upto 1/100th of a degree.

4
 Fig. Bomb Calorimeter

Working: A known mass (about 0.5 to 1.0 g) of the given fuel is taken in a clean crucible. The
crucible is then supported over the ring. A fine magnesium wire, touching the fuel sample is
then stretched across the electrodes. The bomb lid is lightly screwed and is filled with oxygen
to 25 atmospheric pressure. The bomb is then lowered in copper calorimeter, containing a known
amount of water. The initial temperature of the water is noted after thorough stirring. The
electrodes are then connected to 6-Volt battery and circuit is completed. The sample burns and
heat is liberated. Uniform stirring of water is continued and the maximum temperature attained is
recorded.

Calculation: Let X = mass in g of fuel sample taken in crucible W

= mass of water in the calorimeter (in g)

w = water equivalent in g of calorimeter, stirrer, thermometer, bomb etc. (=

Wt. of apparatus X Specific heat)

t1 = initial temperature of water in calorimeter

5
 t2 = final temperature of water in calorimeter

L = higher (or gross) calorific value in fuel in cal/g

Therefore, Heat liberated by burning of fuel = xL

And heat absorbed by water and apparatus etc. = (W + w) (t2 – t1)

But heat liberated by fuel = Heat absorbed by water, apparatus etc.

xL = (W + w) (t2 – t1) or HCV of fuel (L) = (W + w) (t2 – t1) cal/g or kcal/g

x

Higher or gross calorific value (HCV)

It is defined as the total amount of heat liberated, when unit mass or unit volume of the
fuel has been burnt completely and the products of combustion are cooled to room temperature.
Hydrogen is found to be present in almost all fuels and when the calorific value of
hydrogen containing fuel is determined experimentally, the hydrogen is converted into steam. If
the products of combustion are condensed to the room temperature, the latent heat of condensation
of steam also gets included in the measured heat, which is then called “higher or gross calorific
value”.

Lower or net calorific value (LCV)

In actual use of any fuel, the water vapour and moisture etc. escape as such along with
hot combustion gases, since they are not condensed. Hence, a lesser amount of heat is available.
So, net or lower calorific value (LCV) is “the heat produced when unit mass or unit volume of
the fuel is burnt completely and the combustion products are allowed to escape”.

Determination of calorific value

1) By Bomb calorimeter

HCV = (W + w) (t2 – t1) cal/g or kcal/g

X

6
 Where W = mass of water in calorimeter in g
w = water equivalent in g of calorimeter
(= Wt. of apparatus X Specific heat)
t1 & t2 = initial and final temperature of water in calorimeter
x = mass in g of fuel sample taken in crucible
LCV = HCV – Latent heat of water vapours formed
LCV = (L – 0.09H X 587) cal/g or kcal/g
Where Latent heat of steam = 587 cal/g

H = percent of hydrogen in fuel

HCV (or GCV) = (W + w) (t2 – t1 + cooling correction) – (acid + fuse correction)

x
Numerical problems

Q. Calculate the gross (HLV) and net calorific (LCV) value of a coal sample having the
following compositions:

C = 80%, H = 7%, O = 3%, S = 3.5%, N = 2.1% and Ash = 4.4%

Solution:

GVC = 1/100 [8080 x C + 34500 (H – 0/8) + 2240 x S]

= 1/100 [8080 X 80 + 34500 (7 – 3/8) + 2240 X 3.5]

= 8828 kcal/kg.

And NCV = GCV – 0.09H X 587

= 8828 – 0.09 X 7 X 587

= 8458 kcal/kg.

Note: Constituent CV (kcal/g)

Hydrogen 34500

7
 Carbon 8080
Sulphur 2240

Q. A sample of coal containing 89% C, 8% H, 3% Ash. When the coal was tested in the laboratory
for its calorific value in the bomb calorimeter, the following data were obtained:
Weight of the coal burnt = 0.85g
Weight of the water taken = 650 g
Water equivalent of bomb and calorimeter = 2500 g
Rise in temperature = 2.5 0C
Cooling correction = 0.03 0C
Fuse wire correction = 10cal
Acid correction = 50cal
Assuming the latent heat of condensation of steam as 580cal/g, calculate the
(i) Gross and
(ii) Net calorific value of the coal in cal/g

Solution:
(i) GCV (or HCV) = (W + w) (t2 – t1 + cooling correction) – (acid + fuse
correction)
x
= (650 + 2500) (2.5 + 0.03) – (50 + 10)
0.85

= 9205.2 cal/g

(ii) NCV (or LCV) = HCV – 0.09H X 580

= 9205.2 – 0.09 X 8 X 580
= 8787.6 cal/g

..................................................................................................................................................

8
 COAL
Coal is formed from the fossilized remains of animals and plants, hence it is known as
fossil fuel. The factors which are in favour of usage of coals in huge tonnage quantities are –
availability, low cost, least risk of fire hazards and easy storage.
The time required for coalification is of the order 107 and 108 years.
Rank is the qualitative measure of carbon content in coal and is defined as the degree or
extent of maturation. The soft coals (peat, lignite and sub-bituminous coals) have low percentage
of carbon content and are known as low-rank coals. In contrast, hard coals (like bituminous and
anthracite) have high percentage of carbon content and are thus classed as high-rank.
The progressive transformation of wood to anthracite can be written as:

Wood Peat Lignite Bituminous Anthracite

ANALYSIS OF COAL
In order to ascertain the quality of coal, it is subjected to two types of analysis:
(a) Proximate analysis
(b) Ultimate analysis

Proximate analysis: Proximate analysis is so called because the data collected vary with the
procedure adopted. It gives valuable information about the practical utility of coal. It includes
determination of moisture, volatile matter, ash and fixed carbon.

Ultimate analysis: It is useful for combustion calculations. It includes determination of ultimate

constituent present in dry coal like carbon, hydrogen, nitrogen, sulphur, ash and oxygen.

Proximate analysis
Proximate analysis involves in the following determinations:
(1) Moisture content: High percentage of moisture is undesirable because –

9
 (a) It increases the cost of coal and its transportation cost. Hence lesser the moisture
content, better the quality of coal as fuel.
(b) It quenches the fire in the furnace
(c) It evaporates during the burning of coal and it takes some of the liberated heat in the
form of latent heat of evaporation. Therefore, moisture content lowers the effective
calorific value of coal.

Determination of moisture
It is the loss of weight of coal when heated at about 1050C in a crucible. A known amount
of the finely powdered coal sample taken in a silica crucible is heated in an electric hot air oven.
Heating is done at a temperature of 105-1100C for about 1hour. After which the crucible is taken
out with the help of tongs, cooled in a desicator and weighed. The process of heating, cooling and
weighing is repeated till the weight of the crucible containing anhydrous coal becomes constant.
Loss in weight is reported as moisture (on percentage basis).

% of moisture = Loss in weight X 100

Wt. of coal taken

(2) Volatile matter:

(a) The volatile matter present in the coal may be combustible gases (eg. Hydrogen,
methane etc.) or non-combustible gases (like CO2 and N2).
The presence of non-combustible gases is always undesirable, since they do
not add to the heat value.
(b) When a coal has high volatile matter content then a large proportion of fuel distils
over as gas or vapour, a large portion of which escape unburnt. So, higher volatile
content in coal is undesirable.
(c) A high volatile matter containing coal burns with (i) a long flame (ii) high smoke
and (iii) low calorific value. Hence, lesser the volatile matter, better the rank of
the coal.

Determination of percentage of volatile matter content

The moisture free coal is taken in silica crucible and covered with a lid. It is then
placed in a muffle furnace, maintained at 9250 ± 200C for 7minutes. The crucible is then

10
taken out and cooled first in air, then inside desiccators and weighed again. Loss in weight is
reported as volatile matter on percentage basis.
Thus, volatile matter is the loss in weight of moisture-free coal when heated in a
crucible in a muffle furnace at about 9500C for 7minutes.

% of volatile matter = Loss in weight due to removal of volatile matter X 100

Wt. of coal sample taken

(3) Ash: Ash is a non-combustible, useless matter which is left behind when all the
combustible substances have been burnt off from the coal. It is undesirable due to the
following reasons:
(a) It reduces the calorific value of coal
(b) It causes the hindrance to the flow of air and heat, thereby decreasing the efficiency
(c) It also increases transporting, handling and storage costs. There is also an additional
cost involved in its disposal
(d) Clickers (ie. fused ash lumps) block the interspaces of the grate, on which coal is
being burnt. This in turn causes obstruction to air supply. Thereby the burning of coal
becomes irregular. Hence, lower the ash content, better the quality of coal.

Determination of Ash

It is the weight of residue obtained after burning a weighed amount of dry coal in an open
crucible (ie. in presence of oxygen or air) at 700 – 7500C for half an hour in a muffle furnace.
Heating, cooling and weighing is repeated till a constant weight is obtained.

% of ash Weight of ash formed X 100

(4) Fixed carbon: After determination of moisture, volatile matter and ash contents, the
remaining material is known as fixed carbon.

11
 It also represents the quantity of carbon (in coal) that can be burnt by a
primary current of air drawn through the hot bed of a fuel.
Higher the percentage of fixed carbon, greater calorific value, smaller is
percentage of volatile matter, moisture content, ashes content, better the quality of
coal.

Determination of fixed carbon It is determined indirectly by deducting the sum total of

moisture, ash and volatile matter from 100.

Percentage of fixed carbon = 100 - % of (moisture + volatile matter + ash)

Ultimate analysis

(1) Determination of carbon and hydrogen: The amount of carbon, the major combustible
constituent of coal depends on the depends on the type of coal and its percentage increases
with rank from lignites to anthracites. Thus, percentage of carbon forms the basis of
classification of coal. Greater the percentage of carbon and hydrogen, better is the coal in
quality and calorific value.

Determination: A known quantity of coal (about 1 – 2 g) is burnt in a current of dry oxygen when
carbon and hydrogen present in coal are oxidized to CO 2 and H2O, respectively.

The gaseous products of combustion are passed through two bulbs. One containing weighed
amount of anhydrous CaCl2 which absorbs water
CaCl2 + 7H2O CaCl2.7H2O

and the other containing weighed amount of KOH which absorbs carbon-dioxide

2KOH + CO2 K2CO3 + H2O

The weight of CaCl2 and KOH in the bulbs are then determined. The increase in weight of CaCl 2
bulb represents the weight of water formed, while the increase in the weight of KOH bulb
represents the weight of CO2 formed.

C + O2 CO2; H2 + ½ O2 H2 O
12 44 2 18

Wt. of carbon (C) = Atomic wt. of C (= 12)

12
Wt. of CO2 (= increase in wt. of KOH tube) Mol. Wt. of CO2 (= 44)

and % of C =Wt. of C X 100

Wt. of coal
Therefore,

% of C = Increase in wt. of KOH tube X 12 X 100

Wt. of coal sample taken X 44

Similarly,
Wt. of Hydrogen (H2) = Atomic wt. of H2 (= 2)
Wt. of H2O (= increase in wt. of CaCl2 tube) Mol. Wt. of H2O (= 18)

% H = Wt. of Hydrogen X 100

Wt. of coal

% of H = Increase in wt. of CaCl2 tube X 2 X 100

Wt. of coal sample taken X 18

Fig. Carbon and Hydrogen determination

(2) Determination of nitrogen:

Importance: Since nitrogen is an inert and incombustible gas, hence its presence is
undesirable. Thus, a good quality coal should have very little nitrogen content.
13
Determination: Nitrogen estimation is carried out by Kjeldahl’s method.
(a) About 1g of accurately weighed powdered coal is heated with conc. H 2SO4 along
with K2SO4 and CuSO4 in a long-necked flask (called Kjeldahl’s flask)
(b) When clear solution is obtained (ie. when whole nitrogen is converted into
ammonium sulphate), it is treated with excess of NaOH to liberate ammonia
(c) The ammonia thus produced is distilled over and absorbed in a known volume (v 1)
of standard H2SO4 solution (N/10)

N2 + H2SO4 (NH4)2SO4 2NaOH 2Na2SO4 + 2NH3

+ 2H2O

2NH3 + H2SO4 (NH4)2SO4

Fig. Estimation of nitrogen by Kjeldahl’s method

(d) The volume of unused H2SO4 is then determined by titrating against standard NaOH
solution (N/10). Let v2 ml of 0.1N NaOH was required to neutralize excess acid.
Thus, the amount of acid neutralized by liberated ammonia (from coal) is
determined.
Amount of H2SO4 used to neutralize the ammonia evolved -
= N/10 X v1 – N/10 X v2 = 0.1 (v1 –v2)

14
 = 0.1 (v1 –v2)
1000
Wt. of N = 0.1 (v1 –v2) X 14
1000
% of N = Wt. of N X 100
Wt. of coal sample taken (1g)
= 0.1 (v1 –v2) /1000 X 14 X 100 = 0.1 (v1 – v2) X
1.4
1
Therefore, % of N = 0.1 (v1 – v2) X 1.4

(3) Determination of Sulphur

Importance: Although sulphur increases the calorific value, on oxidation it produces
harmful and corrosion causing SO2 and SO3 gases. Oxides of sulphur (formed as
combustion products) pollute the atmosphere. S is usually present to the extent of 0.5
– 3% and is derived from ores like iron pyrites, gypsum etc. mines along with the coal
mines.
Presence of sulphur is highly undesirable in coal to be used for making coke for
iron industry since it is transferred to the iron metal and badly affects the quality and
properties of steel.
Determination: A known amount of coal is burnt completely in bomb calorimeter in a
current of oxygen, by which sulphur present in coal is oxidized to sulphates.
The ash from the bomb calorimeter is extracted with dil. Hydrochloric acid. The
acid extract is then treated with barium chloride solution to precipitate sulphate as BaSO 4.
The precipitate of BaSO4 is filtered, washed, dried and heated to constant weight.
S O2 SO42- BaCl2 BaSO4
32 233

Wt. of S = Atomic wt. of S (32)

Wt. of BaSO4 Mol. Wt. of BaSO4 (233)
Let weight of BaSO4 precipitate is W2 g

15
 Hence, Wt. of S = 32 X W2 g
233
Let wt. of coal taken = W1 g
Therefore,
% of S in coal = Wt. of BaSO4 obtained X 32 X 10
Wt. of coal sample taken in bomb X 233

% of S in coal = W2 X 32 X 100
W1 233

(4) Determination of ash

Determination is carried out as in proximate analysis
(5) Determination of oxygen
Importance: Oxygen is present in combined form with hydrogen in coal and thus,
hydrogen available for combustion is lesser than the actual one.
High oxygen content coals have high inherent moisture and low calorific value.
An increase in 1% oxygen content decreases the calorific value by about 1.7%. Thus, a
good quality coal should have low % of oxygen.
Determination: It is determined indirectly by deducting the combined % of C, H, N, S and
ash from 100.

% of oxygen = 100 - % of (C + H + N + S + ASH)

Numerical problems

Q1. A sample of coal was analyzed as follows:

Exactly 1.5g of coal was weighed into a silica crucible. After heating for 1hour at 1000C, the
residue weighed 1.415g. The crucible was then covered with a vented lid and strongly heated
for exactly 7minutes at 950 ± 200C. The residue weighed 0.528g. The crucible was then heated
without the cover, until a constant weight was obtained. The last residue was found to weigh
0.251g. Calculate

16
 (i) The percentage results of the above analysis
(ii) To which type of analysis does the above description below? Why is the analysis
so named?

Solution:
(i)
(a) Moisture (%) = Loss in weight X 100
Weight of coal taken
= 1.5 – 1.415 X 100
1.5
= 5.67 %

(b) Volatile matter (%)= Loss in weight due to removal volatile matter X 100
Weight of coal sample taken
= 1.415 – 0.528 X 100
1.5
= 59 %

(c) Ash (%) = Weight of ash left X 100

Weight of coal taken
= 0.254 X 100
1.5
= 16.93 %

(d) Fixed carbon (%) = 100 - % of (moisture + volatile matter + ash)

= 100 – (5.67 + 59 + 16.93)
= 18.4 %

(ii) This type of analysis is known as proximate analysis because the data collected
vary with the procedures adopted.

.........................................................................................................

17
 CARBONIZATION

The process of converting coal into coke is called Carbonization. When a coking coal is
heated in the absence of air, the porous, hard and strong residue left is called Coke. Coke is white,
lustrous, dense, porous and coherent mass.
Depending on the behaviour of coal, when it is heated in the absence of air, we can classify
coal into the following categories:
(i) Non-coking coals: Which undergoes practically no fusing effects; such coals are also
called free-burning coals.
(ii) Coking coals: Such coals give porous, hard and strong residue after heating in the
absence of air. The residue is usable for metallurgic purpose, and is known as coke.
Coking coals are suitable for metallurgical purposes because they are quite strong and
do not crush under the weight of ore, flux plus coal in big furnace.
There are some coals which became soft, plastic and fuse together to form a large
coherent mass. Such coals are Caking coals.

COALS

Caking coals Non-caking coals

Non-coking coals Coking coals

All types of coals cannot be converted into coke. Only that coal can be converted
into coke which has a tendency to soften, swell and stick together during strong heating in the
absence of air. This property is found only in bituminous type of coal and hence only bituminous
coal can be coked.

18
 Caking coals with high volatile matter content are used for gas manufacture whereas
caking coals of somewhat lower volatile matter content are used for the manufacture of
metallurgical coke and are thus termed as coking coals.

METALLURGICAL COKE
Good coke for metallurgy should possess the following requisites:
(1) Purity: It should have moisture, ash, sulphur and phosphorus contents as low as possible.
Moisture lowers the calorific value and increases the heating expenses. Excess of ash
hinders the heating process, lowers the calorific value and lead to slag formation. On
burning S and P give undesirable products like SO 2, P2O3, P2O5 which adversely affect
the quality of the metal being produced. Additionally, in presence of sulphur, the coke
brittles.
(2) Porosity: Coal should be porous, so that oxygen can easily come in contact with the carbon
coke, thereby helping in complete combustion at a high rate.
(3) Strength: The coke should be compact, hard and strong to withstand dropping abrasion
as well as the pressure of the over-burden (ore + fuel + flux) in the furnace.
(4) Size: The size of metallurgical coke should be neither too big nor too small. In case the
size is too big, uniformity of heating is never maintained. But on the other hand, if the
coke size is too small, choking will result.
(5) Cost: Coke should be cheap and easily available near the site of the metallurgical plant,
so that the transportation cost is low.
(6) Calorific value: The calorific value of the coal should be high.

TYPES OF CARBONIZATION OF COAL

Depending on the temperature of carbonization, these are two types of carbonization
viz.
(1) Low-temperature carbonization
(2) High-temperature carbonization

Low-temperature carbonization: In this process, the heating of coal is carried out at 500
– 7000C and is mainly carried out for the manufacture of domestic fuel.

High-temperature carbonization: High temperature carbonization is carried out at 900 –

1,2000C and is mainly carried out for the manufacture of metallurgical coke.

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CHARACTERISTICS OF LOW AND HIGH TEMPERATURE CARBONIZATION:

Sl. Characteristics Low temperature High temperature

No. carbonization carbonization
1 Heating temperature 500 – 7000C 900 – 12000C
2 Yield of coke 75 – 80% 65 – 75%
3 Volatile matter content in coke 5 – 15% 1 – 3%
4 Mechanical strength of coke Poor Good
5 Calorific value of gas 6500 – 9500kcal/m3 5400 – 6000kcal/m3
6 Quantity of by product gas produced 130 -150m3/tonne 300 – 390m3/tonne
7 Coke produced Soft Hard
8 Smoke produced on burning coke Smokeless Smoky
9 In gas, % of
(a) Aromatic hydrocarbons Lower Higher
(b) Straight-chain hydrocarbon Higher Lower
10 Use of coke For domestic purposes For metallurgical
purposes

20
 PETROLEUM
(Cracking of hydrocarbon, knocking, octane number and cetane number, synthetic petrol
and petrochemicals and bio-fuels)
Petroleum or crude oil (Latin words, petra = rock; oleum = oil), is a dark greenish- brown,
viscous oil found deep in earth’s crust. It is composed mainly of hydrocarbon compounds
containing oxygen, nitrogen and sulphur.

Cracking of hydrocarbons
Cracking is defined as the decomposition of high molecular weight hydrocarbons of high
boiling points into simpler, low molecular weight hydrocarbons of low boiling points.
C10H22 cracking C5H12 + C5H10
B.P = 1740C n-pentane pentane
B.P = 360C
There are two methods of cracking:
(1) Thermal cracking
(2) Catalytic cracking

Thermal cracking
When the heavy oil is subjected to high temperature and pressure in the absence of
catalyst, it is called “thermal cracking”. In thermal cracking, the bigger hydrocarbons (higher
molecular weight hydrocarbons) break down to give smaller molecules of the paraffins, olefins
plus some hydrogen. It is of two types viz. liquid and vapour phase thermal cracking.

Catalytic cracking
When the heavy oil undergoes cracking at a lower temperature in the presence of catalyst
is called “catalytic cracking”. The quality and quantity of gasoline produced by cracking are
greatly improved by using suitable catalysts like aluminium silicate, Al 2(SiO3)3 or alumina,
Al2O3. Catalytic cracking requires much lower temperature and pressure compared to thermal
cracking. There are two types of catalytic cracking viz. fixed bed and moving bed catalytic
cracking.

21
Advantages of catalytic cracking over thermal cracking
(1) The yield of petrol is higher because catalysts are selective in their action and therefore,
they permit the cracking of only the high boiling hydrocarbons. Thus, the evolution of by-
product gases can be minimized.
(2) The product of catalytic cracking contains a higher amount of aromatics and hence, it
possesses better anti-knocking characteristic.
(3) Isomerisation to branched-chain compounds (iso-paraffins) occur, thereby better petrol
is produced.
(4) The production cost is very low since high temperature and pressure are not needed.
(5) The cracking process can be controlled, so the desired products can be obtained.

Mechanism of cracking process

Thermal and catalytic cracking processes involve free radical and carbonium ion
intermediates, respectively.
(1) Thermal cracking:
Like any other free radical reaction, thermal cracking processes involve three
well defined processes viz. initiation, propagation and termination steps.
(a) Initiation: High molecular weight hydrocarbon (eg. Nonane) undergoes
homolytic cleavage at high temperature of cracking to generate free radicals.

(b) Propagation: The free radicals formed in the initiation steps undergo fission at the β-
position to yield a new radical and an olefin.

The radical having no C – C bond in the β-position give rise to hydrogen free
radical.

22
(c) Termination: These cleavage reactions terminate by the coupling of unstable free
radical intermediates.

CH3 + CH3 CH3CH3

CH3 CH2 + CH3 CH2 CH3CH2CH2CH3

CH3 CH2 + H CH3CH3

(2) Catalytic cracking:

Catalytic cracking is believed to involve carbonium ion intermediates. Due to
thermal cracking, first a small amount of alkenes is formed which gets protonated at the
acidic sites of the catalyst.

The nonyl carbonium ion (II) then undergoes β-cleavage to yield a smaller
carbonium ion and an alkene.

Aromatic systems keep the rings intact and only the side chains are lost as
alkenes.

23
KNOCKING
In an internal combustion engine, a mixture of gasoline vapour and air is used as fuel.
After the initiation of combustion, by spark in the cylinder, the flame should spread rapidly and
smoothly through the gaseous mixture; thereby the expanding gas drives the piston down the
cylinder. The ratio of the gaseous volume (v1) in the cylinder at the end of the suction- stroke to
the volume (v2) at the end of compression stroke of the piston is known as the ‘Compression
ratio’. As v1 ˃ v2 CR = v1/v2 ˃ 1.
The efficiency of an internal combustion engine increases with the increase in
compression ratio which is dependent on the nature of constituents present in the gasoline used.
In certain circumstances, due to the presence of some constituents in the gasoline used, the rate
of oxidation becomes so great that the last portion of the fuel-air mixture gets ignited
instantaneously, producing an explosive violence, known as ‘Knocking’.
Free radical chain reaction leading to cracking and oxidation of the hydrocarbons is
probably the mechanism of chemical reactions that lead to knocking.

Consequences of knocking
 Knocking decreases power output
 Mechanical damage by overheating of the cylinder parts

Knocking tendency decreases in the order –

n-alkanes ˃ mono-substituted alkanes ˃ cyclo alkanes ˃ alkenes ˃ polysubstituted alkenes ˃
aromatics.

OCTANE NUMBER
Octane number (or rating) of a gasoline (petrol) or fuel is the percentage of isooctane in
a mixture of iso-octane, an n-heptane, which matches the fuel under test in knocking
characteristics.

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 In this way, an “80-octane” fuel is the one which is having the same combustion
characteristics as an 80:20 mixture of iso-octane and n-heptane.
It has been found that n-heptane knocks very badly and hence, its anti-knock value has
arbitrarily been given ‘Zero’. On the other hand, iso-octane gives very little knocking, so its
anti-knock value has been given as ‘100’.

IMPROVEMENT OF ANTI-KNOCK CHARACTER OF A FUEL

The octane number of internal combustion fuels can be raised by the addition of such
extremely poisonous materials as Tetraethyl lead, (C2H5)4Pb or TEL and Diethyl telluride,
(C2H5)2Te. In motor spirit (or motor fuel), about 0.5ml and in aviation fuels, about 1.0 to 1.5ml
of TEL is added per litre of petrol.
TEL is converted into a cloud of finely divided lead oxide particles in the cylinder and
these particles react with hydrocarbon peroxide molecules formed, thereby, reducing the chances
of any early detonation. Ironically, deposit of lead oxide is harmful to the engine life.
Consequently, in order to help the simultaneous elimination of lead oxide formed from the engine,
a small amount of ethylene dibromide is also added to petrol. Ethylene dibromide removes lead
oxide as volatile lead bromide along with the exhaust gases. The presence of sulphur compounds
in petrol reduces the effectiveness of the TEL.

Pb + CH2Br – CH2Br PbBr2 + CH2 = CH2

Ethylene dibromide Lead bromide Ethylene

Unleaded Petrol
Unleaded petrol is one where in the enhancement of octane rating (or octane number) is
accomplished without the addition of lead compounds. The main additives are isopentane,
isooctane, methyl tertiary butyl ether (MTBE) etc.
The major advantages of unleaded petrol are that it permits the use of catalytic converted
attached exhaust in automobiles without destroying the active sites.

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CETANE NUMBER AND DIESEL ENGINE
Cetane number
It is a measure of the ease with which a fuel will ignite under compression. It is the
percentage of hexadecane in a mixture of ‘hexadecane’ and ‘2-methylnaphthalene’, which has
the same ignition characteristics as the fuel in question.
The cetane number of a diesel fuel can be raised by the addition of small quantity of
certain ‘pre-ignition dopes’ like ethyl nitrite, iso-amylnitrite, acetone peroxide etc.

Major differences between octane number and cetane number:

No. Octane Number Cetane Number

1 It is the percentage of iso-octane in a It is the percentage of hexadecane and 2-

mixture of iso-octane and n-heptane, methyl naphthalene which have the same
which matches the fuel under test in ignition characteristics of the diesel in
knocking characteristics question.

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2 It is used for finding suitability of It is used for finding suitability of a diesel
gasoline or any other internal fuel.
combustion engine fuel.

3 The octane number of internal The cetane number of diesel fuel can be
combustion (i.c) fuels can be raised by raised by the addition of small quantity of
the addition of tetraethyl lead (C2H5)4Pb certain ‘pre-ignition dopes’ like ethyl
or TEL and diethyl telluride (C2H5)2Te. nitrite, isoamylnitrite, acetone peroxide etc.

4 Hydrocarbons which are poor diesel Ignition quality order among hydrocarbon
fuels are quite good gasoline fuels. constituent of a diesel fuel is as follows:
n-alkanes ˃ naphthalenes ˃ alkenes ˃
branched alkenes ˃ aromatics. Thus,
hydrocarbons which are poor gasoline fuels
are quite good diesel fuels.

5 Straight chain hydrocarbons molecules Straight chain hydrocarbons molecules are

are worst fuels, as they have low octane best as they have high cetane number.
number.

SYNTHETIC PETROL
Petrol is synthesized by any of the following methods:
(1) Polymerization:
The gases obtained as a by-product from cracking of heavy oils etc. contain olefins
(like ethylene, propene and butane) and alkanes (such as methane, ethane, propane and
butane). When this gaseous mixture is subjected to high pressure and temperature, it
polymerizes to form higher hydrocarbons, resembling gasoline called ‘polymer gasoline’.

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The polymerization is of two types:
(i) Thermal polymerization: Polymerization in which the polymerization of cracked
gases is carried out at 500-6000C and 70-350 kg/cm2 pressure. The product is gasoline
and oil mixture, which are separated by fractionation.
(ii) Catalytic polymerization: Polymerization is carried out in the presence of catalyst like
phosphoric acid. In this case, lower temperature of 150-2000C is employed. Products
are gasoline and unpolymerized gas. The latter is separated and recycled for
polymerization.

(2) Fischer-Tropsch method:

Water gas (C + H2O CO + H2), produced by passing steam over heated
coke, is mixed with hydrogen. The gas is purified by passing through Fe 2O3 (to remove
H2S) and then into a mixture of Fe2O3. Na2CO3 (to remove organic sulphur compounds).
The purified gas is compressed to 5 to 25 atm and then led through a converter (containing
a catalyst) maintained at about 200-3000C. A mixture of saturated and unsaturated
hydrocarbon results.

n-CO + 2nH2 C11H2n + nH2O

n-CO + (2n+1) H2 C11H2n+2 + nH2O

The reaction is exothermic, so out-coming hot gaseous mixture is led to a cooler,

where a liquid resembling crude oil is obtained. The crude obtained is then fractionated
to yield:
(i) Gasoline and (ii) High boiling heavy oil

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 Fig. Fischer-Tropsch method

PETROCHEMICALS
Petrochemicals are the chemicals and chemical products which are made from raw
materials derived from petroleum and its fractions. They are also known as ‘petroleum
chemicals’.
Alkanes, alkenes, benzene and its homologous are derived from petroleum and its
fraction. These are used as raw materials for the manufacture of industrially important chemicals
such as ethanol, acetic acid, ammonia, acetone, styrene etc. these chemicals are further used in
industries for the production of solvents, explosives, drug , paints, dyes, fibre, rubbers, plastics
etc.

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