Module-II

FUELS

In this present age of rapid industrial development the power requirement is

increasing day-by-day. Heat energy is the main source of power . Burning of carbon, an
exothermic reaction, produces heat energy. So the carbon compounds have been used as the main
source of heat energy. The primary or main sources of fuels are wood, coal and petroleum. They
are available in the earth’s crust and are called fossil fuels.

A fuel is a substance, which on proper burning gives large amount of heat used for domestic
and industrial purposes. They contain carbon as a main constituent.

Fuel is a combustible substance ,during combustion of it the atoms of C,H,S and

N etc are combine with oxygen with simultaneous liberation of heat and light.
Ex: C + O2 → CO2 +94 K cals
2H2+O2 → 2H2O +68.5 K cals
The main sources of fuels are coal and petroleum oils available in earth crust and they are called
Fossil fuels. The other sources of fuels are
(i) radioactive elements and
(ii) The Sun
Calorific value of a fuel is the total quantity of heat liberated when a unit mass or volume of the
fuel is completely burnt. Heat energy is measured in terms of calorie or kilocalorie Calorie is the
quantity of heat required to raise the temperature of 1 gram of water through 1 C
1kcal=1000 Calories
Gross calorific value of a fuel is defined as the total quantity of heat liberated when a unit mass
of the fuel is completely burnt and the combustion products are cooled to room temperature

Gross calorific value = Heat of reaction + Latent heat of steam

produced + sensible heat obtained by cooling the combustion products to room temperature.

The net calorific value of a fuel is the actual amount of heat available when unit mass of the
fuel is completely burnt and combustion products are allowed to cool.

Net Calorific value = gross calorific value – (Latent heat of steam+ sensible heat on cooling of
the products of combustion)

2.1.6 Liquid Fuels: Refining of Petroleum Process: Products of Petroleum

distillation and their uses :- Petroleum is the naturally available liquid fuel. It is
a dark greenishbrown viscous oil found deep in earth's crust. It is composed of
various hydrocarbons with small amount of other organic compounds as
impurities.
The process of purification and separation of various fractions present in petroleum
by fractional distillation is called refining of petroleum. Refining is done in oil
refineries.
It is the process of separation of various components of a liquid
mixture based on the difference in their boiling points by repeated evaporation and
condensation.
The Crude oil is treated with copper oxide to remove sulphur impurities. Then it is
repeatedly washed with sulphuric acid to remove basic impurities. It is then
washed with sodium hydroxide to remove acidic impurities. Then it is subjected to
Fractional Distillation and various fractions are collected.
[Link] Fractions Temperature Uses
1. Gases Below 30 C o Used as industrial and domestic Fuel
2. Petroleum ether 30oC to 80oC Used as a solvent
3. Gasoline or Petrol 40 to 180 C o o C Used as a solvent fuel and in dry cleaning
4. Kerosene Oil 180 -250 C o o C Used as illuminant and fuel

Petroleum Petroleum or crude oil is a naturally occurring brown to black

coloured viscous oil formed under the crust of earth, on shore or off shore.
Chemically it is a mixture of various hydrocarbons with small amounts of N,
O, S compounds.
The approximate composition of petroleum is C = 80 - 84% H = 10 - 14 % S
= 0.1 - 0.5 % N+ O = Negligible
Classification Petroleum is classified on the basis of various types of
hydrocarbons.
i) Paraffin based oil - Contains mainly n - alkanes (Ex : Pennsylvanian and
gulf coast oil)
ii) Asphalt base oil - Contains aromatic and alicyclic hydrocarbons. (Ex:
Californian oil) iii) Mixed base oil - Contains higher proportion of aromatics
and naphthenes (cyclo alkanes). (Ex : Mexican oil)

Refining of Petroleum (or) Crude Oil

Definition The process of removing impurities and separating out the oil
into various fractions having different boiling points is known as refining of
petroleum.
Cracking Definition: Cracking is a process by which the hydro carbons of high
molecular mass are decomposed into hydrocarbons of low molecular mass by
heating in the presence or absence of a catalyst . Generally Aluminum silicates are
used as catalyst.
Gas oil and Kerosene contain hydrocarbons of high molecular mass and boiling.
They are unsuitable as fuel in automobiles. Hence they are decomposed into
hydrocarbons of low molecular mass and low boiling point.
There are two types of cracking process for engine fuel production :
thermal cracking and, catalytic cracking Vis breaking, and coking are also cracking
procedures for fuel oil etc.
Thermal cracking take place through the creation of HC free radicals by C-to-C
bond scission
The feed is heated to around 500 -600 OC and 70 -100 bars and passed into a
soaking chamber where cracking takes place. The cracked products are
fractionated. The product is relatively unstable and requires the use of antioxidants
and other treatments to prevent gum formation in use. It has relatively poor MON.

Catalytic Cracking:- It is the most important and widely used process for
converting heavy refinery streams to lighter products –to increase the ratio of light
to heavy products from crude oil.
Compared to thermal cracking, it has higher yields, improved quality product for
gasoline (not for diesel fuel) and superior economics.
A fluidized bed of catalyst is used –feed is introduced into it. Catalyst flows from
one vessel to another through a pipe (between reactor and regenerator). Cracked oil
vapor pass to fractionating towers where smaller molecules are separated from
heavier products (gas, catalytic naphtha, cycle oils and residue).
Aluminum silicate known as zeolite is used as a catalyst –has high activity and
suppress the formation of light olefins.
Hydrocracking and steam cracking mechanisms are also used.

Other mechani[Link] Alkylation is a process for producing a high-octane gasoline

component (alkylate) by combining light olefins with isobutane in the presence of
a strongly acidic catalyst (sulfuric or hydrofluoric acid).
Isomerization is a process for converting straight chain paraffins to branch chain –
used to provide isobutane feed for the alkylation process or to convert relatively
low-octane quality of straight paraffins to more valuable branch chain molecules.
eg. n-pentane with RON 62 can be converted to isopentane with RON 92
Process involves contacting HCs with a catalyst (platinum on a zeolite base) and
separating any unchanged straight paraffins for recycle through the unit. The
product is clean burning and has better RON quality.

Polymerization is a process where light olefins such as propene and butanes are
reacted together to give heavier olefins which have good octane quality and low
vapour pressure in gasoline.
Most commonly used catalyst is phosphoric acid on keiselguhr.
The product is almost 100 % olefinic and has relatively poor MON compared with
RON. eg.

CH3CH2CH=CH2 + CH3CH=CH2 → CH3(CH2)4CH=CH2

Butane propene heptene
KNOCKING
The rate of ignition of the fuel gradually increases and the final portion of the fuel-
air mixture gets ignited instantaneously producing an explosive sound known as
“Knocking”.
5.7.1 Causes of knocking in S.I (Petrol) engines
In a petrol engine fuel used as a mixture of gasoline vapor and air at 1:17 ratio
The mixture is compressed and ignited by an electric spark.
The products of combustion increase the pressure and push the piston down the
cylinder.
If the combustion proceeds in a regular way, there is no problem in knocking.
But in some cases, the rate of combustion (oxidation) will not be uniform due
to unwanted chemical constituents of gasoline.
Knocking property of the fuel reduces the efficiency of engine. So a good
gasoline should resist knocking.
5.7.2 Improvement of anti knock characteristics
(i) Blending petrol of high octane number with petrol of low octane number, so
that the octane number of the latter can be improved.
(ii) The addition of anti-knock agents like Tetra-Ethyl Lead (TEL).

5.7.3 OCTANE NUMBER OR OCTANE RATING: - Prior to 1929, fuels were rated
using an engine in which CR could be varied between 2.7:1 to 8:1 - each fuel was
run in this engine at various A/F ratios and ignition timing to obtain conditions for
max power output.
Fuels were assigned values in terms of Highest Useful Compression Ratio, HUCR
in 1929 Octane scale was proposed by Graham Edgar. In this scale two paraffinic
HCs have been selected as standards (PRF, primary reference fuels)- iso-octane
(2-2-4 trimethyl pentane) with very high resistance to knock (arbitrary assigned a
value of 100) and n-heptane with extremely low knock resistance (assigned a
value of 0).

Thus octane number is defined as ‘the percentage of iso-octane present in a

mixture of iso-octane and n-heptanes.’ Octane number is introduced to express the
knocking characteristics of petrol. On the other hand, iso-octane gives very little
knocking and so, its anti-knock value has been given 100.
A mixture of these two compounds containing 95% of 2,2,4-trimethylpentane is
said to have an octane number of 95 (2,2,4-trimethylpentane was formerly known
as iso-octane, hence the terms “octane number” or “octane rating”). A mixture of
compounds with an identical tendency to auto-ignite, under the same conditions of
compression, would thus also be given an octane rating of 95. A compound that is
less likely to auto-ignite than pure 2,2,4-trimethylpentane would have an octane
rating of more than 100
HIGH OCTANE COMPOUNDS
Apart from the use of additives, knocking may also be prevented by using a mixture of high-
octane compounds in petrol manufacture. Certain molecular features are desirable in ensuring
that compounds have high-octane ratings. These are:
a) A high degree of branching
b) Short chain length
c) The existence of rings.

High-octane compounds can be obtained from low by three processes, each involving the use of
catalysts:
a) Isomerisation
b) Dehydrocyclisation
c) Catalytic cracking.
5.7.4ANTI-KNOCK AGENT :-
Tetraethyl lead (TEL) (C2H5)4 Pb is an important additive added to petrol. Thus
the petrol containing tetra ethyl lead is called leaded petrol. TEL reduces the
knocking tendency of hydrocarbon.
Mechanism of Knocking
. Knocking follows a free radical mechanism, leading to a chain growth which
results in an explosion.
If the chains are terminated before their growth, knocking will cease.
TEL decomposes thermally to form ethyl free radicals which combine with the
growing free radicals of knocking process and thus the chain growth is stopped.
Disadvantages of using TEL
When the leaded petrol is used as a fuel, the TEL is converted to lead oxide and metallic
lead.
To avoid this, small amount of ethylene dibromide is added along with TEL.
This ethylene dibromide reacts with Pb and PbO to give volatile lead bromide, which goes
out along with exhaust gases and creates atmospheric pollution.
But now a day‟s aromatic phosphates are used instead of TEL.

5.7.5Causes of knocking in CI (Diesel) engines

In a diesel engine, first air is compressed and raises the temperature of the
cylinder to about 500ċ then the oil is sprayed.
The expanding gases push the piston and power stroke begins.
The combustion of a fuel in a diesel engine is not instantaneous and the time
between injection of the fuel and its ignition is called Ignition lag or Ignition delay
and raising the temperature of vapour to its ignition temperature.
Which undergo explosion during ignition,this is responsible for diesel knock.

5.7.6 CETANE NUMBER OR CETANE RATING

Thus the cetane number is defined as “the percentage of cetane present in a
mixture of cetane and 2-methyl naphthalene which has the same ignition lag
as the fuel under test”.
Cetane number is introduced to express the knocking characteristics of diesel.
Cetane (C16H34) has a very short ignition lag and hence its cetane number is
taken as100. On the other hand, 2-methyl naphthalene has a long ignition lag and
hence its cetane number is taken zero.

CH3-(CH2)14-CH3
n-cetane (cetane no = 100) 2-methyl naphthalene (cetane no = 0)

The cetane number decreases in the following order.

Straight chain paraffin‟s >Cycloparaffins >Olefins >Branched paraffin‟s.

The cetane number of diesel oil can be increased by adding additives called dopes.
Ex: Ethyl nitrate, Iso-amyl nitrate.
More-: In a diesel engine, fuel is exploded not by the spark ignition, but by the
application of high temperature and pressure. Diesel engine fuels consist of longer
chains hydrocarbons than fuels used in internal combustion engine. The main
characteristic of this fuel is that it should ignite easily below compression
temperature and there should be a short induction lag. The suitability of diesel fuel
is determined by its cetane value (or cetane number), which is the percentage of
hexa-decane in a mixture of hexa-decane and 2 – methyl naphthalene, which has
the same ignition characteristics as the diesel fuel in use.