Chapter 7

Fuel

7.1 Definition of fuel

Fuel is a combustible substance, containing carbon as main constituent which on proper burning
gives large amount of heat which can be used economically for domestic and industrial purpose.
The primary or main source of fuels are coals and petroleum oils, the amount of which are
decreasing day-by-day. These are stored fuels available in earth’s crust and are generally called
fossil fuels.

7.1.1 Calorific Value

Calorific value of a fuel is the total quantity of heat liberated when a unit mass or volume of the
fuel is burnt completely.
Usually all fuels contain some hydrogen and when the calorific value of H-containing fuel is
determined experimentally, the hydrogen is converted into steam. If the products of combustion
are condensed at 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(HCV).Thus

• Higher or Gross Calorific Value(HCV/GCV): HCV is the total amount of heat

produced when unit mass/volume of the fuel has been burnt completely and the products
of combustion have been cooled to room temperature.
• Lower or net calorific value : In actual use of any fuel, the water vapor and moisture
etc. are not condensed and escape as such along with hot combustion gases. Hence lesser
amount of heat is available. So LCV is the net heat produced when unit mass/volume of
the fuel is burnt completely and the products of combustion are permitted to escape.

7.1.2 Characteristics of good fuel

• A fuel should have high calorific value.
• Ignition temperature is the minimum temperature at which the fuel in an air-liquid
mixture ignites spontaneously and continues to burn without any external heating. Ignition
temperature should not be either very high or very low. It should be moderate.
Low ignition temperature is dangerous for storage and transport of fuel. High ignition
temperature causes difficulty in igniting the fuel but the fuel is safe during storage, handling
and transport. Hence ideal fuel should have moderate ignition temperature.
• Fuel should have low content of non-combustible(ash) matter and low moisture content.
• Fuel should be readily available in bulk at cheap rate.

83
84 CHAPTER 7. INDUSTRIAL CHEMISTRY:FUEL (PREPARED BY S P MAITY)

7.1.3 Classification of fuel

According to their occurrence fuels are classified as
• Primary fuel which are found in nature as such it is used. e.g. wood, coal, petroleum,
natural gas.
• Secondary fuels are those which are derived from primary fuel. e.g. charcoal, coke, kerosine,
diesel, petrol, producer gas.

7.2 Flash point

The rate of evaporation of liquid fuel increases with increasing temperature but the vapor of fuel
may not catch fire at all temperature. Flash point is the minimum temperature at which the
liquid fuel produces a sufficient concentration of vapor above which it forms an ignitable mixture
with an air and able to produce a flame.
Flash point of a fuel is the lowest temperature at which it is ignitable by an external burning
source. The ignition temperature is the minimum temperature at which the fuel will automat-
ically get ignited in the atmosphere (NTP) without even an external source of burning. In
other words, flash point requires external igniting source while ignition point does not require an
external burning source.

7.3 Coal
Coal is a highly carbonaceous matter that has been formed as a result of alternation of plants
under certain favorable conditions. It is chiefly composed of C,H,N and O besides non com-
bustible inorganic matter. On the basis of degree of alteration (coalification) various type of coal
are recognized.
Wood(%C 50)→ Peat(%C 57)→ Lignite(%C 67)→ Bituminous(%C 83)→ Anthracite(%C
93.5)

7.3.1 Analysis of coal

In order to asses the quality of coal the following two types of analysis are made (i) Proximate
analysis (ii) Ultimate analysis.

Proximate analysis:
It involves the determination of following
1. Moisture content: A known amount (say W1 gm) of finely powdered air dried coal sample
is weighed in a crucible and heated in an electrical hot-air-oven at 105o − 110o C for 1 hour
and then taken out, cooled in a desiccator and weighed(say W2 gm).The loss in weight is a
measure of the moisture content of coal. The loss in weight is expressed in percentage as
W1 − W2
% of moisture = × 100 (7.1)
W1
2. Volatile matter contents: Coal may contain combustible gases like H2 , CO, CH4 or
non combustible gases like CO2 and N2 . Volatile matter does not include moisture of coal.
For determination of volatile matter contents in coal, a known amount of moisture free coal
is taken in a silica crucible covered with a lid and then heated at 950 ± 20o C for about
5 − 10 minutes in a muffle furnace. The crucible is then taken out and cooled first in air,
then inside a desiccator and weighed again.Then
loss in weight due to removal of volatile matter
% of volatile matter = × 100 (7.2)
Weight of coal taken
7.3. COAL 85

*** Coal sample with high % of volatile matter burns with a long flame, high smoke. It
reduces calorific value.

3. Ash content: For determination of ash content, a measured amount of air dried coal is
taken in a open crucible. It is then heated at 700 − 750o C for about half an hour in a muffle
furnace. The solid residue (ash) is cooled and weighed.

weight of the solid residue

% of ash = × 100 (7.3)
Weight of coal taken

4. Fixed carbon:The % of fixed carbon can be obtained by subtracting the total percentage
of moisture contents, volatile matter contents and ash contents from 100.

% of fixed carbon = 100 − % of moisture − % of volatile − % of ash matter (7.4)

Ultimate analysis:
It involves the determination of carbon, hydrogen, nitrogen, sulphur, oxygen and ash content.

1. Carbon and hydrogen:

A known amount of coal in a combustion tube and is burnt in excess pure oxygen. The
carbon and hydrogen of the fuel is converted to CO2 and H2 O respectively. The gaseous
products are passed through two bulbs containing known weights of KOH and CaCl2 re-
spectively. The excess weight of KOH and CaCl2 indicates the amount of CO2 and H2 O
absorbed which are produced from combustion of coal. From this quantity of CO2 and
H2 O % of C and H can be determined as following. In 44 gm CO2 there is 12 gm carbon
and in 18 gm H2 O there is 2 gm hydrogen. Then

Increase in weight of KOH tube × 12

% of C = × 100 (7.5)
weight of coal sample taken × 44
Increase in weight of CaCl2 tube × 2
% of H = × 100 (7.6)
weight of coal sample taken × 18

2. Nitrogen:
Nitrogen is determined by the Kjeldahl method. A known amount of coal is heated with
conc H2 SO4 along with K2 SO4 as catalyst in a long-necked flask (kjeldahl’s flask). The
nitrogen is converted to (NH4 )2 SO4 and the solution becomes clear.

Nitrogen(from coal sample) + H2 SO4 → (N H4 )2 SO4

Now the solution is treated with an excess of NaOH for complete conversion of (N H4 )2 SO4
to ammonia.
2N aOH
(N H4 )2 SO4 −−−−−→ N a2 SO4 + 2N H3 ↑ +2H2 O (7.7)

The ammonia thus liberated is distilled over and absorbed in a known volume (V1 ) of
standard H2 SO4 solution (say N/10).

N H3 + H2 SO4 = (N H4 )2 SO4 (7.8)

The unused acid is then determined by titrating with a standard NaOH solution (N/10),
from which the percentage of nitrogen is calculated. If V2 be the volume of NaOH (N/10)
86 CHAPTER 7. INDUSTRIAL CHEMISTRY:FUEL (PREPARED BY S P MAITY)

required for neutralization of excess acid.

0.1
(V1 − V2 )ml(N/10)H2 SO4 ≡ × (V1 − V2 )equivalent
1000
1 equivalentH2 SO4 ≡ 1 equivalentN H3
≡ 14gm N
0.1 × (V1 − V2 )
So, weight of nitrogen = × 14
1000
0.1 × (V1 − V2 ) × 14
It can be shown that for W gm of sample, % of N = × 100
1000 × W
0.1 × (V1 − V2 )
= × 1.4 (7.9)
W
3. Sulphur:
To determine sulphur in coal, a known amount of coal (W1 ) is burnt in a Bomb calorimeter
in a current of oxygen to oxidize sulphur to sulphates. The residue (ash) in the Bomb
calorimeter is extracted with dilute HCl. Then it is precipitated as BaSO4 by adding
BaCl2 solution. The precipitated BaSO4 is filtered, washed, dried and heated to constant
weight (W2 ) from which percentage of sulphur is calculated.
O BaCl
2
S −−→→ SO42− −−−−→
2
BaSO4
233 gm of BaSO4 ≡ 32gm of sulphur
32 W2
% of sulphur = × × 100 (7.10)
233 W1
4. Ash:
Ash is determined in the same way as in proximate analysis.
5. Oxygen:
% of oxygen = 100 − % of (C+H+N+S+Ash) (7.11)

7.4 Carbonization: Coke

Coke: Coke is the solid, lustrous and porous mass left in the distilling pot after destructive
distillation of coal. The process of converting coal into coke is called carbonization.In this
process, coal is heated in absence of air, to a sufficiently high temperature, under which volatile
are driven off leaving a solid, lustrous,dense, porous mass known as coke. On the basis of
temperature, carbonization is of two types
• Low temperature carbonization (LTC): LTC is carried out at temperature between 500-
700o C.The yield of coke is about 75-80%. The various products of LTC are semicoke, low
temperature tar, spirit and gas. This semicoke which is almost smokeless and soft, has
calorific value 6500-9000 kcal/m3
• High temperature carbonization(HTC): HTC is generally carried out at 900-1200o C
in absence of air. It is used for the production of hard, strong and porous metallurgical
coke. The by-products obtained by this process are coal gas, coke, coal-tar and liquor
ammonia.

7.5 Petroleum
Petroleum is a dark greenish viscous oil found in the earth crust. It consists of a mixture of
paraffinic, olefinic and aromatic hydrocarbon with small quantities of compounds containing
oxygen, sulphur and nitrogen.
7.6. KNOCKING 87

7.5.1 Refining of Petroleum

The crude oil is separated into various fractions by fractional distillation. The resultant fractions
are then finally subjected to purification into desired useful products.The total process is called
refining of petroleum and the plant where these are done is called refinery. The process involves
the following steps:
1. Removal of water:Cottrell’s method
Crude oil remains in the form of stable emulsion of oil and salt water (stabilization is due
to sodium salts of sulfo acids, napthenic acids etc.).Water is removed by allowing the crude
petroleum to flow between very highly charged electrodes. The colloidal water droplets
coalesce to form large size drops and get separated from oil.
2. Removal of sulphur: Excessive salts such as NaCl, MgCl2 which can corrode refining
equipment are removed by washing with water.The sulphur compounds are removed by
treating with CuO. The CuS so formed are removed through filtration.
3. Fractional distillation: The crude petroleum is heated in an iron retort at about 400o C.
All volatile impurities are removed and the hot vapor is allowed to pass through a fraction-
ating column made up of stainless steel.When vapor goes up, it gradually cools down and
fractional condensation occurs at different heights of the column. Higher boiling fraction
condenses first followed by lowered boiling fraction.
The most important fractions collected from the fractionating column by distillation of crude
petroleum are:
1. Petroleum ether:This fraction is obtained in the temperature range of 30o C to 70o C. It
contains mainly C5 to C7 hydrocarbons.
2. Gasoline or petrol: Of all the fractions most important fuel gasoline is obtained in the
temperature range 40o C to 1200o C. It is a mixture mainly pentane and octane (C5 to C8 ).
It’s calorific value is about 11250 kcal/kg. Gasoline which is obtained from direct fractional
distillation of crude petroleum is known as straight run gasoline which is only 20% of total
present demand of gasoline. So the process known as cracking is utilized for conversion of
heavy petroleum to gasoline.Quality of this gasoline which is produced through cracking
found to have better quality. The sulphur containing gasoline is termed as sour petrol.The
sulphur compounds are removed by treating gasoline with sodium plumbite with controlled
addition of sulphur to form lead disulphides known as sweetening. Maximum power is
derived from gasolines when it burns silently and relatively slowly.

N a2 P bO2 + 2RSH → P b(SR)2 + 2N aOH

P b(SR)2 + S → P bS(s) + RSSR(disulphide)

3. Kerosine oil: This fraction is obtained between 180o C to 250o C. It is generally a mixture
of C10 to C16 hydrocarbons. Its calorific value is about 11100 kcal/kg.
4. Diesel oil: This fraction is obtained between 250o C to 320o C. It is generally a mixture of
C15 to C18 hydrocarbons.Its calorific value is about 11000 kcal/kg.

7.6 Knocking
In an internal combustion engine when the rate of oxidation becomes so high that the last portion
of the fuel-air mixture gets ignited instantaneously, producing an explosive violence known as
knocking. a good quality gasoline should resist knocking. The knocking order of different
hydrocarbon are
Straight chain paraffin > branched chain paraffin > olefins > cyclo paraffins > aromatics.
88 CHAPTER 7. INDUSTRIAL CHEMISTRY:FUEL (PREPARED BY S P MAITY)

• Octane number: The resistance offered by gasoline to knocking can not be defined in
absolute terms. It has been found that n-heptane knocks very badly and hence its anti-
knock value has been given ZERO. On the other hand iso-octane gives very little knocking,
so its anti-knock value is given as 100.
Octane number of a gasoline is equal to the percentage by volume of iso-octane in a mixture
of iso-octane and n-heptane having same knocking characteristics as the sample being
tested., under the same set conditions. Greater the octane number, greater is the anti-
knock property of the fuel.
“Octane number 80” means the fuel has the same knocking characteristics as the mixture
of 80 : 20 iso-octane and n-heptane.

• Anti-knock agents: The octane number can be increased by adding certain additives
like tetra ethyl lead (TEL) Pb(Et)4 known as anti-knock agents. Under combustion, TEL
produces Pb and PbO. These particles act as free radical chain inhibitor as they arrest the
propagation of the explosive chain reaction responsible for knocking.But it causes atmo-
spheric pollution as well as reduces engine deficiency. So instead of using TEL nowadays
unleaded petrol where (i) methyl tertiary butyl ether (MTBE) which supplies oxygen
from the ether group for combustion of petrol thus reducing the formation of peroxy com-
pounds, is used,(ii) secondly, reforming i.e. increasing the contents of molecules having
branched chain hydrocarbon like iso-octane, iso-pentane and aromatic hydrocarbon(ethyl
benzene, isopropyl benzene).

• Cetane number: Cetane number of a diesel oil may be defined as the percentage of
cetane (n-hexadecane) in a mixture of cetane and α-methyl napthalene, which will have the
identical ignition characteristics as the fuel under test, under the same set of conditions. It
measures the ease with which the fuel (diesel fuel) will ignite under compression. So higher
the cetane number better is the ignition property of the fuel. The order with decreasing
cetane number is as follows
n-alkanes > napthalene > alkenes > branched alkanes > aromatics
The combustion of fuel in a diesel engine is not instantaneous but there is some lag. The
interval between the start of fuel injection and its ignition is called ignition delay or
induction lag. Cetane has very short ignition delay compared to any diesel fuel whereas
α-methyl napthalene has a longer ignition delay.

7.7 Aviation Fuel

Aviation fuel is a special type of petroleum based fuel with high octane number. It is used in
aircrafts and in racing cars. It is prepared by mixing alkylated branched paraffins with cracked
gasoline containing unsaturated open chain hydrocarbon.

7.8 Liquefied Petroleum Gas (LPG)

LPG are derived from the refinery process, crude oil and natural gas processing plants. The main
constituents are lower hydrocarbons upto C4 , like butanes (major) and isobutanes, isobutylene
and propane etc. LPG is highly inflammable. It can exist as a gas under atmospheric pressure,
but can be readily liquefied under pressure and is done so for easy transportation and storage.It
is cheap , high knock resistant and burns clearly without leaving any residue and so mostly used
as domestic and industrial fuel. It’s calorific value 28000 kcal/kg. It is colorless and odourless. A
strong smelling substance called ethyl mercaptan (C2 H5 SH) or CH3 SH is added to LPG cylinder
to help the detection of gas leakage.
7.9. NATURAL GAS : COMPRESSED NATURAL GAS (CNG) 89

7.9 Natural Gas : Compressed Natural Gas (CNG)

Natural gas is formed under the earth by the decomposition of vegetables matter lying under
water. It is obtained from well dug in the oil bearing regions and coal fields. It is mainly com-
posed of methane, ethane, propane, butane and trace amount of other hydrocarbons along with
hydrogen, carbon dioxide and monoxide.Natural gas with lower hydrocarbons like CH4 and C2 H6
is called dry or lean and with higher hydrocarbon , along with CH4 is called wet or rich. It is
also called marsh gas as the major constituent is methane.
Composition: CH4 (88.5%), C2 H6 (5.%), C3 H8 (3.5%), C4 H10 (2%),
pentane, H2 , CO, CO2 : (0.5%)
Its calorific value 8000-14000 kcal/m3
Use:It is mainly used as domestic and industrial fuel, raw materials for methanol and formalde-
hyde preparation.
Compressed Natural Gas (CNG) is a natural gas under pressure which remains clear, odourless
and non-corrosive.

7.10 Water gas

Water gas is a synthetic gas containing CO (41%) and hydrogen (51%) along with small amount
N2 (4%) and CO2 (4%). It is also known as blue gas as it burns with a blue flame when ignited.
Its calorific value is about 2800 kcal/m3 . It is prepared by passing alternatively steam and little
air through a bed of hot coal or coke, maintained at about 900-1000o C in a reactor.
900−1000o C
C + H2 O −−−−−−−−→ CO + H2 : Δ H= 29 kcal (endothermic)

In order to raise the bed to 1000o C the steam supply is temporarily cut off and air is blown in,
when the following exothermic reactions occur

C + O2 → CO2 : Δ H= -97 kcal (exothermic)

2C + O2 → 2CO : Δ H= - 53 kcal (exothermic)

In order to enhance the calorific value of water gas, it is carburetted by adding gaseous hydrocar-
bons. This mixture of water gas and gaseous hydrocarbons is called carburetted water gas.
It’s composition is H2 (35%), CO(25%), hydrocarbon (35%), N2 and CO2 (5%). This so-called
carburetted water gas has calorific value about 4500 kcal/m3 . It is mainly used for heating and
illumination purpose.

7.11 Producer gas

It is a mixture of CO and N2 .
composition of producer gas is
prepared by passing air mixed
specially designed reactor called
(i) Oxidation:
The calorific value is about 900-1300 kcal/m3 . The average
CO(20-30%), H2 (8-12%), N2 (50-55%) and CO2 (2-3%). It is
with small volume of steam over red hot coke at 1100o C in
‘gas producer’. It is a two step process.

C + O2 → CO2 : Δ H= -97 kcal (exothermic)

2C + O2 → 2CO : Δ H= - 53 kcal (exothermic)

(ii) Reduction:

C + CO2 → 2CO
C + H2 O → CO + H2
C + 2H2 O → CO2 + 2H2
90 CHAPTER 7. INDUSTRIAL CHEMISTRY:FUEL (PREPARED BY S P MAITY)

H2C OCOR1 H2C OH CH3OCOR1

NaOH
HC OCOR2 + 3CH3OH HC OH + CH3OCOR2

CH3OCOR3
H2C OCOR3 H2C OH
bio-diesel
glycerin

Figure 7.1: Bio-diesel preparation

The reduction process is endothermic. Such reactions are allowed to take place deliberately. It
is mainly used as (i) reducing agent in metallurgical process (ii) fuel for open hearth furnaces,
muffle furnace, coke oven plants, etc.

7.12 Bio-diesel
The alternative fuel for diesel engines which are made from vegetable oil or animal fat is known as
bio-diesel. Chemically, bio-diesel molecules are monoalkyl esters produced usually from triglyc-
eride esters. It is prepared through trans-esterification reaction between monohydroxy alcohol
(methanol, ethanol) and triglyceride in presence of catalyst (KOH, NaOH etc.).

7.13 Semi water gas

A mixture of water gas and producer gas is known as semi water gas.It’s calorific value 1700
kcal/m3

7.14 Biogas
It is a methane rich flammable gas that results from the controlled or uncontrolled anaerobic
decomposition of organic waste material.

7.15 Power alcohol

The blend of anhydrous alcohol and petrol is called power alcohol or gasohol. It reduces CO
emission and cause less pollution compared to petrol.