FUELS

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.

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 vapour 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.

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.

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.

Flash point

The rate of evaporation of liquid fuel increases with increasing temperature but the vapour 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 vapour 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 automatically 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.

Coal

Coal is a highly carbonaceous matter that has been formed as a result of alternation of plants under
certain favourable conditions. It is chiefly composed of C,H,N and O besides non-combustible 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)

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 − 110oC 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

% of moisture = W1 − W2/W1 × 100

 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 ± 20oC 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

% of volatile matter = loss in weight due to removal of volatile matter/Weight of coal taken

*** 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 700−750oC for about half an hour in a muffle
furnace. The solid residue (ash) is cooled and weighed.

% of ash = weight of the solid residue/Weight of coal taken × 100

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

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 H2O respectively. The gaseous products are
passed through two bulbs containing known weights of KOH and CaCl2 respectively. The
excess weight of KOH and CaCl2 indicates the amount of CO2 and H2O absorbed which are
produced from combustion of coal. From this quantity of CO2 and H2O % of C and H can be
determined as following. In 44 gm CO2 there is 12 gm carbon and in 18 gm H2O there is 2 gm
hydrogen. Then

% of C = Increase in weight of KOH tube × 12/weight of coal sample taken × 44 × 100

% of H = Increase in weight of CaCl2 tube × 2/weight of coal sample taken × 18 × 100

2. Nitrogen:
Nitrogen is determined by the Kjeldahl method. A known amount of coal is heated with conc
H2SO4 along with K2SO4 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) + H2SO4 → (NH4)2SO4
Now the solution is treated with an excess of NaOH for complete conversion of (NH4)2SO4 to
ammonia.

(NH4)2SO4 2NaOH −−−−−→ N a2SO4 + 2NH3 ↑ +2H2O

The ammonia thus liberated is distilled over and absorbed in a known volume (V1) of standard H2SO4
solution (say N/10).

NH3 + H2SO4 = (NH4)2SO4

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) required for neutralization
of excess acid.

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.
S O2 −−→→ SO2− 4 BaCl2 −−−−→ BaSO4
233 gm of BaSO4 ≡ 32gm of sulphur
% of sulphur = 32/233 × W2/W1 × 100
4. Ash:
Ash is determined in the same way as in proximate analysis
5. Oxygen:
% of oxygen = 100 − % of (C+H+N+S+Ash)

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-
700oC.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 900-1200oC 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.
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.

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 400oC. All volatile impurities are
removed and the hot vapour is allowed to pass through a fractionating column made up
of stainless steel. When vapour 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 30oC to 70oC. 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 40oC to
1200oC. 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 a2P 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 180oC to 250oC. 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 250oC to 320oC. It is generally a mixture of C15 to C18
hydrocarbons. Its calorific value is about 11000 kcal/kg.

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.

• Octane number: The resistance offered by gasoline to knocking cannot be defined in absolute terms.
It has been found that n-heptane knocks very badly and hence its antiknock 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 antiknock 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 atmospheric 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 compounds, 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.
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.

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 (C2H5SH) or CH3SH is added to LPG cylinder to help the detection
of gas leakage.

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 composed 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 C2H6 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%), C2H6(5.%), C3H8(3.5%), C4H10(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 formaldehyde
preparation.

Compressed Natural Gas (CNG) is a natural gas under pressure which remains clear, odourless and
non-corrosive.

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 900-1000oC in a reactor
 C + H2O 900−1000oC −−−−−−−−→ CO + H2 : Δ H= 29 kcal (endothermic)

In order to raise the bed to 1000oC 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 hydrocarbons.
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.

Producer gas

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

(i) Oxidation:
C + O2 → CO2 : Δ H= -97 kcal (exothermic)
2C + O2 → 2CO : Δ H= - 53 kcal (exothermic)
(ii) Reduction:
C + CO2 → 2CO
C + H2O → CO + H2
C + 2H2O → CO2 + 2H2

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.

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 triglyceride
esters. It is prepared through trans-esterification reaction between monohydroxy alcohol (methanol,
ethanol) and triglyceride in presence of catalyst (KOH, NaOH etc.).

Semi water gas

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

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

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.

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