Fuels

• A fuel is a substance that produces useful energy either through combustion or through
nuclear reaction.
• An important property of a fuel is that the energy is released in a controlled manner and can
be harnessed economically for domestic and industrial purposes.
• Wood, coal, charcoal, petrol, diesel, kerosene, producer gas and oil gas are some of the
common examples of fuels.
• Fuels that produce heat energy by combustion are termed as chemical fuels. During
combustion, carbon, hydrogen, sulphur and phosphorus that are present in the fuel combine
with oxygen and release energy.

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 Classification of Fuels
Fuels can be classified on the basis of their (I) occurrence (II) physical state
On the basis of occurrence, fuels are of two types

Primary Fuels or Natural Fuels Secondary Fuels or Derived Fuels

These are found to occur in nature and are These are the fuels that are derived from primary
used as such either without processing or after fuels by further chemical processing, for example,
being processed to a certain extent, which does coke, charcoal, kerosene, producer gas (CO+N2),
not alter the chemical constitution of the fuel. water gas (CO + H2), etc.
These are also known as fossil fuels. Examples
include wood, peat, lignite, coal, petroleum,
natural gas, etc. 3
(II) On the basis of their physical state

Fuels may be classified as follows:

(a) Solid fuels (b) Liquid fuels (c) Gaseous fuels

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 Characteristics of a Good Fuel

1. High Calorific Value: A good fuel should possess high calorific value because calorific value
determines the efficiency of the fuel. Higher the calorific value, greater is the heat liberated per unit
mass or volume.
2. Ignition Temperature: It is the lowest temperature to which a fuel must be preheated so that it starts
burning smoothly. An ideal fuel should have moderate ignition temperature. Low ignition
temperature can cause fire hazards, making storage and transportation difficult. Fuel with low ignition
temperature can burn spontaneously leading to explosion. High ignition temperature, on the other
hand, makes it difficult to kindle (ignite) the fuel.
3. Moisture Content: Moisture content should be low because the presence of moisture lowers the
calorific value of the fuel
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4. Non-combustible Matter: After combustion, the non-combustible matter is left behind as ash.
Non-combustible matter reduces the calorific value of the fuel and also requires additional money
investment for storage, handling and disposal of the waste products produced.
5. Velocity of Combustion: If the velocity of combustion is low, then a part of the liberated heat
may get radiated instead of raising the temperature; hence, the required high temperature may not
be attained. On the other hand, if the velocity of combustion is very high then the rate of
combustion might become uncontrollable. For a continuous supply of heat, fuel must burn with a
moderate rate.
6. Cost of the Fuel: A good fuel should be readily available at a low cost

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7. Combustion Products: The products obtained during combustion of the fuel should be
harmless and non-polluting. Harmful gases such as CO2 , SO2 , H2 S, PH3 and PbBr2 should
not be produced, and also the amount of smoke produced should be less.
8. Storage and Transportation: A good fuel should be easy to handle, store and transport at
low cost.
9. Size: In case of solid fuels, the size should be uniform so that combustion is regular.
10. Combustion Should Be Controllable: The combustion process should be controllable,
that is it can be started or stopped when required.

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Comparison of solid, liquid and gaseous fuel

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 Gross and Net Calorific Value

Gross Calorific Value (GCV) It is also called higher calorific value (HCV) and is defined as the total amount
of heat produced when a unit quantity (mass/volume) of fuel is burnt completely, and the products of
combustion are cooled to room temperature.
• Usually all fuels contain hydrogen. During combustion, the hydrogen present in the fuel is converted into
steam. When the combustion products are cooled to room temperature, the steam gets condensed into water
and heat that equals the latent heat of condensation (The heat emitted when one mole of a substance
condenses is known as the latent heat) of steam is evolved. This heat gets included in the measured heat, and
so its value is high; hence, it is called higher calorific value.

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Low Calorific Value (LCV) It is also termed as net calorific value (NCV) and is defined as
the heat produced when a unit quantity (mass/volume) of a fuel is burnt completely and the hot
combustion products are allowed to escape.
• When a fuel is burnt water vapor escapes along with the hot combustion gases; hence, heat
available is lesser than the gross calorific value. Therefore, this is called low calorific value or
net calorific value.
Thus LCV = HCV – Latent heat of water vapour formed.

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Determination of Calorific Value
Bomb calorimeter
Principle A known amount of
fuel is burnt in excess of oxygen
and the heat liberated is absorbed
in a known amount of water. This
heat liberated is measured by
noting the change in temperature.
Calorific value of the fuel is
then calculated by applying the
following principle:
Heat liberated by fuel = Heat
absorbed by water and the
calorimeter.
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13
 Working

A known amount of fuel (0.5–1 g) is taken in a clean crucible supported over the ring. A fine
magnesium wire, touching the fuel sample, is then stretched across the electrodes. The lid of the
bomb is tightly screwed. The bomb is filled with oxygen at 25 atmospheric pressure and placed in the
copper calorimeter containing a known weight of water. The stirrer is started and the initial
temperature of water is noted. The electrodes are then connected to a 6-volt battery to complete the
circuit. The sample burns and heat is liberated. This heat is absorbed by water. Maximum
temperature shown by the thermometer is recorded. Time taken to cool the water in the calorimeter
from maximum temperature to room temperature is also noted.

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Calculations
Let Weight of fuel sample taken =xg
Weight of water in the calorimeter =Wg
Water equivalent* of calorimeter, stirrer, thermometer, bomb etc =wg
Initial temperature of water in the calorimeter = t1ºC
Final temperature of water in the calorimeter = t2ºC
Higher or Gross calorific value of fuel = H calorie / g
Heat liberated by burning of fuel =x×H
Heat gained by water = W × ∆T × specific heat of water = W (t2 – t1 ) × 1 cal
Heat gained by calorimeter = w (t2 – t1)
Total heat gained = W (t2 – t1 ) + w (t2 – t1) = (W + w) (t2 – t1)

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Net (lower) calorific value

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Corrections

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Corrections

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Examples

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 Boy’s Gas Calorimeter
The Boy’s gas calorimeter is also used to find the calorific value of gaseous and volatile
liquid fuels. It consists of the following parts.

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Boy’s Gas Calorimeter

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Observations

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Problems:

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 Theoretical Calculations:

Dulong's assumed that the heat evolved comes from the combustion of carbon, hydrogen and sulphur
present in the fuel, and the calorific value of the fuel is the sum of the calorific values of these
constituents. The calorific values of C, H and S are found to be 8080, 34500 and 2240 kcal/kg,
respectively

If oxygen is also present, it combines with hydrogen to form H2O. Thus, the hydrogen in 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.

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Examples

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 Solid Fuels
Solid fuel refers to various types of solid materials that are used as fuel to produce energy. The
primary solid fuels commonly used are wood and coal.

Wood: Freshly cut wood contains 25 to 50% moisture which reduces to 15% after drying the
wood in air.
• The average composition of wood is: C = 55%; H = 6%; O = 43%; ash = 1%.
• Its calorific value is about 3500–4500 kcal/kg.
• It burns with a long and non-smoky flame leaving behind small amount of ash.
Destructive distillation of wood at around 500°C produces charcoal which is an excellent
fuel equivalent to the best of fuels.
Coal: Coal is produced when the plant and animal debris are subjected to conditions of high
temperature and pressure over millions of years. Hence, it is regarded as a fossil fuel.
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Classification and rank of coal
starts off
as

After being subjected to heat and pressure for a considerable

amount of time, it is metamorphosed from peat to lignite.

Lignite is referred to as brown coal because it is somewhat light in color and it

remains soft. As time passes, lignite increases in maturity by becoming darker
and harder and is then classified as sub-bituminous coal.

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As this process of continues, more chemical and physical changes
occur and the coal is classified as bituminous. At this point the coal
is dark and hard.

Anthracite is the last stage of coal formation. Anthracite coal is

very hard and shiny.

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 Analysis of Coal
It is necessary to analyze and interpret the results for the purpose of price fixation, commercial
classification and proper industrial utilization.
The quality of coal is analyzed by two ways:
• Proximate analysis
• Ultimate analysis

Proximate Analysis
It is an empirical but important analysis dealing with the determination of moisture content, volatile
matter, ash content and fixed carbon. It is called proximate analysis because the data vary with the
procedure adopted. This analysis provides data for a general assessment of the quality and type of coal. It
involves the following determinations:
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1. Moisture Content

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2. Volatile Matter
The volatile matter present in the coal may be combustible gases such as H2 ,
CO, CH4 and other hydrocarbons or non-combustible gases such as CO2
and N2 . It does not include moisture of the coal.
It is determined by heating a known weight of moisture-free coal in a silica
crucible covered with a vented lid at 950 ± 20 °C for 7 minutes in a muffle
furnace. The crucible is then taken out and cooled inside a dessicator and
weighed again. Complete removal of volatile matter is judged by bubbling
the gas through a water seal. Loss in weight gives the weight of the volatile
matter and the percentage of volatile matter is calculated as follows:

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 3. Ash

• Ash is the non-combustible, useless matter that is left behind when all the combustible
substances have burnt off from coal. Ash usually consists of silica, alumina, iron
oxide and small quantities of lime, magnesia, etc.
• Ash content is determined by heating the residue obtained after removal of moisture
and volatile matter at 700 ± 50 °C for half an hour without a lid in muffle furnace. The
residue left is cooled in a dessicator and weighed. From the weight of residue, the
percentage of ash is calculated as

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4. Fixed Carbon

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 Significance

• High moisture content is undesirable because it reduces the calorific value

• Coal containing high percentage of volatile matter burns with a long flame and high smoke
and has low calorific value. Coals with high percentage of volatile matter ignite easily but
burn very quickly.
• High percentage of ash is undesirable as it reduces the calorific value of the fuel.
• Presence of ash increases the transporting, handling and storage cost.
• Higher the percentage of fixed carbon, greater is the calorific value.

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Example:

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Ultimate Analysis

• It is also called elemental analysis and is used for the determination of carbon,
hydrogen, nitrogen, sulphur and oxygen.
• This analysis requires high degree of skill and the equipment's are expensive.
• However, it gives exact results that are useful in calculating the calorific value of
coal using Dulong’s formula.

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 Carbon and Hydrogen
• Carbon in coal sample occurs in combined form in complex organic matter and can also be
present as mineral carbonates.
• Hydrogen on the other hand is found in organic matter in coal and is also found associated
with the moisture present in coal.
• To estimate carbon and hydrogen accurately weighed coal sample is burnt in a
combustion tube in a current of O2 (free from CO2 and moisture).
• The carbon and hydrogen present in the fuel is converted to CO2 and H2O, respectively. These
are then absorbed by previously weighed tubes containing KOH and anhydrous CaCl2 . The
increase in weights of these tubes gives the amount of CO2 and H2O formed. The percentage
of C and H is then calculated as follows

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 Nitrogen
All the nitrogen present in coal is assumed to occur within the organic matter of coal. Nitrogen
present in coal sample is estimated by Kjehldahl’s method.
• Accurately weighed coal sample is heated with concentrated H2SO4 in the presence of K2SO4
in a long-necked flask known as Kjehldahl’s flask. Nitrogen present in the coal gets converted
to (NH4)2SO4 quantitatively.
The NH3 thus liberated is
NaOH absorbed in a known volume of a
NH3
standard H2SO4 solution (N/10).

The volume of unused H2SO4 is determined by titrating against standard NaOH solution (N/10).
Difference gives the volume of acid used. From the volume of acid used by NH3, the
percentage of nitrogen can be calculated.
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Sulphur

Sulphur is found in coal in three forms, as organic sulphur compounds, as inorganic

sulphides and also as inorganic sulphates.
To estimate the amount of sulphur in the coal sample a known amount of coal is burnt
completely in a bomb calorimeter in a current of oxygen. Sulphur in the coal is oxidised
to sulphates. The ash from the bomb calorimeter is extracted with dilute hydrochloric acid.
The acid extract is then treated with BaCl2 solution to precipitate sulphate as BaSO4 . The
precipitate of BaSO4 is filtered, washed, dried and heated to a constant weight. From the
weight of BaSO4 formed, S is estimated as follows

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 Significance
1. Calorific value of a fuel is directly related to the carbon content; hence, greater the
percentage of carbon, greater is the calorific value of the fuel.
2. High percentage of hydrogen also increases the calorific value of coal. However, hydrogen
is mostly associated with volatile matter and affects the use to which coal is put.
3. Since nitrogen is an inert and incombustible gas with no calorific value, its presence in fuel
is undesirable.
4. Although sulphur increases the calorific value of fuel, yet its presence is undesirable
because it gets oxidised to SO2 and SO3, which causes environmental pollution.

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Questions
Carbonisation of Coal

When coal is heated to a high temperature in the absence of air, it loses volatile matter and
gets converted into a white, dense, lustrous, strong, porous and coherent mass, which is
richer in carbon content than the original fuel. This is known as coke and the process of
converting coal into coke in the absence of air is known as carbonisation of coal.

Types of carbonisation

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Process of carbonisation

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 Caking and coking coals
It is important to note that all types of coals cannot be converted into coke. Some coals soften
and swell at higher temperatures, to form a solid coherent mass with porous structure. Such coals
are called caking coals. The residue so 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. Coking coal is also called
metallurgical coke. This is a unique property of bituminous coal; hence, only bituminous coals
can be converted into coke. Anthracite, sub-bituminous, lignite coals are non-coking coals. All
coking coals are caking coals; however, only some caking coals fall under the category of coking
coals.
Generally, coals with a high percentage of volatile matter, lower ash and higher fixed carbon
content are not fit for ‘coking’. The coals having 20–30% volatile matter are good coking coals.

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Comparison between low and high-temperature
carbonisation
 Metallurgical coke
• A good metallurgical coke should possess the following properties

• The moisture, ash, sulphur and phosphorus contents should be

Purity very low.

• Coal should be porous so that oxygen can come in contact with

carbon, which ensures efficient and complete combustion of the
Porosity fuel in the furnace.

• Coke should be compact, hard and strong enough to withstand

high pressure in the furnace as well as to withstand the abrasive
Strength action of the ores, flux, etc.
 • Metallurgical coke should be of medium size – neither too big nor too small. If the
size is big, uniform heating is not possible, whereas small size of coke results in
Size choking.

Combusti • Coke should burn easily but at the same time it should not be very reactive.
bility

Calorific • The calorific value of coke should be high.

Value

• It should be cheap and easily available.

Cost
Manufacture of metallurgical coke
Metallurgical coke can be manufactured by two methods:
(i) Beehive oven method
(ii) Otto Hofmann’s oven or by-product oven or chamber oven method

Beehive oven method

Otto Hofmann’s oven or by-product oven or
chamber oven method.

Regenerative principle of heat economy is employed to achieve as economical heating as

possible.

Construction: It consists of a number of narrow rectangular chambers made of silica

bricks. Each chamber is 10–12 m long, 3–4 m high and 0.4–0.45 m wide. The chambers are
tightly closed so that no air is admitted. At the top of each chamber, there are holes for
charging the coal. It is also provided with a gas take off (which carries out volatile matter)
and discharging doors at the base for the removal of coke. The ovens (chambers) form a
sort of battery of 10–100 ovens. One single oven is capable of holding 16–24 tons of coal.

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 Working
• Finely crushed coal is introduced
through the charging holes at the
top of the chambers which are
then closed tightly at both ends
to cut off the supply of air. The
ovens are heated to 1200°C by
burning gaseous fuels (such as
producer gas).
• The process of carbonisation
sta rts in coa l adjacent to the
w a l ls a nd m o v e s t o w a r ds t h e
centre.
• As the coal is converted into coke,
there is decrease in volume due to
removal of volatile matter.
• Carbonisation of a charge of coal
takes about 11–18 h. After the
process is complete, red hot coke 59

is pushed out by means of a ram,

• Quenching of red hot coke is carried out either by spraying water (wet quenching)
or by passing inert gas such as N2 from boilers (dry quenching).
• In wet quenching, sensible heat of coke is wasted, whereas in dry quenching the
inert gases after quenching the coke become heated up and are circulated to the boilers
where they generate steam.
• The coke produced by dry quenching is more strong, dense, graphitised and non-
reactive. It is cheaper, dry and contains less dust than the wet quenched coke.

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Recovery of by products

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