Notes by Chikutswi Forbes

TOPIC: FUELS

- determine, experimentally, the heating values of fuels

- explain why some fuels are more efficient than others

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.

Characteristics of good fuel

 A fuel should have high 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

 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.

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. Chemical Fuels are of two types.

(i) Primary Fuels : It occurs in nature e.g coal, petroleum,natural gas.

(ii) Secondary Fuels: It is derived from primary fuels e.g coke, gasoline, coal gas.

Primary and secondary fuels may also be divided into 3 classes namely solid, liquid and
gaseous fuel

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Fossil fuels

 are those, which have been derived from fossil remains of plant and animal life
and are found in the earth’s crust.

 All conventional fossil fuels whether solid, liquid or gaseous (coal, petroleum or
Natural gas) contain basically carbon and / or hydrogen.

Advantages of Solid fuels.

1. Handling and transportation of solid fuels are easy.

2. Solid fuels are cheap and easily available.

3. They have a moderate ignition temperature .

4. This type of fuel can be stored conveniently without any risk.

Disadvantage of solid fuels:

1. During burning, solid fuels produce a large amount of ash and disposal of ash is
a big problem.

2. The calorific value of solid fuel is comparatively low.

3. Since a lot of air is required for complete combustion, its thermal efficiency is
not so high.

4. A large space is required for storage

5. Combustion is a slow process and it cannot be easily controlled.

Advantages of Liquid fuels

1. Liquid fuels do not yield any ash after burning.

2. They require comparatively less storage space.

3. Calorific value of liquid fuel is higher than that of solid fuels.

4. Their combustion is uniform and easily controllable.

Disadvantages of liquid fuels:

1. Liquid fuels are comparatively costlier than the solid fuels.

2. They give unpleasant odour during incomplete combustion.

3. Some amount of liquid fuels will storage.

4. escape due to evaporation during Special type of burners are for effective
combustion.

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Advantages of gaseous fuels:

1.Gaseous fuels can be easily transported through the pipes.

2. They do not produce any ash or smoke during burning.

3. They have high calorific value than the solid fuels.

4. They have high thermal efficiency.

Disadvantages of gaseous fuels

1.They are highly inflammable and hence the chances for fire hazards are high.

2. Since gases occupy a large volume, they require large storage tanks.

Solid Fuels

Wood

 More than two billion people depend on wood energy for cooking and heating,
particularly in households in developing countries.

 In parts of Africa, wood fuels is domestically available and affordable sources of energy
accounting for almost 90 percent of primary energy consumption.

Charcoal

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 is a solid fuel used for heating and cooking that is created through the process of
carbonisation.

 Carbonization is a process where complex carbon substances such as wood or

other biomass are broken down through a slow heating process into carbon and other
chemical compounds.

 During the production of charcoal, wood is cut down into long, cane-sized pieces and
placed in some sort of closed vessel.

 Generally, wood structures known as piles are used, within these piles, the wood is
heated in the absence of air (oxygen) and decompose into charcoal.

Coal

 Coal is an important primary solid fuel that has been formed as a result of
alteration of vegetable matter under some favourable conditions.

 The process of conversion of lignite to anthracite is called coalification (or)

metamorphism of coal.

 Coal is classified on the basis of its rank. The rank of coal denotes its degree of
maturity. Vegetable matter, under the action of pressure, heat and anaerobic
conditions, gets converted into different stages of coal

Wood → Peat → lignite → subbituminous → bituminous → anthracite

With the progress of coal forming reaction, moisture content and oxygen content
reduces and % of carbon increases. Also calorific value increases from peat to
bituminous.

 Peat is the first stage in the formation of coal and its calorific value is about 4000 to
5400 k cal/kg. It is an uneconomical fuel due to its high proportion of 90% moisture
and lower calorific value.

 Lignite is an intermediate stage in the process of coal formation. Its calorific value
is about 6500 to 7100 k cal/kg. Due to the presence of high volatile content, it burns
with long smoky flame.

 Bituminous coal is further sub divided according to its carbon content into three
types I.e; Sub Bituminous coal, semi and Anthracite bituminous coal. Anthracite is
the superior grade classified on the basis of bituminous coal, its volatile,
moisture and ash contents are very less and its calorific value is about 8650 k
cal/kg.

ANALYSIS OF COAL

 The quality of a coal is ascertained by Proximate Analysis and Ultimate Analysis

Proximate Analysis

 indicates the percentage by weight of the fixed carbon, volatiles, ash, and moisture

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content in coal.

 The amounts of fixed carbon and volatile combustible matter directly contribute to the
heating value of coal.

 Fixed carbon acts as a main heat generator during burning and High volatile matter
content indicates easy ignition of fuel.

 The ash content is important in the design of the furnace grate, combustion volume,
pollution control equipment and ash handling systems of a furnace.

Significance of Various Parameters in Proximate Analysis

(a) Fixed Carbon

 Fixed Carbon is the solid fuel left in the furnace after volatile matter is distilled off.

 It consists mostly of carbon but also contains some hydrogen, oxygen, sulphur and
nitrogen not driven off with the gases.

 Fixed carbon gives a rough estimate of heating value of coal.

 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

(b) Volatile Matter

 Volatile Matters are the methane, hydrocarbons, hydrogen and carbon monoxide,
and incombustible gases like carbon dioxide and nitrogen found in coal.

 Thus the volatile matter is an index of the gaseous fuels present.

 Typical range of volatile matter is 20 to 35%.

 The loss in weight of the sample is found out and the % of the volatile matter is
calculated as:

 % of volatile matter in coal = ( loss in weight due to removal of volatile matter

×100)/( weight of coal taken)

 Volatile Matter proportionately increases flame length, and helps in easier ignition of
coal.

(c) Ash Content

 Ash is an impurity that will not burn.

 Typical range is 5 to 40%. After the analysis of volatile matter, the crusible with
residual coal sample is heated without lid as 700 ± 50 oC for 1/2 an hour in a
muffle furnace.

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 The loss in weight of the sample is found out and the % of ash content is calculated
as:

% of ash content in coal = (weight of ash formed × 100)/ (weight of coal taken)

 Ash reduces handling and burning capacity. Increases handling costs.

 Affects combustion efficiency and boiler efficiency

 Causes clinkering and slagging.

(d) Moisture Content

 A known amount of finely powdered air dried coal sample is weighed in a crucible and
heated in an electrical hot-air-oven at 105oC− 110oC for 1 hour and then taken out,
cooled in a desiccator and weighed. The loss in weight is a measure of the moisture
content of coal.

 Moisture in coal must be transported, handled and stored.

 Since it replaces combustible matter, it decreases the heat content per kg of coal.

 Typical moisture range is 0.5 to 10%.

 Moisture increases heat loss, due to evaporation.

 Helps, to a limit, in binding fines.

Ultimate Analysis

 The ultimate analysis indicates the various elementalchemical constituents such as

Carbon, Hydrogen, Oxygen, Sulphur, etc.

 It is useful in determining the quantity of air required for combustion and the
volume and composition of the combustion gases.

 This information is required for the calculation of flame temperature.

(a) Determination of carbon and hydrogen in coal

 A known amount of coal is burnt in presence of oxygen thereby converting carbon and
hydrogen of coal into carbon dioxide and water respectively.

 The products of combustion CO2 and H2O pass over weighed tubes of anhydrous
CaCl2 and KOH which absorb H2O and CO2 respectively.

 The increase in the weight of CaCl2 tube represents the weight of water formed
while the increase in the weight of KOH tube represents the weight of CO2 formed.

 The percentage of carbon and hydrogen in coal can be calculated in the following way

 Consider the following reaction: C + O2 → CO2; 12g of C produces 44g of CO2

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Therefore % of carbon in coal will be determined by 12/44 of (increase in weight of KOH

tube)/(weight of coal sample taken) multiplied by 100.

 Consider the reaction: H2 + O → H2O; 2g of H produces 18g of H2O

% of hydrogen in coal will be determined by 2/18 of (increase in weight of CaCl2 tube)/(weight
of coal sample taken) multiplied by 100.

Nitrogen content

 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 → Na2SO4 + 2NH3 +2H2O

 The ammonia thus liberated is distilled over and absorbed in a known volume of
standard H2SO4 solution

NH3 + H2SO4 = (NH4)2SO4

 The unused acid is then determined by titrating with a standard NaOH solution from
which the percentage of nitrogen is calculated.

Sulphur Content

 To determine sulphur in coal, a known amount of coal 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
from which percentage of sulphur is calculated.

 Typical range is 0.5 to 0.8% normally.

 Sulphur Affects clinkering and slagging tendencies

 Corrodes chimney and other equipment such as air heaters and economizers

 Limits exit flue gas temperature

Carbonization: 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.

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 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.

 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.

Manufacture of Metallurgical Coke by Otto Hoffmann’s Method

 When bituminous coal (coal containing about 90 % carbon) is heated strongly in absence
of air, the volatile matter escapes out and a while, lustrous, dense, strong, porous and
coherent mass is left which is called metallurgical coke.

 In order to save the fuel for heating purpose and recover valuable by-products like coal
gas, ammonia, benzol oil and tar. Otto Hoffmann developed a modern by-product coke
oven.

 The heating is done externally by a portion of coal gas produced during the process
itself. It also utilizes the waste flue gases for heating the checker work bricks.

 The oven consists of a number of narrow silica chambers, each about 10-12 m long, 3-
4m tall and 0.4-0.45 m wide, erected side by side with vertical flues between them to
form a sort of battery. Each chamber has a hole at the top to introduce the charge, a gas
off take and a refractory lined cast iron door at each end for coke discharge.

 The oven works on heat regenerative principle ie. the waste gas produced during
carbonization is utilized for heating.

 The ovens are charged from the top and closed to restrict the entry of air.

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 Coal is introduced into the silica chambers and the chambers are closed. The chambers
are heated to 1200˚C by burning of gaseous fuels (air and producer gas) by passing
them through 2nd and 3rd hot regenerators. Hot flue gases produced during
carbonization come out through 1st and 4th regenerators raising the temperature to
10000oC.

 The fuel gas is now passed through the 1st and 4th regenerators (preheating). Flue
gases come out through the 2nd and 3rd regenerators raise the temperature to 10000oC.
This cycle goes on. This process is known as ‘regenerative system of heat economy

 The time taken for the carbonization process is 11 to 18 hours. When the process is
over, coke is removed from oven and cooled by dry quenching.

How is Petroleum Formed?

 Petroleum is formed from the remains of dead plants and animals that sink and settle
on the seabed millions of years ago and decompose.

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 Due to high temperature and pressure, the organic matter decomposed completely and
formed oil

 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.

 Fractional distillation of crude oil is the process by which we obtain all the various
petroleum products that we rely on from crude oil.

 Products include petrol or diesel that fuels our cars’ engines; the gas oil powering
machinery and furnaces; the jet fuel that fuels aircraft; or domestic and commercial
heating oil that keeps our homes and workplaces warm.

 Petroleum is a broad term that refers to both crude oil and petroleum products.
Petroleum products are the different hydrocarbons groups that occur within crude oil,
and they are obtained through the refinement of crude oil.

Hydrocarbons in crude oil

 Hydrocarbons are chains of carbon and hydrogen that make up all organic material.

 Crude oil is made up of many different types of hydrocarbon chains all mixed together.
When these chains are separated into similar lengths, we have refined the crude oil into
useful products.

 A process called fractional distillation is used in oil refineries to separate (as well as join
or split) the various lengths of hydrocarbon chains to create different petroleum
products from the different distillates.

 The hydrocarbon chains that constitute petroleum fuel products are a family of
hydrocarbons called alkanes, or paraffins, depending on their size.

 Alkanes are hydrocarbon chains with the chemical formula Cn+H2n+2. Alkanes are
stable but versatile, making them safe for use and storage as a range of fuel products.

 The simplest of these alkanes is a gas, methane, with a chemical makeup of CH4 (just
one carbon atom); the next largest is ethane (C2H6), propane (C3H8) and butane
(C4H10). From there, alkanes are named using Greek numerals to easily identify their
structure, for example pentane (C5H12), hexane (C6H14), heptane (C7H16), octane
(C8H18). These alkanes can be hundreds of carbon atoms long.

 Some alkanes are useful to know about at a technical level, specifically octane and
cetane (sometimes called Hexadecane)(C16H34), as they are a measure of the
performance of petrol (the octane number) and diesel fuel (the cetane number in diesel
fuel technical specifications). Alkanes mixtures with a flashpoint of 42℃ are grouped as
fuel oils.

 At the same time, there are also alkenes, naphthenes and aromatics present in crude oil,
which are used in chemical processes. Alkenes and naphthenes refer to hydrocarbons

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with a molecular formula of CnH2n but have different structures – alkanes being formed
in a chain, and naphthenes in a ring.

Fractional distillation and distillates

 The process through which petroleum is refined is called fractional distillation and
occurs in a distillation tower or fractionating column. Outside of the oil industry,
fractional distillation is a process used for separating a mixture of two or more fluids of
different densities by heating the mixture to the point of boiling. These separated fluids
are the ‘distillates’.

 In the context of oil refining, the distillates are the various products we use, such as
petrol or diesel fuels or kerosene. Each of these products has a different density and
form at different stages of the fractionating column – the least dense gases at the top,
and the more dense heavy fuels and bitumen at the bottom.

The most important fractions collected from the fractionating column by distillation of crude

petroleum are:

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 Petroleum ether: This fraction is obtained in the temperature range of 30oC to 70oC. It
contains mainly C5 to C7 hydrocarbons.

 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.

 Maximum power is derived from gasolines when it burns silently and relatively slowly.

Gaseous fuels

1. Natural Gas :

 Compressed Natural Gas (CNG) is formed under the earth by the decomposition of
vegetables matter lying under water. It is obtained 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.

 Its calorific value range from 8000-14000 kcal/m3 and 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.

2. 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.

3. 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

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in specially designed reactor called ‘gas producer’.

3. 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.).

4. Biogas

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

5. 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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