ACCE 1103: Fuels and Combustion

M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

DEFINITION

Fuel is a combustible substance which is able to produce large amount of heat that can be used for
domestic and industrial purpose. Carbon as its major constituent, most of the fuels contain C and H.
Sometimes containing S and N. The combustion involves the oxidation of C to CO2, H to H2O, S if
present oxidized to SO2, while the mineral forms ash.

Combustion refers rapid oxidation of any materials under favourable conditions.

Classifications of Fuel: Fuel can be classified into two types-

(a) On the basis of occurrence

(b) On the basis of physical state

 On the basis of occurrence fuels are further divided into two types-

(a) Natural or primary fuels: Found in nature e.g wood, coal, peat, petroleum, natural gas etc.
(b) Artificial or Secondary fuels: Prepared artificially from primary fuels e.g kerosene, petrol, coal
gas, coke etc.

 On the basis of state of physical state or aggregation fuels are divided into

a) Solid fuels: wood, coal, peat

b) Solid fuels: Mineral oil, Petroleum
c) Gas fuels: Natural gas.

2. CHARACTERISTICS FOR GOOD FUEL: A good fuel should have-

 High calorific value.  Low cost and easy availability.

 Moderate ignition temperature.  Low contents of non-combustible matters.
 Low moisture content.  Combustion should be controllable easily.
 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

 Combustion should be controllable.  Products of combustion should not be

 Easy to transport and readily available at harmful (environment friendly).
low cost.  No offensive odor.

Criteria for selecting a Good fuel:

 Calorific value should be high.

 Miusture content should be low.
 Ash content should be low.
 Sulphur and Phosphorus contents should be low.
 In case of coal size should be uniform.

2.1 Calorific value: It is defined as the amount of heat liberated by the complete combustion of a unit
mass of the fuel.

2.2 Gross or high calorific value (GCV): It is defined as the total heat generated when a unit quantity of
fuel is completely burnt and the products of combustion are cooled to room temperature.

2.3 Net or Lower Calorific Value (NCV)

It is defined as the “net heat produced when a unit quantity of fuel is completely burnt and the products
of combustion are allowed to escape.

NCV = GCV- latent heat of condensation of steam produced.

2.4 Theoretical calculation of calorific value (Dulong‟s formula)

According to Dulong the calorific value of a fuel is the sum of the calorific values of its constituent
elements.

The calorific values of C, H & S are found to be 8080, 34500 and 2240 kcals when 1kg of the fuel is
burnt completely.

Thus, Dulong‟s formulae for GCV is written as

GCV=1/100 [8080(C) + 34500(H-O/8)+ 2240 (S)] Cals /kg.

NCV = [GCV-9/100(H) x 587] Kcals/kg.

The latent heat of steam is 587Kcals/kg.

In Dulong‟s formula C, H, O & S represent the percentage of the corresponding elements.

 [Type the document title] 3
ACCE 1103: Fuels and Combustion

3 SOLID FUEL
Solid Fuels : Solid fuel refers to various types of solid material that are used as fuel to produce energy
and provide heat by combustion.

Types of solid fuel

1. Wood
2. Coal – discussed below.
3. Oil shale = organic rich fine grained sedimentary rocks (like petroleum) containing „Kerogen‟.
From which liquid hydrocarbon can be produced. General composition of oil shales
constitutes inorganic substance and bitumens. It can be refined into many different substances
including disel fuel, gasoline and LPG.
Kerogen: Part of rock that breaks down and release hydrocarbon when heated.
4. Tanbark- is the bark of certain species of trees. Traditionally used for tanning hides into
leather. It is hard, light brown red tinged wood is used for agricultural implements, furniture
and fuel etc.
5. Bagasse – is the dry pulpy fibrous materials remains after crushing sugarcane or sorghum
stalks to extract their juice. Used as a biofuel.
6. Straw
7. Charcoal – is a light weight black carbon residue produced by strongly heating wood in
minimum oxygen (absence of oxygen) to remove all water and volatile constituents. Its
porous material with high carbon content when burned produces little to no smoke. Example:
Common charcoal, sugar charcoal, activated charcoal etc.
8. Coke- a solid carboneous residue derived from low ash, low sulphur bituminous coal from
which the volatile constituents are driven off by heating at 200ºF.

ADVANTAGES OF SOLID FUELS: DISADVANTAGES OF SOLID FUELS:

 Solid fuels are easily available and they are  Combustion process cannot be easily
cheap. controlled.
 Handling and transportation are easy.  The calorific value is comparatively lower.
 They can be stored conveniently without any  They form large amount of ash and its
risk. disposal is a big problem.
 They have a moderate ignition temperature.  A large space is required for storage.

Coal

Coal is one of the fossil fuels. It is a mixture of free carbon and compounds of carbon containing
hydrogen, oxygen, nitrogen and sulphur. Three hundred million years ago, some plants grew into
giant ferns and mosses. These plants got buried into the bottom of the soil. They slowly started to

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

decompose and formed a dense, sponge like material called peat. Over time peat was compressed due
to high temperature and pressure and coal was formed. As coal contains mainly carbon, the slow
process of conversion of dead vegetation into coal is called carbonization.

Extraction of Coal: Coal is extracted from the coal beds found below the surface of the earth. Coal
found inside the earth is broken into pieces by explosives and brought above. Depending on the depth
of the coal bed, coal is extracted in two ways.

Surface mining

If the coal beds lie within 22 feet of the earth‟s

surface, the top soil is removed and coal is dug out.
This is called surface mining.

Underground mining

In some places, coal beds are found very deep

inside the earth. In that case underground
tunnels are made to get this coal. This is called
underground mining or deep mining.

Coal reserves can be found in about 70 countries worldwide. The largest coal reserves are available in
United State, Russia, China, Australia and India. The US is the international leader in coal reserves,
with nearly 30% of the world‟s supply. Coal mining was started in India in 1774. India now ranks
third among the coal producing countries in the world. USA and China have two third of the world‟s
coal reserve.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

2. Types of Coal

Coal is classified into four main categories based on the amounts of carbon it contains and the heat
energy it can produce. They are lignite, sub bituminous, bituminous and anthracite. Among these four
types anthracite is the most desirable one due to its high heat content.

Lignite

Lignite is a brown colored coal of lowest grade. It has the lowest carbon content. The carbon content
of lignite is 25 – 35%. Lignite contains a high amount of water and makes up almost half of our total
coal reserves. It is used for electricity generation. The other uses include generating synthetic natural
gas and producing fertilizer products.

Sub-bituminous

When lignite becomes darker and harder over time sub-bituminous coal is formed. Sub bituminous
coal is a black and dull coal. It has higher heating value than lignite and contains 35-44% carbon. It is
used primarily as fuel for electricity power generation. This coal has lower sulphur content than other
types and burns cleaner.

Bituminous

With more chemical and physical changes, sub-bituminous coal is developed into bituminous coal.
Bituminous coal is dark and hard. It contains 45-86% carbon.

It has high heating value. It is used to generate electricity. Other important use of this coal is to
provide coke to iron and steel industries. By-products of this coal can be converted into different
chemicals which are used to make paint, nylon, and many other items.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Anthracite

Anthracite is the highest grade coal. It has a very light weight and the highest heat content. Anthracite
coal is very hard, deep black and shiny. It contains 86-97% carbon and has a heating value slightly
higher than bituminous coal. It burns longer with more heat and less dust.

3. Uses of Coal

 Coal is used to generate heat and electricity.

 It is used to make derivatives of silicon which are used to make lubricants, water repellents,
resins, cosmetics, hair shampoos, and toothpaste.
 Activated charcoal is used to make face packs and cosmetics.
 Coal is used to make paper.
 Coal helps to create alumina refineries.
 Carbon fibre which is an extremely strong but light weight material is used in construction,
mountain bikes, and tennis rackets.

o Activated carbon, used in filters for water and air purification and in kidney dialysis machines
is obtained from coal.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

4. Products obtained from coal

Coal when heated in the absence of air does not burn but produces many by -products. This process
of heating coal in the absence of air is called destructive distillation of coal. The destructive
distillation of coal can be carried out in the laboratories. The apparatus is as shown in Figure 15. 13.

Finely powdered coal is taken in a test tube and heated. At a particular temperature coal breaks down
to produce coke, coal tar, ammonia and coal gas. Coal tar is deposited at the bottom of the second test
tube and coal gas escapes out through the side tube. Ammonia produced is absorbed in the water,
forming ammonium hydroxide. Finally a black residue called coke is left in the tube.

Thousands of different products have coal or coal by-products as their components. Some of them are
soap, aspirins (tablet), solvents, dyes, plastics, and fibres, such as rayon and nylon. The main by-
products obtained during destructive distillation are coke, coal tar, ammonia and coal gas.

Coke

Coke contains 98% carbon. It is a porous, black and the purest form of coal. It is a good fuel and
burns without smoke. It is largely used as a reducing agent in the extraction of metals from their
ores. It is also used in making fuel gases like producer gas and water gas.

Coal tar

Coal tar is a mixture of different carbon compounds. It is a thick, black liquid with unpleasant
smell. The fractional distillation of coal tar gives many chemical substances like benzene, toluene,
phenol and aniline. They are used in the preparation of dyes, explosives, paints, synthetics fibers,

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

drugs, and pesticides. Another product obtained from coal tar is naphthalene balls which are used to
repel moth and other insects.

Coal gas

Coal gas also known as town gas is mainly a mixture of gases like hydrogen, methane and carbon
monoxide. The gases present in coal gas are combustible and hence, it is an excellent fuel. It has high
calorific value.

Ammonia

The other by product obtained from coal is ammonia. It is used for making fertilizers such as
ammonium sulphate, ammonium superphosphate etc.

It is also known as Black Diamond owing to its precious nature. On destructive distillation, 1000 kg
of coal gives 700 kg of coke, 100 litres of ammonia, 50 litres of coaltar and 400 m3 of coal gas.

Analysis of coal

4.1 Proximate Analysis:

It involves the determination of percentage of following in coal

 Moisture content
 Volatile matter
 Ash content
 Fixed carbon

(a) Moisture content: 1gm of powdered and air-dried coal sample in crucible is heated at 100-150⁰C
in an electric air oven for 1 hour. The loss in weight of the sample is found out and percentage of
moisture is calculated as

% of moisture = (Loss in weight of coal / Weight of air-dried coal) ×100

(b) Volatile matter: In this the crucible with residual coal sample is covered with a lid and heated at
950± 20⁰C for 7mins in a muffle furnace. The loss in weight is found out.

(c) Ash Content: The crucible with residual coal sample is heated without lid at 700 ± 50 ⁰C for
½hour in a muffle furnace. The loss in weight is found out.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

(d) Fixed Carbon: fixed carbon = percentage of (a+b+c)

4.2 Significance of proximate analysis:

 High percentage of moisture content is undesirable.
 High percentage of volatile matter is undesirable.
 High percentage of ash content is undesirable.
 High percentage of fixed carbon content is desirable.

4.3 Ultimate analysis of coal:

Coal is composed primarily of carbon along with variable quantities of other elements, chiefly
hydrogen, sulphur, oxygen, nitrogen. Ultimate analysis is also known as elemental analysis, it is the
method to determine the Carbon,Hydrogen,Nitrogen,Sulphur and Oxygen content present in solid
fuel.

It involves the determination of % of Carbon, Hydrogen, Nitrogen, Sulphur & Oxygen in coal.

1. Carbon & Hydrogen: A known aount of coal sample is burnt with o2 in a combustion apparatus.
In coal carbon & hydrogen are converted into CO2 & H2O & those are absorbed by KOH tubes &
CaCl2 tubes.

2. Nitrogen:

It is carried out by Kjeldahl‟s method. A known amount of coal is heated with Con. H2SO4 in
presence of K2 SO4 catalyst in a long necked flask called Kjeldahl‟s flask. Nitrogen is converted into
ammonium sulphate. Then it is heated with NaOH & absorbed by HCl.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

3. Sulphur: A known amount of coal is completely burnt in a bomb calorimeter. Here sulphur is
converted into sulphate & treated with BaCl2, BaSO4 is obtained.

4. Oxygen: The % of oxygen is calculated as follows,

% of Oxygen in Coal = 100 - % of (C + H+N+S+ash)

Importance or significance of Ultimate analysis:

 Higher % of carbon & hydrogen, better is the quality of coal & higher its calorific value.
 Should have very little nitrogen content.
 Presence of sulphur is undesirable because it forms harmful gases during the combustion.
 Lower of the Oxygen increases the higher its calorific value.

Self practice: Differentiate between Proximate analysis & Ultimate analysis.

5. CARBONISATION OF METALLURGICAL COKE

When coal is heated strongly in the absence of air, it is converted into lustrous, dense, porous and
coherent mass known as coke. This process of converting coal is known as carbonization.

5.1 METALLURGICAL COKE

When bituminous coal is heated strongly in the absence of air, the volatile matter escapes out and
the mass becomes hard, porous and coherent which is called Metallurgical coke.

PREPARATION
5.2 Otto-Hoffman’s method: Significance of Otto-Hoffman‟s method
(i) To increases the thermal efficiency of the carbonization process and,
(ii) To recover the valuable by products (like coal gas, ammonia, benzyl oil, etc).

The oven consists of a number of silica chambers, each chamber is provided with a charging hole at
the top, it is also provided with a gas off take valve and iron door at each end for discharging coke.

Coal is introduced into the silica chamber and the chambers are closed.

The chambers are heated to 1200 o C by burning the preheated air and the producer gas mixture in the
interspaces between the chambers. The air and gas are preheated by sending them through 2nd and 3rd
hot regenerator.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Hot flue gases produced during carbonization are allowed to pass through 1st and 4th regenerators
until the temperature has been raised to 1000ċ.

While 1st and 4th regenerated are heated by hot flue gases, the 2nd and 3rd regenerators are used for
heating the incoming air and gas mixture.

When the process is complete, the coke is removed and quenched with water.

The yield of coke is about 70%.

The valuable by products like coal gas, tar, ammonia, H2S and benzyl, etc. can be recovered from flue
gas.

5.3 Recovery of by-products

(i) Tar: The flue gases are first passed through a tower in which liquor ammonia is sprayed. Tar
and dust get dissolved and collected in a tank below

(ii) Ammonia: The gases are then passed through another tower in which water is sprayed. Here
ammonia gets converted to NH4OH.

(iii) Naphthalene: The gases are again passed through a tower, in which cooled water is sprayed,
naphthalene gets condensed.

(iv) Benzene: The gases are passed through another tower, where petroleum is sprayed, benzene gets
condensed to liquid.

(v) Hydrogen Sulphide: The remaining gases are then passed through a purifier packed with moist
Fe2O3. Here H2S is retained.

The final gas left out is called coal gas which is used as a gaseous fuel.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

5.4 Advantages of Otto Hoffman’s process

o Valuable by products like ammonia, coal gas, Naphthalene etc. are recovered.
o The carbonization time is less.
o Heating is done externally by producer gas.

6 LIQUID FUELS

ADVANTAGES OF LIQUID FUELS:

 They have higher calorific value than solid fuel.

 They occupy less storage space than solid fuels.
 Their combustion is uniform and easily controllable.
 Liquid fuels do not yield any ash after burning.

DISADVANTAGES OF LIQUID FUELS:

 Liquid fuels are more costly than the solid fuels.

 Liquid fuels give unpleasant odor during incomplete combustion.
 Special type of burners is required for effective combustion.
 Some amount of liquid fuels will escape due to evaporation during storage.

6.2 PETROLEUM

 It is naturally occurring liquid fuel.

 It is dark brown or black colored viscous oil.
 Crude oil is a mixture of paraffinic, olefinic and aromatic hydrocarbons with small amounts of
organic compounds like N, O and S.
 The average composition of crude oil is as follows
C = 80-87%
H = 11-15%
S = 0.1-3.5%
N+O = 0.1-0.5% It is classified into three types

1. Paraffinic-Base type crude oil: It contains saturated hydrocarbons from CH4 to C35H72
(Pentatriacontane) with a smaller amount of naphthenes and aromatics.

Note: Cycloalkanes (cycloparaffins or naphthenes) consist of carbon atoms joined by single bonds
in a ring structure. The most abundant cycloalkanes in oil are the single-ring cyclopentane (C5H10)
and cyclohexane (C6H12), and their alkylated (from C1 to C14) homologs (alkyl-cyclopentanes and
alkyl-cyclohexanes).

2. Naphthenic or Asphaltic Base type crude oil: It contains cycloparaffins or naphthenes with a
smaller amount of paraffin and aromatics.

3. Mixed base type crude oil: It contains both paraffinic and asphaltic hydrocarbons.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Note: Asphalt is a black or brown petroleum-like material that has a consistency varying from
viscous liquid to glassy solid. It is obtained either as a residue from the distillation of petroleum or
from natural deposits. Asphalt consists of compounds of hydrogen and carbon with minor proportions
of nitrogen, sulfur, and oxygen. Natural asphalt (also called brea), which is believed to be formed
during an early stage in the breakdown of organic marine deposits into petroleum, characteristically
contains minerals, while residual petroleum asphalt does not.

The use of asphalt is very old, dating back to its use as a water stop between brick walls of a reservoir
at Mohenjo-Daro (about the 3rd millennium bc) in Pakistan. In the Middle East it was extensively
used for paving roads and sealing waterworks, important applications even today. The Pitch Lake on
the island of Trinidad was the first large commercial source, but natural sources have since declined
in importance as petroleum became the major source. Gilsonite, wurzilite, and similar vein asphalts
have special uses in heat-resistant enamels; they are hard and are mined like coal. Petroleum asphalt
is produced in all consistencies from light road oils to heavy, high-viscosity industrial types.

Asphalt softens when heated and is elastic under certain conditions. The mechanical properties of
asphalt are of little significance except when it is used as a binder or adhesive. The principal
application of asphalt is in road surfacing, which may be done in a variety of ways. Light oil “dust
layer” treatments may be built up by repetition to form a hard surface, or a granular aggregate may be
added to an asphalt coat, or earth materials from the road surface itself may be mixed with the
asphalt.

Other important applications include canal and reservoir linings, dam facings, and other harbour and
sea works; asphalt so used may be a thin, sprayed membrane, covered with earth for protection
against weathering and mechanical damage, or thicker surfaces, often including riprap (crushed rock).
Asphalt is also used for roofs, coatings, floor tilings, soundproofing, waterproofing, and other
building-construction elements and in a number of industrial products, such as batteries. For certain
applications an asphaltic emulsion is prepared, in which fine globules of asphalt are suspended in
water.

6.3 REFINING OF PETROLEUM OR CRUDE OIL

The crude oil obtained from the earth is a mixture of oil, water, unwanted impurities and it‟s
subjected to fractional distillation.

During fractional distillation, the crude oil is Thus, the process of removing impurities and separating
the crude oil into various fractions having different boiling points is called Refining of Petroleum.

The process of refining involves the following steps.

Step 1: Separation of water (Cottrell‟s process): The crude oil well is an extremely stable
emulsion. The crude oil is allowed to flow between two highly charged electrodes, where colloidal
water droplets combine to form large drops, which is then separated out form the oil.

Step 2: Removal of harmful sulphur compounds: Sulphur compounds are removed by treating the
crude oil with copper oxide. The copper sulphide formed is separated out by filtration.
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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Step 3: Fractional distillation: The purified crude oil is then heated to about 400ºC in an iron retort,
where the oil gets vaporized.

The hot vapors are then passed into the bottom of a “fractionating column”.

The fractionating column is a tall cylindrical tower containing a number of horizontal stainless steel
trays at short distances.

Each tray is provided with small chimney covered with a loose cap.

When the vapors of the oil go up in the fractionating column, they become and get condensed at
different trays.

The fractions having higher boiling points condense at lower trays whereas the fractions having
lower boiling points condense at higher trays.

The gasoline obtained by this fractional distillation is called straight-run gasoline.

Various fractions obtained at different trays are given in table.

7. KNOCKING

The rate of ignition of the fuel gradually increases and the final portion of the fuel-air mixture gets
ignited instantaneously (unevenly) producing an explosive sound known as “Knocking”.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

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.

7.2: Improvement of anti knock characteristics

Blending petrol of high octane number with petrol of low octane number, so that the octane number
of the latter can be improved. The addition of anti-knock agents like Tetra-Ethyl Lead (TEL).

7.3 OCTANE NUMBER OR OCTANE RATING

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.

7.4 ANTI-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.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

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 di-bromide is added along with TEL.

This ethylene di-bromide reacts with Pb and PbO to give volatile lead bromide, which goes out along
with exhaust gases and creates atmospheric pollution.

But nowadays aromatic phosphates are used instead of TEL.

7.5 Causes of knocking in CI (Diesel) engines

In a diesel engine, first air is compressed and raises the temperature of the cylinder to about 500ºC
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.

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 as 100.
On the other hand 2-methyl naphthalene has a long ignition lag and hence its cetane number is taken
zero.

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.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

7.8 DIESEL INDEX

The quality of diesel oil is indicated by diesel index number using the following.

Aniline point and specific gravity is noted from API (American Petroleum Institute)

Note: The aniline point of an oil is defined as the minimum temperature at which equal volumes of
aniline and lubricant oil are miscible, i.e. form a single phase upon mixing.

Comparison of gasoline oil and diesel oil

Gasoline oil
1. Low boiling fraction of petroleum contains C5-C9 hydrocarbons.
2. Fuel for SI engine
3. Knocking tendency is measured in octane rating
4. Knocking is due to premature ignition
5. Antiknocking is improved by the addition of TEL
6. Its exhaust gases contain higher amount of pollutants
7. More consumption, lower thermal efficiency

Diesel oil
1. High boiling fraction of petroleum contains C15-C18 hydrocarbons.
2. Fuel for Cl engine.
3. Knocking tendency is measured in cetin rating.
4. Knocking is due to ignition lag.
5. Anti knocking is improved by doping with ethyl nitrate.
6. Its exhaust gases contain lesser amount of pollutants.
7. Less consumption, higher thermal efficiency.

Self Activity: Differentiate between Gasoline oil and Diesel Oil.

8. Hydrogenation of coal: The preparation of liquid fuels from solid coal is called Hydrogenation of
coal.

Coal contains about 4.5% of hydrogen compared to about 18% of in petroleum. So, coal is a
hydrogen deficient compound.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

If coal is heated with hydrogen to high temperature under high pressure, it is converted to gasoline.
There are two methods available for the hydrogenation of coal.

 Bergius process (or direct method)

 Fischer- Tropsch Process (or indirect method)

8.1(a)Bergius process (indirect method)

Finely powdered coal + heavy oil+ catalyst powder (tin or nickel) is made into a paste
The paste is pumped along with hydrogen gas into the converter, where the paste is heated to 400-
450ºC under a pressure of 200-250atm.
During this process hydrogen combine with coal to form saturated higher hydrocarbons, which
undergo further decomposition at higher temperature to yield mixture of lower hydrocarbons.
The mixture is led to a condenser, where the crude oil is obtained. The crude oil is then
fractionated to yield. (i) Gasoline (ii) Middle oil (iii) heavy oil.
The middle oil is further hydrogenated in vapour phase to yield more gasoline.
The heavy oil is recycled for making paste with fresh coal dust.
The yield of gasoline is about 60% of the coal.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

8.2 (b) Fischer-tropics process (indirect method)

In this process coal is first converted into coke. Then water gas is produced by passing steam over red
hot coke

The water gas is mixed with hydrogen and the mixture is purified by passing through Fe 2O3 +
Na2CO 3 (to remove sulphur compounds).

The purified gas is compressed to 5 to 25 atm and then led through a converter, which is maintained
at a temperature of 200-300⁰C.

The converter is provided with a catalyst bed consisting of a mixture of 100 parts cobalt, 5 parts
thoria, 8 parts magnesia and 200 parts kieselgurh earth.

A mixture of saturated and unsaturated hydrocarbon is produced as a result polymerization.

The out coming gaseous mixture is led to condenser, where the liquid crude oil is obtained.

The crude oil is fractionated to yield (i) Gasoline and (ii) Heavy oil.

The heavy oil is used for cracking to get more gasoline.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

9 GASEOUS FUELS

 ADVANTAGES OF GASEOUS FUELS:

 Gaseous fuels have high calorific value than solid fuels.
 During burning they do not produce any ash or smoke.
 Compared to solid and liquid fuels, they have high thermal efficiency.
 They can be easily transported through the pipes.

DISADVANTAGES OF GASEOUS FUELS:

 They are highly inflammable and hence the chances for fire hazards are high.
 Since gases occupy a large volume, they require large storage tanks.

9.1. COMPRESSED NATURAL GAS (CNG)

When the natural gas is compressed, it is called compresses natural gas (CNG). The primary
component present in CNG is methane. It is mainly derived from natural gas.

Properties
 CNG is the cheapest, cleanest and least environmentally vehicle impacting alternative fuel.
Vehicles powered by CNG produce less carbon monoxide and hydrocarbon (HC) emission.
 It is less expensive than and diesel.
 The ignition temperature of CNG is about 55ºC.
 CNG requires more air for ignition.

Uses:

 CNG is used to run an automotive vehicle just like LPG.

 Comparison of emission levels between CNG- driven vehicles and petrol driven vehicles.

Other Gases

Apart from natural gas, there are some other gases which are used as fuel. Producer gas, coal gas, bio
gas and water gas are some of them.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Producer Gas

Producer gas is a gaseous mixture of carbon

monoxide and nitrogen. It is produced by passing
air mixed with steam, over red hot coke at a
temperature of 1100 ˚C. It is used as an industrial
fuel for iron and steel manufacturing. It is
calorific value is about 1300 kcal/m3.

Producer gas is known by different names in

different countries. It is referred as Wood gas in
USA and as Suction gas in UK.

Manufacture:

 The reactor used for the manufacture of producer gas is known as gas producer.
 It consists of a tall steel vessel inside of which is lined with refractory bricks.
 It is provided with cup and cone feeder at the top and a side opening for producer gas exists.
 At the bottom, it is provided with an inlet pipe for passing air and steam.
 When a mixture of air and steam is passes over a red hot coke maintained at about 1100ºC in a
reactor, the producer gas is produced.

1. Ash Zone: This is the lowest zone consists mainly of ash. The incoming air and steam
mixture is preheated in this zone.

2. Combustion or oxidation zone: This is the zone next to ash zone. Both the reactions are
exothermic. Hence, the temperature of the bed reaches around 1,100ºC.

3. Reduction Zone: This is the middle zone. Here both CO2 and steam are reduced.

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M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

The above reactions are endothermic. Hence the temperature of the coke bed falls to 1000ºC.

4. Distillation or Drying Zone: This is the upper most of the coke bed. In this zone (400-800ºC)
the incoming coke is heated by the outgoing gases.

Uses:

 It is used as a reducing agent in metallurgical operations.

 It is also used for heating muffle furnaces, open-hearth furnaces etc.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Coal Gas

It is a mixture of gases like hydrogen, methane

and carbon monoxide obtained by the destructive
distillation of coal. Heating coal in the absence
of air is called destructive distillation. It is used
in heating open hearth furnace in the
manufacture of steel. It is also used as a reducing
agent in certain metallurgical operations.

Water Gas

It is a gaseous mixture of carbon monoxide and hydrogen. It is made by passing steam over
incandescent coke at a temperature of 1000°C.

C (g) + H2O(g) ---1000°C→ CO(g) + H2 (g)

It is also called as syngas or synthesis gas as it is used to synthesize methanol and simple
hydrocarbons. It is used as an industrial fuel also.

The average composition of water gas is as follows.

Its calorific value is about 2800kcal/m3

Manufacture

The water gas producer consists of a tall steel vessel, lined inside with refractory bricks. It is provide
with cup and cone feeder at the top and a side opening of water gas exist.

At the bottom on it is provide with two inlet pipes for passing air and steam.

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M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

When steam and little air is passed alternatively over a red hot coke maintained at about 900-1000ċ in
a reactor, water gas is produced.

Step-I: In the first stage, steam is passed through the red hot coke, where CO &H2 are produced. The
reaction is endothermic. Hence, the temperature of the coke bed falls.

In the second stage, in order to raise the temperature of the coke bed to 1000ċ, the steam supply is
temporarily cut off and air blown in; the reaction is

Thus the steam-run and air blow are repeated alternatively to maintain proper temperature.

Uses

 It is used for the production of H2 and in the synthesis of ammonia.

 It is used to synthesis gasoline in Fischer-Tropics process.
 It is also used in the manufacture of power alcohol and carbureted water gas (water gas
oil gas).

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Bio-Gas

Bio-gas is a mixture of methane and carbon

dioxide. It is produced by the decomposition of
plant and animal waste which form the organic
matter. The breaking down of organic matter in
anaerobic condition (ie., in the absence of
oxygen) leads to the formation of biogas. It is
an example for renewable source of energy.

Activity 3

Visit a bio-gas plant in your area with your teacher. Find out how it is prepared. Discuss about the
uses and advantages of bio gas. In what way it will be helpful to the people in rural area?

9.4. LPG- Liquefied Petroleum gas

 It is also known as bottled gas or refinery gas.

 It is obtained by a by-product during the fractional distillation of heavy oil or cracking of
higher hydrocarbons.
 It can easily be liquefied under pressure, but exist as gas at atmospheric pressure.
 LPG consists of the following hydrocarbons containing carbons atoms up to 4(C4).

The average composition of LPG is

Propane - 24.7%
Butane - 38.5%
Isobutene - 37.7%
LPG has the calorific value of about 2500 Kcals/m3.

Uses

LPG is supplied with the trade name like indene bharath gas etc. It is mainly used as domestic and
industrial fuel.

It is also used as motor fuel, because it easily mixes with air and burns without any pollution creating
residue.

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M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Advantages

 It possesses high efficiency and heating rate.

 Burns completely without smoke.
 Needs only little care in maintenance.
 Easily transported using steel cylinder to any places.
 It is very cheaper than gasoline.

Disadvantages

 Handling should be only under pressure.

 User of LPG in engines is possible only if it works under high compression ratio.
 Its response to blending is poor and so its uses are selective.

CNG vs LPG

The key differences between CNG and LPG are provided in this article. CNG is an abbreviation of
“Compressed Natural Gas” whereas LPG is an abbreviation of “Liquefied Petroleum Gas”. The
primary difference between CNG and LPG lies in the components that make up these fuels. While
CNG is primarily made up of Methane, LPG is primarily made up of propane. A few other
differences between CNG and LPG can be found in the tabular column provided below.

Difference between CNG and LPG

One of the major differences between CNG and LPG is that CNG is relatively cheaper than LPG.
However, it is important to note that LPG has a much greater calorific value when compared to CNG.

Difference between CNG and LPG

CNG LPG

It has various uses such as heating and cooking

Its primary use is as an alternative for fuel in
in homes. LPG also has industrial and
automobiles.
agricultural uses.

The primary component in LPG is propane and

The primary component in CNG is methane.
butane.

It produces relatively lower quantities of greenhouse It produces relatively large amounts of carbon
gases (in comparison with LPG). dioxide, a greenhouse gas.

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M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

It is highly flammable as it is much heavier than

It is relatively safe as it disperses rapidly into the air.
air.

The primary source of obtaining CNG is from oil The main source of obtaining LPG is from the
wells, bed methane wells, coal wells and even process of extracting natural gas from
natural gas wells. reservoirs.

Draw backs of presence of S in Coal:

The combustion products of sulphur, SO2 and SO3 are harmful and have corrosion effects on
equipments.

The coal containing sulphur is not suitable for the preparation of metallurgical coke as it affects the
properties of the metal.

Advantages of liquid fuels over solid fuels

Advantages: Disadvantages:
1. Liquid fuel having higher calorific 1. Cost of liquid fuel is high.
value. 2. The storage tank specially designed.
2. Less space is required for storage. 3. It has higher cost.
3. Easy control of combustion by 4. Danger of explosion.
stopping supply of fuel. 5. Liquid fuels mostly we import from other
4. It is very clean fuel, dust free. countries. So, we depends on other
5. Reduction in cost of handling. countries.
6. Easily transported through pipes.
7. During burning it does not form ash.

Gaseous fuels
Advantages of gaseous fuels: Disadvantages:
1. They are free from solid and liquid 1. They are readily inflammable.
Impurity 2. They require large storage capacity.
2. Maximum complete combustion of 3. The cost of gaseous fuel are more.
gaseous fuel is possible.
3. The rate of combustion and temperature
in the combustion chamber can be
easily controlled. 4. For complete
combustion less amount of excess air is

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M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

required.
4. Do not produce ash and smoke.
5. 6. Large amount of heat and
temperature is obtained at a moderate
cost.

Solid fuel
Advantages of solid fuel: Disadvantages:
1. Solid fuel can be stored conveniently 1. Rate of combustion of solid fuel can't be
without any risk of explosion. easily controlled.
2. They can easily transport. 2. Large amount of heat is wasted.
3. They have moderate ignition 3. The ash content of solid fuel is very high.
temperature. 4. The cost of handling of solid fuel is high.
4. Leakage problem is not takes place. 5. After burning it produce large quantity of
smoke.

Merits of liquid fuels over gaseous fuels: (Any four)

1. Required less space for storage.

2. Higher calorific value.
3. Easy control of consumption.
4. Easy handling & transportation.
5. Absences of danger from spontaneous combustion.

SI. Natural liquid fuel Artificial liquid fuel

01 It is obtained from reservoirs in the earth. It is obtained by distillation process of crude oil.

02 Raw material of oil industries. This is the final Product of oil industries.

03 Impure form of fuel. Pure form of fuel.

04 It is cheap. It is costly.

05 Crude petroleum. Gasoline, Kerosene, Lubricating oil, and grease.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

SI.. Solid Fuels Gaseous fuel

01 Required Large space. Required Large space.

02 Low calorific value. Low calorific value.

03 For combustion more air is required. For combustion less air is required.

04 Produce ash & smoke after combustion. Do not Produce ash & smoke after combustion.

05 Low cost. High cost.

06 Impure form. Pure form.

Alternative Fuel

The natural resources in the world have been used by man in a rapid way and they will be exhausted
soon.

Alternative Fuel

The natural resources in the world have been used by man in a rapid way and they will be exhausted
soon. The traditional fuel that we use today including petroleum are non- renewable and they would
be depleted soon. It is estimated that coal will last for 148 years, petroleum for 40 years and natural
gas for 61 years. So we need to find alternative sources of energy. More over fossil fuels emit
harmful gases like carbon dioxide, carbon monoxide and sulphur dioxide which pollute the
atmosphere. Burning fossil fuels also cause temperature rise in the earth‟s atmosphere. Many believe
that fuel which does not cause pollution is needed to enhance the quality of our environment. Some of
the alternative fuels are given below.

Biofuel

Biofuel is a type of renewable energy source derived from microbial, plant, or animal materials.
Examples of biofuels include ethanol (often made from corn in the United States and sugarcane in
Brazil), biodiesel (sourced from vegetable oils and liquid animal fats), green diesel (derived from
algae and other plant sources), and biogas (methane derived from animal manure and other digested
organic material).

Biofuels can be solid, liquid, or gaseous. They are most useful in the latter two forms as this makes it
easier to transport, deliver, and burn cleanly.
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M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

There are two main types of biofuel used in cars: bioethanol and biodiesel. Bioethanol is an alcohol
made from corn and sugarcane, whereas biodiesel is made using vegetable oils and animal fats

Key Takeaways

 Biofuels are a class of renewable energy derived from living materials.

 The most common biofuels are corn ethanol, biodiesel, and biogas from organic byproducts.
 Energy from renewable resources puts less strain on the limited supply of fossil fuels, which
are considered nonrenewable resources.

Limitations of Biofuel

Individuals concerned about energy security and carbon dioxide emissions see biofuels as a viable
alternative to fossil fuels. However, biofuels also have shortcomings.

For example, it takes more ethanol than gasoline to produce the same amount of energy, and critics
contend that ethanol use is extremely wasteful because the production of ethanol actually creates a net
energy loss while also increasing food prices.

Biofuels have also become a point of contention for conservation groups, who argue that bio-crops
would go to better use as a source of food rather than fuel. Specific concerns center around the use of
large amounts of arable land that are required to produce bio-crops, leading to problems such as soil
erosion, deforestation, fertilizer run-off, and salinity

Bio diesel

Bio-diesel is a fuel obtained from vegetable oils such as soya bean oil, jatropha oil, corn oil,
sunflower oil, cotton seed oil, rice-bran oil and rubber seed oil.

Hydrogen - The future fuel Hydrogen could be the best alternative fuel in the future. It is a clean
fuel as it gives out only water while burning. Moreover, it has the highest energy content. It does not
pollute air.

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Wind energy

Wind energy is obtained with the help of wind

mills. When wind blows, they rotate the blades of
the wind mills and electricity is produced by the
dynamo. Wind mills are mostly located at
Kayathar, Aralvaimozhi, Palladam and
Kudimangalam in Tamil Nadu.

Gobar Gas

Biogas or gobar gas is a clean, unpolluted and cheap source of energy in rural areas. It consists of
55−70% methane which is inflammable. Biogas is produced from cattle dung in a biogas plant (in the
absence of air (anaerobic conditions)) commonly known as gobar gas plant through a process called
digestion (fermentation).

In a Gobar gas plant, gobar gas is formed by bacterial fermentation of animal refuse. It mainly
contains methane and its heat of combustion is −809 kJ mol−1 according to the following equation:
CH4+2O2⟶CO2+2H2O;ΔH= −809 kJ

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 ACCE 1103: Fuels and Combustion
M A Samad Azad
Applied Chemistry and Chemical Engineering(ACCE),NSTU

Solar Energy

Sun is the first and foremost energy source that makes life possible on the earth.

Solar Energy

Sun is the first and foremost energy source

that makes life possible on the earth. Solar
energy is the only viable fuel source of non-
depleting nature for sun provides a free and
renewable source of energy. It is the
renewable type of energy without
endangering the environment. It is the
potential source to replace the fossil fuel in
With the advancements in science and technology,
order to meet the needs of the world.
solar energy has become more affordable, and it can
overcome energy crisis. Solar energy is a clean
energy. With the minimum efforts maximum energy
can be harnessed using various equipments.

Applications of Solar Energy

 Solar energy has wider applications in various fields.

o It is used in solar water heater.
o It is used in drying of agricultural and animal products.
o It is used in electric power generation.
o It is used in solar green houses.
o It is used in solar pumping and solar distillation. It is used for solar cooking and solar furnaces
also.

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