Fuels and Combustion

Fuels and Combustion
Universities Press (India) Private Limited
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© Universities Press (India) Private Limited 2009

First Published by Orient Blackswan Private Limited 1974
Second edition 1990
Reprint 1994, 1996, 1998. 2001, 2003, 2005, 2008
Third edition 2009
Reprinted 2010, 2012, 2016
e-edition: First Published 2022
eISBN: 978 93 89211 38 2
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Published by
Universities Press (India) Private Limited
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Hyderabad 500 029 Telangana, India.
Preface
Third Edition
The first edition of the book was published in 1974. It was so well
accepted by students and professional engineers that it necessitated
the publication of an improved edition within a few years. Therefore
the second edition of the book was published in 1990.
I retired from the Indian Institute of Technology, Bombay in
December 1993. At the end of 2007 I was asked by Universities
Press, an associate of Orient Longman Private Limited (now
renamed Orient Blackswan Private Limited) to write the third edition
of the book. Being physically incapacitated I initially declined.
However, the persuasive efforts of Mr Madhu Reddy, who met me in
Kolkata, emboldened me to undertake the revision. The first chapter
has once again been revised to include the most recent data on
global reserves and consumption of fuels. The data in other chapters
have also been updated wherever available. The layout of the book
has been redesigned to give visibility to all sub-topics and improve
readability.
In the process of compilation of the third edition I acknowledge
the help received from the library of Development Consultants
Private Limited (DCPL), Kolkata, Coal India Limited and my son Prof.
Sutanu Sarkar, for his compilation of recent international data about
the conversion of coal to oil throughout the world and other fuel
related information.
I pray that this edition should be useful to students and teachers
in India and abroad.
May 2009 Samir Sarkar
Preface
Second Edition
Primarily meant for students as a textbook, Fuels and Combustion

has been well accepted by professional engineers as well.
The book was out of print for a long time. Repeated requests
have been received for bringing out its second edition.
The first edition has been critically read several times. The bulk of
the text has remained topical after fourteen years of its publication.
However, chapter one has been thoroughly revised. Some of the
topics in other chapters have been updated. The numerical problems
in chapter six and seven have been augmented. All the problems for
practising have been provided with numerical answers.
The statistical data needed close scrutiny. The addition of newer
data has been possible by the help received from the staff of the
Central Fuel Research Institute, Dhanbad, and the Tata Energy
Research Institute, New Delhi. I am indeed thankful to them.
Acknowledgement is due to the Curriculum Development Centre
of the Indian Institute of Technology, Bombay, for financial support in
the preparation of the manuscript.
December 1988 Samir Sarkar

Department of Chemical Engineering
Indian Institute of Technology, Bombay
Preface
First Edition
‘Fuels and Combustion’ forms an integral part of the undergraduate

degree courses in Chemical, Mechanical, Metallurgical and
Aeronautical Engineering. While in the vast majority of courses the
subject retains a distinct identity, there are instances when it is
treated as a minor adjunct to other topics. Apparently this is the
result of hasty distribution of available hours, where the first victim is
the students’ understanding of the subject, leading to difficulties in
the application of the knowledge in later years. Since there can be
no two opinions on the basic need of the subject for the engineering
courses concerned, a definite place has to be found for it in the
academic curriculum.
The subject has two aspects, namely, ‘Fuels’ and ‘Combustion’.
Their relative importance in a given course is a matter of judgement.
However, one should bear in mind that a good treatment of
‘combustion’ can only follow a sound understanding of different
‘fuels’. On the other hand a rigid balance between the different
aspects of the subject cannot constitute a set pattern for all the
courses. Enough flexibility in this regard should be available to the
teacher and the taught. To a chemical engineer, fuels not only supply
energy but also provide basic raw materials for a host of vital
industries. It is, therefore, understandable why much greater stress
should be laid on the processing of fuels for the benefit of chemical
engineering students as compared to those of other branches of
engineering. On the contrary, an Aeronautical Engineering student
may not require more than a cursory treatment of ‘solid fuels’, and
may prefer to raise the ‘combustion’ content of the subject.
I have planned the present textbook in such a way that all those
requiring a course on Fuels and Combustion will find the required
material in it. In consonance with the modern methodology of
teaching I have laid stress on the systematic development of the
subject. The maximum attention has been given to elucidating the
fundamental principles, while the analytic approach has been
exploited to the fullest possible extent. Indian raw materials and
Indian practices have been given due coverage. Numerical problems
have been worked out in many sections of the book and additional
problems have been furnished for further practices. ‘Furnaces and
Boilers’ has been intentionally excluded from the present textbook. A
mere descriptive treatment of this subject is considered uninteresting
and undesirable for the engineering students. In fact ‘Furnace
Design’ has received a separate identity in the curriculum of some
courses, even at the undergraduate level. This requires a separate
textbook on its own.
In preparing the book I have received ample encouragement and
support both from the Director of the Indian Institute of Technology,
Bombay, and from the Head of the Department of Chemical
Engineering, and I am thankful to them. I have benefited from
innumerable books and articles and also by discussions with many
teachers and students. It will not be fair on my part to single them
out. However I must acknowledge the assistance received from TB
Ray, J Eqbal and N Murugesan in the various stages of the
preparation of the book.
I have derived great pleasure in writing this book. If the students
for whom it is primarily meant find it useful, my efforts will have been
more than rewarded. Year after year I have been facing the
questions of my students on the availability of a suitable textbook.
My colleagues have also had a similar experience. I have myself
attempted to provide an answer to this question. Any suggestions for
the improvement of this work will be gratefully welcomed and duly
acknowledged.
ACKNOWLEDGEMENT
I thank my family, especially my wife, who not only inspired me but
also supervised and managed the entire process. My thanks also go
out to all those who have been associated with bringing out this
edition.
Contents
1 Introduction
1.1 Energy and energy resources
1.2 Conventional energy resources
1.3 Energy: Consumption and demand
1.4 Electricity: Consumption and generation
Bibliography
2 Definitions, Units and Measures

2.1 Definitions
2.2 Basis for reporting results of analysis
2.3 Units and conversion factors
2.4 International system (SI) of units
Bibliography
3 Solid Fuels
3.1 Introduction
3.2 Biomass
3.3 Peat
3.4 Lignite or brown coal
3.5 Sub-bituminous coal or black lignite
3.6 Bituminous coal
3.7 Semi-anthracite
3.8 Anthracite
3.9 Cannel coal and boghead coal
3.10 Natural coke/SLY fuel
3.11 Origin of coal
3.12 Composition of coal
3.13 Analysis and properties of coal
3.14 Action of heat on coal
3.15 Oxidation of coal
3.16 Hydrogenation of coal
3.17 Classification of coal
Bibliography
4 Processing of Solid Fuels

4.1 Introduction
4.2 Coal preparation
4.3 Storage of coal
4.4 Carbonisation
4.5 Briquetting of solid fuels
4.6 Gasification of solid fuels
4.7 Liquefaction of solid fuels
Problems
Bibliography
5 Liquid Fuels
5.1 Introduction
5.2 Petroleum
5.3 Liquid fuels from sources other than petroleum
5.4 Storage and handling of liquid fuels
Bibliography
6 Gaseous Fuels
6.1 Introduction
6.2 Types of gaseous fuels
6.3 Cleaning and purification of gaseous fuels
Problems
Bibliography
7 Combustion Process (Stoichiometry and Thermodynamics)

7.1 Combustion stoichiometry
7.2 Examples
7.3 Rapid methods of combustion stoichiometry
7.4 Combustion thermodynamics
Problems
Bibliography
8 Combustion Process (Kinetics)

8.1 Nature of combustion process
8.2 Types of combustion processes
8.3 Mechanism of combustion reactions
8.4 Spontaneous ignition temperature (SIT)
8.5 Velocity of flame propagation
8.6 Limits of inflammability
8.7 Structure of flame
8.8 Flame stability
8.9 Kinetics of liquid fuel combustion
8.10 Kinetics of solid fuel combustion
Problems
Bibliography
9 Combustion Appliances
9.1 Introduction
9.2 Gas burners
9.3 Oil burners
9.4 Coal burning equipment
Bibliography
Appendices
Index
LIST OF TABLES
Table Title
1.1 World total energy consumption by region and fuel, 1990–2030
1.2 World oil reserves by country as of 1 January 2007
1.3 World oil consumption by region, 1990–2030
1.4 World natural gas reserves by country as of 1 January 2007
1.5 World natural gas consumption by region, 1990–2030
1.6 World recoverable coal reserves as of 1 January 2003
1.7 World coal consumption by region, 1990–2030
1.8 Total world delivered energy consumption by end-use sector
and fuel, 2004–2030
1.9 World total energy consumption by region, 1990–2030
1.10 World nuclear energy consumption by region, 1990–2030
1.11 World installed nuclear generating capacity by region, 2003–
2030
1.12 World consumption of hydroelectricity and other renewable
energy (taken together) by region, 1990–2030
1.13 Renewable energy potential and achievements in India, March
2005
2.1 The SI base units
2.2 The SI supplementary units
2.3 Examples of SI derived units expressed in terms of the base
units
2.4 SI derived units having special names or symbols
2.5 Further examples of SI derived units
2.6 Names and symbols for the SI prefixes
3.1 Average composition and properties of hardwoods
3.2 Products of wood carbonisation
3.3 Properties of some non-fossil domestic fuels, air-dried
3.4 Average properties of peat
3.5 Lignite resources of states as on 1 April 2007
3.6 Properties of lignite
3.7 Year-wise lignite production
3.8 Coal resources of states as on 1 January 2005
3.9 Coal resources by category as on 1 January 2007
3.10 World recoverable coal reserves as of 1 January 2003
3.11 Coal production of various states, 1985–86 to 2004–05
3.12 Sector-wise coal consumption in India
3.13 Year-wise coal production
3.14 Properties of Indian bituminous coals
3.15 Properties of anthracitic coals in India
3.16 Properties of cannel coal and boghead coal
3.17 Normal age of coal deposits
3.18 Analysis and fusion range of coal ash
3.19 Classification of Indian coals, their properties and utilization
(IS: 770-1977)
3.20 Regnault–Grüner–Bousquet classification of coal
3.21 Seyler’s classification of coal (1900)
3.22 Grading of Indian bituminous coals (1981)
4.1 Float-and-sink test results
4.2 Estimate of coal washing problem from the amount of near-
gravity material
4.3 Classification of coal cleaning processes
4.4 Performance of washeries/washed coking coal production
during the last five years
4.5 Details of washeries in operation in the country
4.6 Production from coal washeries in India
4.7 All-India production of some coal derivatives
4.8 Company-wise coal production
4.9 Top ten hard coal producers
4.10 Consumer-wise offtake of coal from CIL, SCCL and others for
last five years
4.11 Requirements for industrial coke (IS: 439-1989)
4.12 Requirements for domestic coke (IS:4286-1976)
4.13 Specification for domestic coke (IS 4286-1976)
5.1 Reserves of crude oil in India
5.2 Production of crude oil in India
5.3 Company-wise location and capacity of refineries as on 1 July
2005
5.4 Installed capacity and refinery crude throughput
5.5 Classification of crude petroleum according to Lane and Garton
5.6 Comparison of paraffin-base and asphalt-base crudes
5.7 Characteristic properties of Indian crudes
5.8 Common fractions from crude petroleum
5.9 Specifications for motor gasoline (IS: 2796-2000)
5.10 Specifications for kerosene (IS: 1459-1974)
5.11 Requirements for automotive diesel fuel
5.12 Specifications for fuel oils derived from petroleum or shale (IS:
1593-1982)
5.13 Viscometer conversion factors
5.14 Growth of the Indian petroleum industry
5.15 Properties of coal tar fuels
6.1 IGU gas families
6.2 Production of natural gas
6.3 Reserves of natural gas
6.4 Sectoral consumption of natural gas
6.5 Composition and properties of natural gas
6.6 State-wise consumption of CNG
6.7 Composition and properties of some manufactured gaseous
fuels.
6.8 Composition and properties of wood gas
6.9 Performance of a commercial wood gas producer
6.10 Properties of liquefied petroleum gases
6.11 Specifications for liquefied petroleum gases (IS: 4576-1999)
7.1 Conversion of gross CV(CG) into net CV(CN)
7.2 Calculation of volumes of theoretical air (Ao) and theoretical flue
gases (Vo)
7.3 CO2 content of theoretical dry flue gas
7.4 Heat of combustion of carbon and some gases at 298°K and 1
atm pressure
7.5 Dissociation of carbon dioxide and water vapour
7.6 Maximum adiabatic flame temperature (MAFT)
8.1 Spontaneous ignition temperature in air and oxygen
8.2 Limits of inflammability of some gases and vapours at ordinary
temperature and pressure in air
9.1 Capacity of aerated gas burner (low gas pressure)
LIST OF FIGURES
Figure Title
1.1 World marketed energy consumption, 1980–2030
1.2 World proved oil reserves by geographic region as of 1 January
2007
1.3 OECD and Non-OECD residential sector delivered energy
consumption, 2004–2030
1.4 OECD and Non-OECD commercial sector delivered energy
1.5 OECD and Non-OECD industrial sector delivered energy
1.6 OECD and Non-OECD transportation sector delivered energy
1.7 Average annual change in end-use sector electricity demand,
2004–2030
1.8 World electric power generation, 2004–2030
1.9 Annual growth in electricity generation by region, 2004–2030
1.10 World electricity generation by fuel, 2004–2030
1.11 World natural gas consumption by end-use sector, 2004–2030
1.12 World energy consumption of coal by sector, 2004, 2015 and
2030
3.1 Paraboloidal charcoal kiln
3.2 Inherent moisture and carbon per cent
3.3 Gray–King coke type and percentage of carbon in coal
3.4 Moisture and bulk density of coal
3.5 Porosity and percentage of coal in carbon
3.6 Heat of wetting and percentage of carbon in coal
3.7 Hardgrove grindability and percentage of carbon in coal
3.8 Devolatalisation of coal
3.9 Evolution of gases during carbonisation of coal
3.10 Fluidity and heating temperature of coal
3.11 Seyler’s coal classification chart (simplified)
3.12 Grout–Ralston triaxial diagram
4.1 Washability curves
4.2 Washability characteristic curves
4.3 Pneumatic table
4.4 A two-trough Rheolaveur launder
4.5 Double cone classifier
4.6 Baum jig
4.7 Heavy medium separator
4.8 Flotation cell for coal
4.9 Horizontal cyclone washer
4.10 Lurgi–Spül gas low temperature carboniser
4.11 The Otto underjet hairpin flue oven
4.12 Coke oven with gas gun and crossover flue heating system
4.13 Two alternative flow-sheets for coal preparation
4.14 Flow diagram of semi-direct process
5.1 Vertical cross section of an anticlinal accumulation of oil and gas
5.2 Three-stage distillation of crude oil
5.3 Box-type pipestill
5.4 Fluidised bed (down flow) catalytic cracking process
5.5 Edeleanu process of kerosene purification
5.6 Flow-sheet of a refinery in India
5.7 H-Coal process
5.8 EDS process
5.9 Simplified flow-diagram of Fisher–Tropsch process
5.10 Mobil process for the production of gasoline from methanol
5.11 Ring main system
6.1 Effect of quantity of steam on gas producer performance
6.2 Reaction zones in the fuel bed of a gas producer
6.3 Composition of gases in the fuel bed of a gas producer
6.4 Carburetted water gas unit
6.5 Lurgi gasification unit
6.6 Koppers–Totzek gasifier
6.7 Wood gas producer having a capacity of 70–80 tpd dry wood
6.8 Simplified flow-diagram of (ICI’s) continuous naphtha reforming
plant
7.1 Ostwald chart for coke-oven gas
7.2 Ht-diagram for combustion gases
7.3 Variation of adiabatic flame temperature with composition of
fuel–air mixture
8.1 Explosion limits for H2–O2 reaction, P1, P2, and P3
8.2 Glow and explosion limits for CO–O2 system
8.3 Pressure–temperature diagram of propane–oxygen (1:1)
mixture
8.4 Thermal mechanism of ignition
8.5 Ignition temperature versus pressure
8.6 Ignition temperature versus mixture composition
8.7 Stationary flame in a tube
8.8 Elements of a bunsen burner and method for measuring Vn
8.9 Flame velocity versus composition of gas–air mixture
8.10 Effect of diluents on the limits of inflammability
8.11 Premixed flame of a simple gas burner
8.12 Simple laminar diffusion flame: over-ventilated and under-
ventilated
8.13 Concentration profile of a cross section of a laminar diffusion
flame (schematic)
8.14 Progressive change in flame type with increase in jet velocity
8.15 Combustion of liquid fuel in an open vessel
8.16 Combustion of a liquid fuel droplet
9.1 Atmospheric gas burner (low pressure gas aspiration)
9.2 Air aspiration gas burner
9.3 Combustion with separate gas and air ports: long flame (coke
oven) and short flame
9.4 A blast burner with air register and gas gun
9.5 Fanmix burner
9.6 Surface-combustion tunnel burner
9.7 Pulsating combuster
9.8 Gas burner of submerged combustion type
9.9 Operation characteristics of an aerated burner
9.10 An aerated burner with two-stage aspiration and flame holder
9.11 Pot-type burner
9.12 Wall-wiping flame rotary vaporising burner
9.13 High speed vaporising burner
9.14 Swirl-type oil burner
9.15 Wide range pressure jets: spill type and slot type
9.16 Air register
9.17 Twin-fluid atomisation
9.18 Rotary atomising burner
9.19 Single-retort under-feed stoker
9.20 Travelling-grate stoker with combination-arch furnace (short
front-arch and long rear-arch)
9.21 Spreader stoker
9.22 Downdraft heater
9.23 Principle of downjet firing
9.24 Pulverised coal firing
9.25 Cyclone firing
1 Introduction
1.1 ENERGY AND ENERGY RESOURCES
A fuel is basically a source of heat. The usual method of producing heat

from fuel is by the process of combustion, which is a chemical reaction
between the fuel and the oxidant. In the vast majority of cases, air is the
oxidant, although oxygen, oxygen-enriched air and other chemicals are also
used as oxidants. With the advent of nuclear fuels which generate heat by
nuclear reactions, the common fuels may be termed chemical fuels. Rocket
fuels are different from conventional fuels; the oxidant for combustion of the
fuel is carried by the rocket itself, which therefore does not depend on its
surroundings for propulsion. It should be noted that explosives are not
regarded as fuels.
Depending upon the state of development, energy resources may be
divided into three groups.
The first group comprises those which are currently important in
supply—fossil fuels, hydel energy and nuclear energy from fission.
The second group consists of the resources that are currently us

only play a limited part from the point of view of the general econom
quantities used are small on a global scale, though the role of s
these resources is capable of becoming more important later. These
geothermal energy, aeolian energy (wind), chemical energy (bat
photosynthetic fuels (vegetation and fuel wood), and garbage, mu
wastes and agriresidues.
The third group covers resources which are currently the sub
research and development at various stages. Some of these are l
play an important role in the future, such as solar energy, nuclear
from fusion and energy from the sea (tidal, wave and thermal).
Energy is primarily used by four different sectors.

1. Domestic: Energy is used for cooking, lighting, running appliances,
and heating.
2. Transportation: Energy is used for moving cars, trucks, aircraft, trai
ships.
3. Industrial: Energy is used in factories, industrial complexes, resear

development and trade.
4. Health, education and welfare: Energy is used for supply and distribu
electricity and water, sewage and trash collection and disposa
administration.
The energy requirements of the advanced countries are almost equally

divided among these four heads.
Fuels also have other uses. It is well known that petroleum is also a
storehouse of hydrocarbons that are required for the production of
petrochemicals. The by-products of carbonisation of coal are of great value
in manufacturing chemicals, dyestuffs, pharmaceuticals and perfumery
materials. The coke in blast furnaces not only supplies heat but also takes
part in the chemical reaction of iron and steel production. Both coal and
petroleum are important raw materials in the production of fertilisers, and
play a significant role in the world’s drive for augmenting food output.
Carbon electrodes ultimately depend upon coal and petroleum as the initial
raw material. Numerous other examples may be cited for the non-fuel uses
of substances classified as fuels. In spite of the great importance of these
uses, fuels are primarily recognised as an energy resource.
Currently the energy resources of the world are of great concern
because of two factors: the accelerated rate of growth in population, and the
growing energy requirement per head. The earth now has about 6,000
million people. The population was about 400 million in AD 1550, 1,100
million in AD 1850 and may reach about 8,203 million in 2030 as per the
projection. The annual rate of growth in the world demand per capita for
energy utilisation is projected to be about 2% during 2003–2030. The world
marketed energy consumption was about 283 quadrillion Btu in 1980, 400
in 2000 and is projected to be 702 in 2030 (Fig. 1.1). The total energy
consumption was 29.8 quadrillion kcal in 2003 in the Organisation for
Economic Cooperation and Development (OECD), North America.
Figure 1.1 World marketed energy consumption, 1980–2030
Sources: History: Energy Information Administration (EIA). International
Energy Annual 2004 (May–July 2006), web site www.eia.doe.gov/iea.
Table 1.1 gives data about regional energy consumption from 1990 to
2003 and also projections for 2010 to 2030 (see Appendix 1.1 for regional
definitions). A complete picture of the energy requirement of the world is
available from it. The last column of the table gives the average annual per
cent change from 2003 to 2030.
Table 1.1World total energy consumption by region and fuel. Reference case 1990–
2030 (quadrillion kcal)
1.2 CONVENTIONAL ENERGY RESOURCES
1.2.1 OIL
Table 1.2 shows the estimated world oil resources by country as of 1

January 2007. Out of the total resources of 1,317 billion barrels (Table 1.2;
Fig 1.2), OPEC countries account for 57.3%; out of the remaining 42.7% for
non-OPEC economies, the Middle East contributes the major share; India’s
share is only 1.2%. Historically, estimates of world oil reserves have
generally shown an upward trend. As of 1 January 2007 the proved oil
reserves were estimated at 209 billion kilolitres (1,317 billion barrels) which
are 2.4 billion kilolitres (about 1%) higher than the estimate for 2005.
Table 1.2 World oil reserves by country as of 1 January 2007 (billion barrels)
Country Oil reserves
Saudi Arabia 262.3
Canada 179.2
Iran 136.3
Iraq 115.0
Kuwait 101.5
United Arab Emirates 97.8
Venezuela 80.0
Russia 60.0
Libya 41.5
Nigeria 36.2
Kazakhstan 30.0
United States 21.8
China 16.0
Qatar 15.2
Mexico 12.4
Algeria 12.3
Brazil 11.8
Angola 8.0
Norway 7.8
Azerbaijan 7.0
Rest of World 65.5
World Total 1.317.4
Source: International Energy Outlook 2007. Energy Information Administration, USA.
Figure 1.2 World proved oil reserves by geographic region as of 1 January 2007
Source: International Energy Outlook 2007. Energy Information
Administration, USA.
Oil remains the dominant energy source but its consumption will decline
from 38% in 2003 to 33% in 2030, owing to the rise in oil price (Table 1.1).
World oil use is projected to grow from 12.9 gigalitres per day in 2003 to
15.4 gigalitres per day in 2015, and 18.7 gigalitres per day in 2030 (Table
1.3). The higher price of oil has raised the demand for natural gas.
Table 1.3 World oil consumption by region, Reference case, 1990–2030 (gigalitres per
day)
Table 1.3 shows world oil consumption by region until the year 2030 and
then projections for 2010 to 2030. Out of the total world oil consumption of
12.7 gigalitres per day in 2003, OECD countries accounted for 7.8 gigalitres
per day and non-OECD economies for the rest. India’s share was only 0.4
gigalitre per day in 2003, the shortfall being met by extensive imports. The
situation practically remains the same in the projection for 2010 to 2030.
The average annual per cent change is 2.4 for India, compared to 0.8 for
total OECD, 2.3 for total non-OECD and 1.4 for the total world figure.
1.2.2 NATURAL GAS
The world’s natural gas reserves are estimated to be 6,183 trillion cubic feet
and the top 20 countries account for 5,602 trillion cubic feet. Almost three-
quarters of the world’s natural gas reserves are located in the Middle East
and Eurasia. India contributes a negligible part (Table 1.4).
Table 1.4 World natural gas reserves by country as of 1 January 2007

Country Reserves (trillion cubic feet) Per cent of world
total
World 6,183 100.0
Top 20 countries 5,602 90.6
Russia 1,680 27.2
Iran 974 15.8
Qatar 911 14.7
Saudi Arabia 240 3.9
United Arab 214 3.5
Emirates
United States 204 3.3
Nigeria 182 2.9
Algeria 162 2.6
Venezuela 152 2.5
Iraq 112 1.8
Turkmenistan 100 1.6
Kazakhstan 100 1.6
Indonesia 98 1.6
Norway 82 1.3
China 80 1.3
Malaysia 75 1.2
Uzbekistan 65 1.1
Egypt 59 0.9
Canada 58 0.9
Kuwait 55 0.9
Rest of world 581 9.4
Consumption of natural gas is projected to increase on an average by

2.4% per year from 2003 to 2030 (Table 1.5). The higher natural gas prices
also make coal more cost competitive, especially in the electric power
sector. For many years, natural gas was projected as the fastest growing
energy source in the mid-term; however, higher natural gas prices have
made coal more cost competitive, especially in the electric power sector. As
a result, natural gas use and coal use are projected to increase at similar
rates. Demand for natural gas is projected to rise by an average of 2.4% per
year over the period from 2003 to 2030, and the demand for coal by an
average of 2.5% per year. The consumption of natural gas in 2003 in billion
cubic metres was as follows: world total 2,716.8, OECD total 1,431.9 and
non-OECD total 1,284.9, while India’s share was 28.3 only (Table 1.5). Total
world natural gas consumption is projected to rise from 2,716.8 billion cubic
metres in 2003 to 3,796.0 billion cubic metres in 2015 and to 5,150.4 billion
cubic metres in 2030 (Table 1.5). The average annual per cent change
projected for 2003–2030 is 2.4 for the world, the same for total OECD
countries and 3.3 for total non-OECD economies. India’s rate of increase in
consumption is projected as high as 5.9% per annum, obviously through
large-scale imports. This also shows an improvement in the economy of the
country.
Table 1.5 World natural gas consumption by region, Reference case, 1990–2030 (
billion cubic metres)
Despite high rates of increase in natural gas consumption, particularly
over the past decade, most regional reserves-to-production ratios have
remained high: 66.7 years worldwide, 81.5 years for Russia and more than
100 years for the Middle East. According to the most recent US Geological
Survey estimates, a significant volume of natural gas remains to be
discovered. Russia is already the world’s single largest exporter of natural
gas, with net exports of 7.1 trillion cubicfeet, all of it by pipeline. An
alternative in many countries is to import or export liquefied natural gas
(LNG). Both China and India have limited natural gas reserves and are
projected to rely on imports to meet more than 40% of the natural gas
demand in 2030, both by pipeline and in the form of LNG.
Worldwide, the industrial sector remains the most important end-user for
natural gas, accounting for 52% of the total growth in natural gas use in the
projections; however, natural gas remains an important energy source in the
electric power sector, particularly as a fuel for new generating capacity. The
electric power sector accounts for 39% of the increase in global natural gas
demand over the 2003 to 2030 period.
1.2.3 COAL
The recoverable coal reserves in the world are given in Table 1.6 in terms of
the total quantity of all ranks of coal; India stands fourth with 101.9 billion
tons out of the world total of 1,000.8 and 270.7 for the USA. India is
fortunate to have practically the entire quantity in the form of bituminous
coal and anthracite. The total recoverable reserves of coal around the world
are estimated to last approximately 180 years at the current levels of
consumption (Tables 1.6 and 1.7). Historically, estimates of world
recoverable coal reserves, although relatively stable, have declined
gradually from 1,174 billion tones at the beginning of 1990 to 1,083 billion
tons in 2000 and 1000 billion tons in 2003. The most recent assessment of
world coal reserves includes a substantial downward adjustment for
Germany: from 73 billion tons to 7 billion tons.
Table 1.6 World recoverable coal reserves as of 1 January 2003 (billion short tons)
Region/Country Bituminous and Sub- Lignit Tota
anthracite bituminous e l
United States 123.7 110.3 33.5 267.
5
Russia 54.1 107.4 11.5 173.
0
China 68.6 37.1 20.5 126.
2
India 99.3 0.0 2.6 101.
9
Other Non-OECD Europe and 50.1 18.7 31.3 100.
Eurasia 1
Australia & New Zealand 42.6 2.7 41.9 87.
2
Africa 55.3 0.2 0.0 55.
5
Region/Country Bituminous and Sub- Lignit Tota
anthracite bituminous e l
OECD Euripe 19.5 5.0 18.8 43.
3
Other Non-OECD Asia 1.4 2.0 8.1 11.
5
Brazil 0.0 11.1 0.0 11.
1
Other Central & South America 8.5 2.2 0.1 10.
8
Canada 3.8 1.0 2.5 7.
3
Other 1.8 0.4 0.1 2.
3
World total 528.7 298.1 170.9 997.
7
Table 1.7 World coal consumption by region, Reference case, 1990–2030 (million
short tons)
Although coal deposits are widely distributed, 67% of the world’s
recoverable reserves are located in four countries: the United States (27%),
Russia (17%), China (13%) and India (10%). In 2003, these four countries,
taken together, accounted for 63% of the total world coal production. By
rank, anthracite and bituminous coal account for 53%, sub-bituminous coal
accounts for 30%, and lignite accounts for 17%. Quality and geological
characteristics of coal deposits vary significantly by region and even within
individual coal seams. For example, the International Energy Agency in
2003 estimated that the average calorific value of lignite in major coal
producing countries varies from a low of 1,084 kcal/kg in Greece to a high
of 3,100 kcal/kg in Canada.
Global use of coal is projected to increase by 2.4 billion tons between 2003
and 2015 and by another 2.7 billion tons between 2015 and 2030 (Table
1.7). Japan is an exception, where the electricity sector continues to be
dominated by natural gas and nuclear power generation. World coal
consumption is projected to increase from 5,440 million tons in 2003 to
7,792 million tons in 2015, at an average annual rate of 2.2% (Table 1.7). Of
the coal produced worldwide in 2003, 67% was shipped to electricity
producers, and 30% to industrial consumers. With higher prices for oil and
natural gas making coal more competitive, the IEO 2006 projection for world
coal use in 2025 is 16% higher than in IEO 2005. Consequently, coal’s
share of total energy use is projected to rise from 24% in 2003 to 27% in
2030 and world coal consumption continues to exceed world natural gas
consumption throughout the projections (Table 1.1). The largest increase in
coal use worldwide is projected for China and India, where coal supplies are
plentiful. Together China and India will account for 86% of the rise in non-
OECD coal use and 70% of the world increase in coal demand over the
projection period.
Consumption of coal for non-electricity purposes is projected to double
between 2003 and 2030. The strongest growth in non-electricity
consumption is projected for the non-OECD economies, averaging 3.9%
per year in IEO 2006 reference case. Robust economic growth in many of
the non-OECD countries is expected to boost demand for electricity to run
newly purchased home appliances, for air-conditioning, cooking, space and
water heating, and refrigeration.
Coal consumption in the OECD countries (Table 1.7) is projected to rise
at a relatively even pace in the reference case: from 2.5 billion tons in 2003
to 2.8 billion tons in 2015, and to 3.4 billion tons in 2030. The increase
represents an average growth of 1.2% per year over the entire period and a
slightly higher rate of 1.4% per year from 2015 to 2030. Much of the
increase of 0.9 billion ton in coal consumption projected for the OECD
countries from 2003 to 2030 is the result of the expected strong growth in
US coal demand. In 2003, the United States consumed 1.1 billion tons of
coal, accounting for 92% of coal consumption in North America and 44% of
the OECD total. With substantial coal reserves, the total electricity
generation in the USA depends heavily on it; natural gas cannot compete
with it.
Coal consumption in non-OECD countries is projected to increase by
140% in the IEO 2006 reference case, from 3.0 billion tons in 2003 to 7.1
billion tons in 2030, led by strong economic growth and rising demand for
energy in China and India. China and India are very large countries in terms
of both population and land mass, and both have substantial quantities of
the remaining coal reserves of the non-OECD countries. Together, they
account for 23% of world coal reserves and 67% of non-OECD coal-
reserves, and for 70% of the projected increase in world coal consumption.
Strong economic growth (averaging 6.0% per year in China and 5.4% per
year in India from 2003 to 2030) is projected for both countries and much of
the increase in their demand for energy, particularly in the industrial and
electricity sectors, is expected to be met by coal.
In India, almost 70% of the growth in coal consumption is expected to
be in the electric power sector and most of the remainder in the industrial
sector. In 2003, India’s coal-fired power plants consumed 1.3 quadrillion
kcal of coal, representing 69% of the country’s total coal demand. Coal use
for electricity generation in India is projected to grow by 2.7% per year, to
2.6 quadrillion kcal in 2030, as an additional 94 gigawatts of coal-fired
capacity is brought on line. As a result, India’s coal-fired generating capacity
is expected to more then double in the IEO 2006 projections, from 67
gigawatts in 2003 to 161 gigawatts in 2030. More than 50 gigawatts of new
coal-fired capacity is to be added during India’s eleventh plan period ending
in March 2012.
Currently, there are no coal-to-oil projects under construction in India;
however, a domestic coal-to-liquids industry would represent a viable
means of increasing domestic oil supply. The Indian Oil Corporation is
evaluating the construction of a coal liquefaction facility with an output of
13,000 kilolitres per day, which would be based on the coal-to-liquids
technology developed by South African Company Sasol and would use both
domestic and imported coal as feedstock.
1.3 ENERGY: CONSUMPTION AND DEMAND

On a global scale, energy demand in the industrial sector grows most
rapidly; it is projected to grow at an average rate of 1.8% per year from
2004 to 2030. Slower growth is projected for the buildings sector, while
residential energy use will rise by an average of 1.4% per year and
commercial use by 2.0% per year (Table 1.8). In contrast, the use of energy
for transportation will grow at the same rate as the use of industrial energy,
but faster than energy use in the buildings sector. The higher oil prices are
largely responsible for the slower growth in energy demand by the
transportation sector.
Total world delivered energy consumption by end-use sector and fuel,

Table 1.8
2004–2030 (quadrillion Btu)
The world marketed energy from all sources is projected to increase
over the next two decades on an average of 2.0% per year from 2003–2030
(Table 1.1). World energy consumption is projected to increase by 71% with
fossil fuels continuing to supply much of the energy used worldwide.
Although, increasing world oil prices dampen the growth in demand for oil,
the total world energy use continues to increase as a result of robust
economic growth. Worldwide, total energy use is expected to increase from
446.7 quadrillion Btu in 2004 to 701.6 quadrillion Btu in 2030.
The use of all energy sources increases through 2030. Fossil fuels will
continue to supply much of this increment. Oil will remain the dominant
energy source, given its importance in the transportation and industrial end-
use sectors; however, world oil prices indicate that oil’s share in the energy
market is lessened decreasing in the projection as other fuels replace oil
wherever possible. Renewable energy sources will become more
economically competitive with fossil fuels, and their use expand as rapidly
as consumption of natural gas and coal. Higher fossil fuel prices also
support renewed interest in expanding the use of nuclear power to generate
electricity.
The most rapid growth in energy demand from 2004 to 2030 is projected
for the non-OECD nations. They account for three-fourths of the increase in
world energy use. The energy demand is expected to grow at an average of
3.4% per year for non-OECD Asia (which includes China and India), 2.8%
per year for Central and South America, 2.6% per year for Africa, 2.5% per
year for the Middle East, and 1.4% per year for non-OECD Europe and
Eurasia (Table 1.9). The increases result from projections of strong regional
economic growth. Non-OECD energy use is projected to surpass OECD
energy use by 2015, and in 2030 the total energy demand in non-OECD
nations will exceed that in the OECD countries by 34%. Much of the growth
in energy demand among the non-OECD economies occurs in non-OECD
Asia, which includes China and India. Total primary energy consumption in
the non-OECD countries grows at an average annual rate of 3.0% between
2003 and 2030. The OECD nations, for the most part, are more mature
energy consumers with well-established infrastructures, and their
economies are usually moving away from energy intensive industries
towards services. Consequently, total OECD energy demand increases by
only an average of 0.9% per year over the projection period, as compared
with an average increase of 2.7% per year for the non-OECD nations.
In the OECD, where population growth is generally slow or negative in
many countries over the projection period, the slowest growth in energy use
is projected for the residential sector, at 0.6% per year; and the fastest
growth is in the industrial sector, averaging 1.2% annually. For the non-
OECD regions as a whole, strong growth in demand for energy is projected
for every end-use sector, ranging from 2.3% per year in the transportation
sector to 3.2% per year in the commercial and industrial sectors.
Economic growth is among the most important factors to be considered
in projecting changes in the world energy consumption. The outlook for
medium- to long-term economic growth depends on the underlying
demographic and expected productivity trends in each economy. These in
turn depend on population growth, labour force participation rates,
productivity growth, and national savings and capital accumulation.
1.3.1 RESIDENTIAL SECTOR
The following information is derived from a combination of Tables 1.8 and

1.9, and Figs. 1.3 and 1.4 Households in OECD nations use energy more
intensively than those in non-OECD nations, primarily because of their
higher income levels (Fig. 1.3). Total residential electricity use in the OECD
region accounts for about 80% of the total projected growth is in demand for
residential energy in OECD nations.
Table 1.9World total energy consumption by region, high world oil price case, 1990–
2030 (quadrillion Btu)
Figure 1.3 OECD and Non-OECD residential sector delivered energy
consumption, 2004-2030 (quadrillion Btu)
Figure 1.4 OECD and Non-OECD commercial sector delivered energy
consumption, 2004–2030 (quadrillion Btu)
Household energy use increases more rapidly in the non-OECD

countries than in the OECD countries due to robust economic growth and
expanding population. China and India account for nearly 40% of the total
increase in residential energy use in the non-OECD countries through 2030,
as their economies continue to grow strongly through the projection period.
1.3.2 COMMERCIAL SECTOR
The commercial sector, or the services sector, consists of business

institutions and organisations that provide services, as opposed to those in
manufacturing and agriculture.
Energy consumption by the commercial sector in the OECD nations
increases in the reference case by an average of 1.2% per year from 2004
to 2030 (Fig. 1.4). Natural gas continues to displace petroleum products
and coal as the preferred commercial heating fuel in the OECD region.
Economic growth and commerce are expected to increase rapidly in the
non-OECD nations. Under these circumstances, energy use by the
commercial sector in non-OECD countries will nearby double between 2004
and 2020, with an average annual rate of increase of 3.7%.
Electricity demand for commercial applications is projected to grow
rapidly in the non-OECD nations. The largest increases in commercial
electricity demand are projected for the nations with the rapidly growing
economies, particularly China and India. Increasing commercial activity is
expected to lead to growth in demand for fossil fuels in the non-OECD
nations. Natural gas is an economically attractive choice for commercial
water heating, space heating, and cooking in non-OECD countries,
especially in China and India, which together are expected to account for
around 80% of non-OECD commercial coal use from 2003 through 2030.
1.3.3 INDUSTRIAL SECTOR
Energy is consumed in the industrial sector by several industries, including

manufacturing, agriculture, mining and construction, and for a wide range of
activities, such as process and assembly use, heating and cooling, and
lighting. Energy demand by the industrial sector varies across regions and
countries of the world, based on the level and mix of economic activity,
technological development and population growth, among other factors.
The industrial sector is the largest of the end use sectors, consuming 50%
of delivered energy worldwide in 2004. Industrial energy consumption
increases in all countries and regions; however, its growth rate in the OECD
region—0.6% per year on an average—is slower than the 2.5% average
projected for the non-OECD region.
Electricity accounted for about 16% of OECD industrial sector energy
use in 2004 and its share remains fairly stable throughout the projection
period (Figure 1.5). Oil and natural gas were the most heavily used fuels in
the industrial sector of OECD countries in 2004, together accounting for
two-thirds of the energy consumed in the sector. The two fuels maintain
their overall share in 2030, but consumption of natural gas is expected to
grow almost twice as rapidly as that of oil. Coal makes up the bulk of the
remaining industrial energy consumption, while renewables remain a minor
energy source for the sector.
Figure 1.5 OECD and Non-OECD industrial sector delivered energy
In the non-OECD countries, energy consumption by the industrial sector

is projected to increase by 2.5% per year between 2004 and 2030. China,
the Middle East and India have the most rapid increase in industrial sector
energy consumption from 2004 to 2030. The economies of the OECD
countries have largely moved away from heavy, energy-intensive industries
(such as steel and cement) towards a greater emphasis on light
manufacturing and service activities, but the economies of many of the non-
OECD countries and regions have growing intensive, heavy manufacturing
sectors.
Electricity is expected to become an increasingly important component
of delivered energy demand of the industrial sector in the non-OECD
economies. Oil, coal, and natural gas were the most heavily used fuels in
2004 and are projected to remain so in 2030. Oil use in the non-OECD
industrial sector is projected to increase at a slower rate than natural gas or
coal use.
1.3.4 TRANSPORTATION SECTOR
Energy use in the transportation sector includes fuels consumed for the
purpose of moving people and goods by road, rail and air. The road
transport component consists of both light-duty vehicles (automobiles, sport
utility vehicles, minivans, small trucks and motorcycles, among other small
vehicles) and heavy-duty vehicles (large trucks used for moving freight and
buses for mass transit).
Petroleum products continue to dominate energy use in the
transportation sector; and barring any widespread increase in the
penetration of new technologies, the use of alternative fuels is expected to
remain relatively modest through 2030. Oil is the dominant fuel for
transportation, and currently, there are no other fuels that compete on par
with oil. The IEO 2006 reference case projects a 1.4% average annual
growth rate in demand for petroleum for transportation from 2003 to 2030.
Much of the projected growth in demand for petroleum products is in the
transportation sector of the non-OECD economies. Two-thirds of the
increase in world consumption of liquid fuels is due to the transportation
section. North America and Non-OECD Asia are the largest users.
In general, the transportation sector of the OECD economies is fully
established, with extensive infrastructure that includes highways, airport
facilities and rail systems. Energy demand for transportation in the OECD
region is projected to grow at an average annual rate of 0.9%, from 57.9
quadrillion Btu in 2004 to 63.7 in 2015 and to 73.4 in 2030 (Figs. 1.6 and
1.7). Petroleum products remain the largest source of energy for
transportation in the OECD countries. Although usage of gasoline is
expected to be higher than that of diesel, the product mix for road travel is
dominated by diesel fuel. Most countries are expected to keep taxes on
diesel fuel lower than those for gasoline through 2030, encouraging a
switch to diesel in the mid-term. Fast-paced growth in air travel is expected
to bring about robust growth in demand for aviation fuels in the region.
Figure 1.6 OECD and Non-OECD transportation sector delivered energy
Figure 1.7 Average annual change in end-Use sector electricity demand, 2004–
2030 (per cent per year)
Energy demand in the non-OECD transportation sector as a whole

grows at an average annual rate of 2.9%, from 29.8 quadrillion Btu in 2004
to 42.7 in 2015 and to 63.1 in 2030. As in the OECD economies, the growth
in energy use by the transportation sector is led by greater demand for air
travel. Expanding ownership of private automobiles and the increasing role
of trucking in freight transportation play a significant role in pushing up the
demand for energy. In 2004, the non-OECD economies accounted for about
34% of world energy use for transportation. In 2030, their share is projected
to be 46%, as the gap between the transportation energy consumption in
the non-OECD and OECD economies is expected to narrow substantially
over the projection period.
Non-OECD Asia is poised for strong and significant growth in
transportation sector energy use, with China and India being the primary
contributors to the growth. Infrastructure development is the major hurdle
faced by both China and India. India has an effective and extensive rail
system but its highways system needs development. Work has started on a
highway project to connect India’s major cities and it. is expected to be
completed in the next five years. Similar developments are occurring in
China as well.
In India, energy demand in the transportation sector is projected to grow
at an average rate of 3.3% a year. This could grow even faster if all of the
new highway projects currently under consideration are completed.
1.4 ELECTRICITY: CONSUMPTION AND GENERATION
1.4.1 CONSUMPTION OF ELECTRICITY
The net world electricity consumption is projected to more than double from
2015 to 2030. Most of the growth occurs in the non-OECD nations, where
electricity use increases on an average by 3.9% per year from 2003 to
2030, as compared with 1.5% per year in the OECD nations (Fig. 1.7). Coal
and natural gas remain the most important fuels for electricity production
throughout the projection period.
In 2004, nearly 60% of the total electricity consumption in the OECD
economies was in the buildings sector (residential and commercial). The
remainder was consumed in the industrial sector, except for a small amount
(1%) used by mass transit trains and buses. Overall, net electricity
consumption in OECD countries is projected to increases by 50% from
2004 to 2030, mostly as a result of increasing penetration and
telecommunications technologies. Electricity consumption in the non-OECD
economies is projected to grow at an average annual rate of 3.9% from
2004 to 2030. The average annual growth rate translates to a near tripling
of net electricity consumption in the non-OECD nations over the projection
period. In 2003, non-OECD economies consumed 40% of the world’s
electricity; in 2030, their share is projected to be 56%. The large growth is
mainly due to gross domestic products and population growth.
From 2003 to 2030, residential electricity consumption for the non-
OECD economies as a whole is projected to grow from 23% to 30% of the
total net electricity consumption. In absolute terms, nearly four times as
much electricity will be consumed in the residential sector in 2030 than in
2003, supporting a major transformation in living standards as electric
lighting, appliances, and new technologies become available to an
increasing share of the world’s population. Electricity consumption growth in
the non-OECD industrial sector is somewhat slower than in the buildings
sector, despite the rapid adoption of consumer electronics and computers
for business use. The industrial sector’s share of total non-OECD electricity
demand is projected to decline from 61% in 2003 to 54% in 2030, even as
industrial use of electricity more than doubles.
The increase in residential electricity consumption in non-OECD Asia
region is 6.5% per year. It is by far the fastest in the world, driven by
population growth (see Appendix 1.2) and rising living standards. In 2030,
residential electricity consumption in the region is projected to increase to
nearly four times its 2004 level. In the commercial and industrial sectors,
electricity consumption is projected to grow strongly, at an average annual
rate of 4.8% to 1,291 and 5,653 billion kWh, respectively in 2030. An
extensive expansion of installed generating capacity will be required to
meet the world’s electricity demand. In the reference case, worldwide
installed electricity generating capacity is projected to grow from 16,424
billion kilowatt-hours in 2004 to 30,364 in 2030, at an average rate of 2.0%
per year (Figs. 1.8 and 1.9).
Figure 1.8 World electric power generation, 2004-2030 (billion kilowatt-hours)

Figure 1.9 Annual growth in electricity generation by region, 2004–2030
1.4.2 FUELS USED FOR GENERATION OF ELECTRICITY
The mix of primary fuels used to generate electricity has changed a great
deal over the past two decades on a worldwide basis. Natural gas and
renewable energy sources are expected to increase their individual share of
total world electricity generation in the projections (Fig. 1.10). The natural
gas share of world electricity markets increases from 19% in 2004 to 22% in
2030 and the renewable energy share rises from 18% in 2004 to 20% in
2030, before slightly declining to 19% in 2030. The relative environmental
benefits and efficiency of natural gas make the fuel an attractive alternative
to oil- and coal-fired generation.
Figure 1.10 World electricity generation by fuel, 2004 and 2030 (billion kilowatt-
hours)
Coal has remained a dominant fuel, although electricity generation from

nuclear power increased rapidly from the 1970s through the mid-1980s, and
natural gas-fired generation grew rapidly in the 1980s and 1990s. In
contrast, in conjunction with the high world oil prices, after the oil embargo
of 1973–74 and the Iranian revolution in 1979, the use of oil for electricity
generation has been slowing since the mid-1970s. High world oil prices
encourage switching from oil-fired generation to natural gas and nuclear
power and have reinforced the role of coal in world electric power
generation. Similarly, owing to the relatively high fossil fuel prices of recent
years there is renewed interest in nuclear power and also in making energy
from renewable sources more competitive economically. Rising fossil fuel
prices have also allowed renewable energy sources to compete
economically in the electric power sector (Figures 1.9 and 1.10).
Consumption of hydroelectricity and other grid-connected renewable energy
sources is expected to expand by 2.4% per year—approximately the same
as the rates of growth projected for natural gas and coal—and the
renewable energy share of the world’s total energy consumption from 8% in
2003 to 9% in 2030.
Natural gas
Natural gas is the preferred energy source for electric power generation. In
the IEO 2007 reference case, natural gas-fired generating capacity is
projected to increase by approximately 2.5% per year from 2004 to 2030, as
compared with 2.2% per year for coal and 1.9% per year for renewables
(Table 1.8). Natural gas-fired combined cycle capacity is an attractive
choice for new power plants because of its fuel efficiency, operating
flexibility, relatively short consumption times (months instead of the year
that coal or nuclear power typically require), and lower investment costs.
The major drawback of natural gas capacity is the potential volatility of fuel
costs.
At the world level, natural gas consumption rises from 19% of total fuel
use for electricity generation in 2004 to 22% in 2030 (Table 1.8). Non-OECD
economies on the whole, rely on natural gas and the consumption grows
more than twice as fast as in the OECD countries (Fig. 1.11).
Figure 1.11 World natural gas consumption by end-use sector, 2004–2030
(trillion cubic feet)
In the non-OECD nations, the use of natural gas in generation of total

electricity is projected to rise while the use of oil and renewables is
expected to reduce. Natural gas-fired capacity grows most rapidly in non-
OECD Asia—especially China and India—and natural gas consumption in
the electrical power sector increases by an average of 7.0% per year in
China and 7.1% per year in India from 2004 to 2030.
Coal
Coal retains the largest market share in global electricity generation

(roughly 40%) in the IEO 2006 reference case, despite losing some of its
share to natural gas. Installed coal-fired capacity, as a share of world’s total
capacity, remains at about 30% (Fig. 1.12). Worldwide, coal-fired capacity is
projected to grow by 2.2% per year, slightly faster than the 2.0% average
annual increase for all electricity generation capacity. In 2004, the non-
OECD economies on the whole relied on coal for roughly 43% of
generation, which is slightly more than the OECD economies.
Figure 1.12 World energy consumption of coal by sector, 2004, 2015 and 2030
(per cent)
Regional differences in the use of coal for electricity generation are due
to the availability of coal resources. Regions with large resources of coal
are more likely to use coal for electricity generation, because coal has a
lower energy density (energy per weight) and fewer alternative uses than oil
or natural gas. These factors help keep coal prices, on an energy basis,
lower than oil and natural gas prices. Coal reserves in the United States,
China, India and Australia are among the largest in the world, and these
countries rely on coal to generate 50% to 80% of their electricity.
Nuclear power
Worldwide, the consumption of electricity generated from nuclear power
increases from 3,610 billion kWh in 2003 to 4,030 billion kWh in 2015 (Table
1.10). Higher fossil fuel prices and concerns about security of energy
supplies are expected to improve prospects for nuclear power. Non-OECD
Asia accounts for 69% (gigawatts) of the increase in non-OECD nuclear
capacity generation with an average increase of 6.3% per year from 2003 to
2030. The 51 billion watts of additional installed nuclear generating capacity
projected for non-OECD Asia includes 33 billion watts in China and 12
billion watts in India (Table 1.11). Russia accounts for most of the remaining
non-OECD additions, adding 22 billion watts nuclear capacity over the
period 2003 to 2030. In the IEO 2006 reference case, the world’s total
installed nuclear capacity rises from 361 gigawatts in 2003 to 438 gigawatts
in 2030. The projection for India is 15 gigawatts, while for China it is 39
gigawatts and for Russia it is 43 gigawatts
Table 1.10 World nuclear energy consumption by region, Reference case, 1990–2030
(billion kilowatt-hours)
World installed nuclear generating capacity by region, Reference case,
Table 1.11
2003–2030 (gigawatts)
The world’s nuclear-powered generating capacity increases in the IEO
2006 reference case from 361 gigawatts in 2003 to 438 gigawats in 2030, in
contrast to projections of declines in nuclear power capacity in past IEOs.
The reference case is based on laws and assumes that, for the OECD
economies, in the long term, decommissioning of existing nuclear power
plants as they reach the end of their operating lives will nearly equal the
construction of new ones. This will result in a slight decline in the installed
nuclear capacity towards the end of the projection, after peaking in 2020
(Table 1.11). In contrast, rapid growth in nuclear power capacity is projected
for the non-OECD economies. The non-OECD economies are expected to
add 33 gigawatts of nuclear capacity between 2003 and 2015 and another
42 gigawatts between 2015 and 2030. The largest additions are expected in
China, India and Russia.
Hydroelectricity and renewable energy

The use of hydroelectricity and other grid connected renewable energy
resources continues to expand over the projection period, increasing by
2.4% per year—approximately the same as the growth rates for natural gas
and coal demand in the reference case (Table 1.1). Much of the growth in
renewable energy sources results from large-scale hydroelectric power
projects in non-OECD regions including India (Tables 1.12 and 1.13).
Table 1.12 World consumption of hydroelectricity and other renewable energy (taken
together) by region. Reference case, 1990–2030 (quandrillion Btu)
Table 1.13 Renewable energy potential and achievements in India. March 2005
Source/Technologies Approximat Achievments India’s position
e Potential in the world
Source/Technologies Approximat Achievments
As on As on India’s position
e Potential March March in the world
2004
As on 2005
As on
March March
2004 2005
Wind power, MW 45000 2488 2980 Fifth
Small hydropower upto 25 15000 1603 1693 Tenth
MW
Biomass power/ 19500 613 727 Fourth
congeneration, MW
Biomass gasification, MW Nil 58 62 First
Solar photovoltaies, 20 151 191 -
MW/km2
Solar water heating, million 140 0.8 1.0 -
m2 cellular area
Wastes to energy, MW 1700 41.5 46.5 -
Biogas plants, millions 12 3.7 3.7 First
Improved biogas chulahs 120 33.9 33.9 First
(cooker, stoves), millions
Source: Annual Report 2004/05, Ministry of New and Renewable Energy, Govt. of
India.
The IEO 2006 projections for hydroelectricity and other renewable

energy resources include only on-grid renewables (Table 1.12).
Noncommercial biofuels from plant and animal sources are an important
source of energy, particularly in non-OECD economies, and the
International Energy Agency has estimated that some 2.4 billion people in
developing countries depend on traditional biomass for heating and
cooking.
APPENDIX 1.1
REGIONAL DEFINITIONS
OECD Organisation for Economic Cooperation and Development: North America,
(18% of United States, Canada and Mexico, OECD Europe—Austria, Belgium,
the 2006 Czech Republic, Denmark, Finland, France, Germany, Greece, Hungary
world Iceland, Ireland, Italy, Luxembourg, the Netherlands, Norway, Poland,
populatio Portugal, Slovakia, Spain, Sweden, Poland, Portugal, Slovakia, Spain,
n) Sweden, Switzerland, Turkey, and the United Kingdom. OECD Asia—
Japan, South Korea, Australia, and New Zealand.
Non- Non-OECD Europe and Eurasia
OECD (5% of the 2006 world population)
(82% of Albania, Armenia, Azerbaijan, Belarus, Bosnia and Herzegovia, Bulgaria,
the 2006 Croatia, Estonia, Kazakhstan, Kyrgyzstan, Latvia, Lithuania, Macedonia,
world Malta, Moldova, Romania, Russia, Serbia and Montenegro, Slovenia,
populatio Tajikistan Turkmenistan, Ukraine and Uzbekistan.
n)
Non-OECD Asia
(53% of the 2006 world population)
Afghanistan, Bangladesh, Bhutan, Brunei, Cambodia, China, Fiji, French
Polynesia, Guam, Hong Kong, India, Indonesia, Kiribati, Laos, Malaysia,
Macau, Maldives, Mongolia, Burma, Nauru, Nepal, New Caledonia, Niue,
North Korea, Pakistan, Papua New Guinea, Philippines, Samoa,
Singapore, Solomon Islands, Sri Lanka, Taiwan, Thailand, Tonga, Vanuatu
and Vietnam.
Middle Bahrain, Cyprus, Iran, Iraq, Israel, Jordan, Kuwait, Lebanon, Oman, Qatar,
East (3% saudi Arabia, Syria, the United Arab Emirates and Yemen.
of the
2006
world
populatio
n)
Africa Algeria, Angola, Benin, Botswana, Burkina Faso, Burundi, Cameroon,
(14% of Cape Verde, Central African Republic, Chad, Comoros, Congo
the 2006 (Brazzaville), Congo (Kinshasa), Djibouti, Egypt, Equatorial Guinea,
world Eritrea, Ethiopia, Gabon, Gambia, Ghana, Guinea, Guinea-Bissau, Ivory
populatio Coast, Kenya, Lesotho, Liberia, Libya, Madagascar, Malawi, Mali,
n) Mauritania, Mauritius, Morocco, Mozambique, Namibia, Niger, Nigeria,
Reunion, Rwanda, Sao Tome and Principe, Senegal, Seychelles, Sierra
Leone, Somalia, South Africa, St. Helena, Sudan, Swaziland, Tanzania,
Togo, Tunisia, Uganda, Western Sahara, Zambia and Zimbabwe.
Central Antarctica, Antigua and Barbuda, Argentina, Aruba, Bahamas Island,
and Barbados, Belize, Bolivia, Brazil, British Virgin Islands, Cayman Islands,
South Chile, Colombia, Costa Rica, Cuba, Dominica, Dominican Republic,
America Ecuador, El Salvador, Falkland Islands, French Guiana, Grenada,
(7% of the Guadeloupe, Guatemala, Guyana, Haiti, Honduras, Jamaica, Martinique,
2006 Montserrat, Netherlands, Antilles, Nicaragua, Panama Republic,
world Paraguay, Peru, Puerto Rico, St. Kitts Nevis, St. Lucia, St. Lucia, St.
populatio Vincent/Grenadines, Suriname, Trinidad and Tobago, Turks and Caicos
n) Islands, Uruguay, U.S. Virgin Islands and Venezuela.
Some European Union (EU): Austria, Belgium, Cyprus Czech Republic,
other Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Ireland,
groups Italy, Latvia, Lithuania, Luxembourg, Malta, the Netherlands, Poland,
of Portugal, Slovakia, Slovenia, Spain, Sweden and the United Kingdom.
countries
G8: Canada, France, Germany, Italy, Japan, Russia, the United
Kingdom and the United States.
North American Free Trade Agreement (NAFTA) Member Countries:
Canada, Mexico and the United States.
Organisation of Petroleum Exporting Countries(OPEC): Algeria,
Indonesia, Iran, Iraq, Kuwait, Libya, Nigeria, Qatar, Saudi Arabia, the United
Arab Emirates and Venezuela.
Pacific Rim Developing Countries. Hong Kong, Indonesia, Malaysia,
Philippines, Singapore, South Korea, Taiwan and Thailand.
Persian Gulf Countries: Bahrain, Iran, Iraq, Kuwait, Qatar, Saudi
Arabia and the United Arab Emirates.
APPENDIX 1.2
WORLD POPULATION BY REGION , REFERENCE CASE, 1990–2030

(MILLIONS)
BIBLIOGRAPHY
1. International Energy Outlook 2006, June 2006, Energy Inform

Administration, U.S. Department of Energy, Washington. Internat
Energy Outlook 2007, Energy Information Administration, U.S. Dep
Energy, Washington.
2. International Energy Outlook 2007, June 2006, Energy Inform

Administration, U.S. Department of Energy, Washington. Internat
Energy Outlook 2007, Energy Information Administration, U.S. Dep
Energy, Washington.
3. Advisory Board on Energy, Govt. of India, Towards a Perspective on En

Demand and Supply in India in 2004/5, New Delhi, May, 1985.
4. Huberty MP and Flock WL. Natural Resources, New York: McGraw
1959.
5. Loftness, RL. Energy Handbook, New York: Van Nostrand , 1978.
6. Oil And Gas Journal, 30 December, 1985.
7. Putnam PG. Energy in the Future, Princeton: Van Nostrand, 1985.
8. Reid WT. The Melchet Lecture, 1969. The Energy Explosion, J. Inst.
43: 45–51 (1970).
9. Sutton GP and Ross DM. Rocket Propulasion Elements, Fourth ed.

York: Wiley, 1976.
10. Energy Statistics Yearbook. United Nations. New York, 1985.
11. Van Krevelen, DW. Coal. Amsterdam: Elsevier, 1961.
12. World Coal, Vol 7, No. 7 (Nov./Dec. 1981).

2 Definitions, Units and Measures
2.1 DEFINITIONS
A systematic study of fuels and combustion requires a prior knowledge of

certain frequently used terms.
Proximate analysis
The proximate analysis of a fuel indicates the moisture, volatile matter, fixed
carbon and ash content of the fuel in terms of percentage by weight.
Moisture means the water expelled from the fuel by specified methods
without causing any chemical change to the fuel.
Volatile matter is the total loss in weight minus the moisture when the fuel
is heated out of contact with air to a sufficiently high temperature under
specified conditions.
Ash is the inorganic residue left when the fuel is completely burnt in air
under specified conditions. It is different from the original mineral matter
associated with the coal because of changes that take place during
incineration.
Fixed carbon is the residue obtained by subtracting the sum of the

percentages by weight of moisture, volatile matter and ash from 100. It is
essentially carbon containing minor amounts of nitrogen, sulphur, oxygen
and hydrogen.
Ultimate analysis
The ultimate analysis of a fuel gives its elementary composition. It is the

analysis in terms of the percentage by weight of the elements: carbon,
hydrogen, oxygen, nitrogen and sulphur which constitute the pure fuel, free
from moisture and inorganic constituents.
Combustion
It is the process by which heat is liberated from fuel by its high temperature
reaction with an oxidant which is usually oxygen present in the air. The
quantity of heat evolved by the combustion of unit quantity of fuel is its
calorific value or heating value. There are different ways of expressing the
calorific value.
Gross calorific value (higher heating value) at constant volume is the

quantity of heat liberated by the combustion of a unit quantity of the fuel at
constant volume in oxygen saturated with water vapour, the original material
and final products of combustion being at a reference temperature of 25°C,
and the water obtained from the fuel being in the liquid state.
Gross calorific value at constant pressure is similar to the former

expression except that the combustion takes place at constant pressure
and not at constant volume. In the laboratory determination, solid and liquid
fuels are burnt at constant volume and gaseous fuels are burnt at constant
pressure. In ovens and furnaces, however, the combustion takes place at
constant pressure. The difference in the two corresponding values is small.
For coal, the calorific value at constant pressure exceeds the calorific value
at constant volume by about 5.5 kcal/kg.
Net calorific value (lower heating value) at constant volume is the

quantity of heat evolved when unit quantity of a fuel is burnt at constant
volume in oxygen saturated with water vapour; the original material and
final products of combustion being at a reference temperature of 25°C, and
the water obtained from the fuel being in the vapour state. The net calorific
value is, therefore, less than the gross calorific value by an amount
corresponding to the heat of condensation of water vapour, which at 25°C is
583.5 kcal/kg. For hydrogen this is equal to 5,252 kcal/kg or 468.9 kcal/Nm3
of hydrogen. On approximation, the following formula is used in calculating
the net caloric value from gross calorific value of solid and liquid fuels:
where, CN and CG are the net and gross calorific value in kcal/kg.,
respectively, and H is the percentage of hydrogen in the fuel, including
hydrogen present in moisture and in water of hydration of minerals for fuels
like coal.
For a gaseous fuel, the formula is
Where, CN and CG are equal to net and gross calorific value in kcal/Nm3,
respectively, V = volume percentage (as H2) of total hydrogen of the
gaseous fuel, including the hydrogen obtainable from other combustible
components as well as water vapour in the gas.
Net calorific value at constant pressure is the same as above, except

that the combustion takes place at constant pressure and not at constant
volume.
Ignition point or ignition temperature or spontaneous ignition

temperature: It is the minimum temperature at which a fuel ignites in an
oxidising atmosphere without the help of any external source of fire. It is a
characteristic property of the fuel and also depends upon other factors like
the atmosphere (oxygen or air), method of heating and nature of container.
Flash point and Fire point: These are characteristic properties of liquid
fuels. The flash point is the minimum temperature at which the fuel gives
enough vapours to produce a flash in the atomosphere when an external
point source of fire is brought to it; and fire point is the minimum
temperature at which vapours of the fuel produce a continuous flame
instead of just a flash in momentary contact with a fire source. Fire point is
therefore higher than the flash point. Both these temperatures indicate the
fire risk of a liquid fuel. For highly volatile liquid fuels, the flash and fire
points are much lower than the ignition temperature.
Rank of coal
It is well recognised that coal is derived from vegetable matter by a natural

process giving rise to a transition series of solid fuels. The vegetable matter
first decomposes and forms peat. Subsequently, the peat is progressively
converted into lignite, bituminous coal and anthracite. The process of
conversion of lignite to anthracite is known as metamorphism or
coalification. The position of a coal in this metamorphic series is its rank, or
degree of metamorphism, or degree of maturity.
Carbonisation of coal
It is the process of heating coal without contact with air to a sufficiently high
temperature, so that the coal undergoes decomposition and yields a residue
which is richer in carbon content than the original fuel. A similar but much
slower process takes place in nature also. The natural process is
distinguished by the term coalification. Like coal, many other organic
substances are also subjected to the process of carbonisation.
Gasification
It is the process of converting solid or liquid fuels into gaseous fuels.

Carbonisation is essentially a partial gasification process. In addition to the
main gaseous fuel, some liquid products are also obtained during
gasification. The gaseous product may be directly used as a fuel or may be
used as a raw material for the production of chemicals, fertilisers and liquid
fuels.
Caking and coking
Some coals are capable of producing a lump or cake from a powdery state
by carbonisation. These coals are called caking coals and the phenomenon
is known as the caking of coal. When carbonisation of coal is carried out in
a commercial coke oven at about 1,000°C, and the resultant lumpy product
is sufficiently hard and strong as judged by standard tests, the solid product
is called coke, and the process is known as the coking of coal. While the
process of caking is general, the process of coking is specific. All coking
coals are necessarily caking but only some of the caking varieties fall under
the category of coking. The main use of hard coke is in the feedstock of
blast furnace.
Cracking
It is essentially a thermal decomposition process carried out with or without

a catalyst, in which larger molecules are broken down into smaller ones with
rearrangement of atoms and groups. The process is disproportionate in
nature and forms some complex molecules also. Cracking is universally
practiced in petroleum refining and is also employed in petrochemical
industries on a wide scale. When cracking is performed in the presence of
hydrogen and suitable catalysts, the process is called hydrocracking.
Orsat analysis
The composition of a gaseous fuel may be determined by analysis in a
standard apparatus known as the orsat apparatus. The orsat analysis
normally reports the percentage quantities of carbon dioxide, oxygen,
carbon monoxide and nitrogen. Provisions can also be made for using the
orsat apparatus for more complex analysis, namely, ascertaining the
quantities of hydrogen, methane and unsaturated hydrocarbons. The data
of orsat analysis are always on a dry basis. Moreover, sulphur dioxide is
reported along with carbon dioxide.
Flue gas
It is the gaseous product of combustion of fuels in ovens and furnaces.

When combustion is complete it consists of carbon dioxide, water vapour,
nitrogen and excess oxygen. If the fuel contains sulphur, the flue gas will
also contain sulphur dioxide, and will be reported with carbon dioxide. The
term ‘flue gas’ is derived from the flues that lead the gases from the oven
and furnaces to the chimneys.
2.2 BASIS FOR REPORTING RESULTS OF ANALYSIS
Since fuels are heterogeneous in nature, it is essential to report the

analytical data on an accepted basis. The following forms of basis are in
vogue, especially for solid fuels which are extremely heterogeneous
substances.
run-of-mine (rom)
as-received
air-dried
dry
dry-and-ash-free (daf)
dry-and-mineral-matter-free (dmmf)
moist-mineral-matter-free or, simply, mineral-free

The coal as obtained from a mine is known as run-of-mine coal. When the
data are expressed on this coal as a whole, the basis is termed ‘rom’.
During the handling of the coal in transit, its moisture and mineral matter
changes. The coal also undergoes other changes. Therefore, when the
customer analyses the coal after it is received, the data expressed on this
coal as a whole is termed as-received. The data on an as-received basis
may often be identical to that on an air-dried basis, because the coal
undergoes air drying by exposure to the atmosphere during transit. For
getting accurate and comparable results the air-dried data are obtained
after exposing the coal to an artificial but standard atmosphere at 40°C with
60% relative humidity.
The considerations for any of the other basis are as follows. Coal
consists of moisture, mineral matter and pure coal. When the effect of
moisture content on the analytical data is removed, it is expressed as dry
coal. Similarly the effect of mineral matter is excluded by reporting the data
on a mineral-free basis, taking the pure coal plus moisture as the whole.
However, when it is necessary to calculate the data of the pure coal only,
the effects of moisture and mineral matter are excluded by using dry-and-
mineral-matter-free (dmmf) basis. This basis is also known as unit coal
basis. Since it is difficult to determine the mineral matter content of coal, the
dry-and-ash-free (daf) basis is often used in place of the dmmf basis. For
low ash coals the use of daf basis is justified in assessing the properties of
pure coal. For high ash coals (ash content >10%), the difference between
the dmmf basis and the daf basis is appreciable and the use of the latter
leads to erroneous results. This is particularly so for Indian coals which are
high in ash.
2.3 UNITS AND CONVERSION FACTORS
The units and measures of both common and restricted usage in fuel
technology are included here. Some of the more frequently used conversion
factors are also given.
Gas Constant
R= 1.987 cal/mol K
= 0.082051 1 atm/mol K
= 82.05 ml atm/mol K = 10.726
Length
1 inch (in) = 2.54 cm
1 foot (ft) = 12 in = 30.48 cm
1 metre (m) = 39.37 in = 3.28 ft
1 mile = 1.6093 km
1 micron = 1 micrometre (μm) = 10−6 m = 10−3 mm
1 angstrom (Å) = 0.0001 micron = 10−6 m
Area
1 square inch = 6.45 cm2
1 square foot = 929.03 cm2
1 square metre = 1550 square inches = 10.764 square feet
1 square mile = 640 acres = 259 hectare = 2.59 km2
1 square kilometre = 0.3856 square mile
1 hectare = 10,000 m2
Volume
1 US barrel = 0.159 m3 or 0.159 kl
= 5.615 ft3 = 34.973 UK gallons
= 42 US gallons
1 m3 = 35.315 ft3 = 219.97 UK gallon
= 264.17 US gallons
= 6.290 US barrels
1l = 1000.028 cm3
1 pint = 0.5682 litre = 1/8 UK gallon
Mass
1 gram (g) = 15.432 grains (gr) = 0.0353 ounces (oz)
= 0.002205 pounds (lb)
1 pound = 453.59 g = 0.4536 kg = 7000 gr
1 grain = 0.0648 g
1 tonne (metric) = 1000 kg = 0.984 tons (UK) =1.102 short ton (US
1 short ton (US) = 0.893 tons (UK) = 0.907 metric tonne
1 long ton (UK) = 20 hundred weights (cwt) = 1.106 tonnes (metr
Density and concentration

1 g/ml = 62.426 lb/ft3
= 10.022 lb/UK gal
= 8.345 lb/US gal
1 kg/m3 = 0.06243 lb/ft3
1 lb/ft3 = 16.019 kg/m3
Specific volume
1 m3/kg = 16.0185 ft3/lb
1 ft3/lb = 0.062428 m3/kg
Temperature
1 °F = 5/9 deg C
1 °C = 1.8 deg F
(°F-32)5/9 = °C
(°C × 9/5) + 32 = °F
°C + 273 = kelvin (K)
°F + 460 = rankine (R)
Force
1 gram-force (gf) = 980.665 dyne
1 kg-force (kgf) = 2.2046 lb-force (lbf)
= 70.9316 poundal
1 newton (N) = 105 dyne
Pressure
1 atmosphere (atm) at 0°C = 760 mm Hg = 29.92 in Hg
= 33.9 ft H2O = 1.033 kgf/cm2
= 14.695 lbf/in2 = 2116 lbf/ft2
1 pound-force per square inch (lbf/in2)
= 0.07031 kilogram-force per square centimetre
(kgf/cm2)
1 kgf/cm2 = 14.223 lbf/in2
= 0.036 lbf/in2 = 1.869 mm Hg
= 0.07358 in Hg
1 millibar = 100 N/m2
1 N/m2 = 0.01 millibar
= 10 dyne/cm2
1 torr = 1.333 millibar = 1.316 × 10−3 atm
= 1.360 ×10−3 kgf/cm2
Heat, work and energy

1 kcal = 3.968 Btu
= 2.205 centigrade heat unit (Chu) = 3088 ft lb
= 4186.8 joules (J)
= 0.00116 kWh
1 Btu = 0.252 kcal = 0.5556 Chu
= 778.17 ft lbf
1 Chu = 1.8 Btu = 0.454 kcal
1 therm = 100,000 Btu = 25,200 kcal
= 29.31 kilowatt-hour (kW h)
1 horsepower (hph) = 745.7 W = 0.7457 kW h
1 megawatt (MW) = 1000 kW
1 kWh = 1.341 horse power-hour (hph)
= 3.6 × 106 J
= 859.845 kcal
= 3412.143 Btu
1 MJ = 238.846 kcal = 947.74 Btu
1J =107 ergs
1 eV =1.601 × 10−12 erg = 1.601 × 10−19 J
1 quintillion (Q ) =1000 quadrillion (q) = 1018 Btu
1 q or quad (quadrillion) =1015 Btu
Power
1w = 1.341 × 10−3 hp = 0.10197 m-kgf/s
= 0.73756 ft-lbf/s
1 hp = 745.700 W
1 hph = 0.7457 kWh
Thermal conductivity
Btu in/ h ft2 °F = 0.124 kcal/m h °C
= 0.344 × 10−3 C
1 Btu ft/ h ft2 °F = 1.488 kcal/h m °C
1 kcal/m h °C = 0.672 Btu/ h ft2 °F
= 8.064 Btu in/ h ft2 °F
1 cal/cm s °C = 360kcal/ h m °C
= 241.9 Btu/ h ft °F
= 2902.90 Btu in/ h ft2 °F
1 W/cm °C = 85.985 kcal/m h °C
= 57.779 Btu/ h ft °F
Rate of heat flow or heat flux

1 Btu/h ft2 = 2.7125 kcal/h m2 = 0.31546 × 10−3 W/cm2
1 kcal/h m2 = 0.3687 Btu/h ft2 = 0.1163 × 10−3 W/cm2
1 Btu/h in2 = 390.59 kcal/h m2= 0.045426 W/cm2
Heat transfer coefficient
1 Btu/h ft2 °F = 4.8791 kcal/h m2 °C
1 kcal/ h m2 °C = 0.20495 Btu/h ft2 °F
1 W/cm2 °C(or K) = 8598.45 kcal/h m2 °C
= 1761.1 Btu/h ft2 °F
Dynamic or absolute viscosity

1 poise = 1 dyn s/cm2 = 1 g/cm s
= 0.010197 kgf s/m2
= 2.0885 × 10−3 lbf s/ft2
1 kgf s/m2 = 98.067 poise = 0.20482 lbf s/ft2
1 lbf s/ft2 = 478.8 poise = 4.8824 kgf s/m2
Kinematic viscosity and thermal diffusivity

1 stoke = 1 cm2/s = 0.36 m2/h = 3.875 ft2/h
1 m2/h = 2.7778 stokes = 10.764 ft2/h
1 ft2/h = 0.25806 stokes = 0.0929 m2/h
Calorific value
Solid and liquid fuels
1 Btu/lb = 0.5556 kcal/kg = 0.0224 therm/ton

1 kcal/kg = 1.8 Btu/lb = 0.0403 therm/ton
1 J/g = 0.2388 kcal/kg = 0.4299 Btu/lb
Gaseous fuels
1 Btu/ft3 = 8.899 kcal/m3 at the same temperature and

pressure
1 Btu/ft3 at STP (30 in and 60°F), saturated
= 9.490 kcal/m3 at NTP (760mm and 0°C),
saturated
1 kcal/m3 = 0.1124 Btu/ft3 at the same temperature and
pressure
1 MJ/m3 = 238.846 kcal/m3 = 26.837 Btu/ft3 at the same
temperature and pressure
1 kcal/m3 at NTP, saturated = 0.1054 Btu/ft3 at STP, saturated
Liquid fuels
1 therm/UK gal = 5,543.3 kcal/l
10,000 kcal/l = 1.804 therm/UK gal
Coal equivalents
Sometimes different fuels are expressed in terms of an arbitrary ‘Standard
Coal’ of 7,000 kcal/kg calorific value.
1 kg coal equivalent = 7,000 kcal = 2.9308 × 107 J
1 tonne coal equivalent = 2.9308 kcal × 1016 = 2.9308 × 104 GJ
1 kg oil equivalent = 10,180 kcal = 4.2622 × 107 J
1 tonne oil equivalent = 4.2622 × 104 GJ
2.4 INTERNATIONAL SYSTEM (SI) OF UNITS
The international organisation, General Conference of Weight and

Measures (CGPM), has developed an international system (SI) of units, to
standardise the units of weight and measures all over the world. The SI
units consist of seven base units given in Table 2.1 and two supplementary
units given in Table 2.2. There are many derived units expressed in terms of
base units and supplementary units (Tables 2.3–2.5). There are also
guiding principles for the use of prefixes for forming the multiples and sub-
multiples of units (Table 2.6).
Table 2.1 The SI base units

Quantity Name Unit Definition
of symb
unit ol
Length metre m The metre is the length equal to 1,650,763.73 wave
lengths in vacuum of the radiation corresponding to
the transition of electrons between the 2p10 and
5d5 levels of the krypton 86 atom.
Mass kilogra kg The kilogram is the unit of mass; it is equal to the
m mass of the International Prototype Kilogram (IPK),
which is almost exactly equal to the mass of one
litre of water.
Time second s The second is the duration of 9,192,631,770
periods of the radiation corresponding to the
transition between the two hyperfine levels of
ground state of caesium 133 atom.
Quantity Name Unit Definition
of symb
unit ol
Electricity amper A The ampere is that constant current which, if
e maintained in two straight parallel conductors of
infinite length of negligible circular cross section,
and placed one metre apart in vacuum, would
produce between these conductors a force equal to
2 × 10−7 newton per metre of length.
Thermodynami kelvin K * The kelvin, unit of thermodynamic temperature, is
c temperature the fraction 1/273.16 of the thermodynamic
temperature of the triple point of water.
Luminous candel cd The candela is the luminous intensity in the
intensity a perpendicular direction, of a surface of 1/600,000
square metre of a black body at the temperature of
freezing/platinum under a pressure, of 101.325
newtons per square metre.
The candela is the luminous intensity, in a given
direction, of a source that emits monochromatic
radiation of frequency 540 × 1012 hertz and has a
radiant intensity in that direction of 1/683 watt per
steradian.
Amount of mole mol The mole is the amount of a substance system
substance which contains as many elementary entities as
there are atoms in 0.012 kg of carbon 12.
Note: When the mole is used, the elementary
entities must be specified, and may be atoms,
molecules, ions, electrons, other particles or
specified groups of such particles.
*The unit kelvin and its symbol (K) should be used to express an interval or a
difference of temperature.
Table 2.2 The SI supplementary units

Quantit Name Unit Definition
y of Unit Symb
ol
Plane radian rad The radian is the plane angle between two radii of a
angle circle which cuts off on the circumference an arc equal in
length to the radius. One radian is equal to 360°/2π,
which is approximately 57° 17’44.6”.
Quantit Name Unit Definition
y of Unit Symb
ol
Solid steradia sr The steradian is the solid or 3D angle which, having its
angle n vertex in the centre of a sphere, cuts off an area of the
surface of the sphere equal to that of a square with sides
of length equal to the radius of the sphere.There are 4π,
or approximately 12.5664 steradians in a complete
sphere.
Notes:
(i)There are units for which the CGPM has not stated whether they are base units or
derived units.
(ii)It is sometimes convenient to regard a plane angle and solid angle as each being a
dimensionally independent physical quantity; their units are then base units. It is
sometimes convenient to regard a plane angle as being the quotient of two lengths,
and a solid angle as being an area divided by a length squared; their units are then
derived units.
Table 2.3 Examples of SI derived units expressed in terms of the base units
SI Unit
Quantity Name Symbol
Area square metre m2
Volume cubic metre m3
Speed, Velocity metre per second m/s
Acceleration metre per second squared m/s
2
Wave number 1 per metre 1/m
Density, mass density kilogram per cubic meter kg/
m3
Concentration (of amount of mole per cubic metre mol/
m3
substance)
Activity (radioactive) 1 per second 1/s
Specific volume cubic metre per kilogram m3/
kg
Luminance candela per square metre cd/
m2
Table 2.4 SI derived units having special names or symbols

Quantity Name Symb Expression in Expression in terms of
ol terms of base and supplementary
other SI Units units (see footnote)
Frequency hertz Hz - 1/s
Force newton N - kg m/s2
Pressure* pascal Pa N/m2 kg/m s2
Energy, work, joule J Nm m2 kg/s2
quantity of heat
Power, energy watt W J/s m2 kg/s2
flux
Quantity of coulom C As sA
electricity, b
electric charge
Electric tension, volt V W/A m2 kg/s3 A
electric
potential
Electric farad F C/V m2 kg/s3A
capacitance
Electric ohm Ω V/A m2 kg/s3 A2
resistance
Conductance siemen S A/V s3A2/m2 kg
s
Magnetic flux weber Wb Vs m2 kg/s2 A
Magnetic flux tesla T Wb/m2 kg/s2 A
density
Inductance henry H Wb/A m2 kg/s2 A2
Luminous flux lumen lm cd sr
Illuminance lux lx cd sr/m2
Note: In these expressions there are other equally correct methods of indicating
multiplication and division for example, force can be shown as kg m s−2
*According to ASTM, the basic unit is megapascal, (MPa) = 106 N m2. One bar = 102
Pa = 0.1 MPa
Table 2.5 Further examples of SI derived units [Most of these are usually expressed in
terms of Table 2.4. Expressions in terms of the base (and supplementary) units are
included.]
Quantity Names Symbol Expression in terms of
(see foot- base and supplementary
note) units
Dynamic viscosity pascal second Pa s kg/m s
Moment of force newton metre Nm m2 kg/s2
note) units
Surface tension newton per N/m kg/s2
metre
Heat flux density, watts per W/m kg/s2
irradiance, heat flow square metre
rate
Heat capacity, joule per kelvin J/K m2 kg/s2 k
entropy
Specific heat joule per J/kg m2/s2
capacity, specific kilogram
entropy
Specific energy joule per J/kg m2/s2
kilogram
Thermal conductivity watt per metre W/m K m k g/s3 k
kelvin
Energy density joule per cubic J/m3 kg/m s2
metre
Electric field volt per metre V/m m kg/s3A
strength
Electric charge coulomb per C/m3 s A/m3
density cubic metre
Electric flux density coulomb per C/m2 s A/m2
square metre
Permitivity farad per F/m s4 A2/m2 kg
metre
Current density ampere per A/m2 A/m2
square metre
Magnetic field ampere per A/m A/m
strength metre
Permeability henry per H/m m kg/s2 A2
metre
Molar energy joule per mole J/mol m2 kg/s2 mol
Molar entropy, molar joule per mole J/mol K m2 kg/s2 mol K
heat capacity kelvin
Angular velocity radian per rad/s rad/s
second
Angular acceleration radian per rad/s2 rad/s2
second
squared
Radiant intensity watt per W/sr m2 kg/s2 sr
steradian
note) units
Radiance watt per W/m2 sr kg/s2 sr
square metre
steradian
Note: For each unit in this table, a typical symbol is given. Many other symbols are
equally valid, for example J/m3 =N/m2 = Pa = Ws/m3 = VAs/m3 = VC/m3. Moreover,
sequence is irrelevant, for example, W/m K = W/K m
Table 2.6 Names and symbols for the SI prefixes

Factor Prefix Symbol
1024 yotta Y
1021 zetta Z
1018 exa E
1015 peta P
1012 tera T
109 giga G
106 mega M
103 kilo k
102 hecto h
101 deca da
10-1 deci d
10-2 centi c
10-3 milli m
10-6 micro m
10-9 nano n
10-12 pico p
10-15 femto f
10-18 atto a
BIBLIOGRAPHY
1. International Energy Outlook 2006, Energy Information administration, U

Department of Energy, Washington, DC 20585, June, 2006.
2. Mullin JW. Recent developments in the change-over to the Internatio

System of Units, J. Inst. Fuel, 45: 208, 1972.
3. Rose JW and Cooper JR, (eds.). Technical Data on Fuel, Seventh edit
London: World Energy Conference, London, 1976.
3 Solid Fuels
3.1 INTRODUCTION
Solid materials that are used as a fuel to produce energy by combustion with
oxygen or oxygen-enriched air are known as solid fuels. Both natural and
processed fuels are widely used in domestic and industrial appliances.
Wood, peat, lignite or brown coal, bituminous coal and anthracite are
important natural solid fuels. Charcoal, soft coke, hard coke and carbonised
lignite briquettes are solid fuels derived from natural varieties. Other
examples of widely used solid fuels are animal dung and agricultural and
industrial wastes such as straw, husk, coconut shells, bagasse and sawdust.
3.2 BIOMASS
Atmospheric carbon dioxide is fixed in the form of biomass—the primary

product of photosynthesis in the terrestrial and aquatic regions of the earth.
The secondary products are human, animal and industrial organic wastes
and residues. Both the primary and secondary products constitute the
renewable resources of energy used by human beings around the globe. In
prehistoric times biomass was perhaps the only source of useful energy;
currently it provides 11% of the world’s primary energy. The biomass energy
potential is ten times the world’s annual energy need. More than half of the
energy consumption in India is supported by biomass.
3.2.1 WOOD AND CHARCOAL
Wood has been used as a fuel from ancient times. It is now used extensively
in countries where there are extensive forests, and where other fuels are not
cheap or readily available.
Freshly cut wood contains 25%–50% water. It is normally used in an air-
dried condition with 10%–15% moisture content. Ash content is about 0.6%
or less. The combustible part of wood is mostly made up of cellulose and
lignin, which are organic compounds of carbon, hydrogen and oxygen.
Resins and waxes are also present. The average composition and calorific
value of dry wood are given in Table 3.1. The chemical constitution of dry
wood is fairly constant from different sources.
Table 3.1 Average composition and properties of hardwoods

Group-wise composition, per cent air-dried
Cellulose 45–55
Lignin 25–35
Hemicelluloses 4–6
Fats, waxes and resins 0.5–2
Water 10–15
Ultimate analysis and other properties, per cent dry basis
Carbon 50
Hydrogen 6
Oxygen 43.5
Ash 0.5
Density, kg/m3 650
Calorific value, kcal/kg 4,600
Although ash content is low, the oxygen content of wood is very high.
This makes even dry wood a fuel of low calorific value. However, its ease of
ignition, free burning quality and easy disposal of ash are the points in its
favour.
Wood can be used as a raw material for the carbonisation and
gasification processes. Charcoal is the solid product of carbonisation (so
called destructive distillation), and producer gas is the gaseous product of
the gasification of wood. Charcoal also results from the incomplete burning of
wood.
The carbonisation of wood is characterised by several temperature
regimes.
1. All loosely bound water evaporates between 100°C and 170°C.
2. Gases containing carbon monoxide, carbon dioxide and conde

vapours evolve between 170°C and 270°C.
3. An exothermic step starts at 270–280°C, which can be detected

spontaneous generation of heat and the increase in temperature.
The evolution of the oxides of carbon ceases, but more of the condensable
vapours form. Without any outside source of heat, the temperature continues
to rise slowly until it reaches 400°C to 450°C. A final temperature of 600°C in
practice is achieved by supplying external heat.
Charcoal is the solid product left after the carbonisation of wood. On cooling
the gases and vapours give a non-condensable gas (wood gas) and the
liquids settle into two layers. The upper layer is pyroligneous acid, which is
an aqueous solution of many chemicals, and the lower layer is wood tar.
Except for its use as a supplementary plant fuel, wood gas may be
considered a waste. Acetic acid, methanol and acetone, in various grades of
purity, are recovered from the pyroligneous acid. After acetic acid and water
are recovered from the pyroligneous acid, wood spirit is obtained. This is
further processed for the recovery of methanol. Before the advent of
synthetic processes, wood spirit was the only source of methanol. Wood tar
is often used as a supplementary plant fuel. It is however a potential source
of many chemicals.
Although any wood gives charcoal on carbonisation, some selection is
necessary to get a quality product. Dense charcoal is obtained from the
species of mature dense wood with narrow annular rings, while rotten and
old wood yields a light product. Wood carbonisation may be practised in
open pits, kilns or metal retorts. The primitive open pit method is now
practically obsolete; it accounts for a small fraction of the total production. No
product other than charcoal is recovered. The yield of charcoal is low—about
15% on dry basis and it is of inferior quality.
In most kilns charcoal is the only product, but its yield and quality vary.
There are many designs of charcoal kilns in vogue in India and elsewhere.
Paraboloidal mud-walled kilns are more common in India. No by-products
are recovered. A kiln of this design is built in a paraboloidal shape of radius
2.5–3 m, height 2.5 m and capacity 25–35 m3 of stocked wood. Billets of
wood are stacked on the ground in such a way that a paraboloid results with
the apex at the top (Fig. 3.1). Two interconnecting passages are left in the
stack—a vertical central passage acting as the chimney and a horizontal
passage at the bottom for introducing fire to the centre. The kiln is covered
first with a thick layer of grass, leaves and turf and then plastered with earth
or a mixture of earth and charcoal dust. The initial firing is done with grass
and twigs. Later the wood billets are partly burned to supply heat for the
process. The time taken for carbonisation is about 7 to 10 days. The fire is
extinguished with water and the kiln is allowed to cool for a week or more
before the charcoal is taken out.
Figure Paraboloidal charcoal kiln
3.1
Pits and kilns are located in the forests. Retorts are however used in
factories. The yield of charcoal in retorts is much higher and the by-products
can also be recovered. Some typical yields of by-products of wood
carbonisation in industrial retorts are given in Table 3.2.
Table 3.2 Products of wood carbonization

Products Yields, per cent air-dried
Charcoal 25–30
Pyroligneous acid
8–12
acetic acid
10–20
wood spirit (crude)
10–20
water
Wood tar 8–10

Wood gas 20–23
There are four types of charcoal retorts.

1. Externally fired batch retorts,
2. Externally fired continuous vertical retorts,

3. Internally heated batch vertical retorts,
4. Internally heated continuous vertical retorts.
Internally heated retorts are of recent design, and use forced recirculation of
heated inert gases given off during carbonisation, have high thermal
efficiency and lend themselves to efficient mechanical handling of the wood
and charcoal.
Wood charcoal is a source of fairly pure carbon. It easily ignites and
burns at low rates. For clean and smooth burning in heating ovens, wood
charcoal is a good but costly fuel. It used to be a very important fuel and
reducing agent in metallurgical processes. Coke has now replaced it in most
cases owing to cost and other technical reasons. Charcoal has however
retained its use in some special cases. It is extensively used as a fuel in
blacksmiths’ and metal workers’ forges, and in numerous other cottage
industries. Gasification plants may also use charcoal as the fuel material.
During the Second world war, road vehicles using producer gas obtained
from wood charcoal were used in many countries, including India. In the post
Second world war period, people in industrialised countries rediscovered the
excellent properties of charcoal for barbequing. This is now a major
economic factor in the charcoal industry. With suitable treatment wood
charcoal is widely used as an absorbent in gas purification, solvent recovery
and liquid purification. It has a high surface area of 150–450 m2/g. It remains
the preferred material for the manufacture of carbon disulphide.
Charcoal is also obtained by the carbonisation of other forms of biomass,
for example, sawdust, nutshells, sugarcane bagasse (crushed, chopped and
reduced to small fragments), bark, twigs and coconut shells. The
carbonisation of small particles is very fast and this type of charcoaling is
also referred to as the rapid pyrolysis process. The small-scale rapid
pyrolysis technology has particular importance for the charcoal-maker in
developing countries. Almost all rapid pyrolysis plants can be designed for
the generation of three products, namely, solid charcoal, pyrolysis oil and
converter gas. The biomass char is obtained as a coarse or fine powder and
has to be agglomerated or cast into briquettes for most applications. There is
one charcoal blast furnace at Mysore Iron and Steel Limited (MISL) at
Bhadravati in India with a capacity of 25,000 tonnes of pig iron per annum.
The charcoal consumption is one tonne per tonne of pig iron. The supply of
charcoal is now mostly met from the kilns of the neighbouring forests. The
ferroalloy plant of MISL also uses charcoal as fuel. Some 2 billion people in
the world use firewood and charcoal for cooking and heating.
3.2.2 WOOD WASTES
Small-sized wood wastes, particularly sawdust and wood shavings, find use
as fuel. These can be successfully burnt along with coal and coke. Fuel
briquettes can be made by binding the wastes with an inflammable material
like pitch. Wood wastes can also be converted into charcoal and producer
gas.
3.2.3 BAGASSE
The fibrous material left after the crushing and extraction of juice from sugar
cane is known as bagasse. One of the chief uses of this material is as fuel in
sugar factories. In its air-dried condition it contains 45%–50% moisture and
1% ash, and has a calorific value of 1,500 kcal/kg. It has been estimated that
one tonne of bagasse at 49% moisture burns with 100% excess air to give
the same heat as 160 l of furnace oil. On storing for some months, bagasse
undergoes fermentation and dries to about 15% moisture. The fermented
variety is a better fuel than the raw air-dried bagasse. It has a higher calorific
value, 3,800 kcal/kg, ignites easily and has free burning quality. India
produces 60 million tonnes of raw bagasse annually, out of which about
70%–75% is burnt as fuel; a small quantity is sold for pulp and paper making,
and about 20% is surplus.
3.2.4 DRY LEAVES AND TWIGS
These are collected from the forests and elsewhere and meet the fuel
requirement of the poor in India to a great extent. The moisture, ash and
calorific value of some non-fossil solid fuels are given in Table 3.3.
Table 3.3 Properties of some non-fossil domestic fuels, air-dried

Fuel Moisture, per Ash, per Calorific value,
cent cent kcal/kg
Casuarina leaves 8.4 1.3 4400
Coconut shell 9.3 0.2 4270
Cow dung 8.5 21.7 3290
Cow dung cake 4.3 33.2 3140
Date palm leaves 10.5 4.4 4070
Groundnut shells 12.1 1.3 4200
Mango leaves 9.8 18.0 3390
Palmyra leaves 9.4 1.3 4200
Fuel Moisture, per Ash, per Calorific value,
cent cent kcal/kg
Rice husk 11.6 19.5 3440
Sal wood 10.4 0.3 4480
Sawdust from sal 9.8 1.5 4460
wood
During the Second world war, when petroleum supplies were scarce,
Brazil burned coffee and Argentina burned wheat and corn as fuel.
Power alcohol from farm wastes may be economical in those countries
where sugar crops are easily raised and the cost of imported petroleum is
high.
3.2.5 OTHER AGRICULTURAL WASTES
Besides bagasse, a number of other agricultural wastes also find use as fuel.
The total availability of these in India per year is: rice straw 100 million
tonnes, wheat straw 50 million tonnes, maize straw and cob 20 million
tonnes, cotton stalk 24 million tonnes, and jute stick 2.5 million tonnes. The
straws are used as cattle feed and fuel. The jute stick is mainly used as a
very pleasant and free-burning fuel. Rice husks are higher in ash (>10%)
than the above material. It is used in ovens and furnaces. Coconut shells and
fibres are also employed as fuels. It is estimated that more than 250 million
tonnes of agricultural and forest residues are available in India.
3.2.6 CATTLE DUNG
Unfortunately, cattle dung is widely used as fuel in India. More than 100
million tonnes of dry cattle dung are burnt every year as domestic fuel. It is
equivalent to more than 40 million tonnes of coal. Raw cattle dung is made
into briquettes with straw, leaves, twigs or rice husks and sun dried before
being used as fuel. The more rational use of cattle dung is in the production
of biogas and by product manure. So long as alternative cheap fuels are not
available in abundance, the misuse of cattle dung will continue, especially in
villages and small towns.
3.3 PEAT
Peat is a naturally-occurring solid fuel consisting of partly decomposed plant
material that has accumulated in situ under marshy conditions. Peat bogs
grow at slow, but measurable rates. In general, peat accumulates in an
active swamp at the rate of about 3 m in 2,500 years. It is associated with
very large content of water. In fact, the amount of solid matter in peat bogs is
10%, or less. Near the surface of the deposit, peat is light brown in colour
and highly fibrous in nature. With an increase in the depth, the colour
becomes darker and finally black, when the vegetable origin and structure is
not so obvious. A part of the water content of freshly won peat can be
drained off while a much larger part is removed by drying in air. The air-
drying operation may require 40–50 days.
Peat is not regarded as coal; it represents the first stage in the
conversion of vegetable matter into coal. The other major stages are lignite,
bituminous coal and anthracite. All these fuels together constitute the
humites. Large deposits of peat are found in Russia, Germany, Poland,
Finland, the USA, Sweden, Norway, Ireland, Canada, Indonesia and
Scotland. Russia has 60% of the world’s total reserves of peat. In the
Republic of Ireland, peat is the principal fuel. The only significant deposit of
true peat in India is in the swamps of the Nilgiri hills in southern India at an
elevation of 2,000 m. Peat-like material also occurs at depths of 5–10 m on
the two sides of the Hooghly river in and around Kolkata.
The composition and properties of peat vary widely from place to place,
depending on the nature of the original plant material and the agencies and
extent of decay. Raw peat consists of decayed plant material and peat
humus. The content of montan wax may vary from 3% to 12%. The average
properties of peat are shown in Table 3.4. The lower layers of peat usually
have a higher ash content than the upper layers.
Table 3.4 Average properties of peat
Peat is an important fuel in those countries having large deposits of peat.

It is extracted by an old well-established method of hand-cutting and also by
the mechanised excavation method. Its main use is as domestic fuel, as it is
easy to ignite and burns freely to give a long pleasant flame. Peat is better
used in the form of briquettes. It is also largely used in steam boilers, power
stations and gas producers. The low temperature carbonisation of peat is
practised for getting peat coke and by-products. Peat coke is a valuable fuel
for some metallurgical processes. Peat is also used as a fertiliser or for
making fertilisers. However, about 75% of the world production of peat is
used in heat generation.
3.4 LIGNITE OR BROWN COAL
Lignite occurs in a number of forms distinguished by their physical

characteristics:
1. Woody or fibrous brown coal with the clear structure of plant tissues,
2. Earthy brown lignite, compact but friable,
3. Brown coal showing cleavage and slight woody structure.
A distinction is sometimes made between the terms lignites and brown coals
on the basis of the woody structure, which is predominant in the former and
not obvious in the latter. However, the two terms are often synonymous in
English-speaking countries.
Lignite is characterised by high moisture content ranging from 30% to
50%. On exposure to the atmosphere, the brown colour darkens and the
moisture content reduces to an equilibrium value of 12% to 20%. On drying,
lignite shrinks and breaks up readily in an irregular manner. Hence, it cannot
be transported far from the mine. It is also likely to ignite spontaneously as it
adsorbs oxygen readily and must therefore not be stored in the open without
care.
As already stated, there are extensive deposits of lignite in Russia, the
USA, East Germany, Australia, Canada and India. Table 3.5 gives the lignite
resources in Indian states. The major deposits of true lignite are in Tamil
Nadu and Pondicherry (31,327.02 million tonnes: Neyveli alone accounting
for about 4,200 million tonnes), Rajasthan (4311.43 million tonnes), Gujarat,
Jammu and Kashmir and Kerala. The all India figure is about 38 billion
tonnes. The lignite deposits in many areas are relatively near the earth’s
surface and are quite thick. The deposit at Neyveli occurs about 60 m below
the ground level, is 15–20 m thick and is won by quarrying.
Table 3.5 Lignite resources of states as on 1 April 2007 ( million tonnes)

State Geological reserves
Tamil Nadu and Pondicherry (including NLC) 31327.02
Rajasthan 4311.43
Gujarat 2662.75
Jammu and Kashmir 27.55
Kerala 9.65
W. Bengal 1.15
All India 38339.55
Source: Geological Survey of India, News, 2007. http://www.gsi.gov.in.
As in the case of peat, the composition and properties of lignite also vary
widely. The immature varieties of woody brown coals cannot be easily
distinguished from the mature peat. Likewise, the more mature brown coals
are similar to sub-bituminous coal. The proximate analysis, ultimate analysis
and calorific value of typical lignite of India are given in Table 3.6. The carbon
content is 70%–75% and the oxygen content is 21%–26%. The volatile
matter is often over 50% dmmf and in a large number of cases the ratios of
volatile matter to fixed carbon are approximately 1:1. The high oxygen
content is responsible for relatively low calorific value (6500–7000 kcal/kg
dmmf). On an air-dried basis, the value may be as low as 2,500 kcal/kg due
to the high moisture and ash content. The ash of lignites is generally low.
This is true for India also where the ash of coal is pretty high. However,
Nichahom lignites in Kashmir have a very high ash content up to 50%.
Table 3.6 Properties of lignite

Montan wax is present in lignites ranging from 1% to 10%. Neyveli lignite
yields up to 5% montan wax. The quality of montan wax of Indian lignites is
poor.
Compared to bituminous coal, raw lignite is an inferior fuel owing to its
high moisture, low calorific value, small size and bad weathering properties.
Lignite is of economic importance in those places where it is available and
other fuels do not occur in abundance. Such a situation exists in South India.
Neyveli lignite is used in the generation of electricity in thermal power
stations and for the production of carbonised briquettes which are used as
smokeless fuel. Kashmir lignite is also made into briquettes and used as fuel.
The other important uses of lignite are in gas production and metallurgical
furnaces. The tar obtained by the low temperature carbonisation of lignite is
a valuable raw material for the production of synthetic petroleum and other
liquid fuels. Lignite is extensively used in the manufacture of producer gas. It
is also gasified into synthesis gas for ammonia production.
The year-wise lignite production is given in Table 3.7. The production of
lignite in India was as high as 31.285 million tonnes in 2006–07. Neyveli
Lignite Corporation (NLC) accounted for the major share—67.2%.
Table 3.7 Year-wise lignite production

3.5 SUB-BITUMINOUS COAL OR BLACK LIGNITE
In many countries this fuel is regarded as a variety of mature lignite

resembling true coal in colour and appearance. In India it is regarded as a
separate class and the term sub-bituminous coal is preferred. It is black in
colour with a dull, waxy lustre. It is denser and harder than lignite and has a
lower moisture content of 12% to 25%. Most sub-bituminous coals appear
banded like bituminous coal. The bands are parallel to the bedding plane, but
are poorly jointed and easily split into slabs instead of breaking into
rectangular lumps. Like lignite, sub-bituminous coal disintegrates on
exposure to atmosphere and is therefore difficult to transport.
Sub-bituminous coal is available in the USA, Russia, Germany, Canada,
Australia and India. Some of the tertiary coals in Assam, Kashmir and
Rajasthan are of the sub-bituminous type.
The sub-bituminous coal has 70%–78% carbon, 4.5%–5.5% hydrogen
and about 20% oxygen (all on a dmmf basis). The air-dried moisture is 10%–
20%. The volatile matter is 40% (dmmf) and above. The calorific value is
6800–7600 kcal/kg, dmmf. It ignites easily and may be used in raising steam
for various purposes. If low in sulphur, it may also be used for manufacturing
gaseous fuels.
3.6 BITUMINOUS COAL
This is the most common and widely used variety of solid fossil fuel. The raw
coal ordinarily sold in the market under the Hindi name of koela belongs to
this class. The term ‘bituminous’ is a misnomer. Coal does not contain true
bitumen. Moreover the so-called bitumen extractable from coal with the help
of organic solvents cannot define coal and its properties. The name is
perhaps due to the fact that it burns with a smoky yellow flame similar to that
of bitumen, and that the pitch obtained from coal tar is of a bituminous
nature. The corresponding terms for bituminous coal in German and Russian
imply stone-like coal and do not contain any equivalent for bitumen. The term
coal ordinarily refers to bituminous coal. In the wider sense coal covers all
the solid fossil fuels.
Bituminous coal is black and usually banded. The bands are parallel to
the bedding plane. The coal breaks along vertical joints or cleats into
rectangular, columnar and cubical places. Sometimes the fracture is
conchoidal. The lustre varies from bright to dull. Bituminous coal is denser
and harder than lignite and sub-bituminous coal, and does not disintegrate
into slacks on exposure to atmosphere. Owing to the good heating qualities
and ease of handling, bituminous coal is the major fuel in most countries.
Coal occurs in strata called seams which are bound between the upper
and lower layers of rocks, and have longitudinal and lateral extensions. Coal
seams are parallel to the bedding planes which, may or may not be parallel
to the earth’s surface. The whole of the coal-bearing rocks in a region is
collectively known as the coal measures. The seams vary widely in
thickness, longitudinal and lateral extension and depth of occurrence. For
comfortable mining a seam should be at least a metre in thickness. The
thickest coal seam (156 m) of India has been discovered in Deocha-
Panchmi-Dholkati (Rajmahal coalfield, West Bengal), while the deepest coal
mine (720 m shaft) is at Chinakuri in the Raniganj (West Bengal) coalfield.
Extensive deposits of bituminous coal occur in the USA, Russia,
Germany, China, UK, Poland, India and Canada. Inexplicably, about 95% of
the world’s known coal lies in the northern hemisphere. Asia, including the
old USSR, and North America possess slightly more than four-fifths of the
world’s coal in almost equal amounts. India’s coal resources (proved,
indicated and inferred) in its various states are given in Table 3.8. Out of the
grand total of about 248 billion tonnes, Jharkhand has the largest share of
29%, closely followed by Orissa (24.6%). West Bengal accounts for about
11% only.
Table 3.8 Coal resources of states as on 1 January 2005 (million tonnes)

State Proved Indicated Inferred Total
Andhra Pradesh 8263 6079 2548 16926
Arunachal Pradesh 31 40 19 90
Assam 279 27 34 340
Bihar 0 0 160 160
Chhatisgarh 9373 26191 4411 39975
Jharkhand 35417 30439 6348 72204
Madhya Pradesh 7513 8815 2904 19232
Maharashtra 4653 2309 1620 8582
Meghalaya 117 41 301 459
Nagaland 4 1 15 20
Orissa 15161 30976 14847 60984
Uttar Pradesh 766 296 1062
West Bengal 11383 11876 4554 27813
All India 92960 117090 37797 247847
Source: Annual Report 2004-05, Ministry of Coal 2005, Govt. of India, New Delhi.
Category-wise, non-coking coal contributes the maximum of 87% (Table

3.9). Prime coking coal’s share is only 2%, medium coking coal’s share is
10% and blendable semi-coking coal’s share is less than 1%. Naturally India
has to depend on imports of suitable coal for its coke plants in the iron and
steel industries.
Table 3.9 Coal resources by category as on 1 January 2007 (million tonnes)

Type of coal Proved Indicated Inferred Total
Coking
Prime coking 4614 699 5313
Medium coking 11774 11601 1880 25255
Blendable/semi-coking 482 1003 222 1707
Sub-total 16870 13303 2102 32275
Non-coking 81050 105687 36158 222897
Total 97920 118992 38260 255172
Source: Annual Report 2006-07, Ministry of Coal 2005, Govt. of India, New Delhi.
The world’s proved reserves of bituminous coal and anthracite were

about 998 billion short tons in 2004. The main beneficiaries are the USA
(27%), Russia (17%), China (13%), South Africa (5%), Australia (9%), West
Germany (5.7%) and Poland (5.1%). India’s share is 10%. The world’s
production of coal (including small quantities of anthracite) was 5370 Mt in
2006. Some of the countries leading in coal production are: USA. China,
India, Australia and South Africa.
Table 3.10 World recoverable coal reserves as of 1 January 2003 (billion short tons)
Region/Country Bituminous and Sub- Lignit Tot
Anthracite bituminous e al
World Total 528.8 298.1 170.9 997.
7
United States 123.7 110.3 33.5 267.
6
Russia 54.1 107.4 11.5 173.
1
China 68.6 37.1 20.5 126.
2
India 99.3 0.0 2.6 101.
9
Other Non-OECD Europe 50.1 18.7 31.3 100.
and Eurasia 1
Australia and New Zealand 42.6 2.7 41.9
87.2
Africa 55.3 0.2
55.5
OECD Europe 19.5 5.0 18.8
43.3
Other Non-OECD Asia 1.4 2.0 8.1 11.5
Brazil 0.0 11.1 0.0 11.1
Other Central and South 8.5 2.2 0.1
America 10.8
Canada 3.8 1.0 2.5 7.3
Other 1.8 0.4 0.1 2.1
Source: International Energy Outlook 2006, Energy Information Administration, USA.
The production of coal in India for Industrial purposes dates back to 1775
when the first coal mines were opened in Sitarampur in the Raniganj
coalfield. In those days the mined coal used to be transported to Kolkata
partly by river and partly by road. The production of coal in India was 282 Mt
in 2005–2006 as against 26 Mt in 1947 and 70 Mt in 1973.
There are two modern methods of mining: underground mining and open
cast (or strip) mining from the surface. Modern coal mines are highly
mechanised with sophisticated equipment.
Underground mining
Underground mining has two variants:

1. Board-and-pillar (or pillar and stall), which is used especially in med
thick seams at relatively shallow depth
2. Longwall, a method adaptable to most mining conditions but which

sole technique for mining at great depths.
In the board-and-pillar method, tunnels (galleries) are driven by blasting

along and across the extension of the coal seam. The galleries divide the
seam into many blocks knows as coal pillars. Coal is won by driving galleries
and by depillaring to the extent possible by sand stawing. The coal is moved
underground by conveyor belt and brought to the surface by haulage along
an incline, or by vertical lifts in a pit.
Extraction of coal from the longwall face requires the driving of pairs of
roads which link with pairs of access roads into the area under mining. These
access roads in turn link with a pair of mine shafts (pits). Shafts and roads
are in pairs for the forced circulation of air ventilation. The main machinery
on a longwall face consists of a cutter–loader, a conveyer and a set of
powered supports. The supports are for the roof so that there is no loss of
coal locked up in pillars.
Open cast mining
The technology employed in strip mining is very advanced. It is based mainly

on a huge dragline, with a bucket scooping up tonnes of coal at a time. Large
shovels, bulldozers and bucket-wheel excavators are also used. The top soil
is first removed and placed on one side exposing the coal seams, which are
then progressively extracted. Intervening din bands are separately removed.
Strip mining involves the restoration of the land after extraction of the coal.
More than half the coal in India is raised by open cast mining. The
productivity per manshift in open cast mining is more than five times that in
underground mining. The age old board-and-pillar technique is being
increasingly mechanised and will continue to remain the mainstay of
underground coal production in India. The longwall powered support
technology is restricted to selected mines, where geomining conditions are
conducive to such a method. About 1 Mt of coal was raised by this method in
1985–86.
Coal production in various states for the years 1997–98 and 2005 are
given in Table 3.11. It may be seen that the all India production was 154.4,
289.3 and 382.3 Mt, respectively. Considering the production for 2004–05,
Jharkhand accounted for 20.4% and Chhatisgarh comes next (18.1%).
Orissa was also close (17.3%). If we consider all the years, Madhya Pradesh
produced 29.3% out of a total of 289.3 Mt. West Bengal’s contribution varied
between 12.6% in 1985–86 and 6.2% in 1997–98 and 6.17% in 2004–05.
Table 3.11 Coal production of various states: 1985–86 to 2004–05 (million tonnes)
State 1985–86 1997–98 2004–05 Total per cent
Andhra Pradesh 15.7 28.9 35.3 9.2
Assam 0.9 0.7 0.6 0.2
Bihar 54.3 81.3 − −
Chhatisgarh − − 69.1 18.1
Jharkhand − − 78.0 20.4
Madhya Pradesh 42.6 84.8 52.7 13.8
Maharashtra 11.6 26.2 34.5 9.0
Meghalaya − 3.2 5.6 1.5
Orissa 6.0 42.2 66.1 17.2
Uttar Pradesh 3.9 18.0 16.8 4.4
West Bengal 19.4 18.0 23.6 6.2
All India 154.4 289.3 382.3 100.0
Source: Coal Directory of India (various years), Coal Controller’s Organisation, Ministry
of Coal, Govt. of India, Kolkata.
Table 3.12 gives the sector-wise coal consumption in India. The chief
consumers of coal are the thermal power and coke plants. The most recent
data on year-wise coal production is given in Table 3.13.
Table 3.12 Sector-wise coal consumption in India (million tonnes)

2006–2007
Power 216.472
Steel and coke ovens 12.109
Railways 0.00
Cement 10.942
Fertilisers 2.307
(Soft cokes) LTC 0.000
Brick, kilns, textiles, chemicals, paper and other industries 58.024
Colliery use 0.745
Total offtake 300.599
Source: Annual Report 2006–2007, Ministry of Coal, Govt. of India.
Table 3.13 Year-wise coal production (million tonnes)

Year Coal India All India
1973–74 69.96 78.18
Year Coal India All India
1974–75 78.99 88.41
1975–76 88.98 99.68
1976–77 89.48 101.04
1977–78 88.96 100.98
1978–79 90.05 101.97
1979–80 91.44 103.98
1980–81 100.86 114.01
1981–82 108.94 124.93
1982–83 114.68 130.598
1983–84 121.41 140.242
1984–85 130.81 147.438
1985–86 134.11 154.296
1986–87 144.74 165.686
1987–88 159.02 181.285
1988–89 171.50 196.23
1989–90 178.60 203.361
1990–91 189.68 214.06
1991–92 204.16 232.82
1992–93 211.22 242.00
1993–94 216.10 248.69
1994–95 223.06 257.77
1995–96 237.27 273.42
1996–97 250.62 289.32
1997–98 260.55 300.40
1998–99 256.48 296.51
1999–00 260.58 304.10
2000–01 268.14 313.70
2001–02 279.65 327.79
2002–03 290.69 341.27
2003–04 306.36 361.25
2004–05 323.58 382.62
2005–06 343.39 407.04
2006–07 360.91 430.83
2007–08 379.49 456.37
Source: Coal Directory of India, Part I - Coal Statistics, Ministry of Coal, Govt. of India,
Coal Controller’s Organisation, Kolkata.
It may be noted that the figure 456.37 Mt is for 2007–08. Projecting from
the old data in Table 3.6 of the second edition of the book, we find the state
of Bihar accounted for 35.5% of coal production. Next came Madhya
Pradesh (29.2%). The Raniganj coalfield in West Bengal accounted for only
12.9%.
Table 3.14 shows the properties of Indian bituminous coals. These coals
vary widely in composition and properties. The air-dried moisture varies from
14% to 0.5%. On the dmmf basis, the volatite matter varies from about 45%
down to about 20%, carbon from under 80% to about 92%, hydrogen from
6% to 4%, oxygen from 15% to 0.5% and the calorific value from 8,900 to
7,500 kcal/kg. The limiting figures given are for the bituminous coals of India
and may differ slightly for the coals of other countries. Unlike coals of Europe
and America, Indian coals have a rather high percentage of ash ranging
between 12% and 40%, the usual range being 15% to 30%. In the tertiary
coals of Assam, the ash is often low (3% to 8%) and only in particular areas
is it rather high (24% to 26%).
Table 3.14 Properties of Indian bituminous coals
The caking and coking coals form sub-groups of bituminous coal. A

demerit of the Indian coals is that 82% of the total resources is non-caking.
Again, out of the 18% of the caking coals, only 3.5% is of the prime coking
variety and 14.5% comprises medium coking and weakly caking coals. The
coals of the super seam (X to XVII) of the Jharia coalfield and the Upper and
Lower Karharbari seams of the Giridih coalfield are almost the sole deposits
of truly coking coals in India. There are some coals, for example, the
Dishergarh seam in Raniganj, Mahuda in Jharia and Makum in Assam, which
are highly caking, but do not produce strong coke.
The tertiary coals of India deserve special mention. Geologically the
coals deposited in the tertiary rocks are young and should normally mature to
lignite only. However, due to various reasons, the tertiary coals in the north
eastern region have matured to the bituminous stage and those in Jammu to
the anthracitic stage.
Bituminous coal is the major commercial fuel in most countries, including
India. Its chief use is combustion in domestic ovens, industrial furnaces and
boilers, railway locomotives and thermal power stations. Two other important
uses are carbonisation and gasification, whereby coal is converted into solid
fuels, for example, coke and semi-coke, gaseous fuels like producer gas,
water gas and coal gas, and liquid fuels such as coal tar fuels. Coal is also
the source of a wide range of chemicals, fertilisers and synthetic liquid fuels.
3.7 SEMI-ANTHRACITE
Semi-anthracite is intermediate between bituminous coals and anthracites. It

is harder than the most mature bituminous coal, and ignites more easily than
anthracite to give a short flame changing from yellow to blue. Some of the
properties of semi-anthracite are:
Moisture, per cent air-dried = 1 to 2
Volatile matter, per cent dmmf = 10 to 15
Calorific value, kcal/kg dmmf = 8,500 to 8,800
Semi-anthracites do not occur in India.
3.8 ANTHRACITE
Anthracite is the most mature and hardest form of solid fossil fuel. It has sub-
metallic lustre, sometimes even a graphitic appearance. It does not soil the
hand. Although there is banded structure this is not always obvious.
Anthracites are characterised by low volatile matter, 3% to 10% dmmf, and
high carbon content, over 92% dmmf. The air-dried moisture is 2% to 4%.
The hydrogen content is 2.8% to 3.9% and the calorific value is 8,400 to
8,700 kcal/kg, both on a dmmf basis. Anthracites and semi-anthracites are
non-caking.
The most notable deposits of anthracite are in South Wales, United
Kingdom and Pennsylvania, USA. True anthracites do not occur in India. The
tertiary coals in Jammu and the Lower Gondwana (Permian) coals in
Darjeeling (West Bengal) have properties approaching those of anthracite
and are known as anthracitic coals. There are about 100 to 150 Mt of such
coals in each of the above two deposits. Some of the properties of these
coals are given in Table 3.15.
Table 3.15 Properties of anthracitic coals in India
The chief industrial uses of anthracite are in boilers, domestic stoves and
metallurgical furnaces. It also finds use in small quantities as a component of
coke oven charges. On heating it gives thermo-anthracite which is a useful
raw material in the production of carbon electrodes and other carbon articles.
3.9 CANNEL COAL AND BOGHEAD COAL
Cannel coal and boghead coal (torbanite) are examples of sapropelic coals.
By their nature they cannot be fitted into the series: peat-lignite-bituminous
coal-anthracite which constitutes humic coals. Both humic coals and
sapropelic coals are of vegetable origin—the former being derived from
higher plants and the latter from smaller plant organisms like algae.
Cannel coal and boghead coal have a dull lustre and yield a conchoidal
fracture. They are quite massive, tough and unbanded. A splinter of these
coals can be ignited with a match. Cannel coal owes its name to the word
‘candle’ because it burns with a long and steady flame. Cannel is dull black
in colour while boghead is dull brown.
These coals have higher volatile matter and higher hydrogen than the
corresponding normal (humic) coals. Some typical data are given in Table
3.16. The high hydrogen content is responsible for the high calorific value
and also high yields (45% to 65% dmmf) of tarry products on low
temperature carbonisation.
Table 3.16 Properties of cannel coal and boghead coal

Cannel coal and boghead coal usually occur in isolated bands in rocks of
normal coal seams. When they occur in a separate seam, this is of limited
extent and thickness. These coals do not occur in India. They are
unimportant in other countries also.
In earlier years cannel and boghead were used in the UK extensively for
the manufacture of town gas—a gas of high illuminating power. The advent
of incandescent mantles spoiled this market and the use of these coals has
been discontinued.
3.10 NATURAL COKE/SLV FUEL
The intrusion of igneous rocks into coal seams is a common feature of Indian
coalfields. Natural coke or jhama or special low volatile (SLV) fuel, as it is
commonly known in India is the result of carbonisation of coal in situ by
igneous intrusion. Jhama occurs in many coalfields of India, for example, at
Raniganj, Jharia and Bokaro. Its estimated reserves in the Jharia coalfields
are 400 Mt. It is a material of extremely variable composition and physical
characteristics. The variation depends on the nature of the intrusion, its
proximity to the coal seam and the extent of its effect. Some properties of a
few samples of jhama from Jharia coalfield (seams XV and XVIII) are as
follows: Moisture 1.4%–2.0%, air-dried; ash 21%–35%, air-dried; volatile
matter 5.6%–15.7%, dmmf; carbon 88.7%–94.9%, dmmf and hydrogen
1.4%–4.3% dmmf.
Jhama may find commercial use as a substitute for coke in some cases.
3.11 ORIGIN OF COAL
Chemical and geological studies have conclusively shown that coal is formed
from vegetable material such as trees, vascular plants and spores. The
larger remains like tree trunks, bark, twigs, leaves and some plant residues
can be seen with the naked eye. Small structures such as wood cells, spores
and algae are identified with the help of a microscope. Some lower animal
organisms might have also taken part in the formation of sapropelic coals
and coal shales. The various ranks of coals represent different degrees in
the conversion of the original plant material. The method of accumulation of
the vegetable matter has also influenced the nature and properties of coals.
There are two theories on the origin of coal, namely the autochthonous
(growth in situ) theory and the allochthonous (drift origin) theory. According to
the former, the plants grew and decayed in the same area where the coal is
found today. According to the other view, the vegetable matter was driven
from the original place of occurrence by water into the neighbouring lagoons,
lakes or estuaries. Either theory can account for the wide area occupied by
coal seams and can also explain their relatively uniform thickness.
The in situ theory is favoured by the following points:
1. In the existing peat bogs, for example, the Great Dismal Swamp in
Carolina, USA, the decayed vegetable matter is accumulating in situ.
2. The underclays of the coal bed and sometimes the rocks associate
coal contain upright fossil roots which are sometimes so numerous
suggest the occurrence of a fossil tree forest.
3. The coal seams are fairly constant in composition over a wide area.
The drift theory has the following points in its favour.

1. Large quantities of plant material are carried downstream by rive
sometimes deposited near the estuary, for example, in the deltas
Mississipi and the Ganga.
2. There is a similarity between coal and sedimentary rock. Many sea

stratified and made up of layers of coal with partings of shale,
sandstone, varying from a mere film to an appreciable thic
Carbonaceous shales often pass literally into coal bands.
3. Tree stems without attached roots in a seam are in favour of the tra
character of the trunks and of the vegetable debris generally.
Collected evidences indicate that the majority of coal seams in the world are
of the in situ origin while there is little doubt that some coals have been
formed by the drift method. The characteristic features of the Gondwana coal
seams support the common belief that these coals were formed from plant
materials of terrestrial vegetation which were transported into lakes, river
valleys and estuaries or even into the sea. Many coalfields consist of coal
seams and sedimentary rocks in a sequence that is repeated several times
which corresponds to a cyclic process of accumulation of plant debris and
cover by sedimentary rocks. Such formations of stratified coal seams and
sedimentary rocks are known as coal measures.
There were two important stages in the formation of coal from vegetable
matter
1. Peat stage or biochemical stage,
2. Metamorphism or dynamo-chemical stage.
In the first stage the plant material underwent decay under moist
conditions by bacterial attack. The decay continued until the absence of an
adequate supply of oxygen and the development of exterminative toxins
ended the microbe activities. This could have been caused either by rapid
and complete burial of the peat deposits under a cover of inorganic sediment
or by complete flooding by stagnant water, followed later by a covering of
sedimentary earth.
The agencies causing changes in the dynamochemical stage are
pressure of overburden,
tectonic pressure caused by severe earth movement, for example, dur

folding or buckling of the earth’s strata,
regional temperature increasing by 0.5°C to 3.5°C for every 100 m in

in depth,
contact with igneous intrusions (molten rocks and lava).
These agencies were partly or wholly operative for a very long time, spread
over geological ages. The result has been coals of different maturity or rank.
By and large the rank of coal rises with the increase in the age of the
geological system of the coal deposits (Table 3.17).
Table 3.17 Normal age of coal deposits

Thus bituminous coals are found in paleozoic and mesozoic deposits and
lignite in tertiary deposits. However high tectonic pressure and proximity of
lava might bring about accelerated metamorphism as in the deposits of
anthracitic coals in Jammu and Darjeeling. The effect of depth of occurrence
on the maturity of coals is obvious. Both temperature and pressure rise with
the increase in depth. Again the rate of a chemical change doubles for a rise
of about 10°C. Hence the coals in the lower seams of coal measures are
generally more mature than those in higher seams. This variation of rank
with depth is known as Hilt’s law.
The precise nature of the changes that took place in the gradual
conversion of plant materials into coal is not known. It may however be
inferred that the bacterial attack in the first stage of coal formation brought
about chemical reactions under predominantly oxidising atmosphere, in
which almost all the ingredients of plants took part and produced the humic
acids and other components of peat. Later peat was buried under mineral
rocks and pressed into more compact material. Chemical reactions such as
dehydration, decarboxylation and dehydrogenation, and others, took place
with the result that H2O, CO2, CO2, CH4 and H2S were removed and the
humic acids of peat were converted into mostly neutral substances. The
result was lignite. In contrast to the biochemical stage, the lignite formation
passed through a reducing atmosphere. The aging of lignite into bituminous
coal and then into anthracite was due to further reduction and condensation
reactions.
3.12 COMPOSITION OF COAL
Coal consists of an organic mass with some quantities of inorganic

substances like water and mineral matter. Coal also contains some adsorbed
gases, namely methane, carbon dioxide and carbon monoxide. The organic
mass is a mixture of complex organic compounds of carbon, hydrogen,
oxygen, nitrogen and sulphur. All efforts to completely isolate and identify the
organic compounds of coal have failed. Coal composition is therefore studied
by indirect methods.
Coal appears heterogeneous even to the naked eye. With most coals
differences in texture are apparent, some bands having a bright and others a
dull appearance. These differences are most marked in the case of
bituminous coals but can be traced in sub-bituminous coals, in some lignites
and, to a lesser extent, in anthracitic coals. The heterogeneity of coal is
much more marked under a powerful microscope. An apparently
homogeneous part of coal is found to consist of microscopically identifiable
distinct components.
Coal petrograph is the study of coal components by visual methods, with or

without the help of a micorscope. The components identified with the naked
eye are referred to as macroscopic components or simply macro-
components (rock-type). Similarly, microscopic studies identify microscopic
components or micro-components (maceral).
Macro-components
There are four types of macro-components in coal: vitrain, clarain, durain,

and fusain. This terminology is due to Stopes. According to the terminology
of Thiessen, these components correspond to anthraxylon, translucent
attritus, opaque attritus and fusain, respectively.
Vitrain is the bright, glossy and homogeneous part of coal, having a m
texture and showing characteristic vitreous conchoidal fracture.
Clarain is the semi-bright, heterogeneous material with a banded struc

has a definite and smooth surface when fractured at right angles
bedding plane and these faces have a pronounced gloss or shine.
Durain is the dull and hard band of coal. It is heterogeneous and has
granualar texture. A broken face of durain is never truly smooth but
has a matt surface.
Fusain occurs as patches or wedges of soft, fibrous material rese

charcoal. It is highly friable and can be readily powdered with the f
This material is responsible for the dirty and dusty character of ordina
As a rule, fusain forms only a minor fraction of a coal seam, say abou
5%.
Micro-components
A very large number of macerals of coal have been reported by different

investigators. The more important of these are:
Vitrinite is a major component of vitrain and one of the two p
components of clarain.
Fusinite is a major component of fusain.
Micrinite is one of the two principal components of durain.
Liptinite or exinite is the other principal component of clarain and dura

essentially a mixture of the fossilised remains of spores, cuticles and r
Indian coals are generally dull in appearance, although they are often
interbanded with bright and dull coals as in the seams of the Raniganj and
Jharia coalfields. Fusain is present in small amounts, not exceeding 5%. In
some coalfields, for example, in East Bokaro, sometimes thin but persistent
fusainous bands, locally known as matti, occur and can be traced over wide
areas. With regard to micro-components, the coals are surprisingly high
(over 50%) in vitrinite content in spite of their predominantly dull appearance
and apparently durainous nature.
The petrographic components of coal have different chemical and
physical properties and they can be partly separated by mechanical and
chemical methods. This situation has been gainfully exploited in technology,
for example, in the petrographic preparation of coal for coke production.
The so-called rational analysis of coal determines a number of
components on the basis of the differences in their resistance to nitric acid
and the solubility in some organic solvents. The components studied by the
rational analysis appear to correspond to the micro-components of coal to
some extent. The approximate equivalence is shown below:
Ulmins Vitrinite
Carbonised fibres Fusinite
Opaque matter Micrinite
Spore exins and cuticles Exinite Liptinite
Waxes, resins and hydrocarbons Resinite (Exinite)
The above components are fully developed in bituminous coals. They

gradually lose their identity and converge into a homogeneous mass in
anthracites. These components have been produced from the original plant
material through the peat and lignite stages.
Peat consists of waxes, resins, simple carbohydrates, pectin, hemicellulose,

celulose, lignin and humic acids.
Lignite contains waxes, resins, humic acids and a residual mass composed
of the components corresponding to those of bituminous coal. Humic acids
constitute the major part of lignite.
The exact chemical constitution of the organic content of coal is not
known. It is however generally believed that these compounds are
macromolecular in nature and some structural units repeat in the
macromolecules. Each unit has a nucleus of condensed aromatic rings with
side-chains of an aliphatic, aromatic and naphthenic (hydroaromatic) nature.
The variation in the composition and proportion of the nucleus and side-
chains, and in the number of structural units constituting the macromolecules
gives rise to the different components as they occur in the coals of different
ranks.
For bituminous coals, aromaticity is 70% to 85% of the structure,
hydroaromaticity is 10% to 25% and aliphaticity is below 10%.
3.13 ANALYSIS AND PROPERTIES OF COAL
The chemical and physical properties of coal and the principles of analysis
are discussed here. The detailed methods of analysis and testing vary from
country to country. Those specified in India are available in the relevant
Bureau of Indian Standards (BIS) publications.
The proximate analysis of coal determines moisture, ash, volatile matter
and fixed carbon of coal. The ultimate analysis or elementary analysis
determines the carbon, hydrogen, sulphur, nitrogen and oxygen of pure coal
(organic mass). Based on the reports of these two analyses, a host of
information can be obtained on the properties and probable utilisation of
coal.
The calorific value is the single most important property of all fuels. The
caking properties are of importance for bituminous coals only. Other
chemical and physical properties of coal include solubility, specific gravity,
surface area and porosity, angle of repose, grindability, specific heat,
reflectance and refractive index.
3.13.1 MOISTURE
Owing to its nature, origin and occurrence, coal is always associated with
moisture. It is customary to differentiate between external and inherent
moisture. When wet coal is exposed to the atmosphere, the external
moisture evaporates but the apparently dry coal still contains some moisture
which can be removed only on heating above 100°C. External moisture may
also be called accidental or free moisture, while inherent moisture may be
referred to as equilibrium, or air-dried, or hygroscopic moisture. The quantity
of external moisture depends mainly on the mode of occurrence and
handling of coal, but the air-dried moisture is related to the inherent
hygroscopic nature of the coal.
Excessive quantities of free moisture are undesirable in coal from the
point of view of the customer. Moisture does not contribute to the heating
value of coal and takes away appreciable quantities of heat on conversion to
the vapour form. However, a small amount of free moisture is helpful in some
cases of handling, combustion and coke production.
In order to get reproducible and correct values of air-dried moisture, it is
necessary first to equilibriate the coal sample in a standard atmosphere of
specified temperature and humidity before the actual determination is done.
Air-dried moisture
It is usually determined by observing the loss in weight of the coal sample on

heating to about 105°C. In the case of peat and lignite which start
decomposing at temperatures below 105°C, this method is not applicable
and the Dean and Stark * method is followed.
Air-dried moisture content of coal decreases with increasing rank from a
value of 25% for lignite to a minimum value of 0.5% for a low volatile (15%
VM) bituminous coal. Beyond the minimum, however, the value increases to
about 3% for anthracites (Fig. 3.2). For coals with a moisture content of
above 3%, it is a useful measure of the rank and hence of the other qualities
indicated by the rank (Table 3.18).
Figure Inherent moisture and carbon per cent
3.2
Table 3.18 Analysis and fusion range of coal ash
If coal is exposed to an atmosphere of increasing humidity at a fixed

temperature, it absorbs more and more moisture. The quantity of moisture
held by coal at an approximately saturated atmosphere (96% to 99% relative
humidity) is called near-saturation moisture or capacity moisture or bed
moisture. This is a better measure than the air-dried moisture for the
determination of rank of high volatile bituminous, sub-bituminous and lignite
coals and has found a place, directly or indirectly, as a parameter in some
coal classification systems.
To avoid the effect of variable mineral content, moisture is also expressed
in parts per 100 parts of organic mass or dmmf coal.
3.13.2 ASH AND MINERAL MATTER
Coal contains inorganic mineral substances which are converted into ash by
chemical reactions during the combustion of coal. Ash and mineral matter of
coal are therefore not identical. Depending upon the nature of the source, the
mineral matter in coal is called inherent and extraneous. The inorganic
material of the original vegetable substances is responsible for inherent
mineral matter. The extraneous mineral matter is due to
1. The substances which got associated with the decaying vegetable m
during its conversion into coal,
2. Rocks and dirt getting mixed up during mining and handling of coal.
The former type of extraneous mineral matter is in a fine state and intimately
associated with the organic mass of coal. Hence, it is difficult to remove this
from coal by mechanical methods. The second type of extraneous mineral
matter is more amenable to coal cleaning methods. The inherent mineral
matter cannot be removed by any mechanical means. Fortunately, the
inherent mineral matter content is low (about 2%–3% or less) in all coals.
Indian coals suffer from the great disadvantage that the mineral matter
content is both high and an intimately associated type due to its drift origin.
The bulk of the mineral matter of coal is due to clay or shale consisting of
aluminosilicates of different composition. Other major constituents may be
calcite (calcium carbonate) and pyrites, or related matter. When coal burns,
shale and other hydrated minerals lose water of hydration, while sulphides,
sulphates and carbonates usually decompose, or oxidise, leaving their basic
radicals free to combine with excess of silica, if any. The net result is a loss
of weight so that the ash of coal is always less than the mineral matter
content.
The composition of coal ashes varies widely. The data for some Indian
coals are given in Table 3.17. Generally about 90% or more of coal ash
consists of silica, alumina, iron oxide and lime. The remaining 10% or less
consists mainly of magnesium, sodium and potassium oxides and titania as
basic constituents, and sulphates and phosphates as acidic constituents.
Gallium, germanium, nickel, beryllium, boron and chlorine are among the
trace elements of coal ash.
When heated, coal ash does not melt sharply at any temperature, but
begins to soften at a much lower temperature than that at which it becomes
molten and flows. This necessitates the determination of the fusion range of
temperatures in place of an ash fusion point. The ash fusion characteristic of
coal depends on the composition of the ash. Higher alumina and silica
content make the ash refractory, while lime, magnesia, iron oxides and alkali
oxides have a fluxing effect and lower the ash fusion temperatures. The ash
of Indian coals is generally refractory in nature and the fusion range is mostly
above 1300°C.
The quantity of mineral matter or ash has no relation with the rank or
maturity of coal. Among the macro-constituents of coal, vitrain is of low ash
(1% to 2%), clarain is higher (3% to 5%), and durain is still higher (5% to
8%). Fusain may have high ash. The mineral matter does not contribute to
the calorific value of coal. On the contrary it creates many difficulties in the
efficient utilisation of coal. In a furnace grate the ash may seriously restrict
the passage of air and lower the rate of combustion. High ash leads to large
heat losses and carbon losses and creates such problems as boiler deposits
and clinkering. It has been estimated that 1% rise in coal ash is equivalent to
0.3% to 4% fall in boiler efficiency. High ash is therefore undesirable and
harmful. The content of mineral matter should be reduced by the methods of
coal cleaning. This is particularly important for coals used for making
metallurgical grade coke. High ash coke seriously reduces the efficiency of
blast furnace operations. Coal cleaning is vitally important for high-ash Indian
coking coals.
Apart from the total percentage of ash, its composition and fusion range
also influence the efficiency of coal utilisation. In general, clinkering troubles
are augmented by the lower fusion temperatures. On the other hand, coals of
refractory ash, for example, Indian coals, are a problem to use in slagging
furnaces and slagging gas generators where ash is removed in the molten
state. A non-clinkering ash contains more than 45% of silica and 35%
alumina and less than 15% ferric oxide and 10% calcium oxide.
The coal ash may be used for extracting valuable rare elements. It is
reported that certain coal-based gases produce flue dusts that provide most
of Britain’s germanium.
Enormous quantities of fly ash are produced from coal-based thermal
power stations all over the world. Fly ash is useful in the production of
cement and concrete, bricks, filling material and lightweight aggregates. A
plant at Ennore in Tamil Nadu produces 70 million bricks annually from
cement, lime and fly ash.
The ash of coal is directly determined in the laboratory by completely
burning the coal. It is necessary to know the accurate content of the mineral
matter to determine the content of a pure organic mass of coal. Some
methods are available for this purpose. The Radmacher and Mohrhauer
method essentially consists of dissolving out the mineral substances by
treatment with hydrofluoric acid and hydrochloric acid, and finding the loss of
weight.
Empirical formulae are available for calculating the mineral matter
content from the ash values. The Parr formula is
and the KMC (King, Maries and Crossley) forumula is
where, MM = mineral matter, A = ash, S = total sulphur, Spyr = pyritic sulphur,

CO2= carbon dioxide from carbonates, SO3,ash = sulphate in ash, SO3,coal =
sulphate in pure coal, and Cl = chlorine, all in per cent.
The KMC formula is regarded as the standard of reference, but it involves
too many analytical steps. The Parr formula is quite simple. It recognises
only two losses of consequence during conversion of mineral matter into ash,
namely loss of water of hydration (0.08A) and loss in the conversion of
pyrites into oxides. It further assumes that all the sulphur in coal is in the
inorganic form.
Indian coals in general are low in sulphur and carbonate. A simplified
version of the Parr formula is used for these coals:
MM = 1.1A
The formula assumes that the difference in the weights of mineral matter
and ash is due to the water of hydration which is taken to be 10% of the ash
value (0.1 A).
3.13.3 VOLATILE MATTER AND FIXED CARBON

Volatile matter and fixed carbon are not the constituents of coal. They
represent the volatile and non-volatile products of thermal decomposition of
coal under specified conditions. Volatile matter does not include the moisture
in coal but it contains water that is formed from the hydrogen and oxygen of
coal during the decomposition. When volatile matter is reported on air-dried
and daf (dry and ash-free) basis, it also includes the part of the mineral
matter, for example, water of hydration, which escapes into the gaseous
state. On dmmf basis however, it represents only the volatile products from
the organic mass. Fixed carbon does not include the ash. It is the non-
volatile residue of the organic mass. Furthermore the term ‘fixed carbon’ is a
misnomer: It contains the non-volatile parts of other elements also.
Nonetheless, long usage has shown that the quantities of volatile matter and
fixed carbon are of great scientific and technological value.
The volatile matter and fixed carbon, both expressed as a percentage on
dmmf basis add up to 100 parts of pure coal (organic mass). The higher the
volatile matter, the lower the fixed carbon. There is a correlation between
volatile matter and maturity of coal. With the increase in the maturity or rank
of coal, its volatile matter content decreases. However, there seems to be a
critical value of volatile matter, 32%-33% dmmf, above which this relationship
is not valid. Different macerals of the same coal yield different amounts of
volatile matter. The highest yields are from the exinites and the lowest the
fusinite. Vitrinite occupies an intermediate position.
The physical nature of the residue left after the volatile matter test is an
approximate measure of the caking properties of coal.
The moisture, ash, volatile matter and fixed carbon data of typical Indian
coals are given in Table 3.14.
3.13.4 CARBON
The carbon of coal is not to be confused with its fixed carbon. In anthracites
the volatile matter is very small and the values of fixed carbon and total
carbon are almost equal. In other coals fixed carbon is less than total carbon.
The carbon content is determined by Liebig’s method by completely burning
the coal in a current of pure oxygen and finding the amount of resultant
carbon dioxide. Correction is made for the inorganic carbonates. The carbon
content depends on the nature of coal. It increases with increase in the rank
(Tables 3.14 and 3.19). Among the macerals of the same coal, the exinite
and vitrinite have almost similar carbon content while fusinite has higher
content.
Table 3.19 Classification of Indian coals, their properties and utilisation (IS: 770–1977)
3.13.5 HYDROGEN
Hydrogen is determined together with carbon by completely burning the coal.

From a knowledge of the weight of water formed, the hydrogen content is
calculated. Corrections are made for the moisture of coal and the water of
hydration of minerals. The content of hydrogen in coals from peat to
bituminous stage varies between 4.5% and 6.5% and is not related to the
rank (Tables 3.14 and 3.19). Beyond the bituminous stage, the hydrogen
content sharply decreases to a value of l%−2% in anthracite. Among the
micro-constituents, the exinites are characterised by high hydrogen and the
fusinites by low hydrogen content. Cannel coal and boghead coal also have
high hydrogen content. The hydrogen of coal is responsible for the
production of many useful materials, for example, gaseous hydrogen,
methane and coal chemicals in the carbonisation and gasification industries.
3.13.6 NITROGEN
The Kjeldahl method is used to determine the amount of nitrogen in coal.

The sample is digested with oleum containing a catalyst when nitrogen is
converted into ammonium sulphate. The ammonia is then estimated and the
nitrogen content calculated. The nitrogen content does not bear any relation
to the rank of coal (Table 3.14). In most coals it is between 1% and 2%.
Lower values down to 0.5% and upper values upto 2.5% are also found. The
nitrogen in coal is useful in the carbonisation industries which recover a part
of it as valuable by-products like ammonia, ammonium sulphate and pyridine
bases.
3.13.7 SULPHUR
Sulphur is commonly present in coal in three forms: pyrites, organic sulphur

and sulphate. The occurrence of sulphides and elementary sulphur in coal
have been reported in some cases. Only organic sulphur should be included
in the ultimate analysis. Since most Indian coals contain 0.7 % or less of total
sulphur, it is usually shown as sulphur in the ultimate analysis, without any
corrections.
Total sulphur is determined by Eschka method or Bomb method. In the
former, the entire content of sulphur is converted into soluble sulphates by
heating the coal with an oxidising mixture of magnesium oxide and sodium
carbonate and then estimating the sulphate. In the Bomb method the total
sulphur is converted into soluble sulphates by heating the coal with an
oxidizing mixture of magnesium oxide and sodium carbonate and then
estimating the sulphate. In the Bomb method the total sulphur is also
converted into the sulphate form during the determination of calorific value in
Bomb calorimeter. The pyritic and sulphate sulphur in coal are determined by
the usual methods of analytical chemistry and the organic sulphur is then
calculated by subtracting the inorganic sulphur from the total sulphur.
Although Indian coals are usually low in sulphur (0.7% or less), many
coals of the NorthEastern coalfields have high sulphur content of around 4%.
In general, the coals of most countries of the world are found to contain
between 1% and 3% sulphur. Higher and lower values are also reported. It
has been found that the high sulphur content is generally due to pyrites.
However, North-Eastern coals form an exception where much of the sulphur
is in the organic form.
The sulphur content of coal has no relation to its rank or composition.
Although elementary sulphide, pyritic and organic forms of sulphur contribute
to the calorific value of coal, it is an undesirable constituent. It emits
corrosive sulphur dioxide during combustion and obnoxious hydrogen
sulphide and mercaptans during carbonisation and gasification. A part of the
sulphur can be recovered as a by-product in the coking and gas-making
industries. Since coke always retains a considerable part of sulphur in coal,
metallurgical industries demand coals of low sulphur content in coke making.
3.13.8 OXYGEN
The oxygen in coal is usually determined by the method of difference. The

carbon, hydrogen, nitrogen and sulphur are expressed in per cent on a dmmf
basis and their sum is subtracted from 100. The disadvantage of this
procedure is that the errors of all the other determinations are reflected on
the oxygen value. Direct methods are also available for the determination of
oxygen, but these are laborious and time-consuming. The oxygen content of
coal has a close relation to the rank. The former decreases with the increase
in the latter (Table 3.14). Among the macerals of the same coal, vitrinite has
the highest oxygen content, fusinite the lowest, and exinites the intermediate
value.
3.13.9 PHOSPHORUS
Phosphorus occurs in small quantities in coal. Its determination is important

when the coal is to be used in the production of metallurgical coke. Indian
coking coals have normally less than 0.15% phosphorus which is not a
problem for common use in iron and steel production. The coking coals of
Giridh are even lower in phosphorus, 0.01% to 0.04%, and suitable for
producing coke for making ferro alloys. There are certain areas in the
coalfields of Madhya Pradesh and North-Eastern India where again the coal
contains 0.01 % or less of phosphorus.
3.13.10 CALORIFIC VALUE
This is the basic property of fuels, indicating the quantity of heat evolved by
their complete combustion. Distinction is made between gross and net
calorific values, and between gross calorific values at constant volume and
constant pressure (see Chapter 2). The more generally used property for
coal is the gross calorific value at constant volume. For combustion
calculations, however, the net calorific value is often used with advantage.
The calorific value of coal is determined in a Bomb calorimeter. The complete
combustion is ensured by using powdered coal in a small briquetted form,
and pure oxygen at a moderately high pressure of 25 atm. Precision
equipment under specified conditions and adoption of various correction
factors are necessary for the high accuracy that the test demands.
There are many formulae for the calculation of the calorific value of coal
without actually determining the same in the laboratory. One such formula is
due to Goutal (1902) and is based on proximate analysis
CG = 82F + aV
where CG = gross calorific value, kcal/kg air dried, F = fixed carbon, per cent
air-dried, V = volatile matter, per cent air-dried, and a = a constant,
depending upon the value of volatile matter expressed as per cent daf (V’) as
shown below.
V’ a V’ a V’ a
5 145 20 109 35 94
10 130 25 103 38 85
15 117 30 98 40 80
This formula considers both volatile matter and fixed carbon as

contributing to the calorific value of the coal. The fixed carbon of different
coals is assumed to be of a fixed composition and hence of fixed calorific
value. The composition and calorific value of the volatile matter differ from
coal to coal, and are assumed to depend on the nature of coal as indicated
by the volatile matter on a daf basis. These assumptions limit the utility of the
Goutal formula.
The following formulae have been developed by the Central Fuel
Research Institute (CFRI), Dhanbad, Bihar for the calculation of calorific
value of Indian coals from their proximate analysis:
For low moisture coals, M ≤ 2%
CG = 91.7F + 75.6(V − 0.1 A) − 60M
For high moisture coals, M ≥ 2%
CG = 85.6[100 − (1.1A + M)] −60M
where M, A, V and F denote moisture, ash, volatile matter and fixed carbon,
all in per cent air-dried, respectively.
There are also several formulae that are based upon the ultimate
analysis of coal. The original Dulong formula is:
CG = 80.8C + 344( H − 0/8)
where C, H and O represent carbon, hydrogen and oxygen, respectively, as

per cent of the coal.
The above formula assumes that the heat of formation of coal is zero and
the only heat giving elements are carbon and surplus hydrogen, the latter
meaning the hydrogen in excess of that required to combine with the oxygen
of the coal to form water.
On including sulphur as a heat giving element, the Dulong formula is
amended as
CG = 80.8C + 345(H − 0/8) + 22.2S
where S = sulphur, per cent of coal.

All these formulae are of limited use because the heat of formation of
coal is neither zero nor constant. The modified Dulong formula is, however,
fairly useful for all practical purposes. Seyler has developed a set of formulae
relating the calorific value to the carbon, hydrogen and volatile matter. These
are found to be quite accurate for many coals, excluding those of India.
The calorific value of coal bears a good relationship with the rank (Tables
3.14 and 3.19). The higher the rank, the higher the calorific value.
Anthracites, however, form an exception to this regularity and have lower
calorific values than many bituminous coals. This is due to the sharp fall of
hydrogen content in anthracites, the hydrogen having more than four times
the calorific value of carbon. The high hydrogen content is also responsible
for the relatively high calorific values of cannel coal, boghead coal and the
exinites of humic coals.
3.13.11 CAKING PROPERTIES
Caking coals form a part of the bituminous group: Peat, lignite, sub-
bituminous coal, semianthracite and anthracite are all non-caking. So also
are some of the bituminous coals. A measure of the caking properties is
necessary for coal classification and for selection of coal for different
industries. Caking properties influence not only the production of coke but
also the performance of the coal in combustion and gasification.
Caking, swelling, agglutinating and plastic properties are all interrelated.
Numerous laboratory tests have been proposed for measuring the propensity
of these properties. While some have been developed into standard tests,
others have become either obsolete or are of theoretical interest only. The
standard tests in vogue in different countries are: Free swelling index, Gray-
King (low temperature) Coke type, Caking (agglutinating ) index, Roga index
and Thickness of plastic layer. The appearance of the residue (coke-button)
of the volatile matter test may give an idea of the caking capacity of coal.
This simple test is still in vogue in some countries. The coke-button may
indicate five types: pulverulent, sintered, weakly caked, caked and strongly
caked.
Free swelling index
This is a simple and very useful test. It is one of the three tests standardised
in India. Coal is heated on a flame under specified conditions. The swollen
residue is compared with standard profiles and assigned numbers,
increasing from 0 to 9 by ½ unit. The higher the number, the better the
caking and swelling properties. The limitation is imposed by the maximum
possible number 9 and the very highly swelling coals cannot be differentiated
from one another.
The caking index is the maximum whole number ratio of sand to coal in a
25 g mixture of the two, which on heating under standard conditions
produces a residue capable of supporting a weight of 500 g without
producing more than 5% loose grains. It is a measure of the binding or
agglutinating property of the coal undergoing carbonisation. The higher the
agglutinating propensity, the higher the amount of sand that can be bound by
coal and hence the higher the caking index. It is a modified Grey-Campredon
test and responds well to high-ash Indian coals. The Bureau of Indian
Standards (BIS) has adopted it as one of the three tests for caking
properties. The demerit of the test lies in its trial-and-error approach.
Low temperature Gray-King carbonisation assay
Powdered coal is heated under standard conditions, 600°C. The residue is

visually compared with standard profiles and a letter A to G or G1 to G9 is
assigned. This letter represents the Gray-King (LT) Coke Type. ‘A’ means
non-caking. Letters from ‘B’ to ‘G9’ indicate the increasing order of caking
and swelling capacity. This is one of the three standard tests in India and is
now judged the best suited for Indian coals. If the coal has higher than 17%
ash, then the sample has to be washed before testing.
Roga index
This is a variation of the agglutinating index. A mixture of coal and specified

anthracite in a fixed proportion is carbonised under standard conditions. The
strength of the residue is expressed as a numerical figure called the Roga
index.
Sapozhnikov test
This plastometric test measures the maximum thickness of the plastic layer
that is formed when coal is carbonised under well-defined conditions.
Whatever test is used, the parameter for the caking properties is
significant in defining the nature of coal. The very young coals—peat, lignite
and sub-bituminous—and the very mature ones—semi-anthracite and
anthracite—are completely devoid of cakability. In the case of bituminous
coals, the caking capacity first increases with the rank, attains a maximum
and then decreases with further rise in the maturity (Fig. 3.3). The coals of
the highest coking capacity are often called fat coals. These coals are rare in
India. Among the macerals of the same coal, the fusinite is always found to
be non-caking and the exinites are always good caking. The caking
properties of vitrinite vary with the rank in the same way as those of the
whole coal.
Figure 3.3 Gray-King coke type and percentage of carbon in coal
Why some coals are caking and others non-caking is an interesting

problem for investigation. The caking properties are perhaps due to a
chemical process in which the macromolecular structure of the coal mass is
thermally broken down and some products of relatively low molecular weight
remain in a softened state for a sufficiently long time in the reaction zone. As
a result the entire mass takes the form of a plastic matter which is converted
into a solid lump, resolidified, on further heating. In this way the powdered
caking coals are capable of producing lumpy semicoke and coke. The non-
caking coals cannot produce the plastic state and on carbonisation yield only
a sintered mass in place of coke.
3.13.12 SPECIFIC GRAVITY AND BULK DENSITY
The proportion and nature of both the organic mass and mineral matter
influence the specific gravity of coal. Mineral matter is heavier than pure coal.
Therefore, for the same type of coal, the higher ash coals have higher
specific gravity. The true specific gravity of average bituminous coals
normally varies between 1.27 and 1.45. The following formula is valid for
many coals of India.
g = k + A/100
where, g = specific gravity, k = a constant having an average value of 1.25,

and A = percentage of ash. This formula assumes an overall specific gravity
of 2.25 for the mineral matter of coal.
Among the coals of different types, the specific gravity seems to increase
with maturity: peat 1.15 to 1.25, lignite 1.25 to 1.3, bituminous coal 1.27 to
1.45 and anthracite 1.4 to 1.7.
The bulk density of a material is the overall density of it kept in large
quantities. It depends upon the true density of the material, the pore volume
of the particles (or lumps) and the voidage between the particles (or lumps).
It is therefore a measure of the stowage capacity or the amount which can be
stored in a given volume.
The bulk density of packed coal depends on many factors, the most
important of which are the size analysis of the coal, the size of the container
and the total moisture content of the coal. Other variables are the shape of
the particles or lumps and the method of packing. Depending upon the
various factors, the bulk density of loosely packed dry coal may vary as
Lumpy coal(sized or free from fines) : 600–670 kg/m3

Lumpy coal (with fines) : 690–830 kg/m3
Coal dust : 480–580 kg/m3
Pulverised coal : 400–500 kg/m3
The true density is 1300 kg/m3

The bulk density of small coal decreases with increase of free moisture
content and then reaches a minimum value which may be 16% lower than for
air-dried coal and which may occur at about 6% moisture content. After the
minimum, the bulk density again increases with rise in free-moisture content
but never attains the original value of the dry coal (Fig. 3.4). The variation of
bulk density with the free moisture content is very important in making the
charge for coke ovens.
Figure Moisture and bulk density of coal

3.4
3.13.13 ANGLE OF REPOSE
The angle that a heap of coal forms with the horizontal is of importance in its
storage and in its flow in conveyers and feed hoppers. It is not a reproducible
figure and may vary by 2 to 3 degrees depending upon the roughness of the
surface, moisture content and other factors. In general, the higher the size,
higher the angle of repose. This means that a larger bulk of bigger size coal
may be stored in a heap of given height. Approximate values of angle of
repose for different sizes of dry coal in bulk are:
Size of coal, mm 18–30 12–8 6–12 0–

Angle with horizontal, degrees 41 40 38 32
3.13.14 POROSITY, SURFACE AREA AND HEAT OF WETTING
Coal is a porous substance with a fairly high internal surface area. When it is
brought in contact with a suitable organic liquid such as methanol, the latter
enters the very fine pores and the surface of coal is wetted. The process is
exothermic and heat of wetting is released. There are various methods for
the determination of the porosity and surface area of coal. Heat of wetting is
also a measure of surface area.
Porosity (per cent pore volume), surface area (m2/g coal) and heat of
wetting (cal/g coal) are found to vary with the rank of coal in the same
manner as the moisture varies with the rank. There is initially a fall in the
values till a minimum of 89% to 90% is obtained for coal carbon. The values
again rise in the anthracitic region (Figs 3.2, 3.5 and 3.6). Some average
data are given below.
Figure Porosity and percentage of coal in carbon
3.5
Figure Heat of wetting and percentage of carbon in coal
3.6
I II III
I II III
Carbon, per cent dmmf 80 89 93
Heat of wetting, cal/g dmmf 18–20 2–3 6–8
Surface area, m2/g dmmf 180–200 20–30 60–80
Porosity, per cent dmmf 18–20 2–3 6–8
Approximately, 1 cal/g heat of wetting =10 m2/g surface area =1% porosity.
3.13.15 REFRACTIVE INDEX AND REFLECTANCE
Both these optical properties are found to increase with increase in coal rank.
For vitrain-rich samples, the following values have been reported.
Carbon, per cent dmmf 75 80 84 91 95

Refractive index - 1.6 - 1.9 -
Reflectance, per cent incident light 0.5 0.67 0.92 2.23 4.1
Among the macerals of the same coal, fusinite and micrinite have very
high reflectance and exinite has abnormally low reflectance, the vitrinite
having intermediate values. Reflectance is a good parameter for the
determination of coal rank.
3.13.16 SPECIFIC HEAT
The specific heat of coal increases with increase in the volatile matter and
decrease in the carbon to hydrogen ratio. Typical data on a daf basis at
normal temperature are:
Bituminous coal 0.24–0.26 cal/g°C

Anthracite 0.22–0.23 cal°C
The coal ash has a value of 0.16—0.17 cal/g°C. The relationship

between specific heat and moisture content, and between specific heat and
ash percentage is linear. The specific heat of a coal of given moisture and
ash value can thus be calculated with the help of simple arithmetic.
3.13.17 GRINDABILITY
There are two methods of determining the ease of grinding coal to fine sizes,
namely, (i) ball mill method and (ii) Hardgrove method. The former measures
the amount of work done in grinding a pre-sized material to a given fineness.
The Hardgrove method measures the increase of surface produced by the
application of a standard amount of work and expresses the result as
Hardgrove grindability index, G, which ranges between 20 and 100 for most
coals.
G = 13 + 6.93W
where W = weight of coal in grams passing through a 200-mesh sieve after

50 g of coal of size 16 to 30 mesh are ground in a standard mill for 60
revolutions. The use of a 200-mesh sieve in determining Hardgrove index is
significant because in the pulverised coal, firing the size below 200-mesh is
often specified. A high value of G indicates a soft and easily grindable coal. It
has been established that the Hardgrove grindability index of coal initially
increases with the rank, reaches a maximum of about 105 for bright coals of
89% to 90% carbon, and then falls sharply to about 35 for anthracites (Fig.
3.7). The average Hardgrove index for Indian coals is 55 to 65, but coking
coals of Jharia and Giridih often show higher values up to 75.
Figure 3.7 Hardgrove grindability and percentage of carbon in coal
3.13.18 SOLUBILITY
Peat is slightly soluble in water owing to the presence of simple

carbohydrates and pectin. Lignite and other coals are completely insoluble in
water, cold or hot. Peat and lignite are however soluble in alkali. These fuels
contain humic acid which dissolves forming humates in alkali solutions. They
get precipitated on acidification of the solutions. Higher rank coals normally
do not contain humic acids but produce them on mild oxidation. Oxidised
bituminous coal is therefore partly soluble in alkali solutions. Dilute
hydrochloric acid dissolves the hemi-celluloses present in peat. The
concentrated acid dissolves most of the mineral matter of coals. The so-
called demineralised or ultrapure coal may be prepared by treating coal with
hydrochloric acid. Nitric acid has an oxidising effect on the organic mass of
coal and produces various aliphatic and aromatic carboxylic acids.
Concentrated sulphuric acid decomposes the cellulose present in peat.
Simple organic solvents like benzene, mixture of benzene and alcohol or
chloroform dissolve the waxes and resins which constitute 5% to 20% of peat
and lignite and, generally, 1% or less of higher rank coals. High boiling
solvents like anthracene, phenanthrene, anthracene oil and tetralin, and
basic solvents like pyridine, quinoline, monoethanolamine and ethylene
diamine can extract considerable portions of coal. The organic mass of a
medium rank bituminous coal can be dissolved in tetralin or anthracene oil to
the extent of 85% to 95% on treatment at about, 350°C to 400°C in an
autoclave. The coal extracts obtained in such large yields are of industrial
importance, for example, in the production of liquid fuels or carbon
electrodes. The solubility of anthracite in the above mentioned solvents is
negligible.
3.14 ACTION OF HEAT ON COAL
Studies on the behaviour of coal on heating provide information on the

composition and nature of coal, and supply data for commercial
carbonisation process. When a sample of powdered coal is heated out of
contact with air, it loses occluded gases consisting of methane, ethane,
nitrogen and carbon dioxide at temperatures bellow 100°C. Moisture is
evolved between 100°C and 150°C. The organic mass of coal then starts
decomposing with the evolution of gaseous and vaporous products. The
decomposition is called active when oil appears in the vaporous products.
Peat and young lignites start decomposing at 100°C or less. The initial
temperature of decomposition of bituminous coals is 200°C to 300°C while
active decomposition starts at 300°C to 375°C for these coals.
The evolution of volatile products of thermal decomposition of bituminous
coals is marked by two peaks or maxima, one corresponding to the primary
devolatilisation in the temperature range 350°C to 550°C and the other
corresponding to the secondary devolatilisation around 700°C (Fig. 3.8).
Pyrogenic water, primary tar and gases evolved during the primary, while
gases (mainly hydrogen) are evolved during the secondary devolatilisation
(Fig. 3.9). Peat and lignite show pronounced primary devolatilisation and
insignificant seconday devolatilisation. Anthracite is characterised by the
absence of primary devolatilisation and occurrence of secondary
devolatilisation only. All the three processes—drying, primary devolatilisation
and secondary devolatisation—are endothermic in nature. However, some
investigators have also observed exothermic processes during the thermal
decomposition of coal.
Figure Devolatalisation of coal
3.8
Figure 3.9 Evolution of gases during carbonisation of coal: Coking coal, 1.8°C per
minute, heating rate. The dashed line represents rate of weight loss
against temperature.
While coal undergoes decomposition on heating, the residue becomes

richer in carbon content and exhibits some characteristic physical and
chemical changes. In the case of caking coals, the residue passes through a
plastic state in the range 300°C to 350°C to 500°C to 550°C. The fluidity of
the plastic mass initially increases, attains a maximum and then decreases to
zero (Fig. 3.10). The last point corresponds to the resolidification of the
plastic mass into semi-coke. This is also the upper limit of the primary
devolatilisation process. On further heating, secondary devolatilisation takes
place and semi-coke is converted into true coke. This conversion is marked
by a sudden rise in the electrical conductivity of the solid materials.
Therefore, one method to ensure proper coking is to check the electrical
conductivity of the carbonaceous residue. If coke is heated further, significant
changes take place around 2000°C when graphite-like materials result. This
process is known as graphitisation and is used in the production of graphite
electrodes. Non-caking coals are not amenable to graphitisation.
Figure Fluidity and heating temperature of coal
3.10
The porosity of coal decreases on heating and attains a minimum in the
plastic state. At resolidification, porosity again rises considerably. The
porosity of coke is 40% or above. This property ensures smooth burning of
coke in furnaces. Because of the simultaneous formation of the plastic state
and volatile products of thermal decomposition, the carbonaceous residue
exhibits an initial contraction and fall in porosity followed by swelling,
dilatation and rise in porosity. This phenomenon forms the basis of many
tests for the caking property of coal.
The experiments conducted for determining the yields of various products
of thermal decomposition of coal are known as carbonisation assay. There
are two standard procedures: Gray-King and Fischer. The basic principle of
these assays is to heat coal under specified conditions and collect the gas
after recovering the condensable products, namely tar and liquor. The latter
term is used to denote the resultant aqueous solution of ammonia and other
dissolved substances. The coke is left in the retort.
3.15 OXIDATION OF COAL
The organic mass of coal is quite susceptible to oxidation. Even atmospheric

oxygen brings about oxidation of coal with evolution of heat. The effect is a
fall in the caking capacity, calorific value and tar yield of the coal. Under
adverse circumstances the coal may catch fire in the process. The rate of
oxidation varies inversely with the rank. Oxidation of coal is enhanced by
known oxidising agents such as potassium permanganate solution. Initially
alkali-soluble materials like humic acids are formed. With the progress of
oxidation, one gets benzene carboxylic acids, aliphatic acids and finally
carbon dioxide and water.
The technique of controlled oxidation of coal may be industrially used in
the following cases: (i) production of benzene carboxylic acids, (ii) fuel cells,
and (iii) preparation of coke oven charge from highly swelling coals.
Experiments on coal oxidation have been of great help in elucidating the
nature and composition of coal.
3.16 HYDROGENATION OF COAL
Mild hydrogenation reduces the oxygen content of coal and raises its caking
capacity. This can be achieved by catalytic hydrogenation with molecular
hydrogen or hydrogen donating reagents like tetralin and decalin. Under the
action of heat and high pressure, hydrogen converts coal into liquid products.
This forms the basis of the Bergius process of liquefaction of coal. Once
considered uneconomical, this method now appears economically promising
for the production of liquid fuels from coal (see Chapter 5). Hydrogenation
experiments have also thrown some light on coal constitution. The
susceptibility of coal to hydrogenation decreases with rank. Anthracites resist
hydrogenation.
3.17 CLASSIFICATION OF COAL
The primary function of any classification is to place together things which

are of like nature and to separate those which are of a different nature. Coal
defies any universal classification system owing to the following reasons:
1. Coal is a heterogeneous mixture of organic mass, moisture and
matter in uncertain proportions.
2. The organic mass is itself heterogeneous and consists of a num

macerals, as a result of which, the coals of the same ultimate analysis
necessarily have the same properties, while coals of different comp
may, in some respects, behave alike.
3. The macerals differ from coal to coal with respect to both qual
quantity; the quality of the macerals is determined by the initial plant m
and the coalification process, both of which again vary from place to
and time to time.
4. The mineral matter of coal varies widely in amount and compositio

these factors greatly influence the properties of the whole coal.
Inspite of the above, coal systematics is a vast subject comprising a large

number of proposed classification systems. While some systems are of
scientific and academic interest only, others have been found to be of use in
the commerce and industry of different countries.
A distinction may be made between the terms classification and grading.
The term grade in India generally refers to the commercial degree of purity of
coal, as assessed from the ash and moisture. Coal classification systems
refer to the nature of the organic mass.
The primary basis of coal classification is the nature of the plant debris.
Accordingly, there are three types of coals:
1. Humic coals or humites derived from the higher plant kingdom, for ex
peat, lignite, bituminous coal and anthracite;
2. Sapropelic coals or sapropelites derived from small plant organis

example, cannel coal and boghead coal;
3. Liptobiolites derived from some selected parts of higher plants.
A well-known example of the last type of coal is the papier kohl of the
Moscow basin which originated from a concentration of cuticles in the
Palaeozoic age and bears a superficial resemblance to accumulated sheets
of brown paper. Since only humites are of industrial importance, their
classification is discussed below.
The most important variable in the nature of coal is its rank. A number of
characteristic properties are a function of rank and some of them are used
for determining it. Volatile matter, calorific value and carbon content—singly
or in combination—are used to divide coals into major classes or groups on
the basis of rank. Reflectance is also a good rank parameter. For all practical
purposes this classification into groups is satisfactory for the lignite, sub-
bituminous coal and anthracite. However, it is necessary to sub-divide the
coals of the bituminous stage into sub-classes or sub-groups on the basis of
the caking capacity, as judged from one or more standard tests.
When two parameters representing the rank of coal are plotted on a
graph, the points never fall on a single line. However, nearly all the points fall
within a narrow band of a distinctive shape, see Seyler’s chart (Fig. 3.11).
The band is wider for the young coals and narrows down towards the
anthracites. This has been termed the coal band. The band width is a
measure of the variation of hydrogen in the coal due to the variation in its
petrographic composition.
Figure Seyler’s coal classification chart (simplified)
3.11
3.17.1 REGNAULT-GRÜNER-BOUSQUET
The first real attempt at coal classification was made by Regnault in

France in 1837 on the basis of carbon, hydrogen and oxygen, In 1874
Grüner modified this by adding volatile matter and caking capacity. Further
amendments were made by Grüner’s son and Bousquet in 1911 (Table 3.20).
Table 3.20 Regnault-Grüner-Bousquet classification of coal

This classification recognises six classes of coal but does not include
lignites or any coal containing less than 75% carbon on a daf basis. The
descriptive terminology used by Regnault is still in vogue in many countries
in some form or other. However, the limiting values of the classification
parameters are not applicable to coals of other countries. Various countries
have standardised their coal classification systems on the basis of Regnault-
Grüner classification.
3.17.2 FRAZER
The coals of the USA were divided into four groups by Frazer in 1877 on the
basis of fuel ratio (FR), that is, the ratio of fixed carbon to volatile matter. The
groups were termed: anthracite (FR = 100 to 12), semi-anthracite (FR = 12 to
8), semi-bituminous (FR = 8 to 5) and bituminous (FR = 5 to 0). This system
failed mainly due to much overlapping of the groups.
3.17.3 GROUT AND RALSTON
In 1907 Grout plotted the carbon, hydrogen and oxygen contents of a large
number of American coals on a triaxial diagram and found that the humic
coals lie on a narrow band, with cannel coals, rich in hydrogen, placed well
above the band. In 1915, Ralston extended the findings of Grout. Coals of
equal volatile matter (isovols) and equal calorific value (isocals) were
represented by straight lines inclined at an angel to the C, H and O axes.
The effects of carbonisation and oxidation could also be shown by similar
lines on the triaxial diagram. This classification is of scientific interest but
difficult to use in practice (Fig. 3.12).
Figure Grout-Ralston triaxial diagram
3.12
3.17.4 SEYLER
In 1900 Seyler proposed a coal classification system on the Parr basis, that
is, the basis of ultimate analysis, the assumption being C+H+O = 100 (Table
3.21). Coals were divided into four main groups or species according to
carbon content (anthracitic, carbonaceous, bituminous and lignitous) and the
species were sub-divided into five varieties or genera according to hydrogen
content (per-bituminous, bituminous, semi-bituminous, carbonaceous and
anthracitic). The bituminous species was divided into three subspecies,
namely orthobituminous, meta-bituminous and para-bituminous. The prefix
ortho indicates true, typical or normal. Coals containing more carbon than
those of the ortho-type were given the prefix, meta, and those with a lower
percentage of carbon were indicated by the prefix, para. In a similar way the
lignitous species was divided into ortho-lignitous and meta-lignitous. Again,
coals containing more hydrogen than the normal were called per-hydrous
and indicated by the prefix, per, and those with less hydrogen than the
normal were called sub-hydrous and indicated by the prefix, sub.
Table 3.21 Seyler’s classification of coal (1900)
As with the Regnault-Grüner classification, the lowest carbon content

included in the Seyler classification was 75.0%, thus excluding the lignites.
The Seyler classification has however the important advantage that the
ultimate analysis is correlated with the petrographic composition of the coals.
Thus, members of the bituminous or ortho-hydrous coals contain much
exinite and the sub-hydrous coals contain much fusinite. The low hydrogen in
the semi-bituminous and anthracitic coals is the result of coalification.
Seyler also successfully correlated the ultimate analysis of coals with the
technological properties, namely, volatile matter and calorific value. These
correlations were used in the construction of Seyler’s coal classification chart
(Fig. 3.11). This renowned chart has carbon and hydrogen as rectangular
coordinates, with further axes indicating calorific value and volatile matter at
right angles to each other, but inclined at about 60° to the carbon axis.
Oxygen, moisture and swelling number are indicated by suitable scales.
Seyler has drawn a narrow band on the chart between the carbon limits
of 97% to 70% and hydrogen 2.0% to 5.8%. This band is supposed to
include all normal bright coals within this range of carbon content. Per-
hydrous coals fall above the band and sub-hydrous coals fall below the
same. Isovols and isocals are superimposed on the band. The isovols are
approximately parallel to each other and at right angles to the isocals.
The isocals are also found to be lines of equal air requirements for the
combustion of the coal. These have been correlated with flue gas volumes,
calorific intensity and flame temperature under the conditions of adiabatic
combustion.
Despite its scientific excellence, Seyler’s outstanding coal classification
system is not used in industrial practice, the procedure for ultimate analysis
being too lengthy, and the system itself being too complicated.
3.17.5 CLASSIFICATION OF INDIAN COALS
A Coal Grading Board was constituted by the Government of India in 1924 to

arrange for the grading and certification of exported coal. The grades were
originally meant for the Damodar Valley fields for export purposes. Table 3.22
gives the various grades of Indian coals in operation.
Table 3.22 Grading of Indian bituminous coals (1981)

Serial Class Grade Specification
No.
1. Non-coking coal produced A HU* exceeding 6200 kcal/kg
in all states other than
Assam, Andhra Pradesh,
Meghalaya, Arunachal
Pradesh and Nagaland
B HU exceeding 5600 kcal/kg but
not exceeding 6200 kcal/kg HU
exceeding 4940 kcal/kg but not
exceeding 5600 kcal/kg
C HU exceeding 4200 kcal/kg but
not exceeding 5600 kcal/kg
D HU exceeding 4200 kcal/kg but
E HU exceeding 3360 kcal/kg but
F HU exceeding 2400 kcal/kg but
G HU exceeding 1300 kcal/kg but
2. Non-coking coal produced Not graded
in Assam, Andhra Pradesh,
Meghalaya, Arunachal
Pradesh and Nagaland
3. Coking coal Steel grade I Ash content not exceeding
15%
Serial Class Grade Specification
No.
Steel grade II Ash content exceeding 15%
but not exceeding 18%
Washery grade I Ash content exceeding 18%
but not exceeding 21 %
Washery grade Ash content exceeding 21%
II but not exceeding 24%
III but not exceeding 28%
IV but not exceeding 35%
4. Semi-coking and weakly Semi-coking I Ash plus moisture content not
coking coals exceeding 19%
Semi-coking II Ash plus moisture content
exceeding 19% but not
exceeding 24%
5. Hard coke By-product Ash content not exceeding
premium 25%
By-product Ash content exceeding 25%
ordinary but not exceeding 30%
Beehive Ash content not exceeding
premium 27%
Beehive Ash content exceeding 27%
superior but not exceeding 31%
Beehive Ash content exceeding 31%
ordinary but not exceeding 36%
Source: Burecan of Indian Standards, New Delhi IS:770(1977) classification and
codification of Indian coals and lignite.
*HU = Useful heat value (calorific value).

= 8900 − 138 (ash + moisture)
Note:
1. In the case of coal having moisture less than 2% and VM less than 19
HU is the value arrived at as above reduced by 150 kcal/kg for ea
reduction in VM content below 19%.
2. Moisture at 40°C and 60% relative humidity (RH) is used in evaluation
The classification of Indian coals was first published in 1955 on the

advice of the Planning Commission and subsequently revised several times.
The current classification recognises four classes: lignite, sub-bituminous,
bituminous and anthracite and twelve types consolidate (lignite), high volatile
(sub-bituminous), high volatile (bituminous), medium volatile, high volatile (2
types), medium volatile (2 types), low volatile (2 types), semi-anthracite and
anthracite (Table 3.18). Coals of North-Eastern India, grouped together as B1
constitute a special formation, exhibiting widely different coal characteristics.
All coals are suitable for combustion and many for hydrogenation. The more
common uses are indicated in the classification.
Calorific value, volatile matter and Gray-King coke type are the three
basis parameters of this classification. Moisture, carbon and hydrogen are
the other properties included here. The three-digit basic code numbers of
different coals are shown in a separate column.
The code system is clearly shown in Table 3.19. The group numbers
increase from bottom to top (first digit, calorific value) or from left to right
(second digit, volatile matter). The number of supplementary parameters also
increase from bottom to top in a given group. The third digit is on the basis of
coke type. The fourth digit is provided by the supplementary parameter of
maximum thickness of plastic layer (MTPL) for caking coals or moisture
content for non-caking coals.
Suppose a caking coal with a three-digit basic code number, say 855,
has MTPL subgroup number of 6. The integrated code number of such a
coal will be 8556 which when decoded expresses the following properties:
Calorific value, kcal/kg dmmf 8,505 to 8,700
Volatile matter, per cent dmmf 22.1 to 28.09
G-K/(LT) coke type G3or above
MTPL, mm 26 and above
The above properties of the coal strongly indicate that it is likely to be a

typical prime coking coal. On the other hand, if the basic code number of the
coal remains the same, that is 855, but the MTPL, sub-group is 3 instead of
6, its four-digit integrated code number will be 8533, which would indicate a
coal likely to be somewhat inferior to 8556 in respect of its cokability.
Again, suppose a non-caking coal with a basic code number, say 330,
has a moisture subgroup number 4, the integrated code number will be 3304
and when decoded will expresse the following properties:
Calorific valus, kcal/kg dmmf 7,507 to 7,800
Volatile matter, per cent dmmf 33.1 to 37.0
G-K/(LT) coke type A
Moisture, parts per 100 parts dmmf 9.1 to 11.0
The above properties indicate that the coal is a fairly high moisture, high
volatile, low rank, non-caking coal.
All high volatile non-caking coals giving coke types A and B obviously
have 0 as the third number and are thus readily recongnisable in terms of the
three-digit basic code number. But all such non-caking coals are not
equivalent in their intrinsic/technological properties, and herein lies the
importance of the supplementary parameter—moisture—which subdivides
such coals in terms of different moisture ranges.
Increasing group number means increasing desired property level
depending on use, that is lower moisture, higher CV, lower VM, coke type
towards G and higher MTPL.
The total coal resources of India are estimated to be 158.5 billion tonnes.
As high as 82% of these are estimated to be non-caking and only 18%
caking. Prime coking coals constitute only 3.5% of the total reserves. These
low reserves of prime coking and other caking coals require that India should
adopt all possible technological methods of conserving coal resources and
also import low-ash prime coking coals from abroad.
EXAMPLES
Example I
A XV seam Jharia coal from the Bararee colliery gave the following
proximate analysis: moisture 1.6%, ash 15.7%, volatile matter 27.8% and
fixed carbon 54.9%. Calculate its ash on a dry basis and volatile matter on
daf and dmmf bases.
Solution
The proximate analysis is given on the air-dried basis:
Coal does not contain ‘ash’. Ash comes from the mineral matter (MM)
content. On an average 10% of mineral matter is lost when coal is burnt and
mineral matter is converted into ash (A).
Similarly MM = 1–1 X A
Alternatively, the volatile matter can be calculated through the fixed carbon,
since these two together make-up the whole coal on daf and dmmf bases.
Note: The mineral matter of coal contributes to the volatile matter by an amount
approximately equal to 10% of the ash. Therefore, necessary corrections to the volatile
matter value have to be made while calculating on dmmf basis. Fixed carbon does not
need this correction.
Example 2
The following data are available for a Chanch coal of the Raniganj coalfield.
Calculate its calorific value using at least two different empirical formulae and
compare the computed value with the experimental.
Solution
Goutal and CFRI formulae will be used for calculating calorific value from
the proximate analysis, and modified Dulong formula for calculating from the
ultimate analysis.
Goutal formula
C = 82F + aV
Where a is a constant depending upon the volatile matter expressed as per

cent daf (V’).
Using the known values of a for given values of V from the table on page
Calculation of constant, a
V’ a V’ a V’ a
5 145 20 109 35 94
10 130 25 103 38 85
15 117 30 98 40 80
where V’ is VM, per cent daf
This is higher than the experimental value by (7016 . 6890) or 126 kcal/kg
CFRI* Formula
This is higher than the experimental value by 10 kcal/kg only.

Modified Dulong formula
Therefore, calorific value, kcal/kg dmmf
Therefore, calorific value, kcal/kg air-dried
This figure is higher than the experimental value by 83 kcal/kg.
Thus it is found that all the calculated data are higher than the experimental
value. The best agreement is shown by the CFRI formula.
Example 3
Compare the gross (CG) and net (CN) calorific values of the Chanch coal of
Example 3.2 on air-dried and dry bases.
Solution
Air-dried basis
Therefore, the gross CV is higher than the net by 244 kcal/kg on air-dried
basis.
Dry basis
Therefore, the gross CV is higher than the net by 244 kcal/kg on a dry basis.
Note that when the net CV is to be calculated on a particular basis, first
calculate the gross CV on that basis and then convert it into net CV, taking
into account ‘total hydrogen’ on the basis.
Example 4
From the following data for a Damua coal of the Kanhan valley coalfield, find
out what coal it is according to IS classification system.
Solution
Proximate analysis, per cent air-dried
Out of the supplied date, calorific value, volatile matter and coke type will be
required to obtain the basic code of the coal.
(LT) coke type = F

Therefore, basic code of the coal = 722
From Table 3.19 it may be seen that it is a high volatile, medium caking
bituminous coal B. Its carbon content is likely to be about 85% and hydrogen
content about 5.0% dmmf. Its recommended use is in the preparation of coke
oven blend.
This is in the range 2 to 5 (Table 3.19).

From the MTPL value of 19 mm it is inferred that it belongs to the
subgroup 3. Its integrated code number is 7223 and its blendable property is
confirmed.
BIBLIOGRAPHY
1. Bureau of Indian Standards, New Delhi
a. IS: 437 (1979) Size analysis of coal and coke for marketing
b. IS: 439 (1976) Industrial coke
c. IS: 770 (1977) Classificatioin and codification of Indian coals and lignite
d. IS: 1350 Methods of test for coal and coke
Pt.I (1969) Proximate analysis
Pt.II (1970) Calorific value
Pt.III (1969) Sulphur
Pt.IV (Sec. 1-1974) Ultimate analysis - Determination of carbon and
hydrogen (Sec. 2-1975) Determination of nitrogen
Pt.V (1979) Special impurities
e. IS : 1353 (1959) Methods of test for coal carbonisation caking index,
properties and Gray-King assay (LT) coke types
f. IS : 1354 (1992) Method of test for coke - special test
g. IS : 1355 (1959) Methods of test for ash of coal and coke
h. IS : 4286 (1976) Specification for domestic coke
i. IS : 4311 (1967) Method for the determination of mineral matter in coal

j. IS : 4433 (1979) Method for determination of Hardgrove grindability
coal
k. IS : 5062 Method of test for brown coals and lignites
Pt.I (1969) Moisture content

Pt.II (1969) Ash
Pt.III( 1969) Yields of tar, water, gas and coke by low temperature
carbonization
Pt.IV(1969) Yield of benzene-soluble extract
Pt.V(1973) Acetone-soluble material in benzene extract
l. IS : 6345 (1971) Methods of sampling of coal for float-and-sink analysis
m. IS : 7221 (1974) Methods of determining the moisture holding capa
of hard coals
n. IS : 9127 Methods of petrographic analysis of coal
Pt.I (1979) Definition of terms

Pt. II (1979) Preparation of coal samples
2. Charcoal, The Wealth of India: A Dictionary of Indian Raw Materials
Industrial Products, Council of Scientific and Industrial Research, New D
1951.
3. Coal, The Wealth of India: A Dictionary of Indian Raw Materials
Industrial Products, Vol. 2, Council of Scientific and Industrial Research,
Delhi, 1950.
4. Dryden IGC. Chemical constitution and reactions of coal. In Lowry HH, (

Chemistry of Coal Utilization, Supp. Vol., 232. New York: Wiley, 1963.
5. Elliot MA (ed.), Chemistry of Coal Utilisation, Second Supp. Vol., New Y

Wiley, 1981.
(i) Collcott TG and Smith GB. Mechanical Properties of Coal, 285.

(ii) Gluskoter HJ, Schimp NF and Ruch RR. Coal Analyses, Tr
Elements, and Mineral Matter, 369-424.
(iii) Habermehl D, Orywal F and Beyer H. Plastic Properties of Coal, 317
(iv) Neavel RC. Origin, Petrography and Classification of Coal. 91.
(v) Sharkey AG, Jr, and Mecartney JT. Physical Properties of Coal and
Products, 159.
(vi) Wender I, Heredy LA, Neuworth MB and Dryden IGC. Chem
Reactions and the Constitution of Coal, 425.
6. Emrich W. Handbook of Charcoal Making, Dordrecht (Holland): Reidel, 1
7. Geological Survey of India, News, 2007. http:/gsi.gov.in Ministry of C

Govt. of India, Annual Report 2006–07.
8. Lignite, The Wealth of India: A Dictionary of Indian Raw Materials

Industrial Products, Vol. 6, Council of Scientific and Industrial Research,
Delhi, 1962.
9. International Energy Outlook 2007, http:/www.eia.doe.gov. World

Institute. http:/www.world-coal.org.
10. Mukherjee AK, Chatterjeee CN and Ghosh S. Coal resources of India -

formation, distribution and utilization, Fuel Science and Technology, 1:
34, 1982.
11. Roses JW and Cooper JQ, (eds.). Technical Data on Fuel, Seventh edit
British National Committee, World Energy Conference, London, 1976.
12. Sarkar GG. Introduction to Coal Preparation and Practice, Oxford and
Publishing Company, New Delhi-Mumbai-Kolkaka, 1986.
13. Sarkar S, A New Index for the Caking Capacity of Coal, J. Sc. Inds. R
20D: 401–3, 1961.
14. Van Krevelen DW. Coal, Amsterdam: Elsevier, 1961.
* Coal is heated with an excess of toluene when moisture distills over as an azeotrope
with toluene at 84°C. The vapours are condensed and separated into two layers. The
amount of water is then read off in the graduated receiver.
* CFRI stands for Central Fuel Research Institute, a CSIR organisation, where the
author worked for two years (1956-58). It is located at Jealgone, near the township of
Dhanbad. Bihar.
4 Processing of Solid Fuels
4.1 INTRODUCTION
Solid fossil fuels need treatment after they have been won and before they can
be utilised as a source of energy. Different fuels require different kinds of
treatment. Solid fossil fuels are found associated with minerals, water, gases
and impurities. The associated materials have to be removed to improve the
efficiency of the solid fuel. Solid fuels are usually won in large chunks and
therefore have to be sized or made into usable portions. Peat contains large
amounts of water and is of no use without a major portion of it being removed.
By providing proper drainage in peat bogs, a large quantity of water can be
removed. However, the major portion of the moisture in peat is removed by air-
drying it by spreading on drying fields. Air-dried peat is suitable for firing
directly in domestic ovens and industrial furnaces and boilers. It may also be
used in the form of briquettes. The production of peat briquettes involves size
reduction in disintegrators, further drying in hot gases, and finally briquetting.
Peat is also used in the gasification and carbonisation processes.
Lignite is given treatment such as size reduction, drying (in hot gases or
steam), and briquetting and carbonisation, depending on the final form in which
it is to be fired in domestic ovens and industrial installations. An important use
of lignite is for power generation, in which case it is dried to a low moisture
content and then ground to a fine size for pulverised firing. Air-dried lignite is
suitable for some gasification processes. Cleaning of lignite in heavy media
separators is practised on a limited scale for decreasing the ash when
required.
Depending upon its end use, bituminous coal and anthracite may require
only size reduction and sizing; alternatively they may be subjected to more
complex processing like cleaning, drying, briquetting, carbonisation,
gasification and liquefaction. This chapter discusses the various stages in the
utilisation of solid fossil fuels with emphasis on bituminous coals.
4.2 COAL PREPARATION
The raw coal produced from the mine (run-of-mine or ROM) is unsuitable for
use as such. It is necessary to exercise control over one or more of the
properties like size, and ash, sulphur, phosphorus, moisture and chlorine
content, depending upon the nature of its use. In the simplest case of coal
preparation, it may be sufficient to just separate the fines from the lumps;
whereas, in a modern coke plant, multiple operations such as size reduction,
size separation, cleaning, drying and mixing are carried out on a very large
scale. Coal preparation is costly. Although the treatment of fuel is carried out to
raise the efficiency of its utilisation, the techno-economic considerations finally
dictate to what extent it should be practised.
ROM coal usually has a size of 500–0 mm. The sized coals may be
available in various ranges, such as steam coal: 250–25 mm, rubble: 50–25
mm, smithy: 25–13 mm and slacks: 50–0 mm, 25–0 and 13–0 mm. The
screening of coal is carried out on various types of screens that are revolving,
vibrating and shaking. The screens are necessarily of very large capacity and
all measures are taken to operate them at high speed throughout screening.
Inside the mine or at the surface, visible dirt is removed by hand-picking. The
same method may be used to separate the coal types into bright and dull.
Brights are preferred for domestic use and coke production, while dull coal may
be used in furnaces and boilers. Excepting Raniganj coals, the separation of
coal types by hand-picking is hardly possible in India. By and large, Indian
coals are dull in appearance.
4.2.1 COAL CLEANING
High ash coals need cleaning to raise the efficiency of their utilisation.
Depending upon local conditions, the upper limits of coal ash are fixed for
acceptance by users in various industries. Indian coals are high in ash content.
Therefore, in India, even metallurgical coke producers tolerate as much as
20% ash in coking coals, even though an upper limit of 10% ash is the norm for
corresponding manufacturers abroad. Furthermore, thermal power stations in
India have to tolerate 30% to 35% ash in boiler coals. No doubt this tolerance
is at the cost of efficiency. But there is no other alternative than to depend on
indigenous fuel resources. Indian coals have many problems in washing.
Washing is practised only when it is essential.
With increased coal production, the better coals are being exhausted at a
faster rate; dirtier coals are being raised in greater quantity. The practice of
modem mechanised mining also increases the content of rock in the coal.
Clean coal has higher efficiency of utilisation and many other concomitant
advantages: economy of transport and storage, less ash disposal problem and
lower content of sulphur, phosphorus, chlorine and other harmful elements.
The caking properties of some coals also improve on washing owing to a
decrease in ash percentage and enrichment in vitrain.
The ease of separation of mineral matter from coal depends upon its
nature. These inorganic substances may be grouped into two classes.
1. Substances derived from the coal forming plants,
2. Constituents added to coal from external sources.
The two classes are sometimes known as inherent and extraneous mineral
matter, respectively. A part of the extraneous mineral matter is intimately
associated with the organic mass of coal. This is due to their association with
coal during the early formation stage. The inherent mineral matter cannot be
removed from coal by any mechanical method. Chemical treatment like acid
leaching has to be used for this purpose. Fortunately, the content of inherent
mineral matter in coal is small—less than 3%.
The extraneous mineral matter in coal can be removed by mechanical
means. However, the intimately associated variety can be separated only with
difficulty. A coal is easy to wash when the bulk of its mineral matter is due to
dirt bands and rock particles which get mixed with the coal during mining, or
due to dirt settling on coal during transportation, handling and storage.
Washability curves
The washability characteristics of coal are best evaluated by the float-and-sink

test. The test takes advantage of the fact that the associated minerals have
much higher specific gravity than pure coal. The specific gravities of pure
bituminous coal, shales and pyrites are in the range of 1.28–1.37, 2.0–2.64 and
2.4–4.95, respectively. By using liquids of different specific gravities, the coal
sample is divided into a number of fractions in the increasing order of specific
gravity, and hence of ash value. The percentage of floats and sinks in each
fraction and the ash per cent of the floats and sinks is also determined. Usually
three curves are constructed from the results of the float-and-sink test (Fig 4.1
and Table 4.1):
1. Total floats-ash curve,
2. Total sinks-ash curve,
3. Washability characteristic curve or instantaneous ash curve.

Figure Washability curves
4.1
Table 4.1 Float-and-sink test results
From the first two curves (QGT and QYR) the yield and ash of the clean
product (float), and the heavy waste (sink) at a certain specific gravity of
washing can be found out directly. Similarly, to know the specific gravity at
which the cleaning should be done—with a view to producting the maximum
yield of clean coals within an upper limit of ash value—the total floats–ash
curve is consulted. The yields of sink and its ash are read from the total sinks–
ash curve at the same specific gravity. The third curve gives the washability
characteristics of coal. The curve is constructed by plotting column 8 versus
column 3. It indicates the variation of ash from particle to particle in the
increasing order of higher specific gravity. Hence, this curve clearly shows how
far it is possible to separate the dirt from the clean coal by mechanical
methods. For an easily washable coal, this curve should have a sharp bend.
On the other hand, in the case of a very difficult-to-wash coal, it tends towards
a straight line joining the cleanest and the dirtiest particles (Fig. 4.2).
Figure Washability characteristic curves

4.2
Table 4.2 Estimate of coal washing problem from the amount of near-gravity material
Amount of near-gravity material, per cent Estimate of coal
greater than less than washing problem
0 7 Simple
Amount of near-gravity material, per cent Estimate of coal
greater than less than washing problem
7 10 Moderately difficult
10 15 Difficult
15 20 Very difficult
20 25 Exceedingly difficult
25 − Formidable
Preliminary information about the washability of a coal may be obtained

from the numerical data of the float-and-sink test. If the yield of fractions of
specific gravity between 1.40 and 1.60 is very small, it indicates that the
mineral particles are not intimately associated with organic mass and the coal
is easily washable. If the yields of these fractions are considerable, it means
that much of the mineral matter is intimately associated with the pure coal and
hence difficult to separate.
The specific gravity at which a coal is to be cleaned is determined from the
washability data and economic considerations. The ease of washing at this
specific gravity may be judged from the amount of near-gravity material (ngm)
present in the coal. The amount of this material is defined as the percentage of
the coal that will float in a range ±0.10 of the specific gravity of the separation
value. The presence of ngm causes misplacement of sinks in floats and floats
in sinks. The larger the amount of ngm, the more difficult the cleaning
operation, and vice-versa (Table 4.2).
The commercial methods of coal cleaning are based on differences in
some physical properties of pure coal and the minerals present. Most of the
commercial cleaning processes make use of the difference in the specific
gravity. Coefficients of friction, wettability and resilience are used in a few other
commercial processes. Some methods of coal preparation have been
suggested also on the basis of optical and electrical properties. Coal cleaning
processes are influenced to a greater or lesser extent by the size and shape of
the solid particles.
Depending upon the medium used for cleaning, the various processes are
grouped as dry or wet. Table 4.3 gives the classification of the important coal
cleaning processes. Currently the washeries in India can be broadly divided
into two groups.
1. Pit-head washeries: They treat coal from the same or two or more ad
collieries.
2. Central washeries: They recover their feed supplies from a large num
sources located in specified common areas.
Table 4.3 Classification of coal cleaning processes
Name Basis of separation
Dry processes
1. Pneumatic tables density and friction
2. Spiral separation density and friction
3. Berrisford process resilience and density
4. Air-sand process density
Wet processes
1. Dense or heavy medium separators density, size and shape
2. Jig washers density, size and shape
3. Cyclone washers density, size and shape
4. Trough washers or launders density, size and shape
5. Upward-current classifiers density, size and shape
6. Froth flotation process wettability and density
7. Concentration tables density and friction
8. Oil agglomeration process wettability, size and density
Dry processes
Pneumatic table: It is essentially a perforated and riffled sloping deck which is

rapidly reciprocated (Fig. 4.3). The coal is fed in a thin stream from the upper
comer of the table which is transversely inclined. The table is given a
reciprocating movement and the air blown through the deck. The coal spreads
out over the deck and gets segregated into clean coal and refuse under the
combined action of air flow, reciprocating movement of the table and the friction
resistance of the table. The heavy refuse is trapped in the riffles and
transported to the end of the table. The clean coal passes over the table.
Therefore, middlings and clean coal are collected in separate receivers.
Figure Pneumatic table
4.3
Spiral separator: Coal is fed to the top of a tall, vertical spiral. Owing to a
lower coefficient of friction, the clean coal slides to the outside of the spiral
while the refuse slides down the inside of the spiral.
Berrisford process: This is based upon the difference in the resilience of

clean coal and dirt. The feed is dropped on an inclined plane containing a gap
of chosen width. The clean coal bounces and falls on a receiver while the dirt
falls through the gap.
Air-sand process: In this process a suspension of sand in air is used as the

medium for coal washing. The mixture of air and sand acts as the dense
medium of suitable specific gravity; the clean coal floats and the dirts sink.
The above mentioned processes are the dry processes of coal cleaning.
The chief advantage of these over the wet processes is the elimination of the
cost of drying wet coal and the difficulty of disposal of slurries of water and fine
coal or dust. However, these processes suffer from a great disadvantage—the
requirement of very close limits of screen sizes of the coal feed. Moreover, the
dry processes cannot satisfactorily clean coals of difficult washability. These
considerations greatly limit the use of the dry processes. Among these the
tables are more widely used. There is no coal washery in India based on the
dry cleaning principles.
Wet processes
Concentration tables: The working principle of the concentration tables is

similar to that of the pneumatic tables. Water replaces air and the washing
efficiency is higher, particularly with unsized feeds.
Trough washers: Trough washers or launders are of various designs. The

Rheolaveur system consists essentially of one or more inclined troughs in
which the clean coal and the refuse are separated by alluviation (Fig. 4.4). The
coal feed and water enter at the top of the trough. The heavier dirts tend to
settle at the lower strata of the bed. The lighter clean product remains in the
upper strata and overflows at the lower end of the trough. The flowing refuse at
the lower end is continuously removed through several special pockets called
rheo boxes which are located along the length of the trough. The heavier
material collected in the rheo boxes may be rewashed in another trough for
recovering more clean coal.
Figure A two-trough Rheolaveur launder
4.4
Upward-current classifiers: In the upward-current classifiers, the dirty coal is

fed at the top of an inverted conical vessel and a continuous upward current of
water enters through the base (Fig 4.5). The separation is effected by adjusting
the velocity of water between the terminal velocity of fall of the clean coal
particles and that of the dirts. The settling dirts impart to the bath some of the
properties of a dense medium. Therefore, the size range of the feed can be
greater than would be permitted under typical free settling conditions.
Figure Double cone classifier
4.5
The use of concentration tables, trough washers and upward-current
classifiers is limited to coals that are close in size and have good washability
characteristics. The efficiency of the washers is low in the case of difficult to
wash coals. They are not in use in India.
Jigs and dense medium separators are very widely used in coal washing
plants. Most washeries in India are equipped with these two types of
equipment. Jigs have been the most common type of coal washer the world
over. Recently dense medium separators have become very popular owing to
their better performance in the case of difficult coals. However, jigs are better
adaptable to finer sizes than dense medium separators.
Jig washer: In a jig washer, a coal bed is maintained on a perforated plane

and subjected to the action of periodic upward and downward current of water.
This action stratifies the coal bed mainly according to the specific gravity of the
particles. The clean coal is concentrated largely in the upper strata of the bed
and the dirts accumulated in the lower strata. The pulsaing movement of water
in the jig can be created by different means. The older types of jigs use
reciprocating plungers or diaphragms.
The Baum jig produces pulsations in the water by alternately admitting and
releasing compressed air. It consists of a U-shaped box divided longitudinally
by a vertical partition into washing and air compartments (Fig. 4.6). The former
is sub-divided into two sections by a transverse partition. Each section of the
washing compartment is provided with a sieve. The water pulsation is caused
at the rate of 30 to 60 cycles per minute in the air compartment and relayed to
the adjoining washing compartment. The unclean coal is fed at one end of the
washing compartment. Large pieces of the refuse collect at the bottom of the
first section itself. The clean coal and the smaller sizes of the refuse are carried
forward over the weir into the second section. While the refuse sinks to the
bottom, the clean coal is carried by the flowing water over the discharge weir.
The refuse is periodically removed from the two sections through valves. Fine
dirts fall through the sieves into the bottom of the washer and are removed by a
conveyer.
Figure Baum jig
4.6
The size of coal that can be treated in jigs can be anything between 200
mm and 0.5 mm. However, jigs are now often used to wash small coal, say
below 25 mm—the large sizes being treated in dense medium separators. Jigs
cannot wash fines below 0.5 mm and their efficiency drops sharply when the
content of sizes below 3 mm exceeds 25%. For such fines cyclone washers
are quite suitable. Flotation cells are also used in the washing of coal fines.
When the feed of 200 to 0 mm is jigged, the fines remain unwashed and form a
slurry which needs further treatment for the recovery of combustibles.
The efficiency of jigs is more than 98% for coals with 10% near-gravity
materials. The optimum capacity of jigs is 200 to 400 tonnes per hour (tph).
However, commercial units of 20 as well as 600 tph capacity are known to
exist. Baum jigs have been modified in several ways to increase their capacity
for the same physical space, cope with feed fluctuations and treat fine coals
with high efficiency.
The feldspar jig is an air-pulsated Baum-type jig which utilises a bed of
feldspar (or some hard rock) through which all the waste materials migrate.
With automatic control, this jig can cope with feed flucuations. It is usually used
for the cleaning of –13 mm size coal without desliming. However, little ash
reduction can be accomplished for the –48 mesh (0.29 mm) fraction of the
feed.
The principle of cleaning coal by jigging is the same in the new Batac jigs
as in conventional Baum jigs. However, the Batac jig has improved and
automated methods of air distribution, pulsation and bed control. It provides a
higher capacity in the same physical space. Baum jigs are mainly used for
coarse coal washing, while Batac jigs are used for both coarse and fine coal
cleaning. When cleaning fine coals, feldspar beds are used in some of the cells
of the Batac jig. The performance characteristics of Batac jigs in fine coal
cleaning are similar to those of Baum jigs in coarse coal cleaning.
Dense medium processes: The various dense medium processes are

essentially large scale applications of the float-and-sink test. The separation
can be made to almost correspond to the washability curves. These processes
may be classified on the basis of the type of equipment used:
1. Deep bath: the Chance process and Barvoy’s process,
2. Shallow bath: the Dutch State Mines process and Tromp process,
3. Drum: the Drewboy process and Link belt process.
The present tendency in the design of dense medium washers is to prefer a

shallow bath to deep bath. The advantages of the shallow bath are reduction in
the building height, reduction in the amount of excavation required for the
collecting tank, requirement of much lower volume of liquid media, increase in
the capacity for extracting middlings, and flexibility in flow arrangements. The
drum wash boxes have also similar advantages and find use in newer
installations.
The main point in favour of dense medium processes against jigs is that
coals containing high proportions of near-gravity material (70% to 80% or even
more) can be efficiently washed to about 99% efficiency in almost all types of
dense medium separators. While the jigs are normally efficient in the gravity
range of 1.55 to 1.80, the dense medium washers can efficiently separate at as
low a specific gravity as 1.28 and at any high practical gravity level. The
minimum and maximum capacities of commercial dense medium units are
almost similar to those of jigs.
The dense medium processes are generally inefficient in cleaning small
coals, say, below 6 mm because the effect of viscosity of the media greatly
reduces the capacity of the plant, if an accurate separation is to be maintained.
Moreover, the quantity of the solid media removed with the clean products is
much greater in these sizes and it becomes necessary to regenerate a
relatively greater proportion of the media, and that too with greater difficulty.
The problem of viscosity has been successfully tackled by the addition of
peptisers, such as sodium hexametaphosphate.
A shallow bath of the Tromp process is shown in Fig. 4.7. The bath is made
of mild steel plate. It is provided with a push-plate conveyer (1) to discharge the
cleaned coal and a scraper conveyer (2) to remove separately the middings
and the refuse. A low gravity medium is fed at point (3) and a high gravity
medium at point (4). Both media flow horizontally over the whole width and
depth of the washer. The two conveyers are run in such a way that the swirl of
the media is avoided. The charging of the feed and the collection of the
products are clearly shown in the figure. The middlings may be crushed and
recycled to the bath or used as a by-product fuel.
Figure Heavy medium separator

4.7
The dense media are prepared from the aqueous suspension of finely
ground particles like magnetite, barytes, sand loess, sintered pyrites and froth
flotation tailings. The washery products are separated from these particles by
sieving followed by water spraying on sieves.
Froth flotation process: It is largely used in the beneficiation of mine dust,

slack coal, washing rejects and slurries. It is especially suitable for producing
ultra-pure coal for the manufacture of electrode carbon. The distinctive feature
of this process is its suitability to clean fine coals., say 0.5 mm, which cannot
be treated by other processes. The optimum particle size is 48 to 150 mesh, or
0.29 to 0.10 mm. However, 200 to 325 mesh or 0.074 to 0.43 mm, has also
been processed. It is the only method commercially available for washing –200
mesh size coal. Froth flotation has not been popular in coal washing so far,
owing to high capital and running costs. Its use has recently been encouraged
as a modern trend in washing more and more fine coals.
A froth flotation plant consists of a battery of cells, each with a capacity of 5
to 10 tph. In each cell froth is made by bubbling air through water in the
presence of frothing agents, such as, cresol, pine oil, kerosene and alcohols
(Fig. 4.8). When fine coal is added to such a system, the pure coal particles
adhere to the bubbles of the froth while the dirts are wetted by the water and
sink to the bottom of the cell. The separation is improved by adding collecting
agents, for example, spindle oil, creosote oil, xanthates and soaps to the
system. The cleaned coal is recovered by the vacuum filtration of the froth.
Figure Flotation cell for coal

4.8
Cyclone washers: These were developed during the Second World War in
Holland and, within ten years, found wide application in washing small-sized
coals (Fig. 4.9). The most distinctive features of these washers are a high
quality of separation, and a high flexibility of operation with regard to
percentage of near gravity material, coal particle size, feed rate and separation
gravity. The modern cyclone washers compare favourably with jigs in capital
cost. The slightly higher maintenance cost of the cyclone washer is more than
compensated by the higher efficiency and greater flexibility.
Figure Horizontal cyclone washer
4.9
Cyclone washers operate essentially on the principle of a settling chamber

in which gravitational acceleration is replaced by centrifugal acceleration. Coal
industries use low-pressure horizontal cyclones wherein the centrifugal force is
about 40 times the gravitational force. This low value is sufficient to produce an
accurate and rapid separation of raw coal as small as 0.5 mm in particle size,
overcoming the effect of viscosity caused by 6 mm to 0.5 mm fines. On the
other hand, the use of low feed pressure reduces energy consumption and
simplifies the installation of the cyclone washer. Cyclone washers are usually
built in the normal capacity of 70 to 150 tph.
A pulp of deslimed raw coal and heavy medium such as magnetite make
the feed for a cyclone washer. The overflow contains the sinks. These are
depulped and the products are rinsed with water before final disposal. The
recovered slurry of heavy medium particles is reused after suitable treatment.
Oil agglomeration process: This process of coal cleaning is under

development for early commercialisation. Particles are removed from the liquid
suspension by selective wetting and agglomeration with a second immiscible
liquid. The process relies on surface chemical effects rather than specific
gravity differences as in conventional gravity separation processes. Since coal
particles are essentially hydrophobic in nature, they can be readily
agglomerated with many oils in an agitated aqueous slurry under high shear.
On the other hand, the hydrophilic mineral particles are not affected and
remain suspended in water. Furthermore, since the coal agglomerates of 0.7 to
2 mm are larger than the mineral particles, their removal can be readily
achieved. Thus oil agglomeration is very efficient in handling extremely fine
materials such as coal fines in the –200 mesh range or even –400 mesh, and
materials with considerable amounts of clay slime.
Coal fines are agitated with water and middle distillate oil (5% to 9% of dry
coal) in a flotation cell. No air is used. Heavier oils are avoided because they
have functional oxygen and sulphur groups which can draw minerals also.
Besides agglomeration of fines and partial deashing, dewatering also occurs.
The collecting oil is adsorbed on the surface of the particles, displacing
moisture. Since the surface area of agglomerates is considerably smaller than
that of the starting material, the entrapped moisture content of the product is
lower by 50% of the original coal.
Washer efficiency
The usefulness of a coal cleaning process for a particular coal, or a group of

coals, depends essentially on the efficiency with which it separates the clean
product from dirt. In the ideal case, the separation should be complete and
there should not be any wrong migration of particles—heavier particles to the
product and lighter particles to the tailings. A number of formulae are available
for calculating the washer efficiency, three of which are as follows:
1. Fraser and Yancey
2. Yancey and Geer
3. Anderson
Efficiency, per cent = 100 – (sinks in clean coal + floats in refuse)
The recovery of the clean coal obtained in the washer is best calculated
from the ash balance.
The Fraser and Yancey formula is widely used. It does not, however, allow
for any size degradation taking place in the actual washer operation which
releases more dirt from the pure coal and alters the washability characteristics
of the feed. Moreover, a high recovery of a low grade product may result in an
efficiency greater than 100%. Similarly an exceptionally clean coal with low
recovery will give misleading results.
The Yancey and Geer formula is an improvement upon the first formula. It
is more simple and not likely to give misleading results as it is based upon the
theoretical recovery at the actual ash level and not at the originally fixed
specific gravity. In actual operation, the gravity of separation may differ from
the set value. This formula, however, does not guard against the inaccuracy
resulting from the size degradation of coal in the washer operation.
The demerits of the above two formulae are absent in the Anderson
formula. The separation gravity and the quantity of wrongly migrated particles
(sinks in clean coal and floats in refuse) are determined from the float-and-sink
tests of the clean coal and the refuse. Any alteration in the set value of the
specific gravity and the washability characteristics of the feed during washer
operation is therefore taken into consideration. The Anderson formula however
does not incorporate any term indicating the quantity of the noncombustible
matter carried by the wrongly migrated particles. The total amount of migration
cannot satisfactorily measure the quality of products.
4.2.2 COAL WASHING IN INDIA
Although washability studies were first made in India as early as 1924,

scientific coal preparation developed only recently. The problems in washing
Indian coals are:
large content of intimately associated mineral matter giving rise to
washability characteristics;
presence of high percentage of near-gravity material at the desired de

separation;
wide variation in washability characteristics of coals for different horizon

vertical sections of the same seam;
low average annual production of individual mines.
These problems are solved by using controlled coal crushing for better
release of dirts, employing techniques of coal washing suitable for difficult-to-
wash coal and establishing central washeries fed by a number of collieries.
Jigs, heavy medium separators (shallow bath) and cyclones are the most
widely used coal washers in India. Owing to high ash and difficult washability of
coals, the washeries in India generally produce middlings in addition to the
clean product and the rejects. The middlings have around 30% ash and are
used in thermal power stations. The rejects are sometimes used in thermal
power stations and in the back filling of mines. However, two product schemes
producing a clean coal and a high ash by-product fuel (ash around 45%) are
also recommended. No rejects are obtained in the scheme and the by-product
fuel finds use in modern big thermal power stations and in the production of
soft coke.
Table 4.4 gives the performance of washeries/washed coking coal
production during the last five years, and the location and production figures as
reported in the Annual Report (2006–2007), of the Ministry of Coal, Govt. of
India. The details of washeries in operation in the country as reported by the
same source as above are given in Table 4.5. Both coking and non-coking coal
sectors are covered.
Table 4.4 Performance of washeries/washed coking coal production during the last five
years (in million tonnes)
Table 4.5 Details of washeries in operation in the country

SI. Washery and Operator Capacity Location Consumer
no. (Mty)
no. (Mty)
Coking coal
1 Dudga-II, CIL 2.00 Jharkhand Steel plants
2 Bhojudih, CIL 1.70 West -do-
Bengal
3 Patherdih, CIL 1.60 Jharkhand -do-
4 Moonidih, CIL 1.60 -do- -do-
5 Sudamdih, CIL 1.60 -do- -do-
6 Mahuda, CIL 0.63 -do- -do-
7 Barora *, CIL 0.42 -do- -do
8 Kathara, CIL 3.00 Jharkhand -do-
9 Swang, CIL 0.75 -do- -do-
10 Rajrappa, CIL 3.00 -do- -do-
11 Kedla, CIL 2.60 -do- -do-
12 Nandan, CIL 1.20 -MP- -do-
(A) CIL 20.10
13 Durgapur, SAIL 1.5 WB -do-
14 DCOP, DPL 1.35 WB -do-
15 Chasnala, IISCO 2.0 Jharkhand -do-
16 Jamadoba, TISCO 1.72 -do- -do-
17 West Bokaro-II, TISCO 1.8 -do- -do-
18 West Boakaro-III, TISCO 2.1 -do- -do-
19 Bhelatand 0.8 -do- -do-
20 Govindpur, Auroma Coke Ltd. 1.0 -do- -do-
(B) PSU and Private 12.27
TOTAL (A + B) 32.37
Non-coking coal
1 Dugda-I,CIL 1.00 Jharkhand TPS
2 Lodna,CIL 0.48 -do- TPS
3 Madhuban,CIL 2.50 -do- TPS
4 Gidi,CIL 2.50 -do- TPS
5 Piparwar,CIL 6.50 -do- TPS
6 Kargali,CIL 2.72 -do- TPS
7 Bina,CIL 4.50 UP TPS
(A) CIL 20.20
8 Dipka, Aryan Coal Beneficiation 5.0 Chattisgar RSEB, GEB. PSEB, KPCL,
Pvt. Ltd. h MSEB, cement.
9 Gevra, -do- 6.0 -do- -do-
10 Chandrapur, -do- 2.0 Maharastr MSEB, KPCL
a
no. (Mty)
11 Adilabad, Aryan Energy Pvt. 2.0 AP KPCL
Ltd.
12 Talcher, Aryan Energy Pvt. Ltd. 3.0 Orissa Sponge iron
13 Wani, Kartikay Coal Washeries 2.0 Maharastr TPS
Pvt. a
Ltd. (Aryan)
14 Korba, ST-CLI Coal Washeries 5.0 Chattisgar BSES, GEB, cement
Ltd. h
15 Ramagundam, Gupta Coalfield 2.5 AP KPCL, cement,
&
Washeries Ltd. small industries
16 Sasti, Gupta Coalfield & 2.5 Maharastr RPTS, KPCL
Washeries Ltd. a
17 Wani, Gupta Coalfield & 2.5 Maharastr MSEB
Washeries Ltd. a
18 Umrer, Gupta Coalfield & 0.75 -do- Cement
Washeries Ltd.
19 Bhandara, Gupta Coalfield & 0.75 -do- Sunflag Iron & Steel Co. Ltd.
Washeries Ltd.
20 Parasia, Gupta Coalfield & 0.75 -do- Cement
Washeries Ltd.
21 Bilaspur, Gupta Coalfield & 1.2 Chattisgar Sponge iron
Washeries Ltd. h
22 Ghugus, Gupta Coalfield & 4.0 Maharastr MSEB
Washeries Ltd. a
23 Talcher, Global Coal Mining (P) 2.0 Orissa Sponge iron
Ltd.
24 Wani, Bhatia International Ltd. 3.0 Maharastr MSEB
a
25 Chandrapur, Bhatia 1.0 Maharastr Industries
International Ltd. a
26 Raigarh, Jindal 2.5 Orissa Steel
27 Wani, Indo Unique Flame Ltd. 0.5 Maharastr Sponge iron
a
28 Chattishgarh Power & Coal 1.2 Chattisgar Power and cement
Beneficiation Ltd. h
(B) Private 50.15
TOTAL (A+B) 70.35
Source: Annual Report 2006–2007, Ministry of Coal, Govt. Of India, http://coal.nic.in
The provisions as well as problems of central washeries are in many

respects different from those faced by the pit-head washeries. It is logical to
expect some appreciable variations in the economies of washing for these two
different groups of washeries. For equivalent capacity level the capital cost of a
central washery is obviously higher than that of a pit-head washery. This is
mainly because in a central washery, 20%–30% of the capital cost is incurred
on building elaborate marshalling yard and township, while in a pit-head
washer, only 5%–10% of the capital cost goes towards railway siding and
township.
The operating cost per tonne of throughput in a pit-head washery is about
70% of that incurred in a central washery. The higher cost of washed coal
(cleans) in a central washery is mainly due to the higher freight handling
charge on raw coals drawn from a large number of mines, many of which are
located at a distance from the washery.
Table 4.6 gives the figures of production from more recent washeries in
India in the years 1990–91, 1996–97 and 2003–04. The total raw coal feed for
prime coking coal was 12.47 Mt in 1990–91 and only 4.64 Mt in 2003–04. The
corresponding clean coal production was 6.44 Mt, 5.90 Mt and 2.86 Mt, and
middlings production was 3.08 Mt, 3.70 Mt and 1.01 Mt. Including the medium
coking coal, the total raw coal feed was 20.50 Mt, 22.20 Mt and 15.82 Mt while
the data for clean coal production was 11.10 Mt, 10.90 Mt and 8.20 Mt and
middling production was 5.60 Mt, 6.80 Mt and 4.85 Mt.
Table 4.6 Production from coal washeries in India (million tonnes)

Feed and production 1990–91 1996–97 2003–04
Prime coking coal
Raw coal feed 12.47 12.80 4.64
Clean coal production 6.44 5.90 2.86
Middling production 3.08 3.70 1.01
Medium Coking Coal
Raw coal feed 8.03 9.40 11.18
Total
Raw coal feed 20.50 22.20 15.82
Sources: (1) Coal Directory of India, Government of India, various years. (2) Annual
Report 1997–98, Ministry of Coal, Govt. of India, New Delhi
All-India production of some coal derivatives is given in Table 4.7. The total
hard coke production was increased from 0.6 Mt in 1985–86 to 11.0 Mt in
1995–96 and to as high as 12.39 Mt in 2004–05 in the public sector alone. The
company-wise production of coal is given in Table 4.8.
Table 4.7 All-India production of some coal derivatives (million tonnes)
Item 1985–86 1995–96 2004–05
Soft coke 1.7 0.2 −
Beehive hard coke 0.3 0.1 12.39
By-product hard coke 0.3 10.9 in public sector
Washed coal 10.9 11.9 8.7
Middlings 5.1 6.8 5.2
Total exports 0.2 0.1 1.3
Total imports 2.0 12.5 25.3
Source: Coal Directory of India (various years), Coal Controller’s Organisation, Govt. of
India.
Table 4.8 Company-wise coal production (million tonnes)

Compan Target 2006– Actual Production* Actual Production
y 2007 (April- (2006–2007) (April- (2005–2006) (April-
December) December) December)
CIL 257.367 250.073 241.721
SCCL 27.734 26.097 24.537
OTHERS 17.857 18.978 16.166
TOTAL 302.958 295.148 282.424
* Provisional (figures excluding Meghalaya)
Source: Annual Report: 2006–07, Ministry of Coal, Govt. of India, New Delhi
The National Steel Policy has an ambitions growth plan of 100 Mt coke per
year by 2020, and to convert the country from a coke-importer to a coke-
exporter. As a step towards ensuring the same, it has established long-term
coal supply understanding with a number of reputed Australian coal suppliers.
The coke demand for countries like India will have a continuous upward trend
as the steel and automotive sectors are poised to grow.
The world coke production of the top ten hard coal producers is given in
Table 4.9. Out of them India produced 295.2 million tonnes hard coke in 2006–
2007.
Table 4.9 Top ten hard coal producers (2006)

PR China 2482 Mt
USA 990 Mt
India 427 Mt
Australia 309 Mt
South Africa 244 Mt
Russia 233 Mt
Indonesia 169 Mt
Poland 95 Mt
Kazakhstan 92 Mi
Colombia 64 Mt
Source: World Coal Institute, Coal Facts, http://www.world.org
The sector-wise demand of coal in India is given in Table 4.10 for the years
2001–07 and obviously the power utilities accounted for the lion’s share of the
demand: 216.472 Mt in 2006–07.
Table 4.10 Consumer-wise offtake of coal from CIL. SCCL and others for the last five
years (million tonnes)
The requirements for industrial and domestic cokes are given in Tables
4.11 and 4.12, respectively.
Table 4.11 Requirements for industrial coke (IS: 439–1989)

Table 4.12 Requirements for domestic coke (IS: 4286–1976)
SI.No. Characteristics Requirements
Class 1 Class 2 Class 3
1. Moisture, per cent max 8 8 8
2. Volatile matter, per cent dry 3–10 3–10 3–10
3. Ash, per cent dry max 30 40 50
4. Size range, mm* 100–100 10–100 10–100
5. Shatter index
+ 25 mm per cent min
+ 12.5 mm per cent min 65 65 65
Notes: (1)* Not more than 10% should pass through 100 mm and be retained on 10 mm
sieves.
(2) In the case of domestic coke made from lignite, moisture and volatile matter, not
exceeding 15% each, may be permitted.
4.3 STORAGE OF COAL
Coal consuming industries usually store large quantities of coal at the plant as
a resource to offset interference in supply. During storage coal undergoes a
series of changes on exposure to the atmosphere. This process is known as
the weathering of coal. The extent of changes depends upon the method of
storage and the nature of coal. Weathering is more pronounced with lower rank
coals and greater exposure to air. By storing coal under water and in trenches,
weathering may be minimised. The properties affected by the storage of coal
are (i) size, (ii) friability, (iii) caking capacity, (iv) ultimate analysis, (v) calorific
value, and (vi) yields of carbonisation products.
Weathering tends to reduce the coal size and increase its friability. The
formation of slacks or small sizes of coal is particularly pronounced with sub-
bituminous coal, lignite and peat. This imposes a serious problem in the
handling, transport and storage of these fuels. Anthracite and mature
bituminous coal do not slack.
The caking capacity is very sensitive to aerial oxidation and always
decreases on weathering. A slight decrease in the caking capacity may
improve the coke size in some cases but generally the coking properties
deteriorate during the storage of coal. Other parameters which fall on
weathering are carbon content, hydrogen content, calorific value and tar yield.
The oxygen content and yields of gas and liquor increase by atmospheric
oxidation.
Weathering of coal is essentially a result of mild oxidation and hence, an
exothermic process. If the heat liberated is not completely dissipated, the
temperature of the coal rises. Since the rate of chemical reaction is
approximately doubled by a rise of 10°C, the extent of atmospheric oxidation
continues at an accelerated rate with a greater quantity of heat liberated.
Ultimately the coal may reach its ignition point and burst into flame. This
phenomenon is known as the spontaneous inflammation of coal and is
associated with the storage of coal in bulk, say, 200 tonnes for bituminous coal
and 50 tonnes for lignite.
This hazard may be avoided by decreasing the exposed surface of coal
lumps and suppressing the ventilation. The rate of oxidation appears to
increase proportionally to about the root of the surface area per unit weight of
the coal. The exposed surface area is reduced by avoiding segregation and by
packing the coal tightly and uniformly. Blanketing the pile with fine coal is also
helpful in decreasing the ventilation. Another useful measure is to surround the
coal pile by a wall. All of these constitute a positive measure in minimising the
extent of oxidation—the root cause of spontaneous inflammation. Another
approach is to enhance the ventilation in such a way that the liberated heat is
fast dissipated. This method is not recommended in practice.
Whenever coal is stored in bulk for a long time, its temperature should be
measured at various points of the pile from time to time. Above 70°C, the risk
of spontaneous inflammation is great. Therefore, the coal should be consumed
before this critical temperature is reached. Water spraying helps only in the
initial stages and not after crossing the danger point. As a rule, coal should not
be stored near a source of heat. The problems connected with the storage of
coal also apply to coal in ships’ bunkers and cargo. Here the conditions of
ventilation and proximity of heat source are such that spontaneous
inflammation may occur in piles of smaller quantities, that is, less than 200
tonnes. Therefore greater care must be taken to prevent any rise in
temperature of coal beyond the critical value. Freshly mined coals are most
susceptiable to spontaneous combustion. This hazard usually occurs within
four to five weeks of mining. If coal has been safely stored for more than six
months, it is not usually prone to spontaneous combustion.
4.4 CARBONISATION
The process of carbonisation may be of three categories, namely (i) low

temperature carbonisation (LTC) at 600°C, (ii) medium temperature
carbonisation (MTC) at 800°C, and (iii) high temperature carbonisation (HTC)
at 1000°C. The low temperature process is commercially practiced for the
production of semicoke, which is also called soft coke or char. The high
temperature process is carried out in the production of hard coke and coal gas.
The medium temperature process does not have commercial application.
However, many commercial low temperature carbonisation processes
approach the conditions of MTC. Because of the important use of hard coke in
the blast furnace and cupola, HTC is practised on a much bigger scale than
LTC. Soft coke is mainly used as a smokeless domestic fuel.
4.4.1 Low TEMPERATURE CARBONISATION
Coal and semicoke are poor conductors of heat. In a static bed of externally
heated coal, it is necessary to employ a high temperature gradient to achieve
carbonisation in a reasonable time. This method may seriously affect the
product by over-carbonising the surface layer. Therefore, other methods have
been developed with a view to overcoming this difficulty. The heat transfer rate
is enhanced in these methods by using one or more of the following steps:
direct heating of the charge by hot gases,
movement of the charge by vertical fall,
rotating the carboniser,
using fluidised bed technique.
There are two commercial LTC plants in India, situated at Neyveli (Tamil
Nadu) and Naspur (Andhra Pradesh). Commissioned in 1968, the Neyveli plant
produces 900 tonnes per day (tpd) of carbonised lignite briquettes sold under
the trade name, Leco. The Naspur plant was commissioned in 1979 and has a
capacity of 900 tpd of soft coke. Both these plants are based on internally
heated Lurgi–Spül gas process (Fig. 4.10).
Figure Lurgi–Spül gas low temperature carboniser

4.10
The heart of the Naspur plant is a vertical shaft consisting of three sections
serving as the upper drying zone, the middle carbonising zone and the bottom
coke cooling zone. Coal of size 25 to 125 mm is fed through a hopper. While
falling through the vertical shaft it is successively dried and carbonised. The
drying is effected by the combustion gases from the burner fitted to the drying
zone. The carbonisation is carried out by a mixture of hot gases entering from
the carboniser burner chamber and gases drawn from the coke cooling zone.
The bulk of the gases in the drying zone is kept circulating by a fan while the
rest escape through the chimney at the top. The rich gases from the carboniser
are treated for the recovery of by-products and then sent to the coke cooling
zone and also to various burners. Care is taken to prevent the entry of the
carboniser gases to the dryer and the dryer gases to the carboniser.
The various products of low temperature carbonisation are semicoke, low
temperature tar, liquor, crude low temperature spirit and gas. The quality and
yield of these products depend upon the process and the coal used. LTC plants
normally use low rank coals and lignite. These fuels lead to excessive smoke
formation during burning, but the semicoke obtained from them is a clean fuel.
Some typical yields (dry basis) by the Gray-King assay at 600°C are: semicoke
75%–80%, tar 9%–12%, liquor 5%–7% and gas 100–120 Nm3/tonne. In
commercial plants the yields of semicoke and tar are less and that of gas is
higher. The crude spirit is usually recovered in 0.5%–l% yields.
Semicoke has volatile matter of 8% to 12%, is highly reactive and can be
easily ignited into a smokeless flame. The screened product is an ideal
domestic solid fuel (Table 4.12). The char produced by LTC in a fluidised bed is
converted into suitable briquettes for domestic uses. Other uses of semicoke or
char are production of iron in low shaft furnaces, gasification into fuel gas or
synthesis gas for fertilisers and chemicals, and preparation of coke oven
blends. It may also be used as an industrial fuel.
Low temperature (LT) tar is often known as primary tar since the alteration
by secondary cracking reactions is small due to relatively low temperature
conditions. It is a very complex mixture of higher phenols, substituted aromatic
hydrocarbons and various nitrogenous and oxygenated compounds of carbon
and hydrogen. Many disinfectant preparations are made from this tar.
Chemicals and liquid fuels may be produced from it by employing special
processes. The LT tar has at present a much lower market value than the HT
(high temperature) tar.
The crude spirit corresponds to the crude benzol of HTC but contains larger
proportions of paraffins, naphthenes and olefins. Motor fuel may be produced
by processing the crude spirit.
The properties of the gas obtained by low temperature carbonisation are:
specific gravity (referred to air) 0.6,
calorific value 6500 kcal/Nm3,
composition (in per cent): CO2 4.0, CnHm 4.0, CO 7.0, H2 33.0, Cn H2n
and N2 7.0.
This gas is richer in hydrocarbons and poorer in hydrogen compared to the

gas produced by HTC. Its yield is lower but calorific value is higher. The low
temperature gas is used up in the plant. The gas obtained from a direct heated
LTC plant is a mixture of carbonisation and combustion gases and hence has a
low calorific value of about 1500 kcal/Nm3.
The low temperature carbonisation of coal has a bright future in India as it
can supply the substitute fuel required to replace the large quantities of cattle
dung and other biomass used for domestic hearths. However, the high capital
cost and present poor market value of LT tar hinder the establishment of this
industry. But the so-called bhatta coke is being produced in large quantities in
the Bengal–Bihar coalfield area by a wasteful process. A heap of coal, 15 to 20
te, is set on fire and the volatile products are burnt off. After a suitable time, say
7 to 10 days, the fire is extinguished. The solid residue is essentially a reactive
semicoke with pleasant free-burning characteristics. The Central Fuel
Research Institute (CFRI) at Jealgora near Dhanbad in Bihar has developed a
coking stoker which also produces soft coke by burning off a part of the volatile
matter of coal. Its capital cost is small but no by-products are recovered.
4.4.2 HIGH TEMPERATURE CARBONISATION
This process is commercially practised in coke ovens and to a much lesser

extent in gas retorts. The chief products from these two plants are coke and
gas, respectively. The coke ovens may be of either the beehive type or the by-
product slot-type. The by-products are recovered only in the latter type of coke
ovens while they are burnt off in the former.
The gas obtained by HTC in gas retorts is know as coal gas. Its principal
use is as a town gas. With the advent of natural gas, liquefied petroleum gas
and electricity, the production of town gas by HTC in gas retorts is now more or
less an obsolete process. Further, this retort coke is unsuitable in iron making,
but is reactive and hence a good domestic solid fuel. Therefore, the two-fuel
idea from coal is now staging a come back.
Three types of gas retorts are used in carbonising coal: horizontal retorts,
intermittent vertical retorts and continuous vertical retorts. The presently
defunet town gas plants at Mumbai and Kolkata were using horizontal retorts.
A two-fuel complex using continuous vertical retorts is being installed at
Dankuni, 20 km from Kolkata. The Dankuni coal complex may pave the way for
many such projects in other viable areas in the country.
Continuous vertical retorts
Continuous vertical retorts were developed mainly in the UK during the early
twentieth century. By 1966, there were at least 600 plants throughout the world,
carbonising more than 25 million tonnes of coal per year.
These retorts are narrow vertical brick chambers, rectangular or elliptical in
cross section. Indirect heating is achieved from both sides by burning producer
gas in flues, which may be either horizontal or vertical. The chambers are wider
at the bottom so that the charge can gravitate freely through it. The coal should
ideally be a high-volatile, medium-caking coal or its blend with high volatile
non-caking coal or a non-caking coal alone. It is charged at the top through a
hopper. In its downward movement it is successively dried and carbonised. The
coke is discharged by a mechanical device (coke extractor) into a sealed coke
chamber. It is cooled here by quenching with steam and finally removed from
the retort house. Steaming helps to recover the sensible heat of coke, augment
gas yield by producing water gas and also improve the reactivity of coke by
burning off a part of the coke and opening up its fine pore structure. Since the
water gas so produced has a lower calorific value than the coal gas, it is
obvious that the mixed gas obtained by steaming the coke is poorer than the
coal gas. However, the total heat content of the product gas is increased by
steaming. In other words the thermal efficiency of the plant is greatly enhanced
by steaming due to the conversion of the sensible heat of coke into the
potential heat of water gas.
The gas leaving the retorts is treated for purification from undesirable
components, and for the recovery of valuable by-products. These treatments
constitute the by-product recovery section of the plant. The basic principles of
operation of the by-product recovery sections of the gas and coke plants are
similar and will be discussed under the coke plant. The gas used as town gas
may need an additional step, that is, partial drying because excessive water
vapour causes corrosion and blockages in the distribution pipes. The drying
may be achieved by chilling, compression or treating with dehydrating agents
like concentrated calcium chloride solution. Sometimes crude benzol is not
recovered so that the calorific value of the gas is higher due to the presence of
the benzol hydrocarbons. These considerations also apply to coke oven gas
meant for use through pipelines in places outside the coke plant. The coke
obtained from the gas retorts is known as gas coke. Although a result of high
temperature carbonisation, it is much more reactive than the hard coke
obtained from coke ovens, partly due to the lesser caking properties and lower
rank of the coal carbonised, and partly due to the effect of steaming. The gas
coke is largely used as a fuel in miscellaneous industries and domestic ovens.
Owing to its poorer strength it is not suitable in blast furnace operation.
Beehive coke ovens
These are firebrick chambers with an arched roof and derive their name from
the shape of a beehive. The dimensions of a typical oven are: height 2 m and
base diameter 3.5 m. There is a hole at the centre of the roof and a door at one
side. A number of ovens are built in a row with common walls between
neighbouring ovens. About 5 to 7 tonnes of coal are charged from the top hole
into the hot oven and allowed to form a layer of about 60 to 90 cm depth by
means of a rake. Carbonisation immediately starts and the evolved gases burn
off with the air coming through an opening at the top of the closed door. The
carbonisation proceeds from the top to the bottom of the charge and is
complete in two to three days. Heat transfer is mostly by radiation from the hot
roof to the surface of the charge and then by conduction through the layer of
the charge. Heat is supplied by the burning of the volatile matter and hence no
by-products are recovered. The exhaust gases are allowed to escape to the
atmosphere. In some cases they are passed through flues built in the walls
between the ovens and then released to the surroundings through a chimey.
The thermal efficiency is thus increased and pollution also lessoned.
Sometimes waste heat boilers are also run on the heat produced by the
exhaust gases. When carbonisation is completed, the door is opened and the
coke is quenched with water. The quenched coke is discharged manually or by
a machine. The walls and roof of the emptied oven retain enough heat to
initiate coking of the next charge.
The demerits of beehive coke ovens are:
1. There is no recovery of by-products,
2. There is lower coke yield due to partial combustion,
3. Quality coke can be produced only from good coking coals (blends of
coals cannot be used),
4. There is lack of flexibility of operation.
In spite of these demerits, beehive ovens are still in considerable use in

many countries such as the USA and India. The advantages are:
1. Extremely good quality, strong and blocky coke of the required reac
obtained if the starting coals are of good coking quality.
2. The capital and running costs are low.
3. Coke production is not connected with the availability of a market for

products.
By-product slot-type coke ovens
Coal is indirectly heated in these ovens by combustion chambers separate

from the carbonisation chambers. The ovens are built in a battery of 10–100
ovens, in which the combustion chambers alternate with the carbonisation
chambers. A gaseous fuel is burnt in the combustion chambers for supplying
the heat to the process. Coal is coked in the carbonisation chambers. The
gases and vapours evolved on carbonisation are not permitted to mix with the
combustion gases. The carbonisation gases are treated for the recovery of the
valuable by-products, namely, tar ammonia, crude benzol and coke oven gas.
The carbonisation chamber is a long, narrow parallel piped of usual
dimensions having length 12–14 m, height 4–5 m and width 400–500 mm. The
modern trend is to build very large ovens with a useful capacity of around 40–
50 m3 leading to about 33–40 tonnes of coal per charge and giving about 50–
60 tonnes per day throughout. This has been possible by increasing the height
to 6–7.65 m and length to 15–17.25 m. The width of the oven is not uniform. A
tapering of about 50 mm is maintained for easy pushing of the coke. The two
ends of the chamber are provided with removable doors and the roof is
provided with three to four holes covered with lids for charging coal from the
top. The roof has an additional hole at one end for the escape of volatile
products of carbonisation through a vertical pipe known as the standpipe.
The combustion chamber essentially consists of flues built in the dividing
wall between two neighbouring carbonisation chambers and also in the two
end walls of the battery. Gaseous fuels (usually coke oven gas or blast furnace
gas) are supplied to the heating flues. The hot combustion gases are passed
through regenerators or waste heat boilers and then let out into the
atmosphere through the chimney. Modern coke ovens are always provided with
regenerators which are built underneath the ovens. The heat recovered in the
regenerators is utilised in preheating the air and blast furnace gas. Coke oven
gas cannot be preheated because its hydrocarbons get cracked in the checker
brickwork of the regenerators, resulting in the loss of its heating value and the
blockage of the regenerators by carbon deposits. Regenerators work on the
principle of alternate heating and cooling cycles. This is achieved by
periodically changing the direction of flow of gases through the vertical flues
(reversal) every 30 minutes or so.
The coke ovens are made of silica bricks which are preferred to firebricks
mainly because of the higher stability required at the temperature of the
combustion chamber of about 1350°C to 1450°C. On the other hand,
regenerators are made of firebricks because they can withstand the stress
caused by fluctuating temperatures in the operation cycle.
Each oven cokes a batch of about 20 tonnes or more. The batchwise
carbonisation process is made continuous by building the ovens in a battery. In
a modern coke plant there may be two to three batteries built in one row, with a
total capacity of more than 1 Mt of coke per year. These big plants are attached
to integrated iron and steel mills and are primarily meant for captive
consumption of coke by their own blast furnaces. There are also merchant
coke plants which sell coke to various agencies. These plants may vary widely
in the annual production, the number of batteries and the number and size of
ovens in a battery.
The by-product ovens may be of varying design. While simple ovens bum
only rich gas (coke oven gas), there is provision for burning both rich gas and
lean gas (blast furnace gas) in compound ovens. The coke oven battery may
be supported either directly on the foundation, or on a set of tall columns
erected on the foundation. The latter system constitutes the underjet ovens.
The method of control of gas and air supply differ in the two systems. In the
former type, gun flues are required for gas supply. The heating flues in the
combustion chamber may be horizontal (Semet–Solvay), or vertical (Koppers
cross-regenerative, Simon Carves, Wilputte, Otto, Soviet PVR, Didier,
Koppers–Becker and Soviet PK). The vertical flue ovens again differ in the
manner of grouping of the flues. The most important consideration in the
choice of heating flues is that horizontal flues are points of weakness in the
brick structure. The situation gets worse with the large ovens and particularly
with the compound ovens which need larger diameter flues for the passage of
larger volume of combustion products from the blast furnace gas. Horizontal
flues cannot be completely avoided even in the vertical flue systems because
the combustion gases need a horizontal passage (bus flue) for movement.
Koppers cross-regenerative ovens, Simon Carves (old), Carl Still and Wilputte
ovens suffer from this disadvantage. Twin-flues in Otto, Soviet PVR ovens and
Simon Carves (new) and crossover-flues in Koppers–Becker as well as the
Soviet PK ovens have minimised the weakness of the brick structure by
restructuring the horizontal flue length to the minimum. In the twin-flue system
the combustion gases of the vertical flue leave the combustion chamber
through the neighboring vertical flue (Fig. 4.11). Thus only two neighbouring
flues are connected through a very short horizontal passage at the top. In the
crossover-flue system the vertical flues are combined into six to seven groups
by short horizontal flues at the top and the horizontal flues are each connected
with one crossover flue (Fig. 4.12). The crossover-flues pass through the oven
roof and serve as the connecting links between the two combustion chambers
at the two sides of an oven. All the vertical flues of one of these combustion
chambers serve as the heating flues at one time while those of the other
combustion chamber act as the passage for the flue gases into the regenerator
below. After the reversal, the vertical flues of the two combustion chambers
interchange their function.
Figure The Otto underjet hairpin flue oven
4.11
Figure 4.12 Coke oven with gas gun and crossover flue heating system
The operation of by-product ovens is as follows. The charge for the ovens
is first prepared by an elaborate procedure based on careful considerations
(Fig. 4.13). It consists of a blend of finely ground, say, 100% below 3 mm, and
well mixed coals of different caking and coking properties. The coke oven
charge is stored in service bunkers attached to the battery. Periodically a
charging car receives the required quantity of the coal blend, moves over the
rails laid down on the roof of the battery and releases the charge into an empty
closed-door oven through the charging holes. The charge is levelled at the top
by moving a bar through a hole at the front door. All holes are then closed.
Carbonisation proceeds and the resultant gases and vapours escape through
the standpipe for further treatment. After the coking period, usually 14 to 16
hours, the doors are opened and the glowing coke mass is discharged by the
machine-driven coke pusher, into the coke-quenching car. The emptied oven is
made ready for a fresh charge according to a properly maintained schedule.
The hot coke is quickly quenched by a voluminous water spray and then
dropped on the coke wharf. Dry quenching is also practised by circulating flue
gases over the hot coke. In this case the sensible heat of the coke is partly
recoverable in the form of steam raised in waste heat boilers which are run on
the heated flue gases. From the wharf the coke is sent for screening and then
the screened sizes are properly disposed of.
Figure 4.13 Two alternative flow-sheets, A and B, for coal preparation
In modem coke ovens with a flue temperatures of 1,300–1,350°C, the

productivity is 40 to 50 kg/m3 per hour of oven volume and 9–20 kg/m2 per
hour of oven heating wall surface.
4.4.3 RECOVERY OF BY-PRODUCTS
The gases and vapours leave the ovens at 600—700°C and pass a spray of
flushing liquor at the goose-neck of the standpipe. The gas temperature drops
sharply to about 80°C. Tar and steam are largely condensed here. The liquid
and gas streams enter into a big horizontal pipe (hydraulic main or foul main)
which is connected with all the ovens by the standpipes. The foul main delivers
the streams to the by-product recovery section by a crossover-pipe.
Depending upon how ammonia is recovered, the process of by-product
recovery is called direct, indirect or semidirect. In the direct process ammonia
is fully recovered in the form of ammonium sulphate. In the indirect process it is
recovered fully as an aqueous ammonia solution which may be later converted
into the sulphate. In the semi-direct process, ammonia is recovered partly as
the aqueous solution and partly as the sulphate. Owing to practical difficulties
and production of inferior products, the direct process is not used in practice.
Both the indirect and semi-direct processes are widely used. Figure 4.14 gives
a flow chart of the semi-direct process.
Figure Flow diagram of semi-direct process

4.14
The crossover pipes deliver the liquid and gaseous streams to a down-
comer which separates the two streams. The liquid stream of liquor and
condensed tar is sent to a decanter (settling tank) where they separate into two
layers. The heavier layer of liquor goes to the flushing liquor circulation tank.
The gases are cooled down to about 30°C in the primary cooler which may
work on direct (packed) or indirect (tubular) principle. Almost all the residual tar
vapours in the gas stream are completely condensed here. The water vapours
are also largely condensed during the cooling process. A part of the ammonia
gets dissolved in the liquor. The condensed tar and liquor are sent to a
decanter. The cooled gases enter the exhausters.
The exhausters are essentially turbo-blowers ensuring smooth flow of
gases in the entire by-product recovery section of the plant. The gases from
the exhauster are admitted to the electrostatic preciptators which completely
remove the minute droplets of tar (tar mist or tar fog) remaining suspended in
the gas. The tar-free gas is heated to about 50°C to 60°C in the reheater and
then bubbled through a weak sulphuric acid solution in the saturator. Reheating
of the gas serves to increase its water vapour carrying capacity and keeps the
volume of the saturator solution down to a minimum. Ammonium sulphate is
formed in the saturator and recovered in the form of crystals. The gases
leaving the saturator pass through an acid trap for the removal of the entrained
acid droplets and are then cooled in the final cooler (direct type) to about 20–
25°C before they are ready for the recovery of crude benzol. The cooled gases
are subjected to an absorption treatement in a solvent (wash oil) in packed
towers (benzol scrubbers). The benzolised oil is steam-distilled for the recovery
of crude benzol. The debenzolised oil is recycled.
The gases leaving the benzol scrubbers contain sulphur compounds which
are removed by one of the many processes available for the purpose. The
clean coke oven gas is finally stored in gas holders. If the gas is to be
transmitted over long distances through distribution pipes it should be carefully
treated for minimising the content of naphthalene and water vapour which can
choke and corrode the pipe lines.
The ammonia-containing liquor poses a big handling problem for a coke
plant. The problem is lessened to some extent by using the indirect primary
cooler in place of the direct type. The liquor may be treated in an ammonia-still
for the recovery of ammonia vapours which are either admitted to the main gas
stream before entering the saturator for conversion into ammonium sulphate,
or condensed into concentrated ammonia solutions.
4.4.4 COKE OVENS IN INDIA
Coke was first manufactured in India towards the end of the nineteenth century
in beehive ovens for the iron and steel works at Kulti near Raniganj. Since then
the number of beehive ovens has been on the increase.
About 5000 beehive coke ovens are located in Jharia, Bokaro–Ramgarh–
Karanpura and Raniganj coalfields. The larger batteries are of 20 to 30 beehive
ovens each. The coke yield from a Jharia battery of 20 ovens is about 63%. By
better control of the combustion conditions the yield may be raised to 72% and
the coking time reduced from 72 to 60 hours.
In view of the low capital cost and simplicity of construction and the fact
that beehive ovens can be shut down without any damage to the refractories,
further installation of beehive ovens may be undertaken for the supply of hard
coke to foundries and other consumers.
The first by-product coke plant was built in India in 1909 at Giridih for the
then East India Railway. The first crude benzol recovery unit, however, was
installed in 1920 at the Bararee coke plant. The others are merchant plants for
supplying coke to foundries and to various other consumers. Diverse types of
ovens have been built in the country, namely waste-heat and regenerative,
horizontal-flue and vertical-flue, gun-flue and underjet, twin-flue and cross-
regenerative, compound and rich-gas-fired. Currently the trend is to build twin-
flue, underjet, compound ovens in the big modem coke plants of iron and steel
plants. The total installed coking capacity is about 20 Mt while the coal
throughput is about 14 Mt.
4.4.5 PRODUCTS OF HTC IN COKE OVENS
Coke, tar, crude benzol, ammonia (as concentrated aqueous solution or

ammonium sulphate crystals) and coke oven gas are usually produced by coal
carbonisation in by-product ovens. The typical yields on a dry basis should be
generally, coke 78%–80%, tar 3%, crude benzol 0.8%, ammonia (as sulphate)
1% and coke oven gas 330 Nm3/t. Other recoverable substances include
sulphur (elemental or as sulphuric acid), pyridine, picoline, thiocyanates and
ferrocyanides.
Typical yields from a steel plant coke oven in India are (on a dry charge):
coke 77.3%, tar 2.8%, crude benzol 0.24% and gas 270 Nm3/t.
Given the right type of coals, HT coke is much harder than LT coke, hence,
the former is termed hard coke while the latter is known as soft coke. The hard
coke produced in the coke plant is screened to various size grades, the
nominal sizes being: extra large >100 mm, large 100–25 mm, medium 40–25
mm, small 25–10 mm and fine 10–0 mm. The respective trade names are
foundry coke, blast furnace coke, nut coke, pearl coke and coke breeze. The
large sizes are used in blast furnaces, foundries and water gas generators.
Medium size is also now used in blast furnaces. Excepting coke breeze the
other size grades are used as domestic or industrial fuel. The disposal of coke
breeze is a problem. It may be used in boilers, sintering furnaces, and also in
coke oven charges in small quantities. Typical yields of various size grades of
coke on screening in a coke plant in India are: up to medium 82%, small 6%
and breeze 12%.
Coal tar forms as a result of the secondary cracking reactions of the
primary tar vapours in the high temperature conditions prevailing in the empty
space over the charge and on the surface of coke oven walls. It is a complex
mixture of aromatic and heterocyclic compounds together with small amounts
(less than 5%) of non-aromatic hydrocarbons. Over 500 individual compounds
have been identified and many more minor components await identification.
The composition varies from tar to tar, depending on the nature of the coal and
the coke oven conditions. The concentrations (per cent by weight, dry basis) of
the important components in a typical tar are: benzene 0.25, toluene 0.2,
xylenes 0.2, phenol 0.6, cresols 1.0, naphthalene 8.0, anthracene 1.0,
phenanthrene 6.0, carbazole 1.5 and diphenylene oxide 1.5. Coal tar is rightly
called a storehouse of chemicals.
Direct extraction of the components of coal tar is extremely difficult, if not
impossible. The commercial practice is to distil the tar into several fractions and
then recover the various components either in pure form or as concentrates.
The pure compounds and concentrates obtained fron coal tar are widely
used in the manufacture of dye-stuffs, pharmaceuticals, plastics, explosives,
motor spirits, solvents, disinfectants, absorbants and timber preservatives.
Coal tar and some of its oily fractions act as excellent furnace oils. Pitch is
used in surfacing roads and roofs and also in the production of carbon
electrodes and other carbon articles.
Like coal tar, crude benzol also differs in composition from plant to plant. It
is a mixture of a large number of compounds, of which the following are
important: benzene 65, toluene 15, xylenes 5, naphthalene 1.5, carbon
disulphide 0.5, and unsaturated compounds (such as cyclopentadiene) 10, all
as per cent by weight. These compounds are recovered in various grades of
purity and widely used in diverse fields of the chemical industry. The methods
of recovery involve distillation and subsequent treatment of fractions.
The coke oven gas is also the result of secondary cracking reactions to
which the gases and vapours of carbonisation are subjected and hence
hydrogen forms its principal component. A typical composition is H2 54.0, CH4
28.0, CO 7.4, N2 5.6, CO2 2.0, CnHm 2.6, and O2 0.4%. The corresponding
gross calorific value is 5020 kcal/Nm3 (dry) and 4450 kcal/Nm3 (wet). This gas
is a good source of hydrogen for the production of ammonia, for example, in
the fertiliser plant at Rourkela. Fractions of hydrogen and hydrocarbons are
obtained by compression and liquefaction. The hydrocarbons give additional
hydrogen by partial combustion or reaction with steam. Methanol industries
may also use the hydrogen from coke oven gas. Owing to its high calorific
value, the coke oven gas is widely used as a rich gaseous fuel by itself or in
admixture with lean gases like blast furnace gas in steel mills and other
industries.
4.4.6 PROPERTIES OF COKE
Coke is a hard, porous, carbonaceous material used mainly as a source of

reactive carbon in blast furnaces, foundries and gasifiers and also as a fuel in
boilers and heating appliances. Apart from its size, three important properties
of coke are its purity, strength and reactivity. The purity is ascertained by
determining its moisture, ash, sulphur and phosphorus content. The
percentage of volatile matter is essentially a rough guide of the extent of
carbonisation. The ash and phosphorus are concentrated in coke during
carbonisation while the percentage of sulphur in the fuel may remain practically
the same due to the removal of volatile sulphur together with volatile matter of
coal. The purity of coke is ascertained only by the purity of the coal carbonised.
There are many tests for evaluating the strength and hardness of coke, of
which the Shatter and the Micum tests are the standards in India for evaluating
metallurgical coke. In the Shatter test, a coke sample is dropped from a height
on to a metal-plate and the hardness is reported as a percentage of oversizes
on specified sieves. In the Micum test, the coke samples are put into cylindrical
metal drums which are then rotated about the horizonal axis at a definite rate
for a definite period; angle irons attached to the inner periphery of the drums
carry up some of the coke pieces and drop them from a certain height thus
giving a combined effect of abrasion and shatter. The results of screening
degraded coke are expressed as indices for the strength and hardness of the
original coke. An efficient operation of blast furnace needs minimum voidage of
its charge for the heterogeneous reactions between the solid and gaseous
materials. Out of the three components of the charge, coke has to play the
dominant role in preserving the voidage which is disturbed by the formation of
fines during the downward movement of the charge.
There is no standard test for evaluating the reactivity of coke for
metallurgical uses. However, a specified minimum porosity indirectly ensures
its reasonable reactivity. The porosity is calculated from the true and apparent
specific gravities of the sample.
The reactivity of coke for general uses may be determined with respect to
oxygen or air, carbon dioxide, steam and sulphur. The critical air blast (CAB)
test measures the reactivity to air by determining the minimum rate of air blast
which will maintain combustion of closely graded fuel in an ignited bed of
specified dimensions. The more reactive the coke the lower the CAB value.
This test has been standardised in India together with another test which
indirectly gives a measure of the reactivity from the thermal value of the volatile
matter of the coke. The more reactive cokes have higher thermal values of
their volatile matter.
The IS specifications for domestic coke and industrial coke are given in
Tables 4.11 and 4.13 respectively.
Table 4.13 Specification for domestic coke (IS 4286-1976)
Characteristic Class 1 Class 2 Class 3
Volatile matter, per cent dry 3–10 3–10 3–10
Moisture, per cent max 8 8 8
Ash, per cent max 30 40 50
Note: In the case of processed fuel made from lignite, VM not exceeding 15% may be
permitted.
An important property of coke for its storage and transport is its bulk
density. The values expressed in kg/m3 for different types of cokes are given
below.
Source Sized (18–40 mm) Unsized

Coke oven 417–480 465–513
Horizontal retort 368–417 400–148
Continuous vertical retort 337–453 368
Low temperature retort 305 320
It is noteworthy that the bulk density of coal lumps is 640–800 kg/m3. Thus
coke is much lighter than coal and needs much higher capacity in storage and
handling for the same weight. The true density of coke is, however, quite high
at 1750–2000 kg/m3.
4.5 BRIQUETTING OF SOLID FUELS
The process of briquetting consists in applying pressure to a mass of particles

with or without the addition of a binder and converting it into a compact or
agglomerate. The products are called either briquettes containing binders or
binderless briquettes, as the case may be. The object of briquetting is to
convert a low-grade solid fuel into one of higher quality. Sawdust, peat, lignite,
and coal fines, can all be briquetted into lumps of suitable size, shape and
strength and used as convenient domestic and industrial fuels. Fuel briquettes
in some form or other are almost universally used. Countries manufacturing
fuel briquettes on a commercial scale include East Germany, West Germany,
the old USSR, France, Holland, the UK, Spain, Belgium, the USA, Hungary,
Poland, Czechoslovakia and India. India produces 13.97 Mt per year of lignite
at Neyveli and 6.68 Mt per year in Gujarat.
4.5.1 BRIQUETTING OF LIGNITES

The process of briquetting is most widely used in the case of lignites or brown
coals. Owing to the low structural quality of lignite, considerable amounts of the
fuel are recovered as fines during mining; the coarser pieces disintegrate into
fines after air drying. Briquetting is therefore an essential prerequisite for
burning lignite in domestic ovens and stoker furnaces. However pulverised fuel
combustion as in thermal power stations does not need this preparative step.
Binders are not required in the briquetting of lignite and comparatively low
pressure suffices in achieving the compaction of its particles. These
considerations have contributed to the early commercial success of the
process.
The briquetting of lignite involves three steps—grinding, drying and
pressing. The formation of a good briquette requires that the grains are of a
certain uniform size and optimum moisture content. Under these conditions the
particles can approach very close to each other and allow the cohesive forces
to come into play when an external pressure is applied. The process variables
depend essentially on the nature of the lignite. No universal conditions can be
laid down. The outline of the briquetting plant at Neyveli is given below.
Raw lignite is crushed to below 250 mm size in a blade crusher and stored
in a bunker. This is further ground to below 50 mm in a roller crusher, and
finally to below 8 mm in a hammer mill. The ground, but wet, lignite with a
moisture content of 50%–56% is dried in a steam-tube rotary drier to an
average moisture content of about 9%–l1%. The discharge from the rotary drier
has grain size below 6 mm. Before undergoing final grinding, it needs
pretreatment which involves screening and redrying of the coarse fraction. The
pretreated material is ground to below 1 mm in a hammer mill and then
converted into briquettes by passing through quadruple extrusion presses at a
pressure of about 1000 kg/cm2. No binder is used. The optimum temperature
for briquetting is about 70°C. Cooling of the dried lignite occurs during its
transport from the drier to the press by a conveyor. The temperature rises
during the pressing operation, and therefore it is necessary to allow for cooling
before the briquettes are disposed of.
The lignite briquettes at Neyveli are carbonised at 650°C to 700°C. After
cooling, the carbonised briquettes are sieved over 10 mm screens. The
oversize is marketed under the trade name Leco. The undersize char fines are
also used as industrial fuel.
4.5.2 BRIQUETTING OF BITUMINOUS COAL
Fine coals are produced in large quantities during mining and processing.
Before the advent of pulverised fuel combustion, these fines could be burnt in
ovens and furnaces only after briquetting. Even today the process of
briquetting of coal fines is being increasingly used in many countries since
mechanical mining results in enhanced production of fines and the technique of
pulverised fuel firing is not suitable for domestic ovens and small industrial
furnances.
Briquetting bituminous coal without a binder is difficult. Compared to
lignites, much higher pressures and much finer grain sizes are required.
Therefore, processes that are commercially successful use a suitable binder
like coal tar, pitch or petroleum bitumen. The whole process consists of drying
and grinding the coal, mixing it with the binder, beating the mixture, pressing it
into moulds and cooling the briquettes before final disposal. The moisture
content of the dried coal is maintained at 2%–4%. Pitch and dried coal are
often ground together. The grain size of the ground coal is about 80% less than
0.5 mm and 93% less than 0.88 mm. The pitch content is about 7%–8% of the
coal. The temperature of the mixture is kept at a few degrees within the
softening point of the binder before it is charged into the press. Briquetting
pressure is normally about 150 kg/cm2. The quality of the briquettes depends
upon many factors like the properties of the coal, the properties of the binder,
and the precise way in which the various operations are carried out.
Many binderless briquetting processes have been developed. Economic
considerations stand in the way of their wide commercial exploitation. Hot
briquetting technique consists of preheating a coal blend containing one or
more caking coals to a temperature in the plastic range and then compacting
the mass. The softened coal acts as the binder and the required briquetting
pressure is much lower than in the other binderless briquetting processes for
bituminous coals.
4.5.3 CARBONISED BRIQUETTES
Briquettes of lignites and bituminous coals are carbonised for producing

smokeless lumpy fuel and, to a lesser extent, substitutes for metallurgical coke.
The manufacture of carbonised briquettes requires an additional stage over
and above that required for the conventional coking practice. However, the
process enables the production of coke-like material from lignites, sub-
bituminous coals and non-coking bituminous coals. These are called formed
coke.
There are many processes for the production of carbonised briquettes in
various stages of development. The Lurgi–Spülgas process is one of the most
successful of them. In this process binderless lignite briquettes are first
produced and then carbonised in a three-chamber unit as described in the
section on low temperature carbonisation. The carbonisation temperature may
vary between 500°C and 850°C depending upon the use of the product as
domestic or metallurgical fuel. The higher temperature reduces the volatile
matter and considerably increases the strength of the briquettes. Briquettes
meant for metallurgical fuel production are made at high pressures, about 2000
kg/cm2 in ring-roll presses.
Briquettes are susceptible to deformation, fissuration and crumbling during
carbonisation. The rate of heating during carbonisation is extremely important.
In the case of coal briquettes, the quantity of pitch must not be excessive and
the highly coking coals need pretreatment like oxidation or partial carbonisation
before briquettes are made from them.
The technique of briquetting has also been employed for the production of
agglomerates of fuel with one or both of iron ore and lime. The products,
ferrocoke and fluxed coke are meant for iron production, but are not yet
commercial commodities.
4.6 GASIFICATION OF SOLID FUELS
Solid fuels can be gasified by reaction with air, oxygen, steam, carbon dioxide,
or mixtures of these, into a product that is suitable for use either as a fuel or as
a raw material for making chemicals, liquid fuels or other gaseous fuels.
Carbonisation may be considered as a partial gasification process yielding
solid, liquid and gaseous products from the initial solid fuel. Most of the
gasification processes, however, strive for total gasification of the solid fuel.
The gasification of coal is at present the subject of intense development
activity. It is believed that a considerable portion of the coal consumed in future
will be first gasified. There are many considerations behind the importance
given to gasification: (i) the general advantages of using gaseous fuels (see
Chapter 6), (ii) the product gaseous fuel is cleaner and therefore,
environmentally more acceptable, and (iii) overall rise in efficiency of use of
coal if gasification route is involved.
Gasification processes may be classified in a number of ways:
1. By the method of supplying the heat required
(i) Internal heating

Autothermic, for example, producer gas
Cyclic, for example, water gas
Heat carrying fluids or solids, for example, Koppers process
(ii) External heating or allothermic
2. By the method of contacting reactants

(i) Fixed bed. for example, producer gas, water gas, Lurgi
(ii) Fluidised bed, for example, Winkler
(iii) Suspension of particles in gasifying medium, for example, Koppers
Totzek
3. By the flow of reactants
(i) Cocurrent, for example, Koppers-Totzek

(ii) Countercurrent, for example, producer gas
4. By the gasifying medium
(i) Air with steam, for example, producer gas

(ii) Steam with oxygen or air or oxygen-enriched air, for example, water ga
Koppers–Totzek, Lurgi, Winkler
(iii) Hydrogen in hydrogasification
5. By the condition of the residue removed
(i) Dry ash in nonslagging operation (all the common gasification processe
fall in this group)
(ii) Slag in slagging operation
Some of the more important gasification processes will be taken up later in

Chapter 6.
4.7 LIQUEFACTION OF SOLID FUELS
In analogy to gasification, the term liquefaction of solid fuels is used to cover all
the processes that convert solid fuels into liquid products which may be either
used directly as fuel, or converted into chemicals or other liquid fuels. Owing to
the recovery of crude benzol or coal tar, the carbonisation process may be
described as partial liquefaction of coal. The production of shale oil from shales
by heating in retorts also falls in this category.
Hydrocarbon-type liquid fuels are obtained from solid fuels by the following
routes:
1. Hydrogeneration of coal, for example, Bergius–Pier process,
2. Solvent extraction of coal and hydrogenation of coal extracts,

3. Refining of tar and oil obtained by the carbonisation of various solid fu
oil shales,
4. Gasification of solid fuels into synthesis gas and conversion of the lat
liquid fuels and chemicals, for example, Fischer–Tropsch proces
methanol synthesis.
Much work has been going on to develop these processes into economical
propositions. The world has only one Fischer–Tropsch plant, SASOL in South
Africa, and a few bituminous and brown coal tar refining plants in East
Germany, West Germany and Czechoslovakia. Chapter 5 includes a treatment
of these and other processes for making liquid fuels from solid fuels.
It is a century-old concept that coal fines may be dispersed in fuel oil and
the resultant colloidal fuel may be burnt like a liquid fuel with an added
advantage of high flame emissivity. This dormant concept has been revived in
the seventies to conserve petroleum fuel, and now the liquid medium is offered
by water, oil, methanol or a mixture of any two or all of them. All technological
problems appear to have been nearly solved for the coal–liquid mixture (CLM)
to be a viable alternative fuel to partially displace fuel oil and gas.
Coal should be in a very fine state: for example, 80% below 75 µ, and
100% below 200 µ. This is difficult for Indian coals with poor grindability.
However, larger sizes may be used with suitable dispersants and other
additives. Coal loading of 50%–80% has been achieved—the higher figure with
coal–water mixtures (CWM) and the lower with coal–oil mixtures (COM). Coals
of any rank may be used. CWM system may be easily integrated with a coal
preparation plant and its high potential lies in the fact that the high ash
middlings and tailings may be used as CWM in fluidised bed combustion
systems. COM is already commercialised in many countries. CWM is also a
mature technology approaching commercialisation rapidly. It has a potentially
lower cost than coal liquefaction and gasification due to the lower capital and
operating costs. The main application of COM is in boilers and furnaces. It has
a high potential as injection fuel for blast furnaces and as feedstock for
gasifiers. Heat engines like stationary diesel engines are a potential target; the
coals have to be extra-clean at 2% ash.
Example I
The float-and-sink test data for an Indian coal and European coal are given below.
A European coal crushed below 4 An Indian coal crushed below 3
mm mm
Specific yield per cent ash per cent yield per cent ash per cent
gravity
A European coal crushed below 4 An Indian coal crushed below 3
mm mm
Specific yield per cent ash per cent yield per cent ash per cent
gravity
Below 1.30 37.7 3.2 1.2 2.1
1.30–1.40 31.3 5.8 6.0 9.6
1.40–1.50 2.9 24.9 38.4 19.6
1.50–1.60 2.8 32.3 43.0 25.2
1.60–1.70 1.2 44.1 6.6 34.2
1.70–1.80 0.7 57.5 2.5 41.6
Above 1.80 23.4 78.6 2.3 57.4
Total 100.0 23.6 100.0 23.6
Without drawing the washability curves, what information can you extract
from these data on the ease or difficulty of washing the two coals?
Solution
Yields of fractions between 1.40 and 1.60 specific gravity
European coal: 2.9 + 2.8 = 5.7%

Indian coal: 38.4 + 43.0 = 81.4%
This shows that the Indian coal (even after crushing below 3 mm) contains
large quantities of particles where organic mass and mineral matter are
intimately associated. The European coal contains a very small portion of such
particles. Therefore minerals can be easily separated from the European coal
while this is not so in the case of the Indian coal. This is confirmed by the high
yield of 69% with ash below 5.8%, obtainable from the European coal at a
specific gravity of 1.40. The intimately associated nature of the mineral matter
in the Indian coal is evident from the high ash value between 19.6% and 25.2%
on the 1.40–1.60 fraction with a high yield of 81.4%.
If 1.50 is chosen as the specific gravity of washing, the fraction 1.40–1.60
forms the near gravity material. Table 4.2 shows that the coal washing problem
will be simple for the European coal and formidable for the Indian coal.
However, by tolerating high ash in the clean product if we choose 1.7 as the
specific gravity of washing for the Indian coal,
ngm = 6.6 + 2.5 = 9.1%
Therefore the coal washing problem becomes moderately difficult.

Ash of the product at 1.70 specific gravity.
Example 2
In a central washery in India with a feed coal of 21.0% ash content, the clean
product has an ash content of 18.7% and the sinks have an ash content of
41.2%. If the theoretical recovery is 91.6% for a product of the same ash level,
estimate the performance of the washery.
Solution
Using the ash balance, the plant yield of clean product
PROBLEMS
1. The float-and-sink analysis of an Indian coal is given below. Construct the

important washability curves and comment on the washability characteris
the coal.
Specific gravity Yield per cent Ash per cent

Below 1.30 8.57 3.9
1.30–1.40 47.25 12.6
1.40–1.50 13.31 21.8
1.50–1.60 12.13 30.4
1.60–1.70 12.04 40.1
1.70–1.80 3.30 49.9
Above 1.80 3.40 61.3
2. The following table gives the float-and-sink analysis of a European coal

constructing the washability curves, compare its washability characteristic
those of the Indian coal given in Problem 1.

Below 1.30 66.88 3.75
1.30–1.40 7.22 11.70
1.40–1.50 5.71 21.75
1.50–1.60 2.55 30.70
1.60–1.80 3.44 41.40
Above 1.80 14.20 73.50
3. For the two coals in Problems 1 and 2, choose the suitable specific grav
washing and estimate the ease/difficulty of washing from the amount of
gravity material. (Use Table 4.2).
4. On washing in a plant, the coal of Problem 2 gave a product of 7.3% as

yield of 79.5%. Evaluate its performance.
[Answer: Yancey and Geer η) = 94.4%]

5. The feed to a coal washing plant contains 20.9% ash and its washability
indicates a yield of 77.5% clean coal with 7.9% ash at the chosen sp
gravity. However the actual product has an ash of 9.0% and the rejects
an ash of 67.2%. Evaluate the performance of the washery. (Calcula
plant yield from the ash balance and then the washery efficiency from th
two formulae. For calculating yield at the same ash level, assume
relation between yield and ash).
[Answer: Fraser and Yancey η = 94.0%, Yancey and Geer η = 90.2%]

6. The float-and-sink test data of an American coal are given below. Washin
jig gave a char product of 13.9% ash and refuse of 53.4% ash. Rat
performance of the jig.
[Answer: Yancey and Geer η = 88.4%]

7. An Indian coal gave the following float-and-sink data. A cyclone w
produced a product of 19.3% ash with a yield of 53.0%. How did the cy
perform ?
[Answer: Yancey and Geer η = 90.5%.]

BIBLIOGRAPHY
1. Bureau of Indian Standards, New Delhi.
a. IS: 437 (1979) Size grading of coal and coke for marketing
b. IS: 1354 (1992) Test for coke – special tests.
c. IS: 4023 (1991) Reactivity of coke.

d. IS: 7929 (1975) Determination of electrical resistivity of chemical coke.
2. Coal Carbonisation, The Wealth of India, Industrial Products, Pt. II,128, 195
3. Coal Tar, The Wealth of India, Industrial Products, Pt. II, 142, 1951.
4. Ghosh SR, Sarkar S, Das Gupta NN and Lahiri A. Properties of coal and
for metallurgical uses, Journal of Mines, Metals and Fuels, Special Issu
Coal Carbonisation, 305, 1959.
5. Grainger L and Gibson G. Coal Utilisation – Technology, Economics and P

London: Graham and Trotman, 1981.
6. Lowry HH, (ed.). Chemistry of Coal Utilisation, Vol. 1, New York: Wiley, 194
7. Ratnam CVS. Chemical engineering in the utilisation of lignite, Chemical

of India, Vol..20 (2), 129, 1969.
8. Sarkar S. Kinetics of coal carbonisation reactions in the plastic state, J.

Ind. Res., 19B: 246–8. 1960
9. Sarkar S. Rational utilisation of India’s coal resources, Urja, 143, Aug. 1987
10. Studies on Coal Preparation in India. Central Fuel Research Instit

Dhanbad, 1972
11. Tsai SC. Fundamentals of Coal Beneficiation and Utilisation. Amsterda

Elsevier, 1982.
12. Whitaker JW and Sarkar GG. Studies in Coal Washability, Parts 1, 2, 3 (195
Parts 4, 5, 6 (1951), Parts 7, 8, 9 (1953). Central Fuel Research Instit
Dhanbad.
13. Wilson PJ and Wells JH. Coal, Coke and Coal Chemicals, New York: McG
Hill, 1960.
5 Liquid Fuels
5.1 INTRODUCTION
The importance of liquid fuels is best exemplified by the fact that almost all
internal combustion engines run on them. Life would come to a standstill if
we are denied this commodity, either from nature or from synthetic sources.
The use of liquid fuels in heat generation in ovens and furnaces is
expanding rapidly. The development of highly efficient oil burners of widely
varying burning rates has made this possible. Furthermore, we are
increasingly dependent on petroleum as a source of carbon and hydrogen
for the production of chemicals, fertilisers, dyestuffs, plastics, detergents
and fibres.
Petroleum accounts for the bulk of the liquid fuels. The other liquid fuels
in use are coal tar, crude benzol, synthetic liquid fuels made from coal,
shale oil, alcohol and oil from tar sands.
5.2 PETROLEUM
The term petroleum means oil obtained from the earth. Mineral oil, crude
petroleum, crude oil, crude or simply oil are other names for petroleum.
Petroleum varies widely in appearance. It may be a straw-coloured liquid or
even a black, viscous material. Most petroleums, however, are dark-
coloured, highly mobile liquids in which gas is dissolved and solids are both
dissolved and dispersed. Sometimes, the gas separates naturally and gives
rise to reserves of natural gas. Once the liquid and gas are removed, the
solids are separated on exposure to the surface of the earth and a natural
asphalt deposit results. Harder types of natural asphalt are readily mistaken
for a sapropelic coal.
Petroleum occurs in a reservoir rock which has fluid holding capacity,
porosity and fluid transmitting capacity and permeability. Most reservoir
rocks are sedimentary rocks consisting of coarse-grained minerals, such as,
sand, sandstone, grit, limestone and dolomite. The upward migration of the
fluid from the reservoir rock is prevented by an upper stratum called cap
rock or sealing formation. A cap rock has very fine pores and low
permeability. Typical cap rocks are clays and shales. The migration of the
fluid in other directions is prevented by suitable geological formations of the
reservoir rock and cap rock. These are known as oil traps. In principle, the
boundary between the cap rock and the reservoir rock should be convex
upward. The exact form varies widely. The simplest forms are flat-lying
convex lens and the anticline and dome. The trapping of oil and gas is
facilitated by the presence of water or brine seals (Fig. 5.1).
Figure 5.1 Vertical cross section of an anticlinal accumulation of oil and gas
Exploration for oil reservoirs is conducted by geological and geophysical

techniques. Once promising rock structures are confirmed, the actual
presence of oil is established by drilling. Usually, several deep bores are
drilled to prove the existence or absence of a commercial reservoir.
Petroleum deposits occur in most parts of the world but commercial
quantities are produced mainly in a wide belt stretching from Indonesia
through Myanmar (Burma), India, the Middle East and Central Europe to
North and South America. The most widespread distribution is in the
continent of North America, throughout the United States, Canada and
Mexico. The major oil fields are located in the Middle East (mainly Saudi
Arabia, Iran, Kuwait, Iraq and Abu Dhabi) accounting for about 56.3% of the
world proved reserves of petroleum of about 1.317 billion barrels (Table 1.2
and Fig. 1.2). The other major oil-bearing countries are Russia 8.6%,
Mexico 7%, USA 5%, Venezuela 3.6%, Libya 3% and Nigeria 2.3%.
Petroleum production in India

About 1.4 Mkm2 or about 42% of total land area in India consists of oil
yielding sedimentary rocks. The offshore sedimentary basin exists up to a
water depth of 200 m with an area of 0.4 Mkm2. India’s first oil well, 31m
deep, was drilled with a steam-powered drill near an oil seepage at Nahar
Pong in Assam in 1866. It failed to strike oil. On 26 March 1867, oil was
struck at 35.5 m at Makum in the Digboi area. A few more wells were dug
and commercial production was successful by 1889—only 30 years after
the drilling of the Drake well in the USA. Initially the crude was refined in a
small refinery at Margherita. The first full-fledged refinery was
commissioned at Digboi in 1899, with a capacity of about 90 kl per day.
Through the exploration work of government and semi-government
agencies, several more oil fields have been discovered—Ankleswar, Kalol,
Sanand, Nawagam, North Kadi, and others in Gujarat, Moran-Nahorkatiya,
Hugrijan, Rudrasagar, Lakwa and Galeki in Assam, Bombay High and
Cambay in the western offshore, Palk Strait in the south and the Godavari
offshore in the east. Exploration is going on to ascertain the proved and
recoverable oil deposits in the country.
The story of Bombay High [ONGC (Mumbai High)] is fascinating. The
first step in offshore exploration was taken by the Oil and Natural Gas
Commission (ONGC) in 1962 in the Gulf of Cambay. The Bombay High was
delineated by seismic surveys during 1964–67. Then the pace quickened
and detailed seismic surveys were carried out. In view of the difficult
bydrometeorological and sea-bed conditions, foreign experts were
consulted. The jack up drilling rig, Sagar Samrat, arrived in Bombay in
1973.
Commercial production was started in May 1976 at the rate of 4300
barrels of oil per day (BOPD) or 0.2 million tpy. The contribution of Bombay
High led to a sharp rise in the production figure. Table 5.1 gives the crude
oil reserves up to 2007. The total reserves in 2007 stand up to 726 million
tonnes, out of which 49% was in the onshore area and the remaining 51 %
was in the offshore area.
Table 5.1 Reserves of crude oil in India (million tonnes)

Area 1990 2000 2002 2003 2004 2005 2006 2007
Onshore 307 317 332 339 357 376 387 357
Offshore 432 386 409 422 382 410 369 369
Total 739 703 741 761 739 786 756 726
Source: Ministry of Petroleum and Natural Gas, Govt. of India, Petroleum Statistics, htt
p://petroleum.nic.in/petstat.pdf
The state-wise crude oil production is shown in Table 5.2. The total
production in 2005–06 was 32.190 Mt, out of which Bombay High alone
accounted for 16.309 Mt (or 50.7%). Among the onshore companies, Oil
India Limited accounted for about 3.2 Mt in 2005–06 and ONGC for about
8.1 Mt.
Table 5.2 Production of crude oil in India (thousand tonnes)
It is of interest to note from Table 5.2, compared to Table 5.1, that the
crude oil production in the country is very low in comparison to total
reserves. There is thus a high scope for expansion in the production figures
by expanding the existing refineries/establishing new refineries. According
to the report of the Ministry of Petroleum and Natural Gas, 2005, there were
18 refineries in the country with a total capacity of 127.4 Mt per year, the
throughput being as high as 127.1 Mt so that the per cent utilisation of the
capacity was very high (99.8). Table 5.3 gives the break-up of the refineries
in India. Gujarat has the two largest refineries: Reliance Industries Limited
at Jamnagar (33.0 Mt per year) and the India Oil Corporation at Koyali (13.7
Mt per year). Mention may also be made of the Mangalore refinery in
Karnataka (9.7 Mt per year) and the Manali refinery in Tamil Nadu (9.5 Mt
per year). The Haldia refinery in West Bengal is also mentionable (6.0 Mt
per year).
Table 5.3 Company-wise locations and capacity of refineries as on 1 July 2005
(million metric tonnes per annum)
SI. Name of the company Location of the Capacity
No. refinery (mmtpa)
1. Indian Oil Corporation Ltd. (IOCL) Guwahati 1.00
2. IOCL Barauni 6.00
3. IOCL Koyali 13.70
4. IOCL Haldia 6.00
5. IOCL Mathura 8.00
6. IOCL Digboi 0.65
7. IOCL Panipat 6.00
8. Hindustan Petroleum Corporation Ltd. Mumbai 5.50
(HPCL)
9. HPCL Visakhapatnam 7.50
10. Bharat Petroleum Corporation Ltd. Mumbai 6.90
(BPCL)
11. Chennai Petroleum Corporation Ltd. Manali 9.50
(CPCL)
12. CPCL Nagapattnam 1.00
13. Kochi Refineries Ltd. (KRL) Kochi 7.50
14. Bongaigaon Refinery & Petrochemicals Bongaigaon 2.35
Ltd. (BRPL)
15. Numaligarh Refinery Ltd.(NRL) Numaligarh 3.00
16. Mangalore Refinery & Petrochemicals Mangalore 9.69
Ltd. (MRPL)
17. Tatipaka refinery (ONGC) Andhra Pradesh 0.078
18. Reliance Petroleum Ltd. (RPL) (Pvt. Jamnagar 33.00
Sector)
Total 127.37
Source: Ministry of Petroleum and Natural Gas, Govt. of India, http://petroleum.nic.in/r
efi.htm
5.2.1 ORIGIN OF PETROLEUM
The origin of petroleum is not satisfactorily proved. A large number of

theories have been suggested from time to time. According to some,
petroleum is of inorganic origin, being formed by the action of water on
metallic carbides or by the interaction of water and carbon monoxide on
alkali or alkaline earth metals. According to others, petroleum was formed
from organic sources, animal or vegetable, by a process of destructive
distillation. All these theories have been rejected because they require
some improbable materials or processes.
The vast pool of information gathered by petroleum geologists, chemists
and geophysicists has led to the emergence of some rational views on the
genesis of petroleum. For the sake of convenience four phases of
petroleum genesis are recognised:
embeddment of organic matter in source beds,
conversion of source material into a fluid,
migration of oil into the reservoir rock,
secondary transformation of oil in the reservoir rock.
It is generally accepted that crude has been derived from the organic matter
originally present in marine sediments. The probable sources are plankton,
marine algae, sea grass and larger marine animals. Some terrestrial and
freshwater plants may also have taken part in petroleum formation. The
absence of a reasonable amount of phosphorus in petroleum is an
argument against the involvement of fish in the processes. The dead
organic matter settles down to the bottom of shallow seas and lagoons. The
settling process is facilitated by the presence of mineral particles
transported by flowing water to places where the current is less strong. The
settled debris is attacked by anaerobic bacteria. Most of the organic
compounds are destroyed and lost. Unsaturated fatty oils and fatty acids
which survive the bacterial attack undergo polymerisation into insoluable
solids. These are buried under the steadily increasing cover of sediments,
while anaerobic bacteria continue to act on them. In the process of
compaction, the water content diminishes from 70%–80% to 10% or less.
As a result of continued bacterial decomposition under anaerobic conditions
(reducing atmosphere), the decarboxylation and other reduction processes
take place and the composition of the organic matter becomes more and
more petroleum-like.
The formation of oil from the consolidated organic material of the source
bed needs a considerable degree of degradation. The presence of thermo-
labile and optically active substances like porphyrines and some nitrogen
and sulphur containing complexes in crudes rule out the involvement of high
temperatures, such as, above 200°C, in the genesis of petroleum. The
probable processes by which the degradation of the source material takes
place are
anaerobic bacterial action,
low temperature cracking in presence of clay and mineral catalysts,
irradiation by radioactive materials associated with sedimentary rocks
Low temperature catalytic cracking is believed to be the major process by

which oil was produced from consolidated source material.
Table 5.4 Installed capacity and refinery crude throughput (thousand tonnes)
With the increase in the overburden, the source rocks are subjected to
compression and cause the liquids to migrate to the reservoir rocks. During
migration the composition of oil may change by filtration, solution or
adsorption. Both vertical and lateral migrations are possible. Oil reserves
were built up by migration of oil from a number of source beds. After
reaching the reservoir rocks, oil may or may not have undergone significant
changes in its composition, depending upon its early history and the nature
of the reservoir rock. The agencies for secondary transformations are
radioactivity, bacterial action and catalytic influence of rocks. An additional
factor in the case of shallow layers that are imperfectly sealed at the top is
evaporation.
The reservoir rocks have been found to belong to widely varying
geological eras, namely palaeozoic, mesozoic, teritiary and quanemary,
(see age of coal deposits, Table 3.16). The bulk of the oil fields are from the
mesozoic (120–200 million years) and tertiary (oilgocenemiocene periods,
20–40 million years) eras. Although it has not been possible to establish the
precise ranks or degree of maturity of crudes of different geological ages, it
appears from general observation that crudes from older reservoir rocks are
lighter and more simple in structure and yield larger amounts of distillates
compared to younger crudes. There are, however, exceptions to this. It has
also been generally found that oils become lighter in going basinward in any
horizon (Hilt’s rule).
5.2.2 PETROLEUM PRODUCTION
Occasionally oil may be obtained from surface outcrops, from hand dug
shallow pits or from seepage into mine galleries. However, the usual
production is only from wells. The method that is mostly used for digging a
well is the rotary drilling system which utilises the principle of torsional
grinding or cutting. The equipment assembly is called a drilling rig and it
consists of four main parts:
Derrick, a tall steel structure equipped with hoisting gear for raisi
lowering the drilling equipment;
Drill column or stem consisting of a main section of steel pipes (dri

with at its lower end some extra heavy pipe (drill collars), to which th
attached;
Rotating mechanism at the upper end of the drill column, that is

surface, which is a hollow bar of square or hexagonal cross sectio
kelly or grief stem), and this slides through a square or hexagonal
the machine (rotary table) which provides the rotary movement;
Mud circulation system at the top of the kelly is the so-called swivel t
which a thin mud (drilling fluid) passes from a flexible hose; the botto
of the swivel revolves with the kelly while the top does not, and the
hose is attached to it. The top part of the swivel is also attached
hoisting mechanism.
The hoisting system is controlled from a working platform built within the
derrick above ground level. A central power unit drives the various moving
parts usually by mechanical power transmission. The heart of the fluid
circulation system is the mud pump plant. The mud is pumped down the drill
pipe through the holes of the bit and returned to the pump section via the
annular space between the drill pipe and the walls of the bore hole. The
mud brings the bit cuttings with it. It is thereafter passed through a vibrating
screen and/or settling pits before it returns to the pump section tank.
An efficient mud circulation is perhaps the most important single factor
required to drill an oil well rapidly without accidents and difficulties. The
drilling fluid serves four principal functions, namely (i) cools the bit, (ii)
flushes out the cuttings, (iii) supports the bore wall by hydraulic pressure,
(iv) penetrates porous rock to form a seal of mud cake and (v) prevents the
escape of oil or gas through pores and cracks. Drilling muds are essentially
colloidal clay suspensions with additives to control viscosity.
The main boring is of 20–30 cm in diameter and the depth of a well may
vary from 1.5–4.5 km. Wells of more than 7.5 km have also been drilled
while quite shallow wells also exist. The entire well is provided with a casing
of steel pipes right upto the productive work layer. This prevents the
collapse of the bore walls and ensures that other extraneous fluids do not
enter the well. A steel tubing is suspended from the well-head up to the oil-
bearing rock. It is provided with control valves and outlet pipe at the well-
head.
Oil is normally under pressure in the reservoir. The source of the
pressure may be a body of compressed gas above the oil or a mass of
water underlying the oil. These pressures cause the oil to flow towards the
foot of the well and drive it up the tubing to the surface (natural flow). When
oil pressure is low or it falls as the oil well is depleted, the lifting may be
done by sending gas at high pressure through the annulus between the
casing and the tubing, or by providing a suitable pumping device at the
lower end of the tubing. Water flooding is another method of secondary
recovery of oil; water is injected into the reservoir rock through separate
wells on the periphery of the oil field.
The total production from each well is piped to a gathering station meant
for collecting the production from a number of wells in the area. The gas is
separated by directing the fluid against baffles in cylindrical pressure
vessels. The water and solids are separated either by settling out in tanks
or by centrifuging. The gas is called wet natural gas. It is processed for the
recovery of LPG and natural gasoline and put to other uses. The crude is
sent to the refinery. Rarely is crude oil directly used.
5.2.3 COMPOSITION OF PETROLEUM
Unlike coal, the ultimate analysis of crude petroleum varies within a narrow
range; carbon 83%–87%, hydrogen 11%–14%, sulphur 0.5%–3%, nitrogen
0.1% (rarely up to 1%) and oxygen 2%–3%. The ash of crudes is only 0.1%
or less. Practically all metals have been found in the petroleum ash; the
most widely occurring elements are silicon, iron, aluminium, calcium,
magnesium, nickel and sodium. A few crude oils contain appreciable
quantities of vanadium.
Crude petroleum is essentially a mixture of hydrocarbons. Paraffins,
naphthenes (cycloparaffins) and aromatics are present in all crudes in
widely varying proportions. Only olefins and acetylenes are absent. Olefins
are formed in the processing of petroleum. Only the lower boiling fractions
of crudes contain different types of hydrocarbon as such. The higher
molecular weight hydrocarbons include complex structures containing
aromatic and naphthenic rings with paraffinic side chains. Sulphur, nitrogen
and oxygen are present in the form of derivatives of hydrocarbons, for
example, aliphatic mercaptans and disulphides, aromatic sulphides,
polyalkylated quinolines, isoquinolines and pyridines, fatty acids, naphthenic
acids, phenols and complex asphaltenes and resins.
5.2.4 CLASSIFICATION OF PETROLEUM
The great variations in the nature and concentration of petroleum

components render it very difficult to evolve a simple but satisfactory
classification system. However, a three group classification is sometimes
used by petroleum refiners for commercial practices. According to this
system, the following three types of crudes are recognised:
1. Paraffin-base crude which produces a residue containing both w
asphalt,
2. Asphalt-base crude which yields a black and lustrons residue of asph
3. Mixed-base crude which produces a residue containing both wa

asphalt.
A misnomer ‘naphthene-base’ is sometimes used in lieu of asphalt-base in

the mistaken belief that the asphalt-base crudes consist largely of
naphthemic hydrocarbons. About 90% of the crudes produced at present
fall in the category of mixed-base.
The above classification is based on the principle that the nature of the
residue determines the nature of the whole crude. This is only of limited
validity. Moreover, the grouping of the bulk of the crudes under mixed-base
also give an incomplete picture. These considerations have led to the
development of a number of improved systems. Out of them, the
classification of Lane and Garton is most widely used (Table 5.5). This is
briefly discussed overleaf.
Table 5.5 Classification of crude petroleum according to Lane and Garton

Sl.N Key fraction 1 Sp.gr.60°/60°F Key fraction 2 Sp.gr. 60°/60°F
o. 15.5°/15.5°C °API 15.5°/15.5°C °API
1. Parafffin 0.8251 or less (40 or more) 0.8762 or less (30 or more)
2. Paraffin- 0.8251 or less (40 or more) 0.934–0.8762 (30 to 20)
intermediate
3. Paraffin– 0.8251 or less (40 or more) 0.934 or more (20 or less)
naphthene
4. Intermediate 0.8251–0.8601 (40 to 33) 0.934–0.8762 (30 to 20)
5 Intermediate- 0.8251–0.8602 (40 to 33) 0.8762 or less (30 or more)
paraffin
6 Intermediate- 0.8251–0.8602 (40 to 33) 0.934 or more (20 or less)
naphthene
7 Naphthene 0.8602 or more (33 or less) 0.934 or more (20 or less)
Sl.N Key fraction 1 Sp.gr.60°/60°F Key fraction 2 Sp.gr. 60°/60°F
o. 15.5°/15.5°C °API 15.5°/15.5°C °API
8 Naphthene– 0.8602 or more (33 or less) 0.8762 or less (30 or more)
paraffin
9. Naphthene- 0.8602 or more (33 or less) 0.934–0.8762 (30 to 20)
intermediate
Note: Figures in brackets give density as degree API. vide section 5.2.7.
Two arbitrary fractions are recovered from the crudes on the basis of boiling
range: (i) 250–275°C at 1 atmosphere pressure, and (ii) 275–300°C at a
pressure of 40 mm of mercury. The former is termed key fraction 1 and the
latter, key fraction 2. Each fraction is classified as paraffin, intermediate or
naphthene according to specific gravity, and the crude is classified on the
nature of the key fractions (Table 5.5). Following this system, a crude oil is
called wax-free or wax-bearing according to whether the cloud point of the
key fraction 2 is below or above 5°F(-15°C), respectively. Lane and Garton
have found that 85% of the crudes examined fell into the three simple
namely paraffin, intermediate or naphthene. Paraffin-naphthene or
intermediate-naphthene crudes were not found to exist.
The system of Lane and Garton is an improvement over the three-group
classification in as much as it recognised that one type of hydrocarbon
might predominate in one fraction and another might predominate in
another fraction. However, it characterises the nature of only two fractions
and that too by the approximate method of using specific gravity data. More
detailed studies are necessary for the complete characterisation of crudes.
Not each crude can yield all the products of right quality and in
commercially recoverable quantities. Typical paraffin-base and asphalt-base
crudes differ widely in this respect (Table 5.6). Mixed-base crudes have
properties intermediate between these two. Modern refinery processes,
however, can overcome the deficiencies of crude to a large extent. In
general paraffin-base crudes yield good quality kerosene, diesel fuel,
lubricants and waxes, while asphalt-base crudes yield good quality
gasolines and asphalts. The refinery processes are largely influenced by
the type of crude to be treated.
Table 5.6 Comparison of paraffin-base and asphalt-base crudes

Properties Paraffin-base Asphalt-base
Specific gravity low high
Yield of straight-run gasoline high low
Octane number of gasoline low high
Odour of gasoline sweet or sour aromatic or sour
Sulphur content of fractions low high
Smoke point of kerosene high low
Cetane number of diesel high low
Pour point of diesel high low
Yield of lubricants high low
Viscosity index of lubricants high low
Crude oil from Pennsylvania (USA) and certain fields in Rumania,

Poland and the old USSR may be classified as paraffin-base. Crudes from
California (USA) and some areas in Mexico, Venezuela and the old USSR
serve as examples of asphalt-base oils. The Middle East crudes form a
large group of the mixed-base type.
Some crudes need special mention. Borneo crudes yield gasoline
fractions containing up to 40% simple aromatic hydrocarbons. Another
Indonesian crude (Tarakan) may be used directly as diesel fuel or light
furnace oil. Light Kettleman Hills (California) crude practically consists of
gasoline only.
Nature of Indian crudes
The oil fields of India yield highly waxy and mixed-base crudes. Some of the
characteristic properties of three Indian crudes are given in Table 5.7. The
API gravity varies from 22.3–38.5, the lightest being Bombay High and the
heaviest the Cambay crude. The sulphur content is very low in all Indian
crudes. The crude from Bombay High is almost sulphur-free. The wax
content is hightest for Cambay and lowest for Bombay High.
Table 5.7 Characteristic properties of Indian crudes

Cambay, Nahorkatiya, Bombay High
Gujarat Assam offshore
Specific gravity, 15.5°/15.5°C °API 0.8638 0.8574 0.8324
22.3 33.5 38.5
Water content, per cent v/v 2.60 0.06 –
Salt content, per cent w/w 0.014 nil –
Sulphur content, per cent w/w 0.13 0.17 0.05
Kinematic viscosity at 37.8°C, CS 35.6 4.91 5.1
Calorific value, kcal/kg 10800 – –
Pour point, °C 35.0 30–32 27.0
Distillation characteristics
IBP, °C 62.5 41.0 38.0
Cambay, Nahorkatiya, Bombay High
Gujarat Assam offshore
Up to 150°C, per cent v/v 9.2 23.0 22.0
150–300 °C, per cent v/v 26.5 32.5 33.0
300–465 °C, per cent v/v 35.25 32.2 –
Total up to 465 °C, per cent v/v 70.95 87.7 –
Fraction up to 150°
Sp.gr.(15.5°/15.5°C) 0.7195 0.7471 –
Refractive index, 20°C 1.4041 1.4222
Aromatic content 3–5 20–25
Fraction 150–300 °C
Sp.gr. (15.5°/15.5°C) 0.7920 0.8516
Refractive index, 20°C 1.4404 1.4777
Fraction 300–450°C
Sp.gr. (15.5°/15.5°C) 0.8698 0.9273
Sulphur, per cent w/w 0.05 0.24
Wax content, per cent w/w 32.2 24.4
Short residue (>465°C)
Sp.gr. (15.5°/15.5°C) 0.9554 1.0050
Penetration number 50 16
Softening point (R and B), °C 55 67
Wax (300–465°C), on the basis 16 11 12
of crude, per cent w/w
The yield of straight-run gasoline is more than 20% from Bombay High
and Nahorkatiya and less than 10% from Cambay. The recovery of total
distillates is the lowest from Cambay.
The Bombay High crude is very highly aromatic. Its straight-run gasoline
contains more than 60% aromatics. The corresponding figures for
Nahorkatiya and Cambay are 20–25 and 3%–5%, respectively. The high
aromatic content is a common feature of Southeast Asian crudes.
5.2.5 PETROLEUM PROCESSING
After removal of dirt, water and much of the associated natural gas, the
crude is separated into fractions by distillation and the resultant fractions
are further subject to simple purification treatment or more complex
conversion processes for the manufacture of diverse petroleum products.
All these processes are referred to as petroleum refining and are carried out
in a refinery.
Refinery processes may be conveniently grouped under three main
heads, namely
1. Physical separation processes, for example, distillation and
extraction,
2. Breakdown processes, for example, cracking, visbreaking and coking
3. Rebuilding processes, for example reforming, alkylation, isomerisati

polymerisation.
Various product streams are further refined before marketable products are
obtained. According to the processes used, refineries may be classified as
simple, more complex, or fully integrated.
Simple refineries produce only a limited range of products, mainly
gasolines, kerosenes and aviation turbine fuels, gas and diesel oils, and
fuel oil. Besides a crude oil atmospheric distillation unit, the only other units
are those for reforming and for purification treatment. The additional units in
more complex refineries are usually a vacuum distillation unit and a
cracking plant together with the units for the processing of cracked gases by
polymerisation, alkylation and other methods. Premium motor and aviation
gasolines and bitumen are the notable additional products.
The whole range of petroleum products is obtained in the fully integrated
refineries. The additional units include a high vacuum fractionating unit for
the preparation of lubricating oils, a de-asphalting unit, a solvent extraction
unit, a dewaxing unit, and a coking unit. Since 1950, integrated refineries
which are cheaper to build and operate in the long run have been preferred.
There are export refineries located at, or near the crude oil sources and
market-oriented refineries located near the markets for the petroleum
products. The advent of huge oil tankers, the developments in the piping of
oils and the oil strategy of government have led to the increasing installation
of market-oriented refineries.
A refinery may draw its crude oil supply from a single or many oil fields.
If the crudes are not very different they may be blended before processing.
Those yielding superior distillate fuels may be kept separate from those
producting inferior stocks. Similarly, the oils that yield superior lubricants or
asphalts may be segregated. It is not necessary to extend such segregation
to the cracking of heavier fraction for gasoline production.
Petroleum distillation
The refining of petroleum begins with the separation of the crude by

distillation into a number of fractions. The distillation is carried out first under
atmospheric pressure and the residue from this primary distillation (reduced
crude or long residue) is then distilled under vacuum. The primary
distillation is also known as the topping of the crude oil. The maximum
temperature upto which a crude can be heated without cracking is about
400°C. This sets the limit of the maximum amount of distillate that can be
collected by atmospheric distillation. Steam is used to facilitate the
vaporisation of the high boiling constitutents. The recovery of still heavier
fractions, upto 600°C boiling range, is possible in the vacuum units further
assisted by the admission of steam.
Fractions into which crudes are commonly separated are named in
Table 5.8 with their approximate boiling ranges and uses. Primary distillation
usually recovers fractions upto gas oils, while vacuum distillation recovers
vacuum gas oil, raw lubricating oil distillates and asphalt or bitumen. The
actual practice in a plant considerably varies from plant to plant, depending
upon the type of crude input and the demand of products. On the one hand
the crudes themselves yield fractions of different quality and quantity, and
on the other, the boiling ranges of petroleum products considerably overlap
each other. The nomenclature of the fractions also changes accordingly.
Table 5.8 Common fractions from crude petroleum

Fraction Approximate boiling Uses
range, °C
Fuel gas –162 to –42 containing methane, ethane
and some propane; used
as refinery fuel.
Propane -42 liquefied petroleum gas
(LPG)
Butane –12 to –0.5 LPG component of
gasolines in cold climate
Light naphtha –1 to 150 straight run gasoline,
solvents, depentanised
added to heavy naphtha
feed for reforming
Heavy naphtha 150 to 205 catalytic reformer feed,
component of jet fuels and
solvents
Kerosene 205 to 260 illuminant, fuel
Fraction Approximate boiling Uses
range, °C
Stove oil 205 to 290 fuel
Light gas oil 205 to 315 fuel oil, diesel fuel,
absorbent
Heavy gas oil 315 to 430 catalytic cracking feed
Vacuum gas oil 430 to 540 catalytic cracking feed,
suitable crudes yield
lubricating oils
Residue (short residue) 595 and above heavy fuel oil and asphalt
or bitumen, petroleum coke
making
While vacuum distillation is a one-stage operation, primary distillation

may be run in one or two stages. Figure 5.2 shows a flow-sheet of a
complete three-stage crude distillation unit. The first stage operates at 3 to
4 kgf/cm2 pressure and produces gases and light distillate boiling upto
90°C. The bottoms from the first stage are heated to about 400°C and sent
to the second stage distillation column which operates at atmospheric
pressure. Naphtha is recovered as top stream while kerosene and gas oil
are withdrawn as side streams. The reduced crude is reheated to about
400°C and pumped to the vacuum column (50 to 100 mm Hg pressure).
Here the top stream is a raw lubricating oil. The bottoms are used in making
asphalt or bitumen and heavy furnace oil. Parafffin wax is manufactured
from vacuum gas oil while microcrystalline wax is recovered from certain
types of heavy lubricating oil distillates or residues from paraffinic crudes.
Figure Three-stage distillation of crude oil
5.2
The side streams contain some lighter components as impurities. These

are purified by passing through steam-strippers. Steam carries off the
lighter components back to the main column while the purified fraction is
obtained at the bottom of the stripper.
Fractionating columns vary greatly in size. The usual dimensions are 3 m

diameter and 30 to 35 m height. Plates of various designs are used by
different refineries. Three to five plates, at 0.56 m spacing are usually
sufficient between two neighbouring product streams in atmospheric
columns. This number is two to three for vacuum columns where
fractionation is more efficient owing to the increased difference of vapour
pressure of components and also because of the larger spacing of plates.
In the distillation units, crudes are heated in pipestills. A pipestill is a
special type of furnace with a relatively long but small diameter pipe. The
pipe consists of a large number of tubes connected through bends. The
tubes are housed inside the furnace chamber in single and multiple rows.
The furnace is built in two sections, namely, radiant and convection. The
tubes in the radiant section receive heat directly from the flame and those in
the convection section recover heat from the hot gases travelling to the
stack. There are different designs for pipestills depending upon the
arrangement of tubes and direction of liquid flow. Box-type stills are the
oldest and quite widely used (Fig. 5.3). The furnace is divided into two
chambers by a bridge wall. Separate burners are put on the side walls. The
convection section is separated from the radiant section by a row of tubes.
The crude is pumped into the pipe inlet at the convection section. The final
heating to about 400°C takes place when the preheated crude passes
through the radiant section tubes. High rates of heat transfer are obtained
by radiation and convection and by high liquid flow rates in the pipe. The
high flow rate of the crude also ensures high productivity and prevents local
overheating which might otherwise cause cracking and coke deposition.The
box-type stills have input capacities of 5–20 million kcal/h. The heat flux is
15,000–40,000 kcal/m2 of circumferential tube area per hour and the heat
release is 20,000–45,000 kcal/m3 furnace volume per hour. A high
proportion of the total heat transfer between 55% and 60% is by radiation.
Figure Box-type pipestill

5.3
Stabilisation: Natural gasoline, cracked gasoline and similar stocks contain

dissolved hydrocarbons (gaseous and very highly volatile liquids) which
tend to escape during storage. Stabilisation is the process of removing
these lighter components and making such stocks stable and suitable for
storage and handling. A typical cracked gasoline may contain more than
10% of butane and lighter hydrocarbons. Stabilisers are essentially high
pressure, 8 to 15 kgf/cm2, fractionating columns using 40 to 50 plates and
high reflux rations. The escaping vapours on condensation separate into
gaseous and liquid streams. The liquid is refluxed and also recovered as a
speciality product. The stabilised gasoline is withdrawn from the bottom
through a heat exchanger which preheats the feed. Extra heat is supplied at
the bottom of the tower by means of a reboiler.
Breakdown processes
Cracking: This term refers to the processes by which heavier fractions are
converted into lighter fractions by the application of heat, with or without a
catalyst. The chief application of commercial cracking in refineries is the
production of gasolines from gas oils. Other fields of application are the
production of olefins from naphthas and gas oils for the petrochemical
industry, the reduction of viscosity of straight-run residues (visbreaking), for
fuel oil production, and the conversion of heavy residual products into coke
and lighter products (coking).
When cracking is carried out without any catalyst, the process is called
thermal cracking. This is accomplished by heating the feed upto 450° to
750°C at pressures ranging from 1–70 atm. The important reactions are
decomposition, dehydrogenation, isomerisation and polymerisation. The
paraffinic molecules are first decomposed into lower molecular weight
hydrocarbons, usually a paraffin and an olefin. For example,
While n-decane is a component of gas oil, n-hexane is one of gasoline.

The olefins can then undergo isomerisation, dehydrogenation and
polymerisation reactions. For example,
Iso-octene is again a gasoline component. Owing to various reactions

during cracking, gases and solids (coke) are also produced together with
the liquid products. The ease of cracking depends upon the boiling range
and the chemical nature of the feed. Crackability is higher for the heavier
fractions. Paraffinic feed is more crackable than aromatic.
The use of catalysts not only accelerates the above reactions but
instead introduces new reactions which considerably modify the yield and
nature of the products. Compared with the thermal process, the catalytic
cracking yields less coke, less gas and more liquid products. Moreover, the
gasoline obtained from the catalytic units is far superior in quality owing to
higher content of iso-paraffins and aromatic hydrocarbons. All new cracking
units for gasoline production are based on the catalytic process. Thermal
cracking is now restricted to olefin production, visbreaking and coking.
Conventional thermal cracking units for gasoline production, for example,
the Dubbs process, may still be found in old refineries.
The usual catalysts generally are either synthetic composites of silica
and alumina, or acid-treated natural clays of the montmorillonite group. The
most recent advance is the introduction of zeolites as cracking catalysts
with better activity. The cracking catalysts are used in the form of pellets,
beads or powder. The pellets and beads may be used either as a fixed bed
in a cyclic process, for example, the Houdry process, or as a moving-bed in
a continuous process, for example, thermofor catalytic cracking or TCC
process, Houdriflow process, and others. The power may be used either as
a suspension in the liquid fuel, for example, the suspension process or as a
fluid-bed with the vaporised feed as the fluidising medium. Out of the
various processes now operating, fluid catalytic cracking is by far the most
widely used. The use of catalysts minimises the formation of coke during
cracking, but cannot completely avoid it. The coke particles settle on the
catalyst surface and deactivate.
Catalyst regeneration is therefore vital to the economics of the process.
This is accomplished by the burning of the deposited coke particles in air.
The movement of catalysts from reactor to regenerator and back is much
more easily achieved in the fluid cracking process than in the other
continuous processes. In the fixed bed process, the catalyst is regenerated
in the reactor itself by using a cycle of cracking followed by regeneration
and continuing the cycle till further activation is not possible. The most
obvious demerit of the fixed bed process is the variation of temperature and
activity of the catalyst along the height of the bed and with the progress of
the cycle, causing non-uniformity of the yield and quality of products.
Besides easy catalyst movement, the fluid process has other merits as well,
namely, the fluid bed is essentially an isothermal reactor owing to high heat
transfer rates in the systems, and moreover, high mass transfer rates
between the catalyst surface and gas phase help to increase reaction rates.
Figure 5.4 shows the flow-sheet of a typical down flow fluidised bed
catalytic cracking process. Fresh and recycle gas oil (feed) are mixed with
hot activated catalyst from the regenerator and admitted at the bottom of
the reactor. The catalyst is fluidised in the reactor by the vapours issuing
from the feed line. The cracker gases and vapours are passed through
internal cyclones that remove the entrained catalyst powder and feed it
back to the bed. The gases and vapours enter a large fractionating column
(5 m diameter, 30 m height, 30 to 40 plates) where wet gas, gasoline
(unstablised) and gas oils are recovered. A gas oil stream is recycled.
Reactor conditions are: temperature 470–520°C, pressure 8–15 kgf/cm2,
catalyst-to-oil ratio 5–15 (by weight) and space velocity 1–3 kg oil per hour
per kilogram of catalyst.
Figure 5.4 Fluidised bed (down flow) catalytic cracking process
The spent catalyst is sent from the reactor to the regenerator by a

system of stand-pipes, U-bend transfer lines and risers. It always contains
absorbed oil molecules which are removed by steam-stripping at the leg of
the reactor. Air for catalyst regeneration is injected partly at the catalyst riser
and partly at the regenerator bottom. Regenerator conditions are:
temperature 550–660°C and pressures 1.3–1.7 kgf/cm2. The regenerated
catalyst is sent back to the reactor by a transfer system comprising an
overflow weir, standpipe, U-bend and riser. The combustion gases are led
to the stack.
Cracking is an endothermic process. The heat requirement is met by the
combustion of coke in the regenerator, the heat being transferred as the
sensible heat of the regenerated catalyst. The catalyst size varies and may
consist of particles from 500 μ upper size to fines below 5 μ. Instead of
powder form, catalysts are often used in the form of microspheres of
required sizes. The size degradation due to attrition is very low in the case
of microspheres.
The extent of cracking is deliberately kept at a low level so that coke
and gas formation is minimised. By recycling cracked gas oil streams, the
per cent conversion is raised. There are fluidised bed cracking units in the
refineries at Bombay, Visakhapatnam, Koyali and Mathura.
Visbreaking: Heavy furnace oils are made by blending residues with gas
oils to meet the requirement of viscosity and pour point. The residues are
highly viscous and need large quantities of the valuable blending oils. The
main purpose of visbreaking is to reduce viscosity of the residues by
thermal cracking and thus reduce the consumption of the blending oils.
Visbreaking is carried out by passing the feed through a pipestill at 470 to
520°C at an outlet pressure of 4 to 20 kgf/cm2. It is a one-pass process.
The thermal cracking takes place in the liquid phase. The cracked material
is led into a flash-distillation chamber. A gas, a low quality gasoline and a
light gas oil are recovered from the overhead stream. The liquid products
from the flash chamber are cooled and further fractionated under vacuum
when a heavy gas oil and a tar of reduced viscosity are obtained. This tar is
the main product of visbreaking. It is blended with an oil to give a furnace
fuel while the other products join other corresponding streams of the
refinery for further processing.
Coking: The residual products of the refinery form the feed for coking.
Under relatively severe conditions of thermal cracking, the heavy liquid feed
is converted into gas, naphtha, heating oil, gas oil and coke. Coking is
practised to get either gas oil or coke as the main product. The gas oil is
primarily used as the feed for catalytic cracking while the coke (petroleum
coke) is used as a fuel or in the production of carbon electrodes and
chemicals. There are two methods of coking, namely delayed coking and
fluid coking. Higher coke yield is obtained by the former method while the
fluid coking yields less coke and more gas oil. In delayed coking, the feed is
heated to about 500°C and charged into a chamber called the coke drum.
Coking is continued in this chamber till the cracked products leave the top
and the coke is left behind. The conditions in the coke dram are:
temperature around 425°C, pressure 2 to 6 kgf/cm2. The overhead products
are fractionated and the heavy oil is recycled. The coke is cooled and
removed from the drum by hydraulic cutting.
In fluid coking a spray of the liquid (260° to 360°C) is injected into a
fluidised bed of hot, fine, coke particles (480 to 560°C) at substantially
atmospheric pressure. The material gets cracked. The gases and vapours
are passed through a system of cyclone, scrubber and condenser for
recovering entrained coke particles, gas oil and other products. The coke is
deposited on the fluidised coke particles. It is recovered by withdrawal from
the unit from time to time. The heat of the process is supplied by burning a
part of the coke in a separate chamber (burner). A continuous movement of
the coke is maintained from the reactor to the burner and back.
Reforming: This is the process of preparing high quality gasoline by

heating, with or without a catalyst, the naphtha fractions of the gasoline
boiling range. The upgrading is essentially a result of rearrangement or
reforming of molecules without greatly disturbing the average molecular
weight. The main reactions are the formation of aromatics by the
dehydrogeneration of naphthenes and the dehdrocyclisation of paraffins.
For example,
An important reaction is the isomerisation of methylcyclopentane to

cyclohexane; the latter then dehydrogenates and yields benzene. Other
reactions are the isomerisation of n-paraffins into iso-paraffins and
hydrocracking of higher paraffins into lower ones. Aromatics are the best
gasoline components and iso-paraffins are next to them.
Reforming may be thermal or catalytic as in the case of cracking.
Catalysts not only accelerate the process but also improve the yield and
quality of the resultant gasoline (reformate). Thermal reforming has been
almost completely replaced by catalytic reforming.
Two types of reforming catalysts are used commercially, namely non-
precious metal oxide-type, such as, molybdena or chromia supported on
alumina and the precious metal acid oxide-type, such as, platinum on a
silica-alumina or alumina base. Platinum is more active and selective. It is,
however, easily poisoned by compounds containing sulphur, nitrogen and
arsenic and needs pretreatment of the feed for the removal of the
impurities. The catalyst may be in the form of powder, beads or pellets.
Fixed bed, moving bed and fluid bed processes are in use. Platforming,
catforming, hydroforming, fluid hydroforming and thermofor reforming (TCR)
are the various commercial reforming processes. The feed for catalytic
reforming is drawn from naphthas obtained in the various refinery
processes, for example straight-run distillation, catalytic cracking and
coking. The best results are obtained with the straight-run naphthas of high
naphthene content.
Besides the main product (reformate), reforming also produces lighter
hydrocarbons, hydrogen and traces of very high boiling materials. The
hydrogen-rich gaseous product is recycled with the naphtha feed. The
reformate has a wider boiling range than the original naphtha. The
increased volatiaity is an added advantage gained by the reforming
process.
Reforming is normally a once-through process. The reactor conditions
are: temperature 450 to 520 °C and pressure 15 to 45 kgf/cm2. Fluid bed
and moving bed processes are run at the high temperature ranges using 15
kgf/cm2 pressures. High pressures upto 45 kgf/cm2 are for the fixed bed
process. For the first time in India, the catalytic reforming process was
established at the Bharat Petroleum Refinery at Mumbai. Subsequently this
has been adopted by other refineries at Koyali, Cochin, Chennai and
Haldia.
Rebuilding processes
Polymerisation, Alkylation and Isomerisation: These processes aim at

the production of superior gasolines and are thus complementary to
catalytic cracking and catalytic reforming. The cracker gases in the refinery
are rich in olefins. These compounds undergo polymerisation in the
presence of catalysts, for example, phosphoric acid or sulphuric acid at
suitable temperatures and pressures, and ultimately give products rich in
branched-chain hydrocarbons (polymer gasoline).
In the alkylation process, a gaseous iso-paraffin, for example, iso-butane is

reacted with an olefin (propene or butene) in the presence of sulphuric acid
or hydrofluoric acid as catalyst and the result is a larger iso-paraffin boiling
in the gasoline range (alkylate).
The isomerisation process converts n-paraffins into iso-paraffins in the

presence of aluminium chloride catalysts. Commercially it is mostly
practised to obtain iso-butane from the butane fractions. The iso-butane is
then used in the production of good quality gasoline by the alkylation
process. Pentanes and hexanes are also being increasingly isomerised to
supply excellent high volatile gasoline components, such as, iso-pentances
and iso-hexanes.
The polymerisation and isomerisation processes are also used in the
production of pure petrochemicals.
Hydrogenation: There are essentially three classes of hydrogenation

processes used in petroleum refining, namely, hydrotreating, aromatic
saturation and hydrocracking.
1. Hydrotreating is a mild operation aimed at removing impurities like s
nitrogen, oxygen, halides and trace metals. It is also used to s
petroleum products by saturating olefinic compounds. Hydr
autofining and ultrafining, are the various processes falling into this
Hydrotreating is applied to products of all boiling ranges from light na
to lubricating oils.
2. Aromatics are undesired constituents of kerosene, stove oil, diesel fu

lubricating oil. Saturation of aromatics by hydrogenation results
upgrading of these products. This process is still of limited use in indu
3. Hydrocracking is also known as destructive hydrogenation and leads

formation of saturated compounds of lower molecular weight
cracking of heavy fractions and residues under a substantial pres
hydrogen. Hydrogen suppresses the formation of tar and coke an
raises the crackability of polycyclic aromatic compounds. The proce
achieve high conversions into gasolines and high quality diesel fuels.
hydrocracking of petroleum residues can supply feed for other r
processes.
The important catalysts for the hydrogenation processes are

cobaltmolybdena for hydrotreating, nickel for saturation of aromatics,
tungsten sulphide for vapour-phase hydrocracking and an iron catalyst or
bauxite for liquid-phase hydrocracking.
The normal range of conditions for hydrotreating are: temperature 300–
400°C, pressure 15–17 kgf/cm2, space velocity up to 20 v/v.h. More severe
conditions are required for hydrocracking, namely temperature range of
400–550°C and pressure range of 70–700 kgf/cm2. Hydrocracking of
residues and heavy fractions boiling above 300°C is conducted in the liquid
phase.
The development of the hydrogenation process in refineries has been
possible largely owing to the availabilty of surplus hydrogen-rich gases from
the catalytic reforming of naphthas. Only Chennai and Haldia refineries
have adopted hydrotreating processes. It is planned to have a hydrocracker
at the refinery at Mangalore.
Purification processes
Petroleum products have to reach the consumer in a certain degree of

purity and quality. The impurities and undesired components may come
from the original crude or may be developed during various stages of
processing the crude and its fractions. Even some feedstocks for catalytic
processes require purification so that the catalyst deactivation is minimised.
Depending upon the nature of the crude and the ultimate use of the product,
the required purification may involve a simple treatment or elaborate
processing.
The specific aims of the purification processes are:
1. To minimise (i) acidity, (ii) carbon residue, (iii) catalyst deactivatio
corrosivity, (v) gum formation, (vi) interaction with paints and (vii) n
combustion products;
2. To improve (i) burning characteristics of kerosene and diesel fu

gasoline properties, for example, lead susceptibility and octane rati
colour and colour stability, (iv) odour and (v) pour point of diesel fuel;
3. To purify the product and recover the following for sale or

processing: (i) alkyl phenols, (ii) hydrogen sulphide, (iii) mercapta
naphthenic acids, (v) nitrogen bases and (vi) sulphonates.
The chief components responsible for colour include sulphur compounds,

nitrogen bases and certain hydrocarbons such as high molecular weight
aromatics. Objectionable odours are imparted by hydrogen sulphide,
naphthenics and aliphatic fatty acids which may have originated from the
crudes or appeared during refinery processing. Acidity gives rise to the
problem of corrosion, gum formation and discolouration of products and
interferes during the processing of various feedstocks. Corrosivity may also
be due to non-acidic substances, for example, mercaptans and
polysulphides. Gum formation is promoted by polysulphides, acidic
materials, metallic contaminants, aryl mercaptans and olefinic bodies.
The burning quality of kerosene deteriorates owing to both the presence
of aromatics which cause soot formation, and to the presence of sulphur
compounds, unstable hydrocarbons, metallic naphthenates and
sulphonates which enhance the tendency for the wick to char.
The octane rating indicates the quality of gasoline. Straight-chain
paraffins have poor octane rating while aromatics and isoparaffins have a
very high octane rating. Premier gasoline may be made by removing the
undesired straight-chain paraffins and increasing the content of aromatics.
Gasoline also improves in octane rating by the addition of small quantities
of tetraethyl lead. This property is known as lead susceptibility.
Polysulphides, disulphides and mercaptans seriously reduce the lead
susceptibility of gasoline.
The flow characteristics of diesel are reduced by the dissolved wax
which crystallises out even at ordinary temperatures. This renders the pour
point objectionably high. Methods of dewaxing can improve the quality of
diesel fuel in this respect.
Treatment with acids and alkalis

Sulphuric acid: Owing to its chemical properties, sulphuric acid is the most
versatile refining agent known, as it is also inexpensive and readily
available. Nitrogen bases, asphaltic substances, di-olefins, olefins and
acetylenes are readily removed by sulphuric acid. Aromatics are also
removed at a high concentration. Although many sulphur compounds, for
example, thiophenes, mercaptans and sulphides are also readily removed,
there are some others like elemental sulphur, carbon disulphide and certain
high molecular weight sulphur compounds which are not attacked. By
removing the impurities, sulphuric acid improves colour, stability and odour
and reduces corrosiveness and gum formation of petroleum products.
The use of sulphuric acid in petroleum refining has declined steeply
owing to the development of newer processes. The two major drawbacks of
the sulphuric acid treatment are
1. The large refining losses due to the formation of acid sludge,
2. The problem of disposal of acid sludge.
It is still the most common refining agent. Petroleum products of all boiling
ranges—naphtha to lubricating oil—are given finishing treatment with it.
Acid of 93% strength (66° Be’) finds the most general use. A more dilute
acid is used when the aim is only to improve the colour of light distillates.
Lubricating oils may need up to 98% strength. High temperatures enhance
refining losses. Lower temperatures yield products of a better colour and
are favourable for the removal of sulphur compounds. Gasolines are treated
at 20–30°C. Higher temperatures (30–50°C) are used for treating kerosene
because the removal of aromatics, unsaturated hydrocarbons and asphaltic
materials is favoured at those temperatures. Owing to high viscosity of
lubricating oils, still higher temperatures (40–80°C) are needed to ensure
intimate contact with the acid. Contact time also varies with the nature of
the product. The heavier products need a longer time of contact.
The general procedure for acid treatment is similar. Raw stock and acid
are brought together in desired proportions at a suitable temperature. After
thorough contacting the phases are separated by settling. The oily phase is
neutralised and the spent acid is discarded. The product may need
fractionation to remove high-boiling material produced during acid
treatment.
Other acids: The colour, stability and odour of distillates are improved by
treatment with hydrofluoric acid or acetic anhydride. These reagents
however have limited use.
Caustic soda: A wash with caustic soda is a common treatment after

processing with sulphuric acid. The alkali wash is also widely used to
remove naturally-occuring acidic substances, such as hydrogen sulphide,
carbonyl sulphide, lower aliphatic mercaptans, phenols, aryl mercaptans,
fatty acids and naphthenic acids.
Sweetening processes: Mercaptans and hudrogen sulphide have an
objectionale odour and are said to make an oil sour. By definition, a stock is
sweet if it passes the doctor test. In this test, the oil sample is shaken with
an equal volume of sodium plumbite solution and a small amount of sulphur.
The mercaptans first react with sodium plumbite to form oil soluble lead
mercaptides. The mercaptides on further reaction with elemental sulphur
form sweet smelling, oil soluble disulphides and give a black precipitate of
lead sulphide. The hydrogen sulphide also gives this black precipitate with
the plumbite solution. If the test does not produce even a dark
discolouration at the interface, the sample is sweet. The processes by
which the foul smelling stocks are rendered sweet smelling or odourless are
known as the sweetening processes. In essence these convert mercaptans,
hydrogen sulphide and also elemental sulphur into oil soluble sulphur
compounds without any objectionable odour and thus differ from those
processes where the aim is to materially remove the mercaptans and other
sulphur-containing materials from the stock.
The principle of the doctor test forms the basis of the doctor sweetening
process. There are other processes also using copper chloride, hypochlorite
and lead sulphide, respectively. All these processes are almost obsolete.
Firstly, the disulphides harm lead susceptiblity of gasolines and secondly,
the need for reduction of mercaptans to doctor sweet (0.0004%) is
questioned. However, some cheap sweetening processes, such as air-
inhibitor and air-solutiser processes are still in use. In these processes, air
oxidises the mercaptans in the presence of additives like phenylene
diamine (inhibitor), methanol (solutiser), caustic soda, caustic potash and
doctor solution.
Mercaptan dissolving processes: These remove the mercaptans from the

stock by dissolving out and thus have an advantage over the sweetening
processes where disulphides are left behind. Treatment with caustic soda
removes the lower mercaptans. The high molecular weight mercaptans
have only limited solubility in this reagent. However, some solutisers like
fatty acids, cresols and naphthenic acids markedly enhance the solubility of
the higher mercaptans, particularly in caustic potash. This forms the
underlying principle of a number of commercial processes for the removal of
mercaptans from distillates.
Desulphurisation processes: There are two general methods of reducing

the amount of sulphur compounds in petroleum stocks:
1. Treatment with chemicals and solvents,
2. Catalytic conversion into hydrogen sulphide with or without the su

external hydrogen.
Treatment with acids and alkalis and catalytic hydrotreating were discussed
in the earlier sections. The use of solvent extraction and clay treatment for
desulphurisation will be taken up in the subsequent sub-sections.
Solvent extraction: The difference in solubility of suitable solvents forms

the basis of many refinery processes which either resolve a stock into two
or more products or purify a product from harmful impurities. One of the
oldest processes of petroleum refining—solvent extraction—has quite a few
major uses in modern refineries:
1. Upgrading lubricating oils by removing aromatic materials and s
compounds,
2. Separating reduced crude and residue into lubricating oils and aspha
asphalting),
3. Upgrading kerosene, heating oils and diesel fuels by removing aro

olefines and sulphur compounds,
4. Improving cracker feedstocks by removing asphaltic and other

producing materials (decarbonisation),
5. Separating wax-bearing oils into wax and wax-free oil (dewaxing),
6. Recovering benzene, toluene and xylenes from suitable naphthas an
7. Separating iso-butene from butane–butene streams.
The important solvents employed in one or more of the above uses are
given below.
Liquid sulphur dioxide: It is a versatile solvent applied to a wide variety of
light distillates, for example, heavy naphtha, kerosene and diesel fuel
(Edeleanu process). Mixed with benzene, it is also applicable to lubricating
oils. At its boiling point, –10°C, liquid sulphur dioxide completely dissolves
aromatics, unsaturates, mercaptans and many other sulphur compounds,
but the paraffins and naphthenes remain insoluble in it. A disadvantage is
that moisture cannot be tolerated in the system because the solvent then
becomes highly corrosive.
Furfural: This solvent is being increasingly used in the upgrading of

lubricating oils. It is also applied to light distillates. Aromatics are highly
soluble in it. Low moisture content in the system does not pose a problem.
In fact, a small amount of water is purposefully left in the solvent for
increasing its selectivity.
Phenol: The solvency properties of phenol are similar to those of furfural,

but phenol is toxic and solidifies at ordinary temperatures. However, solvent
recovery is easier and cheaper. Phenol is extensively used in upgrading
lubricating oils. Furthermore, a mixture of phenol and cresols, selectro, is
used as a solvent in the double solvent, Duosol process of upgrading
lubricating oils. Selectro dissolves napthenic hydrocarbons and the other
solvent (liquid propane) dissolves paraffinic hydrocarbons.
Liquid propane: Propane, an abundant material in refineries is a useful

solvent in many ways. It extracts paraffinic hydrocarbons from oils and
precipitates asphaltic or resinous materials. It is widely used in de-
asphalting, dewaxing and upgrading of lubricating oil upgrading (Duosol)
processes. It is also used to facilitate treatment with sulphuric acid.
Methyl ethyl ketone (MEK): It is used in the dewaxing processes. Wax-

bearing oils are dissolved in the solvent and then chilled. The wax
crystallises out in an easily filterable form. The ketone is used as a mixture
with benzene and toluene which increases the solubility of the oil in the
solvent.
Glycol: Aqueous solutions of diethylene glycol (8%–12%) are used in the

extraction of benzene, toluene and xylenes (light aromatics) from the
reformate or cracked naphtha by the well-known Udex process. The product
is used as a premium gasoline or further processed for the recovery of pure
aromatic hydrocarbons.
Dilute sulphuric acid (65%): It is used in the extraction of iso-butene from
butane–butene stream in the refinery. The hydrocarbon is recovered from
the solution by dilution with water to 45% acid, followed by stripping.
A typical sulphur dioxide plant for producing premium kerosene is shown in

Fig. 5.5. The raw feed is first dried and cooled, and then charged to a
packed tower near the bottom. The refrigerated solvent is fed at the top.
Both the overhead raffinate and the bottom extract streams are passed
through triple-effect evaporators for the complete recovery of sulphur
dioxide. The first stage in each of these two evaporators is operated at a
pressure of about 6 to 7 kgf/cm2 which is sufficient to condense the solvent
vapours without compression. The other two stages are operated at much
lower pressures (25 mm Hg in the last stage) and need compression for
liquefying the solvent vapours. There is a small drying tower in the SO2-
stream for the continuous removal of water. This is the only piece of
equipment requiring special corrosion resistant material of construction.
Solvent losses amount to about 0.4 kg per kilolitre of the charge. By using a
solvent-to-feed ratio of 100 and extraction temperature of – 18°C with a
feed of 14% aromatic content, it is possible to get a raffinate of only 2%
aromatics and extract of 82% aromatics in a commercial plant.
Figure Edeleanu process of kerosene purification
5.5
1, 4: High pressure 2, 5: Low pressure 3, 6: Vacuum 7: Extraction
tower
Clay treatment
Clays adsorb asphaltic, resinous and acidic materials from heavy oil and
waxes. This property is utilised to remove traces of asphalts and resins from
low-asphalt content stocks and waxes, and therby improved their colours.
Colour stability, oxidation resistance, and de-emulsibility are also improved.
High asphalt oils are fast de-asphalted by acid treatment or solvent
extraction and then given a clay treatment. Waxes are dissolved in a
solvent like propane and the solution is acid treated. Conventional acid
treatment may be followed by clay treatment for the neutralisation of the
charge by the adsorption of sludge and acidic materials. Clays are also
used to adsorb arsenic compounds from catalytic reformer feeds.
Another use of clays in refineries is for their catalytic properties. Fuller’s
earth and bauxite catalyse the polymerisation of colour forming and gum
forming materials in cracked gasoline. The treated stock is freed from the
polymer by distilling (rerunning). The final product is resistant to
decolourising and gum forming on storage.
Fuller’s earth and bauxite also catalyse the conversion of organic
sulphides and mercaptans to hydrogen sulphide and hydrocarbons at 300–
350°C. They are used to desulphurise straight-run gasolines and
kerosenes. The sulphur in cracked gasoline is largely thiophenic, and
thiophenes are not attacked by clay treatment. Catalytic desulphurisation by
hydrotreating is essentially a variation and improvement of the clay
treatment. External hydrogen enhances the process of desulphurisation and
minimises coke formation.
The liquid phase clay treatment may be carried out either by percola
by contact filtration. The former consists in percolating the liquid
through a fixed or moving bed of the clay. In the filtration method, th
is mixed with the adsorbant and then filtered.
The vapour-phase treatment usually involves passing vapours over

bed of clay. Under desulphurisation conditions, coke deposits deactiv
calalyst. The latter can be regenerated by burning off the coke.
The spent clay from the processes other than desulphurisation are not
usually regenerated. Their disposal is a problem. There is a limited demand
for the spent clay in the manufacture of cinder bricks. Clays may be
regenerated by controlled combustion.
Deasphalting
Crudes contain asphalt in concentrations ranging from 0% to 65%. They are

the highest molecular weight compounds in petroleum. Some of them have
boiling points in the range of lubricating oils and heavy gas oils. Asphalts
readily oxidise and form carbonaceous sludge and hence must be removed
from lubricating oils. These are also undesirable in heavy gas oils to be
used as catalytic cracking feedstock because they form coke. The
processes by which asphalts are removed from heavy stocks are known as
deasphalting. They may be atmospheric distillation, vacuum distillation, acid
treatment and solvent extraction.
Owing to heavy losses of hydrocarbons, acid treatment for deasphalting
is almost obsolete. The bulk of the asphalts are removed by atmospheric
and vacuum distillation. However, a good deal of desirable materials for
lubricating oils is still left in the residue from vacuum distillation. Solvent
deasphlating is the best process from this point.
Dewaxing
Petroleum waxes are solid hydrocarbons (melting point 35–95°C), which

are soluble in crude oils and their fractions. They boil in the wide
temperature range of distillate fuels and lubricating oils, and hence cannot
be separated by distillation. On the other hand, the dissolved waxes
precipitate out at low temperatures and therefore the wax-bearing diesel
fuels and lubricating oils must be dewaxed. Wax is the valuable by-product
of the dewaxing processes.
Dewaxing is done by chilling the oils when wax crystallises out. The wax
crystals are separated by filtration, centrifuging or settling. The separation
stage is difficult, tedious, time-consuming and uneconomical. However, if
the oil is first dissolved in a suitable solvent and the solution chilled, the
crystallised wax can be more conveniently separated from the solution in
vacuum filters. Methyl ethyl ketone (MEK) and propane are the two solvents
that are widely used in dewaxing processes.
There is another method of dewaxing, which is based on the fact that
urea forms solid, filterable complexes, called adducts, with large paraffins
having little or no branching. Urea dewaxing is very effective on lighter
stocks.
Dewaxing processes are particularly important in the refining of the
highly waxy Indian crudes.
Deoiling
A large quantity of oil is left in the crude waxes produced in dewaxing

processes. The oil content may be as high as 50% if the chilling is done
without a solvent. Hence the importance of the deoiling process. A finished
wax should not contain more than 0.5% oil. There are three types of
deoiling processes, namely sweating, resettling and solvent extraction.
1. In the sweating process, the crude wax, slack wax, is melted and ca
thick sheets. These sheets are then subjected to slow heating on pa
a perforated false bottom. As the temperature rises, a mixture of
low-melting wax drains out. The heating is continued until the rem
wax has the desired melting point. The sweating process may be re
for the production of good quality wax.
2. In the resettling process, the slack is diluted with cold naphth

recrystalised by chilling. Final separation of the wax crystals
centrifuging.
3. Propane or a mixture of methyl ethyl ketone and an aromatic solve

be used in the solvent extraction process. These selective solven
better separation than naphtha. The steps in solvent deoiling are sim
those in solvent dewaxing.
5.2.6 IMPORTANT PETROLEUM PRODUCTS
The main products of a petroleum refinery are motor gasoline, a

gasoline, kerosene, jet fuels, diesel fuels and fuel oils.
A few other products are also obtained in large quantities, either

from a refinery or by further processing feedstocks obtained from a re
these are lubricating oils, petroleum wax, bitumen, industrial naphtha
and liquefied petroleum gas (LPG).
A third category of petroleum products includes medicinal oils, trans

oil, spray oils, insecticidal oils, and various types of machine oils.
Petrochemicals form an entirely different class of products.
Gasolines
Gasolines are the liquid fuels used in reciprocating spark-ignition internal

combustion engines. These are broadly of two types: motor gasoline and
aviation gasoline.
Motor gasoline is a mixture of low boiling hydrocarbons with a final boiling

point of about 215°C. It is made in a refinery by blending a number of
products, such as
1. Staiglt-run (virgin) gasoline obtained directly by the distillation of crud
2. Cracked gasoline produced by the cracking of gas oils,
3. Reformate obtained by the reforming of heavy naphtha,
4. Components produced by the alkylation and polymerisation of c

gases,
5. Natural gasoline obtained as a condensate from natural gas.
Butane is added (up to about 10%) to facilitate easy start of cold engines.
Natural gasoline and liquefied petroleum gas are the sources of butane.
Commercial motor gasoline contains a number of additives also. These
are anti-knock agents such as tetraethyl lead (TEL), combustion deposit
modifiers, such as tricresyl phosphate (TCP), and antioxidants, such as 2,
6-ditertiary butyl-4-methyl phenol (2, 6 B4M) and N, N1-disecondary butyl-p-
phenyline diamine, to prevent gum formation. Sometimes a few other
additives are also used. Metal deactivators are used to arrest gum
formation due to trace metals like copper and iron. Cleansing agents are
added to prevent deposits in the fuel supply system. Similarly, anti-rust
agents and anti-icing agents are also added.
Table 5.9 gives the specifications for motor gasoline (IS: 2796-2000).
Gasolines are dyed to impart distinctive colours to different brands and
grades.
Table 5.9 Specifications for motor gasoline (IS: 2796-2000)

Characteristic 83 octane 93 octane
gasoline gasoline
Colour, visual orange red
Octane number (research method), min 83 93
Ledd content (as lead, g/l, max) 0.56 0.80
Distiliation
(i)Initial boiling not limited but to be
reported
point
(ii) Recovey up to 70°C, per cent 2 2
by volume, min
(iii) Recovery up to 125°C, per 10 10
cent by volume, min
(iv) Recovery up to 180°C, per 90 90
cent by volume, min
(v)Final boiling 215 215
point, °C, max
(vi) Residue, per cent by volume, 2 2
max
Reid vapour pressure at 38°C, kgf/cm2, max 0.70 0.70
Sulphur, total per cent by weight, max 0.25 0.20
Residue on evaporation, mg/100 ml , max 4.0 4.0
Oxidation stability, minutes, min 360 360
Copper strip corrosion for 3 hours at 50°C not worse than no. 1
Density at 15°C not limited but to be
reported
Aviation gasolines are characterised mainly by higher volatility and higher

octane rating than the motor gasolines. Although a higher proporation of
TEL may be added, say, upto 4.6 ml per US gallon, the other additives are
lesser in number and quantity. Aviation gasolines are composed mostly of
iso-paraffin alkylates and aromatic reformates.
Kerosene
Kerosene is used mainly in oil lamps, stoves and cookers. The desirable
constituents are paraffins. Therefore, it is obtained as a straight-run distillate
from selected crude oils. No additives are used to improve its quality. The
purification processes are sufficient to yield kerosene with desired
properties (Table 5.10).
Table 5.10 Specifications for kerosene (IS: 1459-1974)

Characteristic Requirement
Acidity, inorganic Nil
Burning quality
(i)Char value, mg/kg of oil 20
consumed, max
(ii) Bloom on glass not darker than
grey
chimney
Colour (Saybolt), min 10
Colour-strip corrosion for 3 hours at 50°C not worse than
no. 1
Distillation
(i)Per cent recovered below 200°C, 20
min
(ii) Final boiling point, °C, 300
max
Flash point (Able),°C, min 35
Smoke point, mm, min 20
Sulphur, total, per cent by mass, max 0.25
Jet fuels
Kerosene-type fuel oils with low freezing point are mainly used in
commercial jet airliners. Military jet aircraft use a 30:70 blend of a kerosene
fraction and a low octane straight-run heavy naphtha fraction. Light gasoline
or butane is added for adjusting the volatility. Antioxidants, metal
deactivators and corrosion inhibitors are employed as additives to jet fuels.
Diesel fuels
Straight-run distillates from paraffin and mixed base crude oils are the most
desired components of diesel fuels; but these are often utilised as cracing
stock for gasoline production. Moreover, there is some overlap in the boiling
ranges of kerosenes and diesel fuels. The latter are, therefore, prepared
from heavy distillates obtained from catalytic cracking units. These
distillates are rich in aromatics and iso-paraffins; the low cetane number is
improved by the use of additives. The suitable volatility is obtained by
blending with light fractions. Residual oils are also used in significant
proportions in meeting the large demand of diesel fuels. The increased cost
of maintenance—due to the use of poor fuels in diesel engines—is more
than offset by the low cost of these fuels (Table 5.11).
Table 5.11 Requirements for automotive diesel fuel

SI. No. Characteristics Requirements
Bharat Stage Bharat Stage
II III
1. Acidity, inorganic nil nil
2. Acidity, total mg of KOH/g, max to report to report
3. Ash per cent by mass, max 0.01 0.01
4. Carbon residue (Ramsbottom) on 10% 0.30 0.30
residue, per cent by mass, max
5. Cetane number, min 48 51
6. Cetane index, min 46 46
7. Pour point, max
(a) Winter 3°C 3°C
(b) Summer 15°C 15°C
8. Copper-strip corrosion for 3 h at 100°C not worse not worse
than No. 1 than No. 1
9. Distillation, per cent (v/v), recovered:
(a) at 350°C, min 85 –
(b) at 360°C, min – 95
(c) at 370°C, min 95 –
SI. No. Characteristics Requirements
Bharat Stage Bharat Stage
II III
10. Flash point
(a) Abel, °C, min 35 35
(b) Pensky-Martens closed cup, °C, min 66 66
11. Kinematic viscosity, centistokes at 40°C 2.0–5.0 2.0–4.5
12. Sediment, per cent by mass, max 0.05 –
13. Total contamination, mg/kg – 24
14. Density at 15°C, kg/m3 820–860 820–845
15. Total sulphur, mg/kg, max 500 350
16. Water content
(a) per cent (v/v) 0.05 –
(b) mg/kg, max – 200
17. Cold filter plugging point (CFPP), max
(a) Winter 6°C 6°C
(b) Summer 18°C 18 °C
18. Total sediments, mg/100 ml, max 1.5 –
19. Oxiidation stability, g/m3 max – 25
20. Polycyclic aromatic hydrocarbon (PAH), per – 11
cent by mass, max
21. Lubricity corrected wear scar diameter (wsd 460 460
1.4) at 60°C, microns, max
22. Oxygen content, per cent by mass, max 0.6 0.6
Fuel oils
The wide range of liquid fuels used in boilers and furnaces is covered by the
term fuel oil (Table 5.12). At one extremity we have a light fuel oil produced
from a cycle gas oil of cracking units, and at the other extremity we have
heavy fuel oils produced from residual stocks of crude distillation units,
catalytic cracking units, thermal cracking units and cokers. Several
intermediate grades of fuel oils may be made by the blending of distillates
and residual stocks. Visbreaking of residual stocks is a very important
process in the production of fuel oils. Cycle gas oil is given such treatment
as filtration through clay and hydrofining. Sludge dispersing agents and
tricresyl phosphate are added to improve the combustion in burners. In the
case of residual fuel oils, magnesium-bearing additives may be used largely
to eliminate corrosion and fouling.
Table 5.12 Specifications for fuel oils derived from petroleum or shale (IS: 1593-1982)
Characteristic Grades
Low Medium Medium High
viscosity viscosity 1 viscosity 2 viscosity
Flash point (Pensky–Martens) 66 66 66 66
(closed),°C, min
Kinematic viscosity, centistokes 80 125 180 370
at 50°C, max
Water content, per cent by 1.0 1.0 1.0 1.0
volume, max
Ash, per cent by mass, max 0.1 0.1 0.1 0.1
Sulphur, total per cent by mass, 3.5 4.0 4.0 4.5
max
Sediment, per cent by mass, max 0.25 0.25 0.25 0.25
Acidity, inorganic nil nil nil nil
Lubricants
Lubricants include a wide range of products. Base oils are obtained as

distillates or residual products in the refinery and are blended to meet
specific requirements of individual operations. The conventional additives
include fatty oils, lard and fatty acids. Some of the additives contain
constituents like sulphur, lead, graphite, molybdenum disulphide or metal
soaps. Antioxidants and anti-corrosion agents are also sometimes added to
protect the metal surfaces from corrosion.
5.2.6 PROPERTIES AND TESTING OF PETROLEUM AND PETROLEUM PRODUCTS
It has been seen in the previous section that the petroleum products include
a wide range of substances. The properties that make them suitable for
specific uses differ from case to case. No single set of test procedures is
therefore available for evaluating them. Some of the common and special
properties of petroleum products and the principle of the corresponding test
procedures are discussed below. Indian specifications for some products
are given in Tables 5.9 to 5.12
Specific gravity
Specific gravity is used in calculations involving weights and volumes.

Because of the closeness of the inherent chemical nature of the main
components of petroleum products, it has been possible to correlate their
specific gravity with other important parameters. Higher specific gravity
means higher concentration of carbon in relation to hydrogen. Hence,
heavier oils have lower calorific value (gross) on a weight basis.
The reverse is true if the calorific value is expressed on a volume basis.
The following equation is useful in the calculation of gross calorific values of
petroleum oils:
where, CG is the gross CV, kcal/kg, and d is the specific gravity at

15.5/15.5°C.
In many empirical correlations, specific gravity is used as Degree API
defined in the following way by the American Petroleum Institute:
This is a slight variation of the Baume scale. Among hydrocarbons, the

aromatics have higher specific gravity than the paraffins. Therefore a
knowledge of specific gravity can appreciably predict the quality of a given
product.
Viscosity
Viscocity is a very important property of fluids and a measure of their

resistance to flow. In petroleum technology, this property is widely used in
design calculations for transportation, combustion in burners and internal
combustion engines and lubrication. It is an important specification
parameter for many petroleum products.
Viscosity may be determined in a U-tube viscometer and other
convenient apparatus. The conventional method for oils is to measure
kinematic viscosity and express this in centistokes or some arbitrary units.
Standard equipment and standard procedure are used to measure the time
required for a fixed volume of oil to flow through an orifice of fixed
dimension at a certain temperature. Different standards vary in the design
of the equipment and the procedural details. The different standard
viscometers used for oils are: Engler, Redwood No. I, Redwood No II,
Saybolt Universal and Saybolt Furol. The result is usually expressed as the
number of seconds required for the flow. In the Engler viscometer, the
viscosity is expressed as a ratio of the time of flow of equal volumes of oil
and water and is called degree Engler. It is possible to convert the data of
one standard into those of another and also into stokes (Table 5.13).
Table 5.13 Viscometer conversion factors
Viscosity is one of the most important criteria of fuel oils. It significantly

influences the ease of handling and transport and the nature of storage.
The viscostiy of the oil supplied to atomising oil burners has a direct effect
on a burner’s performance, and hence on its combustion efficiency.
Residual oils have high viscosity at ordinary temperatures and need
preheating before atomisation. The viscosity of fuel oils falls as the
temperature rises but becomes nearly constant above 120°C. For
atomisation, there is little gain in heating the oil beyond 120°C. The
maximum viscosity for easy atomisation in conventional burners is 25
centistokes or 100 sec Redwood No. I. For easy pumping in usual pipes,
the maximum is 1,200 centistockes or 486 sec Redwood No. II.
There are two opposing effects of oil preheating on the capacity of the
burner. While decreased viscosity facilitates flow of oil through the service
line and atomisation in the burner, decreased density results in the delivery
of lesser weight of oil to the burner. There is therefore an optimum
temperature beyond which additional preheat actually lowers the burner
capactiy.
The performance of diesel fuels also greatly depends upon their
viscosity. Too low a viscosity causes excessive leakage at the injection
pistons while too high a viscosity produces coarse oil droplets which result
in the formation of engine deposits owing to incomplete combustion. The
action of lubricating oils in a particular system depends upon their particular
viscosity. Owing to oxidation and other reasons, viscosity changes
appreciably which necessitates the periodical replacement of the lubricant.
The effect of temperature on viscosity of oils is well known. If a system is
subjected to a variation of temperature, and if the viscosity of the lubricant
varies beyond the tolerable limit, the purpose of lubrication is defeated. It
has been found that the extent of variation in viscosity for a given
temperature fluctuation is not the same for all lubricating oils. Paraffinic
stocks tend to resist alteration in viscosity with temperature change while
naphthenic stocks show large dependence of viscosity on temperature. This
viscosity–temperature relationship of lubricating oils is denoted as the
viscosity index (VI) and is expressed as a number on an arbitrary scale. A
highly paraffinic Pennsylvania oil has a VI of 100 and a naphthenic Gulf
Coast oil has a VI of 0. If L, H and U are the viscosities in CS of the 0 VI,
100 VI and the given oil, respectively, at 100°F.
The viscosity of the two standard oils and the unknown sample must be the
same at 210°F. The kinematic viscosity, U, of the sample is first determined
at 210°F and the values of L and H are then read from the standard ASTM
chart corresponding to that viscosity of the sample.
Oils with a high VI are preferred where a wide variation in temperature is
encountered as in the outdoor use of crank case oils and hydraulic oils.
Certain additives, for example, polybutenes improve the VI of oils. For high
VI oils (VI>100), another parameter called viscosity index extension (VIE) is
used.
At very high pressures the viscosity of oils increases considerably. At a

pressure of 70 kgf/cm2, the increase is by 15%. Most oils begin to solidify at
3,500 kgf/cm2.
Viscosity is not an additive property. Therefore the viscosity of oil blends
has to be experimentally determined or calculated with the help of empirical
blending charts.
Distillation range
Distillation range is the difference in temperature between the temperature

at the initial boiling point and at the end point of a distillation test. It pertains
to distillate products such as gasoline and kerosene. Residual fuel oils are
not normally subjected to a distillation test. The singlemost important
criterion for crudes is their distillation characteristics.
In the distillation test for petroleum products, a measured volume of the
oil is distilled at the specified rate which is suitably increased as the
distillation proceeds. The initial boiling point (IBP) is the temperature when
the first drop falls from the condenser and the final boiling point (FBP) is the
maximum temperature recorded at the end of distillation. Mid-boiling point is
the temperature at which 50% of the oil distills off. Distillation is stopped at
360°C because further heating causes cracking of the residue. If necessary
the distillation may be confined under vacuum. The distillation range is of
value in the evaluation of petroleum products.
Distillation parameters like mid-boiling point often find application in
correlations for other important parameters.
Distillation data are conveniently used to construct very useful curves,
for example, true boiling point (TBP) curves, and equilibrium or flash
vaporisation curves. The TBP curves give the variation of boiling point with
the yields of distillates. Each point in the flash vaporisation curve gives the
total amount of vapour in equilibrium with the liquid at the particular
temeprature. These curves are used in the design of continuous distillation
equipment in refineries.
Flash point and fire point
The flash point is defined as the minimum temperature at which the given
oil evolves just sufficient vapour to form an inflammable mixture with air, as
shown by the formation of a momentary flame (flash) when an external
source of fire is brought in contact with the vapour. The fire point is the
minimum temperature at which the oil vapours will continue to burn instead
of just flashing. For the same product the fire point is higher than the flash
point. It is customary to determine and report both the temperatures,
although the lower temperature (flash point) is itself a measure of the fire
risk of an oil or any inflammable liquid in bulk.
The permissible conditions of storage and use are different for products
with flash points below 23°C (gasoline), between 23°C and 66°C (kerosene)
and above 66°C (fuel oils and gas oils). The oils of the first category are
regarded as dangerous and highly inflammable for transport and storage,
and are subject to strict government regulations. Fuel oils with flash points
above 66°C are regarded as safe.
Besides depending on such inherent properties of the oil as the volatility
and the inflammability limits of the vapour-air mixture, the flash point also
depends upon the design of the apparatus, the test procedure and the
barometric pressure. Two types of apparatus are commonly used:
1. The Pensky–Martens apparatus for oils with flash point above 50 °C,
2. The Abel apparatus for oils with flash points below this temperature.
Kerosene is tested in the Abel, and fuel oil, diesel fuels and gas oils in the
Pensky–Martens apparatus. Both these apparatuses are of the closed-cup
type. The oil is heated in a closed cup under specified conditions and a pilot
flame is introduced into the vapour space by opening a shutter in the lid.
The American Tag apparatus is similar to Abel.
Flash points of lubricating oils, some crude oils and residues are often
determined by the open-cup tests. Either the Pensky–Martens cup or the
Clevelend open-cup is used. The open-cup test is liable to error and gives
only approximate values. The open-cup flash point is higher than the
closed-cup value for the same sample.
The flash point and the fire point give indications of the range and
nature of the boiling point curve. The flash point of lubricants helps to
indicate the relative amount of low-boiling mateial present in it.
These temperatures must not be confused with the completely unrelated
spontaneous ignition temperature (SIT) (see Chapter 8).
Pour point and cloud point
These are used as criteria for fuel oils lubricating oils and diesel fuels used
in cold surroundings. The pour point is defined as the temperature 5°F
(2.8°C) higher than that at which the oil ceases to flow when cooled and
tested according to prescribed conditions. The cessation of flow results from
an increase in viscosity or from the crystallisation of wax from the oil. Heavy
fuel oils have quite a high pour point and heating facilities are usually
necessary in order to ensure the satisfactory flow of the oil. Fuel oils of wax-
bearing crudes have much higher pour point than those derived from crudes
of low wax content. A low pour point is the desired property of an oil in
respect of handling in cold atmosphere.
The cloud point is defined as the temperature at which an oil becomes
cloudy when it is cooled in a specified manner. This temperature is higher
than the pour point (usually by 5°C to 6°C). The cloud is due to wax
crystals. If the oil is moist then also it may become cloudy due to the
immisibility of oil and water at the low temperature. The cloud point is more
significant than the pour point for diesel fuels where the wax crystals can
plug the filters in the fuel injection system and stop the flow even when the
oil is above its pour point.
Asphaltic substances act as pour point depressants, that is, they reduce
the pour point of an oil by inhibiting the growth of wax crystals. Pour points
may also be reduced by increasing the proportion of lighter hydrocarbons in
an oil. In general, naphthenes and aromatics have a lower pour point than
paraffins. Unfortunately the former are the undesired components of fuel
oils and diesel fuels.
Smoke point and char value
These empirical criteria are determined to assess the burning quality of

kerosene as an illuminant or as a fuel. A good quality kerosene should be
clean in respect of smoke in the flame and the deposits, char or toadstool
on the wick. Smoking is due primarily to aromatic hydrocarbons; char
deposits are related to both aromatics and disulphides. The smoking
tendencey of kerosene is determined by the smoke point test, and the
deposit forming tendency by the char value test.
The smoke point is the maximum flame height in millimetres at which
kerosene will bum without smoking in a standard apparatus. Good quality
kerosene shows a smoke point of 20 to 25 mm. Careful acid treatment
raises the smoke point to above 30 mm.
The char value is the amount of char in milligrams, for every kilogram of
kerosene burned, which is formed on the wick of a standard lamp burning
under prescribed conditions. The char value of a high grade kerosene
should not exceed 20 mg/kg.
The formation of smoke and char depends upon the type of burning
appliance also. Some appliances need kerosene of high smoke point and
low char value. Yellow flame, wick-fed appliances, for example, railway
signal lamps which are required to burn for prolonged periods without
attention, fall into this category. Blue flame appliances, for example, space
heaters, can tolerate kerosenes of lower smoke point and higher char value.
The burning quality of kerosene is also judged by its tendency to form a
white or grey deposit or bloom on the glass chimney of lamps, which leads
to a reduction in the illumination power. Disulphides are believed to be
responsible for the bloom.
Carbon residue
This property is important for oils used in gas production, in diesel engines,
in burners and for lubricating oils used in motors. When an oil is heated
both evaporation and cracking set in. The heavier, complex compounds
form, on decompostion, some carbonaceous deposits known as carbon
residue. There are two methods for the determination of this residue,
Conradson’s and Ramsbottom’s. The Conradson test is used for fuel oils
and the Ramsbottom test for lubricating oils. The distillate fuels have a low
carbon residue and the test is applied on the 10% residue after distilling off
90% of the fuels. Kerosenes have so low a residue that this test is
meaningless and the char value is determined in lieu of carbon residue.
Fuels for high speed diesel engines should have a Conradson carbon
residue of not more than 0.1% on a 10% distillation residue. Low and
medium speed engines can tolerate much higher values of Conradson
carbon. The nature of the carbon deposits in diesel engines is very
important. If the deposit is fluffy it is easily removed with the exhaust gases.
On the other hand compact deposits get firmly attached to the engine parts.
Atomising burners are practically insensitive to the carbon residue of the
fuel. However the gas oils used in the vaporising burners should have
Conradson carbon value not exceeding 0.05% on the 10% distillation
residue.
Sulphur content
All crudes contain sulphur. Even after passing through various purification
processes the petroleum products contain sulphur. In general the sulphur
content increases with the increase in the boiling range of the product.
Some typical values are: kerosene 0.05%–0.2%, gas oil and diesel oil
0.3%–1.5% and fuel oil 2%–4%. The high value, 4% is for the heavy
furnace oils of high sulphur crudes.
The sluphur content of oils is best determined by using a bomb
calorimeter. Approximate values are obtained by the lamp method in which
a known weight of the oil is burned in an air current and the combustion
products passed through an alkaline solution, the sulphur being finally
estimated in the solution as sulphuric acid.
The sulphur content should be as low as possible. Sulphur is largely
present in oils in the form of corrosive organic compounds. On combustion
it gives off foul gases.
Moisture
The solubility of water in oils is quite low—0.005% to 0.05% under ordinary

conditions. It may however be present in the dispersed state in residual fuel
oils up to 1%. Water in oils is undesirable. Its separation from oils is
facilitated by preheating. The Dean and Stark method is used for the
determination of moisture in oils. The sample is heated with xylene which
forms an azeotrope with water. The distilled vapours on condensation and
settling give water as a separate layer which can be measured. The Karl
Fischer test can be used to accurately determine water content of 50 to
1000 ppm in oils. The method consists of electrometric titration with a
special reagent.
Ash
The amount of ash in petroleum products is normally very low. The

distillates should have zero ash but certain additives to gasolines or diesel
fuels raise its value. Even a residual fuel should not have ash exceeding
0.1%. Some constituents of petroleum ash have very harmful effects. The
presence of vanadium in fuel oil causes discolouration of the molten glass
tanks, while sodium causes bonding of ash constituents on boiler
superheaters and also attacks refractories.
Calorific value
The ultimate analysis of petroleum fuels does not vary widely. Therefore
their calorific value also varies within a comparatively narrow range,
10,000–11,300 kcal/kg gross, the higher figure being for gasolines and the
lower for heavy furnace oils. Petroleum products are high in hydrogen
content, 11.8% to 14.5%, and hence their net calorific value is less than the
gross by as much as 620–760 kcal/kg. The calorific value of oils is
determined in a bomb calorimeter. Empirical formulae are available for
calculating the calorific value of petroleum fuels from their specific gravity
(Eq. 5.1).
Octane number
Maximum power is derived from gasoline when it bums silently and

relatively slowly. Under certain engine conditions the combustion may begin
smoothly and then the whole of the unburnt fuel may burn rapidly with the
formation of pressure waves (detonation). This leads to knocking of the
gasoline engine. Much of the generated power is wasted and the engine life
is shortened when knocking occurs. A good gasoline should resist
knocking. The anti-knock quality of fuel is measured in a standard engine in
terms of the relative performance of two standard fuels and then expressed
as its octane number. By definition, the octane number of a gasoline is
equal to the percentage by volume of iso-octane (2,2,4-trimethyl pentane) in
a mixture of n-heptane and iso-octane having the same knocking tendency
as the sample being tested. n-Heptane is of poor anti-knock quality and is
assigned zero octane number. On the other hand, iso-octane has excellent
anti-knock quality and is assigned an octane number 100. If a gasoline
matches with a 80/20 blend of iso-octane and n-heptane, its octane number
is 80. Secondary reference fuels are used in practice for experimentally
determining the octane number of gasoline.
The anit-knock quality of a gasoline primarily depends upon the types of
hydrocarbons present. Aromatics have the best anti-knock quality and iso-
paraffins, naphthenes, olefins and n-paraffins follow in succession. All the
refinery processes for the upgrading of gasolines aim at the conversion of
other hydrocarbons into aromatics and iso-paraffins.
A certain minimum anti-knock quality is required for knock-free
operation of a gasoline engine. This requirement primarily depends on the
engine compression ratio. In the USA and Canada, the motor gasoline is
marketed in two grades: regular with octane number 94 and premium with
octane number 100. The motor gasolines in India have 83 and 93 as the
specified octane numbers. Aviation gasolines have octane numbers
exceeding 100.
The octane rating of commercial gasolines is not entirely due to the
hydrocarbons only. Certain additives are put into the gasoline to raise its
octane number. The most effective and common additive is tetraethyl lead
(TEL) which is used in admixture with organic halides. The halides are
added to prevent the deposition of lead by forming volatile lead halides.
Paraffins and naphthenes have higher lead susceptiability than aromatics.
Other anti-knock agents are tetramethyl lead (TML) and tertiary butyl
acetate. Methyl-cyclo-pentadienyl manganese tricarbinol may be used in
conjuction with TEL for boosting the octane number of motor gasoline.
Cetane number
There is a time lag (delay period) between the injection of diesel fuel into
hot compressed air and its ignition. If the delay period is unduly large there
will be accumulation of too much fuel in the cylinder, which will eventually
burn with an undue rapidity. A rapid rise in the cylinder pressure will follow
and cause a ‘diesel knock’. The delay period is inherently connected with
the type of hydrocarbon. The preferred hydrocarbons in the order of
decreasing ignition quality (increasing delay period) are: n-paraffins, olefins,
naphthenes, iso-paraffins and aromatics. This order is the reverse of the
order for gasoline anti-knock quality.
The ignition quality of diesel fuel is measured in a standard engine by
matching against blends of two reference fuels and expresssed in terms of
cetane number. A n-paraffin (n-hexadecane or cetane, C16H34) is given 100
cetane number and an aromatic (d-methyl naphthalene) is given zero
cetane number. If the given fuel matches with a 40/60 blend of cetane and
α-methyl naphthalene, it is assigned a cetane number of 40. In practice,
secondary reference fuels are used in the test because the primary
references are costly and not easily available.
High speed engines, above 1,500 rpm, need high cetane number (45–
50) fuels. A low speed engine is not so demanding since there is more time
available for the combustion. A cetane number of 25 to 30 may suffice.
Diesel fuels are composed largely of distillates. Cracked fractions are
rich in iso-paraffins and aromatics, and hence the amount of cracked
fractions in good diesel fuels should be low.
The cetane number of diesel fuels rich in aromatics and iso-paraffins
may be improved by the addition of alkyl nitrates (amyl and butyl nitrate),
carbamates (isopropyl-n-methyl-n-nitrocarbamate), peroxides (ditertiary
butyl peroxide) and metal-organic compounds. These additives are less
effective towards catalytically cracked stocks than towards straight-run
stocks.
Aniline point
This is defined as the temperature at which a liquid just becomes

completely miscible with an equal volume of aniline. Aromatics are easily
miscible with aniline and have a low aniline point. On the other hand,
paraffins have high aniline point. This test is therefore an indication of the
type of hydrocarbon present in a petroleum product. Hexyl benzene has an
aniline point of -12°C while cetane has a value of 95.1°C. A high aniline
point is an indication of high suitability as a diesel fuel.
The aniline point of a diesel fuel is usually converted into an empirical
diesel index with the help of the following formula:
Numerically the diesel index is usually three units higher than the cetane
number. It is not a very reliable parameter, however its ease of
determination makes it popular in the evaluation of the ignition quality of
diesel fuels.
5.2.7 PETROLEUM REFINING IN INDIA
Petroleum refining in India started in 1893 with the setting up of a small

refinery at Margherita in Assam, which is now non-existent. Set up in 1899,
the Digboi refinery represents the first major refinery in the country. With an
initial refining capacity of 0.25 million tonnes of crude, this was the only
refinery up to 1954 and could meet 7% of the demand of petroleum
products in the country. The crude was available from the Digboi fields.
In the mid 1950s, three coastal refineries were set up by foreign-
controlled oil distributing companies, two on the west coast and one on the
east coast. The crude requirements of these refineries were met by imports.
Following the discovery of oil in new areas in Assam and Gujarat, three
government-controlled refineries were set up between 1962 and 1965 at
Guwahati, Barauni and Koyali in succession. These were all based on
indigenous crudes. In the absence of substantial new oil finds, and with the
growth in the demand of petroleum products in the country, three more
coastal refineries were set up on the basis of imported crudes, two in the
south and one in the east.
After the discovery of the large oil reserves in the Bombay High offshore
areas, the import of crude oil was sharply reduced and many refineries
started operation with indigenous crude. One more refinery was set up at
Bongaigaon in Assam in 1981 and, for the first time, a large refinery was
built at Mathura in Uttar Pradesh in 1984 to process indigenous crude from
Bombay High and Gujarat. The government has approved two more large
refineries, one on the west coast and the other in the deep north. The list of
all the refineries is given in Table 5.3.
The growth of the petroleum industry in India may be judged from
Tables 5.2 and 5.4. Both the production of crude oil and the throughput of
refineries have increased remarkably. The country has to import more than
10 million tonnes of crude from the Middle East while the indigenous
production is hovering around 30 million tonnes. The production of all the
petroleum products taken together is now slightly in excess of their total
consumption of over 40 million tonnes.
There is some imbalance in the patterns of production and consumption
of petroleum products in India (Table 5.14).
Table 5.14 Growth of the Indian petroleum industry
The existing refineries can meet the present requirement except in

certain products like kerosene and lubricants. Compared with other
countries, the per capita production of petroleum products is still very low.
The flow-sheet of a refinery in India is shown in Fig. 5.6
Figure Flow-sheet of a refinery in India
5.6
Lubricating oils are made in the refineries at Digboi. Barauni, HPCL

(Mumbai), Chennai and Haldia. There are two separate lube oil blending
plants, one each at Kolkata and Mumbai.
5.3 LIQUID FUELS FROM SOURCES OTHER THAN
PETROLEUM
5.3.1 COAL TAR AND COAL TAR FUELS
Where distillation facilities are not available, crude coal tar is used as a
furnace fuel. Like other crude fuels, it possesses a number of
disadvantages:
the presence of volatile components which are lost on storage and
increase the fire hazard,
the presence of varying amounts of water which reduce the calorifc

leading to corrosion and irregular combustion,
the presence of solid impurities such as coke dust which may

choking of the burners and pipe lines.
Because of the above considerations and because of the fact that coal tar is
a storehouse of chemicals, its direct use as a fuel is discouraged. It is
preferable to distil the tar into various fractions and then prepare liquid fuels
from certain distillate fractions and their blends with the residual pitch.
These fuels are known as coal tar fuels (CTF).
The coal tar fuels are designated by numbers which are the
temperatures in degrees Fahrenheit to which they must be heated to reach
a condition suitable for atomisation, that is having a maximum viscosity of
25 centistokes. The range of coal tar fuels covers CTF 50, CTF 100, CTF
200, CTF 250, CTF 300 and CTF 400. For example, CTF 200 is the fuel
which is to be preheated to 200° F for ensuring a decreased viscosity for
smooth atomisation. CTF 50 does not need any preheating.
CTF 50 and CTF 100 are the blends of the creosote oil, 230 to 270°C,
and anthracene oil, 270° to 350°C, fractions. CTF 400 is the distillation
residue with a softening point of 75–80°C, that is ‘medium soft’ pitch. CTF
200, 250 and 300 are the blends of the creosote oil, anthracene oil and
residual pitch. While CTF 400 is used as a liquid fuel in installations close to
the site of production, a hard pitch is also manufactured for use as a fuel in
pulverised form.
The most popular coal tar fuel is CTF 200 which is normally a 50:50
pitch-creosote blend. A typical ultimate analysis is: C 89.1, H 6.4, N 1.1, S
0.5, O 2.9 and ash 0.07. Other CTFs show slight variation from these
figures. In general, carbon content increases and hydrogen and oxygen
content decrease in the series CTF 50 to 400. The C:H ratio increases from
11.0 to 16.5 in this series. These high values are due to the aromatic nature
of the coal tar fuels.
Table 5.15 gives the important properties of coal tar fuels. The contents
of sulphur and ash are very low. Besides, the harmful element, vanadium is
negligible in them. The alkali content is also very low.
Table 5.15 Properties of coal tar fuels
Coal tar fuels have two outstanding features—low sulphur content and
high flame emissivity. The latter property is associated with the aromatic
nature of these fuels. Superiority of coal tar fuels to other liquid fuels is best
displayed in open hearth furnaces in many metallurgical processes where
low sulphur content and high flame emissivity are fully exploited. Other
applications of CTFs include the productioin of aluminium and cement in
rotary furnaces, the making of glass and steam raising.
Mention should be made of the use of the light oil fraction, upto 180°C of
coal tar in the production of motor benzol. Motor fuel and diesel fuel are
also obtainable from the creosate oil fraction by suitable treatment of
hydrogenation.
5.3.2 LIQUID FUELS FROM COAL AND COAL TAR FRACTIONS BY

HYDROGENATION
The conversion of coal into oil is essentially a process of raising the H:C
ratio. The destructive hydrogenation of coal in the presence of catalysts
yields oils and is known as the Bergius–Pier process. The first commercial
plant based on this process was installed in Germany in 1927 to convert
brown coals into gasoline. During the Second World War Germany had a
number of such plants which supplied the majority of her liquid fuel
requirements.
The production of liquid fuels by the hydrogenation of coal is not yet
competitive with petroleum refining. Currently there is no commercial plant,
although efforts are being made to improve the technical and economic
aspects of coal hydrogenation.
The conventional coal hydrogenation process operates in two stages:
1. Liquid-phase hydrogenation to produce a middle oil,
2. Vapour-phase hydrogenation of the middle oil to gasoline.
The coal is first ground and made into a paste with a heavy recycle oil and
catalyst which is a compound of iron, tin or molybdenum. The paste is
preheated and then treated with hydrogen at high pressure, 250–350 atm or
more at a temperature of 450°C to 500°C. The unreacted coal is filtered off
and the liquid product distilled. The middle oil is further hydrogenated. The
light oil gives gasoline, while the heavy oil is recycled. The main product of
the second stage—vapour-phase catalytic hydrogenation of the middle oil—
is gasoline. The heavier products are recycled. Diesel fuels and fuel oils
may also be produced if desired, but the cost of these products are much
higher than the corresponding petroleum products under existing
technoeconomic conditions in the world today.
In the new processes of coal hydrogenation under development, the
main objective is to accomplish the process at lower pressures by selecting
a suitable catalyst and by varying the process flow-sheet.
The H-Coal process is an advanced process of coal liquefaction by
catalytic hydrogenation. It has been developed in the USA. A simplified
flow-sheet is given in Fig. 5.7.
Figure H-Coal process
5.7
The H-Coal process is a catalytic hydroliquefaction process using an

ebullated bed reactor. Crushed coal is mixed with recycle oil into a paste,
compressed to 200 bar and added, with hydrogen, first to a preheater and
then to the reactor. The hydrodynamics of the reactor are so maintained
that the catalyst level is well below the slurry level. The hydrogenation takes
place at 450°C and 200 bar. The catalyst is in the form of pellets of cobalt
molybdate on alumina. The products are taken out of the reactor and
separated into gases, liquids and solid residue. The liquids on further
processing give gasoline, diesel, fuel oil and other products. The gases are
treated for hydrogen recovery by steam reforming. The solid residue is
gasified and treated for hydrogen production.
The advantages of the H-Coal process relate mainly to the ebullated
bed reactor which is based on the commercial H-Oil process. The main
criticism is due to the likely contamination and degradation of the catalysts
coming in contact with coal and its mineral content. A variation of the coal
hydrogenation process is the coversion of coal into a solution in tetralin or a
similar solvant (Pott–Broche process) and then treating the solution with
hydrogen in the presence of catalyst under suitable conditions of
temperature and pressure. One advanced process under this category is
the Exxon Donar Solvent (EDS) process developed in the USA.
The EDS process is based on petroleum industry technology and is
stated to be simple and flexible enough to accept a range of coals and
produce a spectrum of products to meet market demands. Figure 5.8 shows
the simplified block diagram. The coal is ground, mixed with recycle solvent
oil, preheated and added with hydrogen to a plug-flow reactor operating up
to 465°C and 130 bar; conditions may be altered to suit coals and product
requirements. The unique feature of the process is that the recycle solvent
is hydrogenated in a separate catalytic reactor before being used for the
slurry preparation. There is no extremal catalyst in the hydrogenation of
coal. Its mineral matter, however, has a catalytic effect. All the products are
recovered by distillation and there is no filtration stage. The primary
products can be hydrogenated further. The distillation residues are
subjected to a patented process, flexicoking. The residues are coked to
produce further liquid hydrocarbon products and the resultant coke is
gasified for the generation of fuel gas and hence, hydrogen. The conversion
of coal may be deliberately limited to 70% to provide enough residue to
balance the hydrogen requirement.
Figure EDS process
5.8
Of the coals of different ranks, the bituminous rank (82%–87%) carbon

are the easiest to hydrogenate. Brown coals need more severe conditions.
Coal tar—both high and low temperature—are easier to hydrogenate owing
to higher H:C ratio than coal. There are a number of commercial
hydrogenation plants in West Germany, East Germany, Czechoslovakia and
Poland for the conversion of coal tar and petroleum residual oils into
gasoline, diesel fuel and other products.
The coal tar is usually hydrogenated in a two-stage process. The first
stage consists of a liquid phase hydrogenation at 250 atm and 460–470°C
in the presence of iron or molybdenum catalyst. The second stage is vapour
phase hydrogenation using fixed bed catalysts, molybdenum or tungsten
compound under the conditions of high temperature (400°C) and pressure
(300 atm). Many variations of the tar hydrogenation process have been
developed. While gasoline is the main target product, it is also intended to
produce diesel fuels and fuel oils by reducing the severity of reactor
conditions.
A novel development in the processing of low temperature tar is its
conversion into a material similar to crude petroleum oil by performing mild
hydrogenation at about 50 atm. This synthetic crude can then be processed
in a petroleum refinery, either alone or in blends, with natural crudes for the
production of high octane gasoline, diesel fuel and other products.
It has also been proposed to convert suitable coals into synthetic crude
in the above line and then process it in a petroleum refinery.
The concept of a coal refinery appears tangible. By using a chosen
route coal may be converted into liquid fuels, chemicals and other products
in such a coal refinery.
5.3.3 LIQUID FUELS FROM COAL BY THE FISHER–TROPSCH PROCESS
The process is based upon the catalytic hydrogenation of carbon monoxide

when the following reactions take place:
By the selection of a suitable temperature, pressure and catalyst, the yields

of hydrocarbons in the boiling range of gasoline and diesel fuel are
maximised. Owing to the straight chains, the gasoline is of a low octane
number and needs catalytic reforming before use. For the same reasons,
the diesel fuel is of excellent quality (cetane number exceeding 100). The
other products range from gaseous hydrocarbons to solid wax.
There are many variations of the original Fischer–Tropsch process. By
changing the process variables, the mixtures of carbon monoxide and
hydrogen are made to yield many chemicals, for example, alcohols, ketones
and fatty acids.
While the catalytic reactions between CO and H2 remain the main basis
of the Fischer–Tropsch process, its commercial success largely depends
upon the methods of preparation of the mixture of CO and H2(synthesis
gas) and its purification from impurities like sulphur compounds, carbon
dioxide, and other compounds which cause serious catalyst poisoning.
About 80% of the operational costs of the process is taken up by the
manufacture and purification of synthesis gas.
Synthesis gas is produced by the gasification of solid fuels like coal and
coke by adjusting the H2:CO ratio to 2:1. The gasification processes will be
discussed in Chapter 6.
The original catalyst for the Fischer–Tropsch synthesis was cobalt. Now
cheaper iron oxide catalysts are used. The process is carried out at 25–30
atm pressure, the temperature being up to 270°C for the Arge fixed-bed
reactor. All the reactions are highly exothermic. Therefore the control of the
reactor temperature is critical.
The Fischer–Tropsch process was developed on a commerecial scale in
Germany before the Second World War and supplied a sizeable proportion
of her liquid fuel requirements during the war. At present there are three
large commercial Fischer–Tropsch plants in the world for the manufacture
of liquid fuels from coal and are located in South Africa (SASOL plants, I, II
and III). Many other countries have investigated the Fischer–Tropsch
process on pilot and semi-commercial scales. The process is in a highly
developed stage and can be widely adopted whenever the economics are
favourable. The SASOL I plant has been on stream since 1955. The three
plants together supply about 70% of South Africa’s motor fuel requirements.
The success of the plant is largely due to the plentiful supply of cheap coal
and the lack of crude oil resources in South Africa.
In the SASOL plants, the raw material is sub-bituminous coal and the
Lurgi process is used to gasify it. The purification of the synthesis gas from
sulphur compounds and CO2 is achieved by washing with methanol at –
60°C at an elevated pressure (Rectisol process). The purified gas contains
56% H2, 27% CO, 14% CH4 and small quantities of carbon dioxide and
nitrogen. It is either passed through an Arge fixed-bed reactor or reformed
with oxygen and steam with the help of nickel catalyst at 20 atm and
1,100°C to convert methane into additional quantities of hydrogen and
carbon monoxide before passing into a Synthol entrained-bed reactor. The
higher temperatures in the Synthol unit give increased yields of gasoline
and comparatively low yields of heavier oils and waxes. The Arge unit uses
lower temperatures and produces a smaller yield of gasoline, but larger
yields of heavier products. The gasoline from the Synthol unit is of much
higher octane rating.
Besides fuels (LPG, gasoline, diesel oil and wax oil), the SASOL plant
also produces chemicals (methanol, ethanol, methy ethyl ketone and
acetone). A simplified flow diagram of this plant is given in Fig. 5.9.
Figure 5.9 Simplified flow-diagram of Fisher-Tropsch process
A recent development of great potential is the production of gasoline

from methanol on a commercial scale by the Mobil process. A new route
has thus been opened up for conversion of coal into synthetic petroleum
products via methanol (Fig. 5.10). Coal is gasified and the raw gas is
treated for generating a mixture of carbon monoxide and hydrogen called
syngas. Methanol is synthesised from the syngas and then converted over
a special zeolite catalyst at about 400°C and 20 atm into gasoline and by-
products. The catalyst may be in the form of fixed bed or fluidised bed.
Hydrocarbons are produced from methanol at a yield of over 99% of the
theoretical, and the share of gasoline in these hydrocarbons is about 80%,
the by-products being liquefied petroleum gas and light gas.
Figure 5.10 Mobil process for the production of gasoline from methanol
There is a 6,00,000 tonnes per year (tpy) gasoline commercial plant,

based on natural gas in New Zealand using the Mobil process. West
Germany has a demonstration scale Mobil plant based on bituminous coal.
5.3.4 MOTOR BENZOL
Crude benzol is a valuable by-product of the coal carbonisation industries. It

contains mainly hydrocarbons together with some acids and bases. A wash
with alkali removes the acids and another with 40% sulphuric acid removes
the bases. The neutral material on distillation gives the first fraction
containing carbon disulphide and some low boiling unsaturated
hydrocarbons. The next fraction, 80–150°C, represents refined benzol and
the heaviest fraction, >150°C, consists mainly of high boiling unsaturated
hydrocarbons.
The refined benzol is essentially a mixture of benzene, toluene and
xylenes. While it can be rectified to get pure aromatic hydrocarbons, there is
a demand for its use as a component of motor gasolines owing to its high
anti-knock quality (about 115 octane number). By blending 50% of motor
benzol, the octane number of a gasoline may be raised from 70 to 80. Motor
benzol is not used as a motor fuel by itself owing to high initial boiling point,
80°C, high freezing point, –50°C and large carbon deposits. Benzol can be
used also as a ternary blend with gasolines and alcohols as motor fuel.
The light oil of coal tar distillation is another source of motor benzol. In
fact crude benzol and the light oil are mixed together before making the
recovery of motor benzol. Crude benzol is water white in colour and is
classified as 90s benzol, 75s benzol, and so on, depending upon the
percentage distilling below 100°C. The gasolines in India do not contain
motor benzol.
5.3.5 ALCOHOLS
Methyl and ethyl alcohols can be used in gasoline engines. Cost

considerations prohibit the use of any alcohol in burners. The octane
numbers of methyl and ethyl alcohols are quite high, 114 and 99,
respectively, but their calorific values are low, 5,335 and 7,120 kcal/kg,
respectively. The flash point is – 1.1°C for methyl alcohol and + 12.8°C for
ethyl alcohol. The lead susceptibility is moderate.
The importance of ethyl alcohol is due to the fact that it is produced from
carbohydrates which are perennially synthesised in nature. Modern
technology produces almost anhydrous alcohol at a reasonable cost. The
consumption of alcohols does not lead to any void, unlike the utilisation of
fossil fuels which exhausts the ‘store’ of the earth.
Alcohols are used in motor gasoline blends up to 10%–20% called
gasohol. They serve to raise the octane rating of straight-run gasolines.
There is a strong case for their large uses in countries where petroleum is
scarce and alcohols are cheap and abundant. The estimated consumption
of ethyl alcohol as fuel in Brazil in 1982 was about 3.7 billion litres out of the
total production of 4.2 billion litres. Ethanol production is predicted to reach
26.4 billion litres in 2008 in Brazil.
5.3.6 SHALE OIL
Shale oil is obtained by the destructive distillation of oil shale. The latter is
widely distributed over the surface of the earth. It is a fragile, agrillaceous
sedimentary rock resembling slate. As mined it is dark brown or grey-to-
black in colour.
The reserves of oil shales in the world amount to well over 20,000
million tonnes. Considerable deposits are in the USA, the old USSR,
France, Sweden, Tasmania, Australia, Manchuria, the UK, and South Africa.
Commercial activities are mostly confined to Estonia (old USSR), Scotland
(UK), Australia, Sweden and Manchuria. The present shale oil production is
negligible owing to the availability of petroleum. Oil shales are very
important standby resources for liquid flels.
Oil shales are essentially a mixture of an organic mass and mineral
matter. The mineral content varies from 33% to above 70%. The organic
mass is called kerogen. It is composed of the remains of a diversity of
vegetable life. Oil shales differ widely from each other in respect of the
nature and content of kerogen. The elementary analysis of the kerogen of
an Estonian shale is: C 76.5–77.5, H 9.1–9.3, S 1.7–2.2, Cl 0.5–0.7, N 0.2–
0.5, and O 10.5–12.0, all in per cent daf.
No appreciable quantity of oil is obtainable by simple solvent extraction
of the shales. A process of thermal decompostion breaks down the complex
structure of kerogen and produces oil. The oil yield depends upon the
nature of the shale and the method of processing and may be as high as
50% of the shale in some cases. More common yields are 10% to 20%.
Shale mining is similar to coal mining. Most of the world’s oil shale is
extracted by the underground method. Opencast mining is also practised.
The run-of-mine shale is prepared through crushing and screening and then
charged into retorts, of which there are many designs. Vertical externally
heated retorts are preferred. The retort temperature varies from 480°C at
the top to 750°C at the base.
The gases and vapours are condensed, and the recovered products
are: crude oil, ammonia liquor, crude naphtha (adsorbed from the gas after
the recovery of oil) and gas. The crude oil is dark green in colour and has a
specific gravity of 0.860 to 0.890. Compared to crude petroleum, it contains
larger amounts of unsaturates, nitrogen bases and phenolic compounds.
Like petroleum, shale oils are also of three types such as paraffin-base,
asphalt-base and mixed-base. The oils from Scottish, Australian and
Manchurian shales are of paraffin base. Those from Estonian, Swedish and
Tasmanian shales are asphaltic. Oils from Colorado shale (USA) may be
classified as of mixed-base.
The refining of crude shale oil is basically similar to petroleum refining.
Motor gasoline and diesel fuel are the main products. These are
comparable to the corresponding petroleum products. Wax is recovered
from the wax-bearing oils.
The disposal of spent shale is a big problem. Brick making is one use.
Very large idle land areas are required for dumping the spent shale.
5.3.7 OIL FROM TAR SANDS
Tar sands are also known as oil sands and bituminous sands. These are
sand deposits impregnated with dense, viscous petroleum-like material or
bitumen. Tar sands are found throughout the world, the largest deposits
being in Athabasca, Canada and in Ornico, Venezuela. The former contains
more than 1,86,000 million kilolitres and the latter more than 1,60,000
million kilolitres of bitumen. The world’s total deposits are about 4,50,000
million kilolitres of bitumen in tar sands.
The production of synthetic crude oil from tar sands is now a
commercial reality. The first venture of 7,200 kl/day design capacity came
on stream in 1967 and the second began in 1978 and nearly approached its
rated capacity of 20,500 kl/day in 1981. Both are in Canada.
The properties of the bitumen recovered from Athabasca tar sand are:
specific gravity (°API) 1.00–1.014 (8–10), viscosity at 60°C, 37 p, pour point
10°C. Elemental analysis: C 83.1, H 10.6, S 4.8 N 0.4, and O 1.1.
Hydrocarbon type: saturated 22%, aromatic 21%, resins 39% and
asphaltenes 18%, respectively; vanadium content 250 ppm and nickel
content 100 ppm. Distillation temperatures: initial boiling point 260°C and
50% boiling point 530°C.
The sands are obtained by surface mining. Bitumen may be recovered
from them by several methods such as (i) direct coking, (ii) anhydrous
solvent extraction, (iii) cold-water separation process, and (iv) hot-water
process. In the hot-water process, the tar sand is heated and mixed with
water to form a pulp of 60%–85% solids at 80–90° C. In a settler the sand
sinks to the bottom and the bitumen floats up in the form of a froth. The
middlings are subjected to froth flotation in air for scavenging another
quantity of bitumen-laden froth. The froth is from the bitumen which
contains l%–2% mineral (dry basis) and 5%–15% water (wet basis).
Bitumen is a hydrogen-deficient oil. The primary upgrading process
improves the H:C ratio by either carbon removal (coking) or hydrogen
addition (hydrocracking) and produces lighter products which are more
easily processed downstream. The secondary upgrading involves further
hydrogenation which causes further cracking and also removal of sulphur
and nitrogen. The upgraded or synthetic crude is finally refined to
marketable products such as gasoline, jet fuel and fuel oil by conventional
means.
Gasification of liquid fuels

Gas oils and residual oils from petroleum refineries are conveniently
converted into gaseous fuels either in separate oil gasification units or in the
carburetted water gas generator units. Naphtha and gas oils are also
converted into synthesis gas for the manufacture of chemicals and
fertilisers.
The different processes of liquid fuel gasification will be taken up in
Chapter 6.
5.4 STORAGE AND HANDLING OF LIQUID FUELS
Liquid fuels of low flash point, such as gasoline, are stored in tanks fitted
with roofs which float on the surface of the liquids. The elimination of any air
space above the fuels reduces fire hazards and evaporation losses. These
fuels are transported from the main installations to the distribution depots
and to consumers either by pipeline or by tankers and other containers. The
storage tanks in the filling stations are sited below ground. All installations
handling liquid fuels with low flash point have to meet various prescribed
requirements.
Liquid fuels with flash point well above room temperature, such as
kerosene, diesel fuel and fuel oils, are stored in tanks provided with fixed
conical shaped roofs. Heating coils are fitted to the storage tanks of the
heavier grades of fuel oils and CTFs to maintain them in an easily
pumpable condition.
All fuel oils contain water which settles to the bottom of the tank and is
removed through a drain cock. In the case of CTF, the water floats on the
fuel and is removed by a draw-off arrangement.
The lighter oils are usually pumped to burners without preheating.
Heavier oils require heating in two stages, first in the storage and then at
the time of delivering to the burners. Tank heating is achieved by low
pressure steam coils situated as low as possible in the tank. No lagging of
these tanks is usually necessary. Hot oil pipe line should be lagged and
there should be electric or steam tracer lines within the lagging to balance
the heat loss from the pipes through the lagging. The preheating of the
heavier oils before pumping and before atomisation should be only up to the
temperature required by viscosity considerations and fixed by plant trials.
Excessive heating should be avoided for attaining heat economy. Steam
heaters are preferred to oil preheaters.
Liquid fuels are supplied to furnaces by gravity feed system or ring main
system. The former comprises either an overhead feed tank or a ground
level feed tank with a pump in the delivery line. The burners get the fuel
through a single feed line. This system is used only when one or two
burners are involved.
The ring main system is preferred for medium and heavy fuel oils burnt
in a number of burners fitted to one or more furnaces. This ensures the
minimum pressure and temperature differences between the burners.
Figure 5.11 shows a typical flow diagram of a ring main system. The oil is
circulated through a ring main round the factory at a rate of two to three
times the actual consumption of the burners. Branch lines are used to feed
the individual burners. There are oil filters both at the suction and the
discharge sides of the pump filter for protecting the pump as well as the
burner nozzles from dirt. There is an oil heater in the ring main and no
separate heating is necessary in the branch lines. The return leg of the ring
main is necessary in the branch lines. It is connected to the suction end of
the pump and not to the storage. This increases the heat economy.
Duplicate pumping, heating and filtering units are provided to ensure
continuous plant operation.
Figure Ring main system

5.11
The oil in the ring main system described above is at the atomisation
temperature. In a variation of this circulation system there is no heating in
the ring main and the oil is kept at a pumpable temperature only. The
branch lines are provided with small heaters to feed the burners with the
oils at the correct atomisation temperature.
In the case of very highly viscous oils, the fuel handling system consists
of concentrically steam-jacketed pipelines, heated pumps and heated filters.
BIBLIOGRAPHY
1. Bureau of Indian Standards, New Delhi
IS: 1447 Pt 1 (2000) Methods of sampling of petroleum and its

products
IS: 1447 Pt. 2 (1992) Sampling of LPG
IS: 1447 Pt. 3 (1992) Sampling of Semi-solid and solid petroleum
products
IS: 1447 Pt. 4 (1989) Sampling of Petroleum Coke for laboratory
analysis
IS: 1448 Methods of test for petroleum and its products (Pts 1–148)
Pt 3 (1984) Aniline point
Pt 4 (1984) Ash, sulphated ash and water soluble ash
Pt 5 (1970) Burning quality
Pt 6 (1984) Calorific value by bomb calorimeter
Pt 7 (2004) Calorific value by calculation
Pt 8 (1967) Carbon residue by Ramsbottom method
Pt 9 (1960) Cetane number
Pt 10 (1970) Cloud point and pour point
Pt 17 (1960) Diesel index
Pt 18 (1991) Distillation
Pt 20 (1998) Flash point by Abel
Pt 21 (1992) Flash point by Pensky–Martens
Pt 23 (1991) Hydrocarbon types by FI adsorption
Pt 25 (1976) Viscosity
Pt 31 (1968) Smoke point
Pt 32(1992) Density
Pt 33 (1991) Sulphur by bomb
Pt 34 (1979) Sulphur by Lamp method
IS: 2796 (2000) Specification for motor gasoline
2. Eqbal J and Sarkar S. Coal Refinery-A Tangible Concept, Petroleum
Hydrocarbons, Vol. 7. 1 (1972).
3. Hobson GD and Pohl W, (eds.). Modern Petroleum Technology, Fo

edition, London: Institute of Petroleum, 1975.
4. Huxtable WH, (ed.). Coal Tar Fuels. Second edition. London: Associatio
Tar Distillers, 1961.
5. Petroleum, The Wealth of India, Raw Materials, Vol. 7, 318. New D

Council for Scientific and Industrial Research, 1966.
6. Petroleum Refining, The Wealth of India, Industrial Products, Pt 6,

New Delhi: Council for Scientific and Industrial Research, 1965.
7. Standard Methods for Testing Petroleum and its Products. London: Ins
of Petroleum, 1960.
8. Williams DA and James G. Liquid Fuels, London: Pergamon, 1963.

6 Gaseous Fuels
6.1 INTRODUCTION
Just as coal powered the industrial revolution of the nineteenth century and
oil fuelled the growth of the twentieth century, gas is emerging as the
preferred source of energy to power the economics of the twenty-first
century, and India is no exception. High growth in population, increasing
urbanisation, rising incomes and standards of living of the people of India
are expected to result in high and steady consumption growth in natural gas
along with petroleum in the country.
The remarkable features of gaseous fuels are the absence of mineral
impurities, the consistency in quality and the convenience and efficiency in
use. On an industrial scale, a gas handling system is the least expensive of
all the fuels. It comprises essentially of a network of piping along with safety
and control equipment. Except in the case of liquefied petroleum gas, no
storage space is usually required as the suppliers are responsible for
delivery. However, large consumers have gas holders and many of them
produce their own gas. Whether purchased from a supplier or made by a
large consumer, the gaseous fuel is available on tap at the actual point of
use by means of distribution pipes. It is an ideal fuel in a region where there
is a concentration of population. The popularity of gaseous fuels may be
judged by the adoption of these fuels in domestic and commercial
undertakings on an ever increasing scale in many countries.
6.2 TYPES OF GASEOUS FUELS
The following classification of fuel gases is based on the mode of

occurrence and the method of production.
Fuel gases occurring in nature
Natural gas and many other variations of it
Methane from coal mines

Fuel gases made from solid fuels
Producer gas
Water gas
Gases from other gasification processes, including substitute natu

(SNG)
Coal gas
Blast furnace gas
Wood gas
Fuel gases made from petroleum

Refinery gases
Liquefied petroleum gas (LPG)
Gases from oil gasification processes
Fuel gases made by fermentation of organic wastes

Two important industrial gaseous fuels are not included in the above list.
These are hydrogen and acetylene which find wide use in metal cutting,
welding, and many other processes. Hydrogen will be taken up later in
detail.
From the utility point of view, the gaseous fuels are often referred to as a
rich gas or lean gas, depending upon whether their calorific value (CV) is
above 4,000 kcal/Nm3 or below about 1,500 kcal/Nm3, respectively.
Hydrocarbon gases and coal gas are examples of a rich gas, while blast
furnace gas and producer gas are examples of a lean gas. Water gas is a
fuel of medium calorific value, about 2,800 kcal/Nm3.
The use of the terms rich gas and lean gas has undergone change
recently with the greater utilisation of very high calorific value gases like
natural gas and LPG. There are now five categories of gases on the basis
of calorific value.
Name of the gas Calorific value

1. Liquefied petroleum gases ~30,000 kcal/Nm3
2. Natural gas and SNG 8,400–9,100 kcal/Nm3
Name of the gas Calorific value
3. Town gas 4,500–5,300 kcal/Nm3
4. Industrial fuel gas (IFG) 2,200–3,100 kcal/Nm3
5. Low calorific value gas (LCVG) 700–1,700 kcal/Nm3
LPG, NG and SNG may be bracketted as high Btu gases, and town gas and
IFG as medium Btu gases, while LCVG may be termed a low Btu gas.
Calorific value alone is not a satisfactory parameter for the technological
classification of gaseous fuels. The thermal output of a heating appliance
depends on the calorific value and gravity of the gas. Both these properties
are combined into one fairly good classification parameter known as the
Wobbe index or Wobbe number which is a dimensional group and thus CV/
√specific gravity depends on the units chosen. The speed of combustion of
a given fuel gas largely depends upon its flame speed, and should be used
as an additional parameter for a rational classification of gaseous fuels.
The International Gas Union (IGU) has classified different gases into
families on the basis of the Wobbe index (Table 6.1.). Each family covers a
range of gas qualities which can be interchanged for a given heating
applicance with the minimum deviation from the designed thermal rating of
the appliance.
Table 6.1 IGU gas families

Family sub-division Wobbe index
kcal/Nm3 MJ/Nm3
Gas family 1 4,250–8,550 17.8–35.8
Coke oven gas
Manufactured gas
Hydrocarbon air mixtures

Gas family 2 8,550–12,824 35.8–53.7
Sub-divsion I 8,550–12,322 35.8–51.6
Sub-division II 12,322–12,824 51.6–53.7
Gas family 3 17,074–20,823 71.5–87.2
LPG
The rich gases—CV above 4,000 kcal/Nm3—may be classified into

three groups on the basis of the flame speed. For this purpose, a flame
speed factor called the Weaver flame speed factor is expressed on an
arbitrary scale in which hydrogen is assumed to have a factor of 100. The
three groups are:
High flame speed gases
CV = 4,000 to 5,000 kcal/Nm3
Weaver flame speed factor = 32 to 45
Low flame speed gases

CV = 7,500 to 10,000 kcal/Nm3
Intermediate type gases

CV = 5,000 to 7,500 kcal/Nm3
Of the various components of a fuel gas, the inert gases (nitrogen and
carbon dioxide) and carbon monoxide reduce the flame speed and the
Wobbe index, whereas, hydrogen does the reverse. Hydrocarbons reduce
the flame speed but raise the Wobbe index.
A proper appraisal of the classification of gaseous fuels is necessary to
derive the best performance of heating appliances. Either the composition
of the fuel or the design of the appliance may be altered if the situation
demands.
6.2.1 NATURAL GAS
Natural gas is a mixture of paraffinic hydrocarbons, in which methane is the

principal component. It occurs in gas fields and also in association with
crude petroleum in oilfields. Natural gas also contains ethane, propane,
butane and pentane in varying proportions. In addition, small quantities of
iso-paraffins and naphthenes may also be present. The vapours of the
hydrocarbons, other than methane and ethane, can be separated out as a
condensate. When the natural gas contains very small quantities of
recoverable condensate, say, less than 15 g/m3, it is known as dry natural
gas. If the content of condensate is appreciable, say, above 50 g/m3, the
gas is known as wet natural gas. The latter is commercially treated for the
recovery of the condensate which is a valuable product known as natural
gasoline and finds wide use as a blending agent for motor fuels. The
recovery of natural gasoline is accomplished by compressing and cooling,
or absorption in an oil, or adsorption on a porous solid. During the process
of recovery, pentane is completely recovered from the gas while small
quantities of butane and propane are left behind in it. The residual gas is in
effect a dry natural gas and known as stripped natural gas to distinguish it
from the naturally occurring dry gas. Similarly, when natural gas comes out
along with crude oil, it is known as associated gas, as in the case of
Bombay High.
The proved reserves of natural gas in the world are about 100 trillion m3
with the following break-up: the old USSR 43.2%, Iran 13.5%, the USA
5.7%, Qatar 4.3%, Saudi Arabia 3.5%, Algeria 3.1% and Norway 3.0%. The
old USSR and the Middle East account for two-thirds of the total reserves.
In the last two decades, natural gas has gained importance in India. The
production of natural gas has increased from almost nil at the time of
Independence to 32 billion cubic metres. The bulk of India’s natural gas
production comes from the western offshore region, particularly from
Bombay High. Assam, Andhra Pradesh and Gujarat are also major
producers of natural gas (see Tables 6.2 and 6.3).
Table 6.2 Production of natural gas (million cubic metres)

Table 6.3 Reserves of natural gas (billion cubic metres)
Area 2003 2004 2005 2006 2007
Onshore 327 339 340 330 270
Offshore 527 584 761 745 785
Total 854 923 1101 1075 1055
Note: The data relate to 1 January 1990 and thereafter 1 April of each year.
Source: Ministry of Petroleum and Natural Gas, Govt. of India, http://petroleum.nic.in/p
etstal.pdf
The sectoral consumption of natural gas is given in Table 6.4. Power

generation consumed about 11.9 billion cubic metres in 2006–07. The
captive use/LPG shrinkage was about 5.6 billion cubic metres.
Table 6.4 Sectoral consumption of natural gas (million cubic metres)

Industry 2003– 2004– 2005– 2006– 2007–
04 05 06 07 08*
Energy purposes
1. Power Generation 11478 12099 11878 11963 12037
2. Industry Fuel 3099 3569 3780 3205 3324
3. Tea Plantation 142 142 151 170 160
4. Domestic Fuel 93 343 75 443
5. Captive use/LPG Shrinkage 4865 4944 5048 5034 5618
6. Others 1263 231 1120 40 1258
Total 20940 21328 22052 20855 22436
Non-energy purposes
1. Fertilizer Industry 7889 8173 7762 8497 9822
2. Petro-Chemicals 1128 1236 1175 1377 1432
3. CNG 1 0 0 0
4. Others 948 38 36 639 638
Total 9966 9447 8973 10513 11892
Grand total 30906 30775 31025 31368 34328
Percentage of grand total Energy 65.4
purposes 67.8 69.3 71.1 66.5
Non-energy purposes 34.6
32.2 30.7 28.9 33.5
*: Provisional.
Source: Ministry of Petroleum and Natural Gas, Govt. of India, http://petroleum.nic.in/p
etstal.pdf
The actual composition of natural gas varies widely from field to field,
the methane content varying from below 50% to above 95%. The
composition of some gases is given in Table 6.5.
Table 6.5 Composition and properties of natural gas

Type
dry and sweet wet and sweet dry and sour
Composition, per cent by volume
CH4 96.91 77.28 45.64
C2H6 1.33 11.18 0.21
C3H8 0.19 5.83 –
Butanes 0.05 2.34 –
Pentanes 0.02 1.18 –
CO2 0.82 0.80 53.93
H2S – – 0.01
N2 0.68 1.39 0.21
Total 100 100 100
Gross calorific value, kcal/Nm3, dry 9,000 11,200 3,260
Specific gravity (air = 1) 0.574 0.741 1.077
Natural gas in certain localities contains large amounts of nitrogen and

carbon dioxide. In some places small but recoverable amounts of helium
are found. Similarly, appreciable amounts of hydrogen sulphide are also
present in some gases which may be treated for the production of elemental
sulphur. Since hydrogen sulphide is corrosive and has a bad odour, gas
containing this compound is known as a foul natural gas. The hydrogen
sulphide-free gas is called a sweet gas.
After delivery from wells, natural gas is processed to remove fine solids.
It is then treated for the recovery of gasoline and liquefied petroleum gas
(LPG). Finally, hydrogen sulphide is removed to obtain gas for distribution.
In cold climates it may be necessary to dehydrate the gas to avoid choking
of lines owing to the formation of crystalline hydrates of methane, ethane,
propane and iso-butane. These hydrates are stable solids below 19°C.
Natural gas is delivered to the consumers by a network of pipelines of
diameter 51–56 cm from the production centre, at pressures usually varying
between 14 and 28 kg/cm2. However, considerable interest has been
shown in the ocean transportation of liquefied natural gas (LNG) from the
countries in which it is a surplus fuel. Successful shipments have been
made of Sahara gas to the UK. Japan also imports LNG in commercial
quantities.
The bulk users are thermal power stations as fuel, and fertiliser
production plants as a source of hydrogen. Natural gas is a preferred
pipeline fuel for domestic and industrial heating in ovens, furnaces and
boilers. Special burners are required to use methane owing to its high
calorific value, high air requirement, moderate specific gravity and low flame
speed. It is widely used as a source of hydrogen and carbon in chemical
industries; in the production of ammonia, methanol, acetylene and carbon
black. Table 6.5 gives the composition and properties of natural gas.
Due to the low energy density, for use as a vehicular fuel, it is
compressed to a pressure of 200–250 bars to facilitate storage in cylinders
mounted in vehicles and so it is called compressed natural gas (CNG).
India’s recoverable resources of more than 690 billion cubic metres
make natural gas a long-term substituted fuel for use in petrol and diesel
engines. Low exhaust emissions, low noise, less maintenance, not prone to
adulteration and driver’s comfort are some of the attractive features of CNG
as an automotive fuel.
Liquefied natural gas is first made from natural gas. It essentially
facilitates storage and transportation of the fuel. This LNG is again reheated
to CNG and filled on board a vehicle for use as fuel.
Given the availability and the infrastructure, CNG qualifies to be one of
the most prominent alternative fuels. It is better than conventional fuels both
in life cycle emissions and vehicle exhaust emissions. Higher octane value
of CNG reduces knocking problems of a vehicle.
Natural gas is neither corrosive nor toxic, its ignition temperature is high,
it is lighter than air, and has a narrow flammability range, making it an
inherently safe fuel compared to other fuel sources. Natural gas cannot
contaminate soil or water. It will always rise into the atmosphere, unlike
other fuels, which are heavier than air and can pool, either as a liquid or a
vapour, upon the ground. Natural gas contains a distinctive odorant
(mercaptan), which allows natural gas to be detected at 0.5% concentration
in air—well below levels that can cause drowsiness due to inhalation and
well below the weakest concentration that can support combustion. Due to
high ignition temperature of natural gas (540°C), simple exposure to a hot
surface (such as exhaust manifold) is unlikely to lead to a fire.
After several trials and field studies by various institutions, and learning
from the experience of other countries, India initiated the use of CNG as an
automotive fuel. Recently large numbers of buses, autos and taxis in Delhi
have switched over to CNG. CNG vehicles are also present in Mumbai and
Vadodora. Other cities are also planning to introduce CNG in a phased
manner. The cost of CNG is about a third of the cost of petrol in terms of
CV. Comparing the emissions from vehicles that use conventional fuel, the
CO emission from vehicles running on CNG is less by 70%–90%,
hydrocarbon emission by 40%–60% and CO2 emission by 10%.
It is also possible to use a bifuel. Vehicles can be operated in the dual
mode like petrol-CNG and diesel-CNG. The major disadvantage is the loss
of luggage space. CNG cylinders take up a lot of storage space and
generally have to be placed in the boot of the car. The body of the cylinders
too have to be made of good grade steel. Finally, based on its
characteristics CNG may slightly hamper vehicle performance.
The sale of CNG in some states of India is shown in Table 6.6. Delhi
accounts for the most (about Rs. 3 lakhs per year). Next comes
Maharashtra (Rs.1.8 to Rs.1.3 lakhs per year). Gujarat sold the least—Rs
4000 in 2004–05 and only Rs. 1000 the previous year.
Table 6.6 State-wise consumption of CNG
6.2.2 HYDROGEN
Hydrogen is the most abundant element in the universe. It is an energy

carrier—it contains the energy that powers the sun which sustains all life on
earth. It is found in all living organisms. Hydrogen is a fuel which can be
used to power internal combustion engines and fuel cells. When hydrogen
is combined with oxygen in a fuel cell, electricity is produced. The water is
usually emitted as a waste product.
As hydrogen is only found combined with other elements, it needs to be
separated from them for use as a fuel for fuel cells.
Methods of hydrogen production
1. Electrolysis of water,
2. Reforming gaseous and liquid hydrocarbon fuels,
3. Gasification of organic and plastic materials into synthetic hydrog

gases,
4. Anaerobic digestion, or biological conversion of hydrocarbons

absence of oxygen— usually by bacteria,
5. Fermentation or biological conversion of hydrocarbons, usually by b

or yeasts,
6. Certain algae emit hydrogen as a waste product from their metabolism
If the electricity used to drive the electrolysis process is derived from

renewable/alternative energy sources, the resulting hydrogen can be called
‘renewable hydrogen’, and therefore carbon-neutral, thus not contributing to
the greenhouse effect and resulting global warming. Renewable hydrogen
can also be produced by gasifying biomass and other materials that do not
contribute to increasing overall carbon levels in the atmosphere.
The key challenges for commercialisation of fuel cells and hydrogen
infrastructure technologies are the following:
1. Cost and durability of fuel cells,
2. Storage of hydrogen,
3. Production and delivery of hydrogen,
4. Public acceptance of hydrogen as a fuel through certified procedur

training manuals for fuel cells.
Fuel cells are an important enabling technology for the hydrogen economy
and have the potential to revolutionise the way we power our nation,
offering cleaner, more-efficient alternatives to the combustion of gasoline
and other fossil fuels.
Fuel cells have the potential to replace the internal combustion engine in
vehicles and provide power in stationary and portable power applications
because they are energy efficient, clean and fuel-flexible. Hydrogen or any
hydrogen-rich fuel can be used by this emerging technology.
6.2.3 METHANE FROM COAL MINES
Methane is associated with coal in situ and its quantity varies from mine to
mine. It is a source of dangerous explosions in gassy mines. This gas is
often known as firedamp. Owing to its porous nature, coal adsorbs methane
formed during coalification. At the time of mining, the gas is gradually
desorbed. Unless this is removed by proper ventilation, explosive mixtures
accumulate inside the mine. This methane-rich gas may be recovered
through a system of boreholes and used as a fuel. In the UK in 1961, about
220 million cubic metres of mine gas were produced. Belgium, Germany
and France have developed processes for the recovery of mine gas.
However, the advent of natural gas from the North Sea has completely
ruined this industry in Europe.
The methane content of coal mine gas is 93%–94%, the other notable
constituents being ethane, carbon dioxide and nitrogen.
6.2.4 PRODUCER GAS
The combustible gaseous mixture obtained by blowing air, or a mixture

of air and steam through an incandescent bed of solid carbonaceous fuel is
known as producer gas and the plant in which it is made is called a gas
producer, or simply a producer. It is a fuel of low calorific value, the principal
components being carbon monoxide and nitrogen. Hydrogen is also present
in significant amounts when air and steam are used in place of air alone.
The advantages of this lean fuel are: (i) advantages of firing gaseous fuel,
(ii) low price and (iii) ease of production. It is the most widely used industrial
fuel gas where cheap solid fuels are abundant while natural gas is not.
Bituminous coal, anthracite and coke are used as the raw material in
gas producers. With suitable variations in the plant, other fuels, namely
peat, lignite and even wood or organic solid waste material may also be
used.
The exact composition of producer gas depends on the type of fuel, the
composition of the blast and other operation variables. The data on some
typical producer gases are given in Table 6.7.
Table 6.7 Composition and properties of some manufactured gaseous fuels
Principal reactions in an air-blown producer
When air Comes in contact with solid amorphous carbon above its ignition
temperature, say, above 500°C, the following two main reactions occur:
The net overall reaction is
As long as oxygen is in excess, carbon dioxide is formed by the reaction

(6.1), which then undergoes reduction into carbon monoxide by reaction
(6.2). Reaction (6.2) is known as the Boudouard reaction and is actually the
single most important reaction controlling the process.
The Boudouard reaction is an endothermic reaction. Its equilibrium
constant greatly increases with the rise in temperature. The content of
carbon monoxide in the equilibrium mixture of carbon monoxide and carbon
dioxide at 1 atm pressure sharply increases beyond 500°C as seen below
Temperature, °C 400 500 600 700 800 900 1000

CO, per cent 0.9 6.5 26.4 63.0 89.5 97.5 99.6
Reaction (6.2) is a heterogeneous reaction. The kinetics are such that the
equilibrium is reached at 1,300°C in a few seconds and at 1,100°C in about
one minute. Only two-thirds of the equilibrium are attained in one minute at
1,000°C.
Increased pressure inhibits the formation of carbon monoxide. But the
effect of pressure is not great and the air blast in normal practice is slightly
above atmospheric pressure. Therefore, the inhibitory effect of pressure is
negligible.
The type of carbon does not practically disturb the equilibrium content of
carbon monoxide but it greatly influences the kinetics of the reaction. In
order of reactivity, charcoal ranks very high, as shown by the following data
on the percentage attainment of equilibrium after one second contact time
at 1,100°C in a given test unit: Charcoal 91.3, coke 13.5 and anthracite
10.5. The lower reactivity of coke and anthracite is overcome in practice by
increasing the contact time by carrying out the reaction at temperatures
above 1,300°C.
The above discussion shows that the producer gas process is favoured
by a high temperature of the fuel bed, adequate time of contact (thick fuel
bed) and reactive fuel. All factors which hinder good contact between
carbon and gaseous reactants must be avoided. If the ash of the fuel is of
low fusion point, say 1,100°C, it melts in the high temperature zone and
then resolidifies into clinker, in the cooler parts. The clinker disturbs the air
distribution, engulfs unburnt carbon and lowers the efficiency of the
process. Similarly, coking coal produces massive lumps in the bed when it
is used as the producer fuel. The process, however, can be carried out by
poking the bed and breaking the masses into small pieces.
After the gases leave the fuel bed, the carbon monoxide partly
dissociates into carbon dioxide and carbon.
This is actually the reversal of the Boudouard reaction and is know as the
Neumann reversal reaction. The result of this reaction is a drop in the
calorific value of the product gas, owing to the conversion of the
combustible carbon monoxide into the non-combustible carbon dioxide in
the gaseous space above the fuel bed.
Demerits of air-blown producer gas

Reaction (6.3) shows that air-blown producer gas is a mixture of about one-
third carbon monoxide and two-thirds nitrogen. The maximum carbon
monoxide content is calculated as only 34.7%, the rest being the inert
nitrogen. By rearranging reactions (6.1) and (6.3) we get
The maximum calorific value of air-blown producer gas is calculated from

this reaction:
This is a very low grade fuel. The yield of this gas is computed from reaction
(6.3).
The maximum cold gas efficiency of the air-blown producer is calculated

from reactions (6.1) and (6.4).
This low cold gas efficiency is a serious demerit of the process.

As much as 30% of the heating value of the carbon is liberated during
the formation of the producer gas. This causes intense local heating which
fuses the ash and leads to serious clinkering problems.
Use of steam in air blast
All the three demerits of the air-blown producer are removed by using a wet
blast, that is, adding steam to the blast of air. The two reactions between
amorphous carbon and steam are
Reaction (6.5)—the water gas reaction—is active at and above 1,000°C
while reaction (6.6) predominates between 500°C and 600°C. Both the
reactions are endothermic and convert a part of the sensible heat liberated
by carbon in the bed into the potential heat in the combustibles formed,
namely CO and H2. Since carbon dioxide is an undesired component of the
product, the reaction (6.6) should be suppressed by maintaining a high bed
temperature.
In the space above the fuel bed the following gaseous reaction—known
as the water gas shift reaction or shift conversion—takes place between
undecomposed steam and carbon monoxide.
This is an undesired reaction which raises the concentration of the inert

CO2 in the product and reduces its calorific value.
Reaction (6.5) produces carbon monoxide and hydrogen in equal
proportions. The equlibrium composition, in per cent of either of these two
components, in the reaction product at different temperatures at
atmospheric pressure is give below:
Temperature, °C 400 500 600 700 800 900 1000

CO or H2, per cent 2.99 12.67 30.61 44.14 48.52 49.58 49.85
Higher pressure inhibits the reaction. But the inhibitory effect of a blast at
slightly above atmospheric pressure is negligible.
In addition to the above reactions, methane formation or a methanation
reaction between carbon and hydrogen also takes place.
This is an exothermic reaction and is therefore largely suppressed by the

high temperature conditions of the bed. However, high pressure favours the
reaction. The equilibrium concentration of methane at 1,000°C is 0.9% at 1
atm, 3.5% at 4 atm and 11.8% at 16 atm. In the usual producer practice, the
methane content of the product is small. High pressure processes have
been developed where methane content is significantly high (10%–13% in
crude gas).*
The advantages derived by the use of air–steam mixture used as the
blast are:
1. The total contents of the combustibles (CO + H2 + CH4) is raised a
inerts (N2 + CO2) content is lowered. The calorific value of the
significantly increased upto about 1,250 kcal/Nm3.
2. A part of the sensible heat liberated by the combustion of car

converted into the potential heat of hydrogen and cabon monoxid
cold gas efficiency of the mixed blast producer is much higher at abo
than that of the air blown producer.
3. The endothermic reactions between steam and carbon prevent the

increase in fuel bed temperature even in localised spots, and hen
tendency of the ash to form clinker is greatly diminished.
The amount of steam blown through the bed is an important factor

affecting the performance of a producer (Fig. 6.1). Initially the increase in
the amount of steam raises the total combustibles content and calorific
value of the gas and also the thermal efficiency of the producer. However,
too much absorption of the heat of the fuel bed by the endothermic
reactions of steam reduces the bed temperatures to below 1,100°C and
hence, lowers the degrees of carbon dioxide reduction and steam
decomposition. Practice has shown that beyond an optimum supply, any
increase in the amount of steam reduces the thermal efficiency of the
producer, the total combustibles content and the calorific value of the gas.
However, if the ash of the fuel has a tendency to clinker, the steam supply
should be increased beyond the optimum value. This step ensures the
smooth continuous running of the producer at the cost of its efficiency and
gas quality.
Figure 6.1 Effect of quantity of steam on gas producer performance
The wet blast may be made either by injecting steam to the air flow or
by blowing air through water in the base of the producer. The first method is
more convenient and is the normal practice. A controlled quantity of steam
is blown into the air blast, raising its temperature to a predetermined level.
This is technically called the blast saturation temperature (BST), on the
assumption that the air is saturated with water vapour at this temperature.
This assumption is valid for all practical purposes.
The amount of steam supply is best controlled by the BST. The optimum
steam supply depends on the nature of the fuel but is usually at 55–62°C
BST which corresponds to 15–22 kg of steam per 100 Nm3 of dry air,
respectively. In terms of the quantity of the solid fuel, the optimum steam
supply is at 0.4–0.5 kg per kilogram of carbon gasified.
Reaction zones in a gas producer
The fuel bed in a normal producer rests on a metallic grate. The former may
be divided into a number of reaction zones: ash zone, oxidation zone,
primary reduction zone, secondary reduction zone, and drying-cum-
carbonisation zone, depending upon the sequences of reactions that take
place in the counter-current movement of the solid fuel and the blast (Fig.
6.2). The air–steam blast is preheated by the ash zone which also serves to
make the blast distribution uniform and protect the grate from intense heat.
The oxygen is consumed within 75–100 mm of the bed, which constitutes
the oxidation zone. Once the reactions start, the compositions of the
gaseous stream go on changing from point to point along the bed depth
(Fig. 6.3). Carbon dioxide forms at the expense of oxygen. Its concentration
reaches a maximum at the top of the oxidation zone when carbon monoxide
begins to appear. The monoxide continues to form by the reactions (6.2)
and (6.5) initially, then by reaction (6.2) alone, and approaches an
equilibrium with the dioxide at the top of the bed. Soon after the appearance
of carbon monoxide, the steam decomposition begins and then vigorously
continues for about 25 mm of the bed depth, which is called the primary
reduction zone. About 40 mm layer of the bed above the zone constitutes
the secondary reduction zone where the steam is decomposed by carbon
monoxide. The uppermost layer of the bed is the drying and carbonisation
zone. The water vapour and the volatile matter of the fuel are added to the
escaping gas. Therefore, fuels with significant yield of volatile matter result
in the production of enriched gases. The top-most zone essentially serves
as the preheating zone for precarbonised fuels like coke.
Figure Reaction zones in the fuel bed of a gas producer
6.2
Figure 6.3 Composition of gases in the fuel bed of a gas producer
The gas composition is slightly changed in the gas space above the fuel
bed. Both Neumann’s reversal reaction and water gas shift reaction are
responsible for a reduction in the calorific value of the final product.
Figure 6.2 is a schematic representation of the zones. In practice there
is no well-defined boundary between two neighbouring zones. Moreover,
the gas flow is not uniform across the bed cross section. It is maximum at
the periphery and minimum at the centre. Therefore, temperature profiles
are concave-shaped—a horizontal section of the bed having the
temperature falling from the periphery to the centre. The reaction zones are
similarly concave-shaped and not horizontal.
Impurities in the raw gas

Where the producer is an internal part of the furnace setting, the hot raw
gas is directly fired in the furnace. In other plants, the gas is cooled and
freed of some impurities and then stored in gas holders.
The usual impurities are undecomposed steam, tar dust, hydrogen
sulphide and ammonia. Most of the steam and tar is condensed on cooling.
Ammonia may be removed and recovered as ammonium sulphate. But
recovery is not economical. No special treatment is normally given for the
removal of hydrogen sulphide and other impurities. Since these are
corrosive and harmful, their content is kept low by using low-sulphur coals
in gas producers. Dust is partly removed with the condensates and should
be completely removed with cyclones or other types of dust catchers.
When raw gas is directly fired in a furnace, the tar contributes to the
calorific value of the gas and raises the temperature and emissivity of the
flame. The dust particles also increase the flame emissivity. But dust is a
major cause for fouling of gas mains carrying hot raw producer gas.
Therefore, some form of a dust catcher is desirable even in producers
supplying hot raw gas to furnaces.
Gasification rate in a producer
The specific gasification rate is expressed as kilograms of fuel gasified per

hour per square metre of the bed cross sectional-area. It is desirable to
achieve a high gasification rate with good gas quality. This is limited by the
following factors:
the form in which ash is discharged,
the use of air with 79% inert nitrogen,
the height of the fuel bed,
the rate of reduction of carbon dioxide and steam.
In normal producers, the ash is removed in the solid form. The ash
fusion point seriously limits the bed temperature and hence the gasification
rate. In high-speed slagging producers, the ash is discharged in the molten
state and therefore the gasification can be carried out at high temperatures
of about 1,500–1,800°C.
The presence of large amounts of nitrogen in the blast leads to high
wastage of heat in the form of sensible heat of the gases leaving the
reaction zone, and hence automatically limits the bed temperature. The use
of oxygen or oxygen-enriched air helps to maintain high bed temperatures
and hence, high gasification rates. The gas quality is also improved. The
operations without inert nitrogen have an unfavourable factor of the
increased partial pressure of the carbon dioxide gas entering the reduction
zone, which displaces the equilibrium of reaction (6.2) towards carbon
dioxide. This effect, however, is more than compensated by the other merits
of a high-oxygen blast.
A conventional producer needs a certain minimum bed height of 0.6–3
m for achieving the desired reduction of carbon dioxide and steam. Deep
beds, however, offer resistance to the blast and hence limit the gasification
rate.
Customary fuels such as coal, coke or anthracite are characterised by
the relatively slow rate of reduction of carbon dioxide and steam. The
situation may be improved by the addition of catalysts (0.01%–0.1% of
Na2CO3, K2CO3 or Ni) to the fuel and the use of highly combustible fuels,
finely divided fuels, or underground fuel beds in situ. The last two methods
involve entirely different types of gasification processes. A preheated blast
increases the gasification rate. However, the benefits of a preheated blast
can be realised only in the slagging producers. Temperature control is the
problem in other processes.
Besides the reactivity, two other properties of the fuel greatly affect the
gasification rate. These are size and size distribution, and hardness.
Uniform size, say 20–40 mm, promotes uniform gas flow across the bed
cross sectional area. The presence of excessive amounts of fines leads to
high carry-over losses and prevents the use of a high blast rate. If the fuel is
soft, it is degraded during handling and operation and thus produces non-
uniform fuel with excessive fines. Modern high capacity producers prefer
closely sized and hard coke as fuel.
Some typical gasification rates for different types of modern producers
are:
slagging ash producer 2.5 t/m2 h

atmospheric and pressure producer 0.2−0.4 t/m2 h
suction producer 0.6−0.9 t/m2 h
The clean gas yield in a large conventional producer may be 4−4.5 Nm3/kg
of dry fuel.
Types of producers
The design of a gas producer may vary in respect of the following features:
(i) direction of travel of blast and fuel, (ii) effective pressure in the producer,
(iii) method of ash removal, (iv) method of blast introduction, (v) fuel feeding
system, (vi) bed stirring devices and (vii) shell construction.
In up-draft producers, the blast travels upwards and the fuel downwards.
Ash is removed from the bottom of the bed and the gas from the top. This is
the most conventional type of gas producer. The earlier discussion on
reaction zones pertains to this. Both the fuel and the blast travel downwards
in the down-draft producers. Hence, the volatile matter of the fuel
undergoes decompostion during its travel through the bed. This is a rare
type of producer. The double-draft producer is also rare—the blast enters
both from the top and the bottom. Another type of producer has found use
in gas-fired vehicles: it has a cross-draft, where the fuel travels downwards
but the blast is introduced on the side of the bed and allowed to travel
practically horizontally before the gas is taken out from the other side.
Depending upon the pressure conditions, there may be atmospheric
(balanced-draft), suction or pressure producers. The atmospheric-type is by
far the most common owing to the elements of safely and control. The
suction-type is of limited capacity and finds use in the manufacture of power
gas and in heating built-in type gas retorts. Pressure producers are used to
supply methane-rich gas to furnaces. The gas pressure at the top of an
atmospheric producer bed is usually slightly positive, 25–125 mm w.g.
In conventional producers, ash is removed in the solid state by a
mechanical ash removing system. The producer shell is placed on a water
pan (seal) and either the shell or the pan is rotated. The ash falls on the pan
and is continuously removed by placing an obstruction in the path of the
relative movement of the ash. When both shell and pan are rotated, the ash
is ploughed from the pan intermittently. Older types of producers have
stationary grates where ash is manually removed at definite intervals. In
slagging producers, ash is allowed to melt and then removed by tapping at
set intervals as in a cupola or blast furnace. Some high-speed producers
allow the ash to be carried away with the gas and collected in dust pockets
in the gas line.
The most common position for feeding of the blast in up-draft producers
is below the grate. The old producers had a flat, inclined or stepped bar
grate. The newer units have a conical-shaped or mushroom-like grate. The
blast inlet is just below the hollow centre of such a grate and enter into the
fuel bed through holes or slots in the grate. The slagging producers receive
a high velocity blast through cooled tuyeres in the side of the producer.
There is no distribution problem in the downward blast.
The producers usually receive intermittent fuel-feeds through hoppers. A
more complicated arrangement such as a worm feed may be necessary for
special fuels. There are variations in the method of uniform distribution of
the fuel and the levelling of the bed. The producer bed needs occasional
stirring to maintain its uniform porosity. The rotation of the shell or water pan
provides agitation. Coking coals need extra stirring from the top by rotary or
oscillating, water-cooled mechanical poking rods.
Producers are usually built of cylindrical steel shells. The shell may be
lined with firebrick and may have a water jacket to protect it from intense
heat. Low pressure and sometimes high-pressure steam is raised in the
water jacket. Larger capacity producers have water-jacketted shells. The
walls of the brick-lined producers should be kept relatively cool to avoid the
formation of wall clinker by the slagging of bricks with coal ash.
An up-draft modern producer may have a height of 2−3 m and a
diameter 1−3.75 m, while the fuel bed may be of 1.75−2.75 m depth. The
brick-lining may be 0.25−0.5 m thick.
Efficiency of a producer
The thermal efficiency of a gas producer may be expressed in one of three

ways.
1. Cold gas efficiency, defined as
2. Hot gas efficiency, defined as
3. Comprehensive efficiency, defined as

where,
Qg = calorific value of gas, gross or net, kcal/Nm3
Qf = calorific value of fuel gasified, gross or net, but same as in Qg, kcal/k
Vg = gas yield, Nm3/kg fuel
C̄p,g = average specific heat of gas, kcal/Nm3, °C
∆tg = gas-temperature above ambient temperature, °C
C̄p,f = average specific heat of fuel, kcal/kg, °C
∆tf = fuel temperature above ambient temperature, °C
In computing hot gas efficiency and comprehensive efficiency it is
necessary to know the particular point in the gas main at which the
reference is made because the gas composition (particluarly with respect to
the contents of tar, undecomposed steam and dust) and temperature vary
accordingly.
The gasification efficiency is often expressed as the carbon efficiency
and is defined as
where,
Cg = carbon content of gas, kg/Nm3
Cf = carbon content of fuel, kg/kg
Vg= gas yield, Nm3/kg
This has only a limited significance since the carbon gasified to carbon
dioxide does not contribute to the heating value of the gas.
The above expressions for the efficiency of gas producers are also
useful in the calculation of efficiency of other gasifiers using solid and liquid
fuels as the raw materials.
6.2.5 WATER GAS

Water gas is a gaseous fuel of medium calorific value, 2,800 kcal/Nm3,
generated by gasifying a solid incandescent source of carbon in
superheated steam. The equipment is known as a water gas generator. The
main reaction of the process is the reaction (6.5) resulting in the production
of hydrogen and carbon monoxide in equal proportions of 50%. In practice it
is impossible to completely exclude the reaction (6.6) which produces
carbon dioxide and hydrogen. Other reactions which occur during the
process are the methanation reaction (6.8), the water gas shift reaction
(6.7) and the Boudouard reaction (6.2). A small amount of nitrogen is
derived from the carbonaceous fuel and also from the air. The composition
and properties of typical water gas are given in Table 6.7 along with other
gaseous fuels.
This gas gives a blue flame owing to the high carbon monoxide content
and is also known as blue water gas, or simply as blue gas.
The two important uses of water gas are in the manufacture of town
gas, and chemicals and fertilisers. In the former case, it is first enriched with
hydrocarbons to give a gas of higher calorific value, called carburetted
water gas. In the production of fertilisers it is essentially used as a source of
hydrogen for ammonia synthesis. Blue water gas may also be used as a
furnace fuel. However, the installation of blue gas generators for the
purpose of supplying fuels only to furnaces is not economical and cannot be
justified.
The decomposition of steam by carbon is a strongly endothermic
process. Attempts to supply the large heat requirement by external heating
has proved uneconomical. The generation of blue gas is therefore an
intermittent process consisting of two main stages:
1. The blow or blasting period during which the fuel bed is heated
blowing air through it,
2. The run or gas-making period during which the blue gas is produ
passing steam through the incandescent fuel.
Reactions (6.1), (6.2) and (6.3) take place during the blow, and reactions
(6.5), (6.6), (6.8), (6.7) and (6.2) take place during the run. The objective,
however, is to accomplish only reaction (6.1) during the blow so that the
maximum possible heat can be evolved by burning a given quantity of
carbon into carbon dioxide. This requires a thin bed. On the other hand, the
objectives during the run are to gasify the greatest possible quantity of
carbon into carbon monoxide and also to decompose the greatest possible
quantity of steam. These require a moderately thick fuel bed ensuring
sufficient time of contact for the reaction (6.5). These requirements of the
blow and the run are to some extent incompatible.
In modern generators, a deep fuel bed is used to achieve a good quality
of blue gas and high productivity of the plant. The formation of carbon
monoxide during the blow is minimised by increasing the air blowing rate.
Moreover, the sensible and potential heat content of the blow gas is
recovered in waste heat boilers. The blow gas of a modern generator may
contain as high as 10% carbon monoxide, the dioxide constituting about
14%.
The fuel bed temperature undergoes fluctuations during the process
cycle. It rises during the blow and falls during the run. The highest
temperature during the blow is limited by the clinkering tendency of the ash,
and the lowest temperature during the run is limited by the requirement of
above 1,100°C of the reaction (6.5). In order to obtain a gas of uniform
composition, the duration of individual stages in the cycle should not be
very large. The working cycle of a six-stage process is shown below:
1. Blow 1.00 min

2. Steam purging 2s
3. Up-run (steaming upwards) 1.25 min
4. Down-run (steaming 1.25 min
downwards)
5. Up-run 0.50 min
6. Air purging 2s
Total 4 min 4s
The change of direction of steaming helps to maintain a uniform bed

temperature. Steam purging prevents the mixing of the blue gas with the
blow gas and air purging ensures complete recovery of the blue gas
remaining in the bed. The control of the cycle by valves is fully automatic.
The normal fluctuation of the fuel bed temperature is 1,400°C at the end of
the blow, to 1,150°C at the end of the run. As much as 45% of the carbon is
consumed during the blow and only 55% during the run. Hence the
importance of heat recovery systems.
Modern blue gas generators may produce as much as 3,00,000
Nm3/day of gas. The shell is water-jacketted as in the case of modern
producers. The plant is operated in conjunction with a waste-heat boiler.
The steam generated in the jacket and waste-heat boiler meets the plant
requirement and also provides some surplus. The gas yield is about 1,800
Nm3/t of daf coke. The steam consumption is about 0.55 kg/Nm3 gas or
about 1.0 kg/kg daf coke. The air requirement is about 1.8 Nm3/Nm3 gas or
3.2 Nm3/kg daf coke.
The cold gas efficiency of a blue gas generator is about 63%. The
overall efficiency, including the recovery of the potential heat of the blow
gas, and the sensible heats of both blow gas and blue gas is about 78%.
The gasification efficiency of a blue gas generator is the lowest of all fixed
bed gasification processes and is below that of the carbonisation process
used in coal gas production.
The blow gas is burnt on the outlet of the generator and the waste
gases are passed through a waste heat boiler to the atmosphere. During
the run the waste heat boiler receives the sensible heat of the blue gas. The
dust in the blue gas is removed by passing it through a washer. Depending
upon the use of the gas, further purification is resorted to for removing tar,
hydrogen, carbon dioxide and other impurities.
The blue gas generation can be made continuous by blowing a mixture
of steam and oxygen through the hot fuel bed. A separate blow period is
thus eliminated. The resulting gas also passes through the hot fuel bed. A
separate blow period is thus eliminated. The resulting gas has a higher
proportion of carbon dioxide than normal blue gas.
When water gas is produced for ammonia synthesis, a proportion of air
is added to the steam so as to get a mixture of hydrogen, carbon monoxide,
carbon dioxide and nitrogen. This is known as semi-water gas. With suitable
treatment, a mixture of nitrogen and hydrogen in a desired proportion is
ultimately made from this gas.
The most common fuel for a water gas generator is hard coke with
uniform lumps and without fines. The ash should be refractory in nature and
its amount should be as small as possible. Where available, anthracite is
also a good raw material for the process. Bituminous coal has the following
disadvantages:
1. Lower capacity of the plant owing to difficulty in keeping the bed i
condition,
2. Formation of fines preventing the use of high blast pressure,
3. Formation of smoke from the volatiles.
Some developments have been made in overcoming these disadvantages

in the total coal gasification processes.
In some processes using bituminous coal, lignite and peat, the blue gas
generation is preceded by precarbonisation in an upper section of the unit.
The gases are separately taken off. The blue gas is mixed with the
carbonisation gas to produce an enriched gaseous fuel called double water
gas or double gas.
The performance data of the semi-water gas generator at the Sindri
fertiliser plant are: Internal hearth diameter: 3.05 m, raw gas produced
6,500 Nm3/h, gasification rate 874 Nm3/m2h raw material consumption per
Nm3 of raw gas, coke 0.60 kg, steam 0.82 kg and air 1.3 Nm3, cold gas
efficiency 60%, carbon efficiency 58%, gas composition (in per cent):
hydrogen 37.1, carbon monoxide 31.3, methane 0.6, nitrogen 23.0 and
carbon dioxide 8.0.
6.2.6 CARBURETTED WATER GAS
The calorific value of blue gas is too low for it to be an effective gaseous
fuel in a town’s distribution system. At best it can act as a diluent of coal
gas. However, it can be enriched with hydrocarbons to make carburetted
water gas. The process is essentially a combination of solid fuel gasification
and liquid fuel gasification. Modern oil gasification processes have
benefitted from the technology of carburetted water gas.
Many petroleum oils undergo cracking at 700–750°C and produce
methane, ethylene, propane and other unsaturated hydrocarbons, all of
which have high calorific values. Carburetted water gas is made by passing
blue gas through a hot chamber, or carburettor into which an oil is sprayed.
The composition of the resultant mixture is obviously dependent upon many
variables. The data for a typical commercial gas is given in Table 6.6. The
carburetted water gas is used as a substitute for coal gas to meet the
seasonal and peak loads of gas supply. Although the calorific value is
similar, its higher specific gravity gives a poorer Wobbe index compared to
coal gas.
A carburetted water gas plant consists of two additional units, namely, a
carburettor and a superheater, besides the blue gas generator and other
accessories. These two units are filled with chequered bricks (Fig. 6.4). The
blow gas is burnt in the carburettor while the combustion is completed in the
superheater. The combustion gases then enter the waste-heat boiler and
finally escape through the chimney. During the run period oil is sprayed into
the brickwork of the carburettor and the blue gas is passed through the
chamber. Cracking is completed in the superheater. Since cracking is an
endothermic process the brickwork temperature falls and this is again
heated up in the blow period. The cyclic process of carburetting blue gas is
well synchronised with the parent gas generation process. The resultant
gas is passed out.
Figure Carburetted water gas unit

6.4
Some of the heat generated by the combustion of blow gas in a

carburettor and superheater is fed back to the fuel bed for carrying out a
back run. Steam is blown through superheater and carburettor into the top
of the fuel bed. Oil is sprayed into the steam. It undergoes severe cracking
on passage through the fuel bed. The back run increases the thermal
efficiency of the plant.
The oil used in carburetting is usually a light petroleum fraction, 200° to
300°C. consisting principally of paraffins. Heavier oils are also used to some
extent. These crack with the formation of coke. The gasification efficiency is
lower but the heavy oils offer cheaper substitutes than the lighter fraction.
The carburettor for heavy oils is often without any chequered bricks.
The requirements for producing 1 Nm3 of a typical carburetted water gas
are: coke 0.45 kg, oil 0.3 kg, steam 0.65 kg and air 1.5 Nm3. The cold gas
efficiency (with light oils) is about 65% which is slightly higher than that of a
blue gas generator.
Complete gasification of coal
Gas-making processes using coke are only partial gasification processes

involving two stages. First the coal is carbonised into coke in coke ovens
and then the coke is gasified in the second stage. The methods of making
producer gas and double water gas from coal are outwardly single-stage
gasification pocesses. However, it is to be noted that carbonisation is
allowed to precede gasification of coke in a separate zone of the same unit.
As a result, large quantities of tar are produced and hence the gasification
efficiency remains below what would have been otherwise. The processes
of complete or total gasification of coal in a single stage maximises the
conversion of coal into gaseous fuel and minimises the formation of tar.
Obviously the gasification efficiency of such processes is higher than that of
those mentioned earlier. Some of these processes are equally suitable for a
wide range of feed material. The classification of various gasification
processes is given in Chapter 4. A brief description of some of the more
important of these follows.
The Lurgi process: This is a single-stage, fixed bed process gasifying a

range of coarse or granular fuels (Fig. 6.5). A Lurgi generator consists of
three main parts: charging box (top), shaft (middle) and ash receiver
(bottom). The shaft is water jacketted. Solid ash is removed by a rotating
grate. With the exception of medium and strongly coking coals, practically
the whole range of solid fuels above 2 mm size are suitable. A mixture of
superheated steam, 450–500°C and oxygen is used as a gasifying medium.
The process is continuous and auto-thermic: the fuel-oxygen reaction
supplying the heat. High pressure at 30 atm favours the methanation
reaction (6.8) which raises the methane content of the gas. The
hydrogenation of the volatile matter of coal under pressure also forms
methane. The methane formation reactions are exothermic. Hence, the
oxygen requirement of the gasification process is reduced.
Figure Lurgi gasification unit
6.5
A high steam-oxygen ratio, say, 10:1, is normally maintained to ensure
that clinkering troubles are avoided. The steam–oxygen ratio is also used to
control the hydrogen–carbon monoxide ratio. The large amount of steam is
responsible for an increased content of carbon dioxide in the gas.
The Lurgi plant produces gas at a high pressure which facilitates its
purification and subsequent distribution through pipes, and its use in the
synthesis of ammonia, methanol and liquid fuel. High pressure also lowers
the gas velocity through the bed and hence, reduces the dust carry-over
from the bed surface and permits a reduction in the grain size of the fuel.
The composition, in per cent of a crude gas and a purified gas from a
commercial Lurgi plant using bituminous coal is given in Table 6.7. The
calorific value of the purified gas is 3,900 kcal/Nm3 and its specific gravity
0.48.
Lurgi plants have been installed in many countries to manufacture fuel
gas for public utility purposes and synthesis gas for the chemical industry.
There is a pilot plant with a capacity of 0.8 tonnes of coal per hour (tph) at
the Central Fuel Research Institute, Dhanbad. A slightly larger pilot plant of
1 tph has recently been installed at the Regional Research Laboratory,
Hyderabad. Of the various complete gasification processes, the Lurgi
pressure gasifier has the largest total installed capacity in the world. An
individual unit has the capacity of 40 tph of coal.
The cold gas efficiency of a commercial Lurgi plant may be about 75%–
80% of the heat in fuel. It may be further raised by recycling the tar in the
gasifier. The rate of gasification may vary from 0.2–1.1 tonnes/m2 per hour.
The consumption of raw materials per Nm3 of refined gas is: fuel (22% ash,
2.5% moisture) 0.85 kg, steam 1.4 kg and oxygen 0.21 Nm3 or 0.3 kg.
The Lurgi gas produced as above is essentially an industrial fuel gas. It
may be further treated for making substitute natural gas (SNG) near natural
gas distribution networks to supplement existing supplies of the latter. Large
demonstration plants have been installed at the individual capacity of, say, 7
tph coal and a pressure of 100 atm in the gasifier. The bed temperature is
allowed to rise to 1,500°C and the ash is disposed off as molten slag. The
specific productivity of such a gasifier is twice that of a standard Lurgi
gasifier. At 100 atm pressure the methane content of the gas may be
increased up to 18%.
The crude gas is treated for the removal of dust and tar, subjected to
shift conversion (6.7) and purified from carbon dioxide and hydrogen
sulphide. The gas is now ready for methanation over a nickel catalyst:
After the condensation of steam the gas is essentially methane (SNG).
The Winkler process: The Winkler gasification process of the fluidised bed
type. The generator is a brick-lined cylindrical shaft. The solid fuel below 8
mm size and 15% moisture is charged by feed worms. The gasification
medium—mixture of oxygen and steam—is blown into the shaft from both
the bottom and above the bed, the latter arrangement being provided for
gasifying some of the entrained fuel particles. The normal bed temperature
is 800–950°C and the space above the fluidised bed attains a temperature
up to 1,000°C. Under these conditions the tar and the gaseous
hydrocarbons are reformed to carbon monoxide and hydrogen. The product
gas contains traces of methane, while phenol is absent. A slightly positive
pressure is maintained inside the system. The hot gas is passed through a
waste heat boiler having a steam superheater and a feed water preheater
and then introduced into cyclones for dust removal. The gas is then sent to
a water scrubber followed by a water seal for cooling and further dust
removal. The final removal of dust is achieved in a Thiessen disintegrator.
Further purification and processing are necessary for preparing synthesis
gas.
The process is suitable for gasifying a wide range of solid fuels having
medium to high reactivity, namely lignite, low temperature coke and char
from coal and lignite and high volatile bituminous coal. High moisture fuels
need predrying. Fuels of low reactivity like anthracite and coke, and fuels of
low ash fusion temperature are unsuitable. The greatest demerit of the
process is high dust carry-over which is as high as 20% even with reactive
fuels. This naturally reduces the gasification efficiency. However, an
elaborate dust recovery system permits the use of the dust in steam raising.
The performance data of a large commercial plant of 60,000 Nm3/h
capacity are given below:
Product gas
Composition, per cent CV Specific gravity
kcal/Nm3 dry (air = 1)
CO H2 CH4 CO2 N2
44.4 36.0 1.6 15.7 2.3 2,600 0.70
Gasification efficiency (carbon conversion) 80%, cold gas efficiency 58%,
consumption per Nm3 gas: lignite 1.1 kg, steam 0.31 kg and oxygen 0.36
Nm3 or 0.51 kg.
Winkler gasifiers of commercial size have been installed in various
countries to produce synthesis gas, water gas and also heating gas. Owing
to its low calorific value and high specific gravity, the Winkler gas is not a
good gaseous fuel and it is more suitable for the manufacture of chemicals,
fertilisers and synthetic liquid fuels.
A Winkler gasification plant with three generators based on lignite was
in operation at Neyveli since 1965. It had a total capacity of 8,60,000 Nm3
gas per day. It supplied synthesis gas to the fertiliser plant. It was shutdown
after the feedstock was changed to naptha.
Low reactivity fuels, and fuels with low ash fusion temperatures can be
successfully gasified in two modified versions of the Winkler process. These
are the Flesch–Winkler and the BASF-Flesh–Demag processes.
The Koppers–Totzek process: This process gasifies pulverised fuel

carried in suspension in oxygen at approximately atmospheric pressure in
the presence of steam. The gasifier is a refractory-lined, horizontal,
cylindrical vessel with conical ends (Fig. 6.6). Two streams of coal dust,
dried to 2% moisture, and size below 0.1 mm in oxygen are fed through
coaxial burners from the two conical ends. A considerable turbulence is
created. Gasification proceeds rapidly at the very high temperature of
1,600°C in the chamber. Superheated steam is introduced around the
burners to shroud the high temperature reaction zone and protect the
burners and gasifier lining from the intense heat, and then to take part in the
reactions.
Figure Koppers–Totzek gasifier
6.6
The product gas leaves the gasifier at 1,000–1,300°C and is passed

through a radiation boiler and a waste-heat boiler for the recovery of the
sensible heat. About half of the ash and one-tenth of the fuel dust is carried
with the gas. This is removed in dust catchers and the fuel is used again.
Half of the ash is deposited on the gasifier wall as a fluid slag. It flows down
and is finally removed from the bottom through a rotating quenching bowl in
a granulated form.
At the high temperature of the reaction zone the volatile matter of the
coal is converted into carbon monoxide, carbon dioxide and hydrogen. The
methane content of the gas is only in traces, below 0.1%. Higher
hydrocarbons are absent. The data about a gas obtained from a
commercial Koppers–Totzek plant using a high ash coal are given below:
Composition, per cent CV Specific gravity
kcal/Nm3 dry (air = 1)
CO H2 CH4 CO2 + H2S N2
55.3 31.1 0.1 12.2 1.3 2,670 0.76
Koppers–Totzek plants have been installed in many countries for making

synthesis gas for ammonia, methanol and others. Owing to high specific
gravity and low calorific value, the gas obtained is not suitable as a fuel.
The cold gas efficiency of the gasifier is 67%, carbon conversion 97% and
the overall efficiency, including waste-heat recovery, 75.5%. The main
points of attraction of the Koppers–Totzek process for the production of
synthesis gas are:
1. Total gasification in a single stage,
2. Very low methane content and absence of tar in the gas,
3. Versatility with regard to the quality of the solid fuel which includes du
slacks produced during mining and handling a coal or lignite,
4. Operation at atmospheric pressure,
5. Simple design of the reactor,
6. Adaptability to the gasification of heavy oils.
There was a pilot plant with a capacity of 115 kg per hour of raw coal at the
Central Fuel Research Institute, Dhanbad, which went into operation in
1959. Two commercial plants have been installed at Talchar in Orissa and
Ramagundem in Andhra Pradesh in 1978 to supply synthesis gas for
ammonia. Each plant has three gasifiers, each with a capacity of 40,000
Nm3 per hour of raw synthesis gas. These are the world’s largest coal
gasifiers.
Some performance data of a commercial Koppers–Totzek plant are: gas
yield 1,530 Nm3/t coal (ash 35%), consumption per Nm3 gas—coal 0.65 kg,
steam 0.35 kg and oxygen 0.36 Nm3 or 0.5 kg.
The Texaco process: The Texaco coal gasifier, which is an entrainment

system, is based on the well-proven Texaco synthesis gas generation
process for the partial oxidation of heavy fuel oil. In the coal version, finely
ground coal <0.074 mm in size is slurried with water and pumped into the
gasifier where it is gasified with oxygen or air at a temperature of about
1,500°C and at pressures which can be up to 150 bar. The jet is directed
downwards from the top of a cylindrical refractory-lined pressure vessel. At
the bottom of the vessel the gas and the molten slag are quenched by a
water spray and a slag quench bath. The gas leaving the reactor is cleaned
and the fines containing carbon recovered for recycling with the coal slurry.
Great care is taken to maintain a constant high solids content. The reactor
temperature which is sensitive to the inputs, is closely controlled in the
range of 1,100–1,370°C to suit the ash fusion temperature. Too high a
temperature results in excessive refractory wear, whereas low temperatures
give rise to slag lumps which would block the exit to the lock hopper. Both
the slurry and oxygen are preheated.
The gas contains about 15% CO2 and very little CH4, and the rest is
mainly H2 and CO in a ratio of about 3:4. The calorific value is about 2,700
kcal/Nm3 when blown with oxygen and about half of that if air is used. The
gasification efficiency is 75%–80% and the oxygen requirement about 0.6–
1.1 kg/kg of coal, depending on the type of coal.
Underground gasification of coal: Coal can be gasified in situ without

raising it from the mine. A number of small commercial plants had been
installed in the old USSR which produced cheap gases of low calorific value
mainly for electricity generation. The production in 1963 was 1.4 billion
cubic metres with an average calorific value of 810 kcal/Nm3 dry. Air and
oxygen were used as the gasifying medium. Bituminous, sub-bituminous
and mature brown coal deposits are suitable for underground gasification.
There are two systems of underground gasification: the shaftless
system and the shaft system. Vertical channels are made in both systems
for supplying the gasifying medium and taking out the product gas. In the
shaftless system, no underground work is required while the shaft system
needs extensive preparatory underground work. The major problem in the
shaftless system is the making of satisfactory links underground between
the inlet and the outlet holes. The natural permeability of the coal bed is not
sufficient. Links can be achieved by establishing electro-links between two
electrodes and carrying out electrical carbonisation of the coal in the path. A
channel of hot coke is formed through which air is passed for gasifying the
fuel between the two vertical boreholes. Another method involves the
development of fractures in the coal mass by hydraulic or pneumatic means
and then creating a path by backward burning.
There are a number of variants of the shaft system. In the. more popular
stream method, horizontal galleries are made at the bottom of the coal
seam. Access galleries connect the horizontal galleries with the mine
shafts. A fire is ignited at the seam bottom along the horizontal gallery and
air is introduced through one access gallery. The product gas is taken out
through the other access gallery. With the progress of gasification, the
reaction zone advances upward along the coal bed. The stream method is
usually adopted with the steeply pitched coal beds.
Another variant of the shaft system is the borehole producer method.
Parallel galleries are constructed within the coal bed and then connected by
making horizontal boreholes through the confined coal mass. Boreholes are
ignited in succession or in small groups. Air is passed through one gallery
and the product gas taken off through the other.
The chief points of attraction of underground gasification of coal are the
elimination of mining and the utilisation of unworkable coal seams and left-
over coal in mines. The product gas may be used not only as a cheap fuel
but also in the manufacture of synthesis gas for ammonia, methanol and
liquid fuels. Large-scale worldwide application of the process will be
possible by the improvement of its technology and also by the ever-
increasing cost of mining and gasification of coal by other routes.
The composition, in per cent, of a lean gas produced by underground
gasification is given below
CO H2 CH4 N2 CO2 CnHm O2

10.7 8.4 1.8 67.4 10.5 0.3 0.9
This gas has a calorific value of 820 kcal/Nm3 dry, and specific gravity of
0.95 (air =1).
6.2.7 COAL GAS
This is produced by the high temperature carbonisation of coal in gas

retorts and coke ovens. Chapter 4 describes the manufacturing process and
gives the average yield, compostion, calorific value and uses of the by-
product coke oven gas; also see Table 6.3. The use of coal carbonisation
processes as the main method of producting town gas or synthesis gas is
rapidly decreasing. What is still attractive is the utilisation of the by-product
gas obtained from coke plants. With a calorific value of 5,000 kcal/Nm3 dry
and specific gravity of 0.4, coal gas is a good fuel for distribution to homes
and industries. It is also suitable for the production of synthetisis gas. Coke
oven gas may be regarded as the cheapest raw material for ammonia
production if the fertiliser plant is located near an integrated iron and steel
plant.
There are two methods for obtaining hydrogen from coke over gas: low
temperature separation and steam reforming. The fertiliser plant at
Rourkela draws the coke oven gas from the steel plant and separates
hydrogen by the low temperature method. The coke oven gas is compresed
to 12–30 atm, Carbon dioxide is removed by water scrubbing and the gas is
gradually cooled to the liquefying temperature. The unsaturates, methane
and carbon monoxide are liquefied. The gaseous hydrogen is purified by
washing with liquid nitrogen and used in the synthesis of ammonia. The
unsaturates may be used in the manufacture of chemicals and the gas
containing methane and carbon monoxide may be used as a rich fuel.
An additional quantity of hydrogen may be obtained from methane by
steam reforming and from carbon monoxide by water gas shift reaction.
6.2.8 BLAST FURNACE GAS
The combustion zone of the blast furnace is near the bottom of the tall
structure. The combustion gases ascend through the descending burden of
coke, ore and flux. Carbon reduces carbon dioxide to carbon monoxide and
decomposes steam into hydrogen and carbon monoxide. The reduction of
iron oxide is achieved mostly by carbon monoxide and partly by hydrogen.
The gases remain in contact with the charge in the upper part of the
furnace, give away part of the sensible heat and leave the furnace top at a
sufficiently high temperature say, 180°C to 200°C. The resultant gas is
known as blast furnace gas.
Blast furnaces may be regarded as gas producers in which a few other
reactions take place in addition to the usual producer reactions. The
resultant gas has higher carbon dioxide content and lower hydrogen content
than the producer gas. A typical gas analysis is shown in Table 6.7.
The gas is produced at a high yield, say, 2,400 Nm3 per tonne of pig
iron. The utilisation of the potential heat of the enormous quantity of the gas
produced in an iron and steel plant is extremely important for the efficiency
of the plant.
The high dust content, upto 20–30 g/m3, is a deterrent to its straight
supply to combustion systems. The heavier particles are removed by dust
catchers or cyclones. If necessary, further cleaning is done in wet cleaning
units like stationary scrubbers, revolving cleaners or centrifugal machines
like the Thiessen disintegrator, bag filters or electrostatic precipitators. The
final degree of cleanliness is about 0.5 g/m3 for industrial burners and 0.01
g/m3 for gas engines. Owing to its low calorific value it is necessary to
preheat the gas and air for obtaining high flame temperatures. It is also
mixed with coke oven gas and used. In a modern iron and steel plant about
20% of the total volume of blast furnace gas is used to preheat the blast,
the surplus gas is frequently used for steam raising purpose and for firing
the open hearth, reheating furnaces and coke ovens.
6.2.9 GASES FROM BIOMASS
Biomass can be coverted to fuel gas as well as synthesis gas for chemicals,
fertilisers and liquid fuels. The present emphasis is on the production of
gasesous fuels from biomass. There are two routes to get gas from
biomass: a thermochemical process and a biochemical process. The term
biogas is reserved for the product obtained by the biochemical conversion
of biomass.
Like coal, biomass can be partially gasified by carbonisation, which is
essentially pyrolysis. This process can be controlled in such a way that
either only charcoal, or charcoal and gas are produced as major products.
In the former variant the medium calorific gas is used up in the charcoal
plant itself. In the other variant, auxiliary fuel is used in firing the charcoal
retort and the gas is released for other consumption. Wood is the main
feedstock used in the carbonisation and total gasification of biomass. If
agriwastes are used in carbonisation, the charcoal emerges in the form of
dust and requires briquetting before it can be put to use. Typical compostion
and properties of gas of wood carbonisation, wood gas, are given in Table
6.8.
Table 6.8 Composition and properties of wood gas

Temperature of carbonisation,°C ~400 ~1000
Yield of gas, Nm3 per tonne of dry wood 125 550
per cent w/w dry wood 14.5 50.8
CV of gas, kcal/Nm3 dry 3,320 3,280
Specific gravity of gas (air =1) 0.68 0.50
Composition, per cent dry
CH2 30 20
C3H10 4 2
CO 25 25
CH4 14 12
H2 20 35
N2 7 6
In order to achieve total gasification it is necessary to use a gasifying
medium like air, oxygen and hydrogen. Air is the most common of the three
and wood logs and chips are the main feedstock for the process which is
widely practised in many countries for producing a cheap fuel gas. The
principle of wood gasification is similar to the principle of obtaining producer
gas from coal. However, the wood producers have longer zones for drying
and carbonisation than the coal producers. The wood producers are also
suitable to gasify peat. A unit with a capacity of 70–80 tpd of dry wood chips
is shown in Fig. 6.7. The performance of a commercial wood gas producer
is given in Table 6.8.
Figure 6.7 Wood gas producer having a capacity of 70–80 tpd dry wood
Crude methyl alcohol may also be recovered in a yield of about 0.5%
dry wood. A typical gas composition, in per cent, is: CO2 6.0, CO 29.0, CH4
2.5, CnHm 0.7, H2 14.5, O2 0.3 and N2 47.0. Its calorific value is 1,660
kcal/Nm3 dry and specific gravity 0.85 (air = 1). About 40% to 50% of the
gas is consumed as a fuel for the producer. The rest is available for, say,
thermal power stations. The liquid products yield chemicals on further
treatment.
Wood gasification based on cheap wood and wood wastes is a process
with sound economics.
Biogas
Anaerobic decomposition of organic wastes by suitable bacteria produces

methan-rich gases known as biogas. Carbonaceous agricultural wastes of
plant or animal origin such as animal dung, straw, hay and fruit peelings,
and municipality sewage constitute organic wastes. Cattle dung, however, is
the largest feedstock for biogas generation.
The anaerobic fermentation of biomass takes place in two stages. First,
the complex organic compounds are decomposed into simple organic acids
and these acids are later converted into methane and carbon dioxide. The
acid-forming and methane-forming bacteria must remain in a state of
dynamic equilibrium.
Fresh dung has a solid content of 20%. It is diluted to 7% to 9% with
water and fed into a pit-like chamber. The temperature is kept at 30°C to
40°C. In the initial acid forming stage, the pH is 6 when much carbon
dioxide is given off. In two to three weeks time, as the volatile acids and
nitrogen compounds are digested and methane is formed, the pH increases
upto 8. Slight mixing improves the gas yield but violent agitation retards the
process.
In a biogas plant the whole system is a continuous operation, that is, the
matter to be fermented is fed in a semifluid form at one end, and the
fermented spent liquor is extracted at the other end periodically, without
disturbing the system. The plant is a composite unit of a digester and gas
holder. The gas holder floats on the top of the digester wherein the gas is
collected and delivered at constant pressure to the gas appliances through
a pipeline.
The composition and yield of biogas depend upon many factors,
including the material used as feed for fermentation. On an average from
cattle dung one gets a gas consisting of 55% to 60% methane and 40% to
45% carbon dioxide with negligible amounts of hydrogen sulphide,
hydrogen and nitrogen. The yield of gas is about 0.092 m3/kg fresh dung in
summer and 0.036 m3/kg in winter. It is necessary to stimulate gas
production in winter by warming up the water used for diluting and mixing
the cattle dung. Some nutrients like urine, oil cakes or molasses may also
be added.
The residual slurry from the digester is rich in nitrogen (1.8%–2.4% as
against 0.75% in fresh dung), phosphorus pentoxide (1.0%–1.2%) and
potassium oxide (0.6%–0.8%). It is a good manure for agriculture.
Biogas is used as a fuel for cooking or for lighting in mantle lamps, or for
running gasoline and diesel engines. It is also possible to use it as a fuel in
industry if available in sufficient quantities.
The future of biogas is very bright in a country like India with a large
population of cows, horses and buffaloes.
6.2.10 REFINERY GASES
The term refinery gas covers a wide range of products and includes gases
obtained during distillation, cracking and other processing of petroleum and
petroleum fractions. These gases contain paraffins like methane, ethane,
propane and butane, olefins like ethylene, propene and butene, hydrogen
sulphide and hydrogen. A possible range of composition may be:
Composition, in per cent
The C4- and C3-hydrocarbons may be separated by liquefaction and sold as

bottled gas. Similarly sulphur may be recovered from the hydrogen
sulphide. The hydrogen and lighter hydrocarbons are best utilised in the
production of chemicals, fertilisers and plastics. These may be used to
enrich town gas also. All these uses and even burnig as a refinery fuel may
not completely consume all the refinery gases produced in a big plant. The
surplus gas is disposed of by burning it in the open.
6.2.11 LIQUEFIED PETROLEUM GASES (LPG)
Out of the gasesous hydrocarbons, the C3- and C4-compounds can be

liquefied at room temperature by the application of moderate pressure and
can therefore be conveniently stored and transported as liquids in light
pressure vessels. These are known as liquefied petroleum gas, or LPG or
bottled gas. In many countries two grades of this product are marketed: one
containing the C3-hydrocarbons—commercial propane—and the other
containing the C4-hydrocarbons—commercial butane—as the chief
components. The latter is safer to handle with storage pressure upto 3 atm
and is freely used for domestic purposes. The C3-hydrocarbons are
liquefied and stored at higher pressures upto 10 atm and used in industrial
heating. Where only one grade is sold, it is a mixture of the two types
containing higher proportion of C4-hydrocarbons. The lighter grade of LPG
contains about 90% propane, below 10% butane–iso-butenes and below
2% ethane–ehylene. The heavier grade contains 80% to 90% butane–iso-
butenes, below 20% propane–propene and below 2% ethane–ethylene.
LPG is prepared from wet natural gas, associated gas and refinery
gases. Indian specifications are given in Table 6.11. The combustion
characteristics of LPG differ greatly from the usual gaseous fuels. They
have high calorific value, high specific gravity, high air requirement and low
flame speeds (Table 6.10). Suitable burners are available for using LPG in
home and industry. Since LPG is odourless it is necessary to add odorants,
such as mercaptans or sulphides, to detect leakage.
Table 6.9 Performance of a commercial wood gas producer
Table 6.10 Properties of liquefied petroleum gases

Type Gross CV Specific gravity Theoretical air
kcal/Nm3 dry (air = 1) requirement Nm3/Nm3
Pure 30,680 2.00 30.94
butane
Pure 23,670 1.52 23.80
propane
Coke 5,020 0.38 4.57
oven gas
Table 6.11 Specifications for liquefied petroleum gases (IS: 4576-1999)

Characteristics Requirements for
commercial use
Butan Butane- Propan
e Propane e
mixture
Vapour pressure at 40°C, kPa, gauge, Max 520 1050 (Note 2) 1550
Composition, liquid volume percentage
(a) C2-Hydrocarbons - Report Report
(b) C3-Hydrocarbons Repor Report 95.0
t Min
(c) C4-Hydrocarbons Repor Report 4.0
t Max
(d) C5-Hydrocarbons and heavier 2.5 2.5 Max 0.2
Max Max
(e) Unsaturated hydrocarbons OR Repor Report Report
t
Volatility: 2.0 2.0 -38.0
Evaporation temperature in °C for 95 per cent by 2.0 2.0 -38.0
volume at 760 mm Hg
pressure, max Total volatile sulphur 150 150 150
ppm, max
Copper strip corrosion at Not
worse
38°C for 1 h than
No. 1
Hydrogen sulphide Pass Pass Pass
Free water content None None None
Bottled gases are becoming increasingly popular as domestic fuel. The

chief point of attraction lies in the fact that a large concentration of thermal
energy is contained in a relatively small and portable vessel which provides
a gaseous fuel that can be piped or directly sent to a gas burner. This is
particularly true in the case of those cities and towns where adequate
central gas distribution systems do not exist. When portable fuels are not
easily available, LPG is quite popular in industrial heating also. LPG has
also found use as a fuel for internal combustion engines of stationary type
and also those attached to vehicles, tractors and locomotives.
Propane and butane gases may be used to enrich the low calorific value
gases in a town gas supply system upto the limits of permissible specific
gravity. Butane may also be diluted with air to get a suitable fuel. A mixture
of 20% butane and 80% air has a CV of 6,136 kcal/Nm3 dry and is well
outside the limits of inflammability of butane in air. Finally propane and
butane may be reformed to get a gaseous fuel or synthesis gas. Propane,
butane and their olefinic counterparts are widely used in refinery processes
and in the production of petrochemicals.
Oil gasification
Liquid fuels are gasified to produce either gaseous fuels or synthesis gas.
Depending upon local conditions, light distillates, middle distillates and
heavy oils are all used as raw materials for gasification processes. Some
have found commercial application.
The C3 - to C15-hydrocarbons are liquids under ambient conditions,
although both lighter and heavier hydrocarbons may remain in solution in
them. The transformation of liquid hydrocarbons into the gaseous form
involves two basic processes:
1. Reduction in the size of the molecules,
2. Reduction in the C/H ratio.
These can be achieved by cracking, addition of hydrogen and removal of

carbon in the form of coke, tar and oxides of carbon.
The C/H ratios by weight of some fuels are: typical coking coal, 15.5:1;
heavy fuel oil, 7.8:1; light distillate feedstock, 5.6:1; natural gas and town
gas; 3:1. If town gas is manufactured from solid and liquid fuels only by
thermal cracking without the addition of hydrogen or oxygen, and if it is
assumed that all the hydrogen goes to the formation of the gas, a simple
calculation will show that only 24% of the solid fuel, 46% of the heavy oil
and as much as 61% of the light oil can be gasified, leaving 76% of the soild
fuel, 54% of the heavy oil and only 39% of the light oil as either carbon or
carbon-rich tar. The total gasification processes aim at converting the
carbon into cabon monoxide and gaseous hydrocarbons by supplying air,
oxygen and steam. This clearly bears out the importance of the lower C/H
ratio of the oils as a technical point in favour of oil gasification as compared
to the gasification of solid fuels.
The overall reactions with oxygen and steam in oil gasification leading to
hydrogen and carbon monoxide formation are
Reaction (6.11) is referred to as partial oxidation and reaction (6.12) as
steam reforming. These reactions are the ultimate goals in the production of
synthesis gas. However, it is desired in fuel gas manufacture to break down
(crack) the oil hydrocarbon molecules to smaller sizes in the gaseous range
so that the gaseous product is rich in hydrocarbons and has a high calorific
value. The cracking reactions have been discussed in Chapter 5. The
resultant gaseous hydrocarbons are predominantly paraffinic, chiefly
methane, and olefinic in nature while aromatics and naphthenes are also
present. The cracking and steam reforming reactions are facilitated by
operation under pressure or by the use of catalysts, the temperature
remaining an important variable. Cracking and steam reforming reactions
(6.13) are highly endothermic while partial oxidation is exothermic.
The heat requirement of the endothermic reaction is supplied by one of

three methods:
1. Cyclic method of dividing the process into blow and run periods as
gas generation,
2. Continuous method of burning a part of the feed in the gasifier using

and steam in place of air and steam,
3. External heating by enclosing the gasifier in a furnace.
The oil gasification process may be classified as follows:

1. Non-catalytic cyclic processes, such as Semet-Solvay,
2. Catalytic cyclic processes, such as Segas and Onia–Gegi,
3. Continuous catalytic reforming, such as ICI and Topsoe.
4. Partial combustion processes, such as Koppers–Totzek, Shell and Te
5. Hydrogenation processes.
Since the oil crisis in the 1970s, the oil gasification processes are restricted
to the production of syngas for chemicals and fertilisers.
Continuous steam reforming of naphtha: Steam reforming of naphtha

has followed the commercial success of steam reforming of natural gas,
refinery gases and LPG for the production of fuel gas, ammonia synthesis
gas, methanol synthesis gas and hydrogen. An incentive for the
development of this process was the availability of cheap surplus naphtha
on a very large scale in the world market.
Contrary to hydrocarbon gases, steam reforming of naphtha deposits
carbon on the catalysts inspite of the use of excess quantities of steam and
operation at comparatively low pressures. However, ICI of Britain have
succeeded in developing a suitable nickel catalyst (specially promoted
nickel oxide on a ceramic base with hydraulic cement bonding) which allows
continuous reforming of desulphurised naphtha at a relativiely high pressure
and with a relatively reduced steam consumption.
Since sulphur seriously deactivates the nickel catalyst, naphtha needs
desulphurisation before steam reforming. Depending upon the purity of the
naphtha, catalytic hydro-desulphurisation is done in a single stage (vapour
phase) or in two-stages (liquid phase followed by vapour phase) process.
The main reactor is in the form of three rows of vertical nickel chrome
alloy steel tubes of 127 mm internal diameter and 8.4 m length charged with
the catalyst. The tubes are heated in a furnace upto 960°C by five rows of
burners installed at the furnace top. The flue gases are used to raise waste
heat steam at 20 atm, superheat the reaction steam and preheat the
combustion air.
A mixture of desulphurised naphtha vapours, surplus hydrogen and
superheated steam (3 mol/mol of feedstock carbon) enters the reactor from
the top. The reaction is carried out at pressures up to 28 atm and
temperatures upto 840°C. The exact temperature and pressure conditions
depend upon the ultimate use of the gas. In a plant for a town’s gas supply
the gas leaves the reactor at 700°C and 19 atm (Fig. 6.8). It is a medium
calorific gas with calorific value of 3,000 kcal/Nm3 (dry) and specific gravity
of 0.46 (air = 1). The sensible heat of the gas is recovered in a waste heat
boiler. It is then passed through a shift converter where carbon monoxide is
reduced to 3% by catalytic shift conversion reaction (6.7). The sensible heat
of the gas is extracted in the waste heat boiler, boiler water preheater and
naphtha with a carbonate lye for carbon dioxide removal. Finally the gas is
enriched and dried before supplying to consumers. Natural gas, refinery
gas, or LPG may be used for enrichment.
Figure 6.8 Simplified flow-diagram of (ICI’s) continuous naphtha reforming plant
When the intention is to make ammonia synthesis gas, the methane

content must not exceed 0.2%. On the other hand, it is not possible to lower
the methane content below 7% to 8% in the steam reformed gas without
using very high temperatures which seriously shorten the reactor tube life.
Therefore, a secondary reformer is used to modify the exit gas from the
primary reformer. Air is mixed with the primary gas in a quantity which
introduces nitrogen in the right proportion to hydrogen in the final synthesis
gas. A part of the combustibles bums and autogenously raises the gas
temperature to 1,200°C when methane–steam reforming is almost complete
over a special nickel catalyst. The gas leaves the secondary reformer at
about 900°C. It is then passed through a waste heat recovery system
before further treatment for ammonia synthesis.
The chief merits of the ICI steam reforming process are low capital cost,
low running cost and well-proved equipment and process design. Its
limitation is non-adaptability to middle and heavy oils. Units of capacity
exceeding 1,00,000 Nm3 per hour gas have been constructed. India has
also adopted this process for ammonia synthesis for her fertiliser production
on quite a large scale for distribution to homes and industries. It is also
suitable for the production of synthesis gas. In addition coke oven gas may
also be regarded as the cheapest raw material for ammonia production if
the fertiliser plant is located near an integrated iron and steel plant.
Partial combustion process: The Shell gasification process is contiguous,
autothermic and non-catalytic. It is mainly used in the production of
synthesis gas although the product gas can be enriched and supplied as
town gas. The feedstock ranges from natural gas to high sulphur heavy oils.
The feedstock, oxygen and steam are separately preheated to about
300°C and then brought together in the reactor at carefully controlled
pressures and flow rates. The reactor is essentially a burner where the
oxygen and steam are rapidly mixed immediately before partial combustion
and a great turbulence is set up in the chamber (Fig. 6.9).
The process operates under pressures of 10–40 atm and at
temperatures of 1,000–1,500°C. The reactor, a cylindrical vessel, is
internally lined with layers of highly refractory and insulating materials. The
exit gas is a mixture of hydrogen, carbon monoxide and carbon dioxide and
contains small quantities of methane and carbon. The carbon produced is
less than 0.05% when methane is the feedstock and 2% to 3% by weight
when liquid hydrocarbons are gasified. It can be removed by washing with
water or scrubbing in light distillates and recovered as a pelleted by-product
fuel. The carbon monoxide is shift converted and then the carbon dioxide is
removed if the gas is to be used in ammonia synthesis or town gas
manufacture. The sensible heat of the gases leaving the reactor at 1,000–
1,200°C is extracted in a waste heat boiler.
The typical product gas composition with a naphtha (liquid) feedstock is;
CO2 4.8%, CO 41.8%, H2 51.7%, CH4 0.3% and others 1.4%, Its calorific
value is 2,870 kcal/Nm3 dry and specific gravity is 0.52 (air =1). The
material requirements per cubic metre of gas, crude but dry are: naphtha
0.3 kg, steam 1 kg and oxygen 0.25 Nm3. Cold gas efficiency is 84% of
feedstock. The high capital cost of the process makes it suitable only for
large capacity installations.
Hydrogenation processes: The process of hydrocracking has been

successfully used in the field of oil gasification. Crude oil and heavy fuel oil
are hydrocracked to give a gas which can be further steam reformed into
synthesis gas.
Preheated streams of the feedstock and a hydrogen-rich gas are fed
into a reactor containing a fluidised bed of coke particles. The reactor
operates at around 700–900°C at pressures up to 50 atm. The aliphatic
contituents are cracked into smaller molecules and the aromatics are
dealkylated to give benzene, toluene, naphthalene and polynuclear
aromatics. The data on the hydrogenation of a crude oil are: Gas
composition in percentage: CO2 0.2, Cn Hm 0.3, CO 2.9, H2 36.3, CH4 45.9,
C2H6 13.5 and N2 0.9. Its calorific value is 7,800 kcal/Nm3 dry and the
specific gravity (air = 1) is 0.44. The cold gas efficiency is 73% of the
feedstock and benzene, toluene and naphthalene are obtained as by-
products.
A characteristic feature of the gas is the high ethane content which
makes it more suitable as a town gas than methane alone. Production of
ethane makes greater room for hydrogen of the gas which therefore has a
higher flame speed.
Light distillates can be subjected to a gas recycle hydrogenation
process to get a rich gas similar to that obtained by the hydrogenantion of
crude oil and heavy oil.
6.3 CLEANING AND PURIFICATION OF GASEOUS FUELS
The gases need cleaning and purification to a much lesser extent than
synthesis gases. Among the fuel gases, greater attention is paid to those
distributed by piping to homes and industries than those used in industrial
furnaces directly after gas generation. The major problem of purifying
gaseous fuels is two-fold: It should not be harmful and obnoxious to the
user and it should not create engineering troubles like corrosion and
choking. Sometimes the gases are upgraded by removing inerts like carbon
dioxide.
The bulk of the steam and tar vapours is removed by condensing in
coolers. Further removal of tar mist is achieved in mechanical detarrers,
although complete removal requires electrostatic precipitators. The water
vapour content of the gases meant for long distance piping is controlled by
cooling down to the desired dew point by the use of refrigerated glycol or
calcium chloride solution.
The methods of dust removal may be classified as dry or wet. Dry
methods include dust chambers, cyclones, bag filters and electrostatic
precipitators; wet methods include packed towers, spray towers and
centrifugal washers, such a Thiessen disintegrator. The maximum limits of
dust content are: < 0.45 g/m3 for use in furnaces and <0.01 g/m3 for use in
gas engines. Electrostatic precipitators and centrifugal washers attain the
latter specification.
The dry method of hydrogen sulphide removal in iron oxide chambers is
widely used in the manufacture of town gas by coal carbonisation. The coke
oven gas is usually purified by wet methods which are also employed in the
removal of hydrogen sulphide from refinery gases and the gases obtained
by various gasification processes using coal and oil.
In the dry method, the gas is passed over moist ferric hydroxide in a
suitable form. When bog iron is used hydrogen sulphide is removed by the
following reaction:
The iron compound is regenerated by adding small quantities of air to

the gas:
Elemental sulphur is formed. The regenerated oxide may be repeatedly

used till the sulphur content of the spent catalyst reaches 60% to 65%. The
sulphur in the spent oxide may be converted to sulphuric acid via sulphur
dioxide.
The basic principle of the wet methods consists in scrubbing the gas
with a suitable reagent which removes hydrogen sulphide by absorption,
with or without a chemical reaction. The spent reagent is regenerated by
oxidation (air blowing) or boiling, when sulphur or hydrogen sulphide
separates. The reagents of some of the processes are given below:
Thylox process: A solution of sodium or ammonium thioarsenate is used.

The reaction during absorption is
The reaction during regeneration (air blowing) is
Seaboard process: A solution of sodium carbonate is used. The reaction

during absorption is
The reaction during desorption (air blowing) is

Girbotal process: Aqueous solutions of aliphatic amines, for example,
monoethanolamine (MEA) and diethanolamine (DEA) are used. CO2 is
removed along with H2S. The reaction during absorption is
The reaction during desorption (steam blowing) is
Shell phosphate process: A solution of tripotassium phosphate is used.

The reaction during absorption is
The reaction during desorption (boiling) is
The following problems will be better appreciated after the completion of

Chapter 7.
Example I
Calculate the gross calorific value and the Wobbe index of a fuel gas having
the following composition, per cent by volume: methane 89.0, ethane 8.0,
propane 2.0 and butane 1.0.
Solution
Using the data in Table 7.4 of Chapter 7, the average calorific value (gross)
of the fuel is calculated.
Average CV (gross) = 9,500 × 0.89 + 16,644 × 0.08 + 23,688 × 0.02 +
30,714 × 0.01
= 10,567 kcal/Nm3
Average molecular weight of = 16 × 0.89 + 30 × 0.08 + 44 × 0.02 + 58 × 0.01
the gas = 18.1
Average molecular weight of = 32 × 0.21 + 28 × 0.79

air = 29 (accepted since CO, is also present in air)
Example 2
In a trial on a producer, the following results were obtained: Gas yield is

3,000 Nm3/te of coke, CV of coke is 5,800 kcal/kg and CV of gas is 1,600
kcal/Nm3. Find its cold gas efficiency.
Solution
Cold gas efficiency of the producer
Example 3
From the data given below, calculate the cold gas efficiency of a gas
producer using a dry blast.
Coal analysis Gas analysis, orsat, per cent
Per cent as charged Per cent, dmmf
Moisture 3.0 C 85.2 CO2 7.0
Coal analysis Gas analysis, orsat, per cent
Ash 14.7 H 5.6 O2 0.7
Volatiles 35.7 N 2.8 CO 20.3
Fixed carbon 46.6 S 0.4 H2 12.5
Total 100.0 O 6.0 C2H4 0.5
Total 100.0 CH4 3.0
N2 56.0
Total 100.0
Clinker analysis, per cent dry: carbon 15.0 and ash 85.0.
Heat of combustion, –∆Hc cal/mol: CO 67,636; H2 68,317; C2H4 337,234
and CH4 212,798.
Solution
Steps of calculation: (i) Convert the ultimate analysis of the coal into ‘as
changed’; (ii) Calculate the dry gas yield from the carbon balance. The
carbon is distributed over the gas, clinker and tar. Assume 10% loss of
carbon with tar. (iii) Calculate the CV of the dry gas from the orsat analysis
and the heats of combustion of the components, (iv) Calculate the CV of the
coal using Dulong’s formula, (v) Compute the cold gas efficiency of
producer.
Converting the ultimate analysis on the ‘as charged’ basis
= 85.2 × 0.808 = 68.9

H = 5.6 × 0.808 = 4.5
N = 2.8 × 0.808 = 2.3
S = 0.4 × 0.808 = 0.3
O = 6.0 × 0.808 = 4.8
Moisture = 3.0
Ash = 14.7
Water of hydration of minerals = 0.1 × 14.7 = 1.5
100.0
For the calculation of gas yield, use 100 kg coal ‘as charged’ as the basis.
Therefore, carbon gasified = 68.9 – (2.6 + 6.89) = 59.41 kg
= 4.95 kmol
Neglecting the SO2 reported with CO2

Carbon in dry gas = 7.0 + 20.3 + 2 × 0.5 + 3.0
= 31.3 kmol per 100 kmol dry gas
CV of dry gas = 67,636 × 0.203 + 68,317 × 0.125 + 3,37,234 × 0.005 + 2,12,798 ×

0.03
= 30,340 kcal/kmol
Therefore, cold gas efficiency of the producer
Example 4
Using the data of Example 6.3, calculate the supply of air and steam per kg
of coal if BST is 60°C. Given: vapour pressure of water at 60°C = 149.40
mm Hg, and 30% of nitrogen in coal is conveted into ammonia.
Solution
The air supply is calculated from the nitrogen balance. Both air and fuel
supply nitrogen, while the gas and ammonia liquor are the recipients of this
element. The gas receives 70% of the nitrogen of the coal while the
ammonia receives 30%.
Applying Dalton’s law of partial pressures and assuming the blast pressure
to be 760 mm,
PROBLEMS
1. Using the gas compositions of Table 6.6 and the calorific values of
7.4, calculate the gross calorific value and the Wobbe index of the
gases.
2. When amorphous carbon is used as the fuel in an air-blown produce

maximum cold gas efficiency is 69.73%. If steam is added in such a
that 0.4 kg steam is decomposed per kilogram of carbon gasified, wh
be the maximum cold gas efficiency of the mixed-blast producer?
values of ∆Hc for CO and H2 are 67,636 and 68,317 kcal/kmol, respec
[Answer: 88.5%]
3. The coal feed to a producer on analysis showed 70% carbon,
moisture, 7.5% ash and negligible nitrogen and sulphur. The product g
analysis showed 8.0% CO2, 16.3% H2, 20.6% CO, 1.0% CH4 and 5
N2. Neglecting tar and clinker losses, calculate (a) gas yield (Nm3/kg
air requirement (Nm3/kg), (c) steam decomposition (kg/kg), (d
hydrogen content of coal in per cent and (e) cold gas efficiency o
producer in per cent.
Note: (i) The steam will include that formed from the oxygen
hydrogen of coal.
(ii) Calculate the calorific value of coal by using the Dulong
formula.
[Answers: (a) 4.41 Nm3/kg (b) 3.02 Nm3/kg (c) 0.253 kg/kg (d) 4.0 per
cent (e) 76.1%]
4. A gas producer gasifies coke containing 10% moisture and 20% ash.
carbon content of the coke is 95% daf and the gas analysis shows
5.3%, CO 25%, H2 12% and CH4 0.5%, calculate the cold gas efficie
the producer. (Neglect other elements in the coke in the calculatio
assume N2 as the remainder in the gas analysis)
[Answer: 87.6%]
5. Perform the ‘simple calculation’ refered to in the third paragraph
gasification, section 6.2.11.
6. Using a naphtha feedstock, a steam reformer produces a gas wit

following composition, per cent dry: CO2 4.4, C2.5H5 4.1, CO 20.0, H2
C2H6 7.7 and N2 14.3. If the naphtha is assumed to be C7H16, calcula
carbon efficienty of the reformer.
[Answer: 92.8%]
BIBLIOGRAPHY
1. Gas Engineers Handbook. New York: Industrial Press, 1966.
2. Gasmaking. London: British Petroleum Co, 1965.

3. Gumz W. Gas Producers and Blast Furnaces. New York: Wiley, 1950
4. Lowry HH, (ed.). Chemistry of Coal Utilization, Vol 2, 1945:1586

Supplementary Volume, 1963:892:1023; Elliott MA, (ed.). S
Supplementary Volume, 1981;1491:1599. New York: Willey.
5. Ministry of Petroleum and Natural Gas, Govt. of India, http://petroleu

n/ng.htm.
6. Nonhebel G. Gas Purification Processes. London: George Newne, 19
7. Pritchard R, Guy JJ and Connor NE. Industrial Gas Utilization, Engin

Principles and Practice. Essex, UK: Bowker Publishing Co., 1977.
8. Paul S. LNG option for India. Ind. Chem. Eng. Section B, 2004;46:4.
* using β-graphite, ∆H= – 94,050 kcal

* Based on β-graphite, the maximum cold gas efficiency is 72%.
* Based on β-graphite, the ∆H values for reactions (6.5), (6.6) and (6.8) are: +31,390
kcal, +21,550 kcal and -17,890 kcal, respectively.
7 Combustion Process
(Stoichiometry and Thermodynamics)
7.1 COMBUSTION STOICHIOMETRY
The combustible elements in solid and liquid fuels are carbon, hydrogen
and sulphur. The combustible components of gaseous fuels are hydrogen,
carbon monoxide, methane and unsaturated hydrocarbons. Higher paraffins
may be present in some fuels such as LPG, carburetted water gas, fuels
obtained from oil gasification and gases from low temperature carbonisation
of coal and lignite. The average molecular formula of paraffins present may
be assumed as:
C1.25H4.5 for low temperature coal gas,
C1.1H4.2 for carburetted water gas and oil gas.
The composition of the unsaturated hydrocarbons may vary from gas to

gas. The following average molecular formulae are representative:
C2H4 for producer gas from coal,
C4H8 for low temperature coal gas and vertical retort coal gas,
C2.5H5 for coke oven gas, horizontal retort coal gas, carburetted wa
and oil gas.
The combustibles undergo complete combustion by the following well-

defined overall chemical reactions.

Gaseous fuels
Paraffins
Unsaturates
In making use of the above reactions in combustion stoichiometry, it is

important to remember the following points:
1. The combustibles in solid and liquid fuels are expressed as the elem
weight per cent. Particular attention should be given to the ba
expression. In Chapter 3 we have seen that the ultimate anal
expressed on a dmmf basis for the high ash Indian coals. This p
problem in combustion calculations because the volatile part of m
matter is included in the combustion products. Under these circumsta
is preferable to express the ultimate analysis in such a way th
following equation holds good:
Since the detailed composition of the mineral matter is not generally

known, it is assumed for convenience that
mineral matter – ash = 0.1 ash
= water of hydration of the minerals
This assumption is also necessary for the calculation of the net
calorific value from the gross. For low-sulphur Indian coals, this
assumption is justified; unless carbonate minerals are present in
significant quantities.
2. The combustibles in gaseous fuels are given in volume or mole pe
Usually a dry basis of expression (orsat analysis) is used. If nec
conversion into a wet basis is done on the assumption that the fuel
saturated with water vapour at the given temperature and pressure.
3. The composition of the products of combustion (flue gas) is first cal

as they are produced and then expressed on a dry basis. Furth
sulphur dioxide and carbon dioxide are reported together as carbon d
since both the components are absorbed in the same absorption pip
the orsat analysis.
4. Theoretical air is the amount of air stoichiometrically required

complete combustion of the combustibles. Similarly, theoretical prod
combustion refer to the flue gas or exhaust gas obtained by the co
combustion of the fuel using theoretical air.
5. Excess air is the amount of air used in excess of the theoretical

expressed as per cent or fraction of the theoretical air. It is impor
remember this definition, particularly when a flue gas contains free
as well as combustibles like carbon monoxide owing to ine
combustion. In this case excess air will correspond to free oxygen
oxygen required for the combustion of the residual combustibles.
6. Useful basis of calculation is 100 kg of solid or liquid fuels and 100

gaseous fuels or flue gas as the case may be.
7. Usually air is assumed dry and CO2-free in combustion calculations.
8. In dry air, the volume (or mole) ratios of the components are
9. Average molecular weight of dry, CO2-free air = 29.0
10.
At 50% excess air, the value of the factor is 1.5.
7.2 EXAMPLES
The following examples illustrate the principles of combustion stoichiometry:
7.2.1 FLUE GAS ANALYSIS FROM FUEL ANALYSIS AND AIR SUPPLY
Example I
Solid fuel: Determine the flue gas analysis, the air-fuel ratio by weight and
the volume of combustion products at 250°C when a Wardha valley coal of
the following composition burns with 50% excess air.
If the burning rate of the coal is 3 t/h, what is the capacity of the air blower
used? Assume complete combustion.
Solution
Basis of calculation: 100 kg air-dried coal.
The steps are:
1. The ultimate analysis is converted from daf to air-dried basis by mul
by the
2. The weights in kilograms are converted into kilomoles by divid

molecular weight or atomic weight as the case may be.
3. Theoretical (stoichiometric) oxygen requirement is calculated fro

combustion equation. The air supply is calculated after deducti
oxygen of the fuel from the total oxygen requirement.
4. The combustion products are also calculated from the chemical equ
Their composition includes excess air. The final analysis of the flue
given on dry basis after combining CO2 and SO2.
5. The calculated values in each step are given below.
Volume of combustion products (flue gas) at 250°C and 1 atm
Flow rate of the flue gas
Assuming 30°C ambient temperature, capacity of air-blower
Flue gas analysis (Problem 1)
Table for solution of Problem 1

Example 2
Liquid fuel: Determine the flue gas analysis and air-fuel ratio by weight
when a medium viscosity fuel oil with 84.9% carbon, 11.4% hydrogen, 3.2%
sulphur, 0.4% oxygen and 0.1% ash is burned with 20% excess air. Assume
complete combustion.
Solution
Basis of calculation: 100 kg fuel oil. No change in the basis of expression is
necessary. The data of the ultimate analysis are converted into kilomoles
(see table on page 256) and the procedure given in the earlier problem is
followed. The results are tabulated below.
Example 3
Gaseous fuel: A furnace burns producer gas with 10% excess air at the rate
of 7200 km3/h and discharges flue gases at 400°C and 760 mm Hg.
Calculate the flue gas analysis, air requirement and volume of flue gases
per hour. The gas is supplied from a gas holder and its orsat analysis is:
CO2 4.0, CnHm 0.4, CO 29.0, H2 12.0, CH4 2.6 and N2 52.0. Ambient
temperature is 30°C and pressure is 760 mm Hg. Assume complete
combustion.
Solution
Basis of calculation: 100 kmol of producer gas as supplied. The steps are:
1. Assume the gas is saturated with water vapour at 30°C and 760 m
Vapour pressure of water (tension of aqueous vapour or aqueous te
at 30°C = 31.89 mm Hg. Content of water vapour in the saturated gas
2. Convert the orsat analysis data into volume per cent wet (saturat
multiplying by
3. Use the combustion equations and tabulate the results as shown o

257.
Table for solution of Problem 2
Combustion calculations (Problem 3)

7.2.2 EXCESS AIR CALCULATION FROM FLUE GAS ANALYSIS
Example 4
Using the calculated orsat analysis of the flue gas in Problem 1, determine
the per cent excess air used in the combustion. No other data are available.
Solution
The orsat analysis of the flue gas is CO2 12.7%, O2 7.1% and N2 80.2%.
There is no combustible in the gas. Hence, the oxygen entirely corresponds
to the excess air. We know
Since the orsat analysis is on a dry basis, the content of water vapour in the
flue gas is not available. Furthermore, the oxygen available from the fuel is
also not known. Therefore, the total air cannot be calculated from the
oxygen balance of the flue gas analysis. The only other course left is to use
the nitrogen balance. In the absence of fuel analysis, one does not know
how much nitrogen is contributed by the fuel itself. From all these
considerations it may be seen that the problem defies any straightforward
solution. However, the contribution of solid and liquid fuels and some
gaseous fuels to the nitrogen content of the respective flue gases is
negligible. The present problem is solved below with the assumption that
the nitrogen of the flue gas is entirely contributed by air and that the fuel
does not contain any oxygen.
Basis of calculation: 100 kmol dry flue gas

Components kmol kmol C accounted kmol O2 accounted
for for
CO2 12.7 12.7 12.7
O2 7.1 - 7.1
N2 80.2 - -
Total 100.0 12.7 19.8
This result is close to the given condition (50% excess air) of Problem 1.
7.2.3 DEW POINT OF FLUE GASES
Flue gases flow through ducts and various other parts of the furnace
system. It is detrimental to have water deposited on them. A knowledge of
dew point of flue gases is therefore desirable.
Example 5
Determine the dew point of the gases obtained in Problems 1, 2 and 3.
Solution
By definition, the dew point of a gaseous mixture is the temperature at
which its water vapour starts condensing. It is therefore the temperature at
which the saturation pressure for water equals the partial pressure of water
vapour in the gaseous mixture.
From the wet flue gas analysis of the three problems, the content of
water vapour is: 5.18%, 9.47% and 9.9%, respectively.
The partial pressure of water vapour in the three gaseous mixtures
(assume gas pressure = 760 mm Hg):
Thermodynamic tables give the following temperatures at which water has

the above saturation pressures (aqueous tension):
For Problem 1: 33.7°C

These are the required dew points.
7.2.4 COMBUSTION CALCULATIONS INVOLVING LOSS OF COMBUSTIBLES WITH

FLUE GASES AND ASH
Example 6
The flue gas from a coal-fired furnace gives the following orsat analysis:
CO2 11.5%, CO 1.5%, and O2 6.5%. A coal from the Dishergarh seam of
the Raniganj field containing carbon 68.0%, nitrogen 1.9%, sulphur 0.3%
and ash 14.7% is used. The dry refuse removed from the furnace has a
combustible content of 40% as carbon. Calculate (a) the volume of air per
kilogram of coal, (b) kilomoles of dry flue gases per 100 kg coal, (c) the
content of surplus hydrogen and water in coal, (d) the volume of flue gases
per kilogram coal and (e) per cent of excess air. Assume dry air, ambient
temperature 30°C, pressure 760 mm and flue gas exit temperature 300°C.
Solution
The steps are
1. Use 100 kg coal as basis of calculation.
2. Calculate the quantity of dry refuse from ash balance between co

refuse. Hence, determine the carbon lost in the refuse and the carbo
to CO2 and CO.
3. Calculate the kilomoles of dry flue gas from carbon balance. Take du
for the sulphur in coal which is burnt to SO2 and reported as CO2 in t
gas.
4. Use nitrogen balance for calculating the quantity of total oxygen su

Calculate the oxygen (sum of free and combined) accounted for in t
gas. The deficit in oxygen is due to the combustion of hydrogen of c
water.
5. The quantity of hydrogen calculated from the oxygen deficit is the

hydrogen in coal. This hydrogen is in excess of that required to co
with the oxygen of coal to form water (vide Dulong’s formula for calc
of CV).
6. The water content of coal is calculated by the method of difference,
100 per cent of (C + S + N2 + ash + surplus H2). This water is the
actual and potential water content of coal. The latter term means the
oxygen in coal and the hydrogen required to combine with it to form w
7. Volume of the flue gas is calculated from the dry flue gas, the water c
and the surplus hydrogen content of coal.
8. The quantity of excess air is finally calculated by the method used in
Basis of calculation: 100 kg coal as fired

Components kg kmol
C 68.0 5.67
N 1.9 0.07
S 0.3 0.01
Ash 14.7 -
84.9
Surplus hydrogen ?
Water ?
100.00
Dry flue gas analysis
1. Basis: 100 kg coal as fired

From (C + S) balance
2. Air contains 79% N2
The number of kilomoles of components in 37.5 kmol dry flue gas and the
total O2 accounted for in it are given in the table above.
This includes the oxygen of coal and the hydrogen required to combine with
it.
7.3 RAPID METHODS OF COMBUSTION STOICHIOMETRY
Detailed methods of combustion stoichiometry should be followed only for

an acquaintance with the subject. Once the principles of combustion
stoichiometry are known, industrial problems are worked out more quickly
by other means. A few of them are presented below.
7.3.1 USE OF FUNDAMENTAL FORMULAE
The formulae are easily derived from combustion equations. They are
useful in a comparatively quick solution of combustion problems.
H2O, C, H2, O2, N2 and S represent the weight per cent of moisture, carbon,
hydrogen, oxygen, nitrogen and sulphur in the fuel, respectively.
Total O2, required for complete combustion of the fuel
Volume of theoretical air required

Volume of theoretical flue gas wet, that is as produced
where,
Volume of theoretical dry flue gas
Analysis of theoretical flue gas wet, per cent:

Orsat analysis of theoretical flue gas dry, per cent:
Excess air (EA) is calculated from the flue gas analysis by using one of the
following formulae:
1. Case of complete combustion
2. Case of incomplete combustion
where, O2, CO, H2, CH4 and N2 represent the per cent of the respective
components in the flue gas. These equations neglect nitrogen in the fuel
and are valid for solid and liquid fuels for all practical purposes.
Excess air factor is defined as
Air supplied
Flue gas produced

Dry flue gas
Flue gas analysis, per cent wet:
Orsat analysis of flue gas, that is per cent dry, is obtained by multiplying wet
per cent of CO2, O2 and N2 by 100/(100 – H2O per cent wet) to get per cent
dry of the respective components.
Gaseous fuels
Let CO2, CH4, Cn Hm, H2, CO, O2 and N2 represent the volume or mole per
cent of the respective components in the fuel gas as fired, that is, wet or
saturated with water vapour at the ambient temperature and pressure.
Volume of theoretical air required
Volume of theoretical wet flue gas produced
where
Volume of theoretical dry flue gas
Excess air ratio, total air supplied and flue gas produced (wet or dry) may
be calculated by the formula (7.14) to (7.23). If the gaseous fuel contains
significant quantities of nitrogen, for example, producer gas and blast
furnace gas, the formulae for excess air calculation are modified as below
In the earlier formulae the symbols with prime denote the content (per cent)
in dry flue gas. The term N2/V’ in the denominator gives the contribution of
the gaseous fuel to the nitrogen in the flue gas.
Example 7
Solve Problem 1 using the formulae given above.
Solution
Analysis of the coal as fired, per cent: C 58.4, H 3.3, O 8.6, N 1.3, S 0.4,
moisture 8.0 and ash 20.0.
Theoretical air
Ao = 0.089C + 0.267H2 + 0.033S - 0.0330
= 0.089 × 58.4 + 0.267 × 3.3 + 0.033 × 0.4 - 0.033 × 8.6
= 5.80 Nm3/kg coal
Carbon dioxide
α = 0.01866C + 0.007S = 0.01866 × 58.4 + 0.007 × 0.4
= 1.09 Nm3/kg coal
Water
β = 0.112H + 0.0125H20 = 0.112 × 3.3 + 0.0124 × 8.0
= 0.47 Nm3/kg coal
Nitrogen
γ = 0.79Ao + 0.008N = 0.79 × 5.80 + 0.008 × 1.3
= 4 60 Nm3/kp coal
Theoretical flue gas (wet)

Vo = σ + β + γ = 1.09 + 0.47 + 4.60
= 6.16 Nm3/kg coal
At n = 0.5,
Air supplied
Flue gas produced (wet)
Flue gas analysis, per cent wet

Example 8
Calculate excess air from the flue gas analysis of Problem 6 by using the
applicable formula.
Solution
Neglecting carbon loss with clinker
7.3.2 USE OF EMPIRICAL CORRELATIONS
Statistical relationships exist between the net calorific value of all industrial
fuels, their theoretical air requirement and the volume of theoretical flue
gases they produce. The net calorific values are themselves related to the
gross calorific values of the respective fuels. Therefore a knowledge of
gross calorific value can be used to calculate Ao and Vo. The empirical
correlations are given in Tables 7.1 and 7.2.
Table 7.1 Conversion of gross CV(CG) into net CV (CN)
Solid fuels, kcal/kg

Coal: CN = 0.954CG + 110 (7.31)
Coke: CN = CG — 40 (7.32)
Liquid fuels, kcal/kg
CN=0.75CG + 2000 (7.33)
Gaseous fuels, kcal/Nm3
Blast furnace gas: CN = 0.99CG (7.34)
Coke oven gas: CN = 0.895CG (7.35)
Water gas : CN = 0.915CG (7.36)
Producer gas: CN = 0.95CG (7.37)
Table 7.2 Calculation of volumes of theoretical air (Ao) and theoretical flue gases (Vo)
Simple empirical relationships are also available for calculating excess air
from a knowledge of the type of fuel gas. From CO2-balance between dry
theoretical and dry actual flue gases, it can be seen that excess air ratio.
For solid and liquid fuels

Therefore,
For gaseous fuels, the ratio varies between 0.9 and 1.95 in regularity
with the variation in net calorific value
Again the content of CO2 in theoretical dry flue gas is approximately

constant for a given class of fuels (Table 7.3). This is the maximum CO2-
content of dry flue gas obtained from that class of fuel. The value of
(CO2)max that is (CO2)theor may also be calculated from the flue gas orsat
analysis.
Table 7.3 CO2 content of theoretical dry flue gas
Fuel (CO2)max, that is,

(CO2)theor, per cent
Bituminous coal 18.7
Lignite, semi-anthracite. 19.5
anthracite, semi-coke
Wood, charcoal 20.5
Fuel oil 15.8
Town gas
CN = 4,900 kcal/Nm3 11.0
4,450 kcal/Nm3 12.0
4.000 kcal/Nm3 13.0
Coke oven gas 11.0
Producer gas from coal 19.0
Producer gas from coke 20.5
Blast furnace gas 24.5

These relationships form the basis of Ostwald charts. The CO2 and O2
contents of the flue gas from the complete combustion of a particular class
of fuel should vary with the amount of excess air in a regular manner. This
regularity is shown in a very simple and clear manner in Ostwald charts.
Each class of fuel has its own Ostwald chart. The two limiting points in the
chart are the (CO2)max and the (O2)max which is 21% (oxygen content of
air). The composition of flue gas containing excess air is shown by a point
in the line joining the two limiting points (Fig. 7.1), perfect combustion line.
Figure Ostwald chart for coke-oven gas

7.1
The Ostwald chart also contains lines of incomplete combustion,
represented by contents of H2 and CO in the flue gas (several experiments
have indicated that when CO is present, it is accompanied by an
approximately equal volume of H2). The chart also includes constant air-
ratio lines. Air-ratio, R, is defined as
where n = excess air factor

Ostwald charts are useful in checking flue gas in combustion
calculations. Each flue gas is represented by a single point in the chart
meant for the particular fuel. The Ostwald charts for various industrial fuels
are available in Reference 5.
Once the excess air factor, n, is known, the volume of actual air supply,
A, and the actual flue gas produced, V, can be calculated.
Example 9
The CO2 content of the products of complete combustion of a coal of 7,200

kcal/kg CV is 12.0% by orsat analysis. Calculate (a) the per cent excess air,
(b) the volume of air supply at 30°C and 760 mm and (c) the volume of flue
gas leaving the furnace at 400°C and 760 mm per kilogram of coal fired.
Solution
From Table 7.1
From Table 7.3

Therefore,
Excess air = 56%
From Table 7.2
Air supply
Volume of flue gas,
7.3.3 USE OF HUMID AIR IN PLACE OF DRY AIR FOR COMBUSTION CALCULATION
If necessary, humidity of atmospheric air may be taken into account in

combustion calculation.
Let the humidity of air = H g/kg of dry air
Volumetric content of water vapour in air
Theoretical humid air consumption for combustion
Actual humid air supply

Product of combustion with humid air
Volume of combustion products (wet)

1. With theoretical humid air
2. With excess air (humid)
Volume of dry combustion products
Therefore, volume of dry combustion products and their orsat analysis

remain unchanged by the use of humid air in place of dry air.
If the humidity is expressed as per cent relative humidity, RH, volume of
water vapour
where, P = atmospheric pressure, mm Hg

ps = vapour pressure of water at the ambient temperature, mm Hg.
Alternatively, humidity, H, is read from psychometric charts at the given RH
and temperature, and then vw is calculated from H.
Example 10
Solve Problem 7 using air of 60% relative humidity at 30°C and 760 mm.
Solution
Water vapour pressure at 30°C = 31.886 mm
Flue gas produced
Water vapour from air
Flue gas analysis, per cent, wet

Orsat analysis will remain unchanged by the use of humid air in place of dry
air.
7.4 COMBUSTION THERMODYNAMICS
Heat of combustion, equilibrium constant of reactions occurring during

combustion, enthalpy of combustion systems and flame temperature are the
thermodynamic functions of the combustion processes which fundamentally
influence the utilisation of fuels in diverse appliances. A brief account of
each of these functions is given below.
7.4.1 HEAT OF COMBUSTION
By applying Hess’s law the heat of combustion of any substance can be

calculated from the heats of formation of reactants and products. Table 7.4
presents the heats of combustion of fuel gas components and carbon at
25°C and 1 atm pressure. The heat of combustion of carbon depends upon
its allotropic form. In physics and thermochemistry, β-graphite is used as a
basis for heat of formation (ΔHf = 0) since it is a well-defined body material.
In technical processes, however, it is preferable to use amorphous carbon,
say, coke carbon as the basis. The data of Table 7.4 relate to solid
amorphous carbon. In relation to β-graphite, the other allotropic forms of
carbon have the following heats of formation: β-graphite = 0, α-graphite =
270 kcal/kmol, diamond = –220 kcal/kmol, amorphous carbon = + 2948.2
kcal/kmol (assumed to get a round figure of 97,000 for – ΔHc).
Table 7.4 Heat of combustion of carbon and some gases at 298°K and 1 atm pressure
Substance Heat of combustion (ΔHc) Calorific value,
kcal/kmol kcal/Nm3 dry
Carbon (solid 97,000 8,083 (kcal/kg)
amorphous)
Hydrogen 68,317.4 3,050 (33,887.6 kcal/kg)
Carbon monoxide 67,636.1 3,020
Methane 212,798 9,500
Ethane 372,820 16,644
Ethylene 337,234 15,055
Acetylene 310,615 13,867
Substance Heat of combustion (ΔHc) Calorific value,
kcal/kmol kcal/Nm3 dry
Propane 530,605 23,688 (11,947 kcal/kg
liquid)
n-Butane 687,982 30,714 (11,749 kcal/kg
liquid)
Propane 491,987 21.964 (11,692 kcal/kg
liquid)
1-Butene 649,757 20,000(11,581 kcal/kg
liquid)
Benzene 789,080 35,227 (9,999 kcal/kg
liquid)
Toluene 943,580 42,124(10,143 kcal/kg
liquid)
Hydrogen sulphide 134,744 6,015
CV can be easily derived from the heat of combustion.
The calorific values of other gases are also given in Table 7.4. When water
is a product of combustion, it is considered in the liquid state for arriving at
the heat of combustion of Table 7.4. Therefore, the figures in the last
column of this table are the gross calorific values of the substances
concerned. The calorific values of commercial fuels are discussed in
Chapters 3, 5 and 6.
The heat of combustion of a fuel is also known as its potential heat. If in
a combustion system there is undeveloped heat, that is loss of combustible
with the flue gas and or solid refuse, the process is obviously inefficient.
The efficiency of combustion is calculated in the following way.
The combustion efficiency is different from the furnace efficiency. The latter
is much more involved. Any meaningful discussion of this term is beyond
the scope of this book.
7.4.2 ENTHALPY OF COMBUSTION SYSTEM
In most practical cases of combustion, heat transfer from the combustion

gases takes place at a fairly constant pressure, not far from the
atmospheric. The heat absorbed by the surroundings from a combustion
system at constant pressure is equal to the decrease in the enthalpy of the
system.
where Q = heat absorbed by surroundings

−∆H = enthalpy decrease of the system in heat units
In other words, enthalpy change is the change of heat content of the system
at constant pressure. It is not necessary to know the absolute enthalpy of a
system. A knowledge of enthalpy in relation to a reference state, say, 0°C
and 760 mm is sufficient. The enthalpy of a gas at a temperature t°C is thus
where C̄p0-t is the mean specific heat between the reference temperature,
0°C, and the given temperature, t°C, expressed as kcal/Nm3 °C (volume
basis) or kcal/kg°C (weight basis). Like Cp, the units of ΔH, may be
kcal/Nm3 or kcal/kg. If molar heat capacity, MCp, is used, ΔHt will be in
kcal/mol.
The values of mean specific heat and enthalpy of gases at different
temperatures with reference to 0°C are given in the Appendices 1-4. The
enthalpy change between two temperatures, t1 and t2 can be determined
from these tables.
Depending upon the particular problem, either the mean specific heat
values, or the enthalpy values are directly used.
The specific heat of a gas is independent of pressure at low pressures
and the average specific heat of a gas mixture is
where (C̄p0-t )A, (C̄p0-t )B,... = mean specific heat of components, A, B ... etc.
xa, xb... volume fraction or weight fraction of components as the case may
be.
The enthalpy of the mixture.
Alternatively the enthalpy of the mixture is calculated from the enthalpy of

its components.
Although normally enthalpy is the product of specific heat and temperature,

it is necessary to take into account some other factors at very high
temperatures above 1500°C for arriving at correct enthalpy values.
The most significant of these factors is the storage of energy by
dissociation reactions — Appendix 3 and Appendix 4 neglect this effect.
Dissociation reactions of combustion systems are discussed below.
Appropriate corrections are to be applied in using the data of Appendix 3
and Appendix 4 above 1,500°C.
The specific heat and enthalpy of combustion gases are used in
calculating flame temperature, heat loss with flue gases and furnace
efficiency. Since the enthalpy data do not include latent heat of
condensation of water vapour, net calorific value of fuel is to be used for
calculating combustion efficiency and furnace efficiency.
Example 11
From the data of Problem 6, calculate the total heat loss with the flue gas
and the potential heat loss with the solid refuse, both expressed as a per
cent of the potential heat (calorific value) in coal. Hence, determine the
combustion efficiency.
Solution
Analysis of coal, per cent as fired: C 68.0, surplus H2 3.9, S 0.3, water
(including water from the oxygen of coal) 11.2, ash 14.7.
By Dulong’s formula
Potential heat loss with the refuse
Flue gas analysis, per cent
Enthalpy of flue gas at 300°C

= 0.064 X 110.0 + 0.108 X 134.7 + 0.014 X 94.4 + 0.753 X 94.2 +
0.061 X 97.2
= 99.9 kcal/Nm3
Let mean specific heat of flue gas at 30°C (datum temperature)
= 0.064 × 0.357 + 0.108 × 0.400 + 0.014 × 0.311 + 0.753 × 0.311 +

0.061 × 0.314
= 0.324 kcal/ Nm3°C
Therefore, enthalpy at 30°C = 0.324 X 30

= 9.72 kcal/Nm3
Therefore, sensible heat loss with the flue gas
= 99.9 – 9.72
= 90.18 kcal/Nm3 gas
Again, potential heat loss with the flue gas
Therefore, combustion efficiency
But, total heat loss with the flue gas
7.4.3 EQUILIBRIUM CONSTANTS OF COMBUSTION REACTIONS

There are a number of reversible reactions which determine the fate of the
combustion process. A proper evaluation of the latter needs consideration
of the equilibrium constants of these reactions. Appendix 5 gives the
equilibrium constants of some of the reactions at the wide temperature
range of 300–4000 K. Out of these, the following reactions are of particular
significance (ΔH values are at 25°C):
Dissociation of water vapour

H2O ⇄ H2 + ½O2 ∆H = + 57,798 kcal
Dissociation of water vapour into hydroxyl group

H2O ⇄ OH + ½H2 ∆H = + 67,858 kcal
Dissociation of carbon dioxide

CO2 ⇄ CO + ½O2 ∆H = + 67,636 kcal
Dissociation of hydrogen
H2 ⇄ 2H ∆H = + 104,178 kcal
Dissociation of oxygen
O2 ⇄ 2O ∆H = + 118,318 kcal
Formation of nitric oxide

½O2 + ½N2 ⇄ NO ∆H = + 21,600 kcal
These reactions are endothermic and convert a part of the sensible heat of
the combustion gases into the potential heat in the form of heat of
combustion of the combustible components formed and the heat of
formation of atomic hydrogen and atomic oxygen. The combustion of fuels
is therefore rendered incomplete at high temperatures. This has two effects:
first, the combustion efficiency is lowered and second, the temperature of
the system falls. The second point is discussed under flame temperature.
Another effect of dissociation is an increase in the volume and number of
moles of the gases.
When the equilibrium constants at different temperatures are known, the
degrees of dissociation at those temperatures can be calculated.
The temperature dependence of the equilibrium constants for CO2
dissociation is given in the following formula, applicable to temperatures
above 1,600K.
A similar formula for H2O dissociation, applicable for all temperatures is

given below
where T is in K.
If x is the fraction of CO2 dissociated at any temperature, the equilibrium
constant at that temperature:
Similarly,
where, y is the fraction of H2O dissociated and P is the total pressure in

atmosphere. In the usual cases of combustion, P = 1. Equations 7.63 and
7.64 are also valid for mixtures containing carbon dioxide and water vapour.
In such cases, partial pressures of these components are to be used for P.
The fraction dissociated is called degree of dissociation, α. Table 7.5
gives the degree of dissociation of carbon dioxide and water vapour in the
temperature range, 1,400−2,900°C. Out of the six reactions written above,
these two reactions are the most significant in usual combustion with air.
Table 7.5 Dissociation of carbon dioxide and water vapour

Example 12
Combustion products (composition of undissociated gas): 11% CO2, 9.5%

H2O, 3.3% O2 and 75.3% N2, leave a combustor at 1,600°C. Calculate the
heat loss due to dissociation of CO2 and H2O per Nm3 of the gas.
Solution
Initial partial pressures
PCO2 =0.119 atm

PH2O = 0.095 atm
Degrees of dissociation at 1,600°C (Table 7.5)
αCO2 = 1.54% at 0.119 atm

αH2O = 0.6% at 0.095 atm
Heat of dissociation
ΔHCO2 = + 67,636 kcal/kmol = + 3,020 kcal/Nm3

ΔHH2O = + 57,798 kcal/kmol = + 2,580 kcal/Nm3
Heat absorbed due to dissociation
= 3020 X 0.0154 X 0.119 + 2580 X 0.006 X 0.095

= 7.02 kcal/Nm3 gas (neglecting the small rise in the volume of the
gas by dissociation)
This is the required heat loss and represents the potential heat of CO and
H2 formed by the dissociation of CO2 and H2O.
7.4.4 ENTHALPY-TEMPERATURE DIAGRAMS
When combustion is complete, the enthalpy of a flue gas is actually the

summation of the enthalpy of theoretical flue gas and that of excess air. For
a given fuel, the composition of its theoretical flue gas is fixed. Therefore,
the enthalpy of its flue gas is a function of two variables only, namely,
temperature and excess air. At temperatures above 1,600°C, the
endothermic effect of dissociation reactions must be taken into account.
These considerations form the basis of the construction of enthalpy-
temperature diagrams. Each class of fuel has its own enthalpy-temperature
diagrams. However it has been found that the theoretical wet flue gases
obtained from all industrial fuels have approximately the same enthalpy
(kcal/Nm3), at the same temperature.
The equilibrium constants hold good for mixtures as well as for the pure
gases. This situation lays the foundation for the well-known Ht-or It-diagram
of Rosin and Fehling (Fig. 7.2). The diagram covers the range from 100 to
2,500 C and shows the relationship between enthalpy and temperature for
different air content of the flue gas. The air content of flue gas,
Figure Ht-diagram for combustion gases
7.2
The diagram takes into account various significant dissociation reactions

occurring above 1,600°C.
Enthalpy–temperature diagrams in general and Ht-diagrams in particular
are very useful in rapidly working out the problems concerning heat loss
with the flue gas and flame temperature.
The full benefits of the Ht-diagram are derived by using a few auxiliary
tables given in Reference 4 of the Bibliography.
Example 13
Using Ht-diagram calculate the enthalpy of the flue gas of Problem 12.
Solution
Air content of flue gas
vA = 3.3 X 4.76 = 15.7%
Therefore, from the Ht-diagram, enthalpy at 1,600°C
= 70 X 8.9 = 623 kcal/Nm3
7.4.5 FLAME TEMPERATURE
The average temperature attained by the combustion products of a mixture

of fuel and oxidant is known as the flame temperature of the inflammable
mixture. Four different types of flame temperature are recognised:
theoretical flame temperature, adiabatic flame temperature, actual flame
temperature and maximum adiabatic flame temperature, or simply
maximum flame temperature. It will be evident that the theoretical flame
temperature is not a tangible concept, while the others are.
When the combustion of the fuel goes to completion and the entire heat
of combustion goes to heat the products of combustion, the resultant
temperature is the theoretical flame temperature. In reality, combustion is
never complete at high temperatures owing to dissociation reactions. When
the endothermic effect of dissociation reactions is taken into account, the
adiabatic flame temperature is obtained. Obviously, this is lower than the
theoretical flame temperature.
In a practical combustion process, adiabatic conditions do not exist.
There is always some heat loss to the surroundings of the system. The
resultant average temperature of the combustion products is termed the
actual flame temperature.
All the three flame temperatures defined above depend upon the
composition of the fuel–oxidant mixture. If the quantity of oxidant is to small,
it will lead to incomplete combustion; if the quantity is too large, it will dilute
the products and take away heat. Both the factors lower the flame
temperature. Theoretical flame temperature has its maximum value at the
stoichiometric composition of fuel and oxidant. Since the degree of
dissociation reactions markedly increases with temperature, the
endothermic effect also rises with it. Heat loss due to this factor increases
with the rise in temperature at an accelerated rate. Therefore, the maximum
adiabatic flame temperature is realised when the fuel is slightly in excess of
the stoichiometric composition (Fig 7.3). Maximum adiabatic flame
temperatures of some fuel gases in air and of a few in oxygen are given in
Table 7.6. It may be seen that with the exception of acetylene which is
somewhat above the range and with a slight exception for hydrogen and
carbon monoxide, all gases listed from 1 to 14 in Table 7.6 have their
maximum flame temperatures around 1,900–1,950°C. This is because an
increase in the calorific value of a fuel is counter-balanced by the additional
air requirement and hence by a greater quantity of products of combustion.
The last two gases, that is, producer gas and blast furnace gas have quite a
low flame temperature owing to very high content of inerts.
Figure 7.3 Variation of adiabatic flame temperature with composition of fuel-air

mixture
Table 7.6 Maximum adiabatic flame temperature (MAFT)

From the few data given for combustion in oxygen, it will be seen that
the flame temperature of a fuel is much higher in oxygen than in air. This is
because of the high nitrogen content of air, which takes away a significant
quantity of heat. It is noteworthy that the depression effect of dissociation on
flame temperature is many times more in oxygen combustion than in air
combustion. For example, methane-oxygen flame, with a stoichiometric
ratio of 1:2 has an adiabatic flame temperature of 2,700°C as against its
theoretical flame temperature of 5,050°C. The drop in flame temperature
due to dissociation is thus as high as 2,310°C. The corresponding values
for stoichiometric combustion in air are: theoretical flame temperature,
2,060°C, adiabatic flame temperature, 1,870°C and the drop due to
dissociation, 190°C, that is, 1/12 of the drop in oxygen. If the products of
combustion of a system are difficult to dissociate at high temperatures the
resultant adiabatic flame temperature should be very high. A cyanogens-
oxygen flame has such products, CO and N2, and gives a temperature of
4,580°C. Similarly, a hydrogen-fluorine flame has a maximum adiabatic
temperature of 4,300°C
In the above discussion and for getting the values of Table 7.6, fuel–
oxidant mixture is taken at room temperature and combustion is assumed to
occur at atmospheric pressure. Flame temperatures can be appreciably
increased if additional heat is supplied to the system in the form of, say,
preheated air and if possible, preheated fuel.
Flame temperatures are calculated by striking a heat balance between
the fuel and air on the one hand and the products of combustion on the
other. Let us take the case of actual flame temperature in air. Heat balance
is given by
CN + ∆Hfuel + A ∆Hair = V ∆Hwg + qdiss + qloss
where,
CN = net CV of fuel, kcal/Nm3 fuel
∆Hfuel = enthalpy of the fuel above the reference temperature, kcal/Nm3
∆Hair = enthalpy of air above reference temperature, kcal/Nm3 air.
∆Hwg = enthalpy of combustion products above reference temperatur
kcal/Nm3 combustion gases.
A = air supplied, Nm3/Nm3 fuel
V = combustion gases producted, Nm3/Nm3 fuel
qdiss = heat loss by dissociation reactions, kcal/Nm3 fuel
qloss = heat loss to surroundings, kcal/Nm3 fuel
But,
∆H =tf C̄pwg, 0–tf – tC̄pwg, 0–t
tf = flame temperature, °C
t = reference temperature, say 25°C
C̄pwg, 0–tf = mean specific heat of combustion products between tf and 0°C
C̄pwg, 0–t = that between t and 0°C
Therefore,
If the fuel and air are supplied at the reference temperature, ∆Hfuel = 0 and
∆Hair = 0. In the case of theoretical flame temperature, qdiss = 0 and qloss =
0. In the case of adiabatic temperature, qloss = 0.
Actual flame temperature may be 250–400°C, lower than the theoretical
temperature.
Flame temperature has a special significance as it governs the thermal
efficiency of the transference of heat from the flames to the heating surface.
From the second law of thermodynamics, this efficiency is given by
Where Tf is the flame temperature and Ts the surface temperature in
absolute scale. The higher the flame temperature, the greater the efficiency.
Hence the special significance of preheating air/ fuel before combustion.
In the calculation of tf, the difficulty lies in its appearance on both sides
of the formulae. The specific heat of waste gases depends upon the
unknown tf. A trial and error method is therefore used. Two approaches are
possible: one through specific heat and another through enthalpy
determinations, as illustrated in the following problems.
Adiabatic flame temperature may be calculated rapidly though less
accurately by using a Ht-diagram.
Example 14
Calculate (a) the theoretical and (b) the adiabatic flame temperatures in the
combustion of methane in stoichiometric air.
Solution
Basis of calculation: 1 Nm3 methane
Stoichiometric combustion
CH4 + 2 (O2 + 3.76N2) → CO2 + 2H2O + 7.52N2

1 Nm3 2 × 4.76 Nm3 1 Nm3 2 Nm3 7.52 Nm3
Volume of combustion products,
V = 1 + 2 + 7.52 = 10.52 Nm3
Theoretical flame temperature

Assume tf = 2100°C
Neglecting the change in the gas composition by dissociation reactions,
we get
Therefore,
Second trial
Assume = 2,070°C. Neglecting the change in the gas composition by
dissociation reactions, we get
This temperature is the same as on the previous trial and may be taken as
the theoretical temperature.
Adiabatic flame temperature
Partial pressures of CO2 and H2O in the undissociated combustion

products.
Assume = 1900°C. Neglecting the change in the gas composition by

dissociation reactions,
At 1,900°C, degrees of dissociation

αCO2 = 8.1% at 0.1 atm
αH2O = 2.2% at 0.2 atm
Neglecting the volume rise by dissociation
Second trial
Third trial
This checks well against the value. However, this temperature is much
higher than the experimental value of the maximum adiabatic flame
temperature 1875°C for methane in air (Table 7.6). The chief reason is the
simplification of the method of calculation.
Example 15
What will be the theoretical flame temperature in the above case if the air is
preheated to 700°C?
Solution
Datum temperature = 25°C
Enthalpy of air at 700° above 0°C
Therefore,
Therefore, ∆Hwg, 0–tf = 10,826 kcal/Nm3 of fuel or 10.52 Nm3 of waste gas
Assume tf = 2500°C
It is slightly less than the required value of enthalpy (10,825 kcal/Nm3 of

fuel) and may be used for further calculation.
Second trial
Assume tf = 2,550°C
∆Hwg, 0–2550 = 1515.6 + 2 × 1242.0 + 7.52 × 927.9
= 10,977.6 kcal/Nm3 of fuel
By interpolation
Example 16
Using a Ht-diagram, calculate the adiabatic flame temperature obtained by

burning coke oven gas (gross CV = 4,800 kcal/Nm3) with 20% excess air
preheated to 600°C. Use appropriate tables in Reference 4.
Solution
Net CV,
CN = 4800 × 0.895 = 4300 kcal/Nm3
Theoretical air,
Theoretical waste gas
Therefore, actual wg = V 0+ nA0 = 5.14 + 0.2 × 4.44

= 6.03 Nm3/Nm3 fuel
Actual air = (1 + n) Ao = 1.2 × 4.44 = 5.33 Nm3/Nm3 fuel

Enthalpy of inlet air above 25 °C
Therefore, enthalpy of waste gas above 25 °C = 165 + 713

= 878 kcal/ Nm3 waste gas
= 98.7 Btu/Nft3
Air content of waste gas
From the Ht-diagram, enthalpy of waste gas at 25 °C above 0°C
= 0.9 Btu/Nft3 waste gas
Therefore, total enthalpy of waste gas at tf °C above 0°C
= 98.7 + 0.9 = 99.6 Btu/Nft3
From the Ht-diagram, tf = 2060°C

Above 1,600°C, the Ht-diagram takes into account the effect of heats of
dissociation reactions. Therefore, this is the required adiabatic flame
temperature.
PROBLEMS
1. A liquid hydrocarbon fuel having a H–C ratio of 0.174 by weight is burn

20% excess air. Calculate (a) the volume of air at 30°C and 740 mm, (
volume of flue gas at 300°C and 740 mm and (c) the weight of water fo
per kilogram of fuel.
[Answer: (a) 15.75m3kg, (b) 31.57 m3/K, (c) 1,332 kg/kg]

2. A natural gas (CO2 0.5%, N2 3.0%, CH4 92.5%, C2H6 4.0%) is burn
15% excess air. Determine (a) the volume of air, (b) the volume of flu
per cubic metre of the gas and also (c) the dew point, (d) compositio
(e) average molecular weight of the combustion products.
[Answer: (a) 12.09 Nm3/Nm3, (b) 11.91 Nm3/Nm3, (c) 563°C, (d) CO2
10.2%, O2 3.0%, N2 86.8%, (e) 27.8)]
3. A Raniganj coal (carbon 88%, hydrogen 4.8%, nitrogen 2.0%, sulphur
and oxygen 4.6% daf; moisture 3% and ash 14.5% as received) is bu
the rate of 300 kg/h. Air supply at 30°C and 740 mm is in 25% exce
theoretical. The flue gas leaves at 300°C and 740 mm. Compute (a
capacity of air blower, (b) the volume of exit gas per minute, (c) the
analysis of flue gas and (d) the dew point of flue gas.
[Answer: (a) 55 m3/min, (b) 313 m3/min, (c) CO2 14.8%, O2 4.3%, N2
80.9% (d) 32.7°C]
4. A gas has the following composition: H2 31%, CO 24% and N245%.
orsat analysis of the combustion products in a furnace is CO2 12.1%
2.8% and CO 0.0%, calculate the amount of excess air used i
combustion.
[Answer: 20.2%]
5. A propane-butane mixture (1:4) is burnt in a Burnsen burner. If the fu
mixture in the mixing tube contains 5.0% fuel, calculate the primary
the mixture as a percentage of the theoretical air.
[Answer: 64.4%]
6. A furnace is fired with a Singareni coal at the rate of 200 kg/h. The
analyses as: carbon 60.5%, hydrogen 3.2%, nitrogen 1.4%, sulphur
oxygen 9.4%, moisture 5.0% and ash 20.0%, air dried. The dry r
contains 20% combustibles. The flue gas has the following orsat ana
CO2 13.6%, O2 5.5% and CO 1.2%. Calculate (a) the hourly heat los
to unburnt combustibles, (b) the capacity of the air blower and (c) vo
flowrate (m3/h) of the flue gas at 250°C and 740 mm.
[Answer: (a) 132,264 kcal/h (b) 30 m3/mm (c) 2,923 m3/h]

7. If octane is burnt with 90% theoretical air, calculate the CO content
exhaust gas. (Assume the reactivity to oxygen in the order of H2 > CO
[Answer: 5.0% dry]

8. A heater burnts fuel oil of specific gravity 0.90 and composition: c
85.5%, hydrogen 12.0% and sulphur 2.5%, at the rate of 170 l/h
combustion is supplemented by a gaseous fuel of orsat analysis: H2 1
N2 62.5%, CH4 2.0%, CO 14.0% and CO2 8.0%. Oil to gas ratio is 2
weight. If 20% excess air is used, calculate the capacity of the fan deli
the air. Assume air at 30°C and 760 mm, and with humidity of 1
moisture per kilogram dry air.
[Answer: 40 m3/min]
9. A flue gas has the following orsat analysis: CO2 8.2%, O2 9.9%, CO
H2 0.4% and N2 81.4%. Calculate (a) the CO2 content of the dry theo
flue gas of the given fuel and (b) the per cent excess air used
combustion.
[Answer: (a) 15.5% (b) 80.4%]

10. The products of combustion of a fuel gas contain CO2 14.2%, H2O
O2 4.0% and the rest N2. If it is at a temperature of 1,000°C and mixe
atmospheric air at 30°C in the volume ratio of 1: 2, calculat
temperature of the mixture.
[Answer: 398°C]
11. Calculate the heat loss with the flue gas in Problems 1 and 3. Expre
result in kcal/kg fuel.
[Answer: 1329 kcal/kg, 882 kcal/kg]

12. The ultimate analysis of a coal tar fuel is C 90.0%, H2 6.0%, S 0.3
1.2% and O2 2.5%. It is burned with 20% excess air and the flue gas l
the combustion chamber at 300°C. Calculate the heat loss with th
gases per kg of dry fuel. (Neglect the ash of coal tar fuel.)
[Answer: 1.041 kcal/kg]

13. Calculate (a) the theoretical and (b) the adiabatic flame temperatu
pure benzene burnt in stoichiometric air.
[Answer: (a) 2,813°C (b) 2,556°C]

14. Determine the amount of heat lost by the dissociation of CO2 and H
the preceding problem.
[Answer: 1.99 kcal/kg benzene]

15. Compute the enthalpy change of the theoretical products of combust
methane in cooling from 1,500°C to 300°C. Express the result
kcal/mol of methane and (b) kcal/Nm3 of the combustion products
[Answer: (a) 1.138 × 105 kcal/mol (b) 482.9 kcal/Nm3]

16. Calculate (a) the theoretical and (b) the adiabatic flame temperatures
combustion of natural gas with 20% excess air. The orsat analysis
gas is: CH4 94.0%, C2H6 1.2%, C2H2 0.7%, C4H10 0.4%, C5H|2 0.2%
0.2% and N3 3.3%. The air is preheated to 800°C. It has a humidity o
g moisture per kilogram of dry air.
[Answer: (a) 2,384°C (b) 2,148°C]

17. A coal-fired furnace emits flue gas at the rate of 52,200 m3/h at 250
the coal analyses as carbon 58.4%, hydrogen 3.3%, nitrogen 1.3%, su
0.4%, oxygen 8.6%, moisture 8.0% and ash 20.0%, and its burning ra
t/h, calculate the orsat analysis of the flue gas.
[Answer:CO2 12.7%, O2 7.1%, N2 80.2%]

18. A gaseous fuel contains CO2 3.4%, C2H4 3.7%, C6H61.5%, O2 0.3%
17.4%, H2 36.8%, CH4 24.9% and N2 12.0%. It is burnt with air in a fur
The CO2 analyser shows 10.0% in the flue gases. Calculate (a) the pe
excess air used and (b) the complete orsat analysis of the flue gases.
[Answer: (a) 37.1% (b) CO2 10.0%, O2 5.9%, N2 84.1%]

19. Burning of carbon monoxide in air at atmospheric pressure gives a g
which the molar ratio of CO to CO2 is unity. The process takes place
insulated chamber, and the products of combustion exit at a temperat
2,430°C. Carbon monoxide enters the furnace at 30°C while the
preheated to the required temperature. Calculate (a) the composition
exit gas, (b) the per cent theoretical air used and (c) the temperature
preheated air.
[Answer: (a) CO2 25.8%, CO 25.8%, N2 48.4%, (b) 50% (c) 2,282°C]
20. A coal analyses carbon 80% and hydrogen 5%. It is burnt with air to
flue gases containing CO2 12.5% and O2 3.5% (orsat analysis).
carbon monoxide is suspected in the flue gases. Estimate (a) the com
orsat analysis of the flue gases and (b) the air/coal ratio by weight.]
[Answer: (a) CO2 12.5%, CO 4.2%, O2 3.5%, N2 79.8%, (b) 11.7]

21. The flue gases from a furnace burning a hydrocarbon fuel enter the s
normal pressure and 200°C and show the following orsat analysi
12.0%, CO 1.4%, O2 3.4% and N2 83.2%. Estimate (a) the per
excess air, (b) the volume of stack gases, expressed as cubic met
kilogram of carbon burnt, (c) the dew point of the stack gases,
atomic ratio of hydrogen to carbon in fuel and (e) the mole of stack
per mole of carbon burnt.
[Answer: (a) 13.9% (b) 27.1m3/kg (c) 47.5°C (d) 1.80 (e) 8.36
mol/mol]
BIBLIOGRAPHY
1. Hougen OA and Watson KM. Material and Energy Balance, Chem

Process Principles, Vol. 1, New York: Wiley,1959.
2. Hougen OA, Watson KM and Ragatz RA. Thermodynamics, Chem

Process Principles, Vol. 2, New York: Wiley, 1959.
3. Lewis B and Von Elbe G. Combustion, Flames and Explosions of Ga

Third edition, Orlando: Academic Press, 1987.
4. Lewis WK, Radasch AH and Lewis HC. Industrial Stoichiometry, Se

edition. New York: McGraw-Hill, 1954.
5. Rose JW and Copper JR. Technical Data on Fuel, Seventh edition, W

Energy Conference, London, 1976.
6. Trinks W and Mawhinney MH. Industrial Furnaces, Fifth edition, New Y

Wiley, 1961.
8 Combustion Process
(Kinetics)
8.1 NATURE OF COMBUSTION PROCESS
The potential energy stored in fuels is released by combustion and made

available in the form of heat and power. The process is essentially chemical
in nature and involves the reaction of fuel components with oxygen. Heat of
reaction is evolved and the temperature of the products is raised. The latter
are in the gaseous and vaporous form and tend to occupy a large volume at
the raised temperature attained, or generate high pressure if the volume is
not allowed to expand. The heat can be directly used for domestic and
industrial purposes, or it can raise steam to
1. Generate electricity (steam turbines),
2. Heat,
3. Supply mechanical power (steam engines).
The energy of the hot combustion products can also be directly used in gas
turbines to do mechanical work or generate electricity.
There are two methods by which the combustion of fuels can generate
electricity without using an alternator: by using fuel cells or a magneto-
hydrodynamic (MHD) generator. In a fuel cell, which is essentially an
electrochemical cell, the free energy of the combustion reaction is directly
converted into electrical energy at a theoretical efficiency of 100%. In a
MHD power generator, an exceedingly high temperature of combustion
products is realised between 2,000°C and 3,000°C, at which temperature
the latter are ionised and the charge of the ions is used to produce electrical
power. The heat remaining in the combustion products is utilised in further
generating electricity through the steam cycle and in preheating the air for
combustion. The total efficiency of such a plant is expected to be 55% as
against only 30% of a thermal power station. Vigorous work is going on in
developing the fields of fuel cells and MHD generators to make them
commercially feasible.
All applied combustion processes are characterised by the formation of
a flame. The term ‘flame’ refers to the heat -and light-emitting gaseous zone
which separates the combustion products from the fuel that is undergoing
combustion. A flame appears just after the fuel is ignited and a sufficiently
high temperature is created which tends to persist slightly beyond the
burning zone till a drop in temperature renders the gases completely non-
luminous. A flame thus covers luminous burning and after-burning zones
and is confined between the ignition zone and the completely non-luminous
combustion gases. A non-luminous Bunsen flame is actually a flame of low
luminosity. The flame front is the surface between the luminous region and
the unburnt fuel. A well-defined flame front is obtainable with gaseous fuels.
Flame thickness or flame length depends upon many factors, namely, types
of fuel, presence of diluent (nitrogen in air, or recirculated flue gases),
intensity of mixing of fuel and oxidant. A fastburning combustion and
luminescence occur almost simultaneously. Since a flame separates the
fuel from the combustion products, it may be significantly defined as the
zone of very steep concentration and temperature gradients. It is this
characteristic which distinguishes flames from chemical reactions in
general.
Because of the luminosity of a flame, some fuels like kerosene are used
as illuminants. Certain devices such as gas mantle are used to augment the
flame luminosity.
8.2 TYPES OF COMBUSTION PROCESSES
There are five general types of combustion processes depending upon the
means of contacting fuel and oxidant and the conditions of the flame. These
are briefly described below.
8.2.1 COMBUSTION WITH STATIONARY FLAMES
This is the usual combustion practiced in ovens and furnaces. The resultant
flame front is more or less stationary in space. A stationary flame may be
further sub-divided as premixed and diffusion. In the former case fuel and
oxidant are premixed before they enter the burning zone. When they are
separately delivered to the burning zone the flame is called a diffusion
flame. In actual practice a part of the total air may be premixed with the fuel
and the remaining may be directly supplied to the combustion area. The
premixed air is known as primary air and the rest is called secondary air.
While solid, liquid and gaseous fuels can all give a premixed flame, a true
diffusion flame is obtained only with gaseous fuels.
A stationary flame may be laminar or turbulent. The velocity of a
premixed system is responsible for its flame being laminar or turbulent. In
the case of a diffusion flame, both the direction of flow and the velocity of
fuel and oxidant determine the nature of the flame. A laminar diffusion flame
is favoured by low and equal velocity and parallel flow of gas and air. When
they flow at an angle to one another with higher and unequal velocity, a
strongly turbulent diffusion flame results.
Generally speaking, diffusion flames are considerably larger than
premixed flames, the other conditions of burning remaining similar. Again
laminar flames are longer than turbulent flames. A highly turbulent flame is
unsteady and irregular in shape. When the air hole of a Bunsen burner is
completely closed, a laminar diffusion flame is obtained. It is long, steady,
quiet, noiseless, well-shaped and luminous. If the big air-hole is fully
opened, a turbulent premixed flame is realised. It is short, unsteady,
flickering, noisy, irregular-shaped and of low luminosity.
The main advantage of the diffusion flame over the premixed one lies in
the fact that one or both of the fuel and air can be preheated before
combustion. On the other hand, when the aim in usual thermal appliances is
an intense combustion in a comparatively short space, a truly laminar,
diffusion flame is rarely used. However, long flames are desired in a coke
oven and open hearth furnace and these are two typical examples where it
is desired to have a long flame, so that an extended zone of uniform
temperature is obtained.
8.2.2 SURFACE COMBUSTION OR FLAMELESS COMBUSTION
At high temperatures all refractory solid surfaces have the property of

accelerating the rate of combustion of fuel gases and air. Some solids, for
example, platinum, can accelerate the process even at low temperatures.
Combustion with a stationary flame is limited by, among other factors, a
range of velocity and concentration conditions of the gas and air. Stable
combustion is possible even outside this range if the reaction is allowed to
proceed in contact with solid surfaces. This phenomenon is known as
surface combustion. Its industrial application is to achieve rapid combustion
of a large quantity of fuel in a comparatively small space with the production
of high temperature and enhanced heat transfer rate. A tunnel burner is a
type of gas burner operating on the surface combustion principle (see
Chapter 9). Well-defined normal flames are absent in surface combustion.
Submerged combustion
This is a special case of the surface combustion process. The burner is

partly or fully submerged in a liquid and the hot combustion gases are
allowed to bubble through it in an agitated condition. A high rate of heat
transfer results from the direct contact of hot gases with the liquid and leads
to a high evaporation rate. Up to 95% of the potential heat of the fuel may
be the useful heat for the process. Submerged combustion finds
commercial application particularly in the evaporation of severely scaling
liquids and highly corrosive solutions.
8.2.3 COMBUSTION WITH EXPLOSION FLAME
This occurs in a homogeneous mixture of fuel and air and is characterised

by the flame front progressing rapidly through the mixture. The process may
be either under constant pressure, for example, mine explosion, or constant
volume, for example, combustion in a gasoline engine. Detonation is a
special type of explosion where the extremely high reaction rate generates
ultra-high velocity pressure waves of 1–4 km/s and an abnormal rate of
pressure rise.
Pulsating combustion
When one end of a long tube is open and the other closed by a non-return
valve, and the air and fuel are introduced at the closed end, pulsating
combustion takes place. On ignition, the pressure in the system tends to
rise sharply at near-constant volume; the rise in pressure prevents the flow
of the air and fuel momentarily. When the exhaust gases leave the tube
through the open end, a fresh supply of air and fuel arrives at the hot zone
and combustion is repeated in the form of pulsations. The frequency of
these pulsations corresponds to the resonant frequency of the combustion
unit. There is no stationary flame in the system. Pulsating combustion is
essentially one specific type of explosion flame. During the operation of a
pulsating combustion unit, a standing pressure wave is produced in the pipe
with a pressure node (velocity antinode) at the exit end, and a pressure
antinode (velocity node) at, or near, the combustion zone. The main interest
in pulsating combustion systems is in obtaining higher rates of combustion
and heat transfer than in a conventional burner. The noise levels of the
pulsating combustors can be lowered by adopting suitable silencers.
8.2.4 SLOW COMBUSTION
This is the general term given to the combustion processes taking place at
sub-flame temperatures below 400°C, at slow and conveniently
determinable rates. Slow combustion of higher hydrocarbons has been
useful in determining chain-reaction rates. In a premixed system of fuel
vapour and air, slow combustion proceeds simultaneously at a number of
points in the whole system. No reaction zone or flame-front is visible. This
process is called homogeneous combustion. It is often characterised by the
appearance of cool flames in succession. These flames emit small
quantities of heat and pale bluish light usually seen only in the dark. Several
cool flames—up to four—may follow one another. Cool flames are a feature
of gas phase oxidation of organic substances below 400°C. Slow
combustion has no direct application in industry. It is indirectly useful in
studying the combustion mechanism.
8.2.5 COMBUSTION OF SOLID FUELS ON GRATE
The process of burning solid fuels in suspension, for example, pulverized

fuel firing or cyclone firing, can more or less fit into one or more of the
combustion processes described above. However, the combustion of lumps
on grate is in a class by itself. An industrial grate essentially consists of
assemblies of firebars mounted parallel to one another. Primary air is
passed through the gap between the neighbouring bars. A glowing fuel bed
with an ash layer underneath is maintained on the grate and fresh charge of
fuel is fed into it from time to time. The rate of feeding corresponds to the
combustion rate. The insulating ash layer serves to protect the firebars from
intense heat and also helps in the distribution of air.
The fresh charge on heating undergoes drying and decomposition. The
combustible volatiles are burnt in the secondary combustion space above
the fuel bed. An additional supply of air— secondary air—is made for this
purpose. This combustion more or less corresponds to the stationary flame
process. The residual solid fuel undergoes true primary combustion on
grate. It is a surface process involving heterogeneous reactions between
carbon and oxygen. The liberated heat converts the fuel into a glowing
mass which radiates heat to the heating surface and also to the fresh
charge of fuel. Carbon monoxide is a product of combustion on grate and
takes part in the secondary combustion.
The above method of burning solid fuels is known as overfeed firing. In
underfeed firing, fresh fuel is fed to the glowing bed from below. In
crossfeed firing, the fuel is fed transversely across the front of the grate.
In down-jet combustion, the grate is dispensed with. A jet of air is
impinged on the surface of the bed of fuel. The sides and bottom of the bed
are enclosed. The combustion products leave the bed through the upper
surface. Fresh fuel is fed from the top while the refuse is periodically
removed from the bottom. The principle of down-jet combustion has not met
with much success in practice. Difficulties in ash removal appear to be the
main hurdle.
8.3 MECHANISM OF COMBUSTION REACTIONS
The most studied combustion reactions are those involving homogeneous

combustion of gases and vapours. Here again the reaction of the
hydrogen–oxygen system has received by far the greatest attention of
researchers in the field. The other systems include carbon monoxide–
oxygen, methane–oxygen and higher hydrocarbons–oxygen. Reaction
mechanisms in high temperature combustion processes differ from
homogeneous combustion in many respects.
Low boiling liquid fuels are burnt in the vapour state. High boiling liquids
undergo cracking on heating and their combustion is essentially a
combination of two processes: combustion of cracked vapour and
combustion of solid carbonaceous material.
Solid fuels also involve two stages; first, the combustion of inflammable
gases and vapours emitted by its heating and oxidation, and secondly, the
combustion of residual coke or char. The solid carbonaceous material from
liquid fuels and the coke and char from solid fuels are mainly composed of
carbon. The mechanism of the carbon-oxygen reaction which has also been
studied in detail is therefore significant in understanding the combustion of
solid and liquid fuels.
The more clearly defined combustion reactions are discussed below
with an initial reference to the characteristics of chain reactions.
8.3.1 CHAIN REACTIONS
The most remarkable feature of rapid combustion and explosion is that,

under certain conditions, the reaction of an almost iso-thermal system can
switch over from one of a slow and finite rate to an infinitely fast and
uncontrollable violent reaction. For usual chemical reactions under
isothermal conditions, the rate depends on the concentration of the
reactants. Since the latter fall with time, the rate also should fall with the
progress of the reaction under isothermal conditions. Herein lies the basic
distinction of combustion reactions.
Combustion reactions of gases and vapours are all chain reactions. Any
chain reaction of finite rate has three consecutive phases: the initiation
phase, the propagation phase and the termination phase. Chain carriers are
formed in the first phase by thermal or other means. These may be atoms
such as H or O, free radicals such as OH, CHO or CH, or even molecules
such as formaldehyde. The chain carriers react with the molecules of the
reactants and produce new chain carriers together with the molecules of
products. The newly formed chain carriers further participate in reactions
and thereby promote the propagation phase. The process is terminated by
chain-breaking reactions in which the chain carriers are eliminated from the
reaction zone by chemical reactions or adsorption on another substance, for
example, on a container surface. When the intermediate reactions in the
propagation phase produce several new chain carriers in one step, each of
the new carriers can initiate a new series of reactions and thus the process
is branched out in several directions. This is known as a chain-branching
reaction. If the carriers are not terminated as fast as they are produced, the
result is the progress of the overall process at a violent rate till all the
reactants are exhausted. Rapid combustion and explosion are brought
about by branched-chain reactions.
where,
F(c) = a function depending on the rate of initial production of chain
carriers
fs and fg = factors depending on the rates of destruction of the carriers
at the surface and in the gas, respectively
α = branching factor, that is the number of chain carriers produced from
one initial carrier
A = a constant or a function of concentration
The condition for overall branching is
α > 1, that is 1 − α = a negative quantity.
If A(α − 1) equals (fs + fg, the reaction rate becomes infinite and brings
about an explosion.
The terms fs and fg are pressure dependent in the opposite way: while fs
increases by a decrease in pressure, the term (fs + fg) will pass through a
maximum. Under certain conditions of diminution of either fs (pressure rise)
or fg (pressure fall), the term fs + fg may become lower than A(I — α). This
suggests that the branched-chain reactions will be terminated and explosion
made impossible at both lower and higher pressures than a certain limiting
value. An explosion may again occur at comparatively high pressures,
particularly at increased temperatures by the formation of new chain
carriers, by other reactions and also by thermal effect.
Besides the branched-chain mechanism of explosion, thermal
mechanism is also recognised in the study of explosion reactions. Heat
liberated by slow combustion may raise the temperatures of the system,
whereupon the reaction rate is accelerated. If the heat generated exceeds
the heat lost to the surroundings, the reaction rate may steadily increase to
a final explosive velocity. Theoretically, a branched-chain explosion can
take place isothermally. A clear-cut distinction of the two mechanisms is not
practically possible.
Combustion is often characterised by an induction period, or delay
period, or ignition lag, or time lag, during which the concentration of chain
carriers builds up. The reaction rate increases exponentially during this
period and ends up in either a steady reaction or an explosion, depending
upon the prevailing conditions.
8.3.2 THERMAL MECHANISM
Non-isothermal systems can be accelerated to an explosive violence by a

thermal mechanism under favourable conditions. The heat liberated by
exothermic reactions is partly lost to the surroundings and the rest raises
the temperature of the system. At the higher temperature, the rate is
accelerated if the opposite effect of the decreased concentration of the
reactants is of lesser significance. This is possible when the reaction is
highly exothermic and the heat loss to the surroundings is much less than
the heat generated. Under adiabatic, or almost adiabatic conditions, the
system may attain a certain temperature (ignition temperature) when the
rate of reaction approaches infinity and the system explodes. The intital
period during which the reaction rate slowly rises with time, and after which
the rate is suddenly accelerated, is the induction period of the system. A
simplified mathematical treatment of the thermal mechanism is given later in
the chapter in Section 8.4.
The thermal mechanism does not exclude the chain mechanism. An
increase in temperature also increases the number of chain carriers in the
system. Thus a thermal mechanism can be complemented by a chain
mechanism. It is also possible that a system is initially of a chain type and
with an increase in temperature gets converted into the thermal type. It is
futile to attempt to explain combustion and explosion by purely thermal or
purely chain mechanisms.
8.3.3 HYDROGEN–OXYGEN REACTION
Active chain carriers may be formed by the following reactions which may
result from intermolecular collision, thermal dissociation or excitation by
electric spark.
These also may be diffused into the unburned gaseous mixture from an
adjacent flame.
It is generally agreed that the low-pressure explosion in the H2–O2
system is due to the following chain-propagating reactions
The last two reactions are of the chain-branching type where each carrier
generates two new carriers. Reaction (8.2) develops one carrier for each
molecule of H2O produced. The new carriers formed can start their own
new chains. If they are not removed as fast as they are produced the
system ends up with an explosion. Chemical calculations show that as little
as 1% branching in the H2–O2 reaction would bring about an explosion.
At low pressures, chain carriers are removed by adsorption on the
container surface. There is a critical pressure below which chain-termination
is predominant and no matter what is its temperature the system does not
explode. This is known as the first explosion limit of the H2–O2 system. The
nature of the surface influences the adsorption process, hence the first
explosion limit depends upon the material of the vessel. Salts such as
iodides of cesium and potassium are powerful chain-breakers and a vessel
coated with one of these salts can raise the first limit by a factor of 10 or
even 100. On the other hand addition of inert gases, or increase in the
vessel diameter, hinders the adsorption on the surface and thus gives lower
values of the first pressure limit.
At pressures above the first limit the chains may be terminated by a
termolecular reaction in the gas phase
where, M represents a molecule present in the system. This molecule takes

away the excess energy produced in the formation of the unstable HO2
whose heat of formation exceeds its heat of decomposition. There is a
critical pressure called second explosion limit above which the reaction (8.5)
is quite predominant; the chain carriers are fast removed from the system
and explosion gives way to slow combustion. HO2 is destroyed on the
surface by the reactions.
The nature of the surface has markedly less effect on the second limit
than on the first limit. The second limit is almost independent of the vessel
diameter. These indicate the validity of the chain-breaking reaction (8.5)
taking place in the gas phase.
At still higher pressures, and particularly with increased temperatures,
another set of chain-branching reactions occur. The process is accelerated
until a third explosion limit is reached.
Explosion in this region of pressure is due to a combustion of chain and

thermal mechanisms. The heat given out by the chain reactions cannot be
dissipated sufficiently fast, so that selfheating occurs, followed by an
explosion.
The three explosion limits, P1, P2 and P3 are schematically shown in
Fig. 8.1 on the plots of pressure versus reaction rate and temperature
versus pressure.
Slow combustion takes place below P1 and between P2 and P3, while
the system explodes between P1 and P2 and above P3. P1 falls slightly with
temperature while P2 rises with it. The effect of temperature on P3 is
remarkable, the limiting pressure falling sharply with a temperature rise. All
these observations are well explained by the mechanism described above.
The chain mechanism is predominant in the process below the second limit.
A combination of chain and thermal mechanism is operative above it.
Figure 8.1 Explosion limits for H2 – O2 reaction, P1, P2 and P3
Depending upon various conditions of the system the values of the three
explosion limits are: P1 0.5 to 9.0 mm, P2 18 to 250 mm and P3 240 to 699
mm Hg. Above atmospheric pressure the system is always explosive.
Figure 8.1b shows the so-called explosion peninsula, the peninsular shape
of the pressure temperature diagram. The system is explosive in the region
of the right-hand side of the curve.
8.3.4 CARBON MONOXIDE-OXYGEN REACTION
The low-pressure ignition of carbon monoxide and oxygen is characterised

by an explosion peninsula (Fig. 8.2). There are two explosion limits. No third
limit has been reported. A pale blue glow is often observed outside the
explosion peninsula. There are two limits of glow, marking what may be
called a glow peninsula.
The mechanism of CO–O2 reaction has been the subject of great
controversy. According to Lewis and von Elbe, the chain propagating
reactions are
The oxygen atom and ozone molelcule serve as chain carriers. Reaction
(8.12) is chain-branching.
According to Semenov, the chain-branching is due to
(* = excited state; To = triplet state)

Figure Glow and explosion limits for CO–O2 system
8.2
At very low pressures, chain carriers are adsorbed by the container surface.
When carrier concentration is built up with rising pressure, a glow is
observed. This is the result of rapid oxidation and formation of CO2
molecules in the gas phase. Explosion is inhibited by products. With further
rise in pressure the heat generated exceeds the heat lost to the wall and
explosion takes place. The lower glow and explosion take place. The lower
glow and explosion limits do not change much with temperature. This may
be due to the small activation energies of both branching and termination
reactions.
The upper glow and explosion limits virtually coincide. The most likely
chain-breaking reaction is
The other reactions are:
(hγ = radiation emitted)
Minute traces of water have a powerful catalytic effect on the combustion of

carbon monoxide*. Several times as much electrical energy is required to
ignite a fully dry CO–O2 mixture as is necessary when traces of water
vapour are present. Water lowers the ignition temperature and raises the
upper explosion limit. The effect is remarkable with only traces of water
vapour. Further addition of water has little effect and sometimes even leads
to a negative effect.
In fact CO–O2 mixture without any trace of hydrogenous impurity may
be virtually non-explosive. The mechanism of a wet CO–CO2 reaction may
involve the following additional chain-branching reactions.
H may be eliminated by
HO2 may react as
The upper limit markedly rises with increasing temperature. This is partly
explained by the reaction energies.
Some values of the two limits are: P1 2.5 to 12.5 mm and P2 40 to 500
mm Hg.
8.3.5 HYDROCARBONS–OXYGEN REACTION
The pressure-temperature diagram (Fig. 8.3) for a 1:1 propane–oxygen

mixture shows some of the characteristics of the reaction of hydrocarbons
with oxygen in the gas phase. The system ignites in the right-hand zone of
the thick line, while the left-hand zone is generally for slow oxidation.
However, in a certain boundary region the system shows faint luminosity,
cool flame, increased luminosity, bright blue flame and finally the
characteristic yellow flame of true ignition—all in succession on either
increasing pressure at a constant temperature or increasing temperature at
a constant pressure.
Figure 8.3 Pressure–temperature diagram of propane–oxygen (1:1) mixture
The oxidation of hydrocarbons involves branched-chain reactions. Long

induction periods (about a minute), slow acceleration and cool flames
indicate that the branching reaction is infrequent and markedly differs from
those in the H2–O2 and CO–O2 systems. The situation is known as
degenerate or delayed branching. In the H2–O2 and CO–O2 systems the
branching is due to reactions of atoms and radicals with fuel or oxygen
molecules. In the hydrocarbon–O2 systems a relatively stable intermediate
product, M, is first formed by a non-branching process. This undergoes
further reactions to give either inert products or new radicals to initiate the
primary chain and produce more carriers.
If RH denotes hydrocarbons, the following give the general mechanism
of the oxidation process.
Formation of R radicals
Formation of peroxide radical RO2
Reactions of RO2 radicals
(R′ = R minus one CH2; R″ = R minus two CH2)

Various intermediate products and radicals are formed from the initial
peroxide radical. Formation of CO and CO2
Termination reaction
In the case of oxidation of methane, the simplest scheme satisfying the

experimental facts is
Formaldehyde is mainly responsible for the degenerate branching at least in
the low temperature, 400 to 450°C oxidation.
In the degenerate branching the number of chains is so low that the
reaction rate of a truly isothermal system cannot be very high. Thermal
factors are involved in the production of cool flames and ignition. When the
heat generated far exceeds the heat lost to the wall, the conditions favour
cool flame and ignition. This explains why cool flames always originate near
the centre of the vessel and spread outwards.
Ozone, peroxides, nitrogen dioxide, organic nitrates and nickel carbonyl
vapour are promoters of ignition of hydrocarbons. Halogen compounds,
such as carbon tetrachloride (CCl4) and bromochloromethane (BrCICH2)
are the retarders.
The phenomenon of ‘knock’ in internal combustion engines is connected
with the chain mechanism of hydrocarbon oxidation. Many substances
enhance the knocking tendency of fuels, for example, ozone, organic
nitrates and nitrites, alkyl peroxides and aldehydes, particularly
formaldehyde. Their pro-knock effect is due to their property to initiate chain
reactions in the process. The anti-knock compounds on the other hand, for
example, tetraethyl lead and iron carbonyl are capable of terminating the
chains. It is well known that the knock-resistance property of fuels directly
varies with the relative rates of their slow combustion.
A knowledge of the reaction mechanism and the effect of various factors
including the container wall permits the prediction of conditions for an
explosion of a reactive mixture of gases in a glass vessel. A different
situation is encountered when the same gas mixture approaches a flame
front. The mixture is first warmed by conduction and convection from the hot
flame gases. It also mixes with new molecules and radicals which diffuse
from the flame towards the cold gas. Thus some reactions will be initiated in
the pre-flame region and further accelerated with rise in temperature and
formation of chain-branching radicals. The bulk of the overall reaction will
take place at the high temperatures in the flame in a very short time. The
gaseous products will finally move away from the flame and the excess
radicals will recombine comparatively slowly with the fall in temperature.
The entire process is complicated by the simultaneous operation of reaction
kinetics, transport phenomena and laws of conservation.
Pyrolysis is an important pre-flame process in the combustion of
hydrocarbons. Except in pyrolysis of several aliphatic compounds at low
temperatures, free radicals play a part in all other pyrolysis processes. The
pyrolyses of methane and acetylene are particularly important, for methane
is a major fuel component while acetylene is formed in high yields by the
decomposition of other hydrocarbons above 1,000°C. In fact acetylene is
the essential precursor to the formation of carbon particles in flames.
Flames are characterised by the presence of ions and such radicals as
CH, C2 and Cn. None of these is found in slow combustion experiments.
8.3.6 COMBUSTION OF ELEMENTARY CARBON
The primary reaction of solid carbon with oxygen is a heterogeneous

reaction in which a complex of indefinite composition is formed at the
surface of carbon by the process of chemisorption. The surface complex
then breaks up into CO and CO2. In the presence of free oxygen, CO then
undergoes homogeneous oxidation into CO2.
The CO2 formed can react with hot carbon to produce CO by the well-
known heterogeneous reaction called the Boudouard reaction
Depending upon the concentration of oxygen in the system, the product will
be rich in CO2 or CO. It has also been shown that certain chlorinated
compounds, for example, POCl3 and CCI4, which are well-known chain
breakers, inhibit the oxidation of CO while water vapour catalyses it.
Therefore, an addition of these chlorinated compounds results in the
product gas being rich in CO. An addition of excess of water vapour can
resume the oxidation of CO and lead to an increase in CO2 concentration.
The reaction mechanism essentially remains the same whether the
carbon is in the form of a bed of lumps or a suspension of powder in air.
Since, however, heterogeneous reactions are involved, diffusion plays a
significant role in the overall kinetics of the process.
8.4 SPONTANEOUS IGNITION TEMPERATURE (SIT)
The minimum temperature to which a combustible system is to be raised for

bringing about rapid combustion or explosion is known as its spontaneous
ignition temperature, or simply ignition temperature. It depends upon the
inherent property of the system and also upon extraneous factors. By
keeping the latter constant, the ignition temperature is obtained as a
characteristic property of the combustible. An expression for SIT of a gas or
vapour is derived below on the basis of the thermal mechanism of
combustion.
The rate of a chemical reaction in gaseous phase is:
where,
=nmole number of product per unit volume
= treaction time
f(p)
= a function of pressure
=Eenergy of activation
=Rgas constant
=Ttemperature of the system in absolute scale.
The rate of heat liberation by a chemical reaction is
where,
Q = heat liberated per mole of product
V = volume of reaction vessel

The rate of heat loss to the vessel wall is
where,
B = a constant = heat transfer coefficient × area
T0 = temperature of vessel wall, K.
Equations [8.63] and [8.64] show that the rate of heat liberation increases
exponentially with temperature while the rate of heat loss does so in a linear
relationship. Figure 8.4 shows the variation of q1 and q11 with temperature.
While there is one curve for q1 for the given combustible, there is a set of
several parallel lines for q11 depending on the vessel wall temperatures T0,
, and so on. The lines at and cut the curve at two points. The
lower point ‘a’ indicates a stable equilibrium. It is easily seen that any
shifting of the system to either side of the point, will bring it back to this
point. The upper point ‘b’ represents an unstable equilibrium practically
impossible to achieve. The line at T0 touches the curve tangentially at c
where the system has unilateral stability. If the system is shifted slightly to a
lower temperature, it comes back to c. On the other hand, any shifting
towards a higher temperature will move the system further away from it.
The point ‘c’ corresponds to the ignition temperature, T.
The two conditions for c are
1. Thermal equilibrium, q1 = q11
2. q11 is tangential to q1
Figure Thermal mechanism of ignition
8.4
that is,
Therefore,
and also
From these two equations (8.65) and (8.66):

Therefore,
This gives two values of the temperature, T. By definition the ignition

temperature is the minimum temperature.
Therefore, ignition temperature
It is thus seen that Ti depends on the inherent properties of the combustible,

E, and also on the conditions of the container, T0. The limiting values of the
container temperature are
If T0 is maximum, that is, ,
Usually, E ≫ T0, (for example, E + 50,000 cal/mol, T0 = 500 – 1000 K)

Hence, by expanding the series in (8.68) we get
Substituting E = 50,000 cal/mol and T0 = 1,000°K,
that is Ti − T0 = 40°C.
This shows that for all practical purposes, T0 may be taken as the
ignition temperature without great error. This analysis justifies the usual
methods of determination of ignition temperature for all practical purposes.
Taking T = Ti, and Ti – T0 = It in equation (8.65)
Since, RT0 ≪ 1, we get the following simplified relation
Taking logarithm
For a bimolecular reaction, F(p) ∝ p2. Writing critical pressure pcr for p, we
finally get
Equation (8.72) is known as Semenov’s equation, giving the relation

between pressure and ignition temperature for successful thermal explosion
of combustible mixtures (Fig. 8.5). Putting Ti = T0 in equations (8.71) and
(8.72), it can be shown that at constant pressure.
Figure Ignition temperature versus pressure

8.5
Q is the heat liberated by combustion. If the fuel–oxidant ratio in the

system is varied between 0 and 1, Q will vary with the maximum near the
stoichiometric composition. Hence, equation (8.73) will lead to Fig. 8.6
which indicates the existence of two limiting compositions of fuel–oxidant
mixture for the system to ignite and explode. These are known as limits of
inflammability (see Section 8.6).
Figure Ignition temperature versus mixture composition
8.6
Equation (8.70) gives an expression for the induction period. The time
required by the system to rise by a temperature difference of gives the
induction period.
It is now clear that the ignition temperature of a fuel is not a
characteristic constant but depends upon circumstances. Some of the
influencing factors are the fuel–oxidant ratio, nature of oxidant, induction
period, vessel wall and presence of promoters or inhibitors. Obviously the
method of determination is of great importance in obtaining the ignition
temperature of substances.
Three principal methods have been used for the determination of SIT of
gases and vapours:
1. Admission of an explosive mixture to an evacuated, heated vessel;
2. Heating of the fuel and oxidant separately and then mixing them in a
vessel;
3. Adiabatic compression of the premixed system until ignition occurs.
The SITs of some gases and vapours are given in Table 8.1. These relate
mainly to the first method.
The ignition temperature of liquid fuels is determined by dropping oil
drops into a heated crucible and observing the minimum temperature at
which a glow occurs followed by explosion or flame. A similar method is
used in the case of coal also. About 5 to 6 g of coal powder is thrown into
the bottom of the vessel heated at a constant rate. The ignition temperature
of coke is determined by a slow method in which a sample of coke is heated
at a constant rate. The temperature at which the rise of coke mass
temperature is suddenly accelerated is recorded as its ignition temperature.
Table 8.1 includes the data on solid and liquid fuels.
Table 8.1 Spontaneous ignition temperature in air and oxygen

Substance In air, °C In oxygen, °C
Acetone 561 485
Acetylene 305 296
Ammonia 651 –
Amyl benzene – 255
Amylene 273 –
Anthracene 472 –
Benzene 580 566
1,3-Butadiene 418 335
Butane 408 283
Bytylene 443 –
Carbon disulphide 120 107
Carbon monoxide 609 588
Cetane 235 –
Creosote 356 –
Cresoie,o 599 –
Cresol, m 626 –
Cyanogen 850 –
Cyclohexane – 296
Cyclopropane 498 454
Cymene 466 –
Decalin 262 –
Decane,n 250 –
Dimethylether 350 252
Dodecane 534 –
Ethane 472 –
Ether, diethyl 193 182
Ethyl alcohol 392 –
Ethyl benzene 477 468
2-ethyl butane – 273
Ethylene 490 485
Gasoline(regular) 280 –
Gasoline 299 –
73 octane
Gasoline (92 octane) 390 –
Gasoline (100 octane) 429 –
Heptane 230 214
Hexane 248 –
Hexane, iso – 284
Hydrocyanic acid 538 –
Hydrogen 572 560
Hydrogen sulphide 292 220
Isodiodecane 500 –
Isoprene 440 –
Kerosene 254 –
Methane 632 556
Methyl alcohol 470 461
2-Methyl butane 420 294
(isopentane)
Methyl chloride 632 –
a-Methyl naphthalene 566 –
2-Methyl propane 462 319
Naphtha 277 –
Napthalene 587 560
Nonane 285 –
Octane 218 208
Pentane 290 258
Petroleum ether 329 –
Phenol 715 500
Propane 493 468
Propylene 458 –
Styrene 490 450
Tolune 552 516
Turpentine 252 –
Xylene, o 496 –
Wood 300 –
Wood charcoal 200–350 –
Peat 220–250 –
Lignite 250–350 –
Bituminous coal 380–120 270–290

Anthracite 500 340
Soft coke 425–500 –
Hard coke 500–650 –
8.5 VELOCITY OF FLAME PROPAGATION
A simple demonstration of flame propagation is furnished by an explosion in

a glass tube. When the combustible mixture is ignited at one end by an
external source of heat, say, a spark, the flame front can be seen to travel
to the other end until the whole mixture is burnt off. Flame propagation is in
fact a characteristic feature of all burning processes. A flame becomes
stationary under favourable circumstances. Let us consider a system with
the combustion surface (flame front) perpendicular to the axis of a
cylindrical tube (Fig. 8.7). The combustible mixture is flowing from the right
to the left. The flame will therefore tend to move from the left to the right
towards the oncoming fresh gas. If the gas velocity is equal to the flame
velocity, the combustion surface will remain stationary. The direction of the
flame velocity is normal to the surface F. It is called the normal velocity of
flame propagation, vn, to differentiate it from the much faster propagation of
flame in detonation (several km/s). The term burning velocity is often used
instead of velocity of flame propagation. In short, it is the velocity, relative to
the unburnt gas, with which a suitably defined flame front travels along the
normal to its surface.
Figure Stationary flame in a tube
8.7
ρe = density of initial mixture

ρn = density of exhaust gases
F = flame front
Vn = normal velocity of flame propagation
Ve = velocity of exhaust gases
Since the mass flow-rate per unit cross-sectional area of the tube is
constant under a steady state, we have
vn ρo = ve ρe
where,
vn = initial gas velocity
ve = velocity of exhaust gas
ρo = density of unburnt gas
ρe = density of exhaust gas
Therefore
As ρo ≫ ρe , therefore ve ≫ vn
It will thus be seen that there is a sharp gradient of gas velocity across
the flame front which is also characterised by the sharp gradients of gas
density, temperature and composition.
In an explosive flame system the flame front moves with a velocity
which is the vector sum of the gas velocity and the normal velocity of flame
propagation. If the mass flow of gases could be prevented in the container
then the actual rate of advance of the flame front into the unburned gas
would be the normal velocity of flame propagation.
A combination of thermal and diffusion mechanisms explains the
phenomenon of flame propagation. The region neighbouring a flame gets
heated up by conduction and convection. Chain carriers are also diffused
from the flame to that region. As a result the pre-flame region becomes the
zone of active reaction, and is converted into the new flame while the
completion of reaction and relatively cooling effect extinguish the luminosity
of the region where the flame existed earlier. The net effect is the
advancement of the flame front.
Numerous attempts have been made to predict flame velocity by purely
thermal mechanism or purely diffusion mechanism or a combination of the
two. There is no universally acceptable formula for calculating flame speed
from the fundamental properties of the system. A simple derivation of vn
from flame propagation by heat conduction alone is given below.
Let us assume a stationary flame in which a fresh well-mixed
combustible gaseous mixture moves continuously in one direction. The rate
of heat flow by conduction per unit surface of gas layer is given by
where, K = average thermal conductivity.

δ = thickness of combustion zone, that is, width of flame front
Tm = temperature of the products of complete combustion
T0 = initial temperature of the fresh gas
The rate of heat consumption by the incipient gas flow is
where, v = gas flow rate = vn for stationary flame

ρ0 = density of fresh gas
vρ0 = mass flow rate per unit area
CP = average specific heat
Equating q1 and q2 and substituting vn for v, we get

where, a = mean thermal diffusivity between T0 and Tm.
Assuming δ = vntr
where, tr = residence time in the reaction zone (reaction time), we finally get
Equation (8.75) gives a very important relationship that the flame velocity is
directly proportional to the square root of thermal diffusivity and inversely
proportional to the square root of the characteristic time of reaction.
where, K = specific reaction rate

K0 = frequency factor
E = energy of activation
R = gas constant
we get
Tm is in fact the flame temperature. The conditions which increase the flame
temperature will thus sharply raise the flame speed.
A more exact expression of Vn includes a factor f which is less than
unity. This factor, in particular, is related to the difference between δ
assumed above and the true width of the reaction zone.
Many experimental techniques have been employed in determining normal

velocity of flame propagation.
Nearly all of them fall under three groups:
1. Bunsen burner method or stationary flame method,
2. Spherical bomb method,

3. Glass tube method.
When proper care is taken and necessary corrections made, all these
methods give comparable and reproducible results. The Bunsen burner
method is briefly discussed here.
Figure 8.8a shows a Bunsen burner with a quiet flame. Fuel gas and
primary air, 50% to 60% of the total air, are mixed in the mixing tube. The
mixture burns with a flame anchored at the burner tip. The flame has an
inner cone and an outer envelope. Combustion proceeds at the inner cone
until the oxygen of the primary air is exhausted. The outer envelope is the
zone of secondary combustion where the remaining combustibles burn in
the secondary air derived from the atmosphere. The flame propagates in a
direction normal to the surface of the inner cone. Since the flame is
stationary, the normal velocity of flame propagation is vectorially equal and
opposite to the velocity of the gas mixture issuing from the burner tip. It can
be calculated from the knowledge of gas velocity and cone angle by using
the vector triangle shown in Fig. 8.8b. The gas velocity varies along the
cross-sectional area of the tube. It is maximum at the tube axis and almost
zero at the wall. The local velocity at a distance of 0.7 times the radius from
the axis represents the average velocity.
Figure 8.8 (a) Elements of a bunsen burner (b) Method for measuring Vn
Let
A = cross-sectional area of the tube, m2

V = flow-rate of the mixture. m3/s
2α = cone angle, degree
Then the normal velocity of flame propagation
The angle α is determined from the angle of the flame projected on a

screen, photographed or viewed through a telescope. The angle between
the tangent to the inner cone surface and the tube axis gives α.
The factors affecting vn are the composition of fuel–oxidant mixture,
temperature, pressure and surface. The flame speed varies with
composition and attains a maximum for a mixture which is slightly richer in
fuel content than the stoichiometric composition (Fig. 8.9). This relationship
is similar to the flame temperature–composition relationship and predictable
from equation (8.76).
Figure 8.9 Flame velocity versus composition of gas–air mixture
Flame speed depends upon the kinetics of combustion reactions and

hence varies from fuel to fuel. The hydrogen flame is the fastest with vn
having a maximum value of about 2.5 m/s. Next comes acetylene, with vn
slightly less than 1.5 m/s. Carbon monoxide, paraffins and benzene have
the maximum value of vn in the range of 0.3–0.4 m/s. Propane is slightly
above this range, while ethylene exceeds 0.6 m/s. All these values are for
fuel–air systems. If oxygen is substituted for air, vn is 5 to 10 times these
values.
Flame speed rises if the initial temperature of the combustible mixture is
increased or the pressure of the system decreased. By preheating the
hydrogen–air mixture to 430°C and methane–air mixture to 680°C, the
maximum value of vn could be increased from 2.5 to 13.0 m/s, and from 0.3
to 3.0 m/s, respectively. According to many investigators, vn appears to vary
as the square of the absolute temperature and inversely as the fourth root
of the pressure.
The surface has a profound effect on flame propagation if the surface-
to-volume ratio of the system is high. By exerting a cooling effect and
adsorbing chain carriers, the container surface slows down the propagation
of flame. In fact combustion can be completely stopped in very narrow
tubes. This was first observed by Davis and formed the basis of his
discovery of the miner’s safety lamp bearing his name.
A knowledge of flame speed is of fundamental importance. It is one of
the basic parameters that affect the rate of heat release in combustion. The
solution of many practical problems in burners and furnaces needs a proper
appreciation of the velocity of flame propagation.
8.6 LIMITS OF INFLAMMABILITY
A fuel–oxidant mixture is called inflammable when combustion liberates

sufficient energy to cause a continued self-propagation of the flame
throughout the unignited regions of the mixture. Like the limits of pressure
(explosion limits) and temperature (ignition temperature), there also exist
concentration limits for a system to be inflammable. These are known as
the limits of inflammability. There are two limits of inflammability—the upper
limit referring to the richest mixture and the lower limit to the leanest mixture
—to propagate a flame when the surface effects are negligible.
An analysis of the mechanism of ignition temperature earlier indicated
the existence of two limits of inflammability. A similar indication can be
obtained from the velocity of flame propagation also. On both the sides of
the optimum fuel–oxidant composition the flame speed declines. There
should be a critical flame speed, actually a range of 10–12 cm/s, below
which flame propagation is not possible owing to the over-whelming effect
of heat loss. The flame should advance at a sufficiently high rate to
compensate for the loss of heat. A mixture below the critical flame speed
may be ignited at a point but the flame will disappear after travelling a short
distance through the combustible mixture. Since the critical flame speed
corresponds to the two compositions on the rich and lean sides, there are
two limits of inflammability.
Inflammability limits are determined in an apparatus consisting of a 75
mm diameter vertical glass tube 1.5 m in height. The mixture is confined in
the tube and then ignited by opening the lower end and applying a spark or
a small flame. The two limiting concentrations are determined at which the
flame just fails to propagate upwards throughout the whole length of the
tube.
The limits of inflammability are influenced by many factors. A reduction
in pressure narrows down the two limits, lowering the upper limit and raising
the lower limit. The upper limit is much more affected than the lower. The
limits tend to join at a critical pressure below which the mixture ceases to be
inflammable at any concentration. The effect of pressure is explained by the
increased diffusivity of chain carriers and other hot products towards the
wall at a reduced pressure.
Ordinary variations of laboratory temperature have no appreciable
influence on the limits. By raising the temperature of the mixture to an
appreciable extent the limits may be widened. The effect is due to the
enhanced flame temperature causing flame propagation in the mixtures of
unfavourable composition.
The container size has negligible effect above 5 cm diameter. In the
case of smaller sizes the limits are narrowed down by decreasing the
diameter. This is the result of wall effect. The minimum tube sizes below
which the flame does not propagate at room temperature and pressure
depend upon the fuel, for H2 it is 0.9 mm, for CO, 2.5 mm and for CH4, 4.0
mm.
The direction of flame propagation affects the limits. The widest limits
are obtained if the flame is to propagate upwards and the lowest limits
result if flame propagates downwards. Intermediate results are provided by
horizontal and inclined tubes. This variation is due to the buoyancy effect.
The limits of inflammability of combustible gases and vapours at
ordinary temperatures and pressures in air are given in Table 8.2.
Hydrogen, acetylene and ethylene oxide have an extremely wide range of
inflammability (H2: 4% to 75%). It is fortunate that petrol vapours and usual
organic solvents (benzene, hexane, ethyl alcohol and acetone) have quite
narrow limits of inflammability (benzene: 1.4% to 7.1 %). Generally, the
higher the maximum normal velocity of flame propagation of a combustible
gas or vapour in air, the wider the limits of its inflammability in air. Carbon
monoxide is the remarkable exception. Although its maximum flame velocity
is less than 0.5 m/s, it has a very wide range of inflammability limits, 12.5%
to 74%.
Table 8.2 Limits of inflammability of some gases and vapours at ordinary temperature
and pressure in air
The inflammability limits of a mixture of combustibles in air may be
approximately calculated by Le Chatelier’s formula
where,
x1 , x2 , x3 =. .volume
. per cent of the combustibles in the
mixture
l1, l2, l3 . . .=limit (lower or upper, as the case may be)
of inflammability of pure combustibles in air,
per cent.
L=limit (lower or upper, as the case may be) of
inflammability of the mixture in air, per cent.
It has been found that the lower limit of a mixture of combustibles can be
accurately calculated but there is often appreciable divergence between the
calculated and experimental values of the upper limit of a mixture. It clearly
shows that the combustibles interact particularly when they are present in
large quantities as in the upper limit of inflammability.
The influence of diluents is illustrated by Fig. 8.10. The very fact that the
curves given by different diluents, namely, N2, CO2, He and Ar do not
coincide shows that the diluents influence flame propagation to a greater or
less extent. The small difference among N2, He and Ar may be explained by
their different thermal properties. However, the exceptional behaviour of
CO2 indicates that it is quite involved in the flame propagation.
Figure Effect of diluents on the limits of inflammability
8.10
Approximate calculation of the inflammability limits of combustibles

containing diluents is based on the fact that the lower limit is actually the
criterion of the combustible concentration while the upper limit is that of the
combustible to oxygen ratio.
If there is no oxygen in the diluent,
If the diluent (other than air) contains O2,
L1 and L2 = lower and upper limits of the pure combustible

and are the limits of the combustible containing diluent
xdil, xcomb , and xO2 are per cent of diluent, combustible and O2 respectively,
in the combustible containing the diluent.
The limits of inflammability of gases and vapours in air are of great practical
significance for precaution against the risks of fire and explosion. In using
solvents and other inflammable substances it is necessary to keep the
concentration of their vapours in the surroundings well outside the
inflammability range. Sometimes nitrogen and carbon dioxide are used as
diluents to bring the atmosphere below the lower limit of inflammability.
Example 1
Calculate the limits of inflammability of a gas mixture containing 25% CO,

40% H2 and 35% CH4.
Solution
From Table 8.2
L1 L2
CO – 12.5 74.0
H2 – 4.0 75.0
CH4 – 5.3 14.0
All the components are combustible. Applying Le Chatelier’s formula (8.79)

Example 2
Calculate the limits of inflammability of a gas containing 25.0% CH4, 45.0%

H2, 10.0% CO, 10.0% CO2 and 10.0% N2.
Solutions
CO2 and N2 are the diluents.
Concentration of diluents = 10 + 10 = 20%
Composition of diluents in free combustible mixture
Limit of inflammability of the diluents-free mixture
Therefore, the limits of inflammability of the given mixture are
8.7 STRUCTURE OF FLAME

The size and shape of a flame depend on its type, namely, premixed or
diffusion, laminar or turbulent, and also on the burner dimensions. An
elementary treatment of the subject is given here.
The premixed flame of a simple gas burner is shown in Fig 8.11. The
burner has a nozzle diameter, d. The distance covered by the initial
boundary of the flame is L, and may be called the zone of inflammation
(height of inner cone). Lf is the flame length and indicates the zone of
complete combustion. In the case of laminar flame, the inflammation zone is
sharply pointed and has a thin surface (flame front). Under turbulent
conditions, the front is distorted and has an appreciable width, δ. The
distance between the visible front and the flame tip, L, represents the
boundary of complete combustion. The most intense combustion takes
place at the flame front while the process is much slower in the zone L,
where diffusion of some air from the atmosphere is involved. The total flame
length is
Lf = Li + δ + Ls
Figure Premixed flame of a simple gas burner

8.11
For a laminar premixed flame, δ = o and

Lf = Li + Ls
The length, Li is related to the process of flame propagation from the
periphery to the centre
where,
v=velocity of flame propagation (laminar or turbulent, as the case
may be)
= rtube radius
v=avaverage linear velocity of the gas at the burner nozzle.
Lf increases with the increase in gas velocity and nozzle diameter and the
decrease in velocity of flame propagation.
For a turbulent flame
v = vav
that is, velocity of turbulent flame propagation is approximately equal to gas
velocity.
The height of the inner cone increases with the increase in gas velocity for a
laminar flame but remains almost constant for a turbulent flame.
Ls is related mainly to the kinetic properties of the combustible mixture.
The width of flame front δ depends upon eddy diffusion.
where,
=εeddy diffusivity
I′=scale of turbulence (analogous to mean free path in molecular
diffusion)
v′=intensity of turbulence (root mean square value of
instantaneous fluctuating velocity)
=vnnormal velocity of flame propagation of the mixture.
The front width increases with increase in eddy diffusivity and decreases in
normal flame speed.
A simple laminar diffusion flame is illustrated in Fig. 8.12. Fuel gas and
air flow separately but at the same linear velocity through two concentric
tubes, the inner tube supplying the fuel jet. The structure of the diffusion
flame is determined mainly by the process of mixing of gas and air, and not
by the velocity of flame propagation. The mixing is achieved by either
molecular diffusion or eddy diffusion, depending upon the laminar or
turbulent conditions of the flame.
Figure 8.12 Simple laminar diffusion flame: (a) over-ventilated and (b) under-
ventilated
Laminar diffusion flame may be of two types. When air is in excess, a
flame of the over-ventilated type is formed (Fig. 8.12a). With excess fuel,
the flame is of the under ventilated type (Fig. 8.12b). The flame boundary is
provided by the surface at which combustion is complete. Since combustion
reactions are rapid it may be assumed that the fuel and air are essentially in
the stoichiometric ratio at the boundary surface. When air is in excess, this
surface closes in towards the axis as the diffusion of gas and air continues.
The length of the flame corresponds to the condition of arrival of sufficient
air at the tip for completing combustion. Beyond this point no fuel gas exists
and the mixing of air and combustion products continues. A normal flame
has the shape of the over-ventilated type. When fuel is in excess, the flame
boundary moves upwards and the flame length corresponds to the arrival of
fuel gas at the outer tube wall. The flame is bell-shaped.
The concentration profile of a cross section of the diffusion flame is
shown in Fig. 8.13. The concentration of fuel gas is highest at the centre
and falls to zero at the boundary. The oxygen is highest at the outer tube
wall and disappears at the flame boundary. The combustion products are
maximum at the boundary and slowly diffuse both towards the flame axis
and the outer wall. The nitrogen is maximum at the wall and slowly drops to
a minimum value at the centre.
Figure 8.13 Concentration profile of a cross section of a laminar diffusion flame
(schematic)
A laminar diffusion flame is converted into the turbulent type by

increasing the gas velocity beyond a critical value. However, the Reynolds
number of the cold gas stream, that is the cold Reynolds number is no
criterion for this conversion. Immediately beyond the burner rim, the
temperature sharply rises and hence the gas viscosity also rises causing a
sharp drop in the Reynolds number. Even when the cold Reynolds number
exceeds 2,300, the value in the flame is much below the critical and the
flame is still laminar. The critical cold Reynolds number for the conversion of
laminar into turbulent flame may vary widely, say, 3,500 to 10,000
depending upon the fuel composition and the quantity of primary air.
Figure 8.14 depicts the transition from laminar to turbulent flame with
the increase in jet velocity. The flame is quiet and possesses strong yellow
luminosity in the laminar region. It is violent, flickery, noisy and devoid of
yellow luminosity in the turbulent region. It may be seen that the flame
length increases with the increase in jet velocity in the laminar region upto a
maximum when flickering is first noted at the flame tip. With the further
increase in gas velocity, a much larger portion of the flame is found to flicker
and the total flame length is decreased. This is the transition stage. In the
turbulent region the flame length remains practically constant with
increasing jet velocity. Above a critical velocity the flame is lifted and finally
it is blown off when the jet velocity increases further.
Figure 8.14 Progressive change in flame type with increase in jet velocity
The difference in the effect of jet velocity on flame length of laminar and
turbulent diffusion flames may be explained in a simple manner.
From the concept of over-ventilated flame, it may be assumed that the
flame length of a laminar diffusion flame corresponds to the condition at the
flame tip on the axis of the jet, where the average depth of penetration of air
into gas is approximately equal to the radius of the burner tube.
From the law of mean square of displacement
x̄2 = 2Dt
where,
x̄ = root mean square of displacement
D = diffusion coefficient
t = time
Since, x̄ = r, the tube radius
r2 = 2Dt
But
where,
L = flame length
v = jet velocity
V = volume flow-rate of jet
For a given fuel and burner, r and D are constant. Hence, the length of a
laminar diffusion flame is directly proportional to its jet velocity. If however,
the volume flow-rate is kept constant by changing the tube diameter with
the jet velocity, the flame length remains costant.
By analogy to the laminar flame, we may write the following relationship
for the length of turbulent diffusion flame
where,
d = burner tube diameter
ε = eddy diffusivity
But, ε = 1′ v′
where 1′ = scale of turbulence
v′ = intensity of turbulence
Experimental data show that
1′ ∝ d and v′∝ v
Therefore, ε ∝ dv
This simple relationship shows that the length of a turbulent diffusion flame
is directly proportional to the nozzle diameter but independent of the
velocity.
Since the flame represents the zone of combustion, its length is a
measure of the reciprocal of the intensity of combustion and, therefore, of
heat release. Flame length studies have great relevance in the rational
design of a combustion chamber, be it for an internal engine or for a
furnace.
8.8 FLAME STABILITY
A freely burning flame is considered stable when there is no flash-back or

blow-off. The essential condition for flame stability is that the normal velocity
of flame propagation is vectorially equal and opposite to the velocity of fuel–
air mixture at the flame front. A consideration of all the factors affecting
these two velocities is necessary for evaluating the conditions of flame
stability.
The important factors to influence vn are: nature of fuel, composition of
fuel–air mixture and its temperature and tube diameter. The temperature of
the mixture at the burner tip depends on heat transfer from the reaction
zone, heat loss to the surroundings and also on the material of construction,
size and shape of the burner wall. The gas velocity depends upon the
desired volume flow-rate and burner nozzle diameter. It also varies along
the cross-sectional area of the nozzle.
Condition for stable flame : vn = vav sinα
Condition for flash-back : vn > vav sinα
Condition for blow-off : vn < vav sinα
The angle α is not constant. Its value depends upon the location of the
flame front. When α > 90°, the flame will be pushed inside the burner tube
and flash-back will occur. Therefore, the minimum gas velocity corresponds
to the normal velocity of flame propagation for the system. On the other
hand, if the flame front is developed at a large distance above the burner
tip, that is, if α → 0°, there will be undue dilution of the combustible mixture
by interdiffusion with the surronding atmosphere. It will cause undue
lowering of the flame velocity and lead to blow-off of the flame. The range of
gas velocity for a stable flame is the result of many variables operating on
the system.
A stable flame may be obtained at high gas velocities either by holding a
wire ring at a considerable distance from the burner tip or by inserting a wire
partly into the burner tube. The gas velocity is slowed down in the vicinity of
the wire in both cases. A conical flame is obtained on the wire ring while the
upper point of the straight wire supports a fan-shaped flame.
An increase in the tube diameter enhances the tendency to flash-back
while a decrease in the tube diameter tends to cause blow-off. Use of
ceramic materials of low thermal conductivity in making the burner tip
prevents the blow-off tendency of turbulent flames. The same, however,
augments the flash-back tendency of laminar flames.
8.9 KINETICS OF LIQUID FUEL COMBUSTION
Liquid fuels do not burn in the liquid state. Vapours of highly volatile liquids
are burnt on the principle of combustion of gaseous fuels. The other liquids
may employ one of two basic principles.
1. In the simpler type the fuel is kept in a shallow, open vessel. Vapours
fuel are formed at the surface on radiation by its own flame and thes
with the air forming a stable flame over the vessel.
2. In the other method of liquid fuel combustion, the fuel is atomised,

divided into fine droplets. The latter are then burnt in air. Each drople
vapours of the fuel on heating and these vapours actually participate
combustion reaction. Vaporisation of liquid fuels before combus
possible owing to their boiling ranges falling below the spontaneous
temperatures. However, some low volatile liquid fuels are cracked
vaporisation and ignition. Their droplets undergo thermal decomp
and form combustible vapours and solid coke particles, both of whic
burn in their respective ways.
The principle of combustion of liquid fuels in an open vessel is illustrated in

Fig. 8.15. The liquid surface receives heat from the flame mainly by
radiation. The vapours formed mix with air by diffusion and then burn at the
flame front. Combustion is completed in the body of the flame. Once the
fuel is ignited, stationary conditions are set up quite fast. Then the burning
rate equals the rate of recession of the liquid, which is constant for the given
conditions. The liquid temperature near the surface coincides with its
average boiling point. The thickness of the heating zone is about 30 to 40
mm. The burning rate increases with the decrease in the latent heat of
vaporisation and increase in the overall rate of heat transfer. The latter
increases with the increase in the difference of flame temperature and
boiling point. The burning rate is found to have a maximum value of 3.5 mm
per minute.
Figure 8.15 Combustion of a liquid fuel in an open vessel
1. Zone of complete combustion 2. Flame front 3. Vapour 4.
Convection current 5. Heating zone 6. Liquid fuel
The combustion of a liquid droplet is schematically shown in Fig. 8.16.
The flame completely engulfs the droplet. The basic mechanism is the
same as above. The droplet surface receives heat from the flame. Vapours
flow in a direction opposite to the heat flow and burn with air at the flame
front. The droplet decreases in size with the progress of combustion until it
is completely converted into products of combustion. A simple relation for
the kinetics of the process is derived in the following.
Figure 8.16 Combustion of a liquid fuel droplet

1. Liquid 2. Vapour layer 3. Combustion zone 4. Diffusion zone
Rate of heat transfer to the liquid per unit surface area is given by
q1 = h(Tg – T1)
where,
=hheat transfer coefficient
=
Tgtemperature of the gaseous medium
T1=temperature of the liquid, which may be considered uniform
throughout the droplet in view of the small size
The chemical kinetics are very high at the high reaction temperature so that
the partial pressure of the vapour at the surface is small and does not
influence the rate of vaporisation. The latter will depend upon the liquid
temperature
w = Ae -L/RT1
where,
w = rate of vaporisation
L = latent heat of vaporisation
A = constant governed by the nature of the liquid
Therefore, the rate of heat consumption per unit surface area is given by
q2 = Lw = LAe -L/RT1
Under equilibrium conditions
This equation may be used to calculate the equilibrium temperature T1 and

hence the rate of vaporisation. Under the conditions of very fast reactions,
the latter gives the rate of combustion.
Therefore, rate of vaporisation
For very small droplets and low values of Reynolds number, it is known that
the Nusselt number Nu ≈ 2
Therefore,
where, k = thermal conductivity and d and r are the diameter and radius,
respectively.
This is the simplified equation for the rate of vaporisation and combustion.
The time of complete combustion, tb, of the droplet may be calculated
from a relation between its radius and the quantity of heat received in a
given time. This relation is
dQ = 4π2h(Tg – T1) dt
where, dq is the heat received by a droplet of radius r in time dt.
The mass vaporised in time dt
Again, dG may be written as

dG = –4π2pdr
where, ρ = liquid density.
tb may be obtained by assuming T1 = constant (boiling point) and

integrating between r = ro, t = to and r = ro, t = tb where ro = initial radius of
the droplet. Writing Tc (combustion temperature) for Tg, we thus get
where, Ko is a constant. This relation is very significant in stating that the

time of burning of a droplet is directly proportional to the square of its initial
diameter do. When tb is in seconds and do in centimetres, the value of Ko is
found to be of the order of 102.
8.10 KINETICS OF SOLID FUEL COMBUSTION
Solid fuels have been studied much more thoroughly than the liquid fuels.
The ignition temperatures of the naturally occurring solid fuels, namely,
wood, peat, ligmite and coal, are higher than the initial temperatures of
active decomposition. These fuels also contain appreciable quantities of
moisture. Therefore, they undergo drying and decomposition before actual
combustion takes place. The volatile matter which contains combustible
gases, vapours and also minute droplets of tarry substances, is thus
evolved. The combustion of theses solid fuels consequently involves the
combustion of the volatile matter and the combustion of the solid
carbonaceous residue. The composition of the volatile matter, and hence its
burning process, varies widely. The residue is essentially carbon. However,
its reactivity depends on the type of fuel and hence its ignition
characteristics also vary. The flame of a solid fuel is due to the combustion
of the volatile matter and the carbon monoxide produced during the
combustion of carbon. The visible indication of the combustion of carbon is
a bright glow of the burning piece.
Carbon furnishes a typical case of heterogeneous combustion, that is,
combustion between two different phases. The fuel is in the solid state and
the oxidant in the gaseous state. This heterogeneous process has two basic
components:
1. Delivery of the gaseous reactant to the surface of the solid by diffusio
2. Chemical reaction of the solid and gas at the surface.
The overall kineties of the process depends in general on the rates of the
two individual steps. When the latter differ considerably the overall kinetics
are governed by the slower of the two. Thus we may have the diffusion-
controlled combustion at high temperatures when the chemical reactions
are extremely fast. Under the conditions of lower temperature, the chemical
kinetics are slowed down and hence these govern the combustion process.
In practical cases both the phenomena may be significant in controlling
combustion.
The chemical kinetics are expressed by an equation of the Langmuir
adsorption isotherm
where,
R
= cspecific reaction rate per unit surface area
=psoxygen concentration at the surface
=k1rate of formation of surface complex of oxygen with carbon
=k2rate of decomposition of the surface complex
This equation has two limiting cases
This variation in the order of the reaction can be achieved also by

temperature variation when k1 and k2 have different temperature
dependences.
The diffusional kinetics are given by the expression
Rd = ko(po – ps )
where,
Rd = rate of diffusion per unit surface area, which is equal to the rate of
reaction per unit area where diffusion controls the process.
ko = velocity constant for diffusion across the boundary layer.
po = oxygen partial pressure in the main stream

D = diffusion coefficient.
δ = boundary layer thickness
If the carbon is porous, the kinetics of pore diffusion are given by
where,
Rp=rate of pore diffusion related to unit area of external surface,
which is equal to the specific reaction rate at the pore surface
related to unit area of external surface
ks=velocity constant for the reaction at the surface, which may be
k1 or k2 depending upon the conditions
=Sinternal surface area per unit volume
=morder of reaction with the limiting values of zero and one.
For a zero order reaction ks = k1 and m = 0
For a first order reaction, ks = k2 and m = 1
The combined kinetics are given by the summation of rates at the surface
and at the pores expressed per unit area of external surface.
Rt = Rs + Rp
where, Rt = total rate of reaction per unit area of external surface
Rs = rate of reaction at the external surface per unit area of external
surface.
Under the conditions of low temperatures, T < 800°C, that is the ignition
range
If Rs >> Rp, Rt = k1, the reaction is of zero order for non-porous carbon.
If Rp >> Rs, Rt ∝ , the reaction is of half order.
Under the conditions of high temperatures, T > 1,200°C, that is in the flame
temperature region
The diffusion across the boundary layer may be assumed to control the
overall kinetics at T > 1200°C, so that
Rd = Rt
We have also obtained,
Eliminating Ps and rearranging, we get
This shows that at high temperatures, the overall reaction is of first order
with respect to the initial oxygen partial pressure; this is true for all cases
whether pore diffusion is relatively important or not.
The above simple derivations confirm the experimental findings in the
two temperature regions with lumps of carbon.
Practical fuel bed can be simultated by carbon channels. Experiments
with single channels have shown that the burning rate is almost
independent of air velocity in the laminar region but increases with it in the
turbulent region; the rate of increase being higher at higher temperatures.
The combustion of pulverized fuel is simulated by the combustion of
carbon particles. The overall kinetics of a single particle is given by
neglecting the pores in the small particles. Assuming relative velocity of the
particles to air negligible, ko = D/r. This bears out the enormous effect of
size reduction in accelerating the process.
As in the case of liquid fuel droplets, the time of complete burning of
carbon particles is found to be proportional to the square of the particle
diameter.
where,
=tbtime of complete burning of the particle
=
d0initial particle diameter
kd=constant of the order of 103 when tb is in seconds and do in
centimetres.
PROBLEMS
1. What percentages of stoichiometric air are present in the two lim

inflammability of the following combustible substances: hydrogen, c
monoxide, acetylene, methane, propane, pentane, acetaldehyde,
alcohol and acetane?
[Answer: 1008.4 and 14.0, 294.1 and 14.8, 327.7 and 2.1, 187.7 and
64.5, 186.8 and 40.0, 172.4 and 31.2, 196.6 and 6.9, 155.9 and 29.9,
169.8 and 42.5]
2. Compute the inflammability limits for a fuel of composition CH4 90%,
4%, C2H4 2%, CO2 2% and N2 2%.
[Answer: 5.3% and 14.6%]

3. The atmosphere in a solvent handling plant contains 2% benzene an
toluene. How much nitrogen is to be added for avoiding fire risk?
[Answer: 115.1 litres N2 per 100 litres polluted air]
BIBLIOGRAPHY
1. Godsave GAE. Studies in the combustion of drops in a fuel spray–

burning of single drops in fuel. Fourth Symposium on Combustion, 1
Cambridge, 1953.
2. Khitrin LN, Fyzika Goreniya i Vzryva (Physics of Combustion
Detonation), Moscow University Press, 1957. English transla
Jerusalem: IPST, 1962.
3. Lewis B and Von Elbe G. Combustion, Flames and Explosions of Ga

Third edition. Orlando: Academic Press, 1987.
4. Minkoff GJ and Tipper CFH. Chemistry of Combustion Reactions. Lon

Butterworths, 1962.
5. Thring MW and Essenthigh RH. Thermodynamics and kinetics of

combustion. In Lowry HH, ed. Chemistry of Coal Utilization, Supp. Vol.
72, New York: Wiley, 1963.
* In fact CO-O2 mixture without any trace of hydrogeneous impurity may be virtually
non-explosive.
9 Combustion Appliances
9.1 INTRODUCTION
The general requirements for smooth and efficient combustion may be

identified as follows:
Fresh charge of fuel should be freely ignited as it enters the burning
zone. Load fluctuations within the specified range should not cause any
ignition problem. Radiation from the flame, hot fuel bed and hot refractory
surface, and convection from hot gases should be adequate to ignite the
fresh fuel. Special care is particularly required in burning solid fuels in
lumps. Direct contact of glowing particles is sometimes used to achieve
proper ignition. The composition of the fuel–primary air mixture must be well
within the limits of inflammability.
Steady combustion is the basis for obtaining the desired rate of heat
release. It is therefore necessary to maintain flame stability throughout the
combustion process. Burners should not be operated below the stipulated
capacity range. The flame should not suddenly come in contact with cold air
or a cold surface. All factors causing flame extinction or flash-back are to be
avoided. Some types of flame holders enhance flame stability.
High temperature combustion is no doubt a fast process but proceeds
with a finite rate. Adequate combustion space should be provided for driving
the process to its completion. In the absence of such space, there will be
loss of combustibles with the exhaust gases, which will also accentuate the
problem of smoke. The smoke may be of two types: brown or black. Brown
smoke is due to unburnt combustible vapours, while black smoke is due to
carbon black produced by the chilling of the flame when it impinges against
a cold surface. Once formed, black smoke is difficult to burn. The shape of
the flame should correspond to the geometry of the furnace and vice versa.
The quantity of air supply is important in achieving proper combustion.
Excepting some premix systems, excess air is always required for complete
combustion. If however, a reducing atmosphere is desired, excess air is to
be avoided. Even otherwise, the quantity of air should be minimum,
consistent with the requirement of a given system. Excess air leads to
increased heat loss in the form of sensible heat of exhaust gases.
The method of air supply is another vital factor of efficient combustion. It
is enough for the required oxygen to be present in the system; it is also
necessary that there is intimate contact between oxygen and the
combustibles. This is achieved by creating intense turbulence in the
combustion space. The method of air supply is a powerful means for this.
Sufficient temperature of the combustion gases should be maintained in
all parts of the combustion chamber. Suitable precautions are to be taken in
the design and operation of the combustion system for this. Temperature is
important for smooth ignition, stable combustion and smoke-free
performance of the system. Theoretically, the most efficient combustion is
that which leads to the maximum temperature possible. It is, however,
advisable in practice to keep the furnace temperature below the maximum
in many cases where other operation factors are important.
Besides the above general requirements, there are special ones for
individual combustion systems. Some of these are discussed below.
9.2 GAS BURNERS
Numerous types of burners have been developed for buring gaseous fuels
in domestic and industrial heating appliances. There are two basic types:
1. Total or partial premix type, in which a part or whole of the combustio
mixed with the gas before it emerges out of the nozzle;
2. Nozzle-mix type, in which, the air is supplied to the burner tip after t
leaves the nozzle.
Atmospheric or aerated gas burners
The kinetic energy of the gas is used to aspirate air from the atmosphere
into a mixing tube which has the burner head at one end. A Bunsen burner
is a typical example. Depending upon the gas pressure, there may be low
pressure gas aspiration at 7.5 to 20 cm wg or high pressure gas aspiration
at 0.25 kg/cm2 gauge and above. A typical aerated gas burner is shown in
Fig. 9.1. Its detailed description is given later in Section 9.2.1.
Figure 9.1 Atmospheric gas burner (low pressure gas aspiration)
Air aspiration gas burners
Air is supplied from a compressor at a medium pressure of 0.15 to 0.35

kg/cm2 gauge or above and its kinetic energy is used to aspirate gas at 7.5
to 20 cm wg into an aspirator body for mixing the two and then the mixture
enters the combustion chamber. The gas is supplied at a constant pressure
controlled by a governor (Fig. 9.2).
Figure Air aspiration gas burner
9.2
Burners with an independent supply of gas and air to the mixer
In this system, the fuel and air are mixed in the desired proportion and the
compressed mixture is then delivered to the combustion chamber under
pressure. This system achieves total premix with high efficiency of mixing.
Typical methods of delivering gas and air in the nozzle-mix systems are
given below.
1. Separate air and gas ports (Fig. 9.3): Streams of air and gas are sep
led into the combustion chamber through ports of suitable size and
The introduction of almost parallel systems of gas and air are used t
diffusion flame for uniform heating of large spaces, for example
overns. By supplying gas and air at an angle and imparting a whirl to
a short intense flame is obtained. When the gas line is in the form of
straight pipe, it is called a gun.
Figure 9.3 Combustion with separate gas and air ports: (a) Long flame (coke
oven), and (b) Short flame
2. Gas ports and air register: The gas is usually supplied by a gas gu
single- or multiple-port head while air is delivered by a forced-drau
register (Fig. 9.4). The air register has controlling air louvers which
rotation of the incoming air and control its quantity. Such units give a
intense and non-luminous flame. A diffuser plate is attached to the
tip to maintain a low gas velocity in the central zone. This helps stea
prompt ignition and flame stabilisation. The diffuser also promote
mixing of air and fuel. These burners are popularly known as blast bu
Figure A blast burner with air register and gas gun
9.4
3. Fanmix burner: Unusually high burning rates are obtainable w

nozzle-mix system using as low as 5% excess air. The straight g
ends in a turbine (spider) having holes drilled on one side of its bla
fan is attached to the turbine (Fig. 9.5).
Figure Fanmix burner
9.5
The emerging gas rotates the turbine and the fan. The latter delivers the
combustion air at right angles to the gas streams. High turbulence results
and leads to a thorough mixing of gas and air. The quantity of air is
controlled by an air shutter.
Depending upon the structure of the flame, gas burners may be of the
following types:
• Torch burner. Each burner gives one flame visibly projected from the
burner tip.
• Ring burner. It is usually an atmospheric burner. The burner head is in
the form of
concentric rings having suitably drilled holes.
Pipe burner. This is also an atmospheric burner. The mixing tube en
pipe with drilled holes or projecting tube ports. There may be sin
multiple-row drilling.
Flameless combustion types: In the surface combustion syste

combustion is localised on the solid surface and no flame is visible.
systems are often referred to as flameless combustors. Surface com
is used at both very high and very low gas velocity which will norma
rise to blow-off and flash-back problems, respectively. Figure 9.6 sh
tunnel burner using the surface combustion principle. A gas–air mix
fed through a port into a circular or rectangular tunnel formed in a ref
block. The incandescent walls of the tunnel bring about surface com
with very high intensity, say 15,000 kcal/h per square centimetre
area. Heat transfer is by radiation from the incandescent refractory
These burners suffer from the disadvantage of noisy operation b
about by the combustion progressing as a series of explosions i
succession inside the tunnel. Tunnel burners are manifold in groups
one gas-air proportioner controls the group. The combustion is co
with the primary air supplied.
Figure Surface-combustion tunnel burner

9.6
Pulsating combustors: They are in a class by themselves. The p

appearance of explosionflames characterise them (Chapter 8). Fig
shows a typical pulsating combustor.
Figure Pulsating combuster
9.7
The following burners are meant for special applications:

Immersion torch burners (pipe in liquid): These are suitable for
solutions, fused metals and salts. Heating tubes are immersed in the
Torch burners fire salts at one end of the heating tubes while the flue
exit from the other end. The liquid is heated indirectly by the heating t
Radiant torch burners (pipe in air or any other gas): The flame is co
within the pipe which heats the air or any other gas. Any contamina
the products of combustion is thus avoided. Radiant burners are ofte
in industrial drying.
Submerged combustion types: Since tunnel burners do not nee

secondary air for combustion; the refractory tunnel may be submerg
liquid without disturbing the combustion. The combustion gases will
through the liquid which will receive heat from these hot gas bubbles.
9.8 shows a simple burner using the submerged combustion principle
intense and more uniform combustion is achieved by providing ad
refractory surface inside the tunnel. The main application of the subm
combustion technique is in crystallising salts for which scaling of th
transfer surface is a serious problem. Burners are built with a rated c
upto 1.3 × 106 kcal/h. Several of these burners may be used in one ta
Figure Gas burner of submerged combustion type
9.8
9.2.1 ATOMOSPHERIC GAS BURNERS
These burners are based on the principle of the Bunsen burner. The
variation occurs mainly in the design of the individual parts. The basic
features of these burners are discussed below with reference to the burner
shown in Fig. 9.1.
The burner consists of a fixed orifice, spud for gas inlet, a controllable
shutter for air supply, a venturi-shaped mixing tube and a burner head with
ports (holes) drilled in it. The narrow zone of the mixing tube is called its
throat which diverges into the hind part called its bell. The gas rate is
controlled by a valve in the gas line. When the gas is admitted through the
orifice, its kinetic energy is increased owing to the high injection velocity and
creates a low static pressure at the throat. Primary air is sucked into the bell
through the air shutter. During flow through the mixing tube from the bell to
the burner head the gas and air mix uniformly and the static pressure is
increased by the slowing down of the fluid stream. The combustible mixture
burns in the form of tiny burner flames anchored on the ports of the burner
head. The primary air is not enough to complete the combustion. Secondary
air is entrained on the flame surface from the surrounding atmosphere by
convection currents. The quantity of primary air depends upon the type of
flame, burner design, input rate and type of gas.
The operation characteristics of an aerated gas burner is shown by a set
of curves in Fig. 9.9; the coordinates are input rates and primary air supply.
Stable burner operation is possible in the middle region confined by the
curves 1, 2, 3 and 4.
Curve 1 represents the conditions of lifting and blow-off and sets the
upper limit of input rate, or gas flow-rate and the primary air supply. This
upper limit varies inversely with the quantity of primary air. A high input rate
therefore requires an increased quantity of secondary air. Curve 2
represents the lower limit of primary air. A low proportion of primary air
gives a long, wavy and yellow flame in aerated burners and leads to the
formation of soot and carbon monoxide by incomplete combustion. The
supply of primary air becomes critical towards the range of high input rate
as shown by the curves 1 and 2 tending to coverage on the right-hand side.
Burner operation is not satisfactory in this region. The proportion of carbon
monoxide in the products of combustion sharply increases for operation to
the right of Curve 4. The conditions of flash-back prevail on the left of Curve
3 which thus sets the lower limit of the input rate.
Figure 9.9 thus clearly shows that a given burner can operate within a
range of gas flowrates. The maximum gas rate is limited by the blow-off,
incomplete combustion or inability to aspirate sufficient primary air. The
minimum is limited by the flash-back. The ratio of maximum to minimum gas
rate obtainable in a burner is called its turndown ratio. A value of 5:1 is
desired in most gas-heated appliances. At a given gas rate, a long luminous
flame is obtained with a low supply of primary air, while a short turbulent
flame is obtained if the quantity of primary air approaches 100% of the
theoretical.
Figure Operation characteristics of an aerated burner
9.9
All premix or partial premix burners give characteristic curves similar to

Fig. 9.9. The relative shape and location of individual curves depend upon
the burner design, the operating temperature and the type of gas used. In
nozzle-mix burners there is no flash-back but the blow-off can be related to
the corresponding conditions of Fig. 9.9. In industrial burners of very high
input rate, either the flame stabiliser in the form of a physical obstruction, a
diffuser, or the principle of surface combustion is used.
Equations and design data for a simple aerated burner
The gas flow-rate through the orifice is given by

where,
V = rate of gas flow, Nm3/h
K = Coefficient of discharge (usually 0.8–0.9 for fixed tubular orifice
spud).
A = orifice (port) area, m2
∆p = pressure drop at the orifice, cm H2O
P = initial gas pressure, cm Hg abs
T = gas temperature, K
S = specific gravity of gas (air = 1)
Knowing the input rate and the desired pressure drop at the orifice, it is
possible to calculate the orifice diameter from equation (9.1). The desired
pressure drop may be calculated from the primary air requirement with the
following empirical equation for the aeration capacity of the burner.
where,
PA = primary air, per cent of theoretical air
P = gas pressure at orifice inlet, cm wg
CN = net CV of gas, kcal/Nm3
Am = average area of mixing tube,
A1 = throat area, m2
A2 = area of mixing tube outlet, m2
Ap = total port area, m2
Q = heat input rate, kcal/h
The first term on the right-hand side of equation (9.2) is a function of the
nature of the gas and its supply pressure. The second term is a function of
the burner dimensions. The third term shows the effect of the temperature
of the mixture.
The nature of application of the burner influences the primary air
requirement. When a long flame is permitted in water heaters and furnaces,
only 35%–40% primary air is recommended with natural gas and most
manufactured gases. The figure is at least 55% with LPG. When a short
flame is required as in cooking ranges, the primary air requirement is
higher. Cooking ranges need 55%–60% and radiant heaters need at least
65%.
The total port area is computed from the design data of specific heat
input rate for the burner, say, 6 X 106 kcal/m2 per hour of port area.
Other design data:

Throat to total port area ratio = 0.20 to 1.0
Air shutter area = 1.25 to 2.25 times the total port area
Distance from gas orifice to throat = 0.5 to 2 times the throat diameter
Length of mixing tube = 6 times the throat diameter
Slope of mixing tube ~ 3°
Area of burner head = 1.5 to 2 times the total port area
It is clear from the above that the aerated burner design is sharply
influenced by the nature of the gas. On the other hand the nature and
quantity of available gases may widely vary. It is therefore necessary to
know the basis of determination of interchangeability of gases.
The burner output rate is given by
Q = ηVCN
where, η = coefficient of combustion efficiency.

Combining equations (9.1) and (9.3), we get.
Furthermore, from equation (9.2), we have the primary air supply
The ratio CN/√S is known as the Wobbe index. It is a useful parameter in

assessing interchangability of gases with respect to aerated burners (see
also Chapter 6). It is a dimensional quantity with the dimensions of calorific
value of gases.
The Wobbe index is of great importance for gases supplied through the
distribution system because aerated burners are widely used by a majority
of customers. It should be realised that this parameter is of limited
significance for other types of burners.
An aeration test burner (ATB) has been specified for evaluating variation
in gas quantity. It is a Teclu burner of 30.5 cm height and 10.26 mm internal
diameter and has a nipple of 0.99 mm diameter. The air shutter is
rectangular and adjustable by a micrometre head. The given gas is burnt in
it. It is aimed at determining the extent of the opening of the air shutter at
which an exact cone of 6.35 cm (2.5 inches) height is obtained. The result is
expressed as the ATB number. A variation of 5 units in the ATB number of a
gas can seriously affect the performance of an aerated burner.
The maximum heat inputs obtainable with aerated burners of low gas
pressure types are given in Table 9.1.
Table 9.1 Capacity of aerated gas burner (low gas pressure)
Aerated burners of high pressure gas aspiration type work on the

principle depicted in Fig. 9.1. However, better mixing and control of gas and
air are obtained with a two-stage aspiration at the orifice (spud) and the
burner throat (Fig. 9.10). This is also provided with a flame holder at the
burner tip, which stabilises the flame by maintaining a zone of relatively low
gas velocity when the gas pressure in the line is quite high.
Figure 9.10 An aerated burner with two-stage aspiration and flame holder
9.3 OIL BURNERS
Basically there are two different classes of oil burners, namely, (i) vaporising
type and (ii) atomising type. The vaporising burners are favoured for heating
units of small size such as portable air heaters, small boilers and cooking
stoves for domestic purposes. These are characterised by low cost and
quiet operation. The atomising burners are used in industrial heating and to
a much lesser extent in some of the big domestic heating appliances.
9.3.1 VAPORISING BURNERS
Vaporising burners are of different designs and they are suitable for oils
ranging from naphtha to light fuel oil. Blow torches and portable gasoline
stoves burn straight-run gasoline. The volatile fuel is passed at a low
pressure through a tube adjacent to the flame, where vaporisation takes
place. The vapour stream issues out of an orifice at a high velocity and
entrains primary air. The fuel–air mixture passes through a mixing tube and
burns at the burner head similar to atmospheric gas burner principle.
Wick-type vaporising burners use superior kerosene. A wick raises
the liquid fuel from a trough by capillary action. Radiation from the flame
and adjacent hot surfaces vaporises the fuel from the wick head. The
vapours are allowed to enter into an annular space between two vertical,
perforated metallic cylinders and burn in the air drawn through the
perforations by natural draught. The combustion takes place throughout the
annular space with a blue flame. These burners are used as cooking
stoves. A variation of the wick-type burner has a capacity upto 5 kg/h and is
suitable in domestic boilers and central heating. Here an asbestos wick
receives the fuel by a gravity-feed which may be regulated within a certain
range. In ordinary wick-type burners, the burning rate is controlled by
varying the length of the exposed portion of the wick; the control is less
satisfactory.
Figure 9.11 shows a pot-type burner: another example of a common-
type vaporising burner. There is a fuel reservoir at the bottom, supplied by
an oil line. The oil surface is heated by radiation from the flame and the hot
walls. The vapours mix with the primary air admitted through a central pillar
and perforations in the pot wall. The fuel-air mixture is too rich at the oil
surface to support combustion. Further up, it is diluted with air and becomes
inflammable. The flame is supported at the top of the pot. These burners
may work on natural or forced draught. Superior kerosene or light fuel oil is
used. Some soot formation cannot be avoided and the pot burner should be
periodically cleaned. The capacity may be upto 10 kg/h.
Figure Pot-type burner

9.11
Wall-wiping flame rotary vaporising burners use coarse atomisation

before the fuel is vaporised. A centrally located centrifugal spinner
distributes the oil in the form of a spray of coarse droplets striking the hot
stainless steel wall of the burner (Fig. 9.12). The vapours are formed and
mixed with the air which is directed towards the wall by a fan. The fuel-air
mixture rises upwards and burns on a stabilising grill with a blue flame. The
flame burns around the inner circumference of the furnace only, and hence
gets its characteristic name. These burners can burn up to 30 kg/h oil. High
combustion efficacy is achieved by the good mixing of fuel and air. Power
requirement is low and the operation noiseless. Kerosene and light fuel oil
are used.
Figure Wall-wiping flame rotary vaporising burner

9.12
The petromax stoves burn kerosene. An upward moving fuel jet is

allowed to strike against a hot metal surface at a high velocity. The vapours
produced burn with a short and intense flame over the metal surface. The
fuel is stored in a small reservoir below the fuel line and the necessary oil
pressure is supplied by compressing air into the reservoir by a hand-driven
piston. These stoves were quite popular in earlier times. Their use has
declined owing to the risk of accidents and noisy operation, and to the
advent of cheaper and safer stoves described in the previous paragraphs.
A high speed vaporising burner is shown in Fig. 9.13. A high rate of
vaporisation is achieved by atomisation of the volatile liquid fuel and
recirculation of hot combustion gases within the burner. This particular
burner clearly bears out the difference between vaporising and atomising
burners. The combustion chamber receives fuel vapours in the former and
fuel droplets in the latter.
Figure High speed vaporising burner

9.13
9.3.2 ATOMISING BURNERS
Atomisation prepares the liquid fuel for combustion by disintergrating it into

droplets. Enormous surface area per unit weight of the fuel is created and
this helps the heterogeneous combustion of the liquid fuel and the gaseous
oxidant. It is well known that a liquid fuel like kerosene in a beaker cannot
be ignited with a match but a spray of the same fuel easily ignites on the
approach of a match flame and continues to burn by itself. Atomising
burners are provided with an arrangement for the atomisation of liquid fuels
before the actual combustion takes place.
There are basically three types of atomising burners differing from one
another on the principle of atomisation. They are
1. Pressure jet atomising burner,
2. Twin-fluid or blast atomising burner,

3. Rotary atomising burner.
The mechanism of atomisation is more or less similar in them. Initially a jet

or a thin film of liquid is obtained and allowed to emerge into the open
atmosphere at a suitable velocity. Both the jet and unsupported film are
unstable and break up into drops. Disturbances like swirling of the jet or
rotation of the film hastens the disintegration process. Viscosity and surface
tension of the liquid are of particular importance in atomisation. Other
factors remaining the same, low viscosity and low surface tension are
desirable for ease of dispersion and formation of small drops. The
atomisation process is further assisted by the resistance, friction and
turbulence of the air. The air resistance and friction become effective when
any ruffling or distortion of the surface of the jet or film occurs. These forces
are particularly significant at combustion chamber conditions owing to
increased air viscosity at high temperatures. Local turbulance in the air
causes deformation and disruption of the drops.
The velocity of the jet or film is one of the most important parameters
influencing the process of atomisation. The higher the liquid velocity, the
greater the disturbance in the liquid and also the resistance, friction and
turbulence of air, and hence the greater the extent of atomisation.
A high speed jet disintegrates into a number of big droplets and a far
greater number of secondary droplets. The big droplets are sub-divided into
small ones during the flow of the spray. The atomisation is never complete
in the immediate vicinity of the orifice, but it proceeds during the penetration
of the spray into the surrounding medium. The resultant spray has a
combination of droplets of various sizes. A considerable proportion of the
droplets is in the extremely small size range, 25 µ or less. These assist in
the initial ignition and promote the stability of the flame. The small droplets
are quickly vaporised, or cracked and ignited. The resultant flame can
support the combustion of the coarser ones. Very large droplets are to be
avoided as far as possible because they may not get completely burnt in the
time available, and they then create complications by depositing themselves
on the walls of the combustion chamber.
The energy required to create a new surface by disintegrating the liquid
into droplets is only a small fraction of the total energy consumed in the
atomisation process. Energy losses (inertial, viscous and those due to
mechanical inefficiency of the equipment) constitute the bulk of the total
energy consumption.
Pressure jet atomisers are of two types. The plain orifice type is most
widely used for fuel injection in diesel and other internal combustion
engines. Very high oil pressures, upto 350 kg/cm2 or even higher are used.
The centrifugal swirl types are most popular in large industrial oil burners.
Much lower oil pressures, 7 to 35 kg/cm2 are required in these.
A simple swirl-type atomiser is shown in Fig. 9.14. The oil enters the
circular swirl chamber (or vortex chamber) through tangentially spaced
ducts or slots (A1 and A2) and rotates in the chamber around an air core
with an angular velocity varying inversely as the radius of the swirl. The
rotating mass of liquid issues through an orifice, C, under the influence of
two main forces. The translation force moves it forward while the centrifugal
or spinning force makes it fly outwards tangentially. The result is the
formation of a hollow, divergently conical and rapidly thinning film which
finally provides a spray of droplets.
Figure Swirl-type oil burner

9.14
The oil viscosity should be about 70 Redwood 1 seconds for small

nozzles and about 100 Redwood 1 seconds for larger nozzles. Heavier fuel
oils should be preheated to this level of viscosity.
The output of a pressure atomiser, Q, increases with the increase in oil
pressure, P, approximately following Q α P0.5, and decreases with the
decrease in oil viscosity. The mean droplet size d increases with viscosity,
varies inversely as P0.35 and increases with the orifice diameter, d0,
approximately following d α d00.5. The droplet size varies between 10 μ and
200 μ.
The spray angle varies as the ratio of the total area of the tangential
ducts or slots to the square root of the product of the orifice outlet diameter,
d0, and the swirl chamber diameter, D.
This angle is independent of the oil pressure and the slope of the
internal surfaces of the swirl chamber. However, the slope of the outlet edge
from which the spray develops influences the spray angle. The spray angle
is widened by rounding the edge.
The simple pressure jet swirl-type atomisers are severely limited in
flexibility owing to the dependence of output on oil pressure. A simple
calculation from Q α P0.5 shows that a wide range of oil pressure between 7
and 35 kg/cm2 allows a ratio of only 1:2.2 between the lowest and the
highest output. This limitation is removed in the modified designs of the
pressure jet atomisers. Two such designs of wide range pressure jets are
shown in Fig. 9.15 in which a turndown ratio of upto 10:1 may be realised.
In the spill-type, the rate of discharge is varied by providing a bypass. In the
other design, this is achieved by having a number of tangential slots for the
entry of oil into the swirl chamber and varying the number of available slots
with a sliding piston.
Figure 9.15 Wide range pressure jets: (a) Spill type and (b) Slot type
Combustion air flows from the windbox through an air register

surrounding the burner (Fig. 9.16). The functions of the air register is to
control the velocity and direction of the mixture of fuel and air, wrap the air
around the flame and finally give a spinning motion to the air. The whirling
air creates a low pressure zone in the vicinity of the nozzle tip and causes a
recirculation of hot combustion gases which help in stabilising the flame. A
diffuser is installed at the end of the burner gun to impart a flow of air
around the oil particles, guide air along the flame and also shield the flame
from high velocity air. It is a hollow metal cone, slotted or pierced with holes
to allow a limited amount of air to promote steady ignition. A refractory
throat is provided at the back of the diffuser. It has an opening which is
concentric with the burner nozzle. Its function is to promote rapid ignition by
radiation from the hot refractory and good mixing of the fuel and air.
Figure Air register
9.16
The pressure jet atomising burners are very quiet and have a low
operating cost. Power requirement is the lowest of all atomisers. These are
perhaps the most widely used of all the atomising burners in existence. A
turndown ratio of 6:1 is expected even in common installations of the wide-
range types. Burners with a capacity upto 4,500 kg/h of oil are obtainable.
Small domestic installations of the pressure jet-type are also available. The
pressure jet atomiser is susceptible to choking by dirt in oil. The latter
should be carefully strained.
Twin-fluid atomisers use an auxiliary fluid (air or steam) to atomise the
oil and are of three main types:
1. Low pressure-type (LP) using air at 35 to 70 cm wg,
2. Medium pressure-type (MP) using air at 0.4 to 1 kg/cm2 gauge
3. High pressure-type (HP) using air or steam at pressures excee

kg/cm2 gauge.
Each of these types may again be either inside-mix or outside-mix type
dedpending on whether the fuel and auxiliary fluid mix within the burner or
beyond the burner outlet. A few inside-and-outside mixing systems are
shown in Fig. 9.17. The inside-mix types are more commonly used. These
provide high efficiency at the high rate of discharge, a high turndown ratio
and a flexible flame structure.
Figure 9.17 Twin-fluid atomisation: (a),(b),(c) Outside-mix types, (d),(e),(f) Inside-

mix types
The general principle in these atomisers is common. Oil flows through a

central tube at a controlled rate and the auxiliary fluid meets it obliquely at a
pre-determined angle as it emerges from the tube. The energy requirement
is met by the auxiliary fluid and the oil pressure need not be more than that
required to ensure a uniform flow through the nozzle.
Approximately the same kinetic energy of the auxiliary fluid is required
for atomisation in the three types of twin fluid atomisers. Therefore, the
higher the pressure of the auxiliary fluid, the lower the quantity required.
High pressure atomisers need only 2% to 3% of the total combination air for
atomisation while this figure is 3% to 15% for MP burners and as high as
20% to 100% for LP burners. On the weight basis, the steam requirement is
similar to air requirement (0.3 kg/ kg oil) in the HP atomisers. Only 2.5% of
the steam that could be generated in a boiler by a high pressure steam
atomising burner is required for achieving the atomisation.
A high turndown ratio of upto 10:1 is obtained with HP and MP burners.
The LP units normally have a low turndown ratio of 2:1 to 5:1, HP and MP
burners use most of the combustion air as secondary air and thus permit
high waste heat recovery by air preheating. The cost of air compression in
HP burners is very high. Therefore, steam is more frequently used to
atomise heavy residual fuels and coal tar fuels which require preheat for
getting the correct viscosity.
LP units are used in domestic and industrial installations. They are quite
versatile and built in wide size ranges. Industrial LP burners with a capacity
of 2,000 kg/h are obtainable, and lighter grades of fuel oils are used.
MP burners are used in boilers and furnaces where greater flexibility
and heat regeneration or recuperation are required.
When steam is substituted for compressed air, the same quality of
atomisation can be obtained at a considerably lower pressure. High
pressure steam burners are widely used in large installations where high
pressure steam is available. These burners may have a capacity upto 3,500
kg/h. Heavy fuel oils are successfully burnt by HP steam atomising burners.
Less preheating of the oil is required when steam is used to atomise it.
Steam should be available at a pressure exceeding the oil pressure. The
admission of the secondary air is through air registers. However, no diffuser
is normally used. The flame shape is altered by changing the nozzle tips.
Rotary atomisers have a central stationary fuel line which delivers the oil
to the inner surface of a rotating hollow tapered cup (Fig. 9.18). The cup is
rotated at speeds of 3,600 to 10,000 rpm by either air-driven impellers or by
an electric motor. Friction between the oil and the cup surface causes the
former to rotate with the cup, and centrifugal force, assisted by the tapering
of the cup causes it to flow towards the brim. Finally the oil is flung off in a
thin film which readily disintegrates into fine droplets. The smoothness and
uniformity of the cup surface results in the production of an even film with
the same velocity at each point of the brim. The result is a higher degree of
uniformity of droplet size than in the other atomisers.
Figure Rotary atomising burner
9.18
About 15% of the combustion air is supplied as primary air by a fan

attached to the rotating shaft of the motor driven cup. This air at a pressure
of 10–25 cm wg gives a forward movement to the spray and also exerts
additional atomising force on the droplets. Secondary air is supplied to the
door underneath or through an opening in a chequered floor, the draught
being provided by the stack. The initial spray angle is 180° and the conical
slope is given by the primary air steam. A fuel droplet size of 50 µ is
claimed.
The oil pressure should be low, 5–8 cm wg and the viscosity should be
in the range of 100–300 Redwood 1 seconds. Rotary atomisers can tolerate
higher viscosity than the others. They may however lose atomising
efficiency at low viscosities. The low viscosities used in a pressure jet
system may cause the oil to ‘slip’ with the cup. The trouble due to choking
by dirt is less. However, there is a greater chance of carbon deposition by
cracking caused by the radiation from the surroundings after the burner is
turned off.
Rotary atomising burners are extensively used in boilers and small
installations. A high turndown ratio of 16:1 can be realised. Capacity up to
800 kg/h is available which is much lower than the maximum capacity of
other atomiser types. Rotary atomising burners are compact (components
combined in an integral unit), efficient and comparatively low in initial cost.
The power requirements are also relatively low.
The rotary units are usually mounted horizontally in the furnace walls,
although a few domestic units have a vertical shaft, producing a flame
shaped like a sunflower.
9.3.3 DRIP FEED SYSTEM IN OIL BURNING
When the combustion chamber is above 600°C and the particular feeding
system can be conveniently provided in the chamber, a very simple and
cheap method of oil burning can be utilised. The fuel is gravity-fed into the
hot environment of the furnace through a suitably shaped piece of metal
tubing. The feed rate is controlled by a valve. The oil droplets fall on a
current of combustion air which is drawn from the chambers undergoing
cooling. The ignition is quite smooth and the combustion is stable. The drip
feed system is particularly suitable for some kilns used in silicate industries.
9.4 COAL BURNING EQUIPMENT
Coal may be burnt by

1. Fixed or agitated beds on a grate,
2. Suspension in air in pulverised fuel burners or cyclone burners,
3. Fluidised bed combustors, in a slurry with water or in suspension i

atomisation burners.
Grate firing is employed in domestic and industrial units and also in thermal
power stations. Pulverised fuel and cyclone burners are used in thermal
power stations and large industrial units. Fluidised bed, coal–water mixture
(CWM) and coal–oil mixture (COM) systems are in an advanced stage of
development with limited number of units already in the market.
Coal may be burnt in a grate by hand firing or by using mechanical
stokers. Domestic appliances, locomotive boilers and small industrial units
use hand firing while medium to large industrial units are fired by
mechanical stokers.
9.4.1 HAND FIRING

The ordinary grates are usually made of iron bars with 6 to 10 mm gaps
between them. There are two accepted methods of hand firing, namely
spreading and coking.
Spreading method: A small quantity of coal is supplied at a time by

spreading over a part of the fuel bed. Care is taken to maintain uniform bed
thickness. Anthracite and free-burning coal are fired by this method.
Coking method: A considerable amount of coal is fed onto a dead plate

just inside the door. The heap of fresh coal is slowly carbonised by the heat
of the glowing bed. The volatile products pass over the bed and get burnt in
the air rising through the grate. The coke is then distributed over the
depleted bed and a fresh charge of coal supplied to the dead plate. Caking
coals are successfully burnt by this method. In a variation of the coking
method, firing is done in alternate sections—either over the front and back
of the grate or to the right and left. This is known as the alternate method of
hand firing.
The success of hand firing largely depends on the skill of the fireman.
The ash is disposed of by shaking or dumping the grates periodically.
However, the bed should be disturbed as little as possible. This precaution
reduces clinker formation and prevents excessive loss of fuels with the
refuse. The amount of air should be controlled with dampers. It should,
however, be obvious that hand firing cannot safeguard the conditions of
efficient combustion.
9.4.2 MECHANICAL STOKERS
The mechanical stokers function on the principle of continuous coal feeding.

The evolution of volatile matter is thus uniform and it becomes easier to
control the air required for the primary and secondary combustion. There
are five types of mechanical stokers, namely,
under-feed stokers,
chain- and travelling-grate stokers,
vibrating-gate stokers,
coking stokers,
spreader stokers.
The last four types come under the general group of overfeed stokers. The
spreader stokers are the correct example of overfeed stokers. The other
three follow cross-feed pattern of fuel and air movement where the fuel
moves horizontally and the air moves upwards at high angles to the fuel
bed.
Under-feed stokers
As their name implies, they introduce the coal into a narrow horizontal retort
or trough beneath the burning fuel bed. The incoming coal progressively
forces the fuel out of the retort and onto the side grates, the rear end being
closed. During its stay beneath the burning bed, the coal undergoes drying
and carbonisation. The volatiles escape through the bed which ensures
their smooth ignition. The coal is fed by means of a plunger or ram or a
reciprocating retort bottom or a worm or screw. This feeding action places
the bed under compression and closes any holes that may tend to form. Air
is supplied through tuyeres (Fig. 9.19). The ash is usually removed by
means of dumping grates at the sides and then discharged into ash pits.
Figure Single-retort under-feed stoker

9.19
The under-feed stokers are of single-retort and multiple-retort types. The

single-retort stokers are widely used for firing medium to small installations
with free-burning to moderately caking coals of high ash fusion point.
Clinkering troubles are experienced if ash fusion point is not sufficiently
high. The multiple retort stokers are meant for large installations.
The burning rate in under-feed stokers is about 100–250 kg of coal per
square metre of the grate area per hour. The grate size in single-retort units
may vary from 1 m2 to 12 m2. Owing to the absence of an ignition problem,
the single-retort units are open or archless. The large multiple-retort units
operate well with a long reach-arch for the avoidance of the drifting of fuel
particles towards the dumping grates which are provided at the rear end of
the multiple-retort units. This action of the rear arch will be discussed under
chain-grate stokers.
Smokeless combustion is easiest to achieve in under-feed stokers.
Such units constitute a major portion of coal firing applications to dwellings
and small commercial enterprises.
Chain- and travelling-grate stokers
In the chain- and travelling-grate stokers the coal is fed on a forward moving
endless grate from a hopper under an adjustable guillotine-type gate, which
controls the thickness of the fuel bed. Ignition of the fresh coal is
accompilished by a combination of three factors:
1. Radiation from a firebrick arch,
2. Hot gases blowing over the charge,
3. Spray of fine glowing fuel particles from the rear end onto the fresh co
Air supply is controlled at different positions on the grate by dividing the air
space beneath into a number of compartments. A dead plate at the front
blocks the air passage and thus prevents spreading of combustion towards
the hopper. A complete combustion of the gases and vapours is ensured by
supplying adequate secondary air and by destroying stratification with the
help of air or steam jets. The moving grate carries ash over the rear end to
an ash pit or other disposal means.
The chain-grate and travelling-grate stokers differ in the construction of
the grate. An endless chain itself forms the grate in the former case, the
individual links of the chain being sufficiently long. The edges of the links
are usually serrated to provide passage for air. The travelling grate is made
of bars which consist of small individual castings or keys. These keys are
carried forward in endless belt fashion on chains, but do not themselves
form a part of the chain. This arrangement is convenient in replacing broken
or damaged keys without dismantling the chain.
The fuel bed in these stokers is not disturbed, and therefore the
clinkering troubles are low. High ash coals with a relatively low ash fusion
point can be successfully burnt. Low ash coals are actually unsuitable as
these grates need a protecting ash layer. The chain- and travelling-grate
stokers are best suited for free burning solid fuels, such as non-caking
bituminous coals, lignite, anthracite and coke breeze. Strongly caking coals
lead to an excessive fuel loss with the refuse.
Although furnaces with these moving grate stokers may be of an open
type or archless, at least a short front arch and often a long rear arch are
most widely used. The radiation from the front arch hinders the secondary
combustion by promoting stratification. On the other hand, when a long rear
arch is located low enough over the fuel bed, sufficient velocity is imparted
to the furnace gas, which causes glowing fines to be carried over and
deposited on the fresh charge. This raining of particles together with the
radiation from the furnace nose maintains smooth ignition while turbulence
created at the furnace throat goes a long way to break the stratification.
Installation of jets at the front wall further improves the secondary
combustion. Figure 9.20 shows a travelling-grate stoker with combination
arch furnace.
Figure 9.20 Travelling-grate stoker with combination-arch furnace (short front-

arch and long rear-arch) 1. Hopper 2. Guillotine-gate 3. Grate 4.
Furnace nose 5. Front-arch 6. Rear-arch 7. Furnace throat (behind
the stoker structure and not visible.)
The burning rate in these stokers is 200–350 kg/m2 per hour. The grate
area may range from 1.5 to 70 m2. The grate width corresponds to the
furnace width and may vary from 1 m to as high as 7.5 m. In addition to
being widely used for boilers of various sizes ranging from small to large,
the moving-grate stokers are also popular for many special furnaces. The
chain-grate stoker is one of the oldest forms of automatic coal firing
appliance.
Vibrating-grate stoker
It consists of a flat inclined grate which is given a periodic forward and

backward vibration in an essentially horizontal plane. This vibration affects
the feeding of coal from the hopper, the movement of the fuel bed down the
grate and finally the discharge of the refuse at the rear end. It also helps in
maintaining a compact and uniform bed. The frequency of vibration is
usually 600 cycles per minute. The stoker is normally vibrated every two
minutes and the vibration lasts for a few seconds at a time. The burning rate
is 150–200 kg/m2 per hour. Vibrating stokers are quite popular in the new
small to medium installations in some of the advanced countries. They are
suitable for a wide range of coals with low-to-high ash and medium-to-high
volatiles, low-to-high ash fusion point and weakly-to-strongly caking.
Coking stokers
The coal is fed by a reciprocating ram on to a reciprocating grate. The rate

of firing is controlled by the speed of the to-and-fro movement of the grate
and the ram, and by the length of travel of the ram. There is a dead plate at
the front end for accomplishing coking of the fresh charge before the fuel is
pushed along the grate bars. The stokers are suitable for medium-to-high
volatile caking coals. Coking stokers and vibrating-grate stokers are similar
in principle.
Spreader stokers
They have provision for continuously projecting coal into the furnace above
the glowing fuel bed on a grate. The fines are partly burnt in suspension,
while the large sizes form the fuel bed. These stokers thus combine the
principles of combustion of coal on grate and in suspension. The coal is fed
from the hopper by a throwing device which may be one of the following
three:
1. Paddle-type underthrow spreader, in which the paddles revolve ar
horizontal axis and throw the coal from their bottom periphery,
2. Paddle-type overthrow spreader, in which the paddles revolve

opposite direction and throw the coal from the top of their periphery,
3. Steam or air jets.
The grate may be stationary, dumping or moving, thus determining the

method of ash disposal. The moving grate is essentially an endless chair
moving from the rear to the front end at a very slow speed, say 10 mm per
minute. As the part of the coal is burnt in suspension, and as the caking
properties of the remaining coal are reduced during the fall, the spreader
stokers successfully burn the strongest caking coal. This is an important
advantage over the chain-grate and travelling-grate stokers. In fact the
spreader stokers have remarkable adaptability to a wide range of coals,
ability to respond quickly to a change of load and relative freedom from slag
and deposit problems. These advantages have contributed to the immense
popularity of spreader stokers in small to large installations. The
disadvantages of fly ash and smoke problems are largely obviated by using
over-fire jets (Fig. 9.21). The spreader stokers are usually of the open- or
archless-type.
Figure Spreader stoker

9.21
High burning rates of 300 to 450 kg/m2 per hour are quite typical in
spreader stokers. By providing a rear arch in the continuous-discharge type
spreader stoker, a very high rate of 750 kg/m2 per hour can be achieved in
locomotive boilers.
Sprinkler stokers
They are similar to spreader stokers. However, less attention is paid to the
suspension combustion in these stokers. Their burning rates are also much
lower, being about 150 kg/m2 per hour. The sprinkler stokers have
stationary grates.
Downdraft heaters and downjet combustors have not been covered in
the above discussions of lump-coal-firing appliances. Figure 9.22 shows the
principles of downdraft combustion. Coal is fed by gravity. The primary air
passes downward and across the bed. Any smoke formed passes through
the hotter portion of the coal and burns, partly in this region and finally by
mixing with the secondary air in the rear combustion chamber. The draft
through the bed is essentially downward from the upper free surface of the
bed to the bottom rear of the unit.
Figure Downdraft heater
9.22
The principle of downjet combustion is shown in Fig. 9.23. The air is

supplied through a jet that impinges on the surface of the fuel bed. The
sides and bottom of the bed are enclosed. Therefore, the gaseous products
of combustion are forced to leave the bed through its upper surface. The
bed depth and other operation variables are controlled in such a way that
the content of combustibles in the exit gas is negligible.
Figure Principle of downjet firing
9.23
9.4.3 PULVERISED COAL FIRING
Most big installations like thermal power stations and cement rotary kilns
fire coal in a powdered form. The combustion appliances used are called
pulverised fuel (PF) burners. These burners can be designed for
exceedingly high capacity. The capacity of such units is limited only by the
size of the combustion space that can be provided. Boilers with more than 1
× 106 kg steam per hour are numerous and these have a huge cathedral-
like size.
The fuel is pulverised in a ball mill or impact mill. The degree of fineness
required depends upon the coal rank: 60% through 200 mesh (0.07 mm) for
brown coals and sub-bituminous coals and upto 85% for anthracites. Not
more than about 2% should be retained on a 50 mesh (0.3mm). Preheated
air at 110–300°C is passed over the coal during grinding. This raises the
capacity of the pulveriser by drying the fuel; the air also serves to transport
the coal to the burner and acts as the primary air which constitutes about
15%–20% of the total combustion air. The temperature of the coal–air
mixture fed to the burners is usually maintained at 70–80°C. The solid
content of the coal–primary air mixture is about 0.5 kg/m3. The old
installations use the central storage or bin-and-feeder system wherein the
prepared coals from several pulverisers were sent to a central bin for further
delivery to individual burners. Current practice employs the unit or direct-
fired system, in which the pulverisers directly feed the burners. The central
storage systems suffer from the risk of explosion of coal–air mixtures and
the tendency of the stored coal fines to granulate.
Depending upon the method of ash removal the PF furnaces may be
dry-bottom or slag-tap type. Dry furnaces are more common of the two. In
the dry-bottom furnace, the ash particles are cooled to below their softening
point. The smaller particles—about 85% of the total ash—are entrained in
the gas stream while the larger particles (15%) settle on the dry bottom of
the combustion chamber. The settled refuse is removed periodically or
continuously by a hydraulic system. Most of the fly ash is trapped in a
collecting system while about 2% of the total ash escapes into the
atmosphere. An electrostatic precipitator can ensure a total trapping of this
ash.
In the slag-tap PF furnace, the ash flows molten from the combustion
chamber into a tank of water below. It is converted into a suitable product
for road filling, as cement aggregate and for brick making. The rest of the
ash leaves the chamber as entrained particles. A collection system taps
most of the fly ash while the loss to the atmosphere is about 2%. With the
slag-tap type, coals with low ash fusion points present no difficulty while the
furnace allows a higher combustion temperature with a high heat release
rate. This type of furnace is not suitable for Indian coals with high ash fusion
points.
There are three different types of PF burners. They are based on the
method of firing: vertical, horizontal or tangential (Fig. 9.24).
Figure Pulverised coal firing
9.24
In vertical firing, several burners are located in the furnace arch. The
nozzle of each burner comprises a long narrow slot through which the coal–
primary air mixture is introduced into the furnace vertically downward. After
penetrating into a certain depth the flame reverses and then flows upward
to attain a fantail shape with large width but small thickness. The long axis
of the fantail is set at right angles to the front wall of the furnace. There are
thus several alternate lanes of flame and air space corresponding to the
number of burners. The nozzle is riffled so as to ensure turbulence.
Secondary air is supplied through ports in the front of the furnace. The
length and intensity of the flame can be widely varied by controlling the
points of secondary air supply. Tertiary air under pressure is admitted
around the nozzles to help regulate the point of ignition. The depth of the
flame travel may be adjusted by controlling the primary and tertiary air.
A horizontal PF burner essentially consists of a central coal nozzle
which has a series of internal directing ribs. The coal nozzle is surrounded
by a housing provided with adjustable vanes. The coal-primary air mixture
enters the nozzle tangentially at the rear. The directing ribs spiral the
mixture and assure its uniform composition over the periphery of the burner
outlet. Secondary air is given a spinning action by the adjustable vanes as it
flows through the housing around the coal nozzle. By controlling the
angularity of these vanes it is possible to control the turbulence and hence
the size and shape of the flame in the furnace. The burners are usually
located in the front or the rear furnace wall. Secondary air is supplied under
pressure.
In tangential firing, burners are located in each of the four corners of the
furnace and tangentially aimed to a small imaginary circle lying at a
horizontal plane at the centre. Intensive mixing occurs where the coal-air
streams meet and promote rapid combustion. Ignition at each burner is
aided by the flame from the preceding one. The whole furnace virtually acts
as the burner. Therefore, it is not necessary to accurately proportion the
coal-air mixture at individual burners. In some boiler designs, the burners
can be tilted up or down, primarily to control the superheated steam
temperature in case of variation in load.
The vertical firing leads to extended and progressive heat release and
thus provide a relatively uniform temperature distribution throughout the
furnace. It also furnishes a longer path of travel for fuel particles. Complete
combustion of low volatile coal is therefore ensured. Vertical firing is
especially good for high, narrow furnaces. These burners are not easily
adaptable for fuels other than coal.
Horizontal PF burners are capable of unusually high capacities—upto
400 kg coal per hour per burner. Therefore a lesser number of horizontal
burners are required compared to other methods of PF firing. This
considerably simplifies coal preparation and delivery system. The horizontal
PF burners can be quickly changed over from one fuel to another including
gas and oil. By installing the horizontal burners in both the front and back
furnace walls, high turbulence can be created and extra-high firing rates
achieved.
Tangential firing is the most effective method of achieving the high rate
of heat release with solid fuels—upto 0.5 million kcal/m3 per hour of the
combustion space. These burners are also readily adaptable for oil or gas
firing.
Although PF firing offers an efficient and intense method of combustion
—85% to 90% efficiency—of solid fuels of even inferior quality, high ash
and low rank coals and permits utilisation of coal slacks obtained during
mining, transportation and washing, it suffers from certain limitations and
undesirable features.
There are two serious disadvantages:
1. Large power requirement and maintenance cost for pulverisers,
2. Problems of fly ash such as erosion of boiler parts and induced dra
cost of collection of entrained particles and pollution of atmosphere.
These have generated increased interest for other methods of burning coal
in large installations.
9.4.4 CYCLONE FIRING
This method of burning coal is similar to PF firing in that it employs the

principle of combustion of coal particles in suspension. It is however, a step
forward and incorporates a number of advantages over PF firing. The
required degree of fineness is 95%, through 0.6 mm, which needs only
simple grinders. The rate of heat release is very high, 5 million kcal/m3 per
hour. The problems of low ash fusion point coal is solved by maintaining
more than 80% of the ash as a molten slag, and the problem of fly ash is
significantly decreased to about 10% of total ash.
A cyclone burner consists of a water-cooled horizontal cylinder of about
2.5 m diameter and 3.5 m length (Fig. 9.25). Coal and primary air, that is,
about 20% of total air, tangentially enter the burner at one end. Coal
particles thus have a whirling motion. Secondary air, which is 75% of total
air, is admitted in the same direction tangentially at the roof of the main
chamber and imparts a further whirling motion to the solid. A very fast
combustion ensures, and owing to the high rate of heat release gas
temperatures exceeding 1,600°C are developed. The ash melts into a liquid
slag and forms a layer on the walls. The incoming coal particles are thrown
by the centrifugal force on to the slag layer and stick to it while the fast
moving gases continue to apply a scrubbing action on them. This
contributes to the achievement of very high rates of heterogeneous
combustion of solid fuel. About 5% of total air is supplied as tertiary air at
the burner axis to aid the burning of coal fines in the core of the vortex
created by the whirling motion.
Figure Cyclone firing
9.25
The exit end of the burner has a re-entrant throat which reverses the
axial motion of the combustion gases and forces them radially inwards
before they leave the cyclone. The molten slag slowly but continually flows
down the wall toward the tap hole at the rear end. It is tapped into a slag
tank and then disposed of. The exit gases entrain relatively small quantities
of fly ash and enter into the main furnace chamber for delivering heat to the
cold surfaces. The particle size of the fly ash is so small that erosion of
heating surface (boiler tubes) is not experienced even at high gas velocities.
Cyclone burners are suitable for almost any grade of coal with minimum
fuel preparation. They are popular in medium to large installations. Although
they have a limited turndown ratio, large furnaces can be provided with a
number of such units. The independent operation of these points offers the
needed flexibility. Since Indian coals are characterised by high ash fusion
points, cyclone furnaces are not used in the country.
9.4.5 FLUIDISED BED COMBUSTION (FBC)
This is another method of burning coal in suspension. The coal is crushed

to an upper size of about 2–6 mm and fed to a refractory lined cylinder to
form a bed 0.5–2.0 m in depth. Air is supplied through a perforated
distributor plate at the bottom at a velocity of 0.4 to 4.0 m/s to form a
fluidised bed. In this state the coal-air system behaves like a fluid; it finds its
own level and has a hydrostatic head. A pressure drop of about 1 mm water
gauge per millimetre depth of bed, equivalent to the weight of particles, is
necessary to sustain fluidisation. Additional mass flow creates turbulence
and bubbles. Accompanying the building, particles are ejected from the bed.
Some fall back to the bed and others are carried out of the vessel with the
air stream. A clearance (freeboard) of about 3 m is provided at the top of
the bed to avoid undue loss of particles by splashing. Coal is continuously
fed to the bed via immersed nozzles fed by pneumatic pipelines.
The turbulence of a fluidised bed causes rapid mixing of the particles.
The rapid relative movement between particles and fluidising medium is
ideal for combustion of the particles. Temperatures range between 750 and
1,000°C, the lower level providing a reasonable margin above the minimum
required for maintenance of combustion and the upper temperature should
be such as to avoid sintering of ash particles. The burning rate of coal is
about 40–400 kg/m2 per hour of bed area, giving a heat release of 0.25 to
2.5 million kcal/m2 per hour. Ash may be removed from the bed by gravity
flow and also as mechanical carry over with the exit gas. Some fine coal is
also elutriated, measuring 2% to 10% of the input. This is recovered in a
cyclone and recycled to the bed. A high combustion efficiency of 97% or
more is achieved.
A distinct advantage in fluidised bed combustion system is that
tubes may be immersed in the bed and approximately half of the he
be removed and recovered by this means. A very high heat t
coefficient, 125 to 430 kcal/m2 C per hour prevails in the bed. The e
of the exit gases can be extracted by usual waste heat boiler systems
There is a great flexibility in the choice of coal feed for FBC system
high ash coals and even washery tailings are easily burnt.
There are several favourable environmental considerations

particulates from the fluidised combustor are coarser than from
burners and are therefore readily trapped in simple cyclones.
The sulphur in the coal is converted to sulphate in the prese

limestone or dolomite fed into the bed. There is therefore no s
emissions in the exit gas.
Since the bed temperature is below 1,000°C, little atmospheric nitro

converted to NOx. This form of pollution is thus less in compariso
conventional combustion.
Fluidised bed combustors are now commercially available in India and

abroad in applications like electricity generation and industrial boilers where
steam is the main product. There are also FBC systems where hot flue
gases are used to dry grass and other material. The FBC units discussed
above operate at atmospheric pressure. Attention is also being given to the
development of pressurised fluidised bed combustors at 6–12 atm for
electricity generation in the combined cycle of gas turbines and steam
turbines. Operation under pressurised conditions improves combustion
efficiency and sulphur retention while lowering the NOx emission; the whole
unit also becomes more compact.
BIBLIOGRAPHY
1. Bureau of Indian Standards, New Delhi.
2. Gas Engineers Handbook. New York: Industrial Press, 1966.
3. Giffen E and Muraszew A. The Atomisation of Liquid Fuels. L

Chapman and Hall, 1953.
4. Johnson AJ and Auth GH. Fuels and Combustion Handbook. New

McGraw-Hill, 1951. Tokyo: Mcgraw-Hill and Kogakusha, 1973.
5. Perry IH. Chemical Engineers’ Handbook, Fifth edition. Tokyo: McGr

and Kogakusha, 1973.
6. Sherman RA and Landry BA. Combustion Processes. In Lowry H

Chemistry of Coal Utilization, Supp. Vol. New York: Wiley, 1963.
7. Shindon L. Gaseous Fuels. Second edition. New York: America

Association, 1954.
8. Williams DA and Jones G. Liquid Fuels. London: Pergamon, 1963.
APPENDIX I
MEAN SPECIFIC HEAT OF GASES AT CONSTANT PRESSURE
BETWEEN 0°C AND T°C (Mass basis, kcal/kg, °C)
Note: Values for the undissociated gas. At temperatures above 1,500°C

dissociation must be taken into account.
APPENDIX 2
MEAN SPECIFIC HEAT OF GASES AT CONSTANT PRESSURE
BETWEEN 0°C AND T°C (Mass basis, kcal/kg, °C)
APPENDIX 3
ENTHALPY OF GASES ABOVE 0°C (Mass basis, kcal/kg)
APPENDIX 4
ENTHALPY OF GASES ABOVE 0°C (VOLUME BASIS, kcal/Nm3)
APPENDIX 5
EQUILIBRIUM CONSTANTS, Kp, OF SOME COMBUSTION
REACTIONS
Note: Carbon, where involved, is in the form of solid 8-graphite.
INDEX
A
aeration test burner, 349
agricultural wastes, 51
air
excess, 251
primary, 296
secondary, 296
tertiary, 366
theoretical, 251
air ports, 343
air ratio, 269, 270
air register, 342, 343, 355, 357
alcohols, 198
alkylation, 166
allochthonous theory, 65
angle of repose, 82
aniline point, 187
anthracite, 63
anti-knock, 186
API gravity, 157
ATB number, 349
atomisation mechanism of, 353
autochthonous theory, 65
B
bagasse, 51
Baum jig, 113
beehive coke oven, 130, 136
benzol
crude, 128, 130, 131, 136, 137, 142, 147, 197
motor, 190, 197
Bergius process, 190
Berrisford process, 110
biogas, 235, 236
biomass, 29, 47
bituminous coal, 56
black lignite, 56
blast furnace gas, 131, 203, 233
blast saturation temperature (BST), 216
blow-off, 331
boghead coal, 63
bomb calorimeter, 76, 184
Boudouard reaction, 212
briquetting, 105, 139
brown coal, 53, 139
bulk density
coal, 81, 82, 139
coke, 139
burner blast, 342
cyclone, 367
gas, 341
oil, 350
PF, 365
by-product coke oven, 233
by-products of coal carbonisation, 2, 49
C
caking, 35, 60, 79
caking index, 79s
calorific value, 34
calorific value of coal, 73, 77
Dulong formula for, 78, 79, 99, 100
Goutal formula for, 78, 99
calorific value
of gases, 349
of oils, 185
cannel coal, 63
carbon efficiency, 223
carbon monoxide–xygen reaction, 303
carbon residue
Conradson, 184
Ramsbottom, 177, 184
carbonisation
coal, 35
low temperature, 126–129, 141
high temperature, 126, 129, 130
wood, 48–50
carbonisation assay, 80, 89
carbonised briquettes, 141
cattle dung, 52
cetane number, 186
chain reactions, 299, 300, 302, 305
char, 50, 126, 140
char value, 183
charcoal, 47, 48
charcoal kiln, 49
chemical fuel, 1
clarain, 67
classifiers, 112
clay treatment, 172
clinker, 214
cloud point, 183
coal
action of heat on, 86
analysis of, 69–86
ash fusion range of, 71–73
burning equipment, 359
classification of, 75. 89, 92, 94, 95
cleaning (washing) of, 72, 73
composition of, 67, 72, 89, 95
consumption of, in India, 60
equivalent, 41
gas, 233
grading of, 96
liquid mixture, 143
measures, 56, 65, 66
mineral matter of, 53, 67, 72–74
oil mixture, 359
origin of, 64, 65
oxidation of, 89
petrography of, 67
preparation of, 105, 109
production of
in India, 58–61
in world, 58
properties of, 69–86
rank of, 35, 66, 70, 74, 76, 83, 90
rational analysis of, 68
refinery, 194
resources
India, 57, 98
world, 25
seam, 56, 59, 64, 67, 232
spontaneous inflammation of, 124, 126
storage of, 122, 124, 126
tar, 188, 194, 197
tar fuels (CTF), 188–191
washability characteristics of, 107, 118, 119
washer, 113
washer efficiency, 117, 118
washeries in India, 119–23
weathering of, 122, 124
coal–water mixture, 143, 359
coalfields in India, major, 64
coalification, 35, 90
coke
blast furnace, 125, 127, 132, 137
foundry, 137
gas, 137
hard, 35, 120, 123, 126, 130, 136, 137, 220, 225, 315
natural, 64
oven
beehive, 130, 136
by-product, 129–136
petroleum, 160, 164
oven gas, 130–138
properties of, 138
soft, 119, 123, 124, 126, 127, 129, 315
coking of coal, 35
by-products of, 131, 135
cold gas efficiency, 214, 222
colloidal fuel, 143
combustion
cyclone, 367
down-jet, 299, 364
efficiency of, 275
empirical correlations in, 267, 268
fluidised bed, 359, 368, 369
heat of, 274, 275, 279, 283
homogeneous, 298, 299
incomplete, 264–69
kinetics of, 319, 331, 333, 335, 336, 338, 339
mechanism of, 299, 303, 305, 306, 308, 310, 311, 321
pulsating, 397, 398
slow, 298, 300, 302, 305, 308, 309, 314
submerged, 297
surface, 297
theoretical products of, 251
thermodynamics of, 274
combustion of
carbon, 335, 338
carbon monoxide, 304
coal–water slurry, 359
hydrocarbons, 309
hydrogen, 299
liquid droplet, 332
liquid fuel in open vessel, 332
combustion on grate, 298
combustion stoichiometry
rapid methods of, 262
Conradson test, 184
cool flame, 305, 306, 308
cracking, 36
critical air blast test (CAB), 138
cross-feed firing, 360
cyclone washer, 116, 146
D
Davis lamp, 320
Dean and Stark method, 70, 185
deasphalting, 158, 170, 171, 173
degree API, 179
delay period, 186, 300
dense medium separator, 112–114
deoiling, 174
desulphurisation, 170, 173
detonation, 185, 297, 316
dew point of flue gases, 259
dewaxing, 158, 168, 171, 173, 174
diesel fuel
specifications for, 177
diesel index, 187
diffuser, 342, 347, 355–57
diffusion mechanism, 316, 317
dissociation reactions, 276, 281–283
distillation of petroleum, 159, 182
doctor test, 169, 170
down-jet combustion, 299
Dulong formula, 78
durain, 67
E
Edeleanu process, 171
EDS process, 193
energy from biomass
energy resources of world, 1
enthalpy of combustion system
of gases, 369
enthalpy–temperature diagrams, 281
equilibrium constants of combustion reactions, 279
Eschka method, 76
excess air factor (ratio), 252, 264, 270, 271
excess air per cent, 258
exinite, 68
explosion
limits, 302–5
peninsula, 303
F
firedamp, 211
fire point, 35, 182
Fischer–Tropsch process, 143, 194
flame
concentration profile of, 328.
cool, 298, 305, 306, 308
diffusion, 296, 297, 327–30
explosion, 297, 298
front, 286–98, 308, 315–17, 325–27, 331–33
holder, 340, 350
laminar, 296, 297, 325, 326–331
length of, 327, 329, 330,
over-ventilated, 327, 329
premixed, 296, 325, 326
propagation of, 316, 320, 322
shape of, 325, 327
stability of, 331
stationary, 296–98, 316–19
structure of, 325, 327
temperature
maximum adiabatic, 283
thickness of, 317
turbulent, 296, 325–31, 338
under-ventilated, 327
velocity of, 315, 316, 318–21, 326, 331
width of, 317, 326
flash-back, 331
flash point, 35
flue gas
dew point of, 259
theoretical, 263–69
flyash, 73, 363
foundry coke, 137
froth flotation, 116
fuel
cell, 295
chemical, 1
conventional, 1, 208, 209
fossil, 1, 13, 15, 17, 23, 25, 56, 63, 105, 198, 211
industrial, 128, 137, 139, 140, 211, 229, 282
non-fossil domestic fuels, 51
nuclear, 1–5, 12–15, 23–28
oil
potential heat of, 215, 216, 222, 224, 234. 275–79, 297
rocket, 1
furnace,
dry-bottom, 365
slag-tap, 365
fusain, 67, 68, 72
fusinite, 68
G
gas
gun, 342, 343, 356
lean, 132, 133, 138, 204, 211, 233
port, 342
rich, 327, 132, 133, 136, 138, 204, 243
burner
aerated (atmospheric), 341, 346, 347, 349, 350,
aeration capacity of, 348
air aspiration, 341, 342
characteristic curves of, 347
fanmix, 343, 344
flameless, 344
nozzle-mix, 341–343, 347
pipe, 342, 344, 345
premix, 340–342, 347
pulsating, 344, 345
ring, 343
submerged, 345, 346
torch, 343, 345
gas oil, 159, 162–65
gas producers, types of, 221
gas retort, 129, 130, 221, 233
gaseous fuel
classification of, 204
cleaning and purification of, 243
composition and properties of, 243
paraffins in, 205
unsaturates in, 233
gasification
complete (total), 227, 228
efficiency of, 227, 228, 231, 234
Koppers–Totzek, 230
liquid fuels, of, 200
Lurgi, 227–29
oil, 238–40
partial combustion (oxidation) process of, 242
rate of, 228
Texaco, 231
underground, 232, 33
Winkler, 229, 30
gasoline
natural, 175, 205
specifications for motor, 175
geothermal energy, 1
Girbotal process, 244
glow limits, 304
Gondwana coalfields, 63, 65
Goutal formula, 78, 99
Gray–King coke type, 80, 95
H
handfiring, 359
hardgrove grindability index, 85
H-coal process, 193
heat of combustion, 274
heat of dissociation, 281
heat of wetting, 82–84
Hilt’s law (rule), 66
hot gas efficiency, 222
Ht-diagram, 282, 283
Houdry process, 162
hydrocarbon–oxygen reaction, 305
hydrocracking, 167
hydrogen–oxygen reaction, 301
hydrogenation of coal, 89
hydrogenation of coal tar, 89
hydrogenation of petroleum, 167, 242
I
ignition lag, 300
ignition temperature, 34
illuminants, 296
induction period, 300, 301, 313, 314
isomerisation, 157, 162, 165–67
It-diagram (see Ht-diagram)
J
jet fuels, 170, 176
jet velocity, 328–30
jhama, 64
jig washer, 113
K
Karlfischer test, 185
kerogen, 198
kerosene
Kjeldahl method, 76
KMC formula, 73
knocking, 185, 186, 208, 308
Koppers–Totzek gasifier, 230
L
Liebig’s method, 74
lignite
black, 56
limits of glow, 303
limits of inflammability, 320–25
Le Chatelier’s formula in, 321, 324
liquefaction of solid fuels, 142
liquefied natural gas (LNG), 9, 208
liquefied petroleum gases (LPG), 237
lubricants, 156, 157, 159, 178, 183, 188
Lurgi–Spiil gas LT carboniser, 128
M
magneto-hydrodynamic (MHD) generator, 295
mechanical stoker, 359, 360
methanation reaction, 215, 223, 227
micrinite, 68, 84
Micum test, 138
montan wax, 52, 55
motor gasoline
N
naphtha, 159
natural coke, 64
natural gas
consumption of, 3–5, 8, 9, 24
world reserves of, 5, 8
near-gravity material, 109, 114, 119, 145
Neumann reversal reaction, 214
non-fossil solid fuels, 51
nuclear power, 25
O
octane number, 185
oil burner, 350
atomising, 352, 353, 356, 357
drip feed system, 358
high-speed vaporising, 352
inside-mix, 356
outside-mix, 356
pot-type, 351
pressure jet atomising, 353, 356
rotary atomising, 353, 357, 358
swirl-type, 354
twin-fluid atomising, 353, 356
vaporising, 350–352
wall-wiping flame-type, 351, 352
wick-type, 350, 351
wide range pressure jet, 355
orsat analysis, 36
Ostwald charts, 269
overfeed firing, 360
P
Parr formula, 73
peat, 52
petroleum
classification of, 155
common fractions of, 160
composition of, 155
consumption of, 188, 190
nature of Indian crudes, 157
occurrence, 147
origin of, 151
processing of, 237
production of, 188
reserves in India, 148
topping of, 159
world proved reserves of, 6, 148
petroleum products
distillation range of, 182
properties and testing of, 178
purification of, 167–74
storage and handling of, 200
petroleum refining in India, 187
pipe-still, 161
pneumatic table, 109
polymerisation, 166
potential heat, 275
pour point, 183
primary tar, 128
producer gas, 211
proximate analysis, 33
pulverised coal firing, 365, 366
horizontal, 366, 367
tangential, 366, 367
vertical, 365–367
pyroligneous acid, 48
R
Ramsbottom test, 184
Rectisol process, 195
reduced crude, 237
refinery gases, 237
reforming
steam, 193, 233, 240, 242
residue (petroleum)
long, 159
short, 158, 160
resinite, 68
retorts
charcoal, 50
continuous vertical, 129
Rheolaveur launder, 111
rocket fuels, 1
run-of-mine (ROM) coal, 36
S
SASOL plant, 195
Seaboard process, 244
Semenov’s equation, 313
semi-anthracite, 63
semi-coke, 61, 88
semi-water gas, 225
shale oil, 198
shatter test, 138
shell phosphate process, 244
SI units, 41
slagging producer, 220, 221
slag-tap furnace, 365
smoke, 340, 341, 364
smoke point, 183
solar energy, 1
solvent extraction, 170
specific heat of coal, 84
spirit, crude, 127
spontaneous ignition temperature (SIT), 309, 315, 332
spontaneous inflammation, 124, 126
spray angle, 354, 358
stabilisation of petroleum products, 161
stoichiometry of combustion, 250
stokers
archless, 361, 363
chain-grate, 361, 362
coking, 362
over-feed, 360
spreader, 360, 363
sprinkler, 363
travelling-grate, 361–63
under-feed, 360, 361
vibrating-grate, 362
storage of
solid fuels, 122
liquid fuels, 200
sub-bituminous coal, 56
substitute natural gas (SNG), 203, 229
sulphur in
coal, 73–78
petroleum, 155, 157, 158
surplus hydrogen, 78
sweating process, 174
sweetening process, 169
swelling index, free, 79
T
tar sand, 199
tetraethyl lead (TEL), 186
Texaco gasification process, 231
theoretical air, 251, 268
theoretical products of combustion, 251
thermal mechanism, 301
Thylox process, 244
tidal power, 1
Tromp shallow bath, 114, 315
turbulence
intensity of, 320, 337
scale of, 326, 330
turndown ratio, 347, 355–58, 368
U
Udex process, 171
ulmins, 68
ultimate analysis, 33
underfeed firing, 299
underground gasification, 232
unit coal, 37
V
rectisol velocity of flame propagation, 315
visbreaking, 164
viscometer conversion factors, 180
viscosity index, 181
vitrain, 67
vitrinite, 68
W
water gas,
blue, 223
carburetted, 200, 223, 225–27, 250, 322
semi-, 225
double, 225, 227
reaction, 215
shift reaction, 233
water of hydration of minerals, 34, 76, 246
weaver flame speed factor, 204
Winkler gasifier, 230
wind power, 29
Wobbe index, 204
wood
charcoal from, 48–50
gas from, 234
wood spirit, 48
wood tar, 48
wood wastes, 50

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Universities Press (India) Private Limited

© Universities Press (India) Private Limited 2009

e-edition: First Published 2022

eISBN: 978 93 89211 38 2

May 2009 Samir Sarkar

Primarily meant for students as a textbook, Fuels and Combustion

December 1988 Samir Sarkar

‘Fuels and Combustion’ forms an integral part of the undergraduate

2 Definitions, Units and Measures

4 Processing of Solid Fuels

7 Combustion Process (Stoichiometry and Thermodynamics)

8 Combustion Process (Kinetics)

1.1 ENERGY AND ENERGY RESOURCES

A fuel is basically a source of heat. The usual method of producing heat

The second group consists of the resources that are currently us

Energy is primarily used by four different sectors.

3. Industrial: Energy is used in factories, industrial complexes, resear

The energy requirements of the advanced countries are almost equally

Table 1.2 shows the estimated world oil resources by country as of 1

1.2.2 NATURAL GAS

Table 1.4 World natural gas reserves by country as of 1 January 2007

Consumption of natural gas is projected to increase on an average by

1.3 ENERGY: CONSUMPTION AND DEMAND

Total world delivered energy consumption by end-use sector and fuel,

1.3.1 RESIDENTIAL SECTOR

The following information is derived from a combination of Tables 1.8 and

Household energy use increases more rapidly in the non-OECD

1.3.2 COMMERCIAL SECTOR

The commercial sector, or the services sector, consists of business

1.3.3 INDUSTRIAL SECTOR

Energy is consumed in the industrial sector by several industries, including

In the non-OECD countries, energy consumption by the industrial sector

Energy demand in the non-OECD transportation sector as a whole

1.4 ELECTRICITY: CONSUMPTION AND GENERATION

1.4.1 CONSUMPTION OF ELECTRICITY

Figure 1.8 World electric power generation, 2004-2030 (billion kilowatt-hours)

1.4.2 FUELS USED FOR GENERATION OF ELECTRICITY

Coal has remained a dominant fuel, although electricity generation from

In the non-OECD nations, the use of natural gas in generation of total

Coal retains the largest market share in global electricity generation

Hydroelectricity and renewable energy

The IEO 2006 projections for hydroelectricity and other renewable

WORLD POPULATION BY REGION , REFERENCE CASE, 1990–2030

1. International Energy Outlook 2006, June 2006, Energy Inform

2. International Energy Outlook 2007, June 2006, Energy Inform

3. Advisory Board on Energy, Govt. of India, Towards a Perspective on En

5. Loftness, RL. Energy Handbook, New York: Van Nostrand , 1978.

6. Oil And Gas Journal, 30 December, 1985.

7. Putnam PG. Energy in the Future, Princeton: Van Nostrand, 1985.

9. Sutton GP and Ross DM. Rocket Propulasion Elements, Fourth ed.

10. Energy Statistics Yearbook. United Nations. New York, 1985.

11. Van Krevelen, DW. Coal. Amsterdam: Elsevier, 1961.

12. World Coal, Vol 7, No. 7 (Nov./Dec. 1981).

A systematic study of fuels and combustion requires a prior knowledge of

Fixed carbon is the residue obtained by subtracting the sum of the

The ultimate analysis of a fuel gives its elementary composition. It is the

Gross calorific value (higher heating value) at constant volume is the

Gross calorific value at constant pressure is similar to the former

Net calorific value (lower heating value) at constant volume is the