FUELS

WHAT IS A FUEL
A fuel is a substance that may be burned in air (or any other oxidant-containing substance), i.e. that so
quickly reacts with oxygen that heat and light is emitted in the form of a sustained flame. Although the
chemical reactions of wood in air, animal-fat in air, coal in air, natural gas in air (approximated by
CH4/O2/N2), hydrogen in oxygen (H2/O2), silicon in oxygen (Si/O2), sodium in chlorine (Na(s)/Cl2(g)),
zirconium powder in carbon dioxide (Zr/CO2), nitrocellulose (-(C6H10O5)n- with n=300..2000) in any
medium, etc., are all of the same chemical type (self-propagating highly-exothermic re-dox reactions, i.e.
combustion processes), usually 'fuels' and 'combustion' only refer to easily flammable substances in air (the air
is the oxidiser needed by a fuel to burn, and it is needed in larger quantities than fuels, so, a first glance on it
seems appropriate).
Some of the basic requirements of a fuel include: high energy density (content), high heat of
combustion (release), good thermal stability (storage), low vapor pressure (volatility) and non-toxicity
(environmental impact).

THE OXIDISER
Oxygen in the air is the basic oxidant for fuels: nitrogen is basically inert, although it combines
endothermically with oxygen at high temperatures to get the unwanted NOx pollutants. The most abundant
element on Earth's crust is oxygen, with 47%wt. It is also the most abundant in the hydrosphere, 86%wt. In
the atmosphere, it is second to nitrogen, with 23%wt. In the whole ecosphere it is the first with 50%wt, and in
the whole planet Earth it has 30%wt, only after Fe, 40%wt). Oxygen is then readily available from Earth's
atmosphere; that is why it is the main oxidiser. Silicon follows as most abundant in the crust (28 %wt), but
most natural Si-compounds are already fully oxidised, as sand (SiO2) and silicate rocks (like CaO3Si); there is
no silane gas (SiH4) free in Nature. Aluminium follows (8 %wt), but again the main Al-compounds are
already fully oxidised, as bauxite (Al2O3) and silicates like Al2O3Si.
As for the fuels, hydrogen, the most abundant element of the Universe, is scarcely available in the
ecosphere, mainly fully oxidised as water in the hydrosphere, where it comprises only a 3%wt, and only
0.9%wt in the whole Earth crust; the ninth most abundant element).

FUEL CLASSIFICATION
Fuels can be classified according to wheter :
1. They occur in nature called primary fuels or are prepared called secondary fuels;
2. They are in solid, liquid or gaseous state.

Table 1. Natural and Manufactured Fuels

1|Page
I. SOLID FUELS are mainly classified into two categories, i.e. natural fuels, such as wood, coal, etc. and
manufactured fuels, such as charcoal, coke, briquettes, etc.
The various advantages and disadvantages of solid fuels are given below:
 Advantages
1. They are easy to transport.
2. They are convenient to store without any risk of spontaneous explosion.
3. Their cost of production is low.
4. They posses moderate ignition temperature.
 Disadvantages
1. Their ash content is high.
2. Their large proportion of heat is wasted.
3. They burn with clinker formation.
4. Their combustion operation cannot be controlled easily.
5. Their cost of handling is high.
NATURAL SOLID FUELS
1. WOODS AND ITS CHARACTERISTICS
The most commonly used and easily obtainable solid fuel is wood. It is the oldest type of fuel which
man had used for centuries after the discovery of the fire itself. Wood is vegetable tissue of trees and
bushes. It consists of mainly cellular tissue and lignin and lesser parts of fat and tar, as well as sugar.
a. Ash The ash content of wood is negligible. The ash consists of mineral water that is found in the
wood itself, with an admixture of some impurities which accure during transportation, etc.
b. Moisture A freshly felled tree anything from 40% to 60% of hygroscopic moisture depending
upon the species of the tree as well as the seasons of the year.
c. Characteristics of Flame The nature of the flame depends on the tar content of wood. The length
of the flame also depends on the tar content.
d. Combustion Characteristics The lighter the wood, the more intensely it burns with a long flame.
e. Ignition Temperature Wood ignites very easily. That is why it is used for lighting other fuels.

2. COALS AND THEIR CHARACTERISTICS

Coal is a heterogeneous mineral consisting principally of carbon, hydrogen and oxygen with lesser
amounts of sulfur and nitrogen. Other constituents are the ash- forming inorganic compounds
distributed throughout coal.
Its main constituents are carbon, hydrogen, oxygen, nitrogen, sulphur, moisture and ash. Coal
passes through different stages during its formation from vegetation. These stages are enumerated and
discussed below :
Plant debris—Peat—Lignite—Brown coal—sub-bituminous coal—Bituminous coal—
Semibituminous coal—Semi-anthracite coal—Anthracite coal—Graphite

Figure 1. Types of Coal

2|Page
 2.1 Types of Coal
a. Peat. It is the first stage in the formation of coal from wood. It contains huge amount of moisture
and therefore it is dried for about 1 to 2 months before it is put to use. It is used as a domestic fuel in
Europe and for power generation in Russia. In India it does not come in the categories of good fuels.

b. Lignites and brown coals. These are intermediate stages between peat and coal. They have a
woody or often a clay like appearance associated with high moisture, high ash and low heat contents.
Lignites are usually amorphous in character and impose transport difficulties as they break easily.
They burn with a smoky flame. Some of this type are suitable for local use only.

c. Bituminous coal. It burns with long yellow and smoky flames and has high percentages of volatile
matter. The average calorific value of bituminous coal is about 31350 kJ/kg. It may be of two types,
namely caking or noncaking.

d. Semi-bituminous coal. It is softer than the anthracite. It burns with a very small amount of smoke.
It contains 15 to 20 per cent volatile matter and has a tendency to break into small sizes during storage
or transportation.

e. Semi-anthracite. It has less fixed carbon and less lustre as compared to true anthracite and gives
out longer and more luminous flames when burnt.

f. Anthracite. It is very hard coal and has a shining black lustre. It ignites slowly unless the furnace
temperature is high. It is non-caking and has high percentage of fixed carbon. It burns either with very
short blue flames or without flames. The calorific value of this fuel is high to the tune of 35500 kJ/kg
and as such is very suitable for steam generation

Table 2. Types of Coal and its Composition

2.2 Coal Properties

The basis of an analysis helps to specify the conditions under which the coal is tested.
The coal sample may be freshly taken from the mine, the as-mined basis. It may have resided in a coal pile
for months, and be analyzed just before burning, the as-fired basis. It may be examined immediately
after transport from the mine, the as-received basis.

a. Moisture content
The moisture content of coals ranges from about 5% to almost 70%. Moisture is an undesirable
constituent of coals because it reduces the heating value (water does not burn!) and its weight adds to
the transportation costs of coal. Moisture content is determined by heating an air-dried coal sample at
105–110 °C (221– 230 °F) under specified conditions until a constant weight is obtained. In general,

3|Page
 the moisture content increases with decreasing rank and ranges from 1 to 40 percent for the various
ranks of coal.

b. Volatile matter content

When a coal sample that has been dried to remove its moisture is heated in the absence of air -
so that it doesn't burn - a further weight loss is observed. The material driven out is called volatile matter. The
volatile matter content of coals, measured in the absence of moisture and ash, ranges from 2% to about
50%. Volatile matter is material that is driven off when coal is heated to 950 °C (1,742 °F) in the
absence of air under specified conditions. It is measured practically by determining the loss of weight.
Consisting of a mixture of gases, low-boiling-point organic compounds that condense into oils upon
cooling, and tars, volatile matter increases with decreasing rank. In general, coals with high volatile-
matter content ignite easily and are highly reactive in combustion applications.

c. Mineral (ash) content

Coal contains a variety of minerals in varying proportions that, when the coal is burned, are
transformed into ash. The amount and nature of the ash and its behaviour at high temperatures affect
the design and type of ash-handling system employed in coal-utilization plants.

d. Fixed-carbon content
Fixed carbon is the solid combustible residue that remains after a coal particle is heated and the
volatile matter is expelled. The fixed-carbon content of a coal is determined by subtracting the
percentages of moisture, volatile matter, and ash from a sample. Since gas-solid combustion reactions
are slower than gas-gas reactions, a high fixed-carbon content indicates that the coal will require a long
combustion time. The fixed carbon content of coals, not including the moisture and ash, ranges
from 50% to about 98%. The anthracites, which contain a high proportion of fixed carbon and are a
popular domestic heating fuel, may be difficult to ignite but they will often burn steadily for a long time with
a short, clean flame.

e. Calorific value
Calorific value, measured in British thermal units or megajoules per kilogram, is the amount of
chemical energy stored in a coal that is released as thermal energy upon combustion. Of the
components determined by proximate analysis, only the volatile matter and the fixed carbon actually
burn and liberate thermal energy. Since the moisture and ash contents of coals can be quite variable
from one coal to another, and will further depend on whether the coal was partially dried or ‘cleaned’
to remove some inorganic debris, any comparison of coals on the basis of the combustible material
must be corrected for the presence of moisture and ash. Similarly, the heating value is lowered by the
presence of non-combustible moisture and ash. Comparing only the combustible part of coals requires
that we know the heating value unaffected by moisture or ash. To make such comparisons, we correct
the values of fixed carbon, volatile matter and calorific value to a moisture- and ash-free basis.
Knowledge of properties of coals on a moisture- and ash-free basis allows us to classify (or rank)
coals. The table below shows the different variation in properties depending upon the type of coal.

Figure 2. Classifications of Coal by Rank

4|Page
2.3 Coal Utilization

There are three major pathways for coal utilization. The principal process by which coal is used is combustion
as shown in the figure below.

Figure 3. Pathways to Coal Utilization

1. Combustion involves burning the coal in air to liberate thermal energy (heat). The heat is used as such for
comfort or to carry out many industrial processes that require high temperatures; it is also used to generate
steam for use in electric power plants.

2. Carbonization is the heating of coal to high temperatures in the absence of air; it is used in manufacturing
coke for the metallurgical industry.

5|Page
3. Conversion uses various chemical processes to transform coal into gaseous or liquid fuels, called synthetic
fuels. Common to all these processes is prior mining of the coal, its preparation (processing) and its
transportation to the consumers.

MANUFACTURED SOLID FUELS

1. Charcoal and its Characteristics
derived from destructive distillation of wood, being left in the shape of solid residue.
-burns rapidly with a clear flame, producing no smoke and developing heat of about 6,050 cal/kg.

2. Coke and its Characteristics

-obtained from destructive distillation of coal, being left in the shape of solid residue.
- Soft coke is obtained as the solid residue from the destructive distillation of coal in the temperature
range of 600-650oC. It contains 5 to 10% volatile matter & burns without smoke.
- Hard coke is obtained as solid residue from the destructive distillation of coal in the temperature
range of 1200-1400oC. It burns with smoke and is a useful fuel for metallurgical process.

3. Briquettes and their Characteristics

The term briquettes is used in respect of the dust, culm, slack and other small size waste remains of
lignite, peat, coke, etc. compressed into different shapes of regular form, with or without binder.

TESTING ANALYSIS OF SOLID FUELS

1. Proximate Analysis determination of the thermal energy released when the coal is burned. Determines the
moisture, volatile combustible matter, fixed carbon and ash content. This analysis of coal gives good
indication about heating and burning properties of coal.

2. Ultimate Analysis This analysis of coal is more precise way to find the chemical composition of coal with
respect to the elements like carbon, hydrogen, oxygen, nitrogen, sulphur and ash. Carbon and hydrogen are the
principal combustible elements in coal. On a weight basis, carbon is the predominant one. It constitutes about
60% to about 95% of the total. For most coals of 90% or less carbon, hydrogen content is generally in the
range of 5%; it drops to about 2% for coals having 95% carbon. Nitrogen content of almost all coals is in the
range of 1-2%. Oxygen content is inversely related to carbon content. For example, coals of 65% carbon may
contain 30% oxygen, while coals of 95% carbon may contain only 2-3% oxygen; this is significant because
the more oxygen a coal contains, the easier it is to start to burn it, or to achieve its ignition. Sulfur content of
coals is seen to be quite variable.

II. LIQUID FUELS

 Advantages
(a) They posses higher calorific value per unit mass than solid fuels.
(b) They burn without dust, ash, clinkers, etc.
(c) They are easy to transport through pipes.

 Disadvantages
(a) The cost of liquid fuel is relatively much higher as compared to solid fuel.
(b) Costly special storage tanks are required for storing liquid fuels.
(c) There is a greater risk of fire hazards, particularly, in case of highly inflammable and volatile liquid fuels.

Petroleum or crude oil is a basic fossil fuel. It is a dark greenish brown, viscous mineral oil, found deep in
earth’s crust. It is mainly composed of various hydrocarbons (like straight chain paraffins, cycloparaffins or
napthenes, olefins, and aromatics) together with small amount of organic compounds containing oxygen
nitrogen and sulphur. Although much depends on its type (paraffinic, naphthenic, asphaltic), an average crude
oil could lead to 20 to 30 % of gasoline 30 to 45 % of intermediate fractions 25 to 50 % of residual fuel oil.
6|Page
2.1 Classification of Petroleum
The chemical nature of crude petroleum varies with the part of the world in which it is found. They appear,
however, to be three principal verities.
 Paraffinic Base Type Crude Petroleum This type of petroleum is mainly composed of the saturated
hydrocarbons from CH4 to C35 H72 and a little of the napthenes and aromatics. The hydrocarbons
from C18 H38 to C35 H72 are sometimes called waxes. 44
 Asphalitc Base Type Crude Petroleum It contains mainly cycloparaffins or napthenes with smaller
amount of parffins and aromatic hydrocarbons.
 Mixed Base Type Crude Petroleum It contains both paraffinic and asphaltic hydrocarbons and are
generally rich in semi-solid waxes.

2.2 Petroleum Products

A fractional distillation column is used to separate petroleum into its various constituents. This process is
shown schematically in Fig. 2. Liquid crude oil is gasified and enters near the bottom of the distillation
column. The heavier fractions have higher boiling points and condense out at the higher temperatures in the
lower part of the column, while the lighter fractions condense out at the lower temperatures in the upper
portion of the column. Some of the common fuels produced in this manner are gasoline, kerosene, jet engine
fuel, diesel fuel, and fuel oil.
Figure 4. Fractional Distillation Column

The products refined from the liquid fractions of crude oil can be placed into ten main categories. These main
products are further refined to create materials more common to everyday life. The main products of
petroleum are:

7|Page
1. Asphalt Asphalt is commonly used to make roads. It is a colloid of asphaltenes and maltenes that is
separated from the other components of crude oil by fractional distillation. Once asphalt is collected, it is
processed in a de-asphalting unit, and then goes through a process called “blowing” where it is reacted with
oxygen to make it harden. Asphalt is usually stored and transported at around 300° Fahrenheit.

2. Diesel Diesel is any fuel that can be used in a diesel engine. Diesel is produced by fractional distillation
between 392° Fahrenheit and 662° Fahrenheit. Diesel has a higher density than gasoline and is simpler to
refine from crude oil. It is most commonly used in transportation.

3. Fuel Oil Fuel oil is any liquid petroleum product that is burned in a furnace to generate heat. Fuel oil is also
the heaviest commercial fuel that is produced from crude oil. The six classes of fuel oil are: distillate fuel oil,
diesel fuel oil, light fuel oil, gasoil, residual fuel oil, and heavy fuel oil. Residual fuel oil and heavy fuel oil are
known commonly as navy special fuel oil and bunker fuel; both of these are often called furnace fuel oil.

4. Gasoline Almost half of all crude oil refined in the United States is made into gasoline. It is mainly used as
fuel in internal combustion engines, like the engines in cars. Gasoline is a mixture of paraffins, naphthenes,
and olefins, although the specific ratios of these parts depends on the refinery where the crude oil is processed.
Gasoline refined beyond fractional distillation is often enhanced with iso-octane and ethanol so that it is
usable in cars. Gasoline is called different things in different parts of the world. Some of these names are:
petrol, petroleum spirit, gas, petrogasoline, and mogas.
5. Kerosene Kerosene is collected through fractional distillation at temperatures between 302° Fahrenheit and
527° Fahrenheit. It is a combustible liquid that is thin and clear. Kerosene is most commonly used as jet fuel
and as heating fuel. In the early days of oil, kerosene replaced whale oil in lanterns. In the early 21st century,
kerosene was used to power New York City Transit buses. Now, kerosene is used as fuel in portable stoves,
kerosene space heaters, and in liquid pesticides.

6. Liquefied Petroleum Gas Liquefied petroleum gas is a mixture of gases that are most often used in heating
appliances, aerosol propellants, and refrigerants. Different kinds of liquefied petroleum gas, or LPG, are
propane and butane. At normal atmospheric pressure, liquefied petroleum gas will evaporate, so it needs to be
contained in pressurized steel bottles.

7. Lubricating Oil Lubricating oils consist of base oils and additives. Mineral oils are manufactured by
special processes called: solvent extraction, catalytic dewaxing, hydrocracking, and isohydromerization.
Different lubricating oils are classified as paraffinic, naphthenic, or aromatic. Lubricating oils are used
between two surfaces to reduce friction and wear. The most commonly-known lubricating oil is motor oil,
which protects moving parts inside an internal combustion engine.

8. Paraffin Wax Paraffin wax is a white, odorless, tasteless, waxy solid at room temperature. The melting
point of paraffin wax is between 117° Fahrenheit and 147° Fahrenheit, depending on other factors. It is an
excellent electrical insulator, second only to Teflon®, a specialized product of petroleum. Paraffin wax is used
in drywall to insulate buildings. It is also an acceptable wax used to make candles for the Jewish Menorah.

9. Bitumen Bitumen, commonly known as tar, is a thick, black, sticky material. Refined bitumen is the
bottom fraction obtained by the fractional distillation of crude oil. This means that the boiling point of
bitumen is very high, so it does not rise in the distillation chamber. The boiling point of bitumen is 977°
Fahrenheit. Bitumen is used in paving roads and waterproofing roofs and boats. Bitumen is also made into
thin plates and used to soundproof dishwashers and hard drives in computers.

9. Petrochemicals Petrochemicals are the chemical products made from the raw materials of petroleum.
These chemicals include: ethylene, used to make anesthetics, antifreeze, and detergents; propylene, used to

8|Page
produce acetone and phenol; benzene, used to make other chemicals and explosives; toluene, used as a solvent
and in refined gasoline; and xylene is used as a solvent and cleaning agent..

10. Jet fuel Jet fuel is a type of aviation fuel designed for use in aircraft powered by gas-turbine engines. It is
clear to straw-colored in appearance. The most commonly used fuels for commercial aviation are Jet A and Jet
A-1 which are produced to a standardized international specification. Jet fuel is a mixture of a large number of
different hydrocarbons. The range of their sizes (molecular weights or carbon numbers) is restricted by the
requirements for the product, for example, freezing point or smoke point. Kerosene-type jet fuel (including Jet
A and Jet A-1) has a carbon number distribution between about 8 and 16 carbon numbers; wide-cut or
naphtha-type jet fuel (including Jet B), between about 5 and 15 carbon numbers.

2.3 Properties of Petroleum

The elemental composition of petroleum is much less variable than that of coal: 83-87% carbon, 11-
16% hydrogen, 0-4% oxygen plus nitrogen, and 0-4% sulfur. Note that most crude oils contain substantially
more hydrogen than coals. Only a brief discussion is needed here regarding the distribution of these elements
among the thousands of compounds found in petroleum

1. Density This is defined as the ratio of the mass of the fuel to the volume of the fuel at a reference
temperature of 15°C. Density is measured by an instrument called hydrometer. The knowledge of density is
useful for quantity calculations and assessing ignition quality. The unit of density is kg/m3 .

2. Specific gravity This is defined as the ratio of the weight of a given volume of oil to the weight of the same
volume of water at a given temperature. The density of fuel, relative to water, is called specific gravity. The
specific gravity of water is defined as 1. Since specific gravity is a ratio, it has no units. The measurement of
specific gravity is generally made by a hydrometer.
Specific gravity is used in calculations involving weights and volumes. The specific gravity of various fuel
oils are given in Table 1.1

3. Viscosity The viscosity of a fluid is a measure of its internal resistance to flow. Viscosity depends on
temperature and decreases as the temperature increases. Any numerical value for viscosity has no meaning
unless the temperature is also specified. Viscosity is measured in Stokes / Centistokes. Sometimes viscosity is
also quoted in Engler, Saybolt or Redwood. Each type of oil has its own temperature - viscosity relationship.
The measurement of viscosity is made with an instrument called Viscometer. Viscosity is the most important
characteristic in the storage and use of fuel oil. It influences the degree of pre-heat required for handling,
storage and satisfactory atomization. If the oil is too viscous, it may become difficult to pump, hard to light the
burner, and tough to operate. Poor atomization may result in the formation of carbon deposits on the burner
tips or on the walls. Therefore pre-heating is necessary for proper atomization.

4. Flash Point The flash point of a fuel is the lowest temperature at which the fuel can be heated so that the
vapour gives off flashes momentarily when an open flame is passed over it. Flash point for furnace oil is 66o
C.

5. Pour Point The pour point of a fuel is the lowest temperature at which it will pour or flow when cooled
under prescribed conditions. It is a very rough indication of the lowest temperature at which fuel oil is readily
pumpable
9|Page
6. Specific Heat Specific heat is the amount of kcals needed to raise the temperature of 1 kg of oil by 1o C.
The unit of specific heat is kcal/kgo C. It varies from 0.22 to 0.28 depending on the oil specific gravity. The
specific heat determines how much steam or electrical energy it takes to heat oil to a desired temperature.
Light oils have a low specific heat, whereas heavier oils have a higher specific heat.

7. Calorific Value The calorific value is the measurement of heat or energy produced, and is measured either
as gross calorific value or net calorific value. The difference being the latent heat of condensation of the water
vapour produced during the combustion process. Gross calorific value (GCV) assumes all vapour produced
during the combustion process is fully condensed. Net calorific value (NCV) assumes the water leaves with
the combustion products without fully being condensed. Fuels should be compared based on the net calorific
value.

8. Sulphur The amount of sulphur in the fuel oil depends mainly on the source of the crude oil and to a lesser
extent on the refining process. The normal sulfur content for the residual fuel oil (furnace oil) is in the order of
2-4 %. The main disadvantage of sulphur is the risk of corrosion by sulphuric acid formed during and after
combustion, and condensing in cool parts of the chimney or stack, air pre heater and economiser.

9. Ash Content The ash value is related to the inorganic material in the fuel oil. The ash levels of distillate
fuels are negligible. Residual fuels have more of the ash-forming constituents. These salts may be compounds
of sodium, vanadium, calcium, magnesium, silicon, iron, aluminum, nickel, etc. Typically, the ash value is in
the range 0.03-0.07 %. Excessive ash in liquid fuels can cause fouling deposits in the combustion equipment.
Ash has erosive effect on the burner tips, causes damage to the refractories at high temperatures and gives rise
to high temperature corrosion and fouling of equipments.

10. Carbon Residue Carbon residue indicates the tendency of oil to deposit a carbonaceous solid residue on a
hot surface, such as a burner or injection nozzle, when its vaporisable constituents evaporate. Residual oil
contains carbon residue ranging from 1 percent or more.

11. Water Content Water content of furnace oil when supplied is normally very low as the product at refinery
site is handled hot and maximum limit of 1% is specified in the standard. Water may be present in free or
emulsified form and can cause damage to the inside furnace surfaces during combustion especially if it
contains dissolved salts. It can also cause spluttering of the flame at the burner tip, possibly extinguishing the
flame and reducing the flame temperature or lengthening the flame.

12. Octane Number

It indicates the tendency of gasoline to knock when the compression ratio n a spark ignition engine is raised.

13. Cetane Number

It ranks fuels according to ignition delay when undergoing standard test.

14. Smoke Point

Measures the tendency of a liquid fuel to from a soot.

15. Ignition Temperature Sometimes called ‘autoignition temperature’, this is the minimum temperature at
which the material will ignite without a spark or flame being present.

16. Flammability Limits in Air The percent concentration in air (by volume) is given for the lower and upper
limit. These values give an indication of relative flammability. The limits are sometimes referred to as ‘lower
explosive limit’ (LEL) and ‘upper explosive limit’ (UEL).

10 | P a g e
17. Fire Point Fire point is the lowest temperature, corrected to one atmosphere pressure (101.3 kPa), at
which the application of a test flame to the oil sample surface causes the vapour of the oil to ignite and burn
for at least five seconds.

18. Reid Vapour Pressure Vapour pressure is an important physical property of volatile liquids. It is the
pressure that a vapour exerts on its surroundings. Its units are kilopascals, corrected to one atmosphere (101.3
kPa). For volatile petroleum products, vapour pressure is used as an indirect measure of evaporation rate.
Vapour pressure can be measured by a variety of methods including Reid, dynamic, static, isoteniscopic,
vapour pressure balance, and gas saturation.

19. Hydrogen Sulphide Unlike other sulphur compounds in crude oils, which tend to accumulate in the
distillation residue, hydrogen sulphide is evolved during distillation or other heating processes.

Alcohols are oxygenated hydrocarbons where a hydrogen atom was replaced by an OH radical Alcohols There
are many alcohols, but the most common are methanol and ethanol Methanol is produced as a product of the
carbonization of wood, or through a synthesis process 2 H 2 + CO → CH 3OH
The process yields about 75% methanol and 25% heavier alcohols, which are then separated by fractional
distillation Ethanol is obtained from fermentation of sugars, followed by fractional distillation.

III. GASEOUS FUELS

Gaseous fuels occur in nature, besides being manufactured from solid and liquid fuels. The advantages and
disadvantages of gaseous fuels are given below:
 Advantages
(a) They can be conveyed easily through pipelines to the actual place of need, thereby eliminating manual
labour in transportation.
(b) They can be lighted at ease. (c) They are free from impurities found in solid and liquid fuels.
 Disadvantages
(a) Very large storage tanks are needed. (b) They are highly inflammable, so chances of fire hazards in their
use are high.
Figure 5. Classifications of Gaseous Fuels

11 | P a g e
 Figure 6. Typical Composition of Gaseous Fuels

Natural gas is generally associated with petroleum deposits and is obtained from wells dug in the oil-bearing
regions. Natural gas is produced from gas wells or oil wells rich in natural gas. Methane is the main
constituent of Natural gas and accounting for about 95% of the total volume. Other components are: Ethane,
Propane, Butane, Pentane, Nitrogen, Carbon Dioxide, and traces of other gases. Very small amounts of
sulphur compounds are also present. Since methane is the largest component of natural gas, generally
properties of methane are used when comparing the properties of natural gas to other fuels.

Characteristics
-It is a fossil fuel formed from plant and animal remains millions of years ago.
-It is hydrocarbon component with methane as a major component.
-It is colorless and odorless. For security during transportation or processing, a commercial odorant is added to
allow users to detect the gas for safety.
-It is lighter than air with a specific gravity of about 0.6-0.8.
-If leaks, it disperses upward and dissipates into the air quickly. It is inflamed during a range of 5-15% by
volume of gas in air.
-The self-ignition temperature of natural gas is 537-540 degree Celsius.
-As it is a clean fuel with cleaner burning nature, natural gas has lower environmental impact when compared
with other types of fuel.

Liquefied petroleum gas (LPG) is a byproduct of natural gas processing or the crude oil refining. It consists
mainly of propane and thus LPG is usually referred to as propane. However, it also contains varying amounts
of butane, propylene, and butylenes.

Manufactured gases are obtained from solid and liquid fuels. Some of the important manufactured gaseous
fuels whose characteristics are discussed in the following sections are coal gas, blast furnace gas, water gas,
producer gas and oil gas.

1. Coal Gas Coal gas is obtained when it is carbonized or heated in absence of air at about 1300oC in
either coke ovens or gas-making retorts. Coal gas is a colourless gas having a characteristic odour. It is
lighter than air and burns with a long smoky flame. It is used in metallurgical operations for providing
reducing atmosphere.
2. Blast Furnace Gas It is a by product flue gas obtained during the reduction of ion ore by coke in the
blast furnace. This gas contains much dust and is usually cleaned before use by dust settlers, cyclones
or electrolytic precipitators.
3. Water Gas Water gas is essentially a mixture of combustible gases CO and H2 with a little fraction of
non-combustible gases. It is made by passing alternatively steam and little air through a bed of red hot
coal or coke maintained at about 900 to 1000oC in a rector, which consists of a steel vessel.

12 | P a g e
 4. Producer Gas Producer gas is essentially a mixture of combustible gases carbon monoxide and
hydrogen associated with non-combustible gases N2, CO2, etc. It is prepared by passing air mixed
with little steam (about 0.35 kg/kg of coal) over a red hot coal or coke bed maintained at about
1100oC in a special reactor called gas producer.
5. Biogas is obtained from the decomposition of organic matter by bacteriological action in closed
digesters, in the absence (or nearly) oxygen. It requires a high moisture content Organic matter
(provided it has high chamber moisture content) can be of various origins, either plant or animal,
being very common the use of organic manure In operation the digesters maintain a temperature
around 30 to 40 °C Since the process is not totally anaerobic, the gas has a significant percentage of
CO2, but the solid waste is a good fertilizer.

Figure 7. Biogas Reactor

6. Town gas (also: low-temperature or lighting gas) is obtained at low- and medium temperature coal
gasification.
7. Coke gas is obtained at the high - temperature coal gasification.
8. Hydrogen is produced on the industrial size by reforming of natural gas (methane). Reforming means
acting of water steam on natural gas in the presence of nickel catalyst at the temperature approx. 800
°C.
Properties of Gaseous Fuels
1. Heating Value is the heat release per unit mass when the fuel initially at 25˚C reacts completely with
oxygen and products returned to 25˚C. The heating value is reported as higher heating value (HHV) when
the water is condensed or as the lower heating value (LHV) when the water is not condensed. LHV is
obtained by:
𝒎𝑯𝟐𝑶
LHV = HHV – 𝒎𝒇𝒖𝒆𝒍 𝒉𝒇𝒈
where hfg is the latent heat of vaporization of water at 25˚C, which equals 2,440 kJ/ kg water. The heating
value of gaseous fuel may be obtained experimentally in a flow calorimeter and can be calculated from
thermodynamics if the composition is known.
HHV (higher/gross heating/calorific value) assumes that the water vapor in the products condenses and thus
includes the latent heat of vaporization of the water vapor in the products.
LHV (ower/net heating/calorific value) does not. contain the latent heat, the water in flue gas remain in
steam form at the initial temperature.

2. Relative density: d = ρgas/ ρair [-]

(important e.g. from explosion safety viewpoints)
Ranges:
d < 0.8 - light gas (e.g. natural gas CH4)
0.8 < d < 1.2 - medium category (e.g. CO)
13 | P a g e
1.2 < d - heavy gas (e.g. LPG - propane-bhutane)

3. Wobbe index (for assessment of gas exchange)

4. Flammability limits, %- Flammability limits, also called flammable limits, give the proportion of
combustible gases in a mixture, between which limits this mixture is flammable.
LFL The lower flammable limit describes the leanest mixture that is still flammable, i.e. the mixture with the
smallest fraction of combustible gas, UFL The upper flammable limit gives the richest flammable mixture.

Renewable fuels
Renewable fuels (biomass) are formed in a year or a few years basis (synthetic fuels may come from fossil or
from renewable sources):
 Gaseous: biogas from anaerobic fermentation or gasogen gas from pyrolysis of biomass.
 Liquid: alcohols, ethers (biopetrol), esters (biodiesel).
 Solid: wood, charcoal, fuel pellets (from wood or vegetable residues), agriculture residues, cattle
manure, urban waste.
In comparison with fossil fuels, particularly with oil and gas, renewable fuels are more
disperse, have less energy content, more moisture and ash content, and require more handling effort
(but they are renewable).

BIOFUELS
The term biofuels, biomass fuels and renewable fuels, may be used indistinctly if they refer to natural
or artificial fuels obtained from renewable sources, although other times distinctions are introduced and then
biofuels may refer to biomass derivatives directly substituting fossil fuels for the same combustor, biomass
may be restricted to unprocessed biomass (forest waste, crops and agriculture waste, animal waste, domestic
waste), and renewable fuel may include fuels like hydrogen obtained by electrolysis and not from biomass.
Some disadvantages of biofuels:
 Biomass fuels are mostly solid, and some pre-processing is needed (gasification, liquefaction) to
produce fluid fuels, the kind of fuel best fitted to both engines and stationary combustors.
 Biomass fuels are less energetic than fossil fuels, because living matter is roughly a water suspension
of oxygenated hydrocarbons, and fossil fuels were slowly 'cooked' over the aeons to separate water
and most of the oxygen. Besides, some biomass fuels have non-fuel components that must be
separated (e.g. soil in forest-waste, metals in industrial waste).
 Biomass fuels are contaminant; not contributing to global warming (because the CO2 produced
compensates with that synthesised from the air during the biomass growth), but producing much more
particulates and new chemical emissions (e.g. dioxins) if not properly treated.

The Biofuels Act or Republic Act (RA) 9367 was signed in January 2007 making the Philippines the first
country in Southeast Asia to have biofuels legislation in place. Sugarcane and molasses are used in Philippine
ethanol production, while coconut oil (CNO), where coconut methyl ester (CME) is derived, is the preferred
biodiesel feedstock. The current blend mandates are 10 percent and two percent for ethanol and biodiesel,
respectively.
Terms:
Bioethanol - refer to ethanol (C2H5OH) produced from feedstock and other biomass;
Biodiesel - refer to Fatty Acid Methyl Ester (FAME) or mono-alkyl esters derived from vegetable oils or
animal fats and other biomass-derived oils that shall be technically proven and approved by the DOE for use
in diesel engines with quality specifications in accordance with Philippine National standards (PNS);
Bioethanol Fuel - refer to hydrous or anhydrous bioethanol suitable denatured for use as motor fuel, with
quality specifications in accordance with the PNS;

14 | P a g e
Biofuel - refer to bioethanol and biodiesel and other fuels made from biomass and primarily used for motive,
thermal and power generation with quality specifications in accordance with the PNS;
Biofuel blends - refer to gasoline or diesel that has been blended with biofuels such as, but not limited to,
bioethanol and biodiesel;
Biomass - refer to any organic matter, particularly cellulosic or lingocellulosic matter, which is available on a
renewable or recurring basis, including basis, including trees, crops and associated residues, plant fiber,
poultry litter and other animal wastes, industrial wastes, and the biodegradable component of solid waste.

Some biofuel production methods considered are:

 Ethanol by fermentation of biomass sugars, starch or cellulose by yeast or bacteria. In Japan, a bacteria
has been bred which produces ethanol from paper or rice-straw without any pre-treatment.
 Methane (actually a biogas mixture) by anaerobic digestion of biomass waste (manure, straw, sewage,
municipal solid waste (MSW)).
 Oils (biodiesel) by reforming oleaginoseous plant seeds (e.g. colza, sunflower, soya). The marine
microscopic algae Botryococcus Braunii has been shown to accumulate a quantity of hydrocarbons
amounting to 75% of their dry weight
 Methanol from wood-waste distillation.
 Hydrogen by reforming other biofuels (e.g. ethanol or methane), or from water electrolysis by solar or
wind energy.

BASIC CHEMISTRY
Before considering combustion problems it is necessary to understand the construction and use of
chemical formulae. This involves elementary concepts which are discussed below briefly.
Atoms. It is not possible to divide the chemical elements indefinitely, and the smallest particle which can take
part in a chemical change is called an ‘atom’. If an atom is split as in nuclear reaction, the divided atom does
not retain the original chemical properties.
Molecules. It is rare to find elements to exist naturally as single atom. Some elements have atoms which exist
in pairs, each pair forming a molecule (e.g. oxygen), and the atoms of each molecule are held together by
stronger inter-atomic forces. The isolation of a molecule of oxygen would be tedious, but possible ; the
isolation of an atom of oxygen would be a different prospect. The molecules of some substances are formed
by the mating up of atoms of different elements. For example, water has a molecule which consists of two
atoms of hydrogen and one atom of oxygen. The atoms of different elements have different masses and these
values are important when a quantitative analysis is required. The actual masses are infinitesimally small, and
the ratios of the masses of atoms are used. These ratios are indicated by atomic weight quoted on a scale
which defines the atomic weight of oxygen as 16.

COMBUSTION
Combustion is the conversion of a substance called a fuel into chemical compounds known as products of
combustion by combination with an oxidizer. The combustion process is an exothermic chemical reaction,
i.e., a reaction that releases energy as it occurs.
Thus combustion may be represented symbolically by:
Fuel + Oxidizer = Products of combustion + Energy
Here the fuel and the oxidizer are reactants, i.e., the substances present before the reaction takes place. This
relation indicates that the reactants produce combustion products and energy.

Three T’s of Combustion

The objective of good combustion is to release all of the heat in the fuel. This is accomplished by
controlling the "three T's" of combustion which are:
(1) Temperature high enough to ignite and maintain ignition of the fuel,
(2) Turbulence or intimate mixing of the fuel and oxygen, and
15 | P a g e
(3) Time sufficient for complete combustion.
Commonly used fuels like natural gas and propane generally consist of carbon and hydrogen. Water
vapor is a by-product of burning hydrogen. This robs heat from the flue gases, which would otherwise be
available for more heat transfer. Natural gas contains more hydrogen and less carbon per kg than fuel oils and
as such produces more water vapor. Consequently, more heat will be carried away by exhaust while firing
natural gas. Too much, or too little fuel with the available combustion air may potentially result in unburned
fuel and carbon monoxide generation. A very specific amount of O2 is needed for perfect combustion and
some additional (excess) air is required for ensuring complete combustion. However, too much excess air will
result in heat and efficiency losses.

Not all of the heat in the fuel are converted to heat and absorbed by the steam generation equipment. Usually
all of the hydrogen in the fuel is burned and most boiler fuels, allowable with today's air pollution standards,
contain little or no sulfur. So the main challenge in combustion efficiency is directed toward unburned carbon
(in the ash or incompletely burned gas), which forms CO instead of CO2.

COMBUSTION EQUATIONS
In a combustion chamber, proportionate masses of air and fuel enter where the chemical reaction takes
place. Then the combustion products pass to the exhaust. By the conservation of mass the mass flow remains
constant (i.e., total mass of products = total mass of reactants), but the reactants are chemically different from
the products, and the products leave at a higher temperature. The total number of atoms of each element
concerned in the combustion remains constant, but the atoms are rearranged into groups having different
chemical properties. This information is expressed in the chemical equation which shows: (i) the reactants and
the products of combustion,
(ii) the relative quantities of the reactants and products.
The two sides of the equation must be consistent, each having the same number of atoms of each
element involved. The oxygen supplied for combustion is usually provided by atmospheric air, and it is
necessary to use accurate and consistent analysis of air by mass and by volume. It is usual in combustion
calculations to take air as 23.3% O2, 76.7% N2 by mass, and 21% O2, 79% N2 by volume. The small traces
of other gases in dry air are included in nitrogen, which is sometimes called ‘atmospheric nitrogen’. Thus for
every 21 moles of oxygen that react when air oxidizes a fuel, there are also 79 moles of nitrogen involved.
Therefore, 79/21 = 3.76 moles of nitrogen are present for every mole of oxygen in the air.

THE COMBUSTION PROCESS

The combustion process consists of the oxidation of constituents in the fuel that are capable of being
oxidized and can therefore be represented by a chemical equation. During a combustion process, the mass of
each element remains the same. Thus, writing chemical equations and solving problems concerning quantities
of the various constituents basically involve the conservation of mass of each element.
During combustion, nitrogen behaves as an inert gas and does not react with other elements, other than
forming a very small amount of nitric oxides. However, even then the presence of nitrogen greatly affects the
outcome of a combustion process since nitrogen usually enters a combustion chamber in large quantities at
low temperatures and exits at considerably higher temperatures, absorbing a large proportion of the chemical
energy released during combustion. Throughout this chapter, nitrogen is assumed to remain perfectly inert.
Keep in mind, however, that at very high temperatures, such as those encountered in internal combustion
16 | P a g e
engines, a small fraction of nitrogen reacts with oxygen, forming hazardous gases such as nitric oxide. Air that
enters a combustion chamber normally contains some water vapor (or moisture), which also deserves
consideration. For most combustion processes, the moisture in the air and the H2O that forms during
combustion can also be treated as an inert gas, like nitrogen. At very high temperatures, however, some water
vapor dissociates into H2 and O2 as well as into H, O, and OH. When the combustion gases are cooled below
the dew-point temperature of the water vapor, some moisture condenses. It is important to be able to predict
the dew-point temperature since the water droplets often combine with the sulfur dioxide that may be present
in the combustion gases, forming sulfuric acid, which is highly corrosive.

Consider first the reaction of carbon with oxygen.

Reactants Product
C + O2 → CO2

This equation states that 1 kmol of carbon reacts with 1 kmol of oxygen to form 1 kmol of carbon
dioxide. This also means that 12 kg of carbon react with 32 kg of oxygen to form 44 kg of carbon dioxide. All
the initial substances that undergo the combustion process are called the reactants, and the substances that
result from the combustion process are called the products.
When a hydrocarbon fuel is burned, both the carbon and the hydrogen are oxidized. Consider the
combustion of methane as an example.
CH4 + 2O2 → CO2 + 2H2O
Here the products of combustion include both carbon dioxide and water. The water may be in the
vapor, liquid, or solid phase, depending on the temperature and pressure of the products of combustion.
Therefore, when the oxygen for the combustion of methane is supplied as air, the reaction can be written as:
CH4 + 2O2 + 2(3.76)N2 → CO2 + 2H2O + 7.52 N2
The minimum amount of air that supplies sufficient oxygen for the complete combustion of all the
carbon, hydrogen, and any other elements in the fuel that may oxidize is called the theoretical/
stoichiometric air. When complete combustion is achieved with theoretical air, the products contain no
oxygen. A general combustion reaction with a hydrocarbon fuel and air is thus written
CxHy + vO2 (O2 + 3.76 N2) → vCO2CO2 + vH2OH2O + vN2N2
with the coefficients to the substances called stoichiometric coefficients. The balance of atoms yields the
theoretical amount of air as:
C: vCO2 = x
H: 2vH2O = y
N2 : vN2 = 3.76 × vO2
O2 : vO2 = vCO2 + vH2O/2 = x + y/4

17 | P a g e