Fuels

Fuel is a combustible substance, containing carbon as a main constituent, which on proper burning gives
large amount of heat, which can be used economically for domestic and industrial purpose. Examples of
fuels are wood, gas, petrol etc. Fuels are also obtained in fossils or in our natural resources. Fossil fuels
are non-renewable energy resources, which were stored millions of years ago by photosynthesis. Fossil
fuels are both energy dense and widespread, so most of the world’s industrial, utility, and
transportation sectors use them as energy sources. Fossil fuels remain to be the dominant energy source
at present and in the foreseeable future. Since The development and deployment of technologies to
harness and utilize renewable energy sources are uneconomic at present, and; Concerns over storage
and/or disposal of spent nuclear fuel and nuclear proliferation. Fuels are classified into to two: Natural
Fuels and Derived Fuels. Natural fuels are fuels that are produced organic materials. Natural fuels can be
either be solid, liquid or gas. Examples of Natural fuels are coal, crude oil, natural gas etc. Derived fuels
are fuels made from combustible components that is manufactured and enhanced by companies. Also
like natural fuels, derived fuels can also be either solid, liquid or gas. Examples of this are charcoal,
petrol, biogas etc. Refer to the picture below:

ADVANTAGES AND DISADVANTAGES: SOLID, LIQUID AND GAS FUELS

Advantages

Solid fuels. This fuels are much more easy to handle and transport. Solid fuels are cheap and easily
available. They have a moderate ignition Temperature This type of fuel can be stored conveniently
without any risk.

Liquid fuels. Fuels like this have a uniform combustion and can be easily controlled. Its calorific value is
higher than that of solid fuels. Compared to solid fuels, liquid fuels has less storage capacity required.
Also liquid fuels do not yield any ash after burning.
Gas fuels or gaseous fuels. This type of fuels are high thermal efficient. They have high calorific value
than the solid fuels. They also do not produce any ash or smoke during burning. And gaseous fuels can
be easily transported through the pipes.

Disadvantages

Solid fuels. During burning, solid fuels produce a large amount of ash and disposal of ash is a big
problem. The calorific value of solid fuel is comparatively low. Since a lot of air is required for complete
combustion, its thermal efficiency is not so high. Solid fuels require large storage capacity. And
combustion is a slow process and it cannot be easily controlled.

Liquid fuels. Liquid fuels are comparatively costlier than the solid fuels. They give unpleasant odor
during incomplete combustion. Some amount of liquid fuels will escape due to evaporation during
storage. Liquid fuels needs special type of burners for an effective combustion.

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

Requirements of a Good Fuel

A good fuel should have the following characteristics:

• High calorific value.

• Moderate ignition temperature.

• Low contents of non-combustible matters.

• Low moisture content.

• Free from objectionable and harmful gases like CO, SOx, H2S.

• Moderate velocity of combustion.

• Combustion should be controllable.

• Easy to transport and readily available at low cost.

COMBUSTION

Combustion is an exothermic chemical reaction, which is accompanied by development of heat and

light at a rapid rate, temperature rises considerably. During the process of combustion, carbon,
hydrogen, etc., combine with oxygen with a liberation of heat. A proper combustion, the substance must
be brought to its kindling (or) ignition temperature, it is the minimum temperature at which the
substance ignites and burns without further addition of heat from outside.

Factors affecting the rate of combustion:

• The concentration of the fuel and air.

• The nature of the combustible substance.

• The temperature.

• With increase in pressure or surface area of the fuel the rate of combustion can be increased.

• It increases with increase in pressure of air.

• It Increases with preheating of fuel and air.

Calorific Value

Heating value or calorific value is the most important characteristic property of any fuel. Calorific value
can be defined as “the amount of heat liberated by the complete combustion of a unit mass of a fuel” or
“the heat produced at constant volume by the complete combustion of a unit quantity of coal”.
There are different expressions of calorific value: Gross or high calorific value (GCV or HCV) includes the
latent heat of vaporization of water in the combustion products, i.e. water is in the form of a liquid. It is
“the total heat generated when a unit quantity of fuel is completely burnt and the products of
combustion are cooled to room temperature.” Otherwise, when the water is not condensed, i.e. is in the
form of a vapor, it is called the Net or Lower Calorific Value (NCV or LCV). It is “the net heat produced
when a unit quantity of fuel is completely burnt and the products of combustion are allowed to escape.
To calculate the calorific value of a solid or liquid fuel can be determined by using bomb calorimeter.
Bomb calorimeter is used by this principle: A known amount of the fuel is burnt in excess of oxygen and
heat liberated is transferred to a known amount of water. The calorific value of the fuel is then
determined by applying the principle of calorimetry i.e. Heat gained = Heat lost. Refer to image below:
Corrections

To have an accurate results the following corrections are also incorporated:

a) Fuse wire correction: As Mg wire is used for ignition, the heat generated by burning of Mg wire is also
included in the gross calorific value. Hence this amount of heat has to be subtracted from the total
value.

b) Acid Correction: During combustion, sulfur and nitrogen present in the fuel is oxidized to their
corresponding acids under high pressure and temperature.

c) Cooling Correction: When the bomb calorimeter is allowed to cool from maximum temperature to
room temperature, some amount of heat is radiated. From the rate of cooling and actual time for
cooling, cooling correction is made and it is added to the temperature difference.
SOLID FUELS

Wood. Wood is derived from trunks and branches of trees. It contains about 15% moisture after air-
drying. It also contains lignocellulose-wood pulp mainly α cellulose and a very small amount of β
cellulose. Its composition on moisture free basis is C= 55%, H = 6%, O = 43%, Ash = 1%. Its calorific value
varies from 4000 to 6400 Btu/lb. Coal. Coal is an important primary solid fuel that has been formed as a
result of alteration of vegetable matter under some favorable conditions. Coal is the generic term
applied to fossil fuels which range from lignite (which is basically a matured or modified peat) to meta-
anthracite which is around 98% carbon). Coal is highly carbonaceous and composed of C, H, N and O,
and non-combustible inorganic matter. Coal is classified on the basis of its rank and the rank of coal
denotes its degree of maturity. Vegetable matter, under the action of pressure, heat and anaerobic
conditions, gets converted into different stages of coal:
Analysis of coal

Ranking of coal is done on:

Importance of Proximate Analysis

Moisture
• High moisture content in coal is undesirable because it,
0.1. Reduces Calorific Value of coal.
0.2. Increases the consumption of coal for heating purpose.
0.3. Lengthens the time of heating.
• Hence, lesser the moisture content, better is the quality of coal.

Volatile Matter

•During burning of coal, certain gases like CO, CO2, CH4, H2, N2, O2, hydrocarbons etc. that
come out are called volatile matter of the coal.

•The coal with higher volatile content,

•Ignites easily (e.g.: it has lower ignition temperature).

•Burns with long yellow smoky flame.

•Has lower Calorific Value.

•Will give more quantity of coal gas when it is heated in absence of air.

Ash

• Ash is the combustion product of mineral matters present in the coal.

•It consists mainly of SiO2, Al2O3 and Fe2O3 with varying amounts of other oxides such as Na 2O,
CaO, MgO etc.

• Ash containing oxides of Na, Ca and Mg melt early. (Low melting ash).

•During coke manufacture, the low melting ash forms a fused lumpy – expanded mass
which block the interspaces of the ‘grate’ and thereby obstructing the supply of air
leading to irregular burning of coal and loss of fuel.

• High ash content in coal is undesirable because it (a) increases transporting, handling, storage
costs, (b) is harder and stronger, (c) has lower Calorific Value.

Fixed Carbon

•It is the pure carbon present in coal.

•Higher the fixed carbon content of the coal, higher will be its Calorific Value
(b) Ultimate Analysis means finding out the weight percentage of carbon, hydrogen, nitrogen, oxygen
and sulfur of the pure coal free from moisture and inorganic constituents. This analysis gives the
elementary constituents of coal. It is useful to the designer of coal burning equipment’s and auxiliaries.

Importance of Ultimate Analysis

Carbon and Hydrogen

• Higher the % of carbon and hydrogen, better the quality of coal and higher is its calorific value.

• The % of carbon is helpful in the classification of coal.

• Higher the % of carbon in coal reduces the size of combustion chamber required.

Nitrogen

• Nitrogen does not have any calorific value, and its presence in coal is undesirable.

•Good quality coal should have very little nitrogen content.

Sulfur

• Though sulfur increases the calorific value, its presence in coal is undesirable

because:

• The combustion products of sulfur, i.e., SO2 and SO3 are harmful and have corrosion
effects on equipment.

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

Oxygen

•Lower the % of oxygen higher is its calorific value.

•As the oxygen content increases its moisture holding capacity increases and the calorific value
of the fuel is required.

LIQUID FUELS

Petroleum or crude oil is a naturally occurring brown to black colored viscous oil formed under the crust
of earth, on shore or off shore. Chemically it is a mixture of various hydrocarbons with small amounts of
N, O, S compounds. The approximate composition of petroleum is C = 80 - 84%, H = 10 - 14 %, S = 0.1 -
0.5 %, N+ O = Negligible.

Classification of Petroleum

1. Paraffinic-base type crude oil

• Contains saturated hydrocarbons from CH4 to C35H72 and a little amount of naphthalenes
and aromatics.

• (e.g. : Pennsylvanian and gulf coast oil)

2. Asphaltic-base type crude oil

• Contains mainly cycloparaffins or naphthalenes with smaller amounts of paraffins and aromatic
hydrocarbons.

• (e.g.: Californian oil)

3. Mixed-base type crude oil

• Contains both paraffinic and asphaltic hydrocarbons and are generally in the form of semi-solid waxes.

• (e.g. : Mexican oil)

Processing of Crude Petroleum

Petroleum is found deep below the earth crust. The oil is found floating over salt water or brine.
Generally, accumulation of natural gas occurs above the oil.

Refining of Petroleum

The process of removing impurities and separating out the oil into various fractions having different
boiling points is known as refining of petroleum. Refining plants are called oil refineries. The process of
refining involves 3 steps: Separation of water, Removal of impurities and Fractional distillation.
Separation of Water. The crude oil from the well is an extremely stable emulsion of oil and salt water.
The crude oil is allowed to flow between 2 highly charged electrodes, where colloidal water droplets
coalesce to form large drops, which is then separated out from the oil. Removal of Impurities. The
presence of NaCl and MgCl2 in the crude oil can corrode the refining equipment, hence these salts are
removed by electrical desalting and dehydration methods. The sulfur compounds present in the crude
oil is removed by treating the oil with copper(II) oxide, which results in the formation of copper sulfide,
which is then removed by filtration. Fractional Distillation. The crude oil is heated to about 400°C,
whereby all volatile substances are evaporated. The hot vapors are then passed up a fractionating
column, which is a tall cylindrical tower containing a number of horizontal stainless steel trays at short
distances. When the vapors of the oil go up the fractionating column, they gradually cool and condense
at different heights of the column. The fractions having higher boiling point condense at lower trays
whereas the fractions having lower boiling points condense at higher trays.
Common Fractions from Crude

Heavy oils on refraction gives:

Some important fractions of petroleum:

1. Petrol or Gasoline (C5-C9)

• It is a low boiling fraction of petroleum obtained between 40 – 120oC.

• It is a mixture of hydrocarbons pentane to nonane (in terms of carbon atoms C5 - C9).

• Its calorific value is about 11,250 kcals/kg.

• It is used as fuel in ICE of automobiles and aero planes.

• Its antiknock value can be improved by the addition of Tetra Ethyl Lead(TEL).

• It is used as a fuel in IC engine and also used in dry cleaning and as a solvent.

2. Naphtha (C9-C10)

• It is a colorless, light fraction obtained between 1200C to 1800C during fractional distillation of
petroleum. It is a mixture of hydrocarbons such as nonane and decane.

• Naphtha is also called as white spirit, which is generally used in dry cleaning and as thinner for
varnish, floor and furniture polishes etc. The lightest portion of the distillate is used as solvent
for fats and rubbers, whereas the heaviest portion of the same is used as a fuel.

3. Kerosene(C10-C16)

• It is relatively a high boiling fraction obtained between 180-250oC during fractional distillation
of petroleum. It is a mixture of hydrocarbons such as decane to hexadecane approximate
composition is C = 84%, H = 16%, > 0.1% S. Its calorific value is about 11,100 kcal/kg.

• It is mainly used as a domestic fuel in stoves and lamps.

• It is also used as jet engine fuel and for making oil gas.

4. Diesel (C15-C18)

• It is also a high boiling fraction obtained between 250-320oC during fractional distillation of
petroleum. It is a mixture of hydrocarbons such as C15H32 to C18H38. Its calorific value is about
11,000 kcal/kg.

• It is used as a very good diesel engine fuel.

5. Heavy oil or Residual fuel oil (C17 – C30)

• The left over portion of petroleum after distilling off all the lighter fractions are called Fuel Oil.

• The approximate composition of fuel oil is C = 86%, H = 12%, S = 1%, H2O = 0.6%; sediments =
0.4%.

• Its calorific value is about 9200 kcal/kg.

• The following fractions are obtained on further vacuum distillation of the fuel oil. i) Light fuel
oil = 350 -420oC ii) Heavy neutral oil = 420-500oC
 • It is used as fuel for ships and also used in metallurgical furnaces.

• Gasoline is also obtained from oil by cracking process.

6. Asphalt

• Asphalts are obtained by:

i) The oxidation of residual heavy oil in presence of air at higher

temperature.

ii) The deep vacuum distillation of residual heavy oil.

• Asphalts are available in the market in liquid, semi-solid and solid forms.

• It is used for road making and making water-proofing roofs.

• It is also used for the manufacture

of water proofing concrete and water proofing paints.

Properties of Liquid Fuels

Standard Ignition Temperature (SIT)

• Flash Point

• It is the lowest temperature that a fuel will ignite without the help of any external flame or
ignition source.

Flash Point

• It is the lowest temperature at which a fuel can be heated so that the vapor gives off flashes
when an open flame is passed over it.

• This gives an indication of the flammability of the fuel.

• Its significance is in the safety aspects of storing and handling the fuel.

Fire Point

• It is the temperature to which the oil must be heated so that the vapor pressure is sufficient to
maintain the flame after the flame source is removed.

Smoke Point

• It is an arbitrary scale related to the height of the flame of the fuel burning in a standard lamp
without smoking.

Cracking is defined as the decomposition of high boiling hydrocarbons of high molecular weight into
smaller, low boiling hydrocarbons of low molecular weight. The crude oil on fractional distillation yields
only about 15 - 20 % gasoline. This is known as Straight Run Gasoline. During cracking: Straight chain
alkanes are converted into branched chain hydrocarbons. Saturated hydrocarbons are converted into
mixture of Saturated and Unsaturated hydrocarbons. Aliphatic alkanes are converted into cyclic alkanes.
All hydrocarbons obtained by cracking have lower boiling point than the parent hydrocarbons.
Two Types of Cracking in Use:

1. Thermal Cracking

• In this process, the heavy oil is subjected in high temperature and pressure, when the bigger
hydrocarbon molecules break down to give smaller molecules of the paraffins, olefins, and
hydrogen.

• The cracked products are then separated by fractional distillation.

2. Catalytic Cracking

• In this process, cracking is carried out in the presence of a catalyst at a lower temperatures
and pressures. The catalysts like aluminum silicate, Al2SiO3, or alumina Al2O3, used in cracking
gives higher yield and better quality of gasoline

Knocking

The rate of ignition of the fuel gradually increases and the final portion of the fuel-air mixture gets
ignited instantaneously producing an explosive sound known as knocking. Knocking property of the fuel
reduces the efficiency of engine. So a good gasoline should resist knocking.

Octane Number or Octane Rating

Octane number is defined as the percentage of iso-octane present in a mixture of iso-octane and n-
heptane. It is introduced to express the knocking characteristics of petrol. It has been found that n-
heptane knocks very badly and hence, its anti-knock value has been given zero (0). On the other hand,
iso-octane gives very little knocking and so, its anti-knock value has been given 100.

Cetane Number or Cetane Rating

Cetane number is defined as the percentage of hexadecane (n-cetane) present in a mixture of

hexadecane and 2-methyl naphthalene, which has the same ignition lag as the fuel under test. It is
introduced to express the knocking characteristics of diesel. Cetane has a very short ignition lag and
hence its cetane number is taken as 100. On the other hand, 2-methyl naphthalene has a long ignition
lag and its cetane number is taken as zero (0). The cetane number decreases in the following order: n-
alkanes > cycloalkanes > alkenes > branched alkanes > aromatics. The cetane number of a diesel oil can
be increased by adding additives called dopes. Some important dopes include ethyl nitrate and iso-amyl
nitrate.

Chemical Structure and Knocking

The knocking tendency of fuel hydrocarbons mainly depends on their chemical structures. The knocking
tendency decreases in the following order: straight-chain paraffins > branched-chain paraffins >
cycloparaffins > olefins > aromatics

Improvement of Antiknock Characteristics

The octane number of fuel can be improved by:

1. Blending petrol of high octane number with petrol of low octane number, so that the octane
number of the latter can be improved

2. The addition of anti-knock agents

Anti-knock properties of a gasoline can be improved by the addition of suitable additives. Tetraethyl
lead or (C2H5)4Pb is an important additive added to petrol. Thus, petrol containing tetraethyl lead is
called leaded petrol. Knocking follows a free radical mechanism, leading to a chain growth which results
in an explosion. If the chains are terminated before their growth, knocking will cease. Lead decomposes
thermally to form ethyl free radicals which combine with the growing free radicals of knocking process
and thus the chain growth is stopped.
GASEOUS FUELS

Natural Gas

Natural gas is always found above the oil in the oil wells. It is also called Marsh gas. It consists of
methane and other saturated hydrocarbons. The average composition of natural gas is as
follows: • Methane = 88.5 %, Ethane = 5.5 %, Propane = 4 %, Butane = 1.5%, Pentane = 0.5%. Its
calorific value varies from 12,000 to 14,000 kcal/m3. If natural gas contains lower hydrocarbons
like methane and ethane it is called lean or dry gas. In the natural gas contains higher
hydrocarbons like propane, butane along with methane it is called rich or wet gas.

Water or Blue Gas

Water gas essentially a mixture of combustible gases like CO, H 2with a little noncombustible
gases like CO2 and N2. Its Calorific Value is 2800 kcals/m 3. The average composition is as follows:
H2= 48 %, CO = 44 %, CO2, N2and CH4= 8 %.
Producer Gas

It is prepared by passing air mixed with a little steam over a red hot coal (or) a coke bed
maintained at above 1100° C in a special reactor called ‘‘Gas Producer’’. • Its Calorific Value is
1800 kcals/m3. The average composition is as follows: N2= 50 %, CO = 30 % • H2 = 10 %, CO2, and
CH4= 10 %.

Liquefied Petroleum Gas (LPG)

It is a mixture of propane and butane.It is obtained as one of the top fractions in the fractional
distillation ofpetroleum.It is easily liquified and so can be economically stored and transportedin
cylinders.Its Calorific Value is 27000 kcals/m3.The approximate composition is as follows: N-Butane = 70
%,Isobutane = 17 %,N-Propane = 11 %,Butylene and Ethane = 2 %.

BOYS OR JUNKERS GAS CALORIMETER

Aims to determine calorific value of gaseous fuel by Junkers gas calorimeter.

Biofuels

• Biogas: from animal manure, other organic wastes, energy crops

• Bioethanol/Ethanol: from sugar/starch

• Biodiesel: from vegetable oils, animal fats

Biogas are gases generally produced by the fermentation of bio wastes, sewage wastes, other organic
wastes and energy crops by anaerobic bacteria. The chief constituent of biogas is methane, so the
process is also called biomethanation. Its Calorific Value is 5400 kcals/m 3. The composition of biogas is
as follow:

Power Alcohol

When ethyl alcohol is used as fuel in an internal combustion engine, it is called power alcohol.
Generally, ethyl alcohol is used as a 5-25% mixture with petrol. Ethyl alcohol has good anti-
knocking property. The addition od ethyl alcohol increases the octane number of petrol. It has
the property of absorbing any traces of water if present in petrol. It contains oxygen atoms,
which help for the complete combustion of power alcohol and largely reduces the polluting
emissions of CO, hydrocarbons, and particulates. It is cheaper than petrol. Ethyl alcohol has a
lower calorific value than petrol. Use of power alcohol significantly reduces the power output.
Ethyl alcohol has high surface tension and its atomization, especially at lower temperature, is
difficult causing starting trouble. It may undergo oxidation reduction to form acetic acid, which
corrodes engine parts. As it contains O atoms, the amount of air required to complete
combustion of power alcohol is less and therefore requiring the modification of the carburetor
and engine.
Production of Ethanol

The basic steps for large-scale production of ethanol are: microbial (yeast), fermentation of
sugars, distillation, dehydration, and denaturing. Prior to fermentation, some crops require
saccharification or hydrolysis of carbohydrates such as cellulose and starch into sugars.
Saccharification of cellulose is called cellulolysis. Enzymes are used to convert starch into sugar.

Production of Ethanol: Fermentation

Ethanol is produced by microbial fermentation of the sugar. Two major components of

plants, starch and cellulose, are both made up of sugars, and can, in principle be
converted to sugars for fermentation. Currently, only the sugar (e.g. sugar cane) and
starch (e.g. corn) portions can be economically converted. There is much activity in the
area of cellulosic ethanol, where the cellulose part of the plant is broken down to sugars
and subsequently converted to ethanol.

Production of Ethanol: Distillation

For ethanol to be usable as fuel, the majority of the water must be removed. Most of the water
is removed by distillation, but the purity is limited to 95-96% due to the formation of a low
boiling water-ethanol azeotrope with maximum 96.5% v/v ethanol and 3.5% v/v water. This
mixture is called hydrous ethanol and can be used as a fuel alone, but unlike anhydrous ethanol,
hydrous ethanol is immiscible in all ratios with gasoline, so the water fraction is typically
removed in further treatment in order to burn in combination with gasoline.

Production of Ethanol: Dehydration

• There are three basic dehydration processes to remove water from

an azeotropic ethanol-water mixture:

• Azeotropic distillation – adding benzene or cyclohexane to the mixture.

• Extractive distillation – adding a ternary component which will increase ethanol’s

relative volatility.

• Molecular sieves – ethanol vapor under pressure passes through a bed of molecular
sieve beads, which absorbs water.
Biodiesel

A fuel derived from organic oils, such as vegetable oil, rather than petroleum. The use
and production of biodiesel are increasing. It is typically used for aircraft, vehicles, and
as heating oil. Grease or cooking oil can be converted to biodiesel and is more
sustainable. It has challenges on its scalability and concerns on competition with food
sources. A fuel derived from organic oils, such as vegetable oil, rather than petroleum.
The use and production of biodiesel are increasing. It is typically used for aircraft,
vehicles, and as heating oil. Grease or cooking oil can be converted to biodiesel and is
more sustainable. It has challenges on its scalability and concerns on competition with
food sources.
Philippines: Biofuels Act of 2006

• Develop and utilize indigenous renewable and sustainably-sourced

clean energy to reduce dependence on imported oil.

• Mitigate toxic and greenhouse gas emissions.

• Increase rural employment and income.

• Ensure the availability of alternative and renewable clean energy

without any detriment to the natural ecosystem, biodiversity and

food reserves of the country.