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Chem 111a Chemistry For Engineers: University of Science and Technology of Southern Philippines
Chem 111a Chemistry For Engineers: University of Science and Technology of Southern Philippines
Chem 111a Chemistry For Engineers: University of Science and Technology of Southern Philippines
TOPIC 7: Fuels
OUTLINE
VII. Fuels
•The Chemistry of Fuels
•Categories of Fuels
•Combustion process
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LEARNING OUTCOMES
• Deduce the concept by which organic compounds become fuel;
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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.
• e.g. wood, charcoal, coal, kerosene, petrol, diesel, producer gas, oil gas
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Fuels
• Fossil fuels are non-renewable energy resources , which were stored millions
of years ago by photosynthesis.
• e.g. coal, crude oil and natural gas
• Fossil fuels are both energy dense and widespread, thus much of the world’s
industrial, utility, and transportation sectors rely on them as energy sources.
Classification of Fuels
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Solid Fuels
ADVANTAGES DISADVANTAGES
Liquid Fuels
ADVANTAGES DISADVANTAGES
1. Liquid fuels do not yield any ash 1. Liquid fuels are comparatively costlier
after burning. than the solid fuels.
2. They require comparatively less 2. They give unpleasant odor during
storage space. incomplete combustion.
3. Calorific value of liquid fuel is higher 3. Some amount of liquid fuels will escape
than that of solid fuels. due to evaporation during storage.
4. Their combustion is uniform and 4. Special type of burners are for effective
easily controllable. combustion.
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Gaseous Fuels
ADVANTAGES DISADVANTAGES
1. Gaseous fuels can be easily 1. They are highly inflammable and hence
transported through the pipes. the chances for fire hazards are high.
2. They do not produce any ash or 2. Since gases occupy a large volume, they
smoke during burning. require large storage tanks.
3. They have high calorific value than
the solid fuels.
4. They have high thermal efficiency.
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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.
Combustion
• For proper combustion, the substance must be brought to its kindling (or)
ignition temperature, which may be defined as:
• The minimum temperature at which the substance ignites and burns without
further addition of heat from outside.
Calorific Value
• Heating value or calorific value is the most important characteristic
property of any fuel.
Calorific Value
• 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.
• “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
Bomb Calorimeter
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Note: The water equivalent of calorimeter is determined by burning a fuel of known calorific value and
using above equation. The fuels used for this purpose is benzoic acid (HCV =6325kcal/kg) and
napthalene (HCV= 9688kcal/kg) .
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Corrections
• For 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 are oxidized to their corresponding acids under high pressure and
temperature.
S + 2H + 2O2 → H2SO4 + Heat
2N + 2H + 3O2 → 2HNO3 + Heat
• Formation of these acids is an exothermic reaction. Hence, these heat
values must be subtracted from HCV.
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Corrections
• For accurate results the following corrections are also incorporated:
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.
9H
[ HCV 587]kcal / kg
100
[ HCV 0.09 H 587]kcal / kg
• where: H = % of H2 in the fuel.
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Example Problem 1:
PROBLEM:
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Example Problem 1:
PROBLEM:
SOLUTION:
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Example Problem 2:
PROBLEM:
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Example Problem 2:
PROBLEM:
SOLUTION:
26.5)
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Example Problem 3:
PROBLEM: On analysis, a coal sample has the following composition by weight;
C = 75 %, O2 = 04 %, S = 05 %, and ash = 3%. Net calorific value of the fuel is
9797.71kcal / kg. Calculate the percentage of hydrogen and gross calorific
value of coal.
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Example Problem 3:
PROBLEM: On analysis, a coal sample has the following composition by weight;
C = 75 %, O = 4 %, S = 5 %, and ash = 3%. Net calorific value of the fuel is
9797.71kcal / kg. Calculate the percentage of hydrogen and gross calorific
value of coal.
SOLUTION:
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Example Problem 3:
SOLUTION:
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Example Problem 3:
SOLUTION:
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SOLID FUELS
Wood
• Wood is derived from trunks and branches of trees.
• Contains about 15% moisture after airdrying.
• Contains lignocellulose-wood pulp mainly α cellulose and a very
small amount of β cellulose.
• Composition of wood on moisture free basis:
• C= 55%, H = 6%, O = 43%, Ash = 1%
• Calorific value varies from 4000 to 6400 Btu/lb.
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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.
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Analysis of coal
Analysis of coal
925 °C
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Analysis of coal
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Significance (or) Importance of Proximate Analysis
• Moisture
• High moisture content in coal is undesirable because it,
• Reduces Calorific Value of coal.
• Increases the consumption of coal for heating purpose .
• 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.
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Significance (or) Importance of Proximate Analysis
• 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 Na2O, 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.
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Analysis of coal
Analysis of coal
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Analysis of coal
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Analysis of coal
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Significance (or) 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.
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• 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.
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LIQUID FUELS
Petroleum
• 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:
• C = 80 - 84%
• H = 10 - 14 %
• S = 0.1 - 0.5 %
• N+ O = Negligible
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Classification of Petroleum
1. Paraffinic-base type crude oil
• Contains saturated hydrocarbons from CH 4 to C35H72 and a little amount of naphthalenes and
aromatics.
• (e.g. : Pennsylvanian and gulf coast oil)
• Generally, accumulation of
natural gas occurs above
the oil.
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Refining of Petroleum
• 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.
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.
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 also used as jet engine fuel and for making oil gas.
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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.
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.
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Properties of
Liquid Fuels
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Properties of Liquid Fuels
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• 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.
• 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.
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Cracking
During cracking:
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
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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.
Leaded Petrol
• 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.
GASEOUS FUELS
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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.
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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.
Example Problem 4:
PROBLEM:
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Example Problem 4:
SOLUTION: Basis: 1m3 of gaseous fuel.
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Example Problem 4:
SOLUTION:
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Example Problem 5:
PROBLEM: The following were obtained in the Boy’s gas calorimeter experiments
Biofuels
• Biogas: from animal manure, other organic wastes, energy crops
Power Alcohol
• Ethyl alcohol has high surface tension and its atomization, especially at
lower temperature, is difficult causing starting trouble.
• 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.
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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.
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LEARNING OUTCOMES
Deduce the concept by which organic compounds become fuel;
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REFERENCES