Unit 5 Fuels
Unit 5 Fuels
Suggested Readings:
1.Engineering Chemistry by Vairam S, Kalyani P.
and Suba R.
2.Engineering Chemistry by Renu Bapna and
Renu Gupta.
Unit Objectives
At the end of the unit, you should be able to:
1.define fuel;
2.describe the properties of fuels;
3.Identify the classification of fuels;
4.discuss calorific value of fuels and its importance;
5.Differentiate solid, liquid and gaseous fuels from one to another.
Definition
Fuels are dense repositories of energy
that are consumed to provide energy
services such as heating, transportation
and electrical generation. Even though
most fuels ultimately get their energy
from the sun
A fuel is a combustible substance
containing carbon as the main constituent
which on proper burning gives large
amount of heat that can be used
economically for domestic and industrial
purposes.
Chemical fuel is a combustible
carbonaceous material which on proper
burning in air gives large amount of heat
that can be used economically for
domestic and industrial purposes
Ex. wood, charcoal, coal, kerosene,
petrol, diesel, producer gas, water gas,
natural gas, etc.
So, carbon compounds have been used for many
centuries as the source of heat and energy.
transport
Classification
A. On the basis of occurrence, fuels are
classified as
primary and secondary fuels
1. Primary fuels occur in nature and
are used
without processing.
2. Secondary fuels are obtained by
chemical
processing of primary fuels.
B. On the basis of physical state, fuels
are classified as solid, liquid and gaseous fuels6
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Calorific Value
• Calorific value of a fuel is "the total quantity of heat
liberated, when a unit mass (or volume) of the fuel is
burnt completely."
Units of heat :
(1) 'Calorie' is the amount of heat required to raise the
temperature of one gram of water through one degree
Centigrade (15-16°C).
(2) "Kilocalorie" is equal to 1,000 calories. It may be
defined as 'the quantity of heat required to raise the
temperature of one kilogram of water through one degree
Centigrade. Thus: 1 kcal = 1,000 cal
(3) "British Thermal unit" (B.T.U.) is defined as "the
quantity of heat required to raise the temperature of one
pound of water through one degree Fahrenheit (60-61°F).
This is the English system unit.
1 B.T.U. = 252 cal = 0.252 kcal 1 kcal = 3.968 B.T.U.
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Calorific Value
Higher or gross calorific value (HCV)
Higher calorific value (HCV) is "the total amount of heat produced,
when unit mass/volume of the fuel has been burnt completely and
the products of combustion have been cooled to room
temperature"(i.e., 15°C or 60°F ).
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Importance of CV
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The higher heating value takes into account the
latent heat of vaporization of water in the
combustion products, and is useful in calculating
heating values for fuels where condensation of
the reaction products is practical (e.g., in a gas-
fired boiler used for space heat).
If the fuel has higher calorific value it will have
tendency to produce more power in the engine.
The fuels with less calorific value tend to burn
inefficiently thus causing lots of exhaust and air-
pollution.
MOST IMORTANT QUALITY INDICATOR OF A
FUEL
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Solid Fuels
COAL
Coal is regarded as a fossil fuel produced from large
accumulations of vegetable debris due to partial decay
and alteration by the action of heat and pressure over
millions of years. Coal is a highly carbonaceous matter
that has been formed as a result of alteration of
vegetable matter (e.g., plants) under certain favourable
conditions. It is chiefly composed of C, H, N, and O,
besides non-combustible inorganic matter.
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Solid Fuels
Classification of Coal
• Coals are classified on the basis of their rank. Rank is
defined as the degree or extent of maturation and is
therefore a qualitative measure of carbon contents. Peat,
lignite and sub-bituminous coals are referred as low rank
coals while bituminous coals and anthracites are classed
as high rank. In European terminology, the lignite and
sub-bituminous coals are called soft coals while
bituminous coals and anthracite coals are termed as hard
coals. In North American terminology, the coal series is
written as
Wood
peat
lignite
bituminous
anthracite.
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Solid Fuels
Analysis of Coal
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1
Solid Fuels
(2) Nitrogen has no calorific value and hence, its presence in coal is
undesirable; thus, a good quality coal should have very little nitrogen
content.
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Solid Fuels
Nitrogen
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Solid Fuels
Sulfur is determined from the washings obtained from the known
mass of coal, used in a bomb calorimeter for determination of a
calorific value. During this determination, S is converted into
sulphate. The washings are treated with barium chloride solution,
when barium sulphate is precipitated. This precipitate is filtered,
washed and heated to constant weight.
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Solid Fuels
(3) Sulphur, although contributes to the heating value of coal, yet on
combustion produces acids (SO2 and SO3), which have harmful effects
of corroding the equipments and also cause atmospheric pollution.
(4) Oxygen content decreases the calorific value of coal. High oxygen-
content coals are characterized by high inherent moisture, low calorific
value, and low coking power. An increase in 1% oxygen content
decreases the calorific value by about 1. 7% and hence, oxygen is
undesirable. Thus, a good quality coal should have low percentage of
oxygen
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Liquid Fuels
Petroleum
Petroleum or crude oil is a dark greenish brown or black
coloured viscous oil found deep in earth's crust. The oil is
usually floating over a brine solution and above the oil,
natural gas is present. Crude oil containing mixture of
paraffinic, olefinic and aromatic hydrocarbons with minor
amounts of organic compounds like N, 0 and S. The
average composition of crude oil is C =80 - 87 %, H =11-
15%, S = 0.1 -3.5%, (N +O) =0.1- 0.5%.
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Liquid Fuels
a) Classification of petroleum
Petroleum is classified into three types based on
variation of chemical nature of crude oil found in the earth.
i) Paraffinic-base type crude oil: It contains saturated
hydrocarbons from CH4 to C35H72 and little amount of
naphthalenes and aromatics.
ii) Asphaltic-base type crude oil: It contains mainly
cycloparaffins or naphthalenes with smaller amount of
paraffins and aromatic hydrocarbons.
iii) Mixed-base type crude oil : It contains both paraffinic
and asphaltic hydrocarbons and are generally in the form of
semi-solid waxes.
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Liquid Fuels
Mining and Refining of Petroleum
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Fractional distillation of Crude oil
Liquid Fuels
Various fractions of crude oil and their composition and uses
Composition
Sn Boiling
Name of the fractions Of Uses
. range (OC)
Hydrocarbons.
As domestic and
1. Uncondensed gases Below 30°C C1 to C4 industrial fuel under
the name LPG
2. Petroleum ether 30 70 °C C5 to C7 As a solvent.
Gasoline (or) petrol. 40 - 120 °C As motor fuel, solvent
3. C5 to C9 and in dry cleaning.
Used in medicines
Petroleum jelly and cosmetics
2. - -
(Vaseline)
Catalytic cracking
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Liquid Fuels
Knocking
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• Improvement of antiknock characteristics
• The octane number of fuel can be improved by
(i)blending petrol of high octane number with
petrol of low octane number, so that the
octane number of the latter can be improved.
(ii) the addition of anti-knock agents like Tetra-
Ethyl Lead (TEL).
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Liquid Fuels
Anti-Knocking agent
LEADED PETROL (ANTI-KNOCK AGENT)
growth is stopped.
Liquid Fuels
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Liquid Fuels
CETANE NUMBER (or) CETANE RATING
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Liquid Fuels
Disadvantages of power alcohol
•As ethyl alcohol contains 'O' atoms, the amount of air require for
complete combustion of power alcohol is lesser and therefore
carburetor and engine need to be modified, when only ethyl
alcohol is used as fuel.
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Liquid Fuels
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.
Fermentation
Ethanol is produced by microbial fermentation of the sugar. Microbial
fermentation will currently only work directly with sugars. 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 a
plant is broken down to sugars and subsequently converted to
ethanol.
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Liquid Fuels
Distillation
• For the ethanol to be usable as a 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 (95.6% m/m (96.5% v/v) ethanol and 4.4%
m/m (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 not miscible in all ratios with gasoline, so the water fraction is typically
removed in further treatment in order to burn in combination with
gasoline.
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Liquid Fuels
Dehydration
•There are basically three dehydration processes to remove the water
from an azeotropic ethanol/water mixture. The first process, used in
many early fuel ethanol plants, is called azeotropic distillation and
consists of adding benzene or cyclohexane to the mixture. When
these components are added to the mixture, it forms a heterogeneous
azeotropic mixture in vapor-liquid-liquid equilibrium, which when
distilled produces anhydrous ethanol in the column bottom, and a
vapor mixture of water, ethanol, and cyclohexane/benzene. When
condensed, this becomes a two-phase liquid mixture. The heavier
phase, poor in the entrainer (benzene or cyclohexane), is stripped of
the entrainer and recycled to the feed, while the lighter phase together
with condensate from the stripping is recycled to the second column.
Another early method, called extractive distillation, consists of adding
a ternary component which will increase ethanol's relative volatility.
When the ternary mixture is distilled, it will produce anhydrous ethanol
on the top stream of the column.
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Liquid Fuels
• With increasing attention being paid to saving energy, many methods have
been proposed that avoid distillation altogether for dehydration. Of these
methods, a third method has emerged and has been adopted by the majority
of modern ethanol plants. This new process uses molecular sieves to
remove water from fuel ethanol.
• In this process, ethanol vapor under pressure passes through a bed of
molecular sieve beads. The bead's pores are sized to allow absorption of
water while excluding ethanol. After a period of time, the bed is regenerated
under vacuum or in the flow of inert atmosphere (e.g. N 2) to remove the
absorbed water. Two beds are often used so that one is available to absorb
water while the other is being regenerated. This dehydration technology can
account for energy saving of 3,000 BTU/gallon (840 kJ/L) compared to
earlier azeotropic distillation.
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Liquid Fuels
Biodiesel
A fuel derived from organic oils, such as vegetable oil, rather than petroleum.
Biodiesel's use and production are increasing. It's typically used for aircraft,
vehicles and as heating oil.
Transesterification
Animal and plant fats and oils are composed of triglycerides, which are esters
containing three free fatty acids and the trihydric alcohol, glycerol. In the
transesterification process, the alcohol is deprotonated with a base to make it
a stronger nucleophile. Commonly, ethanol or methanol are used. As can be
seen, the reaction has no other inputs than the triglyceride and the alcohol.
Under normal conditions, this reaction will proceed either exceedingly slowly
or not at all, so heat, as well as catalysts (acid and/or base) are used to speed
the reaction. It is important to note that the acid or base are not consumed by
the transesterification reaction, thus they are not reactants, but catalysts.
Common catalysts for transesterification include sodium hydroxide,
potassium hydroxide, and sodium methoxide.
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Liquid Fuels
• Almost all biodiesel is produced from virgin vegetable oils using the base-
catalyzed technique as it is the most economical process for treating virgin
vegetable oils, requiring only low temperatures and pressures and
producing over 98% conversion yield (provided the starting oil is low in
moisture and free fatty acids). However, biodiesel produced from other
sources or by other methods may require acid catalysis, which is much
slower.
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Gaseous Fuels
COMPRESSED NATURAL GAS
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Gaseous Fuels
• CNG is often confused with liquefied natural gas (LNG). While both
are stored forms of natural gas, the key difference is that CNG is in
compressed form, while LNG is in liquefied form. CNG has a lower
cost of production and storage compared to LNG as it does not
require an expensive cooling process and cryogenic tanks. CNG
requires a much larger volume to store the same mass of natural
gas and the use of very high pressures (3000 to 4000 lbf/in², or 205
to 275 bar).
Properties
l. CNG is; the cheapest, cleanest and least environmentally impacting
alternative fuel.
2. Vehicles powered by CNG produce less carbon monoxide and
hydrocarbon (HC) emission.
3. It is less expensive than petrol and diesel.
4. The ignition temperature of CNG is about 550°C. CNG requires
more air for ignition.
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