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L-1
Carbon 8080
Hydrogen 34500
Sulphur 2240
If oxygen is also present, it combines with hydrogen to
form H2O. Thus the hydrogen in the combined form is
not available for combustion and is called fixed
hydrogen.
Amount of hydrogen available for combustion = Total
mass of hydrogen-hydrogen combined with oxygen.
1
H 2 O2 H 2O
2
1g 8g 9g
Fixed Hydrogen = Mass of oxygen in the fuel
Therefore, mass of hydrogen available for combustion
= Total mass of hydrogen-1/8 mass of oxygen in fuel
=H-O/8
Dulong’s formula for calculating the calorific value is
given as:
Gross calorific Value (HCV)
1 O
[8080C 34,500( H ) 2,240 S ]kcal / kg
100 8
8470-
Anthracite 90-95 3-4 2-3 0.5-2 3.8-10 1.5-3.5 8800
Analysis of Coal
Coal is analysed in two ways:
1. Proximate analysis
2. Ultimate analysis
The results of analysis are generally reported in the
following ways:
As received basis
Air dried basis
Moisture free basis (oven dried)
Moisture and ash free basis
Proximate Analysis
The data varies with the procedure adopted and
hence it is called proximate analysis.
It gives information about the practical utility of coal.
Proximate analysis of coal determines the moisture,
ash, volatile matter and fixed carbon of coal.
1. Moisture Content: Air dried moisture is
determined by heating a known amount of coal to
105-110 oC in an electric hot air oven for about one
hour. After one hour, it is taken out from the oven
and cooled in a dessicator and weighed.
Percentage of moisture= Loss in weight 100
Weight of coal taken
•Excess of moisture is undesirable in coal.
•Moisture lowers the heating value of coal and takes
away appreciable amount of the liberated heat in the
form of latent heat of vapourisation.
•Excessive surface moisture may cause difficulty in
handling the coal.
•Presence of excessive moisture quenches fire in the
furnace.
2. Volatile Matter: consists of a complex mixture of
gaseous and liquid products resulting from the thermal
decomposition of the coal.
It is determined by heating a known weight of
moisture free coal sample in a covered platinum
crucible at 950 20oC for 7 minutes.
Percentage of volatile matter =
Loss of weight due to volatile matter 100
Weight of coal sample taken
Significance
A high percent of volatile matter indicates that a large
proportion of fuel is burnt as a gas.
The high volatile content gives long flames, high
smoke and relatively low heating values.
For efficient use of fuel, the outgoing combustible
gases has to be burnt by supplying secondary air.
High volatile matter content is desirable in coal gas
manufacture because volatile matter in a coal
denotes the proportion of the coal which will be
converted into gas and tar products by heat.
Ash: Coal contains inorganic mineral substances
which are converted into ash by chemical reactions
during the combustion of coal.
Ash usually consists of silica, alumina, iron oxide and
small quantities of lime, magnesia etc.
Ash content is determined by heating the residue left
after the removal of volatile matter at 700 50oC for
½ an hour without covering
Weight of the residue left 100
Percentage of ash =
Weight of the coal
Significance:
Calorific value of a fuel is directly related to its
carbon content.
A higher percentage of carbon reduces the size of
the combustion chamber
High percentage of hydrogen also increases the
calorific value of coal. The content of hydrogen in
coals varies between 4.5 to 6.5 percent from peat to
bituminous stage.
2. Nitrogen: Nitrogen present in coal sample can be
estimated by Kjeldahl’s method.
Nitrogen H SO Heat
( NH ) SO
2 4 42 4
The contents are then transferred to a round bottomed
flask and solution is heated with excess of NaOH.
The ammonia gas thus liberated is absorbed in a
known volume of a standard solution of acid used.
Fig 4. Estimation of nitrogen by Kjeldahl’s method
NH H SO ( NH ) SO
3 2 4 42 4
Carbonization of Coal (Manufacture of Coke)
It is the process of heating the coal in absence of air to
a sufficiently high temperature, so that the coal
undergoes decomposition and yields a residue which
is richer in carbon content than the original fuel.
Caking and coking of coals: some coals have a
tendency to soften and swell at higher temperatures,
to form a solid coherent mass with porous structure.
Such coals are called caking coals. The residue
formed is called coke. If the coke is hard, porous and
strong, than the coal, from which it is formed, it is
called coking coal.
This property is found only in bituminous type of coal.
Coals with a high percentage of volatile matter are not
fit for coking and are used for gas making. The coals
having 20-30 % volatile matter are good coking coals.
Process of carbonization:
First moisture and occluded gases are driven off.
At about 260-270oC carbon, water, H2S, some low
molecular alkenes and alkanes are evolved.
At about 350oC the decomposition of coal is
accompanied by evolution of gases and elimination of
vapours takes place.
At about 400oC, caking coal becomes soft and plastic.
At about 700oC, hydrogen is evolved
Above 800oC, main gaseous products are evolved
Gases evolved from the plastic mass, expand it to give
foam like appearance.
At further high temperatures this foam like mass
solidifies to form a solid mass with porous structure
called coke.
Types of carbonization
(i) Low temperature carbonization
(ii) High temperature carbonization
(i) Low temperature carbonization: When the
destructive distillation of coal is carried out at
temperatures between 500-700oC.
It is practiced for the production of semi coke. Which
is also called soft coke.
The yield of coke is about 75-80 %.
The coke thus produced contains 5 to 15 % volatile
matter.
The various products of low temperature
carbonization are semi coke, low temperature tar,
crude low temperature spirit and gas.
LTC plants normally use low rank coals. These low
rank coals produce excessive smoke on burning.
Semi coke from LTC is highly reactive and can be
easily ignited into a smokeless flame
The gas which is obtained as a byproduct has higher
calorific value of about 6500-9500 kcal/m3.
(ii) High temperature carbonization: It is carried out
at 900-1200oC. HTC is used for the production of pure,
hard, strong and porous metallurgical coke containing
1-3 % volatile matter. The yield of the coke is 65-75%.
The byproducts-gas and tar have greater amounts of
aromatic hydrocarbons. The gas which is obtained has
lower calorific value of about 5000-6000 kcal/m3 than
that produced in LTC; but the yield of the gas is higher.
The coke obtained is very much harder than the coke
obtained from LTC process and hence is called hard
coke.
Metallurgical coke: The properties of coke depend
on porosity, reactivity and the amount of volatile
matter retained by coke during carbonization. Coke
is mainly used as a heat source and reducing
agent in metallurgy. A good coke in metallurgical
process should possess the following
characteristics:
(i) Purity: The metallurgical coke should contain
lower percentage of moisture, ash, sulphur and
phosphorous.
(ii) Porosity: The coke should be porous so as to
provide contact between carbon and oxygen.
(iii)Strength: The coke used in metallurgical process
should have high strength so as to withstand the
weight of the ore, flux etc. in the furnace.
(iv) size: Metallurgical coke should be of medium
size.
(v) Combustibility: Coke should burn easily. The
combustibility of coke depends on the nature of the
coal, carbonization temperature and reaction
temperature.
(vi) Calorific value: It should be high.
(vii) Reactivity: Reactivity of coke is its ability to react
with CO2, steam, air and oxygen. The reactivity should
not be too high. The reactivity toward CO2 represent
the reduction of CO2
CO ( g ) C (s) 2CO( g )
2
Cost: Coke should be cheap and easily available.
Manufacture of Metallurgical Coke:
(i) Beehive Oven
(ii) Otto Hoffmann oven
(i) Beehive oven: A beehive oven is a fire-brick
chamber having a dome-shaped structure. The
dimensions of a typical oven are 4m and 2.5m high.
The roof is provided with a hole for charging the
coal from the top. Another hole, the discharging
hole is provided in the circumference of the lower
part of the wall. A number of ovens are built in a
row with common walls between neighbouring
ovens.
Beehive coke oven
Demerits of Beehive ovens: The demerits are
•No recovery of byproducts, which are useful
chemicals and are allowed to escape.
•Lower coke yield due to partial combustion
•Lack of flexibility of operation
(ii) Otto-Hoffmann’s oven or By-product Oven: The
beehive ovens have been replaced by chamber ovens
which works on regenerative principle of heat
economy. All the valuable products are recovered
from the outgoing flue gases.
Construction: It consists of no. of narrow rectangular
chambers made of silica bricks.
A single chamber of Otto Hoffmann’s oven
Working: Coal is charged into the chamber.
The coke ovens are heated to 1200oC by burning
gaseous fuels.
The process of carbonization takes place layer by
layer in the coal charge.
As the coal adjacent to the oven walls gets heated, a
plastic zone is formed which moves away from the
walls towards the central zone.
As the coal is converted into coke, there is decrease
in volume. This is because of the removal of volatile
matter in the form of tar and gas at about 500oC. At
further high temperature, the plastic mass solidifies
into hard and porous mass called coke.
Regenerative principle is employed to achieve as
economical heating as possible.
Regenerators are built underneath the ovens.The flue
gases pass their heat to the checker brick work of
regenerators until the temperature rises to 1000oC.
Regenerators work on the principle of alternate
heating and cooling cycles. This is achieved by
periodically changing the direction of flow of gases
through the vertical flues every 30 min or so.
Carbonization of a charge of coal takes about 11-18
hours. After the process is complete, red hot coke is
pushed outside by means of a ram which is electrically
driven. The coke falls into a quenching car. The yield
is 75 % of coal.
Recovery of byproducts: The gases and vapours
evolved on carbonization in coke ovens are not
allowed to mix with the combustion and are collected
separately.The coke oven gas is treated separately
for the recovery of the valuable byproducts.
Saudi Arabia
Russia
United States
Iran
China
Composition:
Pumping of oil
Oil Refining Production
Process
Desalting and Dewatering
Distillation
Cracking
Reforming
Alkylation
Isomerisation
Polymerisation
Hydrotreating
Refining of Petroleum
Crude oil reaching the surface, generally consists of a
mixture of solid, liquid and gaseous hydrocarbons
containing sand and water.
After the removal of dirt, water and much of the
associated natural gas, the crude oil is separated into
a no of useful fractions by fractional distillation.
The resultant fractions are then subjected to
purification known as refining of petroleum.
Steps involved in refining of petroleum:
(i) Demulsification: The crude oil coming out from
the well, is in the form of stable emulsion of oil and
The demulsification is achieved by Cottrell’s process,
in which the water is removed from the oil by electrical
process. The crude oil is subjected to an electrical
field, when droplets of colloidal water coalesce to form
large drops which separate out from the oil.
(ii) Removal of harmful impurities: Excessive salt
content such as NaCl and MgCl2 can corrode the
refining equipment. These are removed by washing
with water.
The objectionable sulphur compound are removed by
treating the oil with copper oxide. The copper sulphide
so formed is separated by filtration.
(iii) Fractional Distillation: It is done in tall fractionating
tower or column made up of steel.
In continuous process, the crude oil is preheated to 350-
380 oC in specially designed tubular furnace known as
pipe still.
Fractional
distillation of crude
petroleum
The hot vapours from the crude are passed through a
tall fractionating column, called bubble tower.
Bubble tower consists of horizontal trays provided with
a no of small chimneys, through which vapours rise.
These chimneys are covered with loose caps, known
as bubble caps. These bubble caps help to provide an
intimate contact between the escaping vapours and
down coming liquid.
The temperature in the fractionating tower decreases
gradually on moving upwards.
As the vapours of the crude oil go up, they become
gradually cooler and fractional condensation takes
place at different heights of column.
The residue from the bottom of the fractionating tower
is vacuum distilled to recover various fractions
Top Flashing
C H Cracking
C H C H
8 18 5 12 3 6
CH 3 CH 2CH 2 CH 2 C H 2 CH 3 CH 2 CH 2
78
Advantages of catalytic cracking over thermal
cracking:
•High temp and pressure are not required in the
presence of a catalyst.
•The use of catalyst not only accelerates the cracking
reactions but also introduces new reactions which
considerably modify the yield and the nature of the
products.
•The yield of the gasoline is higher.
•No external fuel is required for cracking.
•The process can be better controlled so desired
products can be obtained.
•The product contains a very little amount of
undesirable sulphur because a major portion of it
escapes out as H2S gas, during cracking.
•It yields less coke, less gas and more liquid products.
•The evolution of by-product gas can be further
minimized, thereby increasing t he yield of desired
product.
•Catalysts are selective in action and hence cracking
of only high boiling fractions takes place.
•Coke forming materials are absorbed by the catalysts
as soon as they are formed.
Knocking and Anti-knocking
In a spark-ignition petrol engine, a phenomenon that occurs when
unburned fuel-air mixture explodes in the combustion chamber
before being ignited by the spark. The resulting shock waves
produce a metallic knocking sound. Loss of power occurs, which
can be prevented by reducing the compression ratio, re-designing
the geometry of the combustion chamber, or increasing the octane
number of the petrol.(formerly by the use of tetraethyl lead anti-
knock additives, but now increasingly by MTBE – methyl tertiary
butyl ether in unleaded petrol). An antiknock agent is a gasoline
additive used to reduce engine knocking and increase the fuel's
octane rating.
The typical antiknock agents in use are:
Tetra-ethyl lead (phased out)
Methyl cyclo pentadienyl manganese tricarbonyl (MMT)
Ferrocene, Iron pentacarbonyl, Toluene, Isooctane
Octane rating of a spark ignition engine fuel is a
measure of the resistance to detonation or knocking
compared to a mixture of iso -octane (2,2,4-tri methyl
pentane, an isomer of octane) and n- heptane. It is a
numerical representation of the antiknock properties of
motor fuel, compared with a standard reference fuel,
such as isooctane, which has an octane number of 100.
Octane rating does not relate to the energy content of
the fuel .It is only a measure of the fuel's tendency to
burn in a controlled manner, rather than exploding in an
uncontrolled manner.
Octane number: is defined as the percentage of iso
octane present in a mixture of iso-octane and n-
heptane, which has the same knocking characteristics
as that of fuel under examination, under same set of
conditions.
Thus a gasoline with an octane no of 80, would give
the same knocking as a mixture of iso octane and n-
heptane containing 80% of iso octane by volume.
Greater the octane number, greater is the antiknock
property of the fuel.
Cetane Rating: Fuels required for diesel engine are in
contrast to petrol engine fuels, hence a separate scale
is used to grade the diesel oils as they cannot be
graded on octane number scale.
The cetane number of a diesel oil is defined as the
percentage of cetane in a mixture of cetane and a-
methyl naphthalene which will have the same ignition
characteristics as the fuel under test, under same set
of conditions.
Cetane is n-hexadecane
The cetane rating of a fuel depend upon the nature
and composition of hydrocarbon.The straight chain
hydrocarbons ignite quite readily while aromatics do
not ignite easily. Ignition quality order among the
constituents of diesel engine fuels in order of
decreasing cetane no, is as follows:
n-alkanes> naphthenes > alkenes > branched alkanes
> aromatics
Aniline Point
This is an approximate measure of the aromatic content of
a hydrocarbon fuel.
It is defined as the lowest temperature at which a fuel oil is
completely miscible with an equal volume of aniline.
Aniline is an aromatic compound and aromatics are more
miscible in aniline than are paraffins.
Hence, the lower the aniline point, the higher the
aromatics content in the fuel oil.
The higher the aromatics content, the lower the
cetane number of the fuel.
The aniline point can thus be used to indicate the
probable ignition behavior of a diesel fuel.
Diesel Index
The Diesel Index indicates the ignition quality of the
fuel. It is found to correlate, approximately, to the
cetane number of commercial fuels. It is obtained
by the following equation
Diesel Index
aniline po int o F x Degrees API gravity 60o F
100
In API (American Petroleum Institute) scale, water
at 600F has a 0API Of 10.
Diesel Index and cetane number are usually about
50. Lower values will result in smoky exhaust
Gaseous Fuels
Advantages of gaseous fuels
• Least amount of handling
• Simplest burners systems
• Burner systems require least
maintenance
• Environmental benefits: lowest GHG
and other emissions
Gaseous Fuels
Classification of gaseous fuels
Gaseous Fuels
Liquefied Petroleum Gas (LPG)
• Propane, butane and unsaturates, lighter C2
and heavier C5 fractions
• Hydrocarbons are gaseous at atmospheric
pressure but can be condensed to liquid state
• LPG vapour is denser than air: leaking gases
can flow long distances from the source
Applications
Rural heating
Motor fuel
Refrigeration
Cooking
Type of Fuels
Gaseous Fuels
Natural gas
• Methane: 95%
• Remaing 5%: ethane, propane, butane,
pentane, nitrogen, carbon dioxide, other gases
• High calorific value fuel
• Does not require storage facilities
• No sulphur
• Mixes readily with air without producing smoke or
soot
Applications
Power generation
Domestic use
Transportation
Fertilizers
Aviation
Hydrogen
Type of Gaseous Fuels
CNG
Compressed natural gas (CNG) is a fossil fuel substitute for gasoline (petrol), diesel,
or propane/LPG. Although its combustion does produce greenhouse gases, it is a
more environmentally clean alternative to those fuels, and it is much safer than
other fuels in the event of a spill (natural gas is lighter than air, and disperses
quickly when released). CNG may also be mixed with biogas, produced
from landfills or wastewater, which doesn't increase the concentration of carbon in
the atmosphere.
CNG is made by compressing natural gas (which is mainly composed
of methane [CH4]), to less than 1% of the volume it occupies at standard
atmospheric pressure. It is stored and distributed in hard containers at a pressure of
200–248 bar (2900–3600 psi), usually in cylindrical or spherical shapes.
Applications
Cars
Locomotives
Liquefied Natural Gas
Sulphur 3 0.41 -
Oxygen 1 9.89 Trace
Nitrogen Trace 1.22 0.75
Ash Trace 38.63 -
Water Trace 5.98 -
COMBUSTION
Combustion reactions are exothermic reactions
accompanied by evolution of heat and light and the
temperature rises considerably. The amount of oxygen
or air required for combustion of a given sample of fuel
can be calculated.
Solution:
Volume of air supplied = 1.1 × 100/21 × 120/100
= 6.6 m3 = 6600 L
Weight of air supplied = 28.94 × 6600/22.4 =
8.5Kg