Fuels and Combustion

1
 Fuels
Fuels are combustible substance, containing carbon as main
constituents, which on proper burning gives large amount of
heat, which can be used economically for domestic and
industrial purposes.
Alternately, Materials which possess chemical energy is known
as fuel.
For example Wood, Charcoal, coal, Kerosene, petrol diesel, oil
gas etc.

2
During the process of combustion of a fuel, the atom of carbon,
hydrogen etc. combine with oxygen with simultaneous liberation
of Heat at rapid rate. This energy is liberated due to the
“rearrangement of valence electrons” in these atoms, resulting in
the formation of Compounds like CO2 and H2O. Theses
compounds have less energy (heat content) as compared
to reactants.

FUEL + O2 PRODUCTS + HEAT

More heat energy content Lesser heat energy content

C (s) + O2(g) CO2(g) + DH= -94.1Kcal/mole

3
 Classification of Fuels
These can be classified on the basis of their occurrence and
physical state
On the basis of occurrence they are of two types:
Primary Fuels: Fuels which occur in nature as such are
called primary fuels. E.g., wood, peat, coal, petroleum, and
natural gas.
Secondary Fuels: The fuels which are derived from the primary
fuels by further chemical processing are called secondary fuels.
e,g., coke, charcoal, kerosene, coal gas, producer gas etc.
On the basis of physical state these may be classified as:
 Solid Fuels: woods, Peat, Lignite etc.
 Liquid Fuels: Crude oil, Tar, Diesel, Petrol, Kerosene.
4
 Gaseous Fuels: Natural gas, coal gas
Calorific value: The heating value (or energy value or
calorific value) of a substance, usually a fuel or food
(see food energy), is the amount of heat released
during the combustion of a specified amount of it. The
energy value is a characteristic for each substance.
Units of Calorific value:

System Solid/Liquid Gaseous

Fuels Fuels
CGS Calories/gm Calories/cm3
MKS k cal/kg k cal/m3
B.T.U BTU/lb BTU/ft3
5
The quantity of heat can be measured in the following units:
(i) Calorie: It is defined as the amount of heat required to
raise the temperature of 1gm of water by 1oC
1 calorie = 4.184 Joules
(ii) Kilo Calorie: the quantity of heat required to raise the
temperature of one kilogram of water by 1oC
1 k cal = 1000 cal
(iii) British thermal unit: (B. T. U.) It is defined as the amount of
heat required to raise the temperature of 1 pound of water through
1oF.
1 B.T.U. = 252 Cal = 0.252 k cal
(IV) Centigrade heat unit (C.H.U): It is defined as the amount of
heat required to raise the temperature of 1 pound of water through
1oC.
1k cal = 3.968 B.T.U.
6
= 2.2 C.H.U.
 Gross and net calorific Value
Gross Calorific Value: It is the total amount of heat generated
when a unit quantity of fuel is completely burnt in oxygen and
the products of combustion are cooled down to the room
temperature.
As the products of combustion are cooled down to room
temperature, the steam gets condensed into water and latent
heat is evolved. Thus in the determination of gross calorific
value, the latent heat also gets included in the measured heat.
Therefore, gross calorific value is also called the higher
calorific value.
The calorific value which is determined by Bomb calorimeter
gives the higher calorific value (HCV)

7
Net Calorific Value: It is defined as the net heat
produced when a unit quantity of fuel is completely
burnt and the products of combustion are allowed to
escape.
The water vapour do not condense and escape with
hot combustion gases. Hence, lesser amount than
gross calorific value is available. It is also known as
lower calorific value (LCV).
LCV=HCV-Latent heat of water vapours formed
Since 1 part by weight of hydrogen gives nine parts
by weight of water i.e.
H  1O  H O
2 2 2 2
8
Therefore,
LCV=HCV-weight of hydrogen x 9 x latent heat of
steam
= HCV-weight of hydrogen x 9 x 587
Determination of Calorific value
1. Determination of calorific value of solid and non
volatile liquid fuels: It is determined by bomb
calorimeter.
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
9
calorimetery i.e. Heat gained = Heat lost
10
Bomb Calorimeter
Calculations
Let weight of the fuel sample taken = m g
Weight of water in the calorimeter = W g
Water equivalent of the Calorimeter, stirrer, bomb, thermometer
=wg
Initial temperature of water = t1oC
Final temperature of water = t2oC
Specific heat of water = S
Higher or gross calorific value = C cal/g
Heat gained by water = W x Dt x S
= W (t2-t1) S
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 Heat gained by Calorimeter = w (t2-t1) S
Heat liberated by the fuel = m θ cal
Heat liberated by the fuel = Heat gained by water and
calorimeter
m θ = (W+w) (t2-t1) S cal
θ=(W+w)(t2-t1) S cal/g
m

Note: the water equivalent of calorimeter is determined by burning a fuel

of known calorific value and using above equation. The fuel used for this
Purpose is benzoic acid (HCV =6,325cal/g) and napthalene (HCV= 9,622cal/g)
Salicylic acid=5269cal/g

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Net Calorific value:
Let percentage of hydrogen in the fuel = H
Weight of water produced from 1 g of the fuel =
9H/100 g
Heat liberated during condensation of steam
= 0.09H  587 cal
Net (Lower calorific value) = GCV-Latent heat of
water formed
= θ-0.09H  587 cal/gm

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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, sulphur and nitrogen
present in the fuel are oxidized to their corresponding acids
under high pressure and temperature.

S  O  SO
2 2
2SO  O  2H O  2H SO ΔH= -144,000 cal
2 2 2 2 4
2 N  5O  2H O  4HNO
2 2 2 3
ΔH= -57,160,000 cal
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The corrections must be made for the heat liberated in the bomb by the
formation of H2SO4 and HNO3. The amount of H2SO4 and HNO3 is
analyzed by washings of the calorimeter.
For each ml of 0.1 N H2SO4 formed, 3.6 calories should be subtracted.
For each ml of 0.1 HNO3 formed, 1.429 calories must be subtracted.

(C) Cooling correction: As the temperature rises above the room

temperature, the loss of heat does occur due to radiation, and the
highest temperature recorded will be slightly less than that obtained. A
temperature correction is therefore necessary to get the correct rise in
temperature.
If the time taken for the water in the calorimeter to cool down from the
maximum temperature attained, to the room temperature is x minutes
and the rate of cooling is dt/min, then the cooling correction = x  dt.
This should be added to the observed rise in temperature

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Therefore, Gross calorific value

(W+w)(t2-t1)+ cooling correction)- [Acid+fuse correction]

C = Mass of Fuel

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 Some problems

Q:1 0.72 gram of a fuel containing 80% carbon, when burnt in a bomb calorimeter,
Increased the temperature of water from 27.3◦C to 29.1◦C. If the calorimeter contains
250 grm of water and its water equivalent is 150 grms, calculate the HCV of the fuel.
Give your answer in Kj/Kg.

Solution: here X=0.72 g, W=250 g; w=150g; t1= 27.3◦C; t2=29.1◦C

HCV = (W+w)(t2-t1)/X Kcal/Kg

= (250+150)(29.1-27.3)/0.72
= 1,000 kcal/Kg
= 1,000×4.2 KJ/Kg
= 4200KJ/Kg

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 Some problems

On burning 0.83 gram of a solid fuel in a bomb calorimeter, the

temperature of 3500 g water icrease from 26.5˚C to 29.2 ˚C. water
equivalent of calorimeter and latent heat of steam is 385 g and 587 cal/g
respectively. If fuel contain 0.7% hydrogen, calculate the gross and net
Calorific value

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 Some problems

A sample of coal contain c = 93%, H= 6% and ash = 1%. The following

Data were obtained when the above coal was tested in bomb calorimeter
Weight of coal burnt = 0.92 g
Weight of water taken = 550 g
Water equivalent of bomb calorimeter = 2200 g
Rise in temperature = 2.42 ˚C
Fuse wire correction = 10 cal
Acid correction = 50 cal
Calculate gross and net calorific value. Assuming that latent heat of vapor
is s 580 cal/g.

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 Some problems

The following data is obtained in a bomb calorimeter

Weight of crucible = 3.649 g
Weight of crucible and fuel = 4.678 g
Water equivalent of bomb calorimeter = 570 g
Rise in temperature = 2.3 ˚C
Fuse wire correction = 3.6 cal
Acid correction = 3.8 cal
Cooling correction = 0.047 ˚C
Calculate gross and net calorific value if the fuel contain 6.5% hydrogen.

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 Some problems

Determine the water equivalent of the bomb calorimeter apparatus which

gave the following data in the experiments
Weigh of Benzoic acid = 1.346 g
Weight of calorimeter = 1025 g
Weight of calorimeter and water = 3025 g
Initial temperature = 11.872 ˚C
Final Temperature = 14.625 ˚C
Cooling correction = 0.015 ˚C
Heat from fuses = 22 cal
Calorific value of benzoic acid = 6324 cal/g

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 BOYS OR JUNKERS GAS CALORIMETER
AIM :To determine calorific value of gaseous fuel by Junkers gas calorimeter

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23
 BOYS OR JUNKERS GAS CALORIMETER

 AIM :To determine calorific value of gaseous fuel by

Junkers gas calorimeter
 APPARATUS: It consists of following
(i) Bunsen Burner: special type of Burner clamped at the bottom. It can
be pulled out of the combustion chamber or pushed up in chamber
during the carrying out combustion.
(ii) Gasometer: It is employed to measure the volume of gas burning per
unit time. This attached with manometer fitted with the thermometer so
that pressure and temperature of the gas before burning can be read.
(iii) Pressure governor: It can control the supply of quantity of gas at
give pressure.
(iv) Gas Calorimeter/ Combustion chamber: It is a vertical cylinder,
which is surrounded by annular space for heating water and
interchange coils. The entire is covered by an outer jacket in order to
reduce the heat loss by radiation and convection.
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 PROCEDURE:
 Install the equipment on a flat rigid platform near an uninterrupted
continuous water source of ½” size and a drain pipe.
 Connect the gas source to the pressure regulator, gas flow meter
and the burner respectively in series
 Insert the thermometer / temperature sensors, into their respective
places to measure water inlet and outlet temperatures and a
thermometer to measure the flue gas temperature at the flue gas
outlet
 Start the water flow through the calorimeter at a study constant
flow rate and allow it to drain through over flow.
 Start the gas flow slowly and light the burner out side the
calorimeter

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When the steady condition are established, then the reading are taken
simultaneously of:

• The volume of gaseous fuel burnt (V) at given temperature and pressure
in certain period of time (t).

• The quantity of water (W Kg) passing through the annular space during
the same interval of time

• The steady rise in temperature (T2-T1)

• The mass of water (steam) condensed (in Kg) in the outlet water.

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Calculation:
Volume of gas burn at STP in certain time (t)= V
Mass of the cooling water used in time t = W
Temperature of inlet water = T1
Temperature of outlet water = T2
Mass of steam condensed in time t in graduated cylinder = m
Higher calorific value of fuel = L
Specific heat of water = S
Heat absorbed by circulating water = W(T2-T1)×Specific heat of water (s)
Heat produced by combustion of fuel = VL
Thus
VL = W(T2-T1)×S

HCV (L) = W(T2-T1)×S/V

LCV = L - amount of water collected x latent heat

V
m x 587
LCV = L- Kcal/m3
27
V
1 cm3 of water = 1 g of water
 Problem-1

The following were obtained in the Boy’s gas calorimeter experiments

Volume of gas used = 0.1 m3 at NTP

Weight of water heated = 25 Kg
Temp. of inlet water = 20 ˚C
Temp. of outlet water = 33 ˚C
Weight of steam condensed = 0.025 kg
Calculate the gross and net calorific value per m3 at NTP. Take the heat
liberated in condensing water is 580 Kcal/Kg

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 Some problems

During the determination of calorific value of a gaseous fuel by Boy’s

Calorimeter. The following results are obtained
Vol. of gaseous fuel burnt at NTP = 0.093 m3
Weight of water used for cooling the combustion products = 30.5 kg
Weight of steam condensed = 0.031 kg
Temp. of inlet water = 26.1˚C
Temp. of outlet water = 36.5˚C
Determine the gross and net calorific value of the gaseous fuel per cubic
meter at NTP provided that the heat liberated in condensation of water
Vapor is 587cal/g

29
 problems

Calculate the gross calorific value and net calorific value of a

gaseous fuel, 0.012m3 of which when burnt raised the temperature
of 3.5kg of water by 8.2K. Specific heat of water is 4.2 kJ kg-1K-1.
Latent heat of steam is 2.45 kJ kg-1. The volume of water collected
is 6.5cm3 .

V = volume of the gas burnt = 0.015 m3

W = mass of water = 3.5 kg
t2- t1 = rise in temperature = 15.6 K
s = specific heat of water = 4.2kJ kg-1K-1
v = volume of water collected = 6.5 cm3

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Theoretical calculation of Calorific value of a
Fuel: The calorific value of a fuel can be calculated if
the percentages of the constituent elements are
known.
Substrate Calorific value

Carbon 8080

Hydrogen 34500

Sulphur 2240

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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
32
=H-O/8
Dulong’s formula for calculating the calorific value is
given as:
Gross calorific Value (HCV)
1 O
 [8080C  34,500( H  )  2,240S ]kcal / kg
100 8

Net Calorific value (LCV)

9H
 [ HCV   587]kcal / kg
100
 [ HCV  0.09 H  587]kcal / kg

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Calculate the gross and net calorific value of coal having the following
composition carbon = 85%, hydrogen = 8%, sulphur = 1%, nitrogen = 2%,
Ash = 4 %, latent heat of steam 587cal/g.

34
Characteristics of Good Fuel:
(i) Suitability: The fuel selected should be most suitable for
the process. E.g., coke made out of bituminous coal is
most suitable for blast furnace.
(ii) High Calorific value
(iii) Ignition Temperature: A good fuel should have moderate
ignition temperature.
(iv) Moisture content: Should be low
(v) Non combustible matter content
(vi) Velocity of combustion: It should be moderate
(vii) Nature of the products
(viii) Cost of fuel, (ix) Smoke, (x) Control of the process
35
 Solid Fuels:
Wood: Wood has been used as a fuel from ancient times. Due
to large scale deforestation, wood is no longer used.

• Freshly cut wood contains 25-50% moisture.

• Air dried wood contains about 10-15% moisture content.
• The calorific value of air dried wood is about 3500-4500
kcal/kg.
• When wood burns, the ash content is low but the oxygen
content is very high. This makes even dry wood a fuel of low
calorific value.
• Wood charcoal is obtained by destructive distillation of wood.
• The major use of wood charcoal is for producing activated
36 carbon.
 Coal formation

At various times in the geologic past, the Earth had dense forests
in low-lying wetland areas. Due to natural processes such as
flooding, these forests were buried under the soil. As more and
more soil deposited over them, they were compressed. The
temperature also rose as they sank deeper and deeper. As the
process continued the plant matter was protected from
biodegradation and oxidation, usually by mud or acidic water.
This trapped the carbon in immense peat bogs that were
eventually covered and deeply buried by sediments. Under high
pressure and high temperature, dead vegetation was slowly
converted to coal. As coal contains mainly carbon, the
conversion of dead vegetation into coal is called carbonization

37
 The wide, shallow seas of the Carboniferous Period
provided ideal conditions for coal formation, although coal
is known from most geological periods. The exception is
the coal gap in the Permian–Triassic extinction event, where
coal is rare. Coal is known from Precambrian strata, which
predate land plants — this coal is presumed to have
originated from residues of algae

38
39
Coal: coal is highly carbonaceous fossil fuel that has been
produced as a result of vegetable debris under favorable
conditions of high temperature and pressure over million of
years. It is chiefly composed of C, H, N and O besides non-
combustible inorganic matter.
The transformation of the vegetable debris to coal takes place
in two stages:
(a) Biochemical or peat stage: During this stage, the plant
materials were attacked by various micro organisms.
(b) Chemical stage or metamorphism: In this stage, the peat
deposit buried under sedimentary deposits lose moisture
and volatile components under the effect of high
temperature and pressure.
The peat gets enriched in carbon whereas its oxygen content
decreases.
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 Peat, considered to be a precursor of coal, has industrial importance
as a fuel in some regions, for example, Ireland and Finland. In its
dehydrated form, peat is a highly effective absorbent for fuel and oil
spills on land and water. It is also used as a conditioner for soil to
make it more able to retain and slowly release water.

Lignite, or brown coal, is the lowest rank of coal and used almost
exclusively as fuel for electric power generation. Jet, a compact
form of lignite, is sometimes polished and has been used as an
ornamental stone since the Upper Palaeolithic.

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 Sub-bituminous coal, whose properties range from those of
lignite to those of bituminous coal, is used primarily as fuel
for steam-electric power generation and is an important source
of light aromatic hydrocarbons for the chemical synthesis
industry.
Bituminous coal is a dense sedimentary rock, usually black,
but sometimes dark brown, often with well-defined bands of
bright and dull material; it is used primarily as fuel in steam-
electric power generation, with substantial quantities used for
heat and power applications in manufacturing and to make
coke.
“Steam coal" is a grade between bituminous coal and
anthracite, once widely used as a fuel for steam locomotives.
In this specialized use, it is sometimes known as "sea-coal" in
the US. Small steam coal (dry small steam nuts or DSSN) was
used as a fuel for domestic water heating.
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 Anthracite, the highest rank of coal, is a harder, glossy
black coal used primarily for residential and commercial
space heating. It may be divided further into
metamorphically altered bituminous coal and "petrified
oil", as from the deposits in Pennsylvania.

The classification of coal is generally based on the content

of volatiles. However, the exact classification varies
between countries

Graphite, technically the highest rank, is difficult to ignite and is

not commonly used as fuel — it is mostly used in pencils and,
when powdered, as a lubricant.
_____

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Classification of Coal: Coals are mainly classified on the
basis of their degree of coalification from the parent material,
wood. When wood is converted into coal, there is gradual
increase in the concentration of carbon and decrease in the
percentage of oxygen and nitrogen.
Coal is given a ranking depending upon the carbon content of
the coal from wood to anthracite.

Wood Peat Lignite Bituminous coal Anthracite

Increase in carbon contents, Calorific value and hardness

Decrease in H, O, S, N, contents and volatile matter

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Type of Percentage (dry, mineral matter % calorific
coal free basis) moist value
ure
C H O N VM

Wood 45-50 5-6 20-40 0-0.5 - 70-90 4000-

4500
Peat 45-60 3.5-6.5 20-45 0.75-3 45-75 70-90 4125-
5280
Brown Coal 60-75 4.5-5.5 17-35 0.75-2 45-60 30-50 6600-
7100
6600-
Bituminous 75-90 4.0-5.5 20-30 0.75-2 11-50 10-20 8800
coal

8470-
Anthracite
45 90-95 3-4 2-3 0.5-2 3.8-10 1.5-3.5 8800
 Selection of coal

 Calorific value should be high

 Moisture content should be low

 Ash content should be low

 Sulphur and phosphorus contents of coal should be low

 Size of coal should be uniform

46
 Analysis of Coal
In order to assess the quality of coal, the following two types of
analysis are made:
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)

47
 Proximate Analysis
Proximate analysis of coal determines the moisture, ash, volatile matter and
fixed carbon of coal. It gives information about the practical utility of coal.
1. Moisture Content: About 1 g of finely powered air dried coal sample is
weighted in crucible. The crucible is placed in electric hot air oven,
maintained at 105-110 oC. The crucible is allowed to remain in electric
hot air oven for about one hour and then taken out, cooled in a
desiccator and weighed. Loss in weight is reported as moisture
Loss in weight
Percentage of moisture = x 100
Wt. of coal taken
Importance of Proximate analysis:
 Excess of moisture is undesirable in coal.
 Moisture lowers the calorific value of coal because it takes away
appreciable amount of the liberated heat in the form of latent heat of
vaporization.
 Excessive surface moisture may cause difficulty in handling the coal.
48
 Presence of excessive moisture quenches fire in the furnace.
 2. Volatile Matter: It is determined by heating a known weight of moisture
free coal sample in a covered platinum crucible with lid at 950  20oC for 7
minutes in an electrical furnace. The crucible is cooled in a desiccator and
weighed. Loss in weight is reported as volatile matter

Loss in weight
Percentage of volatile matter = x 100
Wt. of coal 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
49converted into gas and tar products by heat.
(3) 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. The crucible
is taken out, cooled first in air, then inside a desiccator and weighed. The
residue is reported as ash on percentage basis.

Wt. of ash left

Percentage of ash = x 100
Significance Wt. of coal taken
The high percentage of ash is undesirable. It reduces the calorific value of
coal.
In furnace grate, the ash may restrict the passage of air and lower the rate
of combustion.
High ash leads to large heat losses and leads to formation of ash lumps.
The composition of ash and fusion range also influences the efficiency of
coal. 50
(4) Fixed Carbon: The percentage of fixed carbon is given by:
Percentage of fixed carbon = 100- [% of moisture + volatile matter + ash]

Significance: Fixed carbon content increases from lignite to anthracite.

Higher the percentage of fixed carbon greater is its calorific value and better
is the quality of coal.
The percentage of fixed carbon helps in designing the furnace and shape of
the fire-box because it is the fixed carbon that burns in the solid state.

51
Ultimate analysis: It is carried out to as certain the composition of
coal.
Ultimate analysis includes the estimation of carbon, hydrogen, sulphur,
nitrogen and oxygen.
Carbon and Hydrogen: A known amount of coal is taken in a combustion
tube and is burnt in excess of pure oxygen. C and H of coal are converted
into CO2 and H2O respectively. Theses gaseous products are absorbed
respectively in KOH and CaCl2 tubes of known weight.

52
Fig. Estimation of carbon and hydrogen
 C + O2 CO2
12 44

H2 +1/2 O2 H2O
2 18 2KOH  CO  K CO  H O
2 2 3 2
CaCl  7 H O  CaCl .7 H O
2 2 2 2

44 g of CO2 contain = 12 g of carbon

Y g of CO2 contain = 12 x Y
44
Percentage of carbon  12  y100
44 weight of coal taken

Percentage of hydrogen  2  z 100

18 weight of coal taken
53
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.

54
    Na SO  2 NH  2H O
( NH ) SO 2NaOH
42 4 2 4 3 2

NH  H SO  ( NH ) SO
3 2 4 42 4
The unused acid is then determined by titrating with NaOH. From the
volume of acid used by NH3 liberated, the percentage of nitrogen can be
calculated.
(3) Sulfur is determined conveniently from the bomb washing from combustion
of a known mass of coal in bomb calorimeter experiment. The washing contain
Sulfur in the form of sulfate which it is precipitate as BaSO4
Weight of barium sulphate obtained x 32 x 100
%S =
Weight of whole sample taken in bomb x 233

(4) Ash is determined as described in proximate analysis

(5) % Oxygen = 100 - % of (C+H+N+Ash)

55
A sample of coal is analyzed as follows: Exactly 2.5 g was weighted into
silica crucible. After heating for an hour at 110˚C, the residue weighed
2.415g. The crucible next was covered with a vented lid and strongly heat
For exactly seven minutes at 950 ˚C. The residue weighed 1.528 g. the
Crucible was then heated without the cover, until a constant weight was
Obtained. The last residue was found to weight 0.245 g. calculate the
percentage result of above analysis.

56
Liquid Fuels: The importance of liquid fuels is the fact that almost all
combustion engines run on them.
Benefits of Liquid fuel:
 They are easy to handle, store and transport.
 After burning they do not leave any applicable amount of ash
 Liquid can easily kindled. The combustion can be started or stopped at
once
 The rate of combustion can easily controlled as desired
 Less excess air is needed in case of liquid fuels as compare to solid fuel
 The furnace space is required is lesser than solid fuel
 Operation is cleaner
The largest source of liquid fuels is petroleum. The calorific value of
petroleum is about 40000 kJ/kg. There are other supplements of liquid fuels
such as coal tar, crude benzol, synthetic liquid fuel made from coal etc.

57
Petroleum: The term petroleum means rock oil. It is also called mineral oil.
Petroleum is a complex mixture of paraffinic, olefinic and aromatic hydrocarbons
with small quantities of organic compounds containing oxygen, nitrogen and
sulphur.
Composition:
Carbon = 79.5% to 87.1%
Hydrogen = 11.5% to 14.8%
Sulphur = 0.1% to 3.5%
Nitrogen and oxygen = 0.1% to 0.5%
Sulphur is present in the form of derivatives of hydrocarbons such as
alkylsulphides, aromatic sulphides etc. Nitrogen is present in the form of
pyridine, quinoline derivatives, pyrrole etc. Combined oxygen is present as
carboxylic acids, ketones and phenols.
The ash of the crude oil is 0.1%.Metals e.g., Silicon, iron, aluminium, calcium,
magnesium, nickel and sodium.
58
 Classification of crude petroleum:

(1) Paraffinic base type crude oil: These category of oil is mainly
composed of saturated hydrocarbons from CH4 to C35H72 and little of
naphthalene and aromatics. The hydrocarbon from C18H38 to C35H72 are
semi solids called waxes.

(2) Asphaltic Base type crude oil: these category of oil contains mainly
cycloparaffinis, or naphthalene with smaller amount of paraffinis and
aromatic hydrocarbons.

(3) Mixed-based type crude oil: these category of oil contains both
paraffinic and asphaltic Hydrocarbons and are generally rich in semi
solid waxes.

59
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.

Fig. : Pumping of oil

60
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 number of useful fractions by fractional distillation and
finally converted into desired specific products. The process of refining
involves the following steps
Step 1: Separation of water (Demulsification): The crude oil coming out
from the well, is in the form of stable emulsion of oil and salt water, which is
yellow to dark brown in color. 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.
Step 2: 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 (solid) so formed is
separated by filtration
61
(iii) Fractional distillation is the separation of a mixture into its component or
fractions on the basis of their boiling point by heating them to a temperature at
which one or more fractions of the compound will vaporize.
It is done in tall fractionating tower or column made up of steel. Fractional
column consists of horizontal trays provided with a no of small chimneys,
through which vapors rise. These chimneys are covered with loose caps,
known as bubble caps. These bubble caps help to provide an intimate contact
between the escaping vapors 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.

62
 Below 30˚C

30-70˚C

40-120˚C

120-180˚C

180-250˚C

250-320˚C

320-400˚C
63
64
The residue from the bottom of the fractionating tower
is vacuum distilled to recover various fractions

Fig. 11: Vacuum distillation of residual oil

65
 Cracking
Gasoline (petrol, C4-C12)) is the most important fraction of crude petroleum.
The yield of this fraction is only 20% of the crude oil. The yield of heavier
petroleum fraction is quite high. Therefore, heavier fractions are converted
into more useful fraction, gasoline. This is achieved by a technique called
cracking.
“Cracking is the process by which heavier fractions are converted into
lighter fractions by the application of heat, with or without catalyst.
Cracking involves the rupture of C-C and C-H bonds in the chains of
high molecular weight hydrocarbons.”
C H Cracking  C H
 C H
10 22 5 12 5 10
Decane n -pentane pentene
B.Pt 174οC B.Pt  36οC

C H Cracking C H
 C H
8 18 5 12 3 6
Nearly 50% of today’s gasoline is obtained by cracking. The gasoline
66obtained by cracking is far more superior than straight run gasoline.
The process of cracking involves the full chemical
changes:
 Higher hydrocarbons are converted to lower
 Hydrocarbons by C-C cleavage. The product obtained on cracking have
low boiling points than initial reactant.
 Formation of branched chain hydrocarbons takes place from straight
chain alkanes.
 Unsaturated hydrocarbons are obtained from saturated hydrocarbons.
 Cyclization may takes place.
 Cracking can also be used for the production of olefins from naphtha's,
oil gas from kerosene.

67
Cracking can be carried out by two methods
Thermal Cracking:. The heavy oils are subjected to high temperature and
pressure, when the bigger hydrocarbons break down to give smaller
molecules of paraffins, olefins etc. this process can be carried either liquid
phase or vapour phase

(a) Liquid Phase thermal cracking: The heavy oil is cracked at a suitable
temperature 475-530oC and under pressures of the range 30-100
kg/cm2. The cracked products are then separated in a fractionating
column. The important fractions are: Cracked gasoline (30-35%),
Cracking gases (10-45%); Cracked fuel oil (50-55%).
(b) Vapour phase thermal cracking: by this methods, only those oils can
be cracked which vapourised at low temperature. The cracking oil is first
vapourised and then crackred at about 600-650oC and under a low
pressures of 10-20 kg/cm2.

68
Catalytic cracking: Cracking is brought about in the presence of a catalyst
at much lower temperatures and pressures. The catalyst used is mainly a
mixture of silica and alumina. Most recent catalyst used is zeolite. The
quality and yield of gasoline is greatly improved by this method.

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.
 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
69
takes place.
There are two methods for catalytic cracking:
(a) Fixed bed catalytic cracking:
Cracked
vapour Cooler
Dissolved gas

Gasoline

Heavy Heavy
oil charge oil Gasoline +
Pre Heater Catalyst chamber Fractionating Dissolved gas
(425-450˚C) (425-450˚C) Stabilizer
column

The heavy oil are heated in a pre heater to cracking temperature (425-450˚C) and then
forced through the catalytic chamber (containing artificial clay and mixed with zirconium
Oxide) maintained at 425-450˚C and 1.5 Kg/cm2 pressure. During their passage through
the tower about 40% heavy oil converted into gasoline and about 2-4% carbon formed.
The vapour produced then passes through fractionating column, where heavy oil fraction
condensed. The vapour are then led through a cooler, where some of the gas are condense
along with the gasoline and uncondensed gas move on. The gasoline containing gas is
then sent to stabilizer, where the dissolved gas are removed and pur gasoline are obtained
70
(b) Moving-bed catalytic cracking:

71
72
Procedure:
(1) The solid catalyst is very finely powered, so that it behave almost as a fluid,
which can be circulated in a gas stream.
(2) The vapours of cracking stocks mixed with fluidized catalyst is forced up into a
large reactor in which heavier molecules are cracked into lighter molecules. Near the
top of he reactor, there is a centrifugal separator (called cyclone), which allow only
the cracked oil vapours to pass on to fractionating column, but retain all the catalyst
powder in the reactor itself
(3) The catalyst powder gradually becomes heavier, due to coating with carbon and
settles to the bottom from where it is forced by an air blast to regenerator (maintained
600˚C)
(4) In regenerator, carbon is burnt and the regenerated catalyst then flow through a
stand pipe for mixing with fresh batch of incoming cracking oil.
(5) At the top of regenerator, there is an separator, which permits only gases (CO2
etc.) to pass out, but holds back catalyst.

73
 Zeolites
Zeolites are microporous, aluminosilicate minerals commonly
used as commercial adsorbents

74
 Reforming
Reforming is a process of bringing about the structural modification in
components of straight run gasoline (prepared by the fractional distillation
of the crude oil), with primary object of improving the octane number.
Reforming can be accomplished by increasing in volatility (reduction of
molecular size) or by the conversion on n-paraffins to isoparafins, olefins,
Aromatics and naphthens to aromatics.

Reforming is carried out either thermally or in the presence of catalyst:

(1) Thermal reforming: thermal reforming is carried out in a reactor, heated at

500-600˚C and a pressure of 85atm. The fed stock is straight run gasoline. To avoid
the formation of gas (at the expanse of gasoline), the condition are controlled by
quenching (rapid cooling) the products by spread of cold oil.
(2) Catalytic reforming: To get better grade and yield of gasoline, catalyst reformin
[Pt (0.75%) supported on alumina] is carried out by using either fixed bed or fluid
bed methods at 460-530˚C and 35-50 atm. The following are the main reaction during
75catalyst reforming:
 Isomerization:
CH3-(CH2)4-CH3 CH3-CH-CH2-CH2-CH3
CH3
n-Hexane
2-methyl pentane
Dehydrogenation:
-3H2

Cyclohexane Benzene

CH3 CH3
-3H2

Methyl-cyclohexane Toluene

Dehydrocyclization:
CH3
CH2 CH3 CH3
H2 C CH3 -H2 -3H2
H2 C CH2
C
H2
Hydrocracking:
[Pt]
CH3-(CH2)8-CH3 + H2 CH3-(CH2)5-CH3
76 n-Decane n-Pentane
 Knocking
In an internal combustion engine, a mixture of gasoline vapours and air is used as fuel.
After the initiation of the combustion reaction by spark in the cylinder, the flame should
be spread rapidly and smoothly through the gaseous mixture, thereby the expanding gas
drive the piston down the cylinder.

The power output and efficiency of an IC engine depends on the Compression ratio
which is the ratio of the volume of the cylinder at the end of the suction stroke to the
volume of the cylinder at the end of the compression stroke.

Volume of cylinder at end of suction stroke

Compression ratio =
Volume of cylinder at end of compression stroke

The efficiency of IC engine increase with increase in compression ratio, which is

dependent upon the nature of constituents present in gasoline.

77
Under ideal conditions, The hydrocarbons in gasoline undergo complete
combustion and the flame propagates smoothly.

“In certain circumstances, the rate of oxidation becomes so great that the
last portion of fuel-air mixture gets ignited instantaneously, producing an
explosive violence, known as Knocking.” the knocking results in loss of
efficiency.

What is reason behind knocking?

78
 Due to deposits of carbon on the walls of the cylinder, some
hydrocarbons of gasoline converted into peroxy compounds. These
accumulated peroxides decompose suddenly and burst into flames
producing shock waves. The shock wave hits the walls of the engine
and the piston with a rattling sound.
The reactions that take place in an IC engine are as given below (taking
ethane as an example for the hydrocarbon present in gasoline):
Under ideal conditions

C2H6 + 7/2 O2  2 CO2 + 3H2O

Under knocking conditions

C2H6 + O2  CH3 –O-O- CH3

(Dimethyl peroxide)
CH3 –O-O- CH3  CH3CHO + H2O
CH3CHO + 3/2 O2  HCHO + CO2 + H2O
9 HCHO + O2  H2O + CO2
The tendency of fuel constituents to knock in the following order:

Straight chain paraffins > Branched chain paraffins > olefins >
cycloparaffins (i.e. naphthalenes) > aromatics

Thus, olefines of the same carbon chain length possess better anti-knocking
Properties than the corresponding paraffins and so one

Effects of knocking:

 Decreases life of engine

 Consumption of fuel is more

80
 Improvement of anti-knocking characteristics of fuel
(Anti-knocking agents)
Addition of tetraethyl led (TEL):
Tetraethyl lead is converted into lead oxide particles in the cylinder and
these particles reacts with the hydrocarbon peroxides molecules formed,
thereby slowing down the chain oxidation reactions and thus decrease the
chances of knocking.
In the process, lead gets deposited on the inner walls of the engines and
at spark plugs, which is harmful for the engine life. Hence
dichloroethane and dibromoethane are added along with tetraethyl lead.

Pb + BrCH2-CH2Br PbBr2 + H2C CH2

These convert the lead into lead halides, which are volatile and escape with
exhaust gases. But, elease of lead compounds pollutes the atmosphere.
Catalytic converters (rhodium catalyst) are used in IC engines to convert
CO in the exhaust to CO2. Lead tetraethyl used as anti knocking agent
poisons the catalyst and hence leaded petrol is not advisable in such IC
engines.
81
Addition of MTBE (Unleaded petrol):
Methyl terta-butyl ether (MTBE) is added to petrol instead of TEL
to boost its octane number. The oxygen of MTBE brings about
complete combustion of petrol preventing peroxide formation and
hence knocking is prevented.
Power alcohol: When ethyl alcohol is used as fuel in internal
combustion engine, it is called as power alcohol. Generally ethyl
alcohol is used as its 5-25% mixture with petrol.

Advantages of power alcohol:

(1) Ethyl alcohol has good anti-knocking property and its octane
number is 90, while the octane number of petrol is about is 65.
Therefore, addition of ehtyl alcohol increases the octane number
of petrol.
(2) Alcohol has property of absorbing any traces of water if present
in petrol.
(3) Alcohol contains higher percentage of oxygen than MTBE and
82hence brings about complete oxidation of petrol more effectively.
 Octane rating of a engine fuel is a measure of the resistance to
knocking.

It as been found that n-heptane knock very badly and hence its anti-knock value
has been given zero, while on the other hand isooctane (2,2,4-trimethyl pentane)
gives very little knocking, so its anti knocking value has been given as 100.

Octane number is the percentage of isooctane present in a mixture of isooctane

and n-heptane has the same knocking characteristics as that of fuel under
examination, under same set of conditions.

 It is a numerical representation of the antiknock properties of motor fuel,

compared with a standard reference fuel.
 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.
 Greater the octane number, greater is the antiknock property of the fuel.

83
 Cetane Number: The suitability of diesel fuel is defined by its cetane
number. The cetane number of a diesel oil is defined as the percentage
of n-hexadecane in a mixture of n-hexadecane and 2-methyl
naphthalene which will have the same ignition characteristics as the
fuel under test, under same set of conditions.
H H H
CH3
H C C C H

H H H

14
2-methyl naphthalene (C.N. =0) n-Hexadecane (C. N. = 100)
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:
4 n-alkanes> naphthenes > alkenes > branched alkanes > aromatics
 Synthetic Petrol
Synthetic petrol can be produced from coal by the following methods
(1) Fisher-Tropsch Process:
In this process, coke is heated and steam is passed over it, thereby, water
gas (CO + H2) is formed
C + H2O (CO + H2)

Water gas is purified by passing through the Fe2O3 (to remove H2S) and
then into Fe2O3 . Na2O3 (to remove organic sulfur compounds).

This purified gas is compressed to 5 to 25 atm and then led through

convertor (containing a catalyst, consisting of a mixture of 100parts cobal
5 parts thoria, 8 parts magnesia) maintained at about 200-300˚C. A mixtur
of saturated and unsaturated hydrocarbons results
n CO + 2n H2 CnH2n + n H2O

85 n CO + (2n+1) H2 CnH2n+2 + n H2O

(1) Bergius Process:

The low ash coal is finely powered and made into a paste with heavy oil
and then a catalyst (composed of tin and nickel oleate) is incorporated.

The whole is heated with hydrogen at 450˚C and under pressure 200-250
atm for about 1.5 h, during which hydrogen combines with coal to form
saturated and unsaturated hydrocarbon, which decompose at prevailing at
high temperature and pressure to yield low boiling liquid hydrocarbons.

The issuing gas are led to condenser, where a liquid resembling crude oil
is obtained, which fractionated to get (a) gasoline (b) middle oil (c) heavy
Oil.
The heavy oil is used again for making paste with fresh coal

86
 Producer gas
Producer gas is essentially a mixture of combustible gases, CO, H2 etc.
associated with large percentage of non combustible gas like CO2, N2 etc.
It is prepared by passing air mixed with little steam (about 0.35 kg/kg coal) over a hot
coke maintained at 1100˚C in special a reactor called ‘gas producer’. It consists of steel
vessels about 3m dia and 4 m in height. The vessel is lined inside with refractory bricks.
coke

Producer gas outlet

Distillation zone
Reduction zone
Combustion zone Coal at 1100˚C

Air mixed with

little steam Exit for ash

87
The producer gas production reactions can be divided into four zone as follows
(a) Ash zone: It is lowest zone consisting mainly of ash. The ash protects the grate
from the intense heat of combustion. Moreover the temperature of supplied air
and steam is increased as they pass through this zone.

(b) Combustion zone: It is the zone next to the ash zone. It is also known as a
oxidation zone. Here carbon burn and forms CO and CO2. the temperature of this
zone is about 1100˚C.
C + O2 CO2 + 97 Kcal

C + 1/2 O2 CO + 29.5 Kcal

(c) Reduction zone: In this zone, CO2 and steam combines with red-hot coke and
liberated free hydrogen and CO.
CO2 + C 2CO -36 Kcal

C + H2O CO + H2 -29 Kcal

C + 2 H2O CO2 + 2H2 -19 Kcal

88
(d) Distillation Zone: In this zone (400-800˚C), the down coming coal is heated by
the out going gases, since the gases give their sensible heat to the coal. The heat give
by the gases and heat radiated from reduction zone helps to distill the fuel.

Compositions:

CO = 22-30%
H2 = 8-12%
N2 = 52-55%
CO2 = 3%
Calorific values = 1300 Kcal/m3

89
 Water Gas (Blue Gas)
Water gas is mixture of combustible gases, CO and H2 with little amount
of non combustible gas like CO2 and N2.
It can be made by passing alternatively steam and little air through a bed
of red hot coal or coke maintained at about 900 to 1000˚C in a reactor,
which consists of steel vessels
coke

Water gas outlet

Coal at 1000˚C

Steam supply Air supply

Exit for ash

90
 Reactions:

(1) Supplied steam reacts with red hot coal at 900-1000˚C to form carbon
monoxide and hydrogen. The reaction is endothermic , so the
temperature of bed falls.
C + H2O CO + H2 -29 Kcal

(2) In order to rise the coal bed at about 1000˚C, the steam supply is
temporarily blown in, when the following exothermic reaction occurs.
C + O2 CO2 + 97 Kcal

2 C + O2 2 CO + 59 Kcal

The temperature again rise bed to about 1000˚C. the cycles of steam run
and air blow are thus repeated alternatively to maintain proper temperature
91
 Average composition of water gas :

H2 = 51%
CO = 41%
N2 = 4%
CO2 = 4%

92
Natural gas
Natural gas is obtained from wells dug in the oil bearing regions. When
natural gas occurs along with petroleum in oil wells is called “wet gas’.
The wet gas is treated to remove propane, propene, butane and butene,
which are used as LPG. When the gas is associated with the crude oil,
It is called dry gas.

The approximate composition of natural gas

CH4= 70-90%
C2H6= 5-10%
H2= 3%
CO+CO2= rest
Calorific value= 12000 to 14000 kcal/m3

93
 H2S gas, if present in natural gas, is removed by scrubbing with
Monoethanol amine (NH2-CH2-CH2-OH)

2 NH2-CH2-CH2-OH + H2S  (NH2-CH2-CH2-OH)2.H2S

Use
(i) It is an excellent domestic fuel and can be conveyed over very large
distances in pipelines.
(ii) It has recently been used in the manufacture of number of chemicals
by synthetic processes.
(iii) It is also used as raw material for the manufacture of carbon black (a
filler for rubber) and hydrogen (used for ammonia synthesis).

94
Compressed natural gas (CNG) is a fossil fuel substitute for
gasoline (petrol), Diesel fuel, and propane/LPG. Although CNG's
combustion does produce greenhouse gases, it is widely considered a
more environmentally "clean" alternative to conventional fuels; plus,
it is much safer than other fuels in the event of a spill (as natural gas
is lighter than air, and disperses quickly when released). CNG may
also be mixed with biogas (produced from landfills or wastewater).

95
 C (s) + O2(g)  CO2 (g)
(12) 32 44

2H2 (g) + O2(g)  2H2O (g)

(2X2=4) 32 2X18=36

S (s) + O2(g)  SO2 (g)

32 32 64

96
Air contains 21% of oxygen by volume and mass percentage is 23

97
98