F UE LS AND C OM B US TION

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 S U B TOPIC S

• Fuels –Introduction, definition, classification, calorific value, Gross and

Net, theoretical calculation (Dulong’s formula)
• Bomb Calorimeter AND Boy’s Calorimeter
• Solid fuel- Coal- classification ,Analysis- Proximate and ultimate
• Carbonisation process-Metallurgical coke-Manufacture of coke by Otto
Hoffmann process.
• Liquid fuel- Refining,cracking: thermal & catalytic, Knocking Octane
and cetane number
• Gaseous fuels - CNG, LPG, NG, Coal gas, Oil gas, Water gas and a
producer gas.

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 I N TRO DUC TI ON

Fuels –Introduction, definition, classification, calorific value,

Gross and Net, theoretical calculation.

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. During the
process of combustion of a fuel, the atoms of carbon, hydrogen, etc
combine with oxygen with simultaneous liberation of heat. The calorific
value of a fuel depends mainly on the two elements.
Eg- Wood, Kerosene, Petrol

• C + O2 CO2 + 94 kcals.
• 2H2 + O2 2H2 O + 68.5 kcals.
The main source of fuel is coal and petroleum. These are stored fuels available in earth’s
crust and are generally called fossil fuels.

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 C L A SSI F I C ATI O N O F F UE L S

• 1. Primary fuels which occur in nature as such, e.g. coal, petroleum and
natural gas.
• 2. Secondary fuels which are derived from the primary fuels, e.g. coke,
gasoline, coal gas, etc.
• Both primary and secondary fuels may be further classified based upon their
physical state as
• (i) solid fuels (ii) liquid fuels and (iii) gaseous fuels

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 CHARACTERISTICS OF A GOOD
FUEL

• i) Fuel should have high calorific value.

• ii) Must have moderate ignition temperature.
• iii) Fuel should have low moisture content.
• iv) Available in bulk at low cost.
• v) Should not burn spontaneously.
• vi) Fuel should burn efficiently, without releasing hazardous
pollutants.
• vii) Handling, storage and transportation should be easy

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 C ALORIFIC 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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 HC V A N D L C V

Higher or gross calorific value:

Gross or 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 ).

Lower or net calorific value (LCV):

Net or lower calorific value (LCV) is "the net heat produced, when unit mass
volume of the fuel is burnt completely and the products are allowed to escape".

 Net calorific value= GCV - Mass of hydrogen per unit weight of the fuel burnt x
0.09 x Latent heat of condensation of water vapour

 NCV=GCV-0.09*H*587 cal/g

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 BO MB C A LOR IMETER

• Bomb calorimeter is used to determine calorific value of solid and liquid fuels
experimentally. A bomb calorimeter contains a cylindrical bomb made by stainless steel.
Combustion takes place in this cylinder.The copper calorimeter also contains electrically
operated stirrer and Beckmann’s thermometer (take reading with temperature difference
up to 0.01oC.

• Calculation: Mass of fuel (solid or liquid)= x g

• Mass of water taken = W g Water equivalent of calorimeter = w g
• Initial temperature of water in calorimeter = T1 K
• Final temperature of water in calorimeter = T2 K
• High or gross calorific value = (𝑾+𝒘)(𝐓𝟐−𝐓𝟏) 𝒙 cal/g

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 CORRECTIONS

• 1. Fuse-wire correction
• 2. Cooling Correction
• 3. Acid Correction

• GCV= (W+w)(T2-T1+Cooling correction)-

(Acid correction+ fuse-wire correction)/x(mass
of fuel)

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 BOY ’ S C A LOR IMETER

• Boy’s Gas Calorimeter Method: This calorimeter is used for determining the calorific value of
gaseous and volatile liquid fuels.
• Principle: The calorific value of gaseous fuels is determined by burning a known volume of gas
sample in a combustion chamber. The released heat is quantitatively absorbed by cooling water,
circulated through the copper coils surrounded the combustion chamber. The mass of the cooling
water and its rise in temperature are noted. The mass of water produced by condensation of steam
is also recorded. The calorific value of the gas sample is then calculated from these data.

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 C ALCULATIONS

Volume of gas burnt = V(m3)

Weight of water= W(kg)
Weight of water condensed=m(kg)
Rise in temperature=(T2-T1)

Heat lost=Heat gain

C=W(T2-T1)/V

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 THEORITICAL CALCULATION

• Dulong's formula for calorific value from the chemical composition of fuel
is :

• HCV = 1/100 [8,080 C + 34,500 (H – O/8)+ 2,240 S] cal/g

• where C, H, O, and S are the percentages of carbon, hydrogen, oxygen and

sulphur in the fuel respectively. In this formula, oxygen is assumed to be
present in combination with hydrogen as water, and

• LCV = [ HCV - 9H/100 x 587] kcal/kg = [HCV - 0.09 H x 587] kcal/kg

• This is based on the fact that 1 part of H by mass gives 9 parts of H2O, and
latent heat of steam is 587 kcal/kg.

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 S OL I D F U EL

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.
• It is chiefly composed of C, H, N, and O, besides non-combustible
inorganic matter.
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.
• The coal series is written as
• Wood peat lignite bituminous

anthracite.

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 ANALYSIS OF COAL

 In order to assess the quality of coal the following two types of analysis
are made.

 1. Proximate Analysis It includes the determination of moisture, volatile

matter, ash and fixed carbon. This gives quick and valuable information
regarding commercial classification and suitability for a particular
industrial use.

 2. Ultimate Analysis It includes the determination of carbon, hydrogen,

nitrogen, sulphur and oxygen in coal.

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Proximate analysis

 (1) Moisture: About 1 g of finely powered air-dried coal sample is weighed in

a crucible. The crucible is placed inside an electric hot air-oven, maintained at
105° - 110°C. The crucible is allowed to remain in oven for 1 hour and then
taken out, cooled in a desiccator and weighed. Loss in weight is reported as
moisture (on percentage-basis).

 % of moisture = Loss in weight x 100

Wt. of coal taken
 (2) Volatile matter: The dried sample of coal left in the crucible in (1) is then
covered with a lid and placed in an electric furnace (muffle furnace),
maintained at 925°± 20°C.

% of volatile matter = Loss in weight due to removal of volatile matter x 100

Wt. of coal sample taken

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(3) Ash: The residual coal in the crucible in (2) is then heated without lid
in a muffle furnace at 700 ± 50° C for 1/2 hour.

%of ash = Wt. of ash left x 100

Wt. of coal taken

(4) Fixed carbon: Percentage of fixed carbon = 100 - % of (moisture +

volatile matter + ash)
 high percentage of fixed carbon is desirable.

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 ULTIM ATE ANALYS IS

Carbon and hydrogen: About 1-2 g of accurately weighed coal sample is burnt
in a current of oxygen in a combustion apparatus.

• % of C = Increase in weight of KOH tube x 12 x 100

Weight of coal sample taken x 44

% of H = Increase in weight of CaCl2 tube x 2 x 100

Weight of coal sample taken x 18

Nitrogen: About 1 g of accurately weighed powdered 'coal is heated with

concentrated H2SO4 along-with K2S04(catalyst) in a long-necked
flask(called Kjeldahl's flask). After the solution becomes clear, it is treated
with excess of KOH and the liberated ammonia is distilled over and absorbed
in a known volume of standard acid solution.
% of N = Volume of acid used x Normality x 1.4
Weight of coal taken

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Sulphur 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.

 % of S = Weight of BaSO4 obtained x 32 x 100

 Weight of coal sample taken x 233

Ash determination is carried out as in proximate analysis.

Oxygen: It is obtained by difference.
 % of O = 100 - % of (C + H + S + N + ash)

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 C O A L V E R S U S C O K E I N M E TA L L U R GI C A L P R O C E S S E S

(1) Coal does not possess as much strength and porosity as coke.
(2) By coking, much of undesirable sulphur is removed.
(3) Coke burns with short flame, due to expulsion of much of its
volatile matter during carbonization.
Because of these reasons, "coke is preferred to coal for metallurgical
purposes", particularly in blast furnaces. On the other hand, coal burns with a
long flame, which is suitable only for reverberatory furnaces.

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TYPES OF COALS

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 MAN U FACTURE O F ME TAL L U RGICAL C O K E
• Otto Hoffman's by-product oven:

• In order to: (1) increase the thermal efficiency of the carbonization process, and
(ii) recover valuable by-product (like coal gas, ammonia, benzol oil, tar, etc.),
Otto Hoffman developed modern by-product coke oven which, unlike beehive
oven, is heated externally by a portion of coal gas produced during the process
itself or by producer gas or by blast furnace gas. Moreover, the heating is done on
the basis of "regenerative system of heat economy", i.e., utilizing the waste flue
gases for heating the checker-work of bricks.

• The by-product coke oven consists of number of narrow silica chambers.

• Each chamber is provided with a charging hole at the top, a gas off-take and a
refractory-lined cast iron door at each ends for discharging coke.

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• A charge consisting of finely crushed coal is introduced through the charging
holes at the top of chambers, which are then closed tightly at both ends to
prevent any access of air.
• The coke ovens are heated to 1,200°C by burning gaseous fuel (like producer
gas) and usually employing a regenerative principle to achieve as economical
heating as possible. The flue gases produced during combustion, before
escaping to chimney, pass on their sensible heat to one of the two sets of
checker brick-work, until this brick-work has been raised to a temperature
of about 1,000°C.
• The flow of heating gases is then reversed and the inlet gases are passed
through the heated checker brick-work, which thus serves to preheat the inlet
gases. The flue gases are then allowed to pass through the second set of
checker bricks to heat it.
• Thus, this cycle goes on. The heating is actually continued, till the evolution
of volatile matter ceases completely. Carbonization of a charge of coal takes
about between 11 to 18 hours.

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It is subsequently quenched by a water spray ('wet quenching’).

In place of wet quenching, "dry quenching" offers advantages, because

the coke produced is more strong, dense, graphitized and non-reactive.
In this method, the red hot coke is placed in a chamber and cooled by
passing inert gases from boilers (like nitrogen).

The heated inert gases are then circulated to boilers, where they
generate steam. The coke produced by 'dry quenching' is cheaper, drier
and contains lesser dust than ‘wet quenched' coke.

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 R E C O V E RY O F B Y- P R O D U C TS

(i)Recovery of tar : The gas is first passed through a tower in which liquor
ammonia is sprayed. Here dust and tar get collected in a tank below, which is
heated by steam coils to recover back ammonia sprayed. The ammonia is used
again.
• (ii) Recovery of ammonia: The gases from the chamber are then passed
through a tower in which water is sprayed. Here ammonia goes into solution
as NH4OH
• (iii) Recovery of naphthalene: The gases are then passed through another
tower in which water at very low temperature is sprayed. Here naphthalene
gets condensed.
• (iv) Recovery of benzene: The gases are then sprayed with petroleum, when
benzene and its homologues are removed.
• (v) Recovery of H2S: The gases are then passed through a purifier, packed
with moist Fe2O3. Here H2S is retained.

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 L I Q UI D F UE L S

The important liquid fuels are petroleum, petroleum products, tar, alcohols. These
are naturally found under the sea surface. Liquid fuels find extensive use in
domestic and industrial purposes.
Petroleum
• Petroleum or crude oil is a dark greenish brown or black coloured viscous oil found
deep in earth's crust.
• The crude oil obtained from the earth crust contains water, sulphur and some
unwanted impurities. After removal of water, sulphur and these impurities, the crude
oil is separated into various useful fractions by fractional distillation and finally
converted into desired specific products.
• This process is called "Refining of Petroleum" and the refining plants are called
"Oil refineries". The process of refining involves the following steps:
 Step -I: Separation of water (Cottrell's process)
 Emulsifying agents are used in which water is removed by Electrical Process. The
crude oil is
 allowed to flow between two highly charged electrodes, where colloidal water
droplets coalesce
 to form large drops, which is then separated out from the oil.

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 ST E P S F O R R E F I NI NG

Step - II: Removal of harmful impurities

 a) The presence of NaCI and MgCI in the crude oil can corrode the refining equipment, hence
 these salts are removed by electrical desalting and dehydration methods.
 b) The sulphur compounds present in the crude oil is removed by treating oil with copper oxide,
 which results in the formation of copper sulphide (solid), which is then removed by filtration

• Step - III: Fractional distillation

The crude oil is then heated to about 400°C in an iron retort, whereby all volatile substances (except asphalt or coke) are
evaporated. The hot vapors are then passed up a fractionating column, which is a tall cylindrical tower containing a
number of horizontal stainless steel trays at short distances. Each tray is provided with small chimney covered with a
loose cap.

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 C R AC KING

• The decomposition of bigger hydrocarbon molecules into simpler, low boiling

hydrocarbons of lower molecular weight is called cracking.
• The gasoline obtained from the fractional distillation of petroleum, has the
highest demand as a motor fuel, but the yield of this fractions is only 20-30%
(Crude oil).
• The cracked gasoline gives better engine performance i.e., they are suitable for
spark -ignition engines of automobiles. In cracking process, higher saturated
hydrocarbon molecules are converted into simpler molecules such as paraffinic
and olefinic hydrocarbons,
• There are two methods of cracking in use
• 1. Thermal cracking
• 2. Catalytic cracking

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THERMAL V/S CATALYTIC CRACKING

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F I XE D BE D V / S MOV I NG BE D C ATALYTIC
CR ACKING

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 K N O C KING

• Knocking is defined as a sharp metallic sound similar to rattling of hammer,

which is produced in the internal combustion engine due to immature ignition
of the air gasoline mixture.

• Disadvantages of knocking:
i) Knocking increases the engine noise and engine runs roughly, due to crank
shaft vibrations.
ii) If knocking is high, it may break the piston.
iii) It decreases power output and efficiency of the machine.
iv) Deposition of unburnt carbon increases in the engine increases due to
knocking.

• .

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 ANTI-KNOCKING AGENTS

Anti-Knocking Agents are the chemical compounds added in small quantities to

motor fuels to improve the antiknock ratings of the fuel.

Some of the Anti-knocking agents are:

1.Tetraethyl lead (TEL) is an important additive added to petrol. Thus the petrol
containing tetra ethyl lead is called leaded petrol.
2. Benzole : A combination of Benzene, Toluene and Xylene.
3. Methyl tertiary Butyl Ether (MTBE): most adaptable for enhancing with
unleaded gasoline. But is not widely accepted because of Environmental
concerns.

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 O C TA N E N U M B E R ( O R ) O C TA N E R ATI N G

Octane number is introduced to express the knocking characteristics of petrol. It

has been found that n-heptane knocks very badly and hence, its anti-knock value
has been given zero. On the other hand, iso-octane gives very little knocking and
so, its anti-knock value has been given 100.

• Thus octane number is defined as 'the percentage of iso-octane present in a

mixture of iso-octane and n-heptane.‘

Iso-octane (Octane number = 100)

• CH3 – CH2 – CH2 – CH2 – CH2 – CH2 - CH3
• n - heptane (Octane number = 0)

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 C E TAN E N U MB E R ( O R ) C E TAN E R AT IN G

• Cetane number is introduced to express the knocking characteristics of diesel. Cetane has
a very short ignition lag and hence its cetane number is taken as 100. On the other hand 2-
methyl naphthalene has a long ignition lag and hence its cetane number is taken as zero.
• CH3 – (CH2)14 – CH3 CH
3

• n-cetane (hexa decane)

• cetane number = 100

• 2-methyl naphthalene (cetane number = 0)

• Thus the cetane number is defined as "the percentage of hexa decane present in a mixture
of hexa decane and 2-methyl napthalene, which has the same ignition lag as the fuel under
test".
• The cetane number decreases in the following order.
• n-alkanes > Cycloalkanes > alkenes >branched alkanes >aromatics
• The cetane number of a diesel oil can be increased by adding additives called dopes.
• Important dopes: Ethyl nitrate, Iso-amyl nitrate.
•

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 G AS E O U S F U E L S

• NATURAL GAS(NG) :
• Natural Gas is obtained from wells dug in the oil bearing regions. When natural gas occurs along with petroleum in oil wells, it is called as ‘wet
gas’ and contains gaseous hydro carbons from C1 to C4. The wet gas is then suitably treated to remove propane, propene, butan e and butane,
which is used as LPG.
• COMPRESS ED NATURAL GAS(CNG):
• When the natural gas is compressed, it is called Compressed Natural Gas (CNG). The primary component present in CNG is methan e. It is
mainly derived from natural gas.
• The natural gas can either be stored in a tank of a vehicle as compressed natural gas (CNG) at 3,000 or 3,600 psi or as liquified natural gas (LNG)
at typically 20-150 psi. A suitably designed natural gas engine may have a higher output compared with a petrol engine because t he octane
number of natural gas is higher than that of petrol.

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Properties of CNG:
• 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.

• Liquified Petroleum Gas (LPG)

LPG or bottled gas or refinery gas is obtained as a by-product during the cracking of
heavy oils or from natural gas. LPG is dehydrated, desulphurised and traces of odorous
organic sulphides (mercaptans) are added to give warning of gas leak.
LPG is supplied under pressure in containers under the trade name like Indane, Bharat
gas, etc.
Its calorific value is about 27,800 kcal/m3 .

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PRODUCER GAS:
• Producer gas is a mixture of combustible gases, CO(30%) and H2(15%) with large amount
of non combustible gases N2(56%) and CO2(3%). Its calorific value is 1300 kcal/m3
It is prepared by passing air mixed with a little steam over a red hot coke maintained at about
l100°C in a special reactor called gas producer.

COAL GAS:
It is a colorless gas with a characteristic odour. Lighter than air and burns with a long smoky
flame.
Obtained when coal is heated in absence of air.

WATER GAS:
It burns with a blue flame and is often termed as ‘blue gas’. It is a mixture of carbon monoxide
and hydrogen with little amount of non-combustible gases such as carbon dioxide and
nitrogen.

OIL GAS:
It is obtained by the cracking of kerosene oil. It is used as a laboratory gas.
Also, used to improve the calorific value of water.

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