Introduction

 A fuel is a substance that produces large amount heat energy either through combustion or through nuclear reaction. This
large amount of heat energy can be used economically for domestic and industrial purposes.
 Fuel that produces heat energy by combustion are termed as “chemical fuels”. . During the process of combustion of a
chemical fuel the atoms of Carbon, Hydrogen, Sulphur etc combine with oxygen with simultaneous liberation of heat. In
the process of combustion, the chemical energy of fuel is converted into heat energy. The concept generally applied to
those materials whivh storing energy in the form of chemical energy that could be released through combustion only
when needed. For example Wood, Coal , charcoal coke petrol etc.

 However combustion is not always necessary for a fuel to produce heat. Energy can also be liberated by fission or fusion
of nuclei. This energy is much greater than the energy released by chemical fuel and such type of fuel are known as
nuclear fuel. For example plutonium, uranium etc.
 CLASSIFICATION OF FUEL
Fuel can be classified on the basis of their (i) occurrence and (ii) Physical state
(i) On the basis of occurrence fuel are also classified in to two categories.
(a) Primary Fuel or Natural Fuels: These are found to occur in nature and are used either processing to a certain extent or
without processing but the chemical comical constitution of fuel does not alter. These are also known as fossil fuels. For
example: Wood, peat, lignite, coal, petroleum, natural gas etc.
(b) Secondary fuel or derived fuel: These are the fuel that are derived from primary fuels by further chemical processing .
For example coke, kerosene, producer gas, water gas etc.

Both primary and secondary fuels may be further classified based upon their physical state as
(a) Solid fuels.
(b) Liquid fuels.
(c) Gaseous fuels.
 CLASSIFICATION OF FUEL
FUEL

OCCURENCE PHYSICAL STATE

PRIMARY OR SECONDARY OR
NATURAL FUEL ARTIFICIAL FUEL

SOLID LIQUID GASEOUS

Characterized by mass, composition, Characterized by composition,
Characterized by composition,
Specific heat, combustion residue and Volume, pressure and thermal
density, Specific heat and other
Other thermal properties properties
Thermal properties
 FUEL

Primary Fuels Secondary fuels

Solid Liquid
Eg- Wood, peat, Gas
Eg- crude
Lignite, Coal Eg- Natural
petroleum,
gas
Natural Gasoline

Liquid
Solid
Eg- Tar Petroleum Distillates- Gas
Eg- Coke,
Gasoline, Kerosene, Gas Oils Eg- Producer gas,
charcoal
Petroleum Residues- Fuel oils, Alcohol water gas, CNG

4
 CHARACTERISTICS OF GOOD FUEL
1. HIGH CALORIFIC VALUE:
A good fuel should have high calorific value i.e. it should produce large amount of heat on burning.
2. MODERATE IGNITION TEMPERATURE:
Ignition temperature: the lowest temperature to which fuel must be preheated so that it starts burning smoothly. If ignition temp.
is low, the fuel catches fire easily. Low ignition temperature is dangerous for storage and transportation of fuel. High temperature
causes difficulty in handling. So ,a good fuel should have moderate ignition temperature.
3. LOW MOISTURE CONTENT:
A good fuel should have low moisture content as moisture content reduces the calorific value.
4. LOW NON-COMBUSTIBLE MATTER CONTENT:
A good fuel should have low contents of non-combustible material as non-combustible matter is left in form of ash which
decreases the calorific value of fuel
5. MODERATE RATE OF COMBUSTION:
The temperature of combustion of fuel depends upon the rate of combustion. If the rate of combustion is low, then required high
temperature may not be reached soon. On the other hand, too high combustion rate causes high temperature very quickly.
 CHARACTERISTICS OF GOOD FUEL
6. MINIMUM SMOKE AND NON-POISONOUS GASES:
On burning, fuel should not give out objectionable and poisonous gases. In other words, gaseous products should not
pollute the atmosphere. Gases like CO, SO2, H2S etc. are some of harmful gases.
7. CHEAP:
A good fuel should be cheap and readily available.
8. EASY TRANSPORTATION:
A good fuel should be easy to handle and transport at low cost
9. CONTROLLABLE COMBUSTION:
Combustion of fuel should be easy to start or stop when required.
10. NON SPONTANEOUS COMBUSTION:
Combustion of fuel should be non-spontaneous otherwise it can cause fire hazards.
11. LOW STORAGE COST:
A good fuel should be easily stored at low cost.
 Comparison of solid, liquid and gaseous fuel
PROPERTY SOLID FUELS LIQUID FUELS GASEOUS FUELS
CALORIFIC VALUE Less calorific value (CV) and High CV and TE than solid High CV and TE than solid
thermal efficiency (TE) due to fuels fuels
high ash and moisture content

CONTROL OF Not easily controlled. Easily controlled by regulating Easily controlled by

COMBUSTION They possess moderate liquid flow. For liquid fuel temperature variation and air
ignition temperature. combustion takes place supply. Combust is very fast
Combustion is slow but it can readily. for gaseous fuel.
not controlled.
APPLICATIONS Not used in Internal Used in ICE Used in ICE
combustion engine (ICE)
MERITS 1. Have moderate ignition 1. Combustion products are 1. Complete combustion
temperature clean and dust and soot occurs so no release of
2. Low production cost as are free smoke or ash particles
not easily explosive so 2. Need less air for complete 2. Preheating can be done to
easily transported and combustion overcome the heat of
stored 3. Easily fired and combustion
extinguished
 Comparison of solid, liquid and gaseous fuel
PROPERTY SOLID FUELS LIQUID FUELS GASEOUS FUELS

DEMERITS 1. Need excess air for 1. High production cost so 1. High production cost so
combustion so not stored easily not stored easily
uncontrollable 2. Require special 2. Highly inflammable so
2. They block air combustion burners risky
circulation during thus releasing offensive
combustion thus odour
accelerates corrosion
3. Flue gases are released
containing dust and soot
particles
 CALORIFIC VALUE
It is defined as the total amount of heat (expressed in calories or kilo calories) liberated
when a unit mass (1gm or 1kg) or volume of the fuel is burnt completely.

It depends upon the nature of the fuel and the relative proportions of the elements present. If
moisture is present there is considerable reduction the calorific value of a fuel. The calorific
value may be theoretically calculated from the chemical composition of the fuel.
If both hydrogen and oxygen are present, it may be assumed that all the oxygen are already
combined with 1/8 of its weight of hydrogen to form water. This fraction is then deducted from
the hydrogen content of the fuel in the calculation. Thus for a fuel containing carbon, hydrogen,
oxygen and sulphur, the calorific value of the fuel is given by DULONG FORMULA
Determination of calorific value from Dulong formula (Theoretically)
Calorific value =1/100 [8080 C + 34500 {H − O/8 } +2240 S] kcal/kg
Where, C = % of Carbon, CV = 8080
H = % of Hydrogen, CV = 34500
O = % of Oxygen, and
S = % of Sulphur, CV = 2240
UNITS FOR heat
BTU –The amount of heat needed to raise the temperature of 1 lb (pound) of water by 10F.
1 BTU = 252 Cal = 1054.6 J = 1054.6 X 107 erg
2. Calorie – The amount of heat needed to raise the temperature of 1 g of water by 10 C.
1 Calorie = 4.815 J = 4.815 X107 erg
3. Kilocalories: The amount of heat needed to raise the temperature of 1 kg of water by 10C.
1 Kcal = 1000 Cal
 GROSS AND NET CALORIFIC VALUE
With fuels containing hydrogen, two calorific values are distinguished, the gross and the
net calorific value
GROSS OR HIGH CALORIFIC VALUE (GCV OR HCV)
(Gross calorific value also known as higher calorific value).
It is defined as the total amount of heat produced when a unit quantity (mass or
volume) of fuel is burnt completely and the products of combustion are cooled to
room temperature.
Usually all fuel contains hydrogen. During combustion, the hydrogen present in the fuel is
converted in to steam. When the combustion products are cooled to room temperature, the
steam gets condensed in to water and heat that equals to the latent heat of condensation
of the steam evolved. This heat gets included in the measured heat and so its value is high.
Hence ,it is called higher calorific value.
 NET OR LOWER CALORIFIC VALUE (NCV OR LCV)
Net calorific value is the heat produced when unit quantity (mass/volume) of a fuel is
burnt completely and the products of combustion are allowed to escape.

Under normal working conditions, when a fuel is burnt water vapour escape along with hot
combustion gases. Hence heat available lesser than the gross calorific value. So net
calorific value also known as low calorific value.
 GROSS CALORIFIC VALUE AND NET CALORIFIC VALUE

Dulong's formula for calorific value from the chemical composition of fuel is :
𝟏 𝑶
HCV = 𝟏𝟎𝟎 [8,080 C + 34,500 ( 𝟖
)+ 2,240 S] kcal/kg

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 - x 587] kcal/kg

LCV = [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.

14
Example 1: 2kg of coal sample was burnt in a bomb calorimeter. The heat liberated was estimated and found to be 14114 Kcal.
Calculate the calorific value of the coal samole.

Ans: Heat liberated on burning of 2 kg coal = 14114 Kcal

𝟏𝟒𝟏𝟏𝟒
Therefore, heat liberated on the combustion of 1Kg coal = 𝟐 = 7057 Kcal.

Example 2 : The gross calorific value of a fuel containing 8% of hydrogen was found to be 9230 Kcal/kg. calculate net calorific
value.

Ans :
𝑁𝐶𝑉 = 𝐺𝐶𝑉 − 0.09 × 𝐻 × 𝐿𝑎𝑡𝑒𝑛𝑡 ℎ𝑒𝑎𝑡 𝑜𝑓 𝑠𝑡𝑒𝑎𝑚

[As we know latent heat of steam is 587 Kcal/kg]

𝑁𝐶𝑉 = [9230 − 0.09 × 8 × 587] Kcal/kg

= 9230 − 422.64

= 8808.36 Kcal/kg
Exmple3: Calculate the gross and net calorific values of a coal sample having the following composition
C = 80%; H = 7%;O = 3%; S = 3.5%; N = 2.5% and ash 4.4%
Solution
(I) G.C.V = 1/100[8080 C+34500(H - O/8)+2240 S] Kcal/kg
= 1/100[8080 X 80 + 34500(7 - 3/8)+2240 X3.5] Kcal/kg
~ 8828.0 Kcal/kg
,,
(II) N.C.V = G.C.V – [0.09H X 587] Kcal/kg

= 8828 – [0.09 X 7 X 587] Kcal/kg

= 8458.2 k cal/kg
 Bomb Calorimeter
It is used to calculate Calorific Value of solid and non- volatile liquid fuels experimentally.
Principle: A known mass of a fuel is burnt in presence of excess oxygen and the heat liberated is absorbed in a known amount of
water. This heat liberated is measured by observing the change in temperature. The calorific value of the fuel can be calculated
using following principle
Heat liberated by the fuel = Heat absorbed by water and the calorimeter.
Thus the quantity of heat produced by burning a unit mass of the fuel is calculated.

Generally Bomb calorimeter

• Generally Bomb calorimeter used to measure enthalpy changes of combustion reactions at a constant volume
• In Bomb calorimeter there is tiny inner metal chamber which is knownas a bomb
•The bomb contains pure oxygen, the reactants are ignited using an electric coil
•A known quantity of water surrounds the bomb and absorbs energy that is released by the reaction
•To obtain precise heat measurements, we must know or find out the heat capacity of the bomb calorimeter
•Heat capacity takes into account all the parts of the calorimeter that can lose or gain.
ctotal= cwater + cthermometer + cstirrer + ccontainer
and qcal= Ctotal Δ T
Ctotal= heat capacity of the calorimeter
CONSTRUCTION:
 CONSTRUCTION:
(i) Stainless steel bomb: It consists of a cylindrical vessel called bomb, made of stainless steel, in which the combustion
of fuel occurs. The bomb is provided with lid, which can be screwed to the body of bomb so as to make a perfect gas
tight seal. The lid is provided with electrodes and an oxygen inlet value. To one of the electrodes, a small ring is
attached. This ring is utilized to support a nickel or stainless steel crucible in which fuel burnt. A small length of a
platinum/ Mg wire is framed in a loop dipping in the fuel and connected to the electrodes which are joined to the
terminal of a battery. The role of Pt is in bomb calorimeter is to resist corrosive action of HNO3 and H2SO4 vapours
formed because of burning of fuel So the inner side of bomb designed such a way that it resist high pressure and
corrosion which may be caused during the combustion.
(ii) Copper calorimeter: This bomb is placed in the copper calorimeter containing a known weight of water.. An accurate
thermometer, which can read the accurate temperatures up to 1/100oC, is fitted to the lid. An electrified operating stirrer
is provided to stir in the copper calorimeter thoroughly.
(iii) Air jacket and water jacket: The copper calorimeter is surrounded by an air jacket along with a water jacket to
prevent loss of heat due to radiation.
 Working:

A known amount of the fuel ( generally 0.5-1gm) is taken in the crucible. A fine Mg wire, touching the
fuel sample is then stretched across the electrodes. About 10 mL of distilled water is introduced into the
bomb to absorb vapors of sulfuric acid and nitric acid formed during combustion. The bomb lid is tightly
screwed. The bomb is filled with oxygen at 25 atmospheric pressure and placed in a copper calorimeter
containing a known weight of water. The initial temperature (T1) of the water is noted after thorough
stirring. The electrode then connected with 6-volt battery to complete the circuit. The sample burns and
heat is liberated. This heat is absorbed by water. Maximum temperature of thermometer is recorded.
Time taken to cool the water in the calorimeter from maximum temperature to room temperature is also
noted.
 CALCULATIONS:
Let,
Weight of fuel sample taken = x gm
Weight of water in the calorimeter = W gm
Water equivalent of calorimeter , stirrer, thermometer , bomb etc = w gm
Initial temperature of water in calorimeter = t10C.
Final temperature of water in calorimeter = t20C.
Higher calorific value of fuel = H caloric/gm
Heat liberated by burning of fuel =𝑥×𝐻
Heat gained by water = 𝑊 × ∆𝑇 × specific heat of water.
= 𝑊 × (𝑡 − 𝑡 ) × 𝑆𝑤𝑎𝑡𝑒𝑟
=𝑊× 𝑡 −𝑡 ×1 =𝑊× 𝑡 −𝑡
Hear gain by calorimeter =w × 𝑡 − 𝑡
Total heat gained =𝑊× 𝑡 −𝑡 +w× 𝑡 −𝑡
= (W + w) × 𝑡 − 𝑡
But
Hear liberated by the fuel = Heat absorbed by water and calorimeter
So, 𝒙 × 𝑯 = (𝐖 + 𝐰) × 𝒕𝟐 − 𝒕𝟏
 CALCULATIONS:

𝒙 × 𝑯 = (𝐖 + 𝐰) × 𝒕𝟐 − 𝒕𝟏

(𝐖 + 𝐰) × 𝒕𝟐 − 𝒕𝟏
𝑯=
𝒙
Generally H is known as gross calorific value (GCV) or high calorific value (HCV)

Now net calorific value (NCV) or lower calorific value (LCV) will be

LCV = HCV – 0.09 H × 587 cal/gm

Heat taken by water in converting steam = 587 cal/gm

CORRECTIONS:
1. Fuse wire corrections (FWC): The gross calorific value calculated above includes the heat liberated by the ignition of Mg fuse wire.
Hence this amount of heat has to be subtracted from the total value.
2. Acid corrections (AC): when fuels containing S and N are oxidized to high temperatures they form H2SO4 and HNO3 releasing energy
(exothermic) that must be considered. The formation of acids is exothermic and this should be subtracted from the obtained value of GCV.
 CORRECTIONS:

[Link] corrections: Heating and cooling are simultaneous process. As the temperature rises above the room
temperature, the loss of heat occurs due to radiation and higher temperature recorded will be slightly less than
the obtained if there was no heat loss. A temperature correction (cooling correction) is therefore necessary to get
the correct rise in temperature.
If the time taken for the water in the calorimeter to cool from maximum temperature attained to room
temperature is x minutes and the rate of cooling is dt/min, then the cooling correction is
= 𝑥 × 𝑑𝑡
And this is added to the rise in temperature.

𝑾+𝒘 𝒕𝟐 − 𝒕𝟏 + 𝒄𝒐𝒐𝒍𝒊𝒏𝒈 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏 − (𝑨𝒄𝒊𝒅 + 𝒇𝒖𝒔𝒆 𝒘𝒊𝒓𝒆 𝒄𝒐𝒓𝒓𝒆𝒄𝒕𝒊𝒐𝒏)

𝑯𝑪𝑽 𝒐𝒇 𝒇𝒖𝒆𝒍 𝑯 =
𝑴𝒂𝒔𝒔 𝒐𝒇 𝒕𝒉𝒆 𝒇𝒖𝒆𝒍 (𝒙)
Numerical problem 3: A coal sample has the following composition by weight. C = 90%, O = 3%, S = 0.5%, N = 0.5 % and ash =
2.5%. Net calorific value of the fuel was found to be 8490 kcal/kg. Calculate the % of H and GCV.
 Solid fuel: Coal

Solid fuel: Solid fuel refers to several types of solid materials that are used to produced energy. For example
wood, coal etc.
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, S and O, besides non-combustible inorganic matter.

Types 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.
 Analysis of Coal
There are two methods: proximate analysis and ultimate analysis.

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 determination of suitability for a particular industrial use.

2. Ultimate Analysis: It includes the determination of carbon, hydrogen, nitrogen, sulphur and oxygen in coal. It is used for
the determination of elements present in the coal and also known elemental analysis. This analysis gives exact results and are
useful in calculating the calorific value of coal using Dulong's formula.

Proximate analysis
1. Moisture Content (MC) : 1gm of powdered and air-dried coal sample in crucible is heated at 105-110⁰C in an electric
air oven for 1 hour. Then the sample is cooled to room temperature and weighed again. The loss in weight represents
moisture. The loss in weight of the sample is found out and percentage of moisture is calculated as % of moisture.
 Proximate analysis
Calculation:
Let the weight of coal sample = W gm
Weight after heating for 1 hour =W1 gm
Loss in weigh that is weight of moisture = (W − W )
( )
% of Moisture = × 100%

= × 100%

Significance of Moisture content

(i) Moisture in coal evaporates during the burning of coal and it takes some of the burning of coal and it takes some of the
liberated heat in the form of latent heat of evaporation. Therefore, moisture lowers the effective calorific value of coal.
(ii) Moisture quenches the fire in the furnace. Hence, lesser the moisture content, better the quality of coal as a fuel.
(iii) It increases the consumption of coal for heating purpose. So presence of higher amount of moisture in coal lengthens the
time of heating.
(iii) However, presence of moisture, up to 10%, produces a more uniform fuel-bed and less of "fly-ash".
 Proximate analysis

2. Volatile matter: The volatile matter present in the coal may be combustible gases such as H2, CO, CH4, and other
hydrocarbons or non combustible gases such as CO2 and N2. It does not include moisture of the coal.
It is determined by heating known weight of moisture free coal in a silica crucible covered with a vented lid at 950± 200C
for 7 min in a muffle furnace. The crucible is then taken out and cooled inside a desiccator and weighed again. Complete
removal of volatile matter is judged by bubbling the gas through a water seal. Loss in weight give the weight of the volatile
matter and % of volatile mater is calculated.
Let the weight of coal sample = W gm
Let the weight of coal sample after heating for 1 hr that is weight after removal of moisture is = W g
Let the weight of sample after removal of volatile matter = W gm
( )
So, % of volatile matter = × 100

= × 100
 Proximate analysis
Significance of volatile matter:
 Volatile matters are the CH4, Hydro carbons, and CO, and incombustible gases like CO2 and NO2 in coal. Thus the
volatile matter is an index of the gaseous fuels present. Typical range of volatile matter is 20 to 35%.
 Coal containing high % of volatile matter burns with a long flame, high smoke and low calorific value
 A high % of volatile matter indicates that a large amount of fuel is burnt as gas.
 Presence of non-combustible gases in undesirable since they do not add to the heat value.
 For efficient use of fuel the outgoing combustible gas (volatile matter) has to be burnt by supplying secondary air. This
requires a large combustion space.
 If the furnace volume is small or flame is short, a large amount of volatile matter will escape unburnt
 Coal with greater % of volatile matter (Say more than 40%) do not form coke well. Presence of low volatile matter
(less than 10%) do not cake at all end and not form good quality coke. Coal having medium (20-30%) volatile matter
are capable of forming hard and strong coke during carbonization.
 High volatile mater containing coal useful in coal gas manufacture because volatile mater in a coal denotes the
proportion of coal that will be converted into gas and tar products by heat. Where as for preparation of metallurgical
coke, coal with low volatile matter is preferred.
 Proximate analysis

3. Analysis of Ash:

After the removal of moisture and volatile matter the residual coal in the crucible in is further heated without lid in a

muffle furnace at 700 ± 50° C for hour. The crucible is then taken out, cooled first in air, then in desiccator and

weighed. The heating, cooling and weighing is to be repeat untill a constant weight is obtained. The residue is reported
as ash on percentage-basis. % of Ash can be calculated as

Let the weight of coal sample = W gm

Let the weight of ash formed = W3 gm

% of ash = × 100

Weight of ash left

% of Ash = × 100
Weight of coal sample taken
 Proximate analysis
Significance of Ash
(i) Ash in the combination product of mineral matter in the coal. It consists mainly SiO2, Al2O3 and Fe2O3
with varying amount of other oxides such as Na2O, CaO, MgO etc. High ash content in coal is undesirable
because it has lower calorific value.
(ii) Ash is a useless, non-combustible matter, which reduces the calorific value of coal. Moreover, ash causes
the hindrance to the flow of air and heat, thereby lowering the temperature. Presence of higher amount of ash
in coal causes obstruction to air supply; thereby the burning of coal becomes irregular. Hence, lower the ash
content, better the quality of coal.
(ii) The presence of ash also increases transporting, handling and storage costs. The presence of ash also
causes early wear of furnace walls, burning of apparatus and feeding mechanism.
 4. Fixed Carbon (FC)
The amount of carbon left is burnt by a primary current of air from hot bed of the fuel.
Fixed carbon: Percentage of fixed carbon = 100 - % of (moisture + volatile matter + ash)

Significance Fixed carbon: Higher the percentage of fixed carbon, greater is its calorific and better the quality
coal. Greater the percentage of fixed carbon, smaller is the percentage of volatile matter. This also represents
the quantity of carbon (in coal) that can be burnt by a primary current of air drawn through the hot bed of a
fuel.
 ULTIMATE ANALYSIS OF COAL
It includes the determination of carbon, hydrogen, nitrogen, sulphur and oxygen in coal. It is used for the
determination of elements present in the coal and also known elemental analysis. This analysis gives exact
results and are useful in calculating the calorific value of coal using Dulong's formula.

1. Carbon and hydrogen: About 1-2 g of accurately weighed coal sample is burnt in a current of oxygen in a
combustion apparatus. C and H present in the coal sample are converted into CO2 and H2O respectively. The
gaseous products of combustion are absorbed respectively in KOH and CaCl2 tubes of known weights. The
increase in weights of these are then determined.
Calculations:
 ULTIMATE ANALYSIS OF COAL
Similarly

Significance of Carbon and hydrogen: Greater the percentage of carbon and hydrogen better is the coal in quality and
calorific value. However, hydrogen is mostly associated with the volatile matter and hence, it affects the use to which the
coal is put. Also higher percentage of carbon in coal reduces the size of combustion chamber required. The amount of
carbon, the major combustible consti1fent of coal, depends on the type of coal and its percentage increases with rank from
lignite to anthracite. Thus, percentage of carbon forms the basis of classification of coal.
 ULTIMATE ANALYSIS OF COAL

Analysis of Nitrogen: Nitrogen present in coal sample is estimated by Kjeldahl’s Method.

About 1 g of accurately weighed powdered 'coal is heated with concentrated H2SO4 along-with K2SO4(catalyst) in a
long-necked flask(called Kjeldahl's flask). Nitrogen present in the coal gets converted to (NH4)2SO4 quantitatively.

After the solution becomes clear, it is treated with excess of NaOH or KOH and the liberated ammonia is distilled over

and absorbed in a known volume of standard H2SO4 (say ~ !

) solution. The unused acid is then determined by back

titration with standard NaOH solution. From the volume of acid used by ammonia liberated, the percentage of N in coal is
calculated.
 ULTIMATE ANALYSIS OF COAL
Analysis of Nitrogen:
 ULTIMATE ANALYSIS OF COAL
Analysis of Nitrogen calculation:
Let the weight of the coal sample = Wgm
Volume ofH2SO4is = V1 mL
Normality of acid = N1
As we know, Equivalents of H2SO4 used = Equivalent of NH3 formed.
Equivalents ofH2SO4 used = N1V1.
Equivalents of NH3 formed.= N1V1.
Generally 1N solution of NH3 fmean 1 gm equivalentNH3 in 1 Litre

Since, 1000 mL 1 N solution of NH3 contains 17 gm NH3 = 14 gm of N

N1V1 of NH3 will contain = × N 1V 1
14 N1V1
% of N = × × 100
1000 W

Volume of H2SO4 × Normality of H2SO4 × 1.4

% of nitrogen =
Weight of coal sample taken
Significance of Nitrogen: Nitrogen has no calorific value and hence its presence in coal is undesirable. Thus, a good
quality coal has very little nitrogen content.
 ULTIMATE ANALYSIS OF COAL
3. Analysis of Sulphur: A known amount of coal is burnt completely in a bomb calorimeter in a current of oxygen. Sulphur
in the coal is oxidized to sulphates. The ash form of the bomb calorimeter is extracted with dilute HCl. The acid extract is the
treated with BaCl2 solution to precipitate sulphate as BaSO4. This precipitate is filtered, washed and heated to constant
weight. From the weight of BaSO4 formed, S is estimated as follows,
 ULTIMATE ANALYSIS OF COAL
Significance of S:
 Although Sulphur increases the calorific value of fuel, yet its presence is undesirable because it gets oxidized to SO2 and
SO3 which causes environmental pollution.

 Sulphur containing coal is not suitable for preparing metallurgical coke. Presence of Sulphur in coke used in the iron
industry affects the quality and properties of steel.
4. Determination of Ash: determination is carried out as in proximate analysis.

5. Determination of Oxygen: Percentage of O = 100 - Percentage of (C + H + S + N + ash)

Significance of Oxygen:
 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.

 Moreover, oxygen is in combined form with hydrogen in coal and thus, hydrogen available for combustion is lesser than
actual one. 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
 Liquid fuel: petroleum
 Liquid fuels are used extensively in industrial and domestic purpose. Application of liquid fuel in internal
combustion engines makes them very essential fuels. The main source of liquid fuel is petroleum fuel. The term
petroleum means rock oil. (In Latin Perra means rock and oleum means oil).
 Petroleum is a fossil fuel because it is made from the remains of plants and animals buried millions of years ago.
Petroleum is a dark, greenish brown, viscous liquid that is found underground. It comprises hydrocarbons such as:
1. It contains straight paraffins or cycloparaffins like methane, ethane, propane, butane, isobutane, pentane,
hexane Olefins like ethene, butene etc
2. Aromatics like benzene etc
[Link] organic compounds containing N, O, S
 . Due to the presence of sulphur, it has an unpleasant smell. It also contains impurities of sand, brine or sea water.
Hence it is called crude oil.

Element Carbon Hydrogen Sulphur Nitrogen Oxygen

% ~75.5 -87.1 ~11.5- 14.8 ~01 -3.5 ~04-3.5 ~0.1-0.9

 Classification of petroleum

Petroleum is classified into three categories according to its composition.

1. Paraffinic base petroleum: It is mainly composed of straight chain saturated
hydrocarbons from CH4 to C35H72 along with small amount of naphthene’s and aromatic
hydrocarbons.
2. Naphthenic or asphaltic base petroleum: It contains mainly cycloparaffins or
naphthenes as main constituent along with smaller amount of paraffins and aromatic
hydrocarbons.
3. Mixed base petroleum: It contains both paraffins and asphatic hydrocarbons.
 Mining and Refining of Petroleum
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
conveI1ed into desired specific products having different boiling points. The 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 or demulsification (Cottrell's process )

The crude oil from the oil well is an extremely stable emulsion of oil and salt water. 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.
Step - II: Removal of harmful impurities
(a) The presence of NaCl and MgCl2 in the crude oil can corrode the refining equipment, hence these salts are
removed by electrical desalting and dehydration methods.
(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.
 Mining and Refining of Petroleum
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.
When the vapours of the oil go up in the fractionating column, they become gradually cooler and get
condensed at different heights of column. The fractions having higher boiling points condense at lower
trays whereas the fractions having lower boiling points condense at higher trays.
Fractional Distillation
Various fractions of crude oil and their composition and uses

-
 Various fractions recovered from Heavy Oil

Boiling Composition
Sl No. Name of the fractions range (OC) of Hydrocarbons Uses
.

1. Lubricating oil - C17 to C20 Used as lubricants

Used in medicines and

2. Petroleum jelly (Vaseline) - - cosmetics

Paraffin wax - Used in candles, wax

3. C20 to C28 paper, boot polish, etc

Used as lubricants.
4. Grease - -
Used for making roads,
water proof roofing,
5. Asphalt or bitumen Above 400°C C30 and above etc
 Cracking
Cracking is decomposition of high molecular weight hydrocarbon (with high boiling points) to low molecular weigh
hydrocarbon with low boiling points).The lower boiling fractions are suitable for internal combustion engines of automobiles.

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) and also quality as straight-run gasoline which is not good enough to use in
automobile industry hence is used only after proper blending. To overcome these difficulties, the higher boiling fractions
(e.g. fuel oil and gas oil) are converted into lower boiling fractions gasoline (petrol) by cracking process.
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
 Thermal cracking
When the cracking process is carried out without any catalyst at high temperature (~ 4500C -7500C) at high pressure (~10-
100 kg/cm2) is known as thermal cracking. In thermal cracking the bigger hydrocarbons breakdown to give smaller
molecules of paraffins, olefins and some hydrogen. This process may be carried out either in liquid phase or in vapour
phase. The important reactions of thermal cracking are decomposition, dehydrogenation, isomerization and polymerization.
.
 Thermal cracking:
Thermal cracking also classified into two categories
(a)Liquid phase thermal cracking: By this method any type of oil (residue, fuel oil or gasoline) can be cracked. The
charge is kept in liquid form by applying high pressure (~ 100 kg/cm2) at a suitable temperature ~ 4500C - 5300C. The
cracked product are separated in a fractional column. The octane rating of the product is 65-70.
(b)Vapour phase thermal cracking: This method is suitable for oil which can be readily vaporized. The oil is first
vaporized and then cracked at about ~ 6000C -6500C and under comparatively low pressure ~ 10 -20 kg/cm2. It required
less time than the liquid phase method. Petrol obtained from vapour phase cracking has better antiknock properties but very
poor stability as compared to petrol obtained form liquid phase cracking.
Comparison of liquid phase and vapour phase thermal cracking:
Characteristic Liquid phase thermal cracking Vapour phase thermal cracking
Cracking temperature ~450- 5300C ~600- 6500C

Pressure ~100 kg/cm2 ~10-20 kg/cm2

Octane rating of petrol 65-70 Greater than 70

Type of oil used under cracking Any heavy oil can be cracked Oil should be readily vaporized
 Catalytic cracking
In this process, cracking is carried out in presence of a catalyst at lower temperature (300°C to 450°C) and pressures (l to
5 kg/cm2). The use of catalyst during cracking accelerates the reaction at the same time modifies the yield and the nature
of products. The catalyst like aluminum silicate [Al2(SiO3)] or alumina [A12O3] used in cracking gives higher yield and
better quality of gasoline.
There are mainly two types of catalytic cracking.
(a)Fixed bed catalytic cracking
(b)Moving bed or Fluidized-bed catalytic cracking

Fixed bed catalytic cracking

In fixed bed catalytic cracking the heavy oil is passed through the heater, where the oil is vaporized and heated to 420 to
450°C and then passed through a catalytic champers containing the catalyst of silica alumina gel (SiO2, Al2O3) or bauxite
mixed with clay and zirconium oxide maintained at 425 to 450°C and 1.5 kg/cm2 pressure. During their passage through
the tower, cracking takes place about 30-40% of the charge is converted into gasoline and about 3- 4% carbon is formed
which gets deposited on the catalytic bed.
 Fixed bed catalytic cracking
The vapours produced are then passed through a fractionating column, where heavy oil fractions condensed. The vapours
are then admitted into a cooler, where some of the gaseous products are condensed along with gasoline and uncondensed
gases move on. The gasoline containing some dissolved gases is then sent to a stabilizer, where the dissolved gases are
removed and pure gasoline is obtained.
When substantial amount of carbon is deposited on the catalyst bed, during cracking, the catalyst stops functioning. It is
reactivated by burning off the deposited carbon in a stream of hot air. During the reactivation of catalyst, the vapours are
diverted through another catalyst chamber so that the reaction proceeds continuously .
 Moving bed or Fluidized-bed catalytic cracking
In this process, solid catalyst is finely powdered, so that it behaves almost as a fluid, which can be circulated in gas stream.
The vapours of cracking stock (gas oil, heavy oil, etc.,) mixed with fluidized catalyst is forced up into a large reactor bed in
which cracking of the heavier molecules into lighter molecules occurs at a temperature of ~500°C and pressure of about to
~5 kg/cm2. The top of the reactor, there is a centrifugal separator, which, allows the low boiling lighter molecules move up
to the top of the reactor and enter into the fractionating column but retains all the catalyst powder in the reactor itself. The
catalyst powder gradually becomes heavier due to coating with carbon formed and settles at the bottom. This is called
spent catalysis and is forced by a blast of air to the regenerator maintained at 6000C. The carbon deposited on the catalyst
powder are burnt off in the regenerator and the catalyst is reactivated. The regenerated catalyst is then flows through a
standpipe to get mixed with fresh charge. The cyclone at the top of the regenerator allows to escape CO2 along with other
gases to escape retaining the catalyst particles. The cracked gases and gasoline are removed from the top of the
fractionating column and sent to a cooler, where gasoline is condensed. It is then sent to a stabilizer to recover pure
gasoline. The product contains a higher proportion of aromatics and iso-paraffins.
 Advantage of catalytic cracking over thermal cracking

(i) The quality and yield of petrol in better

(ii) External fuel is not necessary since the coal embedded in the catalyst supplies the heat.
(iii) Operating pressure is lower
(iv) Byproduct gas evolution being low, yield of petrol is higher
(v) Due to higher aromatics content, the anti-knocking properties are higheer.
(vi) Greater portion of S escape as H2S , so residual S content of the oil is low.
(vii) Gum- forming compound are very low.
(viii) In presence of specific catalyst preferentially the cracking of naphthenic meterials takes place. So it
become richer in paraffinic compounds.
(ix) Only the high-boiling hydrocarbons and the side chain of the aromatics are decomposed preferentially.
 Petroleum Processing

1. Polymerisation: In this method small molecule of hydrocarbon are combine to larger molecules like gasoline. During

cracking large quantities of olefins or unsaturated hydrocaron (like ettylene, propane, and butane) and alkanes (Such as
methane, etahne and butane) are obtained as by products. The gasoline obtained by polymerisation reaction known as
polymer gasoline. It has high octane number.
Polymerisation is carried out in two ways.
i. Thermal Polymerization: In this polymerization of cracked gases is carried out at 500-6000C at 70-350 kg/ cm2 pressure.
The product is gasoline and gas oil which are separated by fraction distilation.
ii. Catalytic Polymerization: It is carried out in the presence of catalyst like phosphoric acid and sulphuric acid. The
process carried out at low temperature (150-2000C).
2. Alkylation: This method used to convert olefins to gasoline. In this process, alkane and alkene are combined together in
the presence of a catalyst under proper temperature and pressure. The most important exmple is the reaction of isobutane and
isobutene in the presence of anhydrous HF at room temperature to give isooctane. This process is used to produce gasoline
of improved quality.
 Synthesis of Gasoline

The gasoline obtained from the fractional distillation of crude petroleum oil is not
enough to meet the requirement of the present community due to vast increase of
automobiles. Hence an alternate source need of finding out to manufacture synthetic petrol.
Synthetic petrol can be manufactured by the process of hydrogenation of coal. The
preparation of liquid fuels from solid coal is called hydrogenation of coal.
• Gasoline is synthesized by the following methods.

• 1. Fischer- Tropsch process.

• 2. Bergius process.

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 Fischer- Tropsch process

This process is based on the catalytic hydrogenation of carbon monoxide. In this process, coal is first converted into
coke. Then water gas is produced by the action of steam over red hot coke.

Water gas is purified by passing over Fe2O3 to remove H2S, then passing over a mixture of Fe2O3, Na2CO3 to remove
organic S compounds. The purified gas is compressed to 5 to 25 atmosphere at 2000 – 3000C passed through a converter
containing catalyst which is a mixture 100 parts cobalt, 5 parts thorium, 8 parts magnesium and 200 parts kieselguhr.

The reactions are strongly exothermic. Hence, the hot out coming gaseous mixture is led to a cooler where a liquid
resembling crude oil is obtained. This is then subjected to fractional distillation to yield gasoline, diesel oil and heavy oil.
The heavy oil can be reuse for cracking to obtained more gasoline. The gasoline formed by Fischer – Tropsch process is rich
in straight chain hydrocarbons, and hence its octane number is only 40. However, the diesel oil obtained is excellent quality.
Fischer- Tropsch process
Bergius process.
Bergius process.
 Refining of gasoline
The straight run gasoline obtained from fractional of crude petroleum or by synthesis contains substance such as
(i) Unsaturated olefines (ii) Sulphur. These substances are undesirable because
 Olefines undergoes oxidation and polymerization leading to gum and sludge formation which stop the function of
engine.
 The Sulphur compounds lead to corrosion of internal combustion engine and H2S gives bad order and make oil sour.
Removal of S related compound (Desulfurization): The S containing gasoline is termed as sour gasoline and the process
of removal of S is known as “ sweetening”. It is accomplished by treating gasoline with sodium plumbite with controlled
addition of S. The S compound are converted into PbS and disulfides. The above process is termed as “Doctors process”.
 Knocking
Knocking is a kind of explosion due to rapid pressure rise occurring in an IC engine.

In a petrol engine, a mixture of gasoline vapour and air at 1: 17 ratio is used as fuel. This
mixture is compressed and ignited by an electric spark. The products of oxidation reaction
(combustion) increases the pressure and pushes the piston down the cylinder. If the
combustion proceeds in a regular way, there is no problem in knocking. But in some cases, the
rate of combustion (oxidation) will not be uniform due to unwanted chemical constituents of
gasoline. The rate of ignition of the fuel gradually increases and the final portion of the fuel-
air mixture gets ignited instantaneously producing an explosive sound known as "Knocking".
Knocking property of the fuel reduces the efficiency of engine. So a good gasoline should
resist knocking.

64
Knocking
Knocking in Spark Ignition Engines
Petrol is used in spark ignition engines. The rapid compression of the fuel-air mixture heats the engine, and it
detonates without the spark being passed. This causes a violent jerk to the piston giving a metallic sound called
knocking.

 Chemical structure and knocking

 The knocking tendency of fuel hydrocarbons mainly depends on their chemical structures. The knocking tendency
decreases in the following order.
 Straight chain paraffins> Branched chain paraffins> Cycloparaffins > Olefins > Aromatics.
 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).
 Anti-Knocking agent

LEADED PETROL (ANTI-KNOCK AGENT)

The anti-knock properties of a gasoline can be improved by the addition of suitable additives.
Tetraethyl lead (TEL) or (C2H5)4 Pb is an important additive added to petrol. Thus the petrol
containing tetra ethyl lead is called leaded petrol.

TEL reduces the knocking tendency of hydrocarbon. Knocking follows a free radical
mechanism, leading to a chain growth which results in an explosion. If the chains are terminated
before their growth, knocking will cease. TEL decomposes thermally to form ethyl free radicals
which combine with the growing free radicals of knocking process and thus the chain growth is
stopped.

66
 OCTANE NUMBER (or) OCTANE RATING

• 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.‘

67
 CETANE NUMBER (or) CETANE RATING

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 α-methyl naphthalene has a long ignition lag and hence its cetane
number is taken as zero.
Thus the cetane number is defined as "the percentage of hexa decane present in a mixture of hexa decane and α -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.