UNIT – IV

Fuels and Combustion

DEPARTMENT OF CHEMISTRY
KONGU ENGINEERING COLLEGE
PERUNDURAI
5-Mar-21
 UNIT – IV

Fuels and Combustion:

Introduction – classification of fuels - characteristics of a good fuel -

combustion - calorific values – gross and net calorific values - Dulong‘s formula
(simple problems) - Flue gas analysis by Orsat‘s method - ignition temperature -
spontaneous ignition temperature - explosive range - solid fuels - coal and its
varieties – proximate and ultimate analysis – significance – metallurgical coke -
Otto-Hoffman byproduct method - liquid fuel - refining of petroleum –
manufacture of synthetic petrol - hydrogenation of coal - Bergius process -
knocking - octane number – cetane number - gaseous fuel - water gas
Fuels: Any substance used to produce heat or power by combustion. Any chemical process
accompanied by the evolution of light or heat is called combustion.

Fuel + Oxygen → Combustion products + Heat

Example of Fuels:
wood
Charcoal
Coal
Kerosene
Petrol
Diesel
Producer gas
Oil gas
Solid fuel (e.g., wood, coal)
 Characteristics of Good Fuels:

• High Calorific Values

• Moderate Ignition Temperature
• Low Moisture Content
• Low Ash Content
• Moderate Velocity of Combustion
• Should not produce harmful products
• Low Cost
• Easy Storage & Transportation
• Easily Controllable
 Combustion
Combustion is defined as the process of burning of a substance in the presence of air or
oxygen with the liberation of light and heat.

Ignition
temperature
Explosive
range

Concepts
Flame
Calorific Value:

It is defined as “the total amount of heat liberated, when a unit mass of

fuel is burnt completely”.

• It is used to identified “the Efficiency of a Fuel.

• The amount of heat can be measured by the following units :

Calorie
Kilocalorie
British Thermal Unit (B.T.U)
Centigrade Heat Unit (C.H.U)

Calorie: It is the amount of heat required to raise the temperature of 1g of

water by 1˚C (i.e. 15 to 16 ˚C)
Ignition Temperature Spontaneous Ignition Temperature
•The lowest temperature at which a substance •The minimum temperature at which a substance
catches fire is called its ignition temperature. catches fire spontaneously without external initiator
such as a flame or a spark.

Explosive range
•The minimum and maximum amounts of fuel
vapour that needs to be present in air for the fuel
vapour to ignite.

(Upper explosive limit)

(Lower explosive limit)
TYPES OF CALORIFIC VALUES

♦ Higher or Gross Calorific Value

♦ Lower or Net Calorific Value

Higher or Gross C.V.

It is defined as the total amount of heat liberated, when one unit of fuel is burnt completely and the
combustion products are cooled to room temperature.

Dulong formula can be expressed as

(• If both hydrogen and oxygen are present, it may be assumed that all the oxygen are already
combined with 1/8 (i.e., 1:8 ratio) of its weight of hydrogen to form water.
The surplus hydrogen available for combustion is H-O/8 (i.e., H/1 – O/8)
• This fraction is then deducted from the hydrogen content of the fuel in the calculation)
Lower or net C.V.

It is defined as the amount of heat liberated, when one unit of the fuel is burnt
completely and the combustion product are allowed to escape.

Net or Low C.V. = Gross C.V. – loss due to water formed

Or

LCV=Gross C.V – Mass of hydrogen ´ 9 ´ Latent heat of steam (587 cal/g)

• (Because 1 part by weight of hydrogen produces 9 parts (1 + 8) by mass of water )

H2 + ½ O2 H2O
1 8 9
part parts parts
Problem:
Calculate the grass and net calorific values of coal sample containing 84% carbon, 1.5% sulphur,
6% nitrogen, 5.5% hydrogen and 8.4% oxygen. The calorific values of carbon, hydrogen and
sulphur are 8080 kcal/kg, 34500 kcal/kg and 2240 kcal/kg, respectively, and latent heat of steam is
587 kcal/g.
Solution:
According to Dulong’s formula for calculating calorific value,
where C, O, H, S are % of carbon, oxygen, hydrogen and sulphur, respectively.
Given that C = 84%, O = 8.4%, H = 5.5% and S = 1.5%. Subtracting these in the above equation:

[8080 * 84 + 34,500 (5.5 – 8.4/8) + 2,240 * 1.5]

=
100

Gross calorific value = 8356.05 kcal/kg

Therefore,

Net calorific value = Gross calorific value – 0.09H * 587

= 8356.05 – 0.09 * 5.5* 587

= 8065.485 kcal/kg
 FLUE GAS ANALYSIS
(ORSAT APPARATUS)

INTRODUCTION

 The mixture of gases like CO2, O2, CO etc., coming-out from the combustion

chamber is called flue gases.

 The analysis of a flue gas will give an insight into the complete or incomplete

combustion process and also the efficiency of the engine.

 The flue gases are estimated by using Orsat’s method.

 Construction and working of Orsat’s Apparatus
 It consists of a horizontal tube having a 3-way stopcock at one end and water-jacketed

measuring burette at the other end.

 The horizontal tube also connected to 3-different absorption bulbs for the absorption of

CO2, O2 and CO respectively. The lower end of the burette is connected to water

reservoir (rubber tube)

 The bulb I: Potassium hydroxide solution.

 The bulb II: Alkaline pyrogallol solution.

 The Bulb III: Ammonical cuprous chloride solution

ORSAT’S APPARATUS
Absorption of gases in reagent bottles:

 It is quite necessary to follow the order of absorbing the gases, CO 2 - first, O2 - second and CO -

last.

 This is because the absorbent used for O2 (i.e: alkaline pyrogallol) can also absorb some amount

of CO2 and the % of CO2 left would be less.

(i) Absorption of CO2: CO2 present in the flue gas is absorbed by KOH.

(ii) Absorption of O2 : O2 present in the flue gas is absorbed by alkaline pyrogallol.

(iii) Absorption of CO: CO present in the flue gas is absorbed by ammonical cuprous chloride.
 Significance of Flue-gas Analysis

 This analysis gives an idea about the complete or incomplete combustion process.

 The presence of a high % of CO in the flue gases shows incomplete combustion of

the fuel and also indicates the short supply of oxygen.

 If the flue gases contain considerable amount of oxygen it indicates an excess

supply of oxygen and possibility of complete combustion.

 Classification
of solid fuels
• Solid fuels refers to various forms of solid material
that can be burnt to release energy, providing heat and
light through the process of combustion.
Naturally Man-made
•Common examples of solid fuels include wood, occurred fuel
charcoal, peat, coal etc.

•Solid fuels have been used throughout human history

to create fire and solid fuel is still in widespread use
Wood, peat, Coke, charcoal
throughout the world in the present day. coal etc. etc.
•Also called black gold.

•Found in sedimentary layers of soil.

•Contains carbon, volatile matter, moisture and ash.

•Mostly used for power generation and metallurgy.

•Coal reserves are six times greater than oil and petroleum reserves.
 Classification of Coal
 Coal is classified on the basis of its rank.
Coalification or metamorphism of coal
 The rank of coal denotes its degree of
maturity.
The process of transformation (coalification)
 Based on carbon, moisture, calorific value
of lignite to anthracite
and ash content coal is classified as follows:
Contd…..
 Peat-Peat is not actually coal, but rather the precursor of coal.
 Lignite- Also known as brown coal, is the lowest grade coal with the least concentration of
carbon. Used for generating electricity. Principle reserves is Neyveli in Tamil Nadu.
 Sub-bituminous coal- Sub-bituminous coal is black in color and has a higher heating value
than lignite, primarily as fuel for steam electric power generation.
 Bituminous coal- Bituminous coal is a middle rank coal between sub-bituminous and
anthracite. Bituminous usually has a high heating value and is the most common type of coal used in
electricity generation.
 Anthracite- The highest rank of coal. It is a hard, brittle, and black lustrous coal, often
referred to as hard coal, containing a high percentage of fixed carbon and a low percentage
of volatile matter.

Peat is the most immature coal, hence it is lowest in rank whereas

anthracite is the most matured coal, and hence it is highest in rank.
 To assess the quality of coal

Analysis of
coal

Proximate Ultimate
analysis analysis

To determine the To determine the

moisture, ash, chemical
volatile matter and composition of
fixed carbon coal- C,H,N,S
 Proximate analysis

Estimation of moisture content

It is determined by heating about 1g of finely powdered coal at 100◦ C to 105 ◦C for an hour in a
hot-air oven. The loss in weight is reported as due to moisture.

% of moisture in coal = [loss in weight of coal/weight of coal initially taken]×100

= 0.1/1 *100 = 10%

Significance
 Decreases calorific value of fuel
 Lengthens the time of heating

The lesser the moisture content, the better the quality

of coal
Contd…..

Estimation of volatile matter

For determining volatile matter, a known weight of moisture free coal is taken in a crucible with
properly fitting lid. It is then heated at 950 ◦C ±20 ◦C for exactly seven minutes in previously
heated muffle furnace. The loss in weight is due to volatile matter which is calculated as

% of volatile matter in coal = [loss in weight of moisture free coal/weight of coal sample]×100
= 0.1/1 * 100 = 10 %

Significance
 Decreases calorific value of fuel
 Forms smoke and pollutes air
A good quality coal should have lesser volatile matter
Contd…..

Estimation of ash in coal

A known weight of coal is taken in a crucible and the coal is burnt completely at 700 ◦C-750
◦C in muffle furnace until a constant weight is obtained. The residue left in the crucible is

ash content in coal which is calculated as

% of ash in coal = [weight of ash formed/weight of coal sample taken]×100

= 0.2/1 * 100 = 20 %
Significance
 Decreases calorific value as it is non combustible matter
 Ash disposal is a problem

A good quality coal should have lesser ash content

Contd…..

Estimation of Fixed Carbon

% of Fixed Carbon = 100 - [% of moisture + % of VM + % of ash]

= 100 – [10 % + 10 % + 20 %]
= 60 %
In any good sample of coal, the percentages of moisture, ash,
volatile matter should be as low as possible and thus the
percentage of fixed carbon should be as high as possible.

Higher the fixed carbon content, higher will be its calorific

value.
  Ultimate Analysis
Estimation of Carbon and Hydrogen
Combustion tube Coal sample

•A known amount of coal is burnt in the presence of oxygen as shown above

•C CO2 & H H2 O
• KOH and CaCl2 absorbs CO2 and H2O respectively.
•Increase in weight of the tubes are noted.
Contd….
Let X- the weight of coal sample taken
Y- increase in weight of KOH tube
Z- increase in weight of CaCl2 tube

C + O2 CO2 & H2 +1/2 O2 H2O

12 32 44 2 16 18

% of Carbon in coal = Increase in weight of KOH tube ×12 ×100

weight of coal sample taken ×44

% of Hydrogen in coal = Increase in weight of CaCl2 tube × 2 ×100

weight of coal sample taken ×18
 Estimation of Nitrogen

Coal +Conc H2SO4+K2SO4

•A known amount of powdered coal is heated with conc.H2SO4 and K2SO4 in

Kjeldahl’s flask

•It is heated with excess NaOH.

• (NH4) 2 SO4 + 2NaOH Na 2 SO4 + 2NH3

•Liberated ammonia is distilled over and absorbed in a known volume of standard

solution of acid.
Contd….
 Unused acid is determined by back titration with standard NaOH.
 Thus, the amount of acid neutralized by liberated ammonia from coal is determined.
Let, weight of coal taken = W gm
Volume of 0.1N HCl initially taken = X ml
Volume of unused HCl = Y ml
Acid neutralised by ammonia = (X-Y) ml
1000 ml of 1N HCl = 1 mole of HCl= 1 mole of NH3= 14g of N2

(X-Y) ml of 0.1N HCl = 14 × (X-Y) × 0.1 g of N2

1000 × 1N
14 × (X-Y) × 0.1
W gm of coal sample contains = 1000 × 1N
g of N2

% of nitrogen = Volume of acid used × normality ×1.4

weight of coal taken
Estimation of Sulphur
 It is determined from the washings obtained from the known mass of coal, used in bomb calorimeter
for determination of a calorific value. During this determination, S is converted into sulphate.
 The washings are treated with barium chloride solution when barium sulphate is precipitated.
 This precipitate is filtered, washed and heated to constant weight.
Let, weight of coal taken in bomb = W gm
weight of BaSO4 formed = X gm
S + 2O2 SO4 BaSO4
32 233
233 g of BaSO4 contains 32 g of sulphur.
1 g of BaSO4 contains 32/233 g of sulphur.

% of sulphur = X x 32 x 100
233 x W
Significance and importance of ultimate analysis
Carbon and Hydrogen
 Greater the percentage of C and H better the quality of coal
Nitrogen
 Nitrogen is an inert and noncombustible gas, its presence is not desirable.
Sulphur
 Oxidation products of Sulphur (SO2 and SO3) , have corrosive effect on the
equipment and also cause atmospheric pollution.
 Presence of sulphur is not desirable in coal.
Oxygen
 High oxygen content coals are characterized by high moisture content.
 A good quality coal should contain lesser moisture content.
Carbonisation of coal
 It is the process of heating the coal in the absence of air to a high temperature to produce a residue coke.
Metallurgical coke
 When bituminous coal is heated strongly in the absence of air, the dense, strong, porous mass obtained
is called metallurgical coke.
 Characteristics of Metallurgical coke:-
i) Purity: -It should contain less percentage of moisture, ash, phosphorus and sulphur.
ii) Porosity: -It should be porous, so that combustion should be uniform and complete.
iii) Strength: -The mechanical strength of coke should be very high.
iv)Size:-Coke should be have medium size.
v) Calorific value:-Coke should possess a very high calorific value.
vi) Cost:-Coke should be cheap and easily available.
vii)Combustibility:-Coke should burn easily.
viii) Reactivity:-The reactivity of coke should not be very high.
Metallurgical coke is superior to coal for the following reasons:
•Coke is stronger and more porous than coal.
•Coke contains lesser amount of sulphur than coal.
•Coke does not contain much volatile matter.
Manufacture of Metallurgical coke by Otto-Hoffmann’s method:
Significance of Otto-Hoffman’s method :
To increases the thermal efficiency of the carbonization process.
 To recover the valuable by products (like coal gas, ammonia, benzyl oil, etc).
Working :
•Coal is charged into the chamber having a size of about 10-12m long, 3-4m height and 0.4-0.45m wide.
•The coke ovens are heated to 1200°C by burning gaseous fuels and usually employ a regenerative
principle to attain economical heating.
•The flue gases produced during combustion are passed to the regenerators that takes up the heat and gets
heated to about 1000°C.
•The flow of heating gases is reversed so that the hot flue gases preheat the other chambers.
•Carbonization time is about 12-18 hours.
•Yield is 70%.
Otto-Hoffman by-product coke oven

By-products recovery

Advantages
Removal of H2S
High thermal efficiency
Lesser carbonization time Fe2O3+ 3 H2S --------> Fe2S2+ 3H2O
By-products recovery
Heating is done externally by producer gas
 Liquid fuels – Petroleum
 Petroleum is made from the remains of plants and animals
buried millions of years ago.
 It is a non-renewable resource.
 It contains straight or cycloparaffins.
 Olefins
 Aromatics
 Other organic compounds containing N, O, S.

Constituents Percentage (%)

C 80 – 87
H 11 – 15
S 0.1 – 3.5
N+O 0.1 – 0.5
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  Composition

 Petroleum is a dark, greenish brown, viscous liquid that is found

underground. It comprises hydrocarbons such as:

1. Straight paraffins or cycloparaffins such as methane, ethane,

propane, butane, isobutane, pentane, hexane.
2. Olefins such as ethylene, butene, isobutene and acetylene,
butadienes.
3. Aromatics such as benzene, naphthalene, cyclohexane, methyl
cyclopentane.
4. Some organic compounds containing nitrogen, oxygen and sulphur.

5-Mar-21
 REFINING OF PETROLEUM CRUDE OIL
 The crude oil obtained from the earth is a mixture of oil, water and unwanted
impurities. After the removal of water and other impurities, the crude oil is subjected to
fractional distillation. During fractional distillation, the crude oil is separated into
various fractions.

Step : 1 Separation of water

(Cottrell’s Process)
 The crude oil from 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 combine to form large drops, which is then separated

out from the oil

5-Mar-21
 Step 2: Removal of harmful sulphur compounds & Salts
 Sulphur compounds are removed by treating the crude oil with copper oxide.

The copper sulphide formed is separated out by filtration.

 Electrical desalting are used to remove NaCl and MgCl2

Step 3: Fractional distillation
 The purified crude oil is then heated to about 400°C in an iron retort, where the
oil gets vapourised. The hot vapours are then passed into the bottom of a
“fractionating column” .

 The fractionating column 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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5-Mar-21
  When the vapours of the oil go up in the fractionating column, they
become cooler and get condensed at different trays.

 The fractions having higher boiling points condense at lower trays

whereas the fractions having lower boiling points condense at higher
trays.

 The gasoline obtained by this fractional distillation is called straight-run

gasoline. Various fractions obtained at different trays are given in table

5-Mar-21
 Various fractions, compositions and their uses

5-Mar-21
 SYNTHETIC PETROL
The gasoline, obtained from the fractional distillation of crude
petroleum oil, is called straight run petrol.
As the use of gasoline is increased, the amount of straight run
gasoline is not enough to meet the requirement of the present
community.
Hence, we are in need of finding out a method of synthesizing
petrol.
 Hydrogenation of coal (or) Manufacture of
synthetic petrol
Coal contains about 4.5% hydrogen compared to about 18% in petroleum.
Coal is a hydrogen deficient compound. If coal is heated with hydrogen to
high temperature under high pressure, it is converted to gasoline.
The preparation of liquid fuels from solid coal is called hydrogenation of
coal (or) synthetic petrol.

There are two methods available for the hydrogenation of coal

Bergius process (or direct method).
Fischer-Tropsch process (or indirect method).
 1.Bergius process (direct method)
In this process the finely powdered coal is made into a
paste with heavy oil and a catalyst powder (tin or nickel oleate)
is mixed with it.
The paste is pumped along with hydrogen gas into the
converter, where the paste is heated to 400 − 450°C under a
pressure of 200 − 250 atm.
 Synthetic Petrol

Synthetic petrol is a mixture of alkanes with composition resembling that of petrol, obtained
artificially from coal.

Bergius Process
 During this process hydrogen combines with coal to form saturated
higher hydrocarbons, which undergo further decomposition at higher
temperature to yield mixture of lower hydrocarbons.
The mixture is led to a condenser, where the crude oil is obtained.

The crude oil is then fractionated to yield

(i) Gasoline
(ii) Middle oil
(iii) Heavy oil.
The middle oil is further hydrogenated in vapour phase to yield more
gasoline. The heavy oil is recycled for making paste with fresh coal dust. The
yield of gasoline is about 60% of the coal used.
 KNOCKING
Definition
Knocking is a kind of explosion due to rapid pressure rise occurring
in an CI engine.

Causes of knocking in S.I (Spark Ignition) Engine [Petrol engines]

In a petrol engine, a mixture of gasoline vapour and air at 1:17 ratio
is used as fuel.
 Chemical Structure and Knocking

The knocking tendency decreases as follows

n-alkanes isoparaffins olefins naphthenes aromatics

(aromatics have highest antiknock value whereas n-alkanes have lowest antiknock value)

So, the presence of maximum quantity of aromatics and minimum quantity of n-

alkanes is desirable in petrol.
 Octane Number
 Octane number is used for gasoline (petrol).

Definition:
It is the % of iso-octane in a mixture of iso-octane and n-heptane.
Octane Number is rated from 0 to 100.

• Comparisons are made with blends of two pure hydrocarbons,

n-heptane and iso-octane (2,2,4-trimethylpentane).
 Octane Number
 Higher octane number fuel will have lesser chance of knocking. Hence such fuel can be
compressed to higher extent without observing any knocking.

 Lesser octane number fuel will have higher chance of knocking. Hence such fuel can't be
compressed to higher extent.

 Octane number actually measures the resistance to auto-ignition. Higher the Octane
Number, Higher will be the resistance to auto-ignition.

For example,
Gasoline with a knocking ability that matches that of a blend of
90% isooctane and 10% n-heptane
has an octane number of 90 •
 How octane number of a fuel can be increased ?
1. By putting special additives into the fuel which discourage auto ignition.
2. By blending high-octane fuels in with the ordinary petrol.

Anti-knocking additives
• Anti-knocking additives are substances which reduce the tendency of a fuel to auto-ignite,
and so increase the octane number.
• Small amounts of lead compounds have been used as economical and effective anti-
knock additives. tetraethyl lead (TEL)
• But it damage the environment.

 Other Additives
 Toluene , Xylene, tertiary-butyl-ether (MTBE) , Methanol or Ethanol Alcohol and Tertiary
Butyl Alcohol
 CI Engine
In a CI engine,
 Air alone gets compressed.
 Diesel is sprayed which must ignite spontaneously
 The product of combustion increases pressure and pushes
the piston out and expels the exhaust gases from the
cylinder.
 Knocking in CI Engine
In Diesel Engine,

Sometimes, in some cases,

 Even after the compression stroke is over and even after the diesel oil is sprayed, burning
may not start.

 So more and more fuel is injected automatically and sudden ignition may occur . This is
called delayed-ignition.

 This delayed ignition causes explosive.

 This is called knocking.

 Chemical Structure and Knocking

The knocking tendency increases as follows

n-alkanes isoparaffins olefins naphthenes aromatics

(n-alkanes have highest antiknock value whereas aromatics have lowest antiknock value)

So, the presence of maximum quantity of n-alkanes and minimum quantity of

aromatics is desirable in diesel.
 Cetane Number
 Cetane number is used for diesel.

Definition:
It is the % of n-hexadecane (n-cetane) in a mixture of n-hexadecane and 1-methyl
naphthalene.

Cetane Number is rated from 0 to 100.

Comparisons are made with blends of n-hexadecane and 1-methyl naphthalene.

 Additives (Improvement of cetane number)
 Ethyl nitrate and iso amyl nitrate

CONCLUSION
OCTANE NUMBER AND CETANE NUMBER

 Octane Number and Cetane Number are the standards to measure the tendency of fuel
to ignite spontaneously.

 Octane number measures the performance of gasoline while Cetane number measure
the performance of the diesel.

 The fuel having high octane number has the low cetane number and high cetane number
fuel has low octane number.

 This is one reason why we can’t use petrol in a diesel engine and diesel in petrol engine.
Comparison of gasoline oil and diesel oil
 Gaseous Fuel
WATER GAS
It is a mixture of CO and H2 with small amount of N2.
 The average composition of water gas is as follows

Constituents Percentage (%)

CO 41
H2 51
N2 4
CO2 + CH4 Rest

Its calorific value is about 2800 kcal/m3

 Manufacture
 The water gas producer consists of a tall steel vessel, lined
inside with refractory bricks.
 It is provided with cup and cone feeder at the top and a side
opening for water gas exit.
 At the bottom it is provided with two inlet pipes for passing
air and steam.

C + H2O+28 kcal −−−> CO + H2

When steam and little air is passed alternatively over a red hot coke
maintained at about 900 −1000°C in a reactor, water gas is produced.
 Various Reactions
The reactions of water gas production involves the following two
steps.
I - Step
In the first stage, steam is passed through the red hot coke,
where CO & H2 gases are produced. The reaction is endothermic.
Hence, the temperature of the coke bed falls.

C + 2H2O−−−> CO2 + 2H2 - 19 kcal

 II - Step
In the second stage, in order to raise the temperature of the
coke bed to 1000°C, the steam supply is temporarily cut off and air
is blown in. The reaction is exothermic.
C + O2 −−−> CO2 +97 kcal
2C + O2 −−−> 2CO +59 kcal

Thus the steam-run and air-blow are repeated alternatively to

maintain proper temperature.
 Since both CO2 and H2 burn with a non-luminous or blue flame,
water gas some times known as “blue gas”

Properties:
 High Calorific values
 Burns with non-luminous flame
 Flame is short but very hot

5-Mar-21
 Uses
It is used for the production of H2 and in the synthesis of
ammonia.
It is used to synthesis gasoline in Fischer Tropsch process.
It is used as an illuminating gas and a fuel.
It is also used in the manufacture of power alcohol and
carburetted water gas (water gas + oil gas).