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FUELS AND COMBUSTION

INTRODUCTION

Fuel is a Combustible substance containing Carbon as the major Constituent which on proper
burning gives large amount of heat that can be used for domestic and industrial purposes.

(or)

Fuel is a source of heat energy. Ex : Wood, Coal, Charcoal, kerosene, petrol, Producer gas etc.

During the Process of Combustion of a fuel, the atoms of Carbon, hydrogen etc combine with
oxygen with liberation of heat.

C + O2 → CO2 + 94kcals.

2H2 + O2 → 2H2O + 68.5kcals

Definition
Fuel is a substance which by Combustion on air gives large amount of heat that can be utilized
economically for industrial and domestic purposes.

COAL
Coal is an important Solid fuel. The process of Conversion of vegetable matter to Anthracite is
called Coalification (or) Metamorphism of Coal.

CLASSIFICATION OF COAL
Coal is classified on the basis of percentage of Carbon, Moisture and the amount of heat content
present in it. The various types of Coals are

WOOD → PEAT → LIGNITE → BITUMINOUS → ANTHRACITE COAL.

The progressive transformation of wood to Anthracite results in

 Decrease in moisture content


 Decrease in Volatile matter content
 Decrease in H2, O2, N2,S contents.
 Increase in C content.
 Increase in Hardness.
 Increase in Calorific Value.

ANALYSIS OF COAL
In order to assess the quality of coal, the following two types of analysis are made.

(i) Proximate Analysis


(ii) Ultimate Analysis

PROXIMATE ANALYSIS
It involves the determination of % of

(i) Moisture Content


(ii) Volatile Matter
(iii) Ash content
(iv) Fixed carbon in coal

Moisture Content

About 1 gm of powdered air-dried coal sample is taken in a crucible, and is heated at


100-105˚ C in an electric hot-air oven for 1 hr. The loss in weight of the sample is found out
and the % of moisture is calculated as

% of moisture in coal = Loss in weight of the coal / Weight of the air-dried

Coal ×100

Volatile matter

After the analysis of moisture content the crucible with residual coal sample is covered with
lid, and is heated at 950±20°C for 7 minutes in a muffle furnace. The loss in weight of the
sample is found out and the % of volatile matter is calculated as

% of volatile matter in coal = Loss in weight of the coal/ weight of air-dried coal ×100
Ash content
After the analysis of volatile matter, the crucible with residual coal sample is heated without
lid at 700±50°C for half an hour in a muffle furnace. The loss in weight of the sample is found out
and the % of content is calculated as

% 0f Ash content in coal = Weight of ash formed / weight of air-dried coal×100.

Fixed carbon
It is determined by subtracting the sum, total of moisture, volatile, and ash contents from 100.

% of fixed carbon in coal = 100 – % of ( moisture content + volatile matter + ash content)

SIGNIFIANCE (OR) IMPORTANCE OF PROXIMATE ANALYSIS


(i) Moisture content
High percentage of moisture is undesirable because

(i) It reduces the Calorific value of Coal


(ii) Moisture in coal consumes more heat in the form of latent heat of
evaporation and hence more heat is to be supplied to the coal
(iii) It increases the transport cost.
(ii) Volatile matter
High % of volatile matter is undesirable because

(i) It reduces the Calorific value of Coal


(ii) Large proportion of fuel on heating will distill over as vapour, which
escapes out unburnt.
(iii) Coal with high % of volatile matter burns with a long flame with high
smoke.
(iv) The coal containing high % of volatile matter do not coke well.
(iii) Ash content
High % ash content is undesirable because,

(i) It reduces the Calorific value of Coal

(ii) Ash causes hindrance to heat flow as well as produces clinkers which blocks the
air supply through the fuel.
(iii) It increases the transporting handling and storage costs
(iv) It involves additional cost in ash disposal.
(iv) Fixed carbon
(i) High % of fixed carbon is desirable because higher the % of fixed carbon in a
coal, greater is its Calorific value.
(ii) The % of fixed carbon helps in designing the furnace and the shape of the fire-
box.

ULTIMATE ANALYSIS
It involves the determination of percentage of

(i) Carbon & Hydrogen content


(ii) Nitrogen content
(iii) Sulphur content
(iv) Ash content
(v) Oxygen content

1. CARBON & HYDROGEN CONTENT

A known amount of the coal sample is burnt in a current of oxygen in a combustion apparatus.
The carbon & hydrogen , present in the coal sample, are converted in to CO2 and H2O
respectively, according to the following equations.

C + O2 → CO2↑

H2 + ½ O2 –→ H2O↑

The liberated CO2 & H2O vapours are absorbed respectively in KOH and anhydrous CaCl2 tubes of
known weights. The increase in wt of KOH tube is due to the formation of CO2 while increase in
weight of CaCl2 tube is due to the formation of H2O.

From the weights of CO2 & H2O formed, the percentage of carbon & hydrogen present in the coal
can be calculated as follows

2KOH + CO2 → K2CO3 + H2O

CaCl2 + 7H2O → CaCl2.7H2O

Let m = weight of the coal sample taken

X = Increase in weight of KOH tube

Y = Increase in weight of CaCl2 tube.

% of Carbon

C + O2 → CO2

12 44
44gms of CO2 contains 12gms of carbon

Therefore X gms of CO2 contains = 12 × x / 44 gms of carbon.

‘m’ gms of coal contains = 12 × x /44 gms of carbon

100gms of coal contains = 12 × x /44 × 100/m gms of carbon

Therefore % of carbon in coal = 12 × x /44 × 100/m

% of carbon in coal = Increase in weight of KOH tube / weight of coal sample taken ×12/44× 100

% of hydrogen

H2 + ½ O2 →H2O

18 gms of water contains 2gms of hydrogen.


‘y’ gms of water contains = 2 × y /18 gms of H2

‘m’ gms of coal contains = 2 × y /18 gms of H2

Therefore 100gms of coal contains = 2 × y /18 ×100/m gms of H2

Therefore % of hydrogen in coal = 2 × y /18 ×100/m

% of hydrogen = Increase in weight of CaCl2 tube / weight of coal sample taken ×2/18
×100

2. NITROGEN CONTENT
The determination of nitrogen content is carried out by kjeldahl’s method. Aknown amount of
powered coal sample is heated with conc.H2SO4 in presence of K2SO4 (catalyst) in a long necked
flask (kjeldahl’s flask). Nitrogen in the coal is converted in to ammonium sulphate and a clear
solution is obtained.

2N + 3 H2 + H2SO4 → (NH4)2SO4

The clear solution is then heated with excess of NaOH and the liberated ammonia is distilled over
and is absorbed in a known volume of standard N/10 HCl.

(NH4)2SO4 + 2NaOH → 2NH3 + Na2 SO4 + 2H2O

NH3 + HCl → NH4 Cl


The volume of unused N/10 HCl is then determined by titrating it against standard N/10 NaOH.
Thus the amount of acid neutralized by liberated NH3 from coal is determined. From this the % of
N2 is calculated as follows.

CALCULATION

Let the weight of the coal sample taken = ‘m’ gms

Initial volume N/10 HCl = V1 ml

Volume of unused N/10 HCl = V2 ml

Therefore the acid neutralized by NH3 = (V1 –V2)ml

We know that

1000ml of 1N HCl ≡ 1 mole of HCl ≡ 1 mole of NH3 [ HCl + NH 3 → NH4Cl]

1mole 1 mole

≡ 14 gms of N2 (or) [17gms of NH3]

Therefore (V1 –V2) ml of N/10 HCl = 14 × (V1 –V2) × n/10 / 1000 × 1N gms of N2

‘m’ gms of coal sample contains = 14 × (V1 –V2) × n/10 / 1000 × 1N gms of N2

100 gms of coal sample contains = 14 × (V1 –V2) × n/10 / 1000 × 1N ×100/m gms of N2

% of nitrogen in coal = 14 × volume of acid consumed × Normality / 1000 × Weight of the coal
sample × 1

(or)

% of nitrogen in coal = 1.4 × volume of acid consumed × Normality / 1000 × Weight of the coal
sample .

3. SULPHUR CONTENT
A known amount of coal sample is burnt completely in a bomb calorimeter. During this process
sulphur is converted in to sulphate, which is extracted with water. The extract is then treated with
BaCl2 solution. So that sulphates are precipitated as BaSO4. The precipitate is filtered, dried and
weighed.
From the weight of BaSO4 obtained, the sulphur present in coal is calculated as follows.

CALCULATION

Let, the weight of coal sample = m gms

Weight of BaSO4 obtained = x gms

S + 2O2 →SO4 2-→BaSo4↓

32 233

233 gms of BaSO4. contains 32 gms of sulphur

32 x x
 x gms of BaSO4. contains = gms of S
233

32 x x
‘m’ gms of coal sample contains = gms of S
233

32 x x 100
100 gms of coal sample contains = × gms of S
233 m

32 x x
 % of sulphur in coal = ×100
233 x m

% of sulphur in coal = 32 ×wt of BaSO4 obtained / 233× wt of coal sample ×100

Ash content

Determination of ash content is carried out as in proximate Analysis.

Oxygen content

The % of oxygen is calculated as follows.

% of oxygen in coal = 100 - % of (C + H


+ N + S +ash)

SIGNIFANCE (OR) IMPORTANCE OF ULTIMATE ANALYSIS


(1) Carbon & hydrogen contents
(i) Higher the % of C & H , better is the quality of coal and higher is its calorific value.
(ii) The % of carbon is helpful in the classification of coal.
(iii) Higher the % carbon in coal reduces the size of combustion chamber required.

(2) NITROGEN CONTENT

(i) Nitrogen does not have any calorific value, and its presence in coal is undesirable.
(ii) Good quality of coal should have very little nitrogen content.

(3) SULPHUR CONTENT

Though sulphur increases thr calorific value, its presence in coal is undesirable
because,

(i) The combustion products of S, SO2, & SO3 are harmful and have corrosion effects on
equipments.
(ii) The coal containing sulphur is not suitable for the preparation of metallurgical coke as it
affects the properties of the metal.
(4) OXYGEN CONTENT
(i) Lower the percentage of oxygen higher is its calorific value.
(ii) As the oxygen content increases its moisture holding capacity increases, and the
calorific value of the fuel is reduced.

CALORIFIC VALUE
The Calorific value of a fuel is defined as “ The total quantity of heat liberated, when a unit mass
of fuel is burnt completely in presence of oxygen”.

(i) CALORIE (OR) GRAM CALORIE

The amount of heat required to raise the temperature of 1 gm of water through 1˚C (15 to 16˚C)

1 Calorie = 4.185 joules

(ii) KILOCALORIE (OR) KILOGRAM

The amount of required to raise the temperature of 1kg of water through 1˚C (15 to 16˚C)

1 kilocalorie = 1000 calorie

(iii) BRITISH THERMAL UNIT (B.T.U)

The amount of required to raise the temperature of 1 lb of water through 1˚F


1 B.T.U = 1054.6 joules

= 1054.6 × 107 ergs

(iv)CENTIGRADE HEAT UNIT (C.H.U)

The amount of required to raise the temperature of 1 lb of water through 1˚C (15 to 16˚C)

1 k.calorie 1000 calories = 3968 BTU = 2.2CHU

1 BTU = 252 calories = 0.252k.cal.

CLASSIFICATION OF CALORIFIC VALUES

HIGHER (OR) GROSS CALORIFIC VALUE (GCV)

The total amount of heat produced, when a unit of mass of fuel is completely burnt and the
products of combustion are cooled to room temperature.

LOWER (OR) NET CALORIFIC VALUE(NCV)

The net heat produced when unit mass of fuel is burnt completely and the products are
permitted to escape.

CLASSIFICATION OF COAL
Wood → Peat → Bituminous coal → Anthracite.

1. WOOD
Wood is obtained from forests, which burns producing a long and non-smoky flame and
leaves behind little amount of ash. The air dried & moisture free wood have the calorific value
about 3500 to 4500 kcal/ kg. wood is largely used as a domestic fuel.

2. PEAT
(i) Peat is the first stage in the coalification of wood.
(ii) It is brown, fibrous jelly like mass and its calorific value is about 5450kcal/kg.
(iii) It is uneconomical fuel due to its higher proporation (80 -90%) of moisture and on
air drying it burns freely.
3. LIGNITE
(i) Lignites are soft, brown coal, the intermediate stage in the process of coalification
consist of vegetable matter
(ii) It burns with long smoky flame due to the presence of volatile matter.
(iii) Its calorific value is about 6500 to 7000 kcal/kg ( On air-dry basis)
(iv) It is mostly used in the manufacture of producer gas.
4. BITUMINOUS COAL
It is common coal dark-grey, which usually soil hands. Bituminous coal are further sub-
classified in to 3 types based on carbon content.

Property Sub-bituminous Bituminous coal Semi-bituminous


coal coal

Moisture & high low Very low


volatile matter

Carbon 75- 83% 78- 90% 90-95%


content

Calorific 7000 8000-8500 8500-8600


value(kcal/kg)

5. ANTHRACITE COAL
(i) It is obtained in the last stage of coalification.
(ii) It is highest rank coal, containing highest % of carbon (92- 98%)
(iii) It has lowest volatile matter, moisture content & ash contents.
(iv) They possess no caking power and their calorific value is about 8650kcal/kg.

Metallurgical coke

When bituminous coal is heated strongly in the absence of air, the volatile matter escapes

out and the mass becomes hard, strong, porous and where which is called metallurgical coke.

How does it differ from coal

(i)Coke is stronger and more porous than coal.

(ii)Coke contains lesser amount of sulphur than coal.

(iii)Coke does not contain much volatile matter than coal.

Manufacturing

Metallurgical coke is manufactured by Otto Hoffman’s by- product oven.


The over consists of a no of

silica chambers. Each chamber

is about 10-12m long 3-4m

height and 0.4 – 0.45m wide.

Each chamber is

provided a charging hole at the

top, it also provided with a gas

off take valve and iron door at

each end for discharging coke.

Coal is introduced into

the silica chamber and the

chambers are closed. The

chambers are heated to 1200˚C by during the preheated air and the producer gas mixture in the

interspaces between the chambers.

The air & gas are preheated by sending them thro’ 2nd & 3rd hot regenerators. Hot flue gases

produced during carbonization are allowed to pass thro’ 1st & 4th regenerators until the temp has

been raised to 1000C while 1st & 4th regenerators are heated by hot flue gases, the 2nd & 3rd

regeneration are used for heating the incoming air & gas mixture.
For economical heating, the direction of inlet gases & flue gases are changed frequently.

The above system of recycling flue gases to produce heat energy is known as the regenerative

system of heat economy.

When the process is complete, the coke is removed & quenched with H20.

Time taken for complete carbonization is about 12 – 20hrs. The yield of coke is about 70%.

The valuable by-products like coal gas, tar, ammonia, H2S, benzene etc.. can be recovered

from flue gas.

Recovery of by – products

i) Tar:-

The flue gases are first passed. thro’ a tower in which liquor NH3 is sprayed. Tar & dust get

dissolved & collected in a tank below.

ii) Ammonia

The gases are passed thro’ tower in which water is sprayed. Ammonia recovered as

NH4OH.

iii) Naphthalene

The gas passed thro’ tower in which cooled water sprayed naphthalene gets condensed.

iv) Benzene: -

The gases passed thro’ tower in which petroleum is sprayed benzene gets condensed to

liquid.

v) H2S:-

The remaining gases passed thro’ the purifier packed moist Fe203. Here H2S is retained.

The final gas left out is called coal gas which is used as a gaseous fuel.

Advantages
1. Valuable by – products are recovered.

2. The carbonization time is less.

3. Heating is done externally by producer gas.

PETROLEUM REFINERY PROCESS

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 the crude

oil is separated into various fractions.

Thus, the process of removing impurities and separating the crude oil into various fractions

having different boiling points is called refining of petroleum.

The process of refining involves the follow steps:

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.

Step 2: Removal of harmful sulphur compounds

Sulphur compounds are removed by treating the crude oil with copper oxide. The copper

sulphide formed is separated out by filtration.

Step 3: Fractional distillation

The purified crude oil is then heated to abort 4000C in an iron retort, where the oil gets

vapourized. The hot vapours are then passed into the bottom of a “fractioning column” (Fig).
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

When the vapours of the oil go up in the fractional

column, they become cooler and get condensed at

different trays.

The fractions having higher boiling 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;

S.No Name of the fraction Boing range 0C Range of C-atoms Uses

1. Uncondensed gases Below 30 C1-C4 As a fuel under the

name of LPG
2. Petroleum ether 30 – 70 C5 – C7 As a solvent

3. Gasoline (or) petrol 40 – 120 C5 – C9 Fuel for IC engines

4. Naphtha (or) Solvent 120 – 180 C9 – C10 As a solvent in paints

spirit and in dry cleaning

5. Kerosene oil 180 – 250 C10 – C16 Fuel for stoves and jet

engines

6. Diesel oil 250 – 320 C15 – C18 Diesel engine fuel

7. Heavy oil 320 – 400 C17 – C30 Fuel for ships and for

production of gasoline

by cracking

Heavy oils on refraction gives

S.No Name of the fraction Uses

1. Lubricating oils As lubricants

2. Petroleum jelly (or) Vaseline Used in medicines cosmetics

3. Grease Used as lubricant

4. Paraffin wax Used in candles, boot polishes etc..

5. Pitch at above 4000C Used for making roads water proof roofing etc.

CRACKING

Def:

Cracking is defined as “the decomposition of high boiling hydrocarbons of high molecular

weight into simplex, low boiling hydrocarbons of low mol-wt.


C10H22 → C5H12 + C5H10

Necessity for cracking:

The crude oil on fractional distillation yields only about 15 – 20% gasoline. This is known

as straight run gasoline the quality of straight run gasoline is not so good. It contains mainly straight

chain paraffin’s, which ignite readily and move rapidly than any other hydrocarbons and hence it

produces knocking (unwanted sound) is IC engines.

In order to overcome these difficulties and also improve the quality and quantity of gasoline,

high boiling fractions are cracked into more valuable low boiling fractions suitable for SI engines.

Thus gasoline obtained by cracking is called cracked gasoline. During cracking the following

changes take place.

(i) Straight chain alkanes are converted to branched chain hydrocarbons.

(ii) Saturated higher hydrocarbons are converted to mixture of saturated and unsaturated lower

hydrocarbons.

(iii) Aliphatic alkanes may also be converted to cyclic compounds.

(iv) All the hydrocarbons obtained by cracking have lower boiling point than the parent

Hydrocarbons.

Types of cracking

There are two types of cracking

1. Thermal cracking

2. Catalytic cracking

Thermal cracking
If the cracking is carried out at higher temperature and pressure without any catalyst, it is

called thermal cracking. There are 2 types of thermal cracking.

(i) Liquid phase thermal cracking

In this method, the heavy oil is cracked at a temp of 475 – 5300C under high pressure of

100kg/Cm2 to keep the reaction product in liquid State. The cracked products are then separated in

to various fractions in a fractioning column. The yield of gasoline is about 50 – 60% and the octane

number is 65 – 70.

(ii) Vapour phase thermal cracking

In this method, the heavily oil is first vapourized and then cracked at a temp of 600 – 6500C

under a lower pressure of 10 – 20kg/Cm2. The yield of gasoline is about 70%. This process is

suitable only for those oils which are readily vapourized.

Catalytic cracking

If the cracking is carried out at lower temp & pressure in the presence of suitable catalyst, it

is called catalytic cracking. The catalyst used are aluminum silicate (or) alumina.

There are two types of catalytic cracking

(i) Fixed bed catalytic cracking

The heavy oil vapour is heated to 420 – 4500C in a preheater. The hot vapours are then

passed thro’ a catalytic chamber maintained at 425 – 4500C and 1.5kg/Cm2 pressure, where catalyst

[artificial clay mixed with zirconium oxide] are kept in fixed beds.

During this passage, through the catalytic chamber, about 40% of the heavy oil is converted

into gasoline and about 2 – 4% carbon is formed. The carbon gets adsorbed on the catalyst bed. The

cracked vapours are then pass through the fractionating column, where heavy oil gets condensed at

the bottom.
The vapours of gasoline are then bent through the cooler where gasoline gets condensed

along with some gases the gasoline containing some dissolved gases is then sent to a stabilizer,

where the dissolved gases are removed and pure gasoline is recovered.

After 8 – 10 hrs, the catalyst loses its activity due to the deposition of carbon. It is

reactivated by burning off the deposited carbon.


Moving bed catalytic cracking

In this process, the solid catalyst is finely powdered, so that it behaves as a fluid, which can be

circulated in oil vapour.

The heavy oil vapour is heated to 420 – 4500C in a preheater and it is mixed with the

catalyst powder. Then this mixture is forced into the reactor, which is maintained at a temperature

of 5000C and a pressure of 5 kg/Cm2, where cracking takes place.

Near the top of the reactor, there is a centrifugal separator called (cyclone) which allows

only the cracked oil vapours to pass on to the fractionating column leaving behind the catalyst

powder in the reactor itself. The catalyst powder gradually becomes heavier due to coating of

carbon and it settles down at the bottom of the reactor. Then it is forced into the regenerator

maintained at 600˚C, where carbon is burnt and the regenerated catalyst is again recirculated along

with the heavy oil vapour.


From the reactor the cracked oil vapours are passed into the fractionating column, where heavy

oil settles down and the vapours are then passed through the cooler where gasoline condenses along

with some gases. The dissolved gases are separated from gasoline by passing it through a stabilizer.

Advantages of catalytic cracking over thermal cracking:

1. The yield of petrol is higher

2. The quality of petrol produced is better


3. The production cost is very less, since high temp and high pressure are not required

4. No external fuel is necessary for cracking the heat required for cracking is desired by burning the

carbon deposited on the catalyst

5. The % of gum and gum forming compounds is very low

6. The products contain less sulphur compounds.

7. The octane number of cracked gasoline is higher when compared to straight – run gasoline. This

is due to the presence of branched paraffin’s and aromatic Hydrocarbons, in cracked gasoline.

8. The cracking process can be easily controlled, so the desired products can be maintained.

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. So, coal is a

hydrogen deficient compound.

If coal is heated with hydrogen to high temp 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 2 methods available for the hydrogenation of coal.

1. Bergius process (Direct method)

2. Fischer – Tropsch process (indirect method)


Bergius process (or) 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 – 4500C under a pressure of 200 – 250 atm.

During this process hydrogen combines with coal to form saturated higher hydrocarbons,

which undergo further decomposition, at higher temperature to yield mixture of tower

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.
Fischer – Tropsch process (or) Indirect method

In this process coal is first converted into coke. Then water gas (C0+H2) is produced by

passing steam over red hot coke.

1200˚c

C + H2O → CO + H2

(coke) (steam) water gas

The water gas is mixed with H2 and the mixture is purified by passing through Fe203 [to

remove H2S] and then into a mixture of Fe203 + Na2C03 [To remove organic sulphur compounds].

The purified gas is compressed to 5 to 25 atm and then led through a converter, which is maintained

at a temp of 200 – 3000C.


The converter is provided with a catalyst bed consisting of a mixture of 100 parts cobalt, 5

parts thoria, 8 parts magnesia and 200 parts keiselghur earth. A mixture of saturated and

unsaturated hydrocarbon is produced as a result of polymerization.

nCO+ 2n H2 – Cn H2n + nH2 0.

nCO + (2n+1) H2 → CnH 2n+2 + n H2O.

The out coming gaseous mixture is led to a condenser, where liquid crude oil is obtained the

crude oil is fractionated to yield

(i) Gasoline
(ii) Heavy oil

The heavy oil is used for cracking to get more gasoline.

KNOCKING

Def:

Knocking is a kind of explosion due to rapid pressure rise occurring in an IC engine.

Causes of knocking is 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.

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.

[IC: Internal combustion engine]

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.

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 paraffin’s > Branched chain paraffin’s > Cyclo paraffin’s > Olefins > Aromatics
Thus olefins of the same carbon-chain length possess better anti-knock properties than the

corresponding paraffin’s.

Improvement of anti-knock 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 [TEL]

iii) Now a days aromatic phosphates are used as antiknock agent because it avoids lead pollution.

OCTANE NUMBER

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.

Def:

“Thus octane number is defined as “The percentage of iso-octane present in a mixture

of iso-octane and n-heptane”


CH3- CH2 -CH2 -CH2 - CH2 -CH2 -CH3

n-heptane (octane number = 0)

LEADED PETROL [ANTI-KNOCK AGENT]

The anti-knock properties of a gasoline can be improved by the addition of suitable

additives. Tetra ethyl lead (TEL) (C2H5)4 Pb is an important additive added to petrol. Thus the

petrol containing tetra ethyl lead is called leaded petrol.

CETANE NUMBER

Cetane number is introduced to express the knocking characteristics of diesel.

Cetane (hexa decane) C16 H34 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.

Def:

Thus the cetane number is defined as “The percentage of hexadecane present in a

mixture of hexadecane and α-methyl naphthalene, which has the same ignition lag as the fuel

under test”.

The cetane number decreases in the following order.

Straight chain paraffin’s > Cyclo paraffin’s > Olefins > Branched paraffin’s > Aromatics.
The cetane number of a diesel oil can be increased by adding additives called dopes.

Important dopes: Ethyl nitrate, Iso-amyl nitrate.