1

Unit-V Fuels and Combustion

Lecture 28 : Topics : Fuels – Definition, classification, Calorific value, Gross and
Net Calorific value – Dulong’s formula with problem

INTRODUCTION

A fuel is a combustible substance containing carbon as the main constituent

which on proper burning gives large amount of heat that can be used economically for
domestic and industrial purposes. During the process of combustion of a fuel, the atoms
of carbon, hydrogen, etc combine with oxygen with simultaneous liberation of heat. The
calorific value of a fuel depends mainly on the two elements.

C + O2 CO2 + 94 kcals.

2H2 + O2 2H2 O + 68.5 kcals.

So, carbon compounds have been used for many centuries as the source of heat and
energy. The main source of fuel is coal and petroleum. These are stored fuels available
in earth's crust and are generally called fossil fuels because they were formed from the
fossilised remains of plants and animals.

CLASSIFICATION

1. Primary fuels which occur in nature as such, e.g. coal, petroleum and natural gas.

2. Secondary fuels which are derived from the primary fuels, e.g. coke, gasoline,
coal gas, etc.

Both primary and secondary fuels may be further classified based upon their
physical state as

(i) solid fuels

(ii) liquid fuels
(iii) gaseous fuels.

CALORIFIC VALUE

Calorific value of a fuel is "the total quantity of heat liberated, when a unit
mass (or volume) of the fuel is burnt completely."

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Units of heat :

(1) 'Calorie' is the amount of heat required to raise the temperature of one gram of
water through one degree Centigrade (15-16°C).

(2) "Kilocalorie" is equal to 1,000 calories. It may be defined as 'the quantity of heat
required to raise the temperature of one kilogram of water through one degree
Centigrade. Thus: 1 kcal = 1,000 cal

(3) "British Thermal unit" (B.T.U.) is defined as "the quantity of heat required to raise
the temperature of one pound of water through one degree Fahrenheit (60-61°F). This
is the English system unit.

1 B.T.U. = 252 cal = 0.252 kcal

1 kcal = 3.968 B.T.U.

Higher or gross calorific value (HCV)

Usually, all fuels contain some hydrogen and when the calorific value of
hydrogen-containing fuel is determined experimentally, the hydrogen is converted into
steam. If the products of combustion are condensed to the room temperature (15°C or
60°F), the latent heat of condensation of steam also gets included in the measured
heat, which is then called "higher or gross calorific value". So, gross or higher calorific
value (HCV) is "the total amount of heat produced, when unit mass/volume of the
fuel has been burnt completely and the products of combustion have been cooled
to room temperature"(i.e., 15°C or 60°F ).

Lower or net calorific value (LCV)

In actual use of any fuel, the water vapour and moisture, etc., are not condensed
and escape as such along-with hot combustion gases. Hence, a lesser amount of heat
is available. So, net or lower calorific value (LCV) is "the net heat produced, when
unit mass /volume of the fuel is burnt completely and the products are permitted
to escape".

Net calorific value = Gross calorific value - Latent heat of condensation of water
vapour produced

= GCV – (Mass of hydrogen per unit weight of the fuel burnt x 9 x

Latent heat of condensation of water vapour)

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

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

where C, H, 0, and S are the percentages of carbon, hydrogen, oxygen and sulphur in
the fuel respectively. In this formula, oxygen is assumed to be present in combination
with hydrogen as water, and

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

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

Lecture 29 : Topics : Solid fuel- Coal- Varieties of coal, Proximate analysis of coal
and its significance

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, and 0, besides non-combustible inorganic matter.

CLASSIFICATION

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. In North American terminology, the coal series is written as

Wood peat lignite bituminous anthracite.

ANALYSIS OF COAL

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

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

ash and fixed carbon. This gives quick and valuable information regarding com-

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mercial 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. Since it is used for the determination of elements
present in the coal, it is also called 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:
About 1 g of finely powered air-dried coal sample is weighed in a crucible. The
crucible is placed inside an electric hot air-oven, maintained at 105° - 110°C. The
crucible is allowed to remain in oven for 1 hour and then taken out, cooled in a
desiccator and weighed. Loss in weight is reported as moisture (on percentage-
basis).

Percentage of moisture = Loss in weight x 100

Wt. of coal taken
(2) Volatile matter:
The dried sample of coal left in the crucible in (1) is then covered with a lid and
placed in an electric furnace (muffle furnace), maintained at 925°± 20°C. The
crucible is taken out of the oven after 7 minutes of heating. The crucible is cooled
first in air, then inside a desiccator and weighed again. Loss in weight is reported
as volatile matter on percentage-basis.

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

Wt. of coal sample taken
(3) Ash:
The residual coal in the crucible in (2) is then heated without lid in a muffle
furnace at 700 ± 50°C for 1/2 hour. The crucible is then taken out, cooled first in
air, then in desiccator and weighed. Heating, cooling and weighing is repeated, till
a constant weight is obtained. The residue is reported ash on percentage-basis.

Percentage of ash = Wt. of ash left x 100

Wt. of coal taken

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

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Importance of proximate analysis

Proximate analysis provides following valuable informations in assessing the quality of

coal:

(1) Moisture:
Moisture lowers the effective calorific value of coal. Moreover, it quenches
the fire in the furnace. Hence, lesser the moisture content, better the quality of
coal as a fuel. However, presence of moisture, up to 10%, produces a more
uniform fuel-bed and less of "fly-ash".

(2) Volatile matter:

A high volatile matter containing coal burns with a long flame, high smoke
and has low calorific value. Hence, lesser the volatile matter, better the rank of
the coal. Higher volatile content in coal is undesirable. A high volatile matter
content means that high-proportion of fuel will be distilled and burned as a gas
or vapour. The volatile matter present in the coal may be combustible gases
(such as methane, hydrogen, carbon monoxide and other hydrocarbons) or non-
combustible gases (like CO2 and N2). Volatile matter content is of special
significance in coal gas manufacture and in carbonization plants, particularly
when by-product recovery is the main object. Thus, high-volatile matter
containing coals do not cake well; whereas medium-volatile matter content coals
are capable of yielding hard and strong coke on carbonization.

(3) Ash :
It 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. Also, it often causes. trouble during firing by forming
clinker), which block the inters paces of the grate. This in-turn causes
obstruction to air supply; thereby the burning of coal becomes irregular. Hence,
lower the ash content, better the quality of coal. 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:

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. Hence, high

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percentage of rued carbon is desirable.

Lecture 30 : Topics : Ultimate analysis of coal and its significance, Carbonization

process, Types, Otto Hoffmann process – Recovery of by products.

ULTIMATE ANALYSIS

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 of the coal 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.

C + O2 CO2

12 44

2 KOH + CO2 K2CO3 + H2O

H2 + ½ O2 H2O

2 18

CaCl2 + 7H2O CaC12.7H2O

Increase in weight of KOH tube x 12 x 100

Percentage of C = Weight of coal sample taken x 44

Increase in weight of CaCl2 tube x 2 x 100

Percentage of H = Weight of coal sample taken x 18

Nitrogen

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

H2SO4 along-with K2S04(catalyst) in a long-necked flask(called Kjeldahl's flask). After
the solution becomes clear, it is treated with excess of KOH and the liberated ammonia
is distilled over and absorbed in a known volume of standard acid solution. The unused

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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 as follows:

Volume of acid used x Normality x 1.4

Percentage of N = . Weight of coal taken

Sulphur

It is determined from the washings obtained from the known mass of coal, used
in a bomb calorimeter for determination of a calorific value. During this determination, S
is converted into sulphate. The washings are treated with barium chloride solution,
when barium sulphate is precipitated. This precipitate is filtered, washed and heated to
constant weight.

Weight of BaS04 obtained x 32 x 100

Percentage of S = Weight of coal sample taken x 233

Ash

It is carried out as in proximate analysis.

Oxygen:

It is obtained by difference.

Percentage of O = 100 - Percentage of (C + H + S + N + ash)

Significance of ultimate analysis:

(1) 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.

(2) Nitrogen
It has no calorific value and hence, its presence in coal is undesirable;
thus, a good quality coal should have very little nitrogen content.

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(3) Sulphur
It although contributes to the heating value of coal, yet on combustion
produces acids (S02 and S03), which have harmful effects of corroding the
equipments and also cause atmospheric pollution. Sulphur is, usually, present to
the extent of 0.5 to 3.0% and derived from ores like iron pyrites, gypsum, etc.,
mines along-with the coal. Presence of sulphur is highly undesirable in coal to
be, used for making coke for iron industry, since it is transferred to the iron metal
and badly affects the quality and properties of steel. Moreover, oxides of sulphur
(formed as combustion products) pollute the atmosphere and leads to corrosion.

(4) Oxygen
The 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.

METALLURGICAL COKE

Good coke for metallurgy should possess the following requisites:

(1) Purity: It should have moisture, ash, sulphur and phosphorus contents as low
as possible. A low percentage of moisture helps in keeping down the heating
expenses. Excess of ash hinders the heating and also helps in slag formation,
which is not desirable in fuels. According to Dr. Mott, 2% of excess coke is required
for the removal of 1 % ash. Presence of S and P gives on burning, undesirable
products like SO2 P203 and P2O5, which adversely affect the quality of the metal
being produced. Moreover, presence of sulphur makes the coke brittle.

(2) Porosity : Coal should be porous, so that oxygen can easily come in contact
with the carbon of coke, thereby helping in complete combustion at a high rate.

(3) Strength: The coke should be quite compact, hard, strong to withstand dropping
abrasion as well as the pressure of the over-burden (ore + fuel + flux) in the
furnaces. It would be useless to employ weak coke in blast furnaces, as the weight
of ore, etc., would crush the coke to breeze and thus prevent the essential passage
of gases up the furnace.

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(4) Size: The size of metallurgical coke should be neither too big nor too small. In
case the size is too big, the uniformity of heating is never maintained, but on the
other hand, if the coke size is too small, choking will result.

(5) Cost: Coke should be cheap and easily available near the site of the
metallurgical plant, so that the transportation cost is low.

(6) Combustibility: Coke should burn easily. The combustibility of coke depends
upon the nature of the coal, carbonization temperature and reaction temperature.
Cokes obtained from strongly coking coals are not as combustible as those derived
from weakly caking and non-caking coals. At a given temperature, cokes obtained
by high-temperature carbonization process are less combustible compared to those
obtained by low-temperature carbonization. However, at high combustion
temperatures (800° - 900°C), all cokes appears to be equally reactive. At about
1,000°C, it appears that the rate of combustion depends only on the rate of
oxygen/air supply.

(7) Calorific value: The calorific value of coke should be high.

(8) Low ash, S and P contents to avoid the incorporation of these in the metal to be
extracted.

(9) Reactivity to steam: Reactivity towards steam increases with the reaction
temperature and varies inversely with carbonizing temperature at which the coke
was produces. Moreover, coke derived from non-caking coals are more reactive to
steam than those derived from taking coals.

Coal versus coke in metallurgical processes:

(1) Coal does not possess as much strength and porosity as coke.

(2) By coking, much of undesirable sulphur is removed.

(3) Coke burns with short flame, due to expulsion of much of its volatile matter
during carbonization.

Because of these reasons, "coke is preferred to coal for metallurgical purposes",

particularly in blast furnaces. On the other hand, coal burns with a long flame, which
is suitable only for reverberatory furnaces.

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Coking quality:

The coals which on heating, in the absence of air, becomes soft, plastic and
{use together to large coherent masses, are called caking coal. Consequently,
such coals are difficult to be oxidized. If the residue (i.e.: coke) obtained after
heating is porous, hard, strong and usable for metallurgical purpose, the original
coal, is known as coking coal

TYPES OF CARBONIZATION OF COAL

These are two types of carbonization of coal:

(1) Low-temperature carbonization:

In this process, the heating of coal is carried our at 500 - 700°C. The yield
of coke is about 75-80% and it contains about 5-15% volatile matter. It is not
mechanically strong, so it cannot be used as a metallurgical coke. However, it
burns easily giving practically a smokeless, hot and radiant fire. Hence, it is
suitable for domestic purposes. The by-product gas produced (about 130-150
m3/tonne) by this process is richer in heating value (about 6,500-9,500 kcal/m3)
and is, therefore, a more valuable gaseous fuel.

(2) High-temperature carbonization:

It is carried out at 900 - 1,200°C with the object of producing coke of the
right porosity, hardness, purity, strength, etc., so that it can be used in
metallurgy. Nearly all the volatile matter of coal is driven off and the yield of coke
is about 65-75%, containing only 1-3% volatile matter. The by-product gas
produced is high in volume (about 300-390 m3/tonne), but its calorific value is
low (about 5,400-6,000 kcal/m3).

MANUFACTURE OF METALLURGICAL COKE

Otto Hoffman's by-product oven process

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

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The by-product coke oven consists of number of narrow silica chambers (each
about 10 to 12 m long, 3 to 4 m high and 0.40 to 0.45 m wide) erected side-by-side with
vertical flues in-between them to form a sort of battery. Each chamber is provided with a
charging hole at the top, a gas off-take and a refractory-lined cast iron door at each
ends for discharging coke.

A charge consisting of finely crushed coal is introduced through the charging holes
at the top of chambers, which are then closed tightly at both ends to prevent any access
of air. The coke ovens are heated to 1,200°C by burning gaseous fuel (like producer
gas) and usually employing a regenerative principle to achieve as economical heating
as possible. The flue gases produced during combustion, before escaping to chimney,
pass on their sensible heat to one of the two sets of checker brick-work, until this brick-
work has been raised to a temperature of about 1,000°C.

Otto Hoffman's by-product oven

The flow of heating gases is then reversed and the inlet gases are passed
through the heated checker brick-work, which thus serves to preheat the inlet gases.
The flue gases are then allowed to pass through the second set of checker bricks to
heat it. This checker-work then serves to preheat the inlet gases. Thus, this cycle goes
on. The heating is actually continued, till the evolution of volatile matter ceases
completely. Carbonization of a charge of coal takes about between 11 to 18 hours.
When carbonization is completed, a massive ram pushes the red hot coke into a truck.
It is subsequently quenched by a water spray ('wet quenching'). In place of wet
quenching, "dry quenching" offers advantages, because the coke produced is more
strong, dense, graphitized and non-reactive. In this method, the red hot coke is placed
in a chamber and cooled by passing inert gases from boilers (like nitrogen). The heated

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

Recovery of by-products :

The gas coming out from the oven is known as "coke oven gas" and is mainly
composed of ammonia, H2S, naphthalene, benzene, tar, moisture, etc.

(i)Recovery of tar : The gas is first passed through a tower in which liquor ammonia is
sprayed. Here dust and tar get collected in a tank below, which is heated by steam coils
to recover back ammonia sprayed. The ammonia is used again.

(ii) Recovery of ammonia: The gases from the chamber are then passed through a
tower in which water is sprayed. Here ammonia goes into solution as NH4OH.

(iii) Recovery of naphthalene: The gases are then passed through another tower in
which water at very low temperature is sprayed. Here naphthalene gets condensed.

(iv) Recovery of benzene: The gases are then sprayed with petroleum, when benzene
and its homologues are removed.

(v) Recovery of H2S : The gases are then passed through a purifier, packed with moist
Fe2O3. Here H2S is retained.

Fe2O3 + 3 H2S Fe2O3 + 3 H2O

After some time, when all Fe2S3 is changed into Fe2O3, the purifier is exposed to
atmosphere, when Fe2O3 is regenerated,

Fe2S3 + 4 O2 2 FeO + 3 SO2

4FeO + O2 2 Fe2O3

Lecture session 31: Liquid fuel – Petroleum – Classification, Refining of crude oil
– fractions and uses.

Liquid Fuels: The important liquid fuels are petroleum, petroleum products, tar,
alcohols. These are naturally found under the sea surface. Liquid fuels are also
obtained synthetically from' hydrogenation of coat. Liquid fuels find extensive use in
domestic and industrial fields.

Petroleum: Petroleum or crude oil is a dark greenish brown or black coloured viscous

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oil found deep in earth's crust. The oil is usually floating over a brine solution and above
the oil, natural gas is present. Crude oil containing mixture of paraffinic, olefinic and
aromatic hydrocarbons with minor amounts of organic compounds like N, 0 and S. The
average composition of crude oil is C =80 - 87 %, H =11-15%, S = 0.1 -3.5%, (N +O)
=0.1- 0.5%.

a) Classification of petroleum

Petroleum is classified into three types based on variation of chemical nature of crude
oil found in the earth.

1. Paraffinic-base type crude oil: It contains saturated hydrocarbons from CH 4 to

C35H72 and little amount of naphthalenes and aromatics.
2. Asphaltic-base type crude oil: It contains mainly cycloparaffins or naphthalenes
with smaller amount of paraffins and aromatic hydrocarbons.
3. Mixed-base type crude oil : It contains both paraffinic and asphaltic hydrocarbons
and are generally in the form of semi-solid waxes.

Mining of Petroleum

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 (Cottrell's process)

The crude oil from the oil well is an extremely stable emulsion 0 f 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

 The presence of NaCI and MgCI in the crude oil can corrode the refining
equipment, hence these salts are removed by electrical desalting and
dehydration methods.
 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.

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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. (Figure )

Fractional distillation of Crude oil

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. The gasoline obtained by the fractional distillation is
called straight - run gasoline. Various fractions obtained at different trays are given in
table.

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Various fractions of crude oil and their compositions and uses

Name of the Boiling Composition

Sn. O Uses
fractions range ( C) of Hydrocarbons
As domestic and
1. Uncondensed gases Below 30°C C1 to C4 industrial fuel under
the name LPG
2. Petroleum ether 30-70 °C C5 to C7 As a solvent.
Gasoline (or) petrol. 40-120 °C As motor fuel, solvent and in
3. C5 to C9
dry cleaning.
Naphtha ( or}solvent As solvent and in dry
4. 120-180 °C C9 to C10
spirit cleaning.
As fuel for jet engines
5. Kerosene oil. 180-250 °C C10 to CI6
and an illuminant.
6. Diesel oil (or) gas oil 250-320 °C C10 to CI8 As Diesel engine fuel.
Production of gasoline by
7. Heavy oil. 320 - 400 °C C17 to C30 cracking
process.
Various fractions recovered from Heavy Oil

Boiling Composition
Name of the O
Sn. range ( C) of Uses
fractions
Hydrocarbons
1. Lubricating oil - C17 to C20 Used as lubricants
Petroleum jelly Used in medicines and cosmetics
2. - -
(Vaseline)
Paraffin wax - Used in candles, wax paper, boot
3. C20 to C28
polish, etc
4. Grease - - Used as lubricants.
Above Used for making roads, water
5. Asphalt or bitumen C30 and above
400°C proof roofing, etc

Lecture session 32: Synthetic petrol – Manufacture by Bergius process. Knocking

– Octane and cetane number - improvement.

Bergius process.

This method was developed by Bergius in Germany during the First World War.

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The low ash coal is finely powdered and made into a paste with heavy oil and then a
catalyst (composed of tin or nickel oleate) is incorporated. The whole is heated with
hydrogen at 450°C and under a pressure 200-250 atm for about 1.5 hours, during which
hydrogen combines with coal to form saturated hydrocarbons, which decompose at
prevailing high temperature and pressure to yield low-boiling liquid hydrocarbons.

The issuing gases (from the reaction vessel) are led to condenser, where a liquid
resembling crude oil is obtained, which is then fractionated to get:

(i) gasoline,

(ii) middle oil, and

(iii) heavy oil.

The latter is used again for making paste with fresh coal dust. The middle oil is
hydrogenated in vapour-phase in presence of a solid catalyst to yields more gasoline.
The yields of gasoline in about 60% of the coal dust used.

Bergius process

 Catalyst-tin or nickel oleate

 Reaction condition- 450°C and under a pressure 200-250 atm
 Middle oil obtained.
 Hydrogenated in vapour-phase in presence of a solid catalyst to yield gasoline.

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Knocking

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

Causes of knocking in S.I

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.
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 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).

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

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ethyl free radicals which combine with the growing free radicals of knocking process
and thus the chain growth is stopped.

Disadvantages of using TEL

When the leaded petrol is used as a fuel, the TEL is converted to lead oxide and
metallic lead. This lead deposits on the spark plug and on cylinder walls which is
harmful to engine life.

To avoid this, small amount of ethylene dibromide is added along with TEL. This
ethylene dibromide reacts with Pb and PbO to give volatile lead bromide, which goes
out along with exhaust gases.

But this creates atmospheric pollution. So nowadays aromatic phosphates are used
instead of TEL

Nowadays aromatic phosphates are used as antiknock agent because it avoids

lead pollution.

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.'

iso-octane (Octane number = 100) n-heptane (Octane number = 0)

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

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hand 2-methyl naphthalene has a long ignition lag and hence its cetane number is taken
as zero.

CH3 – (CH2)14 – CH3

n-cetane (hexa decane) 2-methyl naphthalene

cetane number = 100 (cetane number = 0)

Definition

Thus the cetane number is defined as "the percentage of hexa decane present in a
mixture of hexa decane and 2-methyl napthalene, which has the same ignition lag as
the fuel under test".

The cetane number decreases in the following order.

n-alkanes > Cycloalkanes > alkenes >branched alkanes >aromatics

The cetane number of a diesel oil can be increased by adding additives called
dopes. Important dopes: Ethyl nitrate, Iso-amyl nitrate.

Lecture session 33: Gaseous fuels – CNG, LPG, Water gas and producer gas –
composition, manufacture and uses

COMPRESSED NATURAL GAS

Natural Gas is obtained from wells dug in the oil bearing regions. When natural
gas occurs along with petroleum in oil wells, it is called as ‘wet gas’ and contains
gaseous hydro carbons from C1 to C4.

Properties

1. CNG is the cheapest, cleanest and least environmentally impacting alternative

fuel.

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2. Vehicles powered by CNG produce less carbon monoxide and hydrocarbon (HC)
emission.
3. It is less expensive than petrol and diesel.
4. The ignition temperature of CNG is about 550°C. CNG requires more air for
ignition.

Uses

CNG is used to run an automobile vehicle just like LPG

LIQUEFIED PETROLEUM GAS

LPG – Liquefied Petroleum Gas – describes flammable hydrocarbon gases including

propane, butane and mixtures of these colourless, low carbon gaseous fuels.

Constituents %

n-Butane 38.5

Iso Butane 37

Propane 24.5

Uses

1. It is used as a domestic and industrial fuel

2. It is also used as a motor fuel

PRODUCER GAS

Producer gas is a mixture of combustible gases,

CO 30%
H2 15%
large amount of non combustible gases N2 56%
CO2 3%

Its calorific value is 1300kcal/m3

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It is prepared by passing air mixed with a little steam over a red hot coke maintained at
about l100°C in a special reactor called gas producer. It consists of a steel vessel of (3
m in diameter, 4 m in height) inside lined with refractory bricks. It is provided with cup
and cone feeder at the top and a side opening for produced gas exit. At the bottom, it
has inlets for passing air and steam.

Manufacture of producer gas

Various Reactions

The reactions of producer gas production can be divided into four zones as follows.

(i) Ash Zone

This is the lowest zone consists mainly of ash. The incoming air and steam mixture
is preheated in this zone.

(ii) Combustion or Oxidation Zone

This is the zone next to ash zone. Here the coke is oxidised to CO and CO2. Both
the reactions are exothermic. Hence, the temperature of the bed reaches around
1,100°C.

C +O2  CO exothermic H + 95 k cal

C + 1/2O2  CO2 exothermic H + 29 k cal

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(iii) Reduction Zone

This is the middle zone. Here both CO2 and steam combine with red hot coke and
liberate H2 and CO. The reduction reactions are endothermic and the temperature in the
zone is about 1000°C. If no steam is supplied, the temperature of the producer raise
and this may fuse the ash and refractory lining.

C + CO2  2CO endothermic – 36 k cal

C + H2O  CO + H2 endothermic – 29 k cal

(iv) Distillation or Drying Zone

In this zone (400 - 800°C) the down coming coal is heated by the outgoing gases.
The heat given by the gases and the heat coming out from the reduction zone will distill
the fuel.

Uses

1. It is used as a reducing agent in metallurgical operations.

2. It is also used for heating muffle furnaces, open-hearth furnaces etc.

WATER GAS

It is a mixture of combustible gases,

CO 41%

H2 51%

N2 4%

CO2 4%

Its calorific value is about 2800 kcal/m3

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Manufacture of water gas

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

When steam and little air is passed alternatively over a red hot coke maintained at
about 900 - l000°C in a reactor, water gas is produced.

Reactions

The reactions of water gas production involves the following two steps.

Step 1

In the first step, steam is passed through the red hot coke, where CO & H 2 gases
are produced. The reaction is endothermic. Hence, the temperature of the coke bed
falls.

C + H2O  CO + H2 endothermic – 29 k cal

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Step 2

In the second step, 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 exothermic H + 95 k cal

2C + O2  2CO exothermic H + 59 k cal

Thus the steam – run and air blow are repeated alternatively to maintain proper
temperature.

Uses: It is used for the production of H2 and in the synthesis of ammonia. It is also used
as a source of and illuminating gas and fuel gas.

Lecture session 34: Combustion- Theoretical calculation of air by weight –

problems
Combustion of fuel

Combustion is a process of rapid exothermic oxidation, in which a fuel burns in

the presence of oxygen with the evolution of heat and light.

Aim of combustion is to get the maximum amount of heat from a combustible

substance in shortest time. Most of the combustible substances are enriched with carbon
and hydrogen

C + O2 → CO2; Exothermic

2H2 + O2 → 2H2O; Exothermic

Since, the above reactions are exothermic large quantity of heat is given out.

Theoretical calculation of calorific value

1. Elements always combine in definite proportions to give the products. For

example 12 gm of carbon combines with 32 gm of oxygen to give 44 gm of CO 2

C + O2 → CO2

12 32 44

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Similarly, 4gm of hydrogen combines with 32gm of oxygen to give 36gm of H 2O.

2 H2(g) + O2(g) → 2H2O(g)

4 32 36

2. At STP (273 K, 1 atm) one mole of all gases occupy a volume of 22.4 litres.
Hence at S.T.P. 22.4 liters of CO2 will have a weight of 44gm, its molecular
weight.

3. Air contains 21 % of oxygen by volume and 23 % of oxygen by weight, Hence

1 m3 of oxygen will be supplied by

1 x l00/21 = 4.76 m3 of air

Similarly 1 kg of oxygen will be supplied by 1 x 100/23 = 4.35 kg of air.

4. Molecular weight of air is 28.94mol-1.

1. Minimum oxygen required = (Theoretical O2 required) - (O2 present in fuels).

2. The mass of flue gas is calculated by balancing the carbon in the fuel and the
carbon in the flue gas.

3. Minimum O2 required is calculated on the basis of complete combustion of fuel. If

as a result incomplete combustion or CO is formed then O 2 is calculated for the
conversion of CO to CO2.

4. If the fuel contains both O2 and H2, the amount of hydrogen and oxygen may be
present in the form of as H2O, which is a non-combustible substance. The
remaining available hydrogen takes part in the combustion reaction.

2 H2(g) + O2(g) 2H2O + heat

32 gm of oxygen combines with 4gm of hydrogen, Hence 1 part of hydrogen

combines with 8 parts of oxygen.

Available oxygen = Mass of hydrogen - (Mass of hydrogen/8)

Hence, theoretical amount of oxygen required for complete combustion of 1 kg of

fuel is given by the equation,

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C, H and S are masses of carbon. Hydrogen and sulphur respectively per kg of

the fuel. Since 1 kg of air-contains 23%of oxygen by weight, the amount of air
required theoretically to burn 1 kg of fuel completely is given by equation.

According to Dulong's formula for the theoretical calculation of calorific value is,

Where C, H, O and S represent the % of the corresponding elements in the fuel. It is

based on the assumption that the calorific value of C, H and S are found to be 8080,
34500 and 2240 kcal, when 1 kg of the fuel is burnt completely.

However, all the oxygen in the fuel is assumed to be present in combination with
hydrogen in the ratio H:O as 1:8 by weight. So the surplus hydrogen available for
combustion is' H – (O/8).

Theoretical calculation of minimum air requirement for combustion of a fuel

Combustion is the process of burning any combustible substance in the presence

of oxygen, which liberates energy in the form of heat and light. For efficient combustion,
it is essential that the fuel must be brought into intimate contact with sufficient quantity
of air or oxygen.

The combustible substances usually present in fuels, which enter into the
combustion, are mainly C, H, S and O. But N, CO2 and ash are incombustible matters
present in the fuel, .do not take any oxygen during combustion.

For the complete combustion of a given quantity of fuel can be calculated by

considering the following point. Substances always combine in definite proportions,
which are determined by the molecular weights of the substances.

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iv. Combustion Sulphur

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Lecture session 35: Theoretical calculation of air by volume - problems

Calculate the Minimum volume of air required for the complete combustion of 1m 3 of a
gaseous fuel containing the following composition by volume CO: 23%; H 2 : 12% ; CH4 :
3%; CO2 :5 %; N2 :55% and O2:2%

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A sample of coal was found to contain: C=80%; h=5%; O2=1%; N=2%; remaining being
ash. Calculate the amount of minimum air required for complete combustion of 1 kg of
coal sample.

Solution

1 kg of coal contains

80/100 = 0.8 kg of C

5/100 = 0.05 kg of H

1/100 = 0.01 kg of O2

2/100 = 0.02 kg of N2

N2 is non combustible constituent, it does not born and not require any O2

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The combustion reactions are

C + O2 → CO2

12 32 44

H2 + O2 → H2O

2 16 18

(a) 12 kg of C requires 32 kg of O2

0.8 kg of C requires = (32/12) x 0.8 = 2.133 kg of O2

(b) 2 kg of C requires 16 kg of O2

0.05 kg of H2 requires = (16/2) x 0.05 = 0.4 kg of O2

Total amount of O2 required = 2.133 + 0.4 = 2.533 kg

But, the amount of O2 already present in the fuel = 0.01 kg

So Net O2 required = 2.533 – 0.01 = 2.523 kg

We Know That

23 kg of O2 is supplied by 100 kg of air

So

2.523 kg of O2 is supplied by = (100/23) x 2.523 = 10.9695 kg of air

Thus, min. quantity of air required for complete combustion of 1 kg of coal is = 10.9695
kg

Lecture session 36: Flue gas analysis by Orsat method and its significance.

Flue Gas Analysis (Orsat's method)

The mixture of gases such as CO2, O2, CO, etc., coming out from the combustion
chamber is called flue gases. The analysis of a flue gas would give idea about the
complete or incomplete combustion process. If the flue gases contain considerable
amount of CO, it indicates that incomplete combustion and it contain a considerable
amount of oxygen indicates, complete combustion. The analysis of flue gas is carried
out by using Orsat's apparatus.

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Description of Orsat's Apparatus

It consists of a horizontal tube, having 3 way stopcock. At one end of this tube,
U-tube containing fused CaCl2 is connected. The other end of this tube is connected
with a graduated burette. The burette is surrounded by a water-jacket to keep the
temperature of gas constant. The lower end of the burette is connected to a water
reservoir by means of a rubber tube. The level of water in the burette can be raised or
lowered by raising or lowering the reservoir. The horizontal tube is also connected with
three different absorption bulbs I, II and III for absorbing CO2, O2 and CO.

Bulb- I : It contains 'potassium hydroxide' solution, and it absorbs only CO2

Bulb - II: It contains 'alkaline pyrogallol' solution, and it absorbs only O 2

Bulb.:III : It contains 'ammoniacal cuprous chloride' solution, and it absorbs only CO.

Orsat's Apparatus

Working

The 3-way stopcock is opened to the atmosphere and the reservoir is raised, till
the burette is completely filled with water and air is excluded from the burette. The 3-
way stopcock is now connected to the flue gas supply, the flue gas is sucked into the
burette, and the volume of flue gas is adjusted to 100 cc by raising and lowering the
reservoir. Then the 3-way stop cock is closed.

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a) Absorption of CO2

The stopper of the bulb-1 containing KOH solution is opened and all the gas is
passed into the bulb-1 by raising the level of water in the burette. The gas enters into
the bulb-I, where CO2 present in the flue gas is absorbed by KOH. The gas is again
sent to the burette. This process is repeated several times to ensure complete
absorption of CO2.The decrease in volume of the flue gas in the burette indicates the
volume of CO2 in 100 cc of the flue gas.

b) Absorption of O2

Stopcock of bulb-I is closed and stopcock of bulb-II is opened. The gas is again
sent into the absorption bulb-II, where O2 present in the flue gas is absorbed by alkaline
pyrogallol (925 g of pyrogallol + 200g of KOH in 500 ml distilled water). The decrease in
volume of the flue gas in the burette indicates the volume of O2.

c) Absorption of CO.

Now stopcock of bulb-II is closed and stopcock of bulb-Ill is opened. The

remaining gas is sent into the absorption bulb-III, where CO present in the flue gas is
absorbed by ammoniacal cuprous chloride (100 g CuCl2 + 125 mL liquor ammonia +
375 mL distilled water). The decrease in volume of the flue gas in the burette indicates
the volume of CO. The remaining gas in the burette after the absorption of CO2, O2 and
CO is taken as nitrogen.

Significance of Flue Gas Analysis

Precautions

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