2-20 FUELS AND COMBUSTION

light oil, tar, ammonium sulphate, finely divided sulphur and ammonium thiocyana
can be recovered from the byproduct-oven gases.
(1) Recovery of tar. Gas from the coke ovens is passed through a tower wher
liquor ammonia trickles from the top. Tar and dust settles down in a tar tank. Tar and
ammonia are recovered.
(2) Recovery of ammonia. The gases are sent to another tower where water i
sprayed. Ammonia goes into solution forming ammonium hydroxide. Sometimes
instead of water dilute H,SO, is sprayed, where ammonium sulphate is recovered.
NH, +H 0 ’NH,OH
2NH,OH+ H,SO4(NH, SO4 + 2H,O
(3) Recovery of naphthalene. The gases are then passed to a cooling tower
where water at a low temperature is sprinkled. Condensation of some gases taken
place and naphthalene is recovered.
(4) Recovery of benzole. The gases are then passed through an oil (petroleum)
scrubber where benzene and its homologues are recovered.
(5) Recovery of H,S. The gases then enter a purifying chamber packed with
moist Fe,O3
Fe,O3 + 2H,S ’ Fe,S3 +3H,0
After all the Fe,0, exhausted, it is exposed to atmospheric air to recover the
sulphur (as SO2), and regenerate Fe,0s.
Fe,O3 + 3 0 ’2FeO + 2S02
4FeO + O2’2Fe,03
(6) Recovery of gas. The gas after passing through the various scrubbers and
condensers to remove the various byproducts is finally collected in a gasholder. The
gas has calorific value of about 5000 Kcal/m'.
2.11 LIQUID FUELS
The liquid fuels are characterised by low flash point, high calorific value,
low viscosity at ordinary temperature and low moisture and sulphur contents. The
important liquid fuels include petroleum, petroleum products, tar, alcohols and
colloidal fuels. Liquid fuels find extensive use in domestic and industrial fields.
Petroleum. As it is found in rocks it is called petroleum, derived from the Latin
Petra (rock) and oleum (oil). Thus, petroleum means rock oil. Petroleum is often called
liquid gold, because modern civilization has found it to be more valuable than precious
gold. It is a dark coloured viscous liquid found deep in the earth's crust.
The average composition of crude oil is as follows :
C= 80-87%, H= 11.1-15.0%, S =0. 1-3.5%, 0=0.1-0.9%, N = 0.4-0.9%.
 FUELS AND COMBUSTION 2-21

Cassification of petroleum. Petroleum is classified into three categories

according to its composition.
1. Paraffin base oil. Which mainly consist of staturated paraffinic hydrocarbons
Enm methane to solid waxes) together with smaller amounts of aromatic naphthenes
and hydrocarbons. These oils on distillation leave a residue of solid paraffin wax. (It
is worth mentioning here that a lubricating oil obtained from parafin-base oils usually
have lower specific gravity and higher viscosity index than that obtained from
asphaltic base oils. Also, more solid waxes separate from the paraffin has lubricating
oils on cooling.)
2. Asphalticbase oils. Which principally consist of non-paraffinic hydrocarbons
such as aromatic and naphthenic hydrocarbons. These oils on distillation leave behind
asphalt or bitumen.
3. Mixed base oils. Which are intermediate between the paraffin and asphaltic
base oils and hence contain varying proportions of asphlatic, naphthenic, and aromatic
hydrocarbons.
Refining of petroleum. Crude oil coming out from the well generally consists
of a frothing mixture of solid, liquid and gaseous hydrocarbons containing sand and
water in suspension. Hence, it is not of commercial use. It can be separated into a
number of useful fraction by fractionaldistillation. This process of dividing petroleum
into different useful fractions with different boiling ranges is called refining of
petroleum.The process of refining involves the following steps :
Step I. Separation of water (Cottrell's process). The crude ols is an emulsion
of oil and salt water (brine). The process of separating water from oil consists in
allowing the crude to flow between two highly charged electrodes. The colloidal water
droplets coalesce to form large drops, which separate out from oil.
Step II. Removal of sulphur compounds. This involves the treatment of oil
with copper oxide. A reaction occurs with sulphur compounds which results in the
formation of copper sulphide (precipitate) which is then removed by filration.
Step IIL. Fractional distillation. The crude oil is then heated to about
400-430°C in an iron retort whereby all volatile constituents are evaporated. The
components like tar and asphalt do not vapourize and they settle at the bottom of the
column. The hot vapours are then passed through a distillation column.
The various principal fractionation products thus obtained are given in Table 2.1
 2-22 FUELS AND COMBUSTIO,
Table 2.1. Fractions by distillation of crude
S Name of raction Boiling range Approx. Uses
No. composition
1. Uncondensed gases Upto 30°C Ci-Cs Domestic fucl (LPG), synthesis of
organic chemicals, production of
carbon black.
2, Petroleum cither 30-70°C As a solvent for oil, vamish.
Cs-C7
3. Gasoline or Petrol 40-120°C Cs-C10 Fuel for internal combustion engine of
automobiles, acroplanes, solvent and
dry cleaning.
4. Naphtha 120-180°C Co-Cio As solvent and dry cleaning.
5. Kerosene 180-250'C Cio-C16 Illuminant, fuel for stoves.
6. Diesel oil 250-320°C C1o-C18 Fuel for diesel engines.
7. Heavy oil on 320-400C Lubrication.
C17-C30
refractionation gives
() Lubricating oil Lubricant, cosmetics,
(i) Petroleum jelly Medicines
(üi) Grease Lubricant
(iv) Paraffin waX Candles, boot polish, wax paper,
tarpolin cloth etc.
Residue pitch or above 400'C C30 and Water proofing of roofs, road making
Petroleum coke above As fuel

2.11.1. Other Liquid Fuels

) Kerosene and jet fuels. Kerosene is defined as a refined petroleum distillate,
less volatile than gasoline, and boiling between 150°C and 300°C. Itsdistillation range
Overlaps that of gasoline.
(k) Rocket fuels. In rocket propulsion, the fuel is consumned at a much faster
rate than in the gas turbine or jet engine and temperatures are much higher. Gas
temperatures in the rocket motor run from 5000°F to 6000°F whereas jet aircraft
engine operates at about 1800°F Conventional fuels for jets are mainly kerosenes and
for rockets, liquid organic compounds which are burnt with either liquid oxygen or
concentrated H,0.
The various rocket fuels include alcohol, thiokol, hydrazine, certain borides,
some polymers, hydrogen, lithium hydride, aniline and boranes, with suitable
Oxidizers.
(üi) Fuel oils. The high molecular weight petroleum fractions are called "fuel
oils". Their calorific values are of the order of 10,000 kcals/kg. Just like coal tars and
tar oils, fuel oils are also used for steam raising and heating furnaces.
(iv) Colloidals fuel or oil-coal mixture. It consist of suspension of solid fuel
like coal into liquid oil. This mixture does not separate out on storage at
atmospheric
FUELS AND COMBUSTION 2-23
pressure and temperature. This is due to the fact that it is stabilized by some stabilizing
agent.
The proportion of oil-coal in the colliodal fuel is 40: 60, sothat it can be used
as liquid fuel. The calorific value of this fuel is very high and it can be handled easily
like liquid fuel.
(v) Benzol. It is an important product of carbonization of coal which is used as
a liquid ftuel. It distills in the temperature range of 70° to 150°C. Its composition is
as follows:
Benzene 70%
Toluene 18%
Xylenes 6%
Other hydrocarbons 6%
lts calorific value is about 10,000kcals/kg and its octane rating is as high as 90.
It is generally blended with gasoline and used as a fuel for internal combustion
engines.
(P) Power alcohol. Ethyl alcohol is an important fuel and when it is used in an
internal combustion engine it is called power alcohol". Blends of alcohol with
gasoline or with gasoline plus benzol or with eithers and water were used as motor
fuel.
2.11.2. Gaseous Fuels
Gaseous fuels are classified into natural and artificial gases:
I. Natural gas. Natural gas which is a mixture of methane, ethane, propane,
butane, pentanes, carbon dioxide, nitrogen etc. is the most important fuel found mainly
in the vicinity of coal mines or oil fields. The natural gas derived from oil wells may
be either dry or wet. When natural gas occurs along with petroleum in oil wells it is
called wet gas. The wet gas is treated to remove propane, propene, butane and butene
which are used as LPG. On the other hand when the gas is associated with crude oil
it is called dry gas. The approx. composition of natural gas is
CH, =70-90%,C,H, = 5-109%, C,Hg = 3.7%, CaHÍ = 1.8%,
H, =3%, CO + CO, = rest.
II. Artificial gases :
1. Liquefied (or Liquid) petroleum gas (LPG). LPG consists of light
hydrocarbons (upto Ca) like propane (CHs), propene (C3H) and butane (C¡Hio) which
can be readily liquefied under pressure but can exist as gases under atmospheric
pressure. LPG is mainly used at present as a domestic fuel and to a large extent as
industrial fuel also. It is usually supplied in cylinders under pressure, with different
trade names. LPG can be used as a motor fuel as it easily mixes with air and burns
cleanly without residue and is knock-resistant. However, it has to be handled under
pressure and can be better used only with engines working under high compression
 2-24 FUELS AND COMBUSTION
ratios. Liquid butane js mainly used for domestic purposes whereas liquid propane i
mainly used for industrial purposes because of its higher pressure. LPG (chien
C,H) has the calorific value of about 25000 kcals/m".
2. Coal gas. Coal gas is produced during the carbonisation of coal, i.e., whe
coal is heated in the absence of air. The coal is fed in closed silica retorts which a
then heated to about 13,00°C. The heating is carried out by burning producer gas andi
air mixture.
1300°C
Coal In absence of aBr
Coke + Coal gas

The average composition of coal gas is,

H, =40% N2= 4%
CH, =32% CO, = 1%
CO =7% other = 4%

CH, = 2%
CH =3%
Its calorific value is about 4,900 kcal/m'.
Coal gas is used for illumination purpose. It is also used as a fuel.
3. Oil gas. Oil gas consists of a mixtures of hydrocarbons. It is prepared by
cracking of kerosence oil. Agood oil gas appears in golden colour.
The composition of the oil gas depends on the nature of the oil used. Its average
composition is as follows :
CHË- 25 to 30%
H,- 50 to 55%
CO- 11%
CO)-3%
The calorific value of oil gas is about 6700 kcal/m'. It is used as a laboratory
gas. Itis also used to improve the calorific value of water gas and the mixture of the
two gases is called carburetted water gas.
4. Producer gas. Producer gas is essentially a mixture of carbon monoxide and
nitrogen. It is prepared by passing a mixture of air and steam over a bed of
incandescent coke, anthracite coal, high volatile non-coking coal or lignite.
It is used for heating open-hearth furnance/glass furnance, muffle furnace etc. It
is used as a reducing agent in metallurgical operations. It is also used as fuel in the
manufacture of ceramics and refractories.
5. Water gas (or Blue gas). Water gas is essentially a mixture of CO (40 to
42%)and H2 (48-51%). It is prepared by passing steam over red hot coke. The water
gas is also known as blue gas because it burns with a blue flame due to the combustion
FUELS AND COMBUSTION 2-25
of carbon monoxide.
Water gas is prepared by reacting steam over red hot coke in a cyclic process
comprising of the following two main steps :
() Air is passed through the coke bed when carbon burns to CO and the
(emperaure of the fuel bed increases to over 1000°C.
C+ (O; +3.76 N2) ’ CO+3.76 N,+96.7 kcal
Air (Exothermic)

The outgoing gases containing CO; and Nare used to preheat the incoming air
and steam.

(2) Steam is now blow through the red hot coke when CO and H, are produced.
At higher temperatures :
C+ H,0 C0+ H,- 28.7 kcal (Endothermic)
At lower temperatures :
C+ H;0 CO, + 2H2 - 18.6 kcal (Endothermic)
The calorific values of water gas is about 2580-2670 kcal/m'. The normal
composition of water gas is as follows :
CO= 40-42%, Hh = 48-51%, CO, = 3-5%, CH, = 0.10.5%, N2 =3-6%.
Water gas can be used for heating purposes in industrial operations. Water gas
is used for the production of hydrogen and in synthesis of ammonia. It is used as a
fuel in many industrial processes such as enamelling, annealing etc., in glass and
ceramic industries.

2.12 CRACKING
With the increasing demand of automobile industry, demand of gasoline is rising.
An average crude oil on fractional distillation yields only 20 - 30% gasoline, 40-45%
immediate oils and 25-50% residual oil. The quality of gasoline or "straight run
petrol" is not so good and can be used only after proper blending. Because of these
reasons a process is developed by means of which higher fractions or heavy oils are
converted to more useful and valuable lower boiling oils suitable for spark - ignition
engines of automobiles.
Cracking
Clo H¡2 ’ Cs Hi2 +Cç Hio
Decane n-pentane pentene

Hence, breaking down of higher hydrocarbons in lower hydrocarbons is known

as cracking. It is usually done by two methods :
2.12.1. Thermal Cracking
This is older method. In this, higher hydrocarbons are broken down to lower
hydrocarbons of paraffinic and olefinic series by applying high temperature and
 2-26 FUELS AND COMBUSTION

pressure. The cracked products are subjected to fractional distillation. There are two
types of thermalcracking :
A. Liquid - Phase Thermal Cracking, Any type of oil viz. Residues, fuel oils
can be cracked by this process. The charge in the form of liquid is maintained
in the range of, 420°C to 550°C and a pressure of about - 15 to
100 Kg/cm is applied. The yield is around 50 - 60% and octane rating is
about 65-70.
B. Vapour - Phase Thermal Cracking. This method is applicable only to the
oils, which can vaporize at low temperature., The oil is heated at about 600
to 650°C and subjected to a pressure of 10-20 Kg/cm. The products so
obtained have poor stability but the octane rating is higher than the prior
method i.e., anti knocking properties are better.
2.12.2. Catalytic Cracking
In this method, cracking is done in presence of a catalyst at much lesser
temperature and pressure. There are two main types of catalytic cracking:
1. Fixed Bed Catalytic Cracking, and
2. Moving Bed Catalytic Cracking.
One carried out only in the presence of a catalyst (porous solid particles of
definite composition and structure); the other in presence of a catalyst, but in a
hydrogen atmosphere at a slightly reduced temperature but higher pressure. The latter
is called "hydro-cracking".
Earlier acid clays were used as catalysts, but now, they are replaced by
crystalline alumino-silicates (zeolites). In these, alumina and silica are the major
constituents, but they also contain minor amounts of oxides of Ca, Mg, Na, Fe, Cr
and rare earths. The important characteristics of alumino-silicate catalysts for
petroleum cracking are :
1. Activity, which determines the yield of the end-product, relative to the starting
material used,
2. Selectivity, which is ameasure of its ability to accelerate the desired reactions
and suppress the rate of unwanted reactions,
3. Ageing, as a result of which the catalyst may gradually lose its activity and
to some extent, selectivity. The process of ageing may be accelerated, if the
conditions are more rigid and if the catalyst comes into contact with
compounds containing S, heavy metals (e.g., V, Ni) etc. Catalysts can be
regenerated to restore their activity and selectivity by burning off the coke
deposited on the catalyst particles.
In the cracking process, the contact of crude petroleum fractions with a catalyst
results in the formation of gas, gasoline, coke and other liquid products due to various
reactions such as dehydrogenation, isomerization, hydrogenation and polymerization.