Refining of crude oil: The petroleum obtained by mining is viscous and dark colored liquid.

Due to the presence

of sulphur, it has an unpleasant smell. It also contains impurities of sand, brine or sea water. Hence it is called
crude oil. The process of refining involves the following steps.
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.
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.
Fractional distillation :
The crude oil is then heated to about 400°C in an iron retort, whereby all
volatile substances (except asphalt or coke) are evaporated. The hot vapors
are then passed up a fractionating column, which is a tall cylindrical tower
containing a number of horizontal stainless steel trays at short distances.
Each tray is provided with small chimney covered with a loose cap.When the
vapors 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.
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.
Octane rating is the measure of fuel’s ability to resist knocking. Introduced by Edger in 1872, found that
n-heptane knocks badly and its anti knock value given zero. On the other hand, isooctane gives very little
knocking and its anti knock value given 100.
Octane number of a gasoline is the percentage of isooctane present in the mixture of isooctane and n-heptane,
which matches the fuel under test.

Improvement of antiknock characteristics: The octane number of fuel can be improved by 1) Blending petrol
of high octane number with petrol of low octane number, so that the octane number of the latter can be
improved. 2) The addition of anti-knock agents like Tetra-Ethyl Lead (TEL).
→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.
Cetane Number:Cetane number is introduced to express the knocking characteristics of diesel. Cetane has a
very short ignition lag and hence its cetane number is taken as 100. On the other hand 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) = 100 CH3
→cetane number is defined as "the percentage of hexa decane
2-methyl naphthalene
present in a mixture of hexa decane and 2-methylnapthalene ,which (cetane number = 0)
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.
Liquefied Petroleum Gas(LPG):LPG is obtained as a byproduct, during cracking of heavy oil or from natural
gas.LPG is dehydrated, desulphurized and traces of organic sulphides are added to give warning of gas leak. LPG
is also known as Bottled gas or Refinery gas. It consists of lighter hydrocarbons like Propane (C3H8), Butane
(C4H10) and Iso-butane, which can be readily liquified under applied pressure but can exist as gases under
atmospheric pressure. LPG is mainly used at present as a domestic fuel and also to a large extent as industrial
fuel. It is usually supplied in cylinder under pressure. It is available under different trade names like Indane, HP,
Bharat Gas etc.LPG can be used as a motor fuel as it is easily mixed with air and burns cleanly without residue
and it is knock resistant. Liquid butane is mainly used for the domestic purposes; whereas liquid propane is
mainly used for industrial purposes because of its higher pressure.LPG has the calorific value of about 27800
k.cal/m³.
Advantages of LPG as Motor Fuel: 1.It is cheaper than gasoline, 2.It gives better manifold distribution and
mixes easily with air,3.It is highly knock resistant,4. The residue and oil contamination is small, 5.Burns cleanly
and 6.It enhances the engine life
Disadvantages of LPG as Motor Fuel:1. It has a faint odour, 2.Its handling has to be done under pressure and 3.
Its response to blending is poor.
Compressed Natural Gas (CNG):
CNG is Natural gas compressed under a high pressure of about 1000 atmosphere. A 15 kg steel cylinder
containing of about 20m³ of natural gas at one atmospheric pressure. Now-a-days CNG is being in use as a
substitute to petrol and diesel oil, as it causes less air pollution. In some metropolitan cities use of CNG is
mandatory for city buses, taxis and autos.
Advantages:1.Its octane number is about 130 and hence no anti knocking additives are needed, 2.lt is a light
weight gas with a high ignition temperature, 3.Emission of CO and other un burnt hydrocarbons is minimum,
4.It enables regular combustion ,5.It does not carbonize spark plugs, 6.It does not remove the lubricant films,
7.When CNG is used as a fuel, the engine has a long life, 8. It has less starting problems in cold conditions, and
9. Unlike petrol, CNG is almost insoluble in engine oil. Therefore, the oil can serve longer.
Disadvantages:1.CNG requires large trunk space 2.CNG requires heavy cylinders for storing the natural gas at
high pressure.3. CNG driven vehicles have shortest operating range as compared to petrol expensive driven
vehicles, and 4. Refueling networks for CNG are very
Synthesis of Gasoline:The gasoline obtained from the fractional distillation of crude petroleum oil is not
enough to meet the requirement of the present community due to vast increase of automobiles. Hence an
alternate source need of finding out to manufacture synthetic petrol.
→Synthetic petrol can be manufactured by the process of hydrogenation of coal. The preparation of liquid
fuels from solid coal is called hydrogenation of coal.
→Gasoline is synthesized by the following methods.1 .Fischer- Tropsch process. 2 .Bergius process.
Fischer- Tropsch process :In this process, water gas (CO+H2) is produced by the action of steam over red hot
coke. The gas is purified by passing through Fe2O3 to remove sulphur.
→It is mixed with hydrogen and the mixture is compressed to 5-25 atmospheres. The compressed gases are
then led through a converter which is maintained at a temperature of 200-300°C.
→The converter is provided with a suitable catalyst consisting of a mixture of 100 parts cobalt, 5 parts thoria, 8
parts magnesia and 200 parts kieselguhr. A mixture of saturated and unsaturated hydrocarbons occurs as a
result of polymerisation.
n CO + 2 n H2 CnH2n + n H2O n CO + (2 n + 1) H2 CnH2n+2 + n H2O
Bergius process:This method was developed by Bergius in Germany during the First World War. 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 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 heavy oil 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.

Otto Hoffmann's by-product Oven process:This method is superior over Beehive oven method as it can recover valuable
byproducts and regenerate the heat. The byproduct coke oven consists of number of narrow silica chambers 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 end for discharging coke. A charge consisting of finely
crushed coal. It is introduced through the charging holes at the top of chamber, which are then closed tightly at both
ends to prevent any access of air. The coke ovens are heated to 1200°C by burning gaseous fuel and usually employ a
regenerative principle to achieve heat economy. 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 1000°C. The flow of heating gases is then reversed and the inlet gases pass through the heated
checker brickwork, which serves to preheat the inlet gases. The flue gases are then allowed to pass through the second
set of checker bricks to heat it. The heating is actually continued, till the evolution of volatile matter ceases completely.
Carbonization of a charge of coa! takes about 11 to 18 hours. When carbonization is completed, a massive ram pushes
the red-hot coke into a truck. A water spray subsequently quenches it. The gas coming out from the oven is known as
Coke oven gas and is mainly composed of ammonia, H₂S, naphthalene, benzene, tar etc.
Recovery of By-products:
1.Recovery of Tar: The gas from the coke oven is passed through a tower where liquor ammonia is sprayed from the top.
Tar and dust are removed into a tar tank. Tar and ammonia are recovered. Ammonia liquor is again sent to the top of the
trickling tower.
2.Recovery of Ammonia: The gases now enter another tower where water is sprayed. Ammonia goes into solution
forming ammonium hydroxide. Sometimes instead of water dil H₂SO4 is sprayed when ammonium sulphate is recovered.
NH3 + H2O + NH4OH 2NH4OH + H₂SO4 → (NH4)2SO4+ 2H₂O
3.Recovery of Naphthalene: The gases are then passed to a cooling tower where water at low temperature is sprayed.
Condensation of some gases takes place and naphthalene is recovered.
4.Recovery of Benzene: The gases are then sprayed with petroleum, where benzene and its homologues are recovered.
5.Recovery of H₂S: The gases are then passed to a purifying chamber packed with moist Fe₂O3 to absorb H₂S.
Fe₂O3 +3 H₂S → Fe₂S3 + 3 H₂O
After all the Fe₂O3 is exhausted, it is exposed to atmospheric air to recover the sulphur and regenerate the Fe₂O3.
Fe₂S3 + 4022FeO + 3SO₂ 4FeO + O₂ → 2Fe₂O3
Advantages:1.Increase thermal efficiency of the carbonization process, and 2.Recovery of valuable by products
Applications:1. For metallurgical process particularly iron and steel, 2. As a reducing agent in steel manufacturing
process,3. As a smoke less fuel for domestic purpose, 4. Fuel gases like producer gas, water gas etc are formed from coke
and 5. Coke is used as a raw material for the preparation of synthetic petrol.
Petroleum: Petroleum is made from the remains of plants and animals buried millions of years ago.It is a non-
renewable resource.
Composition
Petroleum is a dark, greenish brown, viscous liquid that is found underground. It comprises hydrocarbons such
as:→Straight paraffins or cycloparaffins such as methane, ethane, propane,butane, isobutane, pentane,
hexane.→Olefins such as ethylene, butene, isobutene and acetylene, butadienes.
→Aromatics such as benzene, naphthalene, cyclohexane, methyl cyclopentane.Some organic compounds
containing nitrogen, oxygen and sulphur.
→The average composition of crude oil is C =80 - 87 %, H =11-15%, S = 0.1 -3.5%, (N +O) =0.1- 0.5%.
Classification of petroleum:
Petroleum is classified into three types based on variation of chemical nature of crude oil found in the earth.
→Paraffinic-base type crude oil: It contains saturated hydrocarbons from CH4 to C35H72 and little amount of
naphthalenes and aromatics.
→Asphaltic-base type crude oil: It contains mainly cycloparaffins or naphthalenes with smaller amount of
paraffins and aromatic hydrocarbons.
→Mixed-base type crude oil : It contains both paraffinic and asphaltic hydrocarbons and are generally in the
form of semisolid waxes.
Coke: the process of coverting coal into coke Is called carbonization ,when a coking coal is heated in the
absence of air the porous, hard and strong residue left is called coke.coke is pure ,stronger and more porous
than coal.