Cracking , reforming and

chemical conversion
reactions
These techniques are used for further refining of
the fractional distillation products and to increase
the yield and quality of petrol.
 Cracking

It involves the breaking or decomposition of

bigger hydrocarbon molecules through the
rupture of C-C and C-H bonds, to yield
smaller molecules. E.g.
C10H22 ----------> C5H12 + C5H10
It is carried out either by thermal
cracking(high temp. and high pressure) or
catalytic cracking(using catalysts).
Thermal cracking
It depends upon the thermal stability of heavier
hydrocarbons. It is carried out either in liquid phase
or in vapour phase.
In general the thermal stability of hydrocarbons
increases in the order :

paraffins < naphthenes(alicyclics) < aromatics

Cracking of the side chains of the alicyclic and

aromatics also occur and in the case of alicyclics
even ring opening may occur. The cracked products
are then subjected to fractionation to separate the
different products.
Thermal cracking is carried out either in liquid phase
or in vapour phase. In liquid phase thermal cracking
the heavy oil is cracked at temperatures in the range
of 450-5500C and at pressures upto 100 kg/cm2. to
yield 50-60% of petrol of octane rating 65-70.

Vapour phase thermal cracking involves vaporising the

oil and cracking at about 600-6500C and pressures of
10-20 kg/cm2 to yield petrol of better anti-knock
characteristic but less stability compared to petrol
obtained by liquid phase cracking.
Catalytic cracking :
It occurs in the presence of catalysts. It requires less severe
conditions of temp. and pressure. It is more economical and
provides better quality of gasoline (containing less alkenes)
and gives higher yield of C-3 and C-4 alkanes and alkenes and
desired liquid hydrocarbons.
Catalytic cracking is carried out either in (i) fixed bed
catalytic reactors or (ii) fluidized bed catalytic reactors.
Catalysts such as activated montmorillonite clay or molecular
sieves are used as catalysts. Modern cracking uses zeolites as
catalyst. These are complex alumino silicates (large lattices of
Al, Si and O carrying a negative charge). They are associated
with positive ions, such as sodium. The alkane is brought into
contact with the catalyst at a temp. of about 500◦C.
In fixed bed catalytic cracking the catalyst used in the
form of pellets or powder. It gives lower yield of
cracked products.

In fluidized bed catalytic cracking the catalyst is finely

divided and maintained in a fluid state. It gives higher
yield of cracked product with higher octane no. This
method enables better contact between the catalyst
and the crude oil facilitating efficient heat transfer.
Reforming
It is the rearrangement of the molecular
structure of the feed hydrocarbons to make the
product more suitable as a fuel for IC (internal
combustion) engine. This is done to improve the
quality of petrol. The main reactions that occur
during reforming process include (i)
dehydrogenation (ii) dehydrocyclization (iii)
hydrocracking (iv) isomerisation.
Dehydrogenation :

Dehydrocyclization :
2C7H16 -----------> C7H14 + C7H8 + 3H2
n-heptane methyl toluene
cyclohexane
Hydrocracking :

Isomerisation :

The hydrogen formed in the dehydrogenation reaction is

utilised to promote hydrocracking of bigger alkane molecules
and also to remove sulphur in the feed as H2S.
Aromatization :
Chemical conversion reactions :
Processing of the cracked/reformed gasoline involves
chemical conversion reactions such as polymerisation,
hydrogenation, isomerisation and alkylation. Alkenes are
polymerised to high mol. wt. hydrocarbons using acidic
catalysts, which are then hydrogenated to yield branched
chain alkanes.

2CH3C(CH3)=CH2 ------> CH3C(CH3)2CH2C(CH3)=CH2

iso-butylene diiso-butylene

--------->
Isomerisation reaction involves a structural rearrangement
within the molecule generally involving the conversion of
straight chain n-alkanes to branched chain iso-alkanes
catalysed by anhydrous AlCl3 activated by anhyd. HCl gas.

CH3(CH2)2CH3 ---------------> CH3CH(CH3)CH3

n-butane 2-methylpropane(iso-butane)

Alkylation is yet another reaction useful in the conversion of

straight chain hydrocarbons to branched ones.

CH3CH(CH3)CH3 + CH3C(=CH2)CH3----->CH3C(CH3)2CH2CH(CH3)2
iso-butane iso-butylene iso-octane