Aromatic Production

Catalytic reforming and pyrolysis gasoline are the two major source of
aromatics.
Catalytic reforming transform low octane naphtha into high octane

motor

gasoline blending stock and aromatics rich in benzene, toluene and xylene with
hydrogen and petroleum gas as byproduct.
Feedstock for catalytic reforming is naptha in the boiling point range of 60180oC.
Catalytic reforming is a major conversion process in petroleum refinery
petrochemical industries
Pyrolysis gasoline available from naphtha cracker.
Pyrolysis gasoline contain 50-70% of aromatics

and

Reaction in catalytic reforming

1) Dehydrogenation
) The conversion of napthenes to aromatics is the
primary napthene reaction
) Rate of dehydrogenation reaction increases with
increase in temperature and decreases with pressure.
) These reaction are highly endothermic

Isomerization
In isomerization two types of reaction are involved.
i) isomerization of normal paraffins to isoparaffins
ii) isomerization of cyclopentanes to cyclohexane plus
subsequent conversion into benzene.
Isomerization reaction are exothermic and reversible.

Dehydrocyclization
It is most critical reaction in reforming are much
slower and are favoured by high temperature and low
pressure.
A minimum six carbon chain is needed to cyclize to
form aromatics.

Process variable in catalytic reforming

1) FeedstockLight fraction have poor napthene and aromatic
content. Hence heavy fraction feedstock are preferred
for reforming.
2) Temperature Reforming reactor temperature is maintained around
470-550oC.
Temperature below 420oC or above 550oC result in
lower performance yield.

3) Space velocity Lowering the space velocity results in increase in octane

number, decreases yield and increase coke deposit.
Highly naphthenic feedstock require high space velocity.
4) Pressure Decreasing pressure increases dehydrogenation of napthene and
dehydrogenation of paraffins which result in higher production
of aromatics and hydrogen.
Higher pressure causes higher rates of hydro cracking but
reducing performance yield.

5) Catalyst poisoning Temporary and permanent poisions are present in the

reformer feed which affect the reformer performance.

Temporary poisons are those which can be removed

from the catalyst without shut down.

Temporary poisons are sulphur, halogens, organic

nitrogen and water.

Permanent poisons are arsenic, lead, copper, iron

mercury, nickel.

Pyrolysis gasoline
Benzene, toluene and xylene are the main component of
pyrolysis gasoline.
Pyrolysis gasoline needs treatment before aromatic
separation as they contain dieneic and sulphur
compounds
It is carried out in two stage hydrogenation column.
In the first stage selective hydrogenation of diolefin take
place in the presence of nickel or palladium catalyst at
temperature 80-160oC and 10-40 atm.
The objective of first stage hydrogenation is
i) to eliminate unsaturated hydrocarbon such as diolefin
and alkenyl aromatics

ii) to provide hydrogenated pyrolysis gasoline with better

stability properties
iii) to avoid gum formation in second stage
Diolefin + H2
Olefin
Alkenyl aromatics + H2

Alkyl aromatics

Second stage is selective hydrogenation of olefin and

hydrodesulphurization of C5-C6 cut carried out at
temperature in the range of 280-350oC and pressure of
15 atm in the presence of composite sulphide of
molybdenum and cobalt on alumina.
Second stage eliminates olefins and sulphur compounds.
olefin + Hydrogen
Paraffin
Cycloolefin + Hydrogen
Naphthene

Sulphur compounds + H2
Paraffin + H2S
Separation of aromatics from aromatic and non
aromatics is done by extraction , extractive distillation,
adsorption and crystallization operation.

P-xylene manufacturing from catalytic reforming