Unit Iv

Petrochemical Engineering-I
UNIT-IV
AROMATIC PRODUCTION
Introduction
Aromatic
hydrocarbons especially Benzene (80.1 0C),

Toluene (110.60C), Xylene [m-xylene (139.10C), p- Xylene
(138.40C), o-Xylene (144.40C)], Ethyl benzene (136.20C)
are major feedstock for a large number of intermediates
which are used in the production of synthetic fibers,
resins,
synthetic
rubber,
explosives,
pesticides,
detergent, dyes, intermediates, etc.
Styrene, linear alkyl benzene and cumene are the major
consumer of benzene.
Benzene also finds application in the manufacture of a
large number of aromatic intermediates and pesticides.
As per CMAI, demand for benzene is forecast to grow at
an average annual rate of 2.8% per year through 2020
resulting in nearly 57 million tonnes of demand by 2020.
Major application of toluene is as solvent.
Other uses are in the manufacture of benzoic

acid, chloro derivatives, nitro toluenes,
toluene sulphonic acid, toluene
sulphonamide, benzaldehyde, etc.
Xylenes are another important aromatics.
Amongst the xylenes, about 80% of the
production is of p-xylene. Finds application in
the manufacture of Terephthalic acid/DMT.
o-Xylene used in the manufacture of phthalic
anhydride and m-xylene Isophthalic acid.
Various Sources of
Aromatics
Process
Description
Coal
Carbonization
From coke oven plant during carbonization,

light oil is obtained as by product which
contains about 2-8 kg, 0.5-2 kg, 0.1-0.5 kg
of benzene, toluene and xylene
respectively per ton of coal.
Steam cracking
of
hydrocarbons
Steam cracking of naphtha and light

hydrocarbon like ethane and propane
produce liquid product (pyrolysis gasoline)
rich in aromatics containing about 65%
aromatics about 50% of which is benzene.
About 30-35% of benzene produced
worldwide is from pyrolysis gasoline.
Process
Description
Catalytic
Reforming
Catalytic reforming is a major conversion

process, which converts low octane
naphtha to high-octane gasoline and
produce aromatics rich in BTX.
Major reactions involved are
dehydrogenation of naphthalenes to
aromatics,
dehydrocyclisation of paraffins to
aromatics,
isomerisation of paraffins and naphthenes,
and hydrocracking of paraffins.
BP-UOP Cyclar
Process
In this process, BTX is produced by

dearomatisation of propane and butane.
The process consists of reaction system,
continuous regeneration of catalyst, and
product recovery.
Catalyst is a proprietary zeolite
incorporated with a non noble metal
promoter.
Process
Description
Dearomatisatio Process consists of extraction of aromatics from

n of
high aromatic naphtha feed without prior
naphtha
reforming.
The process is useful for naphtha having high
aromatics.
Hydro
dealkylation
and
disproportionat
ion
Hydrodealkylation: It involves production of

benzene by dealkylation of toluene either by
catalytic or thermal process.
Catalytic process: Hydeal, Deltol
Thermal process: HAD (ARCO), THDC Gulf Oil
Disproportionation: It involves conversion of
toluene into benzene and xylenes.
Isomerization
process
This process consists of conversion of C8 stream

into valuable o- and p-xylene having
isomerisation and isomer separation stage.
Process
Description
Mitsubishi's This process uses a metallosilicate zeolite catalyst to

Z-forming
promote
Process
dehydrogenation of paraffins followed by
oligomerisation and dehydrocyclisation of paraffins
followed by oligomerisation.
KTI
Pyroformin
g
This process uses a shape selective catalyst to

convert C2 and C3 paraffins to aromatics.
Cheveron's
Aromax
process
It is similar to conventional catalytic reforming

processes and L-type zeolite catalyst.
Petroleum feedstock for aromatic hydrocarbons

Catalytic reforming and pyrolysis of gasoline
are the two major sources of aromatics.

aromatic content of the crude oils varies
from source to source of the crude.
Pyrolysis gasoline may contain around 5070% of aromatics.
Aromatic
Crude
content
various crude
oil
ParaffinsofNaphthenes
Aromatics
Assam Mix, Vol%
32-40
52-43
16-17
Gujart(North),
Vol%
52.50
42.00
5.30
Gujart
(Ankleshwar),
Vol%
70.80
25.00
4.20
Bombay High, Vol

%
53.70
25.00
21.30
Aromatic hydrocarbon production

Catalytic reforming and pyrolysis gasoline are the major
sources for aromatics.

Some of the other aromatic conversion processes commonly
used include toluene disproportionation to produce
benzene and xylene, hydrodealkyaltion of toluene to
produce benzene.
The main processing scheme in catalytic reforming involves:
Catalytic reforming of naphtha or steam reforming of naphtha
for production of pyrolysis gasoline.

Solvent extraction for separation of non-aromatics from
aromatics.
Pre-treatment of pyrolysis gasoline, which includes two-stage
selective hydrogenation.
Separation of benzene, toluene and C8 fractions.
Further separation of C8 hydrocarbons Xylene and ethyl
benzene which includes separation of ethyl benzene by
superfractionaction and separation of p-xylene by either
crystallization or by selective adsorption.
Pyrolysis Gasoline as aromatic feedstock

During Naphtha, pyrolysis gasoline having
boiling point range 20-2000C is obtained as

byproduct which contains a high proportion of
aromatic hydrocarbon.
Typical aromatic product distribution from
pyrolysis gasoline may be about 5-7% aromatics
of which roughly 50% is benzene, 30% toluene
and 20% m-xylene, including ethyl benzene.
Before aromatic separation pyrolysis gasoline
need two-stage hydrogenation treatment
process because they contain dienic and sulphur
compounds
In the first stage selective hydrogenation of
di-olefins takes place under mild conditions in

the presence of nickel or palladium catalyst
at temperature and pressure of 80-1600C and
10 atm and here the aromatic hydrocarbons are
not affected.
Second step is the selective hydrogenation
of olefins and hydrodesulphurization of C5-C6
cut carried out at temperature and pressure of
280-3500C and 15 atm in the presence of
composite sulphide of molybdenum and
cobalt on alumina.
After hydrogenation process, the pyrolysis
gasoline is distilled to give fractions containing
benzene, toluene, and xylene.
The objective of first stage hydrogenation is:

To eliminate unsaturated hydrocarbons such as diolefins and
alkenyl aromatics.
To provide hydrogenated pyrolysis gasoline with better stability
properties.
To avoid gum formation in the second stage.
Diolefin + H2 Olefins
Alkenyl aromatic + H2 Alkyl aromatic
Catalyst is palladium which is sensitive to a number of impurities
The second stage hydrogenation aims to eliminating the
olefins and sulphur compounds.
Olefin + Hydrogen Paraffins
Cycloolefin + Hydrogen Naphthene
Sulphur compounds + Hydrogen Paraffins + H2S
Here some of the contaminants which acts as poisons are organic
chlorides, existing gases, inorganic chlorides and other miner
salts, As, Sb, Pb, Si etc.,
Aromatic Separation from reformate and

pyrolysis gasoline
Catalytically reformed Naphtha is a mixture of benzene, toluene,
xylene and close boiling non-atomic components especially alkanes

and cycloalkanes.
Separation of aromatics from non-aromatics presents difficulties in
product isolation because of their close boiling points.
Here also the separation of xylene(139 0C) and ethyl benzene
(1360C) difficult due to their close boiling point.
The main processing steps involved are:
Separation of aromatics from non-aromatics using solvent
extraction.
Separation of the aromatics from each other.
The following options are available for the separation of aromatics
Solvent extraction for separation of aromatics form nonaromatics.
Superfractionaction for separation of ethyl benzene from xylene.
Separation of p-xylene from m-xylene using adsorption or
crystallization process.
1. Liquid-liquid extractor
column
4. Water wash column
column
2. Extractive distillation column

5. Clay treatment
3. Solvent recovery
6. Benzene recovery
Selection of the solvent

Solvent selectivity
Recoverability of solvent
Density difference between dispersed and
continuous phase
Viscosity
Melting point
Interfacial tension
Corrosion
Toxicity
Thermal and chemical stability
Low miscibility with feed solution
These are some of the solvents are used for

separation of aromatics from non-aromatics:
N-Methyl Pyrollidene (2040C)
N-Fromylmoropholine (2440C)
Dimethylformamide (1530C)
Sulpholane (2880C)
Tetraethylene Glycol (2870C)
Triethylene Glycol (3280C)

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Petrochemical Engineering-I

hydrocarbons especially Benzene (80.1 0C),

Major application of toluene is as solvent.

Other uses are in the manufacture of benzoic

From coke oven plant during carbonization,

Steam cracking of naphtha and light

Catalytic reforming is a major conversion

In this process, BTX is produced by

Dearomatisatio Process consists of extraction of aromatics from

Hydrodealkylation: It involves production of

This process consists of conversion of C8 stream

Mitsubishi's This process uses a metallosilicate zeolite catalyst to

This process uses a shape selective catalyst to

It is similar to conventional catalytic reforming

Petroleum feedstock for aromatic hydrocarbons

are the two major sources of aromatics.

Assam Mix, Vol%

Bombay High, Vol

Aromatic hydrocarbon production

sources for aromatics.

for production of pyrolysis gasoline.

Pyrolysis Gasoline as aromatic feedstock

boiling point range 20-2000C is obtained as

In the first stage selective hydrogenation of

di-olefins takes place under mild conditions in

The objective of first stage hydrogenation is:

Aromatic Separation from reformate and

xylene and close boiling non-atomic components especially alkanes

2. Extractive distillation column

Selection of the solvent

These are some of the solvents are used for

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