Petrochemical Engineering-I

UNIT-IV
AROMATIC PRODUCTION
 Introduction
Aromatic hydrocarbons especially Benzene (80.10C), 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 Steam cracking of naphtha and light hydrocarbon
hydrocarbons 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 Catalytic reforming is a major conversion
Reforming 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 In this process, BTX is produced by
Process 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
Dearomatisation of Process consists of extraction of aromatics from high
naphtha aromatic naphtha feed without prior reforming.
The process is useful for naphtha having high aromatics.

Hydro Hydrodealkylation: It involves production of benzene

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

Isomerization This process consists of conversion of C8 stream into

process valuable o- and p-xylene having isomerisation and
isomer separation stage.
 Process Description
Mitsubishi's This process uses a metallosilicate zeolite catalyst to promote
Z-forming dehydrogenation of paraffins followed by oligomerisation
Process and dehydrocyclisation of paraffins followed by
oligomerisation.
KTI This process uses a shape selective catalyst to convert C2 and
Pyroforming C3 paraffins to aromatics.

Cheveron's It is similar to conventional catalytic reforming processes and

Aromax L-type zeolite catalyst.
process
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 50-70% of aromatics.
Aromatic content of various crude oil
Crude Paraffins Naphthenes Aromatics
Assam Mix, Vol% 32-40 52-43 16-17
Gujart(North), 52.50 42.00 5.30
Vol%
Gujart (Ankleshwar), 70.80 25.00 4.20
Vol%
Bombay High, Vol% 53.70 25.00 21.30
Iranian, Wt% 57.50 31.20 11.40
 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(1390C) 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 non-aromatics.
Superfractionaction for separation of ethyl benzene from xylene.
Separation of p-xylene from m-xylene using adsorption or crystallization
process.
1. Liquid-liquid extractor 2. Extractive distillation column 3. Solvent recovery column
4. Water wash column 5. Clay treatment 6. Benzene recovery column
7. Toluene recovery column 8. Xylene & Ethyl benzene column
9. Ethyl benzene recovery column
 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)