AROMATICS

Dr I.D.Mall
Department of Chemical Engineering
Indian Institute of Technology Roorkee

AROMATICS
Aromatic hydrocarbons especially benzene, toluene,
xylene, ethyl benzene are major feedstock for 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
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.
Originally, the aromatics were produced from coal tar
distillation, which is byproduct of destructive distillation
(carbonisation).

AROMATICS
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.
m-xylene Isohthalic acid
Xylenes
Toluene
Gasoline
Nitrotoluene
Trinitrotoluene
Benzoic acid
Solvents
p-cresol
m-xylene
o-xylene
p-xylene
Toluene
diisocyanate
Isophthalic
acid
Phthalic
anhydride
TPA,
DMT
Motor gasoline
Polyurethane (Rigid foam,
flexible foam, surface coatings)
Explosives
Caprolactam, pharmaceuticals
and flavors, phthalates,
terephthalic acid.
Phenol, sodium benzoate - food
preservatives.
Resins, unsaturated
polyesters, plasticizers,
other esters.
Plasticizers, polyester resins,
alkyl resins, dyes and pigments,
herbicides, isatoic anhydride,
polyester polyols,
phthalimide-fungicides.
Polyester fibers, films,
polyethylene, terephthalate.
Di-tert-butyl-p-cresol (antioxidants)
To
Benzene
Product Profile
of Aromatics
Catalyst
Reforming
Extractor
Raffinate
wash
column
Water
Non Aromatics
Raffinate Wash
Column
Naphtha
Extractive
Stripper
Extract Reflux
Olefin
Hydro
Desulphurisation
Diene
Hydrogenetics
Pyrolysis
Gasoline
Solvent
Recovery
Steam
Clay
Treater
B
e
n
z
e
n
e

C
o
l
u
m
n
T
o
l
u
e
n
e

C
o
l
u
m
n
C
8

C
o
l
u
m
n
Heavy
End
Benzene
Toluene
Xylenes,
Ethyl
Benzene
Waste
Naphtha
Pyrolysis Gasoline
Solvent
Non-Aromatics
T
o
l
u
e
n
e

Benzene
Heavy
End Product
Ethyl
Benzene
Column
m-xylene
column
o-xylene
column
Crystallisation p-xylene
Adsorption
Parex
Mixed Xylene
Isomerisation
L
i
g
h
t

e
n
d

c
o
l
u
m
n
Recycle for
p-xylene
recovery
To flare
p-xylene
Isomerisation
Section
Heavy end
Xylene
separation
Toluene
disprop
ortionati
on
reactor
Xylene
Column
C
9
+
Aromatics
p-xylene
rich
stream
Hydrogen
m- and p- xylene
Ethyl
Benzene
Toluene Disproportionation Section
Xylenes,Ethyle
Benzene
Toluene
Processes Description
Coal Carbonis-
ation
(Coke oven plant)
From coke oven plant during carbonisation, 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 tonne of coal.
Steam cracking of
hydrocar-bons
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.
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,
isomerisation of paraffins and naphthenes,
dehydrocyclisation of paraffins to aromatics, and
hydrocracking of paraffins.
BTX PRODUCTION TECHNOLOGY
Processes Description
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.
Dearomatisation
of naphtha
Process consists of extraction of aromatics from
high aromatic naphtha feed without prior
reforming. The process is useful for naphtha
having high aromatics.
Hydro
dealkylation and
disproportionati
on
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.
BTX PRODUCTION TECHNOLOGY

Processes Description
Isomerisation
and Isomer
process
This process consists of conversion of C
8
stream
into valuable o- and p- xylene having isomerisation
and isomer separation stage.
Mitsubishi's
Zforming
Process
This process uses metallosilicate zeolite catalyst to
promote dehydrogenation of paraffins followed by
oligomerisation and dehydrocyclisation of paraffins
followed by oligomerisation.
KTI
Pyroforming
This process uses a shape selective catalyst to
convert C
2
and C
3
paraffins to aromatics.
Cheveron's
Aromax
process
It is similar to conventional catalytic reforming
processes and L-type zeolite catalyst.
BTX PRODUCTION TECHNOLOGY
BTX FROM PETROLEUM
First step in making BTX is to distill off a suitable
fraction rich in naphthenes which serves as precursors
for aromatics
Catalytic reforming or steam cracking to produce an
aromatic and pyrolysis gasoline.
Preliminary treatment of this cut : fractionation and/or
selective hydrogenations (essentially pyrolysis gasoline)
Solvent extraction to eliminate non-aromatics
Distillation to produce pure benzene and toluene, and in
case of reformates used alone or blended with a pyrolysis
gasoline
Distillation aromatic C8 to yield by superfractionation
ethyl benzene and o-xylene, after passage through a
separation column in a light cut and a heavy cut (splitter)
Production of p-xylene at low temperature, with a mother
liquor by product rich in m-xylene.




Typical yield of benzene, toluene, xylene in kg per tonne of coal
carbonised is about 2.8, 0.5-2, and 0.1-0.5 kg
Potential Availability of Selected Chemicals
Chemicals Per cent availability
Benzene
Toluene
Xylenes
Naphthalenes
Methyl naphthalene
Phenol
Cresols & Xylenes
Diphenyl oxide
0.70
0.20
0.05
0.30
0.06
0.02
0.04
0.04
Aromatic Content of Various Crude Oil
Crude Paraffins Naphthenes Aromatics
Assam Mix, vol.% 32-40 43-52 16-17
Gujarat (North), vol.% 52.50 42.00 5.3
Gujarat (Ankleshwar),
vol.%
70.80 25.00 4.2
Bombay High, vol.% 53.70 25.00 21.3
Iranian, wt.% 57.50 31.20 11.4
Typical Composition of Hydrotreated Pyrolysis Gasoline Feed
Characteristics Hydrotreated C6-C8 Heart cut to Benzene Extraction Unit
Component Wt.%
C
5
s 1.0 wt.% max.
C
9
-204
o
C 1.0 wt.% max.
Cyclopentane 1.00
C
6
Paraffins 10.63
Methyl cyclopentane 10.15
Cyclohexane 2.85
Benzene 24.16
C
7
Paraffins 4.90
1,1-dimethyl cyclo, C
5
0.17
Cis-1,3-dimethyl cyclo, C
5
0.37
Trans-1,3-dimethyl cyclo, C
5
0.30
Cis-1,2- dimethyl cyclo, C
5
0.13
Continue
Continue
Trans-1,2- dimethyl cyclo, C
5
0.54
Methyl cyclohexane 1.12
Ethyl cyclopentane 0.64
Toluene 23.02
C
8
Paraffins 1.64
Total dimethyl cyclohexane 0.33
Ethyl cyclohexane 0.03
n-propyl cyclopentane 0.10
Isopropyl cyclopentane 0.07
Total trimethyl cyclopentane 0.57
Ethyl benzene 6.55
Xylenes 9.73
C
9
plus 1.00
TOTAL 100.00
Major Units of Aromatic Complex

Heavy Naphtha Pre-treatment Unit
Platformer Unit
CCR Unit (Continuous Catalyst
Regenerator)
Recovery Plus.
PSA (Pressure Swing Adsorption)
BTX separation
Xylene Fractionation Unit
p-xylene and m-xylene separation
Crystalisation, Adsorption

Separation of Aromatics

Liquid-liquid extraction (DEG, TEG,
Tetramethylene sulfono NMP-EG,
Monomethyl formamide, Morpholine,
DMF, n-methyl pyrolidone NMP
Extractive or azeotropic distillation
Adsorption
Crystallization
PROCESS FLOW

Feed Preparation (Removal of
contaminants S, N, As, Pb)
Temp. control 550
0
C
Reactors
Product recovery
Aromatic production

Reactions Involved

Dehydrogenation
Methyl cyclohexane Toluene + H
2
MCP Benzene + H
2
Isomerisation
n-Hexane Neohexane
Dehydrocyclisation of paraffins, i-paraffins to
aromatics
n-heptane toluene + H
2
Hydrocracking
Process Variables

Temperatures
Space velocity
Pressure,
Hydrogen-hydrocarbon ratio,
Catalyst type,
Water/chloride content.
N + 2A
Catalyst
Monometallic(Pt),
Bimetallic (Pt, Rhenium)
Multimetallic
Acid Activity : Halogens/silica incorporated in
alumina base.
Metallic Function: To promote dehydrogenation and
hydrogenation. Also contribute to
dehydrocyclisation and isomerisation.
Acid Function : Promotes isomerisation, the initial
step in hydrocracking, participate in paraffin
dehydrocyclisation.
p-Xylene plant
Pretreatment Unit
Reformer Unit
Fractionation Units
Parex Unit
Isomerisation

p-Xylene plant
Pretreatment Unit: This unit is used for
reducing sulphur content to 5 ppm (max.) by
dehydro - desulphurisation which takes
place at 330370
o
C and 24 kg/cm
2
pressure
in presence of cobalt molybdenum catalyst.
Reformer Unit: To get maximum amount of
C
8
aromatics by reforming process (Process
similar to described earlier).
Fractionation Units: For separation of o-, m-,
and p-xylenes from combined C
8
reformate
and isomerisate from isomerisation unit
(after clay treatment).
p-Xylene plant
Parex Unit: This unit is for the separation of
p-xylene by selective adsorption using
molecular sieve followed by desorption.
Other method for separation of p-xylene is by
crystallisation process.
Isomerisation: Isomerisation of C
8
stream
from Parex unit rich in m- and o-xylene and
ethyl benzene to p-xylene, which is sent to
fractionation unit for separation of high
component. The bottom of the column is
recycled for further recovery of xylenes.

p-Xylene from Catalytic Reforming
Preheating
3 Stage Reactor
with interheater
400-450
o
C
Stabilisation
Section
Deheptaniser
Clay
Treatment
o-xylene
column
Adsorber
Crystallisation
Preheating Isomerisation
p-xylene
Naphtha
110-145
o
C
Cut
Reforming of
Naphtha
Fuel gas
Light
reformate
o-xylene
p- and m-xylenes
m-xylene
p-Xylene Separation Processes
Processes Description
Chevron process Uses crystallisation process for separation. It
is characterised by the use of direct
contact cooling. This is accomplished by
injecting liquid CO
2
with feed to
crystallise.
Krupp Process Crystallisation process is used to crystalliser-
scrapped chiller.
Amco Process p-xylene is incorporated using two-stage
crystallisation process with its direct
cooling.
Arco process It uses either two stage or single stage
crystallisation process for separation of p-
xylene followed by toluene distillation
column.
Marazen Process Two stage crystallization process using
ethylene gas as a direct refrigerant.
Continue.
Parex Process
(UOP)
p-xylene is separated by selective adsorption
using zeolite base adsorbent. It uses
simulated moving bed, countercurrent and
liquid phase adsorption. Desorbent is toluene
or p-diethyl benzene.
Aromax Process
(Toray
Industries)
This process also uses selective liquid phase
adsorption using a series of horizontally
situated chambers that are isolated from one
another.
IFPs Eluxyl
Process
Adsorption process is used for separation.
Hybrid Process
(IFP & Chevron)
This process combines the best feature of
adsorption and crystallisation.
The parex process has four major streams that are
distributed to the adsorbent chamber by rotary
valve.
These streams include:
Feed in: Mixed xylene.
Dilute extract out: p-xylene product diluted with
desorbent.
Dilute raffinate out: ethyl benzene, m-xylene, and o-
xylene diluted with desorbent.
Desorbent in: recycle desorbent from the
fractionation column.
At any time, only four of the bed lines are active, carrying the net
streams into and out of the adsorbent chamber. The rotary valve
periodically switches the position of the liquid feed and
withdrawals points as the composition profile moves down the
chamber
1
2
3
4
5
6
7
8
9
10
11
12
R
a
f
f
in
a
t
e
Extract
D
e
s
o
r
b
e
n
t
F
e
e
d
I
IV
II
III
Rotary
Valve
Extract
Column
Raffinat
e
column
Desorbent
Feed from
xylene unit
Light
End
Column
Light ends
p-xylene
Raffinate
D
e
s
o
r
b
e
n
t

P
u
r
i
f
i
c
a
t
i
o
n
Heavy ends
Desorbent
recycle
Pump

Aromatic Conversion Processes
Hydrodealkylation
Isomerisation
Dismutation and Trans alkylation
Disproportionation (Vapor or liquid
phase)
Disproportionation
Transfer of the alkyl group between two
similar molecule producing a lower and
a higher homologue is
disproportionation.
Trimethyl benzene to toluene
Xylene
Propylene Ethylene + Butene
CH
3
CH
3
CH
3
+
2
Dealkylation

C H
3
CH
3
O
2
+
CO
2

+
H
2
+
CO
2

+
H
2
Steam
+
H
2
+ CH
4
Detachment of alkyl group
Toluene Benzene + Xylene
Methyl
Cyclar Process
Cyclar process selectively converts liquefied petroleum
gas to high value benzene, toluene and xylene.

First commercial scale plant has been in case of the
refineries of British Petroleum located at Gragemouth,
Scotland

Special features of Cyclar process are:
Inexpensive and plentiful LPG.
Requires minimal feed pretreatment and product
purification equipments.
Simplicity in process.
BPs Cyclar process is a real break through to
aromatics and dependence on naphtha for
reforming or cracking is reduced.
The selectivity of aromatics is said to be high at
65% with hydrogen as a valuable co-product
which are around 6%.
In the process for conversion of LPG to
petroleum grade aromatics, LPG is continuously
converted to aromatics in four radial flow
reactors arranged in vertical stack using zeolite
catalyst with a non-metal.
The BP-UOP Cyclar Process
In the aromatization reaction, bifunctional
catalyst mainly ZSM-5 type catalyst is used
with non noble metal promoter like Zn, Ga,
etc.
Acidic nature of the catalyst is produced by
zeolite.
Aromatization is a complex reaction, which
involves
Dehydrogenation,
Oligomerisation,
Cyclisation,
Dealkylation
Alkylation
The BP-UOP Cyclar Process
Reactions in Cyclar Process
UOP-BP Cyclar Process for LPG aromatization
Stripper
Stripper
off gas
C
6
+
Aromatic
product
Gas
recovery
station
Booster
compressor
Hydrogen
Net fuel
gas
Charge and Interheaters
Fresh Feed
Recycle to Reactor
From
Reactor
LP
Separator
Catalyst
Regeneration
Stacked reactors
Cyclar Aromatic Product Distribution
Toluene
43%
C9+ Aromat ics
9%
Xylenes
21%
Benzene
27%
Benzene
22%
Xylenes
25%
C9+ Aromat ics
9%
Toluene
44%
Dearomatising of Naphtha
Dearomatising of naphtha is another option for
production of aromatics from naphtha rich in
aromatics.
The process step involves includes
Feed preparation,
Extraction of aromatics
Extractive stripping
Raffinate washing
Solvent recovery
Clay treatment,
Fractionation to produce pure benzene and
toluene
Feed preparation involves separation of 65-110
o
C
cut from C5 -140
o
C naphtha in a series of two
fractionators.
Extraction of aromatics is done by using sulpholane.