AROMATICS

DERIVATIVES

AND

ISOMAR PROCESS
TM

APPLICATION
UOPs Isomar process is used to maximize the recovery
of a particular xylene isomer from a mixture of C8 aromatic isomers.The Isomar process is most often applied
to para-xylene recovery, but it can also be used to maximize the recovery of ortho-xylene or meta-xylene. The
term mixed xylenes is used to describe a mixture of
C8 aromatic isomers containing an equilibrium distribution of para-xylene, ortho-xylene, meta-xylene, and
ethyl benzene (EB). In the case of para-xylene recovery, a mixed xylenes feed is charged to a ParexTM
process unit where the para-xylene isomer is preferentially extracted at 99.9 wt-% purity and 97 wt-% recovery per pass. The raffinate from the Parex unit, almost
entirely depleted of para-xylene, is then sent to the
Isomar unit. The Isomar unit re-establishes an equilibrium distribution of xylene isomers, essentially creating
additional para-xylene from the remaining ortho- and
meta isomers. Effluent from the Isomar unit is then
recycled back to the Parex unit for recovery of additional para-xylene. In this way, the ortho-and
meta- isomers and EB are recycled to extinction.

Typical Parex-Isomar Loop

Light Ends

para-Xylene
Toluene
Clay
Treater

Mixed
Xylenes

Parex

Xylene
Splitter

H2

Isomar

Dehept
Column

Clay
Treater

A9+

PROCESS CHEMISTRY
There are two broad categories of xylene isomerization
catalysts: EB isomerization catalysts, which convert

ethyl benzene into additional mixed xylenes and EB

dealkylation catalysts, which convert ethyl benzene to a
valuable benzene co-product.
UOP offers I-9TM and I-210TM EB isomerization catalysts
and I-100TM and I-300TM EB dealkylation catalysts. The
selection of the isomerization catalyst depends on the

Process Chemistry
Xylene Isomerization:
CH3
CH3 Acid

CH3

CH3

Acid

CH3

Ortho-xylene

EB Dealkylation:
C2H5
Acid

CH3
Para-xylene

Meta-xylene

+ C2H4

Metal
H2

+ C2H6

configuration of the aromatics complex, the composition

of the feedstocks, and the desired product slate. I-9 or
I-210 catalysts are typically chosen when the primary
goal of the complex is to maximize production of paraxylene. Alternatively, I-100 and I-300 catalysts can be
used to debottleneck an existing Parex unit or crystallizer
by converting more EB per pass through the isomerization unit and eliminating the requirement for naphthene
intermediate circulation around the Parex-Isomar recycle loop.
EB isomerization is an equilibrium-limited reaction
usually limited to approximately 30 wt-% EB conversion per pass. EB dealkylation reaction is not equilibrium limited, allowing for up to 70 wt-% or greater EB
conversion per pass. The reduction in the size of the
Parex-Isomar loop with an I-100 or I-300 reload comes
at the expense of lower para-xylene yields, since all the

EB in the feed is being converted to benzene rather than

additional para-xylene.
All xylene isomerization catalysts exhibit some loss of
aromatic rings across the reactor. A large portion of the
total feed to the xylene column is from the Isomar unit. A
typical Parex-Isomar loop exhibits a combined feed ratio
of about 3.5. Therefore, a small reduction in the per-pass
ring loss across the Isomar unit translates to a large yield
advantage. The Isomar process exhibits minimal loss of
valuable aromatics rings. The precise level of expected C8
ring loss varies with catalyst type and operating severity,
but it is normally in the range of 1.5-4.0 wt-% per pass.
The lower end of the range is representative of operation
with I-100, I-300 and I-210 catalysts. The upper end of the
range is representative of operation with I-9 catalyst. The
low ring loss characteristics of the I-210 catalyst, which
was commercialized in early 1998, further improves the
amount of para-xylene yield from a given quantity of
xylene feedstock.
The new I-300 high activity catalyst offers the simplicity
of a single catalyst system. The Isomar process requires
about half as much I-300 catalyst as I-100 catalyst, and
the use of I-300 catalyst eliminates multiple beds of different catalysts with complicated loadings and distributors.
Unlike some EB dealkylation catalysts, it does not require
continuous addition of ammonia to achieve desired activity
and selectivity. As of mid-1999 there are two units in
operation.

PROCESS DESCRIPTION
An Isomar unit is always combined with a recovery unit
for one or more xylene isomers. Usually it is combined
with the Parex process for recovery of para-xylene, as
shown in the Parex-Isomar flow scheme. In the ParexIsomar flow scheme, fresh mixed xylenes are fed to the
xylene column, which can be designed either to recover
ortho-xylene in the bottoms or simply reject C9+ aromatic
components in order to meet feed specifications to the
Parex unit. The xylene column overhead is then directed
to the Parex unit, where 99.9 wt-% para-xylene is produced at 97 wt-% recovery per pass. The raffinate form
the Parex unit, containing less than 1 wt-% para-xylene, is
sent to the Isomar unit.

The general flow scheme of the Isomar unit is shown in the

flow diagram. The feed to the Isomar unit is first combined
with hydrogen-rich recycle gas and makeup gas to replace
the small amount of hydrogen consumed in the Isomar
reactor. The combined feed is then preheated by exchange
with reactor effluent, vaporized in a fired heater and raised
to reactor operating temperature. The hot feed vapor is then
sent to the reactor, where it is passed radially through a
fixed bed of catalyst. The reactor effluent is cooled by
exchange with the combined feed, then sent to the product
separator. Hydrogen-rich gas is taken off the top of the
product separator and recycled back to the reactor. A small

Isomar Process
Parex
Raffinate

Fuel Gas

Charge
Heater

Purge
Gas

Reactor

Separator
To Platformer
Debut

Deheptanizer

Steam

Clay
Treater

Makeup
Hydrogen

To
Xylene
Splitter

portion of the recycle gas is purged to remove accumulated

light ends from the recycle gas loop. Liquid from the bottom of the product separator is charged to the deheptanizer
column. The C7- overhead from the deheptanizer is cooled
and separated into gas and liquid products. The deheptanzier overhead gas is exported to the fuel gas system. The
overhead liquid is recycled back to the Platforming unit
debutanizer column so that any benzene in this stream may
be recovered in the Sulfolane or BT extraction unit. The
C8+ fraction from the bottom of the deheptanizer is clay
treated, combined with fresh mixed xylenes feed and recycled back to the xylene column.

PROCESS PERFORMANCE
The best way to compare xylene isomerization catalyst is to
measure the overall para-xylene yield from the Parex-

ECONOMICS

Isomar loop. The para-xylene yield, based on fresh mixed

xylenes feed to the Parex-Isomar loop, for the I-9, I-100 /
I-300, and I-210 catalyst systems are presented in the following chart:

A summary of the investment cost and the utility consumption for a typical I-210 Isomar unit is shown in the
table below. The basis for this case is an Isomar unit processing 1,840 KMTA (40,000 BPSD) of a raffinate from a
Parex unit. The investment cost is limited to the Isomar
unit, deheptanizer column, and downstream clay treater.
The estimated inside battery limits erected cost for the
unit assumes construction on a U.S. Gulf Coast site in
1999. The scope of the estimate includes engineering,
procurement, erection of equipment on site, and the initial
load of I-9 catalyst.

Parex-Isomar Yields
Based on Fresh Mixed Xylenes Feed
Product Yield, wt% of Feed

100
91.1

90

84.5

87.3

91.0

84.0

80

76.5

70

Estimated ISBL Cost, US$ MM

(including initial catalyst inventory)

60
50

I-9 Catalyst

I-100/I-300
Catalyst

Mixed Xylene Feed: 17% EB, 18% PX

97% PX Recovery in Parex Unit
I-100 Severity: 65% EB Conversion
I-8, I-210 Severity: 22.1% PX/X

Utility Consumption
Electric power, kW
High pressure steam, MT/hr
Cooling water, m3/h
Fuel fired, Gcal/hr

I-210 Catalyst

Para-xylene
Benzene

743
15
824
22

COMMERCIAL EXPERIENCE

The basis for the comparison is the above Parex-Isomar

flow scheme, processing a mixed fresh xylenes feed consisting of 17 wt-% EB, 18 wt-% para-xylene, 40 wt-%
meta-xylene, and 25 wt-% ortho-xylene. The operating
severity for the I-9 and I-210 catalysts is 22.1 wt-% paraxylene of the total xylenes from the Isomar unit. The
operating severity for the I-100 and I-300 catalysts are 65
wt-% conversion of EB per pass. With the I-9 catalyst, the
overall yield of para-xylene is 84 wt-% of the fresh
mixed xylenes feed. Since it has lower ring loss per pass,
the I-100 catalyst exhibits a higher overall yield of benzene + para-xylene, but the yield of para-xylene is only
76.5 wt-%. This means that more mixed xylenes are
required to produce a target amount of para-xylene with
I-100 catalyst. The I-210 catalyst relies on the same reaction chemistry as I-9 catalyst, but is more selective and
exhibits lower ring loss: about 1.5 wt-% compared to 4
wt-% for I-9 catalyst. With I-210 catalyst, the overall
yield of para-xylene is 7 wt-% higher than with I-9 catalyst, at 91 wt-% of fresh mixed xylenes feed.

UOP has licensed more isomerization units than any other

licensor in the world. The first Isomar unit went on stream
in 1967. Since that time, UOP has licensed a total of 54
Isomar units throughout the world. Forty-four Isomar
units have been commissioned, and the remaining 10 are
in various stages of design and construction. UOP is the
only licensor of xylene isomerization technology to offer
both EB isomerization and EB deakylation catalysts. This
choice of catalyst gives UOP increased flexibility to
design an aromatics complex to meet any customers
desired product distribution.

FOR MORE INFORMATION

For more information, contact your UOP representative or
UOP at:
Phone: 1-847-391-2000
Fax:
1-847-391-2253

uop

1999 UOP LLC. All rights reserved.

This information is not to be taken as a warranty or representation for which UOP
assumes legal responsibility nor as permission or recommendation to practice any
patented invention without a license. It is offered solely for your consideration.
UOP 2699C-15 899AD1P

29

TM

UOP L L C
25 East Algonquin Road
Des Plaines, Il 60017-5017
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