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AROMATICS

AND

DERIVATIVES

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.

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 CH3 Acid

Ortho-xylene

Meta-xylene

CH3 Para-xylene

EB Dealkylation: C2H5 Acid

+ C2H4

Metal H2

+ C2H6

Typical Parex-Isomar Loop


para-Xylene Toluene Clay Treater
Parex Isomar Light Ends H2

Dehept Column

Mixed Xylenes

Xylene Splitter

Clay Treater

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

A9+

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

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.

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 Reactor

Purge Gas

Separator
To Platformer Debut

Deheptanizer

Steam

Clay Treater

Makeup Hydrogen

To Xylene Splitter

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.

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-

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:

ECONOMICS
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. Estimated ISBL Cost, US$ MM (including initial catalyst inventory) Utility Consumption Electric power, kW High pressure steam, MT/hr Cooling water, m3/h Fuel fired, Gcal/hr 29

Parex-Isomar Yields
Based on Fresh Mixed Xylenes Feed
100
Product Yield, wt% of Feed 91.1

90 80 70 60 50

84.5 84.0

87.3

91.0

76.5

I-9 Catalyst

I-100/I-300 Catalyst

I-210 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

Para-xylene
Benzene

743 15 824 22

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.

COMMERCIAL EXPERIENCE
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

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

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