Catalyst – solid sorbent – or support therefor: product or process – Zeolite or clay – including gallium analogs – And additional al or si containing component
Reexamination Certificate
2000-12-21
2003-06-10
Dunn, Tom (Department: 1725)
Catalyst, solid sorbent, or support therefor: product or process
Zeolite or clay, including gallium analogs
And additional al or si containing component
C502S064000, C502S067000, C502S071000, C502S074000, C502S077000, C502S213000, C502S214000
Reexamination Certificate
active
06576581
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to catalytic hydrocarbon conversion, and more specifically to the use of an improved molecular-sieve catalyst system in aromatics isomerization.
GENERAL BACKGROUND AND RELATED ART
The xylenes, para-xylene, meta-xylene and ortho-xylene, are important intermediates which find wide and varied application in chemical syntheses. Para-xylene upon oxidation yields terephthalic acid which is used in the manufacture of synthetic textile fibers and resins. Meta-xylene is used in the manufacture of plasticizers, azo dyes, wood preservers, etc. Ortho-xylene is feedstock for phthalic anhydride production.
Xylene isomers from catalytic reforming or other sources generally do not match demand proportions as chemical intermediates, and further comprise ethylbenzene which is difficult to separate or to convert. Paraxylene in particular is a major chemical intermediate with rapidly growing demand, but amounts to only 20-25% of a typical C
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aromatics stream. Adjustment of isomer ratio to demand can be effected by combining xylene-isomer recovery, such as adsorption for para-xylene recovery, with isomerization to yield an additional quantity of the desired isomer. Isomerization converts a non-equilibrium mixture of the xylene isomers which is lean in the desired xylene isomer to a mixture approaching equilibrium concentrations.
Various catalysts and processes have been developed to effect xylene isomerization. In selecting appropriate technology, it is desirable to run the isomerization process as close to equilibrium as practical in order to maximize the para-xylene yield; however, associated with this is a greater cyclic C
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loss due to side reactions. The approach to equilibrium that is used is an optimized compromise between high C
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cyclic loss at high conversion (i.e. very close approach to equilibrium) and high utility costs due to the large recycle rate of unconverted C
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aromatics. Catalysts thus are evaluated on the basis of a favorable balance of activity, selectivity and stability
Catalysts containing molecular sieves have become prominent for xylene isomerization in the past quarter-century or so. U.S. Pat. No. 3,856,872 (Morrison), for example, teaches xylene isomerization and ethylbenzene conversion with a catalyst containing ZSM-5, -12, or -21 zeolite U.S. Pat. No. 4,740,650 (Pellet et al.) teaches xylene isomerization using a catalyst containing at least one non-zeolitic molecular sieve which preferably is a silicoaluminophosphate. U.S. Pat. No. 4,899,011 teaches isomerization of C
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aromatics using two zeolites, each of which is associated with a strong hydrogenation metal. U.S. Pat. No. 5,240,891 (Patton et al.) discloses a MgAPSO molecular sieve having a narrow ratio of framework magnesium and its use in xylene isomerization. U.S. Pat. No. 5,898,090 (Hammerman et al.) teaches isomerization of a mixture of xylenes and ethylbenzene using an SM-3 silicoaluminophosphate molecular sieve. Although these references teach individual elements of the present invention, none of the art suggests combination of the elements to obtain the critical features of the catalyst system and its use of the present invention.
Catalysts for isomerization of C
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aromatics ordinarily are classified by the manner of processing ethylbenzene associated with the xylene isomers. Ethylbenzene is not easily isomerized to xylenes, but it normally is converted in the isomerization unit because separation from the xylenes by superfractionation or adsorption is very expensive. A widely used approach is to dealkylate ethylbenzene to form principally benzene while isomerizing xylenes to a near-equilibrium mixture. An alternative approach is to react the ethylbenzene to form a xylene mixture via conversion to and reconversion from naphthenes in the presence of a solid acid catalyst with a hydrogenation-dehydrogenation function. The former approach commonly results in higher ethylbenzene conversion and more effective xylene isomerization, thus lowering the quantity of recycle in a loop of isomerization/para-xylene recovery and reducing concomitant processing costs, but the latter approach enhances xylene yield by forming xylenes from ethylbenzene. A catalyst system and process which combines the features of the approaches, i.e., achieves ethylbenzene isomerization to xylenes with high conversion of both ethylbenzene and xylenes, would effect significant improvements in xylene-production economics.
SUMMARY OF THE INVENTION
A principal object of the present invention is to provide a novel catalyst and process for the isomerization of alkylaromatic hydrocarbons. More specifically, this invention is directed to a catalyst system for isomerization of C
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aromatic hydrocarbons to obtain improved yields of desired xylene isomers.
This invention is based on the discovery that a catalyst system comprising a combination of a non-zeolitic molecular-sieve catalyst and a zeolitic aluminosilicate catalyst having critically defined characteristics demonstrates improved conversion and selectivity in C
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aromatics isomerization.
Accordingly, a broad embodiment of the invention is directed toward a catalyst system useful for the isomerization of alkylaromatics comprising a combination of a first catalyst comprising a non-zeolitic molecular sieve and a platinum-group metal and a second catalyst comprising a zeolitic aluminosilicate and a platinum-group metal in a substantially lower concentration than in the first catalyst. The non-zeolitic molecular sieve preferably is a silicoaluminophosphate (SAPO) molecular-sieve, more preferably an SM-3 and/or a MgAPSO molecular sieve which preferably comprises a MgAPSO-31 molecular sieve. Platinum is the preferred platinum-group metal, and is in a concentration on the second catalyst of no more than about 30% of the concentration on the first catalyst; preferably, this relative concentration is no more than about 20%, and optionally no more than about 10% of platinum on the second catalyst relative to platinum on the first catalyst. The optimal catalysts generally comprise an inorganic-oxide binder, usually alumina and/or silica.
In one embodiment, the non-zeolitic molecular sieve and the zeolitic aluminosilicate are staged, preferably with a bed of the non-zeolitic molecular sieve preceding a bed of the zeolitic aluminosilicate. In another aspect of the invention, the non-zeolitic molecular sieve and zeolitic aluminosilicate are contained on separate particles which comprise a physical mixture.
A further embodiment of the invention is an alkylaromatics-isomerization process, stock using a catalyst system comprising a combination of a first catalyst comprising a non-zeolitic molecular sieve and a platinum-group metal and a second catalyst comprising a zeolitic aluminosilicate and a platinum-group metal in a substantially lower concentration than in the first catalyst to isomerize a feed mixture to obtain an isomerized product. Preferably the isomerization is effected by the steps of contacting the feed mixture with a non-zeolitic molecular-sieve catalyst to obtain an isomerized intermediate which then is contacted with a zeolitic aluminosilicate to increase the proportion of at least one xylene isomer in an isomerized product. Preferably the process comprises isomerization of a feedstock comprising a non-equilibrium mixture of xylenes and ethylbenzene at isomerization conditions to obtain a product having an increased para-xylene content relative to that of the feed.
These as well as other objects and embodiments will become evident from the following detailed description of the invention.
REFERENCES:
patent: 3856872 (1974-12-01), Morrison
patent: 4351979 (1982-09-01), Chester et al.
patent: 4740650 (1988-04-01), Pellet et al.
patent: 4818739 (1989-04-01), Gortsema et al.
patent: 4899011 (1990-02-01), Chu et al.
patent: 5149421 (1992-09-01), Miller
patent: 5240891 (1993-08-01), Patton et al.
patent: 5612273 (1997-03-01), Prada et al.
patent: 5770542 (1998-06-01), Brandes et al.
patent: 5833837 (1998-11-01), Miller
patent: 5898090 (1999-04-0
Imrie Aaron J.
Sharma Sanjay B.
Dunn Tom
Ildebrando Christina
McBride, Jr. Thomas K.
Molinaro Frank S.
Tolomei John G.
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