Catalyst – solid sorbent – or support therefor: product or process – Zeolite or clay – including gallium analogs – And additional al or si containing component
Reexamination Certificate
1999-03-03
2001-10-09
Griffin, Steven P. (Department: 1754)
Catalyst, solid sorbent, or support therefor: product or process
Zeolite or clay, including gallium analogs
And additional al or si containing component
C502S064000, C502S074000, C502S085000, C502S086000
Reexamination Certificate
active
06300270
ABSTRACT:
BACKGROUND OF THE INVENTION
The invention relates to catalyst compositions useful in hydrocarbon upgrading processes and to methods for their production and use.
In another aspect, this invention relates to processes for converting hydrocarbons to aromatic hydrocarbons with a reduction in sulfur resulting from the conversion of such hydrocarbons in the presence of such catalyst compositions.
It is known to catalytically crack non-aromatic hydrocarbons to lower olefins and aromatic hydrocarbons in the presence of catalysts which contain a zeolite (such as ZSM-5), as is described in an article by N. Y. Chen et al. in Industrial and Engineering Chemistry Process Design and Development, Volume 25, 1986, pages 151-155. However, there are ever present incentives for the development of new, more effective and/or more practical catalyst compositions and methods of preparing them.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a novel catalyst composition effective for at least partially converting a hydrocarbon mixture comprising at least one hydrocarbon having in the range of from about 10 to about 25 carbon atoms per molecule to at least one hydrocarbon having less than about 10 carbon atoms per molecule and for reducing the sulfur concentration of the hydrocarbon mixture.
It is a further object of this invention to provide a method of making a novel catalyst composition, effective for at least partially converting a hydrocarbon mixture comprising at least one hydrocarbon having in the range of from about 10 to about 25 carbon atoms per molecule to at least one hydrocarbon having less than about 10 carbon atoms per molecule and for reducing the sulfur concentration of the hydrocarbon mixture, which is economical and efficient.
It is a further object of this invention to employ this novel catalyst composition in at least partially converting a hydrocarbon mixture comprising at least one hydrocarbon having in the range of from about 10 to about 25 carbon atoms per molecule to at least one hydrocarbon having less than about 10 carbon atoms per molecule and for reducing the sulfur concentration of the hydrocarbon mixture.
The inventive catalyst composition comprises a zeolite, silica, a sulfide, and at least one transition metal including, but not limited to, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and combinations of any two or more thereof.
The catalyst composition can be prepared by the method of:
incorporating at least one transition metal into a calcined zeolite-silica material to thereby form a transition metal-incorporated calcined zeolite-silica material;
calcining the transition metal-incorporated calcined zeolite-silica material to thereby form a calcined transition metal-incorporated calcined zeolite-silica material; and
contacting the calcined transition metal-incorporated calcined zeolite-silica material with ammonium sulfide to thereby form the catalyst composition.
The inventive catalyst composition can be used in the conversion of at least a portion of a hydrocarbon or hydrocarbon mixture to at least one aromatic by contacting, under conversion conditions, a hydrocarbon feedstock with the inventive catalyst composition.
Other objects and advantages of the invention will become apparent from the detailed description and the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
The silica material used in preparing the inventive catalyst composition can be any silica which has a surface area in the range of from about 300 to about 750 m
2
/gram. The preferred form of silica is colloidal silica.
The zeolite material used in preparing the inventive catalyst composition can be any zeolite that is effective in the conversion of non-aromatic hydrocarbons to aromatic hydrocarbons when contacted under suitable reaction conditions with non-aromatic hydrocarbons. Preferably, the zeolite has a constraint index (as defined in U.S. Pat. No. 4,500,417, the disclosure of which is incorporated herein by reference) from less than about 2.0, preferably in the range from about 0.5 to less than about 2.0. Generally, the molar ratio of SiO
2
to Al
2
O
3
in the crystalline framework of the zeolite is at least about 10:1 and can range up to infinity. Preferred zeolites include, but are not limited to, beta zeolite, zeoliteY, mordenite and zeolites ZSM-3, ZSM-4, ZSM-18, ZSM-20 and mixtures or combinations of any two or more thereof. The presently most preferred zeolite is beta zeolite.
In the preparation of the inventive catalyst composition, a zeolite and silica are combined to thereby form a zeolite-silica material. Any suitable method for mixing/combining the zeolite and silica components can be used to provide a homogeneous mixture of such components. Suitable types of solids-mixing machines for mixing the components of zeolite and silica can include, but are not limited to, tumblers, stationary shells or troughs, muller mixers, which are either batch type or continuous type, impact mixers, and the like.
Following the mixing of the zeolite and silica, the resulting zeolite-silica material is extruded into pellets or tablets followed by calcining under conditions sufficient to provide a calcined zeolite-silica material. Generally, such conditions can include a temperature in the range of from about 250° C. to about 1000° C., preferably from about 350° C. to about 750° C., and most preferably from 450° C. to 650° C.; and a pressure in the range of from about 0 to about 50 atmospheres (atm), preferably from about 0.1 to about 30 atm, and most preferably from 0.5 to 10 atm; for a time period in the range of from about 1 to about 30 hours, preferably from about 2 to about 20 hours, and most preferably from 3 to 15 hours.
Following the calcination of the zeolite-silica material, at least one transition metal is incorporated into the calcined zeolite-silica material by any suitable means or method known in the art for incorporating metallic elements into a material to thereby form a transition metal-incorporated calcined zeolite-silica material.
The at least one transition metal includes, but is not limited to, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and combinations of any two or more thereof, preferably molybdenum and/or tungsten, and most preferably molybdenum.
It is preferred to use any standard incipient wetness technique for impregnating the calcined zeolite-silica material with at least one transition metal. A preferred method uses a liquid impregnation solution containing the desirable concentration of at least one transition metal in the form of at least one transition metal compound. It is particularly desirable to use an aqueous solution formed by dissolving at least one transition metal compound in water.
Examples of suitable transition metal compounds include, but are not limited to, chromium boride, chromium diboride, chromium (III) bromide hexahydrate, chromium (II) chloride, chromium (III) chloride, chromium (III) chloride hexahydrate, chromium (II) fluoride, chromium (III) fluoride, chromium (III) fluoride hydrate, chromium (III) nitrate nonahydrate, ammonium molybdate tetrahydrate, ammonium tetrathiomolybdate (VI), ammonium heptamolybdate tetrahydrate, molybdenum (III) chloride, molybdenum (V) chloride, molybdenum (VI) fluoride, molybdenum (II) iodide, molybdenum (IV) oxide, molybdenum (VI) oxide, molybdenum (IV) sulfide, ammonium tetrathiotungstate, tungsten boride, tungsten (IV) chloride, tungsten (VI) chloride, tungsten (VI) fluoride, tungsten (VI) oxide, tungsten (IV) sulfide, tungstic acid, iron (II) bromide, iron (II) bromide hydrate, iron (III) bromide, iron (II) chloride, iron (II) chloride hydrate, iron (III) chloride hexahydrate, iron disulfide, iron (II) iodide, iron (III) nitrate nonahydrate, iron (III) oxide, iron (III) oxide monohydrate, iron (II) sulfide, ammonium hexachlororuthenate (IV), chloropentaammineruthenium (III) chloride, hexaammineruthenium (III) chl
Drake Charles A.
Wu An-hsiang
Anderson Jeffrey R.
Griffin Steven P.
Ildebrando Christina
Richmond, Hitchcock, Fish & Dollar
Stewart Charles W.
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