Chemistry of hydrocarbon compounds – Aromatic compound synthesis – By ring formation from nonring moiety – e.g. – aromatization,...
Reexamination Certificate
2000-02-23
2001-01-09
Wood, Elizabeth D. (Department: 1755)
Chemistry of hydrocarbon compounds
Aromatic compound synthesis
By ring formation from nonring moiety, e.g., aromatization,...
C585S407000, C585S410000, C585S411000, C585S415000, C585S416000, C585S417000, C585S418000, C585S422000, C208S115000, C208S118000, C208S199000, C208S120050, C208S120350, C208S133000, C208S134000, C208S137000, C208S138000, C208S139000, C208S141000
Reexamination Certificate
active
06172273
ABSTRACT:
The invention relates to catalyst systems useful in hydrocarbon upgrading processes and to methods for their production and use. In another aspect, this invention relates to processes for reforming saturated hydrocarbons employing the novel catalyst systems of this invention.
Catalysts for reforming saturated hydrocarbons are well known by those skilled in the art, and are described in the patent literature, e.g. in U.S. Pat. Nos. 4,298,504, 4,165,276, and 4,157,989. However, there are ever present incentives for the development of new, more effective and/or more practical catalyst systems and methods of preparing them.
SUMMARY OF THE INVENTION
It is an object of this invention to provide a novel hybrid catalyst system effective for at least partially reforming saturated hydrocarbons to aromatics.
It is another object of this invention to provide a method of preparing a novel hybrid catalyst system effective for at least partially reforming saturated hydrocarbons to aromatics.
It is a further object of this invention to employ this novel hybrid catalyst system as a catalyst in the at least partial reforming of saturated hydrocarbons.
It is still another object of the present invention to increase the efficiency of the conversion of saturated hydrocarbons to aromatics.
Yet another object of the present invention is to provide an improved reforming process of increased efficiency.
It is a further object of this invention to provide an improved method of preparing a catalyst system, effective for at least partially reforming saturated hydrocarbons to aromatics, which is economical and efficient.
It is a specific object of this invention to provide a novel hybrid catalyst system comprising a platinum group metal (including platinum, iridium, osmium, ruthenium, rhodium, palladium or mixtures of any two or more thereof), a rhenium component, optionally, a halogen component, a porous carrier material, bismuth and silica effective for at least partially reforming saturated hydrocarbons to aromatics.
According to a first embodiment of the present invention, a catalyst system which can be used for at least partially converting a hydrocarbon or a hydrocarbon mixture to an aromatic hydrocarbon is provided. The novel catalyst system comprises a first solid material comprising a platinum group metal, a rhenium component, optionally, a halogen component and a porous carrier material, and a second solid material comprising bismuth and silica.
According to a second embodiment of the present invention, a method which can be used for producing a catalyst system is provided. The method comprises the steps of:
incorporating a platinum group metal, rhenium and, optionally, a halogen component into a porous carrier material to form the first solid material;
incorporating bismuth into silica to form the second solid material; and
blending the first and second solid materials to form the novel catalyst system.
According to a third embodiment of the present invention, a process is provided for the conversion of saturated hydrocarbons to aromatics by contacting under conversion conditions the saturated hydrocarbons with a novel catalyst system prepared by the method of the second embodiment.
According to a fourth embodiment of the present invention, a process is provided for the conversion of saturated hydrocarbons to aromatics by contacting under conversion conditions the saturated hydrocarbons with a first solid material comprising a platinum group metal, a rhenium component, optionally, a halogen component and a porous carrier material producing an intermediate stream, and contacting the intermediate stream with a second solid material comprising bismuth and silica.
According to a fifth embodiment of the present invention, a method is provided for preparing a catalyst system, effective for at least partially reforming saturated hydrocarbons, comprising placing a first solid material comprising a platinum group metal, a rhenium component, optionally, a halogen component and a porous carrier material into a contacting vessel directly above a second solid material comprising bismuth and silica.
Other objects and advantages will become apparent from the detailed description and the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
According to the first embodiment of the present invention the catalyst system can comprise, consist essentially of, or consist of a first solid material comprising a platinum group metal, a rhenium component, a porous carrier material and, optionally, a halogen component and a second solid material comprising, or consisting of, or consisting essentially of, bismuth and silica. The term “metal” used herein also includes a compound of the metal.
Considering first the first solid material, it is preferred that the porous carrier material be a porous, adsorptive, high surface area support having a surface area of about 25 to about 500 m
2
/g. Examples of suitable porous carrier materials include, but are not limited to, aluminas such as for example &agr;-alumina and &ggr;-alumina; silicas; alumina-silica; aluminum phosphate; aluminum chlorohydrate; clays such as kaolinite, halloysite, vermiculite, chlorite, attapulgite, smectite, montmorillonite, illite, saconite, sepiolite, palygorskite; activated carbon; coke; charcoal; crystalline zeolitic aluminosilicates (such as ZSM-5); and spinels such as MgAl
2
O
4
, FeAl
2
O
4
, ZnAl
2
O
4
and CaAl
2
O
4
, and combinations of any two or more thereof. Because these porous carrier materials are well known to one skilled in the art, description of which is omitted herein. The presently preferred porous carrier material is alumina because it is readily available.
An essential ingredient of the first solid material is a platinum group metal. It is an essential feature that substantially all of this platinum group metal is uniformly distributed throughout the porous carrier material in the elemental metallic state prior to the incorporation of the rhenium. This platinum group metal may be present in the first solid material in any amount that is catalytically effective. Generally, the amount of platinum group metal present in the first solid material is in the range of from about 0.01 to about 2 weight %, preferably in the range of from about 0.05 to about 1 weight % based on the total weight of the first solid material, measured on an elemental platinum group metal basis. Particularly preferred mixtures of these platinum group metals for use in the first solid material are: (1) platinum and iridium and (2) platinum and rhodium.
Optionally, a halogen component may be incorporated into the platinum group metal-containing porous carrier material prior to incorporation of rhenium. This halogen may be fluorine, chlorine, iodine, bromine, or mixtures of any two or more thereof. It is customary in the art to refer to the halogen component as being combined with the porous carrier material, or with the platinum group metal in the form of the halide. This halogen component may be in the first solid material in any amount that is catalytically effective. Generally, the amount of halogen component present in the first solid material will be in the range upwardly to about 10 weight %, preferably from about 0.5 to about 5 weight %, and most preferably from 0.5 to 1.5 weight % based on the total weight of the first solid material, measured on an elemental halogen basis.
Another essential ingredient of the first solid material is a rhenium component. The rhenium component present in the first solid material is preferably a pyrolyzed rhenium carbonyl component. The pyrolyzed rhenium carbonyl component can be either the pure pyrolyzed rhenium carbonyl component itself or a substituted pyrolyzed rhenium carbonyl component such as a pyrolyzed rhenium carbonyl halide component including the chlorides, bromides, iodides and mixtures of any two or more thereof. This rhenium component may be present in the first solid material in any amount that is catalytically effective. The preferred amount of rhenium component present in the first solid material is in the
Drake Charles A.
Wu An-hsiang
Anderson Jeffrey R.
Phillips Petroleum Company
Wood Elizabeth D.
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