Mineral oils: processes and products – Chemical conversion of hydrocarbons – Cracking
Reexamination Certificate
2000-08-31
2002-11-19
Griffin, Walter D. (Department: 1764)
Mineral oils: processes and products
Chemical conversion of hydrocarbons
Cracking
C208S113000, C208S119000, C585S653000
Reexamination Certificate
active
06482313
ABSTRACT:
BACKGROUND
This invention relates to catalyst components and compositions and methods of making and using the composition which comprises a crystalline microporous oxide having a promoter metal compound that promotes dehydrogenation and increases Lewis acidity without increasing the unit cell size of the crystalline microporous oxide.
Crystalline microporous oxides, such as zeolitic materials, have been in commercial use in a variety of industries for many years. These materials are especially valuable for their fluid separation ability as molecular sieves, as well as for their ability to act as a catalyst.
Crystalline microporous oxides are particularly useful as catalysts which convert the large paraffin molecules of a hydrocarbon mixture into smaller more unsaturated molecules such as olefins and aromatics. Typical conversion processes include fluid catalytic cracking and hydrocracking. To maximize this conversion process, many structural properties of the catalyst have to be balanced, such as pore size, pore volume, Lewis acidity, and Brøsted acidity. If the structural properties of the conversion catalyst are not properly balanced, conversion of the hydrocarbon mixture to product may be low, product quality may be poor, or the conversion catalyst may be rapidly deactivated.
It would be of particular benefit to obtain a crystalline microporous oxide catalyst high in catalytic activity by balancing the Brøsted acidity and the Lewis acidity of the framework and non-framework portions of the catalyst. By balancing the composition of the framework and non-framework portions of the crystalline structure, catalytic activity can be efficiently optimized. In the case of a cracking catalyst, olefin forming reactions of large paraffin molecules can be more efficiently coupled with the subsequent scission reactions which form the smaller molecules in the final product.
SUMMARY
One embodiment of the present invention comprises a catalyst comprising (i) a matrix material, and (ii) a crystalline microporous oxide incorporated into/with the matrix material. The crystalline microporous oxide comprises a non-framework portion and has a unit cell size. The non-framework portion comprises a promoter metal compound incorporated only into the non-framework portion of the crystalline microporous oxide. The promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
In another embodiment of the catalyst, the crystalline microporous oxide comprises a Y zeolite incorporated into the matrix material. The Y zeolite comprises a non-framework portion, has a unit cell size greater than about 24.30 Å, and comprises aluminum oxide incorporated only into the non-framework portion of the crystalline microporous oxide, such that the aluminum oxide increases Lewis acidity but does not substantially increasing the unit cell size of the zeolite.
In another embodiment of the catalyst, the crystalline microporous oxide comprises a non-framework portion comprising a promoter metal compound capable of increasing Lewis acidity incorporated only into the non-framework portion of the crystalline microporous oxide, such that the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
The embodiments of the catalyst can be used in an FCC unit, an isomerization unit, or a hydrocracker by contacting the catalyst with a suitable feedstock.
Another embodiment of the present invention comprises a process for making a catalyst. The process comprises (a) contacting a crystalline microporous oxide and a promoter precursor comprising a promoter metal capable of forming a promoter metal compound, said crystalline microporous oxide comprising a non-framework portion and having a unit cell size; and, (b) heating the mixture of step (a) to a temperature between 150° C. and 550° C.; wherein a promoter metal compound comprising said promoter metal is incorporated only into the non-framework portion of the crystalline microporous oxide and wherein the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
Another embodiment of the present invention is a process comprising: (a) contacting a crystalline microporous oxide and a promoter precursor, the crystalline microporous oxide comprising a non-framework portion and having a unit cell size and the promoter precursor comprising a promoter metal capable of forming a promoter metal compound; (b) decomposing said promoter precursor thereby forming a promoter metal compound comprising an oxide form of said promoter metal; (c) dispersing said promoter metal compound only into the non-framework portion of said crystalline microporous oxide; wherein the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
Another embodiment of the present invention is a process comprising: (a) calcining a zeolite comprising a non-framework portion and having a unit cell size; (b) contacting the zeolite with a promoter precursor comprising a promoter metal capable of forming a promoter metal compound, wherein said promoter metal is selected from the group consisting of magnesium, chromium, iron, lanthanum, gallium, manganese and aluminum and wherein said promoter precursor is selected from the group consisting of aluminum acetylacetonate, aluminum isopropyloxide, aluminum hexafluoroacetylacetonate, aluminum dichlorohydrol, aluminum ethoxides, tris[2,2,6,6-tetramethyl-3-5, heptanedianoto]aluminum-III[Al(TMHD)
3
], aluminum acetate, aluminum nitrate, aluminum propoxide, magnesium acetylacetonate, chromium acetylacetonate, iron acetylacetonate, gallium acetylacetonate, manganese acetylacetonate, and lanthanide acetylacetonate; (c) heating the mixture of step (b) to a temperature between 150° C. and 550° C.; (d) incorporating the product of step (b) into a matrix material, wherein a promoter metal compound comprising said promoter metal is incorporated only into the non-framework portion of the zeolite and wherein the promoter metal compound does not substantially increase the unit cell size of the zeolite.
Another embodiment of the present invention is a process comprising: (a) contacting a calcined crystalline microporous oxide and a promoter precursor comprising a promoter metal capable of forming a promoter metal compound, said crystalline microporous oxide comprising a non-framework portion and having a unit cell size; and, (b) activating said promoter metal compound, wherein said promoter metal compound is incorporated only into the non-framework portion of the crystalline microporous oxide and wherein the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
Another embodiment of the present invention is a process comprising: (a) calcining a crystalline microporous oxide, the crystalline microporous oxide comprising a non-framework portion and having a unit cell size; (b) contacting an aluminum alkyl selected from the group consisting of trimethylaluminum, triethylaluminum, tri(t-butyl)aluminum; and tri(i-butyl)aluminum; (c) treating the product of step (b) with an oxygen-containing material to form a promoter metal compound, wherein the promoter metal compound does not substantially increase the unit cell size of the crystalline microporous oxide.
Other embodiments of the present invention include the products produced by the processes of the present invention. These products may or may not be incorporated into a matrix material, but are preferably incorporated into a matrix material before used in a process unit.
DETAILED DESCRIPTION
The catalytic activity of a crystalline microporous oxide, such as a zeolite, can be improved by effectively incorporating a promoter metal compound that promotes dehydrogenation and increases Lewis acidity of the crystalline microporous oxide without increasing its unit cell size. Although the crystalline microporous oxide can be used as a catalyst alone, the crystal
Schuette Darlene
Schuette William L.
Schweizer Albert E.
Cromwell Michael A.
ExxonMobil Research and Engineering Company
Griffin Walter D.
Hughes Gerard J.
Schuette Darlene
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