Mesoporous zeolite catalyst supports
View Patent ↗Compositions and methods for preparing a catalyst composition containing mesoporous materials are described herein. In particular, various embodiments described herein relate to the preparation of catalytic compositions containing a mesoporous zeolite and one or more catalytic nanoparticles dispersed therein. In various embodiments described herein, such catalyst compositions can be used in various catalytic conversion processes, such as hydrocracking.
1. A method for modifying a catalyst composition, said method comprising:
(a) incorporating one or more catalytic nanoparticles into a mesoporous zeolite to thereby form an initial catalytic zeolite, wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume in the range of 0.05 to 0.70 cc/g; and
(b) heating at least a portion of said initial catalytic zeolite at a temperature of at least 150° C. to thereby form a heat-modified catalytic zeolite, wherein at least 20 weight percent of the total amount of said catalytic nanoparticles associated with said heat-modified catalytic zeolite are located within the mesopores of said heat-modified catalytic zeolite.
2. The method of claim 1 , wherein at least 75 weight percent of the total amount of said catalytic nanoparticles associated with said heat-modified catalytic zeolite are located within the mesopores of said heat-modified catalytic zeolite.
3. The method of claim 1 , wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume in the range of 0.10 to 0.60 cc/g.
4. The method of claim 1 , wherein said mesoporous zeolite is a mesostructured zeolite.
5. The method of claim 1 , wherein at least 75 weight percent of said catalytic nanoparticles within the mesopores of said heat-modified catalytic zeolite have an average particle size in the range of 5 to 100 nm as measured using high magnification transmission electron microscopy (“TEM”).
6. The method of claim 1 , wherein said catalytic nanoparticles comprise a transition metal.
7. The method of claim 6 , wherein said transition metal is selected from the group consisting of Ni, Co, W, Mo, Pd, Pt, Ru, Rh, Os, Ir, Nb, and combinations thereof.
8. The method of claim 1 , wherein said catalytic nanoparticles comprise cerium oxide, cobalt oxide, nickel oxide, or combinations thereof.
9. The method of claim 1 , wherein said incorporating of step (a) comprises subjecting said mesoporous zeolite to ion exchange with one or more ions of said catalytic nanoparticles to thereby form an ion-exchanged catalytic zeolite.
10. The method of claim 1 , wherein said incorporating of step (a) comprises contacting said mesoporous zeolite with an acid or base to form said initial catalytic zeolite.
11. The method of claim 1 , further comprising combining said heat-modified catalytic zeolite with at least one binder to form a catalyst composition.
12. A method for making a catalyst composition, said method comprising:
(a) subjecting a mesoporous zeolite to ion-exchange with one or more ions of a catalyst metal to form an ion-exchanged catalytic zeolite, wherein said ion exchange incorporates at least a portion of said catalyst ions into the mesopores of said mesoporous zeolite, wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume in the range of 0.05 to 0.70 cc/g; and
(b) contacting said ion-exchanged catalytic zeolite with one or more pH additives to thereby form a catalytic zeolite, wherein at least 20 weight percent of the total amount of said catalyst metal associated with said catalytic zeolite is located within the mesopores of said catalytic zeolite.
13. The method of claim 12 , wherein at least 75 weight percent of the total amount of said catalyst metal associated with said catalytic zeolite is located within the mesopores of said catalytic zeolite.
14. The method of claim 12 , wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume in the range of 0.10 to 0.60 cc/g.
15. The method of claim 12 , wherein said mesoporous zeolite is a mesostructured zeolite.
16. The method of claim 12 , wherein at least 75 weight percent of said catalyst metal within the mesopores of said catalytic zeolite has an average particle size in the range of 5 to 100 nm as measured using high magnification transmission electron microscopy (“TEM”).
17. The method of claim 12 , wherein said catalyst metal comprises a transition metal selected from the group consisting of Ni, Co, W, Mo, Pd, Pt, Ru, Rh, Os, Ir, Nb, and combinations thereof.
18. The method of claim 12 , wherein said ion exchange occurs at a temperature in the range of 25 to 150° C. and for a time period in the range of 1 to 24 hours.
19. The method of claim 12 , further comprising (c) calcining at least a portion of said catalytic zeolite at a temperature in the range of 300 to 1,000° C. to form a calcined catalytic zeolite.
20. The method of claim 19 , further comprising combining said calcined catalytic zeolite with at least one binder to form a catalyst composition, wherein said binder is selected from the group consisting of alumina, silica, titania, zirconia, clays, boron oxide, and combinations thereof.
21. The method of claim 12 , further comprising contacting said catalytic zeolite with hydrogen gas or one or more sulfides in order to at least partially reduce the catalyst metal within said catalytic zeolite into its elemental form.
22. A method for modifying a catalyst composition, said method comprising:
(a) incorporating one or more catalytic nanoparticles into mesopores of a mesoporous zeolite to thereby form an initial catalytic zeolite, wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume in the range of 0.05 to 0.70 cc/g; and
(b) heating at least a portion of said initial catalytic zeolite at a temperature of at least 150° C. to thereby form a heat-modified catalytic zeolite, wherein at least 75 weight percent of said catalytic nanoparticles originally associated with said initial catalytic zeolite are maintained within the mesopores of said heat-modified catalytic zeolite.
23. The method of claim 22 , wherein said mesoporous zeolite has a total 20 to 80 Å diameter mesopore volume in the range of 0.10 to 0.60 cc/g.
24. The method of claim 22 , wherein said mesoporous zeolite is a mesostructured zeolite.
25. The method of claim 22 , wherein at least 75 weight percent of said catalytic nanoparticles within the mesopores of said heat-modified catalytic zeolite have an average particle size in the range of 5 to 100 nm as measured using high magnification transmission electron microscopy (“TEM”).
26. The method of claim 22 , wherein said catalytic nanoparticles comprise a transition metal selected from the group consisting of Ni, Co, W, Mo, Pd, Pt, Ru, Rh, Os, Ir, Nb, and combinations thereof.