Modified zeolites that include zirconium hydride moieties and methods for making such

Patent metadata

Field	Value
Publication number	US-12434229-B2
Application number	US-202318335732-A
Country	US
Kind code	B2
Filing date	Jun 15, 2023
Priority date	Jun 15, 2023
Publication date	Oct 7, 2025
Grant date	Oct 7, 2025

Abstract

Modified zeolites may include a microporous framework including a plurality of micropores having diameters of less than or equal to 2 nm. The microporous framework may include at least silicon atoms and oxygen atoms. The modified zeolite may include a plurality of mesopores having diameters of greater than 2 nm and less than or equal to 50 nm, wherein the plurality of mesopores are ordered with cubic symmetry. The modified zeolite may include a plurality of zirconium hydride moieties each bonded to at least two bridging oxygen atoms, wherein a zirconium atom of the zirconium hydride is bonded to the bridging oxygen atom, and wherein the bridging oxygen atom bridges the zirconium atom of the zirconium hydride moiety and a silicon atom of the microporous framework.

First claim

The invention claimed is:

1. A modified zeolite comprising:
a microporous framework comprising a plurality of micropores having diameters of less than or equal to 2 nm, wherein the microporous framework comprises at least silicon atoms and oxygen atoms; and
a plurality of mesopores having diameters of greater than 2 nm and less than or equal to 50 nm, wherein the plurality of mesopores are ordered with cubic symmetry; and
a plurality of zirconium hydride moieties each bonded to at least two bridging oxygen atoms, wherein a zirconium atom of the zirconium hydride is bonded to the bridging oxygen atom, and wherein the bridging oxygen atom bridges the zirconium atom of the zirconium hydride moiety and a silicon atom of the microporous framework.

2. The modified zeolite of claim 1 , wherein the modified zeolite comprises from 0.01 mmol/g to 0.45 mmol/g zirconium.

3. The modified zeolite of claim 1 , wherein the zirconium atom is bonded to two hydrogen atoms and two bridging oxygen atoms.

4. The modified zeolite of claim 1 , wherein the zirconium atom is bonded to one hydrogen atom and three bridging oxygen atoms.

5. The modified zeolite of claim 1 , wherein the mesopores are ordered with cubic symmetry having an Ia-3d, Fm-3m, Pm-3n, Pn-3m or Im-3m space group.

6. The modified zeolite of claim 1 , wherein the microporous framework further comprises aluminum atoms.

7. The modified zeolite of claim 6 , wherein a ratio of silicon atoms to aluminum atoms is from 1.5 to 1500.

8. The modified zeolite of claim 1 , wherein the modified zeolite is an FAU framework type zeolite.

9. The modified zeolite of claim 1 , wherein the modified zeolite is an USY zeolite.

10. The modified zeolite of claim 1 , wherein a surface area of the modified zeolite is from 200 m 2 /g to 1500 m 2 /g.

11. The modified zeolite of claim 1 , wherein a total pore volume of the modified zeolite is from 0.01 to 1.5 cm 3 /g.

12. The modified zeolite of claim 1 , wherein the modified zeolite further comprises silicon hydride moieties each bonded to bridging oxygen atoms.

13. The modified zeolite of claim 12 , wherein the silicon hydride moiety comprises:
a silicon atom bonded to one hydrogen atom and three bridging oxygen atoms; or
a silicon atom bonded to two hydrogen atoms and two bridging oxygen atoms.

14. A method of cracking a hydrocarbon feedstock, the method comprising contacting the hydrocarbon feedstock with a catalyst comprising the modified zeolite of claim 1 and cracking at least a portion of the hydrocarbon feedstock to form a product.

15. The method of claim 14 , wherein the cracking comprises hydrocracking or fluid catalytic cracking.

16. A method of making the modified zeolite of claim 1 , the method comprising:
reacting an organometallic chemical with a dehydroxylated zeolite, wherein the dehydroxylated zeolite comprises isolated terminal silanol functionalities comprising hydroxyl groups bonded to silicon atoms of the dehydroxylated zeolite, wherein reacting the organometallic chemical with the dehydroxylated zeolite forms an intermediate zeolite comprising organometallic moieties each bonded to an oxygen atom of the intermediate zeolite, and wherein each organometallic moiety comprises a portion of the organometallic chemical; and
reacting the intermediate zeolite with hydrogen to form the modified zeolite of claim 1 , wherein reacting the intermediate zeolite with hydrogen converts at least a portion of the organometallic moieties to zirconium hydride moieties.

17. The method of making the modified zeolite of claim 16 , wherein the modified zeolite comprises from 0.01 mmol/g to 0.450 mmol/g zirconium.

18. The method of making the modified zeolite of claim 16 , wherein reacting the intermediate zeolite with hydrogen converts at least 50% of the organometallic moieties to zirconium hydride moieties.

19. The method of making the modified zeolite of claim 16 , further comprising dehydroxylating an initial zeolite to from the dehydroxylated zeolite, wherein the initial zeolite primarily comprises vicinal silanol functionalities, and wherein dehydroxylating the initial zeolite forms the isolated terminal silanol functionalities.

20. The method of making the modified zeolite of claim 18 , wherein:
dehydroxylating the initial zeolite comprises heating the initial zeolite at a temperature of 650° C. to 1100° C.; and
dehydroxylating the initial zeolite is under vacuum.

Assignees

• Saudi Arabian Oil Co
• Univ King Abdullah Sci & Tech

Inventors

• Hodgkins Robert Peter
• Koseoglu Omer Refa
• Huang Kuo-Wei
• Rueping Magnus
• Samantaray Manoja K
• Parsapur Rajesh Kumar
• Sedjerari Anissa Bendjeriou

Classifications

• B01J35/647

  2-50 nm · CPC title

• B01J35/643

  less than 2 nm · CPC title

• B01J35/638

  more than 1.0 ml/g · CPC title

• B01J35/635

  0.5-1.0 ml/g · CPC title

• B01J35/633

  less than 0.5 ml/g · CPC title