IP Library › Granted Patent US 12,434,229
Granted Patent B2
US 12,434,229 · App. 18/335,732 · Granted Oct 7, 2025

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

Inventors: Robert Peter Hodgkins (Dhahran, SA); Omer Refa Koseoglu (Dhahran, SA); Kuo-Wei Huang (Thuwal, SA); Magnus Rueping (Thuwal, SA); Manoja K. Samantaray (Thuwal, SA); Rajesh Kumar Parsapur (Thuwal, SA); Anissa Bendjeriou Sedjerari (Thuwal, SA)
Assignee: Saudi Arabian Oil Company
B01J29/088B01J35/394B01J35/615B01J35/617B01J35/618B01J35/633B01J35/635B01J35/638B01J35/643B01J35/647B01J37/08B01J37/30C01B39/026C01B39/24C10G47/20B01J2229/186B01J2229/34C01P2002/54C01P2002/72C01P2002/76C01P2002/77C01P2002/82C01P2002/86C01P2004/04C01P2006/12C01P2006/14C01P2006/17
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Quick Facts
Patent No.
US 12,434,229
App. No.
18/335,732
Granted
Oct 7, 2025
Kind
B2
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.

Claims (29)

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.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 15, 2023
From: HUANG, KUO-WEI; RUEPING, MAGNUS; SAMANTARAY, MANOJA KUMAR; PARSAPUR, RAJESH KUMAR; SEDJERARI, ANISSA BENDJERIOU
To: KING ABDULLAH UNIVERSITY OF SCIENCE AND TECHNOLOGY
Reel/Frame 063966/0758 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jun 15, 2023
From: HODGKINS, ROBERT PETER; KOSEOGLU, OMER REFA
To: SAUDI ARABIAN OIL COMPANY
Reel/Frame 064006/0026 →
Continuity (1)
Related Publication 20240424487A1 · Dec 26, 2024
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