Hydrocracking catalyst containing zeolite USY and low acidity and large domain size zeolite beta

Patent metadata

Field	Value
Publication number	US-10913054-B2
Application number	US-201816057778-A
Country	US
Kind code	B2
Filing date	Aug 7, 2018
Priority date	Aug 11, 2015
Publication date	Feb 9, 2021
Grant date	Feb 9, 2021

Abstract

A hydrocracking catalyst comprising a zeolite beta having an average domain size from 800 to 1500 nm2; a zeolite USY; a catalyst support; and at least one metal selected from the group consisting of elements from Group 6 and Groups 8 through 10 of the Periodic Table. The zeolite beta has an OD acidity of 20 to 50 μmol/g and the catalyst support comprises an amorphous silica aluminate and a second support material when the weight percentage content of the zeolite beta is less than the weight percentage of the zeolite USY, and, when the weight percentage content of the zeolite beta is greater than the weight percentage of the zeolite USY, the zeolite beta has an OD acidity of 20 to 400 μmol/g, the zeolite beta content is from 0.5 to 10 wt. % and the zeolite USY has an ASDI between 0.05 and 0.12 with a corresponding zeolite USY content of from 0 to 5 wt. %. A process for hydrocracking a hydrocarbonaceous feedstock using the catalyst is also described as is a method for making the hydrocracking catalyst.

First claim

What is claimed:

1. A hydrocracking catalyst comprising:
a zeolite beta having an average domain size from 800 to 1500 nm 2 ;
a zeolite USY;
a catalyst support; and
at least one metal selected from the group consisting of elements from Group 6 and Groups 8 through 10 of the Periodic Table,
wherein,
the zeolite beta has an OD acidity of 20 to 50 μmol/g and the catalyst support comprises an amorphous silica aluminate and a second support material when the weight percentage content of the zeolite beta is less than the weight percentage of the zeolite USY; and
the zeolite beta has an OD acidity of 20 to 400 μmol/g and the zeolite beta content is from 0.5 to 10 wt. % and the zeolite USY has an ASDI between 0.05 and 0.12 and the zeolite USY content is from 0 to 5 wt. % when the weight percentage content of the zeolite beta is greater than the weight percentage of the zeolite USY.

2. The hydrocracking catalyst of claim 1 , wherein the zeolite beta has a SiO 2 /Al 2 O 3 ratio (SAR) from 50 to 200.

3. The hydrocracking catalyst of claim 1 , wherein the zeolite beta OD acidity is from 30 to 40 μmol/g when the weight percentage content of the zeolite beta in the catalyst is less than the weight percentage of the zeolite USY.

4. The hydrocracking catalyst of claim 1 , wherein the zeolite beta OD acidity is from 30 to 100 μmol/g when the weight percentage content of the zeolite beta in the catalyst is greater than the weight percentage of the zeolite USY.

5. The hydrocracking catalyst of claim 1 , wherein the average domain size is from 900 to 1250 nm 2 .

6. The hydrocracking catalyst of claim 1 , wherein the zeolite beta has more large domains that have a domain size from 1200 to 2000 nm 2 than small domains that the domain size from 200 to 600 nm 2 .

7. The hydrocracking catalyst of claim 1 , wherein the zeolite beta has a standard deviation of domain sizes greater than 700 nm 2 .

8. The hydrocracking catalyst of claim 1 , wherein a weight ratio of the zeolite beta to the zeolite USY is from 0.10 to 0.95.

9. The hydrocracking catalyst of claim 1 , wherein the wt. % of the zeolite beta is from 1 to 5 wt. % higher than the wt. % of the zeolite USY.

10. The hydrocracking catalyst of claim 1 , wherein the zeolite USY has an ASDI between 0.05 and 0.12.

11. The hydrocracking catalyst of claim 1 , wherein the second support is a pseudo-boehmite alumina.

12. The hydrocracking catalyst of claim 1 , wherein the zeolite USY has a total Brönsted acid sites content determined by FTIR after H/D exchange of 0.080 to 0.200 mmol/g.

13. The hydrocracking catalyst of claim 1 , comprising at least one Group 6 metal and at least one metal selected from Groups 8 through 10 of the Periodic Table.

14. A process for hydrocracking a hydrocarbonaceous feedstock, comprising contacting the hydrocarbonaceous feedstock with a hydrocracking catalyst under hydrocracking conditions to produce a hydrocracked effluent that comprises middle distillates; wherein the hydrocracking catalyst comprises:
a zeolite beta having an average domain size from 800 to 1500 nm 2 ;
a zeolite USY;
a catalyst support; and
at least one metal selected from the group consisting of elements from Group 6 and Groups 8 through 10 of the Periodic Table,
wherein,
the zeolite beta has an OD acidity of 20 to 50 μmol/g and the catalyst support comprises an amorphous silica aluminate and a second support material when the weight percentage content of the zeolite beta is less than the weight percentage of the zeolite USY; and
the zeolite beta has an OD acidity of 20 to 400 μmol/g and the zeolite beta content is from 0.5 to 10 wt. % and the zeolite USY has an ASDI between 0.05 and 0.12 and the zeolite USY content is from 0 to 5 wt. % when the weight percentage content of the zeolite beta is greater than the weight percentage of the zeolite USY.

15. The process of claim 14 , wherein the hydrocarbonaceous feedstock has a TBP within 700 to 1200° F. (371 to 649° C.).

16. The process of claim 14 , wherein the zeolite beta has a SiO 2 /Al 2 O 3 ratio (SAR) from 50 to 200.

17. The process of claim 14 , wherein the zeolite beta OD acidity is from 30 to 40 μmol/g when the weight percentage content of the zeolite beta in the catalyst is less than the weight percentage of the zeolite USY.

18. The process of claim 14 , wherein the zeolite beta OD acidity is from 30 to 100 μmol/g when the weight percentage content of the zeolite beta in the catalyst is greater than the weight percentage of the zeolite USY.

19. The process of claim 14 , wherein the average domain size is from 900 to 1250 nm 2 .

20. The process of claim 14 , wherein the zeolite beta has more large domains that have a domain size from 1200 to 2000 nm 2 than small domains that have the domain size from 200 to 600 nm 2 .

21. The process of claim 14 , wherein the zeolite beta has a standard deviation of domain sizes greater than 700 nm 2 .

22. The process of claim 14 , wherein a weight ratio of the zeolite beta to the zeolite USY is from 0.10 to 0.95.

23. The process of claim 14 , wherein the wt. % of the zeolite beta is from 1 to 5 wt. % higher than the wt. % of the zeolite USY.

24. The process of claim 14 , wherein the zeolite USY has an ASDI between 0.05 and 0.12.

25. The process of claim 14 , wherein the second support is a pseudo-boehmite alumina.

26. The process of claim 14 , wherein the zeolite USY has a total Brönsted acid sites content determined by FTIR after H/D exchange of 0.080 to 0.200 mmol/g.

27. The process of claim 14 , comprising at least one Group 6 metal and at least one metal selected from Groups 8 through 10 of the Periodic Table.

28. The process of claim 14 , wherein the hydrocracked effluent comprises
from greater than 50 vol % to 95 vol % of a heavy middle distillate having a TBP of 380-700° F. (193-371° C.) when the weight percentage content of the zeolite beta in the catalyst is less than the weight percentage of the zeolite USY; or
from greater than 30 vol % to 50 vol % of a heavy middle distillate having a TBP of 380-700° F. (193-371° C.) when the weight percentage content of the zeolite beta in the catalyst is greater than the weight percentage of the zeolite USY.

29. A method for making a hydrocracking catalyst, comprising:
mixing together a zeolite beta having an average domain size from 800 to 1500 nm 2 ; a zeolite USY; a catalyst support; and enough liquid to form an extrudable paste;
wherein,
the zeolite beta has an OD acidity of 20 to 50 μmol/g and the catalyst support comprises an amorphous silica aluminate and a second support material when the weight percentage content of the zeolite beta is less than the weight percentage of the zeolite USY; and
the zeolite beta has an OD acidity of 20 to 400 μmol/g and the zeolite beta content is from 0.5 to 10 wt. % and the zeolite USY has an ASDI between 0.05 and 0.12 and the zeolite USY content is from 0 to 5 wt. % when the weight percentage content of the zeolite beta is greater than the weight percentage of the zeolite USY;

extruding the extrudable paste to form an extrudate base;
impregnating the extrudate base with a metal impregnation solution containing at least one metal selected from the group consisting of elements from Group 6 and Group 8 through 10 of the Periodic Table to make a metal-loaded extrudate; and
post-treating the metal-loaded extrudate by

Assignees

• Chevron Usa Inc

Inventors

• Zhang Yihua
• Maesen Theodorus Ludovicus Michael
• Hao Yalin
• Rea Thomas Michael
• Bushee Don Ramon

Classifications

• B01J35/30

  characterised by their physical properties · CPC title

• B01J35/80

  characterised by their amorphous structures · CPC title

• B01J2235/10

  Infrared [IR] · CPC title

• B01J2235/30

  Scanning electron microscopy; Transmission electron microscopy · CPC title

• B01J29/7815

  Zeolite Beta · CPC title