Processes for producing fluorided solid oxides and uses thereof in metallocene-based catalyst systems

Patent metadata

Field	Value
Publication number	US-11731122-B2
Application number	US-202217855874-A
Country	US
Kind code	B2
Filing date	Jul 1, 2022
Priority date	Sep 27, 2018
Publication date	Aug 22, 2023
Grant date	Aug 22, 2023

Abstract

Disclosed herein are methods for preparing fluorided solid oxides by contacting an acidic fluorine-containing compound with an inorganic base to form an aqueous mixture having a pH of at least 4, followed by contacting a solid oxide with the aqueous mixture to produce the fluorided solid oxide. Also disclosed are methods for preparing fluorided solid oxides by contacting an acidic fluorine-containing compound with a solid oxide to produce a mixture, followed by contacting the mixture with a inorganic base to produce the fluorided solid oxide at a pH of at least about 4. The fluorided solid oxide can be used as an activator component in a catalyst system for the polymerization of olefins.

First claim

We claim:

1. A fluorided solid oxide comprising:
a silica-coated alumina;
from about 0.5 to about 15 wt. % F; and
from about 0.5 to about 15 wt. % Zn;
wherein the fluorided solid oxide comprises ZnSiF 6 .

2. A catalyst composition comprising a metallocene compound, the fluorided solid oxide of claim 1 , and an optional co-catalyst.

3. The composition of claim 2 , wherein a catalyst activity of the catalyst composition is greater than about 6000 grams of polyethylene per gram of the fluorided solid oxide per hour, under slurry polymerization conditions, with a triisobutylaluminum co-catalyst, using isobutane as a diluent, and with a polymerization temperature of 95° C. and a reactor pressure of 400 psig.

4. An olefin polymerization process, the process comprising:
contacting the catalyst composition of claim 2 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

5. The fluorided solid oxide of claim 1 , wherein the fluorided solid oxide comprises from about 2 to about 9 wt. % F, and from about 0.5 to about 5 wt. % Zn.

6. The fluorided solid oxide of claim 1 , wherein the fluorided solid oxide further comprises from about 0.3 to about 1 wt. % B.

7. The fluorided solid oxide of claim 1 , wherein the fluorided solid oxide has:
a total pore volume from about 0.5 to about 2.5 mL/g;
a BET surface area from about 150 to about 700 m 2 /g; and
an average (d50) particle size from about 20 to about 100 microns.

8. The fluorided solid oxide of claim 1 , wherein:
the silica-coated alumina contains from about 25 to about 50 wt. % silica, based on the weight of the silica-coated alumina.

9. The fluorided solid oxide of claim 1 , wherein the fluorided solid oxide comprises from about 3 to about 7 wt. % F, and from about 1 to about 5 wt. % Zn.

10. The fluorided solid oxide of claim 9 , wherein the fluorided solid oxide has:
a total pore volume from about 0.5 to about 2.5 mL/g;
a BET surface area from about 150 to about 700 m 2 /g; and
an average (d50) particle size from about 20 to about 100 microns.

11. The fluorided solid oxide of claim 10 , wherein the silica-coated alumina contains from about 25 to about 50 wt. % silica, based on the weight of the silica-coated alumina.

12. The fluorided solid oxide of claim 1 , wherein the fluorided solid oxide comprises from about 4 to about 10 wt. % ZnSiF 6 .

13. A fluorided solid oxide comprising:
a silica-coated alumina;
from about 0.5 to about 15 wt. % F;
from about 0.5 to about 15 wt. % Zn; and
from about 0.2 to about 1.2 wt. % B.

14. The fluorided solid oxide of claim 13 , wherein the fluorided solid oxide comprises:
from about 2 to about 9 wt. % F; and
from about 0.5 to about 5 wt. % Zn.

15. The fluorided solid oxide of claim 13 , wherein the fluorided solid oxide has:
a total pore volume from about 0.5 to about 2.5 mL/g;
a BET surface area from about 150 to about 700 m 2 /g; and
an average (d50) particle size from about 20 to about 100 microns.

16. The fluorided solid oxide of claim 13 , wherein the fluorided solid oxide comprises Zn(BF 4 ) 2 .

17. The fluorided solid oxide of claim 13 , wherein:
the silica-coated alumina contains from about 25 to about 50 wt. % silica, based on the weight of the silica-coated alumina.

18. A catalyst composition comprising a metallocene compound, the fluorided solid oxide of claim 13 , and an optional co-catalyst.

19. The composition of claim 18 , wherein a catalyst activity of the catalyst composition is greater than about 6000 grams of polyethylene per gram of the fluorided solid oxide per hour, under slurry polymerization conditions, with a triisobutylaluminum co-catalyst, using isobutane as a diluent, and with a polymerization temperature of 95° C. and a reactor pressure of 400 psig.

20. An olefin polymerization process, the process comprising:
contacting the catalyst composition of claim 18 with an olefin monomer and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an olefin polymer.

21. The fluorided solid oxide of claim 13 , wherein the fluorided solid oxide comprises:
from about 3 to about 7 wt. % F;
from about 1 to about 5 wt. % Zn; and
from about 0.3 to about 1 wt. % B.

22. The fluorided solid oxide of claim 21 , wherein the fluorided solid oxide has:
a total pore volume from about 0.5 to about 2.5 mL/g;
a BET surface area from about 150 to about 700 m 2 /g; and
an average (d50) particle size from about 20 to about 100 microns.

23. The fluorided solid oxide of claim 22 , wherein the silica-coated alumina contains from about 25 to about 50 wt. % silica, based on the weight of the silica-coated alumina.

24. The fluorided solid oxide of claim 13 , wherein the fluorided solid oxide comprises from about 4 to about 10 wt. % Zn(BF 4 ) 2 .

25. The fluorided solid oxide of claim 13 , wherein:
the silica-coated alumina contains from about 25 to about 50 wt. % silica, based on the weight of the silica-coated alumina; and
the fluorided solid oxide comprises Zn(BF 4 ) 2 .

26. A fluorided solid oxide comprising:
a silica-coated alumina; and
Zn(BF 4 ) 2 , ZnSiF 6 , or a combination thereof.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Mcdaniel Max P
• Clear Kathy S
• Yang Qing
• Crain Tony R

Classifications

• C08F2410/00

  Features related to the catalyst preparation, the catalyst use or to the deactivation of the catalyst · CPC title

• C01B33/10

  Compounds containing silicon, fluorine, and other elements · CPC title

• C01F7/021

  After-treatment of oxides or hydroxides · CPC title

• C08F10/02

  Ethene · CPC title

• C08F4/65916 Primary

  supported on a carrier, e.g. silica, MgCl2, polymer · CPC title