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

Patent metadata

Field	Value
Publication number	US-11998902-B2
Application number	US-202318351546-A
Country	US
Kind code	B2
Filing date	Jul 13, 2023
Priority date	Sep 27, 2018
Publication date	Jun 4, 2024
Grant date	Jun 4, 2024

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 catalyst composition comprising:
a metallocene compound;
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 ; and

a co-catalyst.

2. The composition 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.

3. The composition of claim 1 , wherein the co-catalyst comprises an aluminoxane compound.

4. The composition of claim 1 , wherein the co-catalyst comprises an organoaluminum compound.

5. The composition of claim 4 , 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 from about 4 to about 10 wt. % ZnSiF 6 .

6. A catalyst composition comprising:
a metallocene compound;
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; and

a co-catalyst.

7. The composition of claim 6 , wherein the co-catalyst comprises an aluminoxane compound.

8. The composition of claim 6 , wherein the co-catalyst comprises an organoaluminum compound.

9. The composition of claim 6 , 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.

10. The composition of claim 6 , 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 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 composition of claim 6 , wherein the metallocene compound is an unbridged metallocene compound.

12. The composition of claim 6 , wherein the metallocene compound is a bridged metallocene compound.

13. The composition of claim 6 , wherein the composition comprises two or more metallocene compounds.

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

a co-catalyst.

15. The composition of claim 14 , wherein the fluorided solid oxide comprises Zn(BF 4 ) 2 .

16. The composition of claim 14 , wherein the fluorided solid oxide comprises from about 4 to about 10 wt. % Zn(BF 4 ) 2 .

17. The composition of claim 14 , wherein the fluorided solid oxide comprises ZnSiF 6 .

18. The composition of claim 14 , wherein the fluorided solid oxide comprises from about 4 to about 10 wt. % ZnSiF 6 .

19. The composition of claim 14 , wherein the co-catalyst comprises an aluminoxane compound and/or an organoaluminum compound.

20. The composition of claim 19 , wherein the metallocene compound is an unbridged metallocene compound.

21. The composition of claim 19 , wherein the metallocene compound is a bridged metallocene compound.

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