Particle size control of supported chromium catalysts in loop slurry polymerization reactors

Patent metadata

Field	Value
Publication number	US-11999807-B2
Application number	US-202318463380-A
Country	US
Kind code	B2
Filing date	Sep 8, 2023
Priority date	Dec 8, 2020
Publication date	Jun 4, 2024
Grant date	Jun 4, 2024

Abstract

Supported chromium catalysts containing a solid oxide and 0.1 to 15 wt. % chromium, in which the solid oxide or the supported chromium catalyst has a particle size span from 0.5 to 1.4, less than 3 wt. % has a particle size greater than 100 μm, and less than 10 wt. % has a particle size less than 10 μm, can be contacted with an olefin monomer in a loop slurry reactor to produce an olefin polymer. Representative ethylene-based polymers produced using the chromium catalysts have a HLMI of 4 to 70 g/10 min, a density from 0.93 to 0.96 g/cm 3 , from 150 to 680 ppm solid oxide (such as silica), from 1.5 to 6.8 ppm chromium, and a film gel count of less than 15 catalyst particle gels per ft 2 of 25 micron thick film and/or a gel count of less than or equal to 50 catalyst particles of greater than 100 μm per five grams of the ethylene polymer.

First claim

We claim:

1. A supported chromium catalyst comprising a solid oxide and from 0.1 to 15 wt. % chromium, wherein the supported chromium catalyst is characterized by:
(A1) an amount of the supported chromium catalyst with a particle size greater than 100 μm of less than or equal to 3 wt. %;
(A2) a particle size span ((d90-d10)/d50) in a range from 0.5 to 1.4; and
(A3) a d50 average particle size from 15 to 60 μm;
wherein the catalyst contains, independently, less than 0.1 ppm of Mg, V, Ti, Zr, and Hf.

2. The catalyst of claim 1 , wherein:
the solid oxide is silica, silica-alumina, silica-coated alumina, silica-boria, aluminophosphate-silica, or any combination thereof; and
the catalyst comprises from 0.5 to 2 wt. % chromium.

3. The catalyst of claim 2 , wherein the catalyst is further characterized by a d10 particle size in a range from 11 to 22 μm.

4. The catalyst of claim 3 , wherein the solid oxide is silica.

5. A polymerization process comprising contacting the supported chromium catalyst of claim 1 and an optional co-catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system comprising a loop slurry reactor under polymerization conditions to produce an olefin polymer.

6. The process of claim 5 , wherein the supported chromium catalyst is contacted with ethylene and an olefin comonomer comprising a C 3 -C 10 alpha-olefin.

7. The process of claim 5 , wherein the olefin polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.

8. A supported chromium catalyst comprising a solid oxide and from 0.1 to 15 wt. % chromium, wherein the supported chromium catalyst is characterized by:
(B1) an amount of the supported chromium catalyst with a particle size greater than 100 μm of less than or equal to 0.5 wt. %;
(B2) an amount of the supported chromium catalyst with a particle size less than 10 μm of less than or equal to 7 wt. %; and
(B3) a d50 average particle size from 15 to 60 μm; and
wherein the supported chromium catalyst contains, independently, less than 0.1 ppm of Mg, V, Ti, Zr, and Hf.

9. The catalyst of claim 8 , wherein:
the solid oxide is silica, silica-alumina, silica-coated alumina, silica-titania, silica-titania- magnesia, silica-zirconia, silica-magnesia, silica-boria, aluminophosphate-silica, or any combination thereof; and
the catalyst comprises from 0.5 to 2 wt. % chromium.

10. The catalyst of claim 8 , wherein less than or equal to 3 wt. % of the supported chromium catalyst has a particle size less than 10 μm.

11. The catalyst of claim 8 , wherein the catalyst is further characterized by a d10 particle size in a range from 11 to 22 μm.

12. The catalyst of claim 8 , wherein the catalyst is further characterized by a particle size span from 0.6 to 1.35.

13. The catalyst of claim 8 , wherein the catalyst contains less than or equal to 3 wt. % carbon.

14. The catalyst of claim 8 , wherein at least 80 wt. % of the chromium is present in an oxidation state of three or less.

15. The catalyst of claim 8 , wherein at least 60 wt. % of the chromium is present in an oxidation state of six (Cr+6).

16. The catalyst of claim 8 , wherein the catalyst is further characterized by:
a pore volume from 1 to 3 mL/g; and
a BET surface area from 250 to 550 m 2 /g.

17. The catalyst of claim 8 , wherein:
the d50 average particle size is from 17 to 32 μm; and
the catalyst is further characterized by a d95 particle size from 30 to 55 μm.

18. A polymerization process comprising contacting the supported chromium catalyst of claim 8 and an optional co-catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system comprising a loop slurry reactor under polymerization conditions to produce an olefin polymer.

19. The process of claim 18 , wherein the supported chromium catalyst is contacted with ethylene and an olefin comonomer comprising a C 3 -C 10 alpha-olefin.

20. The process of claim 18 , wherein the olefin polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.

21. A supported chromium catalyst comprising a solid oxide and from 0.1 to 15 wt. % chromium, wherein the supported chromium catalyst is characterized by:
(B1) an amount of the supported chromium catalyst with a particle size greater than 100 μm of less than or equal to 0.5 wt. %;
(B2) an amount of the supported chromium catalyst with a particle size less than 10 μm of less than or equal to 7 wt. %;
(B3) a d50 average particle size from 15 to 60 μm; and
(B4) a particle size span in a range from 0.6 to 1.35.

22. The catalyst of claim 21 , wherein the solid oxide is silica.

23. The catalyst of claim 21 , wherein less than or equal to 3 wt. % of the supported chromium catalyst has a particle size less than 10 μm.

24. The catalyst of claim 21 , wherein the catalyst comprises from 0.5 to 2 wt. % chromium.

25. The catalyst of claim 21 , wherein at least 80 wt. % of the chromium is present in an oxidation state of three or less.

26. A polymerization process comprising contacting the supported chromium catalyst of claim 21 and an optional co-catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system comprising a loop slurry reactor under polymerization conditions to produce an olefin polymer.

27. A supported chromium catalyst comprising a solid oxide and from 0.1 to 15 wt. % chromium, wherein the supported chromium catalyst is characterized by:
(B1) an amount of the supported chromium catalyst with a particle size greater than 100 μm of less than or equal to 0.5 wt. %;
(B2) an amount of the supported chromium catalyst with a particle size less than 10 μm of less than or equal to 7 wt. %; and
(B3) a d50 average particle size from 15 to 60 μm; and
wherein the supported chromium catalyst contains less than or equal to 3 wt. % carbon.

28. The catalyst of claim 27 , wherein the solid oxide is silica.

29. The catalyst of claim 27 , wherein less than or equal to 3 wt. % of the supported chromium catalyst has a particle size less than 10 μm.

30. The catalyst of claim 27 , wherein the catalyst comprises from 0.5 to 2 wt. % chromium.

31. The catalyst of claim 27 , wherein at least 80 wt. % of the chromium is present in an oxidation state of three or less.

32. A polymerization process comprising contacting the supported chromium catalyst of claim 27 and an optional co-catalyst with an olefin monomer and an optional olefin comonomer in a polymerization reactor system comprising a loop slurry reactor under polymerization conditions to produce an olefin polymer.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Mcdaniel Max P
• Ash Carlton E
• Clear Kathy S
• Schwerdtfeger Eric D
• Cruz Carlos A
• Praetorius Jeremy M

Classifications

• C08F10/02 Primary

  Ethene · CPC title

• B01J8/08

  with moving particles (with fluidised particles B01J8/18) · CPC title

• B01J19/2455

  provoking a loop type movement of the reactants (tubular loop-type reactors B01J19/2435; loop reactors having moving elements inside B01J19/1868) · CPC title

• C08K3/08

  Metals · CPC title

• C08K3/36

  Silica · CPC title