Methods for making supported chromium catalysts with increased polymerization activity

Patent metadata

Field	Value
Publication number	US-11673120-B2
Application number	US-202217750524-A
Country	US
Kind code	B2
Filing date	May 23, 2022
Priority date	Sep 24, 2018
Publication date	Jun 13, 2023
Grant date	Jun 13, 2023

Abstract

Methods for making a supported chromium catalyst are disclosed, and can comprise contacting a silica-coated alumina containing at least 30 wt. % silica with a chromium-containing compound in a liquid, drying, and calcining in an oxidizing atmosphere at a peak temperature of at least 650° C. to form the supported chromium catalyst. The supported chromium catalyst can contain from 0.01 to 20 wt. % chromium, and typically can have a pore volume from 0.5 to 2 mL/g and a BET surface area from 275 to 550 m2/g. The supported chromium catalyst subsequently can be used to polymerize olefins to produce, for example, ethylene-based homopolymers and copolymers having high molecular weights and broad molecular weight distributions.

First claim

We claim:

1. An ethylene polymer characterized by:
a Mw in a range from about 300,000 to about 600,000 g/mol;
a relaxation time in a range from about 10 to about 45 sec; and
a CY-a parameter in a range from about 0.08 to about 0.17.

2. An ethylene polymer characterized by:
a Mw in a range from about 300,000 to about 600,000 g/mol;
a ratio of Mw/Mn in a range from about 10 to about 25;
a ratio of Mz/Mw in a range from about 4 to about 10;
a HLMI of less than or equal to about 10 g/10 min;
a relaxation time in a range from about 10 to about 45 sec; and
a CY-a parameter in a range from about 0.08 to about 0.17.

3. The ethylene polymer of claim 1 , wherein the ethylene polymer has a HLMI of less than or equal to about 6 g/10 min.

4. The ethylene polymer of claim 1 , wherein the ethylene polymer has a ratio of Mw/Mn in a range from about 12 to about 22.

5. The ethylene polymer of claim 1 , wherein the ethylene polymer has a ratio of Mz/Mw in a range from about 5 to about 8.

6. An article of manufacture comprising the ethylene polymer of claim 2 .

7. The ethylene polymer of claim 1 , wherein the ethylene polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof.

8. An article of manufacture comprising the ethylene polymer of claim 7 .

9. The ethylene polymer of claim 7 , wherein the ethylene polymer has:
a ratio of Mw/Mn in a range from about 10 to about 25;
a ratio of Mz/Mw in a range from about 4 to about 10; and
a HLMI of less than or equal to about 10 g/10 min.

10. The ethylene polymer of claim 7 , wherein the ethylene polymer has:
a ratio of Mw/Mn in a range from about 12 to about 22;
a ratio of Mz/Mw in a range from about 4.5 to about 9; and
a HLMI of less than or equal to about 6 g/10 min.

11. An article of manufacture comprising the ethylene polymer of claim 10 .

12. The ethylene polymer of claim 7 , wherein:
the Mw is in a range from about 325,000 to about 550,000 g/mol; and
the CY-a parameter is in a range from about 0.09 to about 0.15.

13. The ethylene polymer of claim 12 , wherein the ethylene polymer has:
a ratio of Mw/Mn in a range from about 14 to about 20; and
a ratio of Mz/Mw in a range from about 5 to about 8.

14. The ethylene polymer of claim 13 , wherein the ethylene polymer has a HLMI of less than or equal to about 3 g/10 min.

15. An article of manufacture comprising the ethylene polymer of claim 13 .

16. An ethylene polymer characterized by:
a Mw in a range from about 300,000 to about 800,000 g/mol;
a HLMI of less than or equal to about 6 g/10 min;
a relaxation time in a range from about 5 to about 50 sec; and
a CY-a parameter in a range from about 0.05 to about 0.2.

17. The ethylene polymer of claim 16 , wherein the ethylene polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, an ethylene/1-octene copolymer, or a combination thereof.

18. An article of manufacture comprising the ethylene polymer of claim 17 .

19. The ethylene polymer of claim 17 , wherein the ethylene polymer has:
a ratio of Mw/Mn in a range from about 10 to about 25; and
a ratio of Mz/Mw in a range from about 4 to about 10.

20. The ethylene polymer of claim 19 , wherein:
the relaxation time is in a range from about 10 to about 45 sec; and
the CY-a parameter is in a range from about 0.09 to about 0.15.

21. An article of manufacture comprising the ethylene polymer of claim 20 .

22. The ethylene polymer of claim 17 , wherein the ethylene polymer has:
a ratio of Mw/Mn in a range from about 14 to about 20; and
a ratio of Mz/Mw in a range from about 5 to about 8.

23. An article of manufacture comprising the ethylene polymer of claim 22 .

24. The ethylene polymer of claim 22 , wherein:
the relaxation time is in a range from about 10 to about 45 sec; and
the CY-a parameter is in a range from about 0.09 to about 0.15.

25. The ethylene polymer of claim 17 , wherein the HLMI is less than or equal to about 3 g/10 min.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Mcdaniel Max P
• Clear Kathy S

Classifications

• B01J37/0213

  Preparation of the impregnating solution · CPC title

• B01J37/0045

  Drying a slurry, e.g. spray drying · CPC title

• C08F4/22

  of chromium, molybdenum or tungsten · CPC title

• C08F2500/12

  Melt flow index or melt flow ratio · CPC title

• B01J27/132

  with chromium, molybdenum, tungsten or polonium · CPC title