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

Patent metadata

Field	Value
Publication number	US-11814449-B2
Application number	US-202218046212-A
Country	US
Kind code	B2
Filing date	Oct 13, 2022
Priority date	Dec 8, 2020
Publication date	Nov 14, 2023
Grant date	Nov 14, 2023

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. An ethylene polymer having:
a high load melt index (HLMI) in a range from 4 to 70 g/10 min;
a density in a range from 0.93 to 0.96 g/cm 3 ; and
a gel count of less than or equal to 30 catalyst particles of greater than 100 μm per 5 grams of the ethylene polymer; and
wherein the ethylene polymer contains from 150 to 680 ppm solid oxide and from 1.5 to 6.8 ppm chromium.

2. An article comprising the polymer of claim 1 .

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

4. The polymer of claim 3 , wherein:
the ethylene polymer contains from 200 to 500 ppm solid oxide and from 2 to 5 ppm chromium; and
the solid oxide is silica and/or silica-titania.

5. The polymer of claim 4 , wherein the gel count is less than or equal to 10 catalyst particles of greater than 100 μm per 5 grams of the ethylene polymer.

6. The polymer of claim 4 , wherein the gel count is less than or equal to 2 catalyst particles of greater than 100 μm per 5 grams of the ethylene polymer.

7. An article comprising the polymer of claim 4 .

8. An article comprising the polymer of claim 4 , wherein the article has a gel count of less than or equal to 20 catalyst particles of greater than 100 μm per 5 grams of the article.

9. The polymer of claim 3 , wherein the ethylene polymer contains:
from 200 to 600 ppm solid oxide; and
from 2 to 6 ppm chromium.

10. The polymer of claim 9 , wherein the solid oxide is silica and/or silica-titania.

11. The polymer of claim 3 , wherein the polymer contains, independently, less than 0.1 ppm of Mg, V, Ti, Zr, or Hf.

12. The polymer of claim 3 , wherein the ethylene polymer has:
a Mw in a range from 100,000 to 275,000 g/mol; and
a CY-a parameter in a range from 0.10 to 0.23.

13. An article comprising the polymer of claim 12 , wherein the article has a gel count of less than or equal to 20 catalyst particles of greater than 100 μm per 5 grams of the article.

14. The polymer of claim 1 , wherein the gel count is less than or equal to 10 catalyst particles of greater than 100 μm per 5 grams of the ethylene polymer.

15. The polymer of claim 14 , wherein the ethylene polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.

16. The polymer of claim 15 , wherein:
the HLMI is in a range from 6 to 36 g/10 min; and
the density is in a range from 0.934 to 0.956 g/cm 3 .

17. The polymer of claim 16 , wherein the gel count is less than or equal to 2 catalyst particles of greater than 100 μm per 5 grams of the ethylene polymer.

18. The polymer of claim 17 , wherein the ethylene polymer contains:
from 200 to 500 ppm solid oxide; and
from 2 to 5 ppm chromium.

19. An article comprising the polymer of claim 18 .

20. An ethylene polymer having:
a high load melt index (HLMI) in a range from 4 to 70 g/10 min;
a density in a range from 0.93 to 0.96 g/cm 3 ; and
a film gel count of less than or equal to 10 catalyst particle gels per ft 2 of 25 micron thick film, wherein film gels are of a size greater than 200 μm caused by the catalyst particles;
wherein the ethylene polymer contains from 150 to 680 ppm solid oxide and from 1.5 to 6.8 ppm chromium.

21. An article comprising the polymer of claim 20 .

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

23. The polymer of claim 22 , wherein:
the film gel count is less than or equal to 5 catalyst particle gels per ft 2 of 25 micron thick film; and
the ethylene polymer contains from 200 to 600 ppm solid oxide and from 2 to 6 ppm chromium.

24. The polymer of claim 23 , wherein:
the solid oxide is silica and/or silica-titania; and
the ethylene polymer has a Mw in a range from 100,000 to 275,000 g/mol.

25. The polymer of claim 23 , wherein:
the ethylene polymer contains from 200 to 500 ppm solid oxide and from 2 to 5 ppm chromium; and
the solid oxide is silica and/or silica-titania.

26. An article comprising the polymer of claim 25 .

27. An ethylene polymer having:
a high load melt index (HLMI) in a range from 4 to 70 g/10 min;
a density in a range from 0.93 to 0.96 g/cm 3 ; and
(A) a film gel count of less than Y1 catalyst particle gels per ft 2 of 25 micron thick film, wherein film gels are of a size greater than 200 μm caused by catalyst particles, wherein Y1=0.80*(5,580,000× 1.61 ), and x is the weight fraction of ash in the ethylene polymer, and
(B) a film gel count of less than Y catalyst particle gels per ft 2 of 25 micron thick film, wherein film gels are of a size greater than 200 μm caused by catalyst particles, wherein Y=0.80*(−1,950,000x 3 +324,000x 2 −11,300x+121), and x is the weight percentage of ash in the ethylene polymer; and
wherein the ethylene polymer contains from 150 to 680 ppm solid oxide and from 1.5 to 6.8 ppm chromium.

28. The polymer of claim 27 , wherein:
the ethylene polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer;
the HLMI is in a range from 6 to 36 g/10 min; and
the density is in a range from 0.934 to 0.956 g/cm 3 .

29. The polymer of claim 28 , wherein the ethylene polymer contains:
from 200 to 600 ppm solid oxide; and
from 2 to 6 ppm chromium.

30. The polymer of claim 29 , wherein the ethylene polymer has:
a Mw in a range from 100,000 to 275,000 g/mol; and
a CY-a parameter in a range from 0.10 to 0.23.

31. An article comprising the polymer of claim 30 .

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
• Yu Youlu

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