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

Patent metadata

Field	Value
Publication number	US-11325997-B1
Application number	US-202117543829-A
Country	US
Kind code	B1
Filing date	Dec 7, 2021
Priority date	Dec 8, 2020
Publication date	May 10, 2022
Grant date	May 10, 2022

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/cm3, 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 ft2 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 50 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. The polymer of claim 1 , wherein the ethylene polymer has a film gel count of less than or equal to 15 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.

3. The polymer of claim 1 , wherein the solid oxide is silica and/or silica-titania.

4. The polymer of claim 1 , wherein the polymer comprises an ethylene homopolymer and/or an ethylene/α-olefin copolymer.

5. The polymer of claim 1 , wherein the polymer contains, independently, less than 0.1 ppm of Mg, V, Ti, Zr, or Hf.

6. An article comprising the polymer of claim 1 .

7. The article of claim 6 , wherein the article has a gel count of less than or equal to 40 catalyst particles of greater than 100 μm per 5 grams of the article.

8. 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=1.20*(5,580,000x 1.61 ), and x is the weight fraction of ash in the ethylene polymer, and/or
(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=−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.

9. The polymer of claim 8 , wherein the solid oxide is silica and/or silica-titania.

10. The polymer of claim 8 , wherein the polymer comprises an ethylene homopolymer, an ethylene/1-butene copolymer, an ethylene/1-hexene copolymer, and/or an ethylene/1-octene copolymer.

11. The polymer of claim 8 , wherein the polymer contains, independently, less than 0.1 ppm of Mg, V, Ti, Zr, or Hf.

12. The polymer of claim 8 , wherein the film gel count is 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, and Y1=0.80*(5,580,000x 1.61 ).

13. The polymer of claim 8 , wherein the film gel count is 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, and Y=0.50*(−1,950,000x 3 +324,000x 2 −11,300x+121).

14. An article comprising the polymer of claim 8 .

15. The article of claim 14 , wherein the article has a gel count of less than or equal to 40 catalyst particles of greater than 100 μm per 5 grams of the article.

16. An ethylene polymer composition characterized by:
(A) less than or equal to 1 wt. % of the composition on a 10 mesh sieve, less than or equal to 6 wt. % of the composition on a 20 mesh sieve, and less than or equal to 4 wt. % of the composition thru a 200 mesh sieve; or
(B) less than or equal to 5 wt. % of the composition with a particle size of less than 100 μm, less than or equal to 5 wt. % of the composition with a particle size of greater than 1000 μm, and a particle size span ((d90−d10)/d50) from 0.6 to 1.5; or
both; wherein:
a range of density across the composition is less than 0.025 g/cm 3 ; and
a range of number of short chain branches per 1000 carbon atoms across the composition divided by the mean of the composition is less than 1.

17. The composition of claim 16 , wherein:
less than or equal to 1 wt. % of the composition is on the 10 mesh sieve;
less than or equal to 6 wt. % of the composition is on the 20 mesh sieve; and
less than or equal to 4 wt. % of the composition passes thru the 200 mesh sieve.

18. The composition of claim 17 , wherein:
less than or equal to 0.5 wt. % of the composition is on the 10 mesh sieve;
less than or equal to 4 wt. % of the composition is on the 20 mesh sieve; and
less than or equal to 3 wt. % of the composition passes thru the 200 mesh sieve.

19. The composition of claim 17 , wherein:
less than or equal to 0.1 wt. % of the composition is on the 10 mesh sieve;
less than or equal to 2.5 wt. % of the composition is on the 20 mesh sieve; and
less than or equal to 1 wt. % of the composition passes thru the 200 mesh sieve.

20. The composition of claim 16 , wherein:
less than or equal to 5 wt. % of the composition has the particle size of less than 100 μm;
less than or equal to 5 wt. % of the composition has the particle size of greater than 1000 μm; and
the particle size span ((d90−d10)/d50) is from 0.6 to 1.5.

21. The composition of claim 20 , wherein:
less than or equal to 4 wt. % of the composition has the particle size of less than 100 μm;
less than or equal to 4 wt. % of the composition has the particle size of greater than 1000 μm; and
the particle size span ((d90−d10)/d50) is from 0.7 to 1.5.

22. The composition of claim 20 , wherein:
less than or equal to 2 wt. % of the composition has the particle size of less than 100 μm;
less than or equal to 2 wt. % of the composition has the particle size of greater than 1000 μm; and
the particle size span ((d90−d10)/d50) is from 0.7 to 1.4.

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

• C08F2410/06

  Catalyst characterized by its size · CPC title

• C08K3/08

  Metals · CPC title

• C08F110/02 Primary

  Ethene · CPC title

• C08K3/36

  Silica · CPC title

• C08F210/16

  Copolymers of ethene with alpha-alkenes, e.g. EP rubbers · CPC title