# US 11,999,807 B2 · Particle size control of supported chromium catalysts in loop slurry polymerization reactors

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 11,999,807 B2
- Document ID: US11999807B2
- Status: Granted
- Kind: B2
- Application number: 18/463,380
- Filed: 2023-09-08
- Published: 2023-12-28
- Granted: 2024-06-04
- Earliest claimed: 2020-12-08
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Max P. McDaniel; Carlton E. Ash; Kathy S. Clear; Eric D. Schwerdtfeger; Carlos A. Cruz; Jeremy M. Praetorius
- Web page: https://patentgrep.com/patent/US11999807B2

## CPC

- C08F 10/02: Ethene
- C08F 110/02: Ethene
- B01J 8/08: with moving particles (with fluidised particles B01J8/18)
- B01J 19/2455: {provoking a loop type movement of the reactants (tubular loop-type reactors B01J19/2435; loop reactors having moving elements inside B01J19/1868)}
- C08F 210/16: Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
- C08K 3/08: Metals
- C08K 3/36: Silica
- C08F 2410/06: Catalyst characterized by its size
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)

## 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.

## Claims

### 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.

### Claim 2 (depends on 1)

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.

### Claim 3 (depends on 2)

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

### Claim 4 (depends on 3)

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

### Claim 5 (depends on 1)

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.

### Claim 6 (depends on 5)

The process of claim 5, wherein the supported chromium catalyst is contacted with ethylene and an olefin comonomer comprising a C3-C10 alpha-olefin.

### Claim 7 (depends on 5)

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.

### Claim 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.

### Claim 9 (depends on 8)

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.

### Claim 10 (depends on 8)

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.

### Claim 11 (depends on 8)

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

### Claim 12 (depends on 8)

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

### Claim 13 (depends on 8)

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

### Claim 14 (depends on 8)

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

### Claim 15 (depends on 8)

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

### Claim 16 (depends on 8)

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 m2/g.

### Claim 17 (depends on 8)

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.

### Claim 18 (depends on 8)

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.

### Claim 19 (depends on 18)

The process of claim 18, wherein the supported chromium catalyst is contacted with ethylene and an olefin comonomer comprising a C3-C10 alpha-olefin.

### Claim 20 (depends on 18)

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.

### Claim 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.

### Claim 22 (depends on 21)

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

### Claim 23 (depends on 21)

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.

### Claim 24 (depends on 21)

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

### Claim 25 (depends on 21)

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

### Claim 26 (depends on 21)

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.

### Claim 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.

### Claim 28 (depends on 27)

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

### Claim 29 (depends on 27)

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.

### Claim 30 (depends on 27)

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

### Claim 31 (depends on 27)

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

### Claim 32 (depends on 27)

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.