# US 11,998,902 B2 · Processes for producing fluorided solid oxides and uses thereof in metallocene-based catalyst systems

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- Number: US 11,998,902 B2
- Document ID: US11998902B2
- Status: Granted
- Kind: B2
- Application number: 18/351,546
- Filed: 2023-07-13
- Published: 2023-11-16
- Granted: 2024-06-04
- Earliest claimed: 2018-09-27
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Max P. McDaniel; Kathy S. Clear; Qing Yang; Tony R. Crain
- Web page: https://patentgrep.com/patent/US11998902B2

## CPC

- B01J 37/0209: {involving a reaction between the support and a fluid}
- C08F 110/02: Ethene
- B01J 23/60: with zinc, cadmium or mercury
- B01J 27/12: Fluorides
- B01J 27/138: with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
- B01J 31/122: {Metal aryl or alkyl compounds}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0213: {Preparation of the impregnating solution}
- C08F 4/65912: {in combination with an organoaluminium compound}
- C08F 2410/06: Catalyst characterized by its size
- C08F 2410/07: Catalyst support treated by an anion, e.g. Cl-, F-, SO42-
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Disclosed herein are methods for preparing fluorided solid oxides by contacting an acidic fluorine-containing compound with an inorganic base to form an aqueous mixture having a pH of at least 4, followed by contacting a solid oxide with the aqueous mixture to produce the fluorided solid oxide. Also disclosed are methods for preparing fluorided solid oxides by contacting an acidic fluorine-containing compound with a solid oxide to produce a mixture, followed by contacting the mixture with a inorganic base to produce the fluorided solid oxide at a pH of at least about 4. The fluorided solid oxide can be used as an activator component in a catalyst system for the polymerization of olefins.

## Claims

### Claim 1

A catalyst composition comprising:
a metallocene compound;
a fluorided solid oxide comprising:
a silica-coated alumina,
from about 0.5 to about 15 wt. % F, and
from about 0.5 to about 15 wt. % Zn,
wherein the fluorided solid oxide comprises ZnSiF6; and
a co-catalyst.

### Claim 2 (depends on 1)

The composition of claim 1, wherein the fluorided solid oxide comprises from about 2 to about 9 wt. % F and from about 0.5 to about 5 wt. % Zn.

### Claim 3 (depends on 1)

The composition of claim 1, wherein the co-catalyst comprises an aluminoxane compound.

### Claim 4 (depends on 1)

The composition of claim 1, wherein the co-catalyst comprises an organoaluminum compound.

### Claim 5 (depends on 4)

The composition of claim 4, wherein:
the silica-coated alumina contains from about 25 to about 50 wt. % silica, based on the weight of the silica-coated alumina; and
the fluorided solid oxide comprises from about 4 to about 10 wt. % ZnSiF6.

### Claim 6

A catalyst composition comprising:
a metallocene compound;
a fluorided solid oxide comprising:
a silica-coated alumina,
from about 0.5 to about 15 wt. % F,
from about 0.5 to about 15 wt. % Zn, and
from about 0.2 to about 1.2 wt. % B; and
a co-catalyst.

### Claim 7 (depends on 6)

The composition of claim 6, wherein the co-catalyst comprises an aluminoxane compound.

### Claim 8 (depends on 6)

The composition of claim 6, wherein the co-catalyst comprises an organoaluminum compound.

### Claim 9 (depends on 6)

The composition of claim 6, wherein the fluorided solid oxide comprises:
from about 3 to about 7 wt. % F;
from about 1 to about 5 wt. % Zn; and
from about 0.3 to about 1 wt. % B.

### Claim 10 (depends on 6)

The composition of claim 6, wherein:
the silica-coated alumina contains from about 25 to about 50 wt. % silica, based on the weight of the silica-coated alumina; and
the fluorided solid oxide has:
a total pore volume from about 0.5 to about 2.5 mL/g;
a BET surface area from about 150 to about 700 m2/g; and
an average (d50) particle size from about 20 to about 100 microns.

### Claim 11 (depends on 6)

The composition of claim 6, wherein the metallocene compound is an unbridged metallocene compound.

### Claim 12 (depends on 6)

The composition of claim 6, wherein the metallocene compound is a bridged metallocene compound.

### Claim 13 (depends on 6)

The composition of claim 6, wherein the composition comprises two or more metallocene compounds.

### Claim 14

A catalyst composition comprising:
a metallocene compound;
a fluorided solid oxide comprising:
a silica-coated alumina, and
Zn(BF4)2, ZnSiF6, or a combination thereof; and
a co-catalyst.

### Claim 15 (depends on 14)

The composition of claim 14, wherein the fluorided solid oxide comprises Zn(BF4)2.

### Claim 16 (depends on 14)

The composition of claim 14, wherein the fluorided solid oxide comprises from about 4 to about 10 wt. % Zn(BF4)2.

### Claim 17 (depends on 14)

The composition of claim 14, wherein the fluorided solid oxide comprises ZnSiF6.

### Claim 18 (depends on 14)

The composition of claim 14, wherein the fluorided solid oxide comprises from about 4 to about 10 wt. % ZnSiF6.

### Claim 19 (depends on 14)

The composition of claim 14, wherein the co-catalyst comprises an aluminoxane compound and/or an organoaluminum compound.

### Claim 20 (depends on 19)

The composition of claim 19, wherein the metallocene compound is an unbridged metallocene compound.

### Claim 21 (depends on 19)

The composition of claim 19, wherein the metallocene compound is a bridged metallocene compound.