# US 11,298,683 B2 · Aqueous methods for titanating a chromium/silica catalyst

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- Number: US 11,298,683 B2
- Document ID: US11298683B2
- Status: Granted
- Kind: B2
- Application number: 16/293,726
- Filed: 2019-03-06
- Published: 2019-07-04
- Granted: 2022-04-12
- Earliest claimed: 2017-11-17
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Max P. McDaniel; Kathy S. Clear; Eric D. Schwerdtfeger; Jeremy M. Praetorius
- Web page: https://patentgrep.com/patent/US11298683B2

## CPC

- B01J 23/26: Chromium
- B01J 21/063: {Titanium; Oxides or hydroxides thereof}
- B01J 21/08: Silica
- B01J 35/40: characterised by dimensions, e.g. grain size (in a colloidal state B01J35/23; crystallite size B01J35/77)
- B01J 35/615: {100-500 m2/g}
- B01J 35/617: {500-1000 m2/g}
- B01J 35/635: {0.5-1.0 ml/g}
- B01J 35/638: {more than 1.0 ml/g}
- B01J 37/0203: {the impregnation liquid containing organic compounds}
- B01J 37/0207: {Pretreatment of the support}
- B01J 37/0209: {involving a reaction between the support and a fluid}
- B01J 37/035: {Precipitation on carriers}
- B01J 37/04: Mixing {(B01J37/0009, B01J37/0018 take precedence)}
- B01J 37/14: with gases containing free oxygen
- C08F 4/18: Oxides
- C08F 4/24: Oxides
- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 10/02: Ethene
- B01J 31/0212: {Alkoxylates}
- B01J 31/0274: {containing silicon (ligands in coordination complexes B01J31/1608)}
- B01J 31/0275: {also containing elements or functional groups covered by B01J31/0201 - B01J31/0269}
- B01J 31/34: of chromium, molybdenum or tungsten
- B01J 31/38: of titanium, zirconium or hafnium
- B01J 2231/12: Olefin polymerisation or copolymerisation
- 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

Methods for synthesizing a water-soluble titanium-silicon complex are disclosed herein. The titanium-silicon complex can be utilized to produce titanated solid oxide supports and titanated chromium supported catalysts. The titanated chromium supported catalysts subsequently can be used to polymerize olefins to produce, for example, ethylene based homopolymer and copolymers.

## Claims

### Claim 1

A titanated chromium supported catalyst comprising:
a solid support; and
from about 0.5 to about 15 wt. % chromium, from about 1 to about 10 wt. % titanium on a surface of the solid support, and less than or equal to about 1 wt. % carbon, based on the total weight of the catalyst;
wherein at least about 90 wt. % of the chromium is present in an oxidation state of three or less; and
wherein the titanated chromium supported catalyst is characterized by:
a total pore volume from about 0.5 to about 5 mL/g;
a BET surface area from about 200 to about 700 m2/g; and
a d50 average particle size from about 10 to about 500 microns.

### Claim 2 (depends on 1)

The titanated chromium supported catalyst of claim 1, wherein:
the solid support is silica; and
the catalyst contains from about 0.5 to about 2.5 wt. % chromium, from about 1 to about 6 wt. % titanium on the surface of the silica, and less than or equal to about 0.5 wt. % carbon, based on the total weight of the catalyst.

### Claim 3

A titanated chromium supported catalyst comprising:
a solid support; and
from about 0.1 to about 15 wt. % chromium, from about 1 to about 10 wt. % titanium on a surface of the solid support, and less than or equal to about 1 wt. % carbon, based on the total weight of the catalyst;
wherein at least about 80 wt. % of the chromium is present in an oxidation state of three or less.

### Claim 4 (depends on 3)

The titanated chromium supported catalyst of claim 3, wherein the catalyst contains from about 0.5 to about 5 wt. % chromium, from about 1 to about 6 wt. % titanium on the surface of the solid support, and less than or equal to about 0.5 wt. % carbon.

### Claim 5 (depends on 3)

The titanated chromium supported catalyst of claim 3, wherein at least about 90 wt. % of the chromium is present in an oxidation state of three or less.

### Claim 6 (depends on 3)

The titanated chromium supported catalyst of claim 3, wherein the catalyst is a titanated chromium/silica catalyst.

### Claim 7 (depends on 3)

The titanated chromium supported catalyst of claim 3, wherein the catalyst is characterized by:
a total pore volume from about 0.5 to about 5 mL/g;
a BET surface area from about 200 to about 700 m2/g; and
a d50 average particle size from about 10 to about 500 microns.

### Claim 8 (depends on 3)

The titanated chromium supported catalyst of claim 3, wherein the solid support is silica, silica-alumina, silica-coated alumina, silica-titania, silica-titania-magnesia, silica-zirconia, silica-magnesia, silica-boria, aluminophosphate-silica, or any combination thereof.

### Claim 9 (depends on 8)

The titanated chromium supported catalyst of claim 8, wherein at least about 90 wt. % of the chromium is present in an oxidation state of three or less.

### Claim 10 (depends on 8)

The titanated chromium supported catalyst of claim 8, wherein the catalyst is characterized by:
a total pore volume from about 1 to about 4 mL/g;
a BET surface area from about 200 to about 550 m2/g; and
a d50 average particle size from about 10 to about 500 microns.

### Claim 11 (depends on 10)

The titanated chromium supported catalyst of claim 10, wherein the catalyst contains from about 0.5 to about 5 wt. % chromium, and from about 1 to about 6 wt. % titanium on the surface of the solid support.

### Claim 12 (depends on 3)

The titanated chromium supported catalyst of claim 3, wherein the catalyst contains from about 87 to about 98 wt. % of the solid support.

### Claim 13 (depends on 12)

The titanated chromium supported catalyst of claim 12, wherein the solid support is silica.

### Claim 14

A titanated chromium/silica catalyst comprising:
silica; and
from about 0.1 to about 15 wt. % chromium, from about 1 to about 10 wt. % titanium on a surface of the silica, and less than or equal to about 1 wt. % carbon, based on the total weight of the catalyst;
wherein at least about 75 wt. % of the chromium is present in an oxidation state of three or less.

### Claim 15 (depends on 14)

The titanated chromium/silica catalyst of claim 14, wherein the catalyst contains from about 92 to about 98 wt. % silica.

### Claim 16 (depends on 14)

The titanated chromium/silica catalyst of claim 14, wherein the catalyst contains from about 0.5 to about 5 wt. % chromium, from about 1 to about 6 wt. % titanium on the surface of the silica, and less than or equal to about 0.5 wt. % carbon.

### Claim 17 (depends on 16)

The titanated chromium/silica catalyst of claim 16, wherein the catalyst contains from about 87 to about 98 wt. % silica, and at least about 90 wt. % of the chromium is present in an oxidation state of three or less.

### Claim 18 (depends on 14)

The titanated chromium/silica catalyst of claim 14, wherein the catalyst is characterized by:
a total pore volume from about 0.5 to about 5 mL/g;
a BET surface area from about 200 to about 700 m2/g; and
a d50 average particle size from about 10 to about 500 microns.

### Claim 19 (depends on 14)

The titanated chromium/silica catalyst of claim 14, wherein the catalyst contains from about 0.5 to about 5 wt. % chromium.

### Claim 20 (depends on 19)

The titanated chromium/silica catalyst of claim 19, wherein the catalyst contains less than or equal to about 0.5 wt. % carbon, and at least about 95 wt. % of the chromium is present in an oxidation state of three or less.