# US 12,758,948 B2 · Zinc(II) and gallium(III) catalysts for olefin reactions

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

- Number: US 12,758,948 B2
- Document ID: US12758948B2
- Status: Granted
- Kind: B2
- Application number: 18/959,708
- Filed: 2024-11-26
- Published: 2025-03-13
- Granted: 2026-10-13
- Earliest claimed: 2019-12-03
- Assignees: Purdue Research Foundation
- Applicants: Purdue Research Foundation
- Inventors: Jeffrey T. Miller; Nicole Libretto; Christopher Russell; Matthew A. Conrad
- Web page: https://patentgrep.com/patent/US12758948B2

## CPC

- B01J 23/06: of zinc, cadmium or mercury
- B01J 23/08: of gallium, indium or thallium
- B01J 29/005: {Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89}
- B01J 35/613: {10-100 m2/g}
- B01J 35/615: {100-500 m2/g}
- B01J 35/617: {500-1000 m2/g}
- B01J 35/643: {less than 2 nm}
- C07C 2/10: with metal oxides
- B01J 2235/00: Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
- C07C 2523/06: of zinc, cadmium or mercury
- C07C 2523/08: of gallium, indium or thallium
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS

## Abstract

Oligomerization catalyst and method for oligomerization using the catalyst. The catalyst comprises a single Zn(II) or Ga(III) metal ion center directly bonded to a support through a shared oxygen atom, the catalyst having at least one M-O bond which forms an active site for oligomerization. The method includes reacting one or more C2 to C12 olefins with the oligomerization catalyst at a temperature of about 200° C. or higher to provide an oligomer product comprising C4 to C26 olefins.

## Claims

### Claim 1

A method for making light hydrocarbon oligomers, comprising:
contacting one or more C2 to C12 olefins with a supported gallium catalyst; and
oligomerizing the one or more C2 to C12 olefins in the presence of the supported gallium catalyst to form an oligomer product comprising one or more olefins having C4 to C26 carbon atoms,
wherein the supported gallium catalyst comprises a single Ga(III) metal ion center directly bonded to a support through a shared oxygen atom, and the gallium is present in an amount ranging from about 0.1 wt % to about 20 wt %, based on the total weight of the catalyst.

### Claim 2 (depends on 1)

The method of claim 1, wherein the support material is silica having a pore size of about 5 Å to about 500 Å, and a surface area of about 25 m2/g to about 600 m2/g.

### Claim 3 (depends on 1)

The method of claim 1, wherein the one or more C2 to C12 olefins and supported gallium catalyst are reacted at a pressure of about 1 Bar to about 100 Bar.

### Claim 4 (depends on 1)

The method of claim 1, wherein the one or more C2 to C12 olefins are selected from the group consisting of ethylene and propylene.

### Claim 5 (depends on 1)

The method of claim 1, wherein the oligomer product contains C4 to C26 olefins.

### Claim 6 (depends on 1)

The method of claim 1, wherein the oligomer product contains C12 to C20 olefins having a boiling point in the range of 170° C. to 360° C.

### Claim 7 (depends on 1)

The method of claim 1, wherein the support has a surface area of about 30 m2/g to about 600 m2/g.

### Claim 8 (depends on 2)

The method of claim 2, wherein the support has a pore size of about 50 Å to about 500 Å.

### Claim 9 (depends on 1)

The method of claim 1, wherein the support is silica oxide, aluminum oxide or silica-aluminum oxide.

### Claim 10

A method for making light hydrocarbon oligomers, comprising:
contacting one or more C2 to C12 olefins with a supported gallium catalyst; and
oligomerizing the one or more C2 to C12 olefins in the presence of the supported gallium catalyst to provide an oligomer product comprising one or more olefins having C4 to C26 carbon atoms, wherein the supported gallium catalyst comprises:
a support; and
at least one Ga(III) metal ion surrounded by four oxygen atoms, wherein:
the at least one Ga(III) metal ion is directly bonded to the support through a shared oxygen atom to form at least one Ga(III)—O bond,
the gallium metal ion center of the at least one Ga(III)—O bond has a +3 oxidation state at the reaction conditions, and
the supported gallium catalyst does not have Ga—O—Ga bonds.

### Claim 11 (depends on 10)

The method of claim 10, wherein the gallium is present in an amount ranging from about 0.1 wt % to about 20 wt %, based on the total weight of the catalyst.

### Claim 12 (depends on 10)

The method of claim 10, wherein the support has a surface area of about 30 m2/g to about 600 m2/g.

### Claim 13 (depends on 10)

The method of claim 10, wherein the support has a pore size of about 5 Å to about 500 Å.

### Claim 14 (depends on 10)

The method of claim 10, wherein the support is silica oxide, aluminum oxide or silica-aluminum oxide, zeolite, aluminum phosphate molecular sieve, silicon-aluminum phosphate molecular sieve, mesoporous molecular sieve.

### Claim 15 (depends on 10)

The method of claim 10, wherein the oligomer product has a boiling point in the range of 170° C. to 360° C.

### Claim 16

A method for making light hydrocarbon oligomers, comprising:
oligomerizing one or more C2 to C12 olefins in the presence of a catalyst at oligomerization conditions comprising a temperature of about 200° C. to about 500° C. and a pressure of about 1 bar to about 68.9 bar to provide an oligomer product one or more olefins having C4 to C26 carbon atoms, wherein the catalyst comprises a gallium containing compound and a support comprising at least one oxygen atom, wherein:
at least one Ga(III) metal ion is surrounded by four oxygen atoms,
the at least one Ga(III) metal ion is directly bonded to the support through a shared oxygen atom to form at least one Ga(III)—O bond,
the gallium metal ion center of the at least one Ga(III)—O bond has a +3 oxidation state at the reaction conditions, and
the catalyst does not have Ga—O—Ga bonds.

### Claim 17 (depends on 16)

The method of claim 16, wherein the gallium is present in an amount ranging from about 0.1 wt % to about 30 wt %, based on the total weight of the catalyst, the support has a surface area of about 30 m2/g to about 600 m2/g, and the support has a pore size of about 5 Å to about 500 Å.

### Claim 18 (depends on 17)

The method of claim 17, wherein the support is silica oxide, aluminum oxide or silica-aluminum oxide, zeolite, aluminum phosphate molecular sieve, silicon-aluminum phosphate molecular sieve, mesoporous molecular sieve.

### Claim 19 (depends on 16)

The method of claim 16, wherein the oligomer product has a boiling point in the range of 170° C. to 360° C.

### Claim 20 (depends on 16)

The method of claim 16, wherein the one or more olefins are derived from natural gas, natural gas liquids, or mixtures of both.