# US 2017/0283356 A1 · Methods for the Production of alpha, beta-Unsaturated Carboxylic Acids and Salts Thereof

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

- Number: US 2017/0283356 A1
- Document ID: US20170283356A1
- Status: Published application
- Kind: A1
- Application number: 15/627,515
- Filed: 2017-06-20
- Published: 2017-10-05
- Earliest claimed: 2014-10-08
- Assignees: Chevron Phillips Chemical Company LP
- Applicants: Chevron Phillips Chemical Company LP
- Inventors: Mark L. Hlavinka; Max P. McDaniel; Pasquale Iacono
- Web page: https://patentgrep.com/patent/US20170283356A1

## CPC

- C07C 51/15: by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
- B01J 31/128: {Mixtures of organometallic compounds}
- B01J 31/143: {of aluminium}
- B01J 31/2234: {Beta-dicarbonyl ligands, e.g. acetylacetonates}
- B01J 31/2295: {Cyclic compounds, e.g. cyclopentadienyls}
- B01J 31/26: containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J 31/38: of titanium, zirconium or hafnium
- C07C 51/09: from carboxylic acid esters or lactones
- C07C 51/377: by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)}
- B01J 2231/321: Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
- B01J 2231/46: C-H or C-C activation
- B01J 2531/847: Nickel
- C07C: ACYCLIC OR CARBOCYCLIC COMPOUNDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

Processes for producing an α,β-unsaturated carboxylic acid, such as acrylic acid, or a salt thereof, using treated solid oxides are disclosed. The treated solid oxides can be calcined solid oxides, metal-treated solid oxides, or metal-treated chemically-modified solid oxides, illustrative examples of which can include sodium-treated alumina, calcium-treated alumina, zinc-treated alumina, sodium-treated sulfated alumina, sodium-treated fluorided silica-coated alumina, and similar materials.

## Claims

### Claim at position 1

1-20. (canceled)

### Claim 21

A process for producing an α,β-unsaturated carboxylic acid, or a salt thereof, the process comprising:
(I) contacting
(i) a transition metal-ligand complex;
(ii) an olefin;
(iii) carbon dioxide (CO2);
(iv) a diluent; and
(v) a treated solid oxide comprising a metal-treated solid oxide; and
(II) forming the α,β-unsaturated carboxylic acid, or the salt thereof;
wherein the treated solid oxide does not have an organic basic moiety that is covalently bound with a linking moiety to the treated solid oxide; and
wherein the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the transition metal of the transition metal-ligand complex, is at least 50%.

### Claim 22 (depends on 21)

The process of claim 21, wherein:
the α,β-unsaturated carboxylic acid, or the salt thereof, comprises acrylic acid, methacrylic acid, 2-ethylacrylic acid, cinnamic acid, sodium acrylate, magnesium acrylate, sodium methacrylate, or a combination thereof; and
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the transition metal of the transition metal-ligand complex, is from 75% to 10,000%.

### Claim 23 (depends on 21)

The process of claim 21, wherein:
the olefin comprises ethylene; and
the α,β-unsaturated carboxylic acid comprises acrylic acid.

### Claim 24 (depends on 23)

The process of claim 23, wherein the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the transition metal of the transition metal-ligand complex, is from 75% to 10,000%.

### Claim 25 (depends on 21)

The process of claim 21, wherein the transition metal of the transition metal-ligand complex is a Group 8-11 transition metal, and the ligand of the transition metal-ligand complex is a neutral electron donor group or Lewis base.

### Claim 26 (depends on 21)

The process of claim 21, wherein the metal-treated solid oxide comprises an alkali metal-treated solid oxide.

### Claim 27 (depends on 26)

The process of claim 26, wherein the metal-treated solid oxide comprises a sodium-treated solid oxide.

### Claim 28 (depends on 21)

The process of claim 21, wherein the metal-treated solid oxide comprises an alkaline earth metal-treated solid oxide.

### Claim 29 (depends on 21)

The process of claim 21, wherein the metal-treated solid oxide comprises a transition metal-treated solid oxide.

### Claim 30 (depends on 21)

The process of claim 21, wherein the metal-treated solid oxide comprises a solid oxide selected from alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania-zirconia, or any combination thereof.

### Claim 31 (depends on 21)

The process of claim 21, wherein the metal-treated solid oxide comprises metal at an amount in a range from 1 to 30 wt. %, based on the total weight of the metal-treated solid oxide.

### Claim 32 (depends on 21)

The process of claim 21, wherein the metal-treated solid oxide comprises sodium-treated alumina, potassium-treated alumina, cesium-treated alumina, sodium-treated aluminophosphate, magnesium-treated alumina, calcium-treated alumina, barium-treated alumina, zinc-treated alumina, zirconium-treated alumina, sodium-tungsten-treated alumina, or a combination thereof.

### Claim 33

A process for performing a metallalactone elimination reaction, the process comprising:
(1) contacting
(a) a metallalactone;
(b) a diluent; and
(c) a treated solid oxide comprising a metal-treated solid oxide; and
(2) forming an α,β-unsaturated carboxylic acid, or a salt thereof;
wherein the treated solid oxide does not have an organic basic moiety that is covalently bound with a linking moiety to the treated solid oxide; and
wherein the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is at least 5%.

### Claim 34 (depends on 33)

The process of claim 33, wherein in step (1), the metallalactone and the diluent contact a fixed bed of the treated solid oxide.

### Claim 35 (depends on 33)

The process of claim 33, wherein:
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is from 50% to 10,000%;
the metallalactone is a nickelalactone; and
the α,β-unsaturated carboxylic acid comprises acrylic acid.

### Claim 36 (depends on 33)

The process of claim 33, wherein prior to step (1), the treated solid oxide is produced by a process comprising contacting a solid oxide and a metal-containing compound and calcining.

### Claim 37 (depends on 33)

The process of claim 33, wherein the metal-treated solid oxide comprises a solid oxide selected from alumina, titania, zirconia, magnesia, boria, calcia, zinc oxide, silica-alumina, silica-coated alumina, silica-titania, silica-zirconia, silica-magnesia, alumina-titania, alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminum phosphate, aluminophosphate, aluminophosphate-silica, magnesium aluminate, titania-zirconia, or any combination thereof.

### Claim 38 (depends on 33)

The process of claim 33, wherein the metal-treated solid oxide comprises an alkali metal-treated solid oxide.

### Claim 39 (depends on 38)

The process of claim 38, wherein the metal-treated solid oxide comprises a sodium-treated solid oxide.

### Claim 40 (depends on 33)

The process of claim 33, wherein the metal-treated solid oxide comprises an alkaline earth metal-treated solid oxide.

### Claim 41 (depends on 33)

The process of claim 33, wherein the metal-treated solid oxide comprises a transition metal-treated solid oxide.

### Claim 42 (depends on 33)

The process of claim 33, wherein the metal-treated solid oxide comprises sodium-treated alumina, potassium-treated alumina, cesium-treated alumina, sodium-treated aluminophosphate, magnesium-treated alumina, calcium-treated alumina, barium-treated alumina, zinc-treated alumina, zirconium-treated alumina, sodium-tungsten-treated alumina, or a combination thereof.