Methods for the production of α,β-unsaturated carboxylic acids and salts thereof

Patent metadata

Field	Value
Publication number	US-9896405-B2
Application number	US-201715627515-A
Country	US
Kind code	B2
Filing date	Jun 20, 2017
Priority date	Oct 8, 2014
Publication date	Feb 20, 2018
Grant date	Feb 20, 2018

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.

First claim

We claim:

1. 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 (CO 2 );
(iv) a diluent; and
(v) a treated solid oxide comprising an alkali metal-treated solid oxide, an alkaline earth metal-treated solid oxide, or a combination thereof; 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%.

2. The process of claim 1 , 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%.

3. The process of claim 1 , wherein:
the olefin comprises ethylene; and
the α,β-unsaturated carboxylic acid comprises acrylic acid.

4. The process of claim 3 , 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%.

5. The process of claim 1 , 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.

6. The process of claim 1 , wherein the treated solid oxide comprises an alkali metal-treated solid oxide.

7. The process of claim 6 , wherein the treated solid oxide comprises a sodium-treated solid oxide.

8. The process of claim 6 , wherein the treated solid oxide comprises a potassium-treated solid oxide.

9. The process of claim 1 , wherein the treated solid oxide comprises an alkaline earth metal-treated solid oxide.

10. The process of claim 1 , wherein the treated solid oxide comprises a solid oxide selected from the group consisting of 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, and combinations thereof.

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

12. The process of claim 1 , wherein:
the 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, 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%.

13. 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 an alkali metal-treated solid oxide, an alkaline earth metal-treated solid oxide, or a combination thereof; 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%.

14. The process of claim 13 , wherein in step (1), the metallalactone and the diluent contact a fixed bed of the treated solid oxide.

15. The process of claim 13 , 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.

16. The process of claim 13 , 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.

17. The process of claim 13 , wherein the treated solid oxide comprises a solid oxide selected from the group consisting of 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, and combinations thereof.

18. The process of claim 13 , wherein the treated solid oxide comprises an alkali metal-treated solid oxide.

19. The process of claim 18 , wherein the treated solid oxide comprises a sodium-treated solid oxide.

20. The process of claim 18 , wherein the treated solid oxide comprises a potassium-treated solid oxide.

21. The process of claim 13 , wherein the treated solid oxide comprises an alkaline earth metal-treated solid oxide.

22. The process of claim 13 , wherein:
the 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, or a combination thereof; and
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is from 50% to 10,000%.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Hlavinka Mark L
• Mcdaniel Max P
• Iacono Pasquale

Classifications

• C07C51/15 Primary

  by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title

• B01J31/38

  of titanium, zirconium or hafnium · CPC title

• B01J31/143

  of aluminium · CPC title

• B01J2531/847

  Nickel · CPC title