Methods for the production of alpha, beta-unsaturated carboxylic acids and salts thereof

Patent metadata

Field	Value
Publication number	US-10155711-B2
Application number	US-201715684992-A
Country	US
Kind code	B2
Filing date	Aug 24, 2017
Priority date	Oct 8, 2014
Publication date	Dec 18, 2018
Grant date	Dec 18, 2018

Abstract

Processes for producing an α,β-unsaturated carboxylic acid, such as acrylic acid, or a salt thereof, using solid promoters are disclosed. The solid promoters can be certain solid oxides, mixed oxides, and clays, illustrative examples of which can include alumina, zirconia, magnesia, magnesium aluminate, sepiolite, and similar materials.

First claim

We claim:

1. A process for performing a metallalactone elimination reaction, the process comprising:
(1) calcining a solid promoter;
(2) contacting
(a) a metallalactone;
(b) a diluent comprising a non-protic solvent; and
(c) the solid promoter; and

(3) forming an α,β-unsaturated carboxylic acid, or a salt thereof;
wherein the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is at least 5%.

2. The process of claim 1 , wherein the solid promoter comprises alumina, zirconia, magnesia, magnesium aluminate, sepiolite, sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, cesium carbonate, cesium hydroxide, magnesium carbonate, magnesium hydroxide, calcium carbonate, calcium hydroxide, aluminum carbonate, aluminum hydroxide, or a combination thereof.

3. The process of claim 1 , wherein the solid promoter comprises alumina, zirconia, magnesia, magnesium aluminate, sepiolite, or a combination thereof.

4. The process of claim 1 , wherein:
the metallalactone comprises a nickelalactone;
the α,β-unsaturated carboxylic acid, or the salt thereof, comprises acrylic acid, methacrylic acid, 2-ethylacrylic 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 metallalactone, is from 5% to 95%.

5. The process of claim 1 , wherein the solid promoter comprises alumina.

6. The process of claim 1 , wherein the solid promoter comprises magnesia.

7. A process for performing a metallalactone elimination reaction, the process comprising:
(1) calcining a solid promoter;
(2) contacting
(a) a metallalactone;
(b) a diluent; and
(c) the solid promoter; and

(3) forming an α,β-unsaturated carboxylic acid, or a salt thereof;
wherein the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is at least 5%; and
wherein the solid promoter has a pore volume from 0.5 to 2.5 mL/g and a BET surface area from 100 to 750 m 2 /g.

8. The process of claim 7 , wherein:
the metallalactone comprises a nickelalactone; and
the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the metallalactone, is from 5% to 95%.

9. The process of claim 8 , wherein the solid promoter has a pore volume from 1 to 2.5 mL/g and a BET surface area from 150 to 350 m 2 /g.

10. A process for producing an α,β-unsaturated carboxylic acid, or a salt thereof, the process comprising:
(I) calcining a solid promoter;
(II) contacting
(i) a transition metal-ligand complex, wherein the transition metal is nickel, palladium, or platinum, and the ligand is a neutral electron donor group or Lewis base;
(ii) ethylene;
(iii) carbon dioxide (CO 2 );
(iv) a diluent; and
(v) the solid promoter; and

(III) forming the α,β-unsaturated carboxylic acid, or the salt thereof;
wherein the molar yield of the α,β-unsaturated carboxylic acid, or the salt thereof, based on the transition metal-ligand complex, is at least 5%.

11. The process of claim 10 , wherein the solid promoter is a Lewis acid and a Bronsted base.

12. The process of claim 11 , 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 5% to 95%.

13. The process of claim 10 , wherein the transition metal is nickel.

14. The process of claim 10 , wherein in step (II), the transition metal-ligand complex, ethylene, carbon dioxide, and the diluent contact a fixed bed of the solid promoter.

15. The process of claim 14 , wherein the diluent comprises a non-protic solvent.

16. The process of claim 10 , wherein
the solid promoter has a pore volume from 0.5 to 2.5 mL/g and a BET surface area from 100 to 750 m 2 /g.

17. The process of claim 16 , wherein the solid promoter comprises alumina, zirconia, magnesia, magnesium aluminate, sepiolite, or a combination thereof.

18. The process of claim 16 , wherein the solid promoter comprises alumina.

19. The process of claim 4 , wherein the solid promoter comprises alumina.

20. The process of claim 8 , wherein the solid promoter comprises alumina, zirconia, magnesia, magnesium aluminate, sepiolite, or a combination thereof.

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Hlavinka Mark L
• Mcdaniel Max P

Classifications

• B01J31/26

  containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 · CPC title

• C07C51/377 Primary

  by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups {(C07C51/36 - C07C51/373 take precedence)} · CPC title

• B01J31/24

  Phosphines {, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands} · CPC title

• B01J2231/46

  C-H or C-C activation · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title