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

Patent metadata

Field	Value
Publication number	US-10155712-B2
Application number	US-201815864018-A
Country	US
Kind code	B2
Filing date	Jan 8, 2018
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 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 a transition metal-treated chemically-modified solid oxide, wherein the transition metal-treated chemically-modified solid oxide comprises a chemically-modified solid oxide comprising fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any 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 4 , wherein the transition metal-treated chemically-modified solid oxide comprises a transition metal, wherein the transition metal comprises titanium, zirconium, hafnium, tungsten, zinc, or any combination thereof.

7. 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 transition metal-treated chemically-modified solid oxide, wherein the transition metal-treated chemically-modified solid oxide comprises a chemically-modified solid oxide comprising fluorided alumina, chlorided alumina, bromided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, bromided silica-alumina, sulfated silica-alumina, fluorided silica-zirconia, chlorided silica-zirconia, bromided silica-zirconia, sulfated silica-zirconia, fluorided silica-titania, fluorided silica-coated alumina, fluorided-chlorided silica-coated alumina, sulfated silica-coated alumina, phosphated silica-coated alumina, or any 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%.

8. The process of claim 7 , wherein in step (1), the metallalactone and the diluent contact a fixed bed of the treated solid oxide.

9. The process of claim 7 , 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.

10. The process of claim 7 , 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 transition metal-treated chemically-modified solid oxide comprises a transition metal, wherein the transition metal comprises titanium, zirconium, hafnium, tungsten, zinc, or any combination thereof.

11. The process of claim 7 , wherein the process further comprises, prior to step (1), the steps of:
contacting a solid oxide and an electron-withdrawing anion and calcining to form the chemically-modified solid oxide; and
contacting the chemically-modified solid oxide with a transition metal-containing compound and calcining to form the transition metal-treated chemically-modified solid oxide.

12. The process of claim 11 , 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.

13. The process of claim 12 , 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%; and
the metallalactone is a nickelalactone.

14. 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 a transition metal-treated chemically-modified solid oxide, wherein the transition metal-treated chemically-modified solid oxide comprises a transition metal-treated fluorided solid oxide and/or a transition metal-treated sulfated 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%.

15. The process of claim 14 , 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%.

16. The process of claim 15 , wherein:
the transition metal-treated chemically-modified solid oxide comprises a transition metal, wherein the transition metal comprises titanium, zirconium, hafnium, tungsten, zinc, or any combination thereof; and
the olefin comprises ethylene.

17. The process of claim 14 , 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%; and
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.

18. The process of claim 17 , wherein:
t

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Hlavinka Mark L
• Mcdaniel Max P
• Iacono Pasquale

Classifications

• C07C51/09

  from carboxylic acid esters or lactones · CPC title

• C07C51/377

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

• B01J31/38

  of titanium, zirconium or hafnium · CPC title

• B01J2231/46

  C-H or C-C activation · CPC title

• B01J31/128

  Mixtures of organometallic compounds · CPC title