Gas phase process for acrylate production from ethylene and carbon dioxide

Patent metadata

Field	Value
Publication number	US-12162829-B2
Application number	US-202117553165-A
Country	US
Kind code	B2
Filing date	Dec 16, 2021
Priority date	Dec 16, 2021
Publication date	Dec 10, 2024
Grant date	Dec 10, 2024

Abstract

Catalysts and catalytic processes for the synthesis of acrylic acid and other α,β-unsaturated carboxylic acids and their salts, which are carried out in a diluent or in the absence of a diluent. In an aspect, ethylene and CO 2 can be contacted with a Group 8-11 transition metal precursor compound or a Group 8-11 transition metal metalalactone compound in the presence of a metal-treated chemically-modified solid oxide (MT-CMSO) or a metal-treated solid oxide (MT-SO), to form a metal acrylate. As the catalytic activity wanes in either the presence or absence of a diluent, pressure cycling—that is, pressurizing the reaction system with CO 2 and an olefin such as ethylene for a time period, releasing the pressure, then re-pressurizing with CO 2 and ethylene—can rejuvenate the catalyst and restore its declining catalytic activity.

First claim

We claim:

1. A process for forming an α,β-unsaturated carboxylic acid or a salt thereof, the process comprising:
(a) contacting in any order (i) a Group 8-11 transition metal precursor compound comprising at least one first ligand, (ii) optionally, at least one second ligand, (iii) a first olefin, (iv) carbon dioxide (CO 2 ), (v) a diluent, and (vi) [A] a metal-treated chemically-modified solid oxide, wherein the chemically-modified solid oxide comprises at least one solid oxide which has been treated with at least one electron-withdrawing anion, or [B] a metal-treated solid oxide, to provide a first reaction mixture,
wherein the contacting is optionally carried out at a total pressure greater than ambient pressure, and
wherein at least a portion of the Group 8-11 transition metal is deposited on the metal-treated chemically-modified solid oxide or the metal-treated solid oxide;
(b) releasing the pressure from the first reaction mixture and removing the diluent from the first reaction mixture to provide the catalyst composition as a solid catalyst composition; and
(c) contacting in any order (i) the solid catalyst composition, (ii) a second olefin, and (iii) carbon dioxide (CO 2 ) at a total pressure greater than ambient pressure to provide a second reaction mixture comprising an α,β-unsaturated carboxylic acid or a salt thereof.

2. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the first reaction mixture or the second reaction mixture, independently, comprises: a metalalactone; or an adduct of a metalalactone and the metal-treated chemically-modified solid oxide or the metal-treated solid oxide.

3. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according claim 1 , further comprising the steps of:
(d) releasing at least a fraction of the total pressure from the second reaction mixture; and
(e) contacting in any order (i) the solid catalyst composition, (ii) the second olefin, and (iii) carbon dioxide (CO 2 ) at a total pressure greater than ambient pressure to provide a subsequent reaction mixture comprising an α,β-unsaturated carboxylic acid or a salt thereof.

4. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 3 , further comprising the step of:
(f) repeating steps (d) and (e) any number of times to provide further subsequent reaction mixtures comprising the α,β-unsaturated carboxylic acid or a salt thereof.

5. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the first olefin and the second olefin independently are selected from ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, or styrene.

6. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the first reaction mixture is pressurized with CO 2 to a CO 2 partial pressure greater than ambient pressure.

7. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the first olefin is ethylene and the first reaction mixture is pressurized with ethylene to an ethylene partial pressure greater than ambient pressure.

8. The process for forming an α,β-unsaturated carboxylic acid according to claim 1 , wherein (a) the solid catalyst composition comprises less than 10 wt. % diluent, and/or (b) the solid catalyst composition comprises a free-flowing solid.

9. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the step of contacting the solid catalyst composition, the second olefin, and carbon dioxide (CO 2 ) is carried out in the substantial absence of a diluent.

10. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the step of contacting the solid catalyst composition, the second olefin, and carbon dioxide (CO 2 ) is carried out in the presence of a diluent.

11. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the metal of the Group 8-11 transition metal precursor compound is a Group 8 metal.

12. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the metal of the Group 8-11 transition metal precursor compound is a Group 9 metal.

13. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the metal of the Group 8-11 transition metal precursor compound is a Group 10 metal.

14. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the first ligand and the second ligand, independently, are selected from a diphosphine ligand, a diamine ligand, a diene ligand, a diether ligand, or dithioether ligand.

15. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the first ligand and the second ligand, independently, is selected from trimethylphosphine, triethylphosphine, tripropylphosphine, tributylphosphine, phenylphosphine, tolylphosphine, diphenylphosphine, ditolylphosphine, triphenylphosphine, tritolylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, ethyldiphenylphosphine, diethylphenylphosphine, tricyclohexylphosphine, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, triisopropyl phosphite, tributyl phosphite and tricyclohexyl phosphite, 2-(di-t-butylphosphino) biphenyl, 2-di-t-butylphosphino-1,1′-binaphthyl, 2-(di-t-butylphosphino)-3,6-dimethoxy-2′,4′,6′-tri-i-propyl-1,l′-biphenyl, 2-di-t-butylphosphino-2′-methylbiphenyl, 2-(di-t-butylphosphinomethyl) pyridine, 2-di-t-butylphosphino-2′,4′,6′-tri-i-propyl-1,l′-biphenyl, 2-(dicyclohexylphosphino) biphenyl, (S)-(+)-(3,5-dioxa-4-phospha-cyclohepta [2,1-a;3,4-a′] dinaphthalen-4-yl) dimethylamine, 2-(diphenylphosphino)-2′-methoxy-1,1′-binaphthyl, 1,2,3,4,5-pentaphenyl-1′-(di-t-butylphosphino) ferrocene, 2,2′-bis (diphenylphosphino)-1,1′-binaphthyl (BINAP), 1,2-bis (dimethylphosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,2-bis (dipropylphosphino)-ethane, 1,2-bis (diisopropylphosphino) ethane, 1,2-bis (di-n-butyl-phosphino) ethane, 1,2-bis (di-t-butyl-phosphino) ethane, 1,2-bis (dicyclohexylphosphino) ethane, 1,3-bis (dicyclohexylphosphino) propane, 1,4-bis (dicyclohexylphosphino) butane, 1,3-bis (diisopropylphosphino) propane, 1,3-bis (diphenylphosphino) propane, 1,3-bis (di-t-butylphosphino) propane, 1,4-bis (diisopropylphosphino) butane, 1,4-bis (diphenylphosphino) butane, 2,2′-bis [bis (3,5-dimethylphenyl) phosphino]-4,4′,6,6′-tetramethoxybiphenyl, 2,6-bis (di-t-butylphosphinomethyl) pyridine, 2,2′-bis (dicyclohexylphosphino)-1,1′-biphenyl, bis (2-dicyclohexylphosphinophenyl) ether, 5,5′-bis (diphenylphosphino)-4,4′-bi-1,3-benzodioxole, 2-t-butylphosphinomethylpyridine, bis (diphenylphosphino) ferrocene, bis (diphenylphosphino) methane, bis (dicyclohexylphosphino) methane, bis (di-t-butylphosphino) methane, TMEDA, 2,2′-bipyridine, or 2-((di-t-butylphosphino) methyl) pyridine.

16. The process for forming an α,β-unsaturated carboxylic acid or a salt thereof according to claim 1 , wherein the first ligand and the second ligand, independently, is selected from:
(1R,1′R,2S,2'S)-2,2′-Di-tert-butyl-2,3,2′,3′-tetrahydro-1H,1′H-(1,1′) biisophosphindolyl (also designated (1R, 1′R,2S,2'S)-DuanPhos);
(3S,3'S,4S,4'S,11bS,11′bS)-(+)-4,4′-Di-t-butyl-4,4′,5,5′-tetrahydro-3,3′-bi-3H-dinaphtho [2,1-c: 1′,2′-e] phosphepin (also designated(S)-BINAPINE);
(1S,1S′,2R,2R′)-1,1′-Di-tert-butyl-(2,2′)-diphos

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Iacono Pasquale
• Sutherland Jamie N
• Ash Carlton E
• Ramanathan Anand

Classifications

• C07C2523/00

  Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 (C07C2521/16 takes precedence) · CPC title

• C07C2521/00

  Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium · CPC title

• B01J2531/847

  Nickel · CPC title

• B01J2231/341

  1,2-additions, e.g. aldol or Knoevenagel condensations · CPC title

• B01J29/041

  Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 · CPC title