Hydrocarboxylation of formaldehyde in the presence of a higher order carboxylic acid and a homogeneous catalyst

• US 8,765,999 B2
• Filed: 03/27/2012
• Issued: 07/01/2014
• Est. Priority Date: 03/27/2012
• Status: Active Grant

• Current Assignee: Eastman Chemical Company
• Original Assignee: Eastman Chemical Company
• Inventors: Barnicki, Scott Donald, Hembre, Robert Thomas, Falling, Stephen Neal, Vetter, Andrew James
• Primary Examiner(s): Zucker, Paul A
• Application Number:
  US13/431,369
• Publication Number:
  US 20130261328A1
• Time in Patent Office: 826 Days
• US Class Current: 562/518
• CPC Class Codes: C07C 51/09 from carboxylic acid esters or lactones
• CPC Class Codes: C07C 51/493 whereby carboxylic acid esters are formed
• CPC Class Codes: C07C 59/06 Glycolic acid
• CPC Class Codes: C07C 67/00 Preparation of carboxylic acid esters
• CPC Class Codes: C07C 67/36 by reaction with carbon monoxide or formates C07C67/02, C07C67/03, C07C67/10 take precedence
• CPC Class Codes: C07C 67/58 by liquid-liquid treatment
• CPC Class Codes: C07C 69/24 esterified with monohydroxylic compounds
• CPC Class Codes: C07C 69/675 of saturated hydroxy-carboxylic acids

Abstract

Disclosed is a process for the production and purification of glycolic acid or glycolic acid derivatives by the carbonylation of formaldehyde in the presence of a homogeneous acid catalyst and a carboxylic acid. This invention discloses hydrocarboxylations and corresponding homogeneous acid catalyst and glycolic acid separations. The homogeneous acid catalyst is readily separated from the hydrocarboxylation reaction effluent and recycled and the carboxylic acid is readily removed from the glycolic acid and the carboxylic acid is recycled.

Claims

1. A process for the preparation of glycolic acid, comprising

(A) feeding carbon monoxide, aqueous formaldehyde, a homogeneous acid catalyst, and a carboxylic acid having 3-6 carbon atoms to a hydrocarboxylation reaction zone to produce an effluent comprising said homogeneous acid catalyst and esters of glycolic and carboxylic acids;

(B) recovering said homogeneous acid catalyst from said effluent by extracting said effluent with a first hydrophilic solvent to form a first aqueous extract phase comprising a major amount of said homogeneous acid catalyst contained in said effluent and a first organic raffinate phase comprising a major amount of said esters of glycolic and carboxylic acids contained in said effluent;

(C) separating said first organic raffinate phase and said first aqueous extract phase; and

(D) recycling said first aqueous extract phase to step (A).

2. The process according to claim 1, wherein said feeding of said carboxylic acid and said aqueous formaldehyde in step (A) occurs at a molar ratio of carboxylic acid:

formaldehyde of from 0.5;

1 to 6;

1 and said feeding of said homogeneous acid catalyst and said aqueous formaldehyde in step (A) occurs at a molar ratio of homogeneous acid catalyst;

formaldehyde of from 0.001;

1 to 0.1;

1.

3. The process according to claim 1, wherein said feeding of said carboxylic acid and said aqueous formaldehyde in step (A) occurs at a molar ratio of carboxylic acid:

formaldehyde of from 0.5;

1 to 4;

1 and said feeding of said homogeneous acid catalyst and said aqueous formaldehyde in step (A) occurs at a molar ratio of homogeneous acid catalyst;

formaldehyde of from 0.01;

1 to 0.07;

1.

4. The process according to claim 1, wherein said feeding of said carboxylic acid and said aqueous formaldehyde in step (A) occurs at a molar ratio of carboxylic acid:

formaldehyde of from 0.5;

1 to 2.5;

1 and said feeding of said homogeneous acid catalyst and said aqueous formaldehyde in step (A) occurs at a molar ratio of homogeneous acid catalyst;

formaldehyde of from 0.01;

1 to 0.07;

1.

5. The process according to claim 1, wherein said first hydrophilic solvent comprises 15 weight percent to 100 weight percent water and 0 weight percent to 85 weight percent glycolic acid, each based on a total first hydrophilic solvent weight basis, wherein said extracting of said effluent occurs further with a first hydrophobic solvent selected from the group consisting of hydrocarbons having from 6 to 20 carbon atoms and ethers having from 4 to 20 carbon atoms thereof.

6. The process according to claim 1, wherein said carboxylic acid is selected from the group consisting of propionic acid, n-butyric acid, i-butyric acid, 2-methyl butyric acid, n-valeric acid, and i-valeric acid.

7. The process according to claim 1, wherein said carboxylic acid is selected from the group consisting of 2-methyl butyric acid, n-valeric acid, and i-valeric acid.

8. The process according to claim 1, wherein greater than 90 weight percent of said esters of glycolic and carboxylic acids are recovered in said first organic raffinate phase and wherein greater than 95 weight percent of said homogeneous acid catalyst is recovered in said first aqueous extract phase.

9. The process according to claim 1, wherein said extracting in step (B) occurs in a continuous counter-current first extractor, wherein said first aqueous extract phase exits the bottom of said first extractor and said first organic raffinate phase exits the top of said first extractor, wherein said first hydrophilic solvent is fed to said first extractor above said effluent, and wherein the feed ratio of said first hydrophilic solvent to said effluent ranges from 0.1:

1 to 20;

1 on a weight basis.

10. The process according to claim 5, wherein said extracting in step (B) occurs in a continuous counter-current first extractor, wherein said first aqueous extract phase exits the bottom of said first extractor and said first organic raffinate phase exits the top of said first extractor, wherein said first hydrophilic solvent is fed to said first extractor above said effluent, and wherein the feed ratio of said first hydrophilic solvent to said effluent ranges from 0.1:

1 to 20;

1 on a weight basis, further comprising feeding said first hydrophobic solvent to said first extractor, wherein the feed ratio of said first hydrophobic solvent to said effluent ranges from 0.01;

1 to 5;

1 on a weight basis, and wherein said hydrophobic solvent is selected from the group consisting of hexane, cyclohexane, heptane, octane, decane, benzene, toluene, xylene, isoparaffinic mixed hydrocarbons having a boiling range between 90 and 325°

C., methyl naphthalene, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ethers, methyl tertiary-butyl ether, and methyl tertiary-amyl ether.

11. The process according to claim 9, wherein said feed ratio of said first hydrophilic solvent to said effluent ranges from 0.5:

1 to 4;

1.

12. The process according to claim 1, wherein said aqueous formaldehyde comprises 35 weight percent to 85 weight percent formaldehyde, based on the total weight of said aqueous formaldehyde, the molar ratio of carbon monoxide to formaldehyde ranges from 1:

1 to 10;

1, and said hydrocarboxylation reaction zone is operated at a pressure of from 35 bar gauge to 200 bar gauge and a temperature of from 120°

C. to 220°

C.

13. The process according to claim 1, wherein said homogeneous acid catalyst is selected from the group consisting of hydrochloric acid, hydrobromic acid, hydriodic acid, hydrofluoric acid, perchloric acid, phosphoric acid, nitric acid, sulfuric acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, fluorosulfonic acid, chlorosulfonic acid, benzenesulfonic acid, toluenesulfonic acid, methylsulfonylmethanesulfonic acid, methanetrisulfonic acid, bis(methylsulfonyl)methanesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, and bis(trifluoromethyl)sulfonylamide.

14. The process according to claim 1, wherein said homogeneous acid catalyst is selected from the group consisting of sulfuric acid, trifluoromethanesulfonic acid, 1,1,2,2-tetrafluoroethanesulfonic acid, bis(trifluoromethyl)sulfonylamide, and nonafluorobutanesulfonic acid.

15. The process according to claim 1, wherein said homogeneous acid catalyst comprises trifluoromethanesulfonic acid.

16. The process according to claim 1, further comprising

(E) hydrolyzing said first organic raffinate phase to produce a hydrolyzed mixture comprising glycolic acid and said carboxylic acid;

(F) recovering said carboxylic acid from said hydrolyzed mixture by extracting said hydrolyzed mixture with a second hydrophobic solvent selected from the group consisting of esters having from 4 to 20 carbon atoms, ethers having from 4 to 20 carbon atoms, ketones having from 4 to 20 carbon atoms, and hydrocarbons having from 6 to 20 carbon atoms to form a second aqueous raffinate phase comprising a major amount of said glycolic acid contained in said hydrolyzed mixture and a second organic extract phase comprising a major amount of said carboxylic acid contained in said hydrolyzed mixture;

(G) separating said second aqueous raffinate phase and said second organic extract phase; and

(H) separating said second organic extract phase into said second hydrophobic solvent and said carboxylic acid, recycling said second hydrophobic solvent to step (F), and recycling said carboxylic acid to step (A).

17. The process according to claim 16, further comprising

(I) reacting a first ethylene glycol with said second aqueous raffinate phase while simultaneously removing water to produce an esterification effluent comprising glycolate ester oligomers and glycolic acid oligomers and an overhead stream comprising water;

and

(J) reacting hydrogen with said esterification effluent to produce a second ethylene glycol, separating said second ethylene glycol into a product ethylene glycol and said first ethylene glycol, and recycling said first ethylene glycol to step (I).

18. The process according to claim 5, wherein said first hydrophobic solvent is separated from said esters of glycolic and carboxylic acids contained in said first organic raffinate phase and said first hydrophobic solvent is recycled to step (B).

19. The process according to claim 16, wherein said first hydrophobic solvent and said second hydrophobic solvent are the same.

20. A process for the preparation of glycolic acid, comprising

(A) feeding carbon monoxide, aqueous formaldehyde, a homogeneous acid catalyst, and carboxylic acid selected from the group consisting of propionic acid, n-butyric acid, i-butyric acid, 2-methyl butyric acid, n-valeric acid, and i-valeric acid to a hydrocarboxylation reaction zone to produce an effluent comprising said homogeneous acid catalyst and esters of glycolic and carboxylic acids;

(B) recovering said homogeneous acid catalyst from said effluent by extracting said effluent with a first hydrophilic solvent comprising 15 weight percent to 100 weight percent water and 0 weight percent to 85 weight percent of glycolic acid, each on a total first hydrophilic solvent weight basis, and optionally with a first hydrophobic solvent selected the group consisting of hexane, cyclohexane, heptane, octane, decane, benzene, toluene, xylene, isoparaffinic mixed hydrocarbons having a boiling range between 90 and 325°

C., methyl naphthalene, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, methyl tertiary-butyl ether, and methyl tertiary-amyl ether to form a first aqueous extract phase comprising a major amount of said homogeneous acid catalyst contained in said effluent and a first organic raffinate phase comprising a major amount of said esters of glycolic and carboxylic acids contained in said effluent;

(C) separating said first organic raffinate phase and said first aqueous extract phase; and

(D) recycling said first aqueous extract phase to step (A).

21. The process according to claim 20, wherein said feeding of said carboxylic acid and said aqueous formaldehyde in step (A) occurs at a molar ratio of carboxylic acid:

formaldehyde of from 0.5;

1 to 4;

1 and said feeding of said homogeneous acid catalyst and said aqueous formaldehyde in step (A) occurs at a molar ratio of homogeneous acid catalyst;

formaldehyde of from 0.01;

1 to 0.07;

1.

22. The process according to claim 20, wherein said feeding of said carboxylic acid and said aqueous formaldehyde in step (A) occurs at a molar ratio of carboxylic acid:

formaldehyde of from 0.5;

1 to 2.5;

1 and said feeding of said homogeneous acid catalyst and said aqueous formaldehyde in step (A) occurs at a molar ratio of homogeneous acid catalyst;

formaldehyde of from 0.01;

1 to 0.07;

1.

23. The process according to claim 20, wherein said extraction occurs with said first hydrophobic solvent and said first hydrophobic solvent is selected from the group consisting of hexane, heptane, toluene, xylene, and methyl tertiary-butyl ether.

24. The process according to claim 20, wherein said carboxylic acid is selected from the group consisting of 2-methyl butyric acid, n-valeric acid, and i-valeric acid.

25. The process according to claim 20, wherein greater than 90 weight percent of said esters of glycolic and carboxylic acids are recovered in said first organic raffinate phase and wherein greater than 95 weight percent of said homogeneous acid catalyst is recovered in said first aqueous extract phase.

26. The process according to claim 20, wherein said extracting in step (B) occurs in a continuous counter-current first extractor, wherein said first aqueous extract phase exits the bottom of said first extractor and said first organic raffinate phase exits the top of said first extractor, wherein said first hydrophilic solvent is fed to said first extractor above said effluent, and wherein the feed ratio of said first hydrophilic solvent to said effluent ranges from 0.5:

1 to 4;

1 on a weight basis.

27. The process according to claim 26, further comprising feeding said first hydrophobic solvent to said first extractor, wherein the feed ratio of said first hydrophobic solvent to said effluent ranges from 0.01:

1 to 5;

1 on a weight basis, and wherein the feed ratio of said first hydrophilic solvent to said effluent ranges from 0.5;

1 to 4;

1 on a weight basis.

28. The process according to claim 20, wherein said aqueous formaldehyde comprises 35 weight percent to 85 weight percent formaldehyde, based on the total weight of said aqueous formaldehyde, the molar ratio of carbon monoxide to formaldehyde ranges from 1:

1 to 10;

1, and said hydrocarboxylation reaction zone is operated at a pressure of from 35 bar gauge to 200 bar gauge and a temperature of from 120°

C. to 220°

C.

29. The process according to claim 20, further comprising

(E) hydrolyzing said first organic raffinate phase to produce a hydrolyzed mixture comprising glycolic acid and said carboxylic acid;

(F) recovering said carboxylic acid from said hydrolyzed mixture by extracting said hydrolyzed mixture with a second hydrophobic solvent selected from the group consisting of n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, s-butyl acetate, methyl propionate, ethyl propionate, i-propyl propionate, methyl tertiary-butyl ether, methyl i-butyl ketone, methyl i-propyl ketone, methyl propyl ketone, and toluene to form a second aqueous raffinate phase comprising a major amount of said glycolic acid contained in said hydrolyzed mixture and a second organic extract phase comprising a major amount of said carboxylic acid contained in said hydrolyzed mixture;

(G) separating said second aqueous raffinate phase and said second organic extract phase; and

(H) separating said second organic extract phase into said second hydrophobic solvent and said carboxylic acid, recycling said second hydrophobic solvent to step (F), and recycling said carboxylic acid to step (A).

30. The process according to claim 29, further comprising

(I) reacting a first ethylene glycol with said second aqueous raffinate phase while simultaneously removing water to produce an esterification effluent comprising glycolate ester oligomers and glycolic acid oligomers and an overhead stream comprising water;

and

(J) reacting hydrogen with said esterification effluent to produce a second ethylene glycol, separating said second ethylene glycol into a product ethylene glycol and said first ethylene glycol, and recycling said first ethylene glycol to step (I).

31. The process according to claim 20, wherein said first hydrophobic solvent is separated from said first organic raffinate phase and recycled to step (B).

32. The process according to claim 29, wherein said first hydrophobic solvent and said second hydrophobic solvent are the same.