Recovery of organic acids

• US 20050256337A1
• Filed: 01/28/2005
• Published: 11/17/2005
• Est. Priority Date: 01/29/2004
• Status: Active Grant

• Current Assignee: ZeaChem, Inc.
• Original Assignee: ZeaChem, Inc.
• Inventors: Verser, Dan W., Eggeman, Timothy J.
• Granted Patent: US 7,601,865 B2
• Time in Patent Office: Days
• US Class Current: 562/508
• CPC Class Codes: C07C 51/02 from salts of carboxylic acids
• CPC Class Codes: C07C 51/48 by liquid-liquid treatment
• CPC Class Codes: C07C 51/487 by treatment giving rise to chemical modification by chemisorption C07C51/47
• CPC Class Codes: C07C 53/02 Formic acid
• CPC Class Codes: C07C 53/08 Acetic acid pyroligneous acid C10C; preparation of vinegar C12J
• CPC Class Codes: C07C 53/122 Propionic acid
• CPC Class Codes: C07C 53/124 Acids containing four carbon atoms
• CPC Class Codes: C07C 55/10 Succinic acid
• CPC Class Codes: C07C 59/06 Glycolic acid
• CPC Class Codes: C07C 59/08 Lactic acid
• CPC Class Codes: C07C 59/10 Polyhydroxy carboxylic acids
• CPC Class Codes: C07C 59/265 Citric acid
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

A method is disclosed for the recovery of an organic acid from a dilute salt solution in which the cation of the salt forms an insoluble carbonate salt. A tertiary amine and CO₂ are introduced to the solution to form the insoluble carbonate salt and a complex between the acid and an amine. A water immiscible solvent, such as an alcohol, is added to extract the acid/amine complex from the dilute salt solution to a reaction phase. The reaction phase is continuously dried and a product between the acid and the solvent, such as an ester, is formed.

Claims

1. A method for recovery of an organic acid from a dilute salt solution comprising an organic acid salt, the cation of which forms an insoluble carbonate salt, comprising:

a. introducing a tertiary amine and CO₂ to the dilute salt solution to form an acid/amine complex and the insoluble carbonate salt;

b. introducing a water immiscible solvent to the dilute salt solution to form a reaction phase comprising the acid/amine complex and the water immiscible solvent;

c. continuously drying the reaction phase; and

d. forming a product of the acid and the water immiscible solvent.

2. The method, as claimed in claim 1, wherein the water immiscible solvent is an alcohol.

3. The method, as claimed in claim 1, wherein the water immiscible solvent is an alcohol and the acid/solvent product is an ester.

4. The method, as claimed in claim 3, wherein the water immiscible solvent has a distribution coefficient of at least about 0.5.

5. The method, as claimed in claim 1, wherein the alcohol is selected from the group consisting of n-octanol, n-hexanol, n-pentanol, and n-butanol.

6. The method, as claimed in claim 1, wherein the water immiscible solvent is a mixed solvent comprising a solvent reactive with the acid portion of the acid/amine complex to form an acid/solvent product and a solvent that is inert with the acid portion of the acid/amine complex.

7. The method, as claimed in claim 1, wherein the water immiscible solvent has a distribution coefficient of at least about 0.5.

8. The method, as claimed in claim 1, wherein the water immiscible solvent has a distribution coefficient of at least about 0.75.

9. The method, as claimed in claim 1, wherein the water immiscible solvent has a distribution coefficient of at least about 1.

10. The method, as claimed in claim 1, wherein the water immiscible solvent has a selectivity value of at least about 8.

11. The method, as claimed in claim 1, wherein the water immiscible solvent has a selectivity value of at least about 15.

12. The method, as claimed in claim 1, wherein the water immiscible solvent has a selectivity value of at least about 20.

13. The method, as claimed in claim 1, wherein the tertiary amine is selected from the group consisting of tributylamine and dicyclohexyl methyl amine.

14. The method, as claimed in claim 1, wherein the organic acid is selected from the group consisting of acetic acid, lactic acid, propionic acid, butyric acid, succinic acid, citric acid, 3-hydroxypropionic acid, glycolic acid, and formic acid.

15. The method, as claimed in claim 1, wherein the step of continuously drying the reaction phase comprises a process selected from the group of removing water as an azeotrope with the solvent by azeotropic distillation and removing water by contacting the reaction phase with a water adsorbent.

16. The method, as claimed in claim 1, wherein the solvent is an alcohol and the step of forming the acid/solvent product comprises forming an ester between the acid and the alcohol by the production of water.

17. The method, as claimed in claim 1, wherein the step of forming the acid/solvent product comprises adding a catalyst to the solvent.

18. The method, as claimed in claim 17, wherein the catalyst is a strong acid catalyst.

19. The method, as claimed in claim 18, wherein the catalyst is selected from the group consisting of acid catalysts having a pKa greater than the organic acid and solid acid catalysts.

20. The method, as claimed in claim 18, wherein the catalyst is selected from the group consisting of sulfuric acid, hydrochloric acid and methane sulfonic acid.

21. The method, as claimed in claim 1, further comprising separating the acid/solvent product, the tertiary amine and the solvent.

22. The method, as claimed in claim 21, wherein the separated tertiary amine is used as the tertiary amine in step (a).

23. The method, as claimed in claim 21, wherein the separated solvent is used as the solvent in step (b).

24. The method, as claimed in claim 21, wherein the step of separating comprises distilling the acid/solvent product from the tertiary amine and the solvent.

25. The method, as claimed in claim 24, wherein the step of separating comprises distilling the solvent from the tertiary amine.

26. The method, as claimed in claim 21, wherein the solvent is an alcohol and the acid/solvent product is an ester and the method further comprises hydrogenating the ester to form an alcohol of the acid and regenerate the solvent alcohol.

27. The method, as claimed in claim 26, further comprising dehydrating the alcohol of the acid to form an olefin product.

28. The method, as claimed in claim 26, wherein the regenerated solvent is used as the solvent in step (b).

29. The method, as claimed in claim 26, wherein the solvent is an alcohol and the acid/solvent product is a first ester and the method further comprises transesterifying the first ester with a second alcohol to form a second ester.

30. The method, as claimed in claim 21, wherein the solvent is an alcohol and the acid/solvent product is an ester and the method further comprises hydrolyzing the ester to form the acid and regenerate the solvent alcohol.

31. The method, as claimed in claim 30, wherein the regenerated solvent is used as the solvent in step (b).

32. A method for recovery of an organic acid from a dilute salt solution comprising a calcium salt of an organic acid, comprising:

a. introducing a tertiary amine and CO₂ to the dilute salt solution to form an acid/amine complex and calcium carbonate;

b. mixing the dilute salt solution with a water immiscible alcohol having a distribution coefficient of at least about 0.5, whereby the acid/amine complex is extracted into the water immiscible alcohol;

c. continuously drying the water immiscible alcohol; and

d. forming an ester from the acid and the water immiscible alcohol to produce a mixture comprising the ester, residual water immiscible alcohol, and the tertiary amine.

33. A method for recovery of an organic acid selected from the group consisting of acetic acid, lactic acid, and propionic acid from a fermentation broth comprising a calcium salt of the organic acid, comprising:

a. introducing a tertiary amine selected from the group consisting of tributylamine and dicyclohexyl methyl amine and CO₂ to the dilute salt solution to form an acid/amine complex and calcium carbonate;

b. mixing the dilute salt solution with a water immiscible alcohol selected from the group consisting of octanol, hexanol, pentanol, and butanol, whereby the acid/amine complex is extracted into the water immiscible alcohol;

c. continuously drying the water immiscible alcohol;

d. forming an ester from the acid and the water immiscible alcohol to produce a mixture comprising the ester, residual water immiscible alcohol, and the tertiary amine;

e. separating the ester, the tertiary amine and the water immiscible alcohol;

f. using the separated tertiary amine as the tertiary amine in step (a);

g. using the separated water immiscible alcohol as the water immiscible alcohol in step (b);

h. treating the ester by a process selected from the group consisting of

i. hydrogenating the ester to form an alcohol of the acid and regenerate the solvent alcohol;

ii. transesterifying the ester with a second alcohol to form a second ester;

iii. hydrolyzing the ester to form the acid and regenerate the solvent alcohol.

34. A method for recovery of an organic acid from an acid/amine complex in an aqueous solution, comprising:

a. introducing a water immiscible solvent to the aqueous solution to form a reaction phase comprising the acid/amine complex and the water immiscible solvent and an aqueous phase;

b. continuously drying the reaction phase; and

c. forming a product of the acid and the water immiscible solvent.