Purification of carboxylic acids by complexation with selective solvents

• US 7,307,188 B2
• Filed: 04/08/2005
• Issued: 12/11/2007
• Est. Priority Date: 04/09/2004
• Status: Expired due to Fees

• Current Assignee: GTC Technology, Inc.
• Original Assignee: GTC Technology, Inc.
• Inventors: Chou, Tai-Li, Wytcherley, Randi Wright
• Primary Examiner(s): Zucker; Paul A.
• Application Number:
  US11/102,242
• Publication Number:
  US 20050228195A1
• Time in Patent Office: 977 Days
• Field of Search: None
• US Class Current: 562/486
• CPC Class Codes: C07C 51/285 with peroxy-compounds
• CPC Class Codes: C07C 51/43 by change of the physical state, e.g. crystallisation
• CPC Class Codes: C07C 51/487 by treatment giving rise to chemical modification by chemisorption C07C51/47
• CPC Class Codes: C07C 63/24 1,3 - Benzenedicarboxylic acid
• CPC Class Codes: C07C 63/26 1,4 - Benzenedicarboxylic acid

Abstract

A method and apparatus for purifying carboxylic acids is disclosed. A mixture containing crude carboxylic acid is contacted with a selective crystallization solvent to form a slurry of a salt complex of the carboxylic acid and the selective crystallization solvent. The salt complex is recovered and optionally processed to recover the free carboxylic acid. The method and apparatus of the invention is particularly suitable for purifying aromatic dicarboxylic acids such as terephthalic acid. The present invention also reduces contamination by carboxybenaldehyde isomers in crude phthalic acids by oxidizing the carboxybenzaldehyde to the corresponding phthalic acid.

Claims

1. A method of purifying a carboxylic acid from a crude mixture comprising one or more carboxylic acids, the method comprising:

contacting the crude mixture with a selective crystallization solvent at a temperature and time effective to form a slurry of a salt complex of the carboxylic acid and the selective crystallization solvent without completely dissolving the carboxylic acid; and

recovering the salt complex.

2. The method of claim 1, wherein the carboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid, orthophtalic acid, and mixtures thereof.

3. The method of claim 1, wherein the selective crystallization solvent is selected from the group consisting of N,N-dimethyl acetamide, N,N-dimethyl formamide, N-formyl piperidine, N-alkyl-2-pyrrolidone, N-mercaptoalkyl-2-pyrrolidone, N-alkyl-2-thiopyrrolidone, N-hydroxyalkyl-2-pyrrolidone, morpholines, carbitols, C₁-C₁₂ alcohols, ethers, amines, amides, esters, and mixtures thereof.

4. The method of claim 1, wherein the selective crystallization solvent is N-methyl pyrrolidone.

5. The method of claim 1, wherein the temperature is about 0 to about 65°

C.

6. The method of claim 1, wherein the time is about 1 minute to about 5 hours.

7. The method of claim 1, further comprising decomposing the salt complex in a selective crystallization solvent to provide free carboxylic acid.

8. The method of claim 7, wherein the salt complex is dissolved in the selective crystallization solvent.

9. The method claim 7, wherein the salt complex forms a slurry in the selective crystallization solvent.

10. The method of claim 7, further comprising stirring the selective solvent with energy sufficient to provide crystallization of the carboxylic acid having globular crystal shape.

11. The method of claim 7, further comprising reducing the temperature of the selective solvent.

12. The method of claim 7, further comprising reducing the volume of the selective solvent by evaporating a portion of said selective crystallization solvent.

13. The method of claim 7, further comprising adding a non-solvent to the selective crystallization solvent.

14. The method of claim 1, wherein the mixture further comprises one or more materials selected from the group consisting of carboxybenzaldehyde, toluic acid, and xylene;

and wherein recovering the salt complex yields a mother liquor that is enriched in one or more of the materials, the method further comprising adding an oxidant to a portion of the mother liquor.

15. The method of claim 14, wherein the oxidant is selected from the group consisting of air, enriched air, pure oxygen, hydrogen peroxide, aqueous hydrogen peroxide, hydrogen peroxide in an organic liquid, ozone, carbon tetrachloride, trichloroacetaldehyde, hexamine, acetone, cyclohexanone, benzophenone, cinnamaldehyde, dimethyl sulfoxide, sulfides, chiral oxidants, glyoxals, organic peroxy acids, such as performic acid, peracetic acid, perbenzoic acid, perpropionic acid, permaleic acid, and perphthalic acid.

16. The method of claim 14, wherein the pH of said portion of the mother liquor is about −

1 to about 7.

17. The method of claim 14, wherein the pH of said portion of the mother liquor is adjusted to −

1 to about 7 by adding acid to said mother liquor.

18. The method of claim 14, further comprising purifying additional carboxylic acid from said portion by contacting said portion with a selective crystallization solvent at a temperature and time effective to form a slurry of a salt complex of the additional carboxylic acid and the selective crystallization solvent and recovering the salt complex.

19. The method of claim 1, wherein the mixture comprises terephthalic acid and isophthalic acid and wherein recovering said salt complex yields a mother liquor, the method further comprising precipitating terephthalic acid from the mother liquor to yield a terephthalic acid-depleted stream and then precipitating isophthalic acid from the terephthalic acid-depleted stream.

20. The method of claim 7, wherein the mixture comprises terephthalic acid and isophthalic acid, the method further comprising reducing the temperature and volume of the second crystallization solvent or adding a non-solvent to the second crystallization in a first stage to selectively recover free terephthalic acid and to produce a terephthalic acid-depleted solution and then reducing the temperature and volume of the terephthalic acid-depleted solution in a second stage to selectively recover isophthalic acid.

21. The method of claim 1, wherein the carboxylic acid is selected from the group consisting of terephthalic acid, isophthalic acid, orthophtalic acid, and mixtures thereof;

wherein the mixture further comprises one or more materials selected from the group consisting of carboxybenzaldehyde, toluic acid, and xylene;

wherein recovering said salt complex yields a mother liquor that is enriched in one or more of said materials; and

wherein the selective crystallization solvent is selected from the group consisting of N,N-dimethyl acetamide and N-methyl pyrrolidone, the method further comprising;

decomposing or dissolving said salt complex in a selective crystallization solvent to form a second slurry or solution and precipitating the free carboxylic acid from said second solution while agitating said second solution with energy sufficient to provide crystallization of the carboxylic acid having globular crystal shape, and adding an oxidant to said mother liquor, wherein the oxidant is selected from the group consisting of air, enriched air, pure oxygen, hydrogen peroxide, aqueous hydrogen peroxide, hydrogen peroxide in an organic liquid, ozone, carbon tetrachloride, trichloroacetaldehyde, hexamine, acetone, cyclohexanone, benzophenone, cinnamaldehyde, dimethyl sulfoxide, sulfides, chiral oxidants, glyoxals, organic peroxy acids, such as performic acid, peracetic acid, perbenzoic acid, perpropionic acid, permaleic acid, and perphthalic acid.

23. The method of claim 19, further comprising adjusting the pH of a portion of the mother liquor to about −

1 to about 7 and adding an oxidant to said portion of the mother liquor, wherein the oxidant is selected from the group consisting of air, enriched air, pure oxygen, hydrogen peroxide, aqueous hydrogen peroxide, hydrogen peroxide in an organic liquid, ozone, carbon tetrachloride, trichloroacetaldehyde, hexamine, acetone, cyclohexanone, benzophenone, cinnamaldehyde, dimethyl sulfoxide, sulfides, chiral oxidants, glyoxals, organic peroxy acids, such as performic acid, peracetic acid, perbenzoic acid, perpropionic acid, permaleic acid, and perphthalic acid; and

recycling said portion of the mother liquor to the first crystallization vessel.

22. A method for recovering purified terephthalic acid from the effluent of a terephthalic acid production process, the method comprising:

contacting said effluent in a first crystallization vessel with a selective crystallization solvent to produce a slurry of a salt complex of terephthalic acid and the crystallization solvent without completely dissolving the terephthalic acid in the selective crystallization solvent;

filtering said slurry to provide a solid salt complex and a mother liquor;

decomposing or dissolving the solid salt complex with a selective crystallization solvent in a second crystallization vessel at a temperature of about 65 to about 300°

C. to yield a second crystallization slurry or solution;

reducing the temperature of the second crystallization solution to about 60 to about 185°

C. to crystallize free terephthalic acid; and

recovering the free terephthalic acid.