Separation of dichlorophenols

Patent metadata

Field	Value
Publication number	US-10343965-B2
Application number	US-201615578869-A
Country	US
Kind code	B2
Filing date	May 31, 2016
Priority date	Jun 3, 2015
Publication date	Jul 9, 2019
Grant date	Jul 9, 2019

Abstract

Various processes for the separation of a mixture containing dichlorophenols are described. In various aspects, the present invention relates to separation processes that produce an extract enriched in 2,4-dichlorophenol content and an extract enriched in 2,5-dichlorophenol content. The present invention further relates to various processes that integrate with these separation processes, such as a process for producing 3,6-dichloro-2-methoxybenzoic acid (dicamba) or salt or ester thereof or a process for producing 2,4-dichlorophenoxyacetic acid (2,4-D) or salt or ester thereof.

First claim

What is claimed is:

1. A process for producing an aqueous extract comprising 2,5-dichlorophenol and/or a salt thereof, the process comprising:
feeding a chlorophenol feed mixture comprising 2,5-dichlorophenol and 2,4-dichlorophenol to a fractional liquid-liquid extraction (FLLE) zone comprising a rectifying section and a stripping section;
feeding an organic solvent to the stripping section of the FLLE zone;
feeding an aqueous solution comprising base to the rectifying section of the FLLE zone;
contacting the feed mixture with the organic solvent and the aqueous solution comprising base in the FLLE zone, wherein at least a portion of the 2,5-dichlorophenol is transferred to an aqueous phase and at least a portion of the 2,4-dichlorophenol is transferred to an organic phase comprising the organic solvent;
feeding an aqueous solution comprising acid into the stripping section of the FLLE zone;
removing the aqueous extract comprising 2,5-dichlorophenol and/or a salt thereof in the aqueous phase from the stripping section of the FLLE zone, wherein the weight ratio of total 2,5-dichlorophenol to total 2,4-dichlorophenol in the aqueous extract is greater than the weight ratio of 2,5-dichlorophenol to 2,4-dichlorophenol in the chlorophenol feed mixture; and
removing an organic extract comprising 2,4-dichlorophenol in the organic phase from the rectifying section of the FLLE zone.

2. The process of claim 1 wherein the rectifying section and/or the stripping section comprises a series of stages.

3. The process of claim 2 wherein the FLLE zone comprises at least one vertical column having a feed location for the chlorophenol feed mixture and wherein the rectifying section is the portion of the column situated above the feed location and the stripping section is the portion of the column situated beneath the feed location.

4. The process of claim 3 wherein the organic solvent is fed into a stage that is positioned within a lower portion of the stripping section.

5. The process of claim 1 wherein the organic solvent comprises xylenes.

6. The process of claim 3 wherein the aqueous solution comprising base is fed into a stage that is positioned within an upper portion of the rectifying section.

7. The process of claim 1 wherein the base comprises potassium hydroxide.

8. The process of claim 3 , wherein the aqueous solution comprising acid is fed into a stage that is positioned with a lower portion of the stripping section.

9. The process of claim 1 wherein the acid comprises hydrochloric acid.

10. The process of claim 1 wherein the molar ratio of acid to base is from about 0.5:1 to about 2:1.

11. The process of claim 1 wherein the pH of the aqueous extract comprising 2,5-dichlorophenol and/or a salt thereof in the aqueous phase exiting the stripping section is maintained between about 8 and about 9.

12. The process of claim 1 wherein the pH of the aqueous phase contacting the organic extract comprising 2,4-dichlorophenol in the organic phase exiting the rectifying section is greater than the pH of the aqueous extract comprising 2,5-dichlorophenol and/or a salt thereof in the aqueous phase exiting the stripping section.

13. The process of claim 1 wherein the pH of the aqueous phase contacting the organic extract comprising 2,4-dichlorophenol in the organic phase exiting the rectifying section is between about 9 and about 10.5.

14. The process of claim 1 wherein the weight ratio of 2,4-dichlorophenol to 2,5-dichlorophenol in the chlorophenol feed mixture to the FLLE zone is from about 1:1 to about 5:1.

15. The process of claim 1 wherein the chlorophenol feed mixture further comprises 2-, 3-, 4-monochlorophenol, 2,6-dichlorophenol, 3,4-dichlorophenol, and/or 2,3-dichlorophenol.

16. The process of claim 1 wherein the total 2,5-dichlorophenol content in the aqueous extract is from about 55 wt. % to about 99 wt. % of the total chlorophenol content in the aqueous extract.

17. The process of claim 1 wherein the weight ratio of total 2,5-dichlorophenol to total 2,4-dichlorophenol in the aqueous extract is from about 10:1 to 200:1.

18. The process of claim 1 wherein the aqueous extract comprising 2,5-dichlorophenol and/or a salt thereof in the aqueous phase further comprises 2,6-dichlorophenol and/or a salt thereof, and wherein the total content of 2,6-dichlorophenol is no more than about 3 wt. % of the total chlorophenol content of the aqueous extract.

19. The process of claim 1 wherein the aqueous extract comprising 2,5-dichlorophenol and/or a salt thereof in the aqueous phase further comprises 2,3-dichlorophenol and/or a salt thereof, and wherein the total content of 2,3-dichlorophenol is no more than about 1 wt. % of the total chlorophenol content of the aqueous extract.

20. The process of claim 1 , further comprising:
carboxylating at least a portion of 2,5-dichlorophenol or salt thereof obtained from the aqueous extract removed from the FLLE zone to form 2-hydroxy-3,6-dichlorobenzoic acid or salt thereof;
methylating 2-hydroxy-3,6-dichlorobenzoic acid or salt thereof with a methylating agent to form 3,6-dichloro-2-methoxybenzoic acid or salt thereof and/or methyl 3,6-dichloro-2-methyoxybenzoate; and
when methyl 3,6-dichloro-2-methyoxybenzoate is formed, saponifying methyl 3,6-dichloro-2-methyoxybenzoate with a base to form a salt of 3,6-dichloro-2-methoxybenzoic acid.

Assignees

• Monsanto Technology Llc

Inventors

• Wan Kam-To
• Casanova Eduardo A
• Ahn John H
• Yang Junqiu

Classifications

• C07C67/31

  by introduction of functional groups containing oxygen only in singly bound form · CPC title

• C07C51/15

  by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis · CPC title

• C07C51/09

  from carboxylic acid esters or lactones · CPC title

• C07C39/30

  the halogen being two chlorine atoms · CPC title

• C07C37/84

  by crystallisation · CPC title