Processes for purification, recovery, and conversion of chlorophenol salts and preparation and recovery of products prepared therefrom

Patent metadata

Field	Value
Publication number	US-11629114-B2
Application number	US-202017136341-A
Country	US
Kind code	B2
Filing date	Dec 29, 2020
Priority date	Dec 7, 2016
Publication date	Apr 18, 2023
Grant date	Apr 18, 2023

Abstract

The present invention generally relates to processes for purification, recovery, and conversion of chlorophenol salts (e.g., 2,5-dichlorophenol and salts thereof). In various aspects, the present invention is related to removing one or more impurities from chlorophenol salt-containing process streams and/or recovering chlorophenol salts from process streams for use of the recovered chlorophenol elsewhere in an integrated process. Process streams that may be treated in accordance with the present invention include those incorporating one or more chlorophenol salts in a feed mixture and also those where one or more chlorophenol salts are present in a product or by-product stream of an integrated process. For example, conversion processes of the present invention are suitable as one piece of an integrated process for producing 3,6-dichloro-2-methoxybenzoic acid (dicamba) or a salt or ester thereof or a process for producing 2,4-dichlorophenoxyacetic acid (2,4-D) or a salt or ester thereof. The present invention further relates to processes for preparation, purification, and recovery of intermediates formed in integrated processes utilizing chlorophenol salts such as 2,5-dichlorophenol as starting material, including the intermediate 3,6-dichlorosalicylic acid (3,6-DCSA) formed during preparation of dicamba from 2,5-dichlorophenol.

First claim

What is claimed is:

1. A process for preparation and recovery of 3,6-dichlorosalicylic acid (3,6-DCSA) and/or a salt thereof, the process comprising:
carboxylating 2,5-dichlorophenol (2,5-DCP) and/or a salt thereof in an organic reaction medium comprising an organic solvent, thereby forming a carboxylation product slurry comprising the organic solvent, 3,6-DCSA and/or one or more salts thereof, unreacted 2,5-DCP and/or a salt thereof, and one or more impurities;
feeding the carboxylation product slurry to a fractional liquid-liquid extraction (FLLE) zone;
feeding an organic solvent to the FLLE zone;
feeding an aqueous medium to the FLLE zone;
contacting the carboxylation product slurry with the organic solvent and the aqueous medium in the FLLE zone, wherein at least a portion of the unreacted 2,5-DCP and/or a salt thereof and the one or more impurities are transferred to an organic phase comprising the organic solvent and at least a portion of the 3,6-DCSA or a salt thereof is transferred to an aqueous phase;
recovering an aqueous phase extract comprising one or more salts of 3,6-DCSA from the FLLE zone, wherein the weight ratio of salts of 3,6-DCSA to 2,5-DCP in the aqueous phase extract is greater than the weight ratio of salts of 3,6-DCSA to 2,5-DCP in the carboxylation feed mixture;
recovering an organic phase extract comprising 2,5-DCP, the organic solvent and one or more impurities from the FLLE zone; and
neutralizing the salts of 3,6-DCSA in the aqueous phase extract to form a product mixture comprising 3,6-DCSA, wherein the FLLE zone comprises at least one vertical column having a feed location for the carboxylation product slurry, a stripping section, and a rectifying section, wherein the stripping section is the portion of the column situated beneath the feed location and the rectifying section is the portion of the column situated above the feed location, wherein the aqueous phase extract is recovered from the stripping section of the FLLE zone, and the organic phase extract is recovered from the rectifying section of the FLLE extraction zone.

2. The process of claim 1 wherein the carboxylation product slurry comprises the organic carboxylation reaction medium, unreacted 2,5-DCP and/or a salt thereof, and product solids comprising one or more salts of 3,6-DCSA.

3. The process of claim 1 wherein the aqueous medium further comprises an acid.

4. The process of claim 1 wherein the aqueous phase extract comprises one or more salts of 3,6-DCSA as solids distributed throughout the aqueous medium of the aqueous phase extract.

5. The process of claim 4 wherein the aqueous phase extract has a pH of from about 4 to about 9.

6. The process of claim 1 , the process further comprising feeding the aqueous phase extract to a mixing vessel, wherein an acid is introduced into the mixing vessel;
mixing the aqueous phase extract with the acid, thereby acidifying the one or more salts of 3,6-DCSA and the one or more salts of 2,5-DCP to form an aqueous mixture comprising water, 3,6-DCSA solids, and 2,5-DCP in the aqueous phase;
heating the aqueous mixture, thereby forming a vapor phase comprising 2,5-DCP over the acidified aqueous phase;
recovering the vapor phase from the mixing vessel, wherein the vapor phase is enriched in 2,5-DCP relative to the aqueous mixture; and
recovering a product slurry from the mixing vessel comprising 3,6-DCSA solids, wherein the product slurry is enriched in 3,6-DCSA relative to the aqueous mixture.

7. The process of claim 1 , the process further comprising:
recovering 2,5-DCP from the organic phase extract, wherein:
recovered 2,5-DCP is fed to an extraction zone for recovery of impurities therefrom and/or fed to a carboxylation reactor for production of the 3,6-dichlorosalicylic acid.

8. The process of claim 1 , the process further comprising:
heating a 2,5-DCP feed mixture to a temperature of at least about 25° C., the 2,5-DCP feed mixture comprising an organic solvent, 2,5-DCP, 2,5-dichloro-4-nitrophenol (2,5-DCNP), and a plurality of chlorophenol dimers;
feeding the 2,5-DCP feed mixture into a first extraction zone;
contacting the feed mixture within the first extraction zone with a first aqueous solution comprising a base, thereby forming a first organic phase extract comprising the organic solvent, 2,5-DCP and the plurality of chlorophenol dimers and forming a first aqueous phase extract comprising 2,5-DCNP and/or salts thereof, the first aqueous phase extract being enriched in 2,5-DCNP and/or salts thereof as compared to the first organic phase extract and the 2,5-DCP feed mixture;
feeding the first organic phase extract into a second extraction zone and contacting the first organic phase extract with a second aqueous solution comprising a base, thereby forming a second organic phase extract comprising the chlorophenol dimers and forming a second aqueous phase extract comprising 2,5-DCP and/or salts thereof, the second organic phase extract enriched in the chlorophenol dimers as compared to the first organic phase extract and the second aqueous phase extract enriched in 2,5-DCP as compared to the first organic phase extract, wherein:
the 2,5-DCP carboxylated in the organic reaction medium comprises 2,5-DCP recovered from the second aqueous phase extract.

9. The process of claim 8 wherein the second aqueous solution comprises the base in a molar ratio to 2,5-DCP present in the first organic phase extract of at least about 0.5:1.

10. The process of claim 8 wherein the concentration of base in the second aqueous solution is from about 1 wt % to about 45 wt %.

11. The process of claim 8 wherein the base constitutes less than about 2 wt % of the first aqueous solution.

12. The process of claim 8 wherein the molar ratio of base to 2,5-DCNP present in the feed mixture is from about 0.5:1 to about 5:1.

13. The process of claim 1 , wherein the 2,5-DCP carboxylated is provided by a process comprising:
providing a feed mixture comprising a chlorophenol salt, water, and an organic solvent;
distilling the feed mixture within a distillation zone, thereby forming an overheads fraction comprising water and a portion of the organic solvent and a bottoms fraction comprising the chlorophenol salt and a portion of the organic solvent, the bottoms fraction being enriched in chlorophenol salt as compared to the overheads fraction;
condensing the overheads fraction to form a recycle stream comprising recovered organic solvent and water;
removing water from the recycle stream; and
feeding the recycle stream comprising recovered organic solvent to the distillation zone.

14. The process of claim 13 wherein the overheads fraction comprises a minimum boiling azeotrope comprising the organic solvent and water, the overheads fraction having a boiling point less than the boiling point of any combination of its constituents.

15. The process of claim 13 wherein water is removed from the recycle stream by a liquid-liquid separation method selected from the group consisting of decanting, extraction, mixing/settling, centrifugation, and combinations thereof.

16. The process of claim 13 , further comprising recovering a chlorophenol salt from the bottoms fraction and wherein the chlorophenol salt is the potassium salt of 2,5-DCP, the process further comprising carboxylating the salt of 2,5-DCP in the recovered bottoms fraction removed from the distillation zone to form a carboxylation product slurry comprising 3,6-dichlorosalicylic acid or a salt thereof.

17. The process of claim 1 , further comprising methylating 3,6-dichlorosalicylic acid or a salt t

Assignees

• Monsanto Technology Llc

Inventors

• Berk Howard C
• De Kort Bruno
• Parlow John Joseph
• Stroman Amy E
• Yang Junqiu

Classifications

• C07C37/78

  by azeotropic distillation · CPC title

• C07C63/10 Primary

  Halides thereof · CPC title

• Y02P20/10

  Process efficiency · CPC title

• C07C37/685 Primary

  Processes comprising at least two steps in series · CPC title

• C07C51/15 Primary

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