Process for the preparation and isolation of carboxylic esters

Patent metadata

Field	Value
Publication number	US-9963414-B2
Application number	US-201415101899-A
Country	US
Kind code	B2
Filing date	Dec 5, 2014
Priority date	Dec 6, 2013
Publication date	May 8, 2018
Grant date	May 8, 2018

Abstract

The disclosed methods for preparing and isolating carboxylic esters ensure a high product purity and minimize technical complexity. These methods are based on the reaction of a carboxylic acid with an alcohol in an aqueous medium. In some examples, the alcohol is used both for the esterification and for the precipitation of the salts, preferably ammonium salts, formed in the synthesis.

First claim

What is claimed is:

1. A method for preparing and isolating carboxylic esters of mono- and dicarboxylic acids, hydroxycarboxylic acids, and fatty acids, the method comprising:
providing an aqueous solution of at least one salt of at least one carboxylic acid;
acidifying the aqueous solution with at least one acid to form a free carboxylic acid and a salt of said at least one acid;
precipitating the salt of said at least one acid, formed in said acidifying step, by adding at least one alcohol to the aqueous solution;
removing the precipitated salt from the aqueous solution;
esterifying the at least one free carboxylic acid by adding at least one alcohol; and
separating at least one carboxylic ester from the aqueous solution.

2. The method of claim 1 wherein the at least one salt of the aqueous solution consists of ammonium salt, calcium salt, potassium salt, sodium salt, or a combination thereof.

3. The method of claim 1 further comprising preparing the at least one carboxylic acid of the aqueous solution by fermentation or another biotransformation process, wherein the aqueous solution comprises a fermentation broth comprising biomass present as a suspension, wherein the carboxylic acid salt of the aqueous solution is prepared by neutralization with a base.

4. The method of claim 3 further comprising removing the biomass including any cells and solids present in the aqueous solution directly before, during, or directly after acidifying the aqueous solution, wherein the removing occurs by way of gravimetric separation, centrifugation, microfiltration, ultrafiltration, nanofiltration, and/or any combination thereof.

5. The method of claim 1 further comprising concentrating the aqueous solution by reverse osmosis or evaporation before acidifying.

6. The method of claim 1 wherein the at least one acid used to acidify the aqueous solution has a pKa value less than a pKa value of the carboxylic acid to be isolated and consists of sulfuric acid, phosphoric acid, nitric acid, salt water, aqua regia, carbonic acid, or combinations thereof.

7. The method of claim 1 , wherein the at least one alcohol added to the aqueous solution is one or more of:
a straight-chain or branched C 1 -C 8 -alcohol, comprising one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and combinations thereof;
a straight-chain or branched C 1 -C 8 -diol, comprising one or more of ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and combinations thereof; or
a straight-chain or branched C l -C 8 -polyol.

8. The method of claim 1 wherein removing the precipitated salt from the aqueous solution comprises using a separation process involving gravimetric separation, centrifugation, or combinations thereof.

9. The method of claim 1 further comprising at least one of washing or drying the precipitated salt that is removed from the aqueous solution.

10. The method of claim 1 , further comprising:
adjusting a ratio of alcohol to water in the esterification from 1:5 to 10:1.

11. The method of claim 1 , further comprising:
during said esterifying step, further adding a catalyst that is one or more of:
a water-soluble protic acid,
a water-insoluble acid,
a lipase, or
a solid acid.

12. The method of claim 1 wherein the esterifying is performed at a temperature of between 5-150 degrees Celsius and/or a pressure of 0.1-10 bar.

13. The method of claim 1 wherein the esterifying comprises adding CO2 as a catalyst.

14. The method of claim 1 wherein the esterifying is performed at a temperature of between 5-90 degrees Celsius and/or a pressure of 1-300 bar.

15. The method of claim 14 wherein the at least one acid used to acidify the aqueous solution is a water-soluble acid and is recyclable in the method.

16. The method of claim 1 , wherein the at least one alcohol used in the esterifying is one or more of:
a straight-chain or branched C 1 -C8-alcohol, comprising one or more of methanol, ethanol, propanol, isopropanol, butanol, isobutanol, pentanol, hexanol, heptanol, octanol, and combinations thereof;
a straight-chain or branched C l -C 8 diol, comprising one or more of ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, and combinations thereof; or
a straight-chain or branched C 1 -C 8 -polyol.

17. The method of claim 16 wherein the at least one alcohol used in the esterifying is identical to the at least one alcohol used in the precipitating such that the at least one alcohol is recyclable in the method.

18. The method of claim 1 wherein the esterifying comprises extracting carboxylic esters with at least one organic solvent.

19. The method of claim 1 wherein the precipitating, the removing the precipitated salt, and the esterifying occur simultaneously.

20. The method of claim 1 wherein the separating the at least one carboxylic ester is effected by distillation, subcritical fluid chromatography, or supercritical fluid chromatography.

21. The method of claim 1 further comprising converting the at least one carboxylic ester into the free carboxylic acid after separating the at least one carboxylic ester.

22. The method of claim 1 , wherein the mono- or dicarboxylic acids are one or more of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, sebacic acid, dodecanedioic acid, or itaconic acid, and/or the hydroxycarboxylic acids are one or more of malic acid, glycolic acid, mandelic acid, lactic acid, tartronic acid, tartaric acid, citric acid, 3-hydroxypropionic acid, hydroxybutyric acid, mevalonic acid, gallic acid, salicylic acid, or hydroxybenzoic acid.

Assignees

• Thyssenkrupp Ind Solutions Ag
• Thyssenkrupp Ag

Inventors

• Fritsch Markus
• Börner Armin
• Shuklov Ivan
• Knez Zeljko

Classifications

• C07C51/02

  from salts of carboxylic acids · CPC title

• C07C51/09

  from carboxylic acid esters or lactones · CPC title

• C07C51/43

  by change of the physical state, e.g. crystallisation · CPC title

• C07C51/493

  whereby carboxylic acid esters are formed · CPC title

• C07C67/08 Primary

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title