Process for the oxidative cleavage of vicinal diols

Patent metadata

Field	Value
Publication number	US-10421925-B2
Application number	US-201716306122-A
Country	US
Kind code	B2
Filing date	Jun 5, 2017
Priority date	Jun 6, 2016
Publication date	Sep 24, 2019
Grant date	Sep 24, 2019

Abstract

This invention relates to a process for obtaining monocarboxylic and dicarboxylic acids from unsaturated carboxylic acids and/or their derivatives. The said process comprises an oxidative cleavage reaction of vicinal diols into which are fed at least some of the aqueous phase separated out at the end of the reaction itself and at least one base so that the pH of the aqueous solution at the start of the oxidative cleavage reaction is between 4 and 7.

First claim

The invention claimed is:

1. A process for the oxidative cleavage of unsaturated carboxylic acids and their derivatives for the obtainment of saturated monocarboxylic and dicarboxylic acids or derivatives thereof comprising the steps of:
a) reacting at least one unsaturated carboxylic acid or derivative thereof, an oxidising compound and a catalyst cap able of catalysing the oxidation reaction of the olefin double bond, in order to obtain an intermediate compound containing vicinal diols, and
b) reacting the said intermediate compound, oxygen or a compound containing oxygen, and a catalyst capable of catalysing the oxidation reaction of vicinal diols to carboxyl groups in the presence of water, obtaining an organic phase comprising saturated monocarboxylic acids and saturated dicarboxylic acids or their derivatives, and an aqueous phase comprising the said catalyst, and
c) separating the said aqueous phase from the said organic phase,
characterised in that at least a part of the said aqueous phase comprising the catalyst and at least one base are fed to step b) so that the mixture of the intermediate compound of step a) with the said part of aqueous phase and the said base has a pH value of between 4 and 7.

2. The process according to claim 1 , in which the said derivatives are esters of unsaturated carboxylic acids with monoalcohols and/or polyalcohols.

3. The process according to claim 2 in which the said derivatives are selected from methyl esters, ethyl esters, propyl esters, butyl esters, monoglycerides, diglycerides, triglycerides, or mixtures thereof.

4. The process according to claim 1 in which the said catalyst in step a) is in homogenous or heterogeneous phase and belongs to the group of transition elements and acids, alkali metal salts and complexes thereof.

5. The process according to claim 1 in which the said catalyst in step b) is in homogeneous phase and belongs to the group of transition elements and acids, alkali metal salts and complexes thereof.

6. The process according to claim 1 in which the said catalyst in step b) is selected from Ce, Cr, Co, Cu, Mn, Mo, Re, Os, V and W and acids, alkali metal salts and complexes thereof.

7. The process according to claim 1 in which the said catalyst in step a) is tungstic or phosphotungstic acid, and in which the said catalyst in step b) is a cobalt salt.

8. The process according to claim 1 in which the ratio by weight between the aqueous phase and the organic phase during step b) is below 5:1.

9. The process according to claim 1 in which the reaction time for each of steps a) and b) is between 2 and 8 hours.

10. The process according to claim 1 in which the said step c) comprises one or more operations selected from: decanting, degassing, heating, filtration, washing with water and/or the addition of organic solvents which are immiscible with water.

11. The process according to claim 1 in which the said aqueous phase separated out in step c) is subjected to one or more concentration treatments before being fed back to step b).

12. The process according to claim 1 in which the said base is selected from alkali metal hydroxydes, alkaline earth hydroxydes, transition metal hydroxides, alkaline earth oxides, alkaline earth carbonates and bicarbonates, acetates and mixtures thereof.

13. The process according to claim 12 in which the said base is selected from sodium hydroxide and potassium hydroxide.

14. The process according to claim 1 in which the aqueous phase separated out in step c) and comprising the catalyst of step b) is fed back to step b) as an alternative to fresh catalyst.

15. The process according to claim 1 in which the aqueous phase separated out in step c) and comprising the catalyst of step b) is fed back to step b) together with fresh catalyst.

16. The process according to claim 2 in which the said catalyst in step a) is in homogenous or heterogeneous phase and belongs to the group of transition elements and acids, alkali metal salts and complexes thereof.

17. The process according to claim 3 in which the said catalyst in step a) is in homogenous or heterogeneous phase and belongs to the group of transition elements and acids, alkali metal salts and complexes thereof.

18. The process according to claim 2 in which the said catalyst in step b) is in homogeneous phase and belongs to the group of transition elements and acids, alkali metal salts and complexes thereof.

19. The process according to claim 3 in which the said catalyst in step b) is in homogeneous phase and belongs to the group of transition elements and acids, alkali metal salts and complexes thereof.

20. The process according to claim 4 in which the said catalyst in step b) is in homogeneous phase and belongs to the group of transition elements and acids, alkali metal salts and complexes thereof.

Assignees

• Novamont Spa

Inventors

• Digioia Francesca

Classifications

• C07C67/333

  by isomerisation; by change of size of the carbon skeleton (introduction or elimination of carboxyl groups C07C67/313, C07C67/32) · CPC title

• C07C67/31 Primary

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

• C07C51/367

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

• C07C51/245

  of keto groups or secondary alcohol groups · CPC title

• B01J23/30

  Tungsten · CPC title