Process for hydrogenolysis of alpha-hydroxy esters or acids using a heterogeneous catalyst

Patent metadata

Field	Value
Publication number	US-10189768-B2
Application number	US-201615739378-A
Country	US
Kind code	B2
Filing date	Jun 23, 2016
Priority date	Jun 25, 2015
Publication date	Jan 29, 2019
Grant date	Jan 29, 2019

Abstract

The present invention relates to a method for hydrogenolysis of alpha-hydroxy esters or acids, comprising reacting the alpha-hydroxy ester or acid in the presence of a heterogeneous catalyst. The present invention also relates to a method for producing propionic acid ester, and the use of any of the methods for the production of propionic acid esters, such as alkyl propionate.

First claim

The invention claimed is:

1. A method for hydrogenolysis of alpha-hydroxy esters or acids, comprising:
reacting the alpha-hydroxy ester or acid in the presence of a solid catalyst and a catalyst support,
wherein the catalyst comprises at least two different metals that are Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt, Au, or Hg, or a combination thereof, and
wherein the catalyst support is a porous solid material with the proviso that if the porous solid material consists of one metal oxide, the metal oxide is not SiO 2 .

2. The method according to claim 1 , wherein the catalyst is a bimetallic compound comprising iron (Fe), or wherein the catalyst is a bimetallic compound comprising rhenium (Re).

3. The method according to claim 1 , wherein the catalyst support comprises one or more metal oxide(s), and/or a thermally stable polymer, and/or activated carbon, and/or wherein the catalyst support is microporous and/or mesoporous.

4. The method according to claims 3 , wherein the metal oxide is selected from the group consisting of: ZrO 2 , TiO 2 , Al 2 O 3 , MgAl 2 O 4 , zeolites, combinations thereof, and any combination with SiO 2 .

5. The method according to claim 1 , wherein the alpha-hydroxy ester or acid has the formula:

wherein R 1 and R 2 are independently selected from the group consisting of: hydrogen, alkyl, halogenated alkyl, aminoalkyl, hydroxyalkyl, alkoxyalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, and heterocycloalkenyl.

6. The method according to claim 5 , wherein the alpha-hydroxy ester is an alkyl lactate.

7. The method according to claim 6 , wherein the alkyl lactate is methyl lactate.

8. The method according to claim 5 , wherein R 1 and R 2 are independently C 1 -C 9 alkyl or hydrogen.

9. The method according to claim 1 , wherein the process is carried out at elevated pressure and temperature, and in the presence of a hydrogen source.

10. The method according to claim 9 , wherein the hydrogen source is a gas comprising H 2 and/or a component decomposing into hydrogen.

11. A method for producing propionic acid ester or acid with the formula:

wherein R 1 is methyl, and
R 2 is selected from the group consisting of hydrogen, alkyl, halogenated alkyl, aminoalkyl, hydroxyalkyl, alkoxyalkyl, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocycloalkyl, and heterocycloalkenyl, comprising the steps of:
(i) providing an alpha-hydroxy ester or acid,
(ii) providing a solid catalyst and a catalyst support,
wherein the catalyst comprises at least two different metals that are Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, Cd, W, Re, Os, Ir, Pt, Au, or Hg, or a combination thereof, and
wherein the catalyst support is a solid material with the proviso that if the porous solid material consists of one metal oxide, the metal oxide is not SiO 2 , and

(iii) reacting the alpha-hydroxy ester or acid in the presence of the catalyst and catalyst support,

whereby the alpha-hydroxy ester or acid is converted into propionic acid ester or propionic acid.

12. The method according to claim 11 , wherein the alpha-hydroxy ester is an alkyl lactate, and/or wherein the propionic acid ester is selected from the group consisting of: alkyl propionate, aryl propionate, and alkenyl propionate.

13. The method according to claim 12 , wherein the alkyl lactate is methyl lactate, and/or wherein the propionic acid ester is methyl propionate.

14. The method according to claim 11 , wherein step (iii) is carried out at elevated pressure and temperature, and in the presence of a hydrogen source.

15. The method according to claim 14 , wherein the hydrogen source is a gas comprising H 2 and/or a component decomposing into hydrogen.

16. The method according to claim 1 , wherein the method is selected from the group consisting of: a batch process, a continuous process, such as a continuous flow fixed-bed process and/or fluidized-bed flow process.

17. The method according to claim 11 , wherein the method is selected from the group consisting of: a batch process, a continuous process, such as a continuous flow fixed-bed process and/or fluidized-bed flow process.

18. The method according to claim 1 , wherein the catalyst is a ferrite.

19. The method according to claim 18 , wherein the catalyst is nickel ferrite (NiFe 2 O 4 ) and/or cobalt ferrite (CoFe 2 O 4 ).

Assignees

• Univ Danmarks Tekniske

Inventors

• Saravanamurugan Shunmugavel
• Khokarale Santosh Govind
• Riisager Anders

Classifications

• C07C67/327 Primary

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

• C07C69/24

  esterified with monohydroxylic compounds · CPC title