Process for isomerization and decarboxylation of unsaturated organic compounds with a metal catalyst or catalyst precursor

Patent metadata

Field	Value
Publication number	US-9868679-B2
Application number	US-201414203686-A
Country	US
Kind code	B2
Filing date	Mar 11, 2014
Priority date	Mar 15, 2013
Publication date	Jan 16, 2018
Grant date	Jan 16, 2018

Abstract

Disclosed is a method for using a metal catalyst or catalyst precursor that catalyzes the isomerization of an unsaturated fatty acid, unsaturated fatty acid derivative, or an unsaturated triglyceride. Also disclosed is a method for using a metal catalyst or catalyst precursor that catalyzes the decarboxylation of an unsaturated organic compound. Also disclosed is a method for using a catalyst or catalyst precursor for the dual function isomerization and decarboxylation of an unsaturated fatty acid to an unsaturated organic compound.

First claim

The embodiment of the invention in which exclusive property or privilege is claimed is defined as follows:

1. A process for the production of a decarboxylated unsaturated organic compound, the process comprising contacting an unsaturated carboxylic acid in the presence of a catalyst or catalyst precursor containing a ruthenium carbonyl carboxylates at a temperature at which decarboxylation occurs and recovering the decarboxylated unsaturated organic compound product; wherein the number of C—C double bonds in said decarboxylated unsaturated organic compound is the same as in said carboxylic acid.

2. The process of claim 1 comprising the additional step of contacting an additional acid to said carboxylic acid in the presence of a catalyst or catalyst precursor.

3. The process of claim 2 wherein the acid is a monocarboxylic acid.

4. The process of claim 3 wherein the monocarboxylic acid is benzoic acid, cinnamic acid, propanoic, acid, undecanoic acid, acetic acid, stearic acid, or oleic acid.

5. The process of claim 1 wherein the decarboxylated unsaturated organic compound product is an olefin.

6. The process of claim 5 wherein the olefin is further subject to an oligomerization or a polymerization reaction.

7. The process of claim 5 wherein the decarboxylated unsaturated organic compound product is a mixture of internal and alpha-olefins.

8. The process of claim 5 wherein the decarboxylated unsaturated organic compound product is a conjugated internal olefin.

9. A process for the isomerization and decarboxylation of an unsaturated carboxylic acid, the process comprising contacting an unsaturated carboxylic acid in the presence of a catalyst or catalyst precursor containing a ruthenium carbonyl carboxylates at a temperature at which the isomerization and decarboxylation occurs and recovering the products which are isomerized and decarboxylated unsaturated olefins, wherein the C—C double bonds in said isomerized and decarboxylated unsaturated olefins are in different locations compared to said unsaturated carboxylic acid, and wherein the number of C—C double bonds in said isomerized and decarboxylated unsaturated olefins are the same as in said unsaturated carboxylic acid.

10. The process of claim 9 comprising the additional step of contacting an additional acid to said unsaturated fatty acid in the presence of a catalyst or catalyst precursor.

11. The process of claim 10 wherein the acid is a monocarboxylic acid.

12. The process of claim 11 wherein the monocarboxylic acid is benzoic acid, cinnamic acid, propanoic acid, undecanoic acid, acetic acid, stearic acid, or oleic acid.

13. The process of claim 9 wherein the isomerized and decarboxylated unsaturated organic compound product is an olefin.

14. The process of claim 13 wherein the isomerized and decarboxylated unsaturated organic compound product is a mixture of internal and alpha-olefins.

15. The process of claim 13 wherein the isomerized and decarboxylated unsaturated organic compound product is a conjugated internal olefin.

16. A process for the production of an isomerized unsaturated vegetable oil, the process comprising contacting a starting unsaturated vegetable oil in the presence of a catalyst or catalyst precursor containing a ruthenium carbonyl carboxylates at a temperature at which isomerization occurs and recovering the isomerized unsaturated vegetable oil product, wherein the C—C double bonds in said isomerized unsaturated vegetable oil are in different locations compared to said starting unsaturated vegetable oil, wherein the branching of said isomerized unsaturated vegetable oil is not increased compared to said starting unsaturated vegetable oil, and wherein the number of C—C double bonds in said isomerized unsaturated vegetable oil is the same as in said starting unsaturated vegetable oil; wherein said catalyst or catalyst precursor does not contain a phosphine ligand.

17. The process of claim 16 comprising the additional step of contacting an additional acid to said vegetable oil in the presence of a catalyst or catalyst precursor.

18. The process of claim 17 wherein the acid is a monocarboxylic acid.

19. The process of claim 18 wherein the monocarboxylic acid is benzoic acid, cinnamic acid, propanoic acid, undecanoic acid, acetic acid, stearic acid, or oleic acid.

20. The process of claim 16 wherein the isomerized vegetable oil is an olefin containing triglyceride.

21. The process of claim 20 wherein the isomerized vegetable oil product is a mixture of internal and alpha-olefin containing triglycerides.

22. The process of claim 20 wherein the isomerized vegetable oil product contains a conjugated internal olefin.

23. The process of claim 20 , wherein said vegetable oil is soybean oil.

24. The process of claim 16 wherein the olefin is further subject to an oligomerization or a polymerization reaction.

Assignees

• Us Agriculture

Inventors

• Murray Rex E
• Doll Kenneth M
• Liu Zengshe

Classifications

• C07C2527/13

  Platinum group metals · CPC title

• C10G3/47

  containing platinum group metals or compounds thereof · CPC title

• C07C2521/06

  Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof · CPC title

• Y02P30/20

  using bio-feedstock · CPC title

• C10G50/00

  Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation · CPC title