Methods of refining and producing dibasic esters and acids from natural oil feedstocks

Patent metadata

Field	Value
Publication number	US-9365487-B2
Application number	US-201314048673-A
Country	US
Kind code	B2
Filing date	Oct 8, 2013
Priority date	Oct 12, 2009
Publication date	Jun 14, 2016
Grant date	Jun 14, 2016

Abstract

Methods and systems for making dibasic esters and/or dibasic acids using metathesis are generally disclosed. In some embodiments, the methods comprise reacting a terminal olefin ester with an internal olefin ester in the presence of a metathesis catalyst to form a dibasic ester and/or dibasic acid. In some embodiments, the terminal olefin ester or the internal olefin ester are derived from a renewable feedstock, such as a natural oil feedstock. In some such embodiments, the natural oil feedstock, or a transesterified derivative thereof, is metathesized to make the terminal olefin ester or the internal olefin ester.

First claim

What is claimed is:

1. A method of making an unsaturated dibasic ester, comprising:
providing a reactant composition comprising a terminal olefin ester and an internal olefin ester, wherein the internal olefin ester is a 9-dodecenoic acid ester; and
reacting the terminal olefin ester with the internal olefin ester in a reactor in the presence of a first metathesis catalyst to form an unsaturated dibasic ester and a first terminal olefin.

2. The method of claim 1 , wherein at least a portion of the first terminal olefin is removed from the reactor during the reacting.

3. The method of claim 1 , wherein the terminal olefin ester is a compound according to the following chemical formula:

wherein,
X is C 3-18 alkylene, which optionally comprises unsaturation; and
R is alkyl, which optionally comprises unsaturation or ether linkages.

4. The method of claim 3 , wherein X is —(CH 2 ) 2 —CH═, —(CH 2 ) 3 —CH═, —(CH 2 ) 4 —CH═, —(CH 2 ) 5 —CH═, —(CH 2 ) 6 —CH═, —(CH 2 ) 7 —CH═, —(CH 2 ) 8 —CH═, —(CH 2 ) 9 —CH═, —(CH 2 ) 10 —CH═, —(CH 2 ) 11 —CH═, —(CH 2 ) 12 —CH═, —(CH 2 ) 13 —CH═, —(CH 2 ) 14 —CH═, or —(CH 2 ) 15 —CH═.

5. The method of claim 4 wherein X is —(CH 2 ) 7 —CH═.

6. The method of claim 3 , wherein R is methyl, ethyl, or isopropyl.

7. The method of claim 1 , wherein the terminal olefin ester is a 4-pentenoic acid ester, a 5-hexenoic acid ester, a 6-heptenoic acid ester, a 7-octenoic acid ester, a 8-nonenoic acid ester, a 9-decenoic acid ester, a 10-undecenoic acid ester, a 11-dodecenoic acid ester, a 12-tridecenoic acid ester, a 13-tetradecenoic acid ester, a 14-pentadecenoic acid ester, a 15-hexadecenoic acid ester, a 16-heptadecenoic acid ester, a 17-octadecenoic acid ester, or any mixtures thereof.

8. The method of claim 7 , wherein the terminal olefin ester is a 9-decenoic acid ester.

9. The method of claim 1 , wherein providing a reactant composition comprises reacting the terminal olefin ester with an internal olefin in the presence of a second metathesis catalyst to form at least a portion of the internal olefin ester in the reaction composition.

10. The method of claim 9 , wherein the internal olefin is 2-butene, 2-pentene, 2-hexene, 3-hexene, 2-heptene, 3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, or any mixture thereof.

11. The method of claim 1 , wherein providing a reactant composition comprises reacting the internal olefin ester with a second terminal olefin in the presence of a third metathesis catalyst to form at least a portion of the terminal olefin ester in the reaction composition.

12. The method of claim 11 , wherein the second terminal olefin is ethylene, propene, 1-butene, or any mixture thereof.

13. The method of claim 1 , wherein the unsaturated dibasic ester is a diester of 9-octadecenedioic acid.

14. The method of claim 13 , wherein the unsaturated dibasic ester is 9-octadecenedioic acid dimethyl ester.

15. The method of claim 1 , wherein at least a portion of the terminal olefin ester is derived from a natural oil feedstock.

16. The method of claim 1 , wherein at least a portion of the internal olefin ester is derived from a natural oil feedstock.

17. A method of making a saturated dibasic ester, comprising:
making an unsaturated dibasic ester using a method of claim 1 ; and
hydrogenating the unsaturated dibasic ester to form a saturated dibasic ester.

Assignees

• Elevance Renewable Sciences

Inventors

• Snead Thomas E
• Cohen Steven A
• Gildon Demond L

Classifications

• C10G2300/1088

  Olefins · CPC title

• C10G29/205

  by reaction with hydrocarbons added to the hydrocarbon oil · CPC title

• C11C3/003

  by esterification of fatty acids with alcohols (C11C3/02 takes precedence) · CPC title

• C07C67/343 Primary

  by increase in the number of carbon atoms · CPC title

• C10L1/02

  essentially based on components consisting of carbon, hydrogen, and oxygen only · CPC title