Methods of refining and producing dibasic esters and acids from natural oil feedstocks
View Patent ↗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.
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.