Methods of refining and producing isomerized fatty acid esters and fatty acids from natural oil feedstocks
View Patent ↗Methods are provided for refining natural oil feedstocks and producing isomerized esters and acids. The methods comprise providing a C4-C18 unsaturated fatty ester or acid, and isomerizing the fatty acid ester or acid in the presence of heat or an isomerization catalyst to form an isomerized fatty ester or acid. In some embodiments, the methods comprise forming a dibasic ester or dibasic acid prior to the isomerizing step. In certain embodiments, the methods further comprise hydrolyzing the dibasic ester to form a dibasic acid. In certain embodiments, the olefin is formed by reacting the feedstock in the presence of a metathesis catalyst under conditions sufficient to form a metathesized product comprising olefins and esters, separating the olefins from the esters in the metathesized product, and transesterifying the esters in the presence of an alcohol to form a transesterified product having unsaturated esters.
1. A method of making an isomerized ester, comprising:
providing a C4-C22 unsaturated fatty acid ester; and
isomerizing the C4-C22 unsaturated fatty acid ester in the presence of heat or an isomerization catalyst to form an isomerized acid ester;
wherein the isomerization catalyst is (PCy 3 ) 2 (Cl)(H)Ru(CO) or a sulfonated tetrafluoroethylene polymer; and
wherein the melting point of the isomerized acid ester is reduced by at least 10° C. in comparison to the C4-C22 unsaturated fatty acid ester.
2. The method of claim 1 , wherein the unsaturated fatty acid ester is derived from transesterifying a natural oil feedstock in the presence of an alcohol to form the unsaturated fatty acid ester.
3. The method of claim 1 , wherein the unsaturated fatty acid ester is selected from the group consisting of: pentenoic acid esters, hexenoic acid esters, heptenoic acid esters, octenoic acid esters, nonenoic acid esters, decenoic acid esters, undecenoic acid esters, dodecenoic acid esters, tridecenoic acid esters, tetradecenoic acid esters, pentadecenoic acid esters, hexadecenoic acid esters, heptadecenoic acid esters, octadecenoic acid esters, and mixtures thereof.
4. The method of claim 1 , wherein the solubility of the isomerized acid ester at ambient temperature is at least 10% higher in comparison to the solubility of the C4-C22 unsaturated fatty acid ester in the same solvent.
5. The method of claim 1 , wherein the isomerizing step is conducted by heating a reactor containing unsaturated fatty acid ester to a temperature greater than 100° C.
6. The method of claim 1 , wherein unsaturated fatty acid ester comprises a terminal olefin ester having the following structure:
wherein X is a C 3 -C 18 saturated or unsaturated alkyl chain, and R is an alkyl group.
7. The method of claim 6 , wherein R is methyl.
8. The method of claim 6 , further comprising, prior to the isomerizing step:
providing an internal olefin; and
reacting the terminal olefin ester with the internal olefin in the presence of a metathesis catalyst to form a dibasic ester, wherein, in the subsequent isomerizing step, forming a isomerized dibasic ester.
9. The method of claim 8 , further comprising hydrogenating the isomerized dibasic ester.
10. The method of claim 8 , further comprising reacting the isomerized dibasic ester with itself or a low-molecular-weight olefin in the presence of metathesis catalyst to form a metathesized dibasic ester.
11. The method of claim 8 , wherein the terminal olefin ester is selected from the group consisting of: 4-pentenoic acid ester, 5-hexenoic acid ester, 6-heptenoic acid ester, 7-octenoic acid ester, 8-nonenoic acid ester, 9-decenoic acid ester, 10-undecenoic acid ester, 11-dodecenoic acid ester, 12-tridecenoic acid ester, 13-tetradecenoic acid ester, 14-pentadecenoic acid ester, 15-hexadecenoic acid ester, 16-heptadecenoic acid ester, 17-octadecenoic acid ester, and mixtures thereof.
12. The method of claim 8 , wherein the terminal olefin is 9-decenoic acid ester.
13. The method of claim 8 , wherein the internal olefin ester is selected from the group consisting of: pentenoic acid esters, hexenoic acid esters, heptenoic acid esters, octenoic acid esters, nonenoic acid esters, decenoic acid esters, undecenoic acid esters, dodecenoic acid esters, tridecenoic acid esters, tetradecenoic acid esters, pentadecenoic acid esters, hexadecenoic acid esters, heptadecenoic acid esters, octadecenoic acid esters, and mixtures thereof.
14. The method of claim 8 , wherein the internal olefin is 9-dodecenoic acid ester.
15. The method of claim 8 , further comprising hydrolyzing the isomerized dibasic ester to form an isomerized dibasic acid.