Metathesis methods involving hydrogenation and compositions relating to same
View Patent ↗Disclosed are improved methods for conducting metathesis utilizing polyunsaturated fatty acid compositions (e.g., polyunsaturated fatty acid polyol esters, polyunsaturated fatty acids, polyunsaturated fatty esters, and mixtures), such as those found in naturally occurring oils and fats, as the starting material. The inventive methods involve hydrogenation of polyunsaturated fatty acid compositions prior to metathesis, thereby providing partially-hydrogenation compositions having a relatively higher amount of monounsaturated fatty acid species. The partially hydrogenated composition can then be subjected to metathesis to provide a metathesis product composition containing industrially useful compounds.
1. A method comprising steps of:
(a) providing a polyunsaturated fatty acid composition;
(b) providing a hydrogenation catalyst;
(c) hydrogenating at least a portion of the polyunsaturated fatty acid composition in the presence of the hydrogenation catalyst to form a partially hydrogenated composition;
(d) providing a metathesis catalyst comprising a transition metal; and
(e) metathesizing at least a portion of the partially hydrogenated composition in the presence of the metathesis catalyst to form a composition comprising a mixture of metathesis products, wherein the metathesizing step comprises cross-metathesizing at least a portion of the partially hydrogenated composition with a small olefin.
2. The method according to claim 1 , wherein the polyunsaturated fatty acid composition comprises a polyunsaturated fatty acid, a polyunsaturated fatty monoester, a polyol ester having one or more polyunsaturated fatty acids, or a mixture thereof.
3. The method according to claim 1 , wherein the polyunsaturated fatty acid composition comprises providing a natural oil.
4. The method according to claim 3 , wherein the natural oil is soybean oil.
5. The method according to claim 1 , wherein the step of providing a hydrogenation catalyst comprises providing a hydrogenation catalyst selected from nickel, copper, palladium, platinum, molybdenum, iron, ruthenium, osmium, rhodium, iridium, zinc, cobalt, or a combination of any of these.
6. A method comprising steps of:
(a) providing a polyunsaturated fatty acid composition;
(b) providing a hydrogenation catalyst;
(c) hydrogenating at least a portion of the polyunsaturated fatty acid composition in the presence of the hydrogenation catalyst to form a partially hydrogenated composition;
(d) providing a metathesis catalyst comprising a transition metal; and
(e) metathesizing at least a portion of the partially hydrogenated composition in the presence of the metathesis catalyst to form a composition comprising a mixture of metathesis products, wherein the step of hydrogenating at least a portion of the polyunsaturated polyol ester composition comprises subjecting the polyunsaturated composition to electrocatalytic hydrogenation.
7. A method comprising steps of:
(a) providing a polyunsaturated fatty acid composition;
(b) providing a hydrogenation catalyst;
(c) hydrogenating at least a portion of the polyunsaturated fatty acid composition in the presence of the hydrogenation catalyst to form a partially hydrogenated composition;
(d) providing a metathesis catalyst comprising a transition metal; and
(e) metathesizing at least a portion of the partially hydrogenated composition in the presence of the metathesis catalyst to form a composition comprising a mixture of metathesis products, wherein the partially hydrogenated composition comprises a partially hydrogenated polyol ester having an acid profile comprising monounsaturated fatty acid groups in an amount of 65 wt % or more.
8. A method comprising steps of:
(a) providing a polyunsaturated fatty acid composition;
(b) providing a hydrogenation catalyst;
(c) hydrogenating at least a portion of the polyunsaturated fatty acid composition in the presence of the hydrogenation catalyst to form a partially hydrogenated composition;
(d) providing a metathesis catalyst comprising a transition metal; and
(e) metathesizing at least a portion of the partially hydrogenated composition in the presence of the metathesis catalyst to form a composition comprising a mixture of metathesis products, wherein the partially hydrogenated composition comprises a partially hydrogenated polyol ester having an acid profile comprising polyunsaturated fatty acid groups in an amount of about 10 wt % or less.
9. A method comprising steps of:
(a) providing a polyunsaturated fatty acid composition;
(b) providing a hydrogenation catalyst;
(c) hydrogenating at least a portion of the polyunsaturated fatty acid composition in the presence of the hydrogenation catalyst to form a partially hydrogenated composition;
(d) providing a metathesis catalyst comprising a transition metal; and
(e) metathesizing at least a portion of the partially hydrogenated composition in the presence of the metathesis catalyst to form a composition comprising a mixture of metathesis products, wherein the partially hydrogenated composition comprises a partially hydrogenated composition having an acid profile comprising saturated fatty acid groups in an amount of 0.5 wt % to 10 wt % higher than the saturated fatty acid groups in the polyunsaturated fatty acid composition.
10. The method according to claim 7 , wherein the polyunsaturated fatty acid composition is derived from soybean oil, and wherein the acid profile comprises monounsaturated fatty acid groups in an amount of 70 wt % or more.
11. The method according to claim 1 , further comprising the step of removing the hydrogenation catalyst prior to the metathesizing step.
12. The method according to claim 1 , wherein the step of providing a metathesis catalyst comprises providing a metal carbene catalyst selected from ruthenium, molybdenum, osmium, chromium, rhenium, tungsten, or a combination of any of these.
13. The method according to claim 1 , wherein the metathesizing step comprises a self-metathesis reaction.
14. The method according to claim 13 , wherein the metathesis products comprise internal olefins, monounsaturated fatty esters, and monounsaturated fatty diesters.
15. The method according to claim 14 , wherein the monounsaturated fatty diesters have a chain length ranging from 8 to 32 carbon atoms.
16. The method according to claim 14 , wherein at least a portion of the monounsaturated fatty esters and monounsaturated fatty diesters are in triglyceride form.
17. The method according to claim 1 , wherein the small olefin is a terminal olefin selected from ethylene, propylene, 1-butene, and 1-pentene.
18. The method according to claim 1 , wherein the metathesis composition comprises (i) monounsaturated fatty esters having terminal double bonds; and (ii) olefins with terminal double bonds.
19. The method according to claim 18 , wherein the monounsaturated fatty esters are in triglyceride form.
20. The method according to claim 18 , wherein the terminal monounsaturated fatty esters have a chain length of 4 to 16.
21. The method according to claim 18 , further comprising
(f) hydrolyzing at least a portion of the monounsaturated fatty esters to form monounsaturated fatty acids.
22. The method according to claim 1 , wherein the hydrogenating step comprises
selectively hydrogenating at least a portion of the polyunsaturated fatty acid composition in the presence of the hydrogenation catalyst, under conditions sufficient to form the partially hydrogenated composition having monounsaturated fatty acids or esters.