Method to make alkanes and saturated polyhydroxy compounds from carbonyl compounds
A catalytic process for converting biomass-derived carbohydrates to liquid alkanes, alkenes, and/or ethers is described. The process uses combinations of self- and crossed-aldol condensation reactions, dehydration reactions, and hydrogenation reactions, over specified metal-containing catalysts, to yield alkane, alkene, and ether products from carbohydrate reactants.
1. A method for making alkanes comprising, in an aqueous reaction solution:
(a) subjecting a carbonyl compound to at least one self-aldol condensation reaction or a crossed-aldol condensation reaction with another carbonyl compound to yield a beta-hydroxy carbonyl compound and/or an alpha-beta unsaturated carbonyl compound; then
(b) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated compounds to yield a saturated polyhydroxy compound; and then
(c) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 6 to C 15 alkane that is immiscible in the aqueous reaction solution.
2. The method of claim 1 , wherein step (a) further comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen.
3. A method for making alkanes comprising, in an aqueous reaction solution:
(a) reducing a carbohydrate reactant to yield at least one carbonyl compound having an alpha-position hydrogen; then
(b) subjecting the carbonyl compound to at least one self-aldol condensation reaction or a crossed-aldol condensation reaction with another carbonyl compound to yield a beta-hydroxy carbonyl compound and/or an alpha-beta unsaturated carbonyl compound; then
(c) hydrogenating the beta-hydroxy carbonyl and/or the alpha-beta unsaturated carbonyl compounds to yield a saturated polyhydroxy compound; and then
(d) dehydrating and hydrogenating the saturated polyhydroxy compound to yield an alkane that is immiscible in the aqueous reaction solution.
4. The method of claim 3 , wherein in step (a) the carbohydrate reactant is a sugar.
5. The method of claim 3 , wherein in step (a), the carbohydrate reactant is derived from biomass.
6. The method of claim 3 , wherein step (b) comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen.
7. A method for making alkanes comprising, in an aqueous reaction solution:
(a) dehydrating a C 6 sugar to yield hydroxymethylfurfural; then
(b) subjecting the hydroxymethylfurfural to at least one crossed-aldol condensation reaction with an aldehyde or a ketone to yield a beta-hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least seven (7) carbon atoms; then
(c) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated carbonyl to yield a saturated polyhydroxy compound; and then
(d) dehydrating and hydrogenating the saturated polyhydroxy compound to yield an alkane having at least seven (7) carbon atoms.
8. The method of claim 7 , wherein in step (a),the C 6 sugar is derived from biomass.
9. The method of claim 7 , wherein step (b) yields a beta -hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least nine (9) carbon atoms; and step (d) yields an alkane having at least nine (9) carbon atoms.
10. The method of claim 7 , wherein step (b) yields a beta -hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least eleven (11) carbon atoms; and step (d) yields an alkane having at least eleven (11) carbon atoms.
11. The method of claim 7 , wherein step (b) yields a beta-hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least thirteen (13) carbon atoms; and step (d) yields an alkane having at least thirteen (13) carbon atoms.
12. The method of claim 7 , wherein step (b) yields a beta-hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least fifteen (15) carbon atoms; and step (d) yields an alkane having at least fifteen (15) carbon atoms.
13. The method of claim 7 , wherein step (b) comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen.
14. A method for making alkanes comprising, in an aqueous reaction solution:
(a) dehydrating a C 6 sugar to yield hydroxymethylfurfural; then
(b) hydrogenating the hydroxymethylfurfural to yield hydroxymethyltetrahydrofurfural; then
(c) subjecting the hydroxymethyltetrahydrofurfural to a self-aldol condensation reaction to yield a C 12 beta-hydroxy ketone and/or a C 12 alpha-beta unsaturated ketone; then
(d) hydrogenating the C 12 beta-hydroxy ketone and/or the C 12 alpha-beta unsaturated ketone to yield a saturated polyhydroxy compound; and then
(e) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 12 alkane.
15. The method of claim 14 , wherein step (c) comprises running the self-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen.
16. A method for making alkanes comprising, in an aqueous reaction solution:
(a) dehydrating a C 6 sugar to yield hydroxymethylfurfural; then
(b) subjecting the hydroxymethyltetrahydrofurfural to a first crossed-aldol condensation reaction with a first carbonyl compound having an alpha-position hydrogen, and then a second crossed-aldol condensation reaction with a second carbonyl compound lacking an alpha-position hydrogen, to yield a di-(beta-hydroxy) carbonyl and/or a di-(alpha-beta unsaturated) carbonyl having at least ten (10) carbon atoms; then
(c) hydrogenating the di-(beta-hydroxy) carbonyl and/or the di-(alpha-beta unsaturated) carbonyl to yield a saturated polyhydroxy compound; and then
(d) dehydrating and hydrogenating the polyhydroxy compound to yield an alkane having at least ten (10) carbon atoms.
17. The method of claim 16 , wherein in step (b) the first carbonyl compound is acetone, and the second carbonyl compound is hydroxymethylfurfural.
18. The method of claim 16 , wherein step (b) comprises running the first crossed-aldol condensation reaction and the second crossed-aldol reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen.
19. A method for making to C 1 to C 15 alkanes comprising, in an aqueous reaction solution:
(a) subjecting a carbonyl compound to at least one self -aldol condensation reaction or a crossed-aldol condensation reaction with another carbonyl compound to yield a beta-hydroxy carbonyl compound and/or an alpha-beta unsaturated carbonyl compound; then
(b) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated compounds to yield a saturated polyhydroxy compound; and then
(c) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 1 to C 15 alkane.
20. The method of claim 19 , wherein step (a) further comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen.
21. A method for making alkanes comprising, in an aqueous reaction solution:
(a) dehydrating a C 5 sugar to yield furfural; then
(b) subjecting the furfural to at least one crossed-aldol condensation reaction with an aldehyde or a ketone to yield a beta-hydroxy carbonyl and/or an alpha-beta unsaturated carbonyl having at least six (6) carbon atoms; then
(c) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated carbonyl to yield a saturated polyhydroxy compound; and then
(d) dehydrating and hydrogenating the saturated polyhydroxy compound to yield an alkane having at least six (6) carbon atoms.
22. A method for making alkanes comprising, in an aqueous reaction solution:
(a) dehydrating a C 5 sugar to yield furfural; then
(b) subjecting the furfural to a first crossed-aldol condensation reaction with a first carbonyl compound having an alpha-position hydrogen, and then a second crossed-aldol condensation reaction with a second carbonyl compound lacking an alpha-position hydrogen, to yield a di-(beta-hydroxy) carbonyl and/or a di-(alpha-beta unsaturated) carbonyl having at least nine (9) carbon atoms; then
(c) hydrogenating the di-(beta-hydroxy) carbonyl and/or the di-(alpha-beta unsaturated) carbonyl to yield a saturated polyhydroxy compound; and then
(d) dehydrating and hydrogenating the polyhydroxy compound to yield an alkane having at least eight (8) carbon atoms.
23. A method for making alkanes comprising, in an aqueous reaction solution:
(a) subjecting tetrahydrofurfural to a self-aldol condensation reaction to yield a C 10 beta-hydroxy ketone and/or a C 10 alpha-beta unsaturated ketone; then
(b) hydrogenating the C 10 beta-hydroxy ketone and/or the C 10 alpha-beta unsaturated ketone to yield a saturated polyhydroxy compound; and then
(c) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 10 alkane.
24. A method for making organic polyhydroxy compounds comprising, in an aqueous reaction solution:
(a) subjecting a carbonyl compound to at least one self -aldol condensation reaction or a crossed-aldol condensation reaction with another carbonyl compound to yield a beta-hydroxy carbonyl compound and/or an alpha-beta unsaturated carbonyl compound; then
(b) hydrogenating the beta-hydroxy carbonyl and/or alpha-beta unsaturated compounds to yield a polyhydroxy compound.
25. The method of claim 24 , wherein in step (b) the beta -hydroxy carbonyl and/or alpha-beta unsaturated compounds are hydrogenated such that the polyhydroxy compound is a saturated polyhydroxy compound.
26. The method of claim 25 , further comprising, after step (b):
(c) dehydrating and hydrogenating the saturated polyhydroxy compound to yield a C 6 to C 15 alkane that is immiscible in the aqueous reaction solution.
27. The method of claim 24 , further comprising, after step (b):
(c) dehydrating the saturated polyhydroxy compound to yield a C 6 to C 15 alkene or ether.
28. The method of claim 24 , wherein step (a) further comprises running the self-aldol condensation reaction or the crossed-aldol condensation reaction in the presence of a catalyst comprising magnesium, zirconium, and oxygen.