Biofuels via hydrogenolysis and dehydrogenation-condensation
View Patent ↗A method comprising providing a carbohydrate feed; contacting at least a portion of the carbohydrate feed directly with hydrogen in the presence of a hydrogenolysis catalyst to produce a first reaction product comprising a stable hydroxyl intermediate; contacting at least a portion of the first reaction product comprising the stably hydroxyl intermediates with a dehydrogenation catalyst to form a second reaction product; and contacting at least a portion of the second reaction product with a condensation catalyst comprising a base functionality to form a fuel blend.
1. A method comprising:
contacting a bio-based feedstock comprising lignin with hydrogen and a hydrogenolysis catalyst in a reactor to produce a first reaction product comprising a stable hydroxyl intermediate,
wherein at least a portion of the bio-based feedstock is converted to a carbohydrate in a hydrolysis reaction and the carbohydrate is converted to the first reaction product in a hydrogenolysis reaction, and
wherein the hydrolysis reaction and the hydrogenolysis reaction are conducted in a single step;
contacting at least a portion of the first reaction product comprising the stable hydroxyl intermediates with a dehydrogenation catalyst to form a second reaction product; and
contacting at least a portion of the second reaction product with a condensation catalyst comprising a base functionality to form a fuel blend.
2. The method of claim 1 further comprising:
contacting at least a portion of the first reaction product with a dehydration catalyst to produce a dehydrated reaction product.
3. The method of claim 1 wherein the carbohydrate is reacted directly with hydrogen in the presence of a hydrogenation catalyst prior to hydrogenolysis.
4. The method of claim 3 wherein the hydrogenolysis catalyst and the hydrogenation catalyst are the same catalyst.
5. The method of claim 1 wherein the dehydrogenation catalyst and the condensation catalyst are present in the same reactor.
6. The method of claim 2 wherein the hydrogenolysis catalyst and the dehydration catalyst are present in the same reactor vessel.
7. The method of claim 1 further comprising contacting at least a portion of the first reaction product with a catalyst comprising an acidic functionality to effect a ring opening reaction.
8. The method of claim 1 further comprising contacting at least a portion of the first reaction product with a catalyst comprising a base functionality to effect a ketonization reaction.
9. The method of claim 1 wherein the condensation catalyst further comprises an acidic functionality.
10. The method of claim 1 further comprising hydrotreating the fuel blend.
11. The method of claim 10 wherein the fuel blend comprises a diesel fuel or a jet fuel.
12. A method comprising:
contacting a bio-based feedstock comprising lignin with hydrogen and a hydrogenolysis catalyst in a reactor to produce a first reaction product comprising a stable hydroxyl intermediate stream comprising higher polyols,
wherein at least a portion of the bio-based feedstock is converted to a carbohydrate in a hydrolysis reaction and the carbohydrate is converted to the first reaction product in a hydrogenolysis reaction, and
wherein the hydrolysis reaction and the hydrogenolysis reaction are conducted in a single step;
separating at least a first portion of the higher polyols from the stable hydroxyl intermediate stream;
recycling the first portion of the higher polyols to the reactor and reacting the higher polyols in a hydrogenolysis reaction to produce additional stable intermediates;
contacting at least a portion of the stable hydroxyl intermediates with a dehydrogenation catalyst to form a second reaction product stream; and
contacting at least a portion of the second reaction product stream with a condensation catalyst comprising a base functionality to form a fuel blend.
13. The method of claim 12 wherein the hydrolysis reaction is carried out in the presence of a hydrolysis catalyst.
14. The method of claim 13 wherein the hydrolysis catalyst comprises at least one catalyst selected from the group consisting of: an acid catalyst, a base catalyst, a metal catalyst, acetic acid, formic acid, levulinic acid, and any combination thereof.
15. The method of claim 12 wherein the carbohydrate is reacted directly with hydrogen in the presence of a hydrogenation catalyst prior to the hydrogenolysis reaction.
16. The method of claim 15 wherein the hydrogenation and hydrogenolysis catalysts are the same catalyst.
17. The method of claim 15 wherein the hydrogenolysis catalyst and the hydrogenation catalyst are present in the same reactor vessel.
18. The method of claim 12 wherein the dehydrogenation catalyst and the condensation catalyst are present in the same reactor vessel.
19. The method of claim 12 wherein the condensation catalyst further comprises an acid functionality.
20. The method of claim 12 further comprises hydrotreating the fuel blend.
21. The method of claim 20 wherein the fuel blend comprises at least one composition selected from the group consisting of: a diesel fuel, and a jet fuel.
22. The method of claim 12 further comprising contacting at least a portion of the first and second reaction products with a hydrogenation catalyst after the condensation catalyst to form the fuel blend.
23. The method of claim 1 wherein the bio-based feedstock comprising lignin comprises a solids feedstock.
24. The method of claim 12 wherein the bio-based feedstock comprising lignin comprises a solids feedstock.
25. The method of claim 1 wherein the first reaction product comprises polyols in an amount of greater than 25% by mole.
26. The method of claim 1 wherein the hydrolysis reaction comprises contacting at least a portion of the bio-based feedstock with an organic acid in said reactor.
27. The method of claim 12 wherein the stable hydroxyl intermediate stream comprises higher polyols in an amount of greater than 25% by mole.