Production of adipic acid and derivatives from carbohydrate-containing materials
The present invention generally relates to processes for the chemocatalytic conversion of a glucose source to an adipic acid product. The present invention includes processes for the conversion of glucose to an adipic acid product via glucaric acid or derivatives thereof. The present invention also includes processes comprising catalytic oxidation of glucose to glucaric acid or derivative thereof and processes comprising the catalytic hydrodeoxygenation of glucaric acid or derivatives thereof to an adipic acid product. The present invention also includes products produced from adipic acid product and processes for the production thereof from such adipic acid product.
1. A process for preparing an adipic acid product, the process comprising:
reacting, in the presence of a hydrodeoxygenation catalyst and a halogen source, a hydrodeoxygenation substrate and hydrogen gas to convert at least a portion of the hydrodeoxygenation substrate to an adipic acid product, wherein the hydrodeoxygenation substrate comprises a compound of formula I
wherein X is independently hydroxyl, oxo, halo, acyloxy or hydrogen provided that at least one X is not hydrogen and R 1 is independently a salt-forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl; or a mono- or di-lactone thereof and wherein the adipic acid product is a compound of formula II
wherein R 1 is as defined for formula I.
2. The process as set forth in claim 1 wherein the hydrodeoxygenation substrate comprises a compound of formula I, wherein X is hydroxyl and R 1 is independently a salt-forming ion, hydrogen, hydrocarbyl, or substituted hydrocarbyl.
3. The process as set forth in claim 1 wherein the hydrodeoxygenation substrate comprises glucaric acid.
4. The process as set forth in claim 1 wherein the adipic acid product comprises adipic acid.
5. The process as set forth in claim 1 wherein at least a portion of the hydrodeoxygenation substrate is solubilized with a weak carboxylic acid.
6. The process as set forth in claim 5 wherein the pKa of the weak carboxylic acid is at least about 4.5.
7. The process as set forth in claim 1 wherein the hydrodeoxygenation catalyst comprises a heterogeneous catalyst.
8. The process as set forth in claim 7 wherein the hydrodeoxygenation catalyst comprises at least one d-block metal at a surface of a support.
9. The process as set forth in claim 8 wherein the d-block metal is selected from the group consisting of Ru, Rh, Pd, Pt, and combinations thereof.
10. The process as set forth in claim 7 wherein the hydrodeoxygenation catalyst comprises a first metal and a second metal, wherein the first metal is selected from the group consisting of Ru, Rh, Pd, Pt, and combinations thereof, and the second metal is selected from the group consisting of Mo, Ru, Rh, Pd, Ir, Pt, and Au, and wherein the second metal is not the same as the first metal.
11. The process as set forth in claim 9 wherein the hydrodeoxygenation catalyst support is selected from the group consisting of carbon, silica and zirconia.
12. The process as set forth in claim 5 wherein the halogen source comprises an ionic, atomic, and/or a molecular form of bromine.
13. The process as set forth in claim 12 wherein the halogen source comprises hydrogen bromide.
14. The process as set forth in claim 3 wherein the molar ratio of halogen source to hydrodeoxygenation substrate is equal to or less than about 1.
15. The process as set forth in claim 1 wherein the reaction mixture is maintained at a temperature of at least about 80° C.
16. The process as set forth in claim 1 wherein the temperature of the reaction mixture is from about 100° C. to about 200° C.
17. The process as set forth in claim 1 wherein the reaction is conducted under a partial pressure of hydrogen ranging from about 25 psia (172 kPa) to about 2500 psia (17237 kPa).
18. The process as set forth in claim 1 wherein the hydrodeoxygenation substrate of formula I is prepared by
reacting glucose with oxygen to convert at least a portion of the glucose to the hydrodeoxygenation substrate of formula I.
19. The process of claim 12 wherein the hydrodeoxygenation catalyst comprises Pt and Rh on a support comprising silica.
20. The process of claim 12 wherein the reaction is conducted at a temperature of at least about 140° C.
21. The process of claim 1 wherein the hydrodeoxygenation substrate comprises glucaric acid, the hydrodeoxygenation catalyst comprises a heterogeneous catalyst comprising at least one d-block metal selected from the group consisting of Ru, Rh, Pd, Pt, and combinations thereof at a surface of a support, and the halogen source comprises an ionic, atomic, and/or a molecular form of bromine.
22. The process of claim 5 wherein the hydrodeoxygenation substrate comprises glucaric acid, the hydrodeoxygenation catalyst comprises a heterogeneous catalyst comprising at least one d-block metal selected from the group consisting of Ru, Rh, Pd, Pt, and combinations thereof at a surface of a support, and the halogen source comprises an ionic, atomic, and/or a molecular form of bromine.
23. The process of claim 1 wherein at least a portion of the hydrodeoxygenation substrate is solubilized with a weak carboxylic acid, the hydrodeoxygenation catalyst comprises a heterogeneous catalyst comprising at least one d-block metal selected from the group consisting of Ru, Rh, Pd, Pt, and combinations thereof at a surface of a support, and the halogen source comprises an ionic, atomic, and/or a molecular form of bromine.
24. The process of claim 23 wherein the hydrodeoxygenation substrate comprises glucaric acid.
25. The process of claim 1 wherein at least a portion of the hydrodeoxygenation substrate is solubilized with a weak carboxylic acid, the hydrodeoxygenation catalyst comprises a heterogeneous catalyst comprising at least one d-block metal selected from the group consisting of Ru, Rh, Pd, Pt, and combinations thereof at a surface of a support, and the halogen source comprises hydrogen bromide.
26. The process of claim 25 wherein the hydrodeoxygenation substrate comprises glucaric acid.
27. The process as set forth in claim 1 wherein the halogen source comprises an ionic, atomic, and/or a molecular form of bromine.
28. The process as set forth in claim 3 wherein the adipic acid product comprises adipic acid.
29. The process as set forth in claim 24 wherein the adipic acid product comprises adipic acid.
30. The process as set forth in claim 6 wherein the halogen source comprises an ionic, atomic, and/or a molecular form of bromine.
31. The process as set forth in claim 1 wherein the temperature of the reaction mixture is from about 100° C. to about 200° C. and wherein the reaction is conducted under a partial pressure of hydrogen ranging from about 25 psia (172 kPa) to about 2500 psia (17237 kPa).
32. The process as set forth in claim 26 wherein the temperature of the reaction mixture is from about 100° C. to about 200° C. and wherein the reaction is conducted under a partial pressure of hydrogen ranging from about 25 psia (172 kPa) to about 2500 psia (17237 kPa).
33. The process as set forth in claim 23 wherein the pKa of the weak carboxylic acid is at least about 4.5.
34. The process as set forth in claim 26 wherein the pKa of the weak carboxylic acid is at least about 4.5.
35. The process of claim 19 wherein the reaction is conducted at a temperature of at least about 140° C.
36. The process of claim 18 wherein at least a portion of the glucose and the hydrodeoxygenation substrate of formula I are solubilized with a weak carboxylic acid.
37. The process of claim 18 wherein glucose is reacted with oxygen in the presence of an oxidation catalyst.
38. The process of claim 18 wherein glucose is reacted with oxygen in the substantial absence of added base.
39. The process as set forth in claim 36 wherein the weak carboxylic acid comprises acetic acid.
40. The process as set forth in claim 36 wherein the pKa of the weak carboxylic acid is at least about 4.5.