Method of selectively oxidizing lignin
A method of selectively reacting lignin or a lignin-derived reactant to yield an aromatic product. The method includes the step of reacting lignin or a lignin-derived reactant with a molybdenum-containing catalyst, in a solvent, and optionally in the presence of an oxidant, for a time and a temperature wherein at least a portion of the lignin or lignin-derived reactant is selectively converted into an aromatic product, preferably coniferaldehyde and/or sinapaldehyde.
1. A method of selectively reacting lignin or a lignin-derived reactant to yield an aromatic product, the method comprising:
reacting lignin or a lignin-derived reactant with a molybdenum-containing catalyst selected from the group consisting of MoO 3 , Na 2 MoO 4 .2H 2 O, MoO 2 Cl 2 , [C 5 H 5 Mo(CO) 3 ] 2 , and Mo(dppf)(CO) 4 , in a solvent, for a time and at a temperature wherein at least a portion of the lignin or lignin-derived reactant is selectively converted into an aromatic product.
2. The method of claim 1 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 250° C.
3. The method of claim 1 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 200° C.
4. The method of claim 1 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 160° C.
5. The method of claim 1 , in which the temperature is established by microwave irradiation.
6. The method of claim 1 , in which the temperature is established by radiant heating.
7. The method of claim 1 , wherein the solvent is selected from the group consisting of dimethyl sulfoxide (DMSO), gamma-valerolactone (GVL), dimethylformamide (DMF), and cyclohexanone.
8. The method of claim 1 , wherein the solvent is DMSO, and the lignin or a lignin-derived reactant is reacted with the molybdenum-containing catalyst in the absence of any additional oxidizing agents.
9. The method of claim 1 , wherein the solvent is not DMSO, and the lignin or a lignin-derived reactant is reacted with the molybdenum-containing catalyst in the presence of an additional oxidizing agent.
10. The method of claim 9 , wherein the lignin or a lignin-derived reactant is reacted with the molybdenum-containing catalyst in the presence of an additional oxidizing agent selected from the group consisting of DMSO, O 2 , hydrogen peroxide, benzoyl peroxide, and ammonium persulfate.
11. A method of selectively reacting lignin or a lignin-derived reactant to yield an aromatic product, the method comprising:
reacting lignin or a lignin-derived reactant with a molybdenum-containing catalyst, in a solvent, for a time and at a temperature wherein at least a portion of the lignin or lignin-derived reactant is selectively converted into an aromatic product;
wherein the aromatic product comprises sinapaldehyde.
12. A method of selectively reacting lignin or a lignin-derived reactant to yield an aromatic product, the method comprising:
reacting lignin or a lignin-derived reactant with a molybdenum-containing catalyst selected from the group consisting of MoO 3 , Na 2 MoO 4 .2H 2 O, MoO 2 Cl 2 , [C 5 H 5 Mo(CO) 3 ] 2 , and Mo(dppf)(CO) 4 , in a solvent, in the presence of an additional oxidizing agent, for a time and at a temperature wherein at least a portion of the lignin or lignin-derived reactant is selectively converted into an aromatic product.
13. The method of claim 12 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 250° C.
14. The method of claim 12 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 200° C.
15. The method of claim 12 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 160° C.
16. The method of claim 12 , in which the temperature is established by microwave irradiation.
17. The method of claim 12 , in which the temperature is established by radiant heating.
18. The method of claim 12 , wherein the solvent is selected from the group consisting of dimethyl sulfoxide (DMSO), gamma-valerolactone (GVL), dimethylformamide (DMF), and cyclohexanone.
19. The method of claim 1 , wherein the solvent is not DMSO.
20. The method of claim 19 , wherein the lignin or a lignin-derived reactant is reacted with the molybdenum-containing catalyst in the presence of an additional oxidizing agent, and wherein the additional oxidizing agent is selected from the group consisting of DMSO, O 2 , hydrogen peroxide, benzoyl peroxide, and ammonium persulfate.
21. The method of claim 12 , wherein the additional oxidizing agent is selected from the group consisting of DMSO, O 2 , hydrogen peroxide, benzoyl peroxide, and ammonium persulfate.
22. A method of selectively reacting lignin or a lignin-derived reactant to yield an aromatic product, the method comprising:
reacting lignin or a lignin-derived reactant with a molybdenum-containing catalyst, in a solvent, in the presence of an additional oxidizing agent, for a time and at a temperature wherein at least a portion of the lignin or lignin-derived reactant is selectively converted into an aromatic product;
wherein the aromatic product comprises sinapaldehyde.
23. The method of claim 22 , wherein the molybdenum-containing catalyst is selected from the group consisting of MoO 2 Cl 2 (DMSO) 2 , MoO 3 , Na 2 MoO 4 .2H 2 O, MoO 2 Cl 2 , [C 5 H 5 Mo(CO) 3 ] 2 , and Mo(dppf)(CO) 4 .
24. The method of claim 22 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 250° C.
25. The method of claim 22 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 200° C.
26. The method of claim 22 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 160° C.
27. The method of claim 22 , in which the temperature is established by microwave irradiation.
28. The method of claim 22 , in which the temperature is established by radiant heating.
29. The method of claim 22 , wherein the solvent is selected from the group consisting of dimethyl sulfoxide (DMSO), gamma-valerolactone (GVL), dimethylformamide (DMF), and cyclohexanone.
30. The method of claim 22 , wherein the additional oxidizing agent is selected from the group consisting of DMSO, O 2 , hydrogen peroxide, benzoyl peroxide, and ammonium persulfate.
31. The method of claim 11 , wherein the molybdenum-containing catalyst is selected from the group consisting of MoO 2 Cl 2 (DMSO) 2 , MoO 3 , Na 2 MoO 4 .2H 2 O, MoO 2 Cl 2 , [C 5 H 5 Mo(CO) 3 ] 2 , and Mo(dppf)(CO) 4 .
32. The method of claim 11 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 250° C.
33. The method of claim 11 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 200° C.
34. The method of claim 11 , wherein the lignin or a lignin-derived reactant is reacted at a temperature of from 120° C. to 160° C.
35. The method of claim 11 , in which the temperature is established by microwave irradiation.
36. The method of claim 11 , in which the temperature is established by radiant heating.
37. The method of claim 11 , wherein the solvent is selected from the group consisting of dimethyl sulfoxide (DMSO), gamma-valerolactone (GVL), dimethylformamide (DMF), and cyclohexanone.
38. The method of claim 11 , wherein the solvent is DMSO, and the lignin or a lignin-derived reactant is reacted with the molybdenum-containing catalyst in the absence of any additional oxidizing agents.
39. The method of claim 11 , wherein the solvent is not DMSO, and the lignin or a lignin-derived reactant is reacted with the molybdenum-containing catalyst in the presence of an additional oxidizing agent.
40. The method of claim 39 , wherein the lignin or a lignin-derived reactant is reacted with the molybdenum-containing catalyst in the presence of an additional oxidizing agent selected from the group consisting of DMSO, O 2 , hydrogen peroxide, benzoyl peroxide, and ammonium persulfate.
41. The method of claim 11 , wherein the solvent is not DMSO.
42. The method of claim 41 , wherein the lignin or a lignin-derived reactant is reacted with the molybdenum-containing catalyst in the presence of an additional oxidizing agent, and wherein the additional oxidizing agent is selected from the group consisting of DMSO, O 2 , hydrogen peroxide, benzoyl peroxide, and ammonium persulfate.