Method of selectively oxidizing lignin

Patent metadata

Field	Value
Publication number	US-10730816-B2
Application number	US-201816217569-A
Country	US
Kind code	B2
Filing date	Dec 12, 2018
Priority date	Dec 12, 2017
Publication date	Aug 4, 2020
Grant date	Aug 4, 2020

Abstract

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.

First claim

What is claimed is:

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 t

Assignees

• Wisconsin Alumni Res Found

Inventors

• Gao Ruili
• Ralph John

Classifications

• C07C45/294

  with hydrogen peroxide · CPC title

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title

• B01J31/20

  Carbonyls · CPC title

• B01J2531/64

  Molybdenum · CPC title

• B01J31/2295

  Cyclic compounds, e.g. cyclopentadienyls · CPC title