IP Library › Granted Patent US 12,215,077
Granted Patent B2
US 12,215,077 · App. 17/436,202 · Granted Feb 4, 2025

Methods of depolymerizing lignin

Inventors: Shannon Stahl (Madison, WI); Hao Luo (Decatur, IL)
Assignee: Wisconsin Alumni Research Foundation
C07C51/313B01J31/183B01J35/56C07C45/59
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Quick Facts
Patent No.
US 12,215,077
App. No.
17/436,202
Granted
Feb 4, 2025
Kind
B2
Abstract

Methods of depolymerizing lignin and products obtained therefrom. The methods include reacting lignin in a liquid solvent comprising an oxidation catalyst with the solvent being in contact with O 2 gas. The solvent can include aprotic polar solvents. The oxidation catalyst can include heterogeneous catalysts. The methods can be used in the oxidative catalytic fractionation of raw biomass to generate soluble aromatic monomers and a solid carbohydrate residue. Depolymerized lignin products include phenolic and benzoquinone monomers, such as p-hydroxybenzoic acid, vanillin, syringaldehyde, vanillic acid, and/or syringic acid.

Claims (43)

1. A method of depolymerizing lignin, the method comprising reacting in a liquid solvent lignocellulosic biomass and an oxidation catalyst with the solvent being in contact with gas comprising O 2 gas, wherein the lignocellulosic biomass comprises the lignin and at least one of cellulose and hemicellulose.

2. The method of claim 1 , wherein the solvent comprises organic solvent.

3. The method of claim 1 , wherein the solvent comprises aprotic solvent.

4. The method of claim 1 , wherein the solvent comprises aprotic solvent in an amount of at least about 90% v/v.

5. The method of claim 4 , wherein the aprotic solvent is a polar aprotic solvent.

6. The method of claim 1 , wherein the solvent is devoid of protic solvent or comprises protic solvent in an amount less than about 10% v/v.

7. The method of claim 1 , wherein the solvent comprises a solvent that is not an alcohol and is not water.

8. The method of claim 1 , wherein the oxidation catalyst is a heterogeneous catalyst.

9. The method of claim 1 , wherein the oxidation catalyst is a metal-based catalyst.

10. The method of claim 1 , wherein the oxidation catalyst comprises a metal other than palladium and ruthenium.

11. The method of claim 1 , wherein the oxidation catalyst comprises a non-noble metal.

12. The method of claim 1 , wherein the oxidation catalyst comprises a first-row transition metal.

13. The method of claim 1 , wherein the oxidation catalyst comprises a metal selected from the group consisting of Mn, Fe, Co, Ni, V, and Cu.

14. The method of claim 1 , wherein the oxidation catalyst is contained within the solvent within a porous cage.

15. The method of claim 1 , wherein the gas comprises O 2 gas in an amount from about 1% v/v to about 10% v/v.

16. The method of claim 1 , wherein the O 2 gas is present at a partial pressure of from about 1 to about 3 bar.

17. The method of claim 1 , wherein the reacting is conducted at a temperature from about 100° C. to about 240° C.

18. The method of claim 1 , wherein the lignocellulosic biomass comprises the lignin in an amount from about 10% w/w to about 80% w/w of the lignocellulosic biomass and at least one of cellulose in an amount from about 5% w/w to about 90% w/w of the lignocellulosic biomass and hemicellulose in an amount from about 5% w/w to about 90% w/w of the lignocellulosic biomass.

19. The method of claim 1 , wherein the reacting is conducted for a time from about 4 hours to about 16 hours.

20. The method of claim 1 , wherein the reacting is conducted for a time sufficient to produce a phenolic or benzoquinone monomer.

21. The method of claim 1 , wherein the reacting is conducted for a time sufficient to produce a phenolic monomer comprising a benzylic carbonyl.

22. The method of claim 1 , wherein the reacting is conducted for a time sufficient to produce p-hydroxybenzoic acid, vanillin, syringaldehyde, vanillic acid, and/or syringic acid.

23. The method of claim 1 , further comprising after the reacting, isolating a phenolic monomer produced during the reacting from the solvent.

24. The method of claim 1 , further comprising separating from the solvent a carbohydrate residue produced during the reacting.

25. The method of claim 24 , wherein the lignocellulosic biomass comprises the lignin in an amount from about 10% w/w to about 80% w/w of the lignocellulosic biomass and at least one of cellulose in an amount from about 5% w/w to about 90% w/w of the lignocellulosic biomass and hemicellulose in an amount from about 5% w/w to about 90% w/w of the lignocellulosic biomass.

26. The method of claim 24 , wherein the lignocellulosic biomass has not been treated with any one or more of chemical pretreatment and physicochemical pretreatment.

27. The method of claim 24 , wherein the lignin is in the form of raw lignocellulosic biomass.

28. A method of depolymerizing lignin, the method comprising reacting in a liquid solvent the lignin and an oxidation catalyst with the solvent being in contact with gas comprising O 2 gas, wherein the solvent is selected from the group consisting of acetone, acetonitrile, and a combination thereof.

29. A method of depolymerizing lignin, the method comprising reacting in a liquid solvent the lignin and an oxidation catalyst with the solvent being in contact with gas comprising O 2 gas, wherein the oxidation catalyst comprises a metal-containing nitrogen-doped carbon catalyst.

30. A method of depolymerizing lignin, the method comprising reacting in a liquid solvent lignocellulosic biomass and an oxidation catalyst with the solvent being in contact with gas comprising O 2 gas, wherein the lignocellulosic biomass comprises the lignin and has not been treated with any one or more of chemical pretreatment and physicochemical pretreatment.

31. The method of claim 30 , wherein the lignin is in the form of raw lignocellulosic biomass.

32. The method of claim 30 , wherein:

the solvent comprises an aprotic solvent selected from the group consisting of acetone, acetonitrile, and a combination thereof in an amount of at least about 90% v/v;

the solvent is devoid of protic solvent or comprises protic solvent in an amount less than about 10% v/v;

the oxidation catalyst is a heterogeneous catalyst comprising a metal selected from the group consisting of Mn, Fe, Co, Ni, V, and Cu;

the oxidation catalyst is contained within the solvent within a porous cage;

the gas comprises O 2 gas in an amount from about 1% v/v to about 10% v/v;

the O 2 gas is present at a partial pressure from about 1 to about 3 bar;

the reacting is conducted at a temperature from about 100° C. to about 240° C.; and

the lignocellulosic biomass has not been treated with chemical pretreatment and has not been treated with physicochemical pretreatment.

33. A method of depolymerizing lignin, the method comprising:

reacting in a liquid solvent the lignin and an oxidation catalyst with the solvent being in contact with gas comprising O 2 gas; and

after the reacting, separating a carbohydrate residue produced during the reacting from the solvent.

Assignments (2)
CONFIRMATORY LICENSE Recorded Mar 18, 2022
From: UNIVERSITY OF WISCONSIN-MADISON
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 060201/0924 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Nov 5, 2021
From: LUO, HAO; STAHL, SHANNON
To: WISCONSIN ALUMNI RESEARCH FOUNDATION
Reel/Frame 058028/0229 →
Continuity (2)
Provisional Application 62814503 · Mar 6, 2019
Related Publication 20220127217A1 · Apr 28, 2022
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