Methods for lignin depolymerization using thiols

Patent metadata

Field	Value
Publication number	US-11267838-B2
Application number	US-201816603328-A
Country	US
Kind code	B2
Filing date	Apr 17, 2018
Priority date	Apr 17, 2017
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

The disclosure relates to a method for depolymerizing lignin. The method includes reacting a lignin compound with a thiol compound to depolymerize the lignin compound and to form a depolymerized lignin product having a reduced molecular weight relative to the lignin compound prior to reacting. The method can further include forming an oxidized thiol reaction product between two thiol groups from one or more thiol compounds, and then reducing the oxidized thiol reaction product to re-form or regenerate the thiol compound for further lignin depolymerization.

First claim

What is claimed is:

1. A method for depolymerizing lignin, the method comprising:
reacting a lignin compound with a thiol compound to depolymerize the lignin compound and to form (i) a depolymerized lignin product having a reduced molecular weight relative to the lignin compound prior to reacting, and (ii) an oxidized thiol reaction product between two thiol groups from one or more thiol compounds; and
reducing the oxidized thiol reaction product to form the thiol compound;
wherein:
the thiol compound comprises a hydrocarbon group having 1 to 8 carbon atoms and being substituted with 1 to 4 thiol groups.

2. The method of claim 1 , wherein the lignin compound comprises a cross-linked phenolic polymer comprising at least one of β-O-4 ether linkages, α-O-4 ether linkages, 4-O-5 ether linkages, β-βcarbon-carbon linkages, β-1 carbon-carbon linkages, β-5 carbon-carbon linkages, and 5-5 carbon-carbon linkages between phenolic monomer units in the cross-linked phenolic polymer.

3. The method of claim 2 , wherein the depolymerized lignin product has 50% or less linkages between phenolic monomer units in the cross-linked phenolic polymer relative to the lignin compound prior to reacting.

4. The method of claim 1 , wherein the depolymerized lignin product has a molecular weight of 50% or less relative to the molecular weight of the lignin compound prior to reacting.

5. The method of claim 1 , wherein the lignin compound prior to reacting has a number-average molecular weight of at least 400 g/mol.

6. The method of claim 1 , wherein the lignin compound prior to reacting has a weight-average molecular weight of at least 10000 g/mol.

7. The method of claim 6 , wherein the depolymerized lignin product has a weight-average molecular weight of 50% or less relative to the weight-average molecular weight of the lignin compound prior to reacting.

8. The method of claim 1 , wherein the depolymerized lignin product comprises at least one of a lignin monomer unit and a lignin oligomer thereof, the lignin monomer unit comprising an aromatic group with one or more substituents selected from the group consisting of alcohol groups, ether groups, aldehyde groups, ketone groups, alkyl groups, carboxyl groups, and combinations thereof.

9. The method of claim 8 , wherein the lignin monomer unit is selected from the group consisting of phenol, cresol, guaiacol, 4-ethyl-guaiacol, eugenol, isoeugenol, methoxyeugenol, syringol, and combinations thereof.

10. The method of claim 8 , wherein the depolymerized lignin product is substantially free from adducts of the thiol compound with the lignin monomer unit or the lignin oligomer thereof.

11. The method of claim 1 , wherein the thiol compound comprises a monothiol compound.

12. The method of claim 1 , wherein the thiol compound comprises a hydrocarbon group having 1 to 6 carbon atoms and being substituted with 1 to 2 thiol groups.

13. The method of claim 1 , comprising reacting the lignin compound with the thiol compound in a solvent reaction medium.

14. The method of claim 13 , where the solvent reaction medium comprises a solvent selected from the group consisting of tetrahydrofuran (THF), dimethylformamide (DMF), acetonitrile (ACN), water, dioxane, and combinations thereof.

15. The method of claim 1 , comprising reacting the lignin compound with the thiol compound at a temperature ranging from 20° C. to 200° C.

16. A method for depolymerizing lignin, the method comprising:
reacting a lignin compound with a thiol compound to depolymerize the lignin compound and to form a depolymerized lignin product having a reduced molecular weight relative to the lignin compound prior to reacting;
wherein:
the lignin compound prior to reacting has a number-average molecular weight of at least 400 g/mol;
the depolymerized lignin product has a number-average molecular weight of 50% or less relative to the number-average molecular weight of the lignin compound prior to reacting; and
reacting the lignin compound with the thiol compound further comprises forming an oxidized thiol reaction product between two thiol groups from one or more thiol compounds.

17. A method for depolymerizing lignin, the method comprising:
reacting a lignin compound with a thiol compound to depolymerize the lignin compound and to form (i) a depolymerized lignin product having a reduced molecular weight relative to the lignin compound prior to reacting, and (ii) an oxidized thiol reaction product between two thiol groups from one or more thiol compounds; and
reducing the oxidized thiol reaction product to form the thiol compound;
wherein:
the thiol compound comprises a dithiol compound.

18. A method for depolymerizing lignin, the method comprising:
reacting a lignin compound with a thiol compound to depolymerize the lignin compound and to form (i) a depolymerized lignin product having a reduced molecular weight relative to the lignin compound prior to reacting, and (ii) an oxidized thiol reaction product between two thiol groups from one or more thiol compounds; and
reducing the oxidized thiol reaction product to re-form the thiol compound;
wherein:
the thiol compound comprises a hydrocarbon group having 1 to 8 carbon atoms and being substituted with 1 to 2 thiol groups;
the lignin compound comprises a cross-linked phenolic polymer comprising β-O-4 ether linkages, and the depolymerized lignin product has fewer β-O-4 ether linkages between phenolic monomer units in the cross-linked phenolic polymer relative to the lignin compound prior to reacting;
the depolymerized lignin product has a molecular weight of 50% or less relative to the molecular weight of the lignin compound prior to reacting; and
the depolymerized lignin product comprises at least one of a lignin monomer unit and a lignin oligomer thereof, the lignin monomer unit comprising an aromatic group with one or more substituents selected from the group consisting of alcohol groups, ether groups, aldehyde groups, ketone groups, alkyl groups, carboxyl groups, and combinations thereof.

Assignees

• Univ Michigan State

Inventors

• Hegg Eric Linke
• Jackson James E
• Klinger Grace Elizabeth

Classifications

• C25B3/07

  Oxygen containing compounds · CPC title

• C25B3/25

  Reduction · CPC title

• C07C37/055 Primary

  the substituted group being bound to oxygen, e.g. ether group · CPC title

• C07C37/54

  by hydrolysis of lignin or sulfite waste liquor · CPC title

• C07C319/14

  of sulfides · CPC title