Lignin processing

Patent metadata

Field	Value
Publication number	US-10407355-B2
Application number	US-201515504788-A
Country	US
Kind code	B2
Filing date	Aug 19, 2015
Priority date	Aug 20, 2014
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

A method of depolymerizing a lignin includes oxidizing the lignin to provide an oxidized lignin wherein benzylic —OH of β-O-4 linkages have been converted to carbonyl. The oxidized lignin is depolymerized with a metal selected from the group consisting of zinc, magnesium, aluminum and titanium or mixtures thereof, in the presence of an ammonium salt or carbon dioxide. Also described are methods for manufacturing phenolic products from lignin and a method for the cleavage of a β-O-4 linkage in a substrate.

First claim

The invention claimed is:

1. A method of depolymerizing a lignin, the method comprising:
oxidizing benzylic OH of β-O-4 linkages of a lignin with molecular oxygen in the presence of a quinone and a source of nitrogen dioxide to provide an oxidized lignin wherein the benzylic OH of β-O-4 linkages have been converted to carbonyl; and
depolymerizing the oxidized lignin with a metal selected from the group consisting of zinc, magnesium, aluminum and titanium or mixtures thereof, in the presence of an ammonium salt or carbon dioxide, and
producing at least one phenol according to any one of formulas I, II, or III:

2. The method of claim 1 , wherein the process is carried out as a one pot process, with both the oxidation and depolymerization steps carried out one after the other.

3. The method of claim 1 , wherein the quinone is selected from the group consisting of: 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), p-chloroanil, o-chloroanil, benzoquinone, 2-chloroanthroquinone, and 1,4,5,8-tetrachloroanthroquinone.

4. The method of claim 1 , wherein the source of nitrogen dioxide is selected from the group consisting of: alkyl nitrites, nitrogen dioxide (NO 2 ), nitrite salts, nitric acid/hydrochloric acid mixtures and nitric oxide (NO).

5. The method of claim 1 , wherein the quinone is employed at an amount of from 2 to 30% by weight of the lignin.

6. The method of claim 5 , wherein the quinone is employed at an amount of from 5 to 20% by weight of the lignin.

7. The method of claim 1 , wherein the oxidizing step is carried out in an alcoholic solvent or mixture comprising an alcoholic solvent.

8. The method of claim 7 , wherein the oxidizing step is carried out in the presence of a co-solvent selected from the group consisting of: alkyl ethers, alkyl nitriles, carboxylic acids and aromatic solvents.

9. The method of claim 7 , wherein the oxidizing step is carried out in a solvent system comprising 2-methoxyethanol, a mixture of 2-methoxyethanol and 1,2-dimethoxyethane, or a mixture of 2-methoxyethanol, 1,2-dimethoxyethane and water.

10. The method of claim 1 , wherein the oxidizing step is carried out in a solvent selected from the group consisting of: water, methanol, ethanol, glycerol, glycol ethers and mixtures thereof.

11. The method of claim 1 , wherein the oxidizing step is carried out at a temperature of from 20° C. to 130° C.

12. The method of claim 1 , wherein an ammonium salt is employed in the depolymerization of the oxidized lignin.

13. The method of claim 12 , wherein the ammonium salt is selected from the group consisting of ammonium chloride, ammonium formate, ammonium acetate, ammonium sulphate and ammonium bisulphate.

14. The method of claim 1 , wherein zinc is employed as the metal in the depolymerization of the oxidized lignin.

15. The method of claim 1 , wherein in the depolymerization of the oxidized lignin is carried out in a solvent comprising water and an alcohol.

16. The method of claim 15 , wherein in the depolymerization of the oxidized lignin is carried out in a solvent comprising water and glycol ether.

17. The method of claim 16 , wherein in the depolymerization of the oxidized lignin is carried out in a solvent comprising water and 2-methoxyethanol.

18. The method of claim 17 , wherein the depolymerization of the oxidized lignin is carried out in a water and 2-methoxyethanol mixture in a ratio of from 9:1 to 7:3 of 2-methoxyethanol:water, by volume.

19. The method of claim 15 , wherein the depolymerization of the oxidized lignin is carried out in the presence of a co-solvent selected from the group consisting of: alkyl ethers, alkyl nitriles, carboxylic acids and aromatic solvents.

20. The method of claim 1 , wherein in the depolymerization of the oxidized lignin is carried out at from 20° C. to 120° C.

21. A method of depolymerizing an oxidized lignin, the method comprising:
reacting an oxidized lignin, wherein benzylic —OH of β-O-4 linkages of the oxidized lignin have been converted to carbonyl, with a metal selected form the group consisting of zinc, magnesium, aluminum and titanium or mixtures thereof, in the presence of an ammonium salt or carbon dioxide;
depolymerizing the oxidized lignin; and
producing at least one phenol according to any one of formulas I, II, or III:

22. A method of manufacture of a phenolic product of general formula Z:

wherein R 1 and R 2 are, independently for each occurrence, —H or —OMe and R 3 is —H or —OH; wherein the method comprises oxidizing a lignin to an oxidized lignin wherein benzylic —OH of the β-O-4 linkages have been converted to carbonyl; and
depolymerizing the oxidized lignin with a metal selected from the group consisting of zinc, magnesium, aluminum, titanium and mixtures thereof, in the presence of an ammonium salt or carbon dioxide.

23. The method of claim 22 , wherein the phenolic product of formula Z is at least one of formulas I, II, or III:

24. A method for the cleavage of a β-O-4 linkage in a substrate, the method comprising:
oxidizing a β-O-4 linkage of the substrate to provide an oxidized product wherein benzylic —OH of the β-O-4 linkage is converted to carbonyl; and
depolymerizing the oxidized product with a metal selected from the group consisting of zinc, magnesium, aluminum, titanium and mixtures thereof, in the presence of an ammonium salt or carbon dioxide to produce at least one phenol according to any one of formulas I, II, or III:

25. A method of producing at least one phenol according to any one of formulas I, II, or III:

the method comprising:
oxidatively converting benzylic —OH of β-O-4 linkages of a lignin to carbonyl with molecular oxygen in the presence of a quinone and a source of nitrogen dioxide to provide an oxidized lignin; and
reacting the oxidized lignin with a metal selected from the group consisting of zinc, magnesium, aluminum and titanium or mixtures thereof, in the presence of an ammonium salt or carbon dioxide; and

cleaving a phenolic ether linkage adjacent the carbonyl.

Assignees

• Univeristy Court Of The Univ Of St Andrews
• Univ Court Univ St Andrews

Inventors

• Westwood Nicholas James
• Lancefield Christopher Stuart
• Tran Fanny

Classifications

• D21C11/0007

  Recovery of by-products, i.e. compounds other than those necessary for pulping, for multiple uses or not otherwise provided for (volatile compounds obtained by decomposition of spent liquors in order to regenerate them D21C11/125; compounds obtained by fractionating the liquors in order to regenerate them D21C11/0042) · CPC title

• C07B41/02

  of hydroxy or O-metal groups · CPC title

• C07G1/00 Primary

  Low-molecular-weight derivatives of lignin (high-molecular-weight derivatives of lignin {C08H6/00}) · CPC title

• C07C45/00

  Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds · CPC title

• C07C49/84

  containing ether groups, [IMAGE cpc-sch-C07C-0958.gif] groups,[IMAGE cpc-sch-C07C-0959.gif] groups, or[IMAGE cpc-sch-C07C-0960.gif] groups · CPC title