Methods to convert lignin to phenolic and carboxylate compounds

Patent metadata

Field	Value
Publication number	US-9775347-B2
Application number	US-201314898442-A
Country	US
Kind code	B2
Filing date	Jun 14, 2013
Priority date	Jun 14, 2013
Publication date	Oct 3, 2017
Grant date	Oct 3, 2017

Abstract

A method of converting lignin to phenolic compounds and dicarboxylates in high yield is described. The method involves the use of peroxy acids to react with lignin at a moderated treatment conditions. The peroxy acids can be used along or in combination of other catalysts that have the capability to lower the molecular weight of lignin. A phenolic compounds yield is achieved (>60%) and these phenolic compounds represents high value precursors for various applications include but not limited to antioxidants, health improvement agents, anticorrosive agents, liquid fuel components and performance enhancing agents, resin and adhesives. Dicarboxylic acids can be used for polymer applications or hydrodeoxygenation to hydrocarbon fuel.

First claim

What is claimed is:

1. A process comprising:
oxidatively depolymerizing a lignin with a peroxy acid at a temperature of not less than about 5° C. to not greater than about 160° C. to yield a mixture of dicarboxylic acid compounds and a mixture of phenolic compounds, wherein the mixture of dicarboxylic acid compounds is in at least about 10% total weight yield, wherein the total weight yield is calculated from the lignin on a contained lignin basis.

2. The process of claim 1 , wherein the mixture of phenolic compounds is in at least about 28% the total weight yield.

3. The process of claim 1 , further comprising:
substantially separating one or more dicarboxylic acid compounds or combination thereof from the mixture of phenolic compounds;
reducing at least one of the dicarboxylic acid compounds to a saturated dicarboxylic acid; and
recovering the one or more dicarboxylic acids or combination thereof in at least about 10% the total weight yield.

4. The process of claim 1 , further comprising:
substantially separating one or more dicarboxylic acid compounds or combination thereof from the mixture of phenolic compounds;
esterifying at least one of the dicarboxylic acid compounds to a dicarboxylate ester; and
recovering one or more dicarboxylate esters or combination thereof in at least about 10% the total weight yield.

5. The process of claim 1 , wherein the mixture of phenolic compounds is in at least about 60% the total weight yield.

6. The process of claim 1 , wherein the mixture of dicarboxylic acid compounds is at least about 25% the total weight yield.

7. The process of claim 1 , wherein the lignin is an alkaline lignin.

8. The process of claim 1 , wherein the oxidatively depolymerizing the lignin with the peroxy acid comprises oxidatively depolymerizing at the temperature of not less than about 40° C. to not greater than about 120° C.

9. The process of claim 1 , wherein the oxidatively depolymerizing the lignin with the peroxy acid comprises oxidatively depolymerizing for at least 3 hours.

10. The process of claim 1 , wherein the peroxy acid comprises peracetic acid, performic acid, or combinations thereof.

11. The process of claim 1 , wherein the peroxy acid is a peroxyaryloic acid.

12. The process of claim 1 , wherein the peroxy acid is a peroxybenzoic acid.

13. The process of claim 1 , wherein the peroxy acid is selected from the group consisting of metachloro-peroxybenzoic acid, peroxymonosulfuric acid, and peroxysulfonic acid.

14. The process of claim 1 , wherein the peroxy acid is generated in-situ from an organic acid and hydrogen peroxide.

15. The process of claim 1 , wherein the mixture of phenolic compounds comprises vanillin, vanillic acid, and gallic acid.

16. The process of claim 4 , wherein recovering the one or more dicarboxylate esters comprises recovering a dicarboxylate ester fraction comprising a dialkyl muconate, a dialkyl succinate, a dialkyl maleate, or a combination thereof.

Assignees

• Washington State Univ Res Found
• Univ Washington State

Inventors

• Zhang Xiao

Classifications

• C07C45/59

  in five-membered rings (from ozonides C07C45/40) · CPC title

• C07C65/21

  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

• A01N31/08 Primary

  Oxygen or sulfur directly attached to an aromatic ring system · CPC title

• Y02P30/20

  using bio-feedstock · CPC title

• A01N37/40

  having at least one carboxylic group or a thio analogue, or a derivative thereof, and one oxygen or sulfur atom attached to the same aromatic ring system · CPC title