Method to produce water-soluble sugars from biomass using solvents containing lactones

Patent metadata

Field	Value
Publication number	US-9725776-B2
Application number	US-201514692018-A
Country	US
Kind code	B2
Filing date	Apr 21, 2015
Priority date	Jan 8, 2013
Publication date	Aug 8, 2017
Grant date	Aug 8, 2017

Abstract

A process to produce an aqueous solution of carbohydrates that contains C6-sugar-containing oligomers, C6 sugar monomers, C5-sugar-containing oligomers, C5 sugar monomers, or any combination thereof is presented. The process includes the steps of reacting biomass or a biomass-derived reactant with a solvent system including a lactone and water, and an acid catalyst. The reaction yields a product mixture containing water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof. A solute is added to the product mixture to cause partitioning of the product mixture into an aqueous layer containing the carbohydrates and a substantially immiscible organic layer containing the lactone.

First claim

What is claimed is:

1. A process to produce an aqueous solution of carbohydrates comprising C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof, the process comprising:
(a) reacting biomass or a biomass-derived reactant with a solvent system comprising (i) an organic solvent selected from the group consisting of beta-, gamma-, and delta-lactones, and combinations thereof, and (ii) at least about 1 wt % water; in the presence of an acid catalyst for a time and under conditions to yield a product mixture wherein at least a portion of water-insoluble C6-sugar-containing polymers or oligomers, or water-insoluble C5-sugar-containing polymers or oligomers, if present in the biomass or biomass-derived reactant, are converted to water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof; then
(b) adding a solute to the product mixture of step (a) in an amount sufficient to cause partitioning of the product mixture into an aqueous layer and a substantially immiscible organic layer, wherein the aqueous layer comprises the water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or combination thereof; and then
(c) upgrading the water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or combination thereof.

2. The process of claim 1 , wherein the organic solvent is miscible with water.

3. The process of claim 1 , wherein the organic solvent can dissolve from 2 wt % to 40 wt % water.

4. The process of claim 1 , wherein the organic solvent is gamma-valerolactone (GVL).

5. The process of claim 1 , wherein the organic solvent is present in a mass ratio with water, organic solvent:water, selected from the group consisting of about 60:40, about 65:35, about 70:30, about 75:25, about 80:20, about 85:15, about 90:10, about 95:5, about 97:3, about 98:2, and about 99:1.

6. The process of claim 1 , wherein the acid catalyst is homogeneous or heterogeneous, and if the acid catalyst is homogeneous it is present in a concentration not greater than 100 mM based on volume of the solvent system, and if the acid catalyst is heterogeneous it is present in a concentration not greater than 1.0 wt % based on weight of the solvent system.

7. The process of claim 6 , wherein the acid catalyst is a mineral acid or an organic acid.

8. The process of claim 6 , wherein the acid catalyst is a solid acid catalyst selected from the group consisting of solid Brønsted acid catalysts, solid Lewis acid catalysts, and combinations thereof.

9. The process of claim 8 , wherein the solid acid catalyst is a heteropolyacid.

10. The process of claim 8 , wherein the solid acid catalyst is an amorphous or mesoporous silica, which may be unfunctionalized or functionalized with acidic modifier.

11. The process of claim 8 , wherein the solid acid catalyst is a zeolite.

12. The process of claim 1 , wherein the solute is a water-soluble, inorganic salt.

13. The process of claim 12 , wherein the salt is added to the product mixture in a saturating amount.

14. The process of claim 12 , wherein the salt is sodium chloride.

15. The process of claim 1 , wherein step (a) is conducted at a temperature range selected from the group consisting of from about 100° C. to about 300° C., about 140° C. to about 240° C., and about 150° C. to about 200° C.

16. The process of claim 1 , wherein step (a) is conducted at a dynamic temperature range.

17. The process of claim 16 , wherein the dynamic temperature range ramps from a first temperature to a second temperature that is higher than the first temperature.

18. The process of claim 16 , wherein the dynamic temperature range changes from a first temperature to a second temperature in a non-linear fashion, a discontinuous fashion or a combination thereof.

19. The process of claim 1 , wherein in step (a) the biomass or a biomass-derived reactant comprises water-insoluble glucose-containing polymers or oligomers, or water-insoluble xylose-containing polymers or oligomers, or any combination thereof, and these, if present, are converted to water-soluble glucose-containing oligomers, glucose monomers, water-soluble xylose-containing oligomers, xylose monomers, or any combination thereof.

20. The process of claim 1 , wherein in step (a), residence time of the reaction is selected from the group consisting of 1 min to 24 hours, 1 min to 20 hours, 1 min to 12 hours, 1 min to 6 hours, 1 min to 3 hours, 1 min to 2 hours, 1 min to 1 hour, and 1 min to 30 min.

21. The process of claim 1 , wherein step (c) comprises dehydrating the water-soluble C6-sugar-containing oligomers, the water-soluble C6-sugar monomers, the water-soluble C5-sugar-containing oligomers, the water-soluble C5-sugar monomers, or the combination thereof.

22. The process of claim 21 , wherein the dehydrating is performed in the presence of an organic phase.

23. The process of claim 21 , wherein the dehydrating is performed in the presence of an organic phase and a phase modifier.

24. The process of claim 21 , wherein the dehydrating is performed in the presence of a Lewis acid.

25. The process of claim 21 , wherein the dehydrating converts glucose to 5-hydroxy-methyl-furfural, xylose to furfural, or glucose to 5-hydroxy-methyl-furfural and xylose to furfural.

26. The process of claim 21 , further comprising, separating C6 compounds selected from the group consisting of the water-soluble C6-sugar-containing oligomers and the water-soluble C6-sugar monomers from C5 compounds selected from the group consisting of the water-soluble C5-sugar-containing oligomers and the water-soluble C5-sugar monomers.

27. The process of 26 , wherein the separating is performed prior to the dehydrating, and wherein the dehydrating comprises dehydrating the separated C6 compounds, the separated C5 compounds, or the separated C6 compounds and the separated C5 compounds.

28. The process of claim 27 , wherein the separated C6 compounds comprise glucose and the separated C5 compounds comprise xylose, and wherein the dehydrating yields 5-hydroxy-methyl-furfural from the glucose, furfural from the xylose, or 5-hydroxy-methyl-furfural from the glucose and furfural from the xylose.

29. The process of claim 1 , wherein step (c) comprises depolymerizing the water-soluble C6-sugar-containing oligomers, the water-soluble C5-sugar-containing oligomers, or the combination thereof.

30. The process of claim 29 , wherein the depolymerizing comprises heating the aqueous layer in the presence of an acid catalyst.

31. The process of claim 30 , wherein the acid catalyst in step (c) is the same acid catalyst in step (a).

32. The process of claim 29 , further comprising, separating C6 compounds selected from the group consisting of the water-soluble C6-sugar-containing oligomers and the water-soluble C6-sugar monomers from C5 compounds selected from the group consisting of the water-soluble C5-sugar-containing oligomers and the water-soluble C5-sugar monomers.

33. The process of claim 1 , wherein step (c) comprises depolymerizing the water-soluble C6-sugar-containing oligomers, the water-soluble C5-sugar-containing o

Assignees

• Wisconsin Alumni Res Found

Inventors

• Dumesic James A
• Luterbacher Jeremy S

Classifications

• C07H3/06

  Oligosaccharides, i.e. having three to five saccharide radicals attached to each other by glycosidic linkages · CPC title

• C13K1/06

  obtained by saccharification of starch or raw materials containing starch · CPC title

• C13K1/02 Primary

  obtained by saccharification of cellulosic materials (manufacture of fodder A23K10/32) · CPC title

• C07D307/50

  Preparation from natural products · CPC title

• C13K13/002

  Xylose · CPC title