Catalytic hydrolysis and dehydration of saccharides

Patent metadata

Field	Value
Publication number	US-11028062-B2
Application number	US-201615568672-A
Country	US
Kind code	B2
Filing date	Apr 22, 2016
Priority date	Apr 23, 2015
Publication date	Jun 8, 2021
Grant date	Jun 8, 2021

Abstract

In one aspect, methods of HMF production are described herein. A method of HMF production, in some embodiments, comprises providing a saccharide feedstock including glucose and bringing the saccharide feedstock into contact with a solid state catalytic structure at a temperature sufficient to effectuate dehydration of the glucose to provide HMF. The solid state catalytic structure comprises a substrate having one or more surfaces functionalized with saccharide solubilization functionalities and acid functionalities, wherein the saccharide solubilization functionalities comprise one or more imidazolium salts pendant along chains of a first polymeric species attached to the substrate surface.

First claim

The invention claimed is:

1. A method of producing hydroxymethylfurfural (HMF) and levulinic acid comprising:
providing a saccharide feedstock including glucose;
bringing the saccharide feedstock into contact with a solid state catalytic structure at a first temperature sufficient to effectuate dehydration of the glucose to provide the HMF; and
bringing the HMF into contact with the solid state catalytic structure at a second temperature sufficient to produce levulinic acid,
wherein the solid state catalytic structure comprises a substrate having one or more surfaces functionalized with saccharide solubilization functionalities and acid functionalities,
wherein the saccharide solubilization functionalities comprise one or more imidazolium halide salts pendant along chains of a first polymeric species attached to the substrate surface, and the acid functionalities are pendant along chains of a second polymeric species attached to the substrate surface, and
wherein the second temperature is higher than the first temperature, wherein the substrate is functionalized according to the reaction scheme of FIG. 1 .

2. The method of claim 1 , wherein the acid functionalities participate in dehydration mechanisms of the glucose.

3. The method of claim 1 , wherein the saccharide feedstock further comprises xylose for dehydration to furfural by the solid state catalytic structure.

4. The method of claim 1 , wherein the first temperature is greater than 130° C.

5. The method of claim 1 , wherein the saccharide feedstock is dissolved in an ionic liquid composition comprising a mixture of ionic liquid and water or aprotic solvent.

6. The method of claim 5 , wherein the aprotic solvent is selected from the group consisting of valerolactone, acetonitrile and dimethylacetamide, and wherein the ionic liquid is present in the mixture in an amount of 20 vol. % to 80 vol. %.

7. A method of producing HMF and levulinic acid comprising:
providing a solution comprising saccharide feedstock including cellulose in an ionic liquid composition at a first temperature;
bringing the saccharide feedstock solution into contact with a solid state catalytic structure comprising a substrate having one or more surfaces functionalized with saccharide solubilization functionalities and acid functionalities, wherein the saccharide solubilization functionalities comprise one or more imidazolium halide salts pendant along chains of a first polymeric species attached to the substrate surface, and wherein the acid functionalities comprise aryl sulfonic acid groups pendant along chains of a second polymeric species attached to the substrate surface;
hydrolyzing the cellulose with the acid functionalities of the solid state catalytic structure to provide glucose feedstock in the ionic liquid composition;
altering the temperature of the ionic liquid composition to a second temperature;
bringing the glucose feedstock into contact with the solid state catalytic structure to effectuate dehydration of the glucose to provide the HMF; and
altering the temperature of the ionic liquid composition to a third temperature and bringing the HMF into contact with the solid state catalytic structure to produce levulinic acid,
wherein the third temperature is higher than the second temperature, wherein the substrate is functionalized according to the reaction scheme of FIG. 1 .

8. The method of claim 7 , wherein the acid functionalities of the solid state catalytic structure participate in dehydration mechanisms of the glucose.

9. The method of claim 7 , wherein the saccharide feedstock further comprises hemicellulose for hydrolysis by the acid functionalities into xylose feedstock.

10. The method of claim 9 , wherein the xylose feedstock is brought into contact with the solid state catalytic structure at the second temperature to effectuate dehydration of the xylose to furfural.

11. The method of claim 7 , wherein the ionic liquid composition comprises a mixture of ionic liquid and water or aprotic solvent.

12. The method of claim 11 , wherein the aprotic solvent is selected from the group consisting of valerolactone, acetonitrile and dimethylacetamide.

13. The method of claim 11 , wherein the ionic liquid is present in the mixture in an amount of 20 vol. % to 80 vol. %.

14. The method of claim 1 , further comprising adding heterogeneous catalyst to the saccharide feedstock or the solid state catalytic structure, the heterogeneous catalyst comprising β-Sn or Sn/W.

15. The method of claim 1 , wherein yield of the HMF is greater than 60%.

16. The method of claim 7 , further comprising adding heterogeneous catalyst to the saccharide feedstock or the solid state catalytic structure, the heterogeneous catalyst comprising β-Sn or Sn/W.

17. The method of claim 1 , wherein the dehydration of the glucose yields the HMF in an amount in excess of 60%.

18. The method of claim 1 , wherein the levulinic acid is produced at a yield of 30-60 percent.

19. The method of claim 7 , wherein the dehydration of the glucose yields the HMF in an amount in excess of 60%.

20. The method of claim 7 , wherein the levulinic acid is produced at a yield of 30-60 percent.

Assignees

• Univ Arkansas

Inventors

• Qian Xianghong
• Wickramasinghe Ranil

Classifications

• C07D307/48

  Furfural · CPC title

• C07B35/06

  Decomposition, e.g. elimination of halogens, water or hydrogen halides · CPC title

• C13K1/02

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

• C13K13/002

  Xylose · CPC title

• C07C53/128

  the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids · CPC title