Methods for cellulose hydrolysis using sulfonated polyaromatic catalysts

Patent metadata

Field	Value
Publication number	US-12303876-B2
Application number	US-201917296591-A
Country	US
Kind code	B2
Filing date	Nov 26, 2019
Priority date	Nov 26, 2018
Publication date	May 20, 2025
Grant date	May 20, 2025

Abstract

A method for hydrolyzing cellulosic material includes combining the cellulosic material with a sulfonated polyaromatic catalyst in water to at least partially hydrolyze the cellulosic material and to form a monosaccharide hydrolysis product, thereby forming a reaction mixture including (i) an aqueous phase with the monosaccharide hydrolysis product in solution therein, and (ii) a dispersed phase including the sulfonated polyaromatic catalyst as well as any non-hydrolyzed cellulosic material. The sulfonated polyaromatic catalyst includes a mixture of partially sulfonated polycyclic aromatic hydrocarbons that is substantially insoluble in the aqueous phase, thus providing it with an affinity for the water-insoluble cellulosic substrate where it preferentially exhibits its catalytic hydrolytic activity. The monosaccharide hydrolysis product can be recovered from the aqueous phase of the reaction mixture.

First claim

What is claimed is:

1. A method for hydrolyzing cellulosic material, the method comprising:
admixing a cellulosic material with a sulfonated polyaromatic catalyst in water under temperature and pressure sufficient to at least partially hydrolyze the cellulosic material and to form a monosaccharide hydrolysis product, thereby providing a reaction mixture comprising (i) an aqueous phase comprising the water and the monosaccharide hydrolysis product in solution therein, and (ii) a dispersed phase comprising the sulfonated polyaromatic catalyst; and,
recovering the monosaccharide hydrolysis product from the aqueous phase of the reaction mixture;
wherein the sulfonated polyaromatic catalyst comprises a mixture of partially sulfonated polycyclic aromatic hydrocarbons that is substantially insoluble in the aqueous phase.

2. The method of claim 1 , wherein polycyclic aromatic hydrocarbons in the mixture of partially sulfonated polycyclic aromatic hydrocarbons have at least 3 aromatic units.

3. The method of claim 1 , wherein polycyclic aromatic hydrocarbons in the mixture of partially sulfonated polycyclic aromatic hydrocarbons are selected from the group consisting of triphenylene, tetraphenylene, pentaphenylene, tetracene, pentacene, hexacene, heptacene, octacene, nonacene, decacene, condensed derivatives thereof, quinone derivatives thereof, hydroxylated derivatives thereof, alkylated derivatives thereof, carbonylated derivatives thereof, carboxylated derivatives thereof, and combinations thereof.

4. The method of claim 1 , wherein the mixture of partially sulfonated polycyclic aromatic hydrocarbons has a degree of sulfonation of about 10 wt. % to about 20 wt. %.

5. The method of claim 1 , wherein polycyclic aromatic hydrocarbons in the mixture of partially sulfonated polycyclic aromatic hydrocarbons are also at least partially oxidized.

6. The method of claim 1 , wherein the sulfonated polyaromatic catalyst is present in the reaction mixture in an amount ranging from about 0.5 wt. % to about 5 wt. %, based on the total weight of the reaction mixture.

7. The method of claim 1 , wherein the cellulosic material is present in the reaction mixture in an amount ranging from about 5 wt. % to about 90 wt. %, based on the total weight of the reaction mixture.

8. The method of claim 1 , wherein the weight ratio of the sulfonated polyaromatic catalyst to the cellulosic material in the reaction mixture is in a range of about 1:5 to about 1:100.

9. The method of claim 1 , wherein the cellulosic material is obtained from a lignocellulosic biomass.

10. The method of claim 1 , wherein the monosaccharide hydrolysis product is selected from the group consisting of glucose, xylose, mannose, galactose, rhamnose, arabinose, and combinations thereof.

11. The method of claim 1 , wherein the cellulosic material comprises at least one of cellulose and hemicellulose.

12. The method of claim 1 , comprising performing the admixing in a pressurized vessel.

13. The method of claim 1 , comprising performing the admixing at a temperature of about 100° C. to about 180° C.

14. The method of claim 1 , comprising performing the admixing for about 3 to about 48 hours.

15. The method of claim 1 , comprising performing the admixing under acidic conditions.

16. The method of claim 1 , wherein about 5 wt. % to about 95 wt. % of the initial cellulose material is converted the monosaccharide hydrolysis product.

17. The method of claim 1 , wherein the aqueous phase of the reaction mixture is substantially free of the sulfonated polyaromatic catalyst.

18. The method of claim 1 , wherein the monosaccharide hydrolysis product is substantially free of the sulfonated polyaromatic catalyst.

19. The method of claim 1 , further comprising:
recovering the sulfonated polyaromatic catalyst from the reaction mixture;
admixing a second cellulosic material with the recovered sulfonated polyaromatic catalyst in water to provide a second reaction mixture having an aqueous phase and a dispersed phase; and,
recovering a second monosaccharide hydrolysis product from the aqueous phase of the second reaction mixture.

20. The method of claim 1 , wherein the mixture of partially sulfonated polycyclic aromatic hydrocarbons is selected from the group consisting of partially sulfonated bitumen, partially sulfonated tar, partially sulfonated pitch, partially sulfonated creosote, fractions thereof, and combinations thereof.

21. The method of claim 1 , wherein the mixture of partially sulfonated polycyclic aromatic hydrocarbons comprises partially sulfonated bitumen.

22. The method of claim 1 , wherein the mixture of partially sulfonated polycyclic aromatic hydrocarbons comprises a fraction of partially sulfonated bitumen.

23. The method of claim 22 , wherein the fraction of partially sulfonated bitumen excludes at least one of non-aromatic components and low molecular weight components from polycyclic aromatic hydrocarbons in the fraction of partially sulfonated bitumen.

24. The method of claim 22 , wherein the fraction of partially sulfonated bitumen is a water-insoluble fraction.

25. The method of claim 1 , wherein:
the monosaccharide hydrolysis product is selected from the group consisting of glucose, xylose, mannose, galactose, rhamnose, arabinose, and combinations thereof;
the method comprises performing the admixing at a temperature of about 100° C. to about 180° C.; and
the mixture of partially sulfonated polycyclic aromatic hydrocarbons comprises at least one of partially sulfonated bitumen and a fraction of partially sulfonated bitumen.

26. The method of claim 25 , wherein:
the sulfonated polyaromatic catalyst is present in the reaction mixture in an amount ranging from about 0.5 wt. % to about 5 wt. %, based on the total weight of the reaction mixture;
the cellulosic material is present in the reaction mixture in an amount ranging from about 5 wt. % to about 90 wt. %, based on the total weight of the reaction mixture;
the weight ratio of the sulfonated polyaromatic catalyst to the cellulosic material in the reaction mixture is in a range of about 1:5 to about 1:100; and
the cellulosic material comprises at least one of cellulose and hemicellulose.

27. The method of claim 26 , wherein:
the mixture of partially sulfonated polycyclic aromatic hydrocarbons has a degree of sulfonation of about 10 wt. % to about 20 wt. %; and
about 5 wt. % to about 95 wt. % of the initial cellulose material is converted the monosaccharide hydrolysis product.

Assignees

• Univ Michigan State

Inventors

• Redko Mikhail
• Jackson James E
• Saffron Christopher M
• Kilponen Kyle Matthew

Classifications

• C08B1/00

  Preparatory treatment of cellulose for making derivatives thereof {, e.g. pre-treatment, pre-soaking, activation} · CPC title

• Y02E50/30

  Fuel from waste, e.g. synthetic alcohol or diesel · CPC title

• B01J31/0225 Primary

  comprising sulfonic acid groups or the corresponding salts · CPC title

• C13K1/02 Primary

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