Process for Fractionating Lignocellulosic Biomass into Liquid and Solid Products

• US 20090176286A1
• Filed: 11/15/2006
• Published: 07/09/2009
• Est. Priority Date: 11/23/2005
• Status: Abandoned Application

• Current Assignee: Cargill, Inc. (Agricultural Services Division)
• Original Assignee: Cargill, Inc. (Agricultural Services Division)
• Inventors: Birk, Robert Henry, Brooks, Rebecca Kerin, Warwick, Jeffrey, Wooley, Robert, O'Connor, Ryan P., Mastel, Beth, Hettenhaus, James R., Ritzenthaler, Jon Michael, Kean, Robert Thomas, Kolstad, Jeffrey John, Glassner, David A.
• Application Number:
  US12/093,630
• Publication Number:
  US 20090176286A1
• Time in Patent Office: Days
• US Class Current: 435/139
• CPC Class Codes: C08B 37/0003 General processes for their isolation or fractionation, e.g. purification or extraction from biomass
• CPC Class Codes: C08B 37/0057 beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof
• CPC Class Codes: C08H 8/00 Macromolecular compounds derived from lignocellulosic materials pretreatment thereof B27N
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

The invention herein is an efficient, flexible biomass fractionation process comprising digesting a lignocellulosic-biomass material at about 120-220° C. and a pH of less than about 4, in an aqueous mixture containing an effective concentration of at least one solvent for lignin, and separating to recover a solid phase that contains a large fraction of the cellulose originally in the starting lignocellulosic material and a liquid phase that contains most of the lignin and hemicellulose originally in the starting lignocellulosic biomass. The process can produce a solid phase that contains at least 75% cellulose and less than 10% lignin. The cellulose-rich solid product can be converted very efficiently to glucose. The solid product can also be used in commercial pulp applications, such as papermaking or fluff pulp. Hemicellulose sugars and lignin can be used directly or converted to other products.

Claims

1. A biomass fractionation process comprising

a) digesting a starting lignocellulosic-biomass material at a temperature of from about 120°

C. to about 220°

C. and a pH of less than about 4, in an aqueous extractant mixture containing an effective concentration of a solvent for lignin, to form a digested mass that includes (1) one or more liquid phases that collectively contain dissolved lignin and, if hemicellulose is present in the starting lignocellulosic-biomass material, hemicellulose in dissolved or hydrolyzed form and (2) a solid phase containing cellulose; and

b) separating said liquid and solid phases to recover a solid phase that contains at least 75% of the cellulose originally in the starting lignocellulosic material and a liquid phase that contains at least 50% of the lignin originally in the starting lignocellulosic material and, if hemicellulose is present in the starting lignocellulosic-biomass material, at least 50% of the hemicellulose originally in the starting lignocellulosic material, in the form of hemicellulose sugars.

2. The process of claim 1, wherein said separation is conducted at a temperature of at least about 120°

C. and under superatmospheric pressure such that the water and the solvent for lignin do not boil.

3. The process of claim 1 wherein the starting biomass material contains hemicellulose.

4. The process of claim 3, wherein the solvent for lignin is at least partially immiscible with water and the digested mass contains multiple liquid phases.

5. The process of claim 4, further comprising separating multiple liquid phases to recover a liquid phase that contains at least 50% of the lignin originally in the starting lignocellulosic material and at least one other liquid phase that contains at least 50% of the hemicellulose originally in the starting lignocellulosic material, in the form of hemicellulose sugars.

6. The process of claim 5 wherein the solid phase contains at least 75% by dry weight cellulose and less than 10% by dry weight lignin.

7. The process of claim 6 wherein the solid phase contains at least 85% by dry weight cellulose and less than 5% by dry weight lignin.

8. The process of claim 5 wherein the recovered solid phase is washed with water, a solvent for lignin, or both.

9. The process of claim 4 comprising the further step of c) recovering lignin from a liquid phase.

10. The process of claim 3, further comprising d) fermenting the hemicellulose sugars.

11. The process of claim 10, wherein the hemicellulose sugars are fermented to ethanol, D-lactic acid, L-lactic acid, or a mixture of two or more thereof.

12. The process of claim 1 further comprising e) drying the solid phase to produce a material having a liquid-absorption capacity of at least 13 g water per g dry solid.

13. The biomass fractionation process of claim 5 wherein step a) is conducted at a pH between about 1.5 and about 3.5.

14. The biomass fractionation process of claim 5 wherein step a) is conducted at a pH between about 2.0 and about 3.0.

15. The process of claim 1, wherein steps a) and b) are performed continuously and the solid and liquid flow cocurrently.

16. The process of claim 1 wherein steps a) and b) are performed continuously and the solid and liquid flow countercurrently.

17. The process of claim 1, wherein the solvent for lignin is ethanol.

18. The process of claim 1, wherein the solvent for lignin includes at least one of methanol, ethanol, 1- and 2-propanol, glycerol, 1- and 2-butanol, cyclohexanol, phenol, cresol, cyclohexanone, methyl ethyl ketone, and diethyl ether.

19. The process of claim 1 wherein the extractant mixture contains sulfuric acid.

20. The process of claim 1 wherein the extractant mixture contains at least one of sulfuric acid, sulfurous acid, hydrochloric acid, trifluoroacetic acid, lactic acid, ethyl lactate, citric acid, glycolic acid, and propionic acid.

21. The process of claim 1, wherein the extractant mixture contains 50-80 wt % water and 50-20 wt % of said solvent, based on the combined weight of water and solvent, and the extractant mixture has a pH of 1.5 to 3.5.

22. The process of claim 21, wherein step b) is conducted at a temperature of at least 120°

C. and under sufficient pressure to keep the water and solvent from boiling.

23. The process of claim 21, wherein the solvent is ethanol and the extractant mixture contains sulfuric acid.

24. The process of claim 23, wherein the solid phase contains less than 5% by weight of hemicellulose.

25. A cellulose-rich solid product having a liquid-absorption capacity of at least 13 g water per g dry solid.

26. A cellulose-rich solid product which can be converted to glucose with at least 80% yield within 24 hours at 50°

C. and 2 wt % solids, in the presence of a cellulase enzyme mixture in an amount of no more than 15 filter paper units (FPU) per g of the solid product.

27. The product of claim 26 which can be converted to glucose with at least 80% yield within 24 hours at 50°

C. and 2 wt % solids, in the presence of a cellulase enzyme mixture in an amount of no more than 5 filter paper units (FPU) per g of the solid product.

28. The product of claim 27 which can be converted to glucose with at least 90% yield within 24 hours at 50°

C. and 2 wt % solids, in the presence of a cellulase enzyme mixture in an amount of no more than 15 filter paper units (FPU) per g of the solid product.

29. A biomass fractionation process comprising

a) digesting a starting lignocellulosic-biomass material at a temperature of from about 160°

C. to about 220°

C. and a pH of up to 3, in an aqueous extractant mixture containing an effective concentration of a solvent for lignin, to form a digested mass that includes (1) a liquid phases that collectively contains dissolved lignin and-hemicellulose in dissolved or hydrolyzed form and (2) a solid phase containing cellulose; and

b) separating said liquid and solid phases to recover a solid phase that contains at least 90% of the cellulose originally in the starting lignocellulosic material and a liquid phase that contains at least 75% of the lignin originally in the starting lignocellulosic material and at least 75% of the hemicellulose originally in the starting lignocellulosic material, in the form of hemicellulose sugars;

wherein the solvent for lignin includes at least one of methanol, ethanol, 1- and 2-propanol, glycerol, 1-butanol, 2-butanol, cyclohexanol, phenol, cresol, cyclohexanone, methyl ethyl ketone, and diethyl ether;

wherein the extractant mixture contains at least one of sulfuric acid, sulfurous acid, hydrochloric acid, trifluoroacetic acid, lactic acid, ethyl lactate, citric acid, glycolic acid, and propionic acid;

and wherein said separation is conducted at a temperature of at least about 120°

C. and under superatmospheric pressure such that the water and the solvent for lignin do not boil.

30. The process of claim 29 wherein the solvent for lignin is ethanol, methanol or a mixture thereof, the extractant mixture contains sulfuric acid, sulfurous acid, hydrochloric acid or a mixture of two or more thereof, and the pH is from 2.0 to 3.0.