Process for treating biomass to derivatize polysaccharides contained therein to increase their accessibility to hydrolysis and subsequent fermentation

• US 8,795,993 B2
• Filed: 02/03/2010
• Issued: 08/05/2014
• Est. Priority Date: 02/03/2009
• Status: Expired due to Fees

• Current Assignee: Hercules, LLC (Ashland Global Holdings, Inc.)
• Original Assignee: Hercules Incorporated (Ashland Global Holdings, Inc.)
• Inventors: Conner, Herbert T., Cowan, Patrick J., Gast, John C.
• Primary Examiner(s): Weber, Jon P
• Assistant Examiner(s): Srivastava, Kailash C
• Application Number:
  US12/699,584
• Publication Number:
  US 20110039309A1
• Time in Patent Office: 1,644 Days
• Field of Search: 435/41, 435/105, 435/147, 435/148, 435/157, 435/160, 435/161, 435/68.1, 435/99, 435/126, 435/128, 435/139, 435/146, 435/158, 435/165, 435/167, 435/168, 536/124, 424/438, 514/554, 514/557
• US Class Current: 435/160
• CPC Class Codes: C08B 11/12 substituted with carboxylic radicals , e.g. carboxymethylcellulose [CMC]
• CPC Class Codes: C12P 19/02 Monosaccharides 2-ketogulonic acid C12P7/60
• CPC Class Codes: C12P 19/14 produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase , e.g. by cellulase, hemicellulase
• CPC Class Codes: C12P 2201/00 Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
• CPC Class Codes: C12P 7/10 substrate containing cellulosic material
• CPC Class Codes: C12P 7/16 Butanols
• CPC Class Codes: D21C 1/00 Pretreatment of the finely-divided materials before digesting of waste paper D21C5/02
• CPC Class Codes: D21C 5/00 Other processes for obtaining cellulose, e.g. cooking cotton linters obtaining fibres for spinning D01C; Processes characterised by the choice of cellulose-containing starting materials
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

A process is described for producing fermentable sugars derivable from biomass that contains polysaccharide, such as cellulose, made increasingly accessible as a substrate for enzymatic degradation or other methods of depolymerization. These fermentable sugars are subsequently able to be fermented to produce various target chemicals, such as alcohols, aldehydes, ketones or acids.

Claims

1. A process for producing fermentable sugars from polysaccharide containing biomass, comprising the steps of:

treating the biomass with a swelling agent to produce a swelled biomass;

contacting the swelled biomass with a derivatization agent to derivatize the polysaccharide contained therein to produce a derivatized polysaccharide with increased accessibility, wherein the derivatized polysaccharide, as compared to a swelled polysaccharide without derivatization, (i) exhibits an increase in a soluble portion as determined by an Enzyme Accessibility Test, and (ii) is substantially insoluble as measured by a Solubility Test; and

converting the derivatized polysaccharide to fermentable sugars by hydrolysis;

fermenting the fermentable sugars with at least one biocatalyst under suitable fermenting conditions to produce a target chemical;

converting a portion of the target chemical into at least one derivatization agent; and

feeding at least a portion of the converted derivatization agent back into the step of contacting the swelled biomass with a derivatization agent.

2. The process of claim 1, further comprising the step of removing the swelling agent after the biomass is contacted with the derivatization agent.

3. The process of claim 1, wherein the derivatization agent reacts with at least one of a hydroxyl, carboxyl, and other functional groups of the polysaccharide to form a derivatized polysaccharide having a degree of substitution greater than 0.1.

4. The process of claim 3, wherein the derivatized polysaccharide has a degree of substitution in a range of from about 0.1 to about 1.2.

5. The process of claim 3, wherein the derivatized polysaccharide has a degree of substitution in a range of from about 0.1 to about 0.6.

6. The process of claim 3, wherein the derivatized polysaccharide is selected from the group consisting of hydroxyethyl cellulose, ethylhydroxyethyl cellulose, carboxymethylcellulose, carboxymethylhydroxyethyl cellulose, hydroxypropylhydroxyethyl cellulose, methyl cellulose, methylhydroxypropyl cellulose, methylhydroxyethyl cellulose, carboxymethylmethyl cellulose, hydrophobically modified carboxymethyl cellulose, hydrophobically modified hydroxyethyl cellulose, hydrophobically modified hydroxypropyl cellulose, hydrophobically modified ethylhydroxyethyl cellulose, hydrophobically modified carboxymethylhydroxyethyl cellulose, hydrophobically modified hydroxypropylhydroxyethyl cellulose, hydrophobically modified methyl cellulose, hydrophobically modified methylhydroxypropyl cellulose, hydrophobically modified methylhydroxyethyl cellulose, hydrophobically modified carboxymethylmethyl cellulose, nitrocellulose, cellulose acetate, cellulose sulfate, cellulose vinyl sulfate, cellulose phosphate, methylol cellulose, cellulose phosphonate, and combinations thereof.

7. The process of claim 6, wherein the derivatized polysaccharide is carboxymethylcellulose.

8. The process of claim 7, wherein the carboxymethylcellulose has a degree of substitution in a range of from about 0.1 to about 0.6.

9. The process of claim 6, wherein the derivatized polysaccharide is hydroxyethylcellulose.

10. The process of claim 9, wherein the hydroxyethylcellulose has a molar substitution in a range of from about 0.1 to about 2.0.

11. The process of claim 1, wherein the derivatization agent is selected from the group consisting of chloroacetic acid, sodium chloroacetate, alkyl halides, anhydrides, aldehydes, compounds containing quaternary cation functionality, epichlorhydrin, and mixtures thereof.

12. The process of claim 11, wherein the derivatization agent is ethylene oxide.

13. The process of claim 1, wherein the derivatization agent is at least one of chloroacetic acid and sodium chloroacetate.

14. The process of claim 1, wherein the derivatized polysaccharide has a molar substitution in a range of from about 0.1 to about 3.0.

15. The process of claim 14, wherein the derivatized polysaccharide has a molar substitution of less than about 1.5.

16. The process of claim 14, wherein the derivatized polysaccharide has a molar substitution of less than about 1.0.

17. The process of claim 1, wherein the biomass comprises cellulose and the fermentable sugars comprise glucose.

18. The process of claim 1, wherein the step of converting the derivatized polysaccharide to fermentable sugars by hydrolysis comprises the step of contacting the derivatized polysaccharide with at least one saccharification enzyme under suitable conditions to produce the fermentable sugars.

19. The process of claim 1, wherein the step of converting the derivatized polysaccharide to fermentable sugars by hydrolysis comprises the step of acid hydrolysis of the derivatized polysaccharide to produce the fermentable sugars.

20. The process of claim 1, wherein the polysaccharide contained within the biomass is selected from the group consisting of cellulose, hemicellulose, chitin, chitosan, guar gum, pectin, alginate, agar, xanthan, starch, amylose, amylopectin, alternan, gellan, mutan, dextran, pullulan, fructan, locust bean gum, carrageenan, glycogen, glycosaminoglycans, murein, bacterial capsular polysaccharides, and combinations thereof.

21. The process of claim 20, wherein the polysaccharide is cellulose.

22. The process of claim 1, wherein the biomass is selected from the group consisting of bioenergy crops, agricultural residues, municipal solid waste, industrial solid waste, sludge from paper manufacturer, yard waste, wood and forestry waste, bamboo, bagasse, flax, hemp, manila hemp, sisal hemp, jute, ramie, kanif corn grain, corn cobs, crop residues, corn husks, corn stover, grasses, wheat, wheat straw, barley, barley straw, hay, rice straw, cotton, cotton linters, switchgrass, post consumer paper, post consumer paperboard, sugar cane bagasse, sorghum, soy, components obtained from milling of grains, trees, branches, roots, leaves, wood chips, sawdust, wood pulp, shrubs and bushes, vegetables, fruits, flowers, animal manure, bacteria, algae, fungi, and combinations thereof.

23. The process of claim 1, wherein the swelling agent is selected from the group consisting of alkali metal oxides, alkali metal hydroxides, alkaline earth metal oxides, alkaline earth metal hydroxides, alkali silicates, alkali aluminates, alkali carbonates, amines, ammonia, ammonium hydroxide, tetramethyl ammonium hydroxide, lithium chloride, N-methyl morpholine N-oxide, urea, and mixtures thereof.

24. The process of claim 23, wherein the swelling agent is at least one of sodium hydroxide and ammonium hydroxide.

25. The process of claim 1, further comprising the step of neutralizing the swelling agent after the biomass is contacted with the derivatization agent.

26. The process of claim 1, wherein the target chemical is selected from the group consisting of alcohols, aldehydes, ketones, acids, and combinations thereof.

27. The process of claim 26, wherein the target chemical is alcohol.

28. The process of claim 27, wherein the alcohol is ethanol.

29. The process of claim 27, wherein the alcohol is butanol.

30. The process of claim 29, wherein butanol is at least one of n-butanol, sec-butanol, isobutanol, tert-butanol, and combinations thereof.

31. The process of claim 1, wherein the target chemical is ethanol and the derivatization agent is ethylene oxide.

32. The process of claim 1, wherein the swelled biomass has disrupted intramolecular and intermolecular hydrogen bonds therein.

33. The process of claim 1, wherein the derivatized polysaccharide is substantially in the amorphous phase.

34. The process of claim 1, wherein the derivatized polysaccharide has a solubility of less than 75%, as measured by the Solubility Test.