Methods and systems for producing sugars from carbohydrate-rich substrates

• US 9,194,012 B2
• Filed: 01/28/2015
• Issued: 11/24/2015
• Est. Priority Date: 02/02/2014
• Status: Active Grant

• Current Assignee: Edward Brian Hamrick
• Original Assignee: Edward Brian Hamrick
• Inventors: Hamrick, Edward Brian
• Primary Examiner(s): Mayes, Melvin C
• Assistant Examiner(s): CALL, DOUGLAS BRYANT
• Application Number:
  US14/608,183
• Publication Number:
  US 20150218663A1
• Time in Patent Office: 300 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C08B 37/0003 General processes for their isolation or fractionation, e.g. purification or extraction from biomass
• CPC Class Codes: C08H 8/00 Macromolecular compounds derived from lignocellulosic materials pretreatment thereof B27N
• CPC Class Codes: C12P 19/00 Preparation of compounds containing saccharide radicals ketoaldonic acids C12P7/58
• 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 2203/00 Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source ethanol C12P7/10
• CPC Class Codes: C12P 7/14 Multiple stages of fermentation; Multiple types of microorganisms or re-use of microorganisms
• CPC Class Codes: C12P 7/16 Butanols
• CPC Class Codes: C13K 1/02 obtained by saccharification of cellulosic materials manufacture of fodder A23K10/32
• CPC Class Codes: C13K 1/06 obtained by saccharification of starch or raw materials containing starch
• CPC Class Codes: C13K 13/00 Sugars not otherwise provided for in this class
• CPC Class Codes: C13K 13/002 Xylose
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 20/582 Recycling of unreacted starting or intermediate materials

Abstract

A method for producing sugars from lignocellulosic biomass is provided. Lignocellulosic biomass is composed of lignocellulosic fibers which are hollow and primarily contain cellulose, hemicellulose and lignin. Lignin is concentrated in the outer fiber wall and glues the fibers into bundles, but the inner fiber wall has a much lower concentration of lignin and has more easily accessible cellulose and hemicellulose. This method uses vacuum infusion to infuse homogeneous reagents into the lumen (hollow center) of lignocellulosic fibers to hydrolyze the hemicellulose and cellulose to produce sugars and oligomers, and then uses cycles of vacuum pressure to pump these homogeneous reagents and sugars and oligomers into and out of the lumen. Some types of reagents are dilute acids, cellulase enzymes, hemicellulase enzymes, Fenton or Fenton-like reagents, and hydrogen peroxide. These reagents are homogenized by mixing the reagents with process water using turbulent mixing to produce a homogeneous reagent.

Claims

1. A process for producing sugar monomers and/or polymers from a carbohydrate-rich substrate, said process comprising the steps of:

(a) providing a carbohydrate-rich substrate and an aqueous solution containing a hydrolysis catalyst, and maintaining a gas pressure above said carbohydrate-rich substrate at an evacuation pressure and for an evacuation time to infuse said hydrolysis catalyst into said carbohydrate-rich substrate at an infusion temperature, thereby generating a reaction mixture;

(b) exposing said reaction mixture to a gas-phase reaction pressure that is higher than said evacuation pressure;

(c) maintaining said reaction mixture at a reaction temperature for a reaction time to generate said sugar monomers and/or polymers within lumen space of said carbohydrate-rich substrate;

(d) exposing said reaction mixture to a gas-phase expulsion pressure that is lower than said reaction pressure, to pump said sugar monomers and/or polymers out of said lumen space and into said aqueous solution;

(e) maintaining said reaction mixture at an expulsion temperature for an expulsion time;

(f) repeating steps (b) to (e) for at least two pressure cycles to remove, by a pumping mechanism, said sugar monomers and/or polymers from said lumen space; and

(g) recovering said sugar monomers and/or polymers from said aqueous solution;

wherein said process does not include steam explosion or ammonia fiber expansion of said carbohydrate-rich substrate.

2. The process of claim 1, wherein said carbohydrate-rich substrate is selected from the group consisting of naturally occurring lignocellulosic biomass, processed lignocellulosic biomass, pulp, paper, paper-based products, carbohydrate-rich industrial waste, and combinations thereof.

3. The process of claim 2, wherein said carbohydrate-rich substrate includes said naturally occurring lignocellulosic biomass selected from the group consisting of size-reduced softwood, sugarcane bagasse, wheat straw, corn stover, switchgrass, miscanthus, and combinations thereof.

4. The process of claim 2, wherein said carbohydrate-rich substrate includes carbohydrate-rich industrial waste selected from the group consisting of food waste, components of municipal solid waste, and combinations thereof.

5. The process of claim 1, wherein said sugar monomers and/or polymers comprise pentose and/or hexose sugars in monomer, oligomer, or polymer form, including one or more of xylose, arabinose, glucose, mannose, galactose, O-acetyl galactoglucomannan, and nanocellulose crystals.

6. The process of claim 1, wherein said hydrolysis catalyst comprises an organic acid, a mineral acid, hydrogen peroxide, or a combination thereof.

7. The process of claim 6, wherein said hydrolysis catalyst comprises sulfuric acid in an amount that results in said aqueous solution having a sulfuric acid concentration of about 10 mM to about 200 mM.

8. The process of claim 1, wherein said hydrolysis catalyst comprises one or more Fenton or Fenton-like reagents including hydrogen peroxide and one or multiple transition metals forming a molar ratio of said hydrogen peroxide to said transition metals of about 20 to about 100.

9. The process of claim 1, wherein said hydrolysis catalyst comprises one or more enzymes each with cellulolytic activity and/or hemicellulolytic activity.

10. The process of claim 1, wherein said aqueous solution in step (a) is a homogeneous mixture, said process further comprising mixing said hydrolysis catalyst with process water using turbulent energy in the range of about 0.5 W/kg to about 5 W/kg to produce said homogeneous mixture.

11. The process of claim 1, wherein said reaction temperature is about 40°

C. to about 95°

C. and/or said reaction time is about 15 minutes to about 8 hours.

12. The process of claim 1, wherein said expulsion time is about 1 second to about 60 minutes.

13. The process of claim 1, wherein said expulsion pressure is from about 100% to about 200% of the water equilibrium pressure at said reaction temperature.

14. The process of claim 1, wherein said number of pressure cycles is from 3 to about 200.

15. The process of claim 1, wherein said infusion temperature is less than or equal to the boiling point of water at said evacuation pressure.

16. The process of claim 1, wherein said infusion temperature is from about 40°

C. to about 90°

C.

17. The process of claim 1, wherein said evacuation pressure is from about 105% to about 200% of the water equilibrium pressure at said infusion temperature.

18. The process of claim 1, wherein said evacuation time is about 1 minute to about 2 hours.

19. The process of claim 1, said process further comprising controlling pH of said reaction mixture by adjusting gas-phase composition above, or in equilibrium with, said aqueous solution.

20. The process of claim 19, wherein said hydrolysis catalyst comprises an organic acid, a mineral acid, or a combination thereof, and wherein said pH is controlled to about 2 or less.

21. The process of claim 19, wherein said hydrolysis catalyst comprises one or more Fenton or Fenton-like reagents and optionally one or more mineral acids, and wherein said pH is controlled between about 1 to about 6.

22. The process of claim 19, wherein said hydrolysis catalyst comprises one or more enzymes each with cellulolytic activity and/or hemicellulolytic activity, and wherein said pH is controlled between about 4 to about 7.

23. A method of producing sugar monomers and/or polymers from a carbohydrate-rich substrate having lumen space, said method comprising hydrolyzing said carbohydrate-rich substrate in the presence of an aqueous solution containing a hydrolysis catalyst, and cycling gas pressure between a reaction pressure and an expulsion pressure for at least three pressure cycles, wherein at said reaction pressure, said sugar monomers and/or polymers are generated within said lumen space, and wherein at said expulsion pressure, said sugar monomers and/or polymers are pumped out of said lumen space and into said aqueous solution, wherein said method does not include steam explosion or ammonia fiber expansion of said carbohydrate-rich substrate.

24. The method of claim 23, wherein the mass-transfer rate of said sugar monomers and/or polymers transporting out of said lumen space is higher than the diffusion rate of said sugar monomers and/or polymers diffusing out of said lumen space.

25. The method of claim 23, wherein reaction rate of generation of said sugar monomers and/or polymers is higher than an otherwise-identical process without a step of cycling said gas pressure.