Pretreatment of densified biomass using liquid ammonia and systems and products related thereto

• US 10,730,958 B2
• Filed: 03/08/2018
• Issued: 08/04/2020
• Est. Priority Date: 03/08/2017
• Status: Active Grant

• Current Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Original Assignee: The Board of Trustees of Michigan State University (Michigan State University)
• Inventors: Balan, Venkatesh, Sousa, Leonardo da Costa
• Primary Examiner(s): Barron, Sean C.
• Application Number:
  US15/916,223
• Publication Number:
  US 20180258190A1
• Time in Patent Office: 880 Days
• CPC Class Codes: A23K 10/14 Pretreatment of feeding-stuffs with enzymes
• CPC Class Codes: A23K 10/30 from material of plant origin, e.g. roots, seeds or hay; from material of fungal origin, e.g. mushrooms obtained by microbiological or biochemical processes, e.g. using yeasts or enzymes, A23K10/10
• CPC Class Codes: C07G 1/00 Lignin; Lignin derivatives
• CPC Class Codes: C08B 15/00 Preparation of other cellulose derivatives or modified cellulose , e.g. complexes
• CPC Class Codes: C08H 6/00 Macromolecular compounds derived from lignin, e.g. tannins, humic acids
• 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: Y02E 50/10 Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02P 60/87 Re-use of by-products of food processing for fodder production

Abstract

A method to convert at least a majority of native cellulose I_β to cellulose III_I in pretreated or untreated densified biomass is disclosed. The densified biomass (cellulosic or lignocellulosic) is pretreated with anhydrous liquid ammonia or liquid ammonia comprising a solution of at least 80% ammonia. The pretreating can be performed at a temperature from about 4° C. to about 140° C. and a pressure from about 14.7 to about 200 psi. In one embodiment, the densified cellulosic converting pretreatment process is followed by lignin extraction (LE). The total moisture content of the densified biomass and the solution is 30% or less and a weight ratio of liquid ammonia to the densified biomass is from about 0.3:1 to about 2:1. Various products and systems are also disclosed.

Claims

1. A method of pretreating biomass comprising:

converting at least a majority of native cellulose I_β

to cellulose III_I in densified biomass by pretreating the densified biomass with liquid ammonia, wherein the densified biomass is densified cellulosic biomass or densified lignocellulosic biomass and the liquid ammonia is anhydrous liquid ammonia or liquid ammonia comprising a solution of at least 80% ammonia, wherein the pretreating is performed at a temperature from about 50°

C. to about 140°

C. and at a pressure from about 14.7 to about 200 psi to generate pretreated/cellulose III-containing densified biomass, wherein total moisture content of the densified biomass and the solution is 10% or less and a weight ratio of liquid ammonia to the densified biomass is from about 0.2;

1 up to less than 2;

1.

2. The method of claim 1 wherein the weight ratio of the liquid ammonia to the densified biomass is from about 0.3:

1 to about 1;

1.

3. The method of claim 1 further comprising a lignin extraction step following the converting step to convert an additional 1% to 4% by weight of glucan.

4. The method of claim 1, wherein substantially all of the cellulose I_β

is converted to cellulose III_I.

5. The method of claim 1, wherein all of the cellulose I_β

is converted to cellulose III_I.

6. The method of claim 2, wherein the densified biomass is densified cellulosic biomass and the pretreated/cellulose III-containing densified biomass is pretreated/cellulose III-containing densified cellulosic biomass or wherein the densified biomass is densified lignocellulosic biomass and the pretreated/cellulose III-containing densified biomass is pretreated/cellulose III-containing lignocellulosic densified biomass or pretreated-LE/cellulose III-containing densified biomass.

7. The method of claim 5, wherein the densified lignocellulosic biomass is selected from corn stover, poplar, switchgrass, sugarcane bagasse, wheat straw, sorghum, energy cane, miscanthus, brewery spent grains, DDGS, soybean meal, and combinations thereof.

8. The method of claim 7, wherein the densified biomass is pretreated with the liquid ammonia for about 15 minutes to about 10 hours.

9. The method of claim 7, wherein the pretreatment is from about 1 to about 8 hours.

10. The method of claim 7, wherein the temperature is from about 50°

C. to about 120°

C.

11. The method of claim 7, wherein the densified biomass is untreated densified biomass or pretreated densified biomass containing no cellulose III_I.

12. The method of claim 11 wherein the pretreated densified biomass is pretreated using a pretreatment selected from ammonia, dilute acid, concentrated acid, steam explosion, alkali, organosolv, ionic liquid, biological, tetrahydrofuran (THF) and combinations thereof.

13. The method of claim 12, wherein the ammonia pretreatment is Ammonia Fiber Expansion (AFEX) and the alkali pretreatment is selected from NAOH, KOH, CaOH, and combinations thereof, and the method further comprises comprising recycling the liquid ammonia in a batch mode, a semi-batch mode or continuously.

14. The method of claim 7, wherein the pretreated/cellulose III-containing densified biomass is redensified to produce animal feed with or without added digestive enzymes.

15. The method of claim 7, further comprising an enzymatic hydrolysis step to hydrolyze the pretreated/cellulose III-containing densified biomass product, wherein said enzymatic hydrolysis step proceeds at a rate that is at least 1.5 times faster than a hydrolysis step performed using densified biomass that has not been pretreated with the liquid ammonia.

16. The method of claim 7, wherein the densified biomass is densified lignocellulosic biomass and the solution includes an organic solvent, wherein extractives present in the densified lignocellulosic biomass are removed during the liquid ammonia pretreatment.

17. The method of claim 7, wherein the pretreated/cellulose III-containing densified biomass is pretreated/cellulose III-containing lignocellulosic densified biomass containing lignin and/or hemicellulose, and the method further comprises extracting at least a portion of the lignin and/or hemicellulose from the pretreated/cellulose III-containing lignocellulosic densified biomass to produce an extracted product containing no cellulose III_I and a pretreated densified biomass product, wherein said extracted product contains the lignin and/or hemicellulose.

18. The method of claim 17, wherein glucan and/or xylan is partially or wholly retained with the pretreated densified biomass product.

19. The method of claim 18, wherein the solvent is water or an organic solvent.

20. The method of claim 19, wherein the organic solvent is selected from acetone, ethanol, methanol, isopropanol, dichloromethane, methyl acetate, ethyl acetate, chloroform, and combinations thereof.

21. The method of claim 20, further comprising recycling the solvent in a batch mode, a semi-batch mode or continuously.

22. The method of claim 17, wherein the lignin is one of a plurality of plant cell wall components which are extracted in the extracting step.

23. The method of claim 22, wherein said plant cell wall components further include hemicellulose, arabinan, and combinations, and degradation products thereof.

24. The method of claim 20, wherein the pretreated/cellulose III-containing densified biomass is redensified to produce animal feed with or without added digestive enzymes.

25. A method of pretreating biomass comprising:

converting at least a majority of native cellulose I_β

to cellulose III_I in densified biomass by pretreating the densified biomass with liquid ammonia for a period from about 15 minutes to 10 hours, wherein the densified biomass is densified cellulosic biomass or densified lignocellulosic biomass and the liquid ammonia is anhydrous liquid ammonia or liquid ammonia comprising a solution of at least 80% ammonia, wherein the pretreating is performed at a temperature from about 50°

C. to about 140°

C. and at pressure from about 14.7 to about 200 psi to generate pretreated/cellulose III-containing densified biomass, wherein total moisture content of the densified biomass and the solution is 10% or less and a weight ratio of liquid ammonia to the densified biomass is from about 0.2;

1 up to less than 2;

1; and

further comprising an enzymatic hydrolysis step to hydrolyze the pretreated/cellulose III-containing densified biomass product, wherein said enzymatic hydrolysis step proceeds at a rate that is at least 1.5 times faster than a hydrolysis step performed using densified biomass that has not been pretreated with the liquid ammonia.

26. The method of claim 25 wherein the pressure is atmospheric pressure.