Process for producing bio-based product from straw hemicellulose and fully utilizing the components thereof

• US 9,309,577 B2
• Filed: 01/28/2011
• Issued: 04/12/2016
• Est. Priority Date: 01/28/2011
• Status: Active Grant

• Current Assignee: Hainan Super Healthy Grain Company
• Original Assignee: Institute of Process Engineering Chinese Academy of Sciences (Chinese Academy of Sciences)
• Inventors: Chen, Hongzhang, Wang, Lan
• Primary Examiner(s): McDonald, Jennifer Pitrak
• Assistant Examiner(s): Xu, Qing
• Application Number:
  US13/992,381
• Publication Number:
  US 20130252293A1
• Time in Patent Office: 1,901 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: C07C 51/00 Preparation of carboxylic acids or their salts, halides or anhydrides of acids by hydrolysis of oils, fats or waxes C11C
• CPC Class Codes: C07C 53/08 Acetic acid pyroligneous acid C10C; preparation of vinegar C12J
• CPC Class Codes: C07D 307/48 Furfural
• CPC Class Codes: C07D 307/50 Preparation from natural products
• CPC Class Codes: C08B 11/08 with hydroxylated hydrocarbon radicals; Esters, ethers, or acetals thereof
• 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 6/00 Macromolecular compounds derived from lignin, e.g. tannins, humic acids
• CPC Class Codes: C08H 8/00 Macromolecular compounds derived from lignocellulosic materials pretreatment thereof B27N
• CPC Class Codes: C12N 1/20 Bacteria; Culture media therefor
• 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
• CPC Class Codes: C12P 3/00 Preparation of elements or inorganic compounds except carbon dioxide recovery of carbon dioxides as by-products C12F3/02
• CPC Class Codes: C12P 5/023 Methane
• CPC Class Codes: C12P 7/16 Butanols
• CPC Class Codes: C12P 7/18 polyhydric
• CPC Class Codes: C12P 7/46 Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
• CPC Class Codes: C12P 7/54 Acetic acid vinegar C12J
• CPC Class Codes: C12P 7/56 Lactic acid
• CPC Class Codes: C13K 1/02 obtained by saccharification of cellulosic materials manufacture of fodder A23K10/32
• CPC Class Codes: C13K 13/00 : Sugars not otherwise provided for in this class
• CPC Class Codes: C13K 13/002 : Xylose
• CPC Class Codes: D21C 1/02 : with water or steam
• CPC Class Codes: D21C 3/04 : with acids, acid salts or acid anhydrides D21C3/003 and D21C3/222 take precedence
• CPC Class Codes: D21H 11/12 : Pulp from non-woody plants or crops, e.g. cotton, flax, straw, bagasse
• CPC Class Codes: Y02E 50/10 : Biofuels, e.g. bio-diesel
• CPC Class Codes: Y02E 50/30 : Fuel from waste, e.g. synthetic alcohol or diesel

Abstract

Provided is a process for producing biomass-based product from straw hemicellulose and utilizing the components thereof thoroughly. Steam-explosion and acid-hydrolysis are combined in the pre-treatment of straw in the process, thus a higher concentration of a sugar liquid can be obtained, and furfural and acetic acid can be recovered. The hemicellulose obtained by the pre-treatment can be used directly as ferment materials for producing butanol, succinic acid, butylene glycol, lactic acid, hydrogen and firedamp, which reduces the cost of these biomass-based products. The cellulose and lignin obtained by extracting the straw with an alkaline solution can produce products, such as sodium hydroxymethyl cellulose etc. In the process, all components in the straw can be utilized thoroughly and waste and pollutant will not be produced.

Claims

1. A process for producing a bio-based product from straw hemicellulose, comprising the steps of:

1) pretreating straw, wherein the straw is soaked in water, wherein a mass ratio of straw to water is from 1;

1 to 1;

3, a soaking temperature is from 15°

C. to 90°

C., and a soaking period is from 10 mins to 60 mins;

2) conducting steam explosion, wherein the straw soaked in step

     1) is fed into a steam-explosion tank, and maintained under a steam-explosion pressure for a steam-explosion period;

then a steam-exploded straw material is released, wherein a steam-explosion pressure is from 0.3 MPa to 2.0 MPa, and a pressure maintenance period is from 1 min to 10 mins;

3) performing an acid treatment, wherein the steam-exploded straw material obtained in step

     2) is fed into an acid-hydrolysis tank pre-filled with a 0.8 to 1.6 wt % dilute acid and subjected to acid hydrolysis to generate a hydrolyzed material, wherein in the acid-hydrolysis tank, a mass ratio of the steam-exploded straw to the dilute acid is from 1;

2 to 1;

7, a reaction temperature is from 75°

C. to 105°

C., and a reaction time is from 10 mins to 60 mins; and

4) collecting the product thus obtained, wherein after the acid hydrolysis in step

     3), the hydrolyzed material obtained in step

     3) is filtered to generate a hydrolyzate liquid, and a hydrolysis residue is collected and extruded using an extruder to obtain a solid material.

2. The process according to claim 1, characterized in that said dilute acid is one or more selected from the group consisting of dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid, and dilute phosphoric acid.

3. The process according to claim 1, characterized in that said straw is one or more selected from corn straw, rice straw, wheat straw, bagasse, corn cobs, sorghum straw, miscanthus sinensis, imperata cylindrica, ramie, jute, abutilon, marijuana, flax, Apocynum, kenaf, cotton stalks, banana stems, pineapple leaf, and ponnisetum hydridum.

4. The process according to claim 1, further comprising the steps of:

a) distilling the hydrolyzate liquid obtained from the step

     4) in claim 1 under a reduced pressure, collecting and refining a distillate to obtain furfural and acetic acid, wherein a distilled residue liquid is a sugar solution at a concentration of 20 g/L-150 g/L by weight of xylose and glucose; and

b) preparing a fermentation medium from the sugar solution obtained in step a) by adding a nitrogen source therein after detoxification treatment, inoculating a seed solution of a fermentation bacterium in the logarithmic growth phase at a concentration of 10% by weight of the fermentation medium to produce a fermentation product, wherein the detoxification treatment is one or more selected from the group consisting of electrodialysis, macroporous resin adsorption, and activated carbon adsorption, the nitrogen source is one or more selected from the group consisting of corn milk, corn extracts, yeast extract, peptone, (NH₄)₂HPO₄, (NH₄)₂SO₄, and ammonium acetate, and the fermentation bacterium is Clostridium acetobutyliucm, Actinobacillus succinogenes, Klebsiella, Lactobacillus, or Clostridium butyricum.

5. The process according to claim 4, characterized in that the processing condition for the electrodialysis includes a temperature of 15 to 30°

C. and a current density of 600-1000 A/m²;

a processing condition for the macroporous resin adsorption includes a volume ratio of 1;

3 to 1;

10 between the sugar solution and a macroporous resin and a processing period of 4-12 hours;

a processing condition for the activated carbon adsorption includes a volume ratio of 1;

3 to 1;

10 between the sugar solution and an activated carbon and a processing period of 4-12 hours.

6. The process according to claim 1, characterized in that the obtained solid material is processed into one or more of lignin, long fibers, and short fibers.

7. The process according to claim 6, characterized in that the lignin is further processed into a chemical product, wherein the chemical product is one or more selected from the group consisting of, a phenolic resin, a rubber reinforcing agent, and a nano-carbon fiber.

8. The process according to claim 6, characterized in that the long fibers and short fibers are further processed into sodium hydroxymethyl cellulose, polyether polyol, and fermentation products.

9. The process according to claim 4, characterized in that the fermentation product includes butanol, succinic acid, butanediol, lactic acid, methane, and hydrogen.

10. The process according to claim 1, wherein the steam-explosion pressure is from 0.5 to 1.0 MPa.

11. The process according to claim 3, wherein said straw is one or more selected from the group consisting of corn straw, corn cobs, bagasse, and marijuana.

12. The process according to claim 7, wherein the phenolic resin is phenolic resin adhesive.