PROCESS FOR PRETREATMENT OF THE LIGNOCELLULOSIC BIOMASS WITH A HYDRATED INORGANIC SALT MAKING IT POSSIBLE TO OBTAIN A CELLULOSIC FRACTION AND A HEMICELLULOSIC FRACTION

• US 20150031092A1
• Filed: 12/11/2012
• Published: 01/29/2015
• Est. Priority Date: 01/18/2012
• Status: Abandoned Application

• Current Assignee: IFP Energies Nouvelles
• Original Assignee: IFP Energies Nouvelles
• Inventors: Vallee, Christophe, Bernard, Didier, Aymard, Caroline, Olivier-Bourbigou, Helene
• Application Number:
  US14/372,617
• Publication Number:
  US 20150031092A1
• Time in Patent Office: Days
• US Class Current: 435/99
• CPC Class Codes: C07D 307/50 Preparation from natural products
• 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: C13K 1/02 obtained by saccharification of cellulosic materials manufacture of fodder A23K10/32
• CPC Class Codes: D21C 1/04 with acid reacting compounds
• CPC Class Codes: D21C 3/04 with acids, acid salts or acid anhydrides D21C3/003 and D21C3/222 take precedence
• CPC Class Codes: D21C 3/18 with halogens or halogen-generating compounds bleaching cellulose pulp D21C9/12
• CPC Class Codes: D21C 3/20 with organic solvents or in solvent environment
• CPC Class Codes: D21C 5/005 Treatment of cellulose-containing material with microorganisms or enzymes
• 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

A method for pretreating lignocellulosic biomass by: a) acid hydrolysis with an acid solution resulting in a liquid fraction and a solid fraction, b) separating the solid fraction and the liquid fraction, c) drying the solid fraction, d) firing the dried solid fraction in a medium comprising at least one hydrated inorganic salt to obtain a solid fraction and a liquid fraction, e) separating the solid fraction and the liquid fraction obtained in d), f) optionally, treating said solid fraction obtained in e), g) enzymatic hydrolysis of said solid fraction obtained in e) and/or f), and wherein at least a portion of the liquid fraction obtained in b) is used to grow microorganisms which produce the enzymes necessary for the enzymatic hydrolysis of g).

Claims

1. Process for pretreatment of the lignocellulosic biomass comprising the following stages:

a) A stage for acid hydrolysis of the biomass by an acid solution leading to a liquid fraction that contains the bulk of the hemicellulose in the form of products of hydrolysis and acid and to a solid fraction containing the bulk of the cellulose and the lignin,

b) A stage for separating the solid fraction and the liquid fraction obtained in stage a),

c) A stage for drying the solid fraction obtained in stage b),

d) A stage for baking the dried solid fraction obtained in stage c) in the presence of or in the absence of an organic solvent, in a medium comprising at least one hydrated inorganic salt of Formula (I);

MX_n′

n′

H₂O

in which

M is a metal selected from the groups 1 to 13 of the periodic table,

X is an anion, and

n is an integer between 1 and 6, and with

n′

being between 0.5 and 12,

making it possible to obtain a solid fraction and a liquid fraction containing the hydrated inorganic salt,

e) A stage for separating the solid fraction and the liquid fraction obtained in stage d),

f) Optionally, a stage for treatment of the solid fraction obtained in stage e),

g) A stage for enzymatic hydrolysis of said solid fraction obtained from stage e) and/or f),

and in which at least a portion of the liquid fraction obtained in stage b) is used for the growth of the microorganism that produces enzymes necessary for the enzymatic hydrolysis of stage g).

2. Process according to claim 1, in which the acid of stage a) is selected from among sulfuric acid, hydrochloric acid, nitric acid, ferric chloride, zinc chloride, phosphoric acid, formic acid, acetic acid, oxalic acid, trifluoroacetic acid, and maleic acid, by itself or in a mixture.

3. Process according to claim 1, in which the concentration of acid of stage a) is between 0.001 mol/L and 1 mol/L.

4. Process according to claim 1, in which stage a) is carried out between ambient temperature and 150°

C.

5. Process according to claim 1, in which the drying stage is carried out at a temperature that is greater than or equal to 50°

C.

6. Process according to claim 1, in which the anion X of the hydrated inorganic salt of Formula (I) is a halide anion, selected from among Cl⁻

, F⁻

, Br⁻

, I⁻

, a perchlorate anion, a thiocyanate anion, a nitrate anion, an acetate anion, a para-methylbenzene sulfonate anion, a sulfate anion, an oxalate anion, or a phosphate anion, and in which the metal M in Formula (I) is selected from among lithium, iron, zinc, or aluminum.

7. Process according to claim 1, in which the baking stage d) is carried out at a temperature of between −

20 and 250°

C., preferably between 20 and 160°

C.

8. Process according to claim 1, in which the baking stage d) is carried out in the presence of one or more organic solvents, selected from among the alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, or tert-butanol;

the diols and polyols such as ethanediol, propanediol or glycerol;

the amino alcohols such as ethanolamine, diethanolamine or triethanolamine;

ketones such as acetone or methyl ethyl ketone;

carboxylic acids such as formic acid or acetic acid, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile; and

the aromatic solvents such as benzene, toluene, xylenes, and alkanes.

9. Process according to claim 1, in which the stage e) for separating the solid fraction is carried out by precipitation by the addition of at least one anti-solvent that is a solvent or a mixture of solvents selected from among water, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol;

diols and polyols such as ethanediol, propanediol or glycerol;

amino alcohols such as ethanolamine, diethanolamine or triethanolamine;

ketones such as acetone or methyl ethyl ketone;

carboxylic acids such as formic acid or acetic acid;

esters such as ethyl acetate or isopropyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and acetonitrile; and

preferably, the anti-solvent is water by itself or in a mixture.

10. Process according to claim 1, in which stage f) for treatment of the solid fraction obtained in stage e) is carried out by one or more washing cycles, neutralization, pressing, and/or drying.

11. Process according to claim 1, in which the enzymatic hydrolysis g) is carried out at a temperature of between 40 and 60°

C. and at a pH of between 4.5 and 5.5.

12. Process according to claim 1, in which at least a portion of the liquid fraction obtained in stage b) is neutralized before being used for the growth of the microorganism that produces enzymes.

13. Process according to claim 1, in which at least a portion of the liquid fraction obtained in stage b) is used in the biotechnological processes for conversion of sugars selected from among:

The fermentation into ethanol of C6 sugars by a yeast,

The fermentation into solvents by a bacterium,

The fermentation into ethanol of C6 and C5 sugars by a yeast, by a bacterium, or by a genetically modified yeast,

The production of filamentous fungi.

14. Process according to claim 1, in which at least a portion of the liquid fraction obtained in stage e) is sent to a purification stage, referred to as stage h), making it possible to concentrate the inorganic salt that is contained in the liquid fraction and to obtain a liquid fraction containing the concentrated inorganic salt and another liquid fraction that is low in inorganic salt, with said liquid fraction containing the concentrated inorganic salt next being at least in part recycled in the baking stage d).

15. Process according to claim 1, in which the acid solution used in stage a) is chemically identical to the hydrated inorganic salt of Formula (I) that is diluted in water.