EP2596110A2 - Procédé de production de sucres a partir de biomasse lignocellulosique prétraitée avec un mélange de sels inorganiques hydratés et de sels métalliques - Google Patents
Procédé de production de sucres a partir de biomasse lignocellulosique prétraitée avec un mélange de sels inorganiques hydratés et de sels métalliquesInfo
- Publication number
- EP2596110A2 EP2596110A2 EP11749870.9A EP11749870A EP2596110A2 EP 2596110 A2 EP2596110 A2 EP 2596110A2 EP 11749870 A EP11749870 A EP 11749870A EP 2596110 A2 EP2596110 A2 EP 2596110A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- anion
- formula
- carried out
- enzymatic hydrolysis
- lignocellulosic biomass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
- C07H1/06—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/02—Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/18—Pulping cellulose-containing materials with halogens or halogen-generating compounds
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C3/00—Pulping cellulose-containing materials
- D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- the present invention is part of a process for producing so-called "second generation" alcohol from lignocellulosic biomass.
- Lignocellulosic biomass is composed of three main polymers: cellulose (35 to 50%), hemicellulose (23 to 32%) which is a polysaccharide essentially consisting of pentoses and hexoses and lignin (15 to 25%) which is a polymer of complex structure and high molecular weight, from the copolymerization of phenylpropenoic alcohols. These different molecules are responsible for the intrinsic properties of the plant wall and are organized in a complex entanglement.
- Biofuel production is an application requiring pretreatment of biomass. Indeed, the second generation of biofuel uses as load vegetable or agricultural waste, such as wood, wheat straw, or plantations with high growth potential such as miscanthus. This raw material is perceived as an alternative, sustainable solution with little or no impact on the environment and its low cost and high availability make it a solid candidate for biofuel production.
- the principle of the process of converting lignocellulosic biomass into biofuel uses a step of enzymatic hydrolysis of the cellulose contained in the plant material to produce glucose. This glucose is then fermented into ethanol, the biofuel.
- the cellulose contained in the lignocellulosic biomass is particularly refractory to enzymatic hydrolysis, especially since the cellulose is not directly accessible to the enzymes.
- a pretreatment step upstream of the enzymatic hydrolysis is necessary.
- Ionic liquids are salts consisting solely of liquid ions at temperatures of less than or equal to 100 ° C and provide highly polar media. They are thus used as solvents or as reaction media for treating cellulose or lignocellulosic materials (WO 05/17252; WO 05/23873). But like other pretreatments, ionic liquids have significant cost issues related to the price of ionic liquids and their often difficult recyclability.
- the present invention relates to a process for converting lignocellulosic biomass to sugars comprising at least three steps.
- the first step is a step of cooking the lignocellulosic biomass in a medium comprising at least one inorganic salt hydrated mixture with at least one other metal salt.
- the second step is a step of separating at least one solid fraction having undergone the firing step and the third step is a step of enzymatic hydrolysis of said solid fraction to convert the polysaccharides to monosaccharides.
- the sugars thus obtained are then fermentable in alcohols.
- Figure 1 shows the kinetics of the enzymatic hydrolysis of wheat straw according to the method of the present invention, implementing a step of baking the biomass in the presence of LiCI.H 2 0 (98%) / ZnCl 2. 2.5 H 2 0 (2%) at 140 ° C.
- FIG. 2 represents the kinetics of the enzymatic hydrolysis of wheat straw according to the method of the present invention, implementing a step of cooking the biomass in the presence of LiCl 2 H 2 O (10%) / ZnCl 2 . 2.5 H 2 O (90%) at 80 ° C.
- FIG. 3 represents the kinetics of the enzymatic hydrolysis of the wheat straw according to the process of the present invention, implementing a step of cooking the biomass in the presence of NaCl 6 H 2 O (10%) / ZnCl 2 . 2.5 H 2 O (90%) at 80 ° C.
- FIG. 4 represents the kinetics of the enzymatic hydrolysis of the wheat straw according to the process of the present invention, implementing a step of cooking the biomass in the presence of NaCl 6 H 2 O (10%) / ZnCl 2 . 2.5 H 2 O (90%) recycled at 80 ° C.
- FIG. 5 represents the kinetics of the enzymatic hydrolysis of wheat straw according to the method of the present invention, implementing a step of cooking the biomass in the presence of LiCl 2 H 2 O (10%) / FeCl 3 . 6 H 2 O (90%) at 60 ° C.
- FIG. 6 represents the kinetics of the enzymatic hydrolysis of the wheat straw according to the process of the present invention, implementing a step of cooking the biomass in the presence of LiCl 2 H 2 O (20%) / FeCl 3 . 6 H 2 O (80%) at 60 ° C.
- Figure 7 shows the kinetics of enzymatic hydrolysis of a native wheat straw, having not undergone any pretreatment.
- Figure 8 shows the kinetics of the enzymatic hydrolysis of wheat straw when pretreated by steam explosion prior to enzymatic hydrolysis.
- the process for converting lignocellulosic biomass into monosaccharides comprises at least:
- X is an anion and M is a metal selected from groups 1 and 2 of the Periodic Table, n is an integer of 1 or 2 and n is between 0.5 and 6
- Y is an anion, identical to or different from X
- m is an integer from 1 to 6 and m' is from 0 to 6.
- This process transforms lignocellulosic biomass into fermentable sugars with excellent yields. It also has the advantage of using inexpensive reagents, widely available and recyclable, thus obtaining a low pretreatment cost, especially compared to a process using ionic liquids. This technology is also simple to implement and makes it easy to envisage an extrapolation at the industrial level.
- the transformation of the lignocellulosic biomass into fermentable sugars is carried out with an excellent yield.
- the firing step carried out according to the process of the present invention makes it possible to reduce the duration of enzymatic hydrolysis with respect to the processes described in the prior art.
- the method according to the present invention makes it possible to achieve high glucose yields with short cooking times, allowing a significant gain in terms of productivity of the products. equipment since it becomes possible to use smaller amounts of enzymes and / or to reduce the size of the enzymatic hydrolysis tanks.
- the process according to the invention makes it possible to carry out the step of cooking the lignocellulosic biomass at moderate temperatures, in the absence of pressure, which constitutes a significant gain in terms of energy costs.
- the medium in which the firing step is carried out consists of one or more hydrated inorganic salts of formula (1) mixed with at least one other metal salt, hydrated or not, of formula (2).
- the lignocellulosic biomass, or lignocellulosic materials used in the process according to the invention is obtained from wood (hardwood and softwood), raw or treated, by agricultural products such as straw, plant fibers, cultures. forestry, residues of alcoholic, sugar and cereal plants, residues of the paper industry, or products of transformation of cellulosic or lignocellulosic materials.
- the lignocellulosic materials can also be biopolymers and are preferably rich in cellulose.
- the lignocellulosic biomass used is wood, wheat straw, wood pulp, rice straw or corn stalks.
- the different types of lignocellulosic biomass can be used alone or in mixture.
- the lignocellulosic biomass is present in an amount of between 0.5% and 40% by weight of the total mass of the lignocellulosic biomass / hydrated inorganic salt / metal salt mixture, preferably in an amount of between 3% and 25% weight.
- the anion X is a halide anion chosen from Cl, F, Br and I, a perchlorate anion (ClO 4 ), a thiocyanate anion (SCN), a nitrate anion (NO 3 ) or an acetate anion (CH 3 ). 3 COO).
- the metal M is preferably selected from lithium, magnesium, calcium, potassium or sodium.
- n ' is between 1 and 6.
- the hydrated inorganic salt having the formula (1) can be prepared in situ by the combination of a salt composed of a cation of groups 1 and 2 of the periodic table and a carbonate anion, hydrogen carbonate or hydroxide with an acid.
- the acid can be used pure or in aqueous solution.
- the anion Y is chosen from anions halides, nitrates, carboxylates, halocarboxylates, acetylacetonates, alkoxides, phenolates, optionally substituted, sulphates, alkyl sulphates, phosphates, alkyl phosphates, fluorosulphonates, alkylsulphonates, for example methylsulphonate, perfluoroalkylsulphonates, for example trifluoromethylsulphonate, bis (perfluoroalkylsulphonyl) amides, for example bis (trifluoromethylsulphonyl) amide of formula N (CF 3 SO 2 ) 2 - , arenesulphonates, optionally substituted with halogen or haloalkyl groups; .
- the anion Y is selected from fluoride anions, chloride, bromide, acetate, and triflate.
- the metal M ' is selected from iron, cobalt, nickel, copper, zinc, aluminum, indium or lanthanum.
- the metal salt of general formula (2) is chosen from FeBr 3 , FeCl 3 , FeCl 3 .6H 2 O, FeF 3 , Fe (NO 3 ) 3 , CoCl 2 , CoCl 2 .6H 2 O, Ni (CH 3 COO) 2 .4H 2 O, NiBr 2 , NiCl 2 NiCl 2 .6H 2 O, Zn (CH 3 COO) 2 .2H 2 O, ZnBr 2 , ZnCl 2 , ZnCl 2 .2,5H 2 O, AIBr 3 , AICI 3 , AICI 3 .6H 2 OLaCl 3 , LaCI 3 .6H 2 O.
- the molar fraction of the hydrated inorganic salt of formula (1) in the mixture of at least one hydrated inorganic salt of formula (1) and of at least one metal salt of formula (2) may be between 0.05 and 1 .
- the step of cooking the biomass may be carried out in a medium consisting of a mixture of different hydrated inorganic salts corresponding to formula (1) and / or different metal salts corresponding to formula (2).
- a medium consisting of a mixture of different hydrated inorganic salts corresponding to formula (1) and / or different metal salts corresponding to formula (2).
- several successive firing steps can be carried out in a medium consisting of at least one hydrated inorganic salt of formula (1) mixed with at least one metal salt of formula (2).
- the firing temperature is preferably between -20 ° C and 250 ° C, preferably between 20 and 160 ° C. Very preferably, the cooking temperature does not exceed 100 ° C.
- the duration of the cooking is between 0.5 minutes and 168 hours, preferably between 5 minutes and 4 hours and even more preferably between 20 minutes and 2 hours.
- the step of cooking the lignocellulosic biomass according to the present invention can be carried out in the presence of an organic solvent.
- the organic solvent may be chosen from alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol, diols and polyols such as ethanediol.
- the step of cooking the lignocellulosic biomass according to the present invention can be carried out in the absence of an organic solvent.
- the second step b) of the process according to the invention consists in separating a solid fraction, which has undergone the firing step a) described above. This separation is generally carried out by adding at least one anti-solvent which causes the precipitation of the solid fraction.
- the separation of this precipitated solid fraction and a liquid fraction containing the hydrated inorganic salt, the metal salt and the anti-solvent can be carried out by the usual solid-liquid separation techniques.
- the separation of the solid fraction having undergone the cooking step can be carried out by filtration or by centrifugation.
- the solid fraction may optionally be subjected to additional treatments before the enzymatic hydrolysis step.
- additional treatments may in particular be intended to eliminate traces of hydrated inorganic salts and / or metal salts in the solid fraction having undergone the cooking step.
- additional treatments may be, for example, washes, carried out with the anti-solvent, with water or with any other flow of the process.
- the liquid obtained after washing contains the fluid used for the additional treatment and traces of hydrated inorganic salts and / or metal salts.
- This liquid can advantageously be recycled for use during the separation step, thus allowing a better recovery rate of salts and better purity of the solid fraction while limiting the consumption of anti-solvent or other washing fluid.
- the solid fraction may optionally be dried or pressed to increase the percentage of dry matter contained in the solid.
- the anti-solvent used is a solvent or a mixture of solvents chosen from 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, dimethylsulfoxide, acetonitrile.
- alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol or tert-butanol
- the anti-solvent is selected from water, methanol or ethanol.
- the anti-solvent is water.
- the hydrated inorganic salt and the metal salt contained in the liquid fraction can be separated from the anti-solvent and recycled, for example to be used during the baking step. This separation can be carried out by any method known to those skilled in the art, such as, for example, evaporation, precipitation, extraction, passage over ion exchange resin, electrodialysis, chromatographic methods, solidification. hydrated inorganic salt and metal salt by lowering the temperature or adding a third body, reverse osmosis.
- the liquid fraction containing the hydrated inorganic salt, mixed with the metal salt, and the anti-solvent may also contain products derived from biomass.
- the liquid fraction may contain hemicellulose (or products derived from hemicellulose) and lignin.
- Biomass products contained in the liquid fraction can be separated before or after separation of the hydrated inorganic salt in admixture with metal salt - anti-solvent.
- the products derived from biomass may for example be extracted by addition of an immiscible solvent with the hydrated inorganic salt mixed with the metal salt or with the mixture of the inorganic salt hydrate mixed with the metal salt - anti-solvent.
- Products derived from biomass can also be precipitated by changing conditions (temperature, pH, etc.) or by adding a third body.
- the hydrated inorganic salt mixed with the metal salt thus recovered can be purified by heating at high temperatures, above 400 ° C, to remove by combustion the organic products derived from biomass potentially still present.
- the third step c) of the process according to the invention is the enzymatic hydrolysis step of the solid fraction obtained in step b).
- the solid fraction also referred to below as pretreated substrate, is subjected to enzymatic hydrolysis to convert the polysaccharides to monosaccharides under the usual conditions normally applied in these conversion processes.
- the pretreated substrate is placed in an aqueous medium to reach dry matter concentrations of between 0.5% and 40%, preferably between 1% and 20% by weight.
- the enzymatic hydrolysis is carried out under mild conditions, at a temperature of the order of 40 to 60 ° C, at a pH of between 4.5 and 5.5. Very preferably, the pH is between 4.8 and 5.2. If a pH adjustment is necessary, it is carried out prior to the enzymatic hydrolysis step, when the pretreated substrate is placed in an aqueous medium, in particular by adding a buffer solution.
- Enzymatic hydrolysis is carried out by means of enzymes produced by a microorganism.
- Microorganisms such as fungi belonging to the genera Trichoderma, Aspergillus, Penicillum or Schizophyllum, or anaerobic bacteria belonging for example to the genus Clostridium, produce these enzymes, notably containing cellulases and hemicellulases, suitable for the extensive hydrolysis of cellulose and hemicelluloses.
- the duration of the hydrolysis step c) varies between 1 h and 150 h, preferably between 2 h and 72 h, preferably between 4 h and 24 h.
- the glucose formed is soluble in water while the optionally unconverted cellulose, lignin or other products remain insoluble.
- the aqueous glucose solution is recovered by filtration.
- the monosaccharide thus obtained is easily converted into alcohol by fermentation with yeasts such as, for example, Saccharomyces cerevisiae.
- yeasts such as, for example, Saccharomyces cerevisiae.
- the fermentation must obtained is then distilled to separate the vinasses and the alcohol produced.
- the enzymatic hydrolysis step is carried out simultaneously with the fermentation.
- the substrate used in these examples is a wheat straw.
- the compositional analysis carried out according to the NREL protocol TP-510-42618 indicates that the composition of the raw substrate is the following (in% of dry matter): 37% cellulose, 28% hemicellulose and 20% lignin. In the examples below, the compositions are given in mole fractions.
- Examples 1 to 5 are in accordance with the invention.
- Example 6 is given by way of comparison, the enzymatic hydrolysis being carried out on a native wheat straw.
- Example 7 is a comparative example, the pretreatment carried out consisting of a steam explosion, currently known as one of the best technologies for fermentable sugars.
- Example 1 Pretreatment of wheat straw by LiCI.H 2 0 (98%) / ZnCl 2 .2.5 H 2 0 (2%) 1 0 ° C and enzymatic hydrolysis
- step a the heating is stopped and 80 ml of distilled water are rapidly added to the mixture: the pretreated straw precipitates.
- the suspension containing the salt mixture, water and biomass is placed in a centrifuge tube and stirred at 9500 rpm for 10 minutes.
- the supernatant containing the salt mixture is then separated from the solid.
- the operation is repeated three times by adding 80 ml of distilled water to the solid part still present in the centrifugation tube. 7.4 g of solid, with a dry matter content of 9%, are recovered.
- the solid recovered after precipitation and washing is subjected to enzymatic hydrolysis.
- Half of the recovered solid is placed in a 100 ml Schott flask. 5 ml of acetate buffer, 10 ml of a 1 wt.% Solution of NaN 3 in water are added and the mixture is then made up to 100 g with distilled water. This solution is then left overnight at 50 ° C for "activation" with stirring of 550 rpm in a STEM dry water bath.
- the known quantities of enzyme are then added to the solution:
- the solution is then stirred at 400 rpm at 50 ° C., still in dry-water baths, and samples are taken after 1 h, 4 h, and 7 h. These samples are placed in centrifuge tubes and rapidly placed for 10 minutes in an oil at a temperature of 103 ° C. to neutralize the enzymatic activity. Centrifuge tubes are stored in a refrigerator at 4 ° C while waiting for glucose measurement. They are then diluted by 5 with distilled water before being assayed using the Analox GL6 analyzer apparatus, called glucostat, which measures by enzymatic assay the glucose concentration in aqueous solutions.
- glucostat Analox GL6 analyzer apparatus
- glucose yield defined as the ratio of the glucose concentration in the solution the theoretical maximum concentration according to the cellulose content of the substrate. This glucose yield therefore represents the percentage of the cellulose actually converted into glucose.
- Example 2 Pretreatment of wheat straw by LiCl 2 H 2 O (10%) / ZnCl 2 .2.5H 2 O (90%) at 80 ° C. and enzymatic hydrolysis
- the protocol is identical to that of Example 1 except that 38 g of LiCl 2 H 2 O (10%) / ZnCl 2 .2.5H 2 O (90%) are used in place of 38 g of LiCI.H 2 0 (98%) / ZnCl 2 .2.5 H 2 0 (2%) and that the pretreatment is carried out at 80 ° C.
- the result of the enzymatic hydrolysis is shown in FIG.
- the protocol is identical to that of Example 1 except that 38 g of NaCl 6 H 2 O (10%) / ZnCl 2 .2.5H 2 O (90%) are used in place of 38 g of LiCI.H 2 0 (98%) / ZnCl 2 .2.5 H 2 0 (2%) and that the pretreatment is carried out at 80 ° C.
- the result of the enzymatic hydrolysis is shown in FIG.
- Example 4 Pre-treatment of wheat straw by NaCI.6H 2 O (10%) / ZnCl 2 .2.5 H 2 O (90%) recycled at 80 ° C and enzymatic hydrolysis
- the water stoichiometry with respect to the salts is adjusted by adding 2 g of water.
- step a) of the process according to the invention After this cooking (step a) of the process according to the invention), the heating is stopped and 80 ml of distilled water are rapidly added to the mixture: the pretreated straw precipitates.
- the suspension containing the inorganic salt, water and biomass is placed in a centrifuge tube and centrifuged at 9500 rpm for 10 minutes.
- the supernatant, containing the Inorganic salt is then separated from the solid.
- the operation is repeated twice by adding 80 ml of distilled water to the solid part still present in the centrifugation tube. 11.2 g of solid, with a solids content of 13%, are recovered.
- the solid recovered after precipitation and washing was subjected to enzymatic hydrolysis.
- Half of the recovered solid is placed in a 100 ml Schott flask.
- the solution is then stirred at 400 rpm at 50 ° C., still in the dry-water baths, and samples are taken after 1 h, 4 h and 7 h. These samples are placed in centrifuge tubes and rapidly placed for 10 minutes in an oil at a temperature of 03 ° C. to neutralize the enzymatic activity. Centrifuge tubes are stored in a refrigerator at 4 ° C while waiting for glucose measurement. They are then diluted by 5 with distilled water before being assayed using the Analox GL6 analyzer apparatus, called glucostat, which measures by enzymatic assay the glucose concentration in aqueous solutions.
- glucostat Analox GL6 analyzer apparatus
- glucose yield defined as the ratio of the glucose concentration in the solution to the theoretical maximum concentration according to the cellulose content of the native wheat straw. This glucose yield therefore represents the percentage of the cellulose contained in the native substrate actually converted into glucose after the pretreatment and enzymatic hydrolysis steps.
- Example 6 Pretreatment of Wheat Straw by LiCl 2 H 2 O (20%) / FeCl 3 .6H 2 O (80%) at 60 ° C. and Enzymatic Hydrolysis
- the protocol is identical to that of Example 1 except that 38 g of LiCl 6 H 2 O (20%) / FeCl 3 H 2 O (80%) are used in place of 38 g of LiCl. H 2 O (98%) / ZnCl 2 .2.5H 2 O (2%) and pretreatment is performed at 60 ° C.
- the result of the enzymatic hydrolysis is shown in FIG.
- Example 7 Enzymatic hydrolysis of native wheat straw (without pretreatment)
- Example 8 Enzymatic hydrolysis of wheat straw resulting from pretreatment by steam explosion.
- the protocol used for the enzymatic hydrolysis is identical to that described in Example 1.
- the wheat straw used was pretreated by steam explosion, pretreatment whose three steps are described below.
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Abstract
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Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1003092A FR2963008B1 (fr) | 2010-07-23 | 2010-07-23 | Procede de production de sucres a partir de biomasse lignocellulosique pretraitee avec un melange de sels inorganiques hydrates et de sels metalliques |
PCT/FR2011/000426 WO2012010750A2 (fr) | 2010-07-23 | 2011-07-19 | Procédé de production de sucres a partir de biomasse lignocellulosique prétraitée avec un mélange de sels inorganiques hydratés et de sels métalliques |
Publications (1)
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EP2596110A2 true EP2596110A2 (fr) | 2013-05-29 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP11749870.9A Withdrawn EP2596110A2 (fr) | 2010-07-23 | 2011-07-19 | Procédé de production de sucres a partir de biomasse lignocellulosique prétraitée avec un mélange de sels inorganiques hydratés et de sels métalliques |
Country Status (6)
Country | Link |
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US (1) | US20130210089A1 (fr) |
EP (1) | EP2596110A2 (fr) |
BR (1) | BR112013001757A2 (fr) |
CA (1) | CA2801831A1 (fr) |
FR (1) | FR2963008B1 (fr) |
WO (1) | WO2012010750A2 (fr) |
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FR2985736B1 (fr) * | 2012-01-18 | 2020-01-10 | IFP Energies Nouvelles | Procede de pretraitement de la biomasse lignocellulosique avec un sel inorganique hydrate permettant d'obtenir une fraction cellulosique et une fraction hemicellulosique |
FR2985737B1 (fr) * | 2012-01-18 | 2020-01-10 | IFP Energies Nouvelles | Procede de pretraitement de la biomasse lignocellulosique avec un sel inorganique hydrate comprenant une etape d'hydrolyse acide preliminaire |
BR112014026267A2 (pt) * | 2012-04-26 | 2017-06-27 | Archer Daniels Midland Co | método para processar biomassa lignocelulósica; composição; e composição obtida pelo método |
FR2999605A1 (fr) * | 2012-12-14 | 2014-06-20 | IFP Energies Nouvelles | Procede de production de solutions de sucres a partir de biomasse lignocellulosique avec traitement complementaire du residu solide par un sel inorganique hydrate |
FR2999604B1 (fr) * | 2012-12-14 | 2017-01-13 | Ifp Energies Now | Procede de production de solutions de sucres et d'alcools a partir de biomasse lignocellulosique avec traitement complementaire du residu solide par un sel inorganique hydrate |
US20160046731A1 (en) * | 2014-08-14 | 2016-02-18 | Api Intellectual Property Holdings, Llc | Production of sugars from biomass using solid catalysts |
CN113289680B (zh) * | 2021-06-02 | 2022-09-13 | 河北科技大学 | 一种双相催化剂及其制备方法和在木质纤维素生物质转化中的应用 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0091221B1 (fr) * | 1982-04-05 | 1987-09-09 | Imperial Chemical Industries Plc | Dissolution et hydrolyse des hydrates de carbone |
US4452640A (en) * | 1982-05-11 | 1984-06-05 | Purdue Research Foundation | Quantitative hydrolysis of cellulose to glucose using zinc chloride |
AU2003904323A0 (en) | 2003-08-13 | 2003-08-28 | Viridian Chemical Pty Ltd | Solvents based on salts of aryl acids |
FI116142B (fi) | 2003-09-11 | 2005-09-30 | Kemira Oyj | Esteröintimenetelmä |
EP2100972A1 (fr) * | 2008-03-13 | 2009-09-16 | BIOeCON International Holding N.V. | Procédé pour convertir les polysaccharides dans un hydrate de sel fondu |
US8236535B2 (en) * | 2008-04-30 | 2012-08-07 | Xyleco, Inc. | Processing biomass |
EP2408782A1 (fr) * | 2009-03-17 | 2012-01-25 | BIOeCON International Holding N.V. | Procede pour la conversion de polysaccharides dans un hydrate de sel fondu inorganique |
-
2010
- 2010-07-23 FR FR1003092A patent/FR2963008B1/fr not_active Expired - Fee Related
-
2011
- 2011-07-19 CA CA2801831A patent/CA2801831A1/fr not_active Abandoned
- 2011-07-19 US US13/811,676 patent/US20130210089A1/en not_active Abandoned
- 2011-07-19 WO PCT/FR2011/000426 patent/WO2012010750A2/fr active Application Filing
- 2011-07-19 BR BR112013001757A patent/BR112013001757A2/pt not_active IP Right Cessation
- 2011-07-19 EP EP11749870.9A patent/EP2596110A2/fr not_active Withdrawn
Non-Patent Citations (1)
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See references of WO2012010750A2 * |
Also Published As
Publication number | Publication date |
---|---|
BR112013001757A2 (pt) | 2016-08-30 |
FR2963008A1 (fr) | 2012-01-27 |
US20130210089A1 (en) | 2013-08-15 |
WO2012010750A3 (fr) | 2012-04-12 |
FR2963008B1 (fr) | 2013-01-04 |
CA2801831A1 (fr) | 2012-01-26 |
WO2012010750A2 (fr) | 2012-01-26 |
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