Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
  • C07D307/40—Radicals substituted by oxygen atoms
  • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
  • C07D307/48—Furfural
  • C07D307/50—Preparation from natural products
• • C—CHEMISTRY; METALLURGY
  • C13—SUGAR INDUSTRY
  • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
  • C13K13/00—Sugars not otherwise provided for in this class
  • C13K13/002—Xylose
• • 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
• • 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
• • 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
• • 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
  • D21C1/00—Pretreatment of the finely-divided materials before digesting
  • D21C1/04—Pretreatment of the finely-divided materials before digesting with acid reacting compounds
• • 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
  • D21C3/04—Pulping cellulose-containing materials with acids, acid salts or acid anhydrides
• • 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
• • 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
• • 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
• • 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 the pretreatment processes of lignocellulosic biomass. It is more specifically part of a pretreatment process for lignocellulosic biomass for the production of so-called "second generation" alcohol.
• Lignocellulosic biomass is composed of three main constituents: 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 macromolecule of complex structure and high molecular weight, derived 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.
• Cellulose the majority of this biomass, is thus the most abundant polymer on Earth and the one with the greatest potential for forming materials and biofuels.
• the potential of cellulose and its derivatives has not, for the moment, been fully exploited, mainly because of the difficulty of extracting cellulose. Indeed, this step is made difficult by the very structure of the plants.
• the technological barriers identified in the extraction and processing of cellulose include its accessibility, its crystallinity, its degree of polymerization, the presence of hemicellulose and lignin. It is therefore essential to develop new methods of pretreatment of the lignocellulosic biomass for easier access to cellulose and its transformation.
• biofuel production is an application requiring pretreatment of biomass.
• the second generation of biofuel uses as load vegetable or agricultural waste, such as wood, 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 by biotechnological methods uses a step of enzymatic hydrolysis of the cellulose contained in plant material to produce glucose.
• the glucose obtained can then be fermented into various products such as alcohols (ethanol, 1,3-propanediol, 1-butanol, 1,4-butanediol, etc.) or acids (acetic acid, lactic acid, 3- hydroxypropionic acid, fumaric acid, succinic acid, etc.).
• 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.
• chemical, enzymatic, microbiological treatment of cellulose-rich materials to enhance the subsequent stage of enzymatic hydrolysis. These methods are for example: steam explosion, organosolv process, dilute or concentrated acid hydrolysis or AFEX ("Ammonia Fiber Explosion”) process.
• AFEX Ammonia Fiber Explosion
• Ionic liquids are liquid salts 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, the processes using ionic liquids present significant cost problems related to the price of ionic liquids, their often difficult recyclability, and their limited availability.
• a process for transforming lignocellulosic biomass into fermentable sugars with excellent yields has recently been described in the FR10 / 03092, FR10 / 03093 and FR1 1/02730 applications of the Applicant.
• This process involves the firing of biomass in hydrated, inexpensive, widely available and recyclable inorganic salts. This technology is simple to implement and makes it easy to envisage an extrapolation at the industrial level.
• compositional analyzes performed on the solid fraction resulting from this pretreatment show that the hemicellulose contained in the biomass is hydrolysed during cooking.
• the products resulting from this hydrolysis are therefore found in the liquid fraction consisting of the anti-solvent and the hydrated inorganic salt.
• the recovery of these hydrolysis products of hemicellulose proves difficult because of the high salt concentration of this solution and requires a complex and expensive process.
• the recycling of inorganic salt is made more complex and requires a high purge rate to limit the accumulation of hydrolysis products of hemicellulose during recycling.
• hydrolysis of hemicellulose is easier than that of cellulose, and hydrolysis of hemicellulose may be the first step in a treatment of lignocellulosic biomass (P. Mâki-Arvela, T. Salmi, B. Holmbom, S. Willfer and D. Yu Murzin, Chem Rev. 2011, 111, 5638-5666).
• lignocellulosic biomass P. Mâki-Arvela, T. Salmi, B. Holmbom, S. Willfer and D. Yu Murzin, Chem Rev. 2011, 111, 5638-5666.
• dilute solutions of hydrochloric acid or ferric chloride is known to carry out the selective hydrolysis of hemicellulose (Marcotullio C, Krisanti E, Giuntoli J. and de Jong de Bongesource Technology, 2011, 102, 5917-5923).
• the object of the present invention is to provide a pretreatment process for optimized recovery of cellulosic and hemicellulosic fractions.
• the pretreatment process according to the invention consists in combining acid hydrolysis under mild conditions with pretreatment with hydrated inorganic salts.
• FIG. 1 is a schematic representation of the process according to the invention comprising an acid hydrolysis step, a separation step, a drying step, a step of cooking the dried solid fraction, a step of separating the solid fraction, and a step of treating said solid fraction.
• Figure 2 is a schematic representation of the method according to the invention according to an embodiment wherein the anti-solvent used in the step of treating the solid fraction is recycled to the separation step.
• FIG. 3 is a schematic representation of the process according to the invention according to an embodiment in which the liquid fraction obtained after the separation step is treated before being recycled to the baking stage and / or the stage of drying. acid hydrolysis.
• Figure 4 shows the kinetics of enzymatic hydrolysis of pretreated wheat straw according to the method of the present invention.
• Figure 5 shows the kinetics of enzymatic hydrolysis of pre-treated poplar according to the method of the present invention.
• Figure 6 shows the kinetics of enzymatic hydrolysis of raw wheat straw (without pretreatment).
• the pretreatment method of lignocellulosic biomass according to the present invention comprises the following steps:
• step b) a step of separating the solid fraction and the liquid fraction obtained in step a),
• step c) a step of drying the solid fraction obtained in step b), d) a step of cooking the dried solid fraction obtained in step c) in the presence or absence of an organic solvent, in a medium comprising at least one hydrated inorganic salt of formula (I):
• M a metal selected from groups 1 to 13 of the Periodic Table
• X is an anion
• n is an integer from 1 to 6 and n being from 0.5 to 12,
• step f) optionally a step of treating the solid fraction obtained in step e).
• the Applicant has discovered that the acid hydrolysis step for selectively solubilizing the hemicellulose can be combined with a firing step using hydrated inorganic salts to obtain reactive cellulose reactive in enzymatic hydrolysis, condition to perform an intermediate drying step.
• the process according to the invention thus makes it possible to obtain a cellulosic fraction as well as a hemicellulosic fraction.
• the acid hydrolysis step makes it possible to solubilize selectively the hemicellulose contained in the lignocellulosic biomass.
• This liquid fraction can be easily recovered later in the form of sugars (fermentable to ethanol) or chemicals (such as furfural).
• the solid fraction containing most of the cellulose and lignin is then separated from the liquid fraction. It should be noted that the cellulose contained in the solid fraction after acid hydrolysis is not reactive in enzymatic hydrolysis.
• the solid fraction containing most of the cellulose and the separated lignin is then dried. It should be noted that the drying step is an essential step in the success of the pretreatment process. Indeed, without drying step intermediate, the baking step does not lead to a reactive cellulose enzymatic hydrolysis.
• the step of firing with hydrated inorganic salts is then carried out on the dried solid fraction containing most of the cellulose and lignin (but without the hemicellulose which has been solubilized during the acid hydrolysis step).
• This solid fraction contains most of the cellulose present in the lignocellulosic biomass. This cellulose has the property of being particularly reactive in enzymatic hydrolysis.
• the liquid fraction obtained after the baking step contains the hydrated inorganic salts in good purity. Indeed, the liquid fraction containing hydrated inorganic salts is no longer "polluted" by hydrolysis products of hemicellulose as is the case without acid hydrolysis step.
• This low organic content in the liquid fraction facilitates the recycling of salts in the cooking step and reduces the purge rate of this recycling.
• the acid solution used in the acid hydrolysis step is chemically identical to the hydrated inorganic salt of the cooking step diluted in water.
• at least a portion of the liquid fraction containing the hydrated inorganic salts obtained in the separation step e) can be used, optionally with addition of additional water, as the acid solution in the acid hydrolysis step.
• the method according to the present invention makes it possible to efficiently transform various types of native lignocellulosic biomass into a pretreated biomass by retaining most of the cellulose present in the starting substrate. It also has the advantage of using inexpensive reagents, widely available and recyclable, thus obtaining a low pretreatment cost. This The technology is also simple to implement and makes it easy to envisage an extrapolation at the industrial level.
• 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, pulp and paper residues, marine biomass (eg, cellulosic macroalgae) or transformation products 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, miscanthus, rice straw or corn stalks.
• the different types of lignocellulosic biomass can be used alone or in mixture.
• the acid hydrolysis step makes it possible to solubilize selectively the hemicellulose contained in the lignocellulosic biomass.
• Acid hydrolysis of hemicellulose can be catalyzed by inorganic acids or by organic acids.
• acids that can be used for the hydrolysis of hemicellulose mention may be made of sulfuric acid, hydrochloric acid, nitric acid, ferric chloride, zinc chloride, phosphoric acid, acid and the like. formic acid, acetic acid, oxalic acid, trifluoroacetic acid and maleic acid, alone or as a mixture.
• the concentration of the acid is generally between 0.001 mol / l and 1 mol / l.
• the concentration of the acid is preferably between 0.01 mol / L and 0.4 mol / L.
• the acidic hydrolysis of hemicellulose can be carried out at a temperature between room temperature and 150 ° C, preferably between 50 ° C and 130 ° C.
• the duration of the acid hydrolysis is between 10 minutes and 24 hours, preferably between 30 minutes and 6 hours.
• the mass concentration of the biomass (expressed as dry matter) in the acid hydrolysis step is between 1% and 30%.
• the acid hydrolysis of hemicellulose is carried out under so-called mild conditions, ie the sugars solubilized in the liquid fraction undergo little degradation reactions (such as the dehydration of xylose in furfural) and that this step does not occur. does not allow to obtain a reactive cellulose in enzymatic hydrolysis.
• mild conditions ie the sugars solubilized in the liquid fraction undergo little degradation reactions (such as the dehydration of xylose in furfural) and that this step does not occur. does not allow to obtain a reactive cellulose in enzymatic hydrolysis.
• Acidic hydrolysis provides a liquid fraction containing most of the hemicellulose, in the form of hydrolysis products (sugars or oligomers of sugars), and the acid, and a solid fraction containing the major part of the cellulose and lignin.
• the liquid fraction can be easily upgraded later.
• This separation step can be carried out by the usual solid-liquid separation techniques, for example by decantation, by filtration or by centrifugation.
• the solid fraction containing most of the cellulose and the separated lignin is then dried.
• the drying step is an essential step in the success of the pretreatment process. In fact, without an intermediate drying step, the cooking step does not lead to a reactive cellulose in enzymatic hydrolysis.
• the drying step can be carried out by any method known to those skilled in the art, for example by evaporation.
• Known technologies for evaporative drying are for example the rotary furnace, the moving bed, the fluidized bed, the heated worm, the contact with metal balls providing the heat.
• These technologies may optionally use a gas flowing at co or countercurrent such as nitrogen or any other gas inert under the conditions of the reaction.
• the drying step is carried out at a temperature greater than or equal to 50 ° C.
• the residual water content is less than 30%, preferably less than 20% and more preferably less than 10%.
• the step of cooking with hydrated inorganic salts makes it possible to obtain a solid fraction which contains most of the cellulose present in the lignocellulosic biomass.
• This cellulose has the property of being particularly reactive in enzymatic hydrolysis.
• a liquid fraction containing the hydrated inorganic salt (s) is also obtained.
• M a metal selected from groups 1 to 13 of the Periodic Table, X is an anion and
• n is an integer between 1 and 6 and
• n between 0.5 and 12.
• Anion X can be a monovalent, divalent or trivalent anion.
• X is a halide anion selected from CI “ , F “ , Br “ and ⁇ , a perchlorate anion (CIO4 “ ), a thiocyanate anion (SCN “ ), a nitrate anion (NO3 “ ), a para anion - methylbenzene sulfonate (CH3-C6H4-SO3 "), an acetate anion (CH 3 COO), a sulfate anion (S0 4 2 '), an oxalate anion (C2O4 2") or a phosphate anion (PO4 3 ").
• the anion X is a chloride.
• the metal M in the formula (I) is chosen from lithium, iron, zinc or aluminum.
• the hydrated inorganic salt is selected from: LiCI.HaO, LiCI.2H 2 0, ZnCl 2 .2,5H 2 0, ZnCl 2 .4H 2 0 and FeCl 3 .6H 2 0.
• the firing temperature is between -20 ° C and 250 ° C, preferably between 20 and 160 ° C.
• the firing temperature is preferably between 100 ° C. and 160 ° C.
• the firing temperature is preferably between 20 ° C. and 100 ° C.
• the duration of the cooking is between 0.5 minutes and 168 hours, preferably between 5 minutes and 24 hours and even more preferably between 20 minutes and 12 hours.
• the firing step can be carried out in the presence of one or more organic solvents, chosen from 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 that formic acid or acid acetic acid, dimethylformamide, dimethylacetamide, dimethylsulfoxide, acetonitrile, aromatic solvents such as benzene, toluene, xylenes, alkanes.
• organic solvents chosen from alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol
• the firing step can be carried out in the absence of an organic solvent.
• the dried solid fraction is present in an amount of between 4% and 40% by weight, based on the dry weight of the total mass of the solid fraction / hydrated inorganic salt mixture, preferably in a quantity of between 5% and 30% by weight. % weight
• a mixture of a solid fraction containing the pretreated cellulosic substrate and a liquid fraction containing the hydrated inorganic salt or salts and optionally an organic solvent are obtained. This mixture is sent in a solid / liquid separation step.
• This separation can be carried out directly on the mixture resulting from the cooking step or after addition of at least one anti-solvent promoting the precipitation of the solid fraction.
• the separation is carried out after addition of at least one antisolvent promoting the precipitation of the solid fraction.
• the separation of a solid fraction and a liquid fraction containing the hydrated inorganic salt and optionally the anti-solvent may be carried out by the usual solid-liquid separation techniques, for example by decantation, by filtration or by centrifugation.
• 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 alone or as a mixture, and preferably alone.
• the solid fraction is composed of solid matter, between 5% and 60%, and preferably between 15% and 45%, and a liquid phase.
• the presence of liquid in this fraction is related to the limitations of liquid / solid separation devices.
• the solid material contains most of the cellulose of the initial substrate, between 60% and 100%, and preferably between 75% and 99% of the cellulose initially introduced.
• the liquid fraction contains the hydrated inorganic salt or salts used during the baking step, and optionally the antisolvent. Due to the elimination of hemicellulose by acid hydrolysis, this fraction contains very little hemicellulose (or products derived from hemicellulose). It may contain lignin.
• the solid fraction obtained at the end of the separation step e) may optionally be subjected to additional treatments (step f). These additional treatments may in particular be intended to eliminate the traces of hydrated inorganic salts in this solid fraction.
• Step f) of treatment of the solid fraction obtained in step e) can be carried out by one or more washes, neutralization, pressing, and / or drying.
• the washes can be carried out with antisolvent or with water.
• the washes may also be made with a stream from a processing unit of products from the pretreatment process of the present invention.
• the process according to the present invention when used as pretreatment upstream of a cellulosic ethanol production unit, the washes can be carried out with a stream coming from this cellulosic ethanol production unit.
• the neutralization can be carried out by suspending the solid fraction obtained in step e) in water and adding a base.
• base we refer to any chemical species which, when added to water, gives an aqueous solution of pH greater than 7.
• the neutralization can be carried out by an organic or inorganic base.
• bases that can be used for the neutralization, mention may be made of soda, potassium hydroxide and ammonia.
• the solid fraction obtained at the end of the separation step e) may optionally be dried or pressed to increase the percentage of dry matter contained in the solid.
• the lignocellulosic biomass is introduced via line (1) into the reactor (2) in which the acid hydrolysis step takes place.
• the acid solution is introduced through line (3).
• the line (4) draws a mixture of a liquid fraction containing most of the hemicellulose in the form of hydrolysis products and the acid, and a solid fraction containing most of the cellulose and lignin.
• This mixture is sent into the liquid / solid separation device (5) in which the separation step b) takes place.
• a so-called solid fraction (6) and a liquid fraction (7) are obtained.
• the solid fraction (6) is then sent to a drying step (8).
• the dried solid fraction is then introduced via line (9) into the cooking reactor (10) in which the cooking step takes place.
• the baking medium comprising one or more hydrated inorganic salts and optionally an organic solvent is introduced via line (11).
• a mixture containing the pretreated lignocellulosic substrate, the hydrated inorganic salt or salts and optionally an organic solvent is withdrawn via line (12).
• This mixture is sent into the liquid / solid separation device (13) in which the separation step e) takes place.
• the optional anti-solvent is added via line (14).
• the solid fraction (15) may optionally be subjected to additional treatments (step f) carried out in the device (17).
• the agents possibly necessary for the treatment (s) carried out in the enclosure (17) are introduced via the pipe (18). Any residues of this treatment (s) are withdrawn by the pipe (19). The treated solid fraction is drawn off by the pipe (20).
• the separation step e) is carried out with the addition of an anti-solvent
• the additional treatment carried out in the enclosure (17) (step f)) consists of one or more washings carried out with the anti-solvent introduced via the pipe (18).
• the liquid after washing contains mainly the anti-solvent and contains hydrated inorganic salt.
• This liquid (14) is used in the separation step e).
• the anti-solvent is preferably water.
• FIG. 3 relates to the recycling of the inorganic salt contained in different liquid fractions obtained during the process.
• step e) (16a) at least a portion of the liquid fraction obtained in step e) (16a) is sent to a purification step (21), called step g), making it possible to concentrate the inorganic salt contained in the fraction liquid and to obtain a liquid fraction containing the concentrated inorganic salt (23a) and another liquid fraction depleted in inorganic salt (25), said liquid fraction containing the concentrated inorganic salt (23a) being then at least partially recycled in the cooking step d).
• the purification step g) may in particular be a separation step of the inorganic salt hydrate and the anti-solvent.
• 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 by lowering the temperature or adding a third body, reverse osmosis.
• the additives that may be necessary for this step are introduced via the pipe (22) into the chamber (21).
• a liquid fraction containing the concentrated inorganic salt (23a) is obtained, which is advantageously recycled at least in part to the cooking reactor (10) (step d).
• water may be added to the stream (23a) through the line (24) to adjust the water stoichiometry to obtain a hydrated inorganic salt of the same composition as that introduced by the line (11).
• the hydrated inorganic salt obtained has the same composition as that introduced by the pipe (11).
• the liquid fraction (23a) may contain all or part of the organic solvent.
• the inorganic salt-depleted liquid fraction (25) may contain the anti-solvent, the organic solvent, residues of biomass-derived products, hydrated inorganic salt.
• the liquid fraction depleted of inorganic salt (25) contains less than 50% of the hydrated inorganic salt initially contained in the fraction (16). Even more preferably, the inorganic salt-depleted liquid fraction (25) contains less than 25% of the hydrated iron salt initially contained in the fraction (16).
• the inorganic salt-depleted liquid fraction (25) obtained in the enclosure (21) may also be a partial purge (25a).
• step e) When step e) is carried out with the addition of an antisolvent, the antisolvent is recovered mainly in the liquid fraction depleted in inorganic salt (25) and can be recycled (not shown) to step e) after any reprocessing, or to step f) in the case of the implementation of FIG.
• the f) treatment step of the solid fraction obtained in step e) is performed by one or more washes to obtain a treated solid fraction (20) and a liquid fraction (19), said liquid fraction being at least partly (19a) sent to a purification step (21) to concentrate the inorganic salt contained in the liquid fraction and to obtain a liquid fraction containing the concentrated inorganic salt (23a) and another fraction a liquid depleted of inorganic salt (25), said liquid fraction containing the concentrated inorganic salt (23a) being then at least partly recycled in the baking step d).
• step f) When step f) is carried out with the addition of an antisolvent, any residues of this treatment (s) are withdrawn by the pipe (19), then either purged (19c) or sent to the enclosure (21) via the pipe (19a).
• the antisolvent (18) added in step f) is separated during the purification step (25) and recycled in step f).
• the process according to the invention makes it possible, by the acid hydrolysis step, to selectively separate hemicellulose, which results in a significant drop in products derived from biomass in the liquid fraction obtained after the firing step d).
• the very small amount of products derived from the biomass still contained in the liquid fraction can be separated before or after the separation of the salt.
• hydrated inorganic and anti-solvent The products derived from biomass may for example be extracted by addition of an immiscible solvent with the hydrated inorganic salt or with the hydrated inorganic salt-anti-solvent mixture. Products derived from biomass can also be precipitated by changing conditions (temperature, pH, etc.) or by adding a third body. Products derived from biomass can also be adsorbed on a solid.
• the acid solution used in step a) is chemically identical to the hydrated inorganic salt of formula (I) of step d) diluted in water.
• the inorganic salt is preferably selected from ferric chloride and / or zinc chloride
• the acidic solution used for step a) is a dilute aqueous solution of ferric chloride and / or zinc chloride.
• the liquid fraction after the firing step is, thanks to the prior acid hydrolysis step, highly concentrated in hydrated inorganic salts without being enriched by a significant portion of hydrolysis products of hemicellulose.
• the salt diluted in water and the acid solution are chemically identical, the recycling of this composition in each of the steps (acid hydrolysis and baking) then becomes possible. In addition, this makes it possible to obtain an even lower pretreatment cost since only one chemical compound is used in the two pretreatment stages.
• At least a portion of the acidic solution used in step a) originates from at least a portion of the liquid fraction obtained in step e) and / or step f), with or without passing through a purification step for concentrating the inorganic salt contained in the liquid fraction (s) and obtaining a liquid fraction containing the concentrated inorganic salt and another liquid fraction depleted in inorganic salt, and or from at least part of the liquid fraction depleted of inorganic salt resulting from the purification step g).
• This case is represented in Figure 3 by dotted arrows. Referring to Figure 3, a portion of the liquid fraction (16b) obtained in step e) can be recycled (without purification step) into the acid hydrolysis chamber (2).
• Another part of the liquid fraction (16a) can be sent to a purification stage implemented in the chamber (21) as described above.
• a liquid fraction containing the concentrated inorganic salt (23a) and (23b) and another inorganic salt-depleted liquid fraction (25), a portion of said liquid fraction containing the inorganic salt, are obtained at the outlet of the enclosure (21).
• concentrate (23b) which can then be recycled in the acid hydrolysis (2), another part of said liquid fraction containing the concentrated inorganic salt (23a) can then be recycled in the cooking step d).
• water may be added to the stream (23b) through line (26) to adjust the amount of water to an acidic solution of the same composition as that introduced by line (3).
• step e) another part of the liquid fraction (16) obtained in step e) can be recycled directly (without purification step) in the cooking step d).
• liquid fraction (19b) obtained in step f) can be recycled (without purification step) into the acid hydrolysis chamber (2).
• Another part of the liquid fraction (19a) can be sent to a purification stage implemented in the chamber (21) as described above.
• a liquid fraction containing the concentrated inorganic salt (23a) and (23b) and another inorganic salt-depleted liquid fraction (25), a portion of said liquid fraction containing the inorganic salt, are obtained at the outlet of the enclosure (21).
• concentrate (23b) which can then be recycled in the acid hydrolysis (2), another part of said liquid fraction containing the concentrated inorganic salt (23a) can then be recycled in the cooking step d).
• the pretreatment process according to the present invention can in particular be followed by a conversion of the solid fraction obtained (20) by enzymatic hydrolysis to convert the polysaccharides to monosaccharides.
• the monosaccharides thus obtained can be transformed by fermentation.
• the fermentation products may be alcohols (ethanol, 1,3-propanediol, 1-butanol, 1,4-butanediol, etc.) or acids (acetic acid, lactic acid, 3-hydroxypropionic acid, fumaric acid, acid succinic, ...) or any other fermentation product.
• monosaccharides can easily be converted to alcohol by fermentation with yeasts such as, for example, Saccharomyces cerevisiae.
• the fermentation must obtained is then distilled to separate the vinasses and the alcohol produced. This distillation step may be thermally integrated with the drying step c) and / or with the purification step g) of the inorganic salt.
• enzymatic hydrolysis and fermentation can be carried out in what is commonly referred to as SSF (Simultaneous Saccharification and Fermentation).
• Two substrates were used in this study: a wheat straw substrate and a poplar substrate.
• compositional analysis carried out according to the NREL protocol TP-510-42618 indicates that the composition of the wheat straw is the following: 37% cellulose, 28% hemicellulose and 20% lignin.
• the partial compositional analysis carried out according to the NREL protocol TP-510-42618 indicates that the poplar contains 43% of cellulose and 19% of hemicellulose.
• the reactivity of the pretreated substrate was evaluated by subjecting it to enzymatic hydrolysis.
• Examples 1 and 2 are in accordance with the invention.
• Example 3 is given for comparison and relates to enzymatic hydrolysis carried out on a native wheat straw.
• Example 1 (according to the invention): Pretreatment of wheat straw
• the heating is stopped and 80 ml of distilled water are rapidly added to the mixture: the pre-treated poplar 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.
• 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, 7 h and 24 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 analyzer apparatus YSI2700, which measures by enzymatic assay the glucose concentration in aqueous solutions.
• 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.
• 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. 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, 7 h and 24 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 analyzer apparatus YSI2700, which measures by enzymatic assay the glucose concentration in aqueous solutions.
• glucose yield defined as the ratio of glucose concentration in the solution on 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 3 Enzymatic hydrolysis of native wheat straw (without pretreatment)
• the protocol used for the enzymatic hydrolysis is identical to that described in Example 1.
• the wheat straw is used native, without any pretreatment.
• the process according to the present invention makes it possible to preserve, after pretreatment, the major part of the cellulose present in the lignocellulosic substrate.
• the effectiveness of the pretreatment is excellent insofar as the glucose yield on the pretreatment + enzymatic hydrolysis steps is greater than 60% in less than 24 hours and for limited enzymatic charges.
• the process according to the present invention improves both the reactivity in enzymatic hydrolysis of a poplar straw substrate and of a poplar substrate.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Zoology (AREA)
• Wood Science & Technology (AREA)
• Biochemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Microbiology (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Biotechnology (AREA)
• Bioinformatics & Cheminformatics (AREA)
• General Engineering & Computer Science (AREA)
• General Health & Medical Sciences (AREA)
• Genetics & Genomics (AREA)
• Polysaccharides And Polysaccharide Derivatives (AREA)
• Processing Of Solid Wastes (AREA)
• Compounds Of Unknown Constitution (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=47666388

Family Applications (1)

Country Status (5)

Cited By (1)

Families Citing this family (5)

Citations (1)

Family Cites Families (12)

• 2012
  • 2012-01-18 FR FR1200157A patent/FR2985737B1/fr active Active
  • 2012-12-11 WO PCT/FR2012/000515 patent/WO2013107948A1/fr active Application Filing
  • 2012-12-11 EP EP12821262.8A patent/EP2804951A1/de not_active Withdrawn
  • 2012-12-11 US US14/372,818 patent/US20140352688A1/en not_active Abandoned
  • 2012-12-11 BR BR112014017596A patent/BR112014017596A8/pt not_active IP Right Cessation

Patent Citations (1)

Also Published As

Similar Documents

Legal Events