WO2014091109A1 - Method for producing sugars and, optionally, alcohols and/or solvents from lignocellulosic biomass with neutralisation of the pre-treated pomace with a high level of dry material - Google Patents

Method for producing sugars and, optionally, alcohols and/or solvents from lignocellulosic biomass with neutralisation of the pre-treated pomace with a high level of dry material Download PDF

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Publication number
WO2014091109A1
WO2014091109A1 PCT/FR2013/052869 FR2013052869W WO2014091109A1 WO 2014091109 A1 WO2014091109 A1 WO 2014091109A1 FR 2013052869 W FR2013052869 W FR 2013052869W WO 2014091109 A1 WO2014091109 A1 WO 2014091109A1
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Prior art keywords
liquid
substrate
neutralizing agent
liquid stream
sugars
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PCT/FR2013/052869
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French (fr)
Inventor
Caroline Aymard
Pierre-Antoine Bouillon
Dominique DECOTTIGNIES
Sylvain Louret
Larissa PEROTTA
Eszter Toth
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IFP Energies Nouvelles
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Publication of WO2014091109A1 publication Critical patent/WO2014091109A1/en

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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
    • 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
    • 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
    • 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 a process for producing sugars and, optionally, alcohols and / or solvents from lignocellulosic biomass.
  • a particular embodiment of the invention relates to a process for producing so-called "second generation" ethanol.
  • Lignocellulosic biomass is one of the most abundant renewable resources on earth.
  • the substrates considered are very varied, since they concern both woody substrates (hardwood and softwood), agricultural by-products (straw) or lignocellulosic waste-generating industries (agro-food industries, paper mills).
  • Lignocellulosic biomass is composed of three main polymers: cellulose (35 to 50%), hemicellulose (20 to 30%) 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, composed of aromatic alcohols connected by ether bonds. These different molecules are responsible for the intrinsic properties of the plant wall and are organized in a complex entanglement.
  • the process for the biochemical transformation of lignocellulosic materials into ethanol generally comprises a physicochemical pretreatment step, followed by an enzymatic hydrolysis step using an enzymatic cocktail, an ethanolic fermentation step of the liberated sugars, and fermentation.
  • ethanolic and enzymatic hydrolysis can be conducted simultaneously, and a step of ethanol purification.
  • An example is given by document FR 2 945 543.
  • Cellulose and possibly hemicelluloses are targets for enzymatic hydrolysis but are not directly accessible to enzymes. This is the reason why these substrates must undergo a pretreatment preceding the enzymatic hydrolysis step.
  • the purpose of the pretreatment is to modify the physical and physicochemical properties of the lignocellulosic material, with a view to improving the accessibility of the cellulose trapped within the lignin and hemicellulose matrix.
  • the pretreatment stage is carried out both by the material balance at the end of the pretreatment (recovery rate of the sugars under form of soluble monomers or oligomers or insoluble polymers) and also by the susceptibility to enzymatic hydrolysis of cellulosic and hemicellulosic residues.
  • the step downstream from the pretreatment that is to say the enzymatic hydrolysis step, is carried out under mild pH conditions, typically between 4 and 8, whereas the step of Pretreatment is conducted under more severe conditions (pH less than 4 or greater than 8), which imposes a prior neutralization step.
  • the document FR2945543 describes an alkaline pretreatment of the biomass, followed by washing or dilution. Then the biomass undergoes a pH setting step by contacting with a pH correction solution. Then the biomass is ready to undergo the enzymatic hydrolysis and fermentation steps. This process requires diluting the biomass in the wash solution or in the corrective solution.
  • the present invention proposes to carry out a separation step between the liquid and the solid of the biomass resulting from the pretreatment stage and to use the liquid obtained by separation to neutralize the pH of the biomass resulting from the pretreatment stage in order to limit the dilution of the biomass and obtain a neutral pH neutralization over the entire substrate.
  • the subject of the present invention is a process for producing sugars and optionally alcohols and / or solvents from a biomass feedstock, in which the following steps are carried out:
  • a pretreatment step is carried out by contacting and heating the biomass feedstock with water and a basic or acidic compound, so as to obtain a pretreated substrate,
  • step b) mixing at least a portion of the liquid stream obtained in step b) with a pH-neutralizing agent so as to obtain a liquid stream comprising the pH-neutralizing agent
  • step d) mixing the liquid flow comprising the pH-neutralizing agent with the pretreated substrate obtained in step a) or with the pretreated liquid-poor substrate obtained in step b) so as to obtain a substrate comprising sugars .
  • the mass flow rate of the neutralization agent stream can be determined so that the substrate comprising the sugars reaches a pH of between 4 and 8.
  • step c) at least one sample can be taken. part of the liquid stream, said part of the liquid stream having the same composition as said stream, and then mixing said portion of the liquid stream with a pH neutralizing agent.
  • said liquid stream comprising the pH-neutralizing agent consists of all of said portion of the liquid stream plus the pH-neutralizing agent.
  • the liquid stream in step b), can be extracted from the pretreated substrate obtained in step a) so as to obtain a liquid depleted substrate and said liquid stream, and in step d), the liquid stream comprising the pH-neutralizing agent can be mixed with the liquid-depleted substrate obtained in step b) so as to obtain the neutralized substrate containing sugars.
  • the liquid stream comprising the pH-neutralizing agent can be mixed with the liquid-depleted substrate obtained in step b) so as to obtain the neutralized substrate containing sugars.
  • an alcoholic fermentation of a second portion of the second liquid stream can be carried out by means of an alcoholic microorganism.
  • step b) it is possible to extract the liquid flux from the substrate comprising sugars obtained in step d) so as to obtain a liquid-depleted substrate and said liquid flow, and to step d), the liquid stream comprising the pH-neutralizing agent can be mixed with the pretreated substrate obtained in step a).
  • step d) we can alcoholic fermentation of a second part of the liquid flow by means of an alcoholic microorganism.
  • said compound can be basic and, in this case, the pH neutralizing agent is acidic.
  • said compound may be acidic and, in this case, the pH neutralizing agent is basic.
  • the acidic or basic compound and the pH-neutralizing agent may be independently selected from: potassium hydroxide, sodium hydroxide, ammonia, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid.
  • the substrate comprising sugars is brought into contact with a cellulolytic and / or hemicellulolytic enzyme so as to obtain a hydrolyzate comprising a solid residue and a liquid phase containing sugars,
  • an alcoholic fermentation of the hydrolyzate is carried out by means of an alcoholic microorganism so as to obtain a fermented wine
  • a step of separating and purifying the fermented wine is carried out so as to obtain at least one purified stream comprising alcohol and / or a solvent.
  • the biomass load may include at least one of the following: wood, plants from dedicated crops, agricultural ligno-cellulosic waste, residues from the lignocellulosic material processing industry
  • FIG. 1 is a schematic representation of a first embodiment of the method according to the invention
  • FIG. 2 is a schematic representation of a second embodiment of the method according to the invention.
  • MS dry matter
  • Total Solids the dry matter (solid and soluble) present in a medium.
  • the solids content is determined according to the ASTM E1756-01 method which consists of a mass loss at 105 ° C. With reference to FIGS. 1 and 2, a charge of biomass C is fed into the pretreatment unit P via the conduit 1.
  • the biomass load may consist of wood, straw or maize cobs, dedicated forest crop products, residues of alcoholic, sugar (eg sugar cane or beet) and cereal plants (eg wheat, wheat. ..), paper products and residues from the paper industry and lignocellulosic material processing products.
  • the filler can be composed of about 35 to 50% cellulose, 20 to 30% hemicellulose and 15 to 25% lignin.
  • a flow of acidic or basic compound A and a flow of water W necessary are respectively brought into the pretreatment unit P through the conduits 2 and 3 in order to carry out a hydrolysis reaction in an acidic or basic medium .
  • the biomass charge C is contacted and mixed with water W and compound A in a reactor.
  • the pretreatment unit P can implement a mechanical action, created for example by means of a twin-screw extruder or a grinding machine.
  • the compound A may be selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid or formic acid.
  • compound A may be selected from potassium hydroxide, sodium hydroxide, ammonia.
  • At least one step is performed for heating the mixture of biomass C, water W and compound A in a reactor.
  • the water W can be introduced in the form of steam.
  • the role of pretreatment is to make cellulose accessible to enzymes by destructuring the lignocellulosic matrix.
  • a pretreated substrate is removed from the unit P. Depending on the type of pretreatment, acidic or basic, implemented, the pretreated substrate is acidic or basic.
  • an alkaline pretreatment is carried out in unit P.
  • unit P it is possible to implement a pretreatment with sodium sulphate, also called Kraft process, conventionally used in the processes of production of paper products, called Kraft or "sulphate pulp", at the end of which we obtain paper pulp.
  • the alkaline chemical pretreatment carried out in the unit P may also be an explosion pretreatment of the ammonia fibers, also called AFEX pretreatment (Ammonia Fiber Explosion) or percolation pretreatment using ammonia with recycle, also called ARP pretreatment ( Ammonia Recycle Percolation).
  • AFEX pretreatment Ammonia Fiber Explosion
  • ARP pretreatment Ammonia Recycle Percolation
  • the sodium sulphate process or Kraft process is based on the use of sodium hydroxide and sodium sulphate.
  • the chemical treatment of the wood chips is at 150-175 ° C for a period of 1 to 7 hours depending on the substrate used.
  • Kraft paper pulps are produced from the most varied biomasses, but more particularly from resinous tree species (softwood such as spruce or pine) or hardwood species (hardwood such as eucalyptus) or agricultural lignocellulosic waste (straw wheat, rice, etc.). They are partially delignified by means of high temperature cooking and in the presence of soda. This delignification is controlled by the operating parameters of the reactors. The cooking is carried out in a vertical reactor, where the chips descend by gravity and meet the various cooking liquors.
  • Sodium sulphide is prepared directly from sodium sulphate by combustion. During cooking, sodium sulphide is hydrolyzed to sodium hydroxide, NaHS and H 2 S. The various sulfur compounds present react with lignin to give thiolignins more easily soluble.
  • the liquor applied to the chips is called white liquor.
  • the liquor extracted from the reactor or digester containing the compounds removed from the wall is called black liquor.
  • the result is the production of a pretreated substrate, enriched in cellulose since it contains between 60 and 90% of cellulose and between 5 and 20% of hemicellulose.
  • the ARP process (Ammonia Recycle Percolation) is a pretreatment process using ammonia with recycling. This type of process is described in particular by Kim et al., 2003, Biores. Technol. 90 (2003) p 39-47.
  • the high temperature of the percolation leads to a partial solubilization of both lignin and hemicellulose, this solution is then heated to recycle ammonia and recover on the one hand lignin extracted, for example for energy recovery, and and soluble sugars from hemicelluloses.
  • the AFEX (Ammonia Fiber Explosion) process involves introducing the lignocellulosic substrate into a high-pressure cooker in the presence of ammonia, then causing an explosive expansion at the outlet of the reactor and then recycling the ammonia in gaseous form. This type of process is described in particular by Teymouri et al., 2005, Biores. Technol. 96 (2005) p.2014-2018. This process leads mainly to a destructuration of the biomass matrix but there is no phasic separation of the lignin, hemicellulose and cellulose compounds at the end of treatment.
  • an acidic pretreatment is carried out in the unit P.
  • the biomass is brought into contact with a strong acid diluted in water, for example sulfuric acid, by using the biomass at low dry matter contents, generally between 5 and 20%. dry matter.
  • the biomass, the acid and the water are brought into contact in a reactor and raised to a temperature, generally between 120 ° C. and 200 ° C.
  • the hemicellulose compounds are mainly hydrolysed into sugars, making it possible to destructure the lignocellulosic matrix.
  • the result is the production of a solid pretreated substrate enriched in cellulose and lignin and a liquid fraction enriched in sugars.
  • a dilute acid for example sulfuric acid
  • an operation is performed to neutralize the pH of the pretreated substrate.
  • the neutralization is carried out in two steps: a neutralization agent is added to a liquid stream which has been extracted from the pretreated substrate from the unit P and the substrate is mixed with the liquid stream in which it has previously been added the neutralization agent.
  • a neutralization agent is added to a liquid stream which has been extracted from the pretreated substrate from the unit P and the substrate is mixed with the liquid stream in which it has previously been added the neutralization agent.
  • FIG. 1 the extraction of the liquid flow is carried out before mixing the substrate with the liquid flow comprising the neutralization agent.
  • the extraction of the liquid stream is carried out after having mixed the substrate with the liquid stream comprising the neutralization agent.
  • a step Ex1 for extracting the liquid contained in the pretreated substrate circulating in the conduit 4 is carried out.
  • the extraction of liquid is carried out in the unit Ex1, which can implement one of the following techniques: centrifugation, spinning or pressing, filtration, decantation, tricantation, etc.
  • Extraction in the unit Ex1 makes it possible to generate a liquid flow discharged through line 13.
  • the pretreated substrate remaining after the extraction step that is to say the pretreated substrate depleted of liquid, is removed from the liquid.
  • Ex1 unit through the conduit 12.
  • the liquid fraction is then sent through the conduit 13 in a mixing step with a neutralizing agent.
  • the liquid fraction circulating in the conduit 13 and the neutralization agent B brought by the conduit 14 are mixed in the unit M.
  • the mixture can be produced in a stirred enclosure, for example using a static mixer or any other mixing technique.
  • the neutralizing agent B is chosen to neutralize the pretreated substrate.
  • the pretreated substrate is acidic, the following compounds can be used: potassium hydroxide, sodium hydroxide, ammonia, etc.
  • the pretreated substrate is basic, the following compounds may be used: sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid etc.
  • the neutralization agent B may be introduced into the chamber M in liquid form, for example in aqueous solution, or in solid form, for example in powder, granules or beads.
  • the flow of neutralization agent B introduced into the unit M is determined so as to neutralize the whole of the pretreated substrate 4.
  • the unit M makes it possible to produce a neutralized liquid stream composed of the liquid fraction of the pretreated substrate and the neutralization agent B.
  • the neutralized liquid flow is sent into the unit N via the conduit 15, where it is brought into contact with the remainder of the pretreated substrate 12.
  • the contacting in the unit N can be carried out from the following procedure: agitation in a tank, percolation or any other liquid / solid mixing technique.
  • the mass flow rate of the neutralizing agent stream B introduced into the unit M is determined in such a way that the mixture originating from the unit N reaches a pH of between 4 and 8, preferably between 4.5 and 7.5.
  • the extracted liquid 13 undergoes only one mixing step with the neutralization agent B before being mixed in the unit N with the remainder of the pretreated substrate arriving via the pipe 12.
  • the stream fed to the N unit has the same composition as the stream flowing in the conduit 13 except for the addition of neutralizing agent B.
  • the stream 15 contains, by weight , all the elements of the stream 13, plus the neutralizing agent B.
  • the liquid extracted by the unit Ex1, flowing in the conduit 13, in the unit M, in the conduit 15 and in the unit N is maintained at a temperature below 100 ° C, see 50 ° C.
  • no heating operation is carried out.
  • no material extraction step for example no extraction of water, no extraction of volatile soluble matter contained in stream 13 is carried out. For example, it is not performed no evaporation or membrane separation step on the flow flowing in the conduit 13.
  • the mixture of the pretreated substrate with the neutralized liquid stream in the unit N makes it possible to produce a neutralized substrate discharged through line 6.
  • the neutralized substrate 6 can be directly sent via line 7 to the enzymatic hydrolysis unit.
  • the neutralized substrate discharged through line 6 is optionally subjected to a liquid extraction step in unit Ex2 so as to produce a liquid flow discharged through line 10 to fermentation unit F2 and a fraction solid evacuated via line 7 to the enzymatic hydrolysis unit H.
  • a portion or all of the liquid fraction obtained can be sampled via the conduit 18 by carrying out the second extraction step in the Ex2 unit.
  • the liquid fraction taken by line 18 may consist of between 5% and 100% by volume of liquid stream 10. The portion of liquid flow is introduced into mixing unit M to dilute neutralization agent B in a single phase. liquid, in order to facilitate the contacting of neutralized liquid flow with the pretreated substrate and, therefore, to improve the homogenization of the neutralized support.
  • the pretreated substrate from the unit P is sent into the contacting unit N with a neutralized liquid stream comprising a neutralization agent.
  • the neutralized liquid flow is introduced into unit N via conduit 17.
  • the neutralized liquid flow is brought into contact with the pretreated substrate from unit P via line 4.
  • the pretreated substrate from the unit P is directly introduced into the unit N, without undergoing liquid extraction operation.
  • the contacting in the unit N can be carried out as follows: stirring in a tank, percolation or any other liquid / solid mixing technique.
  • the mixture of the pretreated substrate with the liquid flow comprising the neutralized agent in the unit N makes it possible to produce a neutralized substrate discharged through line 6.
  • the neutralized substrate 6 is subjected to a liquid extraction step in the Ex3 unit so as to produce a liquid fraction discharged through the conduit 10 and a solid fraction discharged via the conduit 7 to the enzymatic hydrolysis unit H.
  • a portion, or all, of the liquid flow obtained is taken via line 16 by carrying out the extraction step in unit Ex3.
  • the portion of liquid flow taken by line 16 may consist of between 5% and 100% by volume of liquid stream 10.
  • the portion of the liquid stream 10 is then sent through line 16 to a mixing unit M with a neutralization agent B.
  • the liquid fraction circulating in line 16 and the neutralization agent B flowing in line 5 are mixed in the water. unit M.
  • the unit M makes it possible to produce a neutralized liquid stream composed of the liquid fraction of the pretreated substrate and the neutralization agent B of the pH.
  • the liquid flow comprising the pH-neutralizing agent is sent to the unit N via the conduit 17, where it is brought into contact with the remainder of the pretreated substrate arriving via the conduit 4.
  • the portion of the The liquid fraction circulating in the conduit 16 is introduced into the mixing unit M to improve the dilution of the neutralizing agent B in a liquid phase, in order to facilitate the contacting of the neutralizing liquid flow with the pretreated substrate in the N-unit and, therefore, to improve the homogenization of the neutralized support, while limiting the dissolution of the pretreated substrate.
  • the mass flow rate of the neutralizing agent stream B introduced into the unit M is determined in such a way that the mixture originating from the unit N reaches a pH of between 4 and 8, preferably between 4.5 and 7.5.
  • the extracted liquid undergoes only a mixing step with the neutralization agent B before being mixed in the unit N with the pretreated substrate arriving via the pipe 6.
  • the stream 17 sent to the unit N has the same composition as the stream flowing in the line 16 except for the addition of neutralization agent B.
  • the stream 17 contains, by weight, all the elements of the stream 16, plus the weight of the neutralizing agent B.
  • the liquid extracted by the unit Ex3, flowing in the ducts 10 and then 16, in the unit M, in the duct 17 and in the Unit N is maintained at a temperature below 100 ° C, see 50 ° C.
  • no heating operation is carried out.
  • no material extraction step for example no extraction of water, no extraction of volatile soluble material
  • the enzymatic hydrolysis is carried out in unit H by contacting, in a reactor, enzymes E via line 8 with the pretreated substrate arriving via line 7.
  • the E enzymes are produced by a microorganism, for example fungi belonging to the genera Trichoderma, Aspergillus, Penicillium or Schizophyllum, or anaerobic bacteria belonging for example to the genus Clostridium.
  • the enzymes produced by these microorganisms contain in particular cellulases and hemicellulases, suitable for the extensive hydrolysis of cellulose and hemicelluloses.
  • the conditions of the enzymatic hydrolysis mainly the solids content of the mixture to be hydrolysed and the amount of enzymes used, are chosen such that a solubilization of the cellulose is obtained. That is to say the conversion rate of cellulose into sugar, between 20% and 99% by weight, preferably between 30% and 95% by weight (the rate of conversion of cellulose to sugar is equal to the amount by weight of cellulose converted to sugar in relation to the total amount of cellulose introduced into unit H).
  • the water required in unit H is added via a conduit (not shown in FIGS. 1 and 2).
  • the desired solids content in the unit H is generally between 5% and 45% by weight, preferably between 8% and 35% by weight.
  • the enzymatic hydrolysis in unit H is preferably carried out at a pH of between 4 and 6 and at a temperature of between 30 ° C. and 60 ° C., preferably between 40 ° C. and 60 ° C.
  • the hydrolyzate that is to say the product of the enzymatic hydrolysis reaction, is discharged from unit H via line 9 to be introduced into the alcoholic fermentation unit F1.
  • unit F1 the hydrolyzate is contacted with one or more fermentation microorganisms.
  • the fermentable sugars are thus converted into alcohols and / or solvents by the microorganisms.
  • the fermentation step in the F1 unit can be carried out at a temperature between 30 ° C and 35 ° C.
  • a fermentation broth is obtained, evacuated via line 21 of unit F1, comprising suspended solids and a liquid phase in which the desired product or products (alcohols and / or or solvents).
  • the enzymatic hydrolysis and alcoholic fermentation steps are carried out in two reactors H and F1, as represented in FIGS. 1 and 2.
  • This embodiment is commonly called SHF or "Separated”. Hydrolysis and Fermentation ".
  • the enzymatic hydrolysis and alcoholic fermentation steps are carried out simultaneously in the same reactor.
  • This embodiment is commonly referred to as SSF or Simultaneous Saccharification and Fermentation.
  • the temperature in the reactor can be between 30 ° C and 45 ° C.
  • the alcoholic fermentation step may allow the simultaneous fermentation of different types of sugars. This embodiment is commonly referred to as SSCF or Simultaneous Saccharification and CoFermentation.
  • the temperature in the reactor can be between 30 ° C and 45 ° C.
  • the must obtained from the fermentation unit F1 is introduced via the conduit 21 into a separation unit SP which makes it possible to separate the musts into different products: the alcohol or the solvent discharged via the conduit 22, a liquid vinasse, containing unfermented sugars, discharged through the conduit 23 and a solid residue, commonly called marc, discharged through line 24, comprising cellulose, hemicellulose that have not been hydrolysed and lignin.
  • the separation unit SP can implement different separation techniques, for example separation by distillation, decantation, centrifugation, filtration.
  • the liquid stream is contacted in unit F2 with one or more fermentation microorganisms. pentoses and hexoses.
  • the fermentable sugars are thus converted into alcohols and / or solvents by the microorganisms.
  • the fermentation step in the unit F2 can be carried out at a temperature between 30 ° C and 45 ° C. At the end of the fermentation step, a fermentation must is obtained, containing the desired product or products (alcohols and / or solvents).
  • the dry matter MS corresponds to the dry matter of organic origin.
  • Example 1 (not according to the invention)
  • the method according to FIG. 1 is implemented without the extraction units Ex1 and Ex2.
  • the neutralizing agent B is diluted in a flow of liquid water outside the process.
  • the neutralization operation N is carried out in a diluted medium, generally less than 15% DM dry matter in order to guarantee the good diffusion of the agent of neutralization. neutralization in the liquid phase.
  • the method according to FIG. 1 is implemented by implementing the extraction step in the Ex1 unit, but not the extraction step in the Ex2 unit.
  • the introduction of an extraction Ex1 makes it possible to obtain a liquid stream 13 with a low dry matter content MS which makes it possible to correctly homogenize the neutralizing agent B by dispersing it in the liquid phase. Once the neutralizing agent is properly homogenized, the neutralized liquid stream can be mixed with the pomace without causing dilution of the process as shown in Table 2.
  • the implementation of the method according to the invention has here allowed the saving of 100 kg / h of water compared to Example 1.
  • the method according to FIG. 2 is implemented.
  • the liquid necessary for the neutralization of the pretreated flow 4 is obtained by pressing in the unit Ex2 of the flow 6 obtained after said neutralization operation in the unit N
  • This implementation with recycling of liquid upstream of the process makes it possible to carry out the neutralization operation N with lower dry matter contents MS than with the implementation of FIG. 1 without having to add additional water outside the process.
  • This implementation provides an additional advantage by facilitating the implementation of the neutralization in the N unit, in particular by allowing the implementation of a less sophisticated stirring possible low MS dry matter content.
  • Table 3 shows an example of implementation according to FIG. 2.
  • the recycling of neutralized juice 16 at the neutralization stage N makes it possible to carry out operation N at 16% dry MS against 22% DM dry matter in Example 2, without causing a dilution of the flows in the process.
  • the neutralization agent B is added via the conduit 5 to the stream 16 recycled to obtain a good homogenization of the neutralization agent in the liquid phase.
  • the stream obtained 17 is then used in stage N.
  • the neutralization therefore takes place at a low DM solids content (16%) without the addition of additional water.

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Abstract

The invention relates to a method for producing sugars and, optionally, alcohols and/or solvents from a biomass feedstock, said method comprising the following steps: a) a step of pre-treatment P is carried out by bringing the biomass feedstock C into contact with water W and a base or acid compound A and heating same, in such a way as to obtain a pre-treated substrate 4, b) a liquid flow (13) is extracted Exl from the pre-treated substrate, c) at least part of the liquid flow (13) obtained in step b) is mixed with a pH neutralisation agent B in such a way as to obtain a liquid flow (15) comprising the pH neutralisation agent, and d) the liquid flow (15) comprising the pH neutralisation agent is mixed with the pre-treated substrate (12) in such a way as to obtain a substrate (6) comprising sugars.

Description

PROCÉDÉ DE PRODUCTION DE SUCRES ET, ÉVENTUELLEMENT, D'ALCOOLS ET/OU DE SOLVANTS À PARTIR DE BIOMASSE LIGNOCELLULOSIQUE AVEC NEUTRALISATION A HAUTE MATIERE SECHE DU MARC PRETRAITE.  PROCESS FOR THE PRODUCTION OF SUGARS AND, POSSIBLY, ALCOHOLS AND / OR SOLVENTS FROM LIGNOCELLULOSIC BIOMASS WITH HIGH DRY MATERIAL DRAINAGE OF PRETREATED MARC.
La présente invention s'inscrit dans le cadre d'un procédé de production de sucres et, éventuellement, d'alcools et/ou de solvants à partir de biomasse lignocellulosique. Un mode particulier de réalisation de l'invention concerne un procédé de production d'éthanol dit de "seconde génération". The present invention is part of a process for producing sugars and, optionally, alcohols and / or solvents from lignocellulosic biomass. A particular embodiment of the invention relates to a process for producing so-called "second generation" ethanol.
La biomasse lignocellulosique représente une des ressources renouvelables les plus abondantes sur terre. Les substrats considérés sont très variés, puisqu'ils concernent à la fois les substrats ligneux (feuillus et résineux), les sous-produits de l'agriculture (paille) ou ceux des industries génératrices de déchets lignocellulosiques (industries agroalimentaires, papeteries). Lignocellulosic biomass is one of the most abundant renewable resources on earth. The substrates considered are very varied, since they concern both woody substrates (hardwood and softwood), agricultural by-products (straw) or lignocellulosic waste-generating industries (agro-food industries, paper mills).
La biomasse lignocellulosique est composée de trois principaux polymères : la cellulose (35 à 50%), l'hémicellulose (20 à 30%) qui est un polysaccharide essentiellement constitué de pentoses et d'hexoses et la lignine (15 à 25%) qui est un polymère de structure complexe et de haut poids moléculaire, composé d'alcools aromatiques reliés par des liaisons éther. Ces différentes molécules sont responsables des propriétés intrinsèques de la paroi végétale et s'organisent en un enchevêtrement complexe.  Lignocellulosic biomass is composed of three main polymers: cellulose (35 to 50%), hemicellulose (20 to 30%) 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, composed of aromatic alcohols connected by ether bonds. These different molecules are responsible for the intrinsic properties of the plant wall and are organized in a complex entanglement.
Le procédé de transformation biochimique des matériaux ligno-cellulosiques en éthanol comprend en général une étape de prétraitement physico-chimique, suivie d'une étape d'hydrolyse enzymatique utilisant un cocktail enzymatique, d'une étape de fermentation éthanolique des sucres libérés, la fermentation éthanolique et l'hydrolyse enzymatique pouvant être conduites simultanément, et d'une étape de purification de l'éthanol. Un exemple est donné par le document FR 2 945 543.  The process for the biochemical transformation of lignocellulosic materials into ethanol generally comprises a physicochemical pretreatment step, followed by an enzymatic hydrolysis step using an enzymatic cocktail, an ethanolic fermentation step of the liberated sugars, and fermentation. ethanolic and enzymatic hydrolysis can be conducted simultaneously, and a step of ethanol purification. An example is given by document FR 2 945 543.
La cellulose et éventuellement les hémicelluloses sont les cibles de l'hydrolyse enzymatique mais ne sont pas directement accessibles aux enzymes. C'est la raison pour laquelle ces substrats doivent subir un prétraitement précédant l'étape d'hydrolyse enzymatique. Le prétraitement vise à modifier les propriétés physiques et physico-chimiques du matériau lignocellulosique, en vue d'améliorer l'accessibilité de la cellulose emprisonnée au sein de la matrice de lignine et d'hémicellulose.  Cellulose and possibly hemicelluloses are targets for enzymatic hydrolysis but are not directly accessible to enzymes. This is the reason why these substrates must undergo a pretreatment preceding the enzymatic hydrolysis step. The purpose of the pretreatment is to modify the physical and physicochemical properties of the lignocellulosic material, with a view to improving the accessibility of the cellulose trapped within the lignin and hemicellulose matrix.
De nombreuses technologies pour réaliser l'étape de prétraitement existent : cuissons acides, cuissons alcalines, explosion à la vapeur etc. L'efficacité du prétraitement se mesure à la fois par le bilan matière à l'issue du prétraitement (taux de récupération des sucres sous forme de monomères ou d'oligomères solubles ou polymères insolubles) et également par la susceptibilité à l'hydrolyse enzymatique des résidus cellulosiques et hémicellulosiques. Dans la plupart des cas, l'étape en aval du prétraitement, c'est-à-dire l'étape d'hydrolyse enzymatique, est réalisée dans des conditions douces de pH, typiquement entre 4 et 8, alors que l'étape de prétraitement est menée dans des conditions plus sévères (pH inférieur à 4 ou supérieur à 8), ce qui impose une étape de neutralisation préalable. Many technologies to carry out the pretreatment stage exist: acid cooking, alkaline cooking, steam blasting, etc. The effectiveness of the pretreatment is measured both by the material balance at the end of the pretreatment (recovery rate of the sugars under form of soluble monomers or oligomers or insoluble polymers) and also by the susceptibility to enzymatic hydrolysis of cellulosic and hemicellulosic residues. In most cases, the step downstream from the pretreatment, that is to say the enzymatic hydrolysis step, is carried out under mild pH conditions, typically between 4 and 8, whereas the step of Pretreatment is conducted under more severe conditions (pH less than 4 or greater than 8), which imposes a prior neutralization step.
Le document « Lignocellulosic Biomass to Ethanol Process Design and Economies Utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic Hydrolysis for Corn Stover", Aden et al. NREL/TP-510-32438 enseigne la séparation de la biomasse prétraitée en une fraction solide et une fraction liquide. Ladite fraction solide subit ensuite un lavage à l'eau et ladite fraction liquide est neutralisée par chaulage suivi d'un traitement à l'acide sulfurique afin de faire précipiter le gypse. Le gypse est ensuite séparé de la fraction liquide, cette dernière étant remélangée avec ladite fraction solide lavée à l'eau. Cette succession d'opérations induit une consommation importante en agents neutralisants (chaux et acide sulfurique) et conduit à la dégradation de sucres lors des passages à pH élevés après chaulage, ainsi qu'à la perte de sucres lors des étapes de séparation liquide/solide. The document "Lignocellulosic Biomass to Ethanol Process Design and Economics Utilizing Co-Current Dilute Acid Prehydrolysis and Enzymatic Hydrolysis for Corn Stover", Aden et al., NREL / TP-510-32438 teaches the separation of pretreated biomass into a solid fraction and a The solid fraction is then washed with water and the liquid fraction is neutralized by liming followed by treatment with sulfuric acid to precipitate the gypsum.The gypsum is then separated from the liquid fraction. the latter being remixed with said solid fraction washed with water This succession of operations induces a large consumption of neutralizing agents (lime and sulfuric acid) and leads to the degradation of sugars during high pH passages after liming, as well as to the loss of sugars during the liquid / solid separation steps.
Le document "Process Design and Economies for Biochemical Conversion of Lignocellulosic Biomass to Ethanol, Humbird et al., NREL/TP-5100-47764, May 201 1 " enseigne la neutralisation de l'ensemble de l'effluent du prétraitement (une explosion à la vapeur en conditions acides) par de l'ammoniaque. Cette solution nécessite d'ajouter une quantité d'eau importante afin de pouvoir homogénéiser correctement le mélange de l'agent neutralisant et de l'effluent du prétraitement. The document "Process Design and Economics for Biochemical Conversion of Lignocellulosic Biomass to Ethanol, Humbird et al., NREL / TP-5100-47764, May 201 1" teaches the neutralization of all pretreatment effluent (an explosion at steam under acidic conditions) with ammonia. This solution requires adding a large amount of water in order to properly homogenize the mixture of the neutralizing agent and the pretreatment effluent.
Le document FR2945543 décrit un prétraitement alcalin de la biomasse, suivi d'un lavage ou d'une dilution. Puis la biomasse subi une étape de mise au pH par mise en contact avec une solution correctrice de pH. Ensuite, la biomasse est prête pour subir les étapes d'hydrolyse enzymatique et de fermentation. Ce procédé nécessite de diluer la biomasse dans la solution de lavage ou dans la solution correctrice. The document FR2945543 describes an alkaline pretreatment of the biomass, followed by washing or dilution. Then the biomass undergoes a pH setting step by contacting with a pH correction solution. Then the biomass is ready to undergo the enzymatic hydrolysis and fermentation steps. This process requires diluting the biomass in the wash solution or in the corrective solution.
La présente invention propose d'effectuer une étape de séparation entre liquide et solide de la biomasse issue de l'étape de prétraitement et d'utiliser le liquide obtenu par séparation pour neutraliser le pH de la biomasse issue de l'étape de prétraitement afin de limiter la dilution de la biomasse et d'obtenir une neutralisation du pH homogène sur l'ensemble du substrat. De manière générale, la présente invention a pour objet un procédé de production de sucres et éventuellement d'alcools et/ou de solvants à partir d'une charge de biomasse, dans lequel on effectue les étapes suivantes : The present invention proposes to carry out a separation step between the liquid and the solid of the biomass resulting from the pretreatment stage and to use the liquid obtained by separation to neutralize the pH of the biomass resulting from the pretreatment stage in order to limit the dilution of the biomass and obtain a neutral pH neutralization over the entire substrate. In general, the subject of the present invention is a process for producing sugars and optionally alcohols and / or solvents from a biomass feedstock, in which the following steps are carried out:
a) on effectue une étape de prétraitement par mise en contact et chauffage de la charge de biomasse avec de l'eau et un composé basique ou acide, de manière à obtenir un substrat prétraité,  a) a pretreatment step is carried out by contacting and heating the biomass feedstock with water and a basic or acidic compound, so as to obtain a pretreated substrate,
b) on extrait un flux liquide du substrat prétraité de manière à obtenir un flux liquide et un substrat appauvri en liquide,  b) extracting a liquid stream from the pretreated substrate so as to obtain a liquid stream and a liquid-depleted substrate,
c) on mélange au moins une partie du flux liquide obtenu à l'étape b) avec un agent de neutralisation du pH de manière à obtenir un flux liquide comportant l'agent de neutralisation du pH,  c) mixing at least a portion of the liquid stream obtained in step b) with a pH-neutralizing agent so as to obtain a liquid stream comprising the pH-neutralizing agent,
d) on mélange le flux liquide comportant l'agent de neutralisation du pH avec le substrat prétraité obtenu à l'étape a) ou avec le substrat prétraité appauvri en liquide obtenu à l'étape b) de manière à obtenir un substrat comportant des sucres.  d) mixing the liquid flow comprising the pH-neutralizing agent with the pretreated substrate obtained in step a) or with the pretreated liquid-poor substrate obtained in step b) so as to obtain a substrate comprising sugars .
Selon l'invention, le débit massique du flux d'agent de neutralisation peut être déterminé de manière à ce que le substrat comportant les sucres atteigne un pH compris entre 4 et 8. A l'étape c), on peut prélever au moins une partie du flux liquide, ladite partie du flux liquide ayant la même composition que ledit flux, puis on mélange ladite partie du flux liquide avec un agent de neutralisation du pH. Dans ce cas, ledit flux liquide comportant l'agent de neutralisation du pH consiste en l'intégralité de ladite partie du flux liquide plus l'agent de neutralisation du pH. According to the invention, the mass flow rate of the neutralization agent stream can be determined so that the substrate comprising the sugars reaches a pH of between 4 and 8. In step c), at least one sample can be taken. part of the liquid stream, said part of the liquid stream having the same composition as said stream, and then mixing said portion of the liquid stream with a pH neutralizing agent. In this case, said liquid stream comprising the pH-neutralizing agent consists of all of said portion of the liquid stream plus the pH-neutralizing agent.
Selon l'invention, à l'étape b), on peut extraire le flux liquide du substrat prétraité obtenu à l'étape a) de manière à obtenir un substrat appauvri en liquide et ledit flux liquide, et à l'étape d), on peut mélanger le flux liquide comportant l'agent de neutralisation du pH avec le substrat appauvri en liquide obtenu à l'étape b) de manière à obtenir le substrat neutralisé comportant des sucres. Dans ce cas, on peut extraire un deuxième flux liquide du substrat comportant des sucres obtenu à l'étape d), et à l'étape c) on peut mélanger la partie du flux liquide obtenu à l'étape b) et au moins une partie du deuxième flux liquide avec un agent de neutralisation du pH de manière à obtenir ledit flux liquide comportant l'agent de neutralisation du pH. De plus, on peut effectuer une fermentation alcoolique d'une deuxième partie du deuxième flux liquide au moyen d'un microorganisme alcooligène. Alternativement, selon l'invention, à l'étape b), on peut extraire le flux liquide du substrat comportant des sucres obtenu à l'étape d) de manière à obtenir un substrat appauvri en liquide et ledit flux liquide, et à l'étape d), on peut mélanger le flux liquide comportant l'agent de neutralisation du pH avec le substrat prétraité obtenu à l'étape a). Dans ce cas, on peut effectuer une fermentation alcoolique d'une deuxième partie du flux liquide au moyen d'un microorganisme alcooligène. According to the invention, in step b), the liquid stream can be extracted from the pretreated substrate obtained in step a) so as to obtain a liquid depleted substrate and said liquid stream, and in step d), the liquid stream comprising the pH-neutralizing agent can be mixed with the liquid-depleted substrate obtained in step b) so as to obtain the neutralized substrate containing sugars. In this case, it is possible to extract a second liquid stream from the substrate containing sugars obtained in stage d), and in stage c) the part of the liquid stream obtained in stage b) can be mixed with at least one portion of the second liquid stream with a pH-neutralizing agent so as to obtain said liquid stream comprising the pH-neutralizing agent. In addition, an alcoholic fermentation of a second portion of the second liquid stream can be carried out by means of an alcoholic microorganism. Alternatively, according to the invention, in step b), it is possible to extract the liquid flux from the substrate comprising sugars obtained in step d) so as to obtain a liquid-depleted substrate and said liquid flow, and to step d), the liquid stream comprising the pH-neutralizing agent can be mixed with the pretreated substrate obtained in step a). In this case, we can alcoholic fermentation of a second part of the liquid flow by means of an alcoholic microorganism.
Selon l'invention, ledit composé peut être basique et, dans ce cas, l'agent de neutralisation du pH est acide. Alternativement, ledit composé peut être acide et, dans ce cas, l'agent de neutralisation du pH est basique. According to the invention, said compound can be basic and, in this case, the pH neutralizing agent is acidic. Alternatively, said compound may be acidic and, in this case, the pH neutralizing agent is basic.
Le composé acide ou basique et l'agent de neutralisation du pH peuvent être indépendamment choisi parmi : hydroxyde de potassium, hydroxyde de sodium, ammoniaque, acide sulfurique, acide chlorhydrique, acide nitrique, acide acétique, acide formique. The acidic or basic compound and the pH-neutralizing agent may be independently selected from: potassium hydroxide, sodium hydroxide, ammonia, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid.
Selon l'invention, on peut en outre effectuer les étapes suivantes : According to the invention, the following steps can furthermore be carried out:
e) on met en contact le substrat comportant des sucres avec une enzyme cellulolytique et/ou hémicellulolytique de manière à obtenir un hydrolysat comportant un résidu solide et une phase liquide contenant des sucres,  e) the substrate comprising sugars is brought into contact with a cellulolytic and / or hemicellulolytic enzyme so as to obtain a hydrolyzate comprising a solid residue and a liquid phase containing sugars,
f) on effectue une fermentation alcoolique de l'hydrolysat au moyen d'un microorganisme alcooligène de manière à obtenir un vin fermenté,  f) an alcoholic fermentation of the hydrolyzate is carried out by means of an alcoholic microorganism so as to obtain a fermented wine,
g) on effectue une étape de séparation et purification du vin fermenté de manière à obtenir au moins un flux purifié comportant de l'alcool et/ou un solvant.  g) a step of separating and purifying the fermented wine is carried out so as to obtain at least one purified stream comprising alcohol and / or a solvent.
La charge de biomasse peut comporter au moins l'un des éléments suivants : du bois, des plantes issues de cultures dédiées, des déchets ligno-cellulosiques agricoles, des résidus de l'industrie de transformation des matériaux ligno-cellulosiques The biomass load may include at least one of the following: wood, plants from dedicated crops, agricultural ligno-cellulosic waste, residues from the lignocellulosic material processing industry
D'autres caractéristiques et avantages de l'invention seront mieux compris et apparaîtront clairement à la lecture de la description faite ci-après en se référant aux dessins parmi lesquels : Other features and advantages of the invention will be better understood and will become clear from reading the description given below with reference to the drawings among which:
- la figure 1 est une représentation schématique d'un premier mode de réalisation du procédé suivant l'invention, FIG. 1 is a schematic representation of a first embodiment of the method according to the invention,
- la figure 2 est une représentation schématique d'un deuxième mode de réalisation du procédé suivant l'invention. FIG. 2 is a schematic representation of a second embodiment of the method according to the invention.
On désigne sous l'abréviation "MS" les matières sèches (solides et solubles) présentes dans un milieu. Le taux de matières sèches (ou "Total Solids") est déterminé selon la méthode ASTM E1756-01 qui consiste en une perte de masse à 105°C. En référence aux figures 1 et 2, une charge de biomasse C est amenée dans l'unité de prétraitement P par l'intermédiaire du conduit 1 . Under the abbreviation "MS" is meant the dry matter (solid and soluble) present in a medium. The solids content (or "Total Solids") is determined according to the ASTM E1756-01 method which consists of a mass loss at 105 ° C. With reference to FIGS. 1 and 2, a charge of biomass C is fed into the pretreatment unit P via the conduit 1.
La charge de biomasse peut être composée de bois, de pailles ou de rafles de maïs, de produits de cultures forestières dédiées, de résidus de plantes alcooligènes, sucrières (par exemple canne à sucre ou betterave) et céréalières (par exemple mais, blé...), de produits et résidus de l'industrie papetière et des produits de transformation des matériaux ligno- cellulosiques. La charge peut être composée d'environ 35 à 50 % de cellulose, de 20 à 30 % d'hémicellulose et de 15 à 25 % de lignine.  The biomass load may consist of wood, straw or maize cobs, dedicated forest crop products, residues of alcoholic, sugar (eg sugar cane or beet) and cereal plants (eg wheat, wheat. ..), paper products and residues from the paper industry and lignocellulosic material processing products. The filler can be composed of about 35 to 50% cellulose, 20 to 30% hemicellulose and 15 to 25% lignin.
Un flux de composé acide ou basique A et un flux d'eau W nécessaires sont respectivement amenés dans l'unité de prétraitement P par l'intermédiaire des conduits 2 et 3 afin d'y réaliser une réaction d'hydrolyse en milieu acide ou basique. Dans l'unité P, la charge de biomasse C est mise en contact et mélangé avec l'eau W et le composé A dans un réacteur. L'unité P de prétraitement peut mettre en œuvre une action mécanique, créée par exemple au moyen d'une extrudeuse de type bi-vis ou d'une défibreuse.  A flow of acidic or basic compound A and a flow of water W necessary are respectively brought into the pretreatment unit P through the conduits 2 and 3 in order to carry out a hydrolysis reaction in an acidic or basic medium . In unit P, the biomass charge C is contacted and mixed with water W and compound A in a reactor. The pretreatment unit P can implement a mechanical action, created for example by means of a twin-screw extruder or a grinding machine.
Dans le cas d'un agent de neutralisation acide, le composé A peut être choisi parmi de l'acide sulfurique, de l'acide chlorhydrique, de l'acide nitrique, de l'acide acétique ou de l'acide formique. Dans le cas d'un agent de neutralisation basique, le composé A peut être choisi parmi de l'hydroxyde de potassium, de l'hydroxyde de sodium, de l'ammoniaque. In the case of an acidic neutralizing agent, the compound A may be selected from sulfuric acid, hydrochloric acid, nitric acid, acetic acid or formic acid. In the case of a basic neutralizing agent, compound A may be selected from potassium hydroxide, sodium hydroxide, ammonia.
Lors de l'étape de prétraitement dans l'unité P, on effectue au moins une étape de chauffage du mélange de biomasse C, d'eau W et du composé A dans un réacteur. L'eau W peut être introduite sous forme de vapeur. Le rôle du prétraitement est de rendre la cellulose accessible aux enzymes en déstructurant la matrice lignocellulosique. On évacue de l'unité P un substrat prétraité. Selon le type de prétraitement, acide ou basique, mis en œuvre, le substrat prétraité est acide ou basique. During the pretreatment step in the unit P, at least one step is performed for heating the mixture of biomass C, water W and compound A in a reactor. The water W can be introduced in the form of steam. The role of pretreatment is to make cellulose accessible to enzymes by destructuring the lignocellulosic matrix. A pretreated substrate is removed from the unit P. Depending on the type of pretreatment, acidic or basic, implemented, the pretreated substrate is acidic or basic.
Selon un premier mode de réalisation, on réalise un prétraitement alcalin dans l'unité P. Par exemple, dans l'unité P, on peut mettre en œuvre un prétraitement au sulfate de sodium, encore appelé procédé Kraft, classiquement utilisé dans les procédés de production de produits papetiers, dit Kraft ou "pâte au sulfate", à l'issue duquel on obtient des pâtes papetières. Le prétraitement chimique alcalin réalisé dans l'unité P peut également être un prétraitement par explosion des fibres à l'ammoniac, encore appelé prétraitement AFEX (Ammonia Fiber Explosion) ou prétraitement par percolation utilisant de l'ammoniaque avec recycle, encore appelé prétraitement ARP (Ammonia Recycle Percolation). According to a first embodiment, an alkaline pretreatment is carried out in unit P. For example, in unit P, it is possible to implement a pretreatment with sodium sulphate, also called Kraft process, conventionally used in the processes of production of paper products, called Kraft or "sulphate pulp", at the end of which we obtain paper pulp. The alkaline chemical pretreatment carried out in the unit P may also be an explosion pretreatment of the ammonia fibers, also called AFEX pretreatment (Ammonia Fiber Explosion) or percolation pretreatment using ammonia with recycle, also called ARP pretreatment ( Ammonia Recycle Percolation).
Le procédé au sulfate de sodium ou procédé Kraft est basé sur l'utilisation de soude et de sulfate de sodium. Le traitement chimique des copeaux de bois se fait à 150-175 °C pendant une durée de 1 à 7 heures en fonction du substrat utilisé. Les pâtes papetières kraft sont produites à partir des biomasses les plus variées, mais plus particulièrement depuis les espèces arborescentes résineuses (softwood tels que les épicéas ou les pins) ou feuillues (hardwood tels que les eucalyptus) ou encore les déchets lignocellulosiques agricoles (paille de blé, riz, etc.). Elles sont partiellement délignifiées au moyen de cuissons à haute température et en présence de soude. Cette délignification est contrôlée par les paramètres opératoires des réacteurs. La cuisson est réalisée dans un réacteur vertical, où les copeaux descendent par gravité et rencontrent les diverses liqueurs de cuisson. Le sulfure de sodium est préparé directement à partir de sulfate de sodium par combustion. Lors de la cuisson, le sulfure de sodium est hydrolysé en soude, en NaHS et en H2S. Les différents composés soufrés présents réagissent avec la lignine pour donner des thiolignines plus facilement solubles. La liqueur appliquée aux copeaux est appelée liqueur blanche. La liqueur extraite du réacteur ou lessiveur contenant les composés éliminés de la paroi est appelée liqueur noire. A l'issue de ce prétraitement alcalin, on aboutit à la production d'un substrat prétraité, enrichi en cellulose puisqu'il contient entre 60 et 90% de cellulose et entre 5 et 20% d'hémicellulose. The sodium sulphate process or Kraft process is based on the use of sodium hydroxide and sodium sulphate. The chemical treatment of the wood chips is at 150-175 ° C for a period of 1 to 7 hours depending on the substrate used. Kraft paper pulps are produced from the most varied biomasses, but more particularly from resinous tree species (softwood such as spruce or pine) or hardwood species (hardwood such as eucalyptus) or agricultural lignocellulosic waste (straw wheat, rice, etc.). They are partially delignified by means of high temperature cooking and in the presence of soda. This delignification is controlled by the operating parameters of the reactors. The cooking is carried out in a vertical reactor, where the chips descend by gravity and meet the various cooking liquors. Sodium sulphide is prepared directly from sodium sulphate by combustion. During cooking, sodium sulphide is hydrolyzed to sodium hydroxide, NaHS and H 2 S. The various sulfur compounds present react with lignin to give thiolignins more easily soluble. The liquor applied to the chips is called white liquor. The liquor extracted from the reactor or digester containing the compounds removed from the wall is called black liquor. At the end of this alkaline pretreatment, the result is the production of a pretreated substrate, enriched in cellulose since it contains between 60 and 90% of cellulose and between 5 and 20% of hemicellulose.
Le procédé ARP (Ammonia Recycle Percolation) est un procédé de prétraitement utilisant de l'ammoniaque avec recyclage. Ce type de procédé est notamment décrit par Kim et al., 2003, Biores. Technol. 90 (2003) p 39-47. La température élevée de la percolation conduit à une solubilisation partielle à la fois de la lignine et des hémicelluloses, cette solution est ensuite chauffée pour recycler l'ammoniaque et récupérer d'une part la lignine extraite, par exemple pour une valorisation énergétique, et d'autre part les sucres solubles issus des hémicelluloses.  The ARP process (Ammonia Recycle Percolation) is a pretreatment process using ammonia with recycling. This type of process is described in particular by Kim et al., 2003, Biores. Technol. 90 (2003) p 39-47. The high temperature of the percolation leads to a partial solubilization of both lignin and hemicellulose, this solution is then heated to recycle ammonia and recover on the one hand lignin extracted, for example for energy recovery, and and soluble sugars from hemicelluloses.
Le procédé AFEX (Ammonia Fiber Explosion) consiste à introduire le substrat lignocellulosique dans un cuiseur à haute pression en présence d'ammoniac, puis de provoquer une détente explosive en sortie du réacteur et de recycler l'ammoniac alors sous forme gazeuse. Ce type de procédé est notamment décrit par Teymouri et al., 2005, Biores. Technol. 96 (2005) p.2014-2018. Ce procédé conduit principalement à une déstructuration de la matrice de la biomasse mais il n'y a pas de séparation phasique des composés lignine, hémicellulose et cellulose en sortie de traitement. The AFEX (Ammonia Fiber Explosion) process involves introducing the lignocellulosic substrate into a high-pressure cooker in the presence of ammonia, then causing an explosive expansion at the outlet of the reactor and then recycling the ammonia in gaseous form. This type of process is described in particular by Teymouri et al., 2005, Biores. Technol. 96 (2005) p.2014-2018. This process leads mainly to a destructuration of the biomass matrix but there is no phasic separation of the lignin, hemicellulose and cellulose compounds at the end of treatment.
Selon un deuxième mode de réalisation, on réalise un prétraitement acide dans l'unité P. Par exemple, dans l'unité P, on peut mettre en œuvre un prétraitement de type cuisson à l'acide diluée. Dans ce mode de réalisation la biomasse est mise en contact avec un acide fort dilué dans de l'eau, par exemple l'acide sulfurique, en mettant en œuvre la biomasse à de faibles teneurs en matières sèche, généralement compris entre 5 et 20% de matière sèche. La biomasse, l'acide et l'eau sont mis en contact dans un réacteur et monté en température, généralement entre 120°C et 200°C. Lors de ce procélé, les composés hémicellulosique sont principalement hydrolysés en sucres, permettant de déstructurer la matrice lignocellulosique. A l'issue de ce prétraitement acide, on aboutit à la production d'un substrat prétraité solide, enrichi en cellulose et en lignine ainsi qu'une fraction liquide enrichie en sucres. Le procédé nommé "explosion vapeur", ou "SteamEx" ou "Steam Explosion" selon la terminologie anglo-saxonne, est réalisé en milieu acide. C'est un procédé dans lequel la biomasse lignocellulosique est mise en contact avec un acide dilué, par exemple l'acide sulfurique, dans un réacteur à faible temps de séjour, généralement compris entre 2 et 15 minutes et à des températures modérées, généralement entre 120°C et 200 °C. En sortie de du réacteur, la biomasse est détendue dans un récipient séparateur gaz / solide afin de produire une biomasse prétraitée à haute matière sèche, généralement comprise entre 20 et 70% de matière sèche. According to a second embodiment, an acidic pretreatment is carried out in the unit P. For example, in the unit P, it is possible to implement a pretreatment of the dilute acid cooking type. In this embodiment, the biomass is brought into contact with a strong acid diluted in water, for example sulfuric acid, by using the biomass at low dry matter contents, generally between 5 and 20%. dry matter. The biomass, the acid and the water are brought into contact in a reactor and raised to a temperature, generally between 120 ° C. and 200 ° C. During this process, the hemicellulose compounds are mainly hydrolysed into sugars, making it possible to destructure the lignocellulosic matrix. At the end of this acid pretreatment, the result is the production of a solid pretreated substrate enriched in cellulose and lignin and a liquid fraction enriched in sugars. The process called "steam explosion", or "SteamEx" or "Steam Explosion" according to the English terminology, is carried out in acidic medium. It is a process in which the lignocellulosic biomass is brought into contact with a dilute acid, for example sulfuric acid, in a reactor with a short residence time, generally between 2 and 15 minutes and at moderate temperatures, generally between 120 ° C and 200 ° C. On leaving the reactor, the biomass is expanded in a gas / solid separator vessel to produce a pretreated biomass with a high solids content, generally between 20 and 70% of dry matter.
Afin de neutraliser le substrat prétraité issu de l'unité P par le conduit 4, c'est-à-dire amener le pH du substrat prétraité proche de la neutralité, de préférence entre 4 et 8, de façon très préférée entre 4,5 et 7, on effectue une opération de neutralisation du pH du substrat prétraité. Selon l'invention, la neutralisation est effectuée en deux étapes : on ajoute un agent de neutralisation dans un flux liquide qui a été extrait du substrat prétraité issu de l'unité P et on mélange le substrat avec le flux liquide dans lequel on a préalablement ajouté l'agent de neutralisation. Selon un premier mode de réalisation représenté par la figure 1 , l'extraction du flux liquide est réalisée avant de mélanger le substrat avec le flux liquide comportant l'agent de neutralisation. Selon un deuxième mode de réalisation de l'invention représenté par la figure 2, l'extraction du flux liquide est réalisée après avoir mélangé le substrat avec le flux liquide comportant l'agent de neutralisation. In order to neutralize the pretreated substrate from the unit P via line 4, that is to say bring the pH of the pretreated substrate close to neutrality, preferably between 4 and 8, very preferably between 4.5 and 7, an operation is performed to neutralize the pH of the pretreated substrate. According to the invention, the neutralization is carried out in two steps: a neutralization agent is added to a liquid stream which has been extracted from the pretreated substrate from the unit P and the substrate is mixed with the liquid stream in which it has previously been added the neutralization agent. According to a first embodiment represented by FIG. 1, the extraction of the liquid flow is carried out before mixing the substrate with the liquid flow comprising the neutralization agent. According to a second embodiment of the invention represented by FIG. 2, the extraction of the liquid stream is carried out after having mixed the substrate with the liquid stream comprising the neutralization agent.
En référence à la figure 1 , on effectue une étape Ex1 d'extraction du liquide contenu dans le substrat prétraité circulant dans le conduit 4. L'extraction de liquide est effectuée dans l'unité Ex1 , qui peut mettre en œuvre l'une des techniques suivantes : centrifugation, essorage ou pressage, filtration, décantation, tricantation, etc. With reference to FIG. 1, a step Ex1 for extracting the liquid contained in the pretreated substrate circulating in the conduit 4 is carried out. The extraction of liquid is carried out in the unit Ex1, which can implement one of the following techniques: centrifugation, spinning or pressing, filtration, decantation, tricantation, etc.
L'extraction dans l'unité Ex1 permet de générer un flux liquide évacué par le conduit 13. Le substrat prétraité restant après l'étape d'extraction, c'est-à-dire le substrat prétraité appauvri en liquide, est évacué de l'unité Ex1 par le conduit 12. La fraction liquide est ensuite envoyée par le conduit 13 dans une étape de mélange avec un agent de neutralisation. La fraction liquide circulant dans le conduit 13 et l'agent de neutralisation B amené par le conduit 14 sont mélangés dans l'unité M. Le mélange peut être réalisé dans une enceinte agitée, par exemple à l'aide d'un mélangeur statique ou tout autre technique de mélange.  Extraction in the unit Ex1 makes it possible to generate a liquid flow discharged through line 13. The pretreated substrate remaining after the extraction step, that is to say the pretreated substrate depleted of liquid, is removed from the liquid. Ex1 unit through the conduit 12. The liquid fraction is then sent through the conduit 13 in a mixing step with a neutralizing agent. The liquid fraction circulating in the conduit 13 and the neutralization agent B brought by the conduit 14 are mixed in the unit M. The mixture can be produced in a stirred enclosure, for example using a static mixer or any other mixing technique.
L'agent de neutralisation B est choisi pour neutraliser le substrat prétraité. Par exemple si le substrat prétraité est acide, on peut utiliser les composés suivants : hydroxyde de potassium, hydroxyde de sodium, ammoniaque etc. Si le substrat prétraité est basique, on peut utiliser les composés suivants : acide sulfurique, acide chlorhydrique, acide nitrique, acide acétique, acide formique etc. L'agent de neutralisation B peut être introduit dans l'enceinte M sous forme liquide par exemple en solution aqueuse, ou sous forme solide par exemple en poudre, en granulés ou en billes. The neutralizing agent B is chosen to neutralize the pretreated substrate. For example, if the pretreated substrate is acidic, the following compounds can be used: potassium hydroxide, sodium hydroxide, ammonia, etc. If the pretreated substrate is basic, the following compounds may be used: sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid etc. The neutralization agent B may be introduced into the chamber M in liquid form, for example in aqueous solution, or in solid form, for example in powder, granules or beads.
Le flux d'agent de neutralisation B introduit dans l'unité M est déterminé de manière à neutraliser l'ensemble du substrat prétraité 4.  The flow of neutralization agent B introduced into the unit M is determined so as to neutralize the whole of the pretreated substrate 4.
L'unité M permet de produire un flux liquide neutralisé, composé de la fraction liquide du substrat prétraité ainsi que l'agent de neutralisation B.  The unit M makes it possible to produce a neutralized liquid stream composed of the liquid fraction of the pretreated substrate and the neutralization agent B.
Le flux liquide neutralisé est envoyé dans l'unité N par l'intermédiaire du conduit 15, où il est mis en contact avec le restant de substrat prétraité 12. Par exemple, la mise en contact dans l'unité N peut être réalisée de la manière suivante : agitation dans une cuve, percolation ou toute autre technique de mélange liquide / solide. Plus précisément, le débit massique du flux d'agent de neutralisation B introduit dans l'unité M est déterminé de manière à ce que le mélange issu de l'unité N atteigne un pH compris entre 4 et 8, de préférence entre 4,5 et 7,5. De préférence, selon l'invention, le liquide 13 extrait ne subit qu'une étape de mélange avec l'agent de neutralisation B avant d'être mélangé dans l'unité N avec le restant de substrat prétraité arrivant par le conduit 12. C'est-à-dire que le flux 15 envoyé dans l'unité N a la même composition que le flux circulant dans le conduit 13 excepté l'addition d'agent de neutralisation B. Donc dans ce cas le flux 15 contient, en poids, tous les éléments du flux 13, plus l'agent de neutralisation B. De préférence, le liquide extrait par l'unité Ex1 , circulant dans le conduit 13, dans l'unité M, dans le conduit 15 et dans l'unité N est maintenu à une température inférieure à 100°C, voir 50 °C. Pour maittenir la température de ce liquide, de préférence, on n'effectue pas d'opération de chauffage. De manière préférée, on n'effectue pas d'étape d'extraction de matière (par exemple pas d'extraction d'eau, pas d'extraction de matière soluble volatile) contenue dans le flux 13. Par exemple, on n'effectue pas d'étape d'évaporation ou de séparation membranaire sur le flux circulant dans le conduit 13.  The neutralized liquid flow is sent into the unit N via the conduit 15, where it is brought into contact with the remainder of the pretreated substrate 12. For example, the contacting in the unit N can be carried out from the following procedure: agitation in a tank, percolation or any other liquid / solid mixing technique. More specifically, the mass flow rate of the neutralizing agent stream B introduced into the unit M is determined in such a way that the mixture originating from the unit N reaches a pH of between 4 and 8, preferably between 4.5 and 7.5. Preferably, according to the invention, the extracted liquid 13 undergoes only one mixing step with the neutralization agent B before being mixed in the unit N with the remainder of the pretreated substrate arriving via the pipe 12. that is, the stream fed to the N unit has the same composition as the stream flowing in the conduit 13 except for the addition of neutralizing agent B. Thus in this case the stream 15 contains, by weight , all the elements of the stream 13, plus the neutralizing agent B. Preferably, the liquid extracted by the unit Ex1, flowing in the conduit 13, in the unit M, in the conduit 15 and in the unit N is maintained at a temperature below 100 ° C, see 50 ° C. To maintain the temperature of this liquid, preferably, no heating operation is carried out. In a preferred manner, no material extraction step (for example no extraction of water, no extraction of volatile soluble matter) contained in stream 13 is carried out. For example, it is not performed no evaporation or membrane separation step on the flow flowing in the conduit 13.
Le mélange du substrat prétraité avec le flux liquide neutralisé dans l'unité N permet de produire un substrat neutralisé évacué par le conduit 6.  The mixture of the pretreated substrate with the neutralized liquid stream in the unit N makes it possible to produce a neutralized substrate discharged through line 6.
Le fait d'utiliser le flux liquide extrait du substrat prétraité pour diluer l'agent de neutralisation puis d'incorporer ce flux liquide au substrat prétraité permet d'améliorer grandement l'homogénéisation dans l'unité N par l'utilisation d'un volume de liquide important sans créer de dilution.  The fact of using the liquid stream extracted from the pretreated substrate to dilute the neutralization agent and then to incorporate this liquid stream into the pretreated substrate greatly improves the homogenization in the N unit by the use of a volume. of significant liquid without creating dilution.
Le substrat neutralisé 6 peut être directement envoyé par le conduit 7 à l'unité d'hydrolyse enzymatique.  The neutralized substrate 6 can be directly sent via line 7 to the enzymatic hydrolysis unit.
Alternativement, le substrat neutralisé évacué par le conduit 6 est soumis de façon optionnelle à une étape d'extraction de liquide dans l'unité Ex2 de manière à produire une flux liquide évacué par le conduit 10 vers l'unité de fermentation F2 et une fraction solide évacué par le conduit 7 vers l'unité d'hydrolyse enzymatique H. En cas de mise en œuvre de l'unité Ex2, on peut prélever, via le conduit 18, une portion ou la totalité de la fraction liquide obtenue en effectuant la deuxième étape d'extraction dans l'unité Ex2. Par exemple la fraction liquide prélevée par le conduit 18 peut consister entre 5% et 100% volumique du flux liquide 10. La portion de flux liquide est introduite dans l'unité de mélange M pour diluer de l'agent de neutralisation B dans une phase liquide, afin de faciliter la mise en contact de flux liquide neutralisé avec le substrat prétraité et, donc, d'améliorer l'homogénéisation du support neutralisé. Alternatively, the neutralized substrate discharged through line 6 is optionally subjected to a liquid extraction step in unit Ex2 so as to produce a liquid flow discharged through line 10 to fermentation unit F2 and a fraction solid evacuated via line 7 to the enzymatic hydrolysis unit H. In the case of implementation of the Ex2 unit, a portion or all of the liquid fraction obtained can be sampled via the conduit 18 by carrying out the second extraction step in the Ex2 unit. For example, the liquid fraction taken by line 18 may consist of between 5% and 100% by volume of liquid stream 10. The portion of liquid flow is introduced into mixing unit M to dilute neutralization agent B in a single phase. liquid, in order to facilitate the contacting of neutralized liquid flow with the pretreated substrate and, therefore, to improve the homogenization of the neutralized support.
En référence à la figure 2, on envoie le substrat prétraité issu de l'unité P dans l'unité de mise en contact N avec un flux liquide neutralisé comportant un agent de neutralisation.With reference to FIG. 2, the pretreated substrate from the unit P is sent into the contacting unit N with a neutralized liquid stream comprising a neutralization agent.
Le flux liquide neutralisé est introduit dans l'unité N par l'intermédiaire du conduit 17. Dans l'unité N le flux liquide neutralisé est mis en contact avec le substrat prétraité issu de l'unité P par le conduit 4. Dans ce mode de réalisation, le substrat prétraité issu de l'unité P est directement introduit dans l'unité N, sans subir d'opération d'extraction de liquide. Par exemple, la mise en contact dans l'unité N peut être réalisée de la manière suivante : agitation dans une cuve, percolation ou toute autre technique de mélange liquide / solide. Le mélange du substrat prétraité avec le flux liquide comportant l'agent de neutralisé dans l'unité N permet de produire un substrat neutralisé évacué par le conduit 6. The neutralized liquid flow is introduced into unit N via conduit 17. In unit N, the neutralized liquid flow is brought into contact with the pretreated substrate from unit P via line 4. embodiment, the pretreated substrate from the unit P is directly introduced into the unit N, without undergoing liquid extraction operation. For example, the contacting in the unit N can be carried out as follows: stirring in a tank, percolation or any other liquid / solid mixing technique. The mixture of the pretreated substrate with the liquid flow comprising the neutralized agent in the unit N makes it possible to produce a neutralized substrate discharged through line 6.
Le substrat neutralisé 6 est soumis à une étape d'extraction de liquide dans l'unité Ex3 de manière à produire une fraction liquide évacuée par le conduit 10 et une fraction solide évacuée par le conduit 7 vers l'unité d'hydrolyse enzymatique H. The neutralized substrate 6 is subjected to a liquid extraction step in the Ex3 unit so as to produce a liquid fraction discharged through the conduit 10 and a solid fraction discharged via the conduit 7 to the enzymatic hydrolysis unit H.
Selon l'invention, on prélève, via le conduit 16, une portion, ou la totalité, du flux liquide obtenu en effectuant l'étape d'extraction dans l'unité Ex3. La portion de flux liquide prélevée par le conduit 16 peut consister entre 5% et 100% volumique du flux liquide 10.  According to the invention, a portion, or all, of the liquid flow obtained is taken via line 16 by carrying out the extraction step in unit Ex3. The portion of liquid flow taken by line 16 may consist of between 5% and 100% by volume of liquid stream 10.
La portion du flux liquide 10 est ensuite envoyée par le conduit 16 dans une unité de mélange M avec un agent de neutralisation B. La fraction liquide circulant dans le conduit 16 et l'agent de neutralisation B circulant dans le conduit 5 sont mélangés dans l'unité M. The portion of the liquid stream 10 is then sent through line 16 to a mixing unit M with a neutralization agent B. The liquid fraction circulating in line 16 and the neutralization agent B flowing in line 5 are mixed in the water. unit M.
L'unité M permet de produire un flux liquide neutralisé, composé de la fraction liquide du substrat prétraité ainsi que l'agent de neutralisation B du pH. The unit M makes it possible to produce a neutralized liquid stream composed of the liquid fraction of the pretreated substrate and the neutralization agent B of the pH.
Le flux liquide comportant l'agent de neutralisation du pH est envoyé dans l'unité N par l'intermédiaire du conduit 17, où il est mis en contact avec le restant de substrat prétraité arrivant par le conduit 4. Ainsi, la portion de la fraction liquide circulant dans le conduit 16 est introduit dans l'unité de mélange M pour améliorer la dilution de l'agent de neutralisation B dans une phase liquide, afin de faciliter la mise en contact de flux liquide neutraliser avec le substrat prétraité dans l'unité N et, donc, d'améliorer l'homogénéisation du support neutralisé, tout en limitant la dissolution du substrat prétraité. De préférence, le débit massique du flux d'agent de neutralisation B introduit dans l'unité M est déterminé de manière à ce que le mélange issu de l'unité N atteigne un pH compris entre 4 et 8, de préférence entre 4,5 et 7,5. The liquid flow comprising the pH-neutralizing agent is sent to the unit N via the conduit 17, where it is brought into contact with the remainder of the pretreated substrate arriving via the conduit 4. Thus, the portion of the The liquid fraction circulating in the conduit 16 is introduced into the mixing unit M to improve the dilution of the neutralizing agent B in a liquid phase, in order to facilitate the contacting of the neutralizing liquid flow with the pretreated substrate in the N-unit and, therefore, to improve the homogenization of the neutralized support, while limiting the dissolution of the pretreated substrate. Preferably, the mass flow rate of the neutralizing agent stream B introduced into the unit M is determined in such a way that the mixture originating from the unit N reaches a pH of between 4 and 8, preferably between 4.5 and 7.5.
De préférence, selon l'invention, le liquide 10 extrait ne subit qu'une étape de mélange avec l'agent de neutralisation B avant d'être mélangé dans l'unité N avec le substrat prétraité arrivant par le conduit 6. C'est-à-dire que le flux 17 envoyé dans l'unité N a la même composition que le flux circulant dans le conduit 16 excepté l'addition d'agent de neutralisation B. Donc dans ce cas le flux 17 contient, en poids, tous les éléments du flux 16, plus le poids de l'agent de neutralisation B. De préférence, le liquide extrait par l'unité Ex3, circulant dans les conduits 10 puis 16, dans l'unité M, dans le conduit 17 et dans l'unité N est maintenu à une température inférieure à 100 °C, voir50 °C. Pour maintenir la température de ce liquide, de préférence, on n'effectue pas d'opération de chauffage. De manière préférée, on n'effectue pas d'étape d'extraction de matière (par exemple pas d'extraction d'eau, pas d'extraction de matière soluble volatile) contenue dans le flux 16. Par exemple, on n'effectue pas d'étape d'évaporation ou de séparation membranaire sur le flux circulant dans le conduit 16.  Preferably, according to the invention, the extracted liquid undergoes only a mixing step with the neutralization agent B before being mixed in the unit N with the pretreated substrate arriving via the pipe 6. This is that is, the stream 17 sent to the unit N has the same composition as the stream flowing in the line 16 except for the addition of neutralization agent B. In this case, the stream 17 contains, by weight, all the elements of the stream 16, plus the weight of the neutralizing agent B. Preferably, the liquid extracted by the unit Ex3, flowing in the ducts 10 and then 16, in the unit M, in the duct 17 and in the Unit N is maintained at a temperature below 100 ° C, see 50 ° C. To maintain the temperature of this liquid, preferably, no heating operation is carried out. In a preferred manner, no material extraction step (for example no extraction of water, no extraction of volatile soluble material) is carried out in the stream 16. For example, it is not carried out no evaporation or membrane separation step on the flow flowing in the duct 16.
La mise en œuvre des unités N et M, ainsi que le choix de l'agent de neutralisation du mode de réalisation décrit en référence à la figure 2 peuvent être réalisés selon les mêmes critères que ceux énoncés lors de la description du mode de réalisation de la figure 1 . The implementation of the units N and M, as well as the choice of the neutralization agent of the embodiment described with reference to FIG. 2 can be carried out according to the same criteria as those described in the description of the embodiment of the embodiment of Figure 1.
En référence aux figures 1 et 2, l'hydrolyse enzymatique est réalisée dans l'unité H en mettant en contact, dans un réacteur, des enzymes E via le conduit 8 avec le substrat prétraité arrivant par le conduit 7. With reference to FIGS. 1 and 2, the enzymatic hydrolysis is carried out in unit H by contacting, in a reactor, enzymes E via line 8 with the pretreated substrate arriving via line 7.
Les enzymes E sont produites par un microorganisme, par exemples des champignons appartenant aux genres Trichoderma, Aspergillus, Pénicillium ou Schizophyllum, ou les bactéries anaérobies appartenant par exemple au genre Clostridium. Les enzymes produites par ces microorganismes contiennent notamment les cellulases et les hémicellulases, adaptées à l'hydrolyse poussée de la cellulose et des hémicelluloses. The E enzymes are produced by a microorganism, for example fungi belonging to the genera Trichoderma, Aspergillus, Penicillium or Schizophyllum, or anaerobic bacteria belonging for example to the genus Clostridium. The enzymes produced by these microorganisms contain in particular cellulases and hemicellulases, suitable for the extensive hydrolysis of cellulose and hemicelluloses.
Dans l'unité H, les conditions de l'hydrolyse enzymatique, principalement le taux de matière sèche du mélange à hydrolyser et la quantité d'enzymes utilisée, sont choisies de telle façon que l'on obtienne une solubilisation de la cellulose, c'est-à-dire le taux de transformation de la cellulose en sucre, comprise entre 20% et 99% poids, de préférence entre 30% et 95% poids (le taux de transformation de cellulose en sucre est égale à la quantité en poids de cellulose transformé en sucre par rapport à la quantité totale de cellulose introduite dans l'unité H). L'eau nécessaire dans l'unité H est ajoutée par un conduit (non représenté sur les figures 1 et 2). Le taux de matière sèche souhaité dans l'unité H est généralement compris entre 5% et 45% poids, de préférence entre 8% et 35% poids. L'hydrolyse enzymatique dans l'unité H est préférentiellement réalisée à pH compris entre 4 et 6 et à une température comprise entre 30 °C et 60° C, de préférence entre 40 °C et 60 °C. L'hydrolysat, c'est-à-dire le produit de la réaction d'hydrolyse enzymatique, est évacué de l'unité H par le conduit 9 pour être introduit dans l'unité de fermentation alcoolique F1 . In unit H, the conditions of the enzymatic hydrolysis, mainly the solids content of the mixture to be hydrolysed and the amount of enzymes used, are chosen such that a solubilization of the cellulose is obtained. that is to say the conversion rate of cellulose into sugar, between 20% and 99% by weight, preferably between 30% and 95% by weight (the rate of conversion of cellulose to sugar is equal to the amount by weight of cellulose converted to sugar in relation to the total amount of cellulose introduced into unit H). The water required in unit H is added via a conduit (not shown in FIGS. 1 and 2). The desired solids content in the unit H is generally between 5% and 45% by weight, preferably between 8% and 35% by weight. The enzymatic hydrolysis in unit H is preferably carried out at a pH of between 4 and 6 and at a temperature of between 30 ° C. and 60 ° C., preferably between 40 ° C. and 60 ° C. The hydrolyzate, that is to say the product of the enzymatic hydrolysis reaction, is discharged from unit H via line 9 to be introduced into the alcoholic fermentation unit F1.
Dans l'unité F1 , l'hydrolysat est mis en contact avec un ou plusieurs micro-organismes de fermentation. Les sucres fermentescibles sont ainsi transformés en alcools et/ou solvants par les micro-organismes. L'étape de fermentation dans l'unité F1 peut être réalisée à une température comprise entre 30°C et 35°C. A l'issuede l'étape de fermentation, on obtient un moût de fermentation, évacué par le conduit 21 de l'unité F1 , comprenant des matières en suspension et une phase liquide dans laquelle se trouve le ou les produits recherchés (alcools et/ou solvants). In unit F1, the hydrolyzate is contacted with one or more fermentation microorganisms. The fermentable sugars are thus converted into alcohols and / or solvents by the microorganisms. The fermentation step in the F1 unit can be carried out at a temperature between 30 ° C and 35 ° C. At the end of the fermentation step, a fermentation broth is obtained, evacuated via line 21 of unit F1, comprising suspended solids and a liquid phase in which the desired product or products (alcohols and / or or solvents).
Selon un premier mode de réalisation de l'invention, les étapes d'hydrolyse enzymatique et de fermentation alcoolique sont réalisées dans deux réacteurs H et F1 , comme représenté sur les figures 1 et 2. Ce mode de réalisation est couramment nommé SHF ou "Separated Hydrolysis and Fermentation".  According to a first embodiment of the invention, the enzymatic hydrolysis and alcoholic fermentation steps are carried out in two reactors H and F1, as represented in FIGS. 1 and 2. This embodiment is commonly called SHF or "Separated". Hydrolysis and Fermentation ".
Selon un mode particulier de réalisation de l'invention, les étapes d'hydrolyse enzymatique et de fermentation alcoolique sont réalisées simultanément dans un même réacteur. Ce mode de réalisation est couramment nommé SSF ou "Simultaneous Saccharification and Fermentation". La température dans le réacteur peut être comprise entre 30 °C et 45 °C. Selon un autre mode de réalisation de l'invention, l'étape de fermentation alcoolique peut permettre la fermentation simultanée de différents type de sucres. Ce mode de réalisation est couramment nommé SSCF ou "Simultaneous Saccharification and CoFermentation". La température dans le réacteur peut être comprise entre 30°C et 45°C.  According to a particular embodiment of the invention, the enzymatic hydrolysis and alcoholic fermentation steps are carried out simultaneously in the same reactor. This embodiment is commonly referred to as SSF or Simultaneous Saccharification and Fermentation. The temperature in the reactor can be between 30 ° C and 45 ° C. According to another embodiment of the invention, the alcoholic fermentation step may allow the simultaneous fermentation of different types of sugars. This embodiment is commonly referred to as SSCF or Simultaneous Saccharification and CoFermentation. The temperature in the reactor can be between 30 ° C and 45 ° C.
Le moût issu de l'unité F1 de fermentation est introduit par le conduit 21 dans une unité de séparation SP qui permet de séparer le moûts en différents produits : l'alcool ou le solvant évacué par le conduit 22, une vinasse liquide, contenant des sucres non fermentés, évacuée par le conduit 23 et un résidu solide, couramment nommé marc, évacué par le conduit 24, comportant la cellulose, de l'hémicellulose qui n'ont pas été hydrolysées et de la lignine. L'unité de séparation SP peut mettre en œuvre différentes techniques de séparation, par exemple séparation par distillation, décantation, centrifugation, filtration. The must obtained from the fermentation unit F1 is introduced via the conduit 21 into a separation unit SP which makes it possible to separate the musts into different products: the alcohol or the solvent discharged via the conduit 22, a liquid vinasse, containing unfermented sugars, discharged through the conduit 23 and a solid residue, commonly called marc, discharged through line 24, comprising cellulose, hemicellulose that have not been hydrolysed and lignin. The separation unit SP can implement different separation techniques, for example separation by distillation, decantation, centrifugation, filtration.
Dans le cas où, dans le procédé de la figure 1 , on prélève seulement une portion du flux liquide 10 de l'unité d'extraction Ex2 par le conduit 18 ou dans le cas où, dans le procédé de la figure 2, on prélève seulement une portion du flux liquide 10 de l'unité d'extraction Ex3 par le conduit 16, la portion restante de flux liquide peut être introduite dans l'unité de fermentation F2 ou peut être envoyé dans une autre unité extérieur au procédé. In the case where, in the process of FIG. 1, only a portion of the liquid flow 10 from the extraction unit Ex2 is taken via line 18 or in the case where, in the process of FIG. only a portion of the liquid flow 10 of the extraction unit Ex3 through the conduit 16, the remaining portion of liquid flow can be introduced into the fermentation unit F2 or can be sent to another unit outside the process.
Dans le cas où la portion restante de flux liquide est introduit dans l'unité F2, le flux liquide est mis en contact dans l'unité F2 avec un ou plusieurs micro-organismes de fermentation des pentoses et des hexoses. Les sucres fermentescibles sont ainsi transformés en alcools et/ou solvants par les micro-organismes. L'étape de fermentation dans l'unité F2 peut être réalisée à une température comprise entre 30°C et 45°C. A l'issue de l'étape de fermentation, on obtient un moût de fermentation, contenant le ou les produits recherchés (alcools et/ou solvants). In the case where the remaining portion of liquid flow is introduced into unit F2, the liquid stream is contacted in unit F2 with one or more fermentation microorganisms. pentoses and hexoses. The fermentable sugars are thus converted into alcohols and / or solvents by the microorganisms. The fermentation step in the unit F2 can be carried out at a temperature between 30 ° C and 45 ° C. At the end of the fermentation step, a fermentation must is obtained, containing the desired product or products (alcohols and / or solvents).
EXEMPLES  EXAMPLES
Les exemples ci-après illustrent l'invention, sans en limiter la portée.  The following examples illustrate the invention without limiting its scope.
Dans les exemples, la matière sèche MS correspond à la matière sèche d'origine organique. Exemple 1 (non conforme à l'invention)  In the examples, the dry matter MS corresponds to the dry matter of organic origin. Example 1 (not according to the invention)
On met en œuvre le procédé selon la figure 1 , sans les unités d'extraction Ex1 et Ex2. Dans cet exemple, l'agent de neutralisation B est dilué dans un flux d'eau liquide extérieur au procédé. Afin de garantir un bon mélange du flux prétraité 4 avec l'agent de neutralisation 15, l'opération de neutralisation N est effectuée en milieu dilué, généralement inférieur à 15% de matière sèche MS afin de garantir la bonne diffusion de l'agent de neutralisation dans la phase liquide.  The method according to FIG. 1 is implemented without the extraction units Ex1 and Ex2. In this example, the neutralizing agent B is diluted in a flow of liquid water outside the process. In order to guarantee a good mixture of the pretreated flow 4 with the neutralization agent 15, the neutralization operation N is carried out in a diluted medium, generally less than 15% DM dry matter in order to guarantee the good diffusion of the agent of neutralization. neutralization in the liquid phase.
Le tableau suivant résume les flux mis en jeux. On note que 100kg/h d'eau ont été ajoutés au procédé pour obtenir un marc neutralisé à faible MS (1 1 %).  The following table summarizes the flows involved. It is noted that 100 kg / h of water were added to the process to obtain a neutralized low MS (1 1%).
Figure imgf000014_0001
Figure imgf000014_0001
Exemple 2 (conforme à l'invention) Example 2 (in accordance with the invention)
On met en œuvre le procédé selon la figure 1 , en mettant en œuvre l'étape d'extraction dans l'unité Ex1 , mais pas l'étape d'extraction dans l'unité Ex2. La mise en place d'une extraction Ex1 permet d'obtenir un flux liquide 13 à faible teneur en matière sèche MS permettant d'homogénéiser correctement l'agent de neutralisation B en le dispersant dans la phase liquide. Une fois l'agent de neutralisation correctement homogénéisé, le flux liquide neutralisé peut être mélangé avec le marc sans provoquer de dilution du procédé comme le montre le tableau 2.
Figure imgf000015_0001
The method according to FIG. 1 is implemented by implementing the extraction step in the Ex1 unit, but not the extraction step in the Ex2 unit. The introduction of an extraction Ex1 makes it possible to obtain a liquid stream 13 with a low dry matter content MS which makes it possible to correctly homogenize the neutralizing agent B by dispersing it in the liquid phase. Once the neutralizing agent is properly homogenized, the neutralized liquid stream can be mixed with the pomace without causing dilution of the process as shown in Table 2.
Figure imgf000015_0001
La mise en œuvre du procédé selon l'invention a ici permis l'économie de 100kg/h d'eau par rapport à l'exemple 1 . The implementation of the method according to the invention has here allowed the saving of 100 kg / h of water compared to Example 1.
Exemple 3 (conforme à l'invention) Example 3 (in accordance with the invention)
On met en œuvre le procédé selon la figure 2. Dans ce mode de réalisation, le liquide nécessaire à la neutralisation du flux prétraité 4 est obtenu par pressage dans l'unité Ex2 du flux 6 obtenu après ladite opération de neutralisation dans l'unité N. Cette mise en œuvre avec recyclage de liquide en amont du procédé permet de réaliser l'opération de neutralisation N à des teneurs en matière sèche MS plus faible qu'avec la mise en œuvre de la figure 1 sans pour autant devoir ajouter de l'eau extérieur au procédé. Cette mise en œuvre permet un avantage supplémentaire en facilitant la mise en œuvre de la neutralisation dans l'unité N, notamment en permettant la mise en œuvre d'une agitation moins perfectionnée possible à faible teneur en matière sèche MS.  The method according to FIG. 2 is implemented. In this embodiment, the liquid necessary for the neutralization of the pretreated flow 4 is obtained by pressing in the unit Ex2 of the flow 6 obtained after said neutralization operation in the unit N This implementation with recycling of liquid upstream of the process makes it possible to carry out the neutralization operation N with lower dry matter contents MS than with the implementation of FIG. 1 without having to add additional water outside the process. This implementation provides an additional advantage by facilitating the implementation of the neutralization in the N unit, in particular by allowing the implementation of a less sophisticated stirring possible low MS dry matter content.
Le tableau 3 montre un exemple de mise en œuvre selon la figure 2. Le recyclage de jus neutralisé 16 à l'étape de neutralisation N permet de réaliser l'opération N à 16% de manière sèche MS contre 22% de matière sèche MS dans l'exemple 2, sans pour autant provoqué une dilution des flux dans le procédé. L'agent de neutralisation B est ajouté via le conduit 5 au flux 16 recyclé pour obtenir une bonne homogénéisation de l'agent de neutralisation dans la phase liquide. Le flux obtenu 17 est ensuite mis en œuvre à l'étape N. La neutralisation a donc lieu à faible teneur en matière sèche MS (16%) sans ajout d'eau supplémentaire.  Table 3 shows an example of implementation according to FIG. 2. The recycling of neutralized juice 16 at the neutralization stage N makes it possible to carry out operation N at 16% dry MS against 22% DM dry matter in Example 2, without causing a dilution of the flows in the process. The neutralization agent B is added via the conduit 5 to the stream 16 recycled to obtain a good homogenization of the neutralization agent in the liquid phase. The stream obtained 17 is then used in stage N. The neutralization therefore takes place at a low DM solids content (16%) without the addition of additional water.
N ° flux 4 17 6 10 7 16 5 No. flow 4 17 6 10 7 16 5
Marc Agent de Marc Jus Marc Jus Agent de Marc Marc Jus Agent Marc Jus Agent
Description Description
prétraité neutralisation neutralisé neutralisé pressé neutralisé neutralisation pretreated neutralization neutralized neutralized pressed neutralized neutralization
Solide (kg/h) 15 0 15 0 15 0 0Solid (kg / h) 15 0 15 0 15 0 0
MS soluble (kg/h) 7 6,9 13,9 1 1 ,5 2,4 6,9 0MS soluble (kg / h) 7 6.9 13.9 1 1, 5 2.4 6.9 0
Eau (kg/h) 78 78 156 130 26 78 0Water (kg / h) 78 78 156 130 26 78 0
Base (kg/h) 0 10 0 0 0 0 10Base (kg / h) 0 10 0 0 0 0 10
PH 1 ,4 5 5 5 5 PH 1, 4 5 5 5 5
MS 22% 8% 16% 8% 40% 8%  MS 22% 8% 16% 8% 40% 8%

Claims

REVENDICATIONS
1 ) Procédé de production de sucres et éventuellement d'alcools et/ou de solvants à partir d'une charge de biomasse, dans lequel on effectue les étapes suivantes : 1) Process for producing sugars and optionally alcohols and / or solvents from a biomass feed, in which the following steps are carried out:
a) on effectue une étape de prétraitement par mise en contact et chauffage de la charge de biomasse avec de l'eau et un composé basique ou acide, de manière à obtenir un substrat prétraité, a) a pretreatment step is carried out by contacting and heating the biomass feedstock with water and a basic or acidic compound, so as to obtain a pretreated substrate,
b) on extrait un flux liquide du substrat prétraité de manière à obtenir un flux liquide et un substrat appauvri en liquide, b) extracting a liquid stream from the pretreated substrate so as to obtain a liquid stream and a liquid-depleted substrate,
c) on mélange au moins une partie du flux liquide obtenu à l'étape b) avec un agent de neutralisation du pH de manière à obtenir un flux liquide comportant l'agent de neutralisation du pH, c) mixing at least a portion of the liquid stream obtained in step b) with a pH-neutralizing agent so as to obtain a liquid stream comprising the pH-neutralizing agent,
d) on mélange le flux liquide comportant l'agent de neutralisation du pH avec le substrat prétraité obtenu à l'étape a) ou avec le substrat prétraité appauvri en liquide obtenu à l'étape b) de manière à obtenir un substrat comportant des sucres. d) mixing the liquid flow comprising the pH-neutralizing agent with the pretreated substrate obtained in step a) or with the pretreated liquid-poor substrate obtained in step b) so as to obtain a substrate comprising sugars .
2) Procédé selon la revendication 1 , dans lequel le débit massique du flux d'agent de neutralisation est déterminé de manière à ce que le substrat comportant les sucres atteigne un pH compris entre 4 et 8. 2) Process according to claim 1, wherein the mass flow rate of the neutralizing agent stream is determined so that the substrate comprising the sugars reaches a pH of between 4 and 8.
3) Procédé selon la revendication 2, dans lequel à l'étape c), on prélève au moins une partie du flux liquide, ladite partie du flux liquide ayant la même composition que ledit flux, puis on mélange ladite partie du flux liquide avec un agent de neutralisation du pH et dans lequel ledit flux liquide comportant l'agent de neutralisation du pH consiste en l'intégralité de ladite partie du flux liquide plus l'agent de neutralisation du pH. 3) Method according to claim 2, wherein in step c), at least a portion of the liquid flow is taken, said portion of the liquid flow having the same composition as said flow, then said portion of the liquid flow is mixed with a pH neutralizing agent and wherein said liquid stream comprising the pH-neutralizing agent consists of all of said portion of the liquid stream plus the pH-neutralizing agent.
4) Procédé selon l'une des revendications 1 à 3 dans lequel à l'étape b), on extrait le flux liquide du substrat prétraité obtenu à l'étape a) de manière à obtenir un substrat appauvri en liquide et ledit flux liquide et dans lequel à l'étape d), on mélange le flux liquide comportant l'agent de neutralisation du pH avec le substrat appauvri en liquide obtenu à l'étape b) de manière à obtenir le substrat neutralisé comportant des sucres. 4) Method according to one of claims 1 to 3 wherein in step b), the liquid flow is extracted from the pretreated substrate obtained in step a) so as to obtain a liquid-depleted substrate and said liquid flow and wherein in step d), mixing the liquid stream comprising the pH-neutralizing agent with the liquid-depleted substrate obtained in step b) so as to obtain the neutralized substrate containing sugars.
5) Procédé selon la revendication 4, dans lequel, en outre, on extrait un deuxième flux liquide du substrat comportant des sucres obtenu à l'étape d), et dans lequel à l'étape c) on mélange la partie du flux liquide obtenu à l'étape b) et au moins une partie du deuxième flux liquide avec un agent de neutralisation du pH de manière à obtenir ledit flux liquide comportant l'agent de neutralisation du pH. 5) Process according to claim 4, wherein, in addition, a second liquid stream is extracted from the substrate comprising sugars obtained in step d), and wherein in step c) the portion of the liquid stream obtained is mixed. in step b) and at least part of the second liquid stream with a pH neutralizing agent so as to obtain said liquid stream comprising the pH-neutralizing agent.
6) Procédé selon la revendication 5, dans lequel on effectue une fermentation alcoolique d'une deuxième partie du deuxième flux liquide au moyen d'un microorganisme alcooligène. 6) Process according to claim 5, wherein an alcoholic fermentation of a second portion of the second liquid stream is carried out by means of an alcoholic microorganism.
7) Procédé selon l'une des revendications 1 à 3, dans lequel à l'étape b), on extrait le flux liquide du substrat comportant des sucres obtenu à l'étape d) de manière à obtenir un substrat appauvri en liquide et ledit flux liquide, et dans lequel à l'étape d), on mélange le flux liquide comportant l'agent de neutralisation du pH avec le substrat prétraité obtenu à l'étape a). 7) Method according to one of claims 1 to 3, wherein in step b), the liquid stream is extracted from the substrate comprising sugars obtained in step d) so as to obtain a liquid-depleted substrate and said liquid stream, and wherein in step d), mixing the liquid stream comprising the pH neutralizing agent with the pretreated substrate obtained in step a).
8) Procédé selon la revendication 7, dans lequel on effectue une fermentation alcoolique d'une deuxième partie du flux liquide au moyen d'un microorganisme alcooligène. 8) Process according to claim 7, wherein an alcoholic fermentation of a second portion of the liquid stream is carried out by means of an alcoholic microorganism.
9) Procédé selon l'une des revendications 1 à 8 dans lequel à l'étape a), ledit composé est basique et dans lequel l'agent de neutralisation du pH est acide. 9) Method according to one of claims 1 to 8 wherein in step a), said compound is basic and wherein the pH neutralizing agent is acidic.
10) Procédé selon l'une des revendications 1 à 9 dans lequel à l'étape a), ledit composé est acide et dans lequel l'agent de neutralisation du pH est basique. 10) Method according to one of claims 1 to 9 wherein in step a), said compound is acidic and wherein the pH neutralizing agent is basic.
1 1 ) Procédé selon l'une des revendications 1 à 10, dans lequel le composé acide ou basique et l'agent de neutralisation du pH sont indépendamment choisi parmi : hydroxyde de potassium, hydroxyde de sodium, ammoniaque, acide sulfurique, acide chlorhydrique, acide nitrique, acide acétique, acide formique. 1 1) Method according to one of claims 1 to 10, wherein the acidic or basic compound and the pH neutralizing agent are independently selected from: potassium hydroxide, sodium hydroxide, ammonia, sulfuric acid, hydrochloric acid, nitric acid, acetic acid, formic acid.
12) Procédé selon l'une des revendications 1 à 1 1 , dans lequel on effectue en outre les étapes suivantes : 12) Method according to one of claims 1 to 1 1, wherein is further carried out the following steps:
e) on met en contact le substrat comportant des sucres avec une enzyme cellulolytique et/ou hémicellulolytique de manière à obtenir un hydrolysat comportant un résidu solide et une phase liquide contenant des sucres, e) the substrate comprising sugars is brought into contact with a cellulolytic and / or hemicellulolytic enzyme so as to obtain a hydrolyzate comprising a solid residue and a liquid phase containing sugars,
f) on effectue une fermentation alcoolique de l'hydrolysat au moyen d'un microorganisme alcooligène de manière à obtenir un vin fermenté, f) an alcoholic fermentation of the hydrolyzate is carried out by means of an alcoholic microorganism so as to obtain a fermented wine,
g) on effectue une étape de séparation et purification du vin fermenté de manière à obtenir au moins un flux purifié comportant de l'alcool et/ou un solvant. 13) Procédé selon l'une des revendications 1 à 12, dans lequel la charge de biomasse comporte au moins l'un des éléments suivants : du bois, de plantes issues de cultures dédiées, des déchets ligno-cellulosiques agricoles, des résidus de l'industrie de transformation des matériaux ligno-cellulosiques. g) a step of separating and purifying the fermented wine is carried out so as to obtain at least one purified stream comprising alcohol and / or a solvent. 13) Method according to one of claims 1 to 12, wherein the biomass load comprises at least one of the following: wood, plants from dedicated crops, agricultural lignocellulosic waste, residues of the lignocellulosic materials processing industry.
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