WO2020152105A1 - Procede de traitement d'une biomasse lignocellulosique - Google Patents
Procede de traitement d'une biomasse lignocellulosique Download PDFInfo
- Publication number
- WO2020152105A1 WO2020152105A1 PCT/EP2020/051289 EP2020051289W WO2020152105A1 WO 2020152105 A1 WO2020152105 A1 WO 2020152105A1 EP 2020051289 W EP2020051289 W EP 2020051289W WO 2020152105 A1 WO2020152105 A1 WO 2020152105A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- washing
- biomass
- lignocellulosic
- production
- substrate
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- 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
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
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- C—CHEMISTRY; METALLURGY
- 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
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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
- C12P7/16—Butanols
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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
- C12P7/24—Preparation of oxygen-containing organic compounds containing a carbonyl group
- C12P7/26—Ketones
- C12P7/28—Acetone-containing products
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- the present invention falls within the field of processes for the production of sugars from lignocellulosic biomasses. It relates more particularly to a process for treating lignocellulosic biomass for the production of alcohols or solvents useful as biofuels (for example ethanol) or for the synthesis of bio-sourced molecules.
- the treatment process according to the invention can integrate a pretreatment by steam explosion or acid cooking of the lignocellulosic biomass.
- Lignocellulosic biomass is made up of three main constituents: cellulose (35 to 50%), hemicellulose (23 to 32%) which is a polysaccharide essentially made up of pentoses and hexoses and lignin (15 to 25%) which is a macromolecule of complex structure and high molecular weight, obtained from the copolymerization of phenylpropenoic alcohols. These different molecules are responsible for the intrinsic properties of the plant wall and organize themselves into a complex tangle.
- Cellulose the majority in this biomass, is thus the most abundant polymer on Earth and the one with the greatest potential for forming materials and biofuels.
- the potential of cellulose and its derivatives could not, for the moment, be fully exploited, mainly due to the difficulty of extracting cellulose. Indeed, this step is made difficult by the very structure of the plants.
- the technological barriers identified in the extraction and processing of cellulose are in particular its accessibility, its crystallinity, its degree of polymerization, the presence of hemicellulose and lignin.
- the principle of the process for converting lignocellulosic biomass by biotechnological processes uses a step of enzymatic hydrolysis of the cellulose contained in plant materials to produce glucose.
- the glucose obtained can then be fermented into various products such as alcohols (ethanol, 1, 3-propanediol, 1 -butanol, 1, 4-butanediol, ...) or acids (acetic acid, lactic acid, acid 3- hydroxypropionic, fumaric acid, succinic acid, ).
- Cellulose and possibly hemicelluloses are the targets of 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 pretreatment aims 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.
- One of the most effective pretreatments is the explosion steam, which allows almost complete hydrolysis of the hemicellulose and a significant improvement in the accessibility and reactivity of cellulose to enzymes.
- This pretreatment can be preceded by other treatment (s) such as an acid impregnation.
- the biomass impregnated with an aqueous solution, with or without acid is treated continuously with steam in a reactor under pressure and temperature in order to mainly destructure the hemicellulose.
- the pretreated biomass is composed of solids (mainly cellulose and lignin) and water soluble sugars.
- a fraction of the pretreated solid is sent to a soluble sugars extraction step to recover a sweet juice.
- the document "Lignocellulosic Biomass to Ethanol Process Design and economiess 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 liquid fraction. This juice rich in sugars can then be used as a carbon source in the units of enzyme production and yeast propagation.
- the pretreated substrate depleted in soluble sugars can be directed to the enzymatic hydrolysis step together with the raw pomace leaving the pretreatment unit.
- the enzymatic hydrolysis aims to convert the pretreated substrate into monomeric sugars.
- the enzymatic cocktail used for this step is a mixture of cellulolytic and / or hemicellulolytic enzymes capable of breaking down cellulose into a solution of sugars, containing in particular glucose.
- the enzymes of the enzymatic cocktail contain three main types of enzymes according to their activities: endoglucanases, exoglucanases and cellobiases.
- the microorganism most used for the production of the enzymatic cocktail is the fungus Trichoderma reesei.
- the process for producing the enzymatic cocktail begins with a propagation phase, the aim of which is to multiply the filamentous fungus T. reesei.
- an enzymatic cocktail production phase is induced by a change of sweet substrate.
- a must is obtained containing a mixture of enzymes and the filamentous fungus T. reesei. This must can be used directly in enzymatic hydrolysis, or the enzymes can be separated from the fungus and then possibly concentrated.
- Fermentation of sugars resulting from enzymatic hydrolysis into various products such as alcohols, solvents or acids requires the use of biocatalysts (bacteria or yeasts).
- biocatalysts bacteria or yeasts
- the main target of the fermentation step is the conversion of sugars into bioproducts, and the conditions of the fermentation step are chosen to promote this metabolic pathway, the conduct of a fermentation step necessarily involves parallel reactions. aimed at the development and maintenance of microorganisms fermentation. For example, Pasteur showed in the 19th century that about 5% of the sugars are converted into co-products, or used for maintenance and cell growth, in the case of fermentation of glucose to ethanol by yeast Saccharomyces cerevisiae.
- the sweet juice resulting from the step of extracting the pretreated pomace can be used partially or completely for the production of biocatalysts.
- This substrate rich in sugars is brought into contact with an inoculum of yeasts or bacteria under conditions favorable to their multiplication.
- the production of biocatalysts requires the supply of carbon and nitrogen compounds but also mineral elements, vitamins. The needs vary according to the type of biocatalyst considered.
- the obtained must containing the yeasts or bacteria is used directly without separation in the fermentation step, or alternatively this must can be concentrated, for example by centrifugation.
- These alcohol production processes in particular to produce biofuel (ethanol) by fermentation therefore comprise, in a known manner, the succession of following steps: grinding of the biomass, optionally an impregnation of the biomass, then pretreatment by steam explosion or cooking in acidic conditions, enzymatic hydrolysis to produce sugars or bio-sourced molecules and alcoholic fermentation to produce biofuel alcohols such as ethanol or other type of fermentation to produce bio-sourced molecules, ethanol (or biofuels or bio-sourced molecules) then being separated for example by distillation.
- US Patent 8,545,633 describes such a process for producing ethanol with standard operating conditions for these steps, conditions which are known to those skilled in the art. This patent more particularly teaches methods of treating crushed biomass before impregnation.
- a first treatment method is an injection of water vapor (called "pre-steaming" according to a known Anglo-Saxon term) into the particles of crushed biomass to homogenize the biomass and prevent the formation of pockets which are poorly impregnated.
- This treatment is carried out with steam at 110 ° C. or more and at least 1.3 bar absolute (5 psig) at a rate of 10 to 20 kg / h for 5 to 30 minutes.
- a small amount of dilute acid can be introduced, for example 0.5 to 15 g acid / kg of biomass.
- Another method consists in removing the fraction of fine particles rich in ash from the biomass.
- the fines are separated by a physical separation based on particle size, and these fines are richer in "ash” than the initial biomass.
- These “ashes” are minerals: silica, compounds containing calcium, magnesium, sodium, potassium, phosphorus and / or aluminum.
- the ash can consume the acid to form salts, which forces the amount of acid to be increased during impregnation. They represent 1 to 10% by weight of the biomass, part of them is insoluble in acid (silica is the predominant part of the insoluble).
- a method for measuring the ash of lignocellulosic products is for example described in the standard ASTM E1755 “Standard Test Method for Ash in Biomass”. This same document describes two processes for removing this ash, namely washing with water, which is not recommended, and a dry treatment, which is recommended.
- the dry process uses the techniques of separation by air jet or cyclone, by dry sieving, dry filtration, sedimentation in several stages, each separating increasingly fine particles, the ash being found in the smallest particles. smaller.
- 95% of the biomass particles sent for impregnation have a size greater than 250 ⁇ m and at least 60% of them have a size less than 4mm.
- the aim of this type of separation is to obtain, with a view to impregnation, a biomass having an ash content of less than 10% by weight, which corresponds to a reduction of at most 75% of the initial ash content, and of these ashes at least 40% is acid soluble ash (used for impregnation).
- the moisture content of biomass is 20% or less by weight, which corresponds to a dry matter content of at least 80% by weight.
- the process for treating lignocellulosic biomass according to the invention uses washing with water before the impregnation step, with washing which is carried out in given conditions, making it possible to avoid the drawbacks presented above while reducing the consumption of acid used for the impregnation step, in which the waste water resulting from the washing is also advantageously used.
- the subject of the invention is a method for treating lignocellulosic biomass comprising the following successive steps:
- the lignocellulosic biomass is conditioned by at least one grinding step, in particular so as to obtain particles of ground biomass having a size of at most 300 mm;
- said particles are washed with an aqueous solution of pH between 4 and 8.5, at a temperature between 10 and 95 ° C, at atmospheric pressure, and for a period of between 1 and 300 minutes;
- the aqueous solution is separated from the washed biomass particles to obtain, on the one hand, a lignocellulosic substrate having a dry matter content of between 15 and 70% by weight, and, on the other hand, a used aqueous washing solution ;
- said lignocellulosic substrate is impregnated with an acidic liquor, so as to obtain an impregnated lignocellulosic substrate having a pH of between 0.1 and 3;
- a solid / liquid separation is carried out of the impregnated lignocellulosic substrate, to obtain, on the one hand, a lignocellulosic substrate having a dry matter content of between 15% by weight and 70% by weight, and, on the other hand, an effluent liquid;
- step f) said impregnated lignocellulosic substrate resulting from step e) is pretreated by cooking, in particular for a period of between 1 and 120 minutes, so as to obtain a pretreated lignocellulosic substrate,
- step h) fermentation is carried out, by microorganisms of the bacteria or yeast type, of the hydrolyzate obtained from step g) to obtain a fermentation must containing at least one bio-based molecule such as a solvent and / or an alcohol;
- a step of production of enzymes and / or a step of production / propagation of the microorganisms necessary for steps g) or h) is integrated into said process;
- step c) At least part of the spent aqueous washing solution separated in step c) is introduced into a step of said biomass treatment process which is subsequent to pre-treatment step f), and / or in a step of production of enzymes and / or in a stage of production / propagation of microorganisms necessary for stages g) or h) when at least one of these stages of production of enzymes and / or of production / propagation of microorganisms is integrated said biomass treatment process.
- the dry matter content is measured according to standard ASTM E1756-08 (2015) “Standard Test Method for Determination of Total Solids in Biomass”.
- DM dry matter content
- the invention therefore proposes to add a washing of the biomass with an aqueous solution, then a solid / liquid separation, before proceeding with the pretreatment, and, in addition, to exploit the resulting washing water, with a double advantage.
- the biomass thus washed and separated is found depleted in ash, which will significantly reduce the acid consumption of the process during the impregnation step.
- the used washing water will become enriched in ash, and this characteristic allows it to be used in process steps where the presence of minerals in the liquid phase is an asset, as detailed below.
- this washing carried out under the specific conditions recommended in the invention, did not cause excessive overconsumption of water or other processing problems.
- the pH of the washing solution should be adjusted to at least 4 (therefore to a very different minimum pH, much higher than the acidic impregnation pH), and which can be moderately acidic, moderately basic or neutral.
- Such a moderate pH of the washing solution has turned out to be particularly suitable, and in particular justified the choice made in the invention to reuse the washing solution used after the pretreatment step, in steps where the pH n is not very acidic.
- the fact that the washing is carried out at atmospheric pressure ensures that one is indeed in the presence of an aqueous solution in the liquid phase, not of a vapor.
- the washing time at most 300 minutes, makes it possible to obtain the desired depletion of the biomass in ash, without having too much impact on the overall production time.
- the washing temperature is in a range allowing either the use of tools and an aqueous solution at ambient temperature, or of moderately heating, for example, only the aqueous solution, depending in particular on the type of biomass.
- at least some or all of the spent aqueous washing solution separated in step c) is introduced into the enzymatic hydrolysis step g) or into the step fermentation h).
- this introduction can be done directly in the fermentation step h), or can be done upstream of the fermentation step, in the neutralization steps (if this is provided for) or enzymatic hydrolysis: the remaining mineral salts are thus transferred to the fermentation step where they can play their role.
- the salts can however be at least partially modified when they are introduced from the enzymatic hydrolysis or from the neutralization, due to the change in the pH of the reaction medium.
- the minerals are particularly useful for side reactions aimed at the maintenance and / or growth of the microorganism used in the fermentation step.
- the method according to the invention also comprises a step of neutralizing the lignocellulosic substrate pretreated in step f), before or during step g) of enzymatic hydrolysis, and at least one part is introduced, or all of the spent aqueous washing solution separated in step c) in said neutralization step.
- the neutralization step is carried out so that the pH of the enzymatic hydrolysis reaction mixture is preferably between 4 and 6. It is thus seen that the used aqueous solution has a pH compatible with that targeted in this step of neutralization.
- the method also comprises an integrated step of production by microorganisms of the fungal type of the enzymes necessary for the enzymatic hydrolysis of step g), and at least a part, or the all of the spent aqueous washing solution separated in step c) in said enzyme production step.
- a step “integrated” into the process of the invention is understood as a step for producing a compound intended to treat biomass, such as an enzyme or a yeast, before it is brought into contact with said biomass, in the process. same installation or in the vicinity of the installation implementing the treatment of the biomass: it is thus a question of manufacturing "in situ" compounds of biological origin which will be used in the treatment of the biomass (alternatively, these compounds of (biological origin can be produced off-site, and brought to the biomass treatment facility).
- the process according to the invention also comprises an integrated stage of propagation of microorganisms of the bacteria or yeast type necessary for the fermentation of stage h), and at least part of the aqueous washing solution is introduced. waste separated in step c) in said propagation step.
- the use of the used aqueous washing solution is very advantageous, because its moderate pH is compatible with that targeted in the media. reactions involved (especially moderately acidic pH). And in addition, it turns out that this solution enriched in minerals is favorable to the production of the target enzymes or microorganisms, these minerals constituting nutrients for the microorganisms concerned.
- the duration of washing step b) is between 1 and 60 minutes, and preferably between 1 and 15 minutes. It turned out that this washing could be efficient even with a short duration, which is an asset industrially.
- the aqueous solution of step b) for washing the particles has a pH of between 5.5 and 7.5, in particular between 6 and 7.5 or between 6.5 and 7.5.
- the aqueous washing solution is therefore close to neutral pH, which makes it possible to simply use water without adding acid or base, without reducing the washing performance.
- the aqueous solution of step b) for washing the particles is at a temperature between 25 and 95 ° C, in particular between 30 and 60 ° C.
- this washing can therefore be carried out at ambient temperature or with moderate heating, in particular provided by heating the solution before bringing it into contact with the biomass (or by recycling water from another step of the process, water being in fact in this temperature range without additional thermal makeup).
- the amount of aqueous solution brought to washing step b) is between 0.5 and 60 g / g of biomass. It is preferably between 1 and 30 g / g of biomass, and in particular between 1, 5 and 20 g / g of biomass.
- step c) it is also possible to reintroduce a portion of the spent aqueous washing solution separated in step c) into washing step b).
- steps g) of enzymatic hydrolysis and h) of fermentation are concomitant, one then speaks of SSCF for the acronym of “Simultaneous saccharification and co-fermentation” in English.
- part of the liquid effluent from step e) can be introduced into washing step b). Since this effluent is acidic, its contribution should be moderate in order to remain within a pH range appropriate for the washing solution.
- step f) a pretreatment by steam explosion is carried out to obtain a vapor and the pretreated lignocellulosic substrate, the vapor resulting from step f) is condensed so as to produce an acid condensate.
- the pretreatment by steam explosion preferably lasts at most 30 minutes, in particular at most 15 minutes.
- At least part of the acid condensate alone or mixed with water can be introduced in step b) of washing.
- the condensate input should be adjusted so that the washing solution remains within the recommended pH range.
- said biomass particles once ground in step a) have a size of at least 1 mm.
- the lignocellulosic substrate obtained from step c) is sent directly to the impregnation step d).
- the lignocellulosic substrate resulting from step c) preferably has a dry matter content of between 25% to 70% by weight, more preferably between 40% and 65% by weight.
- the impregnation step d) is carried out in a single step with a residence time of 10 seconds to 180 minutes.
- the lignocellulosic substrate resulting from step e) has a dry matter content of between 40 and 65% by weight.
- the method also comprises integrated steps for the production of biocatalysts: fungus, enzymes, bacteria or yeasts.
- These production steps can preferably be carried out with a growth of the microorganism (s) from a sweet juice obtained from the biomass treatment process.
- This sweet juice can be extracted after the pretreatment step f), it then contains monomeric sugars resulting from the solubilization of the hemicelluloses which takes place during the pretreatment f).
- This sweet juice can be extracted after the enzymatic hydrolysis step g), it then also contains the monomeric glucose which is the product of the enzymatic hydrolysis of cellulose.
- the extraction of the sweet juice takes place between the pretreatment stage f) and the enzymatic hydrolysis stage g).
- the extraction of the sweet juice can be done by washing the pretreated substrate.
- at least part of the flow used for washing can be the used washing water obtained from step c).
- the invention therefore optionally provides for the integration of said process with a step for producing enzymes and / or a step for producing / propagating the microorganisms necessary for steps g) or h), and for providing a step for extraction of at least part of the sweet juices obtained after the pre-treatment step f) or after the enzymatic hydrolysis step g), in particular by washing the substrate with an aqueous solution.
- aqueous washing solution from step c) can be introduced for the extraction by washing of the sweet juices.
- the process according to the invention can be implemented for the production of ethanol or of an acetone-butanol-ethanol (ABE) mixture or an isopropanol-butanol-ethanol (IBE) mixture or of any other biobased molecule or solvent, like acetone.
- ABE acetone-butanol-ethanol
- IBE isopropanol-butanol-ethanol
- Figure 1 is a block diagram showing an embodiment of the process for producing solvents and / or alcohols from lignocellulosic biomass incorporating a washing step b) of the crushed biomass according to the invention.
- FIG. 2 is a block diagram showing an embodiment of the process for treating lignocellulosic biomass incorporating a recycling of various acid effluents.
- FIG. 3 is a block diagram showing an embodiment of the process for the production of alcohols and / or solvents from lignocellulosic biomass integrating a recycling of the water used for washing the crushed biomass, in the downstream neutralization steps and / or enzymatic hydrolysis and / or fermentation according to the invention.
- FIG. 4 is a block diagram showing yet another embodiment of the process for the production of solvents and / or alcohols according to the invention which comprises units of in situ production of enzymes and yeasts; integrating recycling of the water used for washing the crushed biomass to the production of biocatalysts and / or for the extraction of a sweet juice at least partly used for the production of biocatalysts.
- Figure 5 shows the acid-base titration curves of the liquors of Example 1.
- FIG. 6 shows the evolution of the pH as a function of the specific volume of sulfuric acid H 2 S0 4 solution added to the used impregnation liquors of Example 2.
- Figure 7 shows the change in absorbance during the growth of yeasts in the culture media with or without minerals of Example 5.
- the treatment process comprises in its first step, a step of conditioning the lignocellulosic biomass with at least one grinding so as to obtain biomass particles having a size of at most 300 mm. It is of course possible to carry out several successive grinding steps in order to reach the target particle size.
- the crushed biomass has a particle size (the largest size) of at most 300 mm, most often at least 1 mm, and often between 2 and 200 mm. Any method known to those skilled in the art can be implemented to carry out this step.
- the straws are crushed with sieves from 5 to 100 mm.
- the wood it is generally shredded into parallelepipedal slabs with a length of between 20 and 160 mm, a width of between 10 and 100 mm and a thickness of between 2 and 20 mm.
- the crushed lignocellulosic biomass is brought to the washing step (zone) by any means known to those skilled in the art, in particular a transfer screw.
- the Applicant has now found that the determining effect on the consumption of acid would not be a basicity effect but rather a buffering effect due to the presence of acetic acid or its salts which are generated by the solubilization of the ash contained. in the crushed lignocellulosic biomass during its contact with the acidic aqueous solution used for the impregnation step.
- acetic acid Due to the high pKa (4.76 at 25 ° C) of acetic acid relative to the pH of the acidic impregnation solution (pH ⁇ 3 and most often less than 2), acetic acid has a buffer on the pH, requiring the supply of large amounts of acid to bring the pH to a value compatible with the acid pretreatment step, which is generally between 0.1 and 3
- a washing step step b) of the particles of crushed biomass with an aqueous washing solution, at a temperature of between 10 and 90 ° C., preferably at atmospheric pressure.
- the pH of the aqueous washing solution is between 4 and 8.5, and more preferably between 6 and 7.5.
- the aqueous washing solution can be acidified, advantageously by the impregnation acid which is used in the impregnation step d) detailed below.
- the optional acid is not added to the washing water by an external make-up, but comes from a process stream containing said acid.
- the aqueous wash solution can also be just water (neutral pH).
- the aqueous solution can be an aqueous stream recycled from the process. It is also noted that, according to the invention, washing step b) is carried out in the absence of water in the vapor state.
- washing modes in one step or in several steps following a co-current, counter-current or cross-current mode are possible.
- the washing can be carried out by soaking, for example by transfer of the biomass through a water bath, or else under flowing water, for example by a distribution of water streaming over the biomass which is possibly set in motion.
- the amount of water involved for this step is preferably as low as possible to obtain the desired effect.
- the washing is carried out using between 0.5 and 60 g of water / g of lignocellulosic biomass, preferably between 1 and 30 g of water / g of biomass and more preferably between 1, 5 and 20 g of water / g of biomass.
- the quantity of washing water to be used can be determined by means of a laboratory test preceding the biomass treatment campaign and consisting in measuring the pH of the used washing water (or filtrate) recovered after the washing step.
- the tool or tools performing the washing do not have heating equipment, and the washing temperature is regulated by the temperature of the aqueous washing solution.
- the temperature of the aqueous washing solution is between 25 ° C and 95 ° C and preferably between 30 ° C and 60 ° C, it can therefore be just at room temperature, or have been heated, for this specific washing step or because it comes from less in part, from the recycling of liquid effluents produced in the process and already in this temperature range.
- the washing duration is between 1 minute and 300 minutes, and preferably between 1 minute and 60 minutes, and even more preferably between 1 minute and 15 minutes.
- the method comprises a step of separating the liquid from the particles of washed lignocellulosic biomass to obtain a lignocellulosic substrate whose dry matter content is between 15 and 70% by weight (measured according to the ASTM E1756 standard), preferably between 25 and 70. % and more preferably between 40% and 65% by weight.
- any liquid / solid separation method can be used, provided that the dry matter content at the end of this step is respected.
- the solid / liquid separation is ensured by a filter press type tool or carried out by draining, for example by gravity.
- the step of separating the used washing water is carried out concomitantly with the transfer of the washed lignocellulosic biomass to the impregnation step, by means of a transport screw comprising a solid / separation zone. liquid by pressing the solid material.
- This type of transfer screw comprises a conical compression zone allowing the formation of a hermetic plug of washed biomass and a perforated zone allowing the disposal of used washing water.
- the dry matter rate (DM) can be determined by calculation: it is then considered that the DM contained in the sample pressed is the difference between the DM of the input washed biomass and the DM present in the juice extracted during pressing, the calculation therefore requires a measurement of the mass flow rates of the washed biomass input and of the extracted juice, and measurements of DM of samples of washed biomass at the inlet and of the juice extracted at the outlet (for example according to the same standard ASTM E1756).
- MS pressed substrate (QBE * % MSBE - QJS * % MSJS) / (QBE - QJS)
- the separation step c) thus makes it possible to provide a used washing water of which at least a part can advantageously be used in a downstream step, in particular the downstream fermentation step, according to the process for treating lignocellulosic biomass according to the invention as described below with reference to FIGS. 1 to 4 detailed below.
- Part of the used washing water can be recycled to washing step b) of the process and the other part used in a downstream step.
- the used washing water can optionally be mixed with another filtrate resulting from another step of the process, before being recycled, for example in step b) of washing.
- the separation step c) can be carried out in one or more steps.
- the separation step c) can also be carried out concomitantly with the washing step b), in a tool allowing the washing and the solid / liquid separation to be carried out in a single step.
- This tool can be for example a rotary drum or a belt filter.
- the lignocellulosic substrate resulting from the step of separating the washed biomass is sent to step d) of impregnating with an acidic liquor.
- the lignocellulosic substrate is sent directly to the impregnation step, that is, it does not undergo any further treatment before the impregnation step.
- the treatment process according to the invention comprises a step d) of impregnating the lignocellulosic substrate with an acidic liquor, so as to obtain a washed and impregnated lignocellulosic substrate, the pH of which is between 0.1 to 3.
- This step aims to prepare the lignocellulosic substrate for the pretreatment step.
- the impregnation is carried out in an impregnation reactor at a temperature between 10 and 90 ° C, and preferably at atmospheric pressure. Preferably, the impregnation is carried out at a temperature between 50 ° C and 85 ° C.
- the residence time of the lignocellulosic substrate in the impregnation reactor is usually 10 seconds to 180 minutes, preferably between 30 seconds and 60 minutes, and even more preferably between 30 seconds and 15 minutes.
- the impregnation step is carried out in a single step.
- the washed and impregnated lignocellulosic substrate has a pH of between 0.9 to 2.5.
- the impregnation reactor or impregnator is generally provided with one or more screws which transfer (s) the lignocellulosic substrate from its inlet to the outlet opening.
- the impregnator is also equipped with one or more pipes to supply the acid liquor as well as, if necessary, one or more pipes to withdraw the acid liquor.
- Said acid liquor inlet and outlet pipes are generally installed so as to operate in co-current or counter-current recycling.
- the acidic liquor is an aqueous solution of a strong acid, which is for example chosen from sulfuric acid, hydrochloric acid, nitric acid, for example with an acid content of between 0.5 and 4% by weight .
- a strong acid which is for example chosen from sulfuric acid, hydrochloric acid, nitric acid, for example with an acid content of between 0.5 and 4% by weight .
- the acid used is sulfuric acid.
- the lignocellulosic substrate impregnated with acid liquor is subjected to a solid / liquid separation step in order to obtain a lignocellulosic substrate having a dry matter content of between 15 % and 70% by weight and a spent acidic liquor.
- the lignocellulosic substrate impregnated with acid liquor is first drained, in order to extract at least part of the free acidic liquor, before being treated by solid / liquid separation.
- the solid / liquid separation step can implement any technique known to those skilled in the art, for example decantation, centrifugation or pressing.
- a pressing of the lignocellulosic substrate is carried out concomitantly with its transfer to pretreatment step f), when the latter implements the steam explosion process which is described below.
- This driving mode of step e) is for example ensured by a screw called “plug screw feeder”, the operation of which has already been described above.
- the formation of a plug of pressed lignocellulosic substrate seals the pressure of the steam explosion reactor, preventing steam leakage.
- the transfer screw is also fitted with one or more pipes for withdrawing the spent liquor (called pressât) separated during pressing.
- pressate can be recycled to step d) of impregnation and / or to step b) of washing.
- the wet biomass obtained at the end of step e) of solid / liquid separation which can be designated by the term “washed and acidified lignocellulosic substrate” has a dry matter content preferably between 25% and 70% by weight. , and more preferably between 40 and 65% by weight.
- the washed and acidified lignocellulosic substrate undergoes a pretreatment step f).
- Cellulose (and possibly hemicelluloses) which are the targets of enzymatic hydrolysis are not directly accessible to enzymes. This is the reason why a pre-treatment of the biomass is carried out before the enzymatic hydrolysis step.
- the pretreatment aims in particular to modify the physical and physicochemical properties of the cellulosic fraction, such as its degree of polymerization and its state of crystallinity.
- pretreatment Various types of pretreatment are known to those skilled in the art, they combine a chemical treatment and a heat treatment. Mention may in particular be made of acidic or basic cooking, the so-called “Organosolv” process, treatments with ionic liquids and the process by steam explosion.
- the preferred pre-treatment process is the steam explosion (“SteamEx” or “Steam Explosion” according to the English terminology) carried out in an acidic medium. It is a process in which the lignocellulosic substrate is rapidly brought to high temperature by injection of pressurized steam. The treatment is stopped by sudden decompression.
- the operating conditions of the steam explosion process are as follows:
- the temperature of the reactor is generally between 150 and 220 ° C, preferably between 170 ° C and 210 ° C,
- the pressure is between 5 and 25 bars absolute, more preferably between 8 and 19 bars absolute.
- the residence time before the relaxation phase varies from 10 seconds to 15 minutes, and preferably between 3 minutes and 12 minutes
- the steam explosion can be carried out in batch or continuously, and the depressurization step which allows the biomass to break down can take place in one or more steps.
- the steam explosion is carried out continuously.
- a pretreated lignocellulosic substrate with a high dry matter content is obtained, generally between 20 and 70% by weight, and more often between 35% and 65%, and a vapor phase which is then condensed.
- steps a) to f) according to the present invention therefore makes it possible to produce a reactive pretreated substrate and a water for washing the used biomass. It has also been demonstrated that the process according to the present invention produces a pretreated substrate depleted in minerals compared to the processes of the prior art, in particular the processes implementing a recycling of the impregnation liquor extracted with step e) to impregnation step d). These minerals are extracted in the waste washing water from step c) of the process according to the present invention.
- the pretreated lignocellulosic substrate obtained at the end of step f) of the treatment process according to the invention is advantageously used as feed in a so-called second generation process for the production of solvents and / or 'alcohols from lignocellulosic biomass which continues the treatment of the biomass according to the successive steps described above.
- the pretreated lignocellulosic substrate generally has a pH lower than that which is compatible with the medium for enzymatic hydrolysis.
- the lignocellulosic substrate treated according to step f) of pretreatment is subjected to a neutralization step to bring its pH to a value between 4 and 6.
- an aqueous solution is used containing a neutralization agent which can be chosen from any weak or strong bases known to those skilled in the art.
- the term base denotes any chemical species which, when added to water, gives an aqueous solution with a pH greater than 7.
- the neutralization agent is chosen from potassium hydroxide, sodium hydroxide, ammonia, lime. Even more preferably, the neutralizing agent is chosen from potassium hydroxide and ammonia, alone or in combination with each other.
- the neutralization agent is used in aqueous solution, with a mass concentration of between 2% and 75%, and even more preferably between 15% and 50%.
- Neutralization takes place at a temperature between 15 ° C and 95 ° C, and preferably between 20 ° C and 70 ° C.
- the temperature of the neutralization step is not precisely controlled and is simply governed by the heat given off by the acid-base reaction of neutralization.
- the neutralization step can be carried out continuously, batchwise or batchwise, called “fed-batch” according to Anglo-Saxon terminology.
- a washing step can advantageously be carried out before or after the neutralization step, on all or part of the pretreated lignocellulosic substrate.
- washing is applied, a liquid stream is contacted with the pretreated lignocellulosic substrate, then the liquid is separated from the solid.
- the washing step can be carried out by percolation, by successive mixing and liquid / solid separation operations, by washing on a band filter or by any other technique known to those skilled in the art.
- the washing liquid used can be water or a process stream.
- the mass ratio between the washing liquid added and the liquid contained in the substrate to be washed is generally between 0.5 and 4.
- the washing step generates a sweet washing juice containing part of the hemicelluloses solubilized during the pretreatment.
- This washing juice can for example be used as a carbon source for the production of biocatalysts (enzymes and / or microorganisms).
- the washing step is generally carried out at a temperature between 10 ° C and 95 ° C, and preferably between 30 ° C and 70 ° C.
- the washing stream is at least partly composed of the used washing water resulting from step c) of solid / liquid separation on the washed biomass.
- the pretreated lignocellulosic substrate is sent to enzymatic hydrolysis step g) of the process.
- the pretreated lignocellulosic substrate which is sent to the enzymatic hydrolysis step has a dry matter content generally of between 15% and 70% by weight.
- the objective of enzymatic hydrolysis is to hydrolyze (depolymerize), by means of biocatalysts, the hemicelluloses and cellulose into fermentable sugars, preferably glucose.
- the enzymatic hydrolysis step is carried out under mild conditions, at a temperature of the order of 40 ° C and 55 ° C, preferably between 45 ° C and 50 ° C and at pH from 4.0 to 5 , 5, and even more preferably between 4.8 and 5.2.
- the dry matter content of the enzymatic hydrolysis medium is between 5 and 45% by weight, preferably between 10 and 30% by weight. It is produced by means of enzymes produced by a microorganism.
- microorganisms such as fungi belonging to the genera Trichoderma, Aspergillus, Penicillium or Schizophyllum, or anaerobic bacteria belonging for example to the genus Clostridium, producing a cocktail of enzymes containing in particular cellulases and hemicellulases, adapted to extensive hydrolysis of cellulose and hemicelluloses.
- the enzymatic hydrolysis can be carried out in continuous or batch mode, or continuously fed (“fed batch"), in one or more reactors.
- the residence time is between 12 hours and 200 hours and preferably between 24 hours and 160 hours and even more preferably between 48 hours and 120 hours.
- a hydrolyzate containing fermentable sugars is recovered from the bioreactor, which is then treated in fermentation step h).
- the hydrolyzate obtained can optionally undergo one or more treatment steps before the fermentation step.
- it may be a return to the pH, a partial purification in order to limit the content of inhibitor compound for the fermentative microorganism, an at least partial separation of the solid residues contained in the hydrolyzate.
- step h) of the process for producing solvents and / or alcohols the hydrolyzate optionally treated is sent to the fermentation step h) allowing conversion by means of one or more microorganisms of different kinds of sugars fermentable in solvent and / or alcohols of interest.
- the fermentation methods are known to those skilled in the art and are described in particular in document US Pat. No. 8,456,633.
- solvent is intended to denote organic compounds other than alcohols, for example organic compounds having a ketone function such as acetone.
- alcohol designates in particular ethanol, propanol, isopropanol and butanol.
- the natural or genetically modified microorganisms can be chosen, for example, from Saccharomyces cerevisiae, Schizosaccharomyces pombe, Saccharomyces uvarum, Saccharomyces diastaticus, Kluyveromyces fragilis, Candida shehatae, Pichia stipitis, Pachysolen tannophilis or the bacteria Zymomonas mobilis, Clostricyli columcherichi, Acetobutichi.
- the fermentation step makes it possible, for example, to produce ethanol alone or as a mixture with butanol, propanol, isopropanol and / or acetone.
- the fermentative microorganism may be capable of producing a so-called “ABE (acetone-butanol-ethanol)” or alternatively “IBE (isopropanol-butanol-ethanol) mixture”.
- the microorganism chosen is a natural or genetically modified yeast of the genus Saccharomyces capable of producing ethanol.
- step h a fermentation must diluted in products of interest is recovered.
- steps g) and h) are carried out at the same time, in at least one and the same bioreactor, so that the enzymatic hydrolysis and the fermentation are carried out simultaneously according to a process designated by the term "Saccharification. and Simultaneous Saccharification and Fermentation (SSF) "or" Simultaneous Saccharification and Fermentation (SSF) "according to English terminology, or” Simultaneous Saccharification and Co-Fermentation "(SSCF) when the microorganism used is capable of jointly assimilating C5 sugars and C6 sugars (eg glucose and xylose).
- SSF Simultaneous Saccharification and Fermentation
- SSF Simultaneous Saccharification and Fermentation
- SSCF Simultaneous Saccharification and Co-Fermentation
- the operating conditions in particular temperature
- the temperature can be lowered between 28 ° C and 45 ° C, and preferably between 30 ° C and 35 ° C, when the fermentation is carried out with a yeast of the genus Saccharomyces.
- the pH is preferably adjusted between 5 and 5.5 in order to promote the performance of the yeasts.
- the used washing water recovered in washing step b) after separation of the biomass is advantageously used at least in part in fermentation step h).
- the used washing water from step c) can be introduced directly into the fermentation step h), or be introduced into the enzymatic hydrolysis step g) or even into the neutralization step. prior to enzymatic hydrolysis when expected.
- the used washing water is then transferred in part with the flow resulting from the hydrolysis which is sent to fermentation.
- the production unit implementing the process according to the invention may comprise, in addition to the installations already described, units for the in situ production of enzymes and / or yeasts.
- units for the in situ production of enzymes and / or yeasts For this type of unit, it is possible to send at least part of the used washing water to these enzyme and / or yeast production units in order to enhance the minerals contained therein.
- the used washing water can be detoxified, in order to remove therefrom the compounds which inhibit microorganisms, and / or readjusted in pH.
- the stages of production of biocatalysts require the supply of substrates making it possible to supply the elements constituting the microorganisms. These elements are mainly carbon, oxygen, hydrogen, then, in a second step nitrogen, phosphorus and sulfur. Finally, minerals are also present in small quantities in microorganisms. Thus, when the cells of microorganisms multiply, they puncture all the elements entering into their constitution in their environment.
- the stages of production of biocatalysts are generally carried out on substrates containing assimilable carbon molecules, such as sugars, and in stirred and aerated reactors, the air making it possible to supply oxygen. In addition, supplements must be put in place to ensure the contributions of other elements such as nitrogen, phosphorus, sulfur and minerals.
- the microorganisms necessary for the bioconversion process are produced in situ from sweet juice resulting from the process. These sweet juices are extracted either by washing the pretreated substrate resulting from the pretreatment step f), or by a solid / liquid separation, optionally coupled with washing, carried out after step g) of enzymatic hydrolysis.
- Stage i) of separation of the solvents and / or alcohols from the fermentation must.
- the method according to the invention can finally comprise a step i) of separating the product (s) of interest from the fermentation must, optionally preceded by a solid / liquid separation step in order to remove at least a fraction of the solid matter. contained in the fermentation must.
- the step of separating the product or products of interest uses one or more distillations, according to a technology well known to those skilled in the art.
- the crushed lignocellulosic biomass particles enter through line 1 into washing zone 2 to carry out washing step b).
- the washing according to the invention is carried out by means of a washing water (water with a pH between 4 and 8.5) supplied by line 3.
- a first filtrate which corresponds to a free used washing water can optionally be separated by example by draining and collected by line 4.
- the washed lignocellulosic biomass is then subjected to step c) of solid / liquid separation (separation zone 5), which preferably involves pressing the wet pulp.
- this solid / liquid separation is carried out concomitantly with the transfer of the washed lignocellulosic biomass to the impregnation zone 6 in order to carry out step d) of the process.
- the solid / liquid separation produces a used washing water which is extracted through line 7 and a washed lignocellulosic substrate whose dry matter content is between 15% and 70% by weight.
- the waste washing water from lines 4 and 7 is optionally mixed in order to be recycled to the washing step via line 25.
- the washed lignocellulosic substrate is then sent to the impregnation zone 6 in which stage d) of impregnation of an acidic liquor is carried out, which is supplied via line 8.
- the impregnation is carried out in a reactor of impregnation at a temperature between 10 and 90 ° C and preferably at atmospheric pressure.
- the residence time of the lignocellulosic substrate in the impregnation reactor is usually 10 seconds to 180 minutes, preferably between 30 seconds and 60 minutes and even more preferably between 30 seconds and 15 minutes.
- the impregnation step is carried out in a single step with a dry matter content of between 1 and 30%.
- the solid / liquid separation preferably implements a pressing which is carried out concomitantly with the transport of the washed and impregnated lignocellulosic substrate to the pretreatment unit 1 1, for example by means of a screw of the "plug screw feeder" type. .
- the used acid liquor (or pressate resulting from the pressing) is recovered in line 9 and is optionally recycled to the impregnation zone 6.
- the impregnation of the acid liquor makes it possible to obtain a product having a dry matter content generally included. between 15 and 70% by weight and whose pH is between 0.1 and 3.
- the pretreatment unit 1 1 shown in Figure 1 implements a steam explosion process.
- the steam is supplied through line 12 while the expanded steam is drawn off through line 13 and is generally condensed in order to provide an acidic condensate.
- the pretreated lignocellulosic substrate is neutralized in the neutralization zone 14 which is supplied through line 15 with a neutralizing solution such as a basic solution.
- a neutralizing solution such as a basic solution.
- the neutralized substrate is then subjected to enzymatic hydrolysis carried out in zone 16 in the presence of an enzymatic cocktail provided by the 6 bis line suitable for hydrolyzing cellulose in particular into fermentable sugars (essentially glucose).
- the product of enzymatic hydrolysis is treated in a fermentation step in fermentation zone 17 in order to convert, in the presence of fermentation microorganisms supplied by line 17a, the sugars into products of interest such as a solvent and / or an alcohol.
- the fermentation step carried out in the presence of microorganisms can be an ethylic fermentation mainly producing ethanol, an ABE or IBE type fermentation.
- the fermentation must which is recovered at the outlet of the fermenter is treated in order to separate the products of interest.
- the recovery of the fermentation products is carried out by distillation by means of a column 18, in a manner known to those skilled in the art. From column 18, a stream 19 having concentrated the products of interest and a vinasse 20 is withdrawn.
- FIG. 2 represents a process diagram for the treatment of lignocellulosic biomass in which flows are represented which can be recycled to the stage of washing b) and of separation c) of the biomass, in addition to the external flow of washing water which is brought by line 3.
- part 21 of the spent acid liquor 9 can be recycled from the solid / liquid separation carried out in zone 10 before pretreatment 1 1, the other part 22 being purged or returned to step impregnation carried out in zone 6,
- the washing step can also use part 23 of the acid condensates 13 resulting from the pretreatment 1 1 while the other part 24 of the condensates is purged.
- part 23 of the acid condensates 13 resulting from the pretreatment 1 1 while the other part 24 of the condensates is purged.
- FIGs 3 and 4 similar to Figure 1, show a process diagram for the production of solvents and / or alcohols from lignocellulosic biomass comprising a step of washing the biomass b) in which the used washing water is not only recycled to the washing step, but also advantageously, in whole or in part, used in downstream steps. Indeed, this used washing water very rich in minerals (ash) can be advantageously used as a source of nutrients for microorganisms and yeasts.
- the pH of the wash water is between 4 and 8.5. Thus, depending on the pH, neutralization should be carried out, if necessary, if this water is intended for the production of enzymes or yeasts or to supplement the enzymatic hydrolysis or fermentation media.
- Figure 3 also shows the different possible uses of the used washing water drawn off by the lines 4 and / or 7. All or part of the used washing water 7 (and / or 4) can be directed to a optional treatment step 30, for example a pH adjustment and / or detoxification treatment step.
- the used washing water or the effluent from the treatment step 30 can be sent to the neutralization step of the pretreated lignocellulosic substrate 14 via line 31, to the enzymatic hydrolysis step of zone 16 via the line 32 and / or to the fermentation step 17 via line 33.
- Figure 4 illustrates the possibilities of using the waste washing water from step c) of separation in the enzyme and / or yeast production steps when they are integrated into the biomass treatment process.
- Figure 4 also shows a possible recycling of the used washing water in an optional washing step (partial or total) of the pretreated lignocellulosic substrate, this washing step being able to precede or follow the step of neutralization of the pretreated lignocellulosic substrate.
- FIG. 4 combines the two types of recycling (production of enzymes and / or yeasts and optional washing step). However, in the context of the invention, it is quite possible to carry out only one of the two types of recycling.
- the pretreated lignocellulosic substrate is sent to the washing step (additional step with respect to FIG. 3) carried out in zone 40, before the step of neutralization of zone 14. washing is provided by line 41. A juice containing soluble sugars and other components is recovered by line 42.
- This juice rich in sugars can be used for the production of enzymes carried out in zone 44 and / or of yeasts carried out in zone 45.
- the enzymes and yeasts produced are added respectively via lines 46 and 47 in step d. 'enzymatic hydrolysis in zone 16 and at the fermentation step in zone 17.
- the used washing water 7 (this is also the case, possibly washing water 4) can be treated in an optional treatment step 30 (detoxification and / or neutralization) and be directed all or in part by the lines 43 and 48 to the washing step 40 of the pretreated lignocellulosic substrate, in addition to or as a replacement for the washing water of the line 41.
- the spent washing water 7 (and possibly also the washing water 4) can also be sent to the enzyme production unit 44 via line 49 and / or to the yeast production unit 45 via the line. line 50.
- the washing water 4 and 7 can be mixed before or after the optional treatment step 30.
- the portion of the used washing water 7 which may not be recycled can be purged through line 26.
- the washing water 7 (and 4) resulting from the washing and the separation b) + c) of the invention can therefore be reintroduced at several stages of the process after the pretreatment and / or during the manufacture of the enzymes and / or of the yeasts, and possibly also partially recycled for washing step b). This choice depends on the type of installation (integrated or non-integrated production of enzymes and yeasts), the type of biomass, etc ... and can therefore fluctuate from one production cycle to another or within the same cycle.
- the neutralization and enzymatic hydrolysis steps are carried out in the same unit.
- the implementation of the step of washing the lignocellulosic biomass has the advantage of reducing the amount of acid required for the impregnation. This reduction therefore makes it possible to limit the additions of basic compounds for the stage of neutralization of the pretreated lignocellulosic substrate, which at the same time reduces the amount of salts formed.
- these salts in particular sulphates
- washing water whose pH is buffered, and which is then recycled, allows savings in terms of operating expenses, while avoiding pH shocks that are harmful to the functioning of microorganisms and enzymes. , as well as for the survival of yeasts.
- the reuse of used washing water is very flexible in implementation depending on the various installation configurations, and brings real gain to very specific stages of the process downstream to the pre-treatment. Examples
- Example 1 Determination of residual acidity in liquors prepared according to the prior art and according to the invention.
- the same crushed straw (30 g) is brought into contact with water at 60 ° C. for 3 minutes simulating a washing of the biomass.
- the dry matter content (DM) is 10% by weight in this mixture.
- the medium is then separated by pressing so as to recover a washed straw and a used washing water (filtrate).
- Experimental losses are noted: less than 0.02% losses during contact with water and around 5% mass losses during separation, linked to the experimental setup (2.2% on a DM basis) .
- Example 2 Readjustment of the pH for recycling liquors prepared according to the prior art and according to the invention
- Example 1 The crushed straw of Example 1 is contacted with water at 60 ° C for 60 min.
- the MS content is 10% by weight in this mixture.
- the medium is then separated by a solid / liquid separation making it possible to recover a washed straw and a washing water (filtrate).
- the experimental losses were nearly 12% mass losses during soaking (certainly by evaporation) and approximately 3% mass losses during separation, linked to the experimental setup.
- the MS balance of the preparation is 96.6%.
- the pH of the used liquors L2 and L4 was readjusted to a target value of 1, 2 by adding a solution of H 2 S0 4 at 0.05 M.
- the evolution of the pH as a function of the volume added is presented on FIG. 6, with, on the abscissa, the number of ml of 0.05M H2SO4 solution per ml of sample.
- the waste liquor prepared according to the invention (Liquor L4) requires a lower amount of acid than the waste liquor obtained after impregnation of unwashed biomass (Liquor L2) to lower its pH, in particular for recycling.
- Example 3 Biomass analyzes before and after the sequence of the impregnation and pretreatment steps (prior art)
- This crushed straw was then pretreated according to a process of the prior art: steam explosion preceded by acid impregnation, with total recycling of the used impregnation liquor.
- the crushed straw is conveyed into an impregnation tool by means of a plug-screw type screw.
- the straw flow rate is 2820 kg / hour, or 2600 kg dry / hour. It is relaxed in a bed of acid liquor and conveyed vertically into the impregnation tool, from which it emerges full of impregnation liquor.
- a vat of acidic liquor is used for the preparation of the liquor which continuously feeds the impregnation tool in order to renew the inventory and maintain the level constant.
- This impregnated straw is then conveyed to a steam explosion tool.
- Example 4 Analysis of biomasses before and after the sequence of the washing, impregnation and pretreatment steps (in accordance with the invention) A wheat straw harvested in 2013 was crushed and then analyzed after crushing. The copper, zinc, magnesium and manganese mineral contents of this batch of straw B are reported in the following table 5, expressed in mg of the element / kg dry straw:
- This crushed straw was then pretreated according to a process according to the invention: washing the biomass with an aqueous solution, then acid impregnation followed by a steam explosion, with total recycling of the used impregnation liquor.
- the crushed straw is sent to a first washing step.
- the straw flow rate is 2,920 kg / hour, or 2,600 kg dry / hour.
- the crushed straw is brought into contact with an aqueous solution of pH 5 for a period of 8 minutes in a rotary tool allowing washing and simultaneous draining of the straw.
- step b) of washing and step c) of liquid / solid separation are carried out in the same tool.
- a first wash stream is extracted from the rotary tool and the drained straw is conveyed to the next impregnation step. It is introduced into the impregnation tool by means of a "plug-screw" type screw.
- step c) Due to the high humidity of the drained straw, the compression in this screw generates a second washing flow: there is therefore here a separation according to step c) in two operations.
- the straw After this solid / liquid separation, the straw has a dry matter content of 55%. It is relaxed in a bed of acid liquor and conveyed vertically into the impregnation tool from which it emerges full of impregnation liquor. A vat of acidic liquor is used for the preparation of the liquor which continuously feeds the impregnation tool in order to renew the inventory and maintain the level constant.
- This impregnated straw is then conveyed to a steam explosion tool. It is introduced into this tool by means of a "plug-screw" type screw.
- the used liquor is expelled (called pressât).
- This liquor is recycled to the acid liquor preparation tank for 95% of its mass flow, and the remaining 5% feeds the aqueous washing solution preparation tank.
- the acid liquor preparation tank is also supplied with water and sulfuric acid H 2 S0 4 , in order to compensate for the loss of the fraction of liquor which is exported with the straw in the steam explosion tool.
- the tank for preparing the aqueous washing solution is supplied with waste liquor and water. After a short cooking time in the reactor, the impregnated and cooked straw is relaxed at the reactor outlet. The mixture of solid, liquid and vapor is separated in a cyclone, allowing the vapor to be separated from the solid / liquid mixture. This solid / liquid mixture constitutes the pretreated straw.
- the conditions applied for washing are chosen to approximate the conditions of dilute static impregnation (i.e. 8% DM on the straw):
- the average flow rate of the acid solution is reported, the fluctuations are 10% around this average flow rate (minimum 58 kg / h, maximum 72 kg / h).
- Example 5 Demonstration of the beneficial effect of minerals on the growth of yeast-type microorganisms
- Example 4 A sample of washed and pretreated straw produced according to Example 4 was used for laboratory work. First, this sample was subjected to a solid / liquid extraction to extract a sweet juice containing 65 g / kg of glucose and xylose sugars.
- This juice was then used as a substrate for a laboratory yeast propagation test.
- the tests are carried out in a baffle flask with a total volume of 250mL, fitted with cellulose stoppers allowing air to pass and placed on a shaken table. Temperature and pH are regulated to the same setpoint for all tests.
- the extracted juice is supplemented:
- composition of the mineral cocktail is given in Table 7 below:
- the juices are inoculated with a yeast of the Saccharomyces cerevisiae type genetically modified to assimilate xylose (C5 sugar), in addition to the natural assimilation of glucose.
- the inoculation is done at the same content on the tests, and the monitoring of cell growth is carried out by measuring the absorbance (OD at 600 nm) during the test, and by measuring the insolubles on a sample for the final time of the test.
- Figure 7 shows the monitoring of absorbance A as a function of time expressed in hours, for test 1, which is represented by squares, and for test 2, which is represented by triangles.
- the final yeast contents are 13.3 g / kg for test 1, against 17 g / kg for test 2. A beneficial impact of minerals on the growth of this Saccharomyces type yeast is thus demonstrated. .
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CA3125497A CA3125497A1 (fr) | 2019-01-24 | 2020-01-20 | Procede de traitement d'une biomasse lignocellulosique |
CN202080010609.0A CN113614239A (zh) | 2019-01-24 | 2020-01-20 | 处理木质纤维素生物质的方法 |
BR112021012936-7A BR112021012936A2 (pt) | 2019-01-24 | 2020-01-20 | Método de tratamento de uma biomassa lignocelulósica |
EP20701442.4A EP3914723A1 (fr) | 2019-01-24 | 2020-01-20 | Procédé de traitement d'une biomasse lignocellulosique |
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FR3069248A1 (fr) * | 2017-07-19 | 2019-01-25 | IFP Energies Nouvelles | Procede de traitement de biomasse ligno-cellulosique . |
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FR2974115B1 (fr) * | 2011-04-14 | 2015-12-11 | IFP Energies Nouvelles | Procede de production d'ethanol et de solvants a partir de biomasse lignocellulosique avec recyclage d'un vin ethylique issu de la fermentation des pentoses |
FR3000106B1 (fr) * | 2012-12-20 | 2015-01-30 | Ifp Energies Now | Procede de production d'oligosaccharides a partir de biomasse lignocellulosique |
US10590449B2 (en) * | 2015-06-09 | 2020-03-17 | GranBio Intellectual Property Holdings | Hydrothermal-mechanical treatment of lignocellulosic biomass for production of fermentation products |
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2019
- 2019-01-24 FR FR1900597A patent/FR3092118B1/fr active Active
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2020
- 2020-01-20 EP EP20701442.4A patent/EP3914723A1/fr active Pending
- 2020-01-20 CN CN202080010609.0A patent/CN113614239A/zh active Pending
- 2020-01-20 BR BR112021012936-7A patent/BR112021012936A2/pt unknown
- 2020-01-20 US US17/425,418 patent/US20240026388A1/en active Pending
- 2020-01-20 CA CA3125497A patent/CA3125497A1/fr active Pending
- 2020-01-20 WO PCT/EP2020/051289 patent/WO2020152105A1/fr active Application Filing
- 2020-01-21 AR ARP200100144A patent/AR117854A1/es unknown
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US8456633B2 (en) | 2001-12-21 | 2013-06-04 | Malvern Instruments Incorporated | Spectrometric process monitoring |
US8545633B2 (en) | 2009-08-24 | 2013-10-01 | Abengoa Bioenergy New Technologies, Inc. | Method for producing ethanol and co-products from cellulosic biomass |
US20130236941A1 (en) * | 2012-03-12 | 2013-09-12 | Cobalt Technologies Inc. | Integrated Biorefinery |
FR3069248A1 (fr) * | 2017-07-19 | 2019-01-25 | IFP Energies Nouvelles | Procede de traitement de biomasse ligno-cellulosique . |
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SE2250042A1 (en) * | 2022-01-19 | 2023-07-20 | Valmet Oy | Method and system for processing biomass material |
WO2023140766A1 (fr) * | 2022-01-19 | 2023-07-27 | Valmet Ab | Procédé et système de traitement d'un matériau de biomasse |
Also Published As
Publication number | Publication date |
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CA3125497A1 (fr) | 2020-07-30 |
FR3092118B1 (fr) | 2024-05-31 |
EP3914723A1 (fr) | 2021-12-01 |
AR117854A1 (es) | 2021-09-01 |
FR3092118A1 (fr) | 2020-07-31 |
US20240026388A1 (en) | 2024-01-25 |
BR112021012936A2 (pt) | 2021-09-14 |
CN113614239A (zh) | 2021-11-05 |
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