EP4189102A1 - Method for producing a sugar syrup from a residual lignocellulosic biomass - Google Patents

Method for producing a sugar syrup from a residual lignocellulosic biomass

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Publication number
EP4189102A1
EP4189102A1 EP21773127.2A EP21773127A EP4189102A1 EP 4189102 A1 EP4189102 A1 EP 4189102A1 EP 21773127 A EP21773127 A EP 21773127A EP 4189102 A1 EP4189102 A1 EP 4189102A1
Authority
EP
European Patent Office
Prior art keywords
syrup
sugar syrup
lignocellulosic biomass
glucose
fermentable sugars
Prior art date
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Application number
EP21773127.2A
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German (de)
French (fr)
Inventor
Benjamin PERCHERON
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Suez International SAS
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Suez International SAS
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Filing date
Publication date
Application filed by Suez International SAS filed Critical Suez International SAS
Publication of EP4189102A1 publication Critical patent/EP4189102A1/en
Pending legal-status Critical Current

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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
    • 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
    • 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
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/44—Polycarboxylic acids
    • C12P7/46—Dicarboxylic acids having four or less carbon atoms, e.g. fumaric acid, maleic acid
    • 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
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/52—Propionic acid; Butyric acids
    • 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
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/54—Acetic acid
    • 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
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
    • C12P7/56—Lactic acid
    • 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
    • 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
    • C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00—Microorganisms ; Processes using microorganisms
    • C12R2001/01—Bacteria or Actinomycetales ; using bacteria or Actinomycetales
    • C12R2001/145—Clostridium
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00—Microorganisms ; Processes using microorganisms
    • C12R2001/01—Bacteria or Actinomycetales ; using bacteria or Actinomycetales
    • C12R2001/185—Escherichia
    • C12R2001/19—Escherichia coli
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    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12R—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES C12C - C12Q, RELATING TO MICROORGANISMS
    • C12R2001/00—Microorganisms ; Processes using microorganisms
    • C12R2001/645—Fungi ; Processes using fungi
    • C12R2001/85—Saccharomyces
    • C12R2001/865—Saccharomyces cerevisiae
    • 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

  • TITLE METHOD FOR PRODUCTION OF A SUGAR SYRUP FROM RESIDUAL LIGNOCELLULOSIC BIOMASS
  • the invention relates to the field of the production of fermentable sugars and relates to the use of waste lignocellulosic resources, for example of the paper/cardboard type, as a substrate for a process for preparing said sugars.
  • the invention describes in particular the process used for the preparation of the raw material and its treatment allowing the production of a sugar syrup, in particular of a purified glucose syrup which can be used as a raw material, in particular in the biofuels industry or biotechnologies.
  • the invention relates to a method for producing a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, from lignocellulosic biomass comprising paper waste, in particular printable paper, printed paper , graph paper, wrapping paper or cardboard.
  • the invention also relates to a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, which can be obtained by said process.
  • the use of the process for producing biosourced molecules or biofuels, preferably ethanol, as well as a process for producing biofuels, in particular ethanol, are also objects of the present invention.
  • the lignocellulosic biomass mainly used as a source of fermentable sugars today on a pilot and industrial scale is the so-called 2G (second generation) biomass, i.e. a plant-type biomass, such as the residues of forestry and agricultural industry (wheat straw, corn cobs and sugarcane bagasse) (Nizami et al., 2017).
  • 2G second generation biomass
  • thermochemical and/or mechanical means By thermochemical and/or mechanical means.
  • Non-biological processes include: concentrated acid processes, gasification, hydropyrolysis and pyrolysis.
  • the first step consists in pretreating the biomass, in order to increase the digestibility of the cellulose and the release of monomeric sugars (mainly glucose).
  • monomeric sugars mainly glucose
  • Processes using biological hydrolysis can be classified into 4 sub-categories, depending on whether or not they include the basic steps of the process (Parisutham et al., 2014):
  • CBP Consolidated Bioprocessing
  • the advantage of implementing a combined process such as SSF, SSCF or CBP is to be able to reduce the number of steps and reactors by bringing together the enzyme(s) capable of depolymerizing the cellulose and the (s) microorganism(s) capable of converting simple sugars into a molecule of interest. This generally makes it possible to reduce the necessary investment and therefore the production cost of the target molecule.
  • the process is developed and optimized specifically for a molecule and a given market. This type of process usually involves genetically modified microorganisms.
  • patent application CN 106520861 implements enzymatic hydrolysis with dilute acid pretreatment.
  • Patent application CN102382909 uses acid hydrolysis with successive use of dilute acid and concentrated acid.
  • the patent application JP2006088136 implements a fine pulverization of the biomass by mechanical pretreatment, without acid cooking.
  • Patent application US2010/0009422 describes a process for preparing ethanol comprising in particular a step of thermal pretreatment with high temperature steam.
  • the object of the invention is to hydrolyze the cellulose and, where appropriate, the hemicellulose contained in the residual lignocellulosic biomass without having recourse to cumbersome pre-treatment and purification processes, thus making it possible to reduce impurities, operational costs linked to the use of chemical catalysts, to simplify the subsequent so-called “downstream processing” stages (eg stages of clarification, purification and concentration), while obtaining an optimum mass yield.
  • the object of the invention is in particular to develop a method for producing a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, from lignocellulosic biomass comprising paper waste, in particular printable paper waste. , printed paper or cardboard.
  • Another object of the invention is to enhance said sugar syrup by producing biosourced molecules or biofuels, preferably ethanol.
  • Another object of the invention is to obtain a platform molecule with high added value (sugars or other) from paper-cardboard waste, and in particular useful for the production of biofuels and chemical molecules with low environmental impact and low cost.
  • the invention relates to a method for producing a sugar syrup comprising fermentable sugars from lignocellulosic biomass comprising paper waste, said method comprising in particular the following steps: a. optionally a step of grinding said lignocellulosic biomass; b. i. an impregnation step and ii. a step of thermal pretreatment of the lignocellulosic biomass, said steps of impregnation and thermal pretreatment being carried out simultaneously or successively according to i. then ii. ; vs. an enzymatic hydrolysis step of the pretreated product; and D. a step for recovering the sugar syrup comprising fermentable sugars.
  • the invention relates to a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, which can be obtained by the process according to the invention.
  • the invention relates to the use of the process or the syrup according to the invention to produce biosourced molecules or biofuels, preferably ethanol.
  • the invention relates to a method for producing biofuels, in particular ethanol.
  • the invention relates to a method for producing a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, from lignocellulosic biomass comprising paper waste, in particular printable paper, printed paper or cardboard.
  • said method comprising the following steps: a. optionally, a step of grinding said lignocellulosic biomass comprising paper waste; bi a step of impregnating said lignocellulosic biomass comprising paper waste or crushed lignocellulosic biomass obtained at the end of step a. in an aqueous medium, preferably in water and at room temperature, and ii.
  • a heat pretreatment step implemented in the absence of addition of acid, at a temperature between 80°C and 150°C, preferably between 90°C and 130°C, more preferably at 100° C. or 120° C., at a pH of between 6.5 and 8.5, in particular between 6.5 and 8, in particular at a pH of between 6.8 and 7.5, preferably at a neutral pH, in order to obtain a pretreated product, said impregnation and heat pretreatment steps being carried out simultaneously or successively according to i. then ii.; vs. a step of enzymatic hydrolysis of the pretreated product obtained at the end of step b.
  • step c in order to convert cellulose and hemicellulose into a sugar syrup comprising fermentable sugars, in particular into a syrup comprising glucose; and D. a step for recovering the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, obtained at the end of step c.
  • the invention relates to a process for producing a syrup comprising glucose from lignocellulosic biomass comprising paper waste, in particular printable paper, printed paper or cardboard comprising the following steps: a. optionally, a step of grinding said lignocellulosic biomass comprising paper waste; b. i. a step of impregnating said lignocellulosic biomass comprising paper waste or crushed lignocellulosic biomass obtained at the end of step a. in an aqueous medium, preferably in water and at room temperature, and ii. a heat pretreatment step implemented in the absence of acid addition, at a temperature between 80° C.
  • steps of impregnation and thermal pretreatment being carried out simultaneously or successively according to i. then ii. ; vs. a step of enzymatic hydrolysis of the pretreated product obtained at the end of step b. to convert cellulose and hemicellulose into a syrup comprising glucose; and D. a step for recovering the syrup comprising the glucose obtained at the end of step c.
  • sucrose syrup refers to a viscous and thick liquid comprising sugars in solution.
  • sugar syrup can be interchanged with the term “sweetened juice”.
  • the sugar syrup comprising glucose also comprises xylose, in a lower proportion with respect to glucose.
  • the sugar syrup comprises 70 to 85% glucose and 10 to 15% xylose.
  • the term “fermentable sugars” refers to simple sugars or their mixtures, for example glucose, fructose, arabinose, mannose, galactose, xylose. These “simple sugars” are likely to be fermented under the action of yeasts or bacteria to produce alcohol. These are in particular monosaccharides (/.e. sugars comprising 5 or 6 carbon atoms), in particular a hexose, such as glucose.
  • the “fermentable sugars” refer to fermentable monomeric sugars, ie comprising a single unit. Even more preferably, the "fermentable sugars" comprise or consist essentially of glucose and in a lesser proportion of xylose.
  • the term “lignocellulosic biomass” refers to a substrate essentially consisting of cellulose (from 30 to 70%), hemicellulose (from 5 to 35%) and lignin (from 5 to 25% ) determined with respect to the dry mass of the lignocellulosic biomass.
  • the lignocellulosic biomass is a substrate essentially consisting of cellulose (from 30 to 70%), hemicellulose (from 5 to 25%) and lignin (from 5 to 25%).
  • the lignocellulosic biomass is a substrate essentially consisting of cellulose (from 30 to 70%), hemicellulose (from 5 to 20%) and lignin (from 5 to 20%).
  • the lignocellulosic biomass is a substrate essentially consisting of cellulose (from 30 to 70%), hemicellulose up to 18% and lignin up to 19%.
  • Cellulose is a polymer of glucose, i.e. hexose
  • hemicellulose is a polysaccharide consisting essentially of pentoses (e.g. xylose and arabinose) and glucose
  • lignin is a macromolecule rich in phenolic units.
  • Cellulose is the main source of fermentable sugars.
  • the "lignocellulosic biomass" used in the invention comprises paper waste.
  • the papermaking waste may have been recycled several times, for example up to 7 times, and the average size of the fibers contained in this papermaking waste is generally between 0 mm and 2 mm, preferably between 0.1 mm and 1.5 mm .
  • the substrate providing the lignocellulosic biomass consists of paper waste.
  • the substrate providing the lignocellulosic biomass comprises paper waste and a co-substrate.
  • the substrate providing the lignocellulosic biomass comprises paper waste and is contained in or constituted by a more complex waste such as the Fermentable Fraction of Household Waste (FFOM).
  • FFOM Fermentable Fraction of Household Waste
  • the level of cellulose in the FFOM is less than 50%, for example from 10 to 40% by weight.
  • the SWOT and more generally the household waste in which it is contained are of variable composition depending on the regions considered in the world.
  • the SWOTs can be implemented within the framework of the invention to provide the lignocellulosic biomass to be treated insofar as their content of cellulose, hemicellulose and lignin, in particular by the contribution permitted by the papermaking waste, provides a substrate whose composition falls within the proportions defined above.
  • a SWOT capable of being treated in accordance with the invention comprises 10% to 20% by weight of paper and/or from 8% to 15% by weight of corrugated and flat cardboard and/or between 3 and 6% by weight of textiles and/or between 15 and 25% by weight of sanitary textiles (considered as dissociated from other textiles), for example around 13%, 10%, 4.6% and 21% by weight respectively, these proportions being determined as a percentage of the dry mass of SWOT considered.
  • the remaining fraction of the SWOT is made up of food waste (from 60% to 80%), if necessary also associated with garden waste, or other types of fibers such as wood residues.
  • the waste constituting the FFOM can be used as a lignocellulosic substrate for carrying out the methods of the invention.
  • household waste can also contain composites, plastics, unclassified fuels, glass, metals, unclassified incombustibles and a minority part of hazardous waste. These non-fermentable wastes are normally discarded in the mechanobiological sorting process allowing the production of the SWOT.
  • the SWOT can therefore be defined by considering how it is obtained: it is the result of the mixed collection of household waste, followed by a mechanical-biological separation stage to retain only the fine organic fraction of this waste.
  • the substrate providing the lignocellulosic biomass comprises paper mill waste and SWOT as co-substrate.
  • the lignocellulosic biomass may alternatively or also comprise residues of plant type.
  • plant-type lignocellulosic biomass are residues from the forestry and agricultural industry such as wheat straw, corn cobs and sugar cane bagasse, residues from the agro-food industry.
  • the proportions respectively of hemicellulose and lignin by weight of the dry matter of the total biomass in the mixture are respectively less than 19% and 18%.
  • the lignocellulosic biomass comprises only little (in% by weight of the dry matter) or no plant-type waste from the forestry or agricultural industry.
  • paper waste comprises or essentially consists of paper and cardboard waste.
  • paper and cardboard waste corresponds to a mixture of paper and cardboard waste, said mixture possibly comprising by weight relative to the weight of the dry matter of the waste between 5 and 60% of gray cardboard, between 5% and 60%, in particular between 10 and 20% by weight of printed paper of the office paper type and between 5% and 100% of corrugated cardboard
  • the paper waste is chosen from the group consisting of paper (in particular printed or printable paper), cardboard, in particular newsprint, magazines and stationery sludge.
  • This waste may contain undesirable impurities such as plastics and metals, as well as constituents of inks, said impurities being present in very small quantities.
  • the paper waste is a mixture of lignocellulosic waste (of the cardboard paper type) of low quality in the following average proportions by weight of the total dry matter (+/- 5%, the percentage total not exceeding 100%):
  • said lignocellulosic biomass before grinding and / or impregnation ie "raw" lignocellulosic biomass consists of paper waste and has a total dry matter content of between 70% and 100%, in particular between 85% and 96% by weight of the biomass.
  • said lignocellulosic biomass before grinding and / or impregnation ie "raw" lignocellulosic biomass consists of FFOM and has a total dry matter content of between 45% and 55%, for example, in particular around 50% by weight of the biomass.
  • the total dry matter content varies between 50 and 96% by weight of the biomass depending on the proportions of substrate and of added co-substrate.
  • the impregnation step (also called pulping) b.i. makes it possible to obtain a relatively homogeneous suspension with no dry and/or floating agglomerates. Indeed, the agglomerates are generally less well or even not hydrolyzed in step c. subsequent enzymatic hydrolysis.
  • the impregnation step b.i. is carried out for a period of between 5 and 30 minutes, preferably for 15 minutes.
  • the impregnation step b.i. may include agitation.
  • mixing may be implemented until the disappearance of the floating blocks, in particular larger than 10 cm, disappearance which may be determined by a visual check carried out at predetermined and/or regular intervals in the reactor.
  • the impregnated biomass obtained at the end of step b.i. typically has a total dry matter content of between 5% and 30%, in particular between 10% and 20%.
  • said method may comprise a step a. grinding said raw lignocellulosic biomass comprising paper waste.
  • the lignocellulosic biomass is supplied in the form of paper waste.
  • the lignocellulosic biomass is supplied in the form of Fermentable Fraction of Household Waste (FFOM).
  • FFOM Fermentable Fraction of Household Waste
  • said method does not include a step of grinding said lignocellulosic biomass comprising paper waste. This allows a better tolerance with respect to the quality of the incoming biomass, plastic or metallic impurities not affecting the efficiency or the smooth running of the process.
  • the lignocellulosic biomass undergoes a thermal pretreatment in order to increase its reactivity to enzymatic hydrolysis and the accessibility of cellulose to enzymes.
  • a chemical agent of the acid or base type is usually added to the lignocellulosic biomass to improve (catalyze) the release of the cellulose.
  • a chemical catalyst generates significant nuisances in terms of purification, strongly impacting the economic viability of the sector.
  • the thermal pretreatment step b.ii. is implemented in the absence of addition of acid, preferably in the absence of chemical catalyst. This makes it possible to avoid the generation of inhibitory molecules (in particular for the fermentation step), to reduce the operational costs linked to the use of these chemical catalysts as well as the complexity of the "downstream processing" solutions, while obtaining a yield optimum mass.
  • the thermal pretreatment step b.ii. is carried out at a pressure of between 1 and 5 bars, preferably between 1.5 and 3 bars, more preferably at a pressure equal to approximately 2 bars.
  • the heat pretreatment step b.ii. is carried out for a period of between 10 minutes and 120 minutes, preferably between 10 minutes and 60 minutes, more preferably for 30 minutes.
  • Said steps of impregnation bi and of thermal pretreatment b.ii can be carried out simultaneously or successively, in particular depending on the compactness of the lignocellulosic biomass.
  • steps of impregnation bi and heat pretreatment b.ii. are carried out simultaneously, these two steps can be implemented for a total duration of between 10 minutes and 120 minutes, preferably between 10 minutes and 60 minutes, more preferably for 30 minutes.
  • the impregnation step b.i. and the heat pretreatment step b.ii. are carried out simultaneously, e.g. within the same reactor, in particular in the presence of very loose lignocellulosic biomasses such as uncompacted paper.
  • the impregnation step b.i. and the heat pretreatment step b.ii. are carried out successively, e.g. in two different reactors.
  • the impregnation step b.i. is therefore followed by a thermal pretreatment step b.ii.
  • the homogenization of the biomass is then better controlled in the impregnation step. This has the advantage of making the biomass more homogeneous and more accessible for the effect of the enzymes, while ensuring the inactivation of the microorganisms (in particular bacteria) present initially.
  • the pretreated product obtained at the end of step b. may also be referred to by the term “dough” or “slurry”. This means, for example, that pieces of paper or cardboard are no longer visible to the naked eye.
  • step b. may be followed by a freezing and/or thawing and/or pasteurization step in order to limit the risks of contamination in the subsequent enzymatic hydrolysis step, which could lead to yield reductions.
  • the enzymatic hydrolysis step c. is carried out by means of an enzymatic cocktail such as a mixture of cellulolytic and/or hemicellulolytic enzymes, in particular a mixture of cellulases and hemicellulases.
  • an enzymatic cocktail such as a mixture of cellulolytic and/or hemicellulolytic enzymes, in particular a mixture of cellulases and hemicellulases.
  • the cellulases can be chosen from the group consisting of endocellulases, exocellulases, b-glucosidases and mixtures thereof.
  • the hemicellulases can be chosen from the group consisting of xylanases, xylosidases, endoglucanases, endoxylanases, endoxylanases and b-xylosidases, as well as certain arabinofuranosidases and esterases, and mixtures thereof.
  • the mixture of cellulolytic and/or hemicellulolytic enzymes is chosen from Ctech3® (Novozymes), Deltazym® (WeissBioTech) and Isobake CX®, more preferably Ctech3®.
  • the hydrolysis step c. is implemented using between 10 and 60 mg of enzymes per g of biomass, preferably between 10 and 60 mg of enzymes per g of cellulose, more preferably between 15 and 25 mg of enzymes per g of cellulose .
  • the yield of the enzymatic hydrolysis is between 40% and 80%, typically between 60% and 70%.
  • the Yield is calculated as the ratio of the amount of monomeric sugar released to the total molar amount initially available.
  • This enzymatic hydrolysis step c hydrolyzes sugars from both cellulosic and hemicellulose fractions.
  • step c. comprises a preliminary step of adjusting the pH in order to obtain an acid pH, for example a pH of approximately 5.
  • the pretreated product obtained at the end of step b. optionally frozen and/or thawed and/or pasteurized, generally has a basic or neutral pH, so that the pH adjustment is generally carried out by means of adding an acid such as sulfuric acid or phosphoric acid, preferably sulfuric acid.
  • the sugar syrup generated after enzymatic hydrolysis contains a lower mineral load, facilitating the purification steps and creating no fermentation inhibitor complex such as Furfural or HMF, while allowing increased yields of sugar release.
  • the sugar syrup comprising fermentable sugars in particular the syrup comprising glucose, recovered at the end of step d. has at least one of the following characteristics:
  • - a total dry matter content of between 5% and 25%, preferably between 5% and 20%, in particular between 10% and 20% by weight;
  • - a ratio of glucose to total sugars of between 60% and 90%, preferably between 80% and 90% by weight of the dry matter.
  • the dry matter content represents all the dry matter present in the product, measured for example according to the protocol described in the ISO 6731 standard.
  • the free glucose content represents the quantity of glucose (in dry mass) relative to the total quantity of material (also in dry mass) present in the product, this parameter being conventionally measured in the liquid phase by HPLC or by an equivalent analytical method then estimated by calculation.
  • said method further comprises the following steps: e. a step of clarifying the sugar syrup comprising fermentable sugars, in particular syrup comprising glucose, recovered at the end of step d. in order to separate the solid residues from the liquid residues, said step of clarifying preferably comprising a step of screening, sieving and/or settling and/or centrifugation; f. a purification step, preferably on activated carbon, of the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, obtained at the end of step e. ; and g. a step for recovering the sugar syrup comprising fermentable sugars, in particular syrup comprising purified glucose obtained at the end of step f.
  • the clarification step e. comprises a sieving and/or decantation and/or centrifugation step.
  • the clarification step e. includes a step of sieving, settling and centrifugation.
  • the purification step f. makes it possible to eliminate residual suspended matter, such as some of the ions and/or salts, and to capture certain soluble contaminants such as metallic salts and ink residues.
  • the purification step f. is carried out by filtration on activated carbon.
  • activated carbon usable in step f. are Colorsorb 620 powder (Jacobi), BGX granular (Chemviron), CPW powder (Chemviron), CXV (old coal).
  • said method further comprising: h. a step of concentrating, preferably by means of a vacuum evaporator, more preferably by means of a forced recirculation or falling film thin film evaporator, the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, purified obtained at the end of step f. or g. ; and i. a step for recovering the sugar syrup comprising fermentable sugars, in particular syrup comprising glucose, purified and concentrated obtained at the end of step h.
  • the concentration step makes it possible in particular to ensure the stability of the product by reducing the risk of development of contamination (bacterial in particular).
  • the sugar syrup comprising fermentable sugars in particular the syrup comprising glucose, recovered at the end of step g. or i., has at least one of the following characteristics:
  • - a free glucose content of between 60% and 75%, typically between 65% and 70% by weight of the dry matter; - a ratio of glucose to total sugars of between 70% and 90%, typically between 75% and 85%, in particular 80% by weight of the dry matter.
  • the method for producing a syrup comprising glucose from lignocellulosic biomass comprising paper waste comprises the following steps: a. optionally, a step of grinding said lignocellulosic biomass comprising paper waste; b. i. a step of impregnating said lignocellulosic biomass comprising paper waste or crushed lignocellulosic biomass obtained at the end of step a. in an aqueous medium, preferably in water and at room temperature, and ii.
  • a heat pretreatment step carried out in the absence of acid addition, at a temperature between 80°C and 150°C, preferably between 90°C and 130°C, more preferably at 100°C C or 120° C., at a pH of between 6.5 and 8.5, in particular between 6.5 and 8, in particular at a pH of between 6.8 and 7.5, preferably at a neutral pH, in order to obtain a pretreated product, said steps of impregnation and thermal pretreatment being carried out simultaneously or successively according to i. then ii.; vs. a step of enzymatic hydrolysis of the pretreated product obtained at the end of step b. to convert cellulose and hemicellulose into a syrup comprising glucose; d.
  • a step for recovering the syrup comprising glucose obtained at the end of step c e. a syrup clarification step comprising glucose recovered at the end of step d. in order to separate the solid residues from the liquid residues, said clarification step preferably comprising a step of screening, sieving and/or decantation and/or centrifugation; f. a step of purification on activated carbon of the syrup comprising glucose obtained at the end of step e. ; g. a step for recovering the syrup comprising purified glucose obtained at the end of step f; h.
  • a concentration step preferably by means of a vacuum evaporator, more preferably by means of a forced recirculation or falling film thin film evaporator, of the syrup comprising purified glucose obtained at the end of the step g. ; and i. a step for recovering the syrup comprising glucose, purified and concentrated obtained at the end of step h.
  • the invention also relates to a sugar syrup comprising fermentable sugars, in particular syrup comprising glucose, which can be obtained by the process according to the invention, characterized in that the said syrup has:
  • HMF hydroxymethylfurfural
  • Said syrup may comprise constituents other than glucose, said constituents being present in proportions of between 10% and 30% by weight of the dry matter.
  • constituents are sugars such as xylose, galactose, arabinose, mannose, traces of solvent, traces of ash.
  • the invention also relates to the use of the method according to the invention, or of the syrup according to the invention to produce biosourced molecules.
  • biosourced molecules are: sugars (monosaccharides), ethanol, isobutene, 1,3-propanediol, 2,3-butanediol, 3-hydroxypropionic acid, acetic acid, butyric acid, capric acid, citric acid, fumaric acid, malic acid, propionic acid, pyruvic acid, succinic acid, levulinic acid, 2,5-furandicarboxylic acid, sorbitol, and xylitol.
  • lactic acid Xu et al., 2014, Yadav et al., 2020
  • lactic acid acetic acid Kondo et al., 1996)
  • butyric acid Flu et al., 2017
  • propionic acid Wang et al., 2013
  • succinic acid Ong et al., 2019
  • l isopropanol Frerreira dos Santos Vieira et al., 2020
  • isobutene US20180057843, US9249430, WO2014086781
  • butanol Choeng et al., 2019; Birgen et al., 2019
  • farnesane W02007139924, W0200886781)045555) .
  • biosourced molecules according to the invention are preferably chosen from the group consisting of lactic acid, acetic acid, butyric acid, proprionic acid, succinic acid, isopropanol and isobutene, even more preferably from the group consisting of lactic acid, acetic acid, butyric acid, proprionic acid and isopropanol.
  • the invention also relates to the use of the process according to the invention, or of the syrup according to the invention to produce biofuels, preferably ethanol.
  • the invention also relates to a method for producing biofuels, in particular ethanol, comprising the steps of the method according to the invention and a subsequent fermentation step in order to convert the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, recovered at the end of step g. Yes. into biofuels, especially ethanol.
  • the fermentation step is carried out using yeasts and/or bacteria.
  • the yeasts can be chosen from the group consisting of yeasts of the genus Saccharomyces, Yarrowia and Leuconostoc.
  • the bacteria can be chosen from the group consisting of bacteria of the genus Bacillus, Lactobacillus, Acetobacter, Escherichia, Clostridium and Zymomonas.
  • the fermentation step is carried out using yeasts of the genus Saccharomyces, preferably Saccharomyces cerevisiae.
  • the bacteria can be chosen from Clostridium acetobutylicum or Escherichia coli.
  • the yeasts or the bacteria are chosen for their ability to carry out the alcoholic fermentation.
  • the fermentation step according to the invention can be carried out using yeasts and/or bacteria capable of fermenting both hexoses and pentoses.
  • This fermentation step converts the sugars from both cellulosic and hemicellulosic fractions into biofuels, in particular ethanol.
  • This fermentation step can take place before the subsequent so-called “downstream Processing” steps, that is to say in particular before the clarification steps e., purification steps f. or concentration h.
  • the fermentation step is carried out in a separate reactor from that of the enzymatic hydrolysis step (SHF process) or simultaneously in the same reactor (SSF, SSCF, CBP processes) , preferably in a separate reactor from that of the enzymatic hydrolysis step (SHF process).
  • the method may comprise, after the fermentation step, a step for purifying the biosourced molecule or the biofuel, for example by distillation, in particular in the case of ethanol, the distillation step being whether or not preceded by a clarification step.
  • Example 1 Sugar syrup obtained at the end of the thermal pretreatment and enzymatic hydrolysis stages.
  • the sugar syrup obtained at the end of the enzymatic hydrolysis step c. of the process according to the invention has the following characteristics:
  • Table 1 below indicates the composition of this sugar juice.
  • Example 2 Sugar syrup obtained at the end of the solid/liquid separation (clarification), purification and concentration stages.
  • the sugar syrup obtained at the end of step i. of the process according to the invention has the following characteristics:
  • Example 9 Comparative fermentation of a sugar syrup according to the invention with a control syrup comprising the same quantity of glucose and xylose from conventional channels
  • a sugar syrup generated from paper and cardboard could be tested on a yeast strain of Saccharomyces cerevisiae capable of producing ethanol marketed by the company Lesaffre for the production of ethanol (strain Cellux 4).
  • the fermentation tests took place in an Erlenmeyer or a Schott bottle at two given sugar concentrations: 140 and 210 g/kg of medium (corresponding to the cumulative quantities of glucose and xylose) named respectively TAV 8 and TAV 12.
  • a sugar syrup control (called 1G) containing the same quantity of glucose and xylose was manufactured and tested under the same conditions.
  • the objective of the comparison of the result of the fermentation was to highlight the quality and the absence of inhibitory effect of the sugar syrup resulting from the invention during the fermentation, compared to the use of a syrup glucose and xylose from conventional channels, i.e. produced from 1 G resource (/.e. 1st generation) consisting in particular of beet, wheat, sugar cane.
  • Ethanol production was monitored using mass loss related to CO2 production , directly correlated to ethanol production. The actual final concentration was also checked at the end of the experiment by HPLiC.

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Abstract

The invention relates to a method for producing a sugar syrup comprising fermentable sugars from lignocellulosic biomass containing paper waste, in particular printable paper, printed paper or cardboard, said method comprising the following steps: a. optionally, a step of shredding said lignocellulosic biomass containing paper waste; b.i. a step of impregnating said lignocellulosic biomass containing paper waste or shredded lignocellulosic biomass obtained on completion of step a. in an aqueous medium, and ii. a thermal pretreatment step implemented, without the addition of acid, at a temperature of between 80°C and 150°C, at a pH between 6.5 and 8.5, in particular between 6.5 and 8, in order to obtain a pretreated product, said impregnation and thermal pretreatment steps being carried out simultaneously or successively according to i. and then ii; c. a step of enzymatic hydrolysis of the pretreated product obtained on completion of step b. in order to convert the cellulose and hemicellulose into a sugar syrup comprising fermentable sugars; and d. a step of recovering the sugar syrup comprising fermentable sugars obtained on completion of step c.

Description

DESCRIPTION DESCRIPTION
TITRE : PROCEDE DE PRODUCTION D’UN SIROP DE SUCRES A PARTIR D’UNE BIOMASSE LIGNOCELLULOSIQUE RESIDUAIRE TITLE: METHOD FOR PRODUCTION OF A SUGAR SYRUP FROM RESIDUAL LIGNOCELLULOSIC BIOMASS
Domaine technique de l’invention Technical field of the invention
L’invention se rapporte au domaine de la production de sucres fermentescibles et concerne l’utilisation de ressources lignocellulosiques résiduaires par exemple de type papiers/cartons en tant que substrat d’un procédé de préparation desdits sucres. L’invention décrit notamment le procédé utilisé pour la préparation de la matière première et son traitement permettant la production d’un sirop de sucres, en particulier d’un sirop de glucose purifié utilisable comme matière première, notamment dans l’industrie des biocarburants ou des biotechnologies.The invention relates to the field of the production of fermentable sugars and relates to the use of waste lignocellulosic resources, for example of the paper/cardboard type, as a substrate for a process for preparing said sugars. The invention describes in particular the process used for the preparation of the raw material and its treatment allowing the production of a sugar syrup, in particular of a purified glucose syrup which can be used as a raw material, in particular in the biofuels industry or biotechnologies.
En particulier, l'invention concerne un procédé de production d’un sirop de sucres comprenant des sucres fermentescibles, en particulier d’un sirop comprenant du glucose, à partir de biomasse lignocellulosique comprenant des déchets papetiers, notamment de papier imprimable, de papier imprimé, de papier graphique, de papier d’emballage ou de carton. L’invention concerne également un sirop de sucres comprenant des sucres fermentescibles, en particulier un sirop comprenant du glucose, susceptible d’être obtenu par ledit procédé. L’utilisation du procédé pour produire des molécules biosourcées ou des biocarburants, de préférence de l’éthanol ainsi qu’un procédé de production de biocarburants, en particulier d’éthanol sont également des objets de la présente invention. In particular, the invention relates to a method for producing a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, from lignocellulosic biomass comprising paper waste, in particular printable paper, printed paper , graph paper, wrapping paper or cardboard. The invention also relates to a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, which can be obtained by said process. The use of the process for producing biosourced molecules or biofuels, preferably ethanol, as well as a process for producing biofuels, in particular ethanol, are also objects of the present invention.
Etat de la technique antérieure State of the prior art
La biomasse lignocellulosique principalement utilisée comme source de sucres fermentescibles aujourd’hui à l’échelle pilote et industrielle est la biomasse dite 2G (de seconde génération), c’est-à-dire une biomasse de type végétal, comme les résidus de l’industrie forestière et agricole (paille de blé, rafles de maïs et bagasse de canne à sucre) (Nizami et al., 2017). A ce jour, les limites suivantes ont été mises en avant : The lignocellulosic biomass mainly used as a source of fermentable sugars today on a pilot and industrial scale is the so-called 2G (second generation) biomass, i.e. a plant-type biomass, such as the residues of forestry and agricultural industry (wheat straw, corn cobs and sugarcane bagasse) (Nizami et al., 2017). To date, the following limitations have been highlighted:
- Faible développement de la filière de collecte et de massification des gisements, - Weak development of the collection and massification of deposits sector,
- Exposition aux variations saisonnières des volumes, de la qualité et de la disponibilité,- Exposure to seasonal variations in volumes, quality and availability,
- Concurrence avec la fertilisation des sols et le couvert végétal des champs, - Competition with soil fertilization and plant cover in fields,
- Teneur importante en hémicellulose et lignine rendant l’accès à la cellulose plus complexe et le rendement en glucose plus faible, - High content of hemicellulose and lignin making access to cellulose more complex and lower glucose yield,
- Nécessité d’appliquer des prétraitements lourds et coûteux, pouvant générer des molécules inhibitrices de la fermentation (HMF, Furfural...) (Soltanian et al., 2020). - Need to apply heavy and costly pre-treatments, which can generate molecules that inhibit fermentation (HMF, Furfural, etc.) (Soltanian et al., 2020).
L’utilisation du papier et du carton permet de s’affranchir d’une grande partie de ces limites et d’accéder à des produits plus riches en cellulose, via des procédés moins intensifs et moins complexes du fait d’un premier prétraitement subi par la matière vierge en amont de sa chaîne de production (en papeterie lors de sa production). L’état de la technique en termes de valorisation de la biomasse lignocellulosique inclut plusieurs types de procédés de traitement. Ces procédés ont tous pour objectif d’hydrolyser la cellulose et/ou l’hémicellulose constituant la biomasse, en monomères. L’hydrolyse peut se faire (Nizami et al., 2017): The use of paper and cardboard makes it possible to overcome a large part of these limits and to access products richer in cellulose, via less intensive and less complex processes due to a first pre-treatment undergone by the virgin material upstream of its production chain (in stationery during its production). The state of the art in terms of upgrading lignocellulosic biomass includes several types of treatment processes. These methods all have the objective of hydrolyzing the cellulose and/or hemicellulose constituting the biomass, into monomers. Hydrolysis can be done (Nizami et al., 2017):
- Par voie biologique ou biochimique, au moyen d’enzymes et/ou de microorganismes ; - Biologically or biochemically, using enzymes and/or microorganisms;
- Par voie thermochimique et/ou mécanique. - By thermochemical and/or mechanical means.
Parmi les procédés par voie non-biologique, on compte : les procédés à l’acide concentré, la gazéification, l’hydropyrolyse et la pyrolyse. Non-biological processes include: concentrated acid processes, gasification, hydropyrolysis and pyrolysis.
Pour les procédés par voie biologique, la première étape consiste à prétraiter la biomasse, afin d’augmenter la digestibilité de la cellulose et la libération de sucres monomériques (glucose principalement). Il existe différentes techniques de prétraitements dont (Soltanian et al., 2020) : For biological processes, the first step consists in pretreating the biomass, in order to increase the digestibility of the cellulose and the release of monomeric sugars (mainly glucose). There are different pre-treatment techniques including (Soltanian et al., 2020):
- les procédés à l’acide dilué, - dilute acid processes,
- les procédés à l’acide solide, - solid acid processes,
- les procédés alkalins, - alkaline processes,
- les procédés AVAP, - AVAP processes,
- les procédés Organosolv, - Organosolv processes,
- l’explosion à la vapeur, - steam explosion,
- les procédés à l’eau supercritique, - supercritical water processes,
- l’extrusion. - extruding.
L’ajout de catalyseurs chimiques comme les acides ou les bases dans l’étape de prétraitement permet d’augmenter fortement l’accessibilité de la cellulose aux enzymes hydrolytiques et donc le rendement de libération des sucres simples comme le glucose. La contrepartie de ce prétraitement, outre son coût, est le risque d’apparition de molécules toxiques comme le furfural ou l’hydroxymethylfurfural (HMF) pouvant rapidement se former à forte température. Par la suite, le catalyseur chimique et ses produits de dégradation, solubles dans l’eau comme les molécules de sucres, doivent être extraits par des méthodes de séparation (dites de « downstream processing ») comme la chromatographie ionique ou l’osmose inverse, générant des coûts et contraintes techniques importantes. The addition of chemical catalysts such as acids or bases in the pre-treatment step makes it possible to greatly increase the accessibility of cellulose to hydrolytic enzymes and therefore the yield of release of simple sugars such as glucose. The counterpart of this pre-treatment, in addition to its cost, is the risk of the appearance of toxic molecules such as furfural or hydroxymethylfurfural (HMF) which can quickly form at high temperature. Subsequently, the chemical catalyst and its degradation products, soluble in water such as sugar molecules, must be extracted by separation methods (known as “downstream processing”) such as ion chromatography or reverse osmosis, generating significant costs and technical constraints.
Pour remédier à cette limitation, des procédés sans catalyseurs chimiques (ou à une charge bien inférieure) ont vu le jour pour le prétraitement des fibres végétales: l’explosion à la vapeur. L’imprégnation de la matrice à haute température/pression, suivie d’une étape de détente à très forte vitesse permet de séparer les polymères de sucres avec une meilleure efficacité. Ce procédé s’applique cependant à un flux de matière dont la granulométrie et la composition doivent être scrupuleusement contrôlés, demandant donc une étape de broyage et tamisage fin. Un gisement de déchets papiers contenant un mélange de matières avec des impuretés plastiques et/ou métalliques risquerait d’endommager rapidement l’outil d’explosion vapeur. La dernière étape est la transformation des sucres (après leur purification). Il s’agit souvent d’une fermentation et distillation pour arriver à un produit final à haute valeur ajoutée comme l’éthanol. To overcome this limitation, processes without chemical catalysts (or at a much lower load) have emerged for the pretreatment of plant fibers: steam explosion. The impregnation of the matrix at high temperature/pressure, followed by a very high speed expansion step makes it possible to separate the polymers from the sugars with better efficiency. However, this process applies to a flow of material whose particle size and composition must be scrupulously controlled, thus requiring a grinding and fine sieving step. A deposit of waste paper containing a mixture of materials with plastic and/or metallic impurities could quickly damage the steam explosion tool. The last step is the transformation of the sugars (after their purification). It is often a question of fermentation and distillation to arrive at a final product with high added value such as ethanol.
Les procédés ayant recours à une hydrolyse par voie biologique peuvent être classés en 4 sous-catégories, selon qu’ils regroupent ou non les étapes élémentaires du procédé (Parisutham et al., 2014): Processes using biological hydrolysis can be classified into 4 sub-categories, depending on whether or not they include the basic steps of the process (Parisutham et al., 2014):
- « Separate Hydrolysis and Fermentation » (SHF), - “Separate Hydrolysis and Fermentation” (SHF),
- « Simultaneous Saccharification and Fermentation » (SSF), - “Simultaneous Saccharification and Fermentation” (SSF),
- « Simultaneous Saccharification and Co-Fermentation » (SSCF), - “Simultaneous Saccharification and Co-Fermentation” (SSCF),
- « Consolidated Bioprocessing » (CBP). - “Consolidated Bioprocessing” (CBP).
L’avantage de mettre en oeuvre un procédé combiné comme le SSF, SSCF ou CBP est de pouvoir réduire le nombre d’étapes et de réacteurs en faisant cohabiter l(es) enzyme(s) capable(s) de dépolymériser la cellulose et le(s) microorganisme(s) capable(s) de convertir les sucres simples en molécule d’intérêt. Ceci permet généralement de réduire l’investissement nécessaire et donc le coût de production de la molécule cible. Dans ce cas, le procédé est développé et optimisé spécifiquement pour une molécule et un marché donné. Ce type de procédé fait la plupart du temps intervenir des microorganismes modifiés génétiquement.The advantage of implementing a combined process such as SSF, SSCF or CBP is to be able to reduce the number of steps and reactors by bringing together the enzyme(s) capable of depolymerizing the cellulose and the (s) microorganism(s) capable of converting simple sugars into a molecule of interest. This generally makes it possible to reduce the necessary investment and therefore the production cost of the target molecule. In this case, the process is developed and optimized specifically for a molecule and a given market. This type of process usually involves genetically modified microorganisms.
La valorisation de papiers en sucres et/ou en autres produits d’intérêt comme l’éthanol a été décrite dans l’art antérieur. Par exemple, la demande de brevet CN 106520861 met en oeuvre une hydrolyse enzymatique avec prétraitement à l’acide dilué. La demande de brevet CN102382909 utilise l’hydrolyse acide avec une utilisation successive d’acide dilué et d’acide concentré. La demande de brevet JP2006088136 met en oeuvre une pulvérisation fine de la biomasse par prétraitement mécanique, sans cuisson acide. La demande de brevet US2010/0009422 décrit un procédé de préparation d’éthanol comprenant notamment une étape de prétraitement thermique à la vapeur à haute température. The recovery of papers into sugars and/or other products of interest such as ethanol has been described in the prior art. For example, patent application CN 106520861 implements enzymatic hydrolysis with dilute acid pretreatment. Patent application CN102382909 uses acid hydrolysis with successive use of dilute acid and concentrated acid. The patent application JP2006088136 implements a fine pulverization of the biomass by mechanical pretreatment, without acid cooking. Patent application US2010/0009422 describes a process for preparing ethanol comprising in particular a step of thermal pretreatment with high temperature steam.
Présentation de l’invention Presentation of the invention
L’invention a pour objectif d’hydrolyser la cellulose et le cas échéant l’hémicellulose contenue(s) dans la biomasse lignocellulosique résiduaire sans avoir recours à des procédés lourds de prétraitement et de purification, permettant ainsi de réduire les impuretés, les coûts opérationnels liés à l’utilisation de catalyseurs chimiques, de simplifier les étapes ultérieures dites de « downstream processing » (e.g. étapes de clarification, de purification et de concentration), tout en obtenant un rendement massique optimum. The object of the invention is to hydrolyze the cellulose and, where appropriate, the hemicellulose contained in the residual lignocellulosic biomass without having recourse to cumbersome pre-treatment and purification processes, thus making it possible to reduce impurities, operational costs linked to the use of chemical catalysts, to simplify the subsequent so-called “downstream processing” stages (eg stages of clarification, purification and concentration), while obtaining an optimum mass yield.
L’invention a notamment pour but de développer un procédé de production d’un sirop de sucres comprenant des sucres fermentescibles, en particulier d’un sirop comprenant du glucose, à partir de biomasse lignocellulosique comprenant des déchets papetiers, notamment des déchets de papier imprimable, de papier imprimé ou de carton. Un autre but de l’invention est de valoriser ledit sirop de sucres en produisant des molécules biosourcées ou des biocarburants, de préférence de l’éthanol. The object of the invention is in particular to develop a method for producing a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, from lignocellulosic biomass comprising paper waste, in particular printable paper waste. , printed paper or cardboard. Another object of the invention is to enhance said sugar syrup by producing biosourced molecules or biofuels, preferably ethanol.
Un autre but de l’invention est d’obtenir une molécule plateforme à haute valeur ajoutée (sucres ou autre) à partir de déchets papiers-cartons, et notamment utile pour la production de biocarburants et de molécules chimiques à faible impact environnemental et à faible coût. Another object of the invention is to obtain a platform molecule with high added value (sugars or other) from paper-cardboard waste, and in particular useful for the production of biofuels and chemical molecules with low environmental impact and low cost.
Résumé de l’invention Summary of the invention
Selon un premier aspect, l’invention concerne un procédé de production d’un sirop de sucres comprenant des sucres fermentescibles à partir de biomasse lignocellulosique comprenant des déchets papetiers, ledit procédé comprenant notamment les étapes suivantes: a. optionnellement une étape de broyage de ladite biomasse lignocellulosique; b. i. une étape d’imprégnation et ii. une étape de prétraitement thermique de la biomasse lignocellulosique, lesdites étapes d’imprégnation et de prétraitement thermique étant réalisées simultanément ou de façon successive selon i. puis ii. ; c. une étape d’hydrolyse enzymatique du produit prétraité ; et d. une étape de récupération du sirop de sucres comprenant des sucres fermentescibles. Selon un second aspect, l’invention concerne un sirop de sucres comprenant des sucres fermentescibles, en particulier un sirop comprenant du glucose, susceptible d’être obtenu par le procédé selon l’invention. According to a first aspect, the invention relates to a method for producing a sugar syrup comprising fermentable sugars from lignocellulosic biomass comprising paper waste, said method comprising in particular the following steps: a. optionally a step of grinding said lignocellulosic biomass; b. i. an impregnation step and ii. a step of thermal pretreatment of the lignocellulosic biomass, said steps of impregnation and thermal pretreatment being carried out simultaneously or successively according to i. then ii. ; vs. an enzymatic hydrolysis step of the pretreated product; and D. a step for recovering the sugar syrup comprising fermentable sugars. According to a second aspect, the invention relates to a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, which can be obtained by the process according to the invention.
Selon un troisième aspect, l’invention concerne l’utilisation du procédé ou du sirop selon l’invention pour produire des molécules biosourcées ou des biocarburants, de préférence de l’éthanol. According to a third aspect, the invention relates to the use of the process or the syrup according to the invention to produce biosourced molecules or biofuels, preferably ethanol.
Selon un quatrième aspect, l’invention concerne un procédé de production de biocarburants, en particulier d’éthanol. According to a fourth aspect, the invention relates to a method for producing biofuels, in particular ethanol.
Description détaillée de l’invention Detailed description of the invention
Toute référence à des intervalles de valeurs dans la description et/ou les revendications implique, sauf mention contraire, que les bornes des intervalles sont incluses. Any reference to intervals of values in the description and/or the claims implies, unless otherwise stated, that the limits of the intervals are included.
L’invention concerne un procédé de production d’un sirop de sucres comprenant des sucres fermentescibles, en particulier d’un sirop comprenant du glucose, à partir de biomasse lignocellulosique comprenant des déchets papetiers, notamment de papier imprimable, de papier imprimé ou de carton, ledit procédé comprenant les étapes suivantes: a. optionnellement, une étape de broyage de ladite biomasse lignocellulosique comprenant des déchets papetiers ; b. i. une étape d’imprégnation de ladite biomasse lignocellulosique comprenant des déchets papetiers ou de la biomasse lignocellulosique broyée obtenue à l’issue de l’étape a. en milieu aqueux, de préférence dans de l’eau et à température ambiante, et ii. une étape de prétraitement thermique mise en oeuvre en l’absence d’ajout d’acide, à une température comprise entre 80°C et 150°C, de préférence entre 90°C et 130°C, de manière plus préférée à 100°C ou 120°C, à un pH compris entre 6.5 et 8.5, notamment entre 6.5 et 8, notamment à un pH compris entre 6.8 et 7.5, de préférence à un pH neutre, afin d’obtenir un produit prétraité, lesdites étapes d’imprégnation et de prétraitement thermique étant réalisées simultanément ou de façon successive selon i. puis ii.; c. une étape d’hydrolyse enzymatique du produit prétraité obtenu à l’issue de l’étape b. afin de convertir la cellulose et l’hémicellulose en un sirop de sucres comprenant des sucres fermentescibles, en particulier en un sirop comprenant du glucose ; et d. une étape de récupération du sirop de sucres comprenant des sucres fermentescibles, en particulier du sirop comprenant du glucose, obtenu à l’issue de l’étape c. The invention relates to a method for producing a sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, from lignocellulosic biomass comprising paper waste, in particular printable paper, printed paper or cardboard. , said method comprising the following steps: a. optionally, a step of grinding said lignocellulosic biomass comprising paper waste; bi a step of impregnating said lignocellulosic biomass comprising paper waste or crushed lignocellulosic biomass obtained at the end of step a. in an aqueous medium, preferably in water and at room temperature, and ii. a heat pretreatment step implemented in the absence of addition of acid, at a temperature between 80°C and 150°C, preferably between 90°C and 130°C, more preferably at 100° C. or 120° C., at a pH of between 6.5 and 8.5, in particular between 6.5 and 8, in particular at a pH of between 6.8 and 7.5, preferably at a neutral pH, in order to obtain a pretreated product, said impregnation and heat pretreatment steps being carried out simultaneously or successively according to i. then ii.; vs. a step of enzymatic hydrolysis of the pretreated product obtained at the end of step b. in order to convert cellulose and hemicellulose into a sugar syrup comprising fermentable sugars, in particular into a syrup comprising glucose; and D. a step for recovering the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, obtained at the end of step c.
Dans un mode de réalisation préféré, l’invention concerne un procédé de production d’un sirop comprenant du glucose à partir de biomasse lignocellulosique comprenant des déchets papetiers, notamment de papier imprimable, de papier imprimé ou de carton comprend les étapes suivantes: a. optionnellement, une étape de broyage de ladite biomasse lignocellulosique comprenant des déchets papetiers ; b. i. une étape d’imprégnation de ladite biomasse lignocellulosique comprenant des déchets papetiers ou de la biomasse lignocellulosique broyée obtenue à l’issue de l’étape a. en milieu aqueux, de préférence dans de l’eau et à température ambiante, et ii. une étape de prétraitement thermique mise en oeuvre en l’absence d’ajout d’acide, à une température comprise entre 80°C et 150°C, à un pH compris entre 6.5 et 8.5, notamment entre 6.5 et 8, afin d’obtenir un produit prétraité, lesdites étapes d’imprégnation et de prétraitement thermique étant réalisées simultanément ou de façon successive selon i. puis ii. ; c. une étape d’hydrolyse enzymatique du produit prétraité obtenu à l’issue de l’étape b. afin de convertir la cellulose et l’hémicellulose en un sirop comprenant du glucose; et d. une étape de récupération du sirop comprenant du glucose obtenu à l’issue de l’étape c. In a preferred embodiment, the invention relates to a process for producing a syrup comprising glucose from lignocellulosic biomass comprising paper waste, in particular printable paper, printed paper or cardboard comprising the following steps: a. optionally, a step of grinding said lignocellulosic biomass comprising paper waste; b. i. a step of impregnating said lignocellulosic biomass comprising paper waste or crushed lignocellulosic biomass obtained at the end of step a. in an aqueous medium, preferably in water and at room temperature, and ii. a heat pretreatment step implemented in the absence of acid addition, at a temperature between 80° C. and 150° C., at a pH between 6.5 and 8.5, in particular between 6.5 and 8, in order to obtaining a pretreated product, said steps of impregnation and thermal pretreatment being carried out simultaneously or successively according to i. then ii. ; vs. a step of enzymatic hydrolysis of the pretreated product obtained at the end of step b. to convert cellulose and hemicellulose into a syrup comprising glucose; and D. a step for recovering the syrup comprising the glucose obtained at the end of step c.
Dans le contexte de l’invention, le terme « sirop de sucres » fait référence à un liquide visqueux et épais comprenant des sucres en solution. Le terme « sirop de sucres » peut être interchangé avec le terme « jus sucré ». Dans un mode de réalisation particulier le sirop de sucres comprenant du glucose comprend également du xylose, en proportion moindre par rapport au glucose. Dans un mode de réalisation particulier le sirop de sucres comprend de 70 à 85% de glucose et de 10 à 15% de xylose. In the context of the invention, the term "sugar syrup" refers to a viscous and thick liquid comprising sugars in solution. The term “sugar syrup” can be interchanged with the term “sweetened juice”. In a particular embodiment, the sugar syrup comprising glucose also comprises xylose, in a lower proportion with respect to glucose. In a particular embodiment, the sugar syrup comprises 70 to 85% glucose and 10 to 15% xylose.
Dans le contexte de l’invention, le terme « sucres fermentescibles » fait référence à des sucres simples ou leurs mélanges, par exemple le glucose, le fructose, l’arabinose, le mannose, le galactose, le xylose. Ces « sucres simples » sont susceptibles d’être fermentés sous l’action de levures ou de bactéries pour produire de l’alcool. Il s’agit en particulier de monosaccharides (/.e. de sucres comprenant 5 ou 6 atomes de carbones), notamment d’un hexose, tel le glucose. De préférence, les « sucres fermentescibles » font référence à des sucres monomériques fermentescibles, i.e. comprenant une seule unité. De manière encore plus préférée, les « sucres fermentescibles » comprennent ou consistent essentiellement en du glucose et en moindre proportion du xylose. In the context of the invention, the term “fermentable sugars” refers to simple sugars or their mixtures, for example glucose, fructose, arabinose, mannose, galactose, xylose. These “simple sugars” are likely to be fermented under the action of yeasts or bacteria to produce alcohol. These are in particular monosaccharides (/.e. sugars comprising 5 or 6 carbon atoms), in particular a hexose, such as glucose. Preferably, the “fermentable sugars” refer to fermentable monomeric sugars, ie comprising a single unit. Even more preferably, the "fermentable sugars" comprise or consist essentially of glucose and in a lesser proportion of xylose.
Dans le contexte de l’invention, le terme « biomasse lignocellulosique » fait référence à un substrat essentiellement constitué de cellulose (de 30 à 70%), d’hémicellulose (de 5 à 35%) et de lignine (de 5 à 25%) déterminés par rapport à la masse sèche de la biomasse lignocellulosique. Dans un mode de réalisation particulier, la biomasse lignocellulosique est un substrat essentiellement constitué de cellulose (de 30 à 70%), d’hémicellulose (de 5 à 25%) et de lignine (de 5 à 25%). Dans un autre mode de réalisation particulier, la biomasse lignocellulosique est un substrat essentiellement constitué de cellulose (de 30 à 70%), d’hémicellulose (de 5 à 20%) et de lignine (de 5 à 20%). Dans un autre mode de réalisation particulier, la biomasse lignocellulosique est un substrat essentiellement constitué de cellulose (de 30 à 70%), d’hémicellulose jusqu’à 18% et de lignine jusqu’à 19%. La cellulose est un polymère de glucose, i.e. hexose, l’hémicellulose est un polysaccharide constitué essentiellement de pentoses (e.g. xylose et arabinose) et de glucose, et la lignine est une macromolécule riche en motifs phénoliques. La cellulose est la principale source de sucres fermentescibles. La « biomasse lignocellulosique » utilisée dans l’invention comprend des déchets papetiers. Les déchets papetiers peuvent avoir été recyclés plusieurs fois, par exemple jusqu’à 7 fois, et la taille moyenne des fibres contenues dans ces déchets papetiers est généralement comprise entre 0 mm et 2 mm, préférentiellement entre 0,1 mm et 1 ,5 mm. Selon un mode de réalisation particulier, le substrat apportant la biomasse lignocellulosique est constitué par des déchets papetiers. In the context of the invention, the term “lignocellulosic biomass” refers to a substrate essentially consisting of cellulose (from 30 to 70%), hemicellulose (from 5 to 35%) and lignin (from 5 to 25% ) determined with respect to the dry mass of the lignocellulosic biomass. In a particular embodiment, the lignocellulosic biomass is a substrate essentially consisting of cellulose (from 30 to 70%), hemicellulose (from 5 to 25%) and lignin (from 5 to 25%). In another particular embodiment, the lignocellulosic biomass is a substrate essentially consisting of cellulose (from 30 to 70%), hemicellulose (from 5 to 20%) and lignin (from 5 to 20%). In another particular embodiment, the lignocellulosic biomass is a substrate essentially consisting of cellulose (from 30 to 70%), hemicellulose up to 18% and lignin up to 19%. Cellulose is a polymer of glucose, i.e. hexose, hemicellulose is a polysaccharide consisting essentially of pentoses (e.g. xylose and arabinose) and glucose, and lignin is a macromolecule rich in phenolic units. Cellulose is the main source of fermentable sugars. The "lignocellulosic biomass" used in the invention comprises paper waste. The papermaking waste may have been recycled several times, for example up to 7 times, and the average size of the fibers contained in this papermaking waste is generally between 0 mm and 2 mm, preferably between 0.1 mm and 1.5 mm . According to a particular embodiment, the substrate providing the lignocellulosic biomass consists of paper waste.
Selon un mode de réalisation particulier, le substrat apportant la biomasse lignocellulosique comprend des déchets papetiers et un co-substrat. According to a particular embodiment, the substrate providing the lignocellulosic biomass comprises paper waste and a co-substrate.
Selon un autre mode de réalisation particulier, le substrat fournissant la biomasse lignocellulosique comprend des déchets papetiers et est contenu dans ou constitué par un déchet plus complexe tel que la Fraction Fermentescible des Ordures Ménagères (FFOM). Dans un mode de réalisation particulier de l’invention mettant en oeuvre un substrat lignocellulosique contenu dans la FFOM, le taux de cellulose dans la FFOM est inférieur à 50%, par exemple de 10 à 40% en poids. Les FFOM et plus généralement les déchets ménagers dans lesquels elle est contenue sont de composition variable suivant les régions considérées dans le monde. Les FFOM peuvent être mises en oeuvre dans le cadre de l’invention pour fournir la biomasse lignocellulosique à traiter dans la mesure où leur teneur en cellulose, hémicellulose et lignine, notamment par l’apport permis par les déchets papetiers, fournit un substrat dont la composition entre dans les proportions ci-dessus définies. A titre d’exemple, une FFOM susceptible d’être traitée conformément à l’invention comprend de 10% à 20% en poids de papiers et/ou de 8% à 15% en poids de cartons ondulés et plats et/ou entre 3 et 6 % en poids de textiles et/ou entre 15 et 25% en poids de textiles sanitaires (considérés comme dissociés des autres textiles), par exemple autour de 13 %, 10%, 4.6% et 21% en poids respectivement, ces proportions étant déterminées en pourcentage de la masse sèche de FFOM considérée. La fraction restante des FFOM est constituée par les déchets alimentaires (de 60% à 80%) , le cas échéant également associés à des déchets de jardin, ou d’autres types de fibres comme des résidus de bois. Ensemble, les déchets constituant la FFOM (également appelée FOR pour Fraction Organique Résiduelle ou Fraction organique issue de TMB (pour Tri Mécano-Biologique)) sont utilisables en tant que substrat lignocellulosique pour la réalisation des procédés de l’invention. Au-delà de la fraction fermentescible les déchets ménagers (OM) peuvent aussi contenir des composites, des plastiques, des combustibles non classés, du verre, des métaux, des incombustibles non classés et une partie minoritaire de déchets dangereux. Ces déchets non fermentescibles sont normalement écartés dans le processus de tri mécanobiologique permettant la production de la FFOM. La FFOM peut donc être définie en considérant son mode d’obtention : elle constitue le résultat de la collecte en mélange des déchets ménagers, suivie d’une étape de séparation mécano-biologique pour ne retenir que la fraction fine organique de ces déchets. According to another particular embodiment, the substrate providing the lignocellulosic biomass comprises paper waste and is contained in or constituted by a more complex waste such as the Fermentable Fraction of Household Waste (FFOM). In a particular embodiment of the invention using a lignocellulosic substrate contained in the FFOM, the level of cellulose in the FFOM is less than 50%, for example from 10 to 40% by weight. The SWOT and more generally the household waste in which it is contained are of variable composition depending on the regions considered in the world. The SWOTs can be implemented within the framework of the invention to provide the lignocellulosic biomass to be treated insofar as their content of cellulose, hemicellulose and lignin, in particular by the contribution permitted by the papermaking waste, provides a substrate whose composition falls within the proportions defined above. By way of example, a SWOT capable of being treated in accordance with the invention comprises 10% to 20% by weight of paper and/or from 8% to 15% by weight of corrugated and flat cardboard and/or between 3 and 6% by weight of textiles and/or between 15 and 25% by weight of sanitary textiles (considered as dissociated from other textiles), for example around 13%, 10%, 4.6% and 21% by weight respectively, these proportions being determined as a percentage of the dry mass of SWOT considered. The remaining fraction of the SWOT is made up of food waste (from 60% to 80%), if necessary also associated with garden waste, or other types of fibers such as wood residues. Together, the waste constituting the FFOM (also called FOR for Residual Organic Fraction or Organic Fraction from TMB (for Mechanical-Biological Sorting)) can be used as a lignocellulosic substrate for carrying out the methods of the invention. Beyond the fermentable fraction, household waste (OM) can also contain composites, plastics, unclassified fuels, glass, metals, unclassified incombustibles and a minority part of hazardous waste. These non-fermentable wastes are normally discarded in the mechanobiological sorting process allowing the production of the SWOT. The SWOT can therefore be defined by considering how it is obtained: it is the result of the mixed collection of household waste, followed by a mechanical-biological separation stage to retain only the fine organic fraction of this waste.
Dans un mode particulier de réalisation de l’invention, le substrat fournissant la biomasse lignocellulosique comprend des déchets papetiers et de la FFOM comme co-substrat. In a particular embodiment of the invention, the substrate providing the lignocellulosic biomass comprises paper mill waste and SWOT as co-substrate.
Selon un mode de réalisation, la biomasse lignocellulosique peut alternativement ou également comprendre des résidus de type végétal. Des exemples non limitatifs de biomasse lignocellulosique de type végétal sont des résidus issus de l’industrie forestière et agricole tels que la paille de blé, les rafles de maïs et la bagasse de canne à sucre, des résidus de l’industrie agro-alimentaire. Dans un mode de réalisation particulier lorsque la biomasse lignocellulosique comprend des déchets de type végétal issus de l’industrie forestière ou agricole, les proportions respectivement d’hémicellulose et de lignine en poids de la matière sèche de la biomasse totale en mélange sont inférieures respectivement à 19% et 18%. Selon un mode de réalisation particulier de l’invention, la biomasse lignocellulosique ne comprend que peu (en % en poids de la matière sèche) ou pas de déchets de type végétal issus de l’industrie forestière ou agricole. According to one embodiment, the lignocellulosic biomass may alternatively or also comprise residues of plant type. Non-limiting examples of plant-type lignocellulosic biomass are residues from the forestry and agricultural industry such as wheat straw, corn cobs and sugar cane bagasse, residues from the agro-food industry. In a particular embodiment when the lignocellulosic biomass comprises plant-type waste from the forestry or agricultural industry, the proportions respectively of hemicellulose and lignin by weight of the dry matter of the total biomass in the mixture are respectively less than 19% and 18%. According to a particular embodiment of the invention, the lignocellulosic biomass comprises only little (in% by weight of the dry matter) or no plant-type waste from the forestry or agricultural industry.
Dans le contexte de l’invention, les déchets papetiers comprennent ou sont essentiellement constitués de déchets papiers et cartons. En général, les déchets papiers et cartons correspondent à un mélange de déchets papiers et cartons, ledit mélange pouvant comprendre en poids par rapport au poids de la matière sèche des déchets entre 5 et 60% de cartonnettes grises, entre 5% et 60%, notamment entre 10 et 20% en poids de papiers imprimés du type des papiers de bureau et entre 5% et 100% de cartons ondulés Dans un mode de réalisation particulier de l’invention, les déchets papetiers sont choisis parmi le groupe constitué par des papiers (en particulier papier imprimé ou imprimable), cartons, notamment papiers journaux, magazines et boues de papeterie. Ces déchets peuvent contenir des impuretés indésirables telles que des plastiques, et des métaux, ainsi que des constituants d’encres, lesdites impuretés étant présentes en très faible quantité. In the context of the invention, paper waste comprises or essentially consists of paper and cardboard waste. In general, paper and cardboard waste corresponds to a mixture of paper and cardboard waste, said mixture possibly comprising by weight relative to the weight of the dry matter of the waste between 5 and 60% of gray cardboard, between 5% and 60%, in particular between 10 and 20% by weight of printed paper of the office paper type and between 5% and 100% of corrugated cardboard In a particular embodiment of the invention, the paper waste is chosen from the group consisting of paper (in particular printed or printable paper), cardboard, in particular newsprint, magazines and stationery sludge. This waste may contain undesirable impurities such as plastics and metals, as well as constituents of inks, said impurities being present in very small quantities.
Dans un mode de réalisation préféré de l’invention, les déchets papetiers sont un mélange de déchets lignocellulosiques (de type papier cartons) de basse qualité dans les proportions moyennes suivantes en poids de la matière sèche totale (+/- 5%, le pourcentage total ne dépassant pas 100%) : In a preferred embodiment of the invention, the paper waste is a mixture of lignocellulosic waste (of the cardboard paper type) of low quality in the following average proportions by weight of the total dry matter (+/- 5%, the percentage total not exceeding 100%):
- Cartonnettes grises : 20% - Gray cards: 20%
- Journaux : 30% - Newspapers: 30%
- Magazines : 20% - Magazines: 20%
- Papiers de bureau : 10% - Office papers: 10%
- Cartons ondulés : 20%. - Corrugated cardboard: 20%.
Dans un mode de réalisation particulier de l’invention, ladite biomasse lignocellulosique avant broyage et/ou imprégnation, i.e. biomasse lignocellulosique « brute » est constituée de déchets papetiers et a une teneur en matière sèche totale comprise entre 70% et 100%, notamment entre 85% et 96% en poids de la biomasse. In a particular embodiment of the invention, said lignocellulosic biomass before grinding and / or impregnation, ie "raw" lignocellulosic biomass consists of paper waste and has a total dry matter content of between 70% and 100%, in particular between 85% and 96% by weight of the biomass.
Dans un autre mode de réalisation particulier de l’invention, ladite biomasse lignocellulosique avant broyage et/ou imprégnation, i.e. biomasse lignocellulosique « brute » est constituée de FFOM et a une teneur en matière sèche totale comprise par exemple entre 45% et 55%, notamment autour de 50% en poids de la biomasse. In another particular embodiment of the invention, said lignocellulosic biomass before grinding and / or impregnation, ie "raw" lignocellulosic biomass consists of FFOM and has a total dry matter content of between 45% and 55%, for example, in particular around 50% by weight of the biomass.
Dans un autre mode de réalisation de l’invention où ladite biomasse lignocellulosique est constituée d’un mélange de déchets papetiers et de FFOM, la teneur en matière sèche totale varie entre 50 et 96% en poids de la biomasse selon les proportions de substrat et de co substrat ajoutées. In another embodiment of the invention where said lignocellulosic biomass consists of a mixture of paper mill waste and SWOT, the total dry matter content varies between 50 and 96% by weight of the biomass depending on the proportions of substrate and of added co-substrate.
L’étape d’imprégnation (aussi appelée pulpage) b.i. permet d’obtenir une suspension relativement homogène ne présentant pas d’agglomérats secs et/ou flottants. En effet, les agglomérats sont en général moins bien voire non hydrolysés dans l’étape c. d’hydrolyse enzymatique subséquente. Dans un mode de réalisation particulier de l’invention, l’étape d’imprégnation b.i. est effectuée pendant une durée comprise entre 5 et 30 minutes, de préférence pendant 15 minutes. L’étape d’imprégnation b.i. peut comprendre une mise sous agitation. The impregnation step (also called pulping) b.i. makes it possible to obtain a relatively homogeneous suspension with no dry and/or floating agglomerates. Indeed, the agglomerates are generally less well or even not hydrolyzed in step c. subsequent enzymatic hydrolysis. In a particular embodiment of the invention, the impregnation step b.i. is carried out for a period of between 5 and 30 minutes, preferably for 15 minutes. The impregnation step b.i. may include agitation.
L’homme du métier sait mettre en oeuvre les actions nécessaires pour obtenir l’homogénéisation désirée. Par exemple, un brassage pourra être mis en oeuvre jusqu’à la disparition des blocs flottants, notamment de taille supérieure à 10 cm, disparition qui pourra être déterminée par un contrôle visuel effectué à intervalle prédéterminé et/ou régulier dans le réacteur. A person skilled in the art knows how to implement the actions necessary to obtain the desired homogenization. For example, mixing may be implemented until the disappearance of the floating blocks, in particular larger than 10 cm, disappearance which may be determined by a visual check carried out at predetermined and/or regular intervals in the reactor.
La biomasse imprégnée obtenue à l’issue de l’étape b.i. présente typiquement une teneur en matière sèche totale comprise entre 5% et 30%, notamment entre 10% et 20%. The impregnated biomass obtained at the end of step b.i. typically has a total dry matter content of between 5% and 30%, in particular between 10% and 20%.
Dans un mode de réalisation particulier de l’invention, notamment dans le cas d’une biomasse brute compacte telle que des balles de papier/carton, ledit procédé pourra comprendre une étape a. de broyage de ladite biomasse lignocellulosique brute comprenant des déchets papetiers. In a particular embodiment of the invention, in particular in the case of a compact raw biomass such as bales of paper/cardboard, said method may comprise a step a. grinding said raw lignocellulosic biomass comprising paper waste.
Selon un mode de réalisation particulier du procédé de l’invention la biomasse lignocellulosique est apportée sous la forme de déchets papetiers. According to a particular embodiment of the process of the invention, the lignocellulosic biomass is supplied in the form of paper waste.
Selon un mode particulier du procédé de l’invention, la biomasse lignocellulosique est apportée sous la forme de Fraction Fermentescible d’Ordures Ménagères (FFOM). According to a particular mode of the process of the invention, the lignocellulosic biomass is supplied in the form of Fermentable Fraction of Household Waste (FFOM).
Dans un mode de réalisation particulier de l’invention, ledit procédé ne comprend pas d’étape de broyage de ladite biomasse lignocellulosique comprenant des déchets papetiers. Cela permet une meilleure tolérance vis-à-vis de la qualité de la biomasse entrante, les impuretés plastiques ou métalliques n’affectant pas l’efficacité ou le bon déroulement du procédé. In a particular embodiment of the invention, said method does not include a step of grinding said lignocellulosic biomass comprising paper waste. This allows a better tolerance with respect to the quality of the incoming biomass, plastic or metallic impurities not affecting the efficiency or the smooth running of the process.
Dans le contexte de l’invention, la biomasse lignocellulosique subit un prétraitement thermique afin d’augmenter sa réactivité à l’hydrolyse enzymatique et l’accessibilité de la cellulose aux enzymes. In the context of the invention, the lignocellulosic biomass undergoes a thermal pretreatment in order to increase its reactivity to enzymatic hydrolysis and the accessibility of cellulose to enzymes.
Dans l’art antérieur, un agent chimique de type acide ou base est habituellement ajouté à la biomasse lignocellulosique pour améliorer (catalyser) la libération de la cellulose. Cependant, la présence d’un catalyseur chimique génère des nuisances importantes en termes de purification, impactant fortement la viabilité économique de la filière. In the prior art, a chemical agent of the acid or base type is usually added to the lignocellulosic biomass to improve (catalyze) the release of the cellulose. However, the presence of a chemical catalyst generates significant nuisances in terms of purification, strongly impacting the economic viability of the sector.
Ainsi, l’étape de prétraitement thermique b.ii. est mise en oeuvre en l’absence d’ajout d’acide, de préférence en l’absence de catalyseur chimique. Cela permet d’éviter la génération de molécules inhibitrices (notamment pour l’étape fermentation), de réduire les coûts opérationnels liés à l’utilisation de ces catalyseurs chimiques ainsi que la complexité des solutions de « downstream processing », tout en obtenant un rendement massique optimum. Avantageusement, l’étape de prétraitement thermique b.ii. est mise en oeuvre à une pression comprise entre 1 et 5 bars, de préférence entre 1.5 et 3 bars, de manière plus préférée à une pression égale à environ 2 bars. Thus, the thermal pretreatment step b.ii. is implemented in the absence of addition of acid, preferably in the absence of chemical catalyst. This makes it possible to avoid the generation of inhibitory molecules (in particular for the fermentation step), to reduce the operational costs linked to the use of these chemical catalysts as well as the complexity of the "downstream processing" solutions, while obtaining a yield optimum mass. Advantageously, the thermal pretreatment step b.ii. is carried out at a pressure of between 1 and 5 bars, preferably between 1.5 and 3 bars, more preferably at a pressure equal to approximately 2 bars.
Typiquement, l’étape de prétraitement thermique b.ii. est mise en oeuvre pendant une durée comprise entre 10 minutes et 120 minutes, de préférence entre 10 minutes et 60 minutes, de manière plus préférée pendant 30 minutes. Typically, the heat pretreatment step b.ii. is carried out for a period of between 10 minutes and 120 minutes, preferably between 10 minutes and 60 minutes, more preferably for 30 minutes.
Lesdites étapes d’imprégnation b.i. et de prétraitement thermique b.ii peuvent être réalisées simultanément ou de façon successive, notamment en fonction de la compacité de la biomasse lignocellulosique. Lorsque les étapes d’imprégnation b.i. et de prétraitement thermique b.ii. sont réalisées simultanément, ces deux étapes peuvent être mises en oeuvre pendant une durée totale comprise entre 10 minutes et 120 minutes, de préférence entre 10 minutes et 60 minutes, de manière plus préférée pendant 30 minutes. Said steps of impregnation bi and of thermal pretreatment b.ii can be carried out simultaneously or successively, in particular depending on the compactness of the lignocellulosic biomass. When the steps of impregnation bi and heat pretreatment b.ii. are carried out simultaneously, these two steps can be implemented for a total duration of between 10 minutes and 120 minutes, preferably between 10 minutes and 60 minutes, more preferably for 30 minutes.
Dans un mode de réalisation particulier de l’invention, l’étape d’imprégnation b.i. et l’étape de prétraitement thermique b.ii. sont réalisées simultanément, e.g. au sein d’un même réacteur, notamment en présence de biomasses lignocellulosiques très déliées telles que du papier non compacté. In a particular embodiment of the invention, the impregnation step b.i. and the heat pretreatment step b.ii. are carried out simultaneously, e.g. within the same reactor, in particular in the presence of very loose lignocellulosic biomasses such as uncompacted paper.
Dans un autre mode de réalisation préféré de l’invention, l’étape d’imprégnation b.i. et l’étape de prétraitement thermique b.ii. sont réalisées de façon successive, e.g. au sein de deux réacteurs différents. L’étape d’imprégnation b.i. est donc suivie d’une étape de prétraitement thermique b.ii. On contrôle alors mieux l’homogénéisation de la biomasse dans l’étape d’imprégnation. Cela présente l’avantage de rendre plus homogène et plus accessible la biomasse pour l’effet des enzymes, tout en assurant l’inactivation des microorganismes (notamment bactéries) présents initialement. In another preferred embodiment of the invention, the impregnation step b.i. and the heat pretreatment step b.ii. are carried out successively, e.g. in two different reactors. The impregnation step b.i. is therefore followed by a thermal pretreatment step b.ii. The homogenization of the biomass is then better controlled in the impregnation step. This has the advantage of making the biomass more homogeneous and more accessible for the effect of the enzymes, while ensuring the inactivation of the microorganisms (in particular bacteria) present initially.
Dans le contexte de l’invention, le produit prétraité obtenu à l’issue de l’étape b. peut être également désigné par le terme de « pâte » ou « slurry ». Cela signifie par exemple que les morceaux de papier ou de carton ne sont plus visibles à l’œil nu. In the context of the invention, the pretreated product obtained at the end of step b. may also be referred to by the term “dough” or “slurry”. This means, for example, that pieces of paper or cardboard are no longer visible to the naked eye.
Optionnellement, l’étape b. peut-être suivie d’une étape de congélation et/ou de décongélation et/ou de pasteurisation afin de limiter les risques de contamination dans l’étape subséquente d’hydrolyse enzymatique, ce qui pourrait entraîner des baisses de rendement. Optionally, step b. may be followed by a freezing and/or thawing and/or pasteurization step in order to limit the risks of contamination in the subsequent enzymatic hydrolysis step, which could lead to yield reductions.
Dans un mode de réalisation particulier de l’invention, l’étape d’hydrolyse enzymatique c. est effectuée au moyen d’un cocktail enzymatique tel qu’un mélange d’enzymes cellulolytiques et/ou hémicellulolytiques, notamment un mélange de cellulases et d’hémicellulases. In a particular embodiment of the invention, the enzymatic hydrolysis step c. is carried out by means of an enzymatic cocktail such as a mixture of cellulolytic and/or hemicellulolytic enzymes, in particular a mixture of cellulases and hemicellulases.
Les cellulases peuvent être choisies dans le groupe constitué par les endocellulases, les exocellulases, les b-glucosidases et leurs mélanges. The cellulases can be chosen from the group consisting of endocellulases, exocellulases, b-glucosidases and mixtures thereof.
Les hémicellulases peuvent être choisies dans le groupe constitué par les xylanases, les xylosidases, les endoglucanases, les endoxylanases, les endoxylanases et les b-xylosidases, ainsi que certaines arabinofuranosidases et esterases, et leurs mélanges. The hemicellulases can be chosen from the group consisting of xylanases, xylosidases, endoglucanases, endoxylanases, endoxylanases and b-xylosidases, as well as certain arabinofuranosidases and esterases, and mixtures thereof.
De préférence, le mélange d’enzymes cellulolytiques et/ou hémicellulolytiques est choisi parmi Ctech3® (Novozymes), Deltazym® (WeissBioTech) et Isobake CX®, de manière plus préférée Ctech3®. Preferably, the mixture of cellulolytic and/or hemicellulolytic enzymes is chosen from Ctech3® (Novozymes), Deltazym® (WeissBioTech) and Isobake CX®, more preferably Ctech3®.
Typiquement, l’étape d’hydrolyse c. est mise en œuvre en utilisant entre 10 et 60 mg d’enzymes par g de biomasse, de préférence entre 10 et 60 mg d’enzymes par g de cellulose, de manière encore préférée entre 15 et 25 mg d’enzymes par g de cellulose. Typically, the hydrolysis step c. is implemented using between 10 and 60 mg of enzymes per g of biomass, preferably between 10 and 60 mg of enzymes per g of cellulose, more preferably between 15 and 25 mg of enzymes per g of cellulose .
Dans un mode de réalisation particulier de l’invention, le rendement de l’hydrolyse enzymatique est compris entre 40% et 80%, typiquement entre 60% et 70%. En théorie, le rendement est calculé comme le rapport de la quantité de sucre monomérique libéré sur la quantité molaire totale disponible initialement. En pratique, les inventeurs ont mesuré la quantité de glucose libéré par rapport au taux de cellulose (taux de cellulose = quantité en poids dans quantité totale de matière brute). In a particular embodiment of the invention, the yield of the enzymatic hydrolysis is between 40% and 80%, typically between 60% and 70%. In theory, the Yield is calculated as the ratio of the amount of monomeric sugar released to the total molar amount initially available. In practice, the inventors have measured the quantity of glucose released relative to the cellulose content (cellulose content=quantity by weight in total quantity of raw material).
Cette étape d’hydrolyse enzymatique c. permet d’hydrolyser les sucres issus à la fois des fractions cellulosiques et hémicellulosiques. This enzymatic hydrolysis step c. hydrolyzes sugars from both cellulosic and hemicellulose fractions.
Dans un mode de réalisation particulier de l’invention, l’étape c. comprend une étape préalable d’ajustement du pH afin d’obtenir un pH acide, par exemple un pH d’environ 5. Le produit prétraité obtenu à l’issue de l’étape b., optionnellement congelé et/ou décongelé et/ou pasteurisé, présente en général un pH basique ou neutre, si bien que l’ajustement de pH est généralement effectué au moyen d’ajout d’un acide tel que l’acide sulfurique ou l’acide phosphorique, de préférence l’acide sulfurique. In a particular embodiment of the invention, step c. comprises a preliminary step of adjusting the pH in order to obtain an acid pH, for example a pH of approximately 5. The pretreated product obtained at the end of step b., optionally frozen and/or thawed and/or pasteurized, generally has a basic or neutral pH, so that the pH adjustment is generally carried out by means of adding an acid such as sulfuric acid or phosphoric acid, preferably sulfuric acid.
Par rapport à une biomasse 2G traitée par les procédés de traitement classiques, par exemple à base d’acide, le sirop de sucres généré après hydrolyse enzymatique contient une charge minérale plus faible, facilitant les étapes de purification et ne créant aucun complexe inhibiteur de fermentation comme le Furfural ou HMF, tout en permettant l’augmentation des rendements de libération des sucres. Compared to a 2G biomass treated by conventional treatment processes, for example acid-based, the sugar syrup generated after enzymatic hydrolysis contains a lower mineral load, facilitating the purification steps and creating no fermentation inhibitor complex such as Furfural or HMF, while allowing increased yields of sugar release.
Dans un mode de réalisation particulier de l’invention, le sirop de sucres comprenant des sucres fermentescibles, en particulier le sirop comprenant du glucose, récupéré à l’issue de l’étape d. présente au moins l’une des caractéristiques suivantes : In a particular embodiment of the invention, the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, recovered at the end of step d. has at least one of the following characteristics:
- une teneur en matière sèche totale comprise entre 5% et 25%, de préférence entre 5% et 20% en particulier entre 10% et 20% en poids; - a total dry matter content of between 5% and 25%, preferably between 5% and 20%, in particular between 10% and 20% by weight;
- une teneur en glucose libre comprise entre 60% et 75%, typiquement entre 65% et 70% en poids de la matière sèche ; - a free glucose content of between 60% and 75%, typically between 65% and 70% by weight of the dry matter;
- un ratio de glucose sur sucres totaux compris entre 60% et 90%, de préférence entre 80% et 90% en poids de la matière sèche. - a ratio of glucose to total sugars of between 60% and 90%, preferably between 80% and 90% by weight of the dry matter.
Dans le contexte de l’invention, la teneur en matière sèche représente l’ensemble des matières sèches présentes dans le produit, mesurée par exemple suivant le protocole décrit dans la norme ISO 6731. La teneur en glucose libre représente la quantité de glucose (en masse sèche) par rapport à la quantité totale de matière (en masse sèche également) présente dans le produit, ce paramètre étant classiquement mesuré en phase liquide par HPLC ou par une méthode analytique équivalente puis estimé par calcul. In the context of the invention, the dry matter content represents all the dry matter present in the product, measured for example according to the protocol described in the ISO 6731 standard. The free glucose content represents the quantity of glucose (in dry mass) relative to the total quantity of material (also in dry mass) present in the product, this parameter being conventionally measured in the liquid phase by HPLC or by an equivalent analytical method then estimated by calculation.
Dans un mode de réalisation particulier de l’invention, ledit procédé comprend en outre les étapes suivantes : e. une étape de clarification du sirop de sucres comprenant des sucres fermentescibles, en particulier du sirop comprenant du glucose, récupéré à l’issue de l’étape d. afin de séparer les résidus solides des résidus liquides, ladite étape de clarification comprenant de préférence une étape de dégrillage, tamisage et/ou de décantation et/ou de centrifugation ; f. une étape de purification, de préférence sur charbon actif, du sirop de sucres comprenant des sucres fermentescibles, en particulier du sirop comprenant du glucose, obtenu à l’issue de l’étape e. ; et g. une étape de récupération du sirop de sucres comprenant des sucres fermentescibles, en particulier du sirop comprenant du glucose, purifié obtenu à l’issue de l’étape f. Avantageusement, l’étape de clarification e. comprend une étape de tamisage et/ou de décantation et/ou de centrifugation. Dans un mode de réalisation particulier, l’étape de clarification e. comprend une étape de tamisage, de décantation et de centrifugation. In a particular embodiment of the invention, said method further comprises the following steps: e. a step of clarifying the sugar syrup comprising fermentable sugars, in particular syrup comprising glucose, recovered at the end of step d. in order to separate the solid residues from the liquid residues, said step of clarifying preferably comprising a step of screening, sieving and/or settling and/or centrifugation; f. a purification step, preferably on activated carbon, of the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, obtained at the end of step e. ; and g. a step for recovering the sugar syrup comprising fermentable sugars, in particular syrup comprising purified glucose obtained at the end of step f. Advantageously, the clarification step e. comprises a sieving and/or decantation and/or centrifugation step. In a particular embodiment, the clarification step e. includes a step of sieving, settling and centrifugation.
L’étape de purification f. selon l’invention permet d’éliminer les matières en suspension résiduelles, telles qu’une partie des ions et/ou sels, et de capter certains contaminants solubles tels que les sels métalliques et les résidus d’encre. The purification step f. according to the invention makes it possible to eliminate residual suspended matter, such as some of the ions and/or salts, and to capture certain soluble contaminants such as metallic salts and ink residues.
Avantageusement, l’étape de purification f. est effectuée par filtration sur charbon actif. Des exemples non limitatifs de charbon actif utilisables dans l’étape f. sont Colorsorb 620 en poudre (Jacobi), BGX en grain (Chemviron), CPW en poudre (Chemviron), CXV (charbon ancien). Ainsi, concernant la purification, la combinaison d’une simple étape de clarification (séparation solide/liquide) et un passage sur charbon actif apparaît suffisante. Cela constitue un avantage par rapport aux procédés de l’art antérieur, et notamment des sucres 2G, qui requièrent habituellement une étape de purification par chromatographie ionique. Advantageously, the purification step f. is carried out by filtration on activated carbon. Non-limiting examples of activated carbon usable in step f. are Colorsorb 620 powder (Jacobi), BGX granular (Chemviron), CPW powder (Chemviron), CXV (old coal). Thus, concerning purification, the combination of a simple clarification step (solid/liquid separation) and passage over activated carbon appears sufficient. This constitutes an advantage compared to the methods of the prior art, and in particular 2G sugars, which usually require a purification step by ion chromatography.
Dans un mode de réalisation particulier de l’invention, après l’étape de purification f. ou de récupération g., ledit procédé comprend en outre : h. une étape de concentration, de préférence au moyen d’un évaporateur sous vide, de manière plus préférée au moyen d’un évaporateur couche mince à recirculation forcée ou à flot tombant, du sirop de sucres comprenant des sucres fermentescibles, en particulier du sirop comprenant du glucose, purifié obtenu à l’issue de l’étape f. ou g. ; et i. une étape de récupération du sirop de sucres comprenant des sucres fermentescibles, en particulier du sirop comprenant du glucose, purifié et concentré obtenu à l’issue de l’étape h. In a particular embodiment of the invention, after purification step f. or recovery g., said method further comprising: h. a step of concentrating, preferably by means of a vacuum evaporator, more preferably by means of a forced recirculation or falling film thin film evaporator, the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, purified obtained at the end of step f. or g. ; and i. a step for recovering the sugar syrup comprising fermentable sugars, in particular syrup comprising glucose, purified and concentrated obtained at the end of step h.
L’étape de concentration permet notamment d’assurer la stabilité du produit en réduisant le risque de développement de contaminations (bactériennes notamment). The concentration step makes it possible in particular to ensure the stability of the product by reducing the risk of development of contamination (bacterial in particular).
Dans un mode de réalisation particulier, le sirop de sucres comprenant des sucres fermentescibles, en particulier le sirop comprenant du glucose, récupéré à l’issue de l’étape g. ou i., présente au moins l’une des caractéristiques suivantes : In a particular embodiment, the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, recovered at the end of step g. or i., has at least one of the following characteristics:
- une teneur en matière sèche totale comprise entre 45% et 75%, de préférence de 50% ou de 60% en poids ; - a total dry matter content of between 45% and 75%, preferably 50% or 60% by weight;
- une teneur en glucose libre comprise entre 60% et 75%, typiquement entre 65% et 70% en poids de la matière sèche ; - un ratio de glucose sur sucres totaux compris entre 70% et 90%, typiquement entre 75% et 85%, notamment de 80% en poids de la matière sèche . - a free glucose content of between 60% and 75%, typically between 65% and 70% by weight of the dry matter; - a ratio of glucose to total sugars of between 70% and 90%, typically between 75% and 85%, in particular 80% by weight of the dry matter.
Dans un mode de réalisation préféré, le procédé de production d’un sirop comprenant du glucose à partir de biomasse lignocellulosique comprenant des déchets papetiers, notamment de papier imprimable, de papier imprimé ou de carton, comprend les étapes suivantes: a. optionnellement, une étape de broyage de ladite biomasse lignocellulosique comprenant des déchets papetiers ; b. i. une étape d’imprégnation de ladite biomasse lignocellulosique comprenant des déchets papetiers ou de la biomasse lignocellulosique broyée obtenue à l’issue de l’étape a. en milieu aqueux, de préférence dans de l’eau et à température ambiante, et ii. une étape de prétraitement thermique mise en oeuvre en l’absence d’ajout d’acide, à une température comprise entre 80°C et 150°C, de préférence entre 90°C et 130°C, de manière plus préférée à 100°C ou 120°C, à un pH compris entre 6.5 et 8.5, notamment entre 6.5 et 8, notamment à un pH compris entre 6.8 et 7.5, de préférence à un pH neutre, afin d’obtenir un produit prétraité, lesdites étapes d’imprégnation et de prétraitement thermique étant réalisées simultanément ou de façon successive selon i. puis ii.; c. une étape d’hydrolyse enzymatique du produit prétraité obtenu à l’issue de l’étape b. afin de convertir la cellulose et l’hémicellulose en un sirop comprenant du glucose ; d. une étape de récupération du sirop comprenant du glucose obtenu à l’issue de l’étape c ; e. une étape de clarification du sirop comprenant du glucose récupéré à l’issue de l’étape d. afin de séparer les résidus solides des résidus liquides, ladite étape de clarification comprenant de préférence une étape de dégrillage, de tamisage et/ou de décantation et/ou de centrifugation ; f. une étape de purification sur charbon actif du sirop comprenant du glucose obtenu à l’issue de l’étape e. ; g. une étape de récupération du sirop comprenant du glucose purifié obtenu à l’issue de l’étape f ; h. une étape de concentration, de préférence au moyen d’un évaporateur sous vide, de manière plus préférée au moyen d’un évaporateur couche mince à recirculation forcée ou à flot tombant, du sirop comprenant du glucose purifié obtenu à l’issue de l’étape g. ; et i. une étape de récupération du sirop comprenant du glucose, purifié et concentré obtenu à l’issue de l’étape h. In a preferred embodiment, the method for producing a syrup comprising glucose from lignocellulosic biomass comprising paper waste, in particular printable paper, printed paper or cardboard, comprises the following steps: a. optionally, a step of grinding said lignocellulosic biomass comprising paper waste; b. i. a step of impregnating said lignocellulosic biomass comprising paper waste or crushed lignocellulosic biomass obtained at the end of step a. in an aqueous medium, preferably in water and at room temperature, and ii. a heat pretreatment step carried out in the absence of acid addition, at a temperature between 80°C and 150°C, preferably between 90°C and 130°C, more preferably at 100°C C or 120° C., at a pH of between 6.5 and 8.5, in particular between 6.5 and 8, in particular at a pH of between 6.8 and 7.5, preferably at a neutral pH, in order to obtain a pretreated product, said steps of impregnation and thermal pretreatment being carried out simultaneously or successively according to i. then ii.; vs. a step of enzymatic hydrolysis of the pretreated product obtained at the end of step b. to convert cellulose and hemicellulose into a syrup comprising glucose; d. a step for recovering the syrup comprising glucose obtained at the end of step c; e. a syrup clarification step comprising glucose recovered at the end of step d. in order to separate the solid residues from the liquid residues, said clarification step preferably comprising a step of screening, sieving and/or decantation and/or centrifugation; f. a step of purification on activated carbon of the syrup comprising glucose obtained at the end of step e. ; g. a step for recovering the syrup comprising purified glucose obtained at the end of step f; h. a concentration step, preferably by means of a vacuum evaporator, more preferably by means of a forced recirculation or falling film thin film evaporator, of the syrup comprising purified glucose obtained at the end of the step g. ; and i. a step for recovering the syrup comprising glucose, purified and concentrated obtained at the end of step h.
L’invention concerne également un sirop de sucres comprenant des sucres fermentescibles, en particulier sirop comprenant du glucose, susceptible d’être obtenu par le procédé selon l’invention, caractérisé en ce que ledit sirop présente: The invention also relates to a sugar syrup comprising fermentable sugars, in particular syrup comprising glucose, which can be obtained by the process according to the invention, characterized in that the said syrup has:
- un ratio de glucose sur sucres totaux compris entre 70% et 90%, ou entre 75% et 85%, de préférence entre 80% et 85% en poids de la matière sèche ; et/ou - a ratio of glucose to total sugars of between 70% and 90%, or between 75% and 85%, of preferably between 80% and 85% by weight of the dry matter; and or
- une teneur en furfural ou hydroxymethylfurfural (HMF) de préférence inférieure à 5000 ppm, avantageusement inférieure à 200 ppm. - a content of furfural or hydroxymethylfurfural (HMF) preferably less than 5000 ppm, advantageously less than 200 ppm.
Ledit sirop peut comprendre des constituants autres que le glucose, lesdits constituants étant présents dans des proportions comprises entre 10% et 30% en poids de la matière sèche. Des exemples non limitatifs desdits constituants sont des sucres tels que le xylose, le galactose, l’arabinose, le mannose, des traces de solvant, des traces de cendres. Said syrup may comprise constituents other than glucose, said constituents being present in proportions of between 10% and 30% by weight of the dry matter. Non-limiting examples of said constituents are sugars such as xylose, galactose, arabinose, mannose, traces of solvent, traces of ash.
L’invention concerne également l’utilisation du procédé selon l’invention, ou du sirop selon l’invention pour produire des molécules biosourcées. The invention also relates to the use of the method according to the invention, or of the syrup according to the invention to produce biosourced molecules.
Des exemples non limitatifs de molécules biosourcées selon l’invention sont : les sucres (monosaccharides), l’éthanol, l’isobutène, le 1 ,3-propanediol, le 2,3-butanediol, l’acide 3- hydroxypropionique, l’acide acétique, l’acide butyrique, l’acide caprique, l’acide citrique, l’acide fumarique, l’acide malique, l’acide propionique, l’acide pyruvique, l’acide succinique, l’acide lévulinique, l’acide 2,5-furandicarboxylique, le sorbitol, et le xylitol. Non-limiting examples of biosourced molecules according to the invention are: sugars (monosaccharides), ethanol, isobutene, 1,3-propanediol, 2,3-butanediol, 3-hydroxypropionic acid, acetic acid, butyric acid, capric acid, citric acid, fumaric acid, malic acid, propionic acid, pyruvic acid, succinic acid, levulinic acid, 2,5-furandicarboxylic acid, sorbitol, and xylitol.
A titre d’exemple, les molécules suivantes peuvent être produites par conversion biologique du glucose et ont été décrites dans l’art antérieur : l’acide lactique (Xu et al., 2014, Yadav et al., 2020), l’acide acétique (Kondo et al., 1996), l’acide butyrique (Fu et al., 2017), l’acide propionique (Wang et al., 2013), l’acide succinique (Ong et al., 2019), l’isopropanol (Ferreira dos Santos Vieira et al., 2020), l’isobutène (US20180057843, US9249430, WO2014086781 ), le butanol (Cheng et al., 2019 ; Birgen et al., 2019) et le farnesane (W02007139924, W02008045555). By way of example, the following molecules can be produced by biological conversion of glucose and have been described in the prior art: lactic acid (Xu et al., 2014, Yadav et al., 2020), lactic acid acetic acid (Kondo et al., 1996), butyric acid (Fu et al., 2017), propionic acid (Wang et al., 2013), succinic acid (Ong et al., 2019), l isopropanol (Ferreira dos Santos Vieira et al., 2020), isobutene (US20180057843, US9249430, WO2014086781), butanol (Cheng et al., 2019; Birgen et al., 2019) and farnesane (W02007139924, W0200886781)045555) .
Les molécules biosourcées selon l’invention sont de préférence choisies dans le groupe constitué par l’acide lactique, l’acide acétique, l’acide butyrique, l’acide proprionique, l’acide succinique, l’isopropanol et l’isobutène, de manière encore plus préférée dans le groupe constitué par l’acide lactique, l’acide acétique, l’acide butyrique, l’acide proprionique et l’isopropanol. The biosourced molecules according to the invention are preferably chosen from the group consisting of lactic acid, acetic acid, butyric acid, proprionic acid, succinic acid, isopropanol and isobutene, even more preferably from the group consisting of lactic acid, acetic acid, butyric acid, proprionic acid and isopropanol.
L’invention concerne également l’utilisation du procédé selon l’invention, ou du sirop selon l’invention pour produire des biocarburants, de préférence de l’éthanol. The invention also relates to the use of the process according to the invention, or of the syrup according to the invention to produce biofuels, preferably ethanol.
L’invention concerne également un procédé de production de biocarburants, en particulier d’éthanol, comprenant les étapes du procédé selon l’invention et une étape subséquente de fermentation afin de convertir le sirop de sucres comprenant des sucres fermentescibles, en particulier le sirop comprenant du glucose, récupéré à l’issue de l’étape g. ou i. en biocarburants, en particulier en éthanol. The invention also relates to a method for producing biofuels, in particular ethanol, comprising the steps of the method according to the invention and a subsequent fermentation step in order to convert the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, recovered at the end of step g. Yes. into biofuels, especially ethanol.
Dans un mode de réalisation particulier de l’invention, l’étape de fermentation est effectuée au moyen de levures et/ou de bactéries. Les levures peuvent être choisies dans le groupe constitué par des levures du genre Saccharomyces, Yarrowia et Leuconostoc. Les bactéries peuvent être choisies dans le groupe constitué par les bactéries du genre Bacillus, Lactobacillus, Acetobacter, Escherichia, Clostridium et Zymomonas. De préférence, l’étape de fermentation est effectuée au moyen de levures du genre Saccharomyces, de préférence Saccharomyces cerevisiae. Les bactéries peuvent être choisies parmi Clostridium acetobutylicum ou Escherichia coli. Dans un mode de réalisation particulier les levures ou les bactéries sont choisies pour leur aptitude à réaliser la fermentation alcoolique. In a particular embodiment of the invention, the fermentation step is carried out using yeasts and/or bacteria. The yeasts can be chosen from the group consisting of yeasts of the genus Saccharomyces, Yarrowia and Leuconostoc. The bacteria can be chosen from the group consisting of bacteria of the genus Bacillus, Lactobacillus, Acetobacter, Escherichia, Clostridium and Zymomonas. Preferably, the fermentation step is carried out using yeasts of the genus Saccharomyces, preferably Saccharomyces cerevisiae. The bacteria can be chosen from Clostridium acetobutylicum or Escherichia coli. In a particular embodiment, the yeasts or the bacteria are chosen for their ability to carry out the alcoholic fermentation.
L’étape de fermentation selon l’invention peut être effectuée au moyen de levures et/ou de bactéries capables de fermenter à la fois les hexoses et les pentoses. The fermentation step according to the invention can be carried out using yeasts and/or bacteria capable of fermenting both hexoses and pentoses.
Cette étape de fermentation permet de convertir les sucres issus à la fois des fractions celulosiques et hémicellulosiques en biocarburants, en particulier en éthanol. This fermentation step converts the sugars from both cellulosic and hemicellulosic fractions into biofuels, in particular ethanol.
Cette étape de fermentation peut avoir lieu avant les étapes ultérieures dites de « downstream Processing », c’est-à-dire notamment avant les étapes de clarification e., de purification f. ou de concentration h. This fermentation step can take place before the subsequent so-called “downstream Processing” steps, that is to say in particular before the clarification steps e., purification steps f. or concentration h.
Dans un mode de réalisation particulier de l’invention, l’étape de fermentation est effectuée dans un réacteur distinct de celui de l’étape d’hydrolyse enzymatique (procédé SHF) ou simultanément dans le même réacteur (procédés SSF, SSCF, CBP), de préférence dans un réacteur distinct de celui de l’étape d’hydrolyse enzymatique (procédé SHF). In a particular embodiment of the invention, the fermentation step is carried out in a separate reactor from that of the enzymatic hydrolysis step (SHF process) or simultaneously in the same reactor (SSF, SSCF, CBP processes) , preferably in a separate reactor from that of the enzymatic hydrolysis step (SHF process).
Si l’étape de fermentation est effectuée simultanément dans le même réacteur que celui de l’étape d’hydrolyse enzymatique, le procédé selon l’invention ne comprend pas d’étape d. Selon un mode de réalisation, le procédé peut comprendre, après l’étape de fermentation, une étape de purification de la molécule biosourcée ou du biocarburant, par exemple par distillation, notamment dans le cas de l’éthanol, l’étape de distillation étant précédée ou non par une étape de clarification. If the fermentation step is carried out simultaneously in the same reactor as that of the enzymatic hydrolysis step, the method according to the invention does not include step d. According to one embodiment, the method may comprise, after the fermentation step, a step for purifying the biosourced molecule or the biofuel, for example by distillation, in particular in the case of ethanol, the distillation step being whether or not preceded by a clarification step.
Tous les modes de réalisation décrits ci-dessus peuvent être combinés entre eux. All the embodiments described above can be combined with each other.
Exemples Examples
Les exemples suivants sont donnés à titre purement illustratif, et ne doivent en rien être interprétés comme limitant l’invention. The following examples are given for illustrative purposes only, and should in no way be interpreted as limiting the invention.
Exemple 1. Sirop de sucres obtenu à l’issue des étapes de prétraitement thermique et d’hydrolyse enzymatique. Example 1. Sugar syrup obtained at the end of the thermal pretreatment and enzymatic hydrolysis stages.
Le sirop de sucres obtenu à l’issue de l’étape d’hydrolyse enzymatique c. du procédé selon l’invention a les caractéristiques suivantes : The sugar syrup obtained at the end of the enzymatic hydrolysis step c. of the process according to the invention has the following characteristics:
- une teneur en matière sèche totale de 6,1%, - a total dry matter content of 6.1%,
- 70,7% de glucose libre, - 70.7% free glucose,
- un ratio de glucose sur sucres totaux de : 84,7%. - a ratio of glucose to total sugars of: 84.7%.
Le Tableau 1 ci-dessous indique la composition de ce jus sucré. Table 1 below indicates the composition of this sugar juice.
[Tableau 1] [Table 1]
Exemple 2. Sirop de sucres obtenu à l’issue des étapes de séparation solide/liquide (clarification), purification et concentration. Example 2. Sugar syrup obtained at the end of the solid/liquid separation (clarification), purification and concentration stages.
Le sirop de sucres obtenu à l’issue de l’étape i. du procédé selon l’invention a les caractéristiques suivantes : The sugar syrup obtained at the end of step i. of the process according to the invention has the following characteristics:
- une teneur en matière sèche totale de 59,79%, - a total dry matter content of 59.79%,
- 70,8% de glucose libre, - 70.8% free glucose,
- un ratio de glucose sur sucres totaux est de : 80,5%. Le Tableau 2 ci-dessous indique la composition de ce jus sucré. - a ratio of glucose to total sugars is: 80.5%. Table 2 below indicates the composition of this sweet juice.
[Tableau 2] [Table 2]
Exemple 3. Différents essais concernant l’étape de prétraitement Example 3. Different tests concerning the pretreatment step
Des essais sur la teneur en acide lors de la phase de prétraitement ont été réalisés, ils montrent que la cuisson sans acide permet d’atteindre un rendement massique optimum (Tableau 3). Tests on the acid content during the pre-treatment phase have been carried out; they show that cooking without acid makes it possible to achieve an optimum mass yield (Table 3).
[Tableau 3] [Table 3]
De ces essais, il apparaît que : From these tests, it appears that:
- La meilleure digestibilité est obtenue à partir du papier cuit à 120°C/60min mais sans acide,- The best digestibility is obtained from paper cooked at 120°C/60min but without acid,
- Viennent ensuite les prétraitements à l’acide phosphorique puis à l’acide sulfurique. Les résultats sont mentionnés dans le Tableau 4. - Then come the pre-treatments with phosphoric acid and then with sulfuric acid. The results are listed in Table 4.
[Tableau 4] [Table 4]
Exemple 4. Etude de sensibilité du pH Example 4. pH Sensitivity Study
Une étude de sensibilité du pH a été menée sur un flux de papiers cartons après cuisson présentant les résultats mentionnés dans le Tableau 5. A pH sensitivity study was carried out on a flow of paperboard after curing with the results mentioned in Table 5.
[Tableau 5] [Table 5]
Exemple 5. Etude de l’effet dose (concentration en enzymes) Example 5. Study of the dose effect (enzyme concentration)
Une étude de l’effet dose a été menée sur un flux de papiers cartons après cuisson présentant les résultats mentionnés dans le Tableau 6. [Tableau 6] A study of the dose effect was carried out on a flow of paperboard after curing, presenting the results mentioned in Table 6. [Table 6]
Exemple 6. Tests avec différents cocktails enzymatiques Example 6. Tests with different enzyme cocktails
3 cocktails différents ont été utilisés sur du papier prétraité repulpé en présence de 20mg de protéines enzymatique/ g de cellulose. Les résultats sont mentionnés dans le Tableau 7. [Tableau 7] 3 different cocktails were used on pretreated paper replumped in the presence of 20mg of enzymatic protein/g of cellulose. The results are listed in Table 7. [Table 7]
Exemple 7. Tests avec différents charbons actifs Example 7. Tests with different activated carbons
4 charbons actifs ont été testés pour la purification du sirop de sucres après hydrolyse et clarification : - Colorsorb 620 en poudre de chez Jacobi 4 activated carbons were tested for the purification of sugar syrup after hydrolysis and clarification: - Colorsorb 620 powder from Jacobi
- BGX en grain de Chemviron - CPW en poudre de chez Chemviron - BGX in grain of Chemviron - CPW powder from Chemviron
- CXV (charbon ancien couramment utilisé sur ARD). Les résultats sont mentionnés dans le Tableau 8. [Tableau 8] - CXV (old coal commonly used on ARD). The results are listed in Table 8. [Table 8]
Exemple 8. Fermentation seule Example 8. Fermentation alone
2 sirops de sucres non purifiés et non concentrés ont été utilisés pour tester la croissance d’une souche sauvage de Saccharomyces cerevisiae permettant la conversion du glucose libre en éthanol. Dans un premier temps, les essais ont été réalisés après clarification du sirop sucré (SHF), dans un second temps la levure a été directement ajoutée en milieu ou en fin d’étape d’hydrolyse afin que la fermentation soit effectuée dans le même réacteur (SSF#2 et SSF#1 respectivement). Les résultats obtenus sont mentionnés dans le Tableau 9. 2 unpurified and unconcentrated sugar syrups were used to test the growth of a wild strain of Saccharomyces cerevisiae allowing the conversion of free glucose into ethanol. Initially, the tests were carried out after clarification of the sweet syrup (SHF), then the yeast was directly added in the middle or at the end of the hydrolysis stage so that the fermentation was carried out in the same reactor. (SSF#2 and SSF#1 respectively). The results obtained are mentioned in Table 9.
[Tableau 9] [Table 9]
Exemple 9 : Fermentation comparée d’un sirop de sucres selon l’invention avec un sirop témoin comportant la même quantité de glucose et xylose issu des filières conventionnelles Example 9: Comparative fermentation of a sugar syrup according to the invention with a control syrup comprising the same quantity of glucose and xylose from conventional channels
Un sirop de sucre généré à partir de papiers et cartons (dit sirop de sucres) a pu être testé sur une souche de levure de Saccharomyces cerevisiae apte à produire de l’éthanol commercialisée par la société Lesaffre pour la production d’éthanol (souche Cellux 4). Les essais de fermentation se sont déroulés en Erlenmeyer ou en bouteille Schott à deux concentrations de sucres données : 140 et 210 g/kg de milieu (correspondant aux quantités de glucose et de xylose cumulées) nommées respectivement TAV 8 et TAV 12. Un sirop de sucres témoin (dit 1G) contenant la même quantité de glucose et de xylose a été fabriqué et testé dans les mêmes conditions. A sugar syrup generated from paper and cardboard (called sugar syrup) could be tested on a yeast strain of Saccharomyces cerevisiae capable of producing ethanol marketed by the company Lesaffre for the production of ethanol (strain Cellux 4). The fermentation tests took place in an Erlenmeyer or a Schott bottle at two given sugar concentrations: 140 and 210 g/kg of medium (corresponding to the cumulative quantities of glucose and xylose) named respectively TAV 8 and TAV 12. A sugar syrup control (called 1G) containing the same quantity of glucose and xylose was manufactured and tested under the same conditions.
L’objectif de la comparaison du résultat de la fermentation était de mettre en évidence la qualité et l’absence d’effet inhibiteur du sirop de sucre issu de l’invention lors de la fermentation, par rapport à l’utilisation d’un sirop de glucose et xylose issu de filières conventionnelles, c’est-à- dire produit à partir de ressource 1 G (/.e. 1 ère génération) constituée notamment de betterave, blé, canne à sucre. The objective of the comparison of the result of the fermentation was to highlight the quality and the absence of inhibitory effect of the sugar syrup resulting from the invention during the fermentation, compared to the use of a syrup glucose and xylose from conventional channels, i.e. produced from 1 G resource (/.e. 1st generation) consisting in particular of beet, wheat, sugar cane.
La production d’éthanol a été suivie grâce à la perte en masse liée à la production de CO2, directement corrélée à la production d’éthanol. La concentration finale réelle a également été vérifiée en fin d’expérience par HPLiC . Ethanol production was monitored using mass loss related to CO2 production , directly correlated to ethanol production. The actual final concentration was also checked at the end of the experiment by HPLiC.
Les résultats sont présentés dans le tableau qui suit. L’observation des rendements de conversion montre de très bonnes performances et souligne le potentiel de ces sucres produits à partir de papiers et cartons pour l’intégration dans les filières industrielles de production d’éthanol. The results are presented in the following table. Observation of conversion yields shows very good performance and underlines the potential of these sugars produced from paper and cardboard for integration into industrial ethanol production chains.
TABLEAU CHART
Références References
Nizami et al., Bioresource Technol. 2017, 241 , 1101-1117 ; Nizami et al., Bioresource Technol. 2017, 241, 1101-1117;
Soltanian et al. Energy Conversion and Management 2020, 212, 112792 ; Parisutham et al. Bioresource Technol. 2014, 161, 431-440 ; Xu et al. Bioresource Technol. 2014, 153, 23-29 ; Soltanian et al. Energy Conversion and Management 2020, 212, 112792; Parisutham et al. Bioresource Technol. 2014, 161, 431-440; Xu et al. Bioresource Technol. 2014, 153, 23-29;
Yadav et al. Bioresource Technol. 2020, 11 , 100423 ; Yadav et al. Bioresource Technol. 2020, 11, 100423;
Kondo et al. J. Ferment. Technol. 1996, 81(1), 42-46 ; Kondo et al. J. Ferment. Technology. 1996, 81(1), 42-46;
Fu et al. Bioresource Technol. 2017, 234, 389-396 ; Fu et al. Bioresource Technol. 2017, 234, 389-396;
Wang et al. Bioresource Technol. 2013, 137, 116-123 ; Ong et al., Biochem Eng. J. 2019, 148, 108-115 ; Wang et al. Bioresource Technol. 2013, 137, 116-123; Ong et al., Biochem Eng. J. 2019, 148, 108-115;
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Claims

REVENDICATIONS
1 . Procédé de production d’un sirop de sucres comprenant des sucres fermentescibles à partir de biomasse lignocellulosique comprenant des déchets papetiers, notamment de papier imprimable, de papier imprimé ou de carton, ledit procédé comprenant les étapes suivantes: a. optionnellement, une étape de broyage de ladite biomasse lignocellulosique comprenant des déchets papetiers ; b. i. une étape d’imprégnation de ladite biomasse lignocellulosique comprenant des déchets papetiers ou de la biomasse lignocellulosique broyée obtenue à l’issue de l’étape a. en milieu aqueux, et ii. une étape de prétraitement thermique mise en oeuvre en l’absence d’ajout d’acide, à une température comprise entre 80°C et 150°C, à un pH compris entre 6.5 et 8.5, notamment entre 6.5 et 8, afin d’obtenir un produit prétraité, lesdites étapes d’imprégnation et de prétraitement thermique étant réalisées simultanément ou de façon successive selon i. puis ii. ; c. une étape d’hydrolyse enzymatique du produit prétraité obtenu à l’issue de l’étape b. afin de convertir la cellulose et l’hémicellulose en un sirop de sucres comprenant des sucres fermentescibles; et d. une étape de récupération du sirop de sucres comprenant des sucres fermentescibles obtenu à l’issue de l’étape c. 1 . Process for producing a sugar syrup comprising fermentable sugars from lignocellulosic biomass comprising paper waste, in particular printable paper, printed paper or cardboard, said process comprising the following steps: a. optionally, a step of grinding said lignocellulosic biomass comprising paper waste; b. i. a step of impregnating said lignocellulosic biomass comprising paper waste or crushed lignocellulosic biomass obtained at the end of step a. in an aqueous medium, and ii. a heat pretreatment step implemented in the absence of acid addition, at a temperature between 80° C. and 150° C., at a pH between 6.5 and 8.5, in particular between 6.5 and 8, in order to obtaining a pretreated product, said steps of impregnation and thermal pretreatment being carried out simultaneously or successively according to i. then ii. ; vs. a step of enzymatic hydrolysis of the pretreated product obtained at the end of step b. to convert cellulose and hemicellulose into a sugar syrup comprising fermentable sugars; and D. a step for recovering the sugar syrup comprising fermentable sugars obtained at the end of step c.
2. Procédé selon la revendication 1 , caractérisé en ce que ladite biomasse lignocellulosique avant broyage et/ou imprégnation a une teneur en matière sèche totale comprise entre 70% et 100%, notamment entre 85% et 96%en poids de la biomasse et est constituée de déchets papetiers ou a une teneur en matière sèche totale comprise entre 45% et 96% notamment entre 50% et 70% en poids de la biomasse et est constituée de déchets composés d’un mélange de déchets papetiers et d’un co-substrat par exemple de FFOM .2. Method according to claim 1, characterized in that said lignocellulosic biomass before grinding and / or impregnation has a total dry matter content of between 70% and 100%, in particular between 85% and 96% by weight of the biomass and is consisting of paper waste or has a total dry matter content of between 45% and 96%, in particular between 50% and 70% by weight of the biomass and consists of waste composed of a mixture of paper waste and a co- substrate for example of SWOT.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l’étape de prétraitement thermique b.ii. est mise en oeuvre à une pression comprise entre 1 et 5 bars, de préférence entre 1 .5 et 3 bars, de manière plus préférée à une pression égale à environ 2 bars. 3. Method according to claim 1 or 2, characterized in that the thermal pretreatment step b.ii. is carried out at a pressure of between 1 and 5 bars, preferably between 1.5 and 3 bars, more preferably at a pressure equal to approximately 2 bars.
4. Procédé selon l’une quelconque des revendications 1 à 3, caractérisé en ce que l’étape de prétraitement thermique b.ii. est mise en oeuvre pendant une durée comprise entre 10 minutes et 120 minutes, de préférence entre 10 minutes et 60 minutes, de manière plus préférée pendant 30 minutes. 4. Method according to any one of claims 1 to 3, characterized in that the thermal pretreatment step b.ii. is carried out for a period of between 10 minutes and 120 minutes, preferably between 10 minutes and 60 minutes, more preferably for 30 minutes.
5. Procédé selon l’une quelconque des revendications 1 à 4, caractérisé en ce que l’étape d’hydrolyse enzymatique c. est effectuée au moyen d’un mélange d’enzymes cellulolytiques et/ou hémicellulolytiques, notamment un mélange de cellulases et d’hémicellulases. 5. Method according to any one of claims 1 to 4, characterized in that the enzymatic hydrolysis step c. is carried out using a mixture of cellulolytic and/or hemicellulolytic enzymes, in particular a mixture of cellulases and hemicellulases.
6. Procédé selon l’une quelconque des revendications 1 à 5, caractérisé en ce que le sirop de sucres comprenant des sucres fermentescibles, en particulier le sirop comprenant du glucose, récupéré à l’issue de l’étape d. présente au moins l’une des caractéristiques suivantes : 6. Method according to any one of claims 1 to 5, characterized in that the sugar syrup comprising fermentable sugars, in particular the syrup comprising glucose, recovered at the end of step d. has at least one of the following characteristics:
- une teneur en matière sèche totale comprise entre 5% et 25%, de préférence entre 5% et 15% en poids ; - a total dry matter content of between 5% and 25%, preferably between 5% and 15% by weight;
- une teneur en glucose libre comprise entre 60% et 75%, typiquement entre 65% et 70% en poids de la matière sèche; - a free glucose content of between 60% and 75%, typically between 65% and 70% by weight of the dry matter;
- un ratio de glucose sur sucres totaux compris entre 60% et 90%, de préférence entre 80% et 90% en poids de la matière sèche. - a ratio of glucose to total sugars of between 60% and 90%, preferably between 80% and 90% by weight of the dry matter.
7. Procédé selon l’une quelconque des revendications 1 à 6, caractérisé en ce que ledit procédé comprend en outre les étapes suivantes : e. une étape de clarification du sirop de sucres comprenant des sucres fermentescibles récupéré à l’issue de l’étape d. afin de séparer les résidus solides des résidus liquides ; f. une étape de purification du sirop de sucres comprenant des sucres fermentescibles obtenu à l’issue de l’étape e. ; et g. une étape de récupération du sirop de sucres comprenant des sucres fermentescibles purifié obtenu à l’issue de l’étape f. 7. Method according to any one of claims 1 to 6, characterized in that said method further comprises the following steps: e. a stage of clarification of the sugar syrup comprising fermentable sugars recovered at the end of stage d. in order to separate the solid residues from the liquid residues; f. a step for purifying the sugar syrup comprising fermentable sugars obtained at the end of step e. ; and g. a step for recovering the sugar syrup comprising purified fermentable sugars obtained at the end of step f.
8. Procédé selon la revendication 7, caractérisé en ce qu’après l’étape de purification f., ledit procédé comprend en outre : h. une étape de concentration du sirop de sucres comprenant des sucres fermentescibles purifié obtenu à l’issue de l’étape f. ; et i. une étape de récupération du sirop de sucres comprenant des sucres fermentescibles purifié et concentré obtenu à l’issue de l’étape h. 8. Method according to claim 7, characterized in that after purification step f., said method further comprises: h. a step for concentrating the sugar syrup comprising purified fermentable sugars obtained at the end of step f. ; and i. a step for recovering the sugar syrup comprising purified and concentrated fermentable sugars obtained at the end of step h.
9. Procédé selon la revendication 7, caractérisé en ce que l’étape de purification f. est effectuée par filtration sur charbon actif. 9. Method according to claim 7, characterized in that the purification step f. is carried out by filtration on activated carbon.
10. Procédé selon l’une quelconque des revendications 1 à 9, dans lequel la biomasse lignocellulosique est apportée sous la forme de déchets papetiers. 10. Method according to any one of claims 1 to 9, in which the lignocellulosic biomass is provided in the form of paper waste.
11. Procédé selon l’une quelconque des revendications 1 à 9, dans lequel la biomasse lignocellulosique est apportée sous la forme de Fraction Fermentescible d’Ordures Ménagères (FFOM). 11. Method according to any one of claims 1 to 9, in which the lignocellulosic biomass is provided in the form of Fermentable Fraction of Household Waste (FFOM).
12. Procédé selon l’une quelconque des revendications 7 à 11 , caractérisé en ce que le sirop de sucres comprenant des sucres fermentescibles récupéré à l’issue de l’étape g. ou i. présente au moins l’une des caractéristiques suivantes : 12. Method according to any one of claims 7 to 11, characterized in that the sugar syrup comprising fermentable sugars recovered at the end of step g. Yes. has at least one of the following characteristics:
- une teneur en matière sèche totale comprise entre 50% et 75%, de préférence de 60% en poids; - a total dry matter content of between 50% and 75%, preferably 60% by weight;
- une teneur en glucose libre comprise entre 60% et 75%, typiquement entre 65% et 70% en poids de la matière sèche; - un ratio de glucose sur sucres totaux compris entre 70% et 90%, typiquement entre 75% et 85%, notamment de 80% en poids de la matière sèche. - a free glucose content of between 60% and 75%, typically between 65% and 70% by weight of the dry matter; - a ratio of glucose to total sugars of between 70% and 90%, typically between 75% and 85%, in particular 80% by weight of the dry matter.
13. Procédé selon l’une quelconque des revendications 1 à 12, caractérisé en ce que le sirop de sucres comprenant des sucres fermentescibles est un sirop comprenant du glucose et le cas échéant du xylose. 13. Method according to any one of claims 1 to 12, characterized in that the sugar syrup comprising fermentable sugars is a syrup comprising glucose and, where appropriate, xylose.
14. Sirop de sucres comprenant des sucres fermentescibles, en particulier un sirop comprenant du glucose, susceptible d’être obtenu par le procédé selon l’une quelconque des revendications 1 à 12, caractérisé en ce que ledit sirop présente : 14. Sugar syrup comprising fermentable sugars, in particular a syrup comprising glucose, obtainable by the process according to any one of claims 1 to 12, characterized in that said syrup has:
- un ratio de glucose sur sucres totaux compris entre 70% et 90%, de préférence entre 75% et 85%, notamment entre 80% et 85% en poids de la matière sèche; et/ou - a ratio of glucose to total sugars of between 70% and 90%, preferably between 75% and 85%, in particular between 80% and 85% by weight of the dry matter; and or
- une teneur en furfural ou hydroxymethylfurfural (H MF) de préférence inférieure à 5000 ppm, avantageusement inférieure à 200 ppm. - a content of furfural or hydroxymethylfurfural (H MF) preferably less than 5000 ppm, advantageously less than 200 ppm.
15. Utilisation du procédé selon l’une quelconque des revendications 1 à 12, ou du sirop selon la revendication 14 pour produire des molécules biosourcées, en particulier des molécules biosourcées choisies dans le groupe constitué par l’acide lactique, l’acide acétique, l’acide butyrique, l’acide proprionique, l’acide succinique, l’isopropanol et l’isobutène. 15. Use of the method according to any one of claims 1 to 12, or of the syrup according to claim 14 to produce biosourced molecules, in particular biosourced molecules chosen from the group consisting of lactic acid, acetic acid, butyric acid, proprionic acid, succinic acid, isopropanol and isobutene.
16. Utilisation du procédé selon l’une quelconque des revendications 1 à 12, ou du sirop selon la revendication 14 pour produire des biocarburants, de préférence de l’éthanol. 16. Use of the process according to any one of claims 1 to 12, or of the syrup according to claim 14 to produce biofuels, preferably ethanol.
17. Procédé de production de biocarburants, en particulier d’éthanol, comprenant les étapes du procédé selon les revendications 1 à 12 et une étape subséquente de fermentation afin de convertir le sirop de sucres comprenant des sucres fermentescibles récupéré à l’issue de l’étape g. ou i. en biocarburants, en particulier en éthanol. 17. Process for the production of biofuels, in particular ethanol, comprising the steps of the process according to claims 1 to 12 and a subsequent fermentation step in order to convert the sugar syrup comprising fermentable sugars recovered at the end of the step g. Yes. into biofuels, especially ethanol.
18. Procédé selon la revendication 17, caractérisé en ce que l’étape de fermentation est effectuée au moyen de levures, notamment du genre Saccharomyces, de préférence Saccharomyces cerevisiae, et/ou de bactéries, notamment Clostridium acetobutylicum ou Escherichia coli. 18. Method according to claim 17, characterized in that the fermentation step is carried out using yeasts, in particular of the genus Saccharomyces, preferably Saccharomyces cerevisiae, and/or bacteria, in particular Clostridium acetobutylicum or Escherichia coli.
19. Procédé selon la revendication 17 ou 18 dans lequel l’éthanol est produit avec un rendement mesuré en HPLiC par rapport au sucre supérieur à 40%, par exemple compris entre 45 et 51%. 19. Process according to claim 17 or 18, in which the ethanol is produced with a measured yield of HPLiC relative to the sugar of greater than 40%, for example between 45 and 51%.
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