WO2013151093A1 - Procédé de production d'acide organique - Google Patents

Procédé de production d'acide organique Download PDF

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Publication number
WO2013151093A1
WO2013151093A1 PCT/JP2013/060214 JP2013060214W WO2013151093A1 WO 2013151093 A1 WO2013151093 A1 WO 2013151093A1 JP 2013060214 W JP2013060214 W JP 2013060214W WO 2013151093 A1 WO2013151093 A1 WO 2013151093A1
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organic acid
producing
water
cellulose
mill
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PCT/JP2013/060214
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English (en)
Japanese (ja)
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伸吾 小山
裕 入江
将宏 野場
大樹 浦川
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花王株式会社
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Publication of WO2013151093A1 publication Critical patent/WO2013151093A1/fr

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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
    • C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic 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
    • 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
    • C12P7/40—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
    • C12P7/56—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
    • 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
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the present invention relates to a method for producing an organic acid from biomass.
  • biorefinery that tries to produce raw materials for fuel and chemicals from biomass attracts attention.
  • industrialized biorefinery uses starch or sugar contained in grains such as corn and sugarcane as raw materials, and there is concern about the impact on food supply. Therefore, lignocellulosic biomass contained in non-edible parts of plants such as sugarcane bagasse and rice straw has begun to attract attention as a raw material.
  • Lignocellulosic biomass is mainly contained in the leaves and stems of plants, and has a structure in which lignin and hemicellulose are firmly bound to cellulose. Therefore, the efficiency of the hydrolysis reaction is extremely low, and the hydrolysis must be performed chemically using a strong alkali or a strong acid.
  • a method for avoiding the use of a strong acid or strong alkali having a large environmental load a method is known in which lignocellulosic biomass is pulverized and then hydrolyzed with a hydrolase.
  • an organic acid such as acetic acid forming an ester with a polysaccharide is known (see, for example, Patent Document 1).
  • Patent Document 1 discloses a method for producing a biomass product such as ethanol, in which biomass is brought into contact with an aqueous solution containing ammonia, solid-liquid separation is performed, an inhibitory factor such as acetic acid is separated, and the remaining solid is used in subsequent steps. Is disclosed.
  • Patent Document 2 discloses a method of removing a low-molecular fermentation inhibitor by membrane filtration after saccharification of biomass.
  • Patent Document 3 discloses a method for producing lactic acid by culturing filamentous fungi as a pellet of cell aggregates. This method describes that it is easy to separate the bacterial cells and the medium after fermentation.
  • the present invention provides a method for producing an organic acid comprising the following steps (a) to (d).
  • (A): Lignocellulosic biomass containing cellulose having a cellulose I-type crystallinity of more than 30% represented by the following calculation formula (1) is pulverized, and the cellulose I-type crystallinity is reduced to 0-30% Step of Crystallinity (%) [(I c ⁇ I a ) / I c ] ⁇ 100 (1)
  • Patent Document 1 In the method of Patent Document 1, not only dangerous ammonia is required, but when an organic acid is used, the yield of the organic acid after fermentation is not sufficient. In Patent Document 2, membrane filtration is required for separation of the fermentation inhibitor, and productivity is low. Furthermore, in patent document 3, there is no description about removing a fermentation inhibitor.
  • the present invention relates to providing a method for removing an fermentation inhibitor and efficiently producing an organic acid by a safe and simple means.
  • the present inventor has studied a selective organic acid production method in which cellulosic biomass is hydrolyzed with an enzyme and then fermented.
  • Cellulose crystals are subjected to a pulverization step before subjecting the cellulosic biomass to enzymatic hydrolysis. It has been found that if cellulose is pulverized strongly until the degree of conversion is reduced to 30% or less, the subsequent hydrolysis of cellulose proceeds efficiently.
  • the saccharified product after hydrolysis was fermented to produce an organic acid, it was found that the selectivity of the organic acid was low and a large amount of alcohol was by-produced.
  • an organic acid can be obtained safely and simply at a high conversion rate and conversion rate using filamentous fungi from a lignocellulosic biomass-derived sugar solution.
  • the present invention is a method for producing an organic acid using lignocellulosic biomass as a raw material, and includes the following steps (a) to (d).
  • (A): Lignocellulosic biomass containing cellulose having a cellulose I-type crystallinity of more than 30% represented by the following calculation formula (1) is pulverized, and the cellulose I-type crystallinity is reduced to 0-30% Step of Crystallinity (%) [(I c ⁇ I a ) / I c ] ⁇ 100 (1)
  • lignocellulose-based biomass means biomass mainly composed of cellulose, hemicellulose, and lignin. Any lignocellulosic biomass can be used without particular limitation as long as it contains the above-mentioned components as main components. Specific examples include palm residues such as rice straw, rice husk, straw, bagasse, coconut husk, corn cob, weed, wood, empty fruit bunch, pulp produced from them, and paper. It can also include food industry, building industry, household waste, etc.
  • the lignocellulosic biomass used in the present invention has a cellulose content of 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more.
  • the cellulose content in the present invention means the total amount of cellulose and hemicellulose in the remaining components obtained by subtracting water from lignocellulosic biomass.
  • the cellulose content is generally 75 to 99% by mass, and other components include lignin and the like.
  • the cellulose I type crystallinity degree of a commercially available sheet-like pulp is 60% or more normally. Cellulose I-type crystallinity of cellulose contained in these lignocellulosic biomass exceeds 30%.
  • the water content of the lignocellulosic biomass used in the present invention can easily reduce the cellulose I type crystallinity of cellulose by the following (a) pulverization step, and the subsequent production of saccharified products and organic acids Is preferably 20% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less.
  • the lignocellulosic biomass is pulverized to reduce the cellulose I-type crystallinity (also referred to as “crystallinity”) of cellulose contained in the lignocellulosic biomass to 0 to 30%.
  • Cellulose type I crystallinity The non-crystallized cellulose prepared in the present invention has a cellulose I type crystallinity reduced to 30% or less.
  • Cellulose type I crystallinity is calculated by the Segal method from the diffraction intensity value by the X-ray diffraction method, and is defined by the following calculation formula (1).
  • Crystallinity (%) [(I c ⁇ I a ) / I c ] ⁇ 100 (1)
  • the crystallinity is 30% or less, the chemical reactivity of cellulose is improved, and hydrolysis in the step (c) is likely to proceed.
  • the crystallization degree of the pulverized product is preferably 25% or less, more preferably 20% or less, more preferably 10% or less, and further preferably 0% in which cellulose I-type crystals are not detected by analysis.
  • the cellulose I type crystallinity defined by the calculation formula (1) may be a negative value in calculation, but the cellulose I type crystallinity in the case of a negative value is 0%.
  • the cellulose I type crystallinity is the ratio of the amount of crystal region of cellulose to the total amount.
  • Cellulose type I is a crystalline form of natural cellulose. Cellulose type I crystallinity is also related to the physical and chemical properties of cellulose.
  • the pulverizer include a high pressure compression roll mill, a roll mill such as a roll rotating mill, a vertical roller mill such as a ring roller mill, a roller race mill or a ball race mill, a rolling ball mill, a vibration ball mill, a vibration rod mill, and a vibration tube.
  • Container driven media mills such as mills, planetary ball mills or centrifugal fluidization mills, tower crushers, stirring tank mills, medium stirring mills such as flow tank mills or annular mills, compaction such as high-speed centrifugal roller mills and angling mills
  • Examples include a shear mill, a mortar, a stone mortar, a mass collider, a fret mill, an edge runner mill, a knife mill, a pin mill, and a cutter mill.
  • a container-driven medium mill or a medium stirring mill is preferable, a container-driven medium mill is more preferable, a vibration ball mill, a vibration rod mill, or a vibration A vibration mill such as a tube mill is more preferable, and a vibration rod mill is more preferable.
  • a preferable vibrating rod mill of the present invention has a cylindrical space, is arranged so that the central axis of the cylindrical space is substantially horizontal, and can vibrate in an in-plane direction substantially perpendicular to the central axis. And a rod (B) which is one or more rod-shaped mediums arranged so as to be able to vibrate so as to be substantially parallel to the central axis of the cylindrical space.
  • the vibrating ball mill includes one or more balls (C) that are spherical media.
  • the outer diameter of the rod (B) or ball (C) is preferably in the range of 0.5 to 200 mm, more preferably 1 to 100 mm, still more preferably 5 to 50 mm.
  • the rod (B) those having a cross section of a quadrangle, a polygon such as a hexagon, a circle, an ellipse or the like can be used.
  • the length of the rod (B) is not particularly limited as long as it is shorter than the length of the pulverizer container. If the size of the rod (B) is within the above range, the desired pulverizing force can be obtained, and the cellulose can be efficiently made amorphous without contaminating the powdered cellulose by mixing fragments of the rod (B). It can be made.
  • the filling ratio of the rod (B) or ball (C) varies depending on the type of vibration mill, but is preferably 10 to 97% by volume, more preferably 15 to 95% by volume.
  • the filling rate refers to the apparent volume of the rod (B) or ball (C) relative to the volume of the cylindrical space inside the container (A).
  • vibration rod mill used in the present invention, a vibration mill manufactured by Chuo Kako Co., Ltd., a small vibration rod mill 1045 type manufactured by Yoshida Seisakusho Co., Ltd., a vibration cup mill P-9 type manufactured by Fritsch, Germany, and Nichito Kagaku Co., Ltd.
  • a small vibration mill NB-O type or the like manufactured by the company can be used.
  • the vibrating ball mill a device similar to the vibrating rod mill, for example, a vibrating mill manufactured by Chuo Kakoki Co., Ltd. can be used.
  • the processing method may be either a batch type or a continuous type.
  • the volume of the material to be crushed filled in the cylindrical space inside the container (A) is changed from the volume of the space to the rod (B) or ball ( It is preferably 99% by volume or less, more preferably 95% by volume or less, and still more preferably 90% by volume or less of the volume excluding the volume of C) (hereinafter referred to as the actual volume in the grinding container). 80% by volume or less is more preferable.
  • the volume of the filled raw material to be ground is preferably 1% by volume or more of the actual volume in the container, more preferably 2% by volume or more, and 3% by volume or more. More preferably.
  • the volume of the material to be crushed filled in the cylindrical space inside the container (A) means the volume obtained by dividing the weight of the material to be crushed by the apparent specific gravity of the material. To do.
  • a preferable aspect of the retention amount of the cylindrical space inside the container (A) of the material to be pulverized is “filling amount of material to be pulverized” when the pulverization process is a batch process. Is stored in the cylindrical space inside the container (A) of the raw material to be crushed, and the volume of the raw material to be crushed is retained in the cylindrical space inside the container (A). It is the same except that it reads as “volume of raw material to be crushed”.
  • the frequency and amplitude of the container (A) during the pulverization process are not particularly limited, but the acceleration given to the container (A) and the rod (B) or ball (C) is increased by increasing the frequency and amplitude.
  • the frequency of the container (A) is preferably 8 Hz or more, more preferably 10 Hz or more, and further preferably 12 Hz or more. Further, the amplitude of the container (A) is preferably 5 mm or more, more preferably 6 mm or more, and further preferably 7 mm or more. On the other hand, from the viewpoint of apparatus load, the frequency of the container (A) is preferably 40 Hz or less, more preferably 35 Hz or less, and further preferably 30 Hz or less. Further, the amplitude of the container (A) is preferably 25 mm or less, more preferably 20 mm or less, and still more preferably 18 mm or less.
  • the processing time of the vibrating rod mill or the vibrating ball mill cannot be determined unconditionally depending on the type of the vibrating rod mill or the vibrating ball mill, the type, size and filling rate of the rod or ball, but is preferably 0 from the viewpoint of reducing the crystallinity. 0.01 to 50 hr, more preferably 0.05 to 20 hr, still more preferably 0.1 to 10 hr.
  • the treatment temperature is not particularly limited, but is preferably 5 to 250 ° C., more preferably 10 to 200 ° C. from the viewpoint of preventing deterioration due to heat.
  • alkali includes sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, and calcium hydroxide, more preferably sodium hydroxide and potassium hydroxide, and still more preferably sodium hydroxide.
  • alkali added in this step include powder, granules, lumps, solutions dissolved in a solvent, or dispersions dispersed in a solvent, preferably powders, granules, or lumps.
  • the amount of alkali used is preferably 1 to 100 parts by weight of lignocellulosic biomass from the viewpoint of reducing cellulose I-type crystallinity and allowing subsequent production of saccharified products and organic acids efficiently. 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 10 parts by mass.
  • a pulverized product of amorphous cellulose having a cellulose I-type crystallinity of 30% or less can be efficiently obtained from the raw lignocellulosic biomass.
  • the pulverized material does not adhere to the surface, and can be processed by a dry method.
  • the average particle size of the pulverized product obtained is preferably 20 to 150 ⁇ m, more preferably 25 to 150 ⁇ m, more preferably from the viewpoint of chemical reactivity and handleability when the pulverized product is used as a raw material in step (c). Is 30 to 100 ⁇ m.
  • the average particle size of the pulverized product refers to an average value obtained by the laser diffraction scattering method according to the volume standard.
  • lignocellulosic biomass having a bulk density of 100 kg / m 3 or more is used from the viewpoint of more efficiently performing pulverization and amorphousization with a vibration mill filled with rods or balls. It is preferably 120 kg / m 3 or more, more preferably 150 kg / m 3 or more.
  • the bulk density is 100 kg / m 3 or more
  • the raw material lignocellulosic biomass has an appropriate volume, so that handleability is improved.
  • the raw material preparation amount to the vibration mill can be increased, the processing capacity is improved.
  • the upper limit of the bulk density is preferably 500 kg / m 3 or less, more preferably 400 kg / m 3 or less, and still more preferably 350 kg / m 3 or less from the viewpoint of handleability and productivity. From these viewpoints, the bulk density is preferably 100 to 500 kg / m 3 , more preferably 120 to 400 kg / m 3 , and still more preferably 150 to 350 kg / m 3 .
  • the present invention it may be preferable to pretreat lignocellulosic biomass to be supplied to the vibration mill.
  • the bulk density of the lignocellulosic biomass can be brought into the preferred range described above.
  • the size of the coarsely pulverized product is preferably 1 to 50 mm, more preferably 1 to 30 mm.
  • the water may be an aqueous solution containing a water-soluble solvent, an acidic aqueous solution, or an alkaline aqueous solution.
  • the water-soluble solvent include alcohols such as methanol, ethanol, propanol and butanol; polyhydric alcohols such as ethylene glycol, propylene glycol and butylene glycol; ketones such as acetone and methyl ethyl ketone; polyethers such as polyethylene glycol; Examples include critical carbon dioxide. These may be used alone or in combination of two or more, and may be repeated by changing the solvent. Among these, water is preferable from the viewpoint of removing an inhibitory factor that inhibits the growth and metabolism of filamentous fungi in step (d) and from the viewpoint of removing other inhibitory factors.
  • the pH of the water used in this step is preferably 4 or more, more preferably 6 or more, from the viewpoint of removing an inhibitory factor that inhibits the growth and metabolism of filamentous fungi in the step (d). On the other hand, from the viewpoint of safety, it is preferably 14 or less, more preferably 9 or less, and still more preferably 8 or less.
  • the pH of water used in this step is preferably 4 to 14, more preferably 4 to 9, and still more preferably 6 to 8.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali carbonates such as sodium carbonate and sodium bicarbonate
  • alkali hydrogen carbonates
  • alkaline earth metal hydroxides such as calcium hydroxide
  • Inorganic alkalis such as alkaline earth metal carbonates such as calcium
  • inorganic acids such as hydrochloric acid, phosphoric acid, nitric acid and sulfuric acid, and organic acids such as lactic acid are preferred.
  • the degree of the washing treatment in the step (b) is preferably managed by the water-soluble component remaining rate.
  • the water-soluble component remaining rate is a value obtained by dividing the mass of the water-soluble component in the pulverized product after the washing step by the mass of the water-soluble component in the pulverized product before the washing step.
  • the pulverized product obtained in the step (a) is preferably washed until the water-soluble component remaining rate is sufficiently small.
  • the pulverized product is dispersed in water placed in a batch-type agitation tank or the like, and filtered or centrifuged from the dispersion.
  • the liquid or supernatant is separated to obtain a solid content.
  • the solid content is dispersed again in water using a batch type stirring tank or the like, and the above-described solid-liquid separation is repeated 1 to n times.
  • w n is the mass of water added to the washed n-th
  • v n is the mass of the liquid present in the precipitated fraction after solid-liquid separation of washed n-th.
  • Formula (2) represents the washing efficiency when assuming an ideal state in which the water-soluble components in the pulverized product are all dissolved in the aqueous phase without being distributed or adsorbed on the precipitate.
  • the pulverized material obtained in step (a) is dispersed in water, the dispersion is filtered, and water is supplied to the solid content remaining in the filter. Repeat the operation.
  • the water-soluble component remaining rate can be calculated from the following formula (2 ′) using the water-soluble component contained in the pulverized product as a tracer substance.
  • the water-soluble component analysis method may be any method as long as it is not affected by the coexisting substance and is suitable for the water-soluble component analysis method, and examples thereof include absorbance, liquid chromatography, gas chromatography, and electrical conductivity. .
  • Water-soluble component residual ratio (when continuously washed) Tracer substance mass after washing / Tracer substance mass after washing (2 ')
  • the water-soluble component residual rate is preferably 0.5 or less from the viewpoint of removing substances that inhibit the growth and metabolism of filamentous fungi in step (d) and increasing the productivity of organic acids, Preferably it is 0.4 or less, More preferably, it is 0.2 or less, More preferably, it is 0.1 or less.
  • the water-soluble component residual ratio is preferably 0.001 or more from the environmental load and economical viewpoint by suppressing the amount of water used.
  • the residual ratio of the water-soluble component is preferably 0.001 to 0.5, more preferably 0.001 to 0.4, still more preferably 0.001 to 0.2, and still more preferably. 0.001 to 0.1.
  • a dispersion comprising pulverized material and water obtained in step (a) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and still more preferably 20 ° C. or higher. Moreover, from a viewpoint of energy efficiency, Preferably it is 100 degrees C or less, More preferably, it is 90 degrees C or less, More preferably, it is 80 degrees C or less. Further, the temperature of the dispersion comprising the pulverized product and water obtained in step (a) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and further preferably 20 to 80 ° C. .
  • step (c) the solid obtained in step (b) is hydrolyzed with a hydrolase to obtain a saccharified product.
  • the hydrolase used in step (c) is not particularly limited as long as it is an enzyme having hydrolytic activity with respect to cellulose or hemicellulose.
  • commercially available cellulase preparations and hemicellulase preparations, cellulases and hemicellulases derived from animals, plants and microorganisms can be used.
  • Cellulases include, for example, Trichoderma reease (Trichoderma luses) from Trichoderma lyase (Trichoderma luses luciferase) such as Cellic Ctec, Cellic Ctec2, Celluclast 1.5L (Novozymes), Accelerase 1000, Accelerase 1500, Accelerase DUET (Genencore). .) Cellulase derived from KSM-N145 (FERM P-19727), Bacillus sp. Cellulase derived from KSM-N252 (FERM P-17474), Bacillus sp.
  • KSM-N115 (FERM P -19726) strain-derived cellulase, Bacillus SP s sp.) Cellulase from KSM-N440 (FERM P-19728) strain, Cellulase from Bacillus sp. KSM-N659 (FERM P-19730) strain, Trichoderma viride, Aspergillus sp.
  • acletus Clostridium thermocellum, Clostridium stercoralium, Clostridium josui, Cellulomonas flocculus Iticus), Irupekkusu Rakuteusu (Irpex lacteus), Aspergillus niger (Aspergillus niger), Humicola insolens (Humicola insolens) derived cellulase mixture, Pyrococcus horikoshii (Pyrococcus horikoshii) heat resistance cellulase derived thereof.
  • a cellulase derived from Trichoderma reesei a cellulase derived from Trichoderma violet, a cellulase derived from Humicola insolens, and a cellulase derived from Humicola insolens are preferable.
  • Cellulase derived from (Trichoderma reesei) is more preferable, and Cellic Ctec, Cellic Ctec2 (Novozymes), Accelerase DUET (Genencore), TP-60 (Meiji Seika Co., Ltd.), or Ultraflo L (Novozymes) is more preferable.
  • hemicellulase examples include, for example, a xylanase derived from the Bacillus sp. KSM-N546 (FERM P-19729) strain, Aspergillus niger, Trichoderma violol, H. Or xylanase from Bacillus alcalophilus, Thermomyces, Aureobasidium, Streptomyces, Clostridium thermother, T ASCUS), Karudoseramu (Caldocellum), or Thermo mono Supora (Thermomonospora) genus xylanase like from like.
  • the enzyme which has hemicellulase activity contained in said cellulase mixture can also be utilized.
  • Hydrolytic enzymes can be used alone, but it is effective to use these enzymes in combination for more efficient sugar production.
  • efficiency of sugar production can be improved by further adding a specific cellulase component such as ⁇ -glucosidase to these enzymes.
  • ⁇ -glucosidase to be added include enzymes derived from Aspergillus niger (for example, Novozymes Novozymes 188 and Megazyme ⁇ -glucosidases), Trichoderma reesei enzymes, and Penicillium penisium. ) Derived enzymes and the like.
  • the solid obtained in the (b) step is suspended in an aqueous medium to prepare a suspension.
  • the aqueous medium is not particularly limited as long as the hydrolase is not deactivated, but water, a buffer solution, an acidic aqueous solution, or an alkaline aqueous solution is preferably used.
  • the reaction conditions in the step (c) can be selected according to the characteristics of the enzyme used.
  • the substrate concentration is 5 to 200 (g / L). It is preferable to add hydrolase to the substrate suspension so that it preferably corresponds to 0.01 to 10% by volume, more preferably 0.1 to 2% by volume.
  • the pH is preferably 2 to 10, more preferably 3 to 7, and further preferably 4 to 6.
  • the reaction temperature is preferably 10 to 90 ° C, more preferably 20 to 70 ° C, and still more preferably 40 to 60 ° C.
  • the reaction time is 30 minutes to 7 days, preferably 0.5 to 5 days.
  • the saccharified product after completion of the hydrolysis reaction may be appropriately filtered of insolubles in the saccharified product, or may be subjected to the next step (d) as it is.
  • the mass of monosaccharides (hereinafter also referred to as “total sugar amount”) contained in the saccharified product produced in the step (c) is determined from the viewpoint of improving the yield of organic acid and the ligno after washing subjected to the hydrolysis reaction.
  • the amount is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably 30 to 70% by mass with respect to the total mass of the pulverized product of cellulosic biomass.
  • monosaccharides include glucose, fructose, mannose, galactose, xylose, and arabinose.
  • step (d) the saccharified product obtained in step (c) is fermented with filamentous fungi.
  • the medium used in step (d) includes the saccharified product produced in step (c).
  • the medium generally contains a carbon source, a nitrogen source, and an inorganic salt, but when the saccharified product produced in step (c) sufficiently contains these nutrient sources necessary for culture.
  • a medium may be prepared by adding a nutrient source in addition to the saccharified product.
  • an organic acid is produced by adding and culturing a filamentous fungus capable of producing an organic acid to the medium.
  • the organic acid according to the present invention is a compound having a carboxyl group as an acidic group.
  • organic acids include lactic acid, fumaric acid, itaconic acid, malic acid, pyruvic acid, tartaric acid, succinic acid, maleic acid, glutaric acid, levulinic acid, propionic acid, gluconic acid, ascorbic acid, citric acid, Examples include kojic acid, dipicolinic acid, and aconitic acid. Of these, lactic acid and fumaric acid are preferred.
  • the organic acid can be produced by culturing filamentous fungi capable of producing them.
  • filamentous fungi examples include microorganisms belonging to the genus Rhizopus. Specifically, Rhizopus oryzae and Rhizopus delemar are preferable from the viewpoint of producing a large amount of L-lactic acid and fumaric acid.
  • the culture temperature is preferably 20 to 40 ° C, more preferably 30 to 37 ° C.
  • the pH of the medium is preferably 2 to 7, and more preferably 4 to 6, from the viewpoints of bacterial cell growth and organic acid productivity.
  • the pH control is preferably performed using calcium hydroxide, sodium hydroxide, calcium carbonate, ammonia, sulfuric acid, hydrochloric acid, or the like.
  • any one of anaerobic conditions and aerobic conditions can be appropriately employed.
  • Specific examples include an aeration and stirring type culture tank, a bubble column type culture tank, a fluidized bed culture tank, and a packed bed culture tank.
  • an aeration stirring type culture tank, a bubble column type culture tank, and a fluidized bed culture tank are preferable.
  • the filamentous fungus is preferably cultivated by forming a pellet (mycelium mass).
  • the filamentous fungal pellet can be extracted from the culture tank together with the culture solution, separated and recovered from the medium by operations such as filtration and centrifugation, and used in step (d). It is also possible to leave the filamentous fungus pellet in the culture tank and perform the step (d) in the same culture tank.
  • alcohol is usually by-produced in addition to the organic acid.
  • steps (a) and (b) by combining the steps (a) and (b), an organic acid is selectively obtained, and the amount of by-product alcohol is reduced.
  • an ester may be produced using the product obtained in the step (d) as a raw material, and the obtained ester may be distilled.
  • the distillation step substances other than the organic acid can be removed from the product obtained in the step (d).
  • the mass ratio (organic acid / alcohol) of the organic acid and alcohol obtained in the step (d) is preferably 1.3 or more, more preferably 2.0 or more, from the viewpoint of the yield of the organic acid. Preferably it is 3.0 or more, More preferably, it is 4.0 or more.
  • the present invention further discloses the following manufacturing method regarding the above-described embodiment.
  • a method for producing an organic acid comprising the following steps (a) to (d):
  • (A): Lignocellulosic biomass containing cellulose having a cellulose I-type crystallinity of more than 30% represented by the following calculation formula (1) is pulverized, and the cellulose I-type crystallinity is reduced to 0-30% Step of Crystallinity (%) [(I c ⁇ I a ) / I c ] ⁇ 100 (1)
  • Step (a) is preferably a pulverizer selected from a vertical roller mill, a container drive medium mill, a medium agitation mill and a compaction shear mill, more preferably a container drive medium mill or a medium agitation mill, and more preferably Is a method for producing an organic acid according to ⁇ 1> or ⁇ 2>, which is performed using a container drive medium mill, more preferably a vibration mill filled with rods or balls.
  • ⁇ 4> The method for producing an organic acid according to any one of ⁇ 1> to ⁇ 3>, wherein an alkali is added in the step (a).
  • the amount of alkali used is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and further preferably 5 to 10 parts by weight with respect to 100 parts by weight of lignocellulosic biomass.
  • the manufacturing method of the organic acid as described in any one of. ⁇ 6> The above ⁇ 4>, wherein the alkali is preferably sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate or calcium hydroxide, more preferably sodium hydroxide or potassium hydroxide, still more preferably sodium hydroxide.
  • the cellulose I type crystallinity after pulverization in the step ⁇ 7> (a) is preferably 25% or less, more preferably 20% or less, still more preferably 10% or less, and further preferably 0%.
  • the residual ratio of the water-soluble component of the pulverized product is preferably 0.5 or less, more preferably 0.4 or less, still more preferably 0.2 or less, and still more preferably 0.1 or less.
  • the method for producing an organic acid according to any one of ⁇ 1> to ⁇ 7>, wherein the organic acid is washed with water until ⁇ 9> The method for producing an organic acid according to any one of ⁇ 1> to ⁇ 8>, wherein in the step (b), the pulverized product is washed with water until the water-soluble component remaining ratio is preferably 0.001 or more.
  • the residual ratio of the water-soluble component of the pulverized product is preferably 0.001 to 0.5, more preferably 0.001 to 0.4, and still more preferably 0.001 to 0.2.
  • the total amount is preferably 1 part by mass, more preferably 3 parts by mass or more, still more preferably 5 parts by mass with respect to 1 part by mass of the solid content of the pulverized product obtained in the step (a). More preferably, the method for producing an organic acid according to any one of ⁇ 1> to ⁇ 10>, wherein the organic acid is washed with 10 parts by mass or more of water.
  • the total amount is preferably 100 parts by mass or less, more preferably 50 parts by mass or less, still more preferably 40 parts by mass with respect to 1 part by mass of the solid content of the pulverized product obtained in the step (a)
  • the total amount is preferably 1 to 100 parts by weight, more preferably 3 to 50 parts by weight, based on 1 part by weight of the solid content of the pulverized product obtained in step (a).
  • the temperature of the dispersion comprising the pulverized product and water obtained in the step (a) is preferably 0 ° C. or higher, more preferably 10 ° C. or higher, and further preferably 20 ° C.
  • the temperature of the dispersion obtained from the pulverized product and water obtained in the step (a) is preferably 100 ° C.
  • the temperature of the dispersion comprising the pulverized product and water obtained in the step (a) is preferably 0 to 100 ° C., more preferably 10 to 90 ° C., and still more preferably 20
  • the water is preferably water, an aqueous solution containing a water-soluble solvent, an acidic aqueous solution or an alkaline aqueous solution, more preferably water or an aqueous solution containing a water-soluble solvent, and further preferably water.
  • the cellulase in the step (c) is preferably a cellulase derived from Trichoderma reesei, a cellulase derived from Bacillus sp.
  • KSM-N145 (FERM P-19727), or a Bacillus sp. ) Cellulase derived from KSM-N252 (FERM P-17474) strain, Bacillus sp. Cellulase derived from KSM-N115 (FERM P-19726) strain, Bacillus sp. KSM-N440 (FERM P- 19728) strain-derived cellulase, Bacillus sp.
  • KSM-N659 (FERM P-19730) -derived cellulase, Trichoderma bili (Trichoderma viride), Aspergillus Akureatasu (Aspergillus acleatus), Clostridium thermocellum (Clostridium thermocellum), Clostridium stercorarium (Clostridium stercorarium), Clostridium josui (Clostridium josui), Cellulomonas Fimi (Cellulomonas fimi), Acremonium cell Lori caustics (Acremonium celluloriticus ), Irpex lacteus, Aspergillus niger, Humicola insolens A heat-resistant cellulase derived from Pyrococcus horikoshii, more preferably a cellulase derived from Trichoderma reesei, a cellulase derived from Trichoderma viride, or an insulase derived from Trichoderma
  • the method for producing an organic acid according to ⁇ 18> which is a cellulase derived from Trichoderma reesei.
  • the organic acid is preferably lactic acid, fumaric acid, itaconic acid, malic acid, pyruvic acid, tartaric acid, succinic acid, maleic acid, glutaric acid, levulinic acid, propionic acid, gluconic acid, ascorbic acid, citric acid, kojji
  • the method for producing an organic acid according to any one of ⁇ 1> to ⁇ 19> which is an acid, dipicolinic acid or aconitic acid, more preferably lactic acid or fumaric acid.
  • the filamentous fungus is preferably a microorganism belonging to the genus Rhizopus, more preferably Rhizopus oryzae or Rhizopus delemar, and more preferably Rhizopus oryzae (Rhizpus).
  • Rhizopus oryzae Rhizopus delemar
  • Rhizopus oryzae Rhizopus oryzae
  • ⁇ Analysis method> [Calculation of crystallinity] Using a “Rigaku RINT 2500VC X-RAY diffractometer” manufactured by Rigaku Corporation, the measurement was performed under the following conditions, and the cellulose I type crystallinity was calculated based on the above formula (1).
  • the measurement sample was prepared by compressing a pellet having an area of 320 mm 2 ⁇ thickness of 1 mm.
  • HPLC analysis conditions were as follows: column: ICSep ICE-ION-300, eluent: 0.0085N sulfuric acid, 0.4 mL / min, detection method: RI (HITACHI, L-2490), column temperature: 40 ° C., injection volume : 20 ⁇ L, retention time: 40 minutes.
  • the retention time of each component in this analytical system was glucose: 16 minutes, xylose: 17 minutes, lactic acid: 23 minutes, fumaric acid: 27 minutes, ethanol: 34 minutes.
  • the moisture content was measured using an electronic moisture meter (MOISTUREBALANCE MOC-120H (manufactured by Shimadzu Corporation)). A sample was placed on the moisture meter and measurement was started. The temperature was raised to 120 ° C., which was a preset temperature, and then held at 120 ° C. The time when the change in the mass of the sample in 30 seconds was less than 0.05% was regarded as the end of measurement. The mass reduction rate from the start of measurement to the end of measurement was taken as the amount of water.
  • MOISTUREBALANCE MOC-120H manufactured by Shimadzu Corporation
  • ⁇ Preparation of pelletized filamentous fungus> [Preparation of spore suspension]
  • the strain is a filamentous fungus R. cerevisiae obtained from the National Institute of Technology and Evaluation (NITE). oryzae NBRC5384 was used. Filamentous fungi are streaked / coated on slanted agar medium (Difco Potato Dextrose Agar, Becton, Dickinson and Company) formed in a test tube, and statically cultured at room temperature, and periodically passaged. Went.
  • slanted agar medium Difco Potato Dextrose Agar, Becton, Dickinson and Company
  • the pelleted filamentous fungus was prepared by the following two-stage culture.
  • a 200 mL baffled Erlenmeyer flask charged with 60 mL of PDB medium (Difco Potato Dextrose Broth, Becton, Dickinson and Company) was sterilized, and the spore suspension prepared by the above method was 1 ⁇ 10
  • the cells were inoculated to 4 spore / mL and cultured for 3 days under a culture condition of 27 ° C. and 100 r / m (PRECI, PRXYg-98R).
  • pellet formation medium glucose (reagent) 10% by mass, magnesium sulfate heptahydrate 0.025% by mass, zinc sulfate heptahydrate 0.009% by mass, ammonium sulfate 0.1% by mass, Sterilize a 500 mL Erlenmeyer flask charged with 100 mL of potassium dihydrogen phosphate (0.06% by mass), inoculate 5.0 g of calcium carbonate and 4 mL of the first stage culture solution at 27 ° C., 170 r / m ( (PRECI, PRXYg-98R) for 1.5 days.
  • the obtained pulverized product was taken out from the vibration mill.
  • the crystallinity of the pulverized product was 6%.
  • the average particle size based on volume was 25 ⁇ m.
  • Second wash After adding the same weight (W 2 ) of distilled water as the supernatant discarded in the first wash to the precipitate fraction obtained in the first wash, mixing and stirring again, the same conditions as in the first wash Centrifugation was performed and the supernatant (W 3 ) was discarded.
  • Wash 3rd Add distilled water of the same weight (W 3 ) as the supernatant discarded in the 2nd wash to the precipitate fraction obtained in the 2nd wash and mix and stir again. Centrifugation was performed and the supernatant (W 4 ) was discarded.
  • Table 2 shows the values of W 1 to W 4 in Examples 1 to 5.
  • Table 3 shows the residual ratio of water-soluble components calculated from these values.
  • Second wash 500 g distilled water was added to the cake fraction obtained in the first wash and mixed and stirred again, followed by filtration under the same conditions as the first, and 480 g of liquid was separated and discarded.
  • 3rd washing 500 g of distilled water was added to the cake fraction obtained in the 2nd washing and mixed and stirred again, followed by filtration and separation under the same conditions as the first, and 480 g of liquid was separated and discarded.
  • Table 3 shows the calculated water-soluble component residual ratio.
  • [Drying process] The sugar cane bagasse obtained in the water washing step was dried at 80 ° C. overnight to obtain a dry sugar cane bagasse having a moisture content of 6% by mass. Table 3 shows the results obtained in steps (c) and (d). Compared with Examples 1 to 5, the total conversion rate to lactic acid and conversion rate to ethanol was low, ethanol production was high, lactic acid production was low, and R was small.
  • Example 6 Effect of water washing of dry alkali mixed pulverized sugarcane bagasse
  • steps (a), (b) and (c) were performed as follows.
  • [Dry alkali mixed pulverization] 50 g of dried sugarcane bagasse and 4.4 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) are put into a vibration mill (Chuo Kako Co., Ltd., “MB-1”, total capacity 3.58 L) as a rod.
  • Second wash 500 g of distilled water was added to the precipitate fraction obtained in the first wash and the mixture was stirred again, then centrifuged under the same conditions as the first, and 502 g of the supernatant was discarded.
  • 3rd washing 500 g of distilled water was added to the precipitate fraction obtained in the 2nd washing and the mixture was stirred again, then centrifuged under the same conditions as in the first, and 498 g of the supernatant was discarded.
  • Table 3 shows the calculated water-soluble component residual ratio.
  • Second wash 540 g of distilled water was added to the precipitate fraction obtained in the first wash and the solid matter on the gauze, mixed and stirred again, then centrifuged under the same conditions as the first, and passed through the gauze. 527 g of supernatant was discarded.
  • Third wash 540 g of distilled water was added to the precipitate fraction obtained in the second wash and the solid matter on the gauze, mixed and stirred again, then centrifuged under the same conditions as the first, and passed through the gauze. 527 g of supernatant was discarded. Table 3 shows the calculated water-soluble component residual ratio. [Drying process] The sugar cane bagasse obtained in the water washing step was dried at 80 ° C.
  • Table 3 shows the results obtained in steps (c) and (d). Compared with Example 6, the total of the conversion rate to lactic acid and the conversion rate to ethanol was low, ethanol production was high, lactic acid production was low, and R was small.
  • Example 7 Effect of water washing on dry pulverized EFB (fruit bunch after removing palm fruit) [drying treatment of biomass]
  • Shredder-treated (COMIX, cross-cut shredder S330) EFB was dried at 80 ° C. overnight to obtain a dry EFB with a moisture content of 5 mass%.
  • the cellulose content of EFB was 36%, and the crystallinity was 40%.
  • Second wash To the precipitate fraction obtained in the first wash, distilled water of the same weight (365 g) as the supernatant discarded in the first wash was added, mixed and stirred again, and centrifuged under the same conditions as the first wash. Separation was performed and 362 g of the supernatant was discarded. 3rd washing: Add the same weight (362 g) of distilled water as the supernatant discarded in the 2nd washing to the precipitate fraction obtained in the 2nd washing, mix and stir again, then centrifuge under the same conditions as the 1st Separation was performed and 361 g of the supernatant was discarded. Table 3 shows the calculated water-soluble component residual ratio.
  • Example 5 (Comparative Example 5)
  • B The same operation as Example 7 was performed except not performing a process.
  • C After the step, the obtained liquid was analyzed by HPLC. Table 3 shows the total concentration (G 0 + X 0 ) of glucose and xylose in the obtained saccharified product. Table 3 shows the results obtained after the step (d). Compared with Example 7, the total of the conversion rate to lactic acid and the conversion rate to ethanol was low, and R was small.
  • Example 8 Effect of water washing on dry pulverized inowara [drying treatment of biomass]
  • the rice bran cut into 5 cm long pieces with a scissors was dried at 80 ° C. overnight to obtain a dry rice bran having a moisture content of 6% by mass.
  • Inowara had a cellulose content of 40% and a crystallinity of 54%.
  • the obtained pulverized product was taken out from the vibration mill.
  • the crystallinity of the pulverized product was 7%.
  • the average particle size based on volume was 25 ⁇ m.
  • Second wash The same amount (410 g) of distilled water as the supernatant discarded in the first wash was added to the precipitate fraction obtained in the first wash, mixed and stirred again, and centrifuged under the same conditions as in the first wash. Separation was performed and 406 g of the supernatant was discarded.
  • 3rd washing Add the same weight (406 g) of distilled water as the supernatant discarded in the 2nd washing to the precipitate fraction obtained in the 2nd washing, mix and stir again, then centrifuge under the same conditions as the 1st Separation was performed, and 410 g of the supernatant was discarded. Table 3 shows the calculated water-soluble component residual ratio.
  • step (C) Step of obtaining a saccharified product using a hydrolase to the solid obtained in the washing step The same operation as step (c) described in Examples 1 to 5 was performed. The obtained liquid was analyzed by HPLC. Table 3 shows the total concentration (G 0 + X 0 ) of glucose and xylose in the obtained saccharified product.
  • Second wash The same amount (373 g) of distilled water as the supernatant discarded in the first wash was added to the precipitate fraction obtained in the first wash, mixed and stirred again, and centrifuged under the same conditions as the first wash. Separation was performed and 373 g of the supernatant was discarded.
  • 3rd washing Add the same weight (373 g) of distilled water as the supernatant discarded in the 2nd washing to the precipitate fraction obtained in the 2nd washing, mix and stir again, and then centrifuge under the same conditions as the 1st Separation was performed and 372 g of the supernatant was discarded. Table 3 shows the calculated water-soluble component residual ratio.
  • Fermentability was evaluated by the method shown in ⁇ Evaluation of fermentability>. The results are shown in Table 3. From the results of Example 9, it was found that the conversion rate of sugar to lactic acid was increased by the introduction of the (c) washing step even when the grinding medium was a ball.
  • Second wash The same amount (380 g) of distilled water as the supernatant discarded in the first wash was added to the precipitate fraction obtained in the first wash, mixed and stirred again, and centrifuged under the same conditions as in the first wash. Separation was performed and 379 g of the supernatant was discarded.
  • 3rd washing Add the same weight (379 g) of distilled water as the supernatant discarded in the 2nd washing to the precipitate fraction obtained in the 2nd washing, mix and stir again, then centrifuge under the same conditions as the 1st Separation was performed and 380 g of the supernatant was discarded. Table 3 shows the calculated water-soluble component residual ratio.
  • Fermentability was evaluated by the method shown in ⁇ Evaluation of fermentability>. The results are shown in Table 3. From the results of Example 10, it was found that if the crystallinity after pulverization was 30% or less, the conversion rate of sugar to lactic acid was high.
  • Second wash The same amount (384 g) of distilled water as the supernatant discarded in the first wash was added to the precipitate fraction obtained in the first wash, mixed and stirred again, and then centrifuged under the same conditions as in the first wash. Separation was performed and 384 g of the supernatant was discarded.
  • 3rd washing Add the same weight (384 g) of distilled water as the supernatant discarded in the 2nd washing to the precipitate fraction obtained in the 2nd washing, mix and stir again, then centrifuge under the same conditions as the 1st Separation was performed and 384 g of the supernatant was discarded. Table 4 shows the calculated water-soluble component residual ratio.

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Abstract

La présente invention concerne un procédé permettant d'éliminer des inhibiteurs de fermentation et de produire de manière efficace un acide organique au moyen d'un procédé simple et sûr. L'invention concerne ainsi un procédé de production d'acide organique comprenant les étapes suivantes (a) à (d) consistant à : (a) broyer une biomasse lignocellulosique contenant de la cellulose présentant un degré de cristallisation de cellulose I représentée par la formule de calcul (1) dépassant 30 % et réduire le degré de cristallisation de cellulose I de 0 à 30 %. Degré de cristallisation (%) = [(Ic - Ia)/Ic] × 100 (1) [Ic représente l'intensité diffractée du plan réticulaire (002) (distance réticulaire = 22,4 nm) dans la diffraction de rayons X et Ia représente l'intensité diffractée de la partie amorphe (distance réticulaire = 27,3 nm)] ; (b) rincer à l'eau le produit broyé obtenu à l'étape (a) ; (c) obtenir un produit saccharifié à partir du solide obtenu à l'étape (b) au moyen d'une hydrolase ; (d) faire fermenter le produit saccharifié obtenu à l'étape (c) à l'aide de champignons filamenteux et obtenir ainsi l'acide organique.
PCT/JP2013/060214 2012-04-04 2013-04-03 Procédé de production d'acide organique WO2013151093A1 (fr)

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WO2018051837A1 (fr) * 2016-09-15 2018-03-22 花王株式会社 Champignon filamenteux mutant, et procédé de fabrication d'acide dicarboxylique en c4 mettant en œuvre celui-ci
CN108138173A (zh) * 2015-10-13 2018-06-08 花王株式会社 C4二羧酸的制造方法
WO2021235419A1 (fr) * 2020-05-19 2021-11-25 東レ株式会社 Procédé de production de protéines à l'aide de coques de maïs
CN115029264A (zh) * 2022-06-14 2022-09-09 中国科学院青岛生物能源与过程研究所 一株耐酸热纤梭菌及其降解木质纤维素的方法

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JP2016202073A (ja) * 2015-04-22 2016-12-08 花王株式会社 フマル酸の製造方法
MY185788A (en) 2016-06-27 2021-06-08 Shinko Tecnos Co Ltd Method for producing a product

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WO2010134455A1 (fr) * 2009-05-22 2010-11-25 独立行政法人農業・食品産業技術総合研究機構 Procédé de conversion pour biomasse lignocellulosique
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JP2012517346A (ja) * 2009-02-11 2012-08-02 キシレコ インコーポレイテッド バイオマスの加工方法
WO2010134455A1 (fr) * 2009-05-22 2010-11-25 独立行政法人農業・食品産業技術総合研究機構 Procédé de conversion pour biomasse lignocellulosique
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CN108138173A (zh) * 2015-10-13 2018-06-08 花王株式会社 C4二羧酸的制造方法
WO2018051837A1 (fr) * 2016-09-15 2018-03-22 花王株式会社 Champignon filamenteux mutant, et procédé de fabrication d'acide dicarboxylique en c4 mettant en œuvre celui-ci
WO2021235419A1 (fr) * 2020-05-19 2021-11-25 東レ株式会社 Procédé de production de protéines à l'aide de coques de maïs
CN115029264A (zh) * 2022-06-14 2022-09-09 中国科学院青岛生物能源与过程研究所 一株耐酸热纤梭菌及其降解木质纤维素的方法
CN115029264B (zh) * 2022-06-14 2023-06-09 中国科学院青岛生物能源与过程研究所 一株耐酸热纤梭菌及其降解木质纤维素的方法

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