WO2013103138A1 - Biomass saccharification method and device, method and device for producing sugar, and method and device for producing ethanol - Google Patents

Biomass saccharification method and device, method and device for producing sugar, and method and device for producing ethanol Download PDF

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WO2013103138A1
WO2013103138A1 PCT/JP2012/084143 JP2012084143W WO2013103138A1 WO 2013103138 A1 WO2013103138 A1 WO 2013103138A1 JP 2012084143 W JP2012084143 W JP 2012084143W WO 2013103138 A1 WO2013103138 A1 WO 2013103138A1
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biomass
saccharification
reactor
end
sugar
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PCT/JP2012/084143
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French (fr)
Japanese (ja)
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北野 誠
佐藤 健治
健太郎 成相
典充 金子
重雄 蔦木
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株式会社Ihi
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Publication of WO2013103138A1 publication Critical patent/WO2013103138A1/en

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    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M21/00Bioreactors or fermenters specially adapted for specific uses
    • C12M21/12Bioreactors or fermenters specially adapted for specific uses for producing fuels or solvents
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M23/00Constructional details, e.g. recesses, hinges
    • C12M23/50Means for positioning or orientating the apparatus
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M27/00Means for mixing, agitating or circulating fluids in the vessel
    • C12M27/02Stirrer or mobile mixing elements
    • C12M27/06Stirrer or mobile mixing elements with horizontal or inclined stirrer shaft or axis
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M45/00Means for pre-treatment of biological substances
    • C12M45/09Means for pre-treatment of biological substances by enzymatic treatment
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12MAPPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
    • C12M45/00Means for pre-treatment of biological substances
    • C12M45/20Heating; Cooling
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/14Preparation 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
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00Preparation of oxygen-containing organic compounds
    • C12P7/02Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/04Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
    • C12P7/06Ethanol, i.e. non-beverage
    • C12P7/08Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
    • C12P7/10Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels
    • Y02E50/16Cellulosic bio-ethanol
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels
    • Y02E50/17Grain bio-ethanol

Abstract

Provided are a method and device for producing sugar and ethanol efficiently and inexpensively wherein the amount of enzyme and the treatment time are reduced during the production of ethanol by saccharification enzyme reaction and fermentation using plant waste as the starting material for biomass ethanol. Particulate biomass is prepared to a water content of 80 to 90 mass%, biomass and saccharification enzyme are introduced from one end of a reactor that extends substantially horizontally, and biomass and saccharification enzyme are moved in succession vertically toward the other end of the reactor while being agitated by a turning operation wherein the vertical direction of the reactor serves as the center axis. As a result, saccharification of the biomass proceeds as the biomass moves vertically. Saccharified liquid is gradually produced by hydrolysis of cellulose and recovered from the other end of the reactor, while the solid residue recovered from the other end is re-introduced from the one end to the reactor. The saccharification enzyme contained in the solid residue is thereby reused. The resulting saccharified liquid is used for ethanol fermentation.

Description

Saccharification process and saccharification apparatus biomass, sugar preparation and the sugar production apparatus and ethanol production process and ethanol production apparatus

The present invention, biomass saccharification process and saccharification apparatus, a manufacturing method and ethanol production apparatus manufacturing method and sugar production apparatus and ethanol sugar using the same, in particular, lignocellulosic plant matter waste such as wood and straw when generating biomass ethanol by using as a system biomass saccharification process and saccharification apparatus cellulose saccharification of cellulose by enzyme reaction, a method for manufacturing and ethanol production apparatus manufacturing method and sugar production apparatus and ethanol sugar using the same .

Lignocellulosic biomass is a renewable energy source derived from woody plants, agricultural waste and other similar non-food crops, mainly comprising cellulose, hemicellulose and lignin, called cellulose resources. Recently, as a solution to the shortage of petroleum resources, is noted ethanol fuel to produce ethanol by fermentation of a microorganism using vegetable matter, various processes have been proposed as a production technology.

Cellulose is a glucose polymer linked to one another by beta-l, 4 bonds, varies depending on the type of plant, generally present in a proportion of 30 to 70 wt%. Hydrolysis of cellulosic biomass by enzymes, cellulose constituting the cellulose resources, the content of hemicellulose and lignin, a complex phenomenon influenced by the reaction conditions of the microstructure and enzymes, to degrade such complexes biomass is, it takes a long time and a large amount of energy, a high production cost.

The following Patent Document 1, describes a ethanol fuel products production method, were subjected to a lignin process, using waste materials such as waste paper containing about 80% cellulose, after generating glucose by cellulase enzymes by fermentation method for obtaining ethanol are disclosed.

Further, the following Patent Document 2, is described saccharification reaction vessel, discloses a saccharification reaction vessel provided inside the separation chamber comprising a mesh or punching metal separating foreign matter mixed into the cellulosic material.

Further, the following Patent Document 3, described ethanol production equipment, discloses a reaction vessel for performing enzymatic saccharification and ethanol fermentation in the same reaction zone.

Japanese Patent 2006-88136 JP Japanese Patent 2010-268705 JP International Publication No. WO 2008/047679

The processing performed in the production of biomass ethanol, physical treatment to proceed decomposed by hydrothermal treatment or the like, a chemical process for the reaction to proceed such as hydrolysis using an acid-base or a catalyst such as, a saccharifying enzyme and fermenting organism There is biochemical process utilizing, but for the catalytic and fermentation microorganisms it is possible to recover and reuse, since the enzymes are generally water soluble, difficult recovery. Moreover, the saccharification enzymes, since the deactivation with the passage of use time, to fully monosaccharification is required replenishment of saccharifying enzymes. In particular, beta-glucosidase contained in the cellulose saccharification enzymes are also subject to the inhibition by glucose, which is finally generated in the saccharification, there is a problem that the production rate decreases as the generation of glucose, in order to solve this beta- there is a need to add-on a-glucosidase. Therefore, the amount of saccharifying enzymes used in the production of biomass ethanol increases, the production cost is high. To produce low cost ethanol by suppressing the production cost, it is important reduction in the amount of saccharifying enzymes. Furthermore, since it takes processing time to monosaccharification by the enzyme reaction, in order to produce efficiently ethanol inexpensive, the shorter treatment time is also important.

Also, generally the reaction system to carry out the enzymatic reaction is a water-based containing substrate and enzyme, the use of large amounts of water in such a reaction system, a great deal in the final purification distillation of the resulting ethanol It would consume heat energy. Therefore, the amount of water used is less is desirable.

An object of the present invention is to solve the above problems, high efficiency cellulose decomposition reaction by saccharifying enzyme saccharification method reduces the available biomass enzyme usage, saccharification apparatus, a manufacturing method and a sugar production apparatus sugar provided, it is to provide an efficient manufacturing method and ethanol production apparatus of ethanol using the same.

Another object of the present invention, recovery of enzyme can be recovered and re-used at least a portion of the enzyme from the difficult saccharification step, lignocellulosic biomass that does not use the amount of water a burden in the subsequent ethanol purification saccharification process and saccharification apparatus is to provide a manufacturing method and a sugar production apparatus sugar, effectively implementing the production method and ethanol production apparatus of ethanol capable out the production of ethanol fuel.

In order to solve the above problems, the present inventors have found, after extensive research, by devising a device structure to advance the saccharification reaction, thereby enabling efficient progression of enzymatic reactions, the use of water reducing the amount found to be capable of recovering the portion of the enzyme used, and have completed the present invention.

According to one aspect of the present invention, the saccharification process biomass is to prepare a particulate biomass hydrated state, the biomass and saccharification enzymes, was charged from a substantially one side of the reaction vessel extending horizontally Te while sequentially moved in the longitudinal direction toward the other end, by stirring the biomass and saccharification enzymes by the rotation motion about axis longitudinal direction of the reactor, the biomass together with longitudinal movement of the biomass saccharification and subject matter to proceed. The biomass of hydrous state, 90 wt% or less, preferably to a water content of 80-90 wt% (percentage of water mass to the total mass).

Further, according to one aspect of the present invention, a method of manufacturing the sugar gradually saccharified solution is produced by hydrolysis of cellulose contained in the biomass by the above method of saccharification, the saccharified solution and the solid residue of the reaction vessel each recovered from the other end, wherein the solid residue was charged again reaction vessel from one end of which is recovered from the other end of the reaction vessel, and the gist of reusing saccharification enzyme contained in the solid residue to.
Furthermore, according to one aspect of the present invention, the production method of ethanol, and summarized in that to produce ethanol by a sugar obtained by the production method of the above sugars and microbial fermentation.

Further, according to one aspect of the present invention, the saccharification apparatus includes a reaction vessel extending substantially horizontally, the particulate biomass solids concentration high moisture condition, the other end from one end of the reactor and biomass supply means for supplying to the interior from one end of the reactor to sequentially move longitudinally towards the side, and enzyme addition means for adding the biomass saccharification enzymes supplied from one end of the reactor, a stirring device for stirring the biomass and saccharification enzymes by the rotation motion about axis longitudinal direction of the reaction vessel, the saccharified solution produced by the saccharification of biomass for moving the reaction vessel in the longitudinal direction progresses and summarized in that and a discharge means for recovering from the other end of the reactor.

Furthermore, according to one aspect of the present invention, the sugar manufacturing apparatus, and the saccharification apparatus, the solid residue is separated from the sugar solution produced by hydrolysis of cellulose contained in the biomass in the reaction vessel of the glycated device, wherein was charged again reaction vessel from one end of the reactor is recovered from the other end of the reactor, it is summarized in that and a reflux system to reuse the saccharification enzyme contained in the solid residue.

Further, according to another aspect of the present invention, the sugar manufacturing apparatus, further allowed to proceed hydrolysis by saccharifying enzyme contained in a saccharified solution is discharged and the saccharification apparatus, from the reaction vessel of the glycated device the the saccharified solution thoroughly summarized in that and a monosaccharification secondary saccharification device.

Further, according to one aspect of the present invention, ethanol production apparatus, and the sugar manufacturing device, a fermenting device sugars produced to produce ethanol by microbial fermentation by the sugar manufacturing device, produced by the fermentation device and summarized in that a distillation apparatus and purifying the ethanol being.

According to the present invention, efficient while reducing water consumption in the cellulose enzymatic degradation by saccharifying enzyme can proceed the enzymatic reaction, and, saccharification method a portion can be recovered reuse of enzyme used, the sugar the method of manufacturing becomes feasible, efficient manufacturable sugar saccharification device and sugar manufacturing device is provided, the manufacturing process and ethanol production apparatus of ethanol using the same are realized. Thus, reduces the amount of enzyme used in saccharification reaction in the production of ethanol fuel production cost is reduced, it is possible to reduce the energy load in the purification of the final ethanol. Therefore, an economically advantageous, is promoted the use of vegetable matter waste as biomass, it is useful to resolve the energy resource problems and waste disposal problems.

Schematic diagram illustrating an embodiment of a sugar manufacturing apparatus according to the present invention. Schematic block diagram for explaining along the configuration of the manufacturing method of saccharification process and sugars according to the present invention the sugar production apparatus. Schematically illustrating the structure of a modification of the sugar production apparatus of FIG. Schematic diagram showing another modification of the sugar production apparatus of FIG.

In the production of ethanol fuel utilizing vegetable matter waste (lignocellulosic biomass) and ethanol fermentation saccharification product by hydrolysis of cellulose and / or hemicellulose. The saccharification of cellulose and hemicellulose, the enzyme reaction using a saccharification enzyme (cellulase and hemicellulase), and the like hydrolyzing catalytic reaction using a catalyst, an enzyme reaction, on doing production of bioethanol efficiently in is a useful reaction.

The enzymatic reaction usually added enzyme water containing substrate, the reaction proceeds with uniform by stirring and mixing. In saccharification of biomass, after the removal or decomposition and removal of hemicelluloses lignin in advance subjected to hot water treatment to biomass material wood material or the like into particles, with the solid particles of the cellulosic is dispersed in water the action of saccharification enzyme. In the reaction using the batch type reaction vessel, since the flowability decreases the amount of water increasing the concentration of solid particles is reduced, the portion which is not mixed remain attached to the wall surface of the reaction vessel of an enzymatic reaction occurs efficiently since but decreases, it is difficult to reduce the water content to the extent that decreases the fluidity than a slurry.

In the present invention, as saccharification apparatus for performing enzymatic reactions, by employing the reactor of elongated horizontal, to proceed efficiently enzyme reaction while reducing the water content. Longitudinal Specifically, as an enzyme reactor, using a reaction vessel extending in the lateral direction (horizontal direction), toward the high concentration of biomass and the other end by introducing a (cellulose material) and saccharification enzymes from one end of the reactor allowed to proceed enzymatic reactions during movement of the reaction vessel in a direction, configured to discharge the reaction products and reaction residues from the other end of the reactor. By stirring and vertical gently (longitudinal direction of the apparatus) the moving direction of the raw material, the vertical movement (rising and falling) with the movement and the transverse direction is associated therewith acts on the raw material, not mixed material portion produce the can be prevented. By performing the stirring gently, but prompted the movement of the moving-diffusion and saccharifying enzyme reaction product, the biomass plug flow in the reactor is substantially maintained, cellulose with longitudinal movement of the biomass decomposition saccharification progresses, this according saccharification of liquid is produced. Therefore, the raw material is the product increases the amount of liquid product as it moves in the longitudinal direction becomes slurry, unreacted or reacted during the biomass is separated from the liquid portion as a solid residue. Saccharification of liquid glucose, soluble oligosaccharides with a polymerization degree of 2 to 6, the degree of polymerization include suspension polysaccharide is a partial degradation product of from 7 to 3000 the flow solution having a viscosity. The solid residue of unreacted cellulose and saccharification enzymes are attached, by cast saccharification reaction again this was separated and recovered, it is possible to recovery and reuse of the saccharification enzyme contained in the solid residue. Incidentally, this arrangement is useful when acting hemicellulase as the enzyme against hemicellulose, a cellulase and hemicellulase also available when acting as an enzyme of the mixed system of cellulose and hemicellulose, lignocellulose, such as wood material it can be widely applied to the case of performing the enzymatic reaction to the system material.

It will be described in detail with reference to the drawings the present invention. In the following description, although specific to be described in the case of saccharifying cellulose by cellulase is not limited thereto, hemicellulose and the like, it is applicable to saccharification of lignocellulosic materials is a matter of course.

Figure 1 is a schematic diagram illustrating an embodiment of a sugar manufacturing apparatus for carrying out a saccharification process according to the present invention. Sugar production apparatus 1 is connected to the reaction vessel 2 of an elongated cylindrical shape which is disposed to extend laterally, on one end side upper portion of the reaction vessel 2 in order to input material (and saccharifying enzyme) into the reaction vessel 2 a hopper 3 which is a pipe 4 for recovering the solid residue of unreacted cellulose from the bottom of the reaction tank 2 and the other end to discharge the sugar solution produced in the reaction tank 2 from the side of the other end of the reaction vessel 2 a pipe 5 for, which connect the solid residue is collected to one side of the reaction vessel 2 to reflux again charged to the reaction vessel 2 and an inlet tube 6, the enzyme contained in the solid residue re reflux system for use is constituted by a pipe 5 and inlet pipe 6. Wall of the reaction vessel 2 in order to hold the inside temperature suitable for enzymatic reactions, are provided in a multilayer structure incorporating a heat insulating material therein, the material inner wall that does not inhibit the enzymatic reaction, for example, stainless steel or PTFE, etc. It is formed by being protected by the fluorine resin such as iron. To control the reaction temperature, may be attached to the heating device as required, for example, may the double jacket to keep warm and passed through a of about 80 ° C. hot water to cover the reaction vessel 2, especially the reaction vessel When 2 of the lower half is disposed so as to cover the (inner wall surface portion in contact with the raw material) it is effective. The reaction vessel 2 has a stirrer 7 for stirring and mixing the raw material and saccharification enzymes, the rotation shaft 8 of stirrer 7 is disposed in the longitudinal direction so as to coincide with the center axis of the reaction vessel 2 rotated to be able to be supported at both ends. By rotating or reciprocating rotation of the rotary shaft 8 of stirrer 7 by a motor 10 which is attached to the end of the reaction vessel 2, a rod-shaped paddle 9 erected in the radial direction from the rotating shaft 8 in the reaction vessel 2 the rotating or pivoting swing concentrically, the raw material and enzyme are moved up and down is agitated by this operation. Each of the pipes 4, 5 and inlet pipe 6, the opening and closing valve 11, 12, 13 for controlling the circulation amount is provided. Further, the supply pipe 14 for replenishing the saccharifying enzyme in the middle of the material to move the reaction vessel 2 is connected to the top of the reaction vessel 2.

In saccharifying biomass by sugar production apparatus of FIG. 1, the biomass material prepared in particle diameter about 5mm or less granular or powder form, in advance, subjected to hot water treatment or the like as appropriate, then water mass for water content (total mass percentage) of less about 90 wt%, preferably prepared sludge-like water-containing high concentrations of 80-90% by weight, fed through a hopper 3 into the reaction vessel 2 with saccharifying enzymes. Saccharification enzymes are generally protein content is available as an aqueous solution of about 1% or less, generally, added at the rate of enzyme solution 10 parts by mass relative to 100 parts by mass of cellulose, the amount of enzyme to be recovered together with the solid residue it may be reduced to the minimum necessary amount in accordance with. Addition form of the enzyme may also intermittently continuous. Material and saccharification enzymes fall into the bath is agitated gently by stirring device 7, by continuing the introduction of the raw material, a mixture of raw material and enzyme are successively pushed out from one end to the other end of the reaction vessel 2 gradually moved in the longitudinal direction. During this time, gradually saccharification and liquefaction of cellulose enzyme reaction proceeds, become a slurry mixture of sugar solution and unreacted starting materials, separation of the solid residue and the sugar solution progresses with increasing sugar solution. Upon reaching the other end of the reaction vessel 2, the solid residue and sugar solution are each discharged from the pipe 4,5. To move and stirring of the raw materials in the reaction vessel 2 progresses efficiently and smoothly, it is preferable that the space on the raw material in the reaction vessel 2 is present, in particular, the filling rate of the raw material in the reaction vessel 2 There it is preferable to adjust the addition rate of the raw material so that about 40 to 70 volume%. At that time, the raw material in the reaction tank 2 so as to move at a constant speed, the balance between the emissions of sugar solution and the solid residue and the input amount of the raw materials is adjusted. Since the optimum temperature of the enzyme reaction according to the type of cellulase to be used is different, the temperature in the reaction vessel 2 was determined following the optimum temperature of the cellulase, the reaction time 24-60 hours approximately at about 30 ~ 70 ° C., preferably in 40 ~ 60 ° C. so that the order of 24-48 hours, the raw material is adjusted by the residence time of within the reaction vessel 2. That is, the raw material of the residence time so that the reaction time, the raw material of the input rate is adjusted by the discharge rate of the sugar solution and solid residue. Thus, 85-90% by glycation rate based on the glucose production from cellulose is achieved. To recover a portion of the saccharifying enzyme, the saccharification rate is left intentionally solid residue by setting the reaction time so that the above-mentioned range. No more glycation rate by extending the reaction time is also possible, it is also possible to completely glycosylated.

Cellulase is known generally as a collection of a plurality of types of saccharifying enzymes include a β- glucanase as a main component. β- glucanase, cellulose water-soluble oligosaccharides are known as hydrolyzing saccharification enzyme (2-6 mers glucose), Other, endoglucanases, have cellobiohydrolase like, each reaction stage It is different. Thus, depending on the progress stage of the enzymatic reaction, good reaction efficiency with the action of suitable types of saccharifying enzymes. Sugar production apparatus of the present invention is configured to allow addition of saccharifying enzyme in the course reactants by the supply pipe 14, by using this, the enzyme added to the reaction initial enzyme supplied from the supply pipe 14 can be adjusted to different types or different content. Also, add-supplemented in consideration of inactivation of the enzyme, homogeneously enzyme may be used for the purpose of adjusting the timing added to the dispersion.

The reaction vessel 2 in the sugar production apparatus 1 of Figure 1 has a cylindrical shape, so may be a shape that agitation is applied uniformly, the lower half of the reaction vessel 2 is equal semi-cylindrical, the cylindrical limited not, it may constitute an upper semi-elliptic cylinder shape and polygonal shape.

Saccharification enzymes are hydrophilic, although uniformly diffused in the large amount of water, cellulose also have a hydrophilic, since saccharifying enzyme has a suction force to the surface of the cellulosic material, the extremely reduced amount of water, saccharifying enzyme is easily contacted closely with the material cellulose. Contacted saccharifying enzyme is easily attached to the cellulose, to cut the cellulosic fibers by advancing the hydrolysis at the site. Further the reaction proceeds, it is necessary to move the enzyme as decomposition and cleavage is possible at other sites. However, the movement distance may be short, but rather the movement in the vicinity of the raw material is preferred, vigorous stirring is not required at high speed. Further, since the raw material is sequentially moved in the reaction vessel 2 in the longitudinal direction, than about 4 rpm, preferably under mild agitation of about 1 ~ 3 rpm, the movement and the longitudinal direction, it is a movement perpendicular vertical and lateral can be mixed well I suitably combined, it can proceed satisfactorily enzymatic reactions. For extremely low fluidity semisolid material, stirring at a high speed is not suitable because rather stay localized agitation.

Slow agitation operation solids concentration is high state, also acts as a pressing or shearing stress to the raw material, the raw material particles to promote the release or absorb the surrounding liquid, the liquid inside to the outside because it has an effect to facilitate the separation and release of enzyme penetration and degradation products into the raw material particles. Accordingly, the height of the solids concentration of the raw material particles are in contact with each other acts very advantageously in this regard. There are also functions to facilitate the formation of a sugar solution phase collected fine droplets with each other occur gradually saccharified solution by the reaction, to facilitate separation of the solid residue with sugar solution in the reaction vessel 2 and the other end. Stirring may also intermittently continuous, may decrease the distribution density of the paddle toward the other to reduce the stirring frequency in accordance with the reaction progress (see FIG. 2). At slow agitation, it is sufficiently effective to eliminate the unevenness of the temperature distribution, even when local temperature changes can be kept within ± 5 ° C.. The shape of the paddle may be one capable of agitation to carry out a proper mass transfer as described above, the rod-shaped paddle as shown in FIG. It is suitable.

Figure 2 shows another embodiment of a sugar manufacturing apparatus according to the present invention, similar to FIG. 1, it employs a reaction vessel 21 of cylindrical shape elongated in the lateral direction. In this figure, in order to describe the progression of processes and enzymatic reactions saccharification method describes schematically the structure. In this embodiment, the sugar solution obtained by the sugar manufacturing apparatus 20 is connected to the secondary saccharification device 40 for applying a further saccharification process. Therefore, even if the proportion of oligosaccharide or suspension polysaccharide sugar solution obtained by the sugar production apparatus 20 is high, it is possible to sufficiently monosaccharification by the secondary saccharification device 40, the saccharification enzyme in sugar production apparatus 20 Additionally or reduce the amount of use, it is possible to shorten the saccharification reaction time can be further promoted the emissions control and recovery and reuse of the device outside of the enzyme.

In saccharifying lignocellulosic biomass, subjected to such pre-hot water treatment granular or powdered biomass feedstock appropriate, (the percentage of water mass to the total mass) water content of 90 mass% or less, preferably 80 to 90 wt% was prepared in a high concentration sludge-like water-containing state of the extent, the biomass starts processing by supplying to the sugar production apparatus 20 in FIG. 2 as cellulose material B. First, by opening the control valve 23, the raw material B was pumped supplied from line L1 to one end of the reaction vessel 21 of cylindrical by the pump 22, fed through the top. At this time, by opening the control valve 36, the addition of a saccharifying enzyme is contained in the container 24 to the raw material B. In this embodiment, by switching the control valve 36 is configured so that it can supply the saccharification enzyme in any of the biomass material B in the L1 or pipe reactor 21, a saccharification enzyme in the reaction vessel 21 supply to be mixed in the tank. The reaction tank 21, the rotation shaft 27 of the stirrer 25 driven by the motor 26 is rotated, rotating or reciprocating pivoting material B and saccharification enzymes stirred and mixed by the radial paddles 28 which are erected on the rotary shaft 27 It is. By introducing the raw material B into the reaction vessel 21 at a constant speed, feed B moves the reaction vessel 21 in the longitudinal direction. During this time, saccharified solution P is produced gradually enzymatic reaction proceeds, with the amount gradually increases, the amount of solid residue R which is a raw material B unreacted gradually decreases. Paddles 28 of the stirrer 25, more to one side of the reaction tank 21 where the raw material B is turned on, provided to be less at the other end, a relatively frequent stirring the reaction in the initial stage of the enzymatic reaction promoting, and is configured of the solid residue by lowering the stirring frequency Once generated sugar solution so easily settling by the reaction proceeds.

The other end side of the reaction tank 21, the discharge of the solid residue R of the bottom is controlled by the control valve 30 and 35, the solid residue R which is discharged from the reactor 21 by pumping of the pump 38 provided in the conduit L3 , it is supplied to the reaction tank 21 through line L2, L3 through the switching valve 31 through the pipe line L1, enzyme contained in the solid residue is re-used. Sugar solution P in the reaction vessel 21 is discharged from the suction pipe 29 through the pipe L4, the discharge of the saccharified solution P is controlled by a control valve 32, 33. Sugar solution P discharged from the reactor 21 is supplied through line L5 via the switching valve 31 from line L4 to the secondary saccharification device 40. Alternatively, by closing the control valve 33, it can be collected from the outlet 34 through conduit L6.

Secondary saccharification device 40 is constituted by a vertical reaction vessel batch having a stirring device to stir the contents by rotation of the rotary shaft 41 in the vertical direction of the stirring device in a motor 42. Therefore, suitable for the processing of low fluidity liquid material viscosity can suitably handle the saccharified solution P supplied from the reaction vessel 21.
The raw material B is continuously supplied to the reaction tank 21 it is necessary to use a pipe L1 at all times. Considering this point, shown in FIGS. 3 and 4 an example of discharge and transport the form of sugar solution P and the solid residue R is changed so as to be suitable for continuous processing in the sugar manufacturing apparatus 20 of FIG. Since the emissions of non-transfer Constitution of sugar solution P and the solid residue R is the same as FIG. 2, those in the description the following description of sugar production apparatus of FIGS.
Sugar production apparatus 20A in Figure 3, the conduit L8 for supplying solid residue R which is discharged from the other end of the reactor 21 separately from the raw material B to one end of the reaction vessel 21 provided separately from the pipe L1 is, the transfer path of the saccharified solution P is not intersect the transfer path of the solid residue R. Specifically, saccharified solution P to be discharged from the reaction tank 21 by the suction pipe 29 is supplied through the conduit L7 into the secondary saccharification device 40, the supply is controlled by a control valve 50. Solid residue R in the reaction vessel 21 is returned solely to one end of the reaction vessel 21 from the sludge chamber 60 provided at the bottom of the reaction vessel 21 and the other end through conduit L8, is reused enzymes contained in the solid residue R that. Thus, the supply of the raw material B by line L1 is not interfered with by refluxing the solid residue R, it enables the continuous supply of stable material B. When solid residue R are supplied to the sludge chamber 60, saccharified solution is entrained in the solid residue R is separated as supernatant, the solid residue R is deposited. Sludge chamber 60, the internal liquid - interface meter 51 for detecting the solid interface is attached, the lower end outlet of the sludge chamber 60 is connected pipe L8 is, the control valve 52 for opening and closing the pipe line L8 It is provided. Interface meter 51 is connected to the control valve 52 and the electrical control valve 52 when the interface has reached a predetermined level of solid residue R of depositing the sludge chamber 60 is opened, the control valve so as to close is less than the predetermined level 52 It is allowed to operate. Less than about 50% of the volume of the solid residue by the opening of the control valve 52 is sludge chamber 60 interior volume, it is preferable that preferably sets a predetermined level so as to maintain below approximately 20%. As the interface meter 51, for example, the vibration-type level switch, for liquids tuning fork limit switch, a vibration wave as such as an ultrasonic type level meter, utilizing an acoustic wave of the acoustic wave such as a surface of the interfacial meter suitably detected utilizing it can. Solid residue R which is discharged from the sludge chamber 60 is pumped a conduit L8 by the pump 53, by the switching of the control valve 54 and 55, either returned to the reaction tank 21, or a tube which is branched from the conduit L8 It is supplied to the tank through the road L9. In a state where saccharification progresses suitably in the sugar manufacturing apparatus 20A of FIG. 3, the control valve 52 is opened intermittently, the solid residue R is glycated again returned from conduit L8 into the reaction vessel 21, the enzyme contained in the residue (cellulases) are reused. If the proportion of undegraded product by reduced activity of the enzyme is increased significantly, the liquid control valve 52 the sludge chamber 60 be opened - solid interface continually becomes equal to or greater than a predetermined level. To avoid this situation, if the saccharification rate decreased, switches the solid residue R of the sludge chamber 60 to transfer once the tank without returning to the reaction tank 21, the solid residue in the tank, the control valve 56 by opening the pumped solid-liquid separator 58 via conduit L10 by driving the pump 57. The solid-liquid separator within 58, saccharified solution contained in the solid residue is separated, sugar solution is supplied through the conduit L11 to the secondary saccharification device 40, the solid residue, the fuel is discharged boiler from the conduit 12 It is effectively utilized as a source or the like. In FIG. 3, the saccharification enzyme of the container 24 has been described as added to the raw material B likewise pipe L1 and FIG. 2, the sugar manufacturing apparatus 20A as also added to the solid residue is refluxed it may be configured.
If added amount of enzyme for the raw material B is sufficient, or, in a case the remaining of the solid residue R to pretreatment conditions of the raw material B is good is low, saccharification sufficiently proceeds, the solid residue R since the main component is the glycation not of lignin, less need to return to the reaction vessel 21. Sugar production apparatus 20B shown in FIG. 4 can be used in such cases. In sugar production apparatus 20B of FIG. 4, is omitted conduit for returning the solid residue R which is separated in the sludge chamber 60 to the reaction vessel 21, the solid residue R may always be stored in the tank through the pipe L13. Except for this, the structure of the sugar manufacturing apparatus 20B is similar to sugar production apparatus 20A of FIG.

As reaction conditions in the above-described configuration, for example, in the reaction vessel 21, 12 to 48 hours at 30 ~ 70 ° C., by preferably for about 12-24 hours at 40 ~ 60 ° C., well in the secondary saccharification device 40 stirred sugar solution mixable state is obtained, in which the secondary saccharification device 40, 12 to 48 hours at 30 ~ 70 ° C., preferably by reacting 12-24 hours at 40 ~ 60 ° C., the glycation rate becomes approximately 85-90%, can also be achieved more glycation rate. Incidentally, the adjustment of such reaction temperature, it is useful to cover the reaction vessel 21 by jacket insulation or heating the heat medium heated as sugar manufacturing apparatus of FIG. 1, sugar 2-4 it may utilize insulation or heating system with such jackets in the manufacturing apparatus.

Cellulase is known generally as a collection of a plurality of types of saccharifying enzymes includes a beta-glucanase as a main component, beta-glucanase, cellulose water-soluble oligosaccharides (2-6 mer glucose It is known as hydrolyzing saccharification enzyme). Also, a portion of the water-soluble oligosaccharides are broken down into glucose by β- glucosidase included in cellulase. That is, the cellulase includes a plurality of types of enzymes acting at different stages in monosaccharification process. Each enzyme may each have substrate specificity, since adsorbed to the material B according to their specificity, the enzyme which acts on the early stages of monosaccharification process, easily bonded to the raw material B, an enzyme that acts on the later stages, the portion easily bonded to decomposed suspension polysaccharides, deviation may occur in the distribution of the enzyme in the solid residue R a sugar solution P. Therefore, by reusing recovered solid residue R from reaction vessel 21, it will be relatively large recovery and reuse of the enzyme which acts on glycated early stage, whereas, is supplied to the secondary saccharification device 40 that saccharified solution P may include relatively large enzymes that act on glycated late stage, which is advantageous in to complete the saccharification reaction. Sugar production apparatus of FIG. 2, divides the saccharification process into two, since a part can be performed by the secondary saccharification device 40, glycation rate in the sugar manufacturing apparatus 20 can be set lower than the above Specifically, glycation rate in the sugar manufacturing apparatus 20 to set the reaction time and the enzyme amount such that about 50 to 90% sugar solution containing the suspension polysaccharides and water-soluble oligosaccharide by partial decomposition the fully monosaccharification using a secondary saccharification device 40. Thus, the ratio of the enzyme contained in the slurry-like solid residue R to be collected and reused increases, useful in enhancing the recovery and re-utilization of the enzyme.

The container 37, saccharifying enzymes for refilling the reaction vessel 21 is housed, can be used to replenish the enzyme deficiency by inactivation or the like. Also, the enzyme solution containing a large amount of enzyme which acts on glycated early stage, and saccharified liquid containing a large amount of enzyme which acts on glycated later stage, housed separately in a container 24 and 37, the supply of the enzyme in accordance with the reaction steps it may be carried out.

In sugar production apparatus as shown in FIG. 1 and 2, may be provided with a stirring blade at the tip or in the middle of the paddle of the stirring device, by easily applied pressing force to the raw material on the stirring blade, the contact between the enzyme and the material , an enzyme from entering the raw material particles, release-diffusion from the raw material particles of the decomposition products is accelerated.

Further, the longitudinal axis of the reaction vessel by slightly inclined, the saccharified solution than the one end side of the raw material is introduced are arranged slightly higher towards the other end side being discharged, the reaction vessel by reaction of the raw material feeding since the raw material can be prevented from disturbing the plug flow causing unintended movement, about 3 ° or less, preferably placed the reaction vessel at a tilt angle of about 1 ~ 2 °.

Describing one embodiment for configuring the ethanol production apparatus using the above-described sugar production apparatus below.

Ethanol production apparatus comprises a monosaccharide apparatus for producing a monosaccharide and saccharified biomass, and fermentor to produce ethanol by fermenting a saccharified product, the distillation apparatus for purifying ethanol by distilling fermented product configured using a monosaccharide manufacturing apparatus, a hot compressed water reactor to advance the selective hydrolysis of the hemicellulose, and solid-liquid separator for separating the decomposition product derived from hemicellulose, cellulose saccharification by enzyme reaction configured using an enzyme reactor. As the enzyme reactor 1 or use sugar production apparatus as shown in FIG. 2, the supplies to the hot compressed water reactor hemicellulose selective hydrolysis-liquefied solid-liquid monosaccharide manufacturing apparatus biomass after separation by the separation device, to supply the solid residue is cellulose raw sugar production apparatus of FIG. 1 or FIG. 2, saccharification by enzyme reaction. When performing full saccharification by enzyme reaction, it is introduced as it fermentor monosaccharides obtained by producing ethanol, may be generated ethanol by distillation. If not completely performed saccharification by enzyme reaction, for example, by attaching a catalytic reactor using a solid acid catalyst, a polysaccharide or oligosaccharide partially decomposed it may be hydrolyzed to monosaccharification in the catalytic reactor. Further, the liquefied product produced by selective hydrolysis of the hemicellulose are the partial degradation product comprising an oligosaccharide and xylose from hemicellulose, so to use it for the production of ethanol, the catalytic reactor using a solid acid catalyst If, additionally provided a fermentor using a microorganism having xylose fermentation capacity. Catalysis by the solid acid catalyst is also effective monosaccharification such as oligosaccharides derived hemicellulose.

With ethanol manufacturing apparatus as described above, a method for producing ethanol from lignocellulosic biomass.

Biomass B used as a raw material may be any cellulosic material, such as wood, thinned wood, wood material or bark, straw, wheat straw, grasses, such as rice husk, pulp and waste paper, cotton cloth, hemp cloth, include fibrous material such as an artificial cellulosic material, in particular, it can be efficiently saccharification and fermentation of vegetable material such as wood material containing hemicellulose. From the viewpoint of reaction efficiency, good idea to pulverized pregranulated such biomass B, and adjusted to a particle size about 5mm or less particle preferred.

In pressurized hot water reactor, containing a quantity of biomass supplied as raw material from the outside, the heater and 200 - 230 ° C. of about prepared using a pump or the like, the pressure of 2 to about 2.5 MPa (subcritical supplying pressurized hot water of the state). When pressurized hot water is added to and act on the biomass hemicellulose contained in the biomass is selectively hydrolyzed solubilized. Wood material is mainly composed of cellulose, a cellulosic biomass containing hemicellulose and lignin, compared cellulose to require temperatures of approximately 240 ~ 300 ° C. in the case of hydrolysis with pressurized hot water, hemicellulose since easily disassembled solubilized at a low temperature of about 200 ~ 230 ° C. from cellulose, reaction products of wood material treated by hot compressed water reactor, polysaccharides including oligosaccharides partially decomposed and solubilized hemicellulose and water liquid, a solid-liquid mixture containing a solid residue of cellulose and lignin which is not decomposed. Supplying form of pressurized hot water may be either batchwise in a continuous flow-through, regulation in the case of flow-through, the water flow rate to the bath residence time of pressurized hot water is about 5 to 120 minutes was reacted for about 10 to 120 minutes. When the action of pressurized hot water of about 120 ~ 200 ° C. before supplying 200 ~ 230 ° C. of about hot water described above, lignin is easily separated, the decomposition of hemicellulose at 200 ° C. or higher is accelerated.

Reaction products of the hot compressed water reactor is supplied to the solid-liquid separator, a liquid portion of the hemicellulose degradation products are separated into a solid residue containing cellulose and lignin.

The solid residue, a water content of about 90 wt%, preferably prepared sludge-like water-containing state of the high concentration of about 80 to 90 wt%, as the cellulose raw material, enzyme reactor, that is, in FIG. 1 or 2 sugar It is supplied to the manufacturing apparatus. At that time, (more than about protein content of 1%) cellulase enzyme solution relative to 100 parts by mass of cellulose was added in an amount of about 10 parts by weight, as described above, the longitudinal raw material in the reaction vessel to continue the supply of the raw material slowly stirring while moving in the direction. The reaction vessel is enzyme is maintained in an active temperature, the cellulose of the solid residue is decomposed by the action of the cellulase, the saccharified solution of cellulose and cellobiose (a dimer of glucose) is a water-soluble oligosaccharides with primary decomposition was obtained. Saccharified solution includes a suspension polysaccharide water-soluble oligosaccharides and water-insoluble, a flow liquid suspension polysaccharide water liquid water soluble oligosaccharides are dispersed, the longer the reaction time is sufficiently complete saccharification to become glucose. Suspension polysaccharide is a partial degradation product of cellulose, 7 a dimer or higher glucose polymers and a hexamer of glucose cellohexaose crystals hydrolysable a glucose by the solid acid catalyst reaction is there.

Saccharifying enzyme used in the enzyme reaction can use common saccharification enzymes available commercially, it may also be used those commercially available as a heat-resistant enzyme. Normal saccharification enzymes, enzyme activity is maximized at about 40 ~ 50 ° C., thermostable enzyme, since the enzyme activity is maximized at about 70 ~ 90 ° C., the temperature of the enzyme reactor, the saccharification enzyme used depending appropriate enzyme activity appropriately adjusted so obtained. To facilitate temperature control of the enzymatic reaction, if necessary, the temperature may be provided a cooler for reducing the solid residue after the pressurized hot water reaction.

If saccharified solution of cellulose produced in the enzymatic reaction comprises an oligosaccharide or a polysaccharide may be monosaccharification is supplied to the catalytic reactor. Catalysis, using a solid acid catalyst to proceed by mixing and stirring the solid acid catalyst at a temperature below 90 ° C. or higher 120 ° C., the oligosaccharide and suspension polysaccharides, good hydrolytic by the action of the solid acid catalyst decomposed by glucose (monosaccharide constituting a cellulose) are produced. The solid acid catalyst, carbon-based, zeolite, alumina, and inorganic solid acids such as silica, such as those obtained by introducing an acid group are exemplified by sulfonation of the organic material such as resin, in order to increase the contact surface area powdered or may be used a particulate solid acid catalyst. In particular, preferably has a sulfonated carbon system obtained by sulfonation treatment after carbonizing the organic carbon material, sulfonated carbon-based solid acid catalysts are inert such as nitrogen organic carbon material such as wood acids or herbs obtained by adding a sulfonic group in the skeleton of carbide by heating obtained by heating treatment in a gas atmosphere amorphous black solid (carbide) in concentrated sulfuric acid or fuming sulfuric acid, washed with hot water . The amount of solid acid catalyst, 400 ~ 500g / L is preferable as the packing density. The reaction time may be a generally 5 to about 15 hours. Saccharified solution mainly composed of glucose as the supernatant a solid acid catalyst in the reaction product was settling is obtained. After sedimentation solid acid catalyst was recovered and used again returned to the mixing device.

Saccharified solution obtained from cellulose as appropriate so that the conditions suitable for fermentation water content and pH was adjusted, by taking the fermentation the microorganisms in the fermentation device was prepared in the fermentation stock, ethanol glucose by the action of fermenting microorganism Convert. The fermenting microorganism for use in the ethanol fermentation, can be a known ethanol fermentation microorganisms, such as yeasts, e.g., Saccharomyces cerevisiae, Schizosaccharomyces pombe, Brettanomyces custersii, Sarcina-Bentorikuri, Kluyveromyces fragilis, Zymomonas mobilis, and the like Kluyveromyces marxianus. Furthermore, the gene having the ability to convert to ethanol may be used bacteria introduced by genetic recombination. With flocculent yeast, since the good sedimentation property are advantageous in the solid-liquid separation after the fermentation, advantageous in using the amino acid yeast is degraded by hydrolytic enzymes of microorganisms of the surrounding such as a nutrient source because some form is also useful in improving the efficiency of fermentation. During the fermentation, the nutrients necessary for breeding and activities of fermenting microorganism was added, it is preferable to adjust the optimum pH. For yeast to activities and proliferation, phosphorus, nitrogen, and essential nutrients such as vitamins, Co, Ni, requires request trace elements such as Zn, In addition, yeast are used in the production of biomass ethanol, or lower ability to synthesize such vitamins or amino acids, or, in some cases lacking. As a nutrient source for the fermentation microorganism to add such required components from the outside, yeast extract, polypeptone, and the like can be generally used. Alternatively, it may be utilized crushed vegetable wastes and algae, such as tea leaves or coffee grounds, available components contained in these cytoplasm as the nutrient source.

Saccharification of the fermentation solution (glucose) concentration is about 1 to 20 wt%, preferably adjusted to be about 10 mass%. The addition amount of the microorganism for nutrients (dry matter basis) is adjusted appropriately according to the type of fermenting microorganisms, typically about 0.1 to 1% by weight, preferably set to about 0.2 to 0.5 mass% Then good. pH of the fermentation stock solution is about 2.5-5.5, preferably adjusted to about 3.0 to 5.5, was inoculated fermenting microorganisms at a rate of about 1 ~ 30 g / L, temperature 30 ~ 37 ° C. fermentation proceeds by holding for about 2 to 48 hours to a degree. For example, using the fermentation stock solution of glucose concentration of about 10 wt%, it is possible to produce ethanol at 20 ~ 25g- ethanol / (L · h) about speed.

Fermented product after the fermentation, if necessary, solid (lignin, fermenting microorganisms) after removal by filtration or the like, the purification of ethanol is obtained by distillation in the distillation apparatus. Without removing the solids from the fermentation product may be directly distilled. Solids are separated from the fermentation product may be introduced into the saccharification of biomass.

On the other hand, saccharified solution from hemicellulose with a catalytic reactor, was hydrolyzed by the catalytic reaction using the same solid acid catalyst as described above, to monosaccharification. The reaction conditions may be the same as described above. Hemicellulose derived oligosaccharides, monosaccharides generates comprising such (pentose constitutes hemicellulose) xylose and arabinose.

Saccharified solution from hemicellulose as appropriate so that the conditions suitable for fermentation water content and pH was adjusted, by taking the fermentation the microorganisms in the fermentation device was prepared in the fermentation stock, ethanol xylose like by the action of fermenting microorganism Convert. The fermenting microorganism for use in the fermentation, Saccharomyces yeast, microorganisms having xylose fermentation capacity, such as Rhizopus fungi (Rhizopus oryzae). Furthermore, the gene having the ability to convert to ethanol may be used bacteria introduced by genetic recombination. With flocculent yeast, since the good sedimentation property are advantageous in the solid-liquid separation after the fermentation, advantageous in using the amino acid yeast is degraded by hydrolytic enzymes of microorganisms of the surrounding such as a nutrient source because some form is also useful in improving the efficiency of fermentation.

Fermentation product from hemicellulose, optionally, solids (lignin, fermenting microorganisms) after removal by filtration or the like, the purification of ethanol is obtained by distillation in the distillation apparatus. Without removing the solids from the fermentation product may be directly distilled. Solids are separated from the fermentation product may be introduced into the saccharification of biomass. Fermentation product from cellulose and fermented product from hemicellulose may be distilled together.

In fermenter, as a fermentation microorganism, Clostridium acetobutylicum, Clostridium beijerinckii, Clostridium O Ranch Bed Chile cam, utilizing microorganisms such as Clostridium Tetanomofamu is possible to produce an alcohol or acetone, such as butanol by fermentation, than ethanol useful alcohols can be applied to the production of ketones. Similarly, it is also applicable to generation of such hydroxymethylfurfural and furfural.

The present invention, in producing ethanol fuel plant waste as biomass, utilizing resources there is no possibility of rising food prices, economically and rationally can be processed, waste treatment and resource since contributing to the production, high availability, it is also possible contribution to the promotion and environmental protection recycling.

Claims (18)

  1. It was prepared particulate biomass hydrous state,
    The biomass and saccharification enzymes, while sequentially moving longitudinally substantially toward horizontal direction by introducing from one end of the reactor which extends to the other end, times that the central axis in the longitudinal direction of the reactor by stirring the biomass and saccharification enzymes by dynamic operation, saccharification method biomass saccharification of biomass progresses with longitudinal movement of the biomass.
  2. Biomass of the water-containing state, the water content is not more than 90 wt%, stirring the biomass, the rotation of the stirring device having a paddle to be erected in the radial direction from the rotational axis extending in the longitudinal direction of the reactor saccharification process biomass according to claim 1 carried out by.
  3. Biomass of the water-containing state with a water content of 80-90 wt%, said reaction vessel, according to claim 1 or one side is disposed to be inclined at an inclination angle of less than the 3 ° so as to be lower than the other end saccharification method of biomass as described in 2.
  4. The biomass is lignocellulosic biomass containing cellulose, wherein the saccharification enzyme saccharification method biomass according to any one of claims 1 to 3, which is a cellulase.
  5. Said particulate biomass in advance, biomass according to any one of claims 1 to 4 using the hemicellulose contained in contact with the hot compressed water to biomass that selectively hydrolyzed to remove saccharification method.
  6. During saccharification of the biomass proceeds, saccharification process biomass according to any one of claims 1 to 4 for additional saccharification enzyme.
  7. Gradually saccharified solution is produced by hydrolysis of cellulose contained in the biomass by saccharification process biomass according to any one of claims 1 to 6,
    Respectively collecting the sugar solution and the solid residue from the other end of the reactor,
    The solid residue was charged again reaction vessel from one side, the production method of the sugar to reuse saccharification enzyme contained in the solid residue is recovered from the other end of the reactor.
  8. Glycation rate generated by the sugar solution from the biomass, from 50 to 90%, according to monosaccharification the sugar solution further allowed to proceed hydrolysis by saccharifying enzyme contained in a saccharified solution is recovered from the reaction vessel method for producing a sugar according to claim 7.
  9. Ethanol production process of producing ethanol sugars obtained by the production method of sugar according to claim 7 or 8 by microbial fermentation.
  10. A reaction vessel substantially horizontally extending,
    Solids concentration of particulate biomass high moisture conditions, the biomass supply means for supplying from one end of the reactor to sequentially move longitudinally toward the other end from one end of the reactor to the interior ,
    And enzyme addition means for adding a saccharification enzyme to the biomass supplied from one end of the reactor,
    A stirring device for stirring the biomass and saccharification enzymes by the rotation motion about axis longitudinal direction of the reaction vessel,
    Saccharification device having a discharge means for collecting the sugar solution produced by the saccharification of biomass for moving the reaction vessel in the longitudinal direction progresses from the other end of the reactor.
  11. The stirring device, saccharification apparatus according to claim 10 having a rotary shaft which is rotatably supported and extends in the longitudinal direction of the reactor, and a paddle erected in radial direction from said rotary shaft .
  12. The reaction vessel, saccharification apparatus according to claim 10 or 11 one end side is arranged inclined at an inclination angle of less than the 3 ° so as to be lower than the other end.
  13. Further, glycation device according to any one of claims 10 to 12 having a replenishing means for replenishing the saccharification enzyme in the middle of biomass for moving the reaction vessel.
  14. Further, the particulate biomass, any claims 10 to 13 having a pressurized hot water reactor for removing selectively hydrolyze the hemicellulose contained in the biomass is contacted with a pre-pressurized hot water or saccharification apparatus according to item 1.
  15. And saccharification apparatus according to any one of claims 10-14,
    Put the solid residue to separate from the sugar solution produced by hydrolysis of cellulose contained in the biomass in the reaction vessel of the saccharification device, again the reaction vessel from one end of the reactor is recovered from the other end of the reactor to sugar production apparatus and a reflux system to reuse the saccharification enzyme contained in the solid residue.
  16. Furthermore, sugar production apparatus according to claim 15 having a monosaccharification secondary saccharification device the sugar solution further allowed to proceed hydrolysis by saccharifying enzyme contained in a saccharified solution discharged from the reaction vessel.
  17. And saccharification apparatus according to any one of claims 10-14,
    Sugar production apparatus and a glycated monosaccharification secondary saccharification device the sugar solution further allowed to proceed hydrolysis by saccharifying enzyme contained in a saccharified solution discharged from the reaction vessel of the apparatus.
  18. Sugar production apparatus according to any one of claims 15-17,
    A fermentor to produce ethanol sugar produced by the sugar production apparatus and microbial fermentation,
    Ethanol production apparatus and a distillation apparatus for purifying ethanol produced by the fermentation device.
PCT/JP2012/084143 2012-01-06 2012-12-28 Biomass saccharification method and device, method and device for producing sugar, and method and device for producing ethanol WO2013103138A1 (en)

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