WO2014106953A1 - 糖液の製造装置及び糖液の製造方法 - Google Patents
糖液の製造装置及び糖液の製造方法 Download PDFInfo
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- WO2014106953A1 WO2014106953A1 PCT/JP2014/050037 JP2014050037W WO2014106953A1 WO 2014106953 A1 WO2014106953 A1 WO 2014106953A1 JP 2014050037 W JP2014050037 W JP 2014050037W WO 2014106953 A1 WO2014106953 A1 WO 2014106953A1
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- Prior art keywords
- reaction tank
- saccharification
- cellulose
- sugar
- producing
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M27/00—Means for mixing, agitating or circulating fluids in the vessel
- C12M27/02—Stirrer or mobile mixing elements
- C12M27/06—Stirrer or mobile mixing elements with horizontal or inclined stirrer shaft or axis
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M23/00—Constructional details, e.g. recesses, hinges
- C12M23/58—Reaction vessels connected in series or in parallel
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M27/00—Means for mixing, agitating or circulating fluids in the vessel
- C12M27/02—Stirrer or mobile mixing elements
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M29/00—Means for introduction, extraction or recirculation of materials, e.g. pumps
- C12M29/04—Filters; Permeable or porous membranes or plates, e.g. dialysis
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M35/00—Means for application of stress for stimulating the growth of microorganisms or the generation of fermentation or metabolic products; Means for electroporation or cell fusion
- C12M35/08—Chemical, biochemical or biological means, e.g. plasma jet, co-culture
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/12—Means for regulation, monitoring, measurement or control, e.g. flow regulation of temperature
- C12M41/14—Incubators; Climatic chambers
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS 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
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/12—Means for regulation, monitoring, measurement or control, e.g. flow regulation of temperature
- C12M41/18—Heat exchange systems, e.g. heat jackets or outer envelopes
- C12M41/24—Heat exchange systems, e.g. heat jackets or outer envelopes inside the vessel
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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
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
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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
- 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
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- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
Definitions
- the present invention relates to a sugar solution production apparatus for obtaining a sugar solution from cellulose-containing biomass and a method for producing the sugar solution.
- the fermentation production process of chemicals using sugar as a raw material is used for the production of various industrial raw materials.
- sugars used as fermentation raw materials those derived from edible raw materials such as sugar cane, starch and sugar beet are currently used industrially.
- a process for producing sugar solution more efficiently from renewable non-edible resources i.e. cellulose-containing biomass.
- the construction of a process for efficiently converting the obtained sugar solution into an industrial raw material as a fermentation raw material is a future problem.
- Cellulose-containing biomass is mainly composed of aromatic polymer lignin and monosaccharide polymer cellulose or hemicellulose.
- the sugar solution is generally obtained using a method based on an enzymatic saccharification reaction.
- the enzymatic saccharification reaction method includes, for example, pretreatment such as lignin-protected cellulose or hemicellulose by mechanical treatment such as pulverization or thermochemical treatment using high-pressure and high-temperature hot water, dilute sulfuric acid, ammonia, or the like. Then, cellulose or hemicellulose is detached from lignin (see, for example, Patent Documents 1 and 2) to obtain pretreated biomass. Thereafter, a saccharification enzyme is mixed with the pretreated biomass, and cellulose or hemicellulose obtained by desorption from lignin is hydrolyzed by the saccharification enzyme to produce a monosaccharide.
- a method for intermittently supplying pretreated biomass for example, see Patent Documents 3 and 4
- a method for once solid-liquid separation and mixing the residue and water to accelerate the reaction for example, see Patent Document 5
- Examples include a method of grinding the residue and performing a saccharification reaction again (for example, see Patent Document 6), a method of adding water to the pretreated biomass to form a slurry (for example, see Patent Document 7), and the like.
- the method of intermittently supplying the pretreated biomass as described in Patent Documents 3 and 4 can increase the sugar concentration at the time of saccharification. Since the reaction time of the saccharification enzyme is different between the treated biomass and the pretreated biomass supplied later, the saccharification efficiency is lowered.
- Patent Document 7 discloses a method of providing a slurrying tank to suppress thermal overdegradation of biomass. However, since the liquid cannot be fed unless the solid content concentration is lowered, the sugar concentration is lowered as a result. There is a possibility.
- an object of the present invention is to provide a sugar solution production apparatus and a sugar solution production method capable of efficiently producing a high concentration sugar solution.
- the present inventors have conducted intensive research on a sugar liquid production apparatus and production method.
- the saccharification reaction of the cellulose-containing biomass with the saccharifying enzyme is improved and the saccharification reaction of the cellulose-containing biomass is improved by adjusting the temperature during the saccharification reaction in a plurality of stages in which the cellulose-containing biomass proceeds in the reactor
- the cellulose-containing biomass and saccharifying enzyme are supplied to the horizontal reaction tank, and the saccharification enzyme is mixed with the cellulose-containing biomass while maintaining the inside of the tank at a predetermined temperature.
- the present invention has the following configurations (1) to (16).
- a sugar solution production apparatus for producing a sugar solution from cellulose-containing biomass, A stirring shaft provided in the horizontal direction inside, and a stirring blade provided on the stirring shaft, and saccharifying by reacting the cellulose-containing biomass and the saccharifying enzyme while stirring the cellulose-containing biomass and the saccharifying enzyme A horizontal reaction tank for obtaining a slurry; A vertical reaction tank for saccharifying the saccharification slurry to obtain a saccharified solution; A saccharification slurry supply line connecting the horizontal reaction tank and the vertical reaction tank; A heating unit provided around or on the wall of the horizontal reaction tank and heating the horizontal reaction tank;
- An apparatus for producing a sugar solution comprising: (2)
- the horizontal reactor is A biomass inlet for supplying the cellulose-containing biomass to one of the horizontal reaction vessels;
- a saccharified solution supply line for discharging the saccharified solution from the vertical reaction tank;
- a solid-liquid separator that separates solids from the saccharified liquid to obtain a sugar liquid;
- the apparatus for producing a sugar solution according to any one of (1) to (7) above characterized by comprising: (9) The apparatus for producing a sugar liquid according to (8), further comprising a hot water supply line that is connected to the solid-liquid separator and supplies hot water into the solid-liquid separator.
- the horizontal reaction tank includes a plurality of the stirring shafts, The apparatus for producing a sugar solution according to any one of (1) to (9), wherein each of the stirring shafts includes a plurality of stirring blades.
- the vertical reaction vessel has a second enzyme supply passage for supplying a saccharifying enzyme therein, The production of a sugar solution according to any one of (1) to (11) above apparatus.
- the apparatus for producing a sugar solution according to (12), wherein the saccharifying enzyme supplied to the horizontal reaction tank and the saccharifying enzyme supplied from the second enzyme supply passage are of different types.
- the dry mass of the cellulose-containing biomass subjected to thermochemical treatment is 15% by mass or more to 50% by mass with respect to the total mass of the saccharification slurry.
- thermochemical treatment is selected from the group consisting of ammonia treatment, hydrothermal treatment, blasting treatment, alkali treatment and dilute sulfuric acid treatment.
- thermochemical treatment is selected from the group consisting of ammonia treatment, hydrothermal treatment, blasting treatment, alkali treatment and dilute sulfuric acid treatment.
- the cellulose-containing biomass is vertically saccharified and slurried by the saccharifying enzyme while the cellulose-containing biomass is progressing in the horizontal direction while maintaining the inside of the tank at a predetermined temperature in the horizontal reaction tank.
- the slurry is preliminarily made into a low-viscosity slurry.
- the reaction efficiency between the cellulose-containing biomass and the saccharifying enzyme can be improved, and saccharification is performed at a high concentration.
- a high-concentration sugar liquid can be efficiently produced at a low cost and in a short time.
- FIG. 1 is a partially cutaway view of a sugar liquid production apparatus according to the first embodiment of the present invention.
- FIG. 2 is a cross-sectional view taken along the line AA in FIG. 3 is a cross-sectional view taken along the line BB of FIG.
- FIG. 4 is a diagram illustrating an example of another configuration of the sugar liquid production apparatus.
- FIG. 5 is a view showing another example of the horizontal reaction tank of the sugar liquid production apparatus.
- FIG. 6 is a view showing another example of the horizontal reaction tank of the sugar liquid production apparatus.
- FIG. 7 is a diagram showing an example of another configuration of the vertical reaction tank of the sugar liquid production apparatus.
- FIG. 8 is a conceptual diagram showing an apparatus for producing a sugar liquid according to the second embodiment of the present invention.
- FIG. 8 is a conceptual diagram showing an apparatus for producing a sugar liquid according to the second embodiment of the present invention.
- FIG. 9 is a conceptual diagram showing a sugar liquid production apparatus according to the third embodiment of the present invention.
- FIG. 10 is a conceptual diagram showing an apparatus for producing a sugar liquid according to the fourth embodiment of the present invention.
- FIG. 11 is a diagram illustrating an example of another configuration of the sugar liquid production apparatus.
- FIG. 1 is a partially cutaway view of a sugar liquid production apparatus according to the first embodiment of the present invention.
- FIG. 2 is a cross-sectional view taken along the line AA in FIG.
- FIG. 3 is a cross-sectional view taken along the line BB of FIG. 1 and shows a partial configuration of the sugar liquid production apparatus.
- a sugar liquid production apparatus 10A includes a horizontal reaction tank (horizontal reaction tank) 11, a jacket (heating unit) 12, a vertical reaction tank (vertical reaction tank) 13, and a saccharification slurry. And a supply line L11.
- the horizontal reaction tank 11 refers to a reaction tank in which a stirring shaft provided inside is provided in the horizontal direction.
- the vertical reaction tank 13 refers to a reaction tank in which a stirring shaft provided inside is provided in the vertical direction.
- the horizontal reaction vessel 11 includes a stirring shaft 21 and a stirring blade 22.
- the stirring shaft 21 is provided in the horizontal direction inside the horizontal reaction tank 11.
- the stirring blades 22 are provided on the stirring shaft 21 at predetermined intervals.
- the agitation shaft 21 is rotated by a motor (drive device) 24 to agitate the cellulose-containing biomass 26 supplied into the horizontal reaction tank 11.
- the rotational speeds of the stirring shaft 21 and the stirring blade 22 are controlled by a motor 24.
- the horizontal reaction tank 11 is provided with a biomass inlet 25 on one end side of the horizontal reaction tank 11.
- Cellulose-containing biomass 26, water 27, and pH adjuster 28 are supplied from the biomass inlet 25 into the horizontal reaction tank 11.
- the biomass species of the cellulose-containing biomass 26 contains cellulose and hemicellulose (hereinafter referred to as “cellulose” as a general term for cellulose and hemicellulose), lignin that is an aromatic polymer, and the like, and contains 5% by mass or more of cellulose. It is not particularly limited as long as it is a biological resource.
- the cellulose-containing biomass 26 is also called lignocellulose because it contains lignin, which is an aromatic polymer, in addition to cellulose. It is not particularly limited as long as it is a biological resource containing 5% by mass or more of cellulose.
- biomass species include, for example, bagasse, switchgrass, napiergrass, Eliansus, corn stover, rice straw, straw, EFB (oil palm empty fruit bunches), herbaceous biomass such as rice husks, trees, waste Examples include woody biomass such as building materials.
- the cellulose-containing biomass 26 is mainly classified into a cellulose component, a hemicellulose component, a lignin component, and an inorganic component, and the ratio of each component varies greatly depending on the biomass species and growth conditions, and is not particularly limited.
- the cellulose-containing biomass 26 is preferably pretreated before being supplied to the horizontal reaction tank 11. By pretreating the cellulose-containing biomass 26, the hydrolysis efficiency by the saccharifying enzyme can be improved.
- the pretreatment method of the cellulose-containing biomass 26 is not particularly limited, and a conventionally known pretreatment method can be used. Examples of pre-treatment methods include hydrothermal treatment, ammonia treatment, alkali treatment, dilute sulfuric acid treatment, etc., fine grinding treatment, explosion treatment, acid treatment, sulfuric acid treatment, caustic soda treatment, subcritical water treatment, steaming treatment, etc. Any of these may be used, and these may be used in combination.
- Water 27 is not particularly limited, such as well water, industrial water, tap water, river water, process wastewater, process reclaimed water, and may be a mixed water thereof.
- the pH adjuster 28 is usually an acid or an alkali.
- the additive is an acid or an alkali depends on the pretreatment method.
- hydrothermal treatment, dilute sulfuric acid treatment, blasting treatment, acid treatment, sulfuric acid treatment, subcritical water treatment, steaming treatment and the like are alkaline agents, and for example, ammonia treatment and alkaline treatment are acids.
- the alkali include sodium hydroxide, ammonia and calcium hydroxide.
- the acid include organic acids such as sulfuric acid, hydrochloric acid, phosphoric acid, and acetic acid.
- buffering agents such as sodium acetate, sodium phosphate, sodium citrate.
- an enzyme supply passage 31 is connected to the downstream side in the flow direction of the cellulose-containing biomass 26 from the biomass inlet 25.
- the saccharification enzyme 32 is supplied from the enzyme supply passage 31 into the horizontal reaction tank 11.
- the enzyme supply passage 31 is connected to the downstream side of the biomass introduction port 25, particularly when the cellulose-containing biomass 26 not adjusted for pH and the saccharifying enzyme 32 react with each other, the saccharifying enzyme 32 is deactivated. This is because the saccharification reaction may not proceed.
- the pH of the cellulose-containing biomass 26 is adjusted to 4 or more and 6 or less, it is not necessary to provide the enzyme supply passage 31 in the horizontal reaction tank 11, and the saccharifying enzyme 32 is supplied from the biomass inlet 25. You may supply.
- the saccharifying enzyme 32 refers to an enzyme component that has an activity of degrading cellulose or hemicellulose or assists in degrading cellulose or hemicellulose.
- Specific examples of the enzyme component include cellobiohydrolase, endoglucanase, exoglucanase, ⁇ -glucosidase, xylanase, xylosidase, and biomass swelling enzyme.
- One or more kinds of saccharifying enzymes 32 may be used.
- the saccharifying enzyme 32 is an enzyme mixture containing a plurality of types of the above enzyme components. Preferably there is.
- the saccharifying enzyme 32 can be suitably used even if it is produced by a microorganism.
- the saccharifying enzyme 32 may include a plurality of enzyme components produced by one kind of microorganism, or may include a mixture of enzyme components produced from a plurality of microorganisms.
- the microorganism that produces saccharifying enzyme 32 is a microorganism that produces saccharifying enzyme inside or outside the cell, and preferably a microorganism that produces saccharifying enzyme outside the cell. This is because saccharifying enzyme recovery is easier for microorganisms produced outside the cell.
- the microorganism that produces the saccharifying enzyme 32 is not particularly limited as long as it produces the above enzyme components.
- filamentous fungi classified into the genus Trichoderma and Acremonium secrete a large amount of various saccharifying enzymes to the outside of the cells, so that they can be particularly suitably used as microorganisms producing saccharifying enzyme 32.
- the saccharifying enzyme 32 may be an unused saccharifying enzyme, or the saccharifying enzyme recovered by the solid-liquid separation device 71 may be reused as will be described later. From the viewpoint of reducing the amount of saccharifying enzyme 32 used, particularly the amount of unused saccharifying enzyme, it is preferable to mix and use both the recovered saccharifying enzyme and the unused saccharifying enzyme.
- the method for supplying the cellulose-containing biomass 26, the water 27, the pH adjuster 28, and the saccharifying enzyme 32 is not particularly limited, but it is preferable to quantitatively and continuously supply the cellulose-containing biomass 26, the water 27, the pH adjuster 28 and the saccharifying enzyme 32.
- the slurry-containing saccharification slurry 33 is produced
- the horizontal reaction tank 11 is provided with a saccharified slurry discharge port 34 on the side opposite to the biomass introduction port 25 and on the downstream side in the flow direction of the cellulose-containing biomass 26 in the horizontal reaction vessel 11.
- the horizontal reaction vessel 11 reacts the cellulose-containing biomass 26 and the saccharifying enzyme 32 while stirring the cellulose-containing biomass 26 and the saccharifying enzyme 32 to generate a saccharification slurry 33.
- the saccharification slurry 33 is discharged from the horizontal reaction tank 11 through the saccharification slurry discharge port 34.
- the jacket 12 is provided on the wall surface 11 a of the horizontal reaction tank 11.
- the jacket 12 warms the inside of the horizontal reaction tank 11 from the outside.
- the jacket 12 is a hollow body through which hot water (heat medium) can pass.
- the jacket 12 is provided on the wall surface 11a.
- the jacket 12 is a hollow body through which hot water can pass.
- the jacket 12 is not limited to this, and the jacket 12 is provided with a heating source such as an electric heater or a very small amount of steam inside. What is necessary is just to be able to heat the horizontal reaction tank 11 from the outside, such as supplying each one or intermittently.
- the jacket 12 is provided on the wall surface 11a.
- the present invention is not limited to this, and any method may be used as long as the inside of the horizontal reaction tank 11 is heated from the outside. It may be provided so as to cover the whole.
- the jacket 12 is used to heat the horizontal reaction tank 11.
- the jacket 12 is not limited to this, and a water pipe or a rod heater is provided on the outer periphery of the horizontal reaction tank 11. It is not particularly limited as long as it can heat the horizontal reaction tank 11 such as a wound system.
- a series of saccharification reaction times for obtaining the saccharified solution 41 can be shortened by heating the inside of the horizontal reaction tank 11.
- the saccharification reaction time can be shortened and the viscosity of the saccharification slurry 33 can be reduced.
- the temperature in the horizontal reaction tank 11 is controlled by the jacket 12.
- the hot water 35 passes through the jacket 12 from the jacket hot water supply passage 36 and is supplied to the jacket hot water discharge passage 37.
- the temperature and the hot water supply speed of the hot water 35 can be set and can be appropriately adjusted according to the temperature in the horizontal reaction tank 11.
- the temperature in the horizontal reaction tank 11 is preferably 37 ° C. or higher, more preferably 40 ° C. or higher and 60 ° C. or lower, and even more preferably 45 ° C. or higher, so that the saccharifying enzyme 32 works effectively. It is 55 degrees C or less. This is because when the temperature in the horizontal reaction tank 11 is 40 ° C.
- the temperature in the horizontal reaction vessel 11 is controlled by the jacket 12, but is not limited to this, and any method may be used as long as the horizontal reaction vessel 11 is heated from the outside. .
- the reaction time for reacting the cellulose-containing biomass 26 and the saccharifying enzyme 32 in the horizontal reaction tank 11 is preferably in the range of 5 minutes to 4 hours, and more preferably in the range of 10 minutes to 1 hour. .
- the reaction time is less than 5 minutes, sufficient saccharification and viscosity reduction do not occur, and there is a possibility that the saccharification slurry 33 discharged from the saccharification slurry discharge port 34 may be disturbed in feeding and stirring. .
- the reaction time in the horizontal reaction tank 11 is controlled by the supply speed of the cellulose-containing biomass 26, the damming section 38, the stirring shaft 21, the number of rotations of the stirring blade 22, and the like.
- the order of mixing the cellulose-containing biomass 26, water 27, pH adjuster 28 and saccharifying enzyme 32 is not particularly limited, and there is the following method.
- water 27 is mixed and saccharifying enzyme 32 is mixed.
- pH adjuster 28 and saccharification are mixed.
- a method of mixing the enzyme 32 with the pH adjusting agent 28 and the saccharifying enzyme 32 in this order a method of mixing the cellulose-containing biomass 26 in a solution obtained by diluting the pH adjusting agent 28 with water 27, and then mixing the saccharifying enzyme 32;
- the method of mixing the water 27 and mixing the saccharifying enzyme 32 is preferable. Specifically, in order to give minimum fluidity to the mixture of the cellulose-containing biomass 26 and the pH adjuster 28 after the cellulose-containing biomass 26 and the pH adjuster 28 are supplied into the horizontal reaction tank 11. Water 27 is supplied.
- the cellulose-containing biomass 26, the pH adjuster 28, and the water 27 in the horizontal reaction tank 11 are stirred and mixed to obtain a mixed liquid of the cellulose-containing biomass 26, the pH adjuster 28, and the water 27.
- the pH of this mixed solution is preferably in the range of 3 to 7, more preferably in the range of 4 to 6.
- the saccharifying enzyme 32 can work suitably.
- the saccharifying enzyme 32 is supplied from the enzyme supply passage 31 into the horizontal reaction tank 11, and the mixed solution containing the cellulose-containing biomass 26, the water 27, and the pH adjusting agent 28 and the saccharifying enzyme are mixed. Saccharification reaction is carried out. Thereby, the hydrolyzate of the cellulose containing biomass 26 is obtained.
- This hydrolyzate is a saccharified solution 41 containing a sugar solution 72 and a solid material, which will be described later.
- the water 27 may not be added to the horizontal reaction tank 11.
- the cellulose-containing biomass 26 is discharged as a saccharified slurry 33 from the saccharified slurry outlet 34 as a reaction product containing a pH adjuster 28, water 27, and a saccharifying enzyme 32.
- the rotational speeds of the stirring shaft 21 and the stirring blade 22 are adjusted by the motor 24.
- the residence part of the cellulose containing biomass 26 does not generate
- the dry mass of the cellulose-containing biomass 26 subjected to thermochemical treatment is 15% by mass or more and 50% by mass or less with respect to the total mass of the saccharification slurry 33. It is preferable. This is because when the dry mass of the cellulose-containing biomass 26 subjected to the thermochemical treatment exceeds 50% by mass, slurrying cannot be performed even if the horizontal reaction tank 11 is used, and the saccharification reaction does not proceed.
- the thermochemical treatment include ammonia treatment, hydrothermal treatment, explosion treatment, alkali treatment, and dilute sulfuric acid treatment.
- the horizontal reaction tank 11 is provided with a damming portion 38 at the saccharified slurry outlet 34.
- the damming portion 38 is a plate-like member provided so as to surround the saccharified slurry discharge port 34 with the damming portion 38 and the wall surface 11 a of the horizontal reaction tank 11.
- the damming portion 38 dampens the flow of the saccharification slurry 33.
- the damming portion 38 only needs to be in the vicinity of the saccharification slurry discharge port 34.
- the damming portion 38 is provided in the same direction as the moving direction of the saccharification slurry 33 in the horizontal reaction tank 11, It is not limited to this, You may provide in the vertical direction of the horizontal reaction tank 11, and the installation location of the damming part 38 is not specifically limited.
- the saccharification slurry 33 when discharging the saccharification slurry 33 from the saccharification slurry discharge port 34, the saccharification slurry 33 is divided into a solid component and a liquid component so that it is not difficult to continuously discharge the saccharification slurry 33.
- the height of the damming portion 38 is adjusted. By making the height of the damming portion 38 high enough to be continuously discharged, the saccharified slurry 33 can be discharged from the saccharified slurry outlet 34 continuously and stably.
- the saccharification slurry supply line L11 connects the horizontal reaction tank 11 and the vertical reaction tank 13.
- the saccharification slurry 33 is supplied from the horizontal reaction tank 11 to the vertical reaction tank 13 through the saccharification slurry supply line L11.
- the horizontal reaction tank 11 is installed horizontally with respect to the installation surface, the horizontal reaction tank 11 is inclined at a predetermined angle (for example, 1 ° to 10 °) downward toward the saccharified slurry discharge port 34. It may be. Thereby, the movement efficiency of the cellulose containing biomass 26 can be improved.
- the vertical reaction tank 13 is a tank that saccharifies the saccharification slurry 33 to generate a saccharified solution 41.
- the vertical reaction vessel 13 includes a stirring blade 42 inside.
- the stirring blade 42 is driven by a vertical stirring drive device (vertical stirring motor) 43.
- the saccharification slurry 33 is stirred by the stirring blade 42 and the saccharification reaction is continuously performed in the vertical reaction tank 13. Thereby, the saccharification slurry 33 becomes the saccharification liquid 41.
- the saccharification slurry 33 is stirred in the vertical reaction tank 13 while moving from the upper side to the bottom side. For this reason, the vertical reaction tank 13 can reduce power compared to moving the saccharification slurry 33 while stirring in the horizontal reaction tank 11, and the saccharification slurry 33 is held in the horizontal reaction tank 11. Since the power can be reduced as compared with the above, the equipment cost can be reduced. Further, since the saccharification slurry 33 has low viscosity and good fluidity, it is not necessary to perform horizontal stirring in the horizontal reaction tank 11, and it is easy to draw out even when transferring to the next step.
- the time for the saccharification reaction of the saccharification slurry 33 in the vertical reaction tank 13 is preferably 1 hour or more and 72 hours or less, more preferably 4 hours or more and 24 hours or less.
- the saccharified solution 41 is discharged from the bottom of the vertical reaction tank 13.
- the method for discharging the saccharified solution 41 is not particularly limited, and the saccharified solution 41 may be discharged continuously or intermittently.
- the vertical reaction tanks 13 may be arranged in multiple stages and may take a reaction form such as a continuous stirred tank reactor (CSTR: Continuous Stirred Tank Reactor).
- CSTR Continuous Stirred Tank Reactor
- a method of discharging the batch for each reaction time as described above, or a solid-liquid separation device provided in the subsequent stage of the vertical reaction tank 13 There is a method of discharging according to the batch processing time of the separator. Accordingly, the speed at which the cellulose-containing biomass 26 is advanced in the vertical direction in the vertical reaction tank 13 may be extremely slow, and may be intermittent in some cases.
- the sugar liquid production apparatus 10A includes the horizontal reaction tank 11, the jacket 12, and the vertical reaction tank 13, and in the horizontal reaction tank 11, the cellulose-containing biomass 26, the water 27, the pH adjuster 28, and The saccharification enzyme 32 is mixed to generate a saccharification slurry 33, and the saccharification liquid 41 is generated from the saccharification slurry 33 in the vertical reaction tank 13.
- the sugar liquid production apparatus 10A performs high-concentration saccharified liquid 41 in a low cost and in a short time by performing a saccharification reaction of the cellulose-containing biomass 26 in two stages of a horizontal reaction tank 11 and a vertical reaction tank 13. Can be manufactured well.
- the saccharification reaction can be performed in the vertical reaction tank 13 at a solid concentration of the saccharified solution 41 as high as 15% by mass or more. Therefore, the sugar liquid production apparatus 10A does not decrease the saccharification rate associated with the saccharification reaction at a high concentration seen in the conventional vertical reaction tank, and can perform the saccharification reaction at a higher concentration. The saccharification reaction can proceed.
- the solid content concentration of the cellulose-containing biomass 26 can only be increased to about 15% by mass, and it has been difficult to obtain a saccharified solution 41 having a high concentration.
- the sugar liquid production apparatus 10 ⁇ / b> A combines the horizontal reaction tank 11 and the vertical reaction tank 13 in series with respect to the flow direction of the cellulose-containing biomass 26.
- the cellulose-containing biomass 26 is saccharified and slurried by the saccharifying enzyme 32 while keeping the inside of the tank at a predetermined temperature while proceeding in the horizontal direction, and the cellulose-containing biomass 26 advances in the vertical direction.
- the reaction efficiency at the time of saccharification in the next vertical reaction tank 13 can be improved.
- the saccharification reaction is further advanced in the vertical reaction tank 13 while the saccharification slurry 33 is advanced in the vertical direction so that the saccharification reaction is performed in two stages.
- the reaction efficiency between the cellulose-containing biomass 26 and the saccharifying enzyme 32 can be improved.
- the saccharification slurry 33 has a low viscosity, it can be saccharified to a high concentration in the vertical reaction tank 13.
- the sugar solution producing apparatus 10A can efficiently react the cellulose-containing biomass 26 and the saccharifying enzyme 32, and therefore can produce the high-concentration saccharified solution 41 efficiently at a low cost.
- the sugar solution production apparatus 10A continuously performs the saccharification reaction with a high solid content concentration and high efficiency compared to the conventional case where saccharification is performed only in a vertical reaction tank. Since the saccharification efficiency of the saccharification reaction can be improved, the concentration cost of the saccharified solution 41 and the fermentation product can be reduced. Further, the sugar liquid production apparatus 10A can be downsized, and the equipment cost can be reduced by shortening the reaction time.
- the jacket 12 heats the horizontal reaction tank 11, but the present embodiment is not limited to this.
- the stirring shaft 21 may be heated by making the inside of the stirring shaft 21 a hollow body capable of passing warm water.
- the horizontal reaction tank 11 has the damming portion 38, but is not limited to this, and when the discharge of the saccharified slurry 33 is stable, the horizontal reaction tank 11 is not limited thereto.
- the tank 11 does not have to include the damming portion 38 in particular.
- the saccharification enzyme 32 is supplied only to the horizontal reaction tank 11, but the present invention is not limited to this. As shown in FIG. Two enzyme supply passages 44 may be provided, and the saccharification enzyme 45 may be supplied into the vertical reaction tank 13. The saccharification reaction of the saccharification slurry 33 can be further accelerated in the vertical reaction tank 13 in the horizontal reaction tank 11.
- the saccharifying enzyme 32 and the saccharifying enzyme 45 are preferably of different types. That is, in the initial stage of the saccharification reaction performed in the horizontal reaction tank 11, polysaccharides such as cellulose and hemicellulose are decomposed into oligosaccharides by the saccharification enzyme 32, and in the vertical reaction tank 13, the saccharification enzyme 45 is separated from the oligosaccharides. By decomposing into sugar, the saccharification reaction of the cellulose-containing biomass 26 contained in the saccharification slurry 33 is promoted.
- the horizontal reaction tank 11 has the stirring blades 22 provided on the entire circumferential surface of the stirring shaft 21.
- the present invention is not limited to this. You may make it have the notch part 22a which has a notch in a part of circumferential direction.
- FIG. 5 is a cross-sectional view of the horizontal reaction tank 11 as viewed from the axial direction. As shown in FIG. 5, since the stirring blade 22 has the notch 22a, the cellulose-containing biomass 26 is stirred by the notch 22a of the stirring blade 22, and the reaction efficiency with the saccharifying enzyme 32 is increased and stirred.
- the reaction can be carried out at the optimum temperature of the saccharifying enzyme 32 via the blades 22.
- the stirring blade 22 is provided with one notch 22a, but is not limited to this, and the notch 22a may be two or more. Further, since the stirring blade 22 has the notch portion 22a, the cellulose-containing biomass 26 and the saccharifying enzyme 32 are pushed by the newly-added cellulose-containing biomass 26 and easily move toward the saccharification slurry outlet 34. be able to. For this reason, the cellulose-containing biomass 26 and the like can continuously move toward the saccharified slurry discharge port 34 from the notch 22 a of the stirring blade 22.
- the horizontal reaction vessel 11 includes one stirring shaft 21, but is not limited thereto, and the horizontal reaction vessel 11 may include a plurality of stirring shafts 21. Good.
- An example when the horizontal reaction tank 11 includes two stirring shafts 21 is shown in FIG.
- FIG. 6 is a cross-sectional view of the horizontal reaction tank 11 when two stirring shafts 21 are provided when viewed from the axial direction.
- the horizontal reaction tank 11 includes stirring shafts 21 ⁇ / b> A and 21 ⁇ / b> B in the horizontal direction with respect to the axial direction of the horizontal reaction tank 11.
- the agitation shafts 21A and 21B are provided with a plurality of agitation blades 22A and 22B at predetermined intervals with respect to the agitation shafts 21A and 21B.
- the heating unit is not provided around the vertical reaction tank 13, but the present invention is not limited to this, and the vertical reaction tank 13 is provided with a heating unit around it. It may be.
- the jacket etc. which are provided so that the wall surface or circumference
- FIG. 7 is a diagram illustrating an example of another configuration of the vertical reaction tank 13.
- the vertical reaction tank 13 includes a jacket 46 on the wall surface.
- the jacket 46 is a hollow body through which warm water can pass. Like the jacket 12, the warm water flowing through the jacket 46 is preferably 40 ° C. or higher and 60 ° C.
- FIG. 8 is a conceptual diagram showing a sugar liquid production apparatus according to the second embodiment of the present invention.
- the horizontal reaction tank 51 of the sugar liquid production apparatus 10 ⁇ / b> B includes a hollow stirring shaft 52, a hollow rotating body hot water supply passage 53, and a hollow rotating body hot water discharge passage 54.
- the hollow stirring shaft 52 is a hollow body through which hot water 55 can pass.
- the hot water 55 is supplied from the hot water supply passage 53 for the hollow rotating body to the hollow stirring shaft 52, passes through the hollow stirring shaft 52, and is discharged to the hot water discharge passage 54 for the hollow rotating body.
- the hot water 35 and 55 can be set to a temperature and a hot water supply speed, respectively, and can be appropriately adjusted according to the temperature in the horizontal reaction tank 51.
- the temperature of the hot water 35, 55 may be the same or different. In particular, from the economic point of view, the temperature of the hot water 35, 55 is preferably the same.
- the hot water supply passage 53 for the hollow rotating body is used as the hot water supply passage 53 for the hollow rotating body. May be supplied to the hollow stirring shaft 52.
- the sugar liquid production apparatus 10 ⁇ / b> B adjusts the temperature in the horizontal reaction tank 51 by passing hot water 55 through the hollow stirring shaft 52. .
- the sugar liquid manufacturing apparatus 10B can adjust the temperature in the horizontal reaction tank 51 easily, the temperature of the cellulose-containing biomass 26 can be adjusted more stably, and the saccharification slurry 33 can be adjusted. It can be generated more stably.
- a sugar liquid production apparatus according to a third embodiment of the present invention will be described with reference to the drawings.
- the structure of the sugar liquid manufacturing apparatus which concerns on this embodiment is the same as that of the sugar liquid manufacturing apparatus which concerns on 1st Embodiment by this invention shown in the above-mentioned FIG. 1, it concerns on 1st Embodiment.
- the same members as those in the sugar liquid production apparatus are denoted by the same reference numerals, and the description thereof is omitted.
- FIG. 9 is a conceptual diagram showing a sugar liquid production apparatus according to the third embodiment of the present invention.
- the sugar liquid production apparatus 10 ⁇ / b> C further includes a biomass supply apparatus (biomass supply unit) 61 in addition to the configuration of the sugar liquid production apparatus 10 ⁇ / b> A.
- biomass supply apparatus biomass supply unit
- the biomass supply device 61 includes a hopper 62, a feeder agitator 63, a feeder agitator motor (feeder agitator drive unit) 64, a transfer device 65, a transfer machine motor (a transfer device drive unit) 66, and a solid content adjustment water supply passage 67.
- the hopper 62 is a tank in which the cellulose-containing biomass 26 and the pH adjuster 28 are stored.
- the feeder agitator 63 is for mixing the cellulose-containing biomass 26 and the pH adjuster 28, and for preventing the cellulose-containing biomass 26 in the hopper 62 from bridging.
- the feeder agitator motor 64 agitates the feeder agitator 63.
- the transfer device 65 is for transferring the cellulose-containing biomass 26 and the pH adjusting agent 28.
- the transfer device 65 is not particularly limited, and examples thereof include a flight type conveyor using a screw feeder or a chain.
- the pH adjusting agent 28 is supplied into the hopper 62, and the water 27 is supplied into the solid content adjusting water supply passage 67, and each is mixed separately with the cellulose-containing biomass 26.
- the water 27 and the pH adjusting agent 28 may be supplied into the hopper 62 or may be supplied from the solid content adjusted water supply passage 67.
- the pH adjuster 28 is supplied from the solid content adjusted water supply passage 67 together with the water 27.
- the sugar liquid production apparatus 10C is configured to move any two or more of the cellulose-containing biomass 26, the water 27, and the pH adjuster 28 by the biomass supply apparatus 61, the cellulose-containing biomass 26, the water 27, and the pH.
- the supply speed of the adjusting agent 28 can be stably supplied to the horizontal reaction tank 11.
- the sugar liquid manufacturing apparatus 10C can quantitatively supply the cellulose-containing biomass 26, the water 27, the pH adjuster 28, and the saccharifying enzyme 32 into the horizontal reaction tank 11, the inside of the horizontal reaction tank 11
- the cellulose-containing biomass 26 can be stably slurried.
- the sugar liquid production apparatus 10C can stabilize the saccharification rate of the cellulose-containing biomass 26, that is, the sugar concentration of the saccharification slurry 33, and thus stabilize the quality of the saccharification slurry 33 discharged from the saccharification slurry outlet 34. be able to.
- a sugar liquid production apparatus according to a fourth embodiment of the present invention will be described with reference to the drawings.
- the structure of the sugar liquid manufacturing apparatus which concerns on this embodiment is the same as that of the sugar liquid manufacturing apparatus which concerns on 1st Embodiment by this invention shown in the above-mentioned FIG. 1, it concerns on 1st Embodiment.
- the same members as those in the sugar liquid production apparatus are denoted by the same reference numerals, and the description thereof is omitted.
- FIG. 10 is a conceptual diagram showing a sugar liquid production apparatus according to the fourth embodiment of the present invention.
- the sugar liquid production apparatus 10 ⁇ / b> D has a configuration of the sugar liquid production apparatus 10 ⁇ / b> A, a solid-liquid separation device 71, a saccharified liquid supply line L ⁇ b> 21, a sugar liquid discharge line L ⁇ b> 22, and a saccharification residue discharge line. L24 and a hot water supply line L23.
- the solid-liquid separation device 71 separates the solid content from the saccharified liquid 41 to obtain a sugar liquid 72.
- the solid-liquid separation device 71 may be any device that can separate the solid content from the saccharified solution 41.
- Examples of the solid-liquid separation device 71 include centrifugal decanters such as screw decanters, separation plate centrifuges, shear press centrifuges, vertical centrifuges, filter presses, pneumatic presses (Pneumapress®), Examples include pressure filtration types such as pressure filters, centrifugal filters, screw presses, belt presses, and suction filtration type devices such as belt filters, precoat filters, drum type filtration filters, and vacuum filtration filters.
- the sugar liquid recovery rate is excellent and more sugar liquid components can be recovered by one solid-liquid separation and a clear filtrate can be easily obtained
- a pressure filtration type filter press it is preferable to use a pressure filtration type filter press.
- mold and suction filtration type solid-liquid-separation apparatus are equipped with the automatic washing
- the number of times of washing is not particularly limited.
- the sugar solution 72 contains glucose derived from cellulose and xylose derived from hemicellulose, but the mixing ratio thereof is not particularly limited because it varies depending on the pretreatment method and pretreatment conditions of the cellulose-containing biomass 26. Further, in addition to the above substances, organic acids such as formic acid and acetic acid generated during decomposition of cellulose and hemicellulose, HMF generated from sugar by high-temperature treatment, furfural, and the like may be included. It also contains lignin-derived vanillin, guaiacol, coumaric acid, ferulic acid, and their reaction products.
- the solid content is one in which the cellulose fraction and the hemicellulose fraction in the cellulose-containing biomass 26 are each preferably hydrolyzed by 50% or more, and the moisture content of the solid content is 40% or more and 80% or less.
- the moisture content of the solid content can be 55% or less.
- the saccharified solution 41 is pumped into a filter chamber provided with a filter cloth and dehydrated, and then the cake is squeezed using a diaphragm in the filter chamber. It is preferable to dehydrate.
- the saccharified solution 41 is pressed into a filter chamber provided with a filter cloth by the solid-liquid separation device 71 and dehydrated. Since it is greatly affected by the biomass species, the enzymatic saccharification efficiency of the biomass, the bulk density, etc., it is not particularly limited and is adjusted as appropriate.
- the pressing pressure is preferably, for example, 0.05 MPa or more, more preferably 0.5 MPa in consideration of the pretreatment method of biomass raw material, biomass species, enzymatic saccharification efficiency of biomass, bulk density, and the like. That's it.
- the higher the pressing pressure the lower the moisture content of the solid content, and the yield of the sugar solution 72 is improved. Therefore, the yield of the sugar liquid 72 can be improved by setting the pressing pressure to 0.05 MPa or more.
- the combustion efficiency of the solid content is improved and higher energy can be obtained.
- the saccharified solution supply line L21 connects the vertical reaction tank 13 and the solid-liquid separator 71.
- the saccharified solution 41 discharged from the vertical reaction tank 13 is supplied to the solid-liquid separator 71 through the saccharified solution supply line L21.
- the saccharified solution supply line L21 is provided with a control valve V11 and a saccharified solution supply pump P11 provided on the downstream side of the control valve V11.
- the supply amount of the saccharified liquid 41 is adjusted by the frequency of the control valve V11 or the saccharified liquid supply pump P11.
- the liquid feeding method does not need to be based on a pump, and for example, a pressure feeding method using compressed gas may be adopted. That is, the saccharified solution 41 may be sent using a pressure difference between the vertical reaction tank 13 and the solid-liquid separator 71.
- the saccharified solution supply line L21 may be provided with a buffer tank or a supply tank.
- the sugar liquid discharge line L22 is connected to the permeate side of the solid-liquid separator 71.
- the sugar liquid 72 from which the solid content has been separated from the saccharified liquid 41 by the solid-liquid separator 71 is discharged from the solid-liquid separator 71 through the sugar liquid discharge line L22.
- the sugar solution discharge line L22 is provided with a control valve V12 and a sugar solution supply pump P12 provided on the downstream side of the control valve V12.
- the supply amount of the sugar liquid 72 is adjusted by the frequency of the control valve V12 or the sugar liquid supply pump P12.
- the liquid feeding method of the sugar liquid 72 does not have to be by a pump, and may be the above-described pressure feeding method or may be transferred by natural falling due to the gravity of the sugar liquid itself.
- the hot water supply line L23 connects the hot water supply tank 73 and the non-permeate side of the solid-liquid separator 71.
- the hot water supply tank 73 is a tank for storing hot water 74 supplied to the solid-liquid separator 71.
- Hot water 74 is supplied to the solid-liquid separator 71 through the hot water supply line L23.
- a control valve V13 and a hot water supply pump P13 provided on the upstream side of the control valve V13 are provided.
- the supply amount of the hot water 74 is adjusted by the frequency of the control valve V13 or the hot water supply pump P13.
- the liquid feeding method of the hot water 74 does not need to be based on a pump, and the above-described pressure feeding method may be used.
- the sugar liquid 72 newly generated by reacting with the saccharifying enzyme 32 adsorbed on the solid content using the hot water 74 is discharged from the solid-liquid separator 71 through the sugar liquid discharge line L22.
- the amount of hot water 74 added is not particularly limited, but when hydrolyzing by reacting the hot water 74 with the saccharifying enzyme 32 adsorbed on the solid content, the solid matter concentration is within the range of 1% by mass to 20% by mass. It is preferable to add so that it becomes. When the solid concentration is higher than 20% by mass or lower than 1% by mass, it is not preferable because it is not efficient from the viewpoint of the production amount of the sugar solution 72 and the recovery rate of the saccharifying enzyme 32.
- the temperature of the hot water 74 is preferably in the range of 30 ° C. to 60 ° C., more preferably in the range of 40 ° C. to 55 ° C., and even more preferably around 50 ° C.
- the time for hydrolysis by reacting the hot water 74 with the saccharifying enzyme 32 adsorbed on the solid content is preferably in the range of 1 minute to 180 minutes. If it is less than 1 minute, the recovery efficiency of the saccharifying enzyme 32 adsorbed on the solid content is low, and the recovery efficiency of the saccharifying enzyme 32 adsorbed on the solid content does not increase even if it is performed for 180 minutes or more. is there.
- the pH of the hot water 74 is preferably in the range of 6.0 to 8.0, more preferably about 5.0. If the pH is less than 6.0, the recovery rate of the saccharifying enzyme 32 adsorbed on the solid content decreases, and if the pH exceeds 8.0, the saccharifying enzyme 32 is deactivated, which is not preferable. Therefore, if the pH is in the range of 6.0 to 8.0, the inactivation of the saccharifying enzyme 32 can be reduced as much as possible, and the recovery efficiency of the saccharifying enzyme 32 can be increased.
- the saccharification enzyme 32 recovered by the solid-liquid separator 71 may be reused. From the viewpoint of reducing the amount of saccharifying enzyme 32 used, particularly the amount of unused saccharifying enzyme, it is preferable to mix and use both the recovered saccharifying enzyme 32 and the unused saccharifying enzyme. Further, in order to increase the recovery efficiency of the saccharifying enzyme 32 to the vertical reaction tank 13, after adding an adsorption inhibitor for blocking the sites that are not adsorbed by the cellulose-containing biomass 26, By adding the saccharifying enzyme used, the recovery efficiency of the saccharifying enzyme 32 can be improved.
- the supply timing of the hot water 74 to the solid-liquid separator 71 is not particularly limited, but from the viewpoint of more efficiently performing the solid-liquid separation of the saccharified liquid 41, for example, the solid-liquid separator 71 is a filter press. In this case, it is more preferable that the hot water 74 is supplied after the dehydrated saccharified solution 41 is further dehydrated by squeezing the cake using a diaphragm. That is, when the saccharified solution 41 is squeezed and the warm water 74 is supplied into the solid-liquid separation device 71, the volume of solids is reduced and the water content is also reduced. This is because the penetration efficiency is improved.
- the saccharification residue discharge line L24 is connected to the non-permeate side of the solid-liquid separator 71.
- the solid content remaining after the hot water 74 is supplied into the solid-liquid separator 71 is discharged as a saccharification residue 75 from the solid-liquid separator 71 through the saccharification residue discharge line L24.
- the saccharification residue discharge line L24 is provided with a control valve V14 and a saccharification residue discharge pump P14 provided downstream of the control valve V14.
- the discharge amount of the saccharification residue 75 is adjusted by the frequency of the control valve V14 or the saccharification residue discharge pump P14.
- the discharging method is preferably a belt conveyor suitable for transferring solid matter, rather than a pipe or a pump.
- the solid-liquid separator 71 is a filter press, a pneumatic press (registered trademark) or the like
- the saccharification residue 75 is discharged by moving the filter cloth, moving the filter cloth, or moving the scraper on the filter cloth. After that, it is preferably transferred by a belt conveyor or the like.
- the saccharified solution 41 includes a saccharified solution 72 and a solid material, and the solid material includes a polysaccharide component such as undegraded cellulose or hemicellulose and a component that cannot be degraded by the saccharifying enzyme 32 such as lignin. Further, the solid is in a state where a relatively large amount of saccharifying enzyme 32 is adsorbed. Therefore, the solid-liquid separation device 71 separates the saccharified solution 41 from the saccharide solution 72 and the solid to obtain the saccharide solution 72 and collects the solid content.
- the solid content separated from the saccharified solution 41 by the solid-liquid separator 71 includes a polysaccharide component and the saccharifying enzyme 32.
- the polysaccharide component and saccharifying enzyme 32 contained in the solid material of the saccharified solution 41 are contained in the warm water 74 supplied into the solid-liquid separation device 71 and are used to generate the sugar solution 72.
- the solid residue that has not been used to generate the sugar liquid 72 is discharged from the solid-liquid separation device 71 as a saccharification residue 75 through the saccharification residue discharge line L24.
- the sugar liquid production apparatus 10D includes the solid-liquid separation apparatus 71, captures the solid content on the non-permeation side of the solid-liquid separation apparatus 71, and obtains the sugar liquid 72 that is a liquid component on the permeation side.
- the sugar liquid production apparatus 10D supplies the warm water 74 into the solid-liquid separation apparatus 71, reacts with the saccharifying enzyme 32 adsorbed on the solid content in the solid-liquid separation apparatus 71, and hydrolyzes the sugar liquid. 72 is generated.
- the saccharifying enzyme 32 added while recovering more saccharified liquids 72 can be used, the newly added saccharifying enzyme 32 can be used efficiently and the saccharified liquids 72 can be produced at low cost. It can be manufactured efficiently.
- the sugar liquid production apparatus 10D can further improve the saccharification efficiency of the cellulose-containing biomass 26 than the first to third embodiments, and can shorten the saccharification reaction of the cellulose-containing biomass 26.
- the hot water 74 is supplied to the solid-liquid separator 71 and then discharged from the sugar liquid discharge line L22.
- the present invention is not limited to this, and the solid-liquid separator 71 is not limited thereto.
- a warm water return line may be provided on the permeate side, and the warm water 74 may be supplied to the warm water supply tank 73 so that the warm water 74 is circulated and reused.
- the hot water return line By providing the hot water return line, the hot water 74 used in the solid-liquid separator 71 can be supplied to the hot water supply tank 73, so the hot water 74 used in the solid-liquid separator 71 is passed through the hot water return line.
- the amount of hot water 74 used can be reduced by recycling and recycling.
- the circulating hot water 74 may finally pass through the solid content in the solid-liquid separator 71 and be extracted from the sugar liquid discharge line L22 as the sugar liquid 72, or the hot water 74 may be solid-liquid separated.
- the sugar solution 72 may be extracted from a line different from the sugar solution discharge line L22.
- the sugar liquid production apparatus 10D has one vertical reaction tank 13, but is not limited to this, and a plurality of vertical reaction tanks 13 are provided in series to continuously saccharify. You may make it react and perform solid-liquid separation.
- FIG. 11 is a diagram illustrating an example of another configuration of the sugar liquid production apparatus 10E. As shown in FIG. 11, in the sugar liquid production apparatus 10E, a vertical reaction tank 13-1 and a vertical reaction tank 13-2 are provided in series. The vertical reaction tank 13-1 and the vertical reaction tank 13-2 are connected by a saccharification liquid supply line L21-1, and the vertical reaction tank 13-2 and the solid-liquid separator 71 are connected to the saccharification liquid supply line L21. -2.
- the saccharified liquid 41A discharged from the vertical reaction tank 13-1 is supplied to the vertical reaction tank 13-2 through the saccharified liquid supply line L21-1.
- the saccharified solution supply line L21-1 is provided with a control valve V11-1 and a saccharified solution supply pump P11-1 provided downstream of the control valve V11-1.
- the saccharified solution 41B discharged from the vertical reaction tank 13-2 is supplied to the solid-liquid separation device 71 through the saccharified solution supply line L21-2.
- the saccharified liquid supply line L21-2 is provided with a control valve V11-2 and a saccharified liquid supply pump P11-2 provided downstream of the control valve V11-2.
- the sugar liquid production apparatus 10E is provided with the solid-liquid separation device 71 and the saccharification residue discharge line L24, so that a plurality of vertical reaction tanks (in this embodiment, the vertical reaction tank 13- 1 and 13-2), the saccharification reaction of the saccharification slurry 33 in each of the vertical reaction tanks 13-1 and 13-2 is promoted, so that each vertical reaction tank 13-1 13-2 makes it possible to continuously process the saccharification slurry 33 while maintaining the saccharification efficiency of one vertical reaction tank.
- the saccharification efficiency of the cellulose-containing biomass 26 can be further improved, and the saccharification reaction of the cellulose-containing biomass 26 can be shortened.
- the saccharified solution supply line L21, the hot water supply line L23, and the saccharification residue discharge line L24 are individually connected to the solid-liquid separation device 71.
- the present invention is not limited to this.
- at least one of the saccharified solution supply line L21, the hot water supply line L23, and the saccharification residue discharge line L24 may be shared.
- the solid-liquid separator 71 is, for example, a filter press, the number of liquid supply ports and discharge ports may be limited due to the configuration of the filter press.
- the solid-liquid separation device 71 can be connected to the liquid supply port and the discharge port like a filter press. Even when the number of tanks is limited, the saccharified liquid 41 can be efficiently solid-liquid separated in accordance with the apparatus configuration used as the solid-liquid separation apparatus 71.
- the saccharified liquid 41 is supplied to the solid-liquid separator 71 and the sugar liquid 72 is extracted, and then hot water 74 is supplied to the solid-liquid separator 71 and adsorbed to the solid content in the solid-liquid separator 71.
- the sugar solution 72 is generated by reacting with the saccharifying enzyme 32. And after reducing sugar content from solid content, it is made to discharge
- FIG. The order of supplying the saccharified liquid 41 and the hot water 74 to the solid-liquid separation device 71 and withdrawing the sugar liquid 72 is not particularly limited, and can be adjusted as appropriate.
- the sugar liquid production apparatus 10A according to the first embodiment of the present invention is used as the sugar liquid production apparatus has been described, but the present embodiment is not limited to this.
- the sugar solution production apparatuses 10B and 10C according to the second and third embodiments may be used.
- Example 1 Preparation and analysis of saccharified solution>
- A. Preparation of pretreated cellulose-containing biomass (1. Explosion treatment of cellulosic biomass) Rice straw was used as the cellulose-containing biomass.
- 100 kg of rice straw was pulverized with a rotary cutter mill RCM-400 (manufactured by Nara Machinery Co., Ltd.) with a screen mesh diameter of 8 mm and rotated at 420 rpm.
- 2 kg of rice straw pulverized using a blasting apparatus (reaction vessel 30L, manufactured by Nippon Electric Heat Co., Ltd.) was subjected to steam blasting. The pressure at that time was 2.5 MPa, and the treatment time was 3 minutes.
- Rice straw was used as the cellulose-containing biomass.
- 1 kg of rice straw was pulverized with a rotary cutter mill RCM-400 (manufactured by Nara Machinery Co., Ltd.) with a screen mesh diameter of 8 mm and rotated at 420 rpm.
- 500 g of rice straw crushed using an autoclave device (reaction vessel 3L, manufactured by Nitto Koatsu Co., Ltd.) was introduced into the autoclave and pure ammonia gas was introduced into the autoclave. Processed. This was performed several times to obtain about 20 kg of pretreated biomass.
- [B. Preparation of saccharified solution] [A. The pretreated biomass obtained in [Preparation of Pretreated Cellulose-Containing Biomass] was fractionated in a dry mass of 2 kg and subjected to a saccharification reaction. A saccharification reaction was continuously performed using a Bono dryer (hold capacity: about 30 L) manufactured by Nara Machinery Co., Ltd. as a horizontal reaction tank. Warm water at 50 ° C. was supplied only to the jacket for saccharification reaction. Pretreatment biomass, pH adjuster (sulfuric acid or sodium hydroxide aqueous solution), enzyme solution (Accellacease (registered trademark) DUET, cellulase manufactured by Danisco Japan Co., Ltd.) Water was added continuously.
- pH adjuster sulfuric acid or sodium hydroxide aqueous solution
- enzyme solution Accellacease (registered trademark) DUET, cellulase manufactured by Danisco Japan Co., Ltd.
- a pH adjuster is added so that pH may be set to 4.8
- an enzyme liquid is added so that 200 mL may be supplied with respect to 1 kg of dry mass of pretreatment biomass, and the addition amount of water is
- the saccharification reaction was performed by adding the pH adjuster and the enzyme solution so that the solids concentration was 10 wt%, 15 wt%, 20 wt%, and 30 wt%. Thereafter, 20 L of the discharged saccharification slurry was collected, and a saccharification reaction was performed using a jacket-type reaction tank having a total volume of 25 L as a vertical reaction tank. In the saccharification reaction, the reaction was stopped after 24 hours and 6 hours after the start of addition of the first pretreated biomass to the bouno dryer, which is a horizontal reaction tank.
- the solid content concentration of the saccharified solution obtained above was measured.
- the solid content is measured by using an infrared moisture meter (“FD-720”, manufactured by Kett Scientific Laboratory), holding the sample containing the saccharified solution at a temperature of 120 ° C., and a stable value and an initial value after evaporation.
- the moisture content which is a value obtained from the difference between the two, was measured, and the value obtained by subtracting the moisture content from 100 wt% was defined as the solid content concentration.
- Table 1 The results are shown in Table 1.
- Example 2 Keeping the stirring shaft warm>
- hot water of 50 ° C. was passed not only through the jacket in the bouno dryer as a horizontal reaction vessel but also through the stirring shaft side [A.
- a saccharification reaction was continuously performed on the pretreated biomass obtained in [Preparation of pretreated cellulose-containing biomass]. The reaction was stopped 6 hours and 24 hours after the start of the addition of the first pretreated biomass to the Buno dryer, which was a horizontal reaction tank, and the sugar concentration was measured. The results are shown in Table 2.
- Example 3 Combined use of filtration type solid-liquid separator> With the saccharified solution obtained in Example 2, the saccharification reaction was stopped after 6 hours, and solid-liquid separation was performed using a filter press (manufactured by Ataca Daiki Co., Ltd.) as a filtration type solid-liquid separation device. After the solid-liquid separation, 5 L of hot water at 50 ° C. was supplied to the filter press for squeezing, and the total amount and concentration of the saccharified liquid and the obtained sugar liquid were measured using the above-mentioned “1. Sugar analysis method”. The results are shown in Table 3.
- the obtained saccharified solution is filtered with a filter press, and hot water at 50 ° C. is supplied to promote the saccharification reaction in the filter chamber of the filter press. It was confirmed that the yield was improved. Moreover, it was confirmed by the saccharification reaction of about 6 hours that the sugar yield can obtain the sugar concentration equivalent to that after 24 hours saccharification, suggesting that the equipment cost can be reduced. Moreover, as for the mass of sugar, when there was no filtration device, the biomass undegraded portion was assumed to be 1 kg, the liquid volume was 19 L, and after washing, it was calculated as 24 L. As a result, it was confirmed that the sugar yield was improved by washing the saccharification residue with warm water.
- the pretreatment biomass, pH adjuster (sulfuric acid or sodium hydroxide aqueous solution), enzyme solution (Accel Race Duet, manufactured by Danisco Japan Co., Ltd.), and water were continuously added in accordance with the hold amount of 30 L and the reaction time was 24 hours.
- the reaction was run for a total of 3 days. Each addition speed is such that the pH adjusting agent is added so that the pH of the saccharified solution is 4.8, the enzyme solution is added so as to supply 200 mL with respect to 1 kg of the dry mass of the pretreated biomass, and water is added.
- the saccharification reaction was carried out by adding the amount of the solid content concentration including the pH adjuster and the enzyme solution to 10 wt%, 15 wt%, 20 wt%, and 30 wt%.
- Example 1 In each of the obtained sugar solutions, solids accumulated at the bottom of the bouno dryer, and a stable sugar solution could not be obtained. In addition, the stirrer stopped rotating due to the solid content accumulated at the bottom. Thus, saccharification could not be processed continuously only by using a horizontal reaction tank. Therefore, in Example 1, it was confirmed that saccharification efficiency can be improved more by sharing a horizontal reaction tank and a vertical reaction tank.
- a pretreatment biomass, a pH adjuster (sulfuric acid or sodium hydroxide aqueous solution), an enzyme solution (Accel Race Duet), and water were continuously added with a reaction time of 30 minutes in accordance with the hold amount of 30 L.
- the addition rate is such that the pH adjuster is added so that the pH is 4.8, the enzyme solution is added so as to supply 200 mL to 1 kg of the dry mass of the pretreated biomass, and the amount of water added is the pH adjuster and
- the saccharification reaction was carried out by adding the enzyme solution so that the solid concentration was 10 wt%, 15 wt%, 20 wt%, and 30 wt%.
- the apparatus for producing a sugar liquid and the method for producing a sugar liquid of the present invention can be suitably used for efficiently producing a high-concentration sugar liquid.
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Abstract
Description
(1) セルロース含有バイオマスから糖液を製造する糖液の製造装置であって、
内部に水平方向に設けられる攪拌軸と、前記攪拌軸に設けられる攪拌翼とを備え、前記セルロース含有バイオマスと糖化酵素とを攪拌しながら、前記セルロース含有バイオマスと前記糖化酵素とを反応させて糖化スラリーを得る水平型反応槽と、
前記糖化スラリーを糖化して糖化液を得る垂直型反応槽と、
前記水平型反応槽と前記垂直型反応槽とを連結する糖化スラリー供給ラインと、
前記水平型反応槽の周囲または壁面に設けられ、前記水平型反応槽を加熱する加温部と、
を有することを特徴とする糖液の製造装置。
(2) 前記水平型反応槽は、
前記水平型反応槽の一方に前記セルロース含有バイオマスを供給するバイオマス導入口と、
前記水平型反応槽の前記バイオマス導入口とは反対側に前記糖化スラリーを排出する糖化スラリー排出口と、
を有することを特徴とする上記(1)に記載の糖液の製造装置。
(3) 前記水平型反応槽は、前記糖化スラリー排出口に前記糖化スラリーの流れをせき止めるせき止め部を有することを特徴とする上記(1)または(2)に記載の糖液の製造装置。
(4) 前記攪拌軸が加熱されることを特徴とする上記(1)から(3)の何れか1つに記載の糖液の製造装置。
(5) 前記攪拌軸と前記加温部との何れか一方または両方は、内部を熱媒体が通ることが可能な中空体であることを特徴とする上記(1)から(4)の何れか1つに記載の糖液の製造装置。
(6) 前記熱媒体の温度が40℃以上60℃以下であることを特徴とする上記(5)に記載の糖液の製造装置。
(7) 前記水平型反応槽の前記バイオマス導入口の前流側にセルロース含有バイオマスを供給するバイオマス供給部を備えることを特徴とする上記(1)から(6)の何れか1つに記載の糖液の製造装置。
(8) 前記垂直型反応槽から前記糖化液を排出する糖化液供給ラインと、
前記糖化液から固形分を分離して糖液を得る固液分離装置と、
を有することを特徴とする上記(1)から(7)の何れか1つに記載の糖液の製造装置。
(9) 前記固液分離装置に連結され、前記固液分離装置内に温水を供給する温水供給ラインを有することを特徴とする上記(8)に記載の糖液の製造装置。
(10) 前記水平型反応槽は、前記攪拌軸を複数備え、
それぞれの前記攪拌軸に複数の攪拌翼を備えることを特徴とする上記(1)から(9)の何れか1つに記載の糖液の製造装置。
(11) 前記攪拌翼が切り欠き部を有することを特徴とする上記(1)から(10)の何れか1つに記載の糖液の製造装置。
(12) 前記垂直型反応槽は、内部に糖化酵素を供給する第2の酵素供給通路を有することを特徴とする上記(1)から(11)の何れか1つに記載の糖液の製造装置。
(13) 前記水平型反応槽に給する糖化酵素と前記第2の酵素供給通路から供給する糖化酵素とは、種類が異なることを特徴とする上記(12)に記載の糖液の製造装置。
(14) 前記水平型反応槽における前記セルロース含有バイオマスと前記糖化酵素との糖化反応は、熱化学処理が施されたセルロース含有バイオマスの乾燥質量が糖化スラリーの総質量に対して15質量%以上50質量%以下で行われることを特徴とする上記(1)から(11)の何れか1つに記載の糖液の製造装置。
(15) 前記熱化学処理が、アンモニア処理、水熱処理、爆砕処理、アルカリ処理および希硫酸処理からなる群から選択されることを特徴とする上記(14)に記載の糖液の製造装置。
(16) 上記(1)から(15)の何れか1つに記載の糖液の製造装置を用いてセルロース含有バイオマスから糖液を製造することを特徴とする糖液の製造方法。
<糖液の製造装置>
本発明の第1の実施形態に係る糖液の製造装置(糖液製造装置)について、図面を参照して説明する。図1は、本発明の第1の実施形態に係る糖液製造装置の一部を切り欠いた図である。図2は、図1のA-A断面図である。図3は、図1のB-B断面図であって、糖液製造装置の一部の構成を示す図である。図1に示すように、糖液製造装置10Aは、水平型反応槽(横型反応槽)11と、ジャケット(加温部)12と、垂直型反応槽(縦型反応槽)13と、糖化スラリー供給ラインL11とを有する。
図1~図3に示すように、水平型反応槽11は、攪拌軸21と、攪拌翼22とを備えている。
ジャケット12は、水平型反応槽11の壁面11aに設けられている。ジャケット12は、水平型反応槽11内を外側から温めている。ジャケット12は、内部を温水(熱媒体)が通ることが可能な中空体である。また、ジャケット12は壁面11aに設けられている。
垂直型反応槽13は、糖化スラリー33を糖化して糖化液41を生成する槽である。垂直型反応槽13は、内部に攪拌翼42を備えている。攪拌翼42は、縦型攪拌駆動装置(縦型攪拌モータ)43により駆動される。糖化スラリー33は、攪拌翼42により攪拌され、垂直型反応槽13内で糖化反応が継続して行われる。これにより、糖化スラリー33は糖化液41となる。
本発明の第2の実施形態に係る糖液製造装置について、図面を参照して説明する。なお、本実施形態に係る糖液製造装置の構成は、上述の図1に示す本発明による第1の実施形態に係る糖液製造装置の構成と同様であるため、第1の実施形態に係る糖液製造装置と同一の部材には同一の符号を付してその説明は省略する。
本発明の第3の実施形態に係る糖液製造装置について、図面を参照して説明する。なお、本実施形態に係る糖液製造装置の構成は、上述の図1に示す本発明による第1の実施形態に係る糖液製造装置の構成と同様であるため、第1の実施形態に係る糖液製造装置と同一の部材には同一の符号を付してその説明は省略する。
本発明の第4の実施形態に係る糖液製造装置について、図面を参照して説明する。なお、本実施形態に係る糖液製造装置の構成は、上述の図1に示す本発明による第1の実施形態に係る糖液製造装置の構成と同様であるため、第1の実施形態に係る糖液製造装置と同一の部材には同一の符号を付してその説明は省略する。
[A.前処理したセルロース含有バイオマスの準備]
(1.セルロース系バイオマスの爆砕処理)
セルロース含有バイオマスとして、稲ワラを使用した。稲ワラ100kgをまず、ロータリーカッターミルRCM-400型(株式会社奈良機械製作所製)にてスクリーンメッシュ径8mmの状態で420rpmで回転させて粉砕した。次に、爆砕装置(反応容器30L、日本電熱株式会社製)を用いて粉砕処理した稲ワラ2kgを水蒸気爆砕処理した。その際の圧力は2.5MPa、処理時間は3分であった。
セルロース含有バイオマスとして、稲ワラを使用した。稲ワラ1kgをまず、ロータリーカッターミルRCM-400型(株式会社奈良機械製作所製)にてスクリーンメッシュ径8mmの状態で420rpmで回転させて粉砕した。次に、オートクレーブ装置(反応容器3L、日東高圧株式会社製)を用いて粉砕処理した稲ワラ500gをオートクレーブ内に純アンモニアガスを導入して、120℃、10分の条件下で攪拌しながらアンモニア処理した。これを複数回行い、前処理バイオマスを約20kg得た。
上記[A.前処理したセルロース含有バイオマスの準備]で得られた前処理バイオマスをそれぞれ乾燥質量で2kg分取し、それぞれ糖化反応を行った。水平型反応槽として株式会社奈良機械製作所製のブーノドライヤ(ホールド容量:約30L)を用いて、連続的に糖化反応を行った。50℃の温水はジャケットのみに供給し糖化反応を行った。ホールド量30Lに合わせて反応時間を30分として前処理バイオマス、pH調整剤(硫酸または水酸化ナトリウム水溶液)、酵素液(アクセルレースデュエット:Accellerase(登録商標)DUET、ダニスコジャパン株式会社製セルラーゼ)、水を連続的に添加した。各々の添加物については、pH調整剤はpHが4.8になるように添加し、酵素液は前処理バイオマスの乾燥質量1kgに対して200mLを供給するように添加し、水の添加量はpH調整剤および酵素液を含めて固形分濃度が10wt%、15wt%、20wt%、30wt%となるように添加して糖化反応を行った。その後、排出された糖化スラリー20Lを分取して、垂直型反応槽として、ジャケット式の全容量25Lの反応槽を用いて糖化反応を行った。糖化反応は、水平型反応槽であるブーノドライヤに最初の前処理バイオマスの添加を開始した時から6時間後、24時間後に反応を停止した。
(1.糖の分析方法)
上記で得られた糖化液の糖濃度(g/L)を測定した。得られた糖化液に含まれる糖濃度は、下記に示す高速液体クロマトグラフィー(High Performance Liquid Chromatography:HPLC)条件で、標品との比較により定量した。結果を表1に示す。
カラム:Luna NH2(Phenomenex社製)
移動相:超純水;アセトニトリル=25:75
流速:0.6mL/min
反応液:なし
検出方法:RI(示差屈折率)
温度:30℃
上記で得られた糖化液の固形分濃度を測定した。固形分濃度は、赤外線水分計(「FD-720」、株式会社ケット科学研究所製)を使用して、糖化液を含む試料を120℃の温度に保持し、蒸発後の安定値と初期値との差分から得られる値である含水率を測定し、100wt%から含水率を差し引いた値を固形分濃度とした。結果を表1に示す。
実施例1と同様の方法で、水平型反応槽としてブーノドライヤにおいてジャケットだけでなく、攪拌軸側にも50℃の温水を通して、上記[A.前処理したセルロース含有バイオマスの準備]で得られた前処理バイオマスに連続的に糖化反応を行った。水平型反応槽であるブーノドライヤに最初の前処理バイオマスの添加を開始してから6時間後、24時間後に反応を停止し、糖濃度を測定した。結果を表2に示す。
実施例2で得られた糖化液で、6時間後に糖化反応を止め、さらにろ過型固液分離装置としてフィルタプレス(アタカ大機株式会社製)を用いて固液分離を行った。固液分離後、50℃の温水5Lをフィルタプレスに供給して圧搾を行い、糖化液と得られた糖液の総量と濃度を、上記「1.糖の分析方法」を用いて測定した。結果を表3に示す。
実施例1~3と同様、上記[A.前処理したセルロース含有バイオマスの準備]で得られた前処理バイオマスをそれぞれ乾燥質量で2kg分取し、垂直型反応槽として、ジャケット式の全容量25Lの反応槽を用いて糖化反応を行った。糖化条件としては、爆砕バイオマスについては水酸化ナトリウムで、アンモニア処理バイオマスについては硫酸を使用して、pHを4.8に調整した後、アクセルレースデュエット(ダニスコジャパン株式会社製)を400mL添加した。固形分濃度は10wt%、15wt%、20wt%になるように水を添加してジャケットは温水を用いて50℃に保って24時間糖化反応を行った。最初の前処理バイオマスの添加を開始してから6時間後、24時間後に反応を停止し、糖濃度を測定した。結果を表4に示す。
実施例1~3と同様、上記[A.前処理したセルロース含有バイオマスの準備]で得られた前処理バイオマスをそれぞれ乾燥質量で2kg分取し、それぞれ糖化反応を行った。糖化槽としては、水平型反応槽として株式会社奈良機械製作所製のブーノドライヤ(ホールド容量:約30L)を用いて連続的に糖化反応を行った。50℃の温水はジャケットのみに供給し糖化反応を行った。ホールド量30Lに合わせて反応時間を24時間として前処理バイオマス、pH調整剤(硫酸または水酸化ナトリウム水溶液)、酵素液(アクセルレースデュエット、ダニスコジャパン株式会社製)、水を連続的に添加した。反応は合計3日間運転した。各々の添加速度は、pH調整剤は糖化液のpHが4.8になるように添加し、酵素液は前処理バイオマスの乾燥質量1kgに対して200mLを供給するように添加し、水の添加量はpH調整剤および酵素液を含めて固形分濃度が10wt%、15wt%、20wt%、30wt%となるように添加して糖化反応を行った。
実施例1~3と同様、上記[A.前処理したセルロース含有バイオマスの準備]で得られた前処理バイオマスをそれぞれ乾燥質量で2kg分取し、それぞれ糖化反応を行った。糖化槽としては、水平型反応槽として奈良機械製作所製のブーノドライヤ(ホールド容量:約30L)を用いて連続的に糖化反応を行った。ジャケットおよび攪拌軸には温水を通水せず温度制御なしに糖化反応を行った。外部の温度は25度であった。ホールド量30Lに合わせて反応時間を30分として前処理バイオマス、pH調整剤(硫酸または水酸化ナトリウム水溶液)、酵素液(アクセルレースデュエット)、水を連続的に添加した。添加速度は、pH調整剤はpHが4.8になるように添加し、酵素液は前処理バイオマスの乾燥質量1kgに対して200mLを供給するように添加し、水添加量はpH調整剤および酵素液を含めて固形分濃度が10wt%、15wt%、20wt%、30wt%となるように添加して糖化反応を行った。その後、排出された糖化スラリー20Lを分取して、垂直型反応槽として、ジャケット式の全容量25Lの反応槽を用いて糖化反応を行った。糖化反応は、水平型反応槽であるブーノドライヤに最初の前処理バイオマスの添加を開始した時から6時間後、24時間後に反応を停止し、糖濃度を測定した。結果を表5に示す。
11、51 水平型反応槽
11a 壁面
12、46 ジャケット(加温部)
13 垂直型反応槽
21、21A、21B 攪拌軸
22、22A、22B、42 攪拌翼
22a 切欠き部
24 モータ(駆動装置)
25 バイオマス導入口
26 セルロース含有バイオマス
27 水
28 pH調整剤
31、44 酵素供給通路
32、45 糖化酵素
33 糖化スラリー
34 糖化スラリー排出口
35、55、74 温水
36 ジャケット用温水供給通路
37 ジャケット用温水排出通路
38 せき止め部
41 糖化液
43 縦型攪拌駆動装置(縦型攪拌モータ)
52 中空攪拌軸
53 中空回転体用温水供給通路
54 中空回転体用温水排出通路
61 バイオマス供給装置(バイオマス供給部)
62 ホッパー
63 フィーダ攪拌機
64 フィーダ攪拌機用モータ(フィーダ攪拌機駆動部)
65 移送機
66 移送機用モータ(移送機用駆動部)
67 固形分調整水供給通路
71 固液分離装置
72 糖液
73 温水供給槽
75 糖化残渣
L11 糖化スラリー供給ライン
L21、L21-1、L21-2 糖化液供給ライン
L22 糖液排出ライン
L23 温水供給ライン
L24 糖化残渣排出ライン
P11 糖化液供給ポンプ
P12 糖液供給ポンプ
P13 温水供給ポンプ
P14 糖化残渣排出用ポンプ
V11~V14 調節弁
Claims (16)
- セルロース含有バイオマスから糖液を製造する糖液の製造装置であって、
内部に水平方向に設けられる攪拌軸と、前記攪拌軸に設けられる攪拌翼とを備え、前記セルロース含有バイオマスと糖化酵素とを攪拌しながら、前記セルロース含有バイオマスと前記糖化酵素とを反応させて糖化スラリーを得る水平型反応槽と、
前記糖化スラリーを糖化して糖化液を得る垂直型反応槽と、
前記水平型反応槽と前記垂直型反応槽とを連結する糖化スラリー供給ラインと、
前記水平型反応槽の周囲または壁面に設けられ、前記水平型反応槽を加熱する加温部と、
を有する糖液の製造装置。 - 前記水平型反応槽は、
前記水平型反応槽の一方に前記セルロース含有バイオマスを供給するバイオマス導入口と、
前記水平型反応槽の前記バイオマス導入口とは反対側に前記糖化スラリーを排出する糖化スラリー排出口と、
を有する請求項1に記載の糖液の製造装置。 - 前記水平型反応槽は、前記糖化スラリー排出口に前記糖化スラリーの流れをせき止めるせき止め部を有する請求項1または2に記載の糖液の製造装置。
- 前記攪拌軸が加熱される請求項1から3の何れか1つに記載の糖液の製造装置。
- 前記攪拌軸と前記加温部との何れか一方または両方は、内部を熱媒体が通ることが可能な中空体である請求項1から4の何れか1つに記載の糖液の製造装置。
- 前記熱媒体の温度が40℃以上60℃以下である請求項5に記載の糖液の製造装置。
- 前記水平型反応槽の前記バイオマス導入口の前流側にセルロース含有バイオマスを供給するバイオマス供給部を有する請求項1から6の何れか1つに記載の糖液の製造装置。
- 前記垂直型反応槽から前記糖化液を排出する糖化液供給ラインと、
前記糖化液から固形分を分離して糖液を得る固液分離装置と、
を有する請求項1から7の何れか1つに記載の糖液の製造装置。 - 前記固液分離装置に連結され、前記固液分離装置内に温水を供給する温水供給ラインを有する請求項8に記載の糖液の製造装置。
- 前記水平型反応槽は、前記攪拌軸を複数備え、
それぞれの前記攪拌軸に設けられる複数の攪拌翼を備える請求項1から9の何れか1つに記載の糖液の製造装置。 - 前記攪拌翼が切り欠き部を有する請求項1から10の何れか1つに記載の糖液の製造装置。
- 前記垂直型反応槽は、内部に糖化酵素を供給する第2の酵素供給通路を有する請求項1から11の何れか1つに記載の糖液の製造装置。
- 前記水平型反応槽に供給する糖化酵素と前記第2の酵素供給通路から供給する糖化酵素とは、種類が異なる請求項12に記載の糖液の製造装置。
- 前記水平型反応槽における前記セルロース含有バイオマスと前記糖化酵素との糖化反応は、熱化学処理が施されたセルロース含有バイオマスの乾燥質量が糖化スラリーの総質量に対して15質量%以上50質量%以下で行われる請求項1から11の何れか1つに記載の糖液の製造装置。
- 前記熱化学処理が、アンモニア処理、水熱処理、爆砕処理、アルカリ処理および希硫酸処理からなる群から選択される請求項14に記載の糖液の製造装置。
- 請求項1から15の何れか1つに記載の糖液の製造装置を用いてセルロース含有バイオマスから糖液を製造する糖液の製造方法。
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Also Published As
Publication number | Publication date |
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US10385302B2 (en) | 2019-08-20 |
JP2014131496A (ja) | 2014-07-17 |
BR112015015884B1 (pt) | 2020-11-03 |
US20150353881A1 (en) | 2015-12-10 |
CA2897289A1 (en) | 2014-07-10 |
CN104884603B (zh) | 2018-09-28 |
CN104884603A (zh) | 2015-09-02 |
EP2942386A1 (en) | 2015-11-11 |
JP6307789B2 (ja) | 2018-04-11 |
BR112015015884A2 (pt) | 2017-07-11 |
EP2942386A4 (en) | 2016-09-07 |
AU2014204215A1 (en) | 2015-07-23 |
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