JP2013141415A - Method and device for producing monosaccharide, and method and device for producing ethanol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method and a device for producing a monosaccharide and ethanol inexpensively and with good efficiency wherein plant waste is used as the starting material for the biomass ethanol and the amount of enzyme used and the treatment time are reduced during the production of ethanol by a saccharification enzyme reaction and fermentation.SOLUTION: The monosaccharide is produced by a primary saccharification that involves exposing a biomass to pressurized hot water in order to selectively decompose the hemicellulose contained in the biomass, beating the solid residue after pressurized hot water reaction, and exposing the beaten solid residue to a saccharification enzyme, and a secondary saccharification that involves exposing the primary saccharification product to a solid acid catalyst. The resulting monosaccharide is subjected to ethanol fermentation and distillation to obtain purified ethanol.

Description

  The present invention relates to a method and apparatus for producing monosaccharides, and a method and apparatus for producing ethanol, and more specifically, by saccharification of cellulosic materials and microbial fermentation using plant waste such as wood and wheat straw as biomass. The present invention relates to a monosaccharide production method and production apparatus for producing sugar and biomass ethanol, and an ethanol production method and production apparatus.

  In recent years, biomass ethanol, which produces ethanol by fermentation of microorganisms using plant matter, has attracted attention as a solution to the depletion of petroleum resources, and various processes have been announced as production techniques thereof. For example, Non-Patent Document 1 below discloses a process for producing ethanol by saccharifying cellulose in biomass into glucose using cellulase, which is widely known as a saccharifying enzyme, and fermenting the obtained glucose. . Patent Document 1 listed below describes a method for producing ethanol in which fine bark that has been subjected to treatment with an alkali solution of bark raw material and refined by mechanical treatment is prepared into a slurry having an appropriate pH and then subjected to concurrent saccharification and fermentation. .

JP 2011-152067 A

Maeko Koseki, Hiroyuki Imanaka, Itsuka Imamura, Masahiro Karayama, Kazuhiro Nakanishi, “Efficient ethanol production from wheat bran combined with enzymatic saccharification and fermentation”, Biotechnology Society, Vol. 87, No. 5, P216-223 2009

  Since the saccharifying enzyme used for the production of biomass ethanol is inactivated with the passage of time of use, supplementation of the saccharifying enzyme is necessary for sufficient saccharification. In particular, β-glucosidase contained in a saccharification enzyme is inhibited by glucose that is finally produced in saccharification, so that there is a problem that the production rate decreases according to the production of glucose. To solve this, β-glucosidase Need to be added. For this reason, the quantity of the saccharifying enzyme used for manufacture of biomass ethanol increases, and production cost becomes high. In order to produce ethanol at low cost while suppressing production costs, it is important to reduce the amount of saccharifying enzyme used. In addition, since the saccharification by the enzyme reaction requires a processing time, it is also important to shorten the processing time in order to produce ethanol efficiently at a low cost.

  An object of the present invention is to solve the above-mentioned problems and to produce a monosaccharide that can reduce the amount of saccharification enzyme used without reducing the yield in saccharification of lignocellulosic biomass, and to produce ethanol using the same. Is to provide a method.

  Another subject of the present invention is a monosaccharide device capable of producing monosaccharides with high yield and reducing production costs, and ethanol production capable of producing biomass ethanol efficiently using the same. Is to provide a device.

  In order to solve the above-mentioned problems, the present inventors have conducted extensive research, and as a result, in a process of saccharifying biomass through pressurized hydrothermal treatment, saccharification enzyme treatment, and solid acid catalyst treatment, before performing saccharification enzyme treatment. In addition to reducing the amount of saccharification enzyme used and the treatment time, the reaction efficiency in the solid acid catalyst treatment was improved, and the present invention was completed.

  According to one aspect of the present invention, a method for producing a monosaccharide includes a pressurized hot water reaction step of selectively decomposing hemicellulose contained in biomass by causing pressurized hot water to act on the biomass, and the pressurized hot water. A beating treatment step for beating a solid residue after the reaction step, a primary saccharification step for allowing a saccharifying enzyme to act on the solid residue after the beating treatment step, and a secondary saccharification for causing a solid acid catalyst to act on a product obtained by the primary saccharification step And having a process.

  Moreover, according to one aspect of the present invention, the gist of the method for producing ethanol includes a fermentation step for producing ethanol by fermenting the monosaccharide obtained by the monosaccharide production method described above.

  Furthermore, according to one aspect of the present invention, the monosaccharide production apparatus includes a pressurized hot water reactor that selectively decomposes hemicellulose contained in biomass by causing pressurized hot water to act on the biomass, and the pressurized heat. A beating machine for beating a solid residue obtained from a reaction product of a water reaction apparatus, an enzyme reaction apparatus for allowing a saccharifying enzyme to act on the solid residue beaten by the beating machine, and a solid acid for the reaction product of the enzyme reaction apparatus The gist of the present invention is to have a catalytic reaction device that causes a catalyst to act.

  Moreover, according to one aspect of the present invention, an ethanol production apparatus includes the above monosaccharide production apparatus and a fermentation apparatus that produces ethanol by fermenting a monosaccharide obtained by the monosaccharide production apparatus. The gist.

  According to the present invention, it is possible to reduce the amount of enzyme used and the processing time in the enzymatic decomposition by providing a beating apparatus for performing the beating treatment before performing the enzymatic decomposition of cellulose with a saccharifying enzyme, and the enzyme can be obtained by enzymatic decomposition. Provided are a monosaccharide production method and a production apparatus for improving the reaction efficiency of secondary saccharification of a primary saccharified solution with a solid acid catalyst and obtaining a monosaccharide in a high yield. As a result, a method for producing monosaccharides with high saccharification efficiency and reduced production costs can be implemented, and a low-cost and efficient ethanol production method and production apparatus using biomass are established. Therefore, it is economically advantageous, the use of plant waste as biomass is promoted, and it is useful for solving energy resource problems and waste disposal problems.

The schematic block diagram which shows one Embodiment of the ethanol manufacturing apparatus which concerns on this invention. It is a bar graph for comparing the saccharide | sugar yield in a simple saccharification process based on the presence or absence of a beating process, (a)-(c) is a case where there is no beating process, (d)-(f) is a beating process. When there is. It is a graph for showing the function of a solid acid catalyst, (a) shows the sugar concentration of the product by a saccharification enzyme reaction and a solid acid catalytic reaction, (b) shows the temperature in solid acid catalytic reaction, and glucose production The relationship between a rate constant and a glucose decomposition rate constant is shown.

  In the production of biomass ethanol using plant waste (lignocellulosic biomass), saccharified products obtained by hydrolysis of cellulose and hemicellulose are ethanol-fermented. In the present invention, saccharification of plant cellulose, that is, hydrolysis, is carried out in three types of steps: pressurized hot water reaction, saccharification enzyme reaction, and solid acid catalyzed reaction. In the pressurized hot water reaction, selective hydrolysis of hemicellulose proceeds, and in the saccharification enzyme reaction, hydrolysis of cellulose, which is a residue of pressurized hot water reaction, proceeds. ~ Partially decomposed polysaccharides are produced (primary saccharification) and some are monosaccharified. By subjecting the primary saccharified solution resulting from the hydrolysis reaction to a solid acid catalytic reaction, it is sufficiently saccharified to produce monosaccharides such as glucose and xylose (secondary saccharification). Monosaccharides obtained by such a saccharification process are fermented to produce ethanol.

  In the above saccharification process, the residue after the pressurized hydrothermal reaction is a fiber lump mainly composed of cellulose, but before the saccharification enzyme is allowed to act on this, beating using mechanical shearing force using a mill or the like. It has been found that when the treatment is performed, the saccharifying enzyme reaction easily proceeds, and even if the amount of the saccharifying enzyme used is reduced, cellobiose and water-soluble oligosaccharide can be satisfactorily produced from cellulose. This is thought to be because slack and gaps between cellulose fibers are generated by shearing force due to beating, and the surface area is significantly increased to become a porous residue, so that the saccharifying enzyme is likely to act. Furthermore, it has been found that not only this but also the efficiency of the solid acid catalyzed reaction performed after the saccharifying enzyme reaction is improved. When this cause is investigated, it is considered that the amount of the partially decomposed polysaccharide in the reaction product of the saccharifying enzyme that has a molecular weight that is easily saccharified in the solid acid-catalyzed reaction increases, and as a result, the yield of the monosaccharide is improved. That is, the beating treatment before the enzyme reaction not only makes the enzyme easy to act, but also affects the properties of the product resulting from the enzyme reaction. Therefore, the beating treatment is very useful for mono-saccharifying cellulose through a saccharifying enzyme reaction and a solid acid catalytic reaction.

  Hereinafter, the present invention will be described in detail with reference to the drawings.

  FIG. 1 is a schematic configuration diagram showing an embodiment of an ethanol production apparatus according to the present invention. The ethanol production apparatus A is a monosaccharide production apparatus that saccharifies biomass B to produce a monosaccharide, a fermentation apparatus that ferments a saccharification product to produce ethanol, and distills the fermentation product to purify ethanol E. And a distillation apparatus 9. The monosaccharide production apparatus includes a pressurized hot water reaction apparatus 1, a solid-liquid separator 2, a beater 3, an enzyme reaction apparatus 4, a first catalytic reaction apparatus 5, and a second catalytic reaction apparatus 7, and the first catalytic reaction. The device 5 hydrolyzes (saccharifies) a partially saccharified product derived from cellulose, and the second catalytic reaction device 7 hydrolyzes (saccharifies) a partially saccharified product derived from hemicellulose. The fermentation apparatus includes a first fermentation apparatus 6 that ferments a saccharified product derived from cellulose to produce ethanol, and a second fermentation apparatus 8 that ferments a saccharified product derived from hemicellulose to produce ethanol, which are generated from each. The fermentation products F1 and F2 are distilled by the distillation apparatus 9 to separate and purify ethanol.

  The pressurized hot water reactor 1 includes a pump 1a, a heater 1b, a water amount adjusting valve 1c, a pressure-resistant reaction tank 1d, and a control device 1e. The pump 1a pressurizes and heats water supplied from the outside. To device 1b. The heater 1b heats the pressurized water flowing from the pump 1a to about 200 to 230 ° C. according to the temperature control signal input from the control device 1e, and pressurizes hot water W ′ (with a pressure of about 0.4 to 12 MPa). This is supplied to the reaction tank 1d containing the biomass via the water amount adjusting valve 1c. The water amount adjusting valve 1c is an electronic control valve whose opening degree can be adjusted in accordance with a flow rate control signal input from the control device 1e, and the flow rate of the pressurized hot water W ′ supplied from the heater 1b to the reaction tank 1d. Adjust appropriately. The control device 1e adjusts the temperature and flow rate of the pressurized hot water W ′ supplied to the reaction tank 1d by the temperature control signal output to the heater 1b and the water amount control signal output to the water amount adjustment valve 1c. The biomass hydrolysis conditions in the reaction tank 1d are controlled as described above. The hydrolysis conditions are, for example, the ratio K (= Q / V) between the supply amount Q (ml) of pressurized hot water W ′ and the biomass supply amount V (g), and the temperature T (° C. of pressurized hot water W ′. ) Can be set. Energy efficiency can be improved by providing a heat exchanger that recovers the thermal energy of hot water discharged from the reaction tank 1d and supplies it to the water supplied to the heater 1b.

  The reaction tank 1d contains a certain amount of lignocellulosic biomass supplied as a raw material from the outside, and is added to and acted on pressurized hot water W ′ supplied through the water amount adjusting valve 1c to the biomass. Hemicellulose is selectively hydrolyzed and solubilized. Compared with the case where cellulose requires a temperature of about 240 to 300 ° C. when hydrolyzed with pressurized hot water, hemicellulose is decomposed and solubilized at about 230 ° C. or lower, which is lower than that of cellulose. By treating the biomass at 150 to 230 ° C. in the apparatus 1, the hemicellulose contained in the biomass is selectively partially decomposed and solubilized to become a polysaccharide-containing liquid containing oligosaccharides, and the reaction product is derived from hemicellulose. It becomes a mixture of a water-containing liquid containing oligosaccharides and a solid residue containing cellulose and lignin that do not decompose. The reaction mode of the reaction tank 1d may be a continuous water type or a batch type, but in the case of the continuous water type, it is configured such that pressurized hot water can stay in the tank for about 5 to 120 minutes.

  The reaction product discharged from the pressurized hot water reactor 1 is supplied to the solid-liquid separator 2 and separated into a liquid saccharified product portion that is a hemicellulose-derived decomposition product and a solid residue S containing cellulose and lignin. The The solid residue S is supplied to the beater 3 and then processed by the enzyme reaction device 4 and the first catalytic reaction device 5. The liquid portion is supplied to the second catalytic reactor value 7 as the primary saccharified solution H1 of hemicellulose.

The beating machine 3 applies a shearing force to the solid residue S supplied from the solid-liquid separator 2, thereby causing slack and gaps between the fibers of the solid residue to be processed into a flexible porous shape. The resulting solid residue S ′ has a significant increase in surface area. Examples of the beating machine 3 include refiners used for defibrating processing, dispersers, and mills such as ball mills used for crushing processing, but are not limited thereto, and shear force can be applied. Things can be used as appropriate. The beating condition may be either dry or wet, but when beating in a water-containing state after the pressurized hot water reaction, the burden on the apparatus is small and the processing efficiency is good. The beating conditions such as the beating time and the applied load may be appropriately set according to the situation of the solid residue S so that the solid residue S ′ after the beating process has a suitable specific surface area. 50 m ² / g approximately or more, more preferably to prepare 80~300m ² / g approximately solid residue S '. In the present invention, the specific surface area of the solid residue is a value measured according to the BET method (N ₂ gas adsorption method) after pre-treatment of the sample by vacuum heating and degassing (60 ° C., 6 hours) See example).

  The solid residue S ′ beaten by the beater 3 is supplied to the enzyme reaction device 4. The enzyme reaction apparatus 4 includes a stirrer and a temperature control mechanism, and adds and mixes cellulase, which is a saccharifying enzyme, to the solid residue S ′ whose water content has been adjusted so that stirring is possible as necessary. The cellulose in the solid residue S ′ is hydrolyzed by the action of cellulase, and the decomposition product mainly consisting of cellobiose (a dimer of glucose), which is a partial saccharification of cellulose, is maintained by stirring the mixture. Obtained as liquid C1. Cellulase is generally known as an aggregate of a plurality of types of saccharifying enzymes, and contains β-glucanase as a main component. β-glucanase is known as a saccharification enzyme that hydrolyzes cellulose into water-soluble oligosaccharides (2 to 6-mer of glucose). The primary saccharified liquid C1 contains a water-soluble oligosaccharide and a water-insoluble suspended polysaccharide, and is a fluid liquid in which the suspended polysaccharide is dispersed in a water-containing liquid of the water-soluble oligosaccharide. The suspended polysaccharide is a partially decomposed product of cellulose, specifically, suspended particles containing cellohexaose crystals which are glucose polymer having a polymerization degree of 7 to 3000 and hexamer of glucose, and the subsequent solid It can be decomposed into glucose by an acid-catalyzed reaction. The temperature of the enzyme reaction apparatus 4 is appropriately adjusted within a range of about 40 to 90 ° C. so that an appropriate enzyme activity is obtained according to the saccharifying enzyme to be used. In order to easily control the temperature of the enzyme reaction apparatus 4, it is preferable that the temperature of the solid residue S ′ introduced into the enzyme reaction apparatus 4 is about 50 to 100 ° C. A cooler for lowering the temperature of the solid residue after the water reaction may be provided at the front stage or the rear stage of the beating machine 3. When a thermostable enzyme is used, the cooling capacity of the cooler can be reduced. In the present invention, since the saccharification of the solid residue S ′ is facilitated by the beating treatment, the amount of saccharifying enzyme used can be reduced, and the amount of enzyme as low as 0.25 g or less per gram of cellulose is used for about 12 hours. Within this range, the unreacted cellulose can be substantially disappeared to terminate the enzymatic decomposition.

  The primary saccharified solution C 1 of cellulose produced in the enzyme reaction device 4 is supplied to the first catalytic reaction device 5. If necessary, a separation device such as a belt press may be provided in front of the first catalytic reactor 5 as a means for removing solid residues (lignin and the like) that may remain in the primary saccharified liquid C1. The first catalytic reaction device 5 includes a first mixing device 5a having a temperature control mechanism and a first solid-liquid separation device 5b, and the primary saccharified solution C1 is 90 ° C. or higher and lower than 120 ° C. in the first mixing device 5a. Mix and stir with solid acid catalyst X at temperature. The oligosaccharide and the suspended polysaccharide of the primary saccharified liquid C1 are hydrolyzed by the action of the solid acid catalyst X to produce glucose (monosaccharide constituting cellulose), and the reaction product contains glucose as a main component. A mixture of the secondary saccharified solution C2 and the solid acid catalyst X is obtained.

  The reaction product that has been hydrolyzed in the first mixing device 5a is charged into the first solid-liquid separation device 5b and is subjected to solid-liquid separation. Thereby, the secondary saccharified solution C2 containing glucose as a main component is separated as a supernatant and sent to the first fermentation apparatus 6. The solid acid catalyst X that has settled and separated is recovered and then returned to the first mixing device 5a to be used again. The 1st solid-liquid separation apparatus 5b should just be what can generally be used as a sedimentation tank.

  The secondary saccharified solution C2 supplied from the first solid-liquid separation device 5b to the first fermentation device 6 is appropriately adjusted in water content and pH so as to be in a condition suitable for fermentation, and inoculated with fermenting microorganisms, and the fermentation stock solution The glucose is converted into ethanol by the action of the fermentation microorganism. As the fermentation microorganisms used for ethanol fermentation, known ethanol fermentation microorganisms such as yeast can be used. It is preferable to add a nutrient source necessary for the propagation and activity of fermenting microorganisms. If necessary, a temperature control mechanism for maintaining the temperature at which fermentation is likely to proceed may be provided.

  The fermentation product F1 discharged from the first fermentation apparatus 5 is supplied to the distillation apparatus 9 and distilled to recover purified ethanol. The fermentation product F1 contains a solid substance, and may be distilled as it is without removing it. If necessary, if a filtration device for removing solids (lignin, fermentation microorganisms, etc.) from the fermentation product F1 is provided, only the liquid product can be distilled. The solid matter separated from the fermentation product F1 by filtration or the like may be introduced into the biomass saccharification step.

  On the other hand, the hemicellulose-derived primary saccharified liquid H1 separated by the solid-liquid separator 2 is supplied to the second catalytic reactor 7. The second catalytic reaction device 7 includes a second mixing device 7a having a temperature control mechanism and a second solid-liquid separation device 7b, and the primary saccharified solution H1 is 90 ° C. or higher and lower than 120 ° C. in the second mixing device 7a. Mix and stir with solid acid catalyst X at temperature. The hemicellulose-derived oligosaccharides in the primary saccharified solution H1 are hydrolyzed by the action of the solid acid catalyst X to produce monosaccharides including xylose, arabinose (pentose sugar constituting hemicellulose), etc., and secondary saccharification including these Since the liquid H2 is obtained, the reaction product is a mixture of the secondary saccharified liquid H2 containing xylose and the solid acid catalyst X. The solid acid catalyst X used in the second catalytic reactor 7 may be appropriately selected from the same or different from those usable in the first catalytic reactor 5.

  The reaction product that has finished the hydrolysis reaction in the second mixing device 7a is charged into the second solid-liquid separation device 7b, and the solid acid catalyst X in the charged reaction product is allowed to settle, so that The secondary saccharified liquid H2 is separated and sent to the second fermentation apparatus 8. The solid acid catalyst X that has settled and separated is recovered and then returned to the second mixing device 7a to be used again. The second solid-liquid separator 7b may be anything that can generally be used as a precipitation tank.

  The secondary saccharified solution H2 supplied from the second solid-liquid separation device 7b to the second fermentation device 8 is appropriately adjusted in water content and pH so as to be in a condition suitable for fermentation, inoculated with fermenting microorganisms, and the fermentation stock solution And xylose or the like is converted into ethanol by the action of the fermentation microorganism. The fermentation microorganism used is a microorganism having xylose fermentation ability. It is preferable to add a nutrient source necessary for the propagation and activity of fermenting microorganisms. If necessary, a temperature control mechanism for maintaining the temperature at which fermentation is likely to proceed may be provided.

  The fermentation product F2 discharged from the second fermentation apparatus 7 is supplied to the distillation apparatus 9 and distilled to recover purified ethanol. Fermentation product F2 contains a solid substance and may be distilled as it is without removing it. If necessary, if a filtration device for removing solids (lignin, fermentation microorganisms, etc.) from the fermentation product F2 is provided, only the liquid product can be distilled. The solid matter separated from the fermentation product F2 by filtration or the like may be introduced into the biomass saccharification step. The distillation of the fermentation product F2 can be performed together with the fermentation product F1 obtained from the first fermentation apparatus 5 or individually.

  Blow water is discharged from the reaction tank 1 d of the pressurized hot water reactor 1. Moreover, the water produced by revision of ethanol fermentation is discharged | emitted from the 1st fermentation apparatus 6 and the 2nd fermentation apparatus 8. FIG. The waste water D is supplied to the waste water treatment apparatus 10 and appropriately subjected to purification treatment, and then discharged to the outside.

  A method for producing monosaccharides and ethanol implemented in the ethanol production apparatus configured as described above will be described below.

  The biomass B used as a raw material may be any lignocellulosic material, for example, woody materials such as wood, thinned wood, bark, herbs such as rice straw, wheat straw, rice husk, pulp, waste paper, cotton cloth, linen And fiber materials such as artificial cellulose materials, and in particular, plant materials such as wood materials containing hemicellulose can be efficiently saccharified and fermented. From the viewpoint of reaction efficiency, it is preferable to pulverize such biomass B in advance, and it is preferable to prepare particles having a particle size of about 10 mm or less, specifically about 5 to 10 mm.

  In the pressurized hot water reactor 1, a certain amount of biomass supplied as a raw material from the outside is accommodated in the reaction tank 1d, the heater 1b is adjusted by a temperature control signal input from the controller 1e, and the pump 1a Is heated to about 150 to 230 ° C. to form pressurized hot water W ′ (subcritical hot water having a pressure of about 0.4 to 12 MPa), and contains biomass via the water amount adjustment valve 1c. It is supplied to the tank 1d. The flow rate of the pressurized hot water W 'supplied from the heater 1b to the reaction tank 1d is adjusted appropriately by adjusting the opening of the water amount adjusting valve 1c by a flow rate control signal input from the control device 1e. When pressurized hot water is added to and acted on biomass, hemicellulose contained in the biomass is selectively hydrolyzed and solubilized and liquefied. The woody material is lignocellulosic biomass containing cellulose as the main component and containing hemicellulose and lignin. When hydrolyzed with pressurized hot water, the cellulose needs hemicellulose compared to the temperature of about 240 to 300 ° C. Is decomposed and solubilized at a temperature of about 150 to 230 ° C. lower than that of cellulose. Therefore, the reaction product obtained by treating the wooden material with a pressurized hydrothermal reactor is a polysaccharide containing oligosaccharide partially decomposed and solubilized from hemicellulose. It becomes a solid-liquid mixture containing a water-containing liquid and a solid residue of cellulose and lignin that does not decompose. Pressurized hot water may be supplied either continuously or batchwise, but in the case of continuous water flow, the water flow rate should be adjusted so that the residence time in the tank of pressurized hot water is about 5 to 120 minutes. Adjust and react for about 10 to 120 minutes.

  The reaction product of the pressurized hot water reactor 1 is supplied to the solid-liquid separator 2 and separated into a liquid saccharified portion of the hemicellulose decomposition product and a solid residue S containing cellulose and lignin. The liquid part is supplied to the second catalytic reactor 7, and the solid residue S is supplied to the beating machine 3.

In the beating machine 3, the solid residue S supplied from the solid-liquid separator 2 is beaten and a shearing force is applied. As a result, slack and gaps are generated between the fibers of the solid residue, resulting in a flexible porous shape. Increase significantly. The solid residue S may be beaten in either a dry or wet state, but if beaten in a water-containing state after the pressurized hot water reaction, the burden on the apparatus is small and the processing efficiency is good. Beating after the solid residue S 'having a specific surface area of preferably 50 m 2 / ^g approximately above, as more preferably a 80~300m 2 / ^g approximately, the beating conditions such as beating time and added load, the solid residue S Set appropriately according to the situation. The specific surface area of the solid residue used in the present invention is a value measured according to the BET method (N ₂ gas adsorption method) after subjecting the sample to pretreatment by vacuum heating and degassing (60 ° C., 6 hours). See example).

  The solid residue S ′ beaten by the beater 3 is supplied to the enzyme reaction apparatus 4, and an aqueous liquid containing cellulase, which is a saccharifying enzyme, is added and mixed to maintain the enzyme at an active temperature. The cellulose in the solid residue S ′ is decomposed by the action of cellulase, and a degradation product mainly containing cellobiose (a dimer of glucose) which is a water-soluble oligosaccharide is obtained as the primary saccharified solution C1 of cellulose. Cellulase is generally known as an aggregate of a plurality of types of saccharifying enzymes, and contains β-glucanase as a main component. β-glucanase is known as a saccharification enzyme that hydrolyzes cellulose into water-soluble oligosaccharides (2 to 6-mer of glucose). A part of the water-soluble oligosaccharide is decomposed into glucose by β-glucosidase contained in cellulase. The primary saccharified liquid C1 contains a water-soluble oligosaccharide and a water-insoluble suspended polysaccharide, and is a fluid liquid in which the suspended polysaccharide is dispersed in a water-containing liquid of the water-soluble oligosaccharide. Suspended polysaccharide is a partial degradation product of cellulose, which is a hexamer or higher glucose polymer or a cellohexaose crystal that is a hexamer of glucose, which can be decomposed into glucose by the subsequent solid acid catalyzed reaction. It is.

  As the saccharifying enzyme used in the enzyme reaction apparatus 4, a general saccharifying enzyme available as a commercial product can be used, and those commercially available as thermostable enzymes can also be used. The normal saccharifying enzyme has the maximum enzyme activity at about 40 to 50 ° C., and the thermostable enzyme has the maximum enzyme activity at about 70 to 90 ° C. Therefore, the temperature of the enzyme reaction apparatus 4 is set at the saccharifying enzyme used Depending on the conditions, appropriate adjustments may be made to obtain an appropriate enzyme activity. In order to facilitate the temperature adjustment of the enzyme reaction apparatus 4, it is preferable that the temperature of the solid residue S ′ introduced into the enzyme reaction apparatus 4 is about 90 to 100 ° C. A cooler for lowering the temperature of the solid residue after the water reaction may be provided at the front stage or the rear stage of the beating machine 3. When a thermostable enzyme is used, the cooling capacity of the cooler can be reduced, and the temperature of the enzyme reaction device 4 and the temperature of the first mixing device 5a can be brought close to each other. Can improve.

  When the solid residue S after the pressurized hot water reaction is subjected to a saccharification enzyme reaction without beating, the degradation rate is reduced by reducing the saccharification enzyme, and the degradation rate is also reduced ((a) to (a) in FIG. 2). (See (c)), however, when the solid residue S ′ subjected to the beating process is subjected to a saccharification enzyme reaction, it is possible not only to maintain the degradation rate to some extent even if the saccharification enzyme is reduced, but also in a suspended state by the saccharification enzyme The rate of degradation into polysaccharides increases and the degradation rate also increases (see (d) to (f) in FIG. 2). The reason for this is not clear, but it is necessary for the saccharifying enzyme in contact with the cellulose surface to move after decomposing at the contact site in order for the degradation reaction to proceed. It is considered that the decomposition into a suspended polysaccharide is facilitated. As a result, even if the amount of saccharifying enzyme used is reduced, cellulose can be exhausted and converted to the primary saccharified liquid C1 without extending the enzyme reaction time, and the primary saccharified liquid C1 can be converted into the primary saccharified liquid C1 by the subsequent solid acid catalytic reaction. The amount of monosaccharide from the suspended polysaccharide increases, and the monosaccharide recovery rate increases. Therefore, the beating treatment of the solid residue is extremely useful in a method for monosaccharideizing cellulose by an enzyme reaction and a solid acid catalytic reaction.

  When the primary saccharified liquid C1 produced in the enzyme reaction apparatus 4 is mixed and stirred with the solid acid catalyst X at a temperature of 90 ° C. or higher and lower than 120 ° C. in the first mixing apparatus 5a, the oligosaccharide and suspension of the primary saccharified liquid C1 are mixed. The polysaccharide is hydrolyzed satisfactorily by the action of the solid acid catalyst X to produce glucose (a monosaccharide constituting cellulose), and a secondary saccharified solution C2 containing glucose as a main component is obtained. Examples of the solid acid catalyst X to be used include inorganic solid acids such as zeolite, alumina and silica, and those in which acidic groups are introduced by sulfonation treatment of organic materials such as resins. A powdered or particulate solid acid catalyst is used. In the present invention, a sulfonated carbon type obtained by carbonizing an organic carbon material and then sulfonated is preferable. The sulfonated carbon-based solid acid catalyst is a solution of an amorphous black solid (carbide) obtained by heat-treating organic carbon materials such as woods and / or herbs in an inert gas atmosphere such as nitrogen. It is obtained by heat treatment in sulfuric acid to add a sulfone group to the carbide skeleton and washing with hot water. Carbonization and sulfonation may be performed at the same time, and the treatment temperature for carbonization and sulfonation is appropriately selected depending on the type of organic substance used. The amount of the solid acid catalyst X used is preferably 5 to 20% by mass with respect to the primary saccharified liquid C1. The reaction time may be about 1 to 10 hours in general.

  The reaction product that has finished the hydrolysis reaction in the first mixing device 5a is supplied to the first solid-liquid separation device 5b to precipitate the solid acid catalyst X in the reaction product. The secondary saccharified solution C2 mainly composed of glucose is separated as a supernatant, sent to the first fermentation apparatus 6, and the solid acid catalyst X separated by settling is recovered and then returned to the first mixing apparatus 5a to be used again. The

  The secondary saccharified solution C2 supplied from the first solid-liquid separation device 5b to the first fermentation device 6 is appropriately adjusted in water content and pH so as to be in a condition suitable for fermentation, and inoculated with fermenting microorganisms, and the fermentation stock solution The glucose is converted into ethanol by the action of the fermentation microorganism. As a fermentation microorganism used for ethanol fermentation, known ethanol fermentation microorganisms such as yeast can be used. Examples include Zymomonas mobilis and Kluyveromyces marxianus. Moreover, you may utilize the bacterium which introduce | transduced the enzyme gene which has the conversion ability to ethanol by gene recombination. The use of flocculent yeast is advantageous in solid-liquid separation after fermentation because of good sedimentation, and it is advantageous for yeast to use amino acids and the like degraded by hydrolyzing enzymes of surrounding microorganisms as nutrient sources. Since it is also a form, it is useful for improving fermentation efficiency. During fermentation, it is preferable to add a nutrient source necessary for the propagation and activity of the fermenting microorganisms and adjust to an optimum pH. In order for yeast to be active and proliferating, essential nutrients such as phosphorus, nitrogen and vitamins, and required trace elements such as Co, Ni, and Zn are necessary, and yeast used for the production of biomass ethanol is The ability to synthesize vitamins or amino acids may be low or lacking. As a nutrient source for fermentation microorganisms to which such necessary components are added from the outside, yeast extract, polypeptone and the like can be generally used. Alternatively, plant waste such as tea husk and coffee husk and algal crushed material may be used, and components contained in these cell protoplasts can be used as the nutrient source.

  The concentration of saccharified product (glucose) in the fermentation stock solution is adjusted to be about 1 to 20% by mass, preferably about 10% by mass. The addition amount of the nutrient source for microorganisms (in terms of dry matter) is appropriately adjusted according to the type of fermenting microorganism, and is generally set to about 0.1 to 1% by mass, preferably about 0.2 to 0.5% by mass. Good. The pH of the fermentation stock solution is adjusted to about 2.5 to 5.5, preferably about 3.0 to 5.5, inoculated with fermenting microorganisms at a rate of about 1 to 30 g / L, and a temperature of 30 to 37 ° C. Fermentation proceeds by holding for about 2 to 48 hours. For example, ethanol can be produced at a rate of about 20 to 25 g-ethanol / (L · h) using a fermentation stock solution having a glucose concentration of about 10% by mass.

  The fermentation product F1 that has undergone fermentation in the first fermentation apparatus 5 as described above is subjected to distillation apparatus 9 after removing solids (lignin, fermentation microorganisms, etc.) from the fermentation product F1 as necessary, by filtration or the like. The ethanol is recovered by distillation at You may distill as it is, without removing solid content from fermentation product F1. You may introduce | transduce into the biomass saccharification process the solid substance isolate | separated from the fermentation product F1.

  On the other hand, the hemicellulose-derived primary saccharified liquid H1 separated by the solid-liquid separator 2 is supplied to the second catalytic reactor 7 and the solid acid catalyst X and the primary acid catalyst X at a temperature of 90 ° C. or higher and lower than 120 ° C. in the second mixing device 7a. Mix and stir. The hemicellulose-derived oligosaccharides in the primary saccharified solution H1 are hydrolyzed by the action of the solid acid catalyst X to produce monosaccharides including xylose, arabinose (pentose sugar constituting hemicellulose), etc., and secondary saccharification including these Liquid H2 is obtained. The solid acid catalyst X used in the second catalytic reactor 7 can be appropriately selected from the same or different from those usable in the first catalytic reactor 5, and is sulfonated after carbonization of wood and / or herbs. The use of a sulfonated carbon material obtained by treatment is preferred. Also about the usage-amount of the solid acid catalyst X, 5-20 mass% is preferable with respect to the primary saccharified liquid H1 similarly to the 1st catalyst reaction apparatus 5, and reaction time should just be about 1 to 10 hours generally.

  The reaction product that has finished the hydrolysis reaction in the second mixing device 7a is charged into the second solid-liquid separation device 7b, where the solid acid catalyst X in the reaction product is allowed to settle, and the secondary saccharified solution H2 is used as a supernatant. To be separated. This is sent to the second fermentation apparatus 8. The solid acid catalyst X that has settled and separated is recovered and then returned to the second mixing device 7a to be used again.

  The secondary saccharified solution H2 supplied from the second solid-liquid separation device 7b to the second fermentation device 8 is appropriately adjusted in water content and pH so as to be in a condition suitable for fermentation, inoculated with fermenting microorganisms, and the fermentation stock solution And xylose or the like is converted into ethanol by the action of the fermentation microorganism. Examples of fermenting microorganisms used for ethanol fermentation include microorganisms having xylose fermentation ability, such as Saccharomyces yeasts and Rhizopus oryzae. Moreover, you may utilize the bacterium which introduce | transduced the enzyme gene which has the conversion ability to ethanol by gene recombination. The use of flocculent yeast is advantageous in solid-liquid separation after fermentation because of good sedimentation, and it is advantageous for yeast to use amino acids and the like degraded by hydrolyzing enzymes of surrounding microorganisms as nutrient sources. Since it is also a form, it is useful for improving fermentation efficiency.

  The fermentation product F2 that has undergone fermentation in the second fermentation apparatus 7 as described above is subjected to distillation apparatus 9 after removing solids (lignin, fermentation microorganisms, etc.) from the fermentation product F2 as necessary, by filtration or the like. Purified ethanol is recovered by distillation in You may distill as it is, without removing solid content from fermentation product F2. The solid separated from the fermentation product F2 may be introduced into the biomass saccharification step. The distillation of the fermentation product F2 can be performed together with or separately from the fermentation product F1 obtained from the first fermentation apparatus 5.

  In the ethanol production apparatus of FIG. 1, if a treatment device for removing lignin is provided before the solid residue S ′ after beating is put into the enzyme reaction device 4, the enzyme reaction device 4 can remove the solid residue S ′ from cellulose. Since the action efficiency of the saccharifying enzyme is improved, the decomposition rate of cellulose can be increased and the saccharification efficiency can be improved.

  Solid acid catalysts include powders and pellets. When pellets are used in the first catalyst reaction device 5 and the second catalyst reaction device 7, the solid acid catalyst may be made of a mesh or the like through which the liquid flows easily. The solid acid catalyst can be held in the permeable container and fixed in the primary saccharified liquids H1 and C1, and the primary saccharified liquid can be flowed between the solid acid catalyst pellets by flowing the primary saccharified liquid. . By adopting such a fixed bed type solid acid catalyst, it is possible to simplify the apparatus configuration relating to solid-liquid separation in the first catalytic reaction apparatus and the second catalytic reaction apparatus.

FIG. 3 (b) shows the relationship between the glucose production rate constant k _GP ⁰ and the glucose decomposition rate constant k _CD ⁰ in the solid acid catalyzed reaction and the temperature. From this graph, the solid acid catalyzed reaction is observed at 90 ° C. or higher. It turns out that it progresses well. It is understood that a reaction temperature of 100 ° C. or higher and lower than 120 ° C. is preferable in order to suppress the decomposition of glucose.

  Therefore, when a general saccharifying enzyme is used in the enzyme reaction apparatus 4, in order to bring the temperature of the enzyme reaction apparatus 4 close to the temperature of the first mixing apparatus 5a from the viewpoint of energy efficiency, the solid in the first mixing apparatus 5a The temperature of the acid catalyst reaction is set to a lower value of about 50 ° C. In this case, the speed of the solid acid catalyst reaction is reduced. To compensate for this, the solid acid catalyst used in the first mixing device 5a Increase X.

  Further, in the first fermentation apparatus and / or the second fermentation apparatus 6, alcohol such as butanol is used as a fermentation microorganism by using microorganisms such as Clostridium acetobutylicum, Clostridium beigelinki, Clostridium auran butyricum, Clostridium tetanomorphum, etc. It is possible to change so that it may manufacture by fermentation, acetone, etc., and it can apply to manufacture of useful alcohols and ketones other than ethanol. Similarly, it can be applied to the production of hydroxymethylfurfural and furfural.

<Saccharification without beating treatment>
(Pressurized hot water reaction of woody biomass)
As woody biomass, a sweet sorghum bagasse (moisture content of 30% by mass) of 300 g finely crushed is prepared and charged into a batch-type pressurized hot water reactor (OML-5 manufactured by Om Labtech Co., Ltd.). 3 L of pressurized hot water was supplied to react for 20 minutes. The reaction product is taken out from the pressurized hot water reactor and centrifuged at 3000 G for 15 minutes to remove the saccharified liquid derived from hemicellulose, and the solid residue S (1382 g-wet, moisture content 84.32 mass) is obtained. %).

(Saccharification enzyme reaction of solid residue S)
1.3 g of solid residue S was put in a vial, 1.7 ml of demineralized water was added, and three types of samples (a) to (c) to which saccharifying enzyme (cellulase CTec2 manufactured by NOVOZYME) was added at different ratios were added. Three pieces were prepared. The ratio of saccharifying enzyme added to each material was (a) 0.1 g-enzyme / g-cellulose, (b) 0.17 g-enzyme / g-cellulose, and (c) 0.25 g-enzyme / g-cellulose. It was. These were mounted on a test tube mixing stirrer (Rabinco Rock and Roller L201) and stirred at a speed of 10 rpm in a constant temperature bath at 50 ° C., and the reaction was allowed to proceed after 6 hours, 24 hours or 48 hours. And the yields of glucose in the sample (indicated by G in the figure), water-soluble cellooligosaccharide (OS), and suspended polysaccharide (PS, glucose polysaccharide having a polymerization degree of 7 to 3000) are as follows. Measured according to the operation. The results are shown in graphs (a) to (c) in FIG.

<Saccharification with beating treatment>
(Beat processing of solid residue)
A solid residue S was similarly prepared according to the above-mentioned pressurized hydrothermal reaction of woody biomass, and 127.55 g-wet was put into a zirconia container of a planetary ball mill (PRISCH P-5). Water is added to the solid residue S to adjust the total amount to 250 g. Using 25 zirconia balls (made by FRISCH) with a diameter of 20 mm, a beating process is performed for 60 minutes at a rotational speed of 250 rpm. Obtained.

(Saccharification enzyme reaction of solid residue S ')
1.3 g of solid residue S was put in a vial, 1.7 ml of demineralized water was added, and three samples (d) to (f) to which saccharifying enzyme (cellulase CTec2 manufactured by NOVOZYME) was added at different ratios were added. Prepared one by one. The ratio of saccharifying enzyme added to each material is (d) 0.1 g-enzyme / g-cellulose, (e) 0.17 g-enzyme / g-cellulose, and (f) 0.25 g-enzyme / g-cellulose. It was. These were mounted on a test tube mixing stirrer (Rabinco Rock and Roller L201) and stirred at a speed of 10 rpm in a constant temperature bath at 50 ° C., and the reaction was allowed to proceed after 6 hours, 24 hours or 48 hours. Was completed, and the yields of glucose (G), water-soluble cellooligosaccharide (OS), and suspended polysaccharide (PS, glucose polysaccharide having a polymerization degree of 7 to 3000) in the sample were measured according to the following procedure. The results are shown in the graphs (d) to (f) in Table 2.

<Measurement of sugar yield>
(Yield of glucose (G) and water-soluble cellooligosaccharide (OS))
The sample was filtered using glass fiber filter paper (manufactured by WHATMAN, model: 1821-047), and glucose and cellooligosaccharide having a polymerization degree of 2 to 6 contained in the obtained filtrate were analyzed using a high performance liquid chromatograph (HPLC). The yield of glucose (G) and water-soluble cellooligosaccharide (OS) was calculated as a mass ratio to the amount of cellulose in the solid residue.

(Yield of suspended polysaccharide (PS))
The sample was allowed to stand for 30 minutes, the supernatant was taken out using a pipette, and the total amount of sugar contained in the supernatant was measured according to the phenol-sulfuric acid method. From this total sugar amount, the amount of glucose and water-soluble cellooligosaccharide determined in the above-mentioned measurement of glucose and water-soluble oligosaccharide is subtracted to obtain the amount of suspended polysaccharide contained in the supernatant, and relative to the amount of cellulose in the solid residue. The yield of suspended polysaccharide (PS) was calculated as a mass ratio.

<Comparison with and without beating process>
Since almost no water-soluble cellooligosaccharide (OS) is found in the measurement result of the sugar yield, the hydrolysis of the oligosaccharide proceeds easily in the above saccharifying enzyme reaction.

  The results of (a) to (c) in FIG. 2 regarding the yield of glucose (G) reveal that when the saccharifying enzyme reaction is carried out without the beating treatment, the amount of added saccharification reduces the saccharification rate. It becomes difficult to shorten the reaction time. Compared to this, in the results of (d) to (f) in FIG. 2 in which the saccharifying enzyme reaction was performed after the beating treatment, the yield of glucose generally increased and the amount of enzyme added was reduced. The sugar yield is difficult to decrease and the saccharification rate can be maintained considerably. Furthermore, when (a)-(c) and (d)-(f) of FIG. 2 are compared about the yield of suspended polysaccharide (PS), in the sample which passed through the beating process, suspension polysaccharide (PS) Since the yield is high, particularly in the case where the amount of the enzyme added is small (d) or in the result of the initial reaction (6 hours), the suspension polysaccharide (PS) is likely to be generated by the beating process. it is obvious. This is because when the sample was allowed to stand in the measurement of the yield of the suspended polysaccharide, the presence of the precipitated solid residue found in the samples (a) to (c) (e), (f) and 24 It can also be understood from the fact that it was hardly seen in the sample of (d) which was subjected to abnormal reaction for a time.

  In the saccharification enzyme reaction, if the reaction time is extended, all can be decomposed into glucose, but this is not efficient because the saccharification rate gradually decreases. In contrast, suspended polysaccharide (PS) and water-soluble cellooligosaccharide (OS) can be easily decomposed into glucose by a solid acid catalyzed reaction (see Example 2). If it decomposes into polysaccharide (PS), it can be monosaccharided by solid acid catalyzed reaction. That is, by performing a saccharification enzyme reaction for 24 hours for the sample (d) and 6 hours for the samples (e) and (f), a primary saccharified solution that can be sufficiently mono-saccharified by a solid acid catalytic reaction is obtained. Therefore, the beating process that can promote the production of suspended polysaccharide in the saccharifying enzyme reaction is extremely useful for the process of mono-saccharifying cellulosic biomass by a combination of saccharifying enzyme reaction and solid acid catalyzed reaction. This is an extremely effective means that can shorten the saccharifying enzyme reaction time and the amount of added enzyme without lowering the pH.

<Specific surface area of solid residue>
The specific surface area of the solid residue S obtained by the pressurized hot water reaction and the solid residue S ′ after the beating treatment was measured according to the following operation.

(Dehydration treatment)
20 ml each of 30%, 50%, 70%, 90%, 95% and 99% (hydrous) ethanol was prepared.

  Remove 10 g of solid residue as a sample, put it in a container, and use it in order from the lowest concentration of ethanol, and remove water from the sample by repeatedly immersing the sample in ethanol (15 minutes) and removing the ethanol by decantation. did. In addition, the container was covered at the time of immersion.

(Immobilization process)
T-Butanol was added to the sample after the dehydration treatment, the sample was immersed, and allowed to stand for 15 minutes. Thereafter, t-butanol was removed by decantation. After repeating this immersion and decantation 5 times, t-butanol was added again to immerse the sample, the container was covered with a lid, sealed, and allowed to stand in the refrigerator for 10 minutes. After confirming that t-butanol had solidified, the container taken out from the refrigerator was transferred into a vacuum desiccator, the lid was removed, and the desiccator was decompressed to distill off t-butanol.

(Specific surface area measurement)
Using AUTO SORB-1MP manufactured by Cantachrome Co., Ltd. as a measuring device, vacuum heating and degassing at 60 ° C. was performed for 6 hours as a pretreatment, and then the specific surface area of the sample was determined by the BET method (N2 gas adsorption method). Was measured (see JIS Z8830).

As a result of the measurement, the specific surface area of the solid residue S not subjected to the beating process was 45 m ² / g, and the specific surface area of the solid residue S ′ subjected to the beating process was 91 m ² / g.

  As woody biomass, a sweet sorghum bagasse (moisture content of 30% by mass) of 300 g finely crushed is prepared and charged into a batch-type pressurized hot water reactor (OML-5 manufactured by Om Labtech Co., Ltd.). 3 L of pressurized hot water was supplied to react for 20 minutes. The reaction product was taken out from the pressurized hot water reactor, and the saccharified solution derived from hemicellulose was removed by centrifuging for 15 minutes by applying a centrifugal force of 3000G. From the obtained solid residue 1382 g (water content 84.32% by mass), 127.55 g of the solid residue was fractionated and used as the solid residue S in the following operation.

  The saccharification enzyme (cellulase CTec2 manufactured by NOVOZYME) was added to the solid residue S at a rate of 1.5 g / L, the temperature was kept at 50 ° C., and the mixture was stirred at a speed of 100 rpm using a stirrer. Proceeded. Samples of reaction products at reaction times of 12 hours and 40 hours were sampled, and the saccharifying enzyme reaction was completed in 40 hours.

  By preparing 75 g of a carbon-based solid acid catalyst obtained by sulfonating amorphous carbide, maintaining the temperature at 90 to 100 ° C. in addition to the product of the saccharifying enzyme reaction described above, and stirring at a speed of 200 rpm using a stirrer The solid acid catalyst reaction was carried out for 5 hours.

  Concentrations of glucose, water-soluble cellooligosaccharides and suspended polysaccharides were measured for samples with saccharifying enzyme reaction times of 12 hours and 40 hours and products after the solid acid catalyzed reaction. The results are shown in the bar graph of FIG.

Also, a cellobiose aqueous solution having a concentration of 10% by mass was prepared, and the same solid acid catalyst as described above was added at a rate of 15% by mass with respect to the cellobiose aqueous solution, and the solid acid catalyst reaction was carried out at a constant reaction temperature for a certain period of time. By measuring the later composition, the glucose production rate constant K _GP ⁰ and the glucose degradation rate constant K _GD ⁰ were calculated. At that time, the reaction temperature was changed within a range of 25 to 130 ° C., and the temperature dependency was examined. The results are shown in FIG.

  According to the graph of FIG. 3 (a), it is understood that the water-soluble oligosaccharide and suspended polysaccharide derived from cellulose are well hydrolyzed by the solid acid catalyst and efficiently monosaccharideized. Therefore, it is possible to efficiently saccharify and to shorten the treatment time by shifting to a solid acid catalyzed reaction in a partially saccharified state, rather than completely saccharifying by saccharifying enzyme reaction time. Considering this result, it is clear that the beating treatment shown in Example 1 is very significant in shortening the saccharifying enzyme reaction time and reducing the amount of enzyme.

  The present invention can be economically and rationally processed using resources that do not cause a rise in food prices when producing biomass ethanol from plant waste as biomass. Therefore, it is highly useful and can contribute to the promotion of recycling and environmental protection.

A: Ethanol production apparatus 1: Pressurized hot water reactor 1a: Pump
1b: heater, 1c: water amount adjustment valve, 1d: reaction tank, 1e: control device,
2: solid-liquid separator, 3: beating machine, 4: enzyme reaction device, 5: first catalytic reaction device,
5a: 1st mixing apparatus, 5b: 1st solid-liquid separation apparatus, 6: 1st fermentation apparatus,
7: second catalytic reaction device, 7a: second mixing device, 7b: second solid-liquid separation device,
8: Second fermentation device, 9: Distillation device, 10: Waste water treatment device,
B: Biomass, E: Ethanol, W: Water, W ′: Pressurized hot water,
X: solid acid catalyst, S, S ′: solid residue, H1, C1: primary saccharified solution,
H2, C2: secondary saccharified solution, F1, F2: fermentation product, D: wastewater.

Claims (15)

A pressurized hot water reaction step of selectively decomposing hemicellulose contained in the biomass by applying pressurized hot water to the biomass;
Beating treatment step of beating the solid residue after the pressurized hot water reaction step;
A primary saccharification step in which a saccharification enzyme is allowed to act on the solid residue after the beating treatment step;
A method for producing a monosaccharide, comprising a secondary saccharification step in which a solid acid catalyst is allowed to act on the product of the primary saccharification step. The method for producing a monosaccharide according to claim 1, wherein a specific surface area of the solid residue is increased to 50 m ² / g or more by the beating treatment step.   The method for producing a monosaccharide according to claim 1 or 2, wherein the beating treatment step is a wet treatment.   The method for producing a monosaccharide according to any one of claims 1 to 3, wherein in the primary saccharification step, the solid residue cellulose is decomposed to produce a liquid containing a suspended polysaccharide having a degree of polymerization of 7 to 3000.   The method for producing a monosaccharide according to claim 4, wherein in the secondary saccharification step, the suspended polysaccharide is decomposed to produce glucose as a monosaccharide.   Furthermore, the manufacturing method of the monosaccharide in any one of Claims 1-5 which has the isolation | separation process which isolate | separates the solid residue after the said pressurized hot water reaction process from the decomposition product of hemicellulose before the said beating process process.   Furthermore, the monosaccharide in any one of Claims 1-6 which has a hemicellulose saccharification process which makes a solid acid catalyst act on the decomposition product of the hemicellulose produced | generated in the said pressurized hydrothermal reaction process, and produces | generates xylose as a monosaccharide. Manufacturing method.   The manufacturing method of ethanol which has a fermentation process which ferments the monosaccharide obtained by the manufacturing method of the monosaccharide in any one of Claims 1-6, and produces | generates ethanol.   Furthermore, the manufacturing method of ethanol of Claim 8 which has the refinement | purification process which refine | purifies ethanol contained in the product by the said fermentation process. A pressurized hot water reactor for selectively decomposing hemicellulose contained in biomass by applying pressurized hot water to the biomass;
A beating machine for beating the solid residue obtained from the reaction product of the pressurized hot water reactor;
An enzyme reaction device for allowing a saccharifying enzyme to act on the solid residue beaten by the beater;
A monosaccharide production apparatus comprising: a catalytic reaction apparatus that causes a solid acid catalyst to act on a reaction product of the enzyme reaction apparatus.   And a separation device for separating the reaction product of the pressurized hot water reaction device into a solid residue and a decomposition product of hemicellulose, and the solid residue separated by the separation device is supplied to the beater. Item 11. A monosaccharide production apparatus according to Item 10.   The monosaccharide production apparatus according to claim 10 or 11, further comprising a separation device for separating and recovering the solid acid catalyst from a reaction product of the catalytic reaction device.   Furthermore, it has a hemicellulose type | system | group catalytic reactor which makes a solid acid catalyst act on the decomposition product of hemicellulose produced | generated by the said pressurized hot water reactor, and produces | generates xylose as a monosaccharide. Monosaccharide production equipment. The monosaccharide production apparatus according to any one of claims 10 to 13,
An ethanol production apparatus comprising: a fermentation apparatus that ferments a monosaccharide obtained by the monosaccharide production apparatus to produce ethanol.   Furthermore, the ethanol production apparatus of Claim 14 which has a distillation apparatus which refine | purifies ethanol contained in the product of the said fermentation apparatus.

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