TWI554611B - Method for producing sugar - Google Patents

Description

Sugar manufacturing method

The present invention relates to a method for producing a highly productive sugar using cellulose-based biomass as a raw material, a sugar, and a device for producing the sugar.

Biomass refers to renewable resources from living organisms and can be defined as “renewable organic resources derived from living organisms other than fossil resources”. Among the raw materials, an unutilized plant such as a stem of a starch-based crop such as thinned wood, a rice stem, a wheat stem, a brown rice shell, a maize or a sugar cane, or an oil coconut shell (EFB) is sought. The effective use of biomass.

Among the components of the plant-derived biomass, many polysaccharides such as starch can be easily decomposed into monosaccharides by an enzyme to be used as an energy source or a foodstuff. Therefore, in order to effectively utilize plant-based biomass, it is important to use a high proportion of cellulose in plant cells to be decomposed into methane or monosaccharide (glucose) for use as an energy source or a foodstuff. However, as is well known, cellulose is formed into a large part of the cell wall, has a strong structure and is difficult to be decomposed, and thus has not been effectively utilized in the present state.

Specifically, cellulose has the following multiple structures in the cell wall. Most of the cellulose forming the cell wall has a quasi-crystalline structure called a microfibril which is linearly adhered. The cellulose (microfibers) having such a quasi-crystalline structure are bonded to each other via a non-cellulose component such as hemicellulose or lignin. These cellulose components (microfibers) and non-cellulosic components are usually arranged in a state of a larger structure called a fibril. This fiber is usually laminated to form a cell wall. Having the above quasi-crystalline structure In the cellulose (microfiber), the polymer chain of cellulose is strongly bonded by hydrogen bonding. By this hydrogen bond, plants can have strong cell walls.

As means for decomposing cellulose having such a structure into methane, there is a method of decomposing and utilizing anaerobic microorganisms. However, the decomposition of cellulose by microorganisms is insufficient in practical use due to reasons such as complicated reaction control.

On the other hand, it is also possible to chemically hydrolyze cellulose into monosaccharides using a catalyst or an enzyme. Monosaccharides obtained by chemical decomposition of cellulose, for example, can be converted into ethanol by fermentation, and can be used as an energy source in an internal combustion engine or a turbine. However, in order to chemically directly hydrolyze cellulose-derived biomass from plants, the efficiency is not good based on the molecular structure of cellulose in the cell wall described above. The reason for this is that we believe that the strong structure of cellulose hinders the entry of water and enzymes into the quasi-crystalline structure, which greatly reduces the effect of cellulolytic enzymes. That is, since the enzyme does not easily enter the inside of the quasi-crystalline structure strongly bonded by hydrogen bonding, the glycoside bond cannot be directly decomposed. Therefore, the enzyme can only be slowly decomposed from the surface, so the hydrolysis of the cellulose-based biomass directly by the enzyme is not efficient.

Therefore, a method of producing a cellulose which is easily hydrolyzed by finely subdividing the cellulose-based biomass before it is hydrolyzed by an enzyme has been proposed. This method basically utilizes the following effects, even if the cellulose having a quasi-crystalline structure is slowly hydrated, thereby hydrating to weaken the chemical interaction of hydrogen bonds between polymer chains of adjacent cellulose, and borrowing Mechanically exerting force to break the cellulose polymer chain by impacting, kneading, etc. the cellulose-based biomass The physical role. For the specific content of the method, for example, (1) stirring the suspension of the cellulose-based green matter-producing particles in the container, and then heating the float of the particles while slowly stirring the water while continuing to stir. The technique of hydrating to produce a fine powder (Japanese Patent Publication No. 2004-526008); (2) mixing and stirring a cellulose-based green material with a water-soluble polymer aqueous solution having a viscosity to cause agitation The mechanical force is effectively transmitted to the cellulose polymer chain, and the cellulose polymer chains are separated from each other to break them (International Publication No. 2009/124072).

However, in the technique of (1), a device for causing fine particles of cellulose-based biomass to exist as a float is complicated, and a large amount of energy is consumed when using this technique, which is not high productivity. On the other hand, in the technique of (2), since a water-soluble polymer for imparting viscosity to an aqueous solution is used, it has been confirmed that the cellulose-based biomass can be easily hydrolyzed to some extent. However, the use of a water-soluble polymer, a gelling agent, etc., has high productivity in raw materials, waste treatment, wastewater treatment, etc., and productivity is low, and the manufacture of the sugar has not been put into practical use.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2004-526008

[Patent Document 2] International Publication No. 2009/124072

The present invention has been accomplished based on the above circumstances, and an object of the invention is to provide a method for producing a highly productive sugar using cellulose-based biomass as a raw material. A sugar obtained by the production method and a device for producing the sugar.

In order to solve the above problems, the method for producing a sugar of the present invention is a method for producing a sugar using a cellulose-based raw material as a raw material, which is characterized in that it has a step of obtaining a cellulose-containing biomass and a hydrophilic polymerization. a step of mixing a mixture of a substance and water, applying a shear force to the mixture to break the cellulosic biomass, and saccharifying the saccharification step of the cellulose by the cellulolytic enzyme The inorganic salt is added to the mixture subjected to the above saccharification step, and the first separation step of the sugar liquid and the first residue is separated, and at least a part of the first residue is further added to the mixture in the mixing step for the reuse step.

According to this production method, the sugar can be easily obtained from the mixture in the state of the sugar liquid by the first separation step. Moreover, in this production method, at least a part of the first residue containing the decomposed cellulose-based biomass or the hydrophilic polymer is reused, so that the raw material cost, the waste disposal fee, and the like can be reduced. Thus, the manufacturing method has excellent productivity.

Further, it has a second separation step of diluting at least a portion of the first residue obtained in the first separation step with an aqueous solvent, and separating into a hydrophilic polymer solution and a second residue, preferably added in the above-mentioned recycling step. At least a portion of the first residue is a hydrophilic polymer dissolved in the second separation step At least a portion of the liquid. By such a second separation step, the hydrophilic polymer or the like contained in the hydrophilic polymer solution can be reused efficiently.

Preferably, the aqueous solvent used in the second separation step is acidic. By using an acidic aqueous solvent (aqueous solution) in the second separation step, the decomposition ability of the solution and the solid component can be improved, and recyclability, productivity, and the like can be improved.

Preferably, the mixture in the above mixing step further contains a gelling agent. By adding a gelling agent to the mixture to gelatinize it, in the subsequent breaking step, since the initial kneading stage of the mixture has high viscosity, the physical effect of the kneading can be effectively transmitted to the cellulose. It is a raw material and can effectively break the cellulose-based biomass into molecular layers. Furthermore, by using a colloidal aqueous hydrophilic polymer solution, the colloidal hydrophilic polymer aqueous solution can enter between the separated cellulose chains and stay, thereby preventing recrystallization of the cellulose chain. Improve the ability to break.

It is preferable to further contact at least a part of the mixture subjected to the saccharification step with an aqueous colloid or an ion exchange resin containing a polyvinyl alcohol-based polymer (hereinafter also referred to as "PVA") as a main component, so that the gelling agent is as described above. A gelling agent separation step for separating the mixture. By having the above-mentioned gelling agent separation step, it is possible to achieve reuse of the separated gelling agent, reduce waste to be treated, and reduce impurities (for example, boric acid, etc.) in the wastewater. Therefore, by using the production method having the gelation agent separation step, the total cost at the time of sugar production can be further reduced, and the productivity is excellent. Further, in the gelling agent separation step, in the case of using an aqueous colloid containing PVA as a main component, the gel can be adsorbed by adsorbing the gelling agent in the aqueous colloid. The agent is separated. In this case, the adsorbed gelling agent (borate or the like) can be detached from the aqueous colloid by being in an acidic state, and the hydrocolloid adsorbing the gelling agent can be directly used in the step of the mixture, and the efficiency is good.

Preferably, in the gelling agent separation step, at least a portion of the mixture in contact with the aqueous colloid or ion exchange resin is at least a portion of the first residue. In this manner, since the gelling agent is separated from at least a part of the first residue, impurities in at least a part of the first residue can be removed, and the range in which the hydrophilic polymer solution or the like is used can be expanded.

It is preferred that at least a part of the first residue used in the gelling agent separation step is the hydrophilic polymer solution. Thus, the hydrophilic polymer solution from which the solid component or the like is removed and the aqueous colloid are brought into contact with the ion exchange resin, whereby the gelation agent can be efficiently separated.

Preferably, the method further comprises a third separation step of separating the second residue into a separation liquid and a third residue by using an aqueous solvent, and at least a part of the mixture in contact with the aqueous colloid or the ion exchange resin in the gelling agent separation step. It is the above separation liquid. By such a step, the recovery rate of the gelling agent can be increased, and the concentration of boric acid in the wastewater in the system (for example, the separation liquid subjected to the third separation step) can be lowered.

Preferably, the aqueous solvent is acidic. By using an acidic aqueous solvent (aqueous solution) in the third separation step, the decomposition ability of the solution and the solid component can be improved, and the recyclability, productivity, and the like can be improved.

It is preferred to further have a gelling agent recycling step of adding at least a part of the gelling agent separated in the above gelling agent separation step to the mixture in the above mixing step. Due to the above-mentioned gelling agent reuse step In turn, the gelling agent can be reused, which can reduce the cost and further improve the productivity.

Preferably, the aqueous gel system described above is formed by chemical crosslinking of PVA. By using an aqueous colloid composed of a crosslinked PVA, durability and the like of the hydrocolloid can be improved, and productivity can be further improved.

The above hydrophilic polymer is preferably PVA. By using PVA as the hydrophilic polymer, work efficiency and the like in the breaking step can be improved, so that productivity can be further improved.

Preferably, the above gelling agent is boric acid or borate. By using boric acid or a borate as a gelling agent, the mixture can be gelled into a preferred state, and the productivity of the sugar in the production method can be further improved.

The inorganic salt is preferably at least one selected from the group consisting of sulfates, carbonates, nitrates, phosphates, and hydrogencarbonates. By using the above-mentioned inorganic salt, the precipitation of the hydrophilic polymer and the gelling agent, and the aggregation and precipitation of the precipitate and the decomposed cellulose-based biomass can be efficiently performed, and the productivity of the sugar can be improved.

The mixing step, the breaking step, the saccharification step, the first separation step, and the reuse step are preferably carried out in sequence, and the plurality of times are repeated. By performing the series of steps in a plurality of times, the recyclability can be improved, and the cost reduction and high productivity can be achieved.

The sugar of the present invention is obtained by the production method. Since the sugar is obtained under a stable and mild condition without a heating process or the like, the content of a high value-added component such as xylose is also high.

The sugar producing apparatus of the present invention is provided to obtain a cellulose-containing biomass, a hydrophilic polymer, and water. a mixing means of the mixture, a cutting means for applying a shear force to the mixture to break the cellulose-based biomass, and the inorganic salt is added to the saccharification means for saccharifying the cellulose-based biomass by the cellulolytic enzyme The mixture of the above saccharification step is separated into a first separation means for the sugar liquid and the first residue.

According to this manufacturing apparatus, the first residue separated by the separation means can be easily added to the mixture in the mixing means, and the cost can be reduced by recycling and the waste can be reduced.

Here, the "part" of the first residue, the mixture or the hydrophilic polymer solution also contains a part of the components contained in the first residue. That is, for example, the "one part of the first residue" may be a part of the first residue in the state obtained by the first separation step, or the first residue may be refined by the second separation step or the like (for example, One part of a hydrophilic polymer solution, etc.).

As described above, according to the method for producing a sugar of the present invention, sugar can be obtained with high productivity by using cellulose-based biomass as a raw material. Therefore, according to the present invention, the biomass raw material of the plant system can be effectively utilized as a food or energy resource, and the practicality of the biomass utilization can be improved.

[Formation of the Invention]

The method for producing the sugar of the present invention, the sugar and sugar producing apparatus will be described in detail below.

<Method of manufacturing sugar>

The method for producing a sugar of the present invention comprises a cellulose-based biomass as a raw material, and has a step of obtaining a mixing step of a mixture containing a cellulose-based biomass, a hydrophilic polymer and water, and applying a shear force to the mixture. a step of dividing the cellulose-based biomass into a saccharification step of saccharifying the cellulose-based biomass by cellulolytic enzyme, adding an inorganic salt to the mixture subjected to the saccharification step, and separating into a sugar liquid And a first separation step of the first residue, wherein at least a portion of the first residue is further added to the reuse step in the mixture in the mixing step.

According to this production method, the sugar can be easily obtained from the mixture in the state of the sugar liquid by the first separation step. Moreover, in this production method, at least a part of the first residue containing the decomposed cellulose-based biomass or the hydrophilic polymer is reused, so that the raw material cost, the waste disposal fee, and the like can be reduced. Thus, the manufacturing method has excellent productivity.

The manufacturing method has a second separation step of diluting at least a part of the first residue obtained in the first separation step with an aqueous solvent, and separating the hydrophilic polymer solution and the second residue, preferably in the above-mentioned recycling step. At least a portion of the first residue is at least a portion of the hydrophilic polymer solution separated in the second separation step. By such a second separation step, the hydrophilicity contained in the hydrophilic polymer solution can be reused efficiently A polymer and a gelling agent added as a preferred component.

Preferably, the manufacturing method further comprises a gelling agent separation step of contacting at least a portion of the mixture subjected to the saccharification step with an aqueous colloid or ion exchange resin containing PVA as a main component to separate the gelling agent from the mixture. By having the above-mentioned gelling agent separation step, it is possible to achieve reuse of the separated gelling agent, reduce waste to be treated, and reduce impurities (for example, boric acid, etc.) in the wastewater. Therefore, by using the production method having the gelation agent separation step, the total cost at the time of sugar production can be further reduced, and the productivity is excellent. Further, in the gelating agent separating step, in the case of using an aqueous colloid containing PVA as a main component, the gelling agent can be separated by adsorbing the gelling agent in the aqueous colloid. In this case, the adsorbed gelling agent (borate or the like) can be detached from the aqueous colloid by being in an acidic state, and the hydrocolloid adsorbing the gelling agent can be directly used in the step of the mixture, and the efficiency is good.

Preferably, the manufacturing method further comprises a third separation step of separating the second residue into a separation liquid and a third residue by using an aqueous solvent, and contacting the aqueous colloid or the ion exchange resin in the gelling agent separation step. At least a portion of the above separation liquid. By such a step, the recovery rate of the gelling agent can be increased, and the concentration of boric acid in the wastewater in the system (for example, the separation liquid subjected to the third separation step) can be lowered.

It is preferred to further have a gelling agent recycling step of adding at least a part of the gelling agent separated in the above gelling agent separation step to the mixture in the above mixing step. By reusing the gelling agent with the above-mentioned gelling agent recycling step, the cost can be reduced and the production can be further improved. Sex.

Further, the mixing step, the breaking step, the saccharification step, the first separating step, and the recycling step are preferably carried out in sequence, and the plurality of times are repeated. By performing the series of steps in a plurality of times, the recyclability can be improved, and the cost reduction and high productivity can be achieved. Further, in the case of the preferred step, in the case where the second separation step, the gelation agent separation step, the third separation step, and the gelling agent reuse step are provided, it is preferred to repeat the steps in combination with these steps.

It is preferable that the production method further includes a cellulose-based raw material raw material cutting step (raw material cutting step) for cutting the cellulose-based raw material to make the cellulose-based biomass suitable. The step of sizing particles.

Referring to Fig. 1, one of the manufacturing methods will be described in the order of the manufacturing steps, for example, as follows.

(1) Cellulose-based raw material cutting step

In this step, in order to efficiently carry out the treatment in the following steps, the cellulose-based raw material is cut into particles of an appropriate size. The cellulose-based raw material to be used herein is not particularly limited, and a plant-derived biomass can be preferably used. Specifically, for example, wood such as thinned wood, rice stem, wheat stem, brown rice shell, maize or A stem of a starch-based crop such as sugar cane, an oil coconut shell (EFB), a shell of a coconut fruit, and the like. When the non-essential components such as soil are removed as much as possible, the cellulose-based raw material is reduced to a particulate form by cutting, breaking, or the like. In the cutting step, for example, a breaker described in JP-A-2004-526008 or a device used for producing pulp can be suitably used.

The size of the cellulose-derived green material subjected to the cutting step is preferably 2 mm or less, more preferably 1 mm or less, particularly preferably 100 μm or less, and even more preferably 20 μm or more and 70 μm or less. By setting the average particle diameter of the cellulose-based green particles to 2 mm or less, the subsequent mixing step, particularly the breaking step, can be efficiently carried out, and cellulose having excellent hydrolyzability can be obtained in a short time.

(2) mixing step

In this step, the cellulose-based biomass, the hydrophilic polymer, and water are mixed to obtain such a mixture. Also, the mixture may further contain other ingredients. The mixing method is not particularly limited, and for example, (2-1) a hydrophilic polymer is dissolved in water to form an aqueous solution (aqueous solution preparation step), and (2-2) a gelling agent is added to the aqueous solution as needed. The gelatinization step (gelation step) and (2-3) addition of the cellulose-based biomass to the aqueous hydrophilic polymer solution (addition step).

(2-1) Aqueous solution preparation step

In this step, the hydrophilic polymer is dissolved in water to form an aqueous solution. The concentration of the hydrophilic polymer aqueous solution is not particularly limited, but is preferably 3% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less. By setting the concentration of the hydrophilic polymer aqueous solution to the above range, it is possible to impart an appropriate viscosity to the aqueous solution. Therefore, by setting the concentration of the hydrophilic polymer aqueous solution to the above range, the permeated aqueous solution can efficiently transmit a physical force to the cellulose-based biomass during kneading, that is, the cellulose chain can be pulled by the aqueous solution. By opening, the cellulose-based biomass can be effectively separated into molecular layers. In the case where the concentration of the aqueous solution of the hydrophilic polymer is less than 3% by mass, since the aqueous solution does not have an appropriate viscosity, there will be It is impossible to give full play to the function of the breaking function that utilizes physical effects. On the other hand, when the concentration of the aqueous solution of the hydrophilic polymer exceeds 30% by mass, the viscosity of the aqueous solution is too high to be kneaded, so that the workability in the breaking step is lowered.

(2-2) Gelation step

Preferably, the gelling agent is added to the hydrophilic polymer aqueous solution to be gelled before the cellulose-based biomass particles obtained by the cellulose-based raw material cutting step are mixed with the hydrophilic polymer aqueous solution. . By using such a gelled hydrophilic polymer aqueous solution, the viscous physical action can be effectively transmitted to the cellulose-based biomass in the subsequent stage of the kneading step in which the mixture is highly viscous. It can effectively break the cellulose-based biomass into molecular layers. Furthermore, by using a colloidal aqueous hydrophilic polymer solution, the colloidal hydrophilic polymer aqueous solution can enter between the separated cellulose chains and stay, thereby preventing recrystallization of the cellulose chain. Improve the ability to break.

The gelling agent is not particularly limited as long as it can gel the hydrophilic polymer aqueous solution, and a known one can be used, and for example, boric acid, borate, titanium acetate, or other metal salt is preferable. Among these, boric acid or borate is preferred. By using boric acid or borate as a gelling agent, the mixture can be gelled to an appropriate state, so that the productivity of sugar can be further improved.

In the case where the aqueous solution of the hydrophilic polymer is gelled by the addition of the borate, for example, 1 to 10 parts by mass of a saturated aqueous solution of sodium tetraborate may be added to 100 parts by mass of the hydrophilic polymer aqueous solution of 5% by mass. The aqueous solution of the hydrophilic polymer thus obtained as a gel has the manufacturing The proper viscosity in the method, and even if it is mixed with the cellulose-based biomass and the kneading viscosity is continued, it does not rise (harden), and the kneading can be performed easily and efficiently. Further, it is preferable that the colloidal hydrophilic polymer aqueous solution is acidic, and specifically, the pH is preferably 4 or more and 7 or less.

(2-3) Adding steps

Next, in the aqueous hydrophilic polymer solution gelatinized by the above-described steps, the cellulose-based biomass which has been cut into a preferred size by the above-described steps is mixed to obtain a mixture containing the above. Further, the cellulose-based biomass may be mixed into the ungelatinized aqueous hydrophilic polymer solution without passing through the (2-2) gelation step, and mixed to obtain a mixture.

The amount of the cellulose-based biomass to be mixed is not particularly limited, and is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less based on the total amount of the cellulose-based biomass of the mixture. the following. When the amount of the cellulose-based biomass is less than 5% by mass, the viscosity of the mixture is low, so that the mechanical function of the breaking function cannot be sufficiently exhibited, and the handling amount of the cellulose-based raw material is low. Reduced work efficiency. On the other hand, when the amount of the cellulose-based biomass is more than 50% by mass, the cellulose-based biomass is highly absorbent, and the viscosity of the mixture is too high to be easily kneaded, so workability is lowered. The viscosity of the mixture is preferably, for example, 5.0 × 10 ⁴ mPa. s above 1.0 × 10 ⁶ mPa. s below.

(3) Breaking step

In this step, the cellulose-based biomass is separated into molecular layers (quasi-crystal structure level) by applying a shear force to the mixture obtained in the above mixing step. That is, the cellulose having a quasi-crystalline structure is partially hydrated, and the hydrophilic polymer enters to weaken the hydrogen bond between the cellulose molecules. The microscopic structure of the cell wall is separated by pulling the cellulose apart from each other by a physical force applying a shear force in a state in which the intermolecular bonds are weakened.

Here, in the case of using an aqueous solution (mixture) of a hydrophilic polymer added as a gelatinous agent, it is possible to make a mixture having a better viscosity since the initial stage of applying the shearing force, and it is efficient. The cellulose-based biomass is separated into sub-layers.

The method of applying shearing force to the mixture in the breaking step is not particularly limited, and examples thereof include a method of kneading a mixture. Moreover, the apparatus used in the breaking step is not particularly limited, and a biaxial extrusion molding machine or the like which is usually used in molding of a thermoplastic resin can be suitably used. The time required for this breaking step can be appropriately set depending on the amount of the mixture or the like, for example, within about 30 minutes to 10 hours. Further, in the case where the viscosity is reduced at the time of the breaking step, the viscosity can be adjusted by appropriately adding an aqueous solution of sodium tetraborate or the like.

(4) Saccharification step

In this step, a cellulolytic enzyme is added to a mixture containing cellulose-based biomass which has been separated by the above-described breaking step, and saccharification is carried out. By this saccharification, the cellulose-based biomass is easily decomposed (saccharified) into glucose and eluted into an aqueous solution. Further, xylose or the like derived from hemicellulose contained in the cellulose-based biomass is also dissolved in the aqueous solution. At this time, the lignin contained in the cellulose-based biomass may exist in the state of insoluble particles, and the lignin may be separated by, for example, filtration or centrifugation. The sugar such as soluble glucose obtained in this manner can be used as ethanol by fermentation, and can be suitably used as a fuel resource or the like.

The cellulolytic enzyme is not particularly limited, and can be used in the week. Known, for example, cellulase, pectinase, hemicellulase, β-polyglucose, polyxylase, polymannase, amylase, meicelase, leucocystis cellulase (by Acremonium) Cellulase obtained from cellulolyticus) and the like. These may be used alone or in combination of two or more.

The amount of the cellulolytic enzyme to be added is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.3 parts by mass or more and 5 parts by mass or less based on 100 parts by mass of the cellulose-based biomass.

Further, it is preferred to carry out saccharification after stirring to add the cellulolytic enzyme to the mixture. The stirring time can be, for example, 1 hour or longer and 12 hours or shorter.

The temperature of the mixture in the saccharification step can be appropriately set depending on the type of the enzyme, and is preferably, for example, 30 ° C or more and 70 ° C or less, preferably 40 ° C or more and 60 ° C or less.

Further, the pH of the mixture in the saccharification step may be appropriately adjusted depending on the type of the enzyme or the like, and is preferably adjusted to, for example, pH 5 to 7. This pH adjustment can be adjusted by adding a well-known acid or base to the mixture.

(5) First separation step

In this step, an inorganic salt is added to the mixture obtained through the above saccharification step, and the mixture is separated into a sugar liquid and a first residue (solid content). By the addition of the above inorganic salt, the hydrophilic polymer and the gelling agent dissolved in the mixture are precipitated, and the precipitates and the undecomposed cellulose-based biomass are aggregated and precipitated.

The inorganic salt is not particularly limited, and is preferably selected from the group consisting of sulfates, carbonates, nitrates, phosphates, and hydrogencarbonates. At least one of them. By using the above-mentioned inorganic salt, the precipitation of the hydrophilic polymer and the gelling agent, and the aggregation of the precipitate and the undecomposed cellulose-based biomass can be efficiently performed, and the sugar productivity can be improved. .

Among these inorganic salts, high solubility in water and precipitation and aggregation precipitation can be carried out more efficiently, and a sulfate is preferable, and ammonium sulfate is more preferable.

Further, after the inorganic salt is allowed to stand for a predetermined period of time, the sugar liquid can be separated from the first residue (solid content) by a known means (filtration or the like).

The separated sugar liquid is an aqueous solution in which sugar such as glucose or xylose is dissolved. This sugar liquid can be separated into individual sugars and can be used individually or fermented into ethanol.

(6) Second separation step

In this step, at least a part of the first residue is diluted with an aqueous solvent to separate into a hydrophilic polymer and a second residue (solid content). Further, in the case of using a gelling agent, in the hydrophilic polymer solution, in addition to the hydrophilic polymer, the above gelling agent is dissolved as a solute. In particular, when boric acid or borate is used as the gelling agent, since the hydrophilic polymer solution is easily dissolved as a solute, boric acid, borate or the like can be efficiently separated from the second residue.

The water-based solvent may, for example, be a mixed solvent of water, water and another solvent (for example, an alcohol such as ethanol), and is preferably water in view of ease of work and cost.

Preferably, the aqueous solvent is acidic. In this step, by using In such an acidic aqueous solvent, the separation property of the hydrophilic polymer solution (gelling agent containing boric acid or the like) and the second residue can be improved to improve productivity. The pH of the mixed solution in a state diluted with the aqueous solvent is preferably 3 or more and 5 or less. By setting the pH of the mixed solution to the above range, the separation energy of the hydrophilic polymer solution and the second residue can be further improved.

As a means for making the aqueous solvent acidic, a method of adding a well-known acid to an aqueous solvent can be mentioned. In other words, an acidic aqueous solution may be used as the aqueous solvent. The above acid may be added with a mineral acid such as sulfuric acid, sulfurous acid, phosphoric acid, phosphorous acid, nitric acid, perchloric acid, perbromic acid or hydrochloric acid, or a carboxylic acid, a phthalic acid, a maleic acid or a p-toluene. A method of using an organic acid such as an acid, methanesulfonic acid or phenolsulfonic acid, but it is preferably an inorganic acid, more preferably sulfuric acid, in view of workability and separation property. Further, the addition of the acid may be added to the aqueous solvent before the first residue is diluted, or may be added to the mixed solution in which the first residue is diluted with the aqueous solvent.

The ratio of use of the aqueous solvent is not particularly limited, and is, for example, about 1 to 100 times the mass ratio of the solid content of the first residue.

In the dilution, in order to increase the separation energy, it is preferred to add the aqueous solvent to the first residue and then stir the mixture by a known method. After the stirring, the mixture may be allowed to stand for a specific period of time, and the hydrophilic polymer and the second residue (solid content) are separated by a known means (filtration, centrifugation, etc.).

(7) Gelling agent separation step (I)

In this step, the hydrophilic polymer solution containing the gelling agent obtained from the second separation step (after the mixture of the saccharification step) A small part) separates the gelling agent. The separation means may be a method in which the hydrophilic polymer solution is brought into contact with an aqueous colloid or an ion exchange resin containing PVA as a main component.

(When using an aqueous colloid containing PVA as a main component)

The contact method between the hydrophilic polymer solution and the aqueous colloid is not particularly limited, and examples thereof include a method of immersing an aqueous colloid in a tank in which the hydrophilic polymer solution is charged, or a solution containing a water-containing solution. A method of performing a colloidal adsorption tower.

The hydrophilic polymer solution when it is in contact with the above aqueous colloid is preferably alkaline, and particularly preferably has a pH of from 8 to 12. The adsorptivity to the hydrocolloid of the gelling agent such as boric acid is improved by making the hydrophilic polymer solution (at least a part of the mixture subjected to the saccharification step) alkaline. On the other hand, after the adsorption, the gelling agent such as boric acid is detached from the aqueous colloid, and the aqueous colloid can be easily detached by immersing it in an acidic aqueous solution. At this time, the pH of the acidic aqueous solution is preferably, for example, 2 to 6. This detached boric acid or the like can be reused in a recycling step or the like which will be described later. Further, by removing boric acid or the like, the aqueous colloid can be used plural times. According to this production method, the adsorption and detachment of the hydrocolloid by a gelling agent such as boric acid can be easily controlled by controlling the liquidity.

The average degree of polymerization of the PVA as the main component of the aqueous colloid is preferably 1,000 or more and 10,000 or less, more preferably 1,500 or more and 5,000 or less. By using PVA composed of the average degree of polymerization in the above range, it is possible to obtain an aqueous colloid excellent in water resistance and adsorptivity.

The degree of saponification of the PVA as the main component of the aqueous colloid is preferably 95 mol% or more, more preferably 98 mol% or more. By making this PVA soap The degree of chemical conversion is in the above range, and the adsorptivity of boric acid or the like can be improved.

The aqueous colloid is not particularly limited as long as it is PVA as a main component, and is preferably a crosslinked PVA. The durability of the aqueous colloid can be improved by using the crosslinked PVA.

The cross-linking of the PVA may be, for example, physical crosslinking by irradiation of electron beams or γ-rays, physical crosslinking by repeated freezing, chemical crosslinking using an aldehyde compound or boric acid, or the like. The above aqueous colloid is preferably formed by chemical crosslinking of PVA. By using an aqueous colloid composed of PVA formed by chemical crosslinking, the durability of the hydrocolloid and the like can be improved, and the productivity of sugar can be further improved.

Further, among the chemical crosslinking, PVA (acetalized PVA) crosslinked by an aldehyde compound is preferred. Crosslinking with an aldehyde compound by PVA can reduce the dissolution of PVA from the aqueous colloid, and also improve durability. An example of a specific production method of an aqueous colloid formed by crosslinking of PVA using an aldehyde compound will be described below.

The above aqueous colloid can be obtained by freezing an aqueous PVA solution below -5 °C. The concentration of the PVA aqueous solution is preferably higher in terms of the strength of the colloid, and the lower the adsorption detachment of boric acid or the like is preferable. Therefore, the concentration of the PVA aqueous solution is preferably from 1 to 40% by mass, more preferably from 3 to 20% by mass.

Next, it is acetalized (chemically crosslinked) by adding an aldehyde compound to PVA gelled by freezing. This acetalization reaction can be carried out in a frozen state, but is preferably carried out after thawing. Further, in order to make the mesh structure strong, it is possible to repeatedly freeze and thaw, or to perform local dehydration under reduced pressure in a frozen state.

Examples of the aldehyde compound include glyoxal, formaldehyde, benzaldehyde, succinaldehyde, malondialdehyde, glutaraldehyde, adipaldehyde, terephthalaldehyde, and sebacaldehyde.

The degree of acetalization (degree of formaldehyde formation) of PVA is preferably from 10 to 50 mol%, more preferably from 20 to 40 mol%. If the degree of acetalization (degree of formaldehyde formation) is too low, the water resistance may be insufficient. Conversely, if the degree of acetalization (degree of formaldehydeization) is too high, there is a concern that PVA is hydrophobized and the mesh structure is collapsed.

Further, the aqueous colloid may contain a known component other than PVA insofar as it does not interfere with the gelation of the PVA.

For example, in order to form the hydrocolloid into an arbitrary shape, a water-soluble polymer polysaccharide may be added. Specific examples thereof include a water-soluble polymer polysaccharide having an alkali metal salt of alginic acid, carrageenan, mannan, and chitosan which have gelation ability by contact with a cation. In this case, in order to form the hydrocolloid into an arbitrary shape, the cation for gelatinizing the water-soluble polymer polysaccharide may be contacted with an aqueous colloid such as calcium ion, magnesium ion, strontium ion, strontium ion or the like. A polyvalent metal such as an alkaline earth metal ion, an aluminum ion, a nickel ion or a cerium ion, a potassium ion, an ammonium ion or the like.

The shape of the aqueous colloid is not particularly limited, and any shape such as a spherical shape, a fibrous shape, a ring shape, a film shape, or a cylindrical shape can be appropriately selected. Since the acetalized PVA hydrocolloid thus obtained has a mesh structure, the adsorption and detachment properties of boric acid and the like are excellent, and PVA eluted from the aqueous colloid is abruptly reduced. Moreover, deterioration of the hydrocolloid is also less likely to occur, and durability is improved.

(in the case of using ion exchange resin)

The method of contacting the hydrophilic polymer solution with the ion exchange resin is not particularly limited, and examples thereof include a method in which the hydrophilic polymer solution is passed through an adsorption column filled with a hydrocolloid. Further, the space velocity (SV) when the solution is passed through the adsorption tower is preferably from 1 to 10 / hour.

As the ion exchange resin, a known one can be suitably used. In the case where boric acid or borate is used as the gelling agent, an ion exchange resin selective for boron can be suitably used. The ion-exchange resin which is selective for boron is not particularly limited as long as it has an adsorption property for boron, and is preferably boron having an N-methylglucamine group as an exchange group. Adsorbent ion exchange resin. For example, DIAION (registered trademark, manufactured by Mitsubishi Chemical Corporation) CRB01, CRB02, and AMPERLITE (registered trademark, manufactured by Rohm and Haas Company) IRA743 can be used as the boron-adsorbing resin having an N-methyl-reducing glucosamine group. , DUOLITE (registered trademark, manufactured by Sumitomo Chemical Industries, Ltd.) A368, etc.

Further, it is preferred to appropriately regenerate the ion exchange resin having a reduced adsorption energy by contact with a hydrophilic polymer solution containing boric acid or the like. The regeneration treatment can be carried out, for example, by bringing the boron detachment liquid into contact with the ion exchange resin. The boron detachment liquid is preferably a dilute mineral acid aqueous solution, more preferably a hydrochloric acid or sulfuric acid aqueous solution having a concentration of about 1 to 10%.

Further, in the case of the hydrophilic solution at this time, it is preferred to use a salt which is removed by electrodialysis and adjusted to have a pH of 6 to 12 by adding a basic compound or the like. By using such a hydrophilic polymer solution, the separation energy of a gelling agent such as boric acid can be further enhanced. The above electrodialysis can be used for multivalent anion permeable membranes, etc. get on. Further, the above basic compound may be sodium hydroxide or the like.

(8) Reuse steps

In this step, at least a part of the gelling agent separated in the above gelling agent separation step and/or the above hydrophilic polymer solution separated by the gelling agent is added to the mixture in the above mixing step. By recycling the hydrophilic polymer and/or the gelling agent by this step, the raw material cost, waste disposal cost, and the like can be reduced. Further, in the gelation agent separation step, since the hydrophilic polymer and the gelling agent are separated, either of them may be reused alone, or the ratio thereof may be appropriately changed and reused. Furthermore, it can also be used for other uses other than this manufacturing method.

At this time, the hydrophilic polymer and the gelling agent used in the mixing step may all be used as the recycler, and a part of the new hydrophilic polymer and the gelling agent may be added.

Further, in the present specification, the step of "adding at least a part of the gelling agent separated in the gelling agent separation step to the mixture in the above mixing step" is specifically referred to as "gelling agent recycling step". Here, the gelling agent added to the mixture in the gelling agent recycling step is preferably from the first residue (that is, the gelling agent recycling step is used as a part of the recycling step) It may also be a mixture from the above-described saccharification step before being separated into a sugar liquid and a first residue. The method for producing the sugar of the present invention may be either a gelling agent recycling step or a recycling step other than the above, or may have two steps at the same time.

(9) Third separation step and gelling agent separation step (II)

In the third separation step, diluting with the aqueous solvent in the second fraction The second residue separated from the step is separated into a separation liquid and a third residue. Most of the second residue is used as a component for waste treatment, but by the third separation step, a gelling agent such as boric acid in the separation liquid and an undissolved hydrophilic polymer can be taken out to improve recyclability. And can reduce the load on the environment. Further, in this third separation step, a portion of the first residue not used in the second separation step may also be added to the second residue for use.

Further, the third residue contains undecomposed cellulose-based biomass, undecomposed lignin, and the like. This third residue can be treated as waste, and can also be utilized as, for example, fertilizer or fuel.

The specific method (the type of the aqueous solvent, the acidity, and the like) in the third separation step is the same as the second separation step described above.

In the gelling agent separation step (II), the separation liquid separated in the third separation step is contacted with an aqueous colloid or an ion exchange resin to separate the gelling agent. The specific method (the type of the aqueous colloid and the ion exchange resin, etc.) regarding the gelation agent separation step (II) is the same as the above gelling agent separation step (I).

In the case where the aqueous colloid is used in the gelling agent separation step (II), the separation liquid in contact with the aqueous colloid is preferably alkaline, specifically, pH 8-12. By making the separation liquid (at least a part of the mixture subjected to the saccharification step) alkaline, the adsorption property of the gelling agent such as boric acid to the aqueous colloid can be improved. On the other hand, after the adsorption, the separation of the gelling agent such as boric acid from the aqueous colloid can be easily carried out by immersing the aqueous colloid in an acidic aqueous solution. In this case, the pH of the acidic aqueous solution is preferably 2 to 6, for example. This detached boric acid or the like can be reused in the recycling step. Further, it can be used plural times by removing boric acid or the like from the aqueous colloid.

By passing through the gelling agent separation step, the concentration of the gelling agent (boric acid or the like) in the separating liquid can be lowered, and the treatment as the discharged water can be efficiently performed. Specifically, the concentration of boric acid in the separation liquid can be lowered to, for example, 8 ppm or less, and the boric acid emission standard in the discharge water in Japan is 10 ppm in terrestrial waters and 230 ppm in sea water.

(hydrophilic polymer)

Here, the hydrophilic polymer used in the production of the sugar of the present invention will be described in detail. The hydrophilic polymer is not particularly limited, and examples thereof include a polyvinyl alcohol polymer, an ethylene-vinyl acetate copolymer, and polyvinylpyrrolidone. Among these, PVA is preferred. Since PVA is used as the hydrophilic polymer described above, work efficiency and the like in the breaking step can be improved, so that productivity can be further improved.

(PVA)

Here, the PVA used for the production of the sugar of the present invention will be described in detail. Moreover, PVA (polyvinyl alcohol type polymer) means polyvinyl alcohol and a vinyl alcohol copolymer.

As the PVA, various PVAs can be used, and it is not particularly limited. Usually, a vinyl ester monomer or a vinyl ester monomer typified by vinyl acetate and ethylene are used in various methods (polymerization by polymerization, solution polymerization using methanol or the like as a solvent). PVA obtained by saponification by a known method (alkali saponification or acid saponification) after polymerization is carried out. Further, as the vinyl ester monomer, in addition to vinyl acetate, vinyl formate, vinyl propionate, vinyl tridecanoate or trimethyl vinyl acetate may be used.

Further, in the PVA of the present invention, a monomer copolymerizable with a vinyl ester monomer may be coexistent and copolymerized within a range not impairing the effects of the present invention. Hehe. Examples of such a monomer include olefins such as ethylene, propylene, 1-butene, and isobutylene; acrylic acid; acrylates; methacrylic acid; methacrylates; methyl vinyl acetate and n-propyl vinyl ester; Vinyl esters of isopropyl vinyl ester, n-butyl vinyl ester, isobutyl vinyl ester, tributyl butyl vinyl ester, lauryl vinyl ester, stearyl vinyl ester, etc.; acrylonitrile, methacrylonitrile Nitriles; allyl compounds such as vinyl chloride and allyl chloride; fumaric acid, maleic acid, itaconic acid, maleic anhydride, phthalic anhydride, and trimellitic anhydride a carboxyl group-containing compound such as itaconic anhydride or an ester thereof; a sulfonic acid group containing vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, 2-propenylamine-2-methylpropanesulfonic acid or the like a compound; a diacetone-based compound such as diacetone acrylamide, diacetone acrylate or diacetone methacrylate; a vinyl decane compound such as vinyltrimethoxydecane; isopropenyl acetate; 3-(methyl Acrylamide, propylaminomethylammonium chloride, and the like.

Further, a terminal ester modified product obtained by polymerizing a vinyl ester monomer such as vinyl acetate in the presence of a thiol compound such as thioacetic acid or hydrazine propionate, and saponifying the same can also be used. Further, a conventionally known post-reaction PVA or the like which is modified by post-reaction of various PVAs such as acetaminophen PVA may be used.

The above PVA is a manufacturer of hydrolyzable cellulose which can be used as a raw material of cellulose-based biomass. Specifically, as described above, an aqueous solution of PVA is mixed with a cellulose-based biomass or the like to form a mixture, and a shear force is applied by kneading the mixture or the like to finely break the cellulose-based biomass into molecules. Level (quasi-crystal structure level). At this time, the viscosity of the above mixture can be maintained in an appropriate state by using this PVA aqueous solution. Its knot In the mixing of the mixture or the like, the cellulose polymer chain is easily pulled apart by the aqueous solution having a viscous sensation, and the water and the PVA efficiently enter the inside of the polymer chain having the quasi-crystalline structure, thereby being weakened. Hydrogen bonds between polymer chains. Furthermore, by thus allowing the PVA to enter between the stretched polymer chains, recrystallization of this structure can be prevented. Further, cellulose which is divided into molecular layers in such a manner can be easily decomposed by hydrolyzing enzymes or the like.

The average degree of polymerization of the PVA is preferably 200 or more and 5,000 or less, more preferably 1,000 or more and 4,000 or less, still more preferably 1,800 or more and 3,500 or less, and particularly preferably 2,000 or more and 3,000 or less. By setting the average degree of polymerization of the PVA to be used in the above range, the PVA can be used as an aqueous solution, and when it is mixed with a cellulose-based biomass or the like, it can be mixed with an appropriate viscosity and efficiently and uniformly. The cellulose polymer chain is effectively separated to form a state in which hydrolysis can be easily performed. Further, by using such a PVA having a high average degree of polymerization, it can be gelled with a small amount of a gelling agent (boric acid or the like).

Here, the "average degree of polymerization" is a value of the viscosity average degree of polymerization (P) measured in accordance with JIS K6726. That is, in the case where the degree of saponification is less than 99.5 mol%, the polyvinyl alcohol-based polymer is further saponified to a degree of saponification of 99.5 mol% or more, and after the refining, the ultimate viscosity [η] measured in water at 30 ° C is obtained. (dL(deciliter)/g) A value obtained by the following formula (1).

P=([η]×1000/8.29) ^(1/0.62) (1)

When the average degree of polymerization of the above PVA is less than 200, since the molecular weight is too small, even if the concentration is adjusted to some extent, sufficient viscosity of the aqueous solution cannot be imparted, and the physical pull-off force of the cellulose chains is weakened during the kneading. Case. On the other hand, if the average degree of polymerization exceeds 5,000, the viscosity is too high, and the workability and the removability in the breaking step are lowered, and The molecular weight is too large to enter the cellulose polymer chain, and the effect of weakening the hydrogen bond is lowered.

The lower limit of the degree of saponification of the PVA is preferably 70 mol%, more preferably 75 mol%, still more preferably 80 mol%, and particularly preferably 85 mol%. On the other hand, the upper limit of the degree of saponification is preferably 99.9 mol%, more preferably 99.5 mol%, still more preferably 99.0 mol%. By setting the saponification degree of the PVA to be used in the above range, the PVA is used as an aqueous solution, and when it is mixed with a cellulose-based biomass or the like, it can be efficiently and uniformly mixed with an appropriate viscosity, and as a result, it can be effectively used. The cellulose polymer chain is divided to form a state in which hydrolysis can be easily carried out.

Here, the "saponification degree" means a value measured in accordance with JIS K6726.

When the degree of saponification of the PVA is less than 70 mol%, the water solubility may be lowered, and sufficient viscosity may not be obtained, and the cellulose breaking property during kneading may be lowered. On the other hand, even if the degree of saponification exceeds 99.9 mol%, the breaking energy of breaking the cellulose polymer chain into molecular layers has reached a peak, and there is a possibility that the removability is lowered.

The lower limit of the molecular weight distribution of the above PVA is preferably 2, more preferably 2.2, still more preferably 2.25. On the other hand, the upper limit of the molecular weight distribution is preferably 5, more preferably 4, and particularly preferably 3.5. By setting the molecular weight of the PVA to the above range, the PVA is used as an aqueous solution, and when it is mixed with a cellulose-based biomass or the like, it can be appropriately and viscously mixed, efficiently and uniformly, and can be efficiently introduced. As a result of the gap between the quasi-crystal structures of cellulose of various sizes, as a result, the cellulose polymer chain can be effectively separated and a state in which hydrolysis can be easily performed can be achieved.

Here, the "molecular weight distribution" means a numerical value calculated from a mass average molecular weight (Mw) / a number average molecular weight (Mn). Further, the mass average molecular weight (Mw) and the number average molecular weight (Mn) are monodisperse polymethyl methacrylate as a standard, and the mobile phase is hexafluoroisopropyl containing sodium trifluoroacetate 20 mil/liter. The alcohol was subjected to gel permeation chromatography (GPC) at 40 °C.

When the molecular weight distribution of the PVA is less than the above lower limit, the difference in molecular weight may not be able to enter the gap of the quasi-crystalline structure of various sizes, and the function of weakening the hydrogen bond may not be sufficiently exhibited. On the other hand, when the molecular weight distribution of the PVA exceeds the above upper limit, the molecular weight may not be too large to correspond to the gap of the quasi-crystalline structure, and the ratio of the inaccessible PVA may be too high, and the function of weakening the hydrogen bond may not be sufficiently exhibited. After that.

The case where the molecular weight distribution of this PVA is to be adjusted can be adjusted, for example, by the following method. That is, (1) a method of mixing PVA having different degrees of polymerization; (2) a method of saponifying a mixture of polyvinyl esters having different degrees of polymerization; (3) polymerizing with an aldehyde, an alkyl halide, a mercaptan, or the like. a method of adjusting a polymerization agent to polymerize a polyvinyl ester, and then saponifying the obtained polyvinyl ester; (4) a method of performing a multistage polyvinyl ester polymerization while adjusting the degree of polymerization, and then saponifying the obtained polyvinyl ester; (5) A method in which the polymerization rate is adjusted to carry out polymerization of a polyvinyl ester, and the obtained polyvinyl ester is saponified.

Further, in the method for producing the sugar, the PVA which has been used once or more can be reused because of the reuse step. In this case, it is preferred to adjust the blending ratio of the reused PVA to the newly added PVA, and the molecular weight distribution of the entire PVA is within the above range.

PVA which is suitable for use in the production method can more effectively separate the cellulose-based biomass into a molecular layer by setting the three factors of the average degree of polymerization, the degree of saponification, and the molecular weight distribution within the above range. That is, by specifying the average degree of polymerization and the degree of saponification, it is possible to impart a suitable viscosity for exerting a physical action, and by specifying a molecular weight distribution, it is possible to exert a chemical action to bring the PVA into a quasi-crystalline structure. Increased, and the hydrogen bonds of the cellulose polymer chains are well balanced. In other words, by making the above-described three elements specific, the PVA can be made to have a more balanced physical and chemical action, and thus cellulose which can be easily hydrolyzed by an enzyme or the like can be obtained.

<sugar>

The sugar of the present invention is obtained by the production method. Since the sugar can be obtained under stable and mild conditions without going through a heating step, the content of a high value-added component such as xylose is also high.

This sugar can also be used as a fuel resource or the like by separating it into glucose, xylose, or the like.

<Sugar manufacturing device>

The apparatus for producing a sugar of the present invention comprises: a means for mixing a mixture containing a cellulose-based biomass, a hydrophilic polymer, and water, and a means for separating the cellulose-based biomass by applying shear force to the mixture a saccharification means for saccharifying the above-mentioned cellulose-based biomass by a cellulolytic enzyme, adding an inorganic salt to the mixture subjected to the saccharification step, and separating into The first separation means of the sugar liquid and the first residue.

With this device, sugar can be efficiently produced using cellulose-based biomass as a raw material. Further, with the manufacturing apparatus, the first residue separated in the first separation step can be easily added to the mixture in the mixing means, thereby achieving cost reduction and waste reduction by recycling.

Preferably, the production apparatus includes a second separation means for diluting at least a part of the first residue with an aqueous solvent and separating the hydrophilic polymer solution and the second residue. By having such a second separation means, the recovery property and the like can be further improved.

Further, preferably, the manufacturing apparatus is provided with a gel which contacts at least a part of the mixture subjected to the saccharification step and an aqueous colloid or ion exchange resin containing a polyvinyl alcohol-based polymer as a main component to separate the gelling agent from the mixture. Chemical separation means. By having such a gelling agent separation means, in the case of using a mixture containing a gelling agent, discharge of water is easier and the productivity is further improved by the separation of the gelling agent.

A well-known machine or the like can be used for each of the above means. As the mixing means, the saccharifying means, the first and second separating means, and the gelling agent separating means, for example, a well-known mixing tank having an inlet port and a discharge port, for example, a well-known biaxial pressing can be used. Forming machine.

Moreover, it is possible to have a plurality of means in one machine. Furthermore, the machines corresponding to the respective means may be connected or separated.

Moreover, the method for producing a sugar, the sugar, and the sugar producing device of the present invention are not limited to the above embodiment. For example, for the mixture after the saccharification step, the gelation agent separation step may be directly carried out without going through the separation step. In this case, the gelling agent can be separated from the mixture first, and then taken out. Sugar, etc., the range of modifications of the manufacturing steps can be amplified. Further, the first residue obtained in the first separation step may be supplied to the gelation agent separation step.

Further, in the case where the unnecessary second separation step and/or the gelation agent separation step are omitted, at least a portion of the unseparated first residue itself and the unseparated hydrophilic polymer solution may be appropriately used in the recycling step. Reuse. By doing so, at least a portion of the hydrophilic polymer or the like can be reused.

[Examples]

The present invention will be described in more detail by way of Synthesis Examples and Examples, but the present invention is not limited thereto.

[Synthesis Example 1] (PVA1)

70.0 kg of vinyl acetate and 30.0 kg of methanol were placed in a 250 L reaction vessel equipped with a stirrer, a nitrogen gas inlet, and an initiator inlet, and heated to 60 °C. The inside of the reactor was replaced with nitrogen for 30 minutes to a nitrogen atmosphere. Thereafter, 2,2'-azobisisobutyronitrile (AIBN) as a polymerization initiator was added to the reaction vessel. The polymerization was carried out at 60 ° C for 4 hours, and the polymerization was carried out for 30% with respect to the vinyl acetate. Then, the mixture was cooled, the polymerization was stopped, and the unreacted vinyl acetate monomer was removed under reduced pressure to obtain a methanol solution of vinyl acetate (PVAc).

Methanol was added to the above PVAc solution to adjust the concentration of the PVAc solution to 30% by mass. The alkali molar ratio (ratio of NaOH molar amount relative to the vinyl ester unit molar amount of the PVAc polymer) was 0.11, and the alkali solution (10% NaOH methanol solution) 51.1 g was added to 333 g (PVAc 100 g) of the PVAc solution. , saponification of PVAc. After maintaining the temperature at 60 ° C and performing a saponification reaction for 1 hour, the product (containing saponification in the saponification reaction) The material was appropriately taken out from the reaction vessel and pulverized by a grinder to obtain a white solid. This white solid was mixed in 1000 g of methanol, and left to stand at room temperature for 3 hours to wash. The above washing was carried out three times, and the white solid was centrifuged, and then dried in a dryer at 70 ° C for two days to obtain PVA1. This PVA1 had an average degree of polymerization of 1,700, a degree of saponification of 98.8 mol%, and a molecular weight distribution (Mw/Mn) of 2.24.

[Synthesis Example 2] (PVA2)

PVA2 was obtained in the same manner as in Synthesis Example 1, except that the alkali ratio (ratio of NaOH molar amount relative to the vinyl ester unit molar amount of the PVAc polymer) was 0.07 and the alkali solution was added to 32.5 g. The PVA2 had an average degree of polymerization of 1,740, a degree of saponification of 86.2 mol%, and a molecular weight distribution (Mw/Mn) of 2.30.

[Synthesis Example 3~10] (PVA3~6, 8~11)

PVA 3~6 and PVA8~11 were obtained in the same manner as PVA1 except that the polymerization conditions and the saponification conditions were changed. The average degree of polymerization, the degree of saponification, and the molecular weight distribution are shown in Tables 1 and 2 below together with the values of PVA1 and PVA2.

[Modulation Example 1] (PVA7)

50 parts by mass of PVA-217 (manufactured by Kuraray Co., Ltd.) and 50 parts by mass of PVA-205 (manufactured by Kuraray Co., Ltd.) were mixed to obtain PVA7. This PVA7 had an average degree of polymerization of 1,740, a degree of saponification of 88.2 mol%, and a molecular weight distribution (Mw/Mn) of 2.75.

Further, the average polymerization degree, saponification degree, and molecular weight distribution of PVA-217 and PVA-205 of PVA-based polymer manufactured by Kuraray Co., Ltd. are shown in Tables 1 and 2.

[Example 1-1]

PVA1 was added to distilled water and heated to 90 ° C while stirring, thereby preparing a 10% by mass aqueous solution of PVA. The viscosity of this PVA aqueous solution is only slightly higher than that of water. After 100 g of this aqueous solution was cooled to room temperature, 2 mL of a saturated aqueous solution of boric acid (H ₃ BO ₃ ) was added and mixed. The pH of the resulting aqueous solution was 5.0. Further, 0.5 mL of a saturated aqueous solution of sodium tetraborate was added to the aqueous solution to mix, whereby the aqueous solution became a viscous colloid. The pH of this colloid was 6.5. Then, 50 g of EFB (20 to 70 μm in diameter) as a cellulose-derived plasmid was added to the gel, and kneaded at room temperature with a mixer of a mixer type. This mixture is a relatively low viscosity at the beginning of the mixing, and while the mixing is ongoing, EFB (cellulose-based particles) absorbs water and increases the viscosity. This compound can be easily stretched and stretched by a roll. Each time a kneading was performed at a specific time, a part of the mixture was taken out, and the size of the particles was confirmed by a microscope. It can be observed that as this breaking step proceeds, the particle size decreases and the cell wall structure is broken.

The fact that the cellulose was sufficiently separated by kneading was confirmed by a microscope to obtain an aqueous solution of hydrolyzable cellulose. Thereafter, distilled water was added to the mixture to lower the viscosity. In order to adjust to the optimum pH of the hydrolyzed enzyme, a sodium hydroxide solution was added to the mixture to adjust the pH to 6.0. This mixture has a viscosity equivalent to about the dissolved chocolate. To the mixture, Meicelase (manufactured by Meiji Seika Co., Ltd.) and Melobacterium leucocephala cellulase (cellulose enzyme obtained from Acremonium cellulolyticus, manufactured by Meiji Seika Co., Ltd.) were added as a hydrolyzed enzyme, and 100 parts by mass relative to EFB. 0.5 parts by mass, at a temperature of 50 ° C in the opposite Stir in the container. Dozens of minutes after the addition of the enzyme, the viscosity of this mixture was significantly reduced. This stirring was carried out for 6 hours to obtain a sugar liquid (mixture).

16 g of ammonium sulfate as an inorganic salt was dissolved in 24 g of water and added to the obtained sugar liquid (mixture), and after stirring, it was allowed to stand for 3 hours. After standing, the mixture was filtered to obtain a solution of the separated sugar (sugar solution).

Repeat this operation 3 times. In addition, the amount of PVA used in the second and third times was set to 10 g (10% of the first usage amount), and 90% of the residue (solid content) separated in the previous final step was added to the gelation. In the pre-PVA aqueous solution. That is, the amount of PVA which was not used in the second and third times was set to 10% of the first time, and the amount of PVA was complemented by adding PVA to the residue.

[Example 1-2~1-15]

Examples 1-2 to 1-15 were carried out in the same manner as in Example 1-1 except that the PVA was changed to the other PVA of Table 1, and the inorganic salts were each using the inorganic salts of Table 1, to obtain a sugar liquid.

[Comparative Example 1-1]

The same operation as in Example 1-1 was carried out except that the residue separated in the previous final step was not added to the PVA aqueous solution before gelation in the second and third times to obtain a sugar liquid.

[Evaluation]

After adding the distilled water (filtered sugar solution) after filtration to 400 mL, 2 mL of the sample solution of the glucose solution (0.5% of the whole solution) was taken, and sterilization was performed at 100 ° C for 5 minutes. After cooling the sample solution, it was centrifuged at 3000 rpm for 30 minutes using a centrifugal separator, and then filtered to remove After the solid component was removed, the filtrate was supplied to a chromatography analyzer to measure the amount of monosaccharides (glucose, etc.). The mass ratio of cellulose and hemicellulose in the EFB (50 g) used was 50%, and the saccharification efficiency (%) was determined by the following formula. The measurement results are shown in Table 1.

Saccharification efficiency = [monosaccharide mass (g) / {50 (g) × 0.005 × 0.5} in the sample solution] × 100 (%)

As shown in Table 1, it can be seen that any of the examples 1-1 to 1-15 can be maintained from the first to the third time by recycling the residue containing PVA and undecomposed cellulose. Saccharification efficiency. In addition, it is considered that the saccharification efficiency of the second and subsequent appearances is increased because the residue to be reused contains undecomposed cellulose-based biomass.

[Example 2-1]

PVA1 was added to distilled water, and the mixture was heated to 90 ° C while stirring, thereby preparing a 10% by mass aqueous PVA solution (A). The viscosity of this PVA aqueous solution (A) is only slightly higher than that of water. After 100 g of this aqueous solution (A) was cooled to room temperature, 2 mL of a saturated aqueous solution of boric acid (H ₃ BO ₃ ) was added and mixed. The pH of the resulting aqueous solution was 5.0. Further, 0.5 mL of a saturated aqueous solution of sodium tetraborate was added to the aqueous solution to mix, whereby the aqueous solution became a viscous colloid. The pH of this colloid was 6.5. Then, 50 g of EFB (20 to 70 μm in diameter) as a cellulose-derived plasmid was added to the gel, and kneaded at room temperature with a mixer of a mixer type. This mixture is a relatively low viscosity at the beginning of the mixing, and while the mixing is ongoing, EFB (cellulose-based particles) absorbs water and increases the viscosity. This compound can be easily stretched and stretched by a roll. Each time a kneading was performed at a specific time, a part of the mixture was taken out, and the size of the particles was confirmed by a microscope. It can be observed that as this breaking step proceeds, the particle size decreases and the cell wall structure is broken.

The fact that the cellulose was sufficiently separated by kneading was confirmed by a microscope to obtain an aqueous solution of hydrolyzable cellulose. Thereafter, distilled water was added to the mixture to lower the viscosity. In order to adjust to the optimum pH of the hydrolyzed enzyme, a sodium hydroxide solution was added to the mixture to adjust the pH to 6.0. This mix The composition has a viscosity equivalent to about the dissolved chocolate. To the mixture, Meicelase (manufactured by Meiji Seika Co., Ltd.) and Melobacterium leucocephala cellulase (cellulose enzyme obtained from Acremonium cellulolyticus, manufactured by Meiji Seika Co., Ltd.) were added as a hydrolyzed enzyme, and 100 parts by mass relative to EFB. The mixture was stirred at a temperature of 50 ° C in an amount of 0.5 parts by mass. Dozens of minutes after the addition of the enzyme, the viscosity of this mixture was significantly reduced. This stirring was carried out for 6 hours to obtain a sugar liquid (mixture).

16 g of ammonium sulfate as an inorganic salt was added to 24 g of water to be added to the obtained sugar liquid (mixture), and after stirring, it was allowed to stand for 3 hours, and precipitation of the residue (first residue) was confirmed. After standing, the mixture was filtered to obtain a solution of the separated sugar (sugar solution).

90 g of water was added to 90% of the above-mentioned first residue (solid content), and dilute sulfuric acid was used as a mixture of pH 4.0. The mixture was stirred for 2 hours to disperse the first residue, followed by filtration to obtain a separated PVA solution (B).

Repeat this operation 3 times. In addition, the amount of PVA used in the second and third times was set to 10 g (10% of the first use amount), and the amount of the saturated aqueous solution of boric acid used was 0.2 mL (10% of the first use amount). The PVA solution (B) separated in the previous final step was added to the PVA aqueous solution (A) before gelation. That is, the amount of PVA and the amount of boric acid which were not used in the second and third times were set to 10% of the first time, and PVA and boric acid were reused by adding the separated PVA solution (B) thereto. , to make up the total amount of PVA.

[Example 2-2~2-15]

In addition to the PVA and inorganic salts used in Table 2, In the same manner as in Example 2-1, Examples 2-2 to 2-15 were carried out to obtain a sugar liquid.

[Examples 2-16 and 2-17]

Except that the amount of dilute sulfuric acid after the first residue was diluted with water was adjusted, and the pH of the mixture was adjusted as shown in Table 2, Examples 2-16 and 2-17 were carried out in the same manner as in Example 2-1. Sugar liquid.

[Comparative Example 2-1]

The same operation as in Example 2-1 was carried out except that the PVA solution (B) separated from the previous final step was not added to the PVA aqueous solution (A) before the gelation in the second and third times. , get the sugar solution.

[Evaluation]

The saccharification efficiency was determined in the same manner as above. The measurement results are shown in Table 2.

As shown in Table 2, it was found that all of Examples 2-1 to 2-17 were able to maintain high saccharification efficiency from the first to the third time by recycling the residue containing PVA and boric acid.

[Production Example 3-1] Aqueous colloid (I)

PVA (average degree of polymerization 1,700, degree of saponification 99.8 mol%) manufactured by Kuraray Co., Ltd. was washed with warm water of 40 ° C for 1 hour, and then water was added to PVA to make the concentration of PVA 8%, in an autoclave. The PVA was dissolved by treating at 121 ° C for 30 minutes. It was cast in a shallow groove to have a thickness of 5 mm, frozen in a freezer at -20 ° C for 12 hours, and then thawed at room temperature. The plate-shaped molded product was immersed in an aqueous solution of 30 g/L of formaldehyde, 200 g/L of sulfuric acid, and 150 g/L of sodium sulfate for 30 minutes, and then washed with water, and cut into 5 mm square to obtain a degree of formaldehydeization of 19 m. % of the water-containing colloid (I).

[Production Example 3-2] Hydrocolloid (II)

The same PVA 8% aqueous solution as in Production Example 1 was cast into a shallow tray to have a thickness of 5 mm, frozen in a freezer at -20 ° C for 12 hours, and then thawed at room temperature to obtain a sheet-like formed product. . This was cut into 5 mm square to obtain an aqueous colloid (II).

[Example 3-1]

PVA1 was added to distilled water, and the mixture was heated to 90 ° C while stirring, thereby preparing a 10% by mass aqueous PVA solution (A). The viscosity of this PVA aqueous solution (A) is only slightly higher than that of water. After 100 g of this aqueous solution (A) was cooled to room temperature, 2 mL of a saturated aqueous solution of boric acid (H ₃ BO ₃ ) was added and mixed. The pH of the resulting aqueous solution was 5.0. Further, 0.5 mL of a saturated aqueous solution of sodium tetraborate was added to the aqueous solution to mix, whereby the aqueous solution became a viscous colloid. The pH of this colloid was 6.5. Then, 50 g of EFB (20 to 70 μm in diameter) as a cellulose-derived plasmid was added to the gel, and kneaded at room temperature with a mixer of a mixer type. This mixture is a relatively low viscosity at the beginning of the mixing, and while the mixing is ongoing, EFB (cellulose-based particles) absorbs water and increases the viscosity. This compound can be easily stretched and stretched by a roll. Each time a kneading was performed at a specific time, a part of the mixture was taken out, and the size of the particles was confirmed by a microscope. It can be observed that as this breaking step proceeds, the particle size decreases and the cell wall structure is broken.

The fact that the cellulose was sufficiently separated by kneading was confirmed by a microscope to obtain an aqueous solution of hydrolyzable cellulose. Thereafter, distilled water was added to the mixture to lower the viscosity. In order to adjust to the optimum pH of the hydrolyzed enzyme, a sodium hydroxide solution was added to the mixture to adjust the pH to 6.0. This mixture has a viscosity equivalent to about the dissolved chocolate. To the mixture, Meicelase (manufactured by Meiji Seika Co., Ltd.) and Melobacterium leucocephala cellulase (cellulose enzyme obtained from Acremonium cellulolyticus, manufactured by Meiji Seika Co., Ltd.) were added as a hydrolyzed enzyme, and 100 parts by mass relative to EFB. The mixture was stirred at a temperature of 50 ° C in an amount of 0.5 parts by mass. Dozens of minutes after the addition of the enzyme, the viscosity of this mixture was significantly reduced. This stirring was carried out for 6 hours to obtain a sugar liquid (mixture).

16 g of ammonium sulfate as an inorganic salt was added to 24 g of water to be added to the obtained sugar liquid (mixture), and after stirring, it was allowed to stand for 3 hours, and precipitation of the residue (first residue) was confirmed. After standing, the mixture was filtered to obtain a solution of the separated sugar (sugar solution).

Adding 90 g of water to the separated first residue (solid component) In 90%, dilute sulfuric acid was used as a mixture of pH 4.0. The mixture was stirred for 2 hours to disperse the first residue, followed by filtration to obtain a separated PVA solution (B).

On the other hand, the remaining 10% of the first residue and the second residue separated from the PVA solution (B) were combined, and 34 g of water was added thereto and stirred. The dispersion was filtered and separated into a separating liquid and a third residue. This separating liquid was added to the above aqueous colloid (I) and allowed to stand for 2 hours. Then, the aqueous colloid is taken out, and the remainder is used as the waste liquid (C). On the other hand, the extracted hydrocolloid was added to water, and the pH was adjusted to 4 or less by adding sulfuric acid to desorb the adsorbed boric acid.

Repeat this operation 3 times. In addition, the amount of PVA used in the second and third times was set to 10 g (10% of the first use amount), and the amount of the saturated aqueous solution of boric acid used was 0.2 mL (10% of the first use amount). The PVA solution (B) separated in the previous final step was added to the PVA aqueous solution (A) before gelation. That is, the amount of PVA and the amount of boric acid which were not used in the second and third times were set to 10% of the first time, and PVA and boric acid were reused by adding the separated PVA solution (B) thereto. , to make up the total amount of PVA.

[Examples 3-2 to 3-3]

The sugar liquids were obtained in the same manner as in Example 3-1 except that the inorganic salts of the inorganic salts were used in Examples 3-2 to 3-3.

[Examples 3-4 to 3-5]

Except that the amount of dilute sulfuric acid after the first residue was diluted with water was adjusted, and the pH of the mixture was adjusted as shown in Table 3, Examples 3-4 and 3-5 were carried out in the same manner as in Example 3-1. Sugar liquid.

[Comparative Example 3-1]

The same operation as in Example 1 was carried out except that the PVA solution (B) separated in the previous final step was not added to the PVA aqueous solution (A) before the gelation in the second and third times. Get the sugar solution.

[Examples 3-6]

Example 3-6 was carried out in the same manner as in Example 3-1, except that the aqueous colloid (II) was used instead of the aqueous colloid (I).

[Reference Example 3-1]

Reference Example 3-1 was carried out in the same manner as in Example 3-1, except that a commercially available ceramic adsorbent (particle size: 3 to 5 mm) was used instead of the aqueous colloid (I).

[Reference Example 3-2]

Reference Example 3-2 was carried out in the same manner as in Example 3-1 except that a commercially available activated carbon adsorbent (particle size: 3 to 5 mm) was used instead of the aqueous colloid (I).

[Evaluation] (glycation efficiency)

The saccharification efficiency (%) was determined in the same manner as above. The measurement results are shown in Table 3.

(boric acid concentration)

In Examples 3-1 and 3-6 and Reference Examples 3-1 and 3-2, the boric acid concentration (in terms of boric acid) of the waste liquid (C) in the first operation was measured. The evaluation results are shown in Table 4. Further, the boric acid concentration of the separation liquid before the addition of the aqueous colloid or the adsorbent was 490 ppm.

As shown in Table 3, it was found that any of Examples 3-1 to 3-5 was recovered from the residue containing PVA and boric acid, so that high saccharification efficiency was maintained from the first time to the third time. Further, as shown in Table 4, it was found that by using the PVA hydrocolloid treatment, the boric acid concentration can reach a low concentration which is in compliance with the Japanese emission standard (10 ppm in terrestrial waters and 230 ppm in seawater).

[Example 4-1]

PVA1 was added to distilled water, and the mixture was heated to 90 ° C while stirring, thereby preparing a 10% by mass aqueous PVA solution (A). The viscosity of this PVA aqueous solution (A) is only slightly higher than that of water. After 100 g of this aqueous solution (A) was cooled to room temperature, 2 mL of a saturated aqueous solution of boric acid (H ₃ BO ₃ ) was added and mixed. The pH of the resulting aqueous solution was 5.0. Further, 0.5 mL of a saturated aqueous solution of sodium tetraborate was added to the aqueous solution to mix, whereby the aqueous solution became a viscous colloid. The pH of this colloid was 6.5. Then, 50 g of EFB (20 to 70 μm in diameter) as a cellulose-based green material was added to the colloidal material, and kneaded at room temperature with a mixer of a mixer type. This mixture is a relatively low viscosity at the beginning of the mixing, and while the mixing is ongoing, EFB (cellulose-based particles) absorbs water and increases the viscosity. This compound can be easily stretched and stretched by a roll. Each time a kneading was performed at a specific time, a part of the mixture was taken out, and the size of the particles was confirmed by a microscope. It can be observed that as this breaking step proceeds, the particle size decreases and the cell wall structure is broken.

The fact that the cellulose was sufficiently separated by kneading was confirmed by a microscope to obtain an aqueous solution of hydrolyzable cellulose. Thereafter, distilled water was added to the mixture to lower the viscosity. In order to adjust to the optimum pH of the hydrolyzed enzyme, a sodium hydroxide solution was added to the mixture to adjust the pH to 6.0. This mixture has a viscosity equivalent to about the dissolved chocolate. To the mixture, Meicelase (manufactured by Meiji Seika Co., Ltd.) and Melobacterium leucocephala cellulase (cellulose enzyme obtained from Acremonium cellulolyticus, manufactured by Meiji Seika Co., Ltd.) were added as a hydrolyzed enzyme, and 100 parts by mass relative to EFB. The mixture was stirred at a temperature of 50 ° C in an amount of 0.5 parts by mass. Dozens of minutes after the addition of the enzyme, the viscosity of this mixture was significantly reduced. This stirring was carried out for 6 hours to obtain a sugar liquid (mixture).

16 g of ammonium sulfate as an inorganic salt was added to 24 g of water to be added to the obtained sugar liquid (mixture), and after stirring, it was allowed to stand for 3 hours, and precipitation of the residue (first residue) was confirmed. After standing, the mixture was filtered to obtain a solution of the separated sugar (sugar solution).

90 g of water was added to 90% of the above-mentioned first residue (solid content), and dilute sulfuric acid was used as a mixture of pH 4.0. Mix this mixture The first residue was dispersed by stirring for 2 hours, and then filtered to obtain a separated PVA solution (B).

On the other hand, the remaining 10% of the first residue and the second residue separated from the PVA solution (B) were combined, and 34 g of water was added thereto and stirred. The dispersion was filtered and separated into a separating liquid and a third residue. This separation liquid was passed through an adsorption column packed with a boron-selective ion exchange resin (DIAION (registered trademark) CRB02, manufactured by Mitsubishi Chemical Corporation), which was washed with distilled water, and 250 mL.

Repeat this operation 3 times. In addition, the amount of PVA used in the second and third times was set to 10 g (10% of the first use amount), and the amount of the saturated aqueous solution of boric acid used was 0.2 mL (10% of the first use amount). The PVA solution (B) separated in the previous final step was added to the PVA aqueous solution (A) before gelation. That is, the amount of PVA and the amount of boric acid which were not used in the second and third times were set to 10% of the first time, and PVA and boric acid were reused by adding the separated PVA solution (B) thereto. , to make up the total amount of PVA.

[Examples 4-2 to 4-3]

Examples 4-2 to 4-3 were carried out in the same manner as in Example 4-1 except that each of the inorganic salts of Table 5 was used to obtain a sugar liquid.

[Examples 4-4 to 4-5]

Except that the amount of dilute sulfuric acid after the first residue was diluted with water was adjusted, and the pH of the mixture was adjusted as shown in Table 5, Examples 4-4 and 4-5 were carried out in the same manner as in Example 3-1. Sugar liquid.

[Comparative Example 4-1]

Except that the PVA solution (B) separated from the previous final step was not added to the PVA aqueous solution (A) before gelation in the second and third times, The same operation as in Example 4-1 was carried out to obtain a sugar liquid.

[Evaluation] (glycation efficiency)

The saccharification efficiency (%) was determined in the same manner as above. The measurement results are shown in Table 5.

(boric acid concentration)

In Example 4-1, the boric acid concentration (converted to boric acid) of the separation liquid before and after passing through the adsorption column was measured. The boric acid concentration before the liquid passage was 490 ppm, and the boric acid concentration after the liquid passage was 4.2 ppm.

As shown in Table 5, it was found that any of Examples 4-1 to 4-5 recovered the residue containing PVA and boric acid, so that high saccharification efficiency was maintained from the first time to the third time. Further, by using an ion exchange resin treatment, the boric acid concentration can reach a low concentration which is in compliance with the Japanese emission standard (10 ppm in terrestrial waters and 230 ppm in sea water).

[Industrial availability]

As described above, according to the present invention, the biomass raw material of the plant system can be effectively utilized as food and energy, and the practicality of the biomass utilization can be improved.

Fig. 1 is a flow chart showing a method of producing sugar according to an embodiment of the present invention.

Claims (14)

A method for producing sugar, which is a method for producing sugar using cellulose-based biomass as a raw material, which comprises the steps of: obtaining a mixture containing a cellulose-based biomass, a hydrophilic polymer, and water. a mixing step of applying a shear force to the mixture to separate the cellulose-based biomass into a saccharification step of saccharifying the cellulose-based biomass by a cellulolytic enzyme, adding an inorganic salt to the passage a mixture of the saccharification step, a first separation step of separating the sugar liquid from the first residue, diluting at least a portion of the first residue obtained in the first separation step with an aqueous solvent, and separating into a hydrophilic polymer solution and a second residue And a second separating step, and a recycling step of adding at least a portion of the hydrophilic polymer solution separated in the second separating step to the mixture in the mixing step. The method for producing a sugar according to the first aspect of the invention, wherein the aqueous solvent used in the second separation step is acidic. The method for producing a sugar according to claim 1 or 2, wherein the mixture in the mixing step further contains a gelling agent. The method for producing a sugar according to claim 3, further comprising contacting at least a part of the mixture subjected to the saccharification step with an aqueous colloid or ion exchange resin containing a polyvinyl alcohol-based polymer as a main component to cause a gelling agent A gelling agent separation step separated from the above mixture. The method for producing a sugar according to the fourth aspect of the invention, wherein in the gelling agent separating step, at least a part of the mixture in contact with the aqueous colloid or ion exchange resin is at least a part of the first residue. The method for producing a sugar according to the fifth aspect of the invention, wherein at least a part of the first residue used in the gelling agent separation step is the hydrophilic polymer solution. The method for producing a sugar according to the fourth aspect of the invention, further comprising a third separation step of diluting the second residue with an aqueous solvent, separating into a separation liquid and a third residue, in the gelling agent separation step, and the above At least a portion of the mixture contacted with the aqueous colloid or ion exchange resin is the above separation liquid. The method for producing a sugar according to the seventh aspect of the invention, wherein the aqueous solvent used in the third separation step is acidic. The method for producing a sugar according to the fourth aspect of the invention, wherein the aqueous gel system is formed by chemical crosslinking of a polyvinyl alcohol-based polymer. The method for producing a sugar according to the fourth aspect of the invention, further comprising a gelling agent recycling step of adding at least a part of the gelling agent separated in the gelling agent separation step to the mixture in the mixing step. The method for producing a sugar according to claim 1 or 2, wherein the hydrophilic polymer is a polyvinyl alcohol polymer. The method for producing a sugar according to the third aspect of the invention, wherein the gelling agent is boric acid or borate. The method for producing a sugar according to claim 1 or 2, wherein the above The inorganic salt is at least one selected from the group consisting of sulfates, carbonates, nitrates, phosphates, and hydrogencarbonates. The method for producing a sugar according to claim 1 or 2, wherein the mixing step, the breaking step, the saccharifying step, the first separating step, the second separating step, and the recycling step are repeated plural times.