JP6931878B2 - Method for producing plant-based biomass-derived products by a two-step process - Google Patents

Description

The present invention relates to a method for producing a plant-based biomass-derived product having a two-step process.

Due to the growing environmental awareness in recent years, raw materials derived from biomass have been desired. However, biomass-derived raw materials, for example, which are particularly remarkable in the production of bioethanol, often use raw materials that compete with food such as starch and sugar, which leads to problems such as an increase in food prices and a decrease in food production. Was pointed out. Therefore, at present, attention is being paid to technology for producing biofuels and biochemicals from cellulosic biomass that does not compete with food.
Cellulosic biomass includes, for example, sorghum tree trunks and bunches, palm palm fruit fibers and seeds, bagasse (sorghum (including high biomass content) sorghum), cane tops (sorghum tops and leaves), rice straw, etc. Straw, paddy husk, corn cob, foliage, corn residue (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, yatrofa seed coat and shell, cashew husk, wood chips, switchgrass, napier grass, erianthus , Energy crops, energy canes, etc. All of these cellulosic biomasses contain lignin in addition to cellulose and hemicellulose that can be converted into sugar.

In order to obtain sugar from cellulosic biomass, a pretreatment step is usually required before the enzymatic saccharification treatment. The pretreatment loosens each component of the biomass or the bonds between the components, making it easier for the enzyme to access the cellulose. However, since the enzyme is adsorbed on the lignin existing in the system and inhibits saccharification, it is necessary to use a large amount of an expensive enzyme in order to obtain sufficient saccharification, so that the lignin is solubilized. It was desired.
In addition, hemicellulose is hyperdecomposed when exposed to high temperatures and is easily converted into a saccharification / fermentation inhibitor such as furfural, and it is necessary to suppress the overdecomposition.
Lignin is usually produced as a residue when converting biomass to ethanol, but it has been limited to use as a fuel because it contains a large amount of impurities such as enzymes and yeast. However, since it has a polyphenol-like structure and can be expected to be converted into chemicals and bioplastics, it is desired to extract lignin.

Patent Document 1 discloses a lignin derivative that undergoes a treatment step of stirring biomass in the presence of a solvent under high temperature and high pressure.
Patent Document 2 states that a cellulose derivative, a lignin derivative, and a hemicellulose derivative can be recovered by placing biomass in the presence of a mixed solvent containing water and an aprotic polar solvent and decomposing them under high temperature and high pressure. It is disclosed.
Patent Document 3 contains a 1,1-diphenylpropane unit in which a phenol derivative is grafted to the α-position of the phenylpropane unit of lignin, and comprises an ester moiety in which one or more hydroxyl groups are acylated. System polymers are disclosed.

Patent No. 5256679 Japanese Unexamined Patent Publication No. 2014-62051 Japanese Unexamined Patent Publication No. 2011-256381

However, many of the lignins obtained in Patent Document 1 have too small a molecular weight, have poor heat resistance for using lignin as a resin, and are secondarily induced in a separate reaction kettle in order to improve workability. It was necessary to change the lignin, and it was difficult to use lignin as it was. Also, there is no detailed description of hemicellulose and cellulose saccharides.
In the method described in Patent Document 2, the decomposition treatment temperature is high and hemicellulose is overdecomposed, so that it is difficult to recover it as a saccharide. There is no detailed description of the properties of cellulose derivatives. It was also disclosed that the material was homogenized by acylation denaturation with the hydroxyl group of lignin, and it was necessary to separately perform secondary degeneration in a reaction vessel. In addition, although the heat resistance is improved, the phenolic hydroxyl group is crushed, so that the reaction point disappears at the same time, which makes it attractive as a material.
Patent Document 3 discloses that the material is homogenized by acylating and denaturing the hydroxyl group of lignin. In this method, secondary derivation is required, and although the heat resistance is improved, the phenolic hydroxyl group is crushed, so that the reaction point disappears at the same time, which makes it attractive as a material.

An object of the present invention is to provide a method for producing a hemicellulose-derived saccharide, a cellulose-containing solid substance in which hyperdecomposition is suppressed, and a biomass-derived product which is a lignin with few impurities from plant-based biomass.

As a result of diligent studies, the present inventors have found that the above problems can be solved by going through the following specific two-step process.
That is, the present invention provides the following [1] to [17].
[1] A treatment step (1) for separating hemicellulose from plant-based biomass, a solid content obtained from the treatment step (1), and a solvent selected from an organic solvent alone or a mixed solvent of an organic solvent and water. A method for producing a plant-based biomass-derived product, which comprises a treatment step (2) of mixing and heat-treating.
[2] The plant-based biomass-derived product according to the above [1], wherein a cellulose-containing solid is obtained as a solid and a lignin-containing solution is obtained as a liquid by performing solid-liquid separation after the treatment step (2). Production method.
[3] The method for producing a plant-based biomass-derived product according to the above [2], wherein a solid lignin is obtained by removing a solvent from the lignin-containing solution.
[4] The method for producing a plant-based biomass-derived product according to any one of the above [1] to [3], wherein the plant-based biomass is a herbaceous biomass.
[5] The method for producing a plant-based biomass-derived product according to any one of the above [1] to [4], wherein hydrothermal treatment is performed as a treatment for separating hemicellulose in the treatment step (1).
[6] The plant according to the above [5], wherein the hydrothermal treatment is at least one selected from the group consisting of hydrothermal treatment using water and / or steam, steam blasting, and hydrothermal treatment using an acidic aqueous solution. A method for producing a product derived from water vapor.
[7] The method for producing a plant-based biomass-derived product according to the above [6], wherein the acidic aqueous solution is an acidic aqueous solution containing at least one selected from an inorganic acid and an organic acid.
[8] The pH of the system after the hemicellulose separation in the treatment step (1) to before the mixing of the solid content and the solvent obtained from the treatment step (1) in the treatment step (2), or the treatment step (2). ), The pH of the system when the solid content obtained from the treatment step (1) and the solvent are mixed is adjusted by using a basic substance, according to any one of the above [1] to [7]. A method for producing a product derived from plant-based biomass.
[9] The plant-based biomass-derived product according to the above [8], which adjusts the pH of the system when the solid content obtained from the treatment step (1) and the solvent are mixed in the treatment step (2). Production method.
[10] The method for producing a plant-based biomass-derived product according to the above [8] or [9], wherein the pH of the system after adjusting the pH using the basic substance is 3 or more and 12 or less.
[11] The organic solvent used in the treatment step (2) is at least one selected from ethanol, 1-butanol, 2-methyl-1-propanol, 2-butanol and acetone. 10] The method for producing a plant-based biomass-derived product according to any one of.
[12] The method for producing a plant-based biomass-derived product according to any one of the above [1] to [11], wherein the treatment step (2) is carried out under the following conditions A to C.
Condition A: The concentration of the solid content obtained from the treatment step (1) with respect to the solvent is 1% by mass or more and 50% by mass or less.
Condition B: The treatment temperature is 100 ° C. or higher and 300 ° C. or lower, and Condition C: The treatment time is 0.1 hour or more and 10 hours or less.
[13] A method for producing glucose, wherein the cellulose-containing solid obtained by the production method according to any one of the above [2] to [12] is enzymatically saccharified to obtain glucose.
[14] A resin composition using the lignin obtained by the method according to any one of the above [2] to [12].
[15] A lignin satisfying the following (11) to (13).
(11): The purity of lignin is 90% or more.
(12): The number average molecular weight is 650 or more, and (13): the 5% thermogravimetric reduction start temperature is 210 ° C. or more.
[16] The resin composition containing the lignin according to the above [15].
[17] A molded product using the resin composition according to the above [14] or [16].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing hemicellulose-derived saccharides, cellulose-containing solids with suppressed hyperdecomposition, and biomass-derived products which are lignins with few impurities from plant-based biomass. According to the present invention, since the first treatment step (1) is performed while suppressing the overdecomposition of hemicellulose, a high sugar yield can be obtained from the hemicellulose-derived saccharides and the cellulose-containing solids.

The method for producing a plant-based biomass-derived product of the present invention includes a treatment step (1) for separating hemicellulose from plant-based biomass, a solid content obtained from the treatment step (1), and an organic solvent alone or an organic solvent. It has a step including a treatment step (2) of mixing a solvent selected from a mixed solvent with water and performing a heat treatment. Hereinafter, embodiments of the present invention will be described in detail.

<Processing process (1)>
In this step, hemicellulose is separated from the plant biomass. The details will be described below.

[Plant-based biomass]
Examples of plant-based biomass include wood-based biomass and herbaceous biomass. Examples of woody biomass include conifers and broad-leaved trees such as Sugi, Hinoki, Hiba, Sakura, Eucalyptus, Beech, and Bamboo.
Herbaceous biomass includes palm tree trunk / air bunch, palm palm fruit fiber and seeds, bagasse (corn and high biomass sorghum), cane top (corn top and leaf), energy cane, rice straw, straw, etc. Corn cob, foliage, residue (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, yatrofa skin and shell, cashew shell, switchgrass, erianthus, high biomass yield crop, energy crop, Examples include energy canes.
Among these, from the viewpoint of availability and compatibility with the production method applied in the present invention, herbaceous biomass is preferable, and palm palm air bunch, straw, corn foliage / residue, bagasse, cane top, etc. Energy canes, residues after extraction of these useful components are more preferred, bagasse, cane tops and energy canes are more preferred, and bagasses, cane tops and energy canes are even more preferred.
As the plant-based biomass, crushed biomass can also be used. It may also be in the form of a block, a chip, or a powder. Further, it may be in either a dry state or a water-containing state.

[Processing conditions]
As the treatment step (1) for separating hemicellulose, a known method for treating plant biomass can be used, but here, it is preferable to perform hydrothermal treatment. Examples of the hydrothermal treatment include at least one selected from the group consisting of hydrothermal treatment using water and / or steam, steam blasting, and hydrothermal treatment using an acidic aqueous solution.
When performing hydrothermal treatment using an acidic aqueous solution, it is preferable to use an acidic aqueous solution containing at least one selected from an inorganic acid and an organic acid. Among them, at least one acid aqueous solution selected from the group consisting of an inorganic acid selected from dilute sulfuric acid, phosphoric acid, dilute hydrochloric acid and dilute nitrate, and an organic acid selected from formic acid, acetic acid, oxalic acid and malic acid. It can be used as an acidic aqueous solution.

In the treatment step (1), the charged concentration of the plant-based biomass as a raw material with respect to the aqueous solvent is usually 1% by mass or more and 95% by mass or less, preferably 3% by mass or more and 80% by mass or less, more preferably 5% by mass. % Or more and 50% by mass or less, and most preferably 5% by mass or more and 20% by mass or less.
When the concentration of the raw material plant-based biomass charged is 1% by mass or more, the amount of energy used for heating the aqueous solvent can be suppressed, and the energy efficiency of the treatment step (1) can be kept good. When the concentration of the raw material plant-based biomass charged is 95% by mass or less, the separation efficiency can be kept good.

The treatment temperature in the treatment step (1) is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 190 ° C. or lower, and further preferably 150 ° C. or higher and 180 ° C. or lower. Hemicellulose can be solubilized at 50 ° C. or higher. If the temperature is 200 ° C. or lower, overdecomposition of hemicellulose can be suppressed.
The treatment time in the treatment step (1) is preferably 1 minute or more and 5 hours or less, more preferably 3 minutes or more and 3 hours or less, further preferably 5 minutes or more and 2 hours or less, and particularly preferably 10 minutes or more and 1 It's less than an hour. If the treatment time is 1 minute or more, hemicellulose can be solubilized. If the treatment time is 5 hours or less, overdecomposition of hemicellulose can be suppressed.
The pressure of the reaction system in the treatment step (1) is preferably 0.1 MPa to 30 MPa. More preferable conditions are appropriately set because they are affected by temperature. Further, the processing step can be performed in an ambient atmosphere.
The treatment method in the treatment step (1) is not particularly limited, and examples thereof include standing and stirring treatment. For example, a general batch reactor, a semi-batch reactor, a pressure vessel, or the like can be used. Further, a method of treating a slurry composed of a plant-based biomass-derived solid and water or an acidic aqueous solution while extruding it with a screw or a pump is also applicable.

Hemicellulose is separated by solid-liquid separation of the reaction product after hydrothermal treatment. As the solid after solid-liquid separation, a solid content containing cellulose and lignin can be obtained.
The treatment step (1) may include a step of washing the obtained solid content with water. For example, water of 100 parts by mass or more and 10,000 parts by mass or less is added to 100 parts by mass of the obtained solid content and stirred, and then the solid content and the liquid phase are separated by filtration. The amount of water used for the washing with water is more preferably 1000 parts by mass or more and 5000 parts by mass or less, and further preferably 1000 parts by mass or more and 2000 parts by mass or less. When the amount of water used for washing with water is 100 parts by mass or more, a sufficient washing effect can be obtained, and when the amount is 10,000 parts by mass or less, it can be carried out without any problem in terms of equipment. By providing this water washing step, water-soluble components such as hemicellulose-derived sugars can be removed from the solid content.
The method for performing solid-liquid separation is not particularly limited, and examples thereof include filtration, filter press, centrifugation, and dehydrator.

<Processing process (2)>
This treatment step is a step of heat-treating by mixing the solid content obtained from the treatment step (1) with a solvent selected from an organic solvent alone or a mixed solvent of an organic solvent and water. In this step, lignin and cellulose are separated.
As the solvent, a solvent selected from an organic solvent alone or a mixed solvent of an organic solvent and water is used.

[Organic solvent]
The organic solvent is not particularly limited, and may be either a saturated or unsaturated linear alcohol or a branched alcohol. In addition, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran, ethylene glycol and polyethylene glycol may be used. Further, the organic solvent may be used alone or in combination of two or more.
Among them, at least one selected from methanol, ethanol, propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, pentanol, hexanol, heptanol, octanol, acetone and tetrahydrofuran. Is preferable, and one or more selected from 1-butanol, 2-methyl-1-propanol, 2-butanol, ethanol, pentanol, hexanol and acetone is more preferable, and 1-butanol and 2-methyl-1- It is more preferably at least one selected from propanol, 2-butanol, ethanol and acetone, further preferably 1-butanol, 2-methyl-1-propanol and 2-butanol, and 1-butanol. Is particularly preferable.

[Mixed solvent]
When the mixed solvent of the organic solvent and water is used, the above-mentioned organic solvent can be used, and the same applies to the preferable ones. As the water, for example, tap water, industrial water, ion-exchanged water, distilled water and the like can be used.
The concentration of the organic solvent in the mixed solvent is preferably 10% by weight or more and 80% by weight or less, more preferably 12% by weight or more and 75% by weight or less, and further preferably 15% by weight or more and 70% by weight or less. If the concentration of the organic solvent in the mixed solvent is within the above range, lignin can be sufficiently separated in the treatment step (2).

Here, the pH of the system from after the separation of hemicellulose in the above treatment step (1) to before mixing of the solid content obtained from the treatment step (1) in the treatment step (2) with the solvent, or in the treatment step (2). It is preferable to adjust the pH of the system when mixing the solid content obtained from the treatment step (1) and the solvent with a basic substance, and then perform the heat treatment in the treatment step (2). In particular, when hydrothermal treatment is performed using an acidic aqueous solution in the treatment step (1), it is preferable to adjust the pH before the heat treatment in the treatment step (2).
Since the treatment conditions of the treatment step (2) are stricter than those of the treatment step (1), if the pH in the system is inclined to acidity, it may cause undesired overdecomposition of the cellulose obtained in the treatment step (2). .. In order to suppress this overdecomposition, it is preferable to adjust the pH in the treatment step (2) until the solid content obtained from the treatment step (1) and the solvent are mixed.
Examples of the basic substance include inorganic bases such as sodium hydroxide, potassium hydroxide and calcium hydroxide, and organic bases such as ammonia. The pH before heating in the treatment step (2) is preferably 3 or more and 12 or less, more preferably 3 or more and 10 or less, further preferably 4 or more and 8 or less, particularly preferably 4 or more and 7 or less, and most preferably 4. Adjust to 6 or less. By setting the pH in the above range, overdecomposition of cellulose can be suppressed and a high sugar yield can be obtained.

[Processing conditions]
As the treatment conditions in the treatment step (2), it is preferable to carry out under conditions that satisfy all of the following conditions A to C.
Condition A
The charging concentration of the solid content obtained from the treatment step (1) with respect to the solvent is preferably 1% by mass or more and 50% by mass or less. When a plurality of organic solvents are used as the solvent, the concentration of the solid content charged is based on the total amount of the solvent. If the concentration of the solid content obtained from the treatment step (1) is 1% by mass or more, the energy efficiency of the lignin removal process is taken into consideration even when the amount of energy used for heating the solvent and removing the organic solvent is taken into consideration. Can be kept good. When the concentration of the solid content charged is 50% by mass or less, the amount of the solvent is sufficient, so that the separation efficiency of lignin can be kept good.
The concentration of the solid content obtained from the treatment step (1) with respect to the solvent is more preferably 3% by mass or more and 20% by mass or less, and further preferably 5% by mass or more and 15% by mass or less.

Condition B
The treatment temperature in the treatment step (2) is preferably 100 ° C. or higher and 300 ° C. or lower. When the treatment temperature is 100 ° C. or higher, the separation of lignin can be sufficiently promoted, and when the treatment temperature is 300 ° C. or lower, the decomposition of cellulose and the formation of impurities such as cork due to the repolymerization of lignin can be suppressed. ..
The treatment temperature is more preferably 150 ° C. or higher and 250 ° C. or lower, and even more preferably 170 ° C. or higher and 230 ° C. or lower.

Condition C
The treatment time in the treatment step (2) is preferably 0.1 hour or more and 10 hours or less. If the treatment time is 0.1 hours or more, the separation of lignin can be sufficiently promoted, and if it is 10 hours or less, the decomposition of cellulose and the production of impurities such as cork due to the repolymerization of lignin are suppressed. Can be done.
The treatment time is more preferably 0.2 hours or more and 8 hours or less, further preferably 1 hour or more and 6 hours or less, and particularly preferably 1 hour or more and 3 hours or less.

As another treatment condition in the treatment step (2), it is desired that the pressure of the reaction system is 0.5 MPa to 30 MPa. However, the preferable range of the pressure of the reaction system is appropriately set because it is affected by the amount and temperature of water and the organic solvent. Further, the processing step (2) can be performed in an ambient atmosphere. It is particularly preferable that the treatment step (2) is performed in an atmosphere in which oxygen is reduced by purging with nitrogen in order to suppress polymerization due to an oxidation reaction.
The treatment method in the treatment step (2) is not particularly limited, and examples thereof include standing and stirring treatment. For example, a general batch reactor, a semi-batch reactor, or the like can be used. Further, a method of treating a solid substance derived from plant biomass and a slurry composed of an organic solvent or water and an organic solvent while extruding them with a screw or a pump is also applicable.

The reaction product obtained after the heat treatment in the treatment step (2) can be solid-liquid separated to obtain a cellulose-containing solid as a solid and a lignin-containing solution as a liquid.
The solid-liquid separation after the treatment step (2) may include a step of washing the solid content obtained by the solid-liquid separation with water. The water washing step can be performed by adding, for example, 100 parts by mass or more and 10,000 parts by mass or less of water to 100 parts by mass of the solid content obtained after the solid-liquid separation and stirring. After stirring, the solid content and the liquid phase are separated by filtration.
As described above, the amount of water used in the washing step is preferably 100 parts by mass or more and 10000 parts by mass or less, more preferably 1000 parts by mass or more and 5000 parts by mass or less, and further preferably 1000 parts by mass or more and 2000 parts by mass or less. When the amount of water used for washing with water is 100 parts by mass or more, a sufficient washing effect can be obtained, and when the amount is 10,000 parts by mass or less, it can be carried out without any problem in terms of equipment. By this washing step, the organic solvent can be further removed, and the water-soluble component adhering to the cellulose-containing solid matter can be removed.

A cellulose-containing solid can be obtained by the solid-liquid separation after the heat treatment in the treatment step (2), or further through the water washing step. According to the production method according to the present embodiment, the cellulose-containing solid contained in the plant-based biomass can be recovered as a solid content obtained as a residue in the aqueous phase.
The separation method in the production method according to the present embodiment is not particularly limited, and examples thereof include filtration, filter press, centrifugation, and dehydrator.

The liquid phase obtained after the heat treatment in the treatment step (2) or after the further washing treatment contains lignin. For example, when a mixed solvent of water and an organic solvent is used and two phases are formed after the treatment, the solvent can be removed by vaporizing the organic phase obtained after separating the aqueous phase to obtain a solid lignin. can. Further, when the organic solvent is used alone, or when a mixed solvent with water is used but it is one phase after the heat treatment in the treatment step (2), the solvent is removed by vaporizing the organic solvent or the like. Solid lignin can be obtained as the remaining solid residue or by filtering the solid matter settled in water.

As described above, according to the production method of the present invention, hemicellulose, cellulose-containing solids and lignin can be produced as plant-based biomass-derived products. Each product will be described in detail below.

<Characteristics of lignin>
The lignin obtained by the production method of the present invention has the following characteristics.
(11): The purity of lignin is 90% or more.
(12): The number average molecular weight is 650 or more, and (13): the 5% thermogravimetric reduction start temperature is 210 ° C. or more.
In the above, the purity of lignin is preferably 92% or more, more preferably 94% or more. The number average molecular weight is preferably 700 or more, more preferably 750 or more. Further, the 5% thermogravimetric reduction start temperature is preferably 215 ° C. or higher, more preferably 220 ° C. or higher.
The methods for measuring the purity of lignin, the number average molecular weight, and the starting temperature for reducing the thermogravimetric analysis by 5% will be described later.

<Characteristics of hemicellulose-derived saccharides and the obtained cellulose-containing solids>
According to the production method of the present invention, the recovery rate of hemicellulose-derived saccharides with respect to hemicellulose in plant-based biomass is 50% by mass or more. When the recovery rate of hemicellulose-derived saccharides is less than 50% by mass, the saccharides that can contribute to fermentation decrease.
The cellulose-containing solid obtained by the production method of the present invention contains 60% by mass or more and 90% by mass or less of the cellulose and the cellulose decomposition product obtained by decomposing the cellulose as the solid content based on the total amount of the cellulose-containing solids. As other substances, lignin is contained in an amount of 5% by mass or more and 30% by mass or less, and hemicellulose and a hemicellulose decomposition product obtained by decomposing hemicellulose are contained in an amount of 0% by mass or more and 5% by mass or less. Further, the recovery rate of cellulose in the cellulose-containing solid matter with respect to the cellulose in the plant-based biomass is 70% by mass or more.
When cellulose and the cellulose decomposition product obtained by decomposing cellulose are less than 60% by mass, or when lignin exceeds 30% by mass, the saccharification rate when glucose is obtained by the enzymatic saccharification treatment is lowered. If hemicellulose and the hemicellulose decomposition product obtained by decomposing hemicellulose exceed 5% by mass, the separation / removal of lignin bound to hemicellulose becomes insufficient, and the saccharification rate when glucose is obtained by enzymatic saccharification treatment decreases. .. Further, when the cellulose recovery rate is less than 70% by mass, the glucose recovery rate with respect to cellulose in the plant-based biomass decreases.

<Use of cellulose-containing solids>
Since the cellulose contained in the cellulose-containing solid obtained by the production method of the present invention has a low lignin content, it is suitably used for saccharification treatment with an acid or an enzyme. Further, the cellulose-containing solid obtained by the production method of the present invention is in a state of being easily defibrated as compared with the cellulose-containing solid obtained by another method. Therefore, it has an advantage that it is easy to develop applications.
Further, ethanol, butanol, acetone and the like can be obtained from the cellulose-containing solid obtained by the production method of the present invention by using a known method.
In addition, from the cellulose-containing solids obtained by the production method of the present invention, rubber and tire reinforcing materials as substitutes for resin-reinforced fibers such as cellulose nanofibers and chemical fibers, food additives such as carboxymethyl cellulose and oligosaccharides, and lactic acid , Chemicals such as succinic acid can be obtained.

<Use of hemicellulose and lignin>
From the hemicellulose obtained by the production method of the present invention, food additives such as oligosaccharides and xylitol, and chemical products such as furfural can be obtained, which is useful.
Further, the lignin obtained by the production method of the present invention can be specifically used as a water repellent material for fuel and cement. It can also be applied to phenol resin, epoxy resin, polyurethane resin base resin raw material, epoxy resin additive (hardener), polyurethane resin modifier (flame retardant), thermoplastic resin additive and the like. This is due to the characteristic that lignin has a phenolic structural unit.
For the use of lignin as a base resin raw material, a conventionally known method can be used. One example is a resin composition in which lignin and a known cross-linking agent typified by hexamethylenetetramine are blended.
Various fillers and industrially obtained general phenol resins may be added to the resin composition in which the lignin and the cross-linking agent are mixed, if necessary. Such resin compositions are used for heat insulating materials for houses, electronic parts, resins for flax sands, resins for coated sands, resins for impregnation, resins for lamination, resins for FRP molding, automobile parts, reinforcing materials for automobile tires, and the like. Can be used.
Further, the introduction of an epoxy group into lignin and the use of lignin as an epoxy resin curing agent make it possible to apply it to an epoxy resin. In addition, by introducing a vinyl group, a maleimide group, an isocyanate group, or the like into lignin using a known method, application to a wider range of industrial resins becomes possible.

Regarding the use as an additive, for example, a conventionally known method described in JP-A-2014-15579, International Publication No. 2016/104634, etc. can be used. Various additives and fillers may be added to the resin composition in which the lignin and the thermoplastic resin are mixed, if necessary.

[Resin composition]
In another embodiment of the present invention, a resin composition containing lignin obtained by the above production method is provided. Further, in addition to the lignin obtained by the above production method, a resin component such as a thermoplastic resin or a thermosetting resin may be contained. Ingredients other than lignin will be described below.

<Thermoplastic resin>
The thermoplastic resin that can be blended in the resin composition according to the present embodiment is an amorphous thermoplastic resin having a glass transition temperature of 200 ° C. or lower, or a crystalline thermoplastic resin having a melting point of 200 ° C. or lower. Is preferable. Examples of the thermoplastic resin include polycarbonate resins, styrene resins, polystyrene elastomers, polyethylene resins, polypropylene resins, polyacrylic resins (polymethyl methacrylate resins, etc.), polyvinyl chloride resins, cellulose acetate resins, and polyamide resins. Low melting point polyester resin (PET, PBT, etc.) typified by a combination of terephthalic acid and ethylene glycol, terephthalic acid and 1,4-butanediol, a copolymer containing polylactic acid and / or polylactic acid, acrylonitrile-butadiene -Sterium resin (ABS resin), polyphenylene oxide resin (PPO), polyketone resin, polysulfone resin, polyphenylene sulfide resin (PPS), fluororesin, silicon resin, polyimide resin, polybenzimidazole resin, polyamide elastomer, etc., and others. Examples thereof include a copolymer with the above-mentioned monomer.
The content of the thermoplastic resin in the resin composition according to the present invention is 30% by mass or more and 99.9% by mass or less with respect to the total amount of the resin composition from the viewpoint of obtaining remarkable fluidity and strength. It is preferable, 40% by mass or more and 99.9% by mass or less is more preferable, 45% by mass or more and 99.9% by mass or less is further preferable, and 50% by mass or more and 99.9% by mass or less is particularly preferable.
In addition to the cellulose-containing solid and the thermoplastic resin described above, the resin composition according to the present embodiment may contain a resin, an additive and / or a filler compatible with the thermoplastic resin composition. good.

<Thermosetting resin>
As a thermosetting resin that can be blended in the resin composition according to the present embodiment, a lignin-reactive compound having a functional group capable of reacting with lignin may be blended. Examples of the compound having a functional group capable of reacting with lignin include a compound having an electrophilic substitution reaction with a phenol compound, a compound having an epoxy group, and a compound having an isocyanate group.
Since lignin has a phenolic structural unit, it can be applied as a base resin raw material such as a phenol resin and an epoxy resin, an additive (curing agent) for an epoxy resin, and the like.
(A compound that causes an electrophilic substitution reaction with a phenol compound)
Examples of the compound that causes an electrophilic substitution reaction with the phenol compound include formaldehyde, a formaldehyde donating curing agent compound, and a formaldehyde equivalent compound. Commercially, hexamethylenetetramine, hexaformaldehyde, and paraformaldehyde can be used.
Further, the resin composition according to the present embodiment may further contain a phenol resin in addition to lignin and hexamethylenetetramine. As described above, since lignin has a phenolic structural unit, the phenol resin is a lignin diluent, bulking agent, etc. within a range that does not deteriorate the physical properties such as processability, strength, and heat resistance of the resin composition. Can be used as.

(Compound with epoxy group)
Compounds having an epoxy group belong to the category of so-called epoxy resins. Examples include 2,2-bis (4'-hydroxyphenyl) propane (called bisphenol A), bis (2-hydroxyphenyl) methane (called bisphenol F), and 4,4'-dihydroxydiphenyl. Sulfur (called bisphenol S), 4,4'-dihydroxybiphenyl, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, these halogen and alkyl group substituents, butanediol, ethylene glycol, Compounds containing two or more hydroxyl groups in the molecule such as erythlit, novolak, glycerin, and polyoxyalkylene, and glycidyl ether epoxy resins synthesized from epichlorohydrin and the like; compounds containing the hydroxyl groups in the molecule. And glycidyl ester-based epoxy resin synthesized from phthalic acid glycidyl ester, etc .; synthesized from primary or secondary amines such as aniline, diaminodiphenylmethane, metaxylene diamine, 1,3-bisaminomethylcyclohexane, and epichlorohydrin. Epoxy resins containing glycidyl groups such as glycidylamine-based epoxy resins; epoxy resins containing no glycidyl groups such as epoxidized soybean oil, epoxidized polyolefins, vinylcyclohexendioxides, and dicyclopentadiendioxides can be mentioned. Among these, cresol novolac type and phenol novolac type epoxy resins having similar chemical structures to lignin and good compatibility are preferable.

Further, the thermosetting resin composition may further contain a phenol resin in addition to the compound containing lignin and an epoxy group.
When the lignin contained in the thermosetting resin composition is a compound containing an epoxy group, a curing accelerator can be appropriately added depending on the purpose of accelerating the curing reaction. Specific examples include imidazoles such as 2-methylimidazole, 2-ethyl imidazole and 2-ethyl-4-methyl imidazole, 2- (dimethylaminomethyl) phenol, and 1,8-diazabicyclo (5,4). 0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, and cetyltrimethylammonium salt, and tri. Examples thereof include quaternary phosphonium salts such as phenylbenzylphosphonium salt, triphenylethylphosphonium salt and tetrabutylphosphonium salt, and metal compounds such as tin octylate. Examples of the counter ion of the quaternary phosphonium salt include halogen, organic acid ion, hydroxide ion and the like, and organic acid ion and hydroxide ion are particularly preferable.

(Compound with isocyanate group)
The compound having an isocyanate group is obtained by reacting polyisocyanate or polyisocyanate with a polyol. Examples of the polyisocyanate include aromatic polyisocyanates such as tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), polypeptide MDI (MDI-CR), and carbodiimide-modified MDI (liquid MDI), and norbornandiisocyanate (NBDI). , Isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4'-methylene-bis (cyclohexyl isocyanate) (hydrogenated MDI), xylylene diisocyanate (XDI) and other aliphatic polyisocyanates, and blocked isocyanates. be able to. Among these, it is preferable to use toluene diisocyanate (TDI) and 4,4'-diphenylmethane diisocyanate (MDI).
Further, the thermosetting resin composition may further contain a phenol resin in addition to the lignin and the isocyanate compound.

A curing accelerator can be appropriately added to the thermosetting resin composition depending on the purpose of accelerating the curing reaction. Examples of the curing accelerator include organometallic catalysts of zirconium and aluminum, dibutyltin laurate, phenol salts of DBU, octylates, amines, imidazoles, etc., but in terms of colorability, organometallic catalysts, etc. For example, aluminum sec-butyrate, ethylacetate acetate aluminum diisopropirate, zirconium tributoxyacetylacetonate, zirconium tetraacetylacetonate and the like are particularly preferable.

(Other resin components)
In addition to lignin, the resin composition according to the present embodiment may contain resins such as phenol resin, urea resin, melamine resin, silicone resin, unsaturated polyester resin, alkyd resin, and polyurethane resin.
Like lignin, it has a phenolic hydroxyl group, can react with lignin, and can be used as a diluent for lignin. Therefore, among the above resins, phenol resin is preferable.

<Inorganic filler, organic filler>
The resin composition according to the present embodiment may contain a filler. The filler may be an inorganic filler or an organic filler.
Examples of the inorganic filler include spherical or crushed molten silica, silica powder such as crystalline silica, alumina powder, glass powder, glass fiber, glass flakes, mica, talc, calcium carbonate, alumina, hydrated alumina, and nitride. Examples thereof include boron, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, magnesium oxide and the like.
Examples of the organic filler include carbon fiber, aramid fiber, paper powder, cellulose fiber, cellulose powder, paddy shell powder, fruit shell / nut powder, chitin powder, starch and the like.
The inorganic filler and the organic filler may be contained alone or in a combination of two or more, and the content thereof is determined according to the purpose.

<Other additives>
Various additives can be added to the resin composition according to the present embodiment as long as the characteristics of the molded product obtained from the resin composition are not impaired. Further, a compatibilizer, a surfactant and the like can be further added depending on the purpose.
As the compatibilizer used together with the thermoplastic resin, a resin obtained by adding maleic anhydride, epoxy, etc. to the thermoplastic resin and introducing a polar group, for example, maleic anhydride-modified polyethylene resin, maleic anhydride-modified polypropylene resin, and various commercially available phases. A solubilizer may be used in combination.
Further, examples of the surfactant include linear fatty acids such as stearic acid, palmitic acid and oleic acid, and branched / cyclic fatty acids with rosins, but are not particularly limited thereto.
Further, as additives that can be blended in addition to the above-mentioned ones, flexible agents, heat stabilizers, ultraviolet absorbers, flame retardants, antistatic agents, defoamers, thixotropy-imparting agents, mold release agents, antioxidants, etc. Agents, plasticizers, low stress agents, coupling agents, dyes, light scatterers, small amounts of thermoplastics, etc.

[Molding]
The molded product according to the embodiment of the present invention is obtained from a resin composition containing lignin obtained by the above-mentioned production method. As an example of a molded product, a cured resin composition in which lignin and a cross-linking agent are blended, and various fillers and industrially obtained general phenol resins are blended as necessary. Examples thereof include those that have been molded into a predetermined shape and then cured, those that have been cured and then molded, and the like.
The method of molding into a predetermined shape is not particularly limited as long as the resin composition can be molded. For example, when the resin composition is a thermosetting resin composition, examples of the method for molding into a predetermined shape include a compression molding method, an injection molding method, a transfer molding method, a medium-sized molding method, and an FRP molding method. When the resin composition is a thermoplastic resin composition, examples of the method for molding into a predetermined shape include an extrusion molding method and an injection molding method.

As an example of the molded product, a cured resin composition in which lignin and a cross-linking agent are blended, and various fillers and industrially obtained general phenol resins are further blended as needed. Examples thereof include those which are molded into a predetermined shape and then cured, those which are cured and then molded, and those in which a resin composition obtained by mixing lignin with a thermoplastic resin is molded. Molded products of such resin compositions include heat insulating materials for houses, electronic parts, resins for flax sands, resins for coated sands, resins for impregnation, resins for lamination, resins for FRP molding, automobile parts, and reinforcement of automobile tires. It can be used for materials, OA equipment, machines, information and communication equipment, industrial materials, and the like.

[Glucose production method]
Glucose can be produced using the cellulose-containing solid obtained by the method for producing a cellulose-containing solid according to the embodiment of the present invention.

In the method for producing glucose according to the present embodiment, the conditions for the enzymatic saccharification treatment are as follows.
The enzyme acting on the cellulose contained in the cellulose-containing solid and the cellulose decomposed product obtained by decomposing the cellulose may be 0.1% by mass or more and 200% by mass or less with respect to the total amount of the cellulose-containing solid. can. The enzyme activity used in the enzyme saccharification treatment can be 100 CUN / g or more and 10000 CUN / g or less. Further, when the treatment temperature in the enzyme saccharification treatment is 30 ° C. or higher and 70 ° C. or lower, the enzyme is activated and the saccharification rate can be improved. If the treatment time in the enzyme saccharification treatment is 12 hours or more and 168 hours or less, the enzyme is activated and the saccharification rate can be improved.

Hereinafter, the present embodiment will be described in more detail with reference to Examples, but the present embodiment is not limited thereto.

[Production example of cellulose-containing solids]
<Manufacturing example 1>
Processing process (1)
Plant-based biomass (for example, plant-based biomass such as bagasse), which is a raw material, is crushed to several mm or less as a pretreatment. After pulverization, water is added to prepare a raw material slurry having a solid substance concentration of about 15% by mass. Phosphoric acid is added to this raw material slurry so that the pH in the raw material slurry becomes 2.0, and the mixture is mixed.
The raw material slurry is supplied to a reactor (pressure vessel) and heated to a supercritical state or a subcritical state. When hydrolyzing hemicellulose in the raw material slurry, it is preferable to hydrolyze it at a temperature of 170 ° C.
Processing process (2)
The solid content obtained from the treatment step (1), a mixed solvent of water and 1-butanol prepared at a 1-butanol concentration of 34% by mass, and sodium hydroxide so as to have a pH of 3, SUS (stainless steel) having an internal volume of 0.92 L. ) Put it in a batch type device. The total amount of solvent was 315 g. The raw material charging concentration was set to raw material / solvent = 1/10 (solid content charging concentration: 9.1% by mass).
After purging the inside of the SUS batch type apparatus with nitrogen, the temperature was raised to 200 ° C., and the treatment was carried out for 2 hours. The treatment time was defined as the elapsed time after reaching 200 ° C. In addition, the temperature was measured with a thermocouple.
After the treatment was completed, the SUS batch type apparatus was cooled, and after the temperature dropped to around room temperature, all the contents were taken out. After the treatment, the solid content and the liquid phase were separated by filtration.
200 g of water was added to the solid content, and after stirring for 30 minutes, the solid content and the liquid phase were separated by filtration. The operation was repeated 3 times to obtain a cellulose-containing solid substance. The liquid phase was liquid / liquid separated into an aqueous phase and a 1-butanol phase by a separating funnel. The solvent of the 1-butanol phase was removed by an evaporator (70 ° C., water bath) and then vacuum dried under the condition of 125 ° C. to obtain lignin.

<Manufacturing example 2>
In the treatment step (2), all were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 4.
<Manufacturing example 3>
All were carried out in the same manner as in Production Example 2 except that the 1-butanol concentration in the mixed solvent in the treatment step (2) was 50% by mass.

<Manufacturing example 4>
The same procedure as in Production Example 3 was carried out except that ethanol was used as the organic solvent constituting the mixed solvent in the treatment step (2). Since the liquid phase after solid-liquid separation was one phase, the solid content precipitated in water due to the decrease in solubility was separated by filtration by removing the organic solvent with an evaporator, and then the condition was 125 ° C. The mixture was vacuum dried to obtain lignin.

<Manufacturing example 5>
Lignin was obtained by the same operation as in Production Example 4 except that acetone was used as the organic solvent constituting the mixed solvent in the treatment step (2).
<Manufacturing example 6>
All were carried out in the same manner as in Production Example 3 except that 2-methyl1-propanol was used as the organic solvent constituting the mixed solvent in the treatment step (2).
<Manufacturing example 7>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 5 in the treatment step (2).
<Manufacturing example 8>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 6 in the treatment step (2).

<Manufacturing example 9>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 7 in the treatment step (2).
<Manufacturing example 10>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 10 in the treatment step (2).
<Manufacturing example 11>
All were carried out in the same manner as in Production Example 1 except that the pH was adjusted to 12 in the treatment step (2).
<Production Example 12> (Only water is used in the treatment step (1), not an acidic aqueous solution)
First, plant-based biomass (for example, plant-based biomass such as bagasse), which is a raw material, is pulverized to several mm or less as a pretreatment. After pulverization, water is added to prepare a raw material slurry having a solid substance concentration of about 10% by mass.
The raw material slurry is supplied to a reactor (pressure vessel) and heated to a supercritical state or a subcritical state. When hydrolyzing hemicellulose in the raw material slurry, it is preferable to hydrolyze it at a temperature of 170 ° C. After that (all were carried out in the same manner as in Production Example 1 except that sodium hydroxide was added and the pH was not adjusted in the treatment step (2).

<Manufacturing example 13>
In the treatment step (2), all were carried out in the same manner as in Production Example 1 except that sodium hydroxide was added and the pH was not adjusted.
<Comparative manufacturing example>
All of the same as in Production Example 13 was carried out except that the plant-based biomass as a raw material was treated with a mixed solvent of water and 1-butanol without going through the treatment step (1) which is a hydrothermal treatment step.

<Analysis of the amount of cellulose in plant biomass and cellulose-containing solids>
The amount of cellulose in the plant biomass and the cell roll-containing solid was calculated according to the constituent sugar analysis after the pretreatment shown below.
[Preprocessing]
As a pretreatment, a raw material as a sample was crushed using a Willey mill and dried at 105 ° C.
[Constitutive sugar analysis]
An appropriate amount of a sample of plant-based biomass or cellulose-containing solid was weighed, 72% sulfuric acid was added, and the mixture was left at 30 ° C. for 1 hour with occasional stirring. The reaction mixture was completely transferred to a pressure-resistant bottle while being mixed with pure water, treated in an autoclave at 120 ° C. for 1 hour, and then the filtrate and the residue were filtered off. The monosaccharides in the filtrate were quantified by high performance liquid chromatography. The C6 polysaccharide (mainly glucan) was defined as cellulose, and the C5 polysaccharide (mainly xylan) was defined as hemicellulose.
[Lignin]
The residue obtained by filtration in the process of constituent sugar analysis was dried at 105 ° C., weighed, and the decomposition residue ratio was calculated. Furthermore, the lignin content was calculated by correcting the ash content.

<Cellulose recovery rate>
Cellulose recovery rate (% by weight) = (recovery amount of cellulose-containing solids (g) x ratio of cellulose in cellulose-containing solids (% by weight) / 100) / amount of cellulose in plant-based biomass (g) x 100
<Hydroxymethylfurfural production rate>
The concentration of hydroxymethylfurfural was calculated by a high performance liquid chromatograph (HPLC1200 series manufactured by Agilent).
Hydroxymethylfurfural production rate (mass%) = hydroxymethylfurfural concentration (mg / L) x 10-6 x solution volume (mL) / plant biomass (g) x 100

In Production Examples 1 to 12, it was found that the production of hydroxymethylfurfural due to overdecomposition was suppressed and a high cellulose recovery rate could be obtained.

Examples 1-13
[Evaluation method for the obtained cellulose-containing solids]
<Enzyme saccharification treatment>
1 g (dry weight) of the cellulose-containing solid was put into a 50 mL centrifuge tube and sterilized at 121 ° C. for 20 minutes. The acetic acid buffer solution subjected to the same sterilization treatment was added to the centrifuge tube so that the liquid volume was about 20 mL and the pH was 5, and then the amount of the enzyme shown in Table 3 (manufactured by Nagase ChemteX Corporation, Cellurizer ACE). Was put in. The centrifuge tube was shaken at 120 rpm for 72 hr in a constant temperature bath at 50 ° C.
When 1 ml of the enzyme was added to 4 ml of a 0.625% solution (pH 4.5) of 0.625% sodium carboxymethyl cellulose and allowed to act at 40 ° C. for 30 minutes, a reduction equivalent to 1 μmol of glucose per minute The activity that produces force is expressed as 1 CUN. The enzyme has an enzyme activity of 1600 CUN / g or more.

<Analysis of the amount of glucose in the obtained xylose + xylooligosaccharide and cellulose-containing solids>
1. 1. Sugar analysis Sugars (xylose, xylooligosaccharide, glucose) were analyzed by HPLC under the following conditions.
Measurement condition column: Showa Denko Shodex SP-G (guard column) + SP0810
Mobile phase: distilled water (HPLC grade)
Detector: RI (60 ° C in the cell)
Column temperature: 80 ° C
Injection volume: 50 μL
2. Sample preparation Using a pipettor, collect 0.2 mL of the sample (solution) in a 10 mL vial.
Add 1.8 mL of distilled water and mix well (10-fold dilution).
Collect in a vial.
3. 3. Calculation method The glucose concentration (g-glucose / L) is calculated using the calibration curve.
Glucose recovery rate (%) = (Glucose amount (g) in cellulose-containing solid enzyme saccharified solution x Cellulose-containing solid recovery rate (mass%) / 100) / Glucose amount in plant biomass (g) x 100

In Examples 1 to 12 using the cellulose-containing solid produced by the production example of the present invention, the glucose recovery rate based on the amount of glucose in the plant-based biomass obtained from the cellulose-containing solid by enzymatic saccharification shows a high value. rice field. In Example 13 using the cellulose-containing solid obtained in Production Example 13 in which the pH was not adjusted in the treatment step (2), the total amount of the recoverable cellulose-containing solid was lower than in other production examples. Therefore, when the amount of enzyme is 0.1 mL, the absolute amount of cellulose decomposed into sugar is low, so that the glucose recovery rate is lower than the others.

Example 9 and Comparative Example 1
(Xylose, xylooligosaccharide, glucose) Recovery rate (%) = (Amount of xylose in hydrothermal solution (g) + Amount of xylose oligosaccharide in hydrothermal solution (g) + (Amount of glucose in cellulose-containing solid enzyme saccharified solution) (G) × Cellulose-containing solid recovery rate (% by mass) / 100)) / (Amount of xylose in plant biomass (g) + Amount of glucose in plant biomass (g)) × 100

According to the production method of the present invention, hemicellulose-derived saccharides (xylose and xylooligosaccharide) can be recovered by suppressing hyperdecomposition, so that the saccharides can be efficiently recovered based on plant biomass.

<Measurement of lignin purity>
The same procedure as above <raw material composition analysis> was performed.
<Number average molecular weight>
The number average molecular weight of the above-mentioned lignin was measured by gel permeation chromatography (GPC) using a tetrahydrofuran solvent (measurement temperature 40 ° C., detector RI). The number average molecular weight is a polystyrene-equivalent number average molecular weight.
<Thermal weight reduction start temperature (Td5)>
The 5% thermogravimetric reduction start temperature (Td5) was measured with EXSTAR6000 TG / DTA6200 manufactured by SII. A sample of about 10 mg was weighed in a Pt pan, and the temperature was measured from a temperature rising rate of 10 ° C./min, a measurement atmosphere: air of 200 mL / min, and a temperature of 35 ° C. to 800 ° C. to determine a temperature at which the weight was reduced by 5%.
<Phenolic hydroxyl group equivalent>
A solvent in which deuterated chloroform, pyridine, and cyclohexanol (internal standard) are mixed is added to purified lignin, and 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxa is used as a derivatizing reagent. Phosphoran was added and heated at 50 ° C. for 1 hour. Then, 31 PNMR measurement was carried out under the following measurement conditions.
Pulse width: 30 °
Repeat time: 2 seconds Measurement range: -60 to 200 ppm
Number of integrations: 200 times The internal standard cyclohexanol-derived signal is 145.2 ppm, 144.7 to 136.6 ppm are assigned as phenolic hydroxyl groups (Ph-OH), and phenolic hydroxyl group equivalents (g / eq) are derived from the integrated values. ) Was calculated.

As can be seen from Table 4, lignin having high heat resistance was obtained. In addition, since this production method does not carry out secondary modification, it has a high amount of phenolic hydroxyl groups. Therefore, it can be suitably used as a material.

Example 9 and Comparative Example 1
[Evaluation of Thermosetting Resin Composition Containing Hexamethylenetetramine]
A thermosetting resin composition was prepared using the lignins obtained in Production Example 9 and Comparative Production Example. In addition, the cured product was prepared and its physical properties were evaluated.
<Formulation of thermosetting resin composition and molding method of cured product>
Each component was placed in a mortar at the compounding ratio shown in Table 2, pulverized at room temperature, mixed, mixed at 100 ° C. for 5 minutes using an open roll kneader, and then cooled to room temperature. The mixture was pulverized in a mortar, sandwiched between aluminum plates coated with a mold release agent, and molded at 150 ° C. for 60 minutes under reduced pressure using a vacuum press. After molding, it was treated at 200 ° C. for 120 minutes to obtain a molded product.
<Bending strength measurement method>
A sample of 5 mm × 50 mm × 1 mm was cut out from the obtained molded product, and the bending strength was measured using Instron 5566 under the conditions of a three-point bending mode, a span of 30 mm, and a speed of 2 mm / min.
<Measurement method of glass transition temperature>
The glass transition temperature was measured by the solid viscoelastic method. A sample of 5 mm × 30 mm × 1 mm is cut out from the obtained molded product, and using DMA8000 (manufactured by Perkin Elmer Japan Co., Ltd.), the temperature rise temperature is 2 ° C./min until the temperature reaches 0 ° C. to 300 ° C. or the limit minimum elastic modulus. The measurement was performed at 1 Hz. The peak temperature of the obtained tan δ was defined as the glass transition temperature (Tg).

As can be seen from the results in Table 5, in Example 13 using the lignin obtained by the production method of the present invention, a molded product having high heat resistance and excellent physical characteristics was obtained.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a method for producing hemicellulose-derived saccharides, cellulose-containing solids with suppressed hyperdecomposition, and biomass-derived products which are lignins with few impurities from plant-based biomass. According to the present invention, since the first treatment step (1) is performed while suppressing the overdecomposition of hemicellulose, a high sugar yield can be obtained from the hemicellulose-derived saccharides and the cellulose-containing solids.

Claims (17)

Treatment step (1) to separate hemicellulose from plant-based biomass,
A treatment step (2) in which the solid content obtained from the treatment step (1) is heat-treated by mixing the organic solvent alone or a solvent selected from a mixed solvent of the organic solvent and water.
Contains and
The pH of the system after the separation of hemicellulose in the treatment step (1) to before mixing of the solid content and the solvent obtained from the treatment step (1) in the treatment step (2), or the treatment in the treatment step (2). A method for producing a plant-based biomass-derived product, wherein the pH of the system when the solid content obtained from the step (1) and the solvent are mixed is adjusted using a basic substance. Treatment step (1) to separate hemicellulose from plant-based biomass,
A treatment step (2) in which the solid content obtained from the treatment step (1) is heat-treated by mixing the organic solvent alone or a solvent selected from a mixed solvent of the organic solvent and water.
Contains and
A method for producing a plant-based biomass-derived product, wherein the treatment temperature in the treatment step (1) is 100 ° C. or higher and 190 ° C. or lower. The pH of the system after the separation of hemicellulose in the treatment step (1) to before mixing of the solid content and the solvent obtained from the treatment step (1) in the treatment step (2), or the treatment in the treatment step (2). The method for producing a plant-based biomass-derived product according to claim 2 , wherein the pH of the system when the solid content obtained from the step (1) and the solvent are mixed is adjusted using a basic substance. The method for producing a plant-based biomass-derived product according to claim 1 or 3 , wherein in the treatment step (2), the pH of the system when the solid content obtained from the treatment step (1) and the solvent are mixed is adjusted. .. The method for producing a plant-based biomass-derived product according to any one of claims 1, 3 and 4, wherein the pH of the system after adjusting the pH using the basic substance is 3 or more and 12 or less. The plant-based biomass-derived product according to any one of claims 1 to 5, wherein a cellulose-containing solid is obtained as a solid and a lignin-containing solution is obtained as a liquid by performing solid-liquid separation after the treatment step (2). Product manufacturing method. The method for producing a plant-based biomass-derived product according to claim 6 , wherein solid lignin is obtained by removing the solvent from the lignin-containing solution. The method for producing a plant-based biomass-derived product according to any one of claims 1 to 7 , wherein the plant-based biomass is a herbaceous biomass. The method for producing a plant-based biomass-derived product according to any one of claims 1 to 8 , wherein hydrothermal treatment is performed as a treatment for separating hemicellulose in the treatment step (1). The plant-based biomass-derived production according to claim 9 , wherein the hydrothermal treatment is at least one selected from the group consisting of hydrothermal treatment using water and / or steam, steam blasting, and hydrothermal treatment using an acidic aqueous solution. How to make things. The method for producing a plant-based biomass-derived product according to claim 10 , wherein the acidic aqueous solution is an acidic aqueous solution containing at least one selected from an inorganic acid and an organic acid. Any one of claims 1 to 11 , wherein the organic solvent used in the treatment step (2) is at least one selected from ethanol, 1-butanol, 2-methyl-1-propanol, 2-butanol and acetone. The method for producing a plant-based biomass-derived product according to the section. The method for producing a plant-based biomass-derived product according to any one of claims 1 to 12 , wherein the treatment step (2) is carried out under the following conditions A to C.
Condition A: The concentration of the solid content obtained from the treatment step (1) with respect to the solvent is 1% by mass or more and 50% by mass or less.
Condition B: The treatment temperature is 100 ° C. or higher and 300 ° C. or lower, and Condition C: The treatment time is 0.1 hour or more and 10 hours or less. A method for producing glucose, wherein the cellulose-containing solid obtained by the production method according to claim 6 is enzymatically saccharified to obtain glucose. A lignin that satisfies the following (11) to (13).
(11): The purity of lignin is 90% or more.
(12): The number average molecular weight is 650 or more, and (13): the 5% thermogravimetric reduction start temperature is 210 ° C. or more. A resin composition comprising the lignin according to claim 15. A molded product using the resin composition according to claim 16.