JPWO2017222084A1 - Production method of plant biomass origin product by two steps process - Google Patents

Abstract

Process step (1) for separating hemicellulose from plant biomass, solid content obtained from process step (1), and solvent selected from organic solvent alone or mixed solvent of organic solvent and water are mixed. A process for producing a plant-based biomass-derived product, comprising a treatment step (2) of heating and treating.

Description

  The present invention relates to a method of producing plant-based biomass-derived products having a two-stage process.

With the recent increase in environmental awareness, biomass-derived raw materials have become desirable. However, although biomass-derived raw materials are particularly prominent in, for example, the production of bioethanol, they often use raw materials that compete with food such as starch and sugar, leading to problems such as increased food prices and decreased food production. Was pointed out. Therefore, technology for producing biofuels / biochemicals from cellulosic biomass that does not compete with food is currently attracting attention.
As cellulosic biomass, for example, palm palm trunk and empty bunches, palm palm fruit fibers and seeds, bagasse (sugarcane (including high biomass amount sugar cane) squeezed), cane top (sugar cane top and leaf), rice straw, Wheat straw, rice husk, corn cobs / stalks / corns residue (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, Jatropha seed coat and shell, cashew shell, wood chips, switchgrass, napiergrass, Erianthus Energy crops and energy cane. 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 prior to enzymatic saccharification treatment. By the pretreatment, the components of the biomass or bonds between the components are loosened, and the enzyme can easily access the cellulose. However, since the enzyme adsorbs to lignin present in the system to inhibit the saccharification, in order to obtain sufficient saccharification, it is necessary to use a large amount of expensive enzyme, so lignin solubilization It was desired.
In addition, hemicellulose is over-decomposed when exposed to high temperature, easily converted to a saccharification / fermentation inhibitor such as furfural, and it is necessary to suppress the over-decomposition.
Although lignin is usually produced as a residue when converting biomass to ethanol, it contains many impurities such as enzymes and yeast, and so has been limited to use as fuel. However, because it has a polyphenol-like structure, conversion to chemicals and bioplastics can be expected, so it is desirable to extract lignin.

Patent Document 1 discloses a lignin derivative which is subjected to a treatment process of stirring biomass under high temperature and high pressure in the presence of a solvent.
In Patent Document 2, a cellulose derivative, a lignin derivative and a hemicellulose derivative are recovered by placing biomass in a mixed solvent containing water and an aprotic polar solvent, and decomposing these under high temperature and high pressure conditions. It is disclosed.
Patent Document 3 discloses a heat-resistant lignin comprising a 1,1-diphenylpropane unit grafted with a phenol derivative at the α-position of a phenylpropane unit of lignin, and an ester moiety acylated with one or more hydroxyl groups. Based polymers are disclosed.

Patent No. 5256679 JP-A-2014-62051 JP, 2011-256381, A

However, lignin obtained in Patent Document 1 is often too low in molecular weight, and the heat resistance is poor when using lignin as a resin, and in order to improve workability, secondary induction in a separate reaction kettle is required. Lignin itself was difficult to use. Also, there is no detailed description of hemicellulose and cellulose sugars.
In the method described in Patent Document 2, the decomposition treatment temperature is high, and hemicellulose is overly decomposed, so recovery as saccharides is difficult. There is no detailed description of the properties of the cellulose derivative. It was also disclosed to homogenize the material by performing acylation modification with the hydroxyl group of lignin, and it was necessary to conduct secondary derivatization separately in a reaction kettle. In addition, although the heat resistance is increased, since the phenolic hydroxyl group is crushed, the reaction point is also lost at the same time, which makes the material attractive.
Patent Document 3 discloses that the material is homogenized by subjecting hydroxyl groups of lignin to acylation modification. In this method, it is necessary to make a secondary derivative, and although the heat resistance is increased, the phenolic hydroxyl group is crushed, so that the reaction point is simultaneously lost, which makes the material attractive.

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

As a result of intensive investigations, the present inventors have found that the above-mentioned problems can be solved by passing through the following specific two-stage process.
That is, the present invention provides the following [1] to [17].
[1] Process step (1) for separating hemicellulose from plant biomass, solid content obtained from process step (1), solvent selected from organic solvent alone or mixed solvent of organic solvent and water And a treatment step (2) of heat-treating the mixture, and a method for producing a plant-based biomass-derived product.
[2] The plant-based biomass-derived product according to the above [1], wherein the cellulose-containing solid is obtained as a solid and the 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 biomass-derived product according to the above [2], wherein solid lignin is obtained by removing the 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 treatment for separating hemicellulose in the treatment step (1).
[6] The plant according to the above-mentioned [5], wherein the hydrothermal treatment is at least one selected from the group consisting of hydrothermal treatment using water and / or steam, steam explosion, and hydrothermal treatment using an acidic aqueous solution. Method of producing biomass-derived products.
[7] The method for producing a plant biomass-derived product according to the above [6], wherein the acidic aqueous solution is an acidic aqueous solution containing at least one selected from inorganic acids and organic acids.
[8] The pH of the system from the hemicellulose separation in the treatment step (1) to the mixing of the solid content obtained from the treatment step (1) in the treatment step (2) and the solvent, or the treatment step (2 PH of the system at the time of mixing solid content obtained from process process (1) in a), and a solvent is adjusted using a basic substance, Any one of said [1]-[7] A method of producing a plant-based biomass-derived product.
[9] A plant-based biomass-derived product according to the above [8], wherein in the treatment step (2), the pH of the system at the time of mixing the solid content obtained from the treatment step (1) and the solvent is adjusted. 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 above-mentioned [1] to [1], 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 manufacturing method of the plant type biomass origin product as described in any one of 10].
[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 performed under the following conditions A to C.
Condition A: The solid concentration obtained from the treatment step (1) is 1% by mass to 50% by mass with respect to the solvent,
Condition B: Treatment temperature is 100 ° C. or more and 300 ° C. or less, and Condition C: Treatment time is 0.1 hour or more and 10 hours or less.
[13] A method for producing glucose, which comprises subjecting the cellulose-containing solid product obtained by the production method according to any one of the above [2] to [12] to an enzymatic saccharification treatment to obtain glucose.
[14] A resin composition comprising lignin obtained by the method according to any one of the above [2] to [12].
[15] 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% thermal weight loss start temperature is 210 ° C. or more.
[16] A resin composition containing lignin as described in [15] above.
[17] A molded article obtained by using the resin composition according to the above [14] or [16].

  According to the present invention, it is possible to provide a method for producing a biomass-derived product which is a hemicellulose-derived saccharide, a cellulose-containing solid with suppressed overdegradation, and lignin with few impurities from plant-based biomass. According to the present invention, since the first treatment step (1) is performed while suppressing the overdegradation of hemicellulose, a high sugar yield can be obtained from the hemicellulose-derived saccharide and the cellulose-containing solid.

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

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

[Plant biomass]
Examples of plant biomass include woody biomass and herbaceous biomass. Examples of woody biomass include conifers such as cedar, cypress, hiba, cherry, eucalyptus, beech and bamboo, and hardwoods.
As herbaceous biomass, there are palm palm trunk / empty, palm palm fiber and seeds, bagasse (sugarcane and high biomass amount sugarcane squeezed), cane top (sugarcane top and leaf), energy cane, rice straw, straw, Corn cobs / stalks / leaves (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, hides and shells of jatropha seeds, cashew shells, switchgrass, erianthus, high biomass yield crops, energy crops, Energy cane etc.
Among them, herbaceous biomass is preferable from the viewpoint of easy availability and compatibility with the production method applied in the present invention, and palm palm empty straw, straw, corn foliage and residue, bagasse, cane top, Energy cane is more preferably the residue after extraction of these useful components, bagasse, cane top, energy cane is more preferable, bagasse, cane top, energy cane is more preferable.
Plant-based biomass can also be used after being crushed. It may also be in the form of blocks, chips or powders. Furthermore, it may be either dry or hydrated.

[Processing condition]
A known method of treating plant biomass can be used as the treatment step (1) for separating hemicellulose, but in this case, it is preferable to perform a 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 explosion, and hydrothermal treatment using an acidic aqueous solution.
When hydrothermal treatment using an acidic aqueous solution is performed, it is preferable to use an acidic aqueous solution containing at least one selected from inorganic acids and organic acids. Among them, at least one aqueous acid solution selected from the group consisting of an inorganic acid selected from dilute sulfuric acid, phosphoric acid, dilute hydrochloric acid and dilute nitric acid, 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 preparation concentration of the plant biomass which is the raw material 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 feed concentration of the plant biomass of the raw material is 1 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 maintained favorably. If the preparation concentration of the plant biomass of a raw material is 95 mass% or less, separation efficiency can be kept favorable.

The treatment temperature in the treatment step (1) is preferably 50 ° C. or more and 200 ° C. or less, more preferably 100 ° C. or more and 190 ° C. or less, and still more preferably 150 ° C. or more and 180 ° C. or less. If it is 50 degreeC or more, hemicellulose can be solubilized. When the temperature is 200 ° C. or less, overdegradation of hemicellulose can be suppressed.
The treatment time in treatment step (1) is preferably 1 minute to 5 hours, more preferably 3 minutes to 3 hours, still more preferably 5 minutes to 2 hours, and particularly preferably 10 minutes to 1 hour. It is less than time. If the treatment time is one minute or more, hemicellulose can be solubilized. If the treatment time is 5 hours or less, overdegradation of hemicellulose can be suppressed.
The pressure of the reaction system in the treatment step (1) is desirably 0.1 MPa to 30 MPa. The more preferable conditions are appropriately set because they are influenced by the temperature. In addition, the treatment process can be performed under an ambient atmosphere.
Although there is no restriction | limiting in particular in the processing system in a process process (1), Static or stirring processing can be mentioned. For example, general batch reactors, semi-batch reactors, pressure vessels and the like can be used. Moreover, the system which processes while extruding the slurry which consists of plant type biomass origin solid substance and water or acidic aqueous solution with a screw or a pump etc. is also applicable.

The hemicellulose is separated by solid-liquid separation of the reaction product after the hydrothermal treatment. In addition, as a solid after solid-liquid separation, solid content containing cellulose and lignin is obtained.
The treatment step (1) may include the step of washing the obtained solid content with water. For example, after adding and stirring 100 mass parts or more and 10000 mass parts or less water with respect to 100 mass parts of solid content obtained, solid content and a liquid phase are separated by filtration. The amount of water used for the above-mentioned water washing is more preferably 1000 parts by mass or more and 5000 parts by mass or less, still more preferably 1000 parts by mass or more and 2000 parts by mass or less. If the amount of water used for water washing is 100 parts by mass or more, a sufficient cleaning effect can be obtained, and by setting the amount to 10000 parts by mass or less, it can be carried out without problems on equipment. By providing the step of washing with water, water-soluble components such as hemicellulose-derived saccharides can be removed from the solid.
Although the method of performing solid-liquid separation is not particularly limited, filtration, filter press, centrifugation, dehydrator and the like can be mentioned.

<Processing step (2)>
The present treatment step is a step of mixing the 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, and performing heat treatment. 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, but may be either a saturated or unsaturated linear alcohol and 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. 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 more preferably at least one selected from 1-butanol, 2-methyl-1-propanol, 2-butanol, ethanol, pentanol, hexanol and acetone; More preferably, it is at least one selected from propanol, 2-butanol, ethanol and acetone, more preferably 1-butanol, 2-methyl-1-propanol, 2-butanol, and 1-butanol. It is particularly preferred.

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

Here, the pH of the system from the hemicellulose separation in the treatment step (1) to the mixing of the solid content obtained from the treatment step (1) in the treatment step (2) and the solvent or in the treatment step (2) It is preferable to perform the heat treatment in the treatment step (2) after adjusting the pH of the system at the time of mixing the solid content obtained from the treatment step (1) with the solvent using a basic substance. In particular, when the hydrothermal treatment is performed using an acidic aqueous solution in the treatment step (1), it is preferable to adjust the pH before heat treatment in the treatment step (2).
Since the treatment conditions of treatment step (2) are severe as compared to treatment step (1), if the pH in the system is inclined to acidity, it may cause undesirable overdecomposition of the cellulose obtained in treatment step (2) . Also in order to suppress this over decomposition, it is preferable to adjust the pH before mixing the solid content obtained from the treatment step (1) and the solvent in the treatment step (2).
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, still more preferably 4 or more and 8 or less, particularly preferably 4 or more and 7 or less, most preferably 4 Adjust to 6 or less. By setting the pH to the above-mentioned range, it is possible to suppress the over-decomposition of cellulose and to obtain a high sugar yield.

[Processing condition]
As processing conditions in processing process (2), it is preferred to carry out on the conditions with which all the following conditions AC are fulfilled.
Condition A
The preparation 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. In addition, when using several organic solvents as a solvent, the preparation density | concentration of said solid content is with respect to the total amount of a solvent. If the preparation concentration of solid content obtained from the treatment step (1) is 1% by mass or more, the energy efficiency of the lignin removal process, even considering the heating of the solvent and the amount of energy used for the removal of the organic solvent Can be kept good. If the preparation concentration of the solid content 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 preparation concentration of the solid content obtained from the treatment step (1) with respect to the solvent is more preferably 3% by mass to 20% by mass, and still more preferably 5% by mass to 15% by mass.

Condition B
The treatment temperature in the treatment step (2) is preferably 100 ° C. or more and 300 ° C. or less. If the treatment temperature is 100 ° C. or more, the separation of lignin can be sufficiently advanced, and if the treatment temperature is 300 ° C. or less, decomposition of cellulose and generation of impurities such as coke due to repolymerization of lignin can be suppressed. .
The treatment temperature is more preferably 150 ° C. or more and 250 ° C. or less, still more preferably 170 ° C. or more and 230 ° C. or less.

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

As another process condition in a process process (2), it is desired that the pressure of a reaction system shall be 0.5 Mpa-30 Mpa. However, the preferable range of the pressure of the reaction system is appropriately set because it is influenced by the amount of water and the organic solvent and the temperature. In addition, the treatment step (2) can be performed under an ambient atmosphere. In addition, in order to suppress the polymerization due to the oxidation reaction, the treatment step (2) is particularly preferably performed under an atmosphere in which nitrogen purge is performed to reduce oxygen.
Although there is no restriction | limiting in particular in the processing system in a process process (2), Static or stirring processing can be mentioned. For example, general batch reactors, semi-batch reactors and the like can be used. Moreover, the system which processes while extruding the slurry which consists of plant type biomass origin solid substance, an organic solvent or water, and an organic solvent with a screw or a pump etc. is also applicable.

The reaction product obtained after the heat treatment of 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 10000 parts by mass or less of water to 100 parts by mass of the solid content obtained after solid-liquid separation and stirring. After stirring, the solid and the liquid phase are filtered off.
The amount of water used in the water washing step is preferably 100 parts by weight or more and 10000 parts by weight or less, more preferably 1000 parts by weight or more and 5000 parts by weight or less, and still more preferably 1000 parts by weight or more and 2000 parts by weight or less. If the amount of water used for water washing is 100 parts by mass or more, a sufficient cleaning effect can be obtained, and by setting the amount to 10000 parts by mass or less, it can be carried out without problems on equipment. This water-washing step allows the further removal of the organic solvent and the removal of water-soluble components adhering to the cellulose-containing solid.

A cellulose-containing solid can be obtained after solid-liquid separation after the heat treatment of the treatment step (2), or further through the above-mentioned water washing step. According to the production method of the present embodiment, the cellulose-containing solid substance 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 a dehydrator.

  The liquid phase obtained after the heat treatment of the treatment step (2) or after the additional water washing contains lignin. For example, when using a mixed solvent of water and an organic solvent and becoming two phases after treatment, the solvent is removed by evaporating the organic phase obtained after separating the aqueous phase to obtain solid lignin it can. In addition, even when an organic solvent is used alone or when a mixed solvent with water is used, when it is one phase after the heat treatment of the treatment step (2), the solvent is removed by evaporating the organic solvent or the like. Solid lignin can be obtained as a solid residue left or by filtering the solid precipitated in water.

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

<Characteristics of lignin>
The lignin obtained by the production method of the present invention has the following features.
(11): The purity of lignin is 90% or more,
(12): the number average molecular weight is 650 or more, and (13): the 5% thermal weight loss 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. Furthermore, the 5% thermal weight loss start temperature is preferably 215 ° C. or higher, and more preferably 220 ° C. or higher.
In addition, each measuring method of the purity of the said lignin, a number average molecular weight, and 5% thermal weight reduction start temperature is mentioned later.

<Characteristics of hemicellulose-derived saccharide and obtained cellulose-containing solid matter>
According to the production method of the present invention, the recovery rate of the hemicellulose-derived saccharide with respect to the hemicellulose in the plant biomass is 50% by mass or more. When the recovery rate of hemicellulose-derived saccharides is less than 50% by mass, 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 based on the total amount of the cellulose-containing solid as solid content. As the other substance, lignin is contained in an amount of 5% by mass to 30% by mass, and hemicellulose and a hemicellulose decomposition product obtained by decomposing the hemicellulose are contained in an amount of 0% by mass to 5% by mass. Moreover, the cellulose recovery rate in the cellulose-containing solid matter with respect to the cellulose in plant-based biomass will be 70 mass% or more.
If the cellulose and the cellulose degradant obtained by decomposing the cellulose are less than 60% by mass, or if the lignin exceeds 30% by mass, the saccharification rate at the time of obtaining glucose by the enzymatic saccharification treatment decreases. When the hemicellulose and the hemicellulose degradation product obtained by degrading the hemicellulose exceed 5% by mass, the separation and removal of lignin bound to the hemicellulose becomes insufficient, and the saccharification rate at the time of obtaining glucose by enzymatic saccharification treatment decreases. . In addition, when the cellulose recovery rate is less than 70% by mass, the glucose recovery rate with respect to the cellulose in the plant biomass decreases.

<Uses 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 the saccharification treatment with an acid or an enzyme. In addition, the cellulose-containing solid obtained by the production method of the present invention is in a state of being easily disintegrated as compared to the cellulose-containing solid obtained by other methods. For this reason, it has the advantage that application development is easy to carry out.
In addition, ethanol, butanol, acetone and the like can be obtained from the cellulose-containing solid obtained by the production method of the present invention using a known method.
In addition, from cellulose-containing solid substances obtained by the production method of the present invention, rubbers and tire reinforcements as substitutes for resin-reinforced fibers and chemical fibers such as cellulose nanofibers, food additives such as carboxymethyl cellulose and oligosaccharides, lactic acid And succinic acid can be obtained.

<Uses of hemicellulose and lignin>
From hemicellulose obtained by the production method of the present invention, oligosaccharides, food additives such as xylitol, and chemicals such as furfural can be obtained, which is useful.
Further, lignin obtained by the production method of the present invention can be specifically used as a water repellent material for fuel and cement. In addition, it can be applied to base resin raw materials of phenol resin, epoxy resin, polyurethane resin, additive of epoxy resin (curing agent), modifier of polyurethane resin (flame retardant), additive of thermoplastic resin, 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, conventionally known methods can be used. One example is a resin composition in which lignin and a known crosslinking agent represented by hexamethylenetetramine are blended.
Various fillers and general phenol resins obtained industrially may be blended into the resin composition in which lignin and a crosslinking agent are blended, as necessary. Such resin compositions are used as heat insulation materials for housing, electronic components, resins for flax sand, resins for coated sand, resins for impregnation, resins for lamination, resins for FRP molding, automobile parts, reinforcements for automobile tires, etc. It can be used.
In addition, the introduction of an epoxy group into lignin and the use of lignin as an epoxy resin curing agent also make it possible to apply to epoxy resins. 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.

  About the use as an additive, the conventionally well-known method mentioned, for example to Unexamined-Japanese-Patent No. 2014-15579, international publication 2016/104634 etc. can be used. Various additives and fillers may be blended into the resin composition, in which lignin and a thermoplastic resin are blended, as necessary.

[Resin composition]
In another embodiment of the present invention, there is provided a resin composition comprising lignin obtained by the above production method. Moreover, resin components, such as a thermoplastic resin and a thermosetting resin, may be contained other than the lignin obtained by the said manufacturing method. The components other than lignin are described below.

<Thermoplastic resin>
The thermoplastic resin that can be added to the resin composition according to the present embodiment is an amorphous thermoplastic resin having a glass transition temperature of 200 ° C. or less, or a crystalline thermoplastic resin having a melting point of 200 ° C. or less Is preferred. The thermoplastic resin includes, for example, polycarbonate resin, styrene resin, polystyrene elastomer, polyethylene resin, polypropylene resin, polyacrylic resin (polymethyl methacrylate resin etc.), polyvinyl chloride resin, cellulose acetate resin, polyamide resin, Low melting point polyester resin (PET, PBT etc.) represented by polyester of a combination of terephthalic acid and ethylene glycol, terephthalic acid and 1,4-butanediol, copolymer containing polylactic acid and / or polylactic acid, acrylonitrile-butadiene -Styrene resin (ABS resin), polyphenylene oxide resin (PPO), polyketone resin, polysulfone resin, polyphenylene sulfide resin (PPS), fluorocarbon resin, silicon resin, polyimide resin, polybenzimide Tetrazole resins, polyamide elastomers, and copolymers thereof with other monomers.
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. 40 mass% or more and 99.9 mass% or less are more preferable, 45 mass% or more and 99.9 mass% or less are more preferable, and 50 mass% or more and 99.9 mass% or less are particularly preferable.
The resin composition according to the present embodiment may contain, in addition to the above-described cellulose-containing solid and thermoplastic resin, a resin compatible with the thermoplastic resin composition, an additive, and / or a filler. Good.

<Thermosetting resin>
A lignin reactive compound having a functional group capable of reacting with lignin may be blended as a thermosetting resin that can be blended in the resin composition according to the present embodiment. Examples of the compound having a functional group capable of reacting with lignin include compounds that cause electrophilic substitution reaction with a phenol compound, compounds having an epoxy group, compounds having an isocyanate group, and the like.
Since lignin has a phenolic structural unit, it can be applied as a base resin raw material such as phenol resin and epoxy resin, an additive (hardening agent) of epoxy resin, and the like.
(Compound that produces electrophilic substitution reaction with phenol compound)
As a compound which produces an electrophilic substitution reaction with a phenol compound, formaldehyde, a formaldehyde donor hardening | curing agent compound, or a formaldehyde equivalent compound etc. are mentioned. Commercially, hexamethylenetetramine, hexaformaldehyde and paraformaldehyde can be used.
In addition to lignin and hexamethylenetetramine, the resin composition according to this embodiment may further contain a phenol resin. As described above, since lignin has a phenolic structural unit, the phenolic resin is a diluent, extender, etc. of lignin within the range that does not reduce physical properties such as processability, strength and heat resistance of the resin composition. It can be used as

(Compound having an epoxy group)
Compounds having an epoxy group belong to a category called so-called epoxy resin. For example, 2,2-bis (4'-hydroxyphenyl) propane (referred to as bisphenol A), bis (2-hydroxyphenyl) methane (referred to as bisphenol F), 4,4'-dihydroxydiphenyl Sulfone (referred to as bisphenol S), 4,4'-dihydroxybiphenyl, resorcine, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylol ethane, their halogen-substituted and alkyl-substituted products, butanediol, ethylene glycol, A glycidyl ether epoxy resin synthesized from a compound containing two or more hydroxyl groups in the molecule, such as ELISLIT, novolac, glycerin, polyoxyalkylene, etc. and epichlorohydrin; a compound containing two or more hydroxyl groups in the molecule And lid Glycidyl ester epoxy resin synthesized from acid glycidyl ester etc .; glycidyl synthesized from primary or secondary amines such as aniline, diaminodiphenylmethane, metaxylene diamine, 1,3-bisaminomethylcyclohexane etc. and epichlorohydrin etc. Epoxy resins containing glycidyl groups such as amine epoxy resins; epoxy resins containing no glycidyl group such as epoxidized soybean oil, epoxidized polyolefins, vinylcyclohexene dioxide, dicyclopentadiene dioxide and the like. Among these, preferred are cresol novolac-type and phenol novolac-type epoxy resins which are similar in lignin and chemical structure and compatible with each other.

The thermosetting resin composition may further contain a phenol resin in addition to the compound containing lignin and an epoxy group.
When lignin contained in the thermosetting resin composition is a compound containing an epoxy group, a curing accelerator can be appropriately added according to the purpose of curing reaction promotion. Specific examples include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,4 0) Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, tetrabutyl ammonium salts, triisopropyl methyl ammonium salts, trimethyl decanyl ammonium salts, quaternary ammonium salts such as cetyl trimethyl ammonium salts, tri Examples thereof include quaternary phosphonium salts such as phenylbenzyl phosphonium salt, triphenylethyl phosphonium salt and tetrabutyl phosphonium salt, and metal compounds such as tin octylate. As a counter ion of quaternary phosphonium salt, halogen, an organic acid ion, a hydroxide ion etc. are mentioned, Especially, an organic acid ion and a hydroxide ion are preferable.

(Compound having isocyanate group)
The compound having an isocyanate group is a polyisocyanate, or one obtained by reacting a polyisocyanate and a polyol. As polyisocyanates, aromatic polyisocyanates such as tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), polymeric MDI (MDI-CR), carbodiimide-modified MDI (liquid MDI) and the like and norbornane diisocyanate (NBDI) Aliphatic polyisocyanates such as isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4'-methylene-bis (cyclohexyl isocyanate) (hydrogenated MDI), xylylene diisocyanate (XDI), and blocked isocyanates be able to. Among these, tolylene diisocyanate (TDI) and 4,4'-diphenylmethane diisocyanate (MDI) are preferably used.
Moreover, the said thermosetting resin composition may further contain the phenol resin other than lignin and an isocyanate compound.

  A curing accelerator can be appropriately added to the thermosetting resin composition according to the purpose of curing reaction promotion. Examples of the curing accelerator include organometallic catalysts of zirconium and aluminum, dibutyltin laurate, phenol salts of DBU, octylate salts, amines, imidazoles and the like, but in terms of colorability, organometallic catalysts, For example, aluminum sec-butylate, ethylacetoacetate aluminum diisopropylate, zirconium tributoxyacetylacetonate, zirconium tetraacetylacetonate and the like are particularly preferable.

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

<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.
As the inorganic filler, for example, spherical or crushed fused silica, silica powder such as crystalline silica, alumina powder, glass powder, glass fiber, glass flake, mica, talc, calcium carbonate, alumina, hydrated alumina, nitrided Boron, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, magnesium oxide and the like can be mentioned.
Examples of the organic filler include carbon fiber, aramid fiber, paper powder, cellulose fiber, cellulose powder, chaff powder, fruit shell / nut powder, chitin powder, starch and the like.
The inorganic filler and the organic filler may be contained singly or in 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 properties of the molded product obtained from the resin composition are not impaired. In addition, compatibilizers, surfactants and the like can be added according to the purpose.
As a compatibilizer to be used together with a thermoplastic resin, a resin obtained by adding maleic anhydride, epoxy or the like to a thermoplastic resin to introduce a polar group, such as maleic anhydride modified polyethylene resin, maleic anhydride modified polypropylene resin, various commercially available phases A solubilizer may be used in combination.
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 not limited thereto.
Furthermore, as additives that can be blended in addition to those described above, flexibilizers, heat stabilizers, UV absorbers, flame retardants, antistatic agents, antifoaming agents, thixotropic agents, mold release agents, antioxidants Agents, plasticizers, stress reducing agents, coupling agents, dyes, light scattering agents, small amounts of thermoplastic resins, etc.

[Molding]
The molded article 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 article, one obtained by curing a resin composition in which lignin and a cross-linking agent are blended, and various fillers and industrially obtainable general phenolic resins are compounded as necessary, What was hardened | cured after shape | molding to a predetermined shape, or what was shape-processed after hardening was mentioned is mentioned.
As a method of shape | molding to a predetermined | prescribed shape, if a resin composition can be shape | molded, it will not be specifically limited. For example, when the resin composition is a thermosetting resin composition, compression molding method, injection molding method, transfer molding method, middle molding, FRP molding method and the like can be mentioned as a method of molding into a predetermined shape. Moreover, when a resin composition is a thermoplastic resin composition, an extrusion molding method, an injection molding method, etc. are mentioned as a method of shape | molding to a predetermined shape.

  As an example of a molded article, one obtained by curing a resin composition in which lignin and a crosslinking agent are blended, various fillers, and an industrially obtainable general phenolic resin are further blended, if necessary. Those obtained by forming into a predetermined shape and then curing, or those obtained by forming and processing after being cured, and those obtained by forming and processing a resin composition obtained by mixing lignin with a thermoplastic resin can be mentioned. Molded articles of such resin compositions are heat insulation materials for housing, electronic parts, resins for flax sand, resins for coated sand, resins for impregnation, resins for lamination, resins for FRP molding, automobile parts, reinforcement of automobile tires It can be used for materials, office automation equipment, machines, information communication equipment, industrial materials, etc.

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

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

  Hereinafter, the present embodiment will be more specifically described by way of examples, but the present embodiment is not limited to these.

[Production Example of Cellulose-Containing Solid]
<Production Example 1>
Treatment process (1)
Plant-based biomass (for example, grass-based biomass such as bagasse), which is a raw material, is ground to several mm or less as pretreatment. After grinding, water is added to make a raw material slurry having a solid concentration of about 15% by mass. Phosphoric acid is added to and mixed with the raw material slurry so that the pH in the raw material slurry becomes 2.0.
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 carry out hydrothermal treatment at a temperature of 170 ° C.
Treatment process (2)
Solid content obtained from treatment step (1), a mixed solvent of water and 1-butanol prepared with 1-butanol concentration of 34% by mass, sodium hydroxide so as to be pH 3, and an inner volume of 0.92 L SUS (stainless steel ) It was placed in a batch-type apparatus. The total amount of solvent was 315 g. The raw material preparation concentration was performed as raw material / solvent = 1/10 (the solid content preparation 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 treatment was performed for 2 hours. The treatment time was an elapsed time after reaching 200 ° C. In addition, the temperature was measured by a thermocouple.
After completion of the treatment, the SUS batch-type apparatus was cooled, and after the temperature dropped to around room temperature, all contents were taken out. After treatment, the solid and the liquid phase were filtered off.
The solid content was added with 200 g of water, and after stirring for 30 minutes, the solid content and the liquid phase were separated by filtration. The said operation was repeated 3 times and the cellulose containing solid was obtained. The liquid phase was liquid / liquid separated into an aqueous phase and a 1-butanol phase by a separatory funnel. After removing the solvent of 1-butanol phase with an evaporator (70 ° C., water bath), vacuum drying was performed at 125 ° C. to obtain lignin.

<Production Example 2>
The same procedure as in Production Example 1 was followed except that the pH was adjusted to 4 in the treatment step (2).
<Production Example 3>
The same procedure as in Production Example 2 was performed except that the 1-butanol concentration in the mixed solvent in the treatment step (2) was 50% by mass.

Production Example 4
The same procedure as in Production Example 3 was performed except that ethanol was used as the organic solvent constituting the mixed solvent in the treatment step (2). In addition, since the liquid phase after solid-liquid separation is one phase, solid content separated in water due to the decrease of solubility is separated by filtration by removing the organic solvent by an evaporator, and the condition of 125 ° C. In vacuo to obtain lignin.

<Production 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).
<Production Example 6>
The same procedure as in Production Example 3 was repeated except that 2-methyl 1-propanol was used as the organic solvent constituting the mixed solvent of the treatment step (2).
Production Example 7
The same procedure as in Production Example 1 was followed except that the pH was adjusted to 5 in the treatment step (2).
<Production Example 8>
The same procedure as in Production Example 1 was followed except that the pH was adjusted to 6 in the treatment step (2).

<Production Example 9>
The same procedure as in Production Example 1 was followed except that the pH was adjusted to 7 in the treatment step (2).
Production Example 10
The same procedure as in Production Example 1 was followed except that the pH was adjusted to 10 in the treatment step (2).
<Production Example 11>
The same procedure as in Production Example 1 was followed except that the pH was adjusted to 12 in the treatment step (2).
<Production Example 12> (In the treatment step (1), not the acidic aqueous solution but only water is used)
First, plant-based biomass (for example, plant-based biomass such as bagasse), which is a raw material, is ground to several mm or less as pretreatment. After grinding, water is added to obtain a raw material slurry having a solid 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 carry out hydrothermal treatment at a temperature of 170 ° C. Thereafter, in the same manner as in Production Example 1 except that sodium hydroxide was added in the treatment step (2) and the pH was not adjusted.

Production Example 13
The same procedure as in Production Example 1 was carried out except that sodium hydroxide was added in the treatment step (2) and the pH was not adjusted.
<Comparative production example>
The same procedure as in Production Example 13 was performed except that the plant biomass as a raw material was treated with a mixed solvent of water and 1-butanol without passing through the treatment step (1) which is the hydrothermal treatment step.

<Analysis of the amount of cellulose in plant biomass and in solid containing cellulose>
The amount of cellulose in plant biomass and in the solid containing cellulose was calculated according to the constituent sugar analysis after the pretreatment described below.
[Preprocessing]
The raw material used as a sample was grind | pulverized using the Willey mill as pre-processing, and it dried at 105 degreeC.
[Constructed sugar analysis]
An appropriate amount of a sample of plant biomass or a 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 solution was completely transferred to a pressure bottle while mixing with pure water, and treated in an autoclave at 120 ° C. for 1 hour, and then the filtrate and the residue were separated by filtration. 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) as hemicellulose.
[Lignin]
The residue obtained by filtering off in the process of component sugar analysis was dried at 105 ° C., weighed, and the decomposition residue rate was calculated. Furthermore, the content of lignin was calculated by ash content correction.

<Cellulose recovery rate>
Cellulose recovery rate (% by weight) = (collected amount of cellulose-containing solid matter (g) × cellulose ratio in cellulose-containing solid body (% by weight) / 100) / cellulose amount in plant biomass (g) × 100
<Hydroxy methyl furfural formation rate>
The concentration of hydroxymethylfurfural was calculated by high performance liquid chromatograph (HPLC 1200 series manufactured by Agilent).
Hydroxymethyl furfural production rate (mass%) = hydroxymethyl furfural concentration (mg / L) × 10-6 × solution volume (mL) / plant biomass (g) × 100

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

Examples 1 to 13
[Method of evaluating obtained cellulose-containing solid matter]
<Enzymatic saccharification treatment>
1 g (dry weight) of a cellulose-containing solid was placed in a 50 mL centrifuge tube and sterilized at 121 ° C. for 20 minutes. Acetic acid buffer solution subjected to the same sterilization treatment is added to a centrifuge tube so that the volume is about 20 mL, pH 5, and then the amounts of enzymes shown in Table 3 (Nagase ChemteX Co., Ltd., Cellizer ACE) Was introduced. The centrifuge tube was shaken at 120 rpm for 72 hours in a thermostat of 50 ° C.
When 1 ml of the enzyme is added to 4 ml of a 0.625% solution of 0.625% sodium carboxymethylcellulose (pH 4.5) and allowed to act at 40 ° C. for 30 minutes, a reduction corresponding to 1 μmol of glucose per minute The activity producing force is denoted as 1 CUN. The enzyme has an enzyme activity of 1600 CUN / g or more.

<Analysis of glucose content in obtained xylose + xylooligosaccharide and cellulose-containing solid>
1. Sugar Analysis Sugars (xylose, xylooligosaccharides, glucose) were analyzed by HPLC using the following conditions.
Measurement condition column: Showa Denko Shodex SP-G (guard column) + SP0810
Mobile phase: distilled water (HPLC grade)
Detector: RI (in-cell 60 ° C)
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 vials.
3. Calculation Method The calibration curve is used to calculate the glucose concentration (g-glucose / L).
Glucose recovery rate (%) = (amount of glucose in cellulose-containing solid matter enzyme saccharification liquid (g) × cellulose-containing solid matter recovery rate (mass%) / 100) / amount of glucose in plant biomass (g) × 100

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

Example 9 and Comparative Example 1
Recovery rate (%) = (xylose amount in hydrothermally treated solution (g) + xylooligosaccharide amount in hydrothermally treated solution (g) + (glucose amount in cellulose-containing solid matter saccharification solution) ((xylose, xylooligosaccharide, glucose) (G) × cellulose-containing solid matter recovery rate (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, it is possible to suppress and overdegrade the hemicellulose-derived saccharides (xylose and xylooligosaccharides), and therefore, saccharides can be efficiently recovered based on plant biomass.

<Measurement of lignin purity>
It carried out similarly to the said <composition analysis of a raw material>.
<Number average molecular weight>
The number average molecular weight of the above 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% thermal weight loss start temperature (Td5) was measured by EXSTAR6000 TG / DTA6200 manufactured by SII. About 10 mg of a sample was weighed in a Pt pan, the temperature was raised to 10 ° C./min, the measurement atmosphere: air was 200 mL / min, the temperature was measured to 35 ° C. to 800 ° C., and the temperature at which the weight decreased by 5% was determined.
<Phenolic hydroxyl equivalent>
A solvent in which heavy chloroform, pyridine and cyclohexanol (internal standard) are mixed is added to the purified lignin, and 2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxa is further added as a derivatization reagent. Phospholane was added and heated to 50 ° C. for 1 hour. Thereafter, 31P NMR measurement was performed under the following measurement conditions.
Pulse width: 30 °
Repeating time: 2 seconds Measuring range: -60 to 200 ppm
Integration number: 200 times The internal standard cyclohexanol-derived signal is 145.2 ppm, 144.7 to 136.6 ppm is assigned as a phenolic hydroxyl group (Ph-OH), and the integral value is equivalent to the phenolic hydroxyl group (g / eq) ) Was calculated.

  As can be seen from Table 4, lignin with high heat resistance was obtained. Moreover, since secondary modification is not performed in this manufacturing method, 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 produced using lignin obtained in Production Example 9 and Comparative Production Example. Moreover, the hardened | cured material was produced and the physical property was evaluated.
<Composition of thermosetting resin composition and molding method of cured product>
Each component was put in a mortar at a compounding ratio shown in Table 2, ground at room temperature, mixed, mixed for 5 minutes at 100 ° C. using an open roll kneader, and cooled to room temperature. The mixture was ground in a mortar, sandwiched between aluminum plates coated with a 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 article.
<Method for measuring bending strength>
A sample of 5 mm × 50 mm × 1 mm was cut out from the obtained molded product, and using Instron 5566, the bending strength was measured under the conditions of 3-point bending mode, span 30 mm, speed 2 mm / min.
<Method of measuring glass transition temperature>
The measurement of glass transition temperature was measured by solid viscoelasticity method. A sample of 5 mm × 30 mm × 1 mm is cut out from the obtained molded product, and a temperature rise temperature of 2 ° C./min until it reaches 0 ° C. to 300 ° C., or a critical minimum elastic modulus, using DMA 8000 (manufactured by Perkin Elmer Japan Co., Ltd.) , Measured at 1 Hz. The peak temperature of the obtained tan δ was taken as the glass transition temperature (Tg).

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

  According to the present invention, it is possible to provide a method for producing a biomass-derived product which is a hemicellulose-derived saccharide, a cellulose-containing solid with suppressed overdegradation, and lignin with few impurities from plant-based biomass. According to the present invention, since the first treatment step (1) is performed while suppressing the overdegradation of hemicellulose, a high sugar yield can be obtained from the hemicellulose-derived saccharide and the cellulose-containing solid.

Claims (17)

Treatment step (1) for separating hemicellulose from plant biomass;
Process step (2) of mixing the solid content obtained from process step (1) with a solvent selected from organic solvents alone or mixed solvents of organic solvents and water, and heat treating
And a method for producing a plant-based biomass-derived product.   The method for producing a plant-based biomass-derived product according to claim 1, wherein solid-liquid separation is performed after the treatment step (2) to obtain a cellulose-containing solid as a solid and a lignin-containing solution as a liquid.   The manufacturing method of the plant-based biomass origin product of Claim 2 which obtains solid lignin by removing a solvent from the said lignin containing solution.   The method for producing a plant-based biomass-derived product according to any one of claims 1 to 3, 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 4, wherein in the treatment step (1), hydrothermal treatment is performed as treatment for separating hemicellulose.   The plant-based biomass-derived product according to claim 5, wherein the hydrothermal treatment is at least one selected from the group consisting of hydrothermal treatment using water and / or steam, steam explosion, and hydrothermal treatment using an acidic aqueous solution. Method of manufacturing objects.   The method for producing a plant-based biomass-derived product according to claim 6, wherein the acidic aqueous solution is an acidic aqueous solution containing at least one selected from inorganic acids and organic acids.   The pH of the system from the hemicellulose separation in the treatment step (1) to the mixing of the solid content obtained from the treatment step (1) in the treatment step (2) and the solvent, or the treatment in the treatment step (2) The plant-derived biomass-derived product according to any one of claims 1 to 7, wherein the pH of the system at the time of mixing the solid content obtained from step (1) and the solvent is adjusted using a basic substance. Manufacturing method.   The method for producing a plant-based biomass-derived product according to claim 8, wherein in the treatment step (2), the pH of the system at the time of mixing the solid content obtained from the treatment step (1) and the solvent is adjusted.   The method for producing a plant-based biomass-derived product according to claim 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.   The organic solvent used in the process step (2) is at least one selected from ethanol, 1-butanol, 2-methyl-1-propanol, 2-butanol and acetone. The manufacturing method of the plant-based biomass origin product as described in a term. The method for producing a plant-based biomass-derived product according to any one of claims 1 to 11, wherein the treatment step (2) is performed under the following conditions A to C.
Condition A: The solid concentration obtained from the treatment step (1) is 1% by mass to 50% by mass with respect to the solvent,
Condition B: Treatment temperature is 100 ° C. or more and 300 ° C. or less, and Condition C: Treatment time is 0.1 hour or more and 10 hours or less.   The manufacturing method of glucose which carries out an enzyme saccharification process of the cellulose containing solid obtained by the manufacturing method as described in any one of Claims 2-12, and obtains glucose.   The resin composition which uses the lignin obtained by the method as described in any one of Claims 2-12. 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% thermal weight loss start temperature is 210 ° C. or more.   A resin composition comprising lignin according to claim 15.   A molded article comprising the resin composition according to claim 14 or 16.