CN109689736A

CN109689736A - Method for producing products derived from plant-based biomass using a two-stage process

Info

Publication number: CN109689736A
Application number: CN201780054650.6A
Authority: CN
Inventors: 小山启人; 广田一晃; 山尾忍; 冈野匡贵; 增田隆夫; 吉川琢也
Original assignee: Hokkaido University NUC; Idemitsu Kosan Co Ltd
Current assignee: Hokkaido University NUC; Idemitsu Kosan Co Ltd
Priority date: 2016-09-09
Filing date: 2017-09-07
Publication date: 2019-04-26
Also published as: WO2017222084A1; JP6931878B2; JPWO2017222084A1

Abstract

A method for producing a product derived from a plant-based biomass, comprising: a treatment step (1) for separating hemicellulose from a plant-based biomass; and a treatment step (2) in which the solid component obtained in the treatment step (1) is mixed with a solvent selected from an organic solvent alone or a mixed solvent of an organic solvent and water, and is subjected to a heat treatment.

Description

The method of the product from department of botany's biomass is manufactured using two-stage process

Technical field

The present invention relates to the manufacturing methods of product with two-stage process, from department of botany's biomass.

Background technique

With the raising that environment in recent years is realized, gradually expectation is originated from the raw material of biomass.But for example, in biological second It is particularly significant that, the raw material from biomass uses starch, sugar etc. to compete with food in most cases in the manufacture of alcohol Raw material, therefore being noted leads to problems such as food price rising, grain-production reduce.So now by not with food competition Cellulose-based biomass manufacture bio-fuel/biochemicals technology is concerned.

As cellulose-based biomass, the trunk of such as oil palm and the fiber of empty fruit cluster, oil palm fruit can be enumerated With seed, bagasse (sugarcane (include high biological quality sugarcane)) marc), the sugarcane tip (top of sugarcane and leaf), rice straw, wheat Straw, rice husk, the cob base of leaf corn residue (corn stalk, corncob, corn lees) of corn, sorghum (including sugar grass) are residual Slag, leprosy tree species skin and shell, cashew nut shell, wood shavings, switchgrass, napier grass, Ravenna grass, energy crop, Energy Sugarcane etc..In addition to containing Have except the cellulose that can be converted to sugar, hemicellulose, these cellulose-based biomass contain lignin.

In order to obtain sugar by cellulose-based biomass, pretreatment procedure usually is needed before enzymatic conversion processing.By this Pre-treatment, the combination between each ingredient or each ingredient of biomass are opened, and enzyme becomes easy close to cellulose.But by Lignin present in system is adsorbed in enzyme and hinders to be saccharified, and therefore, in order to obtain adequately saccharification property, needs largely to use Expensive enzyme, it is therefore desirable for the solubilising of lignin.

In addition, excessive decomposition occurs if being exposed to high temperature for hemicellulose, it is easy to be converted to the saccharification/fermentation of furfural etc Inhibiting substances need to inhibit excessive decomposition.

Usual lignin is generated in the form of residue when biomass is converted to ethyl alcohol, but include a large amount of enzyme/yeast it The impurity of class, therefore be limited to be used as fuel always.But since it is with class polyphenol structure, it can be expected that being converted to Product, biological plastics, thus it is expected to extract lignin.

Disclose lignin derivative in patent document 1, via by biomass in the presence of the solvent, under high temperature and pressure The treatment process being stirred.

Following the description is disclosed in patent document 2: biomass being made to be placed in the mixing comprising water and aprotic polar solvent In the presence of solvent, they are subjected to resolution process at high temperature under high pressure, thus recycled fiber element derivative, lignin derivative And hemicellulose derivative.

Heat resistance Lignins polymer is disclosed in patent document 3, it includes the α of the phenylpropane units in lignin Position is grafted with 1, the 1- diphenyl propane unit of amphyl, and has ester portion obtained by 1 or 2 or more hydroxyl is acylated Position.

Existing technical literature

Patent document

Patent document 1: Japanese Patent No. 5256679

Patent document 2: Japanese Unexamined Patent Publication 2014-62051 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2011-256381 bulletin.

Summary of the invention

Problems to be solved by the invention

However, the most molecular weight of lignin obtained in patent document 1 is too small, poor heat resistance when lignin is used as resin, this Outside, it in order to improve operability, needs separately to carry out secondary derivatization by reaction kettle, lignin is difficult to directly use.In addition, not having There is detailed record relevant to the carbohydrate of hemicellulose and cellulose.

In method described in Patent Document 2, resolution process temperature is high, excessive decomposition occurs for hemicellulose, accordingly, it is difficult to The form of carbohydrate is recycled.It is not documented for the character of cellulose derivative.It also discloses by utilizing lignin Hydroxyl be acylated modified to realize homogenizing for material, need separately to carry out secondary derivatization using reaction kettle.This Outside, although heat resistance improves, phenolic hydroxyl group is consumed, therefore reaction site also disappears simultaneously, damages the glamour as material.

Patent document 3, which is disclosed, realizes homogenizing for material and the hydroxyl of lignin be acylated and is modified.It should It needs to carry out secondary derivatization in method, although heat resistance improves, consumes phenolic hydroxyl group, therefore, reaction site also disappears simultaneously It loses, damages the glamour as material.

The present invention is provided to be contained by the manufacture of department of botany's biomass is originated from the carbohydrate of hemicellulose, excessive decomposition is suppressed The method of the product from biomass of the solid of cellulose and the lignin few as impurity.

The method for solving problem

The inventors of the present invention have made intensive studies, as a result, it has been found that: by being able to solve via following specific two-stage process State project.

That is, the present invention provides following [1] ~ [17].

[1] manufacturing method of the product from department of botany's biomass, contains:

The treatment process (1) of hemicellulose is separated from department of botany's biomass；And

It will be by solid component that treatment process (1) obtains and the mixing selected from individual organic solvent or organic solvent and water is molten Solvent mixing in agent, and the treatment process (2) heated.

[2] manufacturing method of the product according to above-mentioned [1] from department of botany's biomass, wherein in aforementioned processing After process (2), the solid containing cellulose is obtained in solid form and being separated by solid-liquid separation, and with the shape of liquid Formula obtains the solution containing lignin.

[3] manufacturing method of the product according to above-mentioned [2] from department of botany's biomass, wherein by from aforementioned Solvent is removed in solution containing lignin and obtains solid lignin.

[4] manufacturing method of the product according to any one of above-mentioned [1] ~ [3] from department of botany's biomass, In, afore-mentioned plants system biomass is draft system biomass.

[5] manufacturing method of the product according to any one of above-mentioned [1] ~ [4] from department of botany's biomass, In, in aforementioned processing process (1), as the processing of separation hemicellulose, carry out hydro-thermal process.

[6] manufacturing method of the product according to above-mentioned [5] from department of botany's biomass, wherein at aforementioned hydro-thermal Reason is selected from having used the hydro-thermal process of water and/or vapor, steam explosion and used at the hydro-thermal of acidic aqueous solution It is at least one kind of in reason.

[7] manufacturing method of the product according to above-mentioned [6] from department of botany's biomass, wherein aforementioned acid water Solution is to include at least one kind of acidic aqueous solution in inorganic acid and organic acid.

[8] manufacturing method of the product according to any one of above-mentioned [1] ~ [7] from department of botany's biomass, In, it is adjusted using alkaline matter: from after separation hemicellulose in aforementioned processing process (1) into aforementioned processing process (2) Will the solid component that obtained by treatment process (1) mixed with solvent before until system pH or in aforementioned processing process (2) It is middle will system of the solid component that obtained by treatment process (1) when being mixed with solvent pH.

[9] manufacturing method of the product according to above-mentioned [8] from department of botany's biomass, wherein adjustment is aforementioned In treatment process (2) will system of the solid component that obtained by treatment process (1) when being mixed with solvent pH.

[10] manufacturing method of the product according to above-mentioned [8] or [9] from department of botany's biomass, wherein use The pH that aforementioned base substance adjusts the system after pH is 3 or more and 12 or less.

[11] manufacturing method of the product according to any one of above-mentioned [1] ~ [10] from department of botany's biomass, Wherein, organic solvent used in aforementioned processing process (2) be selected from ethyl alcohol, n-butyl alcohol, 2- methyl-1-propyl alcohol, 2- butanol and It is at least one kind of in acetone.

[12] manufacturing method of the product according to any one of above-mentioned [1] ~ [11] from department of botany's biomass, Wherein, aforementioned processing process (2) are carried out using following condition A ~ C.

Condition A: the solid component obtained by treatment process (1) is 1 mass % or more and 50 relative to the feed concentrations of solvent Quality % or less；

Condition B: treatment temperature is 100 DEG C or more and 300 DEG C or less；And

Condition C: the processing time is 0.1 hour or more and 10 hours or less.

[13] manufacturing method of glucose, wherein the manufacturing method described in any one of above-mentioned [2] ~ [12] will be passed through The obtained solid containing cellulose carries out enzymatic conversion processing, obtains glucose.

[14] resin combination uses wood obtained from having the method as described in any one of above-mentioned [2] ~ [12] Quality.

[15] lignin meets following (11) ~ (13).

(11): the purity of lignin is 90% or more；

(12): number-average molecular weight is 650 or more；And

(13): 5% hot loss of weight start temperature is 210 DEG C or more.

[16] resin combination, it includes lignin described in above-mentioned [15].

[17] formed products, using has resin combination described in above-mentioned [14] or [16].

The effect of invention

In accordance with the invention it is possible to provide by the manufacture of department of botany's biomass is originated from the carbohydrate of hemicellulose, excessive decomposition is suppressed The solid containing cellulose and the lignin few as impurity the product from biomass method.According to this hair It is bright, due to carrying out the first treatment process (1) while inhibiting the excessive decomposition of hemicellulose, can be by being originated from half fiber It ties up the carbohydrate of element and the solid containing cellulose obtains high candy output.

Specific embodiment

The manufacturing method of product from department of botany's biomass of the invention has following process, and the process contains: from The treatment process (1) of hemicellulose is separated in department of botany's biomass；And it will be by solid component that treatment process (1) obtains and choosing The processing work for mixing with the solvent of the in the mixed solvent of water from individual organic solvent or organic solvent, and being heated Sequence (2).Hereinafter, detailed description of embodiments of the present invention for needle.

In this process, hemicellulose is separated from department of botany's biomass.It is described in detail below.

[department of botany's biomass]

As department of botany's biomass, woody system's biomass, draft system biomass can be enumerated.As woody system's biomass, can arrange Enumerate the needlebush, leaf wood such as Chinese fir, Japan cypress, cypress, cherry tree, eucalyptus, beech, bamboo.

As draft system biomass, can enumerate the trunk empty fruit cluster of oil palm, the fiber of oil palm fruit and seed, Bagasse (marc of sugarcane and high biological quality sugarcane), the sugarcane tip (top of sugarcane and leaf), Energy Sugarcane, rice straw, wheat straw, jade The cob base of leaf residue (corn stalk, corncob, corn lees) of rice, sorghum (include sugar grass) residue, leprosy tree species skin With shell, cashew nut shell, switchgrass, Ravenna grass, high yield of biomass crop, energy crop, Energy Sugarcane etc..

Among these, from the viewpoint of obtaining easiness, the adaptability with the manufacturing method applied in the present invention, preferably For draft system biomass, base of leaf residue, bagasse, the sugarcane tip, the energy of the more preferably empty fruit cluster, wheat straw, corn of oil palm are sweet Sugarcane, they extract the residue after useful components, more preferably bagasse, the sugarcane tip, Energy Sugarcane, further preferably bagasse, the sugarcane tip, Energy Sugarcane.

Crushed material also can be used in department of botany's biomass.In addition it is also possible to for the arbitrary shape in block, fragment or powder. In turn, the free position in can also being drying or is aqueous.

[treatment conditions]

As the treatment process (1) of separation hemicellulose, the processing method of well known department of botany's biomass can be used, herein, It is preferred that carrying out hydro-thermal process.As hydro-thermal process, can enumerate selected from hydro-thermal process, the water steaming for having used water and/or vapor Gas explosion is fried and has used at least one kind of in the hydro-thermal process of acidic aqueous solution.

When used the hydro-thermal process of acidic aqueous solution, it is preferable to use comprising in inorganic acid and organic acid extremely Few a kind of acidic aqueous solution.Wherein it is possible to by from selected from dilute sulfuric acid, phosphoric acid, dilute hydrochloric acid and dust technology inorganic acid and At least one kind of aqueous acid selected in the organic acid in formic acid, acetic acid, oxalic acid and malic acid is used as acidic aqueous solution.

In treatment process (1), department of botany's biomass as raw material is usually 1 relative to the feed concentrations of water solvent Quality % or more and 95 mass % hereinafter, preferably 3 mass % or more and 80 mass % hereinafter, more preferably 5 mass % or more and 50 matter % is measured hereinafter, most preferably 5 mass % or more, 20 mass % or less.

If the feed concentrations of department of botany's biomass of raw material are 1 mass % or more, it is able to suppress molten for heating water system The quantity of energy of agent can keep the energy efficiency for the treatment of process (1) well.If feeding intake for department of botany's biomass of raw material is dense Degree is 95 mass % hereinafter, can then keep separative efficiency well.

Treatment temperature in treatment process (1) be preferably 50 DEG C or more and 200 DEG C hereinafter, more preferably 100 DEG C or more and 190 DEG C hereinafter, further preferably 150 DEG C or more and 180 DEG C or less.If it is 50 DEG C or more, hemicellulose can be increased It is molten.If it is 200 DEG C hereinafter, being then able to suppress the excessive decomposition of hemicellulose.

The processing time in treatment process (1) be preferably 1 minute or more and 5 hours hereinafter, more preferably 3 minutes or more and 3 hours hereinafter, further preferably 5 minutes or more and 2 hours hereinafter, particularly preferably 10 minutes or more and 1 hour or less.Such as The fruit processing time is 1 minute or more, then can be by hemicellulose solubilising.If processing the time be 5 hours hereinafter, if be able to suppress The excessive decomposition of hemicellulose.

The pressure of reaction system in treatment process (1) is desired for 0.1MPa ~ 30MPa.Preferred condition is by temperature shadow It rings, therefore suitably sets.In addition, treatment process can carry out under surrounding atmosphere.

Processing mode in treatment process (1) is not particularly limited, and can enumerate standing or stir process.It can use Such as general batch reactor, semibatch reactor, pressure vessel etc..In addition it is also possible to using that will include to be originated to plant The solid and water of object system biomass or the slurry of acidic aqueous solution while being squeezed out with screw rod or pump etc. at The mode of reason.

By the way that the reactant after hydro-thermal process to be separated by solid-liquid separation, to separate hemicellulose.It should be noted that making For the solid after separation of solid and liquid, the available solid component containing cellulose and lignin.

It should be noted that may include the process for washing resulting solid component in treatment process (1). For example, relative to resulting 100 mass parts of solid component, adds 100 mass parts or more and 10000 water below the mass and stir After mixing, solid component and liquid phase are separated by filtration.Water used in above-mentioned washing is more preferably 1000 mass parts or more And 5000 below the mass, more than further preferably 1000 mass parts and 2000 below the mass.If used in washing Water is 100 mass parts or more, then sufficient cleaning effect can be obtained, by being set as 10000 below the mass, in equipment side Face can be washed without problems.By the way that the washing step is arranged, it is water-soluble carbohydrate of hemicellulose etc. can will to be originated from Ingredient is removed from solid component.

The method being separated by solid-liquid separation is not particularly limited, and can enumerate filtering, filters pressing, centrifuge separation, dewaterer etc..

Present treatment process is the solid component that will be obtained by treatment process (1) and selected from individual organic solvent or organic solvent The process for mixing, and being heated with the solvent of the in the mixed solvent of water.In this process, lignin and cellulose are carried out Separation.

As solvent, the solvent selected from individual organic solvent or the in the mixed solvent of organic solvent and water is used.

[organic solvent]

Organic solvent is not particularly limited, and can be any one of saturated or unsaturated, straight chain alcohol and branched-chain alcoho.In addition, It can be the ketones such as acetone, methyl ethyl ketone；The ethers such as tetrahydrofuran；Ethylene glycol, polyethylene glycol.In addition, organic solvent can be single Only organic solvent can also mix a variety of.

Wherein, methanol, ethyl alcohol, propyl alcohol, n-butyl alcohol, 2- methyl-1-propyl alcohol, 2- butanol, 2- methyl-2- third are preferably selected from It is at least one kind of in alcohol, amylalcohol, hexanol, enanthol, octanol, acetone and tetrahydrofuran, more preferably it is selected from n-butyl alcohol, 2- methyl-1- One or more of propyl alcohol, 2- butanol, ethyl alcohol, amylalcohol, hexanol and acetone are further preferably selected from n-butyl alcohol, 2- methyl-1- At least one kind of in propyl alcohol, 2- butanol, ethyl alcohol and acetone, further preferably n-butyl alcohol, 2- methyl-1-propyl alcohol, 2- butanol are special It You Xuanwei not n-butyl alcohol.

[mixed solvent]

When using the mixed solvent of above-mentioned organic solvent and water, as organic solvent, above-mentioned organic solvent, preferably object can be used Also identical.As water, can be used such as tap water, industrial water, ion exchange water, distilled water.

The concentration of the organic solvent of in the mixed solvent is preferably 10 weight % or more and 80 weight % or less, more preferably 12 weights Measure % or more and 75 weight % or less, further preferably 15 weight % or more and 70 weight % or less.If in the mixed solvent has The concentration of solvent is that then can be sufficiently separated lignin in treatment process (2) in above range.

It is preferred here that being adjusted using alkaline matter: from after separation hemicellulose in above-mentioned treatment process (1) Until in treatment process (2) will the solid component that obtained by treatment process (1) mixed with solvent before until system pH or In treatment process (2) will system of the solid component that obtained by treatment process (1) when being mixed with solvent pH, then located Heat treatment in science and engineering sequence (2).It is particularly preferred that carrying out hydro-thermal process using acidic aqueous solution in treatment process (1) When, before the heat treatment in treatment process (2) until pre-adjust pH.

Due to treatment process (2) treatment conditions strictly than treatment process (1), if the pH slant acidity in system, It is possible that causing the undesirable excessive decomposition of cellulose obtained in treatment process (2).It is also excellent in order to inhibit the excessive decomposition PH is adjusted during being selected in until mixing the solid component obtained by treatment process (1) with solvent in treatment process (2).

As alkaline matter, the inorganic bases such as sodium hydroxide, potassium hydroxide, calcium hydroxide can be enumerated；The organic bases such as ammonia.It will The pH before heating in treatment process (2) adjusts to preferably 3 or more and 12 or less, more preferably 3 or more and 10 or less, into one Step preferably 4 or more and 8 or less, particularly preferably 4 or more and 7 or less, most preferably 4 or more and 6 or less.By the way that pH is set as Above range is able to suppress the excessive decomposition of cellulose, can obtain high candy output.

[treatment conditions]

As the treatment conditions in treatment process (2), preferably carried out under conditions of all meeting following condition A ~ C.

Condition A

The solid component obtained by treatment process (1) is preferably 1 mass % or more and 50 matter relative to the feed concentrations of above-mentioned solvent Measure % or less.It should be noted that the feed concentrations of above-mentioned solid component are phases as solvent and when using a variety of organic solvents For the concentration of solvent total amount.If the feed concentrations of the solid component obtained by treatment process (1) are 1 mass % or more, i.e., Make to consider quantity of energy used in the heating of solvent, the removal of organic solvent, can also keep the removal work of lignin well The energy efficiency of skill.If the feed concentrations of above-mentioned solid component be 50 mass % hereinafter, if as quantity of solvent be adequately, because This, can keep the separative efficiency of lignin well.

The solid component obtained by treatment process (1) is more preferably 3 mass % or more relative to the feed concentrations of above-mentioned solvent And 20 below mass %, further preferably 5 mass % or more and 15 mass % or less.

Condition B

Treatment temperature in treatment process (2) is preferably 100 DEG C or more and 300 DEG C or less.If treatment temperature be 100 DEG C with On, then can be sufficiently carried out the separation of lignin, if treatment temperature be 300 DEG C hereinafter, if be able to suppress cellulose point The generation for polymerizeing the impurity such as caused coke again of solution, lignin.

Treatment temperature be more preferably 150 DEG C or more and 250 DEG C hereinafter, further preferably 170 DEG C or more and 230 DEG C with Under.

Condition C

The processing time in treatment process (2) is preferably 0.1 hour or more and 10 hours or less.If handling the time is 0.1 small When more than, then can be sufficiently carried out the separation of lignin, if processing the time be 10 hours hereinafter, if be able to suppress cellulose The impurity such as decomposition, coke caused by the polymerizeing again of lignin generation.

Processing the time be more preferably 0.2 hour or more and 8 hours hereinafter, further preferably 1 hour or more and 6 hours with Under, particularly preferably 1 hour or more and 3 hours or less.

As other treatment conditions in treatment process (2), it is expected that the pressure of reaction system is set as 0.5MPa ~ 30MPa. Wherein, the preferred scope of the pressure of reaction system is influenced by water, the amount of organic solvent and temperature, therefore is suitably set.In addition, place Science and engineering sequence (2) can carry out under surrounding atmosphere.It should be noted that in order to inhibit the polymerization as caused by oxidation reaction, processing Process (2) particularly preferably carries out under the atmosphere that progress nitrogen purging reduces oxygen.

Processing mode in treatment process (2) is not particularly limited, and can enumerate standing or stir process.It can use Such as general batch reactor, semibatch reactor etc..In addition it is also possible to using that will include from department of botany's biomass Solid and organic solvent or water and organic solvent the mode that is handled while with extrusions such as screw rod or pumps of slurry.

The reactant obtained after the heat treatment for the treatment of process (2) is separated by solid-liquid separation, can be obtained in solid form To the solid containing cellulose, and the solution containing lignin is obtained in fluid form.

It should be noted that may include that will be obtained by separation of solid and liquid when separation of solid and liquid after treatment process (2) The process washed of solid component.The washing step can be by relative to the solid component 100 obtained after separation of solid and liquid Mass parts add such as 100 mass parts or more and 10000 water and stirring below the mass to carry out.After stirring, by solid at Divide and is separated by filtration with liquid phase.

Water used in washing step be preferably as described above 100 mass parts or more and 10000 below the mass, it is more excellent Be selected as 1000 mass parts or more and 5000 below the mass, it is more than further preferably 1000 mass parts and 2000 mass parts with Under.If water used in washing is 100 mass parts or more, sufficient cleaning effect can be obtained, by being set as 10000 Below the mass, it can be washed without problems in equipment aspect.By the washing step, be able to carry out organic solvent into one Step removal, and remove water-soluble ingredient accompanying by the solid containing cellulose.

After the separation of solid and liquid after the heat treatment for the treatment of process (2), or further via above-mentioned washing step, energy Access the solid containing cellulose.The manufacturing method according to the present embodiment can be used as in water phase with residue The obtained solid component of form and recycle the solid contained in department of botany's biomass containing cellulose.

Separate mode in manufacturing method described in present embodiment is not particularly limited, can enumerate filtering, filters pressing, from Heart separation, dewaterer etc..

Comprising lignin in the liquid phase obtained after the heat treatment for the treatment of process (2) or after further washing process. For example, in the case where two-phase is presented after treatment, being obtained after separating water phase by making using the mixed solvent of water and organic solvent Organic phase gasify etc. and remove solvent, solid lignin can be obtained.In addition, even if organic solvent is used alone Situation, using in the case where the mixed solvent of organic solvent and water, the case where after the heat treatment for the treatment of process (2) being a phase Under, ands making organic solvent gasification etc. can remove solvent and in water as remaining solid residue or by filtering The solid of sedimentation, to obtain solid lignin.

As described above, manufacturing method according to the invention can manufacture half fiber as the product for being originated from department of botany's biomass Dimension element, the solid containing cellulose and lignin.For each product, it is described in detail below.

Lignin obtained from manufacturing method through the invention has following characteristics.

(11): the purity of lignin is 90% or more；

(12): number-average molecular weight is 650 or more；And

(13): 5% hot loss of weight start temperature is 210 DEG C or more.

In above-mentioned record, the purity of lignin is preferably 92% or more, more preferably 94% or more.In addition, the equal molecule of number Amount preferably 700 or more, more preferably 750 or more.In turn, 5% hot loss of weight start temperature is preferably 215 DEG C or more, is more preferably 220 DEG C or more.

It should be noted that each survey of purity, number-average molecular weight and 5% hot loss of weight start temperature for above-mentioned lignin Determine method, is detailed in aftermentioned.

Manufacturing method according to the invention, the carbohydrate from hemicellulose are returned relative to the hemicellulose in department of botany's biomass Yield reaches 50 mass % or more.When the rate of recovery of carbohydrate from hemicellulose is less than 50 mass %, fermentation is potentially contributed to Carbohydrate is reduced.

In the solid containing cellulose that manufacturing method through the invention obtains, in terms of solid component, containing fibre Tie up element solid total amount benchmark in, cellulose and by the content of cellulose decomposition object obtained from cellulose decomposition be 60 matter % or more is measured and 90 mass % hereinafter, the content of lignin is 5 mass % or more and 30 mass % are hereinafter, half fiber as other materials The content of hemicellulose decomposition product obtained from tieing up element and decomposing hemicellulose is 0 mass % or more and 5 mass % or less.This Outside, the cellulose in the solid containing cellulose reaches 70 matter relative to the rate of recovery of the cellulose in department of botany's biomass Measure % or more.

Cellulose and by cellulose decomposition object obtained from cellulose decomposition less than 60 mass % the case where or lignin In the case where more than 30 mass %, handling conversion coefficient when obtaining glucose by enzymatic conversion is reduced.If hemicellulose and general half Hemicellulose decomposition product obtained from cellulose decomposition is more than 5 mass %, then the separation of the lignin in conjunction with hemicellulose/go Except becoming inadequate, handling conversion coefficient when obtaining glucose by enzymatic conversion is reduced.In addition, the cellulose rate of recovery is less than 70 When quality %, glucose is reduced relative to the rate of recovery of the cellulose in department of botany's biomass.

Cellulose contained in solid containing cellulose obtained from manufacturing method through the invention is contained due to lignin Amount is few, therefore is applicable to the saccharification processing based on acid, enzyme.In addition, containing fibre obtained from manufacturing method through the invention The solid of element is tieed up compared with the solid containing cellulose as obtained from other methods, the state for being easy defibering is presented. Therefore, have the advantages that be readily expanded application.

In addition it is possible to use well known method, the solid-state containing cellulose obtained by manufacturing method through the invention Object obtains ethyl alcohol, butanol and acetone etc..

Furthermore, it is possible to obtain cellulose nanometer by the solid containing cellulose that manufacturing method through the invention obtains Fiber etc. is as resin reinforcing fiber/chemical fibre substitute rubber and tire reinforcing material, carboxymethyl cellulose, oligosaccharides etc. The chemicals such as food additives, lactic acid, succinic acid.

The hemicellulose obtained by manufacturing method through the invention can obtain the food additives such as oligosaccharides, xylitol, furfural Equal chemicals, thus it is useful.

In addition, the lignin that manufacturing method through the invention obtains specifically can be used as fuel, cement water repellent material Material.In addition, can also be applied to the additive of phenolic resin, epoxy resin, the base resin raw material of polyurethane resin, epoxy resin The modifying agent (fire retardant) of (curing agent), polyurethane resin, additive of thermoplastic resin etc..This, which is based on lignin, has phenol The feature of structural unit.

About the purposes as basis resin raw material of lignin, conventionally known method can be used.As an example, may be used It enumerates and is combined with lignin and using hexa as resin combination made of the known crosslinking agent of representative.

Can according to need to be combined in resin combination made of lignin and crosslinking agent cooperate various packing materials, The conventional phenolic resin industrially obtained.This resin combination can be used for the heat-insulating material, electronic component, pressure break of house Sand resin, coated sand resin, infiltration resin, stacking resin, FRP molding resin, automobile component, automobile tire Reinforcing material etc..

In addition, by the use as epoxy curing agent for importing epoxy group and lignin into lignin, also It can be applied to epoxy resin.In addition to this, by using well known method, by vinyl, dimaleoyl imino, isocyanates Base etc. is directed into lignin, can further apply the industrial resin of wide scope.

About the use as additive, such as Japanese Unexamined Patent Publication 2014-15579, International Publication No. 2016/ can be used No. 104634 conventionally known methods enumerated in waiting.It can according to need to being combined with made of lignin and thermoplastic resin Cooperate various additives, packing material in resin combination.

[resin combination]

In other embodiments of the present invention, the resin combination comprising lignin obtained from by the above-mentioned manufacture method is provided Object.In addition, may include thermoplastic resin, Thermocurable tree except except through lignin obtained from above-mentioned manufacturing method The resin components such as rouge.About the ingredient other than lignin, it is described below.

As the thermoplastic resin that can cooperate in resin combination described in present embodiment, preferably there are 200 DEG C of glass below The amorphous thermoplastic resin or fusing point of glass transition temperature are 200 DEG C of crystalline thermoplastic resins below.As thermoplastic Property resin, such as polycarbonate-based resin, phenylethylene resin series, polystyrene based elastomers, polyvinyl resin, poly- can be enumerated Allyl resin, polyacrylic based resin (plexiglass etc.), Corvic, acetyl cellulose resins, Eutectic representated by the combined polyester of polyamide, terephthalic acid (TPA) and ethylene glycol, terephthalic acid (TPA) and 1,4- butanediol Point polyester resin (PET, PBT etc.), polylactic acid and/or copolymer, acrylonitrile-butadiene-styrene resin comprising polylactic acid (ABS resin), polyphenylene oxide resin (PPO), polyketone resin, polysulfone resin, polyphenylene sulfide (PPS), fluororesin, silicone resin, Polyimide resin, polybenzimidazole resin, polyamide elastomer etc. and the copolymer of they and other monomers.

Thermoplastic resin from the viewpoint of obtaining significant mobility and intensity, in resin combination of the present invention The content of rouge is preferably 30 mass % or more and 99.9 mass % or less, more preferably 40 relative to total scale of construction of the resin combination Quality % or more and 99.9 mass % or less, further preferably 45 mass % or more and 99.9 mass % or less, particularly preferably 50 Quality % or more and 99.9 mass % or less.

In resin combination described in present embodiment, in addition to the above-mentioned solid containing cellulose, thermoplastic resin it Outside, can also comprising can be compatible with thermoplastic resin composition resin, additive and/or filler.

<heat-curing resin>

As the heat-curing resin that can cooperate in resin combination described in present embodiment, can cooperate have can be with wood Lignin reaction's property compound of the functional group of quality reaction.It can be with the chemical combination of the functional group of lignin reaction as having Object can enumerate and the compound of electrophilic substitution occurs with phenolic compounds, the compound with epoxy group, has isocyanic acid The compound etc. of ester group.

Lignin has the structural unit of phenol, therefore, the applicable base resin for making phenolic resin and epoxy resin etc. Raw material, additive (curing agent) of epoxy resin etc..

(compound that electrophilic substitution occurs with phenolic compounds)

As the compound that electrophilic substitution occurs with phenolic compounds, formaldehyde can be enumerated, for formaldehyde curing agent compound Or formaldehyde isovalent compounds etc..Hexa, pregnancy aldehyde and paraformaldehyde commercially can be used.

It, can also be with other than lignin and hexa in addition, in resin combination described in present embodiment Further include phenolic resin.As described above, lignin has the structural unit of phenol, therefore, phenolic resin can not drop It is used as diluent, the incremental agent etc. of lignin in the range of the physical property such as processability, intensity and the heat resistance of low resin combination.

(compound with epoxy group)

Compound with epoxy group belongs in the scope of referred to as so-called epoxy resin.As an example, can to enumerate 2,2- bis- (4 '-hydroxy phenyl) propane (referred to as bisphenol-A), bis- (2- hydroxy phenyl) methane (referred to as Bisphenol F), 4,4 '-dihydroxydiphenyls Sulfone (referred to as bisphenol S), 4,4 '-dihydroxybiphenyls, resorcinol, saligenin, trihydroxy diphenyldimethyhnethane, four phenolic group second Alkane, their halogen substituents and alkyl substituents, butanediol, ethylene glycol, erythrite, novolaks, glycerol, polyoxy alkylidene Deng the glycidol ether system epoxy resin of compound and the synthesis such as epoxychloropropane in the molecule containing 2 or more hydroxyls；By The intramolecular contains the ethylene oxidic ester system epoxy of the synthesis such as compound and the O-phthalic acid glycidyl ester of 2 or more hydroxyls Resin；By primary amine or secondary amine and table such as aniline, diaminodiphenyl-methane, m-xylene diamine, the bis- aminomethyl cyclohexanes of 1,3- Glycidol amine system epoxy resin of the synthesis such as chloropharin etc. includes the epoxy resin of glycidyl；Epoxidised soybean oil, epoxy Change the epoxy resin that polyolefin, vinyl cyclohexene dioxide, dicyclopentadiene etc. are free of glycidyl.This Among a little, preferably chemical structure and lignin like and the good cresol novolak type of compatibility, phenol novolak type Epoxy resin.

In addition, in hot curing resin composition, it, can be into one other than lignin and comprising the compound of epoxy group Step includes phenolic resin.

It, can be according to rush in the case that lignin contained in hot curing resin composition is the compound comprising epoxy group Into curing reaction purpose and be properly added curing accelerator.As concrete example, 2-methylimidazole, 2- ethyl miaow can be enumerated The imidazoles such as azoles, 2-ethyl-4-methylimidazole, 2-(dimethylaminomethyl) phenol, 1,8- diaza-bicyclic (5,4,0) ten The phosphines such as tertiary amines, the triphenylphosphines such as one carbene -7,4-butyl ammonium, triisopropyl methyl ammonium salt, trimethyldecylammonium ammonium salt, whale The quaternary phosphoniums such as the quaternary ammonium salts such as cerul leptodactyline, triphenylbenzylphosphonium microcosmic salt, triphenyl ethyl microcosmic salt, tetrabutyl microcosmic salt Metallic compounds such as salt, tin octoate etc..As the counter ion counterionsl gegenions of quaternary alkylphosphonium salt, halogen, organic acid anions, hydrogen-oxygen can be enumerated Compound ion etc., particularly preferably organic acid anions, hydroxide ion.

(compound with isocyanate group)

Compound with isocyanate group is polyisocyanates or makes obtained from polyisocyanates and polyol reaction.Make For polyisocyanates, toluene di-isocyanate(TDI) (TDI), 4,4 '-methyl diphenylene diisocyanates (MDI), polymerization can be enumerated MDI(MDI-CR), carbodiimide modified MDI(liquid MDI) etc. aromatic polyisocyanates and norbornene alkyl diisocyanate (NBDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HDI), 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl Isocyanates) (hydrogenation MDI), the aliphatic polyisocyantes such as xylylene diisocyanate (XDI)；Blocked isocyanate.This , it is preferable to use toluene di-isocyanate(TDI) (TDI), 4,4 '-methyl diphenylene diisocyanates (MDI) among a little.

In addition, in above-mentioned hot curing resin composition, it, can be into one other than lignin and isocyanate compound Step includes phenolic resin.

Hot curing resin composition can be properly added curing accelerator according to the purpose for promoting curing reaction.As Curing accelerator can enumerate the organic metal series catalysts, dibutyl tin laurate, the phenates of DBU, octanoic acid of such as zirconium, aluminium Salt, amine, imidazoles etc., from the viewpoint of coloring, particularly preferably organic metal series catalysts, such as secondary butyric acid aluminium, acetyl Ethyl acetate diisopropanol closes aluminium, three butoxy acetylacetone,2,4-pentanedione zirconiums, four acetylacetone,2,4-pentanedione zirconiums etc..

(other resin components)

In resin combination described in present embodiment, other than lignin, phenolic resin, carbamide resin, trimerization may include The resins such as melamine resin, silicone resin, unsaturated polyester resin, alkyd resin, polyurethane resin.

Due to having phenolic hydroxyl group in the same manner as lignin, can react with lignin, it is also possible to make lignin Diluent, therefore, among above-mentioned resin, preferably phenolic resin.

Resin combination described in present embodiment may include packing material.Packing material can be inorganic filling material, It can be organic filler.

As inorganic filling material, fused silica, the crystalline silica of for example spherical or broken shape can be enumerated Equal SiO 2 powders, alumina powder, glass powder, glass fibre, sheet glass, mica, talcum, calcium carbonate, aluminium oxide, water Close aluminium oxide, boron nitride, aluminium nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, magnesia etc..

In addition, carbon fiber, aramid fiber, paper powder, cellulose fibre, cellulose can be enumerated as organic filler material Powder, powdered rice hulls, fruit shell nut powder, chitin powder, starch etc..

Inorganic filling material, organic filler material can individually contain or combine a variety of containing content can be according to mesh Determine.

In resin combination described in present embodiment, in the model for the characteristic for not damaging the formed products obtained by the resin combination In enclosing, various additives can be added.In addition, can further add compatilizer, surfactant etc. according to purpose.

As the compatilizer being used together with thermoplastic resin, the addition maleic acid into thermoplastic resin can be applied in combination Acid anhydride, epoxy group etc. and imported the resin of polar group, such as maleic anhydride modified polyvinyl resin, maleic anhydride modified poly- third Olefine resin, commercially available various compatilizers.

In addition, the straight chain fatty acids such as stearic acid, palmitinic acid, oleic acid can be enumerated as surfactant；Or rosin Equal branches/cyclic fatty acid etc., but it is not particularly limited in this.

In turn, as the additive that can cooperate in addition to that mentioned above, toughener, heat stabilizer, ultraviolet light can be enumerated and inhaled Receive agent, fire retardant, antistatic agent, defoaming agent, thixotropy conferring agents, release agent, antioxidant, plasticizer, low stress agent, idol Join agent, dyestuff, light scattering agent, a small amount of thermoplastic resin etc..

[formed products]

Formed products described in embodiments of the present invention are by the resin combination containing the lignin obtained by the above-mentioned manufacture method Object and obtain.It as an example of formed products, can enumerate: solidify resin combination made of being combined with lignin and crosslinking agent Obtained from formed products；In addition, conventional phenolic resin that is as needed and cooperating various packing materials, industrially obtain, and Make formed products obtained from its solidification after being configured to regulation shape；Or forming obtained from being formed after solidifying it Product etc..

As the method for being configured to regulation shape, as long as being capable of being shaped to resin combination, it is not particularly limited.Example Such as, when resin combination is hot curing resin composition, the method for being configured to regulation shape can enumerate compression forming method, note Penetrate forming process, transmitting forming process, middle contour forming, FRP forming process etc..In addition, when resin combination is thermoplastic resin composition, The method for being configured to regulation shape can enumerate extrusion molding method, injection molding method etc..

It as an example of formed products, can enumerate: solidify resin combination made of being combined with lignin and crosslinking agent Obtained from formed products；In addition, the usual phenolic resin for further cooperating various packing materials as needed, industrially obtaining, And the formed body obtained from solidifying it after being configured to regulation shape；Or obtained from being formed after solidifying it Formed body obtained from processing etc. is formed in the resin combination that lignin and thermoplastic resin mix by formed body. Heat-insulating material, electronic component, fracturing sand resin, the coated sand that the formed products of this resin combination can be used for house are used Resin, infiltration with resin, stacking with resin, FRP molding resin, automobile component, the reinforcing material of automobile tire, OA equipment, Machinery, information communication device, industry goods, materials and equipments etc..

[manufacturing method of glucose]

Contain fibre obtained from manufacturing method using the solid described in embodiment through the invention containing cellulose The solid for tieing up element, can manufacture glucose.

In the manufacturing method of glucose described in present embodiment, the condition of enzymatic conversion processing is as described below.

For cellulose contained in the solid containing cellulose and by cellulose decomposition obtained from cellulose decomposition The enzyme that object works can be set to 0.1 mass % or more and 200 mass % or less relative to the solid total amount containing cellulose.This Outside, enzymatic conversion, which handles used enzymatic activity, can be set to 100CUN/g or more and 10000CUN/g or less.In turn, if enzyme is sugared Treatment temperature in change processing is 30 DEG C or more and 70 DEG C hereinafter, then enzyme activates, and can be improved conversion coefficient.If enzymatic conversion Processing time in processing is 12 hours or more and 168 hours hereinafter, then enzyme activates, and can be improved conversion coefficient.

Embodiment

Hereinafter, further illustrating present embodiment by embodiment, but present embodiment is not appointed by these embodiments What is limited.

[Production Example of the solid containing cellulose]

Treatment process (1)

As pre-treatment, several mm will be crushed to as department of botany's biomass of raw material (such as vegetation system biomass of bagasse etc) Below.After crushing, add water that the raw material slurry that solid concentration is 15 mass % or so is made.Phosphoric acid is added into the raw material slurry, So that the pH in raw material slurry reaches 2.0, and mixed.

Raw material slurry is supplied in reactor (pressure vessel), and is heated to supercriticality or subcritical state is Only.When hemicellulose in raw material slurry is hydrolyzed, hydro-thermal process is preferably carried out with 170 DEG C of temperature.

Treatment process (2)

By the solid component obtained by treatment process (1), the water and n-butyl alcohol that are prepared in such a way that n-butyl alcohol concentration is 34 mass % Mixed solvent, sodium hydroxide is put into in such a way that pH reaches 3 SUS(stainless steel to internal volume for 0.92L) interval of system In formula device.The total amount of solvent is 315g.Raw material feed concentrations be set as raw material/solvent=1/10(solid component feed intake it is dense Degree: 9.1 mass %) Lai Jinhang.

After being purged in the device of the batch-type system of SUS with nitrogen, until being warming up to 200 DEG C, 2 hours places are carried out Reason.The processing time is set as the elapsed time from reaching 200 DEG C.In addition, using thermocouple come measuring temperature.

After treatment, the batch-type system of SUS is cooling, it, then will be interior until temperature drops near room temperature It is tolerant all to take out.After processing, solid component and liquid phase are separated by filtration.

200g water is added into solid component to be separated by filtration solid component and liquid phase after stirring 30 minutes.It should Operation 3 times repeatedly, obtain the solid containing cellulose.Liquid phase is separated into water phase and n-butyl alcohol by separatory funnel liquid liquid Phase.After the solvent of n-butyl alcohol phase is removed using evaporimeter (70 DEG C, water-bath), it is dried in vacuo, is obtained under conditions of 125 DEG C To lignin.

In treatment process (2), pH is adjusted to 4, in addition to this, is all equally carried out with Production Example 1.

The n-butyl alcohol concentration of in the mixed solvent in treatment process (2) is 50 mass %, in addition to this, all same as Production Example 2 It carries out.

As constitute treatment process (2) mixed solvent organic solvent, using ethyl alcohol, in addition to this, with Production Example 3 equally into Row.It should be noted that since the liquid phase after being separated by solid-liquid separation is a phase, by removing organic solvent using evaporimeter, lead to After the solid component precipitated in water because solubility reduces is separated by solid-liquid separation by filtering, carried out under conditions of 125 DEG C Vacuum drying, obtains lignin.

As constitute treatment process (2) mixed solvent organic solvent, using acetone, in addition to this, by with 4 phase of Production Example Same operation, obtains lignin.

As constitute treatment process (2) mixed solvent organic solvent, using 2- methyl 1- propyl alcohol, in addition to this, all with Production Example 3 equally carries out.

In treatment process (2), pH is adjusted to 5, in addition to this, is all equally carried out with Production Example 1.

In treatment process (2), pH is adjusted to 6, in addition to this, is all equally carried out with Production Example 1.

In treatment process (2), pH is adjusted to 7, in addition to this, is all equally carried out with Production Example 1.

In treatment process (2), pH is adjusted to 10, in addition to this, is all equally carried out with Production Example 1.

In treatment process (2), pH is adjusted to 12, in addition to this, is all equally carried out with Production Example 1.

(water is used only without the use of acidic aqueous solution) in<Production Example 12>in treatment process (1)

Firstly, will be crushed as department of botany's biomass of raw material (such as vegetation system biomass of bagasse etc) as pre-treatment To several mm or less.After crushing, add water that the raw material slurry that solid concentration is 10 mass % or so is made.

Raw material slurry is supplied in reactor (pressure vessel), and is heated to supercriticality or subcritical state. When hemicellulose in raw material slurry is hydrolyzed, hydro-thermal process is preferably carried out with 170 DEG C of temperature.Hereinafter, (in processing work In sequence (2), sodium hydroxide is not added with to adjust pH, in addition to this, is all equally carried out with Production Example 1.

In treatment process (2), sodium hydroxide is not added with to adjust pH, in addition to this, is all equally carried out with Production Example 1.

Not after the treatment process (1) as hydro-thermal process process, not using the mixed solvent of water and n-butyl alcohol to as raw material Department of botany's biomass handled, in addition to this, and Production Example 13 is all same carries out.

About the cellulose amount in the cellulose amount in department of botany's biomass and the solid containing cellulose, carry out following shown Pre-treatment after, according to constitute glycan analysis calculated.

[pre-treatment]

The raw material as sample is crushed, is dried with 105 DEG C using wiley mill as pre-treatment.

[constituting glycan analysis]

Measure the sample of suitable department of botany's biomass or the solid containing cellulose, add 72% sulfuric acid, 30 DEG C of one side with When stirring on one side place 1 hour.By the reaction solution on one side with pure water is mixed release while completely and be transferred in pressure bottle, with autoclave with After 120 DEG C are handled 1 hour, filtrate and residue are separated by filtration.About the monosaccharide in filtrate, high performance liquid chromatography is utilized It is quantified.It should be noted that C6 polysaccharide (mainly glucan) is defined as cellulose, (mainly by C5 polysaccharide Xylan) it is defined as hemicellulose.

[lignin]

The residue being separated by filtration during glycan analysis being constituted is dried with 105 DEG C, measures weight, and it is residual to calculate decomposition Slag rate.In turn, by carrying out ash amount correction, the content of lignin is calculated.

The cellulose rate of recovery (weight %)=(solid containing cellulose is returned in yield (g) × solid containing cellulose Cellulose ratios (weight %)/100) cellulose amount (g) × 100 in/department of botany's biomass

Using high performance liquid chromatograph (Agilent corporation, HPLC1200 series), the concentration of hydroxymethylfurfural is calculated.

Hydroxymethylfurfural production rate (quality %)=hydroxymethylfurfural concentration (mg/L) × 10^-6× solution capacity (mL)/plant It is biomass (g) × 100.

[table 1]

。

[table 2]

。

Known to: in Production Example 1 ~ 12, the generation of hydroxymethylfurfural caused by excessive decomposition is suppressed, and can obtain height The cellulose rate of recovery.

Embodiment 1 ~ 13

[evaluation method of the resulting solid containing cellulose]

By the solid 1g(dry weight containing cellulose) investment into 50mL centrifugal separating tube, carries out 121 DEG C, 20 minutes Sterilization treatment.The acetate buffer for implementing identical sterilization treatment is added to centrifugation in such a way that liquid measure reaches about 20mL, pH5 In separating pipe, thereafter, enzyme amount shown in input table 3 (Na ガセケ system テッ Network ス corporation, セ Le ライザー ACE).It should Centrifugal separating tube vibrates 72hr in 50 DEG C of thermostat with 120rpm.

To enzyme 1ml is added in 0.625% solution (pH4.5), 4ml of 0.625% sodium carboxymethylcellulose, made with 40 DEG C When it is acted on 30 minutes, activity when generating reducing power comparable with the glucose of 1 μm of ol at 1 minute is shown as 1CUN.Above-mentioned enzyme Enzymatic activity with 1600CUN/g or more.

1. glycan analysis

Sugared (xylose, wood oligose, glucose) is analyzed using following conditions and using HPLC.

Determination condition

Column: Showa electrician Shodex SP-G(guard column)+SP0810

Mobile phase: distilled water (HPLC rank)

Detector: being 60 DEG C in RI(cuvette)

Column temperature: 80 DEG C

Injection rate: 50 μ L

2. prepared by sample

Using pipettor, 0.2mL sample (solution) is taken into 10mL bottle.

Distilled water 1.8mL is added, (10 times of dilution) is sufficiently mixed.

It takes into bottle.

3. calculation method

Using standard curve, calculate concentration of glucose (g- glucose/L).

The glucose rate of recovery (%)=(glucose amount (g) in the solid enzymatic conversion liquid containing cellulose × contain fiber The solid rate of recovery (quality %)/100 of element) glucose amount (g) × 100 in/department of botany's biomass.

[table 3]

。

[table 4]

。

In the embodiment 1 ~ 12 of the solid containing cellulose manufactured using Production Example through the invention, by containing There is the glucose rate of recovery of glucose amount benchmark of the solid of cellulose in department of botany's biomass as obtained from enzymatic conversion Show high numerical value.It should be noted that containing using as obtained from the Production Example 13 for adjusting pH not in treatment process (2) In the embodiment 13 of the solid of cellulose, the total amount for the solid containing cellulose that can be recycled is more than other Production Examples Low, therefore, if enzyme amount reaches 0.1mL, the absolute magnitude of the cellulose until decomposing to sugar is low, therefore, the glucose rate of recovery with Other rate of recovery are compared and are lower.

Embodiment 9 and comparative example 1

(xylose, wood oligose, glucose) rate of recovery (%)=(wood in xylose amount (g)+hydro-thermal process liquid in hydro-thermal process liquid is few Sugar amount (g)+(glucose amount (g) × solid rate of recovery containing cellulose in the solid enzymatic conversion liquid containing cellulose (quality %)/100))/(glucose amount (g) in xylose amount (g)+department of botany's biomass in department of botany's biomass) × 100.

[table 5]

。

Manufacturing method according to the invention is able to suppress excessively dividing for the carbohydrate (xylose and wood oligose) from hemicellulose Solution and recycled, therefore, using department of botany's biomass as benchmark, can efficiency recycle carbohydrate well.

It is equally carried out with above-mentioned<composition analysis of raw material>.

<number-average molecular weight>

Using having used the gel of tetrahydrofuran solvent to be impregnated with chromatography (GPC), the number-average molecular weight (measurement of above-mentioned lignin is measured Temperature is 40 DEG C, detector RI).Number-average molecular weight is the number-average molecular weight of polystyrene conversion.

5% hot loss of weight start temperature (Td5) is measured using the EXSTAR6000 TG/DTA6200 of SII corporation.To Pt pots The middle sample for weighing about 10mg, with 10 DEG C/min of heating rate, measurement atmosphere: surveying for air 200mL/ minutes from 35 DEG C of temperature Determine until 800 DEG C, finds out the temperature that weight reduces 5%.

Be blended with deuterated chloroform, pyridine, cyclohexanol (internal standard) solvent be added to purification lignin in, in turn, as derivative Materialization reagent and add 2- chloro- 4,4,5,5- tetramethyls -1,3,2- dioxaphospholane, with 50 DEG C heat 1 hour.Thereafter, Implement 31PNMR measurement using following determination conditions.

Pulse width: 30 °

Reciprocal time: 2 seconds

Measurement range: -60 ~ 200ppm

Tired number of calculating: 200 times

It is set as 145.2ppm as the signal of interior target cyclohexanol by being originated from, 144.7 ~ 136.6ppm is attributed to phenolic hydroxyl group (Ph-OH), phenolic hydroxyl group equivalent (g/eq) is calculated by integrated value.

[table 6]

。

As shown in Table 4: the high lignin of heat resistance can be obtained.In addition, do not carried out in this manufacturing method it is twice-modified, because This is with high phenolic hydroxyl group amount.Therefore, material can also be suitably used as.

Embodiment 9 and comparative example 1

[including the evaluation of the hot curing resin composition of hexa]

Using lignin obtained in Production Example 9 and comparison manufacturing example, hot curing resin composition is made.In addition, making it Solidfied material evaluates physical property.

Each ingredient is put into mortar using match ratio shown in table 2, after being crushed, being mixed at room temperature, uses mill Roller kneading machine, after five minutes with 100 DEG C of mixing, until being cooled to room temperature.Mixture is crushed with mortar, is sandwiched in and is coated with demoulding Between the aluminium sheet of agent, using vacuum pressed machine, shaped 60 minutes with 150 DEG C under reduced pressure.After forming, 120 points are handled with 200 DEG C Clock obtains formed products.

5mm × 50mm × 1mm sample is cut out by gained formed products, using Instron 5566, in beam mode, spacing at 3 30mm, under conditions of speed 2mm/ minutes, bending strength is measured.

The measurement of glass transition temperature is measured by solid visco-elasticity method.By gained formed products cut out 5mm × 30mm × The sample of 1mm uses DMA8000(パーキ Application エルマージャパ Application Co. Ltd. system), at 0 DEG C ~ 300 DEG C or to reaching Until the minimum elasticity modulus of the limit, it is measured with 2 DEG C/min of warming temperature, 1Hz.By the peak temperature of resulting tan δ As glass transition temperature (Tg).

[table 7]

* 1: phenolic resin ... PR-53195(Sumitomo ベイー Network ライ De Co. Ltd. system)

* 2: inorganic filling material 1 ... glass fibre CS3E479S(Nitto Boseiki Co., Ltd.'s system).

As shown in Table 5: in the embodiment 13 using lignin obtained from manufacturing method through the invention, energy Access the formed products of heat resistance height and physical properties excellent.

Industrial availability

In accordance with the invention it is possible to provide by the manufacture of department of botany's biomass is originated from the carbohydrate of hemicellulose, excessive decomposition is suppressed The solid containing cellulose and the lignin few as impurity the product from biomass method.According to this hair It is bright, the first treatment process (1) is carried out while inhibiting the excessive decomposition of hemicellulose, it therefore, can be by being originated from hemicellulose Carbohydrate and solid containing cellulose obtain high candy output.

Claims

1. being originated from the manufacturing method of the product of department of botany's biomass, contain:

2. the manufacturing method of the product according to claim 1 from department of botany's biomass, wherein in the treatment process (2) after, the solid containing cellulose is obtained in solid form and being separated by solid-liquid separation, and in fluid form To the solution containing lignin.

3. the manufacturing method of the product according to claim 2 from department of botany's biomass, wherein by containing from described Solvent is removed in the solution of lignin and obtains solid lignin.

4. the manufacturing method of the product described according to claim 1 ~ any one of 3 from department of botany's biomass, wherein described Department of botany's biomass is draft system biomass.

5. the manufacturing method of the product described according to claim 1 ~ any one of 4 from department of botany's biomass, wherein in institute It states in treatment process (1), as the processing of separation hemicellulose, carries out hydro-thermal process.

6. the manufacturing method of the product according to claim 5 from department of botany's biomass, wherein the hydro-thermal process is Selected from having used the hydro-thermal process of water and/or vapor, steam explosion and used in the hydro-thermal process of acidic aqueous solution It is at least one kind of.

7. the manufacturing method of the product according to claim 6 from department of botany's biomass, wherein the acidic aqueous solution To include at least one kind of acidic aqueous solution in inorganic acid and organic acid.

8. the manufacturing method of the product described according to claim 1 ~ any one of 7 from department of botany's biomass, wherein use Alkaline matter adjusts: into the treatment process (2) will be by handling from after separation hemicellulose in the treatment process (1) The solid component that process (1) obtains mixed with solvent before until system pH or will be by the treatment process (2) The pH of system when the solid component that science and engineering sequence (1) obtains is mixed with solvent.

9. the manufacturing method of the product according to claim 8 from department of botany's biomass, wherein adjustment is in the processing In process (2) will system of the solid component that obtained by treatment process (1) when being mixed with solvent pH.

10. the manufacturing method of the product from department of botany's biomass according to claim 8 or claim 9, wherein use the alkali Property substance adjustment pH after system pH be 3 or more and 12 or less.

11. the manufacturing method of the product described according to claim 1 ~ any one of 10 from department of botany's biomass, wherein institute Stating organic solvent used in treatment process (2) is in ethyl alcohol, n-butyl alcohol, 2- methyl-1-propyl alcohol, 2- butanol and acetone It is at least one kind of.

12. the manufacturing method of the product described according to claim 1 ~ any one of 11 from department of botany's biomass, wherein benefit The treatment process (2) are carried out with following condition A ~ C:

Condition A: the solid component obtained by treatment process (1) is 1 mass % or more and 50 matter relative to the feed concentrations of solvent Measure % or less；

Condition C: the processing time is 0.1 hour or more and 10 hours or less.

13. the manufacturing method of glucose, wherein will be as obtained from the manufacturing method described in any one of claim 2 ~ 12 Solid containing cellulose carries out enzymatic conversion processing, obtains glucose.

14. resin combination uses lignin obtained from having the method as described in any one of claim 2 ~ 12.

15. lignin meets following (11) ~ (13):

(11): the purity of lignin is 90% or more；

(12): number-average molecular weight is 650 or more；And

(13): 5% hot loss of weight start temperature is 210 DEG C or more.

16. resin combination, it includes the lignin described in claim 15.

17. formed products, resin combination described in having the right to require 14 or 16 is used.