WO2017222084A1 - Procédé de production d'un produit dérivé d'une biomasse végale, comprenant un processus en deux étapes - Google Patents

Procédé de production d'un produit dérivé d'une biomasse végale, comprenant un processus en deux étapes Download PDF

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Publication number
WO2017222084A1
WO2017222084A1 PCT/JP2017/032386 JP2017032386W WO2017222084A1 WO 2017222084 A1 WO2017222084 A1 WO 2017222084A1 JP 2017032386 W JP2017032386 W JP 2017032386W WO 2017222084 A1 WO2017222084 A1 WO 2017222084A1
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Prior art keywords
biomass
plant
lignin
treatment
treatment step
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PCT/JP2017/032386
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English (en)
Japanese (ja)
Inventor
啓人 小山
一晃 廣田
山尾　忍
匡貴 岡野
隆夫 増田
吉川　琢也
Original Assignee
出光興産株式会社
国立大学法人北海道大学
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Application filed by 出光興産株式会社, 国立大学法人北海道大学 filed Critical 出光興産株式会社
Priority to CN201780054650.6A priority Critical patent/CN109689736A/zh
Priority to JP2018523716A priority patent/JP6931878B2/ja
Publication of WO2017222084A1 publication Critical patent/WO2017222084A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02—Monosaccharides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/14—Hemicellulose; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L97/00—Compositions of lignin-containing materials
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/02—Monosaccharides

Definitions

  • the present invention relates to a method for producing a plant biomass-derived product having a two-stage process.
  • biomass-derived raw materials have been desired.
  • raw materials derived from biomass are particularly prominent in the production of bioethanol, for example, but there are many cases where raw materials that compete with food such as starch and sugar are often used, which leads to an increase in food prices and a decrease in food production.
  • a technology for producing biofuels and biochemicals from cellulosic biomass that does not compete with food is currently attracting attention.
  • Cellulosic biomass includes, for example, palm palm trunks and bunches, palm palm fruit fibers and seeds, bagasse (sugar cane (including high biomass and sugar cane)), cane top (sugar cane top and leaf), rice straw, Straw, rice husk, corn cobs, foliage, corn residue (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, Jatropha seed coat and shell, cashew shell, wood chip, switchgrass, napiergrass, Eliansus Energy crops and energy canes.
  • bagasse bagasse
  • cane cane top
  • rice straw Straw, rice husk, corn cobs, foliage, corn residue (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, Jatropha seed coat and shell, cashew shell, wood chip, switchgrass, napiergrass, Eliansus Energy crops and energy canes.
  • sorghum including sweet sorghum
  • a pretreatment step is usually required before the enzymatic saccharification treatment.
  • each component of the biomass or a bond between the components is loosened, and the enzyme can easily access the cellulose.
  • the enzyme adsorbs to lignin present in the system and inhibits saccharification, it was necessary to use a large amount of expensive enzyme in order to obtain sufficient saccharification, so that lignin was solubilized. It was desired.
  • hemicellulose is excessively decomposed when exposed to high temperature, and is easily converted into a saccharification / fermentation inhibitor such as furfural, and it is necessary to suppress the excessive decomposition.
  • Lignin is usually produced as a residue when biomass is converted to ethanol, but has been limited to use as a fuel because it contains many impurities such as enzymes and yeast. However, since it has a polyphenol-like structure, it can be expected to be converted into chemicals and bioplastics, and therefore it is desired to extract lignin.
  • Patent Document 1 discloses a lignin derivative that undergoes a treatment step in which biomass is stirred in the presence of a solvent under high temperature and high pressure.
  • biomass is recovered in the presence of a mixed solvent containing water and an aprotic polar solvent, and these are decomposed under high temperature and high pressure to recover a cellulose derivative, a lignin derivative, and a hemicellulose derivative.
  • Patent Document 3 includes a 1,1-diphenylpropane unit grafted with a phenol derivative at the ⁇ -position of a phenylpropane unit of lignin, and has an ester site in which one or two or more hydroxyl groups are acylated. Based polymers are disclosed.
  • Patent Document 3 discloses that the material is homogenized by acylating and modifying the hydroxyl group of lignin. In this method, secondary derivatization is required, and although the heat resistance is increased, the phenolic hydroxyl group is crushed. Therefore, the reactive sites are also lost, which is attractive as a material.
  • the present invention is to provide a method for producing a hemicellulose-derived saccharide, a cellulose-containing solid material in which excessive decomposition is suppressed, and a biomass-derived product that is lignin with less impurities from plant-based biomass.
  • the present invention provides the following [1] to [17].
  • the manufacturing method of the plant biomass origin product containing the process process (2) which mixes and heat-processes.
  • Condition A The concentration of the solid content obtained from the treatment step (1) with respect to the solvent is 1% by mass or more and 50% by mass or less.
  • Condition B 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.
  • a resin composition comprising the lignin obtained by the method according to any one of [2] to [12] above.
  • the present invention it is possible to provide a method for producing a hemicellulose-derived saccharide, a cellulose-containing solid material in which excessive decomposition is suppressed, and a biomass-derived product that is lignin with less impurities from plant-based biomass.
  • the first treatment step (1) is performed while suppressing the excessive decomposition 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 biomass-derived product of the present invention includes a treatment step (1) for separating hemicellulose from a plant biomass, a solid content obtained from the treatment step (1), and an organic solvent alone or an organic solvent. It has the process containing the process process (2) which mixes the solvent selected from the mixed solvent with water, and heat-processes.
  • hemicellulose is separated from plant biomass. Details will be described below.
  • Plant biomass examples include woody biomass and herbaceous biomass.
  • woody biomass examples include conifers such as cedar, cypress, hiba, cherry, eucalyptus, beech and bamboo, and broad-leaved trees.
  • Herbaceous biomass includes palm palm trunks and empty bunches, palm palm fruit fibers and seeds, bagasse (sugar cane and high biomass sugar cane squeezed rice cake), cane top (sugar cane top and leaf), energy cane, rice straw, straw, Corn cob, foliage, residue (corn stover, corn cob, corn hull), sorghum (including sweet sorghum) residue, Jatropha seed shell and shell, cashew shell, switchgrass, Elianthus, high biomass yield crop, energy crop, Energy cane etc. are mentioned.
  • the plant biomass can be pulverized.
  • any shape of a block, a chip, or powder may be used.
  • it may be either dry or hydrated.
  • the treatment step (1) for separating hemicellulose a known plant biomass treatment method can be used, but hydrothermal treatment is preferably performed here.
  • 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.
  • hydrothermal treatment using an acidic aqueous solution it is preferable to use an acidic aqueous solution containing at least one selected from inorganic acids and organic acids.
  • At least one acid aqueous solution selected from the group consisting of inorganic acids selected from dilute sulfuric acid, phosphoric acid, dilute hydrochloric acid and dilute nitric acid, and organic acids selected from formic acid, acetic acid, oxalic acid and malic acid, It can be used as an acidic aqueous solution.
  • the charged concentration of the plant-based biomass as the raw material with respect to the aqueous solvent is usually 1% by mass to 95% by mass, preferably 3% by mass to 80% by mass, more preferably 5% by mass. % To 50% by mass, most preferably 5% to 20% by mass. If the feed concentration of the raw material plant biomass is 1% by mass or more, the amount of energy used for heating the aqueous solvent can be suppressed, and the energy efficiency of the treatment step (1) can be kept good. When the feed concentration of the raw material plant-based biomass is 95% by mass or less, the separation efficiency can be kept good.
  • the treatment temperature in the treatment step (1) is preferably 50 ° C. or higher and 200 ° C. or lower, more preferably 100 ° C. or higher and 190 ° C. or lower, and further preferably 150 ° C. or higher and 180 ° C. or lower. If it is 50 degreeC or more, hemicellulose can be solubilized. If it is 200 degrees C or less, the excessive decomposition of hemicellulose can be suppressed.
  • the treatment time in the treatment step (1) is preferably from 1 minute to 5 hours, more preferably from 3 minutes to 3 hours, further preferably from 5 minutes to 2 hours, particularly preferably from 10 minutes to 1 hour. Below time. If the treatment time is 1 minute or longer, hemicellulose can be solubilized.
  • the pressure of the reaction system in the treatment step (1) is desirably 0.1 MPa to 30 MPa. More preferable conditions are appropriately set because they are affected by temperature. Further, the treatment process can be performed in an ambient atmosphere. Although there is no restriction
  • Hemicellulose is separated by solid-liquid separation of the reaction product after hydrothermal treatment.
  • the solid content containing a cellulose and lignin is obtained.
  • the process of washing the obtained solid content with water may be included.
  • 100 parts by mass or more and 10000 parts by mass or less of water are added to 100 parts by mass of the obtained solids and stirred, and then the solids and the liquid phase are separated by filtration.
  • the amount of water used for the water washing is more preferably 1000 parts by mass or more and 5000 parts by mass or less, and still more preferably 1000 parts by mass or more and 2000 parts by mass or less.
  • a method for performing solid-liquid separation is not particularly limited, and examples thereof include filtration, filter press, centrifugal separation, and dehydrator.
  • This treatment step is a step in which 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 are mixed and subjected to heat treatment. In this step, lignin and cellulose are separated.
  • a solvent an organic solvent alone or a solvent selected from a mixed solvent of an organic solvent and water is used.
  • Organic solvent is not particularly limited, and may be a saturated or unsaturated linear alcohol or branched alcohol.
  • 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.
  • 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 further preferably 15% by weight to 70% by weight. If the concentration of the organic solvent in the mixed solvent is within the above-described range, lignin can be sufficiently separated in the treatment step (2).
  • the pH of the system from after the separation of hemicellulose in the processing step (1) until before mixing the solid content and the solvent obtained from the processing step (1) in the processing step (2), or in the processing step (2) It is preferable to perform the heat treatment in the treatment step (2) after adjusting the pH of the system when the solid content obtained from the treatment step (1) and the solvent are mixed with a basic substance.
  • hydrothermal treatment is performed using an acidic aqueous solution in the treatment step (1)
  • the pH before mixing the solid content obtained from the treatment step (1) and the solvent in the treatment step (2) 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).
  • 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, and most preferably 4 Adjust to 6 or less.
  • the treatment conditions in the treatment step (2) are preferably performed under conditions that satisfy all of the following conditions A to C.
  • Condition A The concentration of the solid content obtained from the treatment step (1) with respect to the solvent is preferably 1% by mass or more and 50% by mass or less.
  • concentration of the said solid content is with respect to the total amount of a solvent. If the solid concentration obtained from the treatment step (1) is 1% by mass or more, the energy efficiency of the lignin removal process even if the amount of energy used for heating the solvent or removing the organic solvent is taken into account. Can be kept good.
  • the concentration of the solid content obtained from the treatment step (1) with respect to the solvent is more preferably 3% by mass or more and 20% by mass or less, and further preferably 5% by mass or more and 15% by mass or less.
  • the treatment temperature in the treatment step (2) is preferably 100 ° C. or higher and 300 ° C. or lower. If the treatment temperature is 100 ° C. or higher, the lignin can be sufficiently separated, and if it is 300 ° C. or lower, 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 higher and 250 ° C. or lower, and further preferably 170 ° C. or higher and 230 ° C. or lower.
  • the treatment time in the treatment step (2) is preferably 0.1 hour or more and 10 hours or less. If the treatment time is 0.1 hour or more, the separation of lignin can be sufficiently advanced, and if it is 10 hours or less, the decomposition of cellulose and the generation of impurities such as coke due to repolymerization of lignin are suppressed. Can do.
  • the treatment time is more preferably 0.2 hours or more and 8 hours or less, further preferably 1 hour or more and 6 hours or less, and particularly preferably 1 hour or more and 3 hours or less.
  • the pressure of the reaction system is 0.5 MPa to 30 MPa.
  • the preferable range of the pressure in the reaction system is appropriately set because it is influenced by the amount of water and organic solvent and the temperature.
  • the processing step (2) can be performed in an ambient atmosphere.
  • the treatment step (2) is particularly preferably performed in an atmosphere in which nitrogen purge is performed to reduce oxygen in order to suppress polymerization due to oxidation reaction.
  • nitrogen purge is performed to reduce oxygen in order to suppress polymerization due to oxidation reaction.
  • a general batch reactor, a semi-batch reactor, or the like can be used.
  • the system which processes, extruding the slurry which consists of a plant-derived biomass-derived solid substance and 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 in the treatment step (2) can be subjected to solid-liquid separation to obtain a cellulose-containing solid as a solid and a lignin-containing solution as a liquid.
  • the solid-liquid separation after the processing step (2) may include a step of washing the solid content obtained by the solid-liquid separation with water. This water washing process can be performed by adding 100 mass parts or more and 10000 mass parts or less of water with respect to 100 mass parts of solid content obtained after solid-liquid separation, and stirring. After stirring, the solid content and the liquid phase are separated by filtration.
  • the amount of water used in the washing step is preferably 100 parts by mass or more and 10,000 parts by mass or less, more preferably 1000 parts by mass or more and 5000 parts by mass or less, and further preferably 1000 parts by mass or more and 2000 parts by mass or less. If the amount of water used for water washing is 100 parts by mass or more, a sufficient cleaning effect can be obtained, and if it is 10000 parts by mass or less, it can be carried out without any problems in terms of equipment. By this water washing step, it is possible to further remove the organic solvent and to remove water-soluble components attached to the cellulose-containing solid.
  • a cellulose-containing solid can be obtained after solid-liquid separation after the heat treatment in the treatment step (2), or further through the water washing step.
  • the cellulose-containing solid contained in the plant biomass can be recovered as a solid obtained as a residue in the aqueous phase.
  • the liquid phase obtained after the heat treatment in the treatment step (2) or after further water washing treatment contains lignin.
  • lignin for example, when a mixed solvent of water and an organic solvent is used and two phases are formed after the treatment, the organic phase obtained after separating the aqueous phase can be vaporized to remove the solvent to obtain solid lignin. it can.
  • an organic solvent is used alone or when a mixed solvent with water is used, if the organic solvent is one phase after the heat treatment in the treatment step (2), the solvent is removed by vaporizing the organic solvent or the like. Then, solid lignin can be obtained by filtering the solid residue remaining in the water or by solid matter precipitated in water.
  • hemicellulose, cellulose-containing solid and lignin can be produced as a plant-derived biomass-derived product.
  • hemicellulose, cellulose-containing solid and lignin can be produced as a plant-derived biomass-derived product.
  • Each product is described in detail below.
  • the lignin obtained by the production method of the present invention has the following characteristics.
  • the purity of lignin is preferably 92% or more, and more preferably 94% or more.
  • the number average molecular weight is preferably 700 or more, and more preferably 750 or more.
  • the 5% thermogravimetric decrease starting temperature is preferably 215 ° C. or higher, more preferably 220 ° C. or higher.
  • each measuring method of the purity of the said lignin, a number average molecular weight, and a 5% thermogravimetric decrease start temperature is mentioned later.
  • sugar with respect to the hemicellulose in plant biomass becomes 50 mass% or more.
  • the recovery rate of saccharides derived from hemicellulose 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 a cellulose degradation product obtained by decomposing cellulose and cellulose on the basis of the total amount of the cellulose-containing solid as a solid content.
  • lignin is contained in an amount of 5% by mass to 30% by mass
  • hemicellulose and a hemicellulose decomposition product obtained by decomposing hemicellulose are contained in an amount of 0% by mass to 5% by mass.
  • the cellulose recovery rate in the cellulose containing solid with respect to the cellulose in plant-type biomass will be 70 mass% or more.
  • hemicellulose and the hemicellulose degradation product obtained by decomposing hemicellulose exceed 5% by mass, separation and removal of lignin bound to hemicellulose will be insufficient, and the saccharification rate when obtaining glucose by enzymatic saccharification will decrease. Moreover, when a cellulose recovery rate is less than 70 mass%, the glucose recovery rate with respect to the cellulose in plant-type biomass falls.
  • the cellulose contained in the cellulose-containing solid obtained by the production method of the present invention has a low lignin content, it is suitably used for saccharification treatment with acids and enzymes.
  • the cellulose containing solid obtained by the manufacturing method of this invention is in the state which is easy to be defibrated compared with the cellulose containing solid obtained by other methods. For this reason, it has the advantage that application development is easy. Further, 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.
  • resin and fiber reinforcing materials such as cellulose nanofibers, rubber and tire reinforcing materials as a substitute for chemical fibers, food additives such as carboxymethylcellulose and oligosaccharides, lactic acid Chemical products such as succinic acid can be obtained.
  • ⁇ Uses of hemicellulose and lignin> From the hemicellulose obtained by the production method of the present invention, food additives such as oligosaccharides and xylitol, and chemicals such as furfural can be obtained, which is useful.
  • the lignin obtained by the production method of the present invention can be specifically used as a water repellent material for fuel and cement. Further, it can be applied to phenol resin, epoxy resin, polyurethane resin base resin raw material, epoxy resin additive (curing agent), polyurethane resin modifier (flame retardant), thermoplastic resin additive, and the like. This is due to the characteristic that lignin has a phenolic structural unit.
  • a conventionally well-known method can be used about the use as a base resin raw material of lignin.
  • a resin composition in which a known crosslinking agent typified by lignin and hexamethylenetetramine is blended can be mentioned. You may mix
  • Such a resin composition is used for heat insulating materials for homes, electronic parts, resin for flack sand, resin for coated sand, resin for impregnation, resin for laminating, resin for FRP molding, automobile parts, reinforcing material for automobile tires, etc. Can be used.
  • an epoxy resin is also possible by introducing an epoxy group into lignin and using lignin as an epoxy resin curing agent.
  • introducing a vinyl group, a maleimide group, an isocyanate group or the like into lignin using a known method it can be applied to a wider range of industrial resins.
  • resin composition a resin composition containing lignin obtained by the above production method is provided. 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. Components other than lignin will be described below.
  • thermoplastic resin that can be blended in the resin composition according to the present embodiment is an amorphous thermoplastic resin having a glass transition temperature of 200 ° C. or lower, or a crystalline thermoplastic resin having a melting point of 200 ° C. or lower. Is preferred.
  • thermoplastic resin examples include 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 resins (PET, PBT, etc.) represented by polyesters of combinations of terephthalic acid and ethylene glycol, terephthalic acid and 1,4-butanediol, polylactic acid and / or copolymers containing polylactic acid, acrylonitrile-butadiene -Styrene resin (ABS resin), polyphenylene oxide resin (PPO), polyketone resin, polysulfone resin, polyphenylene sulfide resin (PPS), fluororesin, silicon resin, polyimide resin, polybenzimi Tetrazole resins, polyamide elastomers, and copolymers thereof with other monomers.
  • ABS resin acrylon
  • the content of the thermoplastic resin in the resin composition according to the present invention is 30% by mass or more and 99.9% by mass or less with respect to the total amount of the resin composition from the viewpoint of obtaining remarkable fluidity and strength. It is preferably 40% by mass to 99.9% by mass, more preferably 45% by mass to 99.9% by mass, and particularly preferably 50% by mass to 99.9% by mass.
  • the resin composition according to the present embodiment may contain a resin, an additive and / or a filler compatible with the thermoplastic resin composition in addition to the above-described cellulose-containing solid and thermoplastic resin. Good.
  • ⁇ Thermosetting resin> You may mix
  • the compound having a functional group capable of reacting with lignin include a compound that causes an electrophilic substitution reaction with a phenol compound, a compound having an epoxy group, a compound 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 (curing agent) of epoxy resin, and the like.
  • Examples of the compound that causes an electrophilic substitution reaction with a phenol compound include formaldehyde, a formaldehyde donating curing agent compound, or a formaldehyde equivalent compound. Commercially, hexamethylenetetramine, hexaformaldehyde, and paraformaldehyde can be used.
  • the resin composition according to the present embodiment may further contain a phenol resin in addition to lignin and hexamethylenetetramine.
  • the phenol resin is a lignin diluent, extender, etc., as long as the physical properties such as processability, strength, and heat resistance of the resin composition do not deteriorate. Can be used as
  • the compound having an epoxy group belongs to a category called a so-called epoxy resin.
  • examples include 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, resorcin, saligenin, trihydroxydiphenyldimethylmethane, tetraphenylolethane, halogen-substituted and alkyl-substituted thereof, butanediol, ethylene glycol, A compound containing two or more hydroxyl groups in the molecule such as erythritol, novolak, glycerin, polyoxyalkylene and the like, and a glycidyl ether epoxy resin synthesized from epichlorohydrin, etc .; a compound containing two or more
  • thermosetting resin composition may further contain a phenol resin in addition to the compound containing lignin and an epoxy group.
  • a curing accelerator can be appropriately added according to the purpose of promoting the curing reaction.
  • Specific examples include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza-bicyclo (5,4,4).
  • Tertiary amines such as undecene-7, phosphines such as triphenylphosphine, quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, tri Examples thereof include quaternary phosphonium salts such as phenylbenzylphosphonium salt, triphenylethylphosphonium salt and tetrabutylphosphonium salt, and metal compounds such as tin octylate. Examples of the counter ion of the quaternary phosphonium salt include halogen, organic acid ion, hydroxide ion and the like, and organic acid ion and hydroxide ion are particularly preferable.
  • the compound having an isocyanate group is obtained by reacting polyisocyanate or polyisocyanate with a polyol.
  • Polyisocyanates include aromatic polyisocyanates such as tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), polymeric MDI (MDI-CR), carbodiimide-modified MDI (liquid MDI), 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.
  • IPDI isophorone diisocyanate
  • HDI hexamethylene diisocyanate
  • MDI 4,4′-methylene-bis (cyclohexyl isocyanate)
  • XDI xylylene diisocyanate
  • blocked isocyanates be able to.
  • tolylene diisocyanate (TDI) and 4,4′-diphenylmethane diisocyanate (MDI) are preferably used.
  • the thermosetting resin composition may further contain a phenol resin in addition to lignin and an isocyanate compound.
  • a curing accelerator can be appropriately added to the thermosetting resin composition according to the purpose of accelerating the curing reaction.
  • the curing accelerator include zirconium and aluminum organometallic catalysts, dibutyltin laurate, DBU phenol salts, octylates, amines, imidazoles, and the like.
  • zirconium and aluminum organometallic catalysts include zirconium and aluminum organometallic catalysts, dibutyltin laurate, DBU phenol salts, octylates, amines, imidazoles, and the like.
  • aluminum sec-butyrate, ethyl acetoacetate aluminum diisopropylate, zirconium tributoxyacetylacetonate, zirconium tetraacetylacetonate and the like are particularly preferable.
  • the resin composition according to this embodiment may contain a resin such as a phenol resin, a urea resin, a melamine resin, a silicone resin, an unsaturated polyester resin, an alkyd resin, or a polyurethane resin.
  • a resin such as a phenol resin, a urea resin, a melamine resin, a silicone resin, an unsaturated polyester resin, an alkyd resin, or a polyurethane resin.
  • a resin such as a phenol resin, a urea resin, a melamine resin, a silicone resin, an unsaturated polyester resin, an alkyd resin, or a polyurethane resin.
  • a resin such as a phenol resin, a urea resin, a melamine resin, a silicone resin, an unsaturated polyester resin, an alkyd resin, or a polyurethane resin.
  • phenol resins are preferred among the above resins.
  • the resin composition according to the present embodiment may include a filler.
  • the filler may be an inorganic filler or an organic filler.
  • the inorganic filler for example, silica powder such as spherical or crushed fused silica, crystalline silica, alumina powder, glass powder, glass fiber, glass flake, mica, talc, calcium carbonate, alumina, hydrated alumina, nitriding Examples thereof include boron, aluminum nitride, silicon nitride, silicon carbide, titanium nitride, zinc oxide, tungsten carbide, and magnesium oxide.
  • organic filler examples include carbon fiber, aramid fiber, paper powder, cellulose fiber, cellulose powder, rice husk powder, fruit shell / nut powder, chitin powder, and starch.
  • the inorganic filler and the organic filler may be contained singly or in combination, and the content is determined according to the purpose.
  • thermoplastic resins include resins in which polar groups are introduced by adding maleic anhydride, epoxy, or the like to thermoplastic resins, such as maleic anhydride-modified polyethylene resins, maleic anhydride-modified polypropylene resins, and various commercially available phases. A solubilizer may be used in combination.
  • the surfactant examples include linear fatty acids such as stearic acid, palmitic acid, and oleic acid, and branched / cyclic fatty acids with rosins, but are not particularly limited thereto.
  • additives that can be blended include a flexibilizer, a heat stabilizer, an ultraviolet absorber, a flame retardant, an antistatic agent, an antifoaming agent, a thixotropic agent, a release agent, and an antioxidant. Agents, plasticizers, stress reducing agents, coupling agents, dyes, light scattering agents, small amounts of thermoplastic resins, etc.
  • the molded article which concerns on embodiment of this invention is obtained from the resin composition containing the lignin obtained by the manufacturing method mentioned above.
  • a molded product a cured resin composition in which lignin and a crosslinking agent are blended, and various fillers and industrially obtained general phenol resins are blended as necessary, Examples thereof include those cured after being molded into a predetermined shape, and those molded after being cured.
  • the method for molding into a predetermined shape is not particularly limited as long as the resin composition can be molded.
  • examples of the method for molding into a predetermined shape include a compression molding method, an injection molding method, a transfer molding method, an intermediate molding method, and an FRP molding method.
  • examples of the method for molding into a predetermined shape include an extrusion molding method and an injection molding method.
  • a molded product what is obtained by curing a resin composition in which lignin and a crosslinking agent are blended, various fillers and general phenol resins obtained industrially, if necessary, Examples thereof include those cured after being molded into a predetermined shape, those molded after being cured, and those obtained by molding a resin composition obtained by mixing lignin with a thermoplastic resin. Molded articles of such resin compositions include: heat insulating materials for housing, electronic parts, resin for flack sand, resin for coated sand, resin for impregnation, resin for lamination, resin for FRP molding, automobile parts, reinforcement of automobile tires It can be used for materials, OA equipment, machines, information communication equipment, industrial materials and the like.
  • Glucose can be produced using the cellulose-containing solid obtained by the method for producing a cellulose-containing solid according to the embodiment of the present invention.
  • the conditions for the enzymatic saccharification treatment are as follows.
  • Cellulose contained in the cellulose-containing solid and the enzyme that acts on the cellulose degradation product obtained by decomposing cellulose may be 0.1% by mass or more and 200% by mass or less based on the total amount of the cellulose-containing solid. it can.
  • the enzyme activity used for an enzyme saccharification process can be 100 CUN / g or more and 10000 CUN / g or less.
  • the processing temperature in enzyme saccharification processing is 30 degreeC or more and 70 degrees C or less, an enzyme will activate and it can improve a saccharification rate.
  • the treatment time in the enzyme saccharification treatment is 12 hours or more and 168 hours or less, the enzyme is activated and the saccharification rate can be improved.
  • Plant-based biomass for example, plant-based biomass such as bagasse
  • water is added to obtain a raw material slurry having a solid concentration of about 15% by mass.
  • phosphoric acid is added and mixed so that the pH in the raw slurry becomes 2.0.
  • the raw slurry is supplied to a reactor (pressure vessel) and heated to a supercritical state or a subcritical state.
  • hydrothermal treatment is preferably performed at a temperature of 170 ° C.
  • Processing step (2) Solid content obtained from the treatment step (1), a mixed solvent of water and 1-butanol prepared at a 1-butanol concentration of 34% by mass, sodium hydroxide so that the pH is 3, SUS (stainless steel with an internal volume of 0.92 L) ) Placed in batch-type apparatus.
  • the total amount of solvent was 315 g.
  • the treatment time was the elapsed time after reaching 200 ° C. The temperature was measured with a thermocouple.
  • the SUS batch-type apparatus was cooled, and after the temperature dropped to near room temperature, the entire contents were taken out.
  • the solid content and the liquid phase were separated by filtration.
  • 200 g of water was added to the solid content, and after stirring for 30 minutes, the solid content and the liquid phase were separated by filtration.
  • the said operation was repeated 3 times and the cellulose containing solid substance was obtained.
  • the liquid phase was liquid / liquid separated into a water phase and a 1-butanol phase by a separatory funnel.
  • the solvent of the 1-butanol phase was removed with an evaporator (70 ° C., water bath) and then vacuum-dried at 125 ° C. to obtain lignin.
  • ⁇ Production Example 4> It carried out similarly to manufacture example 3 except having used ethanol as an organic solvent which comprises the mixed solvent of a process process (2). Since the liquid phase after solid-liquid separation was a single phase, the organic solvent was removed with an evaporator, and the solid content precipitated in water due to the decrease in solubility was separated by solid-liquid separation by filtration. And vacuum drying to obtain lignin.
  • a raw material slurry having a solid concentration of about 10% by mass.
  • the raw slurry is supplied to a reactor (pressure vessel) and heated to a supercritical state or a subcritical state.
  • hydrothermal treatment is preferably performed at a temperature of 170 ° C. Thereafter, everything was carried out in the same manner as in Production Example 1 except that sodium hydroxide was not added to adjust the pH in (treatment step (2)).
  • ⁇ Production Example 13> All in the same manner as in Production Example 1 except that sodium hydroxide was not added to adjust the pH in the treatment step (2).
  • ⁇ Comparative production example> The same procedure as in Production Example 13 was performed except that the plant-based biomass as a raw material was treated with a mixed solvent of water and 1-butanol without going through the treatment step (1) which is a hydrothermal treatment step.
  • ⁇ Analysis of cellulose content in plant biomass and cellulose-containing solids The amount of cellulose in the plant biomass and cellulose-containing solid was calculated according to the constituent sugar analysis after the pretreatment shown below.
  • Preprocessing As a pretreatment, a raw material to be a sample was pulverized using a Willet mill and dried at 105 ° C.
  • Component sugar analysis An appropriate amount of a plant-based biomass or cellulose-containing solid sample was weighed, 72% sulfuric acid was added, and the mixture was allowed to stand at 30 ° C. with stirring as needed for 1 hour. The reaction solution was completely transferred to a pressure-resistant bottle while being mixed with pure water, treated in an autoclave at 120 ° C.
  • Cellulose recovery rate (% by weight) (cellulose-containing solids recovered amount (g) ⁇ cellulose ratio in cellulose-containing solids (% by weight) / 100) / cellulose amount in plant biomass (g) ⁇ 100 ⁇ Hydroxymethylfurfural production rate>
  • concentration of hydroxymethylfurfural was calculated using a high performance liquid chromatograph (HPLC 1200 series, manufactured by Agilent).
  • Hydroxymethylfurfural production rate (mass%) hydroxymethylfurfural concentration (mg / L) ⁇ 10 ⁇ 6 ⁇ solution volume (mL) / plant biomass (g) ⁇ 100
  • the enzyme has an enzyme activity of 1600 CUN / g or more.
  • Glucose recovery rate (glucose amount in cellulose-containing solid enzyme saccharified solution (g) ⁇ cellulose-containing solid material recovery rate (mass%) / 100) / glucose amount in plant biomass (g) ⁇ 100
  • Example 1 to 12 using the cellulose-containing solid produced by the production example of the present invention the glucose recovery rate based on the amount of glucose in plant biomass obtained by enzymatic saccharification from the cellulose-containing solid shows a high value. It was.
  • Example 13 using the cellulose-containing solid obtained in Production Example 13 in which the pH was not adjusted in the treatment step (2) the total amount of cellulose-containing solid that can be recovered is lower than in other production examples. Therefore, when the amount of the enzyme is 0.1 mL, the absolute amount of cellulose that is decomposed to sugar is low, so that the glucose recovery rate is lower than others.
  • saccharide can be efficiently recovered on the basis of plant biomass because the hemicellulose-derived saccharides (xylose and xylooligosaccharide) can be suppressed and recovered.
  • thermosetting resin composition containing hexamethylenetetramine A thermosetting resin composition was prepared using the lignin obtained in Production Example 9 and Comparative Production Example. Moreover, the hardened
  • ⁇ Formulation of thermosetting resin composition and molding method of cured product> Each component was put in a mortar at the blending ratio shown in Table 2, pulverized at room temperature, mixed, mixed at 100 ° C. for 5 minutes using an open roll kneader, and then cooled to room temperature. The mixture was pulverized in a mortar, sandwiched between aluminum plates coated with a release agent, and molded at 150 ° C. for 60 minutes under reduced pressure using a vacuum press.
  • Example 13 using lignin obtained by the production method of the present invention, a molded product having high heat resistance and excellent physical properties was obtained.
  • the present invention it is possible to provide a method for producing a hemicellulose-derived saccharide, a cellulose-containing solid material in which excessive decomposition is suppressed, and a biomass-derived product that is lignin with less impurities from plant-based biomass.
  • the first treatment step (1) is performed while suppressing the excessive decomposition of hemicellulose, a high sugar yield can be obtained from the hemicellulose-derived saccharide and the cellulose-containing solid.

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Abstract

L'invention concerne un procédé de production d'un produit dérivé d'une biomasse végétale, qui comprend : une étape de traitement (1) consistant à séparer une hémicellulose d'une biomasse végétale; et une étape de traitement (2) consistant à mélanger le constituant solide obtenu à l'étape de traitement (1) avec un solvant choisi parmi un solvant organique seul ou un solvant mixte composé d'un solvant organique et d'eau, puis à soumettre le mélange à un traitement thermique.
PCT/JP2017/032386 2016-09-09 2017-09-07 Procédé de production d'un produit dérivé d'une biomasse végale, comprenant un processus en deux étapes WO2017222084A1 (fr)

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