WO2012133126A1 - Agent épaississant et procédé de production de cellulose hydrolysable l'utilisant - Google Patents

Agent épaississant et procédé de production de cellulose hydrolysable l'utilisant Download PDF

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Publication number
WO2012133126A1
WO2012133126A1 PCT/JP2012/057395 JP2012057395W WO2012133126A1 WO 2012133126 A1 WO2012133126 A1 WO 2012133126A1 JP 2012057395 W JP2012057395 W JP 2012057395W WO 2012133126 A1 WO2012133126 A1 WO 2012133126A1
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viscosity
imparting agent
cellulose
pva
mol
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PCT/JP2012/057395
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English (en)
Japanese (ja)
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誠二 秦
仲前　昌人
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株式会社クラレ
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Priority to JP2013507470A priority Critical patent/JP5816680B2/ja
Publication of WO2012133126A1 publication Critical patent/WO2012133126A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L5/00—Preparation or treatment of foods or foodstuffs, in general; Food or foodstuffs obtained thereby; Materials therefor
    • 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
    • C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis

Definitions

  • the present invention relates to a viscosity imparting agent used for producing hydrolyzable cellulose using cellulose-based biomass as a raw material, and a method for producing hydrolyzable cellulose using the same.
  • Biomass refers to bio-based renewable resources and can be defined as “renewable, bio-derived organic resources excluding fossil resources”. Among these biomass, effective utilization of unused plant biomass such as wood from thinned wood, rice straw, wheat straw, rice husks, stalks of starch-based crops such as corn and sugarcane, and oil palm empty bunch (EFB) is required. .
  • unused plant biomass such as wood from thinned wood, rice straw, wheat straw, rice husks, stalks of starch-based crops such as corn and sugarcane, and oil palm empty bunch (EFB) is required. .
  • cellulose has the following multiple structure in the cell wall.
  • the cellulose that forms the cell wall has a quasicrystalline structure that adheres in a straight line, most often referred to as microfibrils.
  • the celluloses (microfibrils) having this quasicrystalline structure are bonded to each other via non-cellulose components such as hemicellulose and lignin. These cellulose components (microfibrils) and non-cellulose components are arranged as a larger structure generally referred to as fibrils. These fibrils are usually laminated in a sheet form to constitute a cell wall.
  • the polymer chains of cellulose are strongly bound by hydrogen bonding. This hydrogen bond causes the plant to have a strong cell wall.
  • the apparatus for causing the cellulose-based biomass fine particles to exist as a floating body becomes complicated, and a great amount of energy is consumed when this technique is used, so that the productivity is high. It can not be said.
  • the technique (2) although use of a water-soluble polymer for imparting viscosity to an aqueous solution can improve a certain degree of easy hydrolysis of cellulosic biomass, Further improvement is needed to improve degradability.
  • the present invention has been made on the basis of such circumstances, and by providing a suitable viscosity to an aqueous solution containing cellulosic biomass in the production of hydrolyzable cellulose using cellulosic biomass as a raw material, etc.
  • the viscosity of the cellulosic biomass can be easily divided at the molecular level, and as a result, the viscosity imparting agent capable of efficiently producing hydrolyzable cellulose, and hydrolyzable cellulose using this viscosity imparting agent
  • An object is to provide a manufacturing method.
  • the viscosity-imparting agent of the present invention made to solve the above problems is A viscosity-imparting agent used for the production of hydrolyzable cellulose from cellulosic biomass, It contains a polyvinyl alcohol polymer containing a monomer unit having an alkyl group having 29 or less carbon atoms and 8 or more carbon atoms.
  • the viscosity-imparting agent of the present invention can increase the viscosity of this solution when it is made into an aqueous solution, and the cellulose-based biomass solution when this aqueous solution is mixed with powdered or particulate cellulose-based biomass. Uniform dispersibility (miscibility) can be improved.
  • an appropriate shearing force can be applied to the cellulosic biomass by mixing the viscosity-imparting agent with the cellulosic biomass particles. That is, in the cellulosic biomass fragmentation operation using the viscosity-imparting agent, cellulose polymer chains are easily separated from each other by a viscous aqueous solution, and water and polyvinyl alcohol are contained inside the polymer chain having a quasicrystalline structure. As the polymer enters efficiently, hydrogen bonds between the polymer chains can be weakened. Furthermore, re-quasi-crystallization of the polymer chain can be prevented by the polyvinyl alcohol polymer entering between the polymer chains thus torn.
  • the cellulose polymer chain in cellulosic biomass can be effectively divided at the molecular level, and cellulose that is easily hydrolyzed (saccharified) by an enzyme or the like can be obtained.
  • the number of carbon atoms of the monomer unit is 11 or more, and the ratio of carbon number to oxygen number (carbon number / oxygen number) in the side chain of the monomer unit is larger than 2.5 / 1. preferable.
  • the average degree of polymerization of the polyvinyl alcohol polymer is from 100 to 5,000, the saponification degree is from 60 to 99.99 mol%, and the monomer unit content is from 0.05 to 10 mol%. The following is preferable.
  • the thickening action and the penetration action between the cellulose polymer chains can be more effectively exhibited.
  • the monomer unit is represented by the following general formula (I).
  • R 1 represents a linear or branched alkyl group having 8 to 29 carbon atoms.
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the thickening action and the penetration action between the cellulose polymer chains can be more effectively exhibited.
  • the average degree of polymerization of the polyvinyl alcohol polymer (A) is 200 or more and 5,000 or less, the saponification degree is 60 mol% or more and 99.99 mol% or less, and the content of the monomer unit is 0.05 mol% or more. It may be 5 mol% or less.
  • the viscosity-imparting agent as an aqueous solution and the cellulosic biomass are more suitable for viscosity.
  • the polyvinyl alcohol polymer (A) can be easily and uniformly mixed and can easily enter between the torn cellulose polymer chains. Therefore, cellulose having higher hydrolyzability can be obtained by using such a polyvinyl alcohol polymer (A).
  • the polyvinyl alcohol polymer (A) is obtained by saponifying a copolymer of an unsaturated monomer represented by the following general formula (II) and a vinyl ester monomer. Good.
  • the monomer unit has a polyoxyalkylene group represented by the following general formula (III), It is also preferable that the content of the monomer unit is 0.1 mol% or more and 10 mol% or less.
  • each R 3 independently represents a methyl group or an ethyl group.
  • R 4 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. 0 ⁇ m ⁇ 10, (5 ⁇ n ⁇ 40)
  • the polyvinyl alcohol polymer (B) having such a monomer unit at the above-described content has high viscosity when formed into an aqueous solution, and has a temperature-sensitive gelling property. Therefore, the thickening action of the thickening agent and the penetration action between the cellulose polymer chains can be more effectively exhibited.
  • the average degree of polymerization of the polyvinyl alcohol polymer (B) is preferably 100 to 4,000, and the saponification degree is preferably 70 to 99.99 mol%.
  • the viscosity-imparting agent (polyvinyl alcohol polymer (B) aqueous solution) and the cellulosic biomass are more suitably viscous.
  • the polyvinyl alcohol polymer (B) can be easily and uniformly mixed and can easily enter between the torn cellulose polymer chains. Therefore, cellulose having higher hydrolyzability can be obtained by using such a polyvinyl alcohol polymer (B).
  • the polyvinyl alcohol polymer (B) is obtained by saponifying a copolymer of an unsaturated monomer represented by the following general formula (IV) and a vinyl ester monomer. Good.
  • R 5 is a hydrogen atom or —COOM 1.
  • M 1 is a hydrogen atom, an alkali A metal atom or an ammonium group,
  • R 6 is a hydrogen atom, a methyl group or —CH 2 —COOM 2.
  • M 2 is a hydrogen atom, an alkali metal atom or an ammonium group
  • X is —O—, -CH 2 -O -, - CO - , - CO-O -, - CO-NR 7 - , or -CO-NR 7 -CH 2 - in which .R 7 is a hydrogen atom or an alkyl having 1 to 4 carbon atoms Group.
  • R 5 is a hydrogen atom
  • X is —CO—NR 7 — or —CO—NR 7 —CH 2 —
  • R 7 is a hydrogen atom or carbon number. It is preferably 1 to 4 alkyl groups.
  • the polyvinyl alcohol polymer (B) has the amide structure or the like, it is more suitable for the cellulosic biomass fragmentation work in terms of viscosity when used as an aqueous solution, affinity with cellulose, and the like.
  • the viscosity imparting agent is preferably in the form of a gel.
  • a gel-like viscosity imparting agent polyvinyl alcohol-based polymer aqueous solution
  • the mixture can be made to have a suitable viscosity from the initial stage in the dividing step, and the viscosity can be maintained to a certain degree. Therefore, efficient hydrolyzable cellulose can be produced.
  • the gel-like viscosity-imparting agent can enter and stay between the broken cellulose polymer chains due to the gel-like state, so that the re-crystallization of the cellulose polymer chains can be prevented and the breaking ability can be prevented. Will be improved.
  • the usage-amount of a gelatinizer can be reduced.
  • a method for producing hydrolyzable cellulose using cellulosic biomass as a raw material A mixing step of obtaining a mixture containing the viscosity-imparting agent and cellulosic biomass; A splitting step of splitting cellulosic biomass by applying a shearing force to the mixture.
  • a mixture having an appropriate viscosity can be obtained by mixing the viscosity-imparting agent (aqueous solution of the polyvinyl alcohol polymer) and cellulose biomass. Further, according to the production method, cellulose polymer chains are easily separated from each other by a viscous aqueous solution by applying a shearing force to the mixture, and water and polyvinyl alcohol are contained inside the polymer chain having a quasicrystalline structure. The hydrogen bond between the polymer chains can be weakened by the system polymer entering efficiently.
  • hydrolyzable cellulose it is possible to effectively break the cellulose polymer chain in the cellulosic biomass at the molecular level and obtain cellulose that is easily hydrolyzed (saccharified) by an enzyme or the like.
  • hydrolyzable cellulose is cellulose obtained by using cellulose-based biomass or the like as a raw material and dividing it, and has higher hydrolyzability than the raw material.
  • Aqueous solution refers to a solution using water as a solvent, and is a concept including a gel-like material that loses fluidity.
  • cellulose when producing hydrolyzable cellulose using cellulosic biomass as a raw material, cellulose is provided by imparting a suitable viscosity to a solution containing cellulosic biomass.
  • the molecular level of the biomass can be easily divided, and as a result, hydrolyzable cellulose can be produced efficiently.
  • a hydrolysable cellulose can be manufactured efficiently using cellulosic biomass as a raw material.
  • plant-based biomass raw materials can be efficiently used as food and energy resources, and the feasibility of biomass utilization can be enhanced.
  • the viscosity imparting agent of the present invention contains a polyvinyl alcohol polymer (hereinafter also referred to as “PVA”) containing a monomer unit having an alkyl group having 29 or less carbon atoms.
  • the number of carbons contained in the monomer unit is 8 or more. That is, the PVA is a polymer containing a vinyl alcohol unit and the monomer unit.
  • the said PVA may have another monomer unit in the range which does not impair the meaning of this invention.
  • the alkyl having 29 or less carbon atoms refers to a group represented by C n H 2n + 1 (1 ⁇ n ⁇ 29), methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, octyl group, A decyl group, dodecyl group, hexadecyl group, octadecyl group, icosyl group, hexacosyl group, octacosyl group, etc. can be mentioned.
  • the alkyl group may be linear or branched.
  • the monomer unit may have a plurality of the alkyl groups.
  • the monomer unit may have an alkylene group such as an ethylene group, an aryl group, an arylene group, or the like.
  • Examples of the monomer unit having an alkyl group having 29 or less carbon atoms and 8 or more carbon atoms include ⁇ -olefins such as dodecene, tetradecene, and hexadecene; Vinyl ethers such as hexyl vinyl ether, nonyl vinyl ether, dodecyl vinyl ether, octadecyl vinyl ether; Alkyl (meth) acrylamides such as octylacrylamide; N-alkyl (meth) acrylamide represented by the above general formula (II) and the like; An unsaturated monomer having an oxybutylene unit or an oxypropylene unit represented by the general formula (IV); The monomer unit derived from etc.
  • ⁇ -olefins such as dodecene, tetradecene, and hexadecene
  • Vinyl ethers such as hexyl vinyl ether, nonyl vinyl ether, do
  • the alkyl group having 29 or less carbon atoms is R 1
  • the alkyl group having the general formula (IV) 29 or less carbon atoms.
  • the alkyl group is R 3 .
  • the main chain such as the long chain alkyl group of the monomer represented by the general formula (II), the oxybutylene unit or the oxypropylene unit of the monomer represented by the general formula (IV) is used.
  • the number of carbon atoms of the monomer unit is 11 or more, and the ratio (carbon number / oxygen number) of carbon number (carbon atom number) and oxygen number (oxygen atom number) in the side chain of the monomer unit is It is preferably greater than 2.5 / 1. In addition, as an upper limit of this ratio, it is 100/1, for example, and 50/1 is preferable.
  • the side chain referred to here means a portion branched from a carbon atom that forms a main chain when the monomer unit is polymerized.
  • the carbon number of the monomer unit is a carbon number including not only the side chain but also the carbon number in the main chain.
  • the viscosity-imparting agent of the present invention can increase the viscosity of this solution when it is made into an aqueous solution, and the cellulose-based biomass solution when this aqueous solution is mixed with powdered or particulate cellulose-based biomass. Uniform dispersibility (miscibility) can be improved.
  • an appropriate shearing force can be applied to the cellulosic biomass by mixing the viscosity-imparting agent with the cellulosic biomass particles. That is, in the cellulosic biomass fragmentation operation using the viscosity-imparting agent, cellulose polymer chains are easily separated from each other by a viscous aqueous solution, and water and PVA are efficient inside the polymer chain having a quasicrystalline structure. The hydrogen bond between the polymer chains can be weakened. Furthermore, the re-crystallization of the torn cellulose polymer chain can be prevented by the entry of the PVA having a high interaction with cellulose between the torn cellulose structures.
  • the cellulose polymer chain in cellulosic biomass can be effectively divided at the molecular level, and cellulose that is easily hydrolyzed (saccharified) by an enzyme or the like can be obtained.
  • the lower limit of the content of the monomer unit in the PVA is preferably 0.05 mol%, more preferably 0.1 mol%, 0.15 mol%, and even more preferably 0.2 mol%.
  • the upper limit is preferably 10 mol%, more preferably 8 mol%, 5 mol%, 2 mol%, or even 1 mol%.
  • the monomer unit content (modification rate) is the ratio (mol%) of the number of moles of each monomer unit in the number of moles of all monomer units constituting the PVA.
  • the content of the monomer unit of the PVA in the present invention may be obtained from the PVA or from a vinyl ester polymer that is a precursor thereof, and both can be obtained from proton NMR.
  • a vinyl ester polymer specifically, after reprecipitation and purification of the vinyl ester polymer three or more times with n-hexane / acetone, drying is performed under reduced pressure at 50 ° C. for 2 times. Make a sample for analysis every day. The sample may be dissolved in CDCl 3 or the like and then measured by proton NMR.
  • saponifying a vinyl ester polymer and obtaining PVA the content rate of the said monomer unit normally does not change before and after saponification.
  • the lower limit of the average degree of polymerization (viscosity average degree of polymerization) of PVA is preferably 100, more preferably 500, and even more preferably 1,000.
  • the upper limit is preferably 5,000, and more preferably 4,000.
  • the lower limit of the saponification degree of the PVA is preferably 60 mol%, more preferably 70 mol%, 80 mol%, and even more preferably 96 mol%. On the other hand, as this upper limit, 99.99 mol% is preferable and 99.9 mol% is more preferable. By setting the degree of saponification to the above range, good viscosity, water solubility and the like can be exhibited.
  • the saponification degree of the PVA in the present invention is a value that can be measured according to JIS K6726.
  • PVA PVA (A) and PVA (B) having the following specific monomer units are preferable.
  • PVA (A) and PVA (B) will be described in detail.
  • the PVA (A) has the monomer unit (a) represented by the general formula (I) as the monomer unit. Since the PVA (A) includes the monomer unit (a) having an alkyl group and an amide group having a predetermined size, the intermolecular interaction with water and cellulose can be effectively enhanced. Therefore, the PVA (A) can more effectively exert the thickening action of the viscosity-imparting agent and the penetration action between the cellulose polymer chains.
  • the linear or branched alkyl group represented by R 1 has 8 or more and 29 or less carbon atoms, preferably 10 or more and 25 or less, and more preferably 12 or more and 24 or less.
  • the number of carbon atoms is 8 or more, the interaction between alkyl groups is increased, and the ability to improve viscosity is further improved.
  • this carbon number exceeds 29, the water solubility of PVA (A) falls and it becomes difficult to carry out uniform dispersion
  • R 2 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and is preferably a hydrogen atom or a methyl group from the viewpoint of ease of synthesis.
  • the content of the monomer unit (a) in the PVA (A) is preferably 0.05 mol% or more and 5 mol% or less, more preferably 0.1 mol% or more, and further more preferably 0.2 mol% or more. preferable. Further, the content is preferably 2 mol% or less, and more preferably 1 mol% or less. When the content of the monomer unit (a) is in the above range, thickening and the like can be expressed more effectively.
  • the modified vinyl ester polymer has a structure other than the above structure, the content of the monomer unit can be easily calculated by appropriately changing the peak to be calculated and the calculation formula. it can.
  • the average degree of polymerization of the PVA (A) is preferably 200 or more and 5,000 or less, more preferably 500 or more, and further preferably 1,000 or more.
  • the saponification degree of the PVA (A) is preferably 60 mol% or more and 99.99 mol% or less, more preferably 80 mol% or more and 99.9 mol% or less, and further preferably 96 mol% or more and 99.9 mol% or less. .
  • the saponification degree of the PVA (A) is preferably 60 mol% or more and 99.99 mol% or less, more preferably 80 mol% or more and 99.9 mol% or less, and further preferably 96 mol% or more and 99.9 mol% or less.
  • the method for producing the PVA (A) is not particularly limited, but the alkyl-modified vinyl obtained by copolymerizing the unsaturated monomer represented by the general formula (II) with a vinyl ester monomer.
  • a method of saponifying an ester polymer is preferred.
  • the above copolymerization is preferably performed in an alcohol solvent or without a solvent.
  • unsaturated monomer represented by the general formula (II) include N-octylacrylamide, N-decylacrylamide, N-dodecylacrylamide, N-octadecylacrylamide, N-hexacosylacrylamide, N- Examples include octyl methacrylamide, N-decyl methacrylamide, N-dodecyl methacrylamide, N-octadecyl methacrylamide, N-hexacosyl methacrylamide and the like.
  • N-octadecyl acrylamide, N-octyl methacrylamide, N-decyl methacrylamide, N-dodecyl methacrylamide, N-octadecyl methacrylamide, and N-hexacosyl methacrylamide are preferable, and N-octadecyl acrylamide, N -Dodecyl methacrylamide and N-octadecyl methacrylamide are more preferred.
  • vinyl ester monomers examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl versatate, vinyl caproate, vinyl caprylate, vinyl laurate, and vinyl palmitate. , Vinyl stearate, vinyl oleate, vinyl benzoate and the like, among which vinyl acetate is preferred.
  • the unsaturated monomer represented by the general formula (II) and the vinyl ester monomer are copolymerized, other monomers may be copolymerized within a range not impairing the gist of the present invention.
  • monomers that can be used include: ⁇ -olefins such as ethylene, propylene, n-butene and isobutylene; Vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, 2,3-diacetoxy-1-vinyloxypropane; Nitriles such as acrylonitrile and methacrylonitrile; Vinyl halides such as vinyl chloride and vinyl fluoride; Vinylidene halides such as vinylidene chloride and vinylidene fluoride; Allyl compounds such as allyl acetate
  • the amount of the other monomer used is preferably 20 mol% or less, more preferably 5 mol% or less, and still more preferably 0 mol%, based on all monomers used for copolymerization.
  • the usage-amount of another monomer unit exceeds 20 mol%, the physical property of desired PVA may become difficult to be expressed.
  • the present invention is also intended to adjust the degree of polymerization of the resulting vinyl ester polymer in the copolymerization of the unsaturated monomer represented by the general formula (II) and the vinyl ester monomer.
  • Copolymerization may be carried out in the presence of a chain transfer agent within the range not impairing the gist of the above.
  • Aldehydes such as acetaldehyde and propionaldehyde
  • Ketones such as acetone and methyl ethyl ketone
  • Mercaptans such as 2-hydroxyethanethiol
  • Halogenated hydrocarbons such as trichlorethylene and perchlorethylene
  • phosphinic acid salts such as sodium phosphinate monohydrate, among which aldehydes and ketones are preferably used.
  • the amount of the chain transfer agent to be added is determined according to the chain transfer constant of the chain transfer agent to be added and the degree of polymerization of the target vinyl ester polymer. 1 mass% or more and 10 mass% or less are preferable.
  • the temperature employed when copolymerizing the unsaturated monomer represented by the general formula (II) and the vinyl ester monomer is preferably 0 to 200 ° C, more preferably 30 to 140 ° C.
  • the copolymerization temperature is lower than 0 ° C., it is difficult to obtain a sufficient polymerization rate.
  • polymerization is higher than 200 degreeC, it is difficult to obtain PVA which has the modification
  • the heat generated by the polymerization is balanced with the heat released from the surface of the reactor.
  • Examples thereof include a method and a method of controlling by an external jacket using an appropriate heat medium, but the latter method is preferable from the viewpoint of safety.
  • the polymerization method employed for the copolymerization of the unsaturated monomer represented by the general formula (II) and the vinyl ester monomer is batch polymerization, semi-batch polymerization, continuous polymerization, or semi-continuous polymerization. Either of these may be used.
  • the polymerization method any known method such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, or an emulsion polymerization method can be employed.
  • a bulk polymerization method or a solution polymerization method in which polymerization is performed in a solvent-free or alcohol-based solvent is preferably employed, and an emulsion polymerization method is suitable for the purpose of producing a vinyl ester polymer having a high degree of polymerization. Adopted.
  • alcohol solvent methanol, ethanol, n-propanol or the like can be used, but is not limited thereto. Moreover, these solvents can be used by mixing two or more kinds.
  • azo initiators As the initiator used for copolymerization, conventionally known azo initiators, peroxide initiators, redox initiators and the like are appropriately selected according to the polymerization method.
  • the azo initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (4-methoxy-2,4- Dimethyl valeronitrile) and the like
  • peroxide initiators include perisopropyl compounds such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, diethoxyethyl peroxydicarbonate; t-butyl Perester compounds such as peroxyneodecanate, ⁇ -cumylperoxyneodecanate, and t-butylperoxydecanate; acetylcyclohexylsulfonyl peroxide; 2,4,4-trimethyl
  • the initiator can be combined with potassium persulfate, ammonium persulfate, hydrogen peroxide, or the like to form an initiator.
  • the redox initiator include a combination of the above-described peroxide and a reducing agent such as sodium hydrogen sulfite, sodium hydrogen carbonate, tartaric acid, L-ascorbic acid, Rongalite and the like.
  • an antioxidant such as tartaric acid may be added to the polymerization system in an amount of about 1 to 100 ppm based on the vinyl ester monomer in order to prevent coloring.
  • a known basic catalyst such as sodium hydroxide, potassium hydroxide or sodium methoxide or an acidic catalyst such as p-toluenesulfonic acid is used.
  • An alcoholysis reaction or a hydrolysis reaction can be applied.
  • the solvent that can be used in this reaction include alcohols such as methanol and ethanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene; These can be used alone or in combination of two or more.
  • the PVA (B) contains a monomer unit (b) having a polyoxyalkylene group (POA group) represented by the general formula (III) as the monomer unit. Since the PVA (B) contains the monomer unit (b), the PVA (B) has a high viscosity when used as an aqueous solution and has a temperature-sensitive gelling property. Therefore, the uniform dispersibility (miscibility) in the solution of the cellulosic biomass when the aqueous solution of PVA (B) is mixed with the powdered or particulate cellulosic biomass can be enhanced. In addition, according to the said PVA (B), the usage-amount of the gelatinizer in the case of manufacture of a hydrolysable cellulose can be reduced.
  • POA group polyoxyalkylene group represented by the general formula (III)
  • R 3 is an alkyl group selected from a methyl group or an ethyl group.
  • R 4 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom or a methyl group.
  • m and n each represent the number of oxyalkylene units, and satisfy the relationship of 0 ⁇ m ⁇ 10 and 5 ⁇ n ⁇ 40.
  • a unit whose number is m is a unit 1
  • a unit whose number is n is a unit 2.
  • the arrangement of the unit 1 and the unit 2 may be either random or block.
  • n satisfies the relationship of 5 ⁇ n ⁇ 40, but preferably 10 ⁇ n ⁇ 30.
  • the content of the monomer unit (b) in the PVA (B) is preferably 0.1 mol% or more and 10 mol% or less, more preferably 0.15 mol% or more and 8 mol% or less, and 0.2 mol % To 5 mol% is more preferable. By setting the content of the monomer unit (b) in the above range, thickening and the like can be expressed more effectively.
  • the average degree of polymerization of the PVA (B) is preferably 100 or more and 4,000 or less, more preferably 500 or more, and further preferably 1,000 or more.
  • the saponification degree of the PVA (B) is preferably 70 mol% or more and 99.99 mol% or less, more preferably 80 mol% or more and 99.9 mol% or less, and further preferably 96 mol% or more and 99.9 mol% or less. .
  • the saponification degree of the PVA (B) in the above range, when this PVA (B) is used as an aqueous solution and mixed with the cellulosic biomass, it can be mixed efficiently and uniformly with a suitable viscosity, As a result, the cellulose polymer chain can be efficiently divided and brought into a state where hydrolysis can be easily performed.
  • the method for producing the PVA (B) is not particularly limited, but the vinyl ester type obtained by copolymerizing the unsaturated monomer represented by the general formula (IV) and the vinyl ester type monomer is obtained.
  • a method of saponifying the polymer is preferred.
  • the above copolymerization is preferably performed in an alcohol solvent or without a solvent.
  • R 5 is a hydrogen atom or —COOM 1
  • M 1 is a hydrogen atom, an alkali metal atom, or an ammonium group.
  • alkali metal atom include a sodium atom.
  • R 5 is preferably a hydrogen atom among these.
  • R 6 is a hydrogen atom, a methyl group or —CH 2 —COOM 2
  • M 2 is a hydrogen atom, an alkali metal atom or an ammonium group.
  • the alkali metal atom include a sodium atom.
  • R 6 is preferably a hydrogen atom or a methyl group.
  • R 7 is hydrogen An atom or an alkyl group having 1 to 4 carbon atoms.
  • —CO—NR 7 — or —CO—NR 7 —CH 2 — is preferable.
  • the POA-modified PVA has the above amide structure, it is suitable for a cellulosic biomass fragmentation operation in terms of viscosity when used as an aqueous solution, affinity with cellulose, and the like.
  • R 7 a hydrogen atom, a methyl group or an ethyl group.
  • X is asymmetric, the direction thereof is not particularly limited. However, when the POA group side is “*”, the X may be —CONH— *, —CO—NH—CH 2 — * or —O—. Are preferred, and —CONH— * or —CO—NH—CH 2 — * is more preferred.
  • Examples of the unsaturated monomer include those in which R 4 and R 5 are hydrogen atoms, polyoxyalkylene mono (meth) acrylamide, polyoxyalkylene mono (meth) allyl ether, polyoxyalkylene monovinyl ether, polyoxyalkylene mono Specific examples include (meth) acrylates.
  • the terminal hydroxyl group of the unsaturated monomer exemplified when R 4 is a hydrogen atom is used as the unsaturated monomer having 1 to 8 carbon atoms.
  • the thing substituted by the alkoxy group can be mentioned.
  • Examples of the vinyl ester monomer include those described above.
  • a chain transfer agent can be used as in the case of the PVA (A). Further, the temperature, the polymerization method, the initiator and the antioxidant used in the copolymerization are the same as those in the above-described PVA (A). The saponification method of the obtained copolymer is also the same.
  • the viscosity-imparting agent may be a powder made of only the PVA, or an aqueous solution of the PVA.
  • the other component may be contained in the range which does not inhibit the effect of this invention. Examples of the other components include other water-soluble polymers and gelling agents.
  • the viscosity imparting agent is preferably in the form of a gel.
  • a gel-like viscosity imparting agent PVA aqueous solution
  • the mixture can have a suitable viscosity from the initial stage in the dividing step, and the viscosity can be maintained to a certain degree, so that the efficiency can be maintained. Good hydrolyzable cellulose can be produced.
  • the gel-like viscosity-imparting agent PVA
  • the said PVA with high viscosity in aqueous solution is used, the usage-amount of a gelatinizer can be reduced.
  • the method for producing hydrolyzable cellulose using cellulosic biomass as a raw material includes a mixing step of obtaining a mixture containing the viscosity-imparting agent (hereinafter also referred to as “PVA aqueous solution”) and cellulosic biomass, and applying a shearing force to the mixture. And a dividing step of adding and dividing the cellulosic biomass.
  • PVA aqueous solution the viscosity-imparting agent
  • a dividing step of adding and dividing the cellulosic biomass.
  • the cellulosic biomass raw material Prior to the mixing step, the cellulosic biomass raw material is cut by cutting the cellulosic biomass raw material, and the cellulosic biomass raw material is cut into an appropriately sized particle, the aqueous solution preparation for preparing the viscosity imparting agent (PVA aqueous solution), and the viscosity It is preferable to have the gelatinization process which makes an imparting agent (PVA aqueous solution) into a gel form.
  • PVA aqueous solution aqueous solution
  • it demonstrates in order along the manufacturing process of a hydrolysable cellulose.
  • the cellulosic biomass raw material cutting step in order to make the processing in the subsequent steps efficient, the cellulosic biomass raw material is cut into particles of an appropriate size.
  • the cellulose-based biomass material used here is not particularly limited, and plant-derived biomass can be preferably used. Specifically, for example, wood such as thinned wood, rice straw, straw, rice husk, bagasse, corn, Examples thereof include stalks of starch-based crops such as sugarcane, oil palm bunches (EFB), and coconut shells.
  • Such a cellulosic biomass raw material is reduced to particles by various cutting means such as shearing and beating after removing unnecessary components such as soil as much as possible.
  • a breaker described in JP-T-2004-526008, an apparatus used for producing pulp chips, and the like can be suitably used.
  • the size of the cellulosic biomass particles having undergone this cutting step is preferably 2 mm or less, more preferably 1 mm or less, particularly preferably 100 ⁇ m or less, and particularly preferably 20 ⁇ m or more and 70 ⁇ m or less.
  • the subsequent mixing step, particularly the dividing step can be efficiently performed, and cellulose having excellent hydrolyzability can be obtained in a short time.
  • the said PVA viscosity imparting agent
  • dissolved in water is melt
  • aqueous solution aqueous solution-like viscosity imparting agent.
  • concentration of this PVA aqueous solution 3 mass% or more and 30 mass% or less are preferable, and 5 mass% or more and 20 mass% or less are more preferable.
  • the concentration of the aqueous solution in the above range, during kneading, physical force is effectively transmitted to the cellulosic biomass through the aqueous solution, and as a result, the cellulose polymer chain is peeled off by this aqueous solution, Cellulosic biomass can be effectively divided at the molecular level.
  • concentration of the PVA aqueous solution is less than 3% by mass, the aqueous solution does not have an appropriate viscosity, and there is a possibility that the dividing function due to physical action is not sufficiently exhibited.
  • the concentration of the PVA aqueous solution exceeds 30% by mass, the viscosity of the aqueous solution is so high that it becomes difficult to knead, and the workability in the dividing step may be reduced.
  • concentration as the whole PVA containing the said PVA is the said density
  • other compounds other than PVA may be dissolved or dispersed in this PVA aqueous solution (the viscosity imparting agent).
  • the gelled aqueous solution can enter and stay between the split cellulose polymer chains, so that re-crystallization of the cellulose polymer chains can be prevented, The splitting ability will be improved.
  • Examples of the gelation method of the PVA aqueous solution include a method of cross-linking PVA by adding various chemical substances (gelling agents) such as borate, titanium acetate, and other metal salts. .
  • the said viscosity imparting agent (above-mentioned PVA) is excellent in the viscosity increase in aqueous solution, even if it reduces the addition amount of the said gelling agent, or it does not use a gelling agent, this aqueous solution is moderate. Can provide a good viscosity. That is, according to the said viscosity imparting agent, the usage-amount of a gelatinizer can be reduced.
  • the saturated aqueous solution of sodium tetraborate is 0 to 10 parts by mass, preferably 100 parts by mass of the 5% by mass PVA aqueous solution, It can be performed by adding 0.1 to 5 parts by mass and mixing.
  • the gelled PVA aqueous solution has a suitable viscosity in the production, and is easy and efficient because the viscosity does not easily rise (harden) even if it is mixed and kneaded with the cellulosic biomass. Kneading can be performed.
  • this gel-like PVA aqueous solution is acidic, and specifically, it is preferable that pH is 4-6.
  • the mixing amount of the cellulose-based biomass is not particularly limited, but the mixing amount of the cellulose-based biomass with respect to the entire mixture is preferably 5% by mass or more and 50% by mass or less, and more preferably 10% by mass or more and 40% by mass or less.
  • the mixing amount of the cellulosic biomass is less than 5% by mass, the viscosity of the mixture is low and there is a possibility that the function of dividing by the physical action may not be sufficiently exhibited. descend.
  • the mixing amount of the cellulosic biomass exceeds 50% by mass, the water absorption by the biomass is strong, the viscosity of the mixture is too high, and kneading becomes difficult, so that workability is lowered.
  • the viscosity of the mixture is preferably, for example, from 5.0 ⁇ 10 4 mPa ⁇ s to 1.0 ⁇ 10 6 mPa ⁇ s.
  • Cellulosic biomass is split at the molecular level (quasicrystalline structure level) by applying shearing force to the mixture obtained in the mixing step described above. That is, cellulose having a quasicrystalline structure is partially hydrated, and the PVA enters, hydrogen bonds between the cellulose molecules are weakened. In addition, due to the physical force due to the addition of shear force, intermolecular Cellulose polymers are separated from each other in a state in which the bond between the two is weakened, so that the microscopic structure of the cell wall is divided.
  • the viscosity-imparting agent of the present invention an appropriate viscosity can be imparted to the mixture due to the high affinity between the PVA, water, and cellulose. Both the action and the action of physically separating cellulose molecules by a mechanical operation of applying a shearing force can be effectively exhibited. Moreover, by using the said viscosity imparting agent, this PVA will approach into the clearance gap between the cellulose polymer chains physically separated, and it will become easy to adhere. Therefore, according to the production method using the PVA, re-quasicrystallization of the cellulose polymer chain can be prevented, and hydrolyzable cellulose can be produced more efficiently.
  • a gelled PVA aqueous solution a mixture having a favorable viscosity can be obtained from the first stage of applying shearing force, and cell-based biomass can be efficiently divided at the molecular level. be able to.
  • the method for applying a shearing force to the mixture in the dividing step is not particularly limited, and examples thereof include a method of kneading the mixture.
  • the apparatus used in the dividing step is not particularly limited, but a twin screw extruder generally used for molding a thermoplastic resin or the like is preferably used.
  • the time required for this dividing step is appropriately set according to the amount of the mixture and the like, and is, for example, about 30 minutes to 10 hours.
  • the viscosity may be appropriately adjusted by adding a sodium tetraborate aqueous solution or the like.
  • the cellulose-based biomass becomes cellulose that is easily hydrolyzed with the quasicrystalline structure divided by going through the above-described steps.
  • the hydrolyzable cellulose thus obtained is easily saccharified by adding a hydrolase such as cellulase to the mixture, and the resulting glucose is dissolved in the aqueous solution.
  • a hydrolase such as cellulase
  • the hydrolase include cellulase, pectinase, hemicellulase, ⁇ -glucanase, xylanase, mannase, amylase, mecerase, and acremonium cellulase (cellulase obtained from Acremonium cellulolyticus).
  • hemicellulose-derived xylose and the like contained in the cellulosic biomass are also dissolved in the aqueous solution.
  • the lignin contained in the cellulosic biomass may exist as insoluble particles, but this lignin can be separated by, for example, filtration or centrifugation.
  • the saccharides such as soluble glucose thus obtained can be converted to ethanol by fermentation and can be suitably used as a fuel resource.
  • the PVA obtained by the following production examples was evaluated according to the following method.
  • Modification rate [Content of monomer unit having an alkyl group having 29 or less carbon atoms in PVA (hereinafter also referred to as “modification rate”)] It calculated
  • a monomer solution was prepared by dissolving N-octadecylmethacrylamide in methanol to a concentration of 5% as a delay solution, and the atmosphere was purged with nitrogen by bubbling nitrogen gas.
  • the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization.
  • AIBN 2,2′-azobisisobutyronitrile
  • the delay solution was added dropwise so that the monomer composition (ratio of vinyl acetate and N-octadecylmethacrylamide) in the polymerization solution became constant, polymerization was performed at 60 ° C. for 3 hours, and then the polymerization was stopped by cooling.
  • the total amount of monomers added until the polymerization was stopped was 4.8 g.
  • the solid content concentration at the time of termination of polymerization was 29.9% by mass.
  • unreacted vinyl acetate monomer was removed while sometimes adding methanol at 30 ° C. under reduced pressure to obtain a methanol solution (concentration 35% by mass) of an alkyl-modified vinyl ester copolymer (alkyl-modified PVAc).
  • alkyl-modified PVAc alkyl-modified vinyl ester copolymer
  • 777.9 g of alkyl-modified PVAc methanol solution prepared by adding methanol thereto (200.0 g of alkyl-modified PVAc in the solution) was added 27.9 g of an alkali solution (10% by weight methanol solution of sodium hydroxide).
  • the saponification was carried out (concentration of alkyl-modified PVAc in saponification solution: 25% by mass, molar ratio of sodium hydroxide to vinyl acetate unit in alkyl-modified PVAc: 0.03).
  • a gel-like material was formed in about 1 minute after the addition of the alkaline solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to proceed with saponification. Neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2,000 g of methanol was added thereto, and the mixture was allowed to stand and washed at room temperature for 3 hours.
  • PVA1-1 alkyl-modified PVA
  • PVA1-1 had an average degree of polymerization of 1,700, a degree of saponification of 98.5 mol%, and a modification rate of 0.4 mol%.
  • Production Examples 1-2 to 1-18 Charge amount of vinyl acetate and methanol, polymerization conditions such as kind and addition amount of unsaturated monomer having alkyl group used during polymerization, concentration of alkyl-modified PVAc during saponification, molar ratio of sodium hydroxide to vinyl acetate unit Various alkyl-modified PVAs (PVA1-2 to 1-18) were produced in the same manner as in Production Example 1 except that the saponification conditions such as the above were changed as shown in Table 1.
  • Production Example 1-19 (Production of PVA1-19) A 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen inlet and an initiator addition port was charged with 750 g of vinyl acetate, 250 g of methanol, and 57.3 g of octadecyl vinyl ether, and the inside of the system was kept for 30 minutes while bubbling nitrogen. Replaced with nitrogen. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 1.0 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization. After polymerization at 60 ° C. for 2 hours, the polymerization was stopped by cooling.
  • AIBN 2,2′-azobisisobutyronitrile
  • the solid content concentration when the polymerization was stopped was 30.4% by mass. Subsequently, unreacted vinyl acetate monomer was removed while sometimes adding methanol at 30 ° C. under reduced pressure to obtain a methanol solution (concentration 35% by mass) of an alkyl-modified vinyl ester copolymer (alkyl-modified PVAc). . Furthermore, 7.0 g of an alkaline solution (10% by mass of sodium hydroxide in methanol) was added to 792.9 g of an alkyl-modified PVAc methanol solution prepared by adding methanol thereto (200.0 g of the alkyl-modified PVAc in the solution).
  • PVA1-19 had an average degree of polymerization of 1,700, a degree of saponification of 88.0 mol%, and a modification rate of 0.8 mol%.
  • Production Example 1-20 (Production of PVA1-20) 900 g of vinyl acetate and 100 g of methanol were charged into a 3 L reactor equipped with a stirrer, reflux condenser, nitrogen inlet tube and initiator addition port, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and polymerization was performed at 60 ° C. for 3 hours. After cooling, the polymerization was stopped. The solid content concentration when the polymerization was stopped was 31.0% by mass.
  • AIBN 2,2′-azobisisobutyronitrile
  • unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution (concentration 30% by mass) of unmodified polyvinyl acetate (unmodified PVAc). Furthermore, 27.9 g of an alkaline solution (sodium hydroxide in 10% by mass in methanol) was added to 971.1 g of methanol solution of unmodified PVAc prepared by adding methanol thereto (200.0 g of unmodified PVAc in the solution).
  • an alkaline solution sodium hydroxide in 10% by mass in methanol
  • saponification was carried out (the concentration of unmodified PVAc in the saponified solution was 20% by mass, the molar ratio of sodium hydroxide to the vinyl acetate unit in the unmodified PVAc was 0.03).
  • a gel-like material was formed in about 1 minute after the addition of the alkaline solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to proceed with saponification. Neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2,000 g of methanol was added thereto, and the mixture was allowed to stand and washed at room temperature for 3 hours.
  • PVA1-20 had an average polymerization degree of 3,000 and a saponification degree of 98.5 mol%.
  • Example 1-1 PVA1-1 was added to distilled water and heated to 90 ° C. with stirring to prepare a 10% by mass PVA aqueous solution.
  • This aqueous PVA solution was slightly more viscous than water.
  • 1 mL of a saturated aqueous solution of boric acid (H 3 BO 3 ) was added and mixed.
  • the pH of the obtained aqueous solution was 5.0.
  • 0.5 mL of a saturated aqueous solution of sodium tetraborate was added to and mixed with this aqueous solution, whereby the aqueous solution was made into a viscous gel.
  • the gel-like body had a pH of 6.5.
  • 50 g of EFB particles having a diameter of 20 to 70 ⁇ m
  • cellulosic biomass particles was added to the gel and kneaded using a mixer-type kneader at room temperature.
  • Example 1-2 to 1-18, Comparative Examples 1-1 to 1-2 Examples 1-2 to 1-18 and Comparative Examples 1-1 to 1-2 were performed in the same manner as Example 1-1 except that PVA was changed from PVA 1-1 to the other PVA in Table 2. A hydrolyzable aqueous cellulose solution was obtained, and finally a glucose solution was obtained.
  • Examples 1-1 to 1-16 use alkyl-modified PVA having a specific monomer unit, so that the saccharification efficiency exceeds 80% and cellulose easily It was found that it was divided into hydrolyzed states. On the other hand, in Comparative Example 1-1, it was found that the PVA used was not denatured, so that the cellulose was not sufficiently divided to a state where it was easily hydrolyzed.
  • a monomer solution having a concentration of 20% by mass was prepared by dissolving an unsaturated monomer having a POA group (monomer A) in methanol as a delay solution, and nitrogen substitution was performed by bubbling nitrogen gas.
  • the temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to initiate polymerization.
  • AIBN 2,2′-azobisisobutyronitrile
  • the delay solution was dropped to keep the monomer composition (ratio of vinyl acetate and monomer A) in the polymerization solution constant, polymerization was performed at 60 ° C. for 3 hours and then cooled to stop the polymerization. The total amount of the monomer solution added until the polymerization was stopped was 75 ml.
  • the solid content concentration when the polymerization was stopped was 24.4% by mass.
  • unreacted vinyl acetate monomer was removed while occasionally adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution (concentration 35 mass%) of POA-modified vinyl ester polymer (POA-modified PVAc).
  • POA-modified PVAc methanol solution
  • 55.6 g of an alkaline solution sodium hydroxide in 10% by mass in methanol
  • PVA2-1 POA-modified PVA
  • PVA2-1 had an average degree of polymerization of 1,740, a degree of saponification of 98.5 mol%, and a modification amount of 0.4 mol%.
  • Production Examples 2-2 to 2-24 (Production of PVA 2-2 to 2-24) Charge amount of vinyl acetate and methanol, type of unsaturated monomer having POA group used during polymerization (Table 4), polymerization conditions such as addition amount, concentration of POA-modified PVAc during saponification, hydroxylation to vinyl acetate unit Various POA-modified PVA (PVA2-2 to 2-24) were produced in the same manner as in Production Example 2-1, except that the saponification conditions such as the molar ratio of sodium were changed as shown in Tables 3 and 4. .
  • Production Example 2-25 (Production of PVA2-25) 700 g of vinyl acetate and 300 g of methanol were charged into a 3 L reactor equipped with a stirrer, a reflux condenser, a nitrogen introduction tube and an initiator addition port, and the system was purged with nitrogen for 30 minutes while bubbling nitrogen. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.25 g of 2,2′-azobisisobutyronitrile (AIBN) was added to start polymerization, and polymerization was performed at 60 ° C. for 3 hours. After cooling, the polymerization was stopped. The solid content concentration when the polymerization was stopped was 17.0% by mass.
  • AIBN 2,2′-azobisisobutyronitrile
  • the unmodified PVAc concentration of the saponified solution was 20% by mass, the molar ratio of sodium hydroxide to the vinyl acetate unit in the unmodified PVAc was 0.1).
  • a gel-like material was formed in about 1 minute after the addition of the alkaline solution. This was pulverized with a pulverizer and allowed to stand at 40 ° C. for 1 hour to proceed with saponification. Neutralized. After confirming that the neutralization was completed using a phenolphthalein indicator, a white solid was obtained by filtration, 2,000 g of methanol was added thereto, and the mixture was allowed to stand and washed at room temperature for 3 hours.
  • PVA2-25 had an average degree of polymerization of 1,760 and a degree of saponification of 98.8 mol%.
  • Example 2-1 to 2-24, Comparative Example 2-1 Examples 2-1 to 2-24 and Comparative Example 2-1 were carried out in the same manner as in Example 1-1 except that PVA was changed from PVA 1-1 to other PVA in Table 5, and hydrolyzable cellulose. An aqueous solution was obtained and finally a glucose solution was obtained.
  • Examples 2-1 to 2-19 use POA-modified PVA having a specific monomer unit, the saccharification efficiency exceeds 78% and cellulose easily It was found that it was divided into hydrolyzed states. On the other hand, in Comparative Example 2-1, it was found that the PVA used was not denatured, so that the cellulose was not sufficiently divided into a state where it was easily hydrolyzed.
  • the viscosity-imparting agent of the present invention can be suitably used for producing hydrolyzable cellulose using cellulosic biomass as a raw material. Therefore, according to this invention, a plant-type biomass raw material can be efficiently utilized as a food or energy resource, and the feasibility of utilization of biomass can be improved.

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Abstract

La présente invention concerne un agent épaississant destiné à être utilisé dans le cadre de la production de cellulose hydrolysable à partir d'une matière première comprenant de la biomasse cellulosique, ledit agent étant capable de conférer la viscosité nécessaire à une solution contenant de la biomasse cellulosique afin de faciliter la décomposition de ladite biomasse cellulosique au niveau moléculaire et de permettre une production efficace de cellulose hydrolysable. L'invention concerne également un procédé de production de cellulose hydrolysable faisant appel audit agent épaississant. La présente invention concerne, donc, un agent épaississant destiné à être utilisé dans le cadre de la production de cellulose hydrolysable à partir d'une matière première comprenant de la biomasse cellulosique, ledit agent épaississant étant caractérisé en ce qu'il contient un polymère d'alcool polyvinylique comprenant des motifs monomères portant chacun un groupe alkyle comportant au maximum 29 atomes de carbone et chaque motif monomère comportant au moins 8 atomes de carbone.
PCT/JP2012/057395 2011-03-25 2012-03-22 Agent épaississant et procédé de production de cellulose hydrolysable l'utilisant WO2012133126A1 (fr)

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JPH05507615A (ja) * 1990-06-14 1993-11-04 ノボ　ノルディスク　アクティーゼルスカブ ポリサッカライドヒドロラーゼの活性化
JPH08281092A (ja) * 1995-04-14 1996-10-29 Nippon Synthetic Chem Ind Co Ltd:The 乳化分散安定剤
JPH10295390A (ja) * 1997-04-28 1998-11-10 Tsurunaga Takehisa 植物繊維からのグルコースの製造方法
JPH10338714A (ja) * 1997-06-09 1998-12-22 Kao Corp 新規ポリビニルアルコール誘導体
JP2008274247A (ja) * 2007-03-30 2008-11-13 National Institute Of Advanced Industrial & Technology 微細繊維状セルロース系物質及びその製造方法
WO2009124072A1 (fr) * 2008-04-01 2009-10-08 Biomass Conversions, Llc Procédé simplifié pour la digestion de biomasse cellulosique
JP2010051308A (ja) * 2008-07-28 2010-03-11 National Institute Of Advanced Industrial Science & Technology 酵素液の製造方法及び糖の製造方法

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JPH05507615A (ja) * 1990-06-14 1993-11-04 ノボ　ノルディスク　アクティーゼルスカブ ポリサッカライドヒドロラーゼの活性化
JPH08281092A (ja) * 1995-04-14 1996-10-29 Nippon Synthetic Chem Ind Co Ltd:The 乳化分散安定剤
JPH10295390A (ja) * 1997-04-28 1998-11-10 Tsurunaga Takehisa 植物繊維からのグルコースの製造方法
JPH10338714A (ja) * 1997-06-09 1998-12-22 Kao Corp 新規ポリビニルアルコール誘導体
JP2008274247A (ja) * 2007-03-30 2008-11-13 National Institute Of Advanced Industrial & Technology 微細繊維状セルロース系物質及びその製造方法
WO2009124072A1 (fr) * 2008-04-01 2009-10-08 Biomass Conversions, Llc Procédé simplifié pour la digestion de biomasse cellulosique
JP2010051308A (ja) * 2008-07-28 2010-03-11 National Institute Of Advanced Industrial Science & Technology 酵素液の製造方法及び糖の製造方法

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Publication number Priority date Publication date Assignee Title
WO2014103877A1 (fr) * 2012-12-25 2014-07-03 三洋化成工業株式会社 Accélérateur de réaction de saccharification enzymatique et composition d'accélérateur de réaction de saccharification enzymatique
JPWO2014103877A1 (ja) * 2012-12-25 2017-01-12 三洋化成工業株式会社 酵素糖化反応促進剤及び酵素糖化反応促進剤組成物

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