WO2017142000A1 - 糖アルコールの製造方法 - Google Patents
糖アルコールの製造方法 Download PDFInfo
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- WO2017142000A1 WO2017142000A1 PCT/JP2017/005611 JP2017005611W WO2017142000A1 WO 2017142000 A1 WO2017142000 A1 WO 2017142000A1 JP 2017005611 W JP2017005611 W JP 2017005611W WO 2017142000 A1 WO2017142000 A1 WO 2017142000A1
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- sugar
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- acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/20—Oxygen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C31/18—Polyhydroxylic acyclic alcohols
- C07C31/26—Hexahydroxylic alcohols
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- 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
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
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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
- C13K13/00—Sugars not otherwise provided for in this class
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B61/00—Other general methods
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Definitions
- the present invention relates to a method for producing sugar alcohol from cellulose-containing biomass.
- the chemical synthesis process using sugar as a raw material is used for the production of various industrial raw materials, and the sugar alcohol synthesis process using a hydrogenation reaction of sugar is a typical example.
- sugars used as synthetic raw materials are industrially used from edible raw materials such as sugar cane, starch, sugar beet, etc. From the ethical aspect of competing, a process for producing sugar solution more efficiently than renewable non-edible resources, that is, biomass containing cellulose, or the resulting sugar solution as a synthetic raw material and efficiently converting it into an industrial raw material The construction of the process is a future issue.
- Patent Document 1 A method of hydrolyzing by an enzymatic reaction after pretreatment for improving hydrolysis reactivity is generally known (Patent Document 2). Furthermore, a method for obtaining a sugar solution by purifying a hydrolyzed sugar aqueous solution using an ultrafiltration membrane, a nanofiltration membrane, a reverse osmosis membrane or the like has been reported (Patent Documents 3 to 5).
- a method for producing a xylose polymer reduced product, which is a sugar alcohol is known by hydrogenating a xylose polymer recovered from the non-permeation side at a high temperature and high pressure under a metal catalyst after removal from the permeation side of the nanofiltration membrane. (Patent Document 6).
- catalyst poisons of metal catalysts include low molecular organic substances such as nitrogen compounds, sulfur compounds, and phosphorus compounds, and metals such as Ag, Hg, Pb, Bi, Sn, Cd, and As.
- Non-patent Document 1 these catalyst poisons are generally removed by adsorption and removal by activated carbon treatment or ion-exchange resin treatment (Patent Document 7).
- an object of the present invention is to provide a method for efficiently producing a sugar alcohol from cellulose-containing biomass by simply removing the catalyst poison derived from cellulose-containing biomass.
- the catalyst poison contained in the aqueous sugar solution obtained by hydrolyzing cellulose-containing biomass is not a generally known low-molecular organic substance or metal, but a relatively high-molecular substance.
- the inventors have found that the catalyst poison can be easily removed by a separation membrane, and completed the present invention.
- the present invention includes the following [1] to [9].
- [1] A method for producing sugar alcohol using cellulose-containing biomass as a raw material, Step (1): The aqueous sugar solution obtained by hydrolysis of the biomass containing cellulose is filtered through a separation membrane having a molecular weight cut off of 300 to 800 to remove the catalyst poison on the non-permeating side, and the sugar solution is removed from the permeating side.
- a method for producing a sugar alcohol comprising: [2] The method for producing a sugar alcohol according to [1], wherein the separation membrane in the step (1) is a separation membrane having a fractional molecular weight of 300 to 500.
- [6] A method for producing an anhydrous sugar alcohol, comprising a step of producing a sugar alcohol by the production method according to any one of [1] to [5], and a step of subjecting the sugar alcohol to a dehydration reaction.
- sugar alcohol can be produced from cellulose-containing biomass with high yield.
- Cellulose-containing biomass refers to a biological resource containing 5% by weight or more of cellulose. Specific examples include herbaceous biomass such as bagasse, switchgrass, napiergrass, Eliansus, corn stover, rice straw, and straw, and woody biomass such as trees and waste building materials. These cellulose-containing biomass is also called lignocellulose because it contains lignin and cellulose / hemicellulose which are aromatic polymers.
- hydrolysis treatment of cellulose-containing biomass is carried out by chemical treatment methods such as acid treatment with high-temperature and high-pressure dilute sulfuric acid or sulfite, and alkali treatment with an alkaline aqueous solution such as calcium hydroxide or sodium hydroxide.
- chemical treatment methods such as acid treatment with high-temperature and high-pressure dilute sulfuric acid or sulfite, and alkali treatment with an alkaline aqueous solution such as calcium hydroxide or sodium hydroxide.
- alkali treatment with an alkaline aqueous solution such as calcium hydroxide or sodium hydroxide.
- alkali treatment with an alkaline aqueous solution
- hydrothermal treatment treating with pressurized hot water.
- hydrolysis treatment with a saccharifying enzyme may be performed.
- acid treatment is characterized in that lignin is dissolved and hydrolysis starts from an easily soluble hemicellulose component, and then a hardly soluble cellulose component is decomposed, so that a liquid containing a large amount of xylose derived from hemicellulose is obtained. It is possible.
- the number of treatments is not particularly limited, but by setting two or more acid treatment steps, hydrolysis conditions suitable for hemicellulose and cellulose can be selectively set, improving degradation efficiency and sugar yield. It becomes possible to make it.
- the acid used in the acid treatment is not particularly limited as long as it causes hydrolysis, but sulfuric acid is desirable from the viewpoint of economy.
- the acid concentration is preferably 0.1 to 100% by weight, more preferably 0.5 to 15% by weight.
- the reaction temperature can be set in the range of 100 to 300 ° C., and the reaction time can be set in the range of 1 second to 60 minutes.
- the liquid component after the acid treatment contains a large amount of monosaccharides and oligosaccharides whose main components are components derived from hemicellulose obtained by hydrolysis.
- both hemicellulose and cellulose can be hydrolyzed and hydrolyzed in one step.
- the solid content and liquid component obtained after acid treatment may be performed separately, or may be performed while the solid content and liquid component are mixed.
- the used acid is contained in the solid content and liquid component obtained by an acid treatment, in order to perform a hydrolysis reaction by a saccharifying enzyme, it is preferable to neutralize an acid-treated material beforehand.
- Alkali treatment is a treatment method in which cellulose-containing biomass is reacted with an aqueous alkali solution, specifically, an aqueous solution of a hydroxide salt (excluding ammonium hydroxide).
- a hydroxide salt excluding ammonium hydroxide
- the hydroxide salt used is preferably sodium hydroxide or calcium hydroxide.
- the concentration of the alkaline aqueous solution is preferably in the range of 0.1 to 60% by weight, and this is added to the cellulose-containing biomass and is usually treated at a temperature range of 100 to 200 ° C, preferably 110 to 180 ° C.
- the number of treatments is not particularly limited, and may be performed once or a plurality of times. When performing twice or more, you may implement each process on different conditions.
- the pre-processed product obtained by the alkali treatment contains an alkali, it is preferable to neutralize beforehand, when hydrolyzing by a saccharifying enzyme further.
- Ammonia treatment is a treatment method in which an aqueous ammonia solution or 100% ammonia (liquid or gas) is reacted with cellulose-derived biomass.
- the method described in JP 2008-161125 A or JP 2008-535664 A is used. be able to.
- the reaction efficiency with the saccharifying enzyme is greatly improved by the fact that the crystallinity of cellulose is lost due to the reaction of ammonia with the cellulose component.
- ammonia is added to the cellulose-containing biomass so as to have a concentration in the range of 0.1 to 15% by weight with respect to the cellulose-containing biomass, and the treatment is performed at 4 to 200 ° C., preferably 60 to 150 ° C.
- the number of treatments is not particularly limited, and may be performed once or a plurality of times.
- Hydrothermal treatment is a method of treating cellulose-containing biomass with pressurized hot water at 100 to 400 ° C. for 1 second to 60 minutes.
- the cellulose-containing biomass which is insoluble in water at a normal temperature of 25 ° C. after the treatment, is adjusted to a concentration of 0.1 to 50% by weight with respect to the total total weight of the cellulose-containing biomass and water.
- the pressure is not particularly limited because it depends on the treatment temperature, but it is preferably 0.01 to 10 MPa.
- the elution component into hot water differs depending on the temperature of the pressurized hot water.
- the first group of tannin and lignin flows out from the cellulose-containing biomass first, and then the second group of hemicellulose flows out at 140 to 150 ° C. or higher.
- the temperature exceeds about 230 ° C. the third group of cellulose flows out.
- the hydrolysis reaction of hemicellulose and cellulose may occur simultaneously with the outflow.
- the treatment temperature may be changed to perform multi-stage treatment.
- an aqueous solution containing a component eluted into pressurized hot water is referred to as a hot water-soluble component
- a hot water-soluble component is referred to as a hot water-insoluble component.
- the hot water insoluble content is a solid content mainly containing a disaccharide or higher cellulose (C6) component obtained as a result of elution of many lignin and hemicellulose components.
- C6 disaccharide or higher cellulose
- hemicellulose components and lignin components may be included. These content ratios change with the temperature of the pressurized hot water of hydrothermal treatment, and the kind of process biomass.
- the water content of the hot water insoluble component is 10% to 90%, more preferably 20% to 80%.
- the hot water soluble component is an aqueous solution containing hemicellulose, lignin, tannin and a part of cellulose components eluted in pressurized hot water in a liquid state or a slurry state, and is in a liquid state or a slurry state.
- the hot water-soluble component contains a large amount of hydrolyzed polysaccharides, oligosaccharides and monosaccharides.
- a pulverization process in which fibers are mechanically cut using a cutter mill or a hammer mill, a fine pulverization process using a ball mill or a jet mill, a wet process using a grinder, a mechanochemical A pretreatment such as a steaming / explosion process in which steaming is performed for a short time with treatment and steam, and the pressure is instantaneously released and pulverized by volume expansion may be performed.
- a steaming / explosion process in which steaming is performed for a short time with treatment and steam, and the pressure is instantaneously released and pulverized by volume expansion
- cellobiohydrase and xylanase which are enzyme components contained in the crudely purified cellulase derived from filamentous fungi, are suitable.
- Cellobiohydrase is a general term for enzymes that release cellobiose by hydrolysis of cellulose chains, and an enzyme group belonging to cellobiohydrase is described as EC number: EC 3.2.1.91.
- Xylanase is a general term for enzymes characterized by acting on xylan, which is a main component constituting xylan, and an enzyme group belonging to xylanase is described as EC number: EC 3.2.1.8. .
- the filamentous fungi include Trichoderma, Aspergillus, Cellulomonas, Clostridium, Streptomyces, Humicola, and Humicola. Examples include microorganisms such as the genus Irpex, the genus Mucor, and the genus Talaromyces. Among these filamentous fungi, the genus Trichoderma is preferably used because it produces a large amount of enzyme components having high specific activity in the hydrolysis of cellulose in the culture solution.
- Trichoderma microorganisms are not particularly limited, but Trichoderma reesei QM9414 (Trichoderma reesei QM9414), Trichoderma reesei QM9113 (Trichoderma reesei QM9123), Trichoderma reesei Rutcder R-30 C Trichoderma reesei PC3-7), Trichoderma reesei CL-847 (Trichoderma reesei CL-847), Trichoderma reesei MCG77 (Trichoderma reesei MCG77), Trichoderma reesei MCG80 (TriMCede MCGer 80) Rikoderuma viride QM9123 (Trichoderma viride QM9123) can be exemplified derived.
- Trichoderma reesei is preferable. Further, it may be a microorganism derived from Trichoderma reesei, and a mutant having improved cellulase productivity by performing a mutation treatment with a mutation agent or ultraviolet irradiation.
- the crudely purified cellulase preferably contains an enzyme component other than the cellobiohydrase and xylanase from the viewpoint of improving the hydrolysis efficiency of the cellulosic biomass pretreatment product and improving the yield of xylo-oligosaccharide.
- enzyme component of the crudely purified cellulase in addition to the cellobiohydrase and xylanase, one or more enzyme components selected from the group consisting of endoglucanase and ⁇ -glucosidase, preferably endoglucanase, ⁇ -glucosidase, arabinofuranosidase
- one or more enzyme components selected from the group consisting of xylan esterase and ferulic acid esterase more preferably selected from the group consisting of endoglucanase, ⁇ -glucosidase, arabinofuranosidase, xylan esterase, ferulic acid esterase, mannanase and mannosidase It is preferable to include one or more kinds of enzyme components.
- the weight ratio of each enzyme component of the crude cellulase is not particularly limited.
- the culture solution derived from Trichoderma reesei contains 50 to 95% by weight of cellobiohydrase, and the rest Ingredients include endoglucanase, ⁇ -glucosidase, xylanase, ⁇ -xylosidase and the like.
- Trichoderma microorganisms produce strong cellulase components in the culture solution, while ⁇ -glucosidase has low ⁇ -glucosidase activity in the culture solution because it is retained in the cell or on the cell surface.
- the culture solution derived from Trichoderma reesei to which a different or the same kind of ⁇ -glucosidase is further added as the roughly purified cellulase of the present invention.
- ⁇ -glucosidase derived from Aspergillus
- Examples of ⁇ -glucosidase derived from the genus Aspergillus include Novozyme 188 commercially available from Novozyme.
- the culture solution of the filamentous fungi for example, the culture solution of the filamentous fungi exemplified above, the culture supernatant obtained by removing the cells from the culture solution, or the culture solution containing the disrupted microorganism cells may be used as they are, or they may be concentrated.
- the product obtained may be used as a crudely purified cellulase.
- the method for removing cells from the culture solution include centrifugation, filter press, and microfiltration membrane treatment, and these can be used alone or in combination.
- a method for obtaining a microbial cell lysate suspend the cell isolated by a method such as centrifugation and crush the microbial cell with an ultrasonic homogenizer or bead-type homogenizer to obtain a microbial cell lysate.
- a concentration method include a concentration method by evaporation concentration or ultrafiltration membrane treatment.
- the purified enzyme group For the purification of the enzyme group, known methods such as ammonium sulfate fractionation and column chromatography can be used.
- the purified enzyme added to the filamentous fungus culture solution is used as a crude purified cellulase, the purified enzyme is added in an amount not exceeding the amount of protein in the culture supernatant before the addition of the purified enzyme.
- Crude cellulase can be added to the crude cellulase by purifying the enzyme group using a known method, such as a culture solution of filamentous fungi, a culture supernatant from which the bacterial cells have been removed, a culture solution containing microbial cell disruptions, or a known method.
- a known method such as a culture solution of filamentous fungi, a culture supernatant from which the bacterial cells have been removed, a culture solution containing microbial cell disruptions, or a known method.
- it may be prepared by heat-treating a product formulated by combining at a specific pH and temperature.
- the crude cellulase diluted with an aqueous solvent is heat-treated for a certain time under specific pH and temperature conditions.
- the enzyme concentration during the heat treatment is 0.01 to 10% by weight, more preferably 0.1 to 5% by weight, and still more preferably 0.2 to 1% by weight in terms of protein concentration.
- the stability of most of the enzyme components in the crude cellulase decreases, and most of the enzyme components are deactivated during the heat treatment, so that cellulose
- the hydrolysis efficiency of the system biomass pretreatment product decreases, and the yield of xylo-oligosaccharides decreases.
- the protein concentration exceeds 5% by weight, the stability of the protein increases, the enzyme activity for decomposing xylo-oligosaccharides in the crude cellulase into xylose becomes difficult to decrease, and the xylo-oligosaccharide yield decreases.
- the solid content concentration of the cellulosic biomass pretreatment product is in the range of 1 to 30% by weight, preferably 3 to 20% by weight, more preferably 5 to 10% by weight. It is preferable that The hydrolysis reaction using a saccharifying enzyme is preferably performed in the vicinity of pH 3.0 to 8.0, more preferably in the vicinity of pH 5.5 to 8.0. The hydrolysis reaction using a saccharifying enzyme is preferably performed in 1 to 144 hours, more preferably 3 to 72 hours, and further preferably 6 to 24 hours. Moreover, it is preferable to perform solid-liquid separation at the end of hydrolysis by a saccharifying enzyme to remove undecomposed solid content. Examples of the solid content removal method include a centrifugal separation method and a membrane separation method, but are not particularly limited. Moreover, you may use such solid-liquid separation combining multiple types.
- the aqueous sugar solution obtained in the hydrolysis process of the cellulose-containing biomass has a solid content, tannin, saccharifying enzyme, biomass. It is preferable to remove a water-soluble polymer such as a protein component derived before passing through a separation membrane having a fractional molecular weight of 300 to 800.
- the method for removing these components is not particularly limited, but as a preferable method for removing these components, the aqueous sugar solution is filtered through a microfiltration membrane and / or an ultrafiltration membrane having a fractional molecular weight of more than 2,000, A method of filtering solid content and water-soluble polymer on the permeate side is mentioned.
- the filtration method include pressure filtration, vacuum filtration, and centrifugal filtration, but are not particularly limited.
- the filtration operation is broadly classified into constant pressure filtration, constant flow filtration, and non-constant pressure non-constant flow filtration, but is not particularly limited. Further, the filtration operation may be multistage filtration using a microfiltration membrane or an ultrafiltration membrane having a fractional molecular weight larger than 2,000 twice or more in order to efficiently remove a solid content.
- a microfiltration membrane is a membrane with an average pore diameter of 0.01 ⁇ m to 5 mm, and is abbreviated as a microfiltration membrane, MF membrane, etc., and removes solids contained in an aqueous sugar solution. It is preferably used when The microfiltration membrane used here may be an inorganic membrane or an organic membrane, cellulose, cellulose ester, polysulfone, polyethersulfone, chlorinated polyethylene, polypropylene, polyolefin, polyvinyl alcohol, polymethyl methacrylate, polyvinylidene fluoride, Examples thereof include organic materials such as polytetrafluoroethylene, metals such as stainless steel, and inorganic materials such as ceramic.
- the ultrafiltration membrane is a separation membrane having a fractional molecular weight of 600 to 200,000, and is abbreviated as an ultrafiltration membrane, a UF membrane, or the like.
- the molecular weight cut-off refers to the Membrane Society of Japan, Membrane Experiment Series Volume III, Artificial Membrane Editor / ist Kimura, Shinichi Nakao, Haruhiko Ohya, Tsutomu Nakagawa (Kyoritsu Shuppan, 1993), page 92.
- a plot of data with the molecular weight on the horizontal axis and the rejection rate on the vertical axis is called a fractionated molecular weight curve.
- the molecular weight at which the blocking rate is 90% is called the fractional molecular weight of the membrane. ”Is well known to those skilled in the art as an index representing the membrane performance of the ultrafiltration membrane.
- a water-soluble polymer, particularly a saccharifying enzyme, contained in an aqueous sugar solution can be suitably removed.
- the material of the ultrafiltration membrane is not particularly limited, but cellulose, cellulose ester, polysulfone, sulfonated polysulfone, polyethersulfone, sulfonated polyethersulfone, chlorinated polyethylene, polypropylene, polyolefin, polyvinyl alcohol, poly Examples thereof include organic materials such as methyl methacrylate, polyvinylidene fluoride, and polytetrafluoroethylene, metals such as stainless steel, and inorganic materials such as ceramic. Among these, an organic film is preferable from the viewpoint of removing hydrophobic substances. Of these, polyethersulfone is preferred. More preferably, it is a sulfonated polyethersulfone.
- the form of the ultrafiltration membrane to be used is not particularly limited, and any of a spiral type, a hollow fiber type, a tubular type, and a flat membrane type may be used.
- ultrafiltration membrane used in the present invention examples include DESAL G-5 type, GH type, GK type, Sinder 1 SPE1, KOCH PM1000, PM2000, MPS-36, SR2, and Alpha.
- GR95Pp, ETNA01PP manufactured by Laval examples include NTR-7450 manufactured by Nitto Denko Corporation (see fractional molecular weight 600 to 800, WaterResearch 37 (2003) 864-872), NTR-7410 (fractional molecular weight 1,000 to 2,000, Hygiene Engineering Symposium Proceedings, 5: 246-251 (1997)).
- the filtration pressure in the filtration treatment of the ultrafiltration membrane depends on the concentration of the aqueous sugar solution, but is preferably in the range of 0.1 MPa to 8 MPa. If the filtration pressure is lower than 0.1 MPa, the membrane permeation rate decreases, and if it is higher than 8 MPa, the membrane may be damaged. Moreover, since a membrane permeation
- the membrane permeation flux in the filtration treatment of the ultrafiltration membrane is preferably 0.2 m / D or more and 4.0 m / D or less. This is because if it is 0.2 m / D or less, concentration with an ultrafiltration membrane cannot be performed, and if it is 2.0 m / D or less, fouling of the membrane becomes remarkable. Moreover, if it is 0.5 m / D or more and 2.0 m / D or more, since it becomes easy to perform filtration by an ultrafiltration membrane, it is more preferable.
- the pH of the aqueous sugar solution in the filtration treatment of the ultrafiltration membrane is not particularly limited, but is preferably 5 or less, more preferably 4 or less. If the pH is 1 or less, a large amount of acid is required at the time of pH adjustment. Therefore, it is preferable to set the lower limit of pH to 1 from the viewpoint of economy.
- the pH adjustment of the sugar aqueous solution is remarkable when an aromatic compound such as coumaric acid or ferulic acid and a substance having a carboxylic acid group are included.
- the present invention is characterized in that the aqueous sugar solution obtained by the above method is subjected to a filtration treatment with a separation membrane having a molecular weight cut-off of 300 to 800, preferably 300 to 500 and / or 600 to 800.
- a filtration treatment with a separation membrane having a molecular weight cut-off of less than 300 or more than 800 is not preferable because a catalyst poison that inhibits the later-described sugar alcohol synthesis step cannot be separated.
- the filtration process using the separation membrane may be a filtration process using a plurality of separation membranes.
- a plurality of types of filtration processes may be used even for a single type of separation membrane filtration process. It may be a filtration process.
- the material of the separation membrane is not particularly limited, and a polymer material such as cellulose ester polymer such as cellulose acetate, polyamide, polyester, polyimide, vinyl polymer can be used. It is not limited to the film
- the membrane structure has a dense layer on at least one side of the membrane, and on the asymmetric membrane having fine pores gradually increasing from the dense layer to the inside of the membrane or the other side, or on the dense layer of the asymmetric membrane. Either a composite film having a very thin functional layer formed of another material may be used.
- a composite membrane having a high-pressure resistance, high water permeability, and high solute removal performance and having an excellent potential and a functional layer of polyamide is preferable.
- a structure in which polyamide is used as a functional layer and is held by a support made of a porous membrane or nonwoven fabric is suitable.
- preferable polyamide-based separation membranes used in the present invention include, for example, NFW series manufactured by SYNDER.
- the filtration pressure in the filtration treatment of the separation membrane depends on the concentration of the aqueous sugar solution, but is preferably in the range of 0.1 MPa to 8 MPa. If the filtration pressure is lower than 0.1 MPa, the membrane permeation rate decreases, and if it is higher than 8 MPa, the membrane may be damaged. Moreover, since a membrane permeation
- the sugar solution is recovered from the permeation side of the separation membrane by the filtration treatment, and the catalyst poison of the metal catalyst used for the subsequent hydrogenation reaction is removed from the non-permeation side of the separation membrane.
- the catalyst poison removed from the non-permeating side of the separation membrane has not yet been specified, but it is a substance produced by hydrolysis of cellulose-containing biomass and has a molecular weight exceeding at least 300. It is estimated that As catalyst poisons of metal catalysts, low molecular organic substances such as nitrogen compounds, sulfur compounds and phosphorus compounds, and metals such as Ag, Hg, Pb, Bi, Sn, Cd, As have been known so far. However, these known catalyst poisons are substances having a molecular weight of less than 300-800, and the catalyst poisons produced by hydrolysis of cellulose-containing biomass may be novel catalyst poisons that have not been identified so far.
- the saccharide liquid collected from the permeation side of the separation membrane contains saccharides which are starting materials for the production of sugar alcohols by the subsequent hydrogenation reaction.
- the type of saccharide is not particularly limited, but monosaccharide is preferably the main component, and xylose and / or glucose is preferably the main component.
- the sugar liquid obtained by the above step is subjected to a hydrogenation reaction to synthesize a sugar alcohol.
- a liquid phase containing sugar is brought into contact with a metal catalyst in the presence of hydrogen.
- the metal catalyst may be suspended in the liquid phase (suspension method), or the liquid phase may be passed through a fluidized catalyst bed (fluidized bed method) or a fixed catalyst bed (fixed bed method).
- the metal catalyst used for the hydrogenation reaction is preferably a catalyst containing a metal selected from Group 8 elements of the Periodic Table.
- Group 8 elements of the periodic table refer to elements of the iron, cobalt, nickel, and platinum groups.
- the platinum group element means six elements of ruthenium, rhodium, palladium, osmium, iridium and platinum.
- metals selected from Group 8 elements of the periodic table metals selected from nickel and platinum group elements are more preferable, and ruthenium or nickel is more preferable.
- Specific examples of the metal catalyst containing ruthenium or nickel include a ruthenium catalyst and a Raney nickel catalyst.
- the ruthenium content of the ruthenium catalyst is based on the weight of the support material, and is preferably 0.1 to 5% by weight, more preferably 1 to 5% by weight in terms of ruthenium element.
- the Raney nickel catalyst is obtained by developing a Raney alloy mainly composed of nickel and aluminum with an alkaline aqueous solution.
- the Raney nickel catalyst is applied to the above metal for the purpose of increasing hydrogenation activity or adding resistance to poisonous substances. Other metals may be added.
- the added metal is at least one selected from iron, chromium, cobalt, manganese, and molybdenum.
- the Raney nickel catalyst may be a developed Raney nickel catalyst. Specifically, it is an R-2313A type catalyst available from Nikko Jamaica Corporation.
- the R-2313A type catalyst is a promoter of molybdenum and generally contains about 1.5% molybdenum and 85% nickel.
- a basic compound When using a Raney nickel catalyst, it is preferable to add a basic compound and adjust the reaction solution to pH 7 to 10 in order to prevent melting of nickel. More preferably, the pH is 8-9. What is added is at least one selected from the group consisting of magnesium oxide, sodium borate, potassium borate, and dipotassium hydrogen phosphate.
- the sugar concentration of the sugar solution used for the hydrogenation reaction is not particularly limited, but can basically be freely selected.
- the saccharide concentration is a weight% calculated based on a value obtained by dividing the total weight of glucose, xylose and oligosaccharide (hereinafter referred to as sugar weight) by the total weight of the solution, and is often in the range of 2 to 80% by weight. The preferred range is 20 to 70% by weight.
- the reaction solvent for the hydrogenation reaction is an aqueous solvent, but “aqueous” means 50% by volume or less of water and preferably one or more water-miscible organic solvents, preferably 50% by volume or less, particularly 50% by volume or less. And a mixture of water with a C1-C4-alkanol such as methanol, ethanol, n-propanol or isopropanol. Water is often used as the sole solvent.
- isopropanol serves as a hydrogen atom donor and a hydrogen transfer reaction is expected to proceed with respect to the aldehyde of the sugar, it is preferable to use isopropanol because the yield of the product sugar alcohol is further improved. .
- the hydrogen partial pressure during the hydrogenation reaction is preferably in the range of 0.1 to 15 MPa, preferably 1 to 10 MPa, and more preferably 1 to 5 MPa.
- the reaction temperature is preferably in the range of 80 to 200 ° C, more preferably in the range of 100 to 150 ° C.
- the weight of the sugar solution as the starting material is converted to the sugar weight W1, and the relationship between the ruthenium catalyst amount and the ruthenium equivalent amount W2 is not particularly limited, but the yield of the product is excellent and the economy is also excellent. Therefore, the ratio of W1 to W2 (W1 / W2) is preferably 1 to 100, and more preferably 1 to 20.
- the weight of the sugar liquid as the starting material is converted to the sugar weight W1, and the relationship between the Raney nickel catalyst amount and the nickel equivalent amount W3 is not particularly limited, but the yield of the product is superior and the economy is also excellent.
- the ratio of W1 to W3 is preferably 1 to 100, and more preferably 1 to 20.
- the metal catalyst may be used by being supported on a solid support.
- the solid support for supporting the metal catalyst is suitably at least partially made of a porous material, and it is appropriate that the transition metal is supported on the surface of the porous material. Therefore, it is appropriate that the solid support used in the catalyst of the present invention has at least the surface of the portion on which the transition metal is supported made of a porous material, and the entire solid support is made of a porous material or is not non-conductive.
- a surface of a support made of a porous material may be coated with a porous material.
- the support may be made of another porous material.
- the solid support can be at least partially made of, for example, an inorganic oxide.
- the inorganic oxide is preferably the porous material.
- at least a part of the solid support used in the catalyst of the present invention is preferably a solid support exhibiting acidity, and the solid support exhibiting acidity is preferably the porous material.
- the solid support is preferably one in which hydrogen molecules are dissociated by a metal such as Pt and a proton acid point is expressed on the support.
- solid support examples include silica, alumina, silica-alumina, zeolite, titania, zirconia, and activated carbon.
- the shape and form of the solid carrier are not particularly limited, and may be, for example, powder, particle, granule, pellet, honeycomb, extrusion, ring, column, rib extrusion, or rib ring. it can.
- the carrier in the form of powder, particles, granules, and pellets can be made of, for example, only the porous material, the oxide, or the material exhibiting acidity.
- the carrier having a honeycomb structure may be a non-porous material, for example, a surface of a support made of cordierite or the like, which is coated with the porous material, oxide, or acidic material. Further, as described above, the support may be made of another porous material.
- the sugar alcohol obtained in the present invention is not particularly limited, but since a saccharide contained in the sugar solution is used as a starting material, a reduced product of monosaccharide is preferably the main component, and xylitol and / or sorbitol are the main components. Preferably there is.
- the sugar alcohol obtained by the hydrogenation reaction has a quality suitable for normal food and drink use, and if necessary, by a method such as deionization with an ion exchange resin, adjustment of the content by chromatographic separation, etc. , Refined, and, if necessary, liquid, powder, granule, molded product, and other components through operations such as concentration, spray drying, granulation drying, etc.
- Various types of products such as mixed products can be obtained.
- the sugar alcohol obtained in the present invention can be used alone as a sweetener.
- sugar glucose, glucose, xylose, lactose, honey, flour, isomerized sugar, maltose, maltooligosaccharide, xylooligosaccharide, cellooligosaccharide , Chickenpox, trehalose, cellobiose, palatinose, maple sugar, erythritol, xylitol, mannitol, sorbitol, maltitol, lactitol, maltoteitol, xylobiitol, xylitolitol, xylotetriitol, reduced palatinose, reduced starch hydrolysis ,
- sugars and sugar alcohols such as reduced maltose starch syrup and reduced xylooligosaccharides, various high sweeteners such as stevioside, dihydrochalcone, glycyrrhizin
- the shape is also solid, powder, granule, paste, liquid, etc. It can be selected according to the application, and can be used as a taste improver and a quality improver for taste products, cosmetics, pharmaceuticals and the like.
- sugar alcohol obtained in the present invention can be used to produce polyol derivatives such as ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, and anhydrous sugar alcohol.
- polyol derivatives such as ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, and anhydrous sugar alcohol.
- These sugar alcohol derivatives can also be used as surfactants, emulsifiers, reagents for enzyme reactions, plastics, synthetic bases for chemical fibers, and the like.
- anhydrous sugar alcohol which is a polyol derivative is a mixture characterized by comprising sorbitan and / or xylitan as a main component.
- Sorbitan is 1,4-anhydro-D-sorbitol, 1,5-anhydro-D-sorbitol, 2,5-anhydro-D-sorbitol, 3,6-anhydro-D-sorbitol, 2,5-anhydro- L-mannitol, 2,5-anhydro-L-iditol, etc. are generic names, and the sorbitan in the present invention may be a single component or a mixture of the above components (Applied Catalysis, A: General 492 (2015) 252-261.). .
- Xylitan is a general term for 1,4-anhydro-D-xylitol, 2,5-anhydro-D-xylitol, etc., and the xylitan in the present invention may be a single component or a mixture of the above components (Energy & Fuels, 29 (10) 6529-6535; 2015).
- the anhydrous sugar alcohol can be obtained by subjecting the sugar alcohol of the present invention to heat dehydration in the presence of an acid catalyst.
- the acid catalyst is preferably an organic acid, an inorganic acid, or a Lewis acid, and more preferably methanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid, trichloroacetic acid, Lewis acids such as organic acids such as citric acid, inorganic acids such as hydrochloric acid, concentrated sulfuric acid, sodium sulfate, nitric acid, phosphoric acid, phosphorous acid, oxalic acid, boric acid, fluoroboric acid, iron chloride, aluminum chloride, bismuth triflate It is an acid. More preferred are p-toluenesulfonic acid, methanesulfonic acid, concentrated sulfuric acid, and iron chloride.
- the sugar alcohol concentration in the anhydrous sugar alcohol synthesis is not particularly limited.
- the sugar alcohol concentration is a weight% calculated based on a value obtained by dividing the total weight of sorbitol, xylitol, and oligosaccharide alcohol (hereinafter, sugar alcohol weight) by the total weight of the solution, and in many cases, 50 to 80 weight. %, Preferably 55 to 80% by weight, more preferably 60 to 80% by weight.
- the reaction solvent is an aqueous solvent or no solvent, but preferably no solvent.
- the reaction pressure is preferably in the range of 5 to 300 Pa, and preferably in the range of 10 to 150 Pa.
- the reaction temperature is preferably in the range of 100 to 200 ° C, more preferably in the range of 100 to 160 ° C, and more preferably in the range of 120 to 140 ° C.
- the reaction time is preferably in the range of 0.5 hours to 2 hours, more preferably in the range of 0.8 hours to 1.2 hours in the above temperature range.
- reaction time is too short, the reaction conversion rate decreases, and if it is too long, the excessive dehydration reaction of sorbitol proceeds and becomes isosorbide, both of which lead to a decrease in the yield of sorbitan.
- the range is preferably 0.5 hours to 2 hours, more preferably 0.8 hours to 1.2 hours.
- the sugar alcohol weight as the starting material is converted to the sugar alcohol weight W4, and the relationship with the acid catalyst amount W5 is such that if the ratio of W4 to W5 (W4 / W5) is too large, the reaction conversion rate decreases and is small. If it is too high, the excessive dehydration reaction of sorbitol proceeds and becomes isosorbide, both of which lead to a decrease in the yield of sorbitan. Accordingly, W4 / W5 is preferably 75 to 200, and more preferably 100 to 150.
- sorbitan and / or xylitan which are the main components, are known to be used as moisturizers.
- lotions, creams, emulsions, lotions, cosmetic liquids It can be used in gels or packs. It can also be used in skin care preparations such as body lotions and face wash, makeup preparations, hair care preparations, hand soaps, soaps, hand sanitizers or bath preparations.
- skin care preparations such as body lotions and face wash, makeup preparations, hair care preparations, hand soaps, soaps, hand sanitizers or bath preparations.
- pharmaceuticals, quasi-drugs, and cosmetics In particular, it can be easily applied to external preparations such as pharmaceuticals, quasi-drugs, and cosmetic compositions applied to the skin. It is.
- the anhydrous sugar alcohol obtained in the present invention can be used as a surfactant, an enzyme reaction reagent or the like by condensing with a fatty acid, and a polyethylene glycol chain is added to the condensation product of a fatty acid ester and an anhydrous sugar alcohol.
- PEG can also be used as a surfactant, an enzyme reaction reagent, and the like.
- the fatty acid used in the present invention is not particularly limited, and examples thereof include linear or branched saturated fatty acids and unsaturated fatty acids having 6 to 24 carbon atoms. Specific examples include caproic acid, caprylic acid, capric acid. Lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, lignoceric acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, erucic acid, isostearic acid, 2-ethylhexylic acid and condensed ricinoleic acid. These fatty acids can be used alone or in combination of two or more.
- the amount of fatty acid charged to sugar alcohol or anhydrous sugar alcohol varies depending on the target degree of esterification and is not uniform.
- the degree of esterification the more unreacted sugar alcohol in the reaction product obtained.
- the content of anhydrous sugar alcohol increases. Therefore, the method of the present invention can be particularly effective in reacting, for example, about 0.1 to 1 mol of fatty acid with respect to 1 mol of sugar alcohol or anhydrous sugar alcohol.
- the esterification reaction of a sugar alcohol or an anhydrous sugar alcohol with a fatty acid may be carried out without a catalyst, or may be carried out using an acid catalyst or an alkali catalyst, but is carried out in the presence of an alkali catalyst.
- the acid catalyst include proton acids such as sulfuric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, paratoluenesulfonic acid, and methanesulfonic acid, salts thereof, metal halides, and the like.
- alkali catalyst examples include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, alkali metal hydrogen carbonates, alkali metals and alkaline earth metals. And alkaline earth metal oxides, alkaline earth metal hydroxides, other metals and oxides thereof.
- the amount of the alkali catalyst used is 0.01 to 10.0% by mass, preferably 0.1 to 1.0% by mass, based on the total charged amount (in terms of dry matter).
- the esterification reaction is carried out in a normal reaction vessel equipped with, for example, a stirrer, a heating jacket, a baffle plate, an inert gas blowing tube, a thermometer and a water separator with a condenser, and the like. , And stirring and mixing the catalyst, and heating at a predetermined temperature for a certain period of time while removing water generated by the esterification reaction outside the system in an inert gas atmosphere such as nitrogen or carbon dioxide. Is called.
- the reaction temperature is usually in the range of 150 to 250 ° C, preferably in the range of 200 to 250 ° C.
- the reaction pressure is under reduced pressure or normal pressure, and the reaction time is 0.5 to 15 hours, preferably 1 to 6 hours.
- the end point of the reaction is usually determined by measuring the acid value of the reaction mixture and taking 10 or less as a guide.
- the reaction pressure is preferably in the range of 5 to 300 Pa, and preferably in the range of 10 to 150 Pa.
- the neutralization treatment is preferably performed at a liquid temperature in the range of 180 to 200 ° C.
- the neutralization of the catalyst is, for example, when sodium hydroxide is used as an alkali catalyst and neutralized with phosphoric acid (85% by mass), and the amount of phosphoric acid calculated by the following neutralization reaction formula (1)
- the amount of phosphoric acid (85% by mass) equal to or greater than 0.85 divided by 0.85, preferably 2 to 3 times the amount of phosphoric acid calculated by neutralization reaction formula (1) divided by 0.85 This is done by adding phosphoric acid (85% by weight) to the reaction mixture and mixing well.
- the anhydrous sugar alcohol ester obtained in the present invention is a sorbitan ester and / or a xylitan ester as a main component.
- the sorbitan ester is used for foods, industrial articles such as plastics, rubbers, fibers, paints, pharmaceuticals, aromatics. Since it is widely used as an emulsifier for cosmetics and the like, application for the same use is expected.
- sugar alcohol obtained in the present invention can be used to produce polyol derivatives such as ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, and anhydrous sugar alcohol.
- polyol derivatives such as ethylene glycol, propylene glycol, 1,3-propanediol, glycerol, and anhydrous sugar alcohol.
- These sugar alcohol derivatives can also be used as surfactants, emulsifiers, reagents for enzyme reactions, plastics, synthetic bases for chemical fibers, and the like.
- sugar alcohol derivatives can also be used as surfactants, emulsifiers, enzyme reaction reagents, plastics, synthetic bases for chemical fibers, and the like.
- Trichoderma reesei ATCC 66589 (distributed from ATCC) was inoculated to this preculture medium so as to be 1 ⁇ 10 5 cells / mL, and cultured at 28 ° C. for 72 hours with shaking at 180 rpm to prepare a preculture (shaking).
- Apparatus BIO-SHAKER BR-40LF manufactured by TAITEC).
- DPC-2A DPC-2A containers and autoclaved for 15 minutes at 121 ° C.. After standing to cool, 0.1% each of PE-M and Tween 80 autoclaved at 121 ° C. for 15 minutes, respectively, was added. 250 mL was inoculated. Thereafter, the cells were cultured at 28 ° C., 87 hours, 300 rpm, and aeration volume of 1 vvm.
- ⁇ -Glucosidase Novozyme 188) was added to the culture solution prepared under the aforementioned conditions in an amount of 1/100 as a protein weight ratio, and this was used as a crude purified cellulase.
- Reference Example 2 Hydrolysis process of cellulose-containing biomass (dilute sulfuric acid treatment / saccharifying enzyme treatment) Rice straw was used as the cellulose-containing biomass.
- the cellulose-containing biomass was immersed in a 1% sulfuric acid aqueous solution and autoclaved (manufactured by Nitto Koatsu) at 150 ° C. for 30 minutes. After the treatment, solid-liquid separation was performed to separate into an aqueous sulfuric acid solution and sulfuric acid-treated cellulose. Next, after mixing with sulfuric acid-treated cellulose and dilute sulfuric acid-treated liquid so that the solid content concentration becomes 10% by weight, the pH was adjusted to around 7.0 with sodium hydroxide.
- a crudely purified cellulase derived from Trichoderma reesei was added as a saccharifying enzyme, and a hydrolysis reaction was performed while stirring and mixing at 40 ° C. for 1 day. Thereafter, centrifugation (3000 G) was performed to separate and remove undegraded cellulose or lignin to obtain an aqueous sugar solution.
- Reference Example 3 Pretreatment of cellulose-containing biomass (steaming explosion treatment / saccharification enzyme treatment) Rice straw was used as the cellulose-containing biomass. 100 g of the cellulose-containing biomass is put into a 2 L steaming explosion tester (manufactured by Nippon Electric Heating Co., Ltd.), steam is put into it, the pressure is kept at 2.5 MPa for 2.5 minutes, the inside of the container is opened to the atmosphere at once, and the explosion is performed A sample was collected. The temperature in the container at this time was 225 ° C. The water content of the treated product at this time was 84.4%. Water was added so that the solid concentration was 10% by weight, and a 1N aqueous sodium hydroxide solution was added to adjust the pH to 7.0.
- a crudely purified cellulase derived from Trichoderma reesei was added as a saccharifying enzyme, and a hydrolysis reaction was performed while stirring and mixing at 40 ° C. for 1 day. Thereafter, centrifugation (3000 G) was performed to separate and remove undegraded cellulose or lignin to obtain an aqueous sugar solution.
- Reference Example 4 Hydrolysis process of cellulose-containing biomass (hydrothermal treatment / saccharifying enzyme treatment) Rice straw was used as the cellulose-containing biomass.
- the cellulose-containing biomass was immersed in water and autoclaved (manufactured by Nitto Koatsu Co., Ltd.) at 180 ° C. for 20 minutes while stirring. The pressure at that time was 10 MPa.
- the solution component and the treated biomass component were subjected to solid-liquid separation using centrifugation (3000 G). The pH of the solution was adjusted to around 7.0 with sodium hydroxide.
- a crudely purified cellulase derived from Trichoderma reesei was added as a saccharifying enzyme, and a hydrolysis reaction was performed while stirring and mixing at 40 ° C. for 1 day. Thereafter, centrifugation (3000 G) was performed to separate and remove undegraded cellulose or lignin to obtain an aqueous sugar solution.
- Reference Example 5 Cellulose-containing biomass hydrolysis process (ammonia treatment / saccharification enzyme treatment) Rice straw was used as the cellulose-containing biomass.
- the cellulose-containing biomass was charged into a small reactor (TVS-N2 30 ml, pressure-resistant glass industry) and cooled with liquid nitrogen. A 100% concentration of ammonia gas was introduced into the reactor, and the sample was completely immersed in 100% liquid ammonia.
- the reactor lid was closed and left at room temperature for about 15 minutes. Subsequently, it processed in the 150 degreeC oil bath for 1 hour. After the treatment, the reactor was taken out of the oil bath, and immediately after the ammonia gas leaked in the draft, the reactor was evacuated to 10 Pa with a vacuum pump to dry the cellulose-containing biomass.
- the treated cellulose-containing biomass and pure water were stirred and mixed so that the solid content concentration was 15% by weight, and then the pH was adjusted to around 7.0 with sulfuric acid and sodium oxide.
- a crudely purified cellulase derived from Trichoderma reesei was added as a saccharifying enzyme, and a hydrolysis reaction was performed while stirring and mixing at 40 ° C. for 1 day. Thereafter, centrifugation (3000 G) was performed to obtain an aqueous sugar solution from which undegraded cellulose or lignin was separated and removed.
- Reference Example 6 Hydrolysis process of cellulose-containing biomass (sodium hydroxide treatment / saccharification enzyme treatment) Rice straw was used as the cellulose-containing biomass. It was immersed in an aqueous sodium hydroxide solution so that the amount of alkali added to the cellulose-containing biomass was 10% by weight, and autoclaved (manufactured by Nitto Koatsu Co., Ltd.) at 80 ° C. for 3 hours. After the treatment, solid-liquid separation was performed to separate into an aqueous sodium hydroxide solution and sodium hydroxide-treated cellulose.
- the mixture was stirred and mixed with sodium hydroxide-treated cellulose and sodium hydroxide-treated liquid so that the solid content concentration became 10% by weight, and then the pH was adjusted to around 7 with hydrochloric acid.
- a crudely purified cellulase derived from Trichoderma reesei was added as a saccharifying enzyme, and a hydrolysis reaction was performed while stirring and mixing at 40 ° C. for 1 day. Thereafter, centrifugation (3000 G) was performed to separate and remove undegraded cellulose or lignin to obtain an aqueous sugar solution.
- Reference Example 7 Microfiltration membrane and ultrafiltration membrane treatment of aqueous sugar solution
- the aqueous sugar solution described in Reference Examples 2 to 6 was filtered using a microfiltration membrane (product name: slurry cup, pore size: 0.45 ⁇ m).
- the permeated liquid of the microfiltration membrane was filtered using an ultrafiltration membrane and a flat membrane filtration unit “SEPA-II” (manufactured by GE Osmonix) under the conditions of a membrane surface linear velocity of 20 cm / sec and a filtration pressure of 1 MPa. And filtered until a permeation flux of 0.5 m / day was obtained.
- As the ultrafiltration membrane “M-U1812” (manufactured by Applied Membrane, material: polyethersulfone, molecular weight cut-off: 10,000) was used.
- Reference Example 8 Measurement of sugar concentration The concentration of glucose, xylose, xylobiose, and xylotriose in the sugar solution was measured using the Hitachi high-performance liquid chromatograph “LaChrom Eite” (HITACHI) under the following conditions: glucose, xylose, xylobiose Quantitative analysis was performed based on a calibration curve prepared with a xylotriose preparation.
- Mobile phase Water detection method: RI Flow rate: 0.5 mL / min Temperature: 75 ° C.
- Example 1 Filtration treatment using a separation membrane having a molecular weight cut off of 300 to 500
- the solution was concentrated to a flux of 0.5 m / D under a membrane surface velocity of 20 cm / second and a filtration pressure of 4 MPa. Three times the amount of RO water was added.
- Example 2 Reverse Osmosis Membrane Treatment of Separation Membrane Permeation Liquid with Fraction Molecular Weight 300-500 All the permeation liquids of the separation membrane described in Example 1 were combined, and the reverse osmosis membrane and flat membrane filtration unit “SEPA-II” (GE Osmonics) The product was filtered under the conditions of a membrane surface linear velocity of 20 cm / sec and a filtration pressure of 1 MPa, and the filtration treatment was performed until the permeation flux became 0.5 m / day.
- SEPA-II GE Osmonics
- Example 3 Filtration treatment using a separation membrane having a fractional molecular weight of 600 to 800
- the solution was concentrated to a flux of 0.5 m / D under a membrane surface velocity of 20 cm / second and a filtration pressure of 4 MPa. Three times the amount of RO water was added.
- Example 4 Reverse Osmosis Membrane Treatment of Separation Membrane Permeate with Fraction Molecular Weight 600-800 All the permeate permeation of the separation membrane described in Example 3 were combined, and the reverse osmosis membrane and flat membrane filtration unit “SEPA-II” (GE Osmonics) The product was filtered under the conditions of a membrane surface linear velocity of 20 cm / sec and a filtration pressure of 1 MPa, and the filtration treatment was performed until the permeation flux became 0.5 m / day.
- SEPA-II GE Osmonics
- “FRH-2514” manufactured by ROPUR, material: cross-linked wholly aromatic polyamide, NaCl removal rate: 99%, fractional molecular weight: 100 or less
- the obtained permeate was concentrated to obtain a permeate.
- the permeate was concentrated under reduced pressure to Brix 74 to obtain a sugar solution.
- the composition of the obtained sugar solution is shown in Table 2. This example can also be applied to a permeate obtained according to Reference Examples 7 and 3 using the sugar aqueous solution of any of Reference Examples 2 to 5 as a raw material, and a sugar liquid can be obtained in the same manner.
- Example 5 Examination of hydrogenation reaction of sugar solution using Raney nickel catalyst To the sugar solution (400 mg) described in Example 2, Raney nickel catalyst (R-2313A, 4 mg) manufactured by Nikko Guatemala Co., Ltd. and ion-exchanged water (20 mL) And a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. 30 minutes later, after cooling to room temperature and substituting the system with nitrogen, glucose, xylose, sorbitol, and xylitol in the reaction solution were quantified by the saccharide determination method described in Reference Example 8, and the molar yield of sorbitol from glucose was determined.
- Example 6 Examination of hydrogenation reaction of sugar liquid using 5% activated carbon-supported ruthenium catalyst (Ru / C catalyst)
- Example 6 Hydrogenation of sugar liquid using 5% activated carbon-supported ruthenium catalyst (Ru / C catalyst) Reaction Study 5% Ru / C (manufactured by NE CHEMCAT, AC-4503, 4 mg) and ion-exchanged water (20 mL) were added to the sugar solution (399 mg) described in Example 2, hydrogen pressure 5 MPa, temperature Hydrogenation reaction was performed at 100 degreeC. After 30 minutes, the system was cooled to room temperature, and the system was purged with nitrogen.
- Example 7 Hydrogenation reaction of sugar solution using Raney nickel catalyst To the sugar solution (400 mg) described in Example 4, Raney nickel catalyst (R-2313A, 4 mg) manufactured by Nikko Guatemala Co., Ltd. and ion-exchanged water (20 mL) And a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and substituting the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the molar yield was calculated. As a result, sorbitol was 41% and xylitol was 84% (Table 3). ). Even if the same operation as in this example is carried out using the sugar aqueous solution of any of Reference Examples 2 to 5 as a raw material, the sugar alcohol can be similarly obtained.
- Example 8 Examination of hydrogenation reaction of sugar solution using 5% activated carbon-supported ruthenium catalyst (Ru / C catalyst) 5% Ru / C (NE CHEMCAT) was added to the sugar solution (399 mg) described in Example 4. Manufactured, AC-4503, 4 mg) and ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and substituting the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the molar yield was calculated. As a result, sorbitol was 38% and xylitol was 79% (Table 3). ). Even if the same operation as in this example is carried out using the sugar aqueous solution of any of Reference Examples 2 to 5 as a raw material, the sugar alcohol can be similarly obtained.
- Ru / C catalyst activated carbon-supported ruthenium catalyst
- Ru / C 5% Ru /
- Comparative Example 1 Examination of hydrogenation reaction of catalyst poison-containing sugar solution using Raney nickel catalyst
- the catalyst solution-containing separation membrane non-permeate solution liquid (201 mg) described in Example 1 was added to the sugar solution (202 mg) described in Example 2.
- Raney nickel catalyst (Nikko Rika Co., Ltd., R-2313A, 4 mg) and ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and substituting the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the molar yield was calculated to be sorbitol 7% and xylitol 27% (Table 3).
- Comparative Example 2 Examination of Hydrogenation Reaction of Catalyst Poison-Containing Sugar Liquid Using 5% Ru / C Catalyst
- the separation liquid concentrate (201 mg containing catalyst poison described in Example 1 was added to the sugar liquid described in Example 2 (202 mg).
- 5% Ru / C manufactured by NE CHEMCAT, AC-4503, 4 mg
- ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C.
- Example 3 After 30 minutes, after cooling to room temperature and substituting the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the molar yield was calculated to be sorbitol 7% and xylitol 27% (Table 3). Since the ruthenium catalyst was poisoned by the catalyst poison contained in the concentrate described in Example 1, the molar yield was remarkably reduced. Even when the same operation as in this comparative example is carried out using the aqueous sugar solution of any of Reference Examples 2 to 5 as a raw material, the molar yield similarly decreases.
- Comparative Example 3 Examination of hydrogenation reaction using Raney nickel catalyst after poisoning
- the Raney nickel catalyst used in Comparative Example 1 (R-2313A, R-2313A, 4 mg) was ionized into the sugar solution (202 mg) described in Example 2. It was washed with exchanged water (50 mL), collected, and added again. After dilution with ion-exchanged water (20 mL), a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and nitrogenizing the system, the reaction solution was quantified in the same manner as in Example 5 and the yield was calculated. As a result, sorbitol was 6% and xylitol was 25% (Table 3).
- Comparative Example 4 Examination of hydrogenation reaction with 5% Ru / C catalyst after poisoning 5% Ru / C (manufactured by NE CHEMCAT) used in Comparative Example 2 was added to the sugar solution (202 mg) described in Example 2. , AC-4503, 4 mg) was washed with ion-exchanged water (50 mL), recovered, and added again. After dilution with ion-exchanged water (20 mL), a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, the system was cooled to room temperature, and the system was purged with nitrogen. Then, the reaction solution was quantified in the same manner as in Example 5, and the yield was calculated.
- Comparative Example 5 Examination of hydrogenation reaction of catalyst poison-containing sugar solution using Raney nickel catalyst
- the catalyst solution-containing separation membrane non-permeate liquid solution (201 mg) described in Example 2 was added to the sugar solution (202 mg) described in Example 4.
- Raney nickel catalyst (Nikko Rika Co., Ltd., R-2313A, 4 mg) and ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and substituting the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the molar yield was calculated.
- Comparative Example 6 Examination of Hydrogenation Reaction of Catalyst Poison-Containing Sugar Solution Using 5% Ru / C Catalyst
- the catalyst solution-containing separation membrane concentrate (201 mg) described in Example 3 was added to the sugar solution (202 mg) described in Example 4.
- 5% Ru / C manufactured by NE CHEMCAT, AC-4503, 4 mg
- ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and substituting the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the molar yield was calculated.
- Comparative Example 7 Investigation of hydrogenation reaction using Raney nickel catalyst after poisoning
- the Raney nickel catalyst used in Comparative Example 6 (R-2313A, R-2313A, 4 mg) was ionized in the sugar solution (202 mg) described in Example 4. It was washed with exchanged water (50 mL), collected, and added again. After dilution with ion-exchanged water (20 mL), a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and substituting the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the yield was calculated. As a result, sorbitol was 12% and xylitol was 54% (Table 3).
- Comparative Example 8 Investigation of hydrogenation reaction with 5% Ru / C catalyst after poisoning 5% Ru / C (manufactured by NE CHEMCAT) used in Comparative Example 5 was added to the sugar solution (202 mg) described in Example 4. , AC-4503, 4 mg) was washed with ion-exchanged water (50 mL), recovered, and added again. After dilution with ion-exchanged water (20 mL), a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and substituting the inside of the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the yield was calculated.
- Comparative Example 9 Hydrogenation reaction study of ultrafiltration membrane permeate using Raney nickel catalyst To the ultrafiltration membrane permeate (402 mg) described in Reference Example 7, Raney nickel catalyst (Nikko Jamaica Co., Ltd., R-2313A, 4 mg) ) And ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and substituting the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the molar yield was calculated. As a result, the sorbitol was 28% and xylitol was 71%.
- Comparative Example 10 Examination of Hydrogenation Reaction of Ultrafiltration Membrane Permeate Using 5% Ru / C Catalyst
- the ultrafiltration membrane permeate (402 mg) described in Reference Example 7 was added to 5% Ru / C (NE CHEMCAT, AC-4503, 4 mg) and ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 30 minutes, after cooling to room temperature and substituting the system with nitrogen, the reaction solution was quantified in the same manner as in Example 5 and the molar yield was calculated. As a result, sorbitol was 23% and xylitol was 66%.
- Example 9 Heat dehydration study using a raw material having a sugar alcohol concentration of 80% at a reaction temperature of 140 ° C
- the Raney nickel catalyst (R-2313A, 4mg) manufactured by Nikko Guatemala Co., Ltd. was added to the sugar solution (200mg) described in Example 2.
- ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C.
- Example 10 Heat dehydration study using a raw material having a sugar alcohol concentration of 80% at a reaction temperature of 150 ° C.
- a Raney nickel catalyst (R-2313A, 4 mg) was added to the sugar solution (200 mg) described in Example 2.
- ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C.
- the molar yield of xylitol was calculated and found to be 99% sorbitol and 99% xylitol.
- the reaction solution was filtered through Celite and then concentrated under reduced pressure to a sugar alcohol concentration of 80%. After heating to 150 ° C., concentrated sulfuric acid (manufactured by Kanto Chemical Co., Ltd., special grade, 2 mg) was added, and the pressure was reduced to 300 Pa. After stirring at 150 ° C. for 1 hour, the mixture was cooled to room temperature and returned to atmospheric pressure.
- Example 11 Heat dehydration study using a raw material having a sugar alcohol concentration of 80% at a reaction temperature of 160 ° C.
- the Raney nickel catalyst (R-2313A, 4 mg) was added to the sugar solution (200 mg) described in Example 2. And ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C. After 3 hours, after cooling to room temperature and substituting the system with nitrogen, glucose, xylose, sorbitol, and xylitol in the reaction solution were quantified by the quantitative method described in Reference Example 8, and the molar yield of sorbitol from glucose, xylose was determined. From the above, the molar yield of xylitol was calculated and found to be 99% sorbitol and 99% xylitol.
- the reaction solution was filtered through Celite and then concentrated under reduced pressure to a sugar alcohol concentration of 80%. After heating to 160 ° C., concentrated sulfuric acid (manufactured by Kanto Chemical Co., Ltd., special grade, 2 mg) was added, and the pressure was reduced to 300 Pa. After stirring at 160 ° C. for 1 hour, the mixture was cooled to room temperature and returned to atmospheric pressure. After dilution with ion-exchanged water (10 mL), analysis was performed by the analysis method described in Reference Example 8, and sorbitol to sorbitan, isosorbide molar yield, and xylitol to xylitan molar yield were calculated.
- Example 12 Heat dehydration study using a raw material having a sugar alcohol concentration of 60% at a reaction temperature of 140 ° C.
- Raney nickel catalyst (R-2313A, Nikko Rika Co., Ltd., 4 mg) was added to the sugar solution (200 mg) described in Example 2.
- ion-exchanged water (20 mL) were added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and a temperature of 100 ° C.
- Example 13 Preparation of sorbitan / xylitan laurate mixture
- the anhydrous sugar alcohol solution described in Example 7 was dehydrated at 75 ° C for 10 minutes under a reduced pressure of 400 Pa.
- 212 mg (1.3 mmol) of lauric acid manufactured by Kanto Chemical Co., Inc.
- 5.4 mg (0.1 mmol) of sodium hydroxide was added as a catalyst
- the acid value was 10 at 200 ° C. in a nitrogen gas stream under normal pressure.
- the esterification reaction was carried out for 6 hours until the following.
- the obtained reaction mixture was cooled to 180 ° C., 39.4 mg of phosphoric acid (85% by mass) was added to neutralize the catalyst, and a sorbitan / xylitan lauric acid ester mixture (311 mg) was obtained.
- This product had an acid value of 3.3 and a hydroxyl value of 220 (Table 5). Even when the same operation as in this example is carried out using the sugar aqueous solution of any of Reference Examples 2 to 5 as a raw material, the anhydrous sugar alcohol can be similarly obtained.
- Example 14 Production of sorbitan / xilitan palmitate ester mixture
- the anhydrous sugar alcohol solution described in Example 7 was dehydrated at 75 ° C for 10 minutes under reduced pressure of 400 Pa. Next, 344 mg (1.3 mmol) of palmitic acid (manufactured by Kanto Chemical Co., Inc.) was charged, 5.4 mg (0.1 mmol) of sodium hydroxide was added as a catalyst, and the acid value was 10 at 200 ° C. in a nitrogen gas stream under normal pressure. The esterification reaction was performed for 6 hours until the following.
- the obtained reaction mixture was cooled to 180 ° C., 39.4 mg of phosphoric acid (85% by mass) was added to neutralize the catalyst, and a sorbitan / xilitan palmitate ester mixture (392 mg) was obtained.
- This product had an acid value of 3.8 and a hydroxyl value of 250 (Table 5). Even when the same operation as in this example is carried out using the sugar aqueous solution of any of Reference Examples 2 to 5 as a raw material, the anhydrous sugar alcohol can be similarly obtained.
- Example 15 Preparation of sorbitan / xylitan stearate mixture
- the anhydrous sugar alcohol solution described in Example 7 was dehydrated at 75 ° C for 10 minutes under a reduced pressure of 400 Pa.
- 381 mg (1.3 mmol) of stearic acid manufactured by Kanto Chemical Co., Inc.
- 5.4 mg (0.1 mmol) of sodium hydroxide was added as a catalyst
- the acid value was 10 at 200 ° C. in a nitrogen gas stream under normal pressure.
- the esterification reaction was performed for 6 hours until the following.
- Example 16 Preparation of sorbitan / xylitan oleate mixture
- the anhydrous sugar alcohol solution described in Example 7 was dehydrated at 75 ° C for 10 minutes under reduced pressure of 400 Pa.
- 381 mg (1.3 mmol) of oleic acid manufactured by Kanto Chemical Co., Inc.
- 5.4 mg (0.1 mmol) of sodium hydroxide was added as a catalyst, and the acid value was 200 ° C. in a nitrogen gas stream under normal pressure.
- the esterification reaction was performed for 6 hours until it became 10 or less.
- the obtained reaction mixture was cooled to 180 ° C., and 39.4 mg of phosphoric acid (85% by mass) was added to neutralize the catalyst to obtain a sorbitan / xylitan oleate mixture (392 mg).
- the acid value was 3.7 and the hydroxyl value was 240 (Table 5). Even when the same operation as in this example is carried out using the sugar aqueous solution of any of Reference Examples 2 to 5 as a raw material, the anhydrous sugar alcohol can be similarly obtained.
- an aqueous solution of sugar obtained by hydrolyzing cellulose-containing biomass is filtered through a separation membrane having a molecular weight cut off of 300 to 800, so that the catalyst poison is removed to the non-permeation side, and the sugar solution is introduced from the permeation side. And the resulting sugar solution is hydrogenated under a metal catalyst to produce a sugar alcohol in high yield.
- an anhydrous sugar alcohol can be produced in high yield by subjecting the sugar alcohol to heat dehydration by acting an acid catalyst.
- an anhydrous sugar alcohol ester can be manufactured by heating an anhydrous sugar alcohol in the presence of a fatty acid and a solid base.
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Abstract
Description
[1]セルロース含有バイオマスを原料として糖アルコールを製造する方法であって、
工程(1):セルロース含有バイオマスの加水分解により得られた糖水溶液を分画分子量300~800の分離膜に通じて濾過して、触媒毒を非透過側に除去し、透過側から糖液を回収する工程、および
工程(2):工程(1)で得られた糖液を金属触媒の存在下、水素添加反応する工程、
を含む、糖アルコールの製造方法。
[2]前記工程(1)の分離膜が分画分子量300~500の分離膜である、[1]に記載の糖アルコールの製造方法。
[3]前記工程(1)の分離膜が分画分子量600~800の分離膜である、[1]に記載の糖アルコールの製造方法。
[4]前記工程(2)において、金属触媒がルテニウム触媒またはラネーニッケル触媒である、[1]~[3]のいずれかに記載の糖アルコールの製造方法。
[5]糖アルコールがソルビトールおよび/またはキシリトールを主成分とする、[1]~[4]のいずれかに記載の糖アルコールの製造方法。
[6][1]~[5]のいずれかに記載の製造方法によって糖アルコールを製造する工程、および糖アルコールを脱水反応に供する工程を含む、無水糖アルコールの製造方法。
[7]無水糖アルコールがソルビタンおよび/またはキシリタンを主成分とする、[6]に記載の無水糖アルコールの製造方法。
[8][1]~[5]のいずれかに記載の製造方法によって糖アルコールを製造する工程、[6]に記載の製造方法によって無水糖アルコールを製造する工程、および無水糖アルコールと飽和または不飽和脂肪酸との縮合反応に供する工程を含む、無水糖アルコールエステルの製造方法。
[9]無水糖アルコールエステルがソルビタンエステルおよび/またはキシリタンエステルを主成分とする、[8]に記載の無水糖アルコールエステルの製造方法。
中和式(1):3NaOH+H3PO4→Na3PO4+H2O。
トリコデルマ属由来粗精製セルラーゼは以下の方法で調製した。
コーンスティップリカー5%(w/vol)、グルコース2%(w/vol)、酒石酸アンモニウム0.37%(w/vol)、硫酸アンモニウム0.14(w/vol)、リン酸二水素カリウム0.2%(w/vol)、塩化カルシウム二水和物0.03%(w/vol)、硫酸マグネシウム七水和物0.03%(w/vol)、塩化亜鉛0.02%(w/vol)、塩化鉄(III)六水和物0.01%(w/vol)、硫酸銅(II)五水和物0.004%(w/vol)、塩化マンガン四水和物0.0008%(w/vol)、ホウ酸0.0006%(w/vol)、七モリブデン酸六アンモニウム四水和物0.0026%(w/vol)となるよう蒸留水に添加し、100mLを500mLバッフル付き三角フラスコに張り込み、121℃で15分間オートクレーブ滅菌した。放冷後、これとは別にそれぞれ121℃で15分間オートクレーブ滅菌したPE-MとTween80をそれぞれ0.01%(w/vol)添加した。この前培養培地にトリコデルマ・リーセイATCC66589(ATCCより分譲)を1×105個/mLになるように植菌し、28℃、72時間、180rpmで振とう培養し、前培養とした(振とう装置:TAITEC社製 BIO-SHAKER BR-40LF)。
コーンスティップリカー5%(w/vol)、グルコース2%(w/vol)、セルロース(アビセル)10%(w/vol)、酒石酸アンモニウム0.37%(w/vol)、硫酸アンモニウム0.14%(w/vol)、リン酸二水素カリウム0.2%(w/vol)、塩化カルシウム二水和物0.03%(w/vol)、硫酸マグネシウム七水和物0.03%(w/vol)、塩化亜鉛0.02%(w/vol)、塩化鉄(III)六水和物0.01%(w/vol)、硫酸銅(II)五水和物0.004%(w/vol)、塩化マンガン四水和物0.0008%(w/vol)、ホウ酸0.0006%(w/vol)、七モリブデン酸六アンモニウム四水和物0.0026%(w/vol)となるよう蒸留水に添加し、2.5Lを5L容撹拌ジャー(ABLE社製 DPC-2A)容器に張り込み、121℃で15分間オートクレーブ滅菌した。放冷後、これとは別にそれぞれ121℃で15分間オートクレーブ滅菌したPE-MとTween80をそれぞれ0.1%添加し、あらかじめ前記の方法にて液体培地で前培養したトリコデルマ・リーセイPC3-7を250mL接種した。その後、28℃、87時間、300rpm、通気量1vvmにて培養を行い、遠心分離後、上清を膜濾過(ミリポア社製 ステリカップ-GV 材質:PVDF)した。この前述条件で調製した培養液に対し、β-グルコシダーゼ(Novozyme188)をタンパク質重量比として、1/100量添加し、これを粗精製セルラーゼとした。
セルロース含有バイオマスとして、稲藁を使用した。前記セルロース含有バイオマスを硫酸1%水溶液に浸し、150℃で30分オートクレーブ処理(日東高圧製)した。処理後、固液分離を行い、硫酸水溶液と硫酸処理セルロースに分離した。次に硫酸処理セルロースと固形分濃度が10重量%となるように希硫酸処理液と攪拌混合した後、水酸化ナトリウムによって、pHを7.0付近に調整した。この混合液に、糖化酵素としてトリコデルマ・リーセイ由来の粗精製セルラーゼを添加し、40℃で1日間攪拌混同しながら、加水分解反応を行った。その後、遠心分離(3000G)を行い、未分解セルロースあるいはリグニンを分離除去し、糖水溶液を得た。
セルロース含有バイオマスとして、稲藁を使用した。前記セルロース含有バイオマス100gを2L蒸煮爆砕試験機(日本電熱株式会社製)に投入して蒸気を投入し、2.5MPaで2.5分間保持して容器内を一気に大気開放し、爆砕処理を行いサンプルを回収した。この時の容器内の温度は225℃であった。この時の処理物の含水率は84.4%であった。固形分濃度が10重量%となるように水を加えpHを1規定の水酸化ナトリウム水溶液を添加してpHを7.0に調整した。この混合液に、糖化酵素としてトリコデルマ・リーセイ由来の粗精製セルラーゼを添加し、40℃で1日間攪拌混同しながら、加水分解反応を行った。その後、遠心分離(3000G)を行い、未分解セルロースあるいはリグニンを分離除去し、糖水溶液を得た。
セルロース含有バイオマスとして、稲藁を使用した。前記セルロース含有バイオマスを水に浸し、撹拌しながら180℃で20分間オートクレーブ処理(日東高圧株式会社製)した。その際の圧力は10MPaであった。処理後は溶液成分と処理バイオマス成分に遠心分離(3000G)を用いて固液分離した。水酸化ナトリウムによって、溶液のpHを7.0付近に調整した。この混合液に、糖化酵素としてトリコデルマ・リーセイ由来の粗精製セルラーゼを添加し、40℃で1日間攪拌混同しながら、加水分解反応を行った。その後、遠心分離(3000G)を行い、未分解セルロースあるいはリグニンを分離除去し、糖水溶液を得た。
セルロース含有バイオマスとして、稲藁を使用した。前記セルロース含有バイオマスを小型反応器(耐圧硝子工業株式会社製、TVS-N2 30ml)に投入し、液体窒素で冷却した。この反応器に濃度100%のアンモニアガスを流入し、試料を完全に100%の液体アンモニアに浸漬させた。リアクターの蓋を閉め、室温で15分ほど放置した。次いで、150℃のオイルバス中にて1時間処理した。処理後、反応器をオイルバスから取り出し、ドラフト中で直ちに前記アンモニアガスをリーク後、さらに真空ポンプで反応器内を10Paまで真空引きし前記セルロース含有バイオマスを乾燥させた。この処理セルロース含有バイオマスと固形分濃度が15重量%となるように純水を攪拌混合した後、硫酸によって、酸化ナトリウムによって、pHを7.0付近に調整した。この混合液に、糖化酵素としてトリコデルマ・リーセイ由来の粗精製セルラーゼを添加し、40℃で1日間攪拌混同しながら、加水分解反応を行った。その後、遠心分離(3000G)を行い、未分解セルロースあるいはリグニンを分離除去した糖水溶液を得た。
セルロース含有バイオマスとして、稲藁を使用した。前記セルロース含有バイオマスに対するアルカリ添加量が10重量%になるように、水酸化ナトリウム水溶液に浸し、80℃で3時間オートクレーブ処理(日東高圧株式会社製)した。処理後、固液分離を行い、水酸化ナトリウム水溶液と水酸化ナトリウム処理セルロースに分離した。次に水酸化ナトリウム処理セルロースと固形分濃度が10重量%となるように水酸化ナトリウム処理液と攪拌混合した後、塩酸によって、pHを7付近に調整した。この混合液に、糖化酵素としてトリコデルマ・リーセイ由来の粗精製セルラーゼを添加し、40℃で1日間攪拌混同しながら、加水分解反応を行った。その後、遠心分離(3000G)を行い、未分解セルロースあるいはリグニンを分離除去し、糖水溶液を得た。
参考例2~6記載の糖水溶液を精密濾過膜(製品名:スラリーカップ、孔径:0.45μm)を用いて濾過を行った。次に、精密濾過膜の透過液について限外濾過膜および平膜濾過ユニット“SEPA-II”(GEオスモニクス製)を用いて、膜面線速度20cm/秒、濾過圧1MPaの条件下で濾過を行い、透過流束が0.5m/dayになるまで濾過処理を行って透過液を得た。限外濾過膜は、“M-U1812”(Applied Membrane社製、材質:ポリエーテルスルホン、分画分子量:10000)を使用した。
糖液中のグルコース、キシロース、キシロビオース、キシロトリオースの濃度は、日立高速液体クロマトグラフ“LaChrom Eite”(HITACHI)を用いて、以下の条件でグルコース、キシロース、キシロビオース、キシロトリオースの標品で作製した検量線をもとに、定量分析した。
カラム:KS802、KS803(Shodex)
移動相:水
検出方法:RI
流速:0.5mL/min
温度:75℃。
参考例7記載の糖水溶液を精密濾過膜及び限外濾過膜処理して得られた透過液を分画分子量300~500の分離膜および平膜濾過ユニット“SEPA-II”(GEオスモニクス製)を用いて、膜面線速度20cm/秒、濾過圧4MPaの条件下で、Fluxが0.5m/Dになるまで濃縮し、3倍量のRO水を添加した。同様の方法で濃縮とRO水の添加を二回繰り返した後に、透過流束が0.5m/dayになるまで濃縮し、触媒毒が含有された非透過液と透過液の濾過処理を行った。本実施例は、参考例2~5のいずれかの糖水溶液を参考例7記載の精密濾過膜及び限外濾過膜処理して得られた透過液にも適用できる。
実施例1記載の分離膜の透過液を全て合わせ、逆浸透膜および平膜濾過ユニット“SEPA-II”(GEオスモニクス製)を用いて、膜面線速度20cm/秒、濾加圧1MPaの条件下で濾過を行い、透過流束が0.5m/dayになるまで濾過処理を行った。逆浸透膜は、“FRH-2514”(ROPUR社製、材質:架橋全芳香族ポリアミド、NaCl除去率:99%、分画分子量:100以下)を使用した。得られた透過液をBrix74まで減圧濃縮し、糖液を得た。得られた糖液の組成を表1に示す。本実施例は、参考例2~5のいずれかの糖水溶液を原料として、参考例7及び実施例1に準じて得られた透過液にも適用でき、同様に糖液を得ることができる。
参考例7記載の糖水溶液を精密濾過膜及び限外濾過膜処理して得られた透過液を分画分子量600~800の分離膜および平膜濾過ユニット“SEPA-II”(GEオスモニクス製)を用いて、膜面線速度20cm/秒、濾過圧4MPaの条件下で、Fluxが0.5m/Dになるまで濃縮し、3倍量のRO水を添加した。同様の方法で濃縮とRO水の添加を二回繰り返した後に、透過流束が0.5m/dayになるまで濃縮し、触媒毒が含有された非透過液と透過液の濾過処理を行い、透過液を回収した。分離膜は、“1812F”(SYNDER社製、材質:ポリアミド、分画分子量:600~800)を使用した。本実施例は、参考例2~5のいずれかの糖水溶液を参考例7記載の精密濾過膜及び限外濾過膜処理して得られた透過液にも適用できる。
実施例3記載の分離膜の透過液を全て合わせ、逆浸透膜および平膜濾過ユニット“SEPA-II”(GEオスモニクス製)を用いて、膜面線速度20cm/秒、濾加圧1MPaの条件下で濾過を行い、透過流束が0.5m/dayになるまで濾過処理を行った。逆浸透膜は、“FRH-2514”(ROPUR社製、材質:架橋全芳香族ポリアミド、NaCl除去率:99%、分画分子量:100以下)を使用した。得られた透過液を濃縮し、透過液を得た。透過液をBrix74まで減圧濃縮し、糖液を得た。得られた糖液の組成を表2に示す。本実施例は、参考例2~5のいずれかの糖水溶液を原料として、参考例7及び実施例3に準じて得られた透過液にも適用でき、同様に糖液を得ることができる。
実施例2記載の糖液(400mg)に、ラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、反応液中のグルコース、キシロース、ソルビトール、キシリトールを参考例8に記載の糖類の定量方法によって定量し、グルコースからソルビトールのモル収率、キシロースからキシリトールのモル収率をそれぞれ算出したところ、ソルビトール55%、キシリトール90%であった(表3)。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に糖アルコールを得ることができる。 実施例6:5%活性炭担持ルテニウム触媒(Ru/C触媒)を用いた糖液の水素添加反応検討
実施例6:5%活性炭担持ルテニウム触媒(Ru/C触媒)を用いた糖液の水素添加反応検討
実施例2記載の糖液(399mg)に、5%Ru/C(N.E.CHEMCAT社製、AC-4503、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、モル収率を算出したところ、ソルビトール52%、キシリトール88%であった(表3)。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に糖アルコールを得ることができる。
実施例4記載の糖液(400mg)に、ラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、モル収率を算出したところ、ソルビトール41%、キシリトール84%であった(表3)。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に糖アルコールを得ることができる。
実施例4記載の糖液(399mg)に、5%Ru/C(N.E.CHEMCAT社製、AC-4503、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、モル収率を算出したところ、ソルビトール38%、キシリトール79%であった(表3)。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に糖アルコールを得ることができる。
実施例2記載の糖液(202mg)に、実施例1記載の触媒毒含有の分離膜非透過液液(201mg)、ラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、モル収率を算出したところ、ソルビトール7%、キシリトール27%であり(表3)、ラネーニッケル触媒が実施例1記載の非透過液に含有されていた触媒毒によって被毒されたため、収率は顕著に低下した。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
実施例2記載の糖液(202mg)に、実施例1記載の触媒毒含有の分離膜濃縮液(201mg)、5%Ru/C(N.E.CHEMCAT社製、AC-4503、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、モル収率を算出したところ、ソルビトール7%、キシリトール27%であり(表3)、ルテニウム触媒が実施例1記載の濃縮液に含有されていた触媒毒によって被毒されたため、モル収率は顕著に低下した。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
実施例2記載の糖液(202mg)に、比較例1で用いたラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)をイオン交換水(50mL)で洗浄、回収し、再度添加した。イオン交換水(20mL)で希釈した後に、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素した後に、実施例5と同様に反応液を定量し、収率を算出したところ、ソルビトール6%、キシリトール25%であった(表3)。したがって、比較例1で被毒されたラネーニッケル触媒は洗浄操作を行っても活性は戻らず、モル収率は低下したままであった。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
実施例2記載の糖液(202mg)に、比較例2で用いた5%Ru/C(N.E.CHEMCAT社製、AC-4503、4mg)をイオン交換水(50mL)で洗浄、回収し、再度添加した。イオン交換水(20mL)で希釈した後に、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、収率を算出したところ、ソルビトール7%、キシリトール25%であった(表3)。したがって、比較例2で被毒されたルテニウム触媒は洗浄操作を行っても活性は戻らず、モル収率は低下したままであった。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
実施例4記載の糖液(202mg)に、実施例2記載の触媒毒含有の分離膜非透過液液(201mg)、ラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、モル収率を算出したところ、ソルビトール13%、キシリトール53%であり(表3)、ラネーニッケル触媒が実施例1記載の非透過液に含有されていた触媒毒によって被毒されたため、収率は顕著に低下した。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
実施例4記載の糖液(202mg)に、実施例3記載の触媒毒含有の分離膜濃縮液(201mg)、5%Ru/C(N.E.CHEMCAT社製、AC-4503、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、モル収率を算出したところ、ソルビトール13%、キシリトール55%であり(表3)、ルテニウム触媒が実施例1記載の濃縮液に含有されていた触媒毒によって被毒されたため、モル収率は顕著に低下した。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
実施例4記載の糖液(202mg)に、比較例6で用いたラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)をイオン交換水(50mL)で洗浄、回収し、再度添加した。イオン交換水(20mL)で希釈した後に、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、収率を算出したところ、ソルビトール12%、キシリトール54%であった(表3)。したがって、比較例1で被毒されたラネーニッケル触媒は洗浄操作を行っても活性は戻らず、モル収率は低下したままであった。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
実施例4記載の糖液(202mg)に、比較例5で用いた5%Ru/C(N.E.CHEMCAT社製、AC-4503、4mg)をイオン交換水(50mL)で洗浄、回収し、再度添加した。イオン交換水(20mL)で希釈した後に、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、収率を算出したところ、ソルビトール14%、キシリトール53%であった(表3)。したがって、比較例2で被毒されたルテニウム触媒は洗浄操作を行っても活性は戻らず、モル収率は低下したままであった。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
参考例7記載の限外濾過膜透過液(402mg)に、ラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、モル収率を算出したところ、ソルビトール28%、キシリトール71%であり、限外濾過膜処理では残存してしまう触媒毒によってモル収率が低下する結果となった(表3)。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
参考例7記載の限外濾過膜透過液(402mg)に、5%Ru/C(N.E.CHEMCAT社製、AC-4503、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。30分後、室温まで冷却し、系内を窒素置換した後に、実施例5と同様に反応液を定量し、モル収率を算出したところ、ソルビトール23%、キシリトール66%であり、限外濾過膜処理では残存してしまう触媒毒によってモル収率が低下する結果となった(表3)。参考例2~5のいずれかの糖水溶液を原料として本比較例と同様の操作を実施しても、同様にモル収率が低下する。
実施例2記載の糖液(200mg)に、ラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。3時間後、室温まで冷却し、系内を窒素置換した後に、反応液中のグルコース、キシロース、ソルビトール、キシリトールを参考例8に記載の定量法によって定量し、グルコースからソルビトールのモル収率、キシロースからキシリトールのモル収率をそれぞれ算出したところ、ソルビトール99%、キシリトール99%であった。この反応液をセライト濾過した後に、糖アルコール濃度80%まで減圧濃縮した。140℃まで加熱した後に、濃硫酸(関東化学株式会社製、特級、2mg)を添加し、300Paまで減圧した。140℃で1時間攪拌した後、室温まで冷却し、大気圧に戻した。イオン交換水(10mL)を用いて希釈した後に、参考例8に記載の分析法で分析を行い、ソルビトールからソルビタン、イソソルビドのモル収率、キシリトールからキシリタンのモル収率をそれぞれ算出したところ、ソルビタン73%、イソソルビド13%、キシリタン99%(表4)であった。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に無水糖アルコールを得ることができる。
実施例2記載の糖液(200mg)に、ラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。3時間後、室温まで冷却し、系内を窒素置換した後に、反応液中のグルコース、キシロース、ソルビトール、キシリトールを参考例8に記載の定量法によって定量し、グルコースからソルビトールのモル収率、キシロースからキシリトールのモル収率をそれぞれ算出したところ、ソルビトール99%、キシリトール99%であった。この反応液をセライト濾過した後に、糖アルコール濃度80%まで減圧濃縮した。150℃まで加熱した後に、濃硫酸(関東化学株式会社製、特級、2mg)を添加し、300Paまで減圧した。150℃で1時間攪拌した後、室温まで冷却し、大気圧に戻した。イオン交換水(10mL)を用いて希釈した後に、参考例8に記載の分析法で分析を行い、ソルビトールからソルビタン、イソソルビドのモル収率、キシリトールからキシリタンのモル収率をそれぞれ算出したところ、ソルビタン63%、イソソルビド27%、キシリタン99%(表4)であった。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に無水糖アルコールを得ることができる。 実施例11:糖アルコール濃度80%の原料を用いた反応温度160℃での加熱脱水検討
実施例2記載の糖液(200mg)に、ラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。3時間後、室温まで冷却し、系内を窒素置換した後に、反応液中のグルコース、キシロース、ソルビトール、キシリトールを参考例8に記載の定量法によって定量し、グルコースからソルビトールのモル収率、キシロースからキシリトールのモル収率をそれぞれ算出したところ、ソルビトール99%、キシリトール99%であった。この反応液をセライト濾過した後に、糖アルコール濃度80%まで減圧濃縮した。160℃まで加熱した後に、濃硫酸(関東化学株式会社製、特級、2mg)を添加し、300Paまで減圧した。160℃で1時間攪拌した後、室温まで冷却し、大気圧に戻した。イオン交換水(10mL)を用いて希釈した後に、参考例8に記載の分析法で分析を行い、ソルビトールからソルビタン、イソソルビドのモル収率、キシリトールからキシリタンのモル収率をそれぞれ算出したところ、ソルビタン37%、イソソルビド53%、キシリタン99%(表4)であった。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に無水糖アルコールを得ることができる。 実施例12:糖アルコール濃度60%の原料を用いた反応温度140℃での加熱脱水検討
実施例2記載の糖液(200mg)に、ラネーニッケル触媒(日興リカ株式会社製、R-2313A、4mg)とイオン交換水(20mL)を添加し、水素圧5MPa、温度100℃にて水素添加反応を行った。3時間後、室温まで冷却し、系内を窒素置換した後に、反応液中のグルコース、キシロース、ソルビトール、キシリトールを参考例8に記載の定量法によって定量し、グルコースからソルビトールのモル収率、キシロースからキシリトールのモル収率をそれぞれ算出したところ、ソルビトール99%、キシリトール99%であった。この反応液をセライト濾過した後に、糖アルコール濃度60%まで減圧濃縮した。140℃まで加熱した後に、濃硫酸(関東化学株式会社製、特級、2mg)を添加し、300Paまで減圧した。140℃で5時間攪拌した後、室温まで冷却し、大気圧に戻した。イオン交換水(10mL)を用いて希釈した後に、参考例8に記載の分析法で分析を行い、ソルビトールからソルビタン、イソソルビドのモル収率、キシリトールからキシリタンのモル収率をそれぞれ算出したところ、ソルビタン70%、イソソルビド7%、キシリタン99%(表4)であった。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に無水糖アルコールを得ることができる。
実施例7記載の無水糖アルコール溶液を、400Paの減圧下、75℃で10分間脱水した。次にラウリン酸(関東化学株式会社製)212mg(1.3mmol)を仕込み、触媒として水酸化ナトリウム5.4mg(0.1mmol)を加え、常圧下、窒素ガス気流中200℃ で、酸価10以下となるまで6 時間エステル化反応を行った。得られた反応混合物を180℃まで冷却し、リン酸(85質量%)39.4mgを添加して触媒を中和し、ソルビタン/キシリタンラウリン酸エステル混合物(311mg)を得た。このものは酸価:3.3、水酸基価:220であった(表5)。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に無水糖アルコールを得ることができる。
実施例7記載の無水糖アルコール溶液を、400Paの減圧下、75℃で10分間脱水した。次にパルミチン酸(関東化学株式会社製)344mg(1.3mmol)を仕込み、触媒として水酸化ナトリウム5.4mg(0.1mmol)を加え、常圧下、窒素ガス気流中200℃で、酸価10以下となるまで6時間エステル化反応を行った。得られた反応混合物を180℃ まで冷却し、リン酸(85質量%)39.4mgを添加して触媒を中和し、ソルビタン/キシリタンパルミチン酸エステル混合物(392mg)を得た。このものは酸価:3.8、水酸基価:250であった(表5)。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に無水糖アルコールを得ることができる。
実施例7記載の無水糖アルコール溶液を、400Paの減圧下、75℃で10分間脱水した。次にステアリン酸(関東化学株式会社製)381mg(1.3mmol)を仕込み、触媒として水酸化ナトリウム5.4mg(0.1mmol)を加え、常圧下、窒素ガス気流中200℃で、酸価10以下となるまで6時間エステル化反応を行った。得られた反応混合物を180℃まで冷却し、リン酸(85質量%)39.4mgを添加して触媒を中和し、ソルビタン/キシリタンステアリン酸エステル混合物(392mg)を得た。このものは酸価:3.1、水酸基価:210であった(表5)。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に無水糖アルコールを得ることができる。
実施例7記載の無水糖アルコール溶液を、400Paの減圧下、75℃ で10分間脱水した。次にオレイン酸酸(関東化学株式会社製)381mg(1.3mmol) を仕込み、触媒として水酸化ナトリウム5.4mg(0.1mmol)を加え、常圧下、窒素ガス気流中200℃で、酸価10以下となるまで6時間エステル化反応を行った。得られた反応混合物を180℃まで冷却し、リン酸(85質量%)39.4mgを添加して触媒を中和し、ソルビタン/キシリタンオレイン酸エステル混合物(392mg)を得た。このものは酸価:3.7、水酸基価:240であった(表5)。参考例2~5のいずれかの糖水溶液を原料として本実施例と同様の操作を実施しても、同様に無水糖アルコールを得ることができる。
Claims (9)
- セルロース含有バイオマスを原料として糖アルコールを製造する方法であって、
工程(1):セルロース含有バイオマスの加水分解により得られた糖水溶液を分画分子量300~800の分離膜に通じて濾過して、触媒毒を非透過側に除去し、透過側から糖液を回収する工程、および
工程(2):工程(1)で得られた糖液を金属触媒の存在下、水素添加反応する工程、
を含む、糖アルコールの製造方法。 - 前記工程(1)の分離膜が分画分子量300~500の分離膜である、請求項1に記載の糖アルコールの製造方法。
- 前記工程(1)の分離膜が分画分子量600~800の分離膜である、請求項1に記載の糖アルコールの製造方法。
- 前記工程(2)において、金属触媒がルテニウム触媒またはラネーニッケル触媒である、請求項1~3のいずれかに記載の糖アルコールの製造方法。
- 糖アルコールがソルビトールおよび/またはキシリトールを主成分とする、請求項1~4のいずれかに記載の糖アルコールの製造方法。
- 請求項1~5のいずれかに記載の製造方法によって糖アルコールを製造する工程、および糖アルコールを脱水反応に供する工程を含む、無水糖アルコールの製造方法。
- 無水糖アルコールがソルビタンおよび/またはキシリタンを主成分とする、請求項6に記載の無水糖アルコールの製造方法。
- 請求項1~5のいずれかに記載の製造方法によって糖アルコールを製造する工程、請求項6に記載の製造方法によって無水糖アルコールを製造する工程、および無水糖アルコールと飽和または不飽和脂肪酸との縮合反応に供する工程を含む、無水糖アルコールエステルの製造方法。
- 無水糖アルコールエステルがソルビタンエステルおよび/またはキシリタンエステルを主成分とする、請求項8に記載の無水糖アルコールエステルの製造方法。
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109464919A (zh) * | 2017-09-07 | 2019-03-15 | 旭化成株式会社 | 使用多孔膜的糖化液的制造方法 |
JP2019089719A (ja) * | 2017-11-13 | 2019-06-13 | 株式会社サナス | 糖脂肪酸エステルおよびオイルゲル化剤 |
JP2020172455A (ja) * | 2019-04-09 | 2020-10-22 | 出光興産株式会社 | C5+化合物の製造方法及びc5+化合物 |
Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11506934A (ja) | 1995-06-07 | 1999-06-22 | アーケノール,インコーポレイテッド | 強酸加水分解法 |
JP2001079411A (ja) | 1999-09-20 | 2001-03-27 | Asahi Kasei Corp | 還元糖の水素添加触媒の再生方法 |
JP2001095594A (ja) | 1999-09-30 | 2001-04-10 | Meiji Seika Kaisha Ltd | グルコース及びセロオリゴ糖の製造方法 |
JP2005533494A (ja) * | 2002-06-27 | 2005-11-10 | ダニスコ スイートナーズ オイ | 糖の結晶化 |
JP2008056599A (ja) | 2006-08-30 | 2008-03-13 | Nikken Kasei Kk | キシロース重合体及びその還元物の製造方法 |
JP2008161125A (ja) | 2006-12-28 | 2008-07-17 | Univ Of Tokyo | 糖の製造方法、エタノールの製造方法、及び乳酸の製造方法、並びにこれらに用いられる酵素糖化用セルロース及びその製造方法 |
JP2008535664A (ja) | 2005-04-12 | 2008-09-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 発酵性糖を得るためのバイオマス処理 |
WO2009110374A1 (ja) | 2008-03-05 | 2009-09-11 | 東レ株式会社 | 多糖類系バイオマス由来化合物の製造方法 |
WO2010067785A1 (ja) | 2008-12-09 | 2010-06-17 | 東レ株式会社 | 糖液の製造方法 |
WO2013018694A1 (ja) | 2011-07-29 | 2013-02-07 | 東レ株式会社 | 糖液の製造方法 |
WO2014065364A1 (ja) * | 2012-10-25 | 2014-05-01 | 東レ株式会社 | 有機酸またはその塩の製造方法 |
JP2014128213A (ja) * | 2012-12-28 | 2014-07-10 | Kawasaki Heavy Ind Ltd | 濃縮糖化液製造方法 |
JP2014196294A (ja) * | 2013-03-07 | 2014-10-16 | 国立大学法人 宮崎大学 | バイオマス由来の有機化合物の製造方法 |
JP2016007160A (ja) * | 2014-06-24 | 2016-01-18 | 日東電工株式会社 | 糖液の製造方法及び多糖類系バイオマス由来化合物の製造方法 |
WO2016035875A1 (ja) * | 2014-09-05 | 2016-03-10 | 東レ株式会社 | 糖液の製造方法 |
JP2016079169A (ja) * | 2014-10-09 | 2016-05-16 | 三菱化学株式会社 | 糖アルコールの製造方法および糖液 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3784408A (en) | 1970-09-16 | 1974-01-08 | Hoffmann La Roche | Process for producing xylose |
US4008285A (en) | 1974-04-22 | 1977-02-15 | Melaja Asko J | Process for making xylitol |
US4297290A (en) | 1980-07-17 | 1981-10-27 | Ici Americas Inc. | Process for preparing sorbitan esters |
US5782982A (en) | 1993-03-26 | 1998-07-21 | Arkenol, Inc. | Method of removing silica or silicates from solids resulting from the strong acid hydrolysis of cellulosic and hemicellulosic materials |
US5597714A (en) | 1993-03-26 | 1997-01-28 | Arkenol, Inc. | Strong acid hydrolysis of cellulosic and hemicellulosic materials |
US5562777A (en) | 1993-03-26 | 1996-10-08 | Arkenol, Inc. | Method of producing sugars using strong acid hydrolysis of cellulosic and hemicellulosic materials |
FI111960B (fi) | 2000-12-28 | 2003-10-15 | Danisco Sweeteners Oy | Erotusmenetelmä |
US20050021123A1 (en) * | 2001-04-30 | 2005-01-27 | Jurgen Dorn | Variable speed self-expanding stent delivery system and luer locking connector |
US6982328B2 (en) | 2003-03-03 | 2006-01-03 | Archer Daniels Midland Company | Methods of producing compounds from plant material |
FI120590B (fi) | 2005-10-28 | 2009-12-15 | Danisco Sweeteners Oy | Erotusmenetelmä |
PL1999134T3 (pl) * | 2006-03-09 | 2016-04-29 | Archer Daniels Midland Co | Sposób wytwarzania alkoholi anhydrocukrowych |
WO2014008493A2 (en) | 2012-07-05 | 2014-01-09 | Golden Bear LLC | Externally-powered strapping tool and a strapping tool assembly utilized therein |
WO2015002255A1 (ja) | 2013-07-02 | 2015-01-08 | 三菱化学株式会社 | 糖液の処理方法、水素化処理糖液、有機化合物の製造方法および微生物の培養方法 |
US20170044177A1 (en) * | 2014-04-23 | 2017-02-16 | East China University Of Science And Technology | Methods and systems for producing isosorbide from biomass |
US9920003B2 (en) * | 2014-08-19 | 2018-03-20 | Archer Daniels Midland Company | Non-ionic amphiphiles and methods of making the same |
CN104402676A (zh) * | 2014-11-07 | 2015-03-11 | 宜宾雅泰生物科技有限公司 | 以粘胶纤维压榨碱液为原料生产木糖醇的膜过滤工艺 |
CN104450799A (zh) * | 2014-12-05 | 2015-03-25 | 浙江华康药业股份有限公司 | 一种制备固体山梨醇并联产果葡糖浆的生产工艺 |
ES2850355T3 (es) | 2016-02-19 | 2021-08-27 | Intercontinental Great Brands Llc | Procesos para crear corrientes de múltiples valores de fuentes de biomasa |
-
2017
- 2017-02-16 US US15/999,598 patent/US10487066B2/en active Active
- 2017-02-16 EP EP17753256.1A patent/EP3418269B1/en active Active
- 2017-02-16 JP JP2017511372A patent/JP6844535B2/ja active Active
- 2017-02-16 CA CA3014555A patent/CA3014555C/en active Active
- 2017-02-16 MY MYPI2018702861A patent/MY187470A/en unknown
- 2017-02-16 CN CN201780011699.3A patent/CN108698963B/zh active Active
- 2017-02-16 BR BR112018016739-8A patent/BR112018016739B1/pt active IP Right Grant
- 2017-02-16 WO PCT/JP2017/005611 patent/WO2017142000A1/ja active Application Filing
Patent Citations (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11506934A (ja) | 1995-06-07 | 1999-06-22 | アーケノール,インコーポレイテッド | 強酸加水分解法 |
JP2001079411A (ja) | 1999-09-20 | 2001-03-27 | Asahi Kasei Corp | 還元糖の水素添加触媒の再生方法 |
JP2001095594A (ja) | 1999-09-30 | 2001-04-10 | Meiji Seika Kaisha Ltd | グルコース及びセロオリゴ糖の製造方法 |
JP2005533494A (ja) * | 2002-06-27 | 2005-11-10 | ダニスコ スイートナーズ オイ | 糖の結晶化 |
JP2008535664A (ja) | 2005-04-12 | 2008-09-04 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | 発酵性糖を得るためのバイオマス処理 |
JP2008056599A (ja) | 2006-08-30 | 2008-03-13 | Nikken Kasei Kk | キシロース重合体及びその還元物の製造方法 |
JP2008161125A (ja) | 2006-12-28 | 2008-07-17 | Univ Of Tokyo | 糖の製造方法、エタノールの製造方法、及び乳酸の製造方法、並びにこれらに用いられる酵素糖化用セルロース及びその製造方法 |
WO2009110374A1 (ja) | 2008-03-05 | 2009-09-11 | 東レ株式会社 | 多糖類系バイオマス由来化合物の製造方法 |
WO2010067785A1 (ja) | 2008-12-09 | 2010-06-17 | 東レ株式会社 | 糖液の製造方法 |
WO2013018694A1 (ja) | 2011-07-29 | 2013-02-07 | 東レ株式会社 | 糖液の製造方法 |
WO2014065364A1 (ja) * | 2012-10-25 | 2014-05-01 | 東レ株式会社 | 有機酸またはその塩の製造方法 |
JP2014128213A (ja) * | 2012-12-28 | 2014-07-10 | Kawasaki Heavy Ind Ltd | 濃縮糖化液製造方法 |
JP2014196294A (ja) * | 2013-03-07 | 2014-10-16 | 国立大学法人 宮崎大学 | バイオマス由来の有機化合物の製造方法 |
JP2016007160A (ja) * | 2014-06-24 | 2016-01-18 | 日東電工株式会社 | 糖液の製造方法及び多糖類系バイオマス由来化合物の製造方法 |
WO2016035875A1 (ja) * | 2014-09-05 | 2016-03-10 | 東レ株式会社 | 糖液の製造方法 |
JP2016079169A (ja) * | 2014-10-09 | 2016-05-16 | 三菱化学株式会社 | 糖アルコールの製造方法および糖液 |
Non-Patent Citations (8)
Title |
---|
"Ullmanns Enzyklopadie der Techenischen Chemie [Ullmsnn's Encyclopedia of Industrial Chemistry", vol. 13, pages: 135 |
APPLIED CATALYSIS, vol. 492, 2015, pages 252 - 261 |
CATALYST, vol. 5, 2015, pages 145 - 269 |
ENERGY & FUELS, vol. 29, no. 10, 2015, pages 6529 - 6535 |
P. N. RYLANDER: "Hydrogenation and Dehydrogenation", ULLMAN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY |
SANITARY ENGINEERING SYMPOSIUM ACADEMIC PAPERS, vol. 5, 1997, pages 246 - 251 |
See also references of EP3418269A4 |
WATER RESEARCH, vol. 37, 2003, pages 864 - 872 |
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JP2019089719A (ja) * | 2017-11-13 | 2019-06-13 | 株式会社サナス | 糖脂肪酸エステルおよびオイルゲル化剤 |
JP2020172455A (ja) * | 2019-04-09 | 2020-10-22 | 出光興産株式会社 | C5+化合物の製造方法及びc5+化合物 |
JP7253960B2 (ja) | 2019-04-09 | 2023-04-07 | 出光興産株式会社 | C5+化合物の製造方法 |
Also Published As
Publication number | Publication date |
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CN108698963B (zh) | 2021-12-21 |
BR112018016739A2 (pt) | 2019-04-30 |
CA3014555A1 (en) | 2017-08-24 |
BR112018016739B1 (pt) | 2022-03-15 |
US20190177290A1 (en) | 2019-06-13 |
CA3014555C (en) | 2024-02-13 |
EP3418269A4 (en) | 2019-09-25 |
EP3418269A1 (en) | 2018-12-26 |
MY187470A (en) | 2021-09-23 |
JPWO2017142000A1 (ja) | 2018-12-06 |
JP6844535B2 (ja) | 2021-03-17 |
CN108698963A (zh) | 2018-10-23 |
US10487066B2 (en) | 2019-11-26 |
EP3418269B1 (en) | 2020-11-25 |
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