[go: up one dir, main page]

WO2021049363A1 - Procédé de production d'une lignine soluble dans un solvant organique - Google Patents

Procédé de production d'une lignine soluble dans un solvant organique Download PDF

Info

Publication number
WO2021049363A1
WO2021049363A1 PCT/JP2020/032988 JP2020032988W WO2021049363A1 WO 2021049363 A1 WO2021049363 A1 WO 2021049363A1 JP 2020032988 W JP2020032988 W JP 2020032988W WO 2021049363 A1 WO2021049363 A1 WO 2021049363A1
Authority
WO
WIPO (PCT)
Prior art keywords
organic solvent
soluble lignin
lignin
molecular weight
content
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2020/032988
Other languages
English (en)
Japanese (ja)
Inventor
修 若村
掌 道上
貴章 古屋
渡辺　隆司
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Steel Engineering Co Ltd
Kyoto University NUC
Original Assignee
Nippon Steel Engineering Co Ltd
Kyoto University NUC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Steel Engineering Co Ltd, Kyoto University NUC filed Critical Nippon Steel Engineering Co Ltd
Priority to PH1/2022/550560A priority Critical patent/PH12022550560A1/en
Priority to JP2021545232A priority patent/JP7378742B2/ja
Priority to BR112022004152-7A priority patent/BR112022004152B1/pt
Publication of WO2021049363A1 publication Critical patent/WO2021049363A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G1/00—Lignin; Lignin derivatives
    • 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
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
    • C12P7/22—Preparation of oxygen-containing organic compounds containing a hydroxy group aromatic

Definitions

  • the present invention relates to a method for producing an organic solvent-soluble lignin.
  • the present application claims priority based on Japanese Patent Application No. 2019-165546 filed in Japan on September 11, 2019, the contents of which are incorporated herein by reference.
  • Non-edible biomass includes cellulose, which is the most abundant on the earth, but most of it exists as lignocellulose, which is a complex with aromatic polymers lignin and hemicellulose.
  • ethanol production using lignocellulose-based biomass as a raw material it was obtained in a pretreatment step of thermochemically pretreating the biomass raw material, a saccharification step of enzymatically treating the biomass after the pretreatment step to produce a saccharified solution, and a saccharification step. It comprises a fermentation step of adding a microbial culture solution to a saccharified solution to perform ethanol fermentation, and a purification step of separating ethanol from the fermented solution obtained in the fermentation step by distillation or the like.
  • lignin remains as a solid, there is a problem that a large amount of fermentation residue is generated. This fermentation residue is generally processed by a boiler in an annexed factory, methane fermentation, etc., and is not effectively used at present.
  • lignin-based products black liquor, lignin sulfonate
  • technology for effective utilization has been developed for many years.
  • lignin is affected by sulfonation or chloride, so that it is difficult to use, and most of them are limited to fuel use as a boiler heat source.
  • Patent Document 1 discloses a method for producing a lignin decomposition product by treating a lignin-containing biomass with a mixed solvent having a molar ratio of water to alcohol of 1/1 to 20/1.
  • Patent Document 2 discloses a method for producing low molecular weight lignin by heating lignin-containing biomass in the presence of an acid catalyst in a mixed solvent of hydrocarbon and alcohol.
  • Patent Document 3 lignin-containing biomass is pretreated by combining hydrothermal treatment and pulverization treatment, and the enzymatic saccharification residue generated when the pretreated biomass is enzymatically saccharified is further hydrothermally treated by autoclave, and the treated product thereof.
  • a method for producing a lignin decomposition product by dissolving the solid substance in an organic solvent after obtaining the solid substance from the solid-liquid separation of the above.
  • a lignin-containing biomass is saccharified with an enzyme to obtain a saccharified residue, and the saccharified residue is heated in a mixed solvent containing water and an organic solvent having a solubility in water at 20 ° C. of 90 g / L or more.
  • a method for producing a lignin decomposition product by treating to obtain a heat treatment liquid containing a lignin decomposition product and then solid-liquid separation of the heat treatment liquid to remove insoluble matter is disclosed.
  • the lignin contained in the biomass raw material has a complicated structure, and its characteristics change randomly depending on various conditions in the method for producing the lignin decomposition product. Therefore, the methods described in Patent Documents 1 to 4 and the like cannot obtain lignin having specific properties. Moreover, in order to obtain lignin having a specific property, various conditions in the production method thereof have not been controlled so far.
  • the present invention has been made in view of the above circumstances, and provides a method for producing an organic solvent-soluble lignin having specific properties.
  • the present invention includes the following aspects.
  • a dilute sulfuric acid cooking method is performed so that the ⁇ -O-4 bond content, weight average molecular weight and molecular weight distribution, and hydroxyl group content of the obtained organic solvent-soluble lignin are within predetermined ranges.
  • the content of the thioacidrysis monomer of the organic solvent-soluble lignin quantified by the thioacidrysis method as the content of the ⁇ -O-4 bond is in the range of 95 ⁇ mol / g or more and 248 ⁇ mol / g or less.
  • the treatment intensity by the dilute sulfuric acid cooking method is controlled so that the weight average molecular weight of the organic solvent-soluble lignin quantified by the gel permeation chromatograph method is in the range of 2400 or more and 4200 or less. , (1).
  • the method for producing an organic solvent-soluble lignin (4) In the pretreatment step, the treatment intensity by the dilute sulfuric acid cooking method so that the molecular weight distribution of the organic solvent-soluble lignin quantified by the gel permeation chromatograph method is in the range of 1.0 or more and 2.0 or less.
  • the content of the phenolic hydroxyl group of the organic solvent-soluble lignin quantified by phosphorifying the hydroxyl group as the content of the hydroxyl group by phosphorus 31 nuclear magnetic resonance spectroscopy is 7 mmol / g or more and 32 mmol /.
  • Method for producing soluble lignin. (6) In the pretreatment step, any one of (1) to (4), wherein the treatment intensity by the dilute sulfuric acid steaming method is 1.0 or more and 3.0 or less in terms of CSI represented by the following formula (I). The method for producing an organic solvent-soluble lignin according to one.
  • the CSI was controlled to approach 1.0 in order to increase the ⁇ -O-4 bond content of the organic solvent-soluble lignin, while the organic solvent-soluble lignin was used.
  • the CSI is controlled to approach 1.0 in order to reduce the weight average molecular weight and molecular weight distribution of the organic solvent-soluble lignin, while the weight average molecular weight of the organic solvent-soluble lignin.
  • the CSI is controlled to approach 1.0, while the hydroxyl content of the organic solvent-soluble lignin is adjusted.
  • the method for producing an organic solvent-soluble lignin according to the embodiment of the present invention (hereinafter, may be abbreviated as “the method for producing the present embodiment”) will be described in detail.
  • the meanings of various terms are defined as follows.
  • herbaceous biomass is used as a raw material.
  • a residue generated in the process of producing bioethanol, biobutanol, a biochemical product or the like from cellulose and hemicellulose in the herbaceous biomass may be used.
  • crushed biomass can be used, and any shape such as a block, a chip, or a powder may be used.
  • herbaceous biomass may be simply referred to as "biomass”.
  • Herbaceous biomass includes bamboo, palm tree trunks and bunches, palm palm fruit fibers and seeds; bagasse (sorghum and high biomass sorghum), rice straw, straw, corn cob, foliage and residues (corn stover) , Corn cob, corn hull), sorghum (including sweet sorghum) residue, obtained from grasses such as switchgrass, erianthus, napiergrass; Residues and the like to be used can be mentioned.
  • the herbaceous biomass one obtained from a gramineous plant is preferable, and bagasse or napier grass is more preferable, from the viewpoint of availability and compatibility with the production method of the present embodiment.
  • cellulose includes hexoses having six carbons as constituent units. Therefore, when cellulose is hydrolyzed, it produces a hexose monosaccharide (glucose or the like) composed of 6 carbons or a hexose oligosaccharide (for example, cellobiose or the like) in which a plurality of the monosaccharides are linked.
  • Hemicellulose includes pentose (C5 sugar) having five carbons such as xylose and six carbons such as mannose, arabinose, and 4-O-methylglucuronic acid as constituent units (hexose).
  • Complex polysaccharides such as glucomannan and glucuronoxylan composed of C6 sugar) are included. Therefore, when hemicellulose is hydrolyzed, it is a monosaccharide of pentasaccharide consisting of 5 carbons, an oligosaccharide of pentasaccharide in which a plurality of monosaccharides are linked, a monosaccharide of hexasaccharide consisting of 6 carbons, and the like.
  • a plurality of monosaccharides linked to each other produce an oligosaccharide of hexacarbonate, and an oligosaccharide in which a plurality of monosaccharides of pentasaccharide and a plurality of monosaccharides of hexasaccharide are linked.
  • composition ratio and the amount of monosaccharide or oligosaccharide produced from hemicellulose or cellulose differ depending on the pretreatment method and the type of herbaceous biomass used as a raw material.
  • lignin is a natural polymer that is one of the three major principal components of herbaceous biomass.
  • bagasse contains 5% by mass or more and 30% by mass or less of lignin.
  • the basic skeleton of lignin is composed of aromatic nuclei (benzene nuclei), and lignin is classified into G nuclei, S nuclei and H nuclei based on its structure.
  • the G nucleus has one methoxy group (-OCH 3 ) at the ortho position of the phenol skeleton portion
  • the S nucleus has two methoxy groups at the ortho position
  • the H nucleus is It does not have a methoxy group at the ortho position.
  • lignin in herbaceous biomass such as bagasse contains all of H nucleus, G nucleus and S nucleus as a basic skeleton.
  • the lignin derived from coniferous trees has a G nucleus as a basic skeleton
  • the lignin derived from broad-leaved trees has a G nucleus and an S nucleus as a basic skeleton.
  • Lignin has various intermolecular binding modes, but the most abundant among them is ⁇ -O-4 binding, which is about 50 mol% or more and 70 mol% or less of the total binding mode in the lignin molecule. It is an ether bond that occupies.
  • the ⁇ -O-4 bond is a bond mode represented by the following formula (II) and forms a linear structure of lignin. In the process of polymerizing lignin in plant cells, the ⁇ -position of the side chain of the monomer and the 4-position of the aroma nucleus of the adjacent monomer are continuously linked to polymerize.
  • the "water-soluble lignin” is a lignin that is soluble in water, and specifically, a saccharification product after a saccharification step, a fermentation product after a fermentation step, and a purification step, which will be described later. Indicates the lignin contained in the liquid component when the waste liquid of the above is solid-liquid separated. Since the number average molecular weight of water-soluble lignin is relatively small, about 1000 or less, it is presumed that water-soluble lignin is soluble in water.
  • the "water-insoluble lignin” is a lignin that is insoluble in water, and specifically, a solid solution of a saccharification product after a saccharification step, a fermentation product after a fermentation step, and a waste liquid after a purification step, which will be described later. When separated, it shows the lignin contained in the solid components (ie, saccharification residue, fermentation residue and solid residue). Since the water-insoluble lignin has a relatively large number average molecular weight of more than 1,000 and less than 10,000, it is presumed that it is insoluble in water.
  • the "saccharification product” referred to here includes a saccharified solution which is a liquid component and a saccharified residue which is a solid component, the saccharified solution contains water-soluble lignin, and the saccharified residue contains water-insoluble lignin. included.
  • the "fermentation product” contains a fermentation broth which is a liquid component and a fermentation residue which is a solid component, the fermentation broth contains water-soluble lignin, and the fermentation residue contains water-insoluble lignin.
  • the waste liquid contains a liquid residue which is a liquid component and a solid residue which is a solid component, the liquid residue contains water-soluble lignin, and the solid residue contains water-insoluble lignin.
  • the "organic solvent-soluble lignin” is a lignin that is soluble in an organic solvent. Specifically, in the extraction step described later, water-insoluble lignin is added to the organic solvent, mixed, and then stirred. Shows the lignin contained in the liquid component when solid-liquid separated. Since the number average molecular weight of the organic solvent-soluble lignin is about 1000 or more and 3000 or less, it is presumed that the organic solvent-soluble lignin is insoluble in water while being soluble in the organic solvent.
  • Organic solvent-insoluble lignin refers to lignin contained in a solid component when water-insoluble lignin is added to an organic solvent, mixed, stirred, and then solid-liquid separated in an extraction step described later. Since the organic solvent-insoluble lignin has a relatively large number average molecular weight of more than 3000 and 10000 or less, it is presumed that it is insoluble in water and organic solvents.
  • the number average molecular weight of each lignin can be measured by gel permeation chromatography (GPC).
  • sacharifying enzyme examples include cellulase that decomposes cellulose, hemicellulose that decomposes hemicellulose, and amylase that decomposes starch.
  • the cellulase may be any cellulase that decomposes cellulose into monosaccharides such as glucose or oligosaccharides, for example, endoglucanase (EG), cellobiohydrolase (CBH), and ⁇ -glucosidase ( ⁇ ).
  • EG endoglucanase
  • CBH cellobiohydrolase
  • ⁇ ⁇ -glucosidase
  • BGL has at least one activity of each activity, and an enzyme mixture having each of these activities is preferable from the viewpoint of enzyme activity.
  • the hemicellulase may be any one that decomposes hemicellulose into monosaccharides such as xylose or oligosaccharides, and for example, at least one activity of each activity of xylanase, xylosidase, mannanase, galactosidase, glucuronidase, and arabinofuranosidase. From the viewpoint of enzyme activity, it is preferable that the enzyme mixture has each of these activities.
  • saccharifying enzymes such as cellulase and hemicellulase is not limited, and for example, Trichoderma, Acremonium, Aspergillus, Bacillus, Pseudomonas.
  • Saccharifying enzymes such as cellulases and hemicellulase derived from microorganisms such as the genus Penicillium, Aeromonus, Irpex, Sporotichum, and Humicola can be used.
  • the manufacturing method of this embodiment includes the following steps. Pretreatment step of pretreating herbaceous biomass by dilute sulfuric acid steaming method; A saccharification step of enzymatically saccharifying the pretreated herbaceous biomass obtained in the pretreatment step; Solid-liquid separation step of solid-liquid separation of the saccharification treatment product obtained in the saccharification step to obtain a saccharification residue; Extraction step of adding an organic solvent to the saccharified residue to extract an organic solvent-soluble lignin
  • the ⁇ -O-4 bond content, weight average molecular weight and molecular weight distribution, and hydroxyl group content of the obtained organic solvent-soluble lignin in the pretreatment step are each within a predetermined range. As described above, the treatment intensity by the dilute sulfuric acid cooking method is controlled.
  • the inventors have determined the treatment strength by the dilute sulfuric acid steaming method in the pretreatment step, the content of ⁇ -O-4 bond, the weight average molecular weight and the molecular weight distribution, and the content of hydroxyl group.
  • the present invention was developed by controlling the treatment intensity by the dilute sulfuric acid steaming method in the pretreatment step in order to obtain an organic solvent-soluble lignin whose characteristics are within a predetermined range. It came to be completed.
  • the ⁇ -O-4 bond content of the organic solvent-soluble lignin obtained in the production method of the present embodiment can be expressed by the content of the thioacidrysis monomer of the organic solvent-soluble lignin quantified by the thioacidlysis method.
  • the content of the thioacidrysis monomer is 95 ⁇ mol / g or more and 248 ⁇ mol / g or less, preferably 173 ⁇ mol / g or more and 248 ⁇ mol / g or less, and more preferably 201 ⁇ mol / g or more and 248 ⁇ mol / g or less. It is possible to produce an organic solvent-soluble lignin in the range of.
  • the content of the thioacidlysis monomer can be quantified by the thioacidlysis method, and specifically, it can be measured by using the method shown in Examples described later.
  • the weight average molecular weight of the organic solvent-soluble lignin quantified by the gel permeation chromatography (GPC) method is in the range of 2400 or more and 4200 or less.
  • the weight average molecular weight is the largest among the peaks of the chromatogram obtained by measuring the organic solvent-soluble lignin by the GPC method. It is a measured value of the weight average molecular weight of a certain peak.
  • the weight average molecular weight can be quantified by the GPC method, and specifically, it can be measured by using the method shown in Examples described later.
  • the production method of the present embodiment it is possible to produce an organic solvent-soluble lignin in which the molecular weight distribution of the organic solvent-soluble lignin quantified by the GPC method is in the range of 1.0 or more and 2.0 or less.
  • the weight average molecular weight is the largest among the peaks of the chromatogram obtained by measuring the organic solvent-soluble lignin by the GPC method. It is a value obtained by dividing the measured value of the peak weight average molecular weight Mw by the measured value of the number average molecular weight Mn.
  • the molecular weight distribution can be calculated by measuring the number average molecular weight Mn and the weight average molecular weight Mw by the GPC method and dividing the obtained weight average molecular weight Mw by the number average molecular weight Mn. Specifically, it can be calculated by using the method shown in Examples described later.
  • the hydroxyl group of the organic solvent-soluble lignin examples include an alcoholic hydroxyl group bonded to an aliphatic hydrocarbon group (including a modifying group of a sugar or a related compound) and a hydroxyl group bonded to an aromatic hydrocarbon group (phenol).
  • Various hydroxyl groups such as (sexual hydroxyl group, etc.) and OH group at the end of the carboxy group can be mentioned.
  • it may have many phenolic hydroxyl groups and alcoholic hydroxyl groups. preferable.
  • the phenolic hydroxyl group also includes a hydroxyl group bonded to the benzene ring of syringyl and guaiacyl.
  • the total content of the phenolic hydroxyl group and the alcoholic hydroxyl group of the organic solvent-soluble lignin quantified by phosphorus 31 nuclear magnetic resonance spectroscopy (31 P-NMR method) by phosphorifying the hydroxyl group is 13 mmol /
  • An organic solvent-soluble lignin in the range of g or more and 228 mmol / g or less can be produced.
  • the phenolic hydroxyl group content of the organic solvent-soluble lignin quantified by phosphorus 31 nuclear magnetic resonance spectroscopy (31 P-NMR method) by phosphorifying the hydroxyl group is 7 mmol / g or more and 32 mmol. It is possible to produce an organic solvent-soluble lignin having a range of / g or less and an alcoholic hydroxyl group content of 6 mmol / g or more and 196 mmol / g or less.
  • an organic solvent-soluble lignin having a ⁇ -O-4 bond content, a weight average molecular weight and a molecular weight distribution, and a hydroxyl group content within the above ranges can be obtained.
  • each step of the manufacturing method of the present embodiment will be described in detail below.
  • pretreatment process In the pretreatment step, herbaceous biomass is pretreated by the dilute sulfuric acid steaming method.
  • the dilute sulfuric acid cooking method is a method of heating and pressurizing in the presence of dilute sulfuric acid.
  • the dilute sulfuric acid to be used can be added, for example, so that the pH of the pretreatment solution containing herbaceous biomass is about 0.8 or more and 6.7 or less.
  • lignin undergoes a polycondensation reaction as well as a decomposition reaction, and its structure changes depending on the pretreatment conditions. Therefore, since the chemical structure and degree of shrinkage of lignin change depending on the pretreatment conditions, the water-soluble lignin and water-insoluble content contained in the liquid fraction (saccharified liquid) and solid fraction (saccharified residue) in the solid-liquid separation step.
  • the proportion of lignin, as well as the proportion of organic solvent-soluble lignin and organic solvent-insoluble lignin contained in the liquid fraction (extract) and solid fraction (extraction residue) in the extraction step also changes.
  • the strength of the pretreatment that is, the strength of decomposing lignin, cellulose and hemicellulose can be controlled by three parameters of temperature, time and pH. From this, the processing intensity can be evaluated by the CSI (Combined Severity Index) represented by the following formula (I) with the above three parameters as variables.
  • the larger the CSI value the higher the decomposition strength of biomass tends to be, and the smaller the CSI value, the lower the decomposition strength of biomass tends to be.
  • the CSI value is controlled so that the ⁇ -O-4 bond content, the weight average molecular weight and the molecular weight distribution, and the hydroxyl group content of the organic solvent-soluble lignin are within the above ranges.
  • the larger the CSI value the higher the decomposition strength of the biomass.
  • the CSI value is too large, the ⁇ -O-4 bond content and the hydroxyl group content will be shown in Examples described later.
  • the amount tends to decrease, the weight average molecular weight is relatively large, and the width of the molecular weight distribution tends to increase. This is because the ⁇ -O-4 bond decreases and the side chain increases as the decomposition strength of the biomass increases, the polycondensation reaction becomes more significant than the decomposition reaction and the molecular weight increases, and the modification progresses. It is presumed that this is due to the decrease in phenolic hydroxyl groups and alcoholic hydroxyl groups.
  • the CSI value is set. In order to reduce the content of the thioacidrysis monomer, the CSI value is controlled to be large.
  • the CSI value is controlled to be small, while the CSI value is controlled to be small.
  • the CSI value is controlled to be large.
  • the hydroxyl group content is within the desired range, for example, to increase the total content of phenolic hydroxyl groups and alcoholic hydroxyl groups of the organic solvent-soluble lignin quantified by the 31 P-NMR method by phosphorylating the hydroxyl groups.
  • the CSI value is controlled to be large.
  • the content of the thioacidrysis monomer is 95 ⁇ mol / g or more and 248 ⁇ mol / g or less
  • the weight average molecular weight is 2400 or more and 4200 or less
  • the molecular weight distribution is 1.0 or more and 2.0 or less
  • the total content of phenolic hydroxyl groups and alcoholic hydroxyl groups is 13 mmol / g or more and 228 mmol / g or less (specifically, the content of phenolic hydroxyl groups is 7 mmol / g or more and 32 mmol / g or less, and alcoholic.
  • the CSI is preferably 1.0 or more and 3.0 or less, more preferably 1.2 or more and 2.8 or less. It is preferable, 1.5 or more and 2.7 or less is more preferable, and 1.5 or more and 2.5 or less is particularly preferable.
  • an organic solvent-soluble lignin having a ⁇ -O-4 bond content, a weight average molecular weight and a molecular weight distribution, and a hydroxyl group content within the above range can be produced.
  • the pH is preferably 0.8 or more and less than 1.5, more preferably 0.8 or more and 1.4 or less, and 0.8. More than 1.2 or less is more preferable.
  • the temperature can be, for example, 100 ° C. or higher and 250 ° C. or lower, 120 ° C. or higher and 200 ° C. or lower, and 150 ° C. or higher and 180 ° C. or lower.
  • the time can be, for example, 3 minutes or more and 150 minutes or less, 5 minutes or more and 120 minutes or less, 7 minutes or more and 90 minutes or less, and 8 minutes or more and 40 minutes or less. ..
  • the reaction vessel used in the dilute sulfuric acid cooking method is not particularly limited as long as it is a steam supply type, but has a heating pressure device such as an autoclave having acid resistance, or a heating pressure vessel having acid resistance, and further has a screw. It is conceivable that the feeders are integrated and put into a device or the like capable of continuous processing for processing.
  • the biomass may be crushed using a mill or the like before and after the treatment by the dilute sulfuric acid steaming method.
  • the saccharification reaction is carried out using an enzyme using cellulose and hemicellulose contained in the pretreated herbaceous biomass obtained in the pretreatment step as substrates.
  • the enzyme referred to here is mainly a saccharifying enzyme, and those exemplified in the above “saccharifying enzyme” can be used.
  • the saccharification temperature is preferably 45 ° C. or higher and 70 ° C. or lower, more preferably 45 ° C. or higher and 55 ° C. or lower, and particularly preferably 50 ° C.
  • the saccharification time is preferably 12 hours or more and 120 hours or less, more preferably 24 hours or more and 96 hours or less, and further preferably 24 hours or more and 72 hours or less.
  • the saccharification step is not particularly limited and can be carried out using a known saccharification apparatus. Specific examples thereof include saccharification devices such as a stirring type, a ventilation stirring type, a bubble tower type, a fluidized bed type, and a packed bed type. Further, the saccharification device may be provided with a temperature control device such as a hot water circulation type jacket on the outside of the device in order to keep the temperature inside the device constant.
  • a temperature control device such as a hot water circulation type jacket on the outside of the device in order to keep the temperature inside the device constant.
  • Solid-liquid separation process the saccharification treatment product obtained in the saccharification step is solid-liquid separated and separated into a saccharification solution which is a liquid fraction and a saccharification residue which is a solid fraction to obtain a saccharification residue.
  • This saccharified residue contains water-insoluble lignin.
  • a method for solid-liquid separation a known method for separating solid content and liquid content can be used.
  • a method of filtering with a filter, a vibrating sieve or the like, a centrifugal separation method, a separation method using a screw press, or the like can be used. These are, but are not limited to.
  • the saccharified solution obtained in the solid-liquid separation step may be refined by removing impurities from the saccharified solution and sold as molasses, or the saccharified solution may be used to produce useful components produced by microbial fermentation. You may. Details of the useful ingredient will be described later.
  • extraction process an organic solvent is added to the saccharified residue obtained in the solid-liquid separation step to extract the organic solvent-soluble lignin.
  • the organic solvent one having an affinity for water (hydrophilicity) is preferable.
  • the solubility in water at 20 ° C. is preferably 90 g / L or more, more preferably 100 g / L or more, still more preferably 120 g / L or more.
  • the organic solvent preferably has an SP value of 8 or more and 23 or less, more preferably 8 or more and 16 or less, and further preferably 9 or more and 15 or less, from the viewpoint of improving the extraction rate of the organic solvent-soluble lignin.
  • the "SP value” means a solubility parameter (SP value), and the method of Fedors (Reference 1: “Fedors RF," A Method for Estimating Both the Solubility Parameters and Molar Volumes “. of liquids ”, Polymer Engineering and Science, Vol. 14, No. 2, p147-154, 1974.”), and the value ⁇ [(cal / cm 3 ) 1 / 2 ], which is obtained from the square root of the ratio of the total evaporation energy ( ⁇ ei) of the atom or atomic group of the chemical structure of the compound to the total molar volume ( ⁇ vi).
  • organic solvent examples include alcohols, nitriles, ethers, and ketones. These organic solvents may be used alone or in combination of two or more.
  • alcohols examples include methanol, ethanol, diethylene glycol, n-propanol, isopropanol, 2-butanol, isobutanol, t-butyl alcohol and the like.
  • nitriles examples include acetonitrile and the like.
  • ethers examples include dioxane, tetrahydrofuran (THF) and the like.
  • ketones include acetone, methyl ethyl ketone and the like.
  • organic solvent methanol, ethanol, THF, or acetone is preferable, and acetone is more preferable, because the extraction rate of the organic solvent-soluble lignin is excellent. Since these organic solvents have low solubility of biomass saccharified products such as glucose and xylose and do not dissolve cellulose, hemicellulose, etc., lignin can be efficiently extracted.
  • a mixed solvent of an organic solvent and water can be used.
  • the ratio of water to the organic solvent is preferably more than 0/100 and 40/60 or less, more preferably 10/90 or more and 40/60 or less, and further preferably 20/80 or more and 40/60 or less in terms of mass ratio. When the ratio is within the above range, the organic solvent-soluble lignin can be extracted more efficiently.
  • the water when a mixed solvent of an organic solvent and water is used, the water also contains water contained in the saccharified residue.
  • an organic solvent preferably acetone or ethanol
  • the extraction can be carried out under the conditions within the above range, which is the ratio of water to the organic solvent.
  • the saccharified residue and the organic solvent are mixed and stirred to dissolve the organic solvent-soluble lignin in the organic solvent.
  • the extraction step can be performed using, for example, a known extraction device such as a rotocell type extraction device.
  • the amount of the solvent (organic solvent or mixed solvent of organic solvent and water) added can be 2 times or more and 40 times or less in terms of mass ratio with respect to the dry mass of the saccharified residue, and can be 2 times or more and 30 times or less. It can be 2 times or more and 20 times or less, and can be 5 times or more and 15 times or less, and is not limited to this.
  • the extraction time (time for mixing and stirring the saccharified residue and the organic solvent) can be, for example, 30 minutes or more and 240 minutes or less, and is not limited thereto.
  • the temperature condition until the organic solvent-soluble lignin is dissolved in the organic solvent and the extract is obtained can be carried out under mild temperature conditions equal to or lower than the boiling point of the organic solvent used, for example, room temperature ( Specifically, it can be carried out under the condition of 15 ° C. or higher and 35 ° C. or lower). Other conditions such as the stirring speed can be appropriately set according to the mixing amount of the saccharified residue and the organic solvent.
  • an extract containing an organic solvent-soluble lignin can be obtained.
  • the solid-liquid separation method include the same methods as those exemplified in the above-mentioned “solid-liquid separation step”.
  • the organic solvent-soluble lignin contained in the extract can be obtained as a powdery organic solvent-soluble lignin by removing the organic solvent by a known method such as using a distillation column or the like. At this time, it is preferable that the removed organic solvent is cooled, concentrated, recovered by using a condenser such as a capacitor, and reused.
  • the production method of the present embodiment may further include other steps in addition to the above steps.
  • the production method of the present embodiment may further include a fermentation step after the saccharification step.
  • a fermentation step microorganisms are added to the saccharified solution obtained in the saccharification step, and the fermentation reaction is carried out with stirring.
  • the fermentation reaction when microorganisms ingest monosaccharides such as glucose and xylose and oligosaccharides in the saccharified solution, useful components different from organic solvent-soluble lignin are produced.
  • the production method of the present embodiment may further include a fermentation step after the saccharification step and before the solid-liquid separation step.
  • the fermentation step microorganisms are added to the saccharified products (saccharified liquid and saccharified residue) obtained in the saccharification step, and the fermentation reaction is carried out with stirring.
  • the solid-liquid separation step the fermentation product obtained in the fermentation step is solid-liquid separated to obtain a fermentation residue.
  • an organic solvent is added to the fermentation residue to extract the organic solvent-soluble lignin. Deterioration of the structure of lignin (change in chemical structure and degree of polycondensation) is hardly affected except in the above pretreatment step, and lignin is persistently decomposed.
  • the physical properties and yield of the obtained organic solvent-soluble lignin do not change even after the fermentation step and the purification step described later, and the fermentation residue separated from the fermentation product obtained after the fermentation step and after the purification step.
  • the solid residue separated from the obtained waste liquid can be used as a raw material for extraction of the organic solvent-soluble lignin in the same manner as the saccharified residue.
  • the microorganism used in the fermentation step is not particularly limited as long as it can produce a useful component different from the target organic solvent-soluble lignin.
  • Specific examples thereof include yeast and bacteria, and genetically modified microorganisms are also preferably used.
  • Genetically modified microorganisms are microorganisms that do not have the enzyme genes required for conversion to useful components different from the target organic solvent-soluble lignin such as alcohol, and these genes are introduced by genetic engineering technology into alcohol and the like. It enables the production of useful components different from the target organic solvent-soluble lignin.
  • Examples of the genetically modified microorganism include recombinant Escherichia coli having alcohol fermentability. Among them, yeast is preferable as the microorganism used in the production method of the present embodiment.
  • the culture solution containing the microorganism may be used as it is, or the culture solution containing the microorganism may be concentrated by centrifugation, or may be appropriately used.
  • the amount of microorganisms used may be calculated based on the growth rate of microorganisms, the size of the fermentation apparatus, the amount of saccharified solution used for fermentation, and the like.
  • the fermentation step it is preferable to ferment the saccharification product using yeast as a microorganism to produce alcohol such as ethanol as a useful component different from the organic solvent-soluble lignin.
  • the fermentation step may be appropriately performed based on the prior art.
  • the fermentation temperature is preferably 25 ° C. or higher and 50 ° C. or lower, more preferably 28 ° C. or higher and 35 ° C. or lower, and particularly preferably 32 ° C.
  • the fermentation time is preferably 24 hours or more and 120 hours or less, more preferably 24 hours or more and 96 hours or less, and further preferably 24 hours or more and 72 hours or less.
  • the fermentation step is not particularly limited and can be carried out using a known fermentation apparatus. Specific examples thereof include, but are not limited to, a stirring type, a ventilation stirring type, a bubble tower type, a fluidized bed type, a packed bed type and the like. Further, the fermentation apparatus may be provided with a temperature control device such as a hot water circulation type jacket on the outside of the apparatus in order to keep the temperature inside the apparatus constant.
  • a temperature control device such as a hot water circulation type jacket on the outside of the apparatus in order to keep the temperature inside the apparatus constant.
  • the production method of the present embodiment may further include a purification step after the fermentation step.
  • a purification step useful components different from the organic solvent-soluble lignin are extracted from the fermentation product obtained in the fermentation step.
  • the production method of the present embodiment may further include a purification step after the fermentation step and before the solid-liquid separation step.
  • a useful component different from the organic solvent-soluble lignin is extracted from the fermentation product obtained in the fermentation step.
  • the waste liquid is discharged after the useful components different from the organic solvent-soluble lignin are taken out.
  • the waste liquid contains water-soluble lignin and water-insoluble lignin.
  • the solid-liquid separation step the waste liquid obtained in the purification step is solid-liquid separated to obtain a solid residue in the waste liquid.
  • an organic solvent is added to the solid residue to extract the organic solvent-soluble lignin.
  • the useful component different from the organic solvent-soluble lignin means a compound produced by ingesting monosaccharides and oligosaccharides obtained by decomposing herbaceous biomass by microorganisms such as yeast.
  • useful components include alcohols such as ethanol, butanol, 1,3-propanediol, 1,4-butanediol, and glycerol; pyruvic acid, succinic acid, malic acid, inosinic acid, citric acid, lactic acid, and the like.
  • the compound obtained by fermentation is a monomer such as lactic acid, it may be converted into a polymer by polymerization.
  • ethanol is preferable as a useful component produced in the above-mentioned fermentation step.
  • the purification method includes, for example, a method of distilling the fermentation broth (distillation method).
  • the herbaceous biomass compound is an amino acid
  • an ion exchange method a method for adsorbing and removing foreign substances using activated carbon, and the like can be mentioned.
  • yeast is used as a microorganism to ferment the saccharification product to produce alcohol such as ethanol as a useful component, and then in the purification step, alcohol such as ethanol is produced from the fermentation product by a distillation method. It is preferable to take it out.
  • an epoxy resin can be obtained by subjecting an organic solvent-soluble lignin to an addition reaction of epichlorogenohydrin (for example, epichlorohydrin or the like).
  • a urethane resin can be obtained by reacting an organic solvent-soluble lignin with an isocyanate compound.
  • a phenol resin can be obtained by performing a curing reaction of an organic solvent-soluble lignin using hexamine as a curing agent.
  • organic solvent-soluble lignin contains an aromatic skeleton, it can be used as a raw material having excellent mechanical properties such as fire resistance, heat resistance, and hardness, and the above-mentioned various resins can be used as electric substrate materials, heat-resistant plastic materials, and the like. can do.
  • the organic solvent-soluble lignin since the organic solvent-soluble lignin has excellent dispersibility, it can be used as a surfactant, for example, by modifying the organic solvent-soluble lignin to introduce a long-chain hydrocarbon group or the like.
  • the organic solvent-soluble lignin obtained by the production method of the present embodiment has a ⁇ -O-4 bond content, a weight average molecular weight and a molecular weight distribution, and a hydroxyl group content within a predetermined range. Yes, it is possible to provide a lignin that can meet the above specifications.
  • Example 1 (Examination of conditions for dilute sulfuric acid cooking method) Using napier grass, which is a herbaceous biomass, a dilute sulfuric acid cooking method was carried out under each condition shown in Table 1. Specifically, the treatment by the dilute sulfuric acid cooking method was carried out by adding dilute sulfuric acid to the napier glass so as to have the following pH conditions, and then using a steam supply type pressurized pretreatment apparatus.
  • CSI combined Safety Index
  • I temperature, pH, and treatment time, which are parameters of the conditions of the dilute sulfuric acid cooking method, as variables.
  • the napier grass pretreated under each of the above conditions was saccharified by adding saccharifying enzymes (cellulase and hemicellulase) to obtain a saccharified product.
  • saccharifying enzymes cellulase and hemicellulase
  • the obtained saccharification product was filtered to obtain a saccharification residue.
  • (1) Content of ⁇ -O-4 bond The content of ⁇ -O-4 bond in the organic solvent-soluble lignin was measured by using the thioacidlysis method.
  • a decomposition product containing a thioacidrysis monomer composed of syringyl and guaiacyl is produced by cleaving the ⁇ -O-4 bond, and by analyzing the decomposition product, ⁇ -O- contained in lignin is produced.
  • Quantify 4 bonds That is, the content of the thioacidrysis monomer is quantified as the content of ⁇ -O-4 bond.
  • a pyridine solution of N, O-Bis (trimethylsilyl) trifluoroacetamide (BSTFA) was added to the concentrate as a silylating agent, and the mixture was stirred at room temperature for 30 minutes or more and 60 minutes or less to prepare a derivatized sample.
  • the derivatized sample was measured by gas chromatography-mass spectrometry (GC-MS) under the measurement conditions shown below, and the content of the thioacidrysis monomer composed of syringyl (S) and guaiacyl (G) was calculated.
  • GC-MS gas chromatography-mass spectrometry
  • FIG. 1 “thioacidrysis S + G” is the content ( ⁇ mol / g) of the thioacidlysis monomer composed of syringyl (S) and guaiacyl (G).
  • FIG. 2A is a gel permeation chromatograph of organic solvent-soluble lignin obtained using napier glass pretreated under the conditions of CSI of 1.27, 1.87, 2.36, 2.66 and 2.95. It is a chromatogram obtained by measuring by the method.
  • the weight average molecular weight Mw, the number average molecular weight Mn, and the molecular weight distribution Mw / Mn at each peak of each chromatogram shown in FIG. 2A are shown in Table 2 below.
  • FIG. 2B is a graph showing the measured values of the weight average molecular weight of the peak having the largest weight average molecular weight (peak 1 in Table 2 above) among the peaks of the chromatogram shown in FIG. 2A.
  • the weight average molecular weight increases, the width of the molecular weight distribution increases, and the weight average molecular weight of the entire organic solvent-soluble lignin is about 200 or less, which is a low molecular weight organic solvent.
  • the proportion of soluble lignin was a tendency for the proportion of soluble lignin to decrease.
  • the measured value of the weight average molecular weight of the peak having the maximum weight average molecular weight Mw among the peaks of the chromatogram shown in FIG. 2A is 2453 or more and 4151 or less.
  • the molecular weight distribution Mw / Mn was 1.32 or more and 1.86 or less.
  • organic solvent-soluble lignin obtained using napier grass pretreated under the conditions of CSI of 1.27, 1.57, 2.36 and 2.95 was used.
  • the content of hydroxyl groups in the organic solvent-soluble lignin was quantified by phosphorus 31 nuclear magnetic resonance spectroscopy (31 P-NMR method) after phosphorylation of the hydroxyl groups.
  • organic solvent-soluble lignin 25 mg
  • 2-Chromium4,5,5-tetramethyl-1,3,2-dioxaphosphorane 115 mg (100 ⁇ L: excess amount)
  • Measuring device JEOL JNM-LA400MK Observation frequency: 400MHz Number of integrations: 409 6 times Measurement temperature: 16 ° C (room temperature) Solvent used: Pyridine / deuterated chloroform mixture (mass ratio 8: 5)
  • the content of (including hydroxyl groups) was 7.03 mmol / g or more and 31.24 mmol / g or less.
  • the content of alcoholic hydroxyl groups was 6.04 mmol / g or more and 195.7 mmol / g or less. From these facts, it was suggested that the control of CSI is effective for obtaining the organic solvent-soluble lignin in which the content of hydroxyl groups, particularly the total content of phenolic hydroxyl groups and alcoholic hydroxyl groups, is in a specific range.
  • an organic solvent-soluble lignin having specific properties can be produced.

Landscapes

  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Zoology (AREA)
  • Biotechnology (AREA)
  • Microbiology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Compounds Of Unknown Constitution (AREA)

Abstract

La présente invention concerne un procédé de production d'une lignine soluble dans un solvant organique qui comprend une étape de prétraitement consistant à prétraiter une biomasse herbacée par un procédé de digestion par acide sulfurique dilué, une étape de saccharification consistant à saccharifier la biomasse herbacée prétraitée obtenue dans l'étape de prétraitement avec une enzyme, une étape de séparation solide-liquide consistant à effectuer une séparation solide-liquide du produit de traitement de saccharification obtenu dans l'étape de saccharification pour obtenir un résidu de saccharification, et une étape d'extraction consistant à ajouter un solvant organique au résidu de saccharification pour extraire une lignine soluble dans un solvant organique, dans l'étape de prétraitement, l'intensité de traitement par le procédé de digestion d'acide sulfurique dilué est régulée de telle sorte que la teneur en liaison β-O-4, le poids moléculaire moyen en poids, la distribution de poids moléculaire et la teneur en groupes hydroxyle de la lignine soluble dans un solvant organique obtenue sont dans des plages prédéfinies.
PCT/JP2020/032988 2019-09-11 2020-09-01 Procédé de production d'une lignine soluble dans un solvant organique Ceased WO2021049363A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
PH1/2022/550560A PH12022550560A1 (en) 2019-09-11 2020-09-01 Method for producing organic solvent-soluble lignin
JP2021545232A JP7378742B2 (ja) 2019-09-11 2020-09-01 有機溶媒可溶性リグニンの製造方法
BR112022004152-7A BR112022004152B1 (pt) 2019-09-11 2020-09-01 Método para produzir lignina solúvel em solvente orgânico

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2019165546 2019-09-11
JP2019-165546 2019-09-11

Publications (1)

Publication Number Publication Date
WO2021049363A1 true WO2021049363A1 (fr) 2021-03-18

Family

ID=74866934

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2020/032988 Ceased WO2021049363A1 (fr) 2019-09-11 2020-09-01 Procédé de production d'une lignine soluble dans un solvant organique

Country Status (3)

Country Link
JP (1) JP7378742B2 (fr)
PH (1) PH12022550560A1 (fr)
WO (1) WO2021049363A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015157792A (ja) * 2014-02-25 2015-09-03 国立研究開発法人産業技術総合研究所 リグニン分解物の製造方法
US20160273011A1 (en) * 2013-12-06 2016-09-22 Iogen Corporation Process for hydrolyzing a pretreated feedstock and recovering lignin

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20160273011A1 (en) * 2013-12-06 2016-09-22 Iogen Corporation Process for hydrolyzing a pretreated feedstock and recovering lignin
JP2015157792A (ja) * 2014-02-25 2015-09-03 国立研究開発法人産業技術総合研究所 リグニン分解物の製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUAN, S. ET AL.: "An optimum combined severity factor improves both the enzymatic saccharification yield and the functional lignin structure", CELLUL O SE, vol. 26, - 23 April 2019 (2019-04-23), pages 4731 - 4742, XP036774996, DOI: 10.1007/s10570-019-02442-9 *

Also Published As

Publication number Publication date
BR112022004152A2 (pt) 2023-10-31
JP7378742B2 (ja) 2023-11-14
JPWO2021049363A1 (fr) 2021-03-18
PH12022550560A1 (en) 2023-03-20

Similar Documents

Publication Publication Date Title
Paz et al. Enzymatic hydrolysis of brewer’s spent grain to obtain fermentable sugars
Eliana et al. Effects of the pretreatment method on enzymatic hydrolysis and ethanol fermentability of the cellulosic fraction from elephant grass
US10927388B2 (en) Method for preparing sugar, bioethanol or microbial metabolite from lignocellulosic biomass
CN101815788B (zh) 用于从预处理过的木质纤维素原料产生醇和葡萄糖的基于纤维素酶的方法
US9133278B2 (en) Methods for detoxifying a lignocellulosic hydrolysate
Li et al. Ethanol organosolv pretreatment of bamboo for efficient enzymatic saccharification.
WO2010059796A2 (fr) Procédé de préparation d'une solution de sucres par saccharification chimique et enzymatique combinée d'une biomasse enrichie en polysaccharides
EP2207888A1 (fr) Traitement enzymatique sous vide de matières lignocellulosiques
Fan et al. Vacuum-assisted black liquor-recycling enhances the sugar yield of sugarcane bagasse and decreases water and alkali consumption
MX2014012867A (es) Separacion liquido / liquido de biomasa lignocelulosica para producir jarabes de azucar y fracciones de lignina.
EP2785853A2 (fr) Compositions et procédés pour liquéfaction de biomasse
CA2974747A1 (fr) Procede comprenant un pretraitement avec du dioxyde de soufre et/ou de l'acide sulfureux et hydrolyse enzymatique
WO2015081439A1 (fr) Procédé d'hydrolyse d'une charge de départ prétraitée et de récupération de lignine
Klinpratoom et al. Improvement of cassava stem hydrolysis by two-stage chemical pretreatment for high yield cellulosic ethanol production
WO2014190294A1 (fr) Séparation de sucres et purification à partir de biomasse
KR101039792B1 (ko) 바이오 연료 및 바이오 화학물질 제조용 전처리 장치, 및 이를 이용한 전처리 공정과 바이오 연료 및 바이오 화학물질의 제조 공정
Buyukkileci et al. Organosolv pretreatment of corncob for enzymatic hydrolysis of Xylan
JP5745237B2 (ja) セルロース系バイオマスからの糖およびアルコールの製造方法
CN116568816A (zh) 由残余木质纤维素生物质产生糖浆的方法
KR102062715B1 (ko) 목질계 바이오매스의 효소 반응성을 높이는 방법
JP7378742B2 (ja) 有機溶媒可溶性リグニンの製造方法
JP7357875B2 (ja) 有機溶媒可溶性リグニンの製造方法
Zhuang et al. Liquid hot water pretreatment for lignocellulosic biomass biorefinery
BR112022004152B1 (pt) Método para produzir lignina solúvel em solvente orgânico
Desouky et al. Establishing an Effective Multi-Function System for Sugarcane Bagasse Bio-degradation

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20863473

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
ENP Entry into the national phase

Ref document number: 2021545232

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 20863473

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 112022004152

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20220307