WO2009110499A1 - 水の浄化方法、水の浄化装置、及び水の浄化セット - Google Patents

水の浄化方法、水の浄化装置、及び水の浄化セット Download PDF

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WO2009110499A1
WO2009110499A1 PCT/JP2009/054051 JP2009054051W WO2009110499A1 WO 2009110499 A1 WO2009110499 A1 WO 2009110499A1 JP 2009054051 W JP2009054051 W JP 2009054051W WO 2009110499 A1 WO2009110499 A1 WO 2009110499A1
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group
molecule
general formula
independently
water
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PCT/JP2009/054051
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English (en)
French (fr)
Japanese (ja)
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満 近藤
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国立大学法人静岡大学
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Priority to CN2009801076541A priority Critical patent/CN101959803B/zh
Priority to JP2010501932A priority patent/JP5448195B2/ja
Publication of WO2009110499A1 publication Critical patent/WO2009110499A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C07D233/61—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with hydrocarbon radicals, substituted by nitrogen atoms not forming part of a nitro radical, attached to ring nitrogen atoms

Definitions

  • the present invention relates to a water purification method, a water purification device, and a water purification set.
  • perchlorate is a substance that damages the thyroid gland that controls metabolic effects in adults and promotes physical development in children.
  • perchlorate ion (ClO 4 ⁇ ) exhibits high solubility in water, and since it hardly interacts with the cation among all the anions, it is difficult to remove from the aqueous solution as a precipitate or the like. Ion.
  • perchlorate As a technique for removing perchlorate from waste liquid contaminated with perchlorate (or perchlorate ions), perchlorate is concentrated, and KCl is added to the concentrated perchlorate solution to perchlorate.
  • a method is known in which acid potassium (KClO 4 ) is produced, cooled and crystallized (see, for example, Japanese Patent Publication No. 9-504472).
  • a water treatment system for removing perchlorate using a resin for example, Japanese Patent Application Laid-Open No. 2004-346299 and “NEDO Overseas Report, No.
  • the above-mentioned method for producing potassium chlorate from perchlorate and crystallizing it has a concentration step of evaporating the solvent from the solution, so that the perchlorate ions in the solution are retained while maintaining the state of the solution. It cannot be captured.
  • the above-described method of removing perchlorate using a resin has a problem of poor selectivity in terms of perchlorate ion trapping as well as costly regeneration of the resin.
  • perchlorate ions cannot be selectively captured from a system in which a plurality of anions are present. Therefore, it is necessary to develop a purification method that selectively captures specific molecules such as perchlorate ions and reduces the concentration of the captured molecules in water.
  • the present invention has been made in view of the above, and an object of the present invention is to provide a water purification method, a water purification device, and a water purification set capable of purifying water with few trapped molecules.
  • Means for solving the above-mentioned problems are as follows. ⁇ 1> Contacting a compound represented by the following general formula (I) and a capture agent containing a metal ion capable of planar tetracoordination or regular octahedral coordination with water containing a molecule to be captured, and porous A method for purifying water, comprising bringing a solid material into contact with water containing a molecule to be captured having a molecular size of 1 nm or less.
  • R 2, R 3, and one of R 4 is in the meta or para to R x R y, R x and R y are following heterocyclic independently of one another Represents a substituent,
  • R 1 , R 2 , R 3 , R 4 and R 5 the remainder excluding R y is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a sulfonic acid Represents a group, but is not simultaneously a hydrogen atom.
  • R 6 and R 7 each independently represent a hydrogen atom or a methyl group, and A contains at least one nitrogen atom. Represents a 5-membered or 6-membered heterocyclic group.
  • ⁇ 2> The water purification method according to ⁇ 1>, wherein the molecule to be trapped has a molecular size of 1 nm or less.
  • ⁇ 3> The method for purifying water according to ⁇ 1>, wherein the water after contact with the scavenger is brought into contact with the porous solid.
  • ⁇ 4> The water purification method according to ⁇ 1>, wherein the porous solid is at least one selected from the group consisting of activated carbon, zeolite, ion exchange resin, clay, and silica gel.
  • R y is in a para position with respect to R x .
  • ⁇ 6> The water purification method according to ⁇ 1>, wherein in the general formula (I), R 6 and R 7 are both hydrogen atoms.
  • R 3 is R y
  • R 1 , R 2 , R 4 and R 5 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 10 carbon atoms.
  • R 3 is R y
  • R 1 , R 2 , R 4 and R 5 are each independently a substituted or unsubstituted hydrocarbon group having 1 to 6 carbon atoms.
  • R 3 is R y
  • R 1 , R 2 , R 4, and R 5 are each independently a substituted or unsubstituted hydrocarbon group having 1 or 2 carbon atoms.
  • A is an imidazolyl group.
  • the scavenger is a coordination compound including a compound represented by the general formula (I) and a metal ion capable of planar tetracoordination or regular octahedral coordination. is there.
  • a water purification apparatus comprising a filtration part containing a compound represented by the following general formula (I) and a metal ion capable of planar tetracoordination or regular octahedral coordination, and a porous solid: It is.
  • R 2, R 3, and one of R 4 is in the meta or para to R x R y, R x and R y are following heterocyclic independently of one another Represents a substituent,
  • R 1 , R 2 , R 3 , R 4 and R 5 the remainder excluding R y is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a sulfonic acid Represents a group, but is not simultaneously a hydrogen atom.
  • R 6 and R 7 each independently represent a hydrogen atom or a methyl group, and A contains at least one nitrogen atom. Represents a 5-membered or 6-membered heterocyclic group.
  • the filtration unit includes a capturing unit including the capturing agent and an adsorption unit connected to the capturing unit and including the porous solid.
  • a water purification set comprising a compound represented by the following general formula (I) and a scavenger containing a metal ion capable of planar tetracoordination or regular octahedral coordination, and a porous solid.
  • R 2, R 3, and one of R 4 is in the meta or para to R x R y, R x and R y are following heterocyclic independently of one another Represents a substituent,
  • R 1 , R 2 , R 3 , R 4 and R 5 the remainder excluding R y is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a sulfonic acid Represents a group, but is not simultaneously a hydrogen atom.
  • R 6 and R 7 each independently represent a hydrogen atom or a methyl group, and A contains at least one nitrogen atom. Represents a 5-membered or 6-membered heterocyclic group.
  • the present invention it is possible to provide a water purification method, a water purification device, and a water purification set that can purify water with few molecules to be trapped.
  • FIG. 4 is a diagram showing a state in which one capture capsule type molecule according to a reference example of the present invention includes one perchlorate ion (ClO 4 ⁇ ) molecule, ignoring the atomic radius. It is the figure which represented the mode that one capture capsule type molecule concerning a reference example of the present invention encapsulates one molecule of perchlorate ion (ClO 4 ⁇ ) in consideration of the van der Waals radius.
  • the water purification method of the present invention comprises a scavenger containing a compound represented by the following general formula (I) and a metal ion capable of planar tetracoordination or regular octahedral coordination, and water containing a molecule to be captured. And contacting the porous solid with water containing the molecule to be captured.
  • a scavenger containing a compound represented by the following general formula (I) and a metal ion capable of planar tetracoordination or regular octahedral coordination and water containing a molecule to be captured.
  • a metal ion capable of planar tetracoordination or regular octahedral coordination
  • the molecule to be captured and the capture capsule type molecule are adsorbed to the porous solid.
  • the concentration of molecules to be captured in water can be effectively reduced, and the water can be purified to have few molecules to be captured.
  • the molecule to be captured is not particularly limited as long as it is a molecule that can be captured by the capturing agent. However, from the viewpoint of obtaining the above effect more effectively, the molecule to be captured is preferably a molecule having a molecular size of 1 nm or less.
  • the molecular size of 1 nm or less means that the maximum diameter of the molecule is 1 nm or less.
  • the maximum diameter of a molecule refers to a value obtained from the average of the longest distances between the atoms at the ends constituting the molecule based on a structural model prepared in consideration of the van der Waals radius.
  • the “molecule” in the present invention may be any of a cation, an anion, and a neutral molecule.
  • molecules to be captured in the present invention are shown below.
  • anions perchlorate ion (ClO 4 ⁇ ), trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), tetrafluoroborate ion (BF 4 ⁇ ), azide ion (N 3 ⁇ ), phosphate ion (PO 4 3- ), and the like.
  • neutral molecules include benzene, toluene, xylene, cyclohexane, and cyclohexene.
  • perchlorate ion (ClO 4 ⁇ ), trifluoromethanesulfonate ion (CF 3 SO 3 ⁇ ), and tetrafluoroborate ion (BF 4 ⁇ ) are preferable from the viewpoint of removal efficiency.
  • water containing a molecule to be captured in the present invention may contain other components as long as the molecule to be captured is contained in water.
  • Water containing molecules to be trapped includes, for example, drinking water, industrial water, waste water, and various aqueous solutions, colloidal solutions (milk, etc.), suspensions containing food, soil, and the like.
  • the scavenger in the present invention contains a compound represented by the following general formula (I) and a metal ion capable of planar tetracoordinate or regular octahedral coordination.
  • Examples of the form of the scavenger in the present invention include a form of a coordination compound containing the compound represented by the general formula (I) and the metal ion, and a form of a mixture containing the coordination compound and other components.
  • a compound represented by the general formula (I) that exists independently that is, does not take the form of the coordination compound
  • a metal containing the metal ion And a salt form a compound represented by the general formula (I) that exists independently (that is, does not take the form of the coordination compound) and a metal containing the metal ion And a salt form.
  • R 2, R 3, and one of R 4 is in the meta or para to R x R y, independently R x and R y are each heterocyclic-substituted below Represents a group,
  • R 1 , R 2 , R 3 , R 4 and R 5 the remainder excluding R y is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a sulfonic acid Represents a group, but not simultaneously a hydrogen atom,
  • R 6 and R 7 each independently represent a hydrogen atom or a methyl group
  • A represents a 5-membered or 6-membered heterocyclic group containing at least one nitrogen atom.
  • the compound represented by the general formula (I) contacts a metal ion capable of planar tetracoordinate or octahedral coordination with a molecule to be captured in a liquid sample, a plurality of the compounds are collected together with the metal ion.
  • the molecules are taken in to form capsule molecules (self-assembly reaction; see, for example, FIGS. 3 and 4 described later).
  • Specific examples of the molecules to be captured are as described above.
  • a capsule molecule incorporating a molecule to be captured is referred to as a “captured capsule molecule”.
  • the capture capsule type molecule can also capture the captured molecule by coordination bond outside the capture capsule type molecule (two metal ions). Therefore, one molecule of the capture capsule type molecule can capture three molecules to be captured. Furthermore, it has been confirmed that one capture capsule type molecule captures another molecule to be captured with another capture capsule type molecule in addition to three molecules to be captured. That is, it is known that one capture capsule type molecule can capture up to four molecules to be captured. The above forms can be confirmed by, for example, single crystal structure analysis and visible / ultraviolet spectrum.
  • the self-assembly reaction by the compound represented by the general formula (I) shows extremely high selectivity for the molecule to be captured, when the molecule to be captured is present in the liquid, it is efficiently and reliably captured. A molecule can be captured.
  • the compound represented by the general formula (I) when the compound represented by the general formula (I) is in contact with the metal ion and an anion other than the molecule to be captured, it is not such a capture capsule type molecule but a coordination compound described later. Such a polymer structure is easily formed.
  • R y is in the para position with respect to R x , that is, R 3 is R y , does not leave the trapped molecule and forms a capture space without a gap. Therefore, it is preferable.
  • R y and R x are the same heterocyclic substituent from the viewpoint of being able to limit the number of isomers of the captured capsule type molecule to be generated and easily identifying the product.
  • R 6 and R 7 are preferably both hydrogen atoms from the viewpoint of forming a trapped capsule molecule without causing steric hindrance with other substituents of the aromatic ring.
  • R 1 , R 2 , R 3 , R 4 and R 5 the remainder excluding R y is independently a hydrogen atom, a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms, or a sulfonic acid Represents a group but is not simultaneously a hydrogen atom.
  • R 1 and R 2 may be bonded to each other to form a ring (aromatic ring or aliphatic ring).
  • R 4 and R 5 may also be bonded to each other to form a ring (aromatic ring or aliphatic ring).
  • R 1 , R 2 , R 3 , R 4 and R 5 the remainder excluding R y is preferably a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms.
  • the compound represented by the general formula (I) is sterically hindered from the viewpoint of ease of synthesis. 1 to 10 is preferable, 1 to 6 is more preferable, and 1 to 2 is particularly preferable from the viewpoint of forming a capsule without becoming and preventing anion from leaving the capsule.
  • Examples of the substituent that can be substituted on the hydrocarbon group include a halogen atom, a sulfonic acid group, a nitro group, a hydroxyl group, and an alkyl halide group. From the viewpoint of ease of synthesis, stability, and insolubility in water. Therefore, a fluorine atom or a perfluoroalkyl group is preferable.
  • the heterocyclic group represented by A may be substituted with a substituent such as an alkyl group having 1 to 6 carbon atoms or a sulfonic acid group.
  • the heterocyclic group may contain an oxygen atom or a sulfur atom in addition to the nitrogen atom.
  • Examples of the heterocyclic group represented by A include a heterocyclic group capable of coordinating with the metal ion.
  • Such heterocyclic groups include pyrrolyl groups other than pyrrol-1-yl groups, 2H-pyrrolyl groups other than 2H-pyrrol-1-yl groups, imidazolyl groups, pyrazolyl groups, and isothiazol-1-yl groups.
  • Isothiazolyl groups isoxazolyl groups other than isoxazol-1-yl groups, pyrrolidinyl groups other than pyrrolidin-1-yl groups, imidazolidinyl groups, pyrazolidinyl groups, pyridyl groups other than pyridin-1-yl groups, pyrazyl groups, pyrimidinyl groups, pyridazinyl
  • Preferred are a group, a piperidinyl group other than a piperidin-1-yl group, a piperazinyl group, a morpholinyl group other than a morpholin-4-yl group, and a group represented by the following structural formula.
  • pyrrolyl groups other than pyrrol-1-yl groups imidazolyl groups
  • pyridyl groups other than pyridin-1-yl groups represented by the following structural formula More preferred are the groups
  • the imidazolyl group is particularly preferable.
  • the particularly preferred form of the compound represented by the general formula (I) is R from the viewpoint of ease of synthesis, prevention of formation of isomers, and formation of a capsule space that does not release the trapped molecule.
  • 3 is R y
  • R 1 , R 2 , R 4 and R 5 each independently has 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, more preferably 1 or 2 carbon atoms).
  • the compound represented by the general formula (I) includes the following general compounds from the viewpoint of ease of synthesis, prevention of isomer formation, and formation of a capsule space that does not release the trapped molecule.
  • a compound represented by the formula (II) is also preferable.
  • R 1 , R 2 , R 4 , and R 5 are the matters described above for R 1 , R 2 , R 4 , and R 5 in the general formula (I) except that R y is not R y . Can be applied as is.
  • a 1 has the same meaning as A in formula (I), and preferred ranges are also the same.
  • the compound of the present invention includes, for example, reacting a halogen-substituted aromatic compound with a compound corresponding to A in the general formula (I) in the presence of an alkali metal salt to replace the halogen atom with A.
  • a halogen-substituted aromatic compound with a compound corresponding to A in the general formula (I) in the presence of an alkali metal salt to replace the halogen atom with A.
  • 1,4-bis (imidazol-1-yl-methyl) benzene can be synthesized by heating and reacting imidazole and ⁇ , ⁇ '-dibromo-p-xylene in the presence of sodium hydride. Examples of such a synthesis method include C.-H. Zhou, R.-G. Xie, and H.-M. Zhao, Organic. Preparations and Procedures Int., 1996, 28 (3), 345 Has been.
  • exemplary compounds exemplary compounds (a) to (h)) of the compound represented by the general formula (I) are shown.
  • the present invention is not limited to these.
  • the exemplified compound (a) or the exemplified compound (b) is more preferable.
  • Metal ion capable of planar tetracoordinate or octahedral coordination in the present invention examples include Zn 2+ , Cu 2+ , Ni 2+ , Co 2+ , Fe 2+ , Mn 2+ , Ag + , Pd 2+ , and Pt 2+. It is done. Among these, Zn 2+ , Cu 2+ , Ni 2+ , Pd 2+ , and Pt 2+ are preferable, and Cu 2+ is particularly preferable from the viewpoint of the formation of trapping capsule type molecules and the formation of coordination compounds.
  • the coordination compound in the present invention is a compound containing the compound represented by the aforementioned general formula (I) and the aforementioned metal ion.
  • the coordination compound When the coordination compound is brought into contact with the trapped molecule in a liquid sample, the compound represented by the general formula (I) and the metal ion constituting the coordination compound capture the trapped molecule. Reconstituted into capsule-type molecules. For this reason, like the case where the compound represented by the general formula (I) is used as a simple substance, the molecule to be captured can be captured with high selectivity.
  • the coordination compound of the present invention a polymer complex in which a plurality of compounds represented by the general formula (I) are coordinated with each of a plurality of metal ions contained in the coordination compound. Structure is mentioned.
  • the structure of the polymer complex include a two-dimensional sheet structure in which four molecules of the compound represented by the general formula (I) are coordinated with each metal ion.
  • the compound represented by each general formula (I) is arranged between two metal ions, and is coordinated to one metal ion at a nitrogen atom portion in one heterocyclic ring. And is coordinated to the other metal ion at the nitrogen atom in the other heterocyclic ring (see, for example, FIGS. 5 and 6 described later).
  • the coordination compound of the present invention may contain an anion other than a water molecule and the trapped molecule, and these water molecule and anion may be coordinated to the metal ion, It may not be coordinated to the metal ion.
  • an example in which an anion is coordinated to a metal ion is, for example, “A layer” in FIG. 5 described later.
  • examples of water molecules coordinated to metal ions include “B layer” in FIG. 6 to be described later.
  • the anion in the two-dimensional sheet type structure is (1) a metal ion in another two-dimensional sheet type structure.
  • the structure of the coordination compound is a three-dimensional structure in which a plurality of two-dimensional sheet-type structures are stacked (for example, see FIG. 7 described later).
  • two-dimensional sheet-type structures in which water molecules are coordinated to metal ions are anions (for example, sulfate ions). ) May also be included.
  • water molecules in the two-dimensional sheet type structure interact with water molecules in another two-dimensional sheet type structure via anions.
  • the structure of the coordination compound described above has been clarified by, for example, elemental analysis or single crystal structure analysis.
  • Examples of anions other than the trapped molecule that may be contained in the coordination compound of the present invention include OH ⁇ , SO 4 2 ⁇ , CO 3 2 ⁇ , NO 3 ⁇ , CH 3 COO ⁇ , C 2 O 4 2 ⁇ , HCOO ⁇ , Cl ⁇ , Br ⁇ , F ⁇ , PF 6 ⁇ , acetylacetonato (C 5 H 7 O 2 ⁇ ), SiF 6 2 ⁇ , and the like.
  • NO 3 ⁇ , SO 4 2 ⁇ , OH ⁇ , and CO 3 2 ⁇ are preferable, and SO 4 2 ⁇ is more preferable from the viewpoint of the formation of coordination compounds.
  • the metal ion (component A) and the compound represented by the general formula (I) (component B) have a molar ratio [component A / component B] of 1.
  • the method of making it react in the ratio used as / 2 is mentioned.
  • a metal salt composed of the A component and an anion other than the molecule to be trapped (specific examples are as described above) is used as a solvent (for example, water, dimethyl ester).
  • a solvent for example, water, dimethyl ester.
  • Formamide, methanol, ethanol, propanol, acetonitrile, acetone, etc. are dissolved in solution A, and component B is dissolved in another solvent (eg, dimethylformamide, methanol, ethanol, propanol, acetonitrile, acetone, etc.).
  • solvent for example, water, dimethyl ester.
  • component B is dissolved in another solvent (eg, dimethylformamide, methanol, ethanol, propanol, acetonitrile, acetone, etc.).
  • the component A and the component B may be dissolved and reacted in the same solvent.
  • a single solvent such as methanol, dimethylformamide, or ethanol may be used as the solvent.
  • a mixed solvent such as water / acetonitrile, water / dimethylformamide, water / methanol, water / ethanol, methanol / dimethylformamide, ethanol / dimethylformamide or the like may be used.
  • the scavenger in the present invention includes a compound represented by the general formula (I) that exists independently (does not take the form of a coordination compound), and a metal salt, in addition to the form containing the coordination compound. It may be in the form of a mixture.
  • the metal salt the above-mentioned “metal salt composed of the component A and an anion other than the trapped molecule” can be used.
  • porous solid examples include activated carbon, zeolite, ion exchange resin (cation exchange resin or anion exchange resin), clay (clay), silica gel, glass fiber, nonwoven fabric, filter paper, and the like.
  • activated carbon, zeolite, ion exchange resin, clay (clay), and silica gel are preferable, and activated carbon, zeolite, ion exchange resin, and clay (clay) are more preferable.
  • the activated carbon examples include crushed activated carbon, granular activated carbon, and powdered activated carbon. Among them, granular activated carbon and crushed activated carbon are preferable, and crushed activated carbon is more preferable from the viewpoint of the passing speed of the aqueous solution to be treated. preferable.
  • Natural zeolite and synthetic zeolite can be used as the zeolite.
  • zeolite 3A, zeolite 4A, zeolite 5A, and zeolite 13X can be mentioned.
  • zeolite 5A and zeolite 13X are preferable, and zeolite 13X is more preferable.
  • anion exchange resin examples include acrylic anion exchange resins, styrene anion exchange resins, and dimethylamine anion exchange resins. Among them, styrene anion exchange resins and dimethylamine type An anion exchange resin is preferred, and a dimethylamine anion exchange resin is more preferred.
  • cation exchange resin examples include styrene cation exchange resins, methacrylic acid cation exchange resins, and acrylic acid cation exchange resins. Among them, methacrylic acid cation exchange resins are preferable.
  • the pore size of the porous solid in the present invention is not particularly limited, but is preferably 0.4 nm to 1.5 nm, particularly preferably 0.6 nm to 1.0 nm, from the viewpoint of adsorptivity depending on the size of the molecule to be captured.
  • the method of bringing the capturing agent into contact with water containing the molecule to be captured may be a method of adding a capturing agent to the water containing the molecule to be captured or a method of passing water containing the molecule to be captured through the capturing agent.
  • the method of bringing the porous solid into contact with the water containing the molecule to be trapped is the method of adding the porous solid to the water containing the molecule to be trapped. The method of letting it pass may be used.
  • the capturing agent and water containing the molecule to be captured are contacted (hereinafter also referred to as “treatment A”). Further, contacting the porous solid and water containing the molecule to be captured (hereinafter, also referred to as “treatment B”) may be performed simultaneously or separately.
  • the form in which the treatment A and the treatment B are simultaneously performed is a form in which the capture agent and the porous solid are added to a liquid sample (independently or as a mixture),
  • Examples include a form in which a liquid sample is passed through a mixture containing a capture agent and the porous solid.
  • the form in which the process A and the process B are separately performed includes a form in which the process A is performed in the order of the process B and a form in which the process B is performed in the order of the process A.
  • the form in which the process A and the process B are performed independently is the form in which the process A is performed in the order of the process B out of the two forms (that is, the capture agent).
  • the liquid sample after contact with the porous solid is preferably brought into contact with the porous solid.
  • by performing in order from the process A to the process B not only the density
  • processing A to process B the liquid sample is passed through a capture agent (process A), and the liquid sample that has passed through the capture agent is further passed through a porous solid (process B).
  • a capturing agent is added to the liquid sample (processing A), and the unreacted capturing agent is filtered from the liquid sample to which the capturing agent is added.
  • Examples include a form in which a porous solid is added to the liquid sample that has been removed and the capture agent has been removed (Process A).
  • the time for contacting the scavenger and water containing the molecule to be captured is not particularly limited, but is preferably 2 hours or longer, more preferably 6 hours or longer, and particularly preferably 10 hours or longer.
  • the upper limit is not particularly limited, but is, for example, 30 hours.
  • the time for contacting the porous solid with water containing the molecule to be trapped is not particularly limited, and is preferably 2 hours or more, more preferably 6 hours or more, and more preferably 10 hours, although it depends on the kind of the porous solid. The above is particularly preferable.
  • the upper limit is not particularly limited, but is, for example, 30 hours.
  • the liquid sample is heated. May be.
  • the heating temperature varies depending on the type of metal salt, the type of compound represented by formula (I), the type of coordination compound, etc., but is preferably 0 to 100 ° C., more preferably 20 to 70 ° C. .
  • the temperature of the liquid sample in the treatment B varies depending on the kind of the porous solid and the like, but is preferably 5 to 40 ° C., more preferably 20 to 30 ° C. from the viewpoint of adsorptivity.
  • the water purification method of this invention performs other processes, such as a pre-process, a middle process, a post-process. May be included.
  • a pre-process for example, when a liquid sample shows acidity or alkalinity, the liquid sample is passed through a buffer (or a buffer is added to the liquid sample), so that the liquid sample A process to bring it close to sex.
  • the buffer include soil.
  • the post-treatment include filtration with a known filter.
  • the water purification apparatus of the present invention comprises a filtration unit comprising a compound represented by the general formula (I) and a scavenger containing a metal ion capable of planar tetracoordinate or regular octahedral coordination, and a porous solid.
  • a filtration unit comprising a compound represented by the general formula (I) and a scavenger containing a metal ion capable of planar tetracoordinate or regular octahedral coordination, and a porous solid.
  • the water purification device 10 has a filtration unit 12 including a scavenger 14 and a porous solid 16.
  • the filtration unit 12 has a supply port 22 and a discharge port 24, and the flow rate adjusting unit 18 is connected to the discharge port 24.
  • a filter 15 is provided on the downstream side of the capture agent 14 (the discharge port 24 side, hereinafter the same), and a filter 17 is provided on the downstream side of the porous solid 16.
  • the arrangement of the capture agent 14 and the porous solid 16 is the capture agent 14 on the upstream side (the supply port 22 side, hereinafter the same), and the porous solid 16 on the downstream side.
  • a liquid sample is supplied to the filtration part 12 from the direction of arrow I, and the supplied liquid sample contacts the capture agent 14 in the filtration part 12 (the processing A).
  • the molecule to be captured in the liquid sample is captured by the capture agent 14 (that is, a capture capsule type molecule is formed).
  • the liquid sample passes through the filter 15 and comes into contact with the porous solid 16 (process B).
  • the trapped capsule molecules formed as described above are also adsorbed to the porous solid 16.
  • the liquid sample after the above purification treatment passes through the filter 17, the discharge port 24 and the flow rate adjustment unit 18 and is discharged in the direction of the arrow O.
  • the contact time between the liquid sample and the capture agent 14 and the contact time between the liquid sample and the porous solid 16 can be collectively adjusted by the flow rate adjusting unit 18.
  • a preferable range of the contact time is as described above.
  • known means such as an operation valve and an adjustment valve can be used.
  • the structure of the filtration unit 12 include a structure in which the capture agent 14 and the porous solid 16 are placed in a hollow container.
  • a hollow container For example, a well-known column, a filter housing, etc. can be used.
  • the amount of the scavenger 14 is not particularly limited.
  • the upper limit is not particularly limited, but is, for example, 500 g.
  • the amount of the porous solid 16 is not particularly limited.
  • the upper limit is not particularly limited, but is, for example, 500 g.
  • a well-known filter can be used as the filter 15 and the filter 17 provided in the downstream of the capture
  • the water purification device 10 is not limited to the form in which the capture agent 14 and the porous solid 16 are directly put into the hollow container, and the cartridge containing the capture agent 14 and the cartridge containing the porous solid 16 are mounted in the hollow container. It may be a form to do.
  • the trapping agent 14 that is, the trapping portion
  • the porous solid 16 that is, the adsorbing portion
  • the trapping agent 14 and the porous solid 16 are divided into two filtration portions. 14 and the porous solid 16 may be mixed to constitute one filtration unit.
  • a capturing agent 14 as a capturing part upstream and a porous solid 16 as an adsorbing part downstream as shown in FIG. .
  • a flow rate adjusting unit may be provided on the upstream side of the filtering unit 12 in the liquid sample flow path so that the supply rate of the liquid sample can be adjusted.
  • the water purification device 30 includes a capturing unit 32 having the capturing agent 14 and an adsorption unit 42 including the porous solid 16.
  • the capturing unit 32 and the adsorbing unit 42 constitute a filtering unit.
  • the matters described for the filtering unit 12 in the water purifier 30 can be applied as they are.
  • the preferred amounts of the scavenger 14 and the porous solid 16 are the same as in the case of the water purification device 10.
  • the capturing unit 32 has a supply port 36 and a discharge port 37.
  • a filter 35 is provided on the downstream side of the capture agent 14 (on the discharge port 37 side, the same applies hereinafter).
  • the filter 35 can be omitted.
  • the adsorbing part 42 has a supply port 46 and a discharge port 47, and a filter 45 is provided on the downstream side of the porous solid 16 (the discharge port 47 side, the same applies hereinafter).
  • the filter 45 can be omitted.
  • the discharge port 37 of the capturing unit 32 and the supply port 46 of the suction unit 42 are connected by a connection unit 40.
  • the connection unit 40 may have a flow rate adjusting function as will be described later.
  • a flow rate adjusting unit 50 is connected to the discharge port 47 of the adsorption unit 42.
  • water liquid sample
  • a liquid sample is supplied to the capturing unit 32 from the direction of the arrow I, and the supplied liquid sample contacts the capturing agent 14 in the capturing unit 32 (Processing A).
  • the molecule to be captured in the liquid sample is captured by the capture agent 14 (that is, a capture capsule type molecule is formed).
  • the liquid sample after contacting the capture agent 14 is transferred to the adsorption unit 42 through the filter 35, the discharge port 37, the connection unit 40, and the supply port 46.
  • the transferred liquid sample comes into contact with the porous solid 16 (Process B).
  • the contact time between the liquid sample and the capture agent 14 and the contact time between the liquid sample and the porous solid 16 can be collectively adjusted by the flow rate adjusting unit 50.
  • a preferable range of the contact time is as described above.
  • known means such as an operation valve and an adjusting valve can be used.
  • the means similar to the flow volume control part 50 can also be provided in another location.
  • the term “between the capture unit 32 and the adsorption unit 42 in the flow path of the liquid sample” refers to, for example, the downstream side of the capture unit 32 (for example, the vicinity of the discharge port 37) and the upstream side of the adsorption unit 42 (for example, supply) The vicinity of the mouth 46), and the like.
  • connection part 40 may have a flow volume adjustment function.
  • a flow rate adjusting unit may be provided on the upstream side of the capturing unit 32 (for example, in the vicinity of the supply port 36) in the liquid sample flow path so that the supply rate of the liquid sample can be adjusted.
  • connection between the capture unit 32 and the suction unit 42 is not limited to using the independent connection unit 40 shown in FIG.
  • the end part of the capture part 32 and the end part of the suction part 42 may be provided with a mutually connectable mechanism (such as a screw mechanism), and the capture part 32 and the suction part 42 may be connected by this mechanism. .
  • the water purification apparatus of this invention is not limited to the said 2 examples. Absent.
  • a structure such as a known water purifier can be used without particular limitation.
  • the water purification set of the present invention comprises a scavenger containing a compound represented by the general formula (I) and a metal ion capable of planar tetracoordinate or octahedral coordination, and a porous solid.
  • the water purification method of the present invention can be performed using the water purification set. That is, the process A can be performed using a scavenger, and the process B can be performed using a porous solid.
  • An advantage of using the water purification set is that the capturing agent can be easily brought into contact with the liquid sample for an arbitrary time. For example, after the capture agent is filled in a glass filter container, it is possible to perform an operation such as immersing in a liquid sample for an arbitrary time, and subsequently immersing activated carbon or an ion exchange resin in an aqueous solution for an arbitrary time.
  • the water purification set there is a form of a set in which the scavenger and the porous solid are combined in a state where they are individually put in a container.
  • a set in which one type of capture agent and porous solid is combined may be used, or a set including a plurality of types of capture agent and / or porous solid (that is, depending on conditions such as a molecular species to be captured).
  • a set in which a combination of a capturing agent and a porous solid can be selected.
  • the capture agent and the porous solid can be used out of the container at the time of use.
  • a set form in which a capturing member including a capturing agent and an adsorption member including a porous solid are combined is also suitable.
  • a set in which one type of capture member and adsorption member is combined may be used, or a set including a plurality of types of capture members and / or adsorption members (that is, capture is performed according to conditions such as the species to be captured). It may be a set in which a combination of a member and an adsorbing member can be selected.
  • the capturing member and the adsorbing member members having the same structure as the capturing unit 32 and the adsorbing unit 42 described for the water purification device 30 described above can be applied.
  • the process A can be performed using a capturing member
  • the process B can be performed using an adsorption member.
  • the water purifier of this invention can be obtained by connecting the said capture member and the said adsorption member.
  • the connection may be performed using an independent connection member, or by providing a mechanism (screw mechanism or the like) that can be connected to each other at the end of the capturing means and the end of the suction means. You may go.
  • the obtained purple crystals were collected, and the structure of the purple crystals was confirmed by single crystal structure analysis and mass spectrometry measurement.
  • Single crystal structure analysis was performed using a structure analysis apparatus (Mercury two-dimensional detector system) manufactured by Rigaku Corporation and collecting X-ray reflection data using a molybdenum K ⁇ radiation source at room temperature.
  • the structural analysis was performed using the Crystal Structure program manufactured by Rigaku Corporation.
  • the mass spectrometry measurement was performed using the LCT mass spectrometer made from Micromass.
  • FIGS. 3 and 4 show the structure of the trapped capsule molecule, which has been clarified from the single crystal structure analysis data and the mass spectrometry measurement.
  • the structure of the trapping capsule molecule is a structure in which a capsule skeleton formed by two copper (II) ions and four bit4 molecules encloses one molecule of perchlorate ion.
  • perchlorate ions are coordinated to both copper (II) ions one molecule at a time from the outside of the capsule.
  • the size of the space formed by two copper (II) ions and the bitb4 molecule is 6.5 0.6 (0.65 nm) ⁇ 6.5 ⁇ (0.65 nm) ⁇ 5.0 ⁇ ( 0.50 nm), and was a size that contained perchlorate ions so as not to be detached.
  • hydrogen atoms are omitted.
  • the obtained purple crystals were dissolved in any of dimethylformamide, methanol, ethanol, acetonitrile, and acetone. This result also shows that the purple crystal has the structure of a trapped capsule molecule.
  • the resulting blue crystal was subjected to single crystal structure analysis.
  • the blue crystal was not soluble in the solvent and could not be subjected to mass spectrometry, the ratio of carbon, hydrogen, and nitrogen in the blue crystal was confirmed by elemental analysis and matched with the single crystal structure analysis result. It was confirmed.
  • the obtained blue crystal is not a capture capsule type molecule as in Reference Example 2, but a coordination compound ( ⁇ [Cu (bitb) 2 (H 2 O) 2 ] ⁇ It was found to be a polymer complex represented by [Cu (bitb) 2 (SO 4 ) 2 ] ⁇ ⁇ ; hereinafter also referred to as “Cu-bitb polymer”). The detailed structure of the coordination compound will be described later.
  • the obtained blue crystals did not dissolve in any of water, dimethylformamide, methanol and ethanol.
  • This result also shows that the blue crystals are not the structure of the trapped capsule molecule, but the coordination compound ( ⁇ [Cu (bitb) 2 (H 2 O) 2 ] ⁇ [Cu (bitb) 2 (SO 4 ) 2 ] ⁇ ⁇
  • the coordination compound ⁇ [Cu (bitb) 2 (H 2 O) 2 ] ⁇ [Cu (bitb) 2 (SO 4 ) 2 ] ⁇ ⁇
  • the reason why the blue crystal takes the structure of the coordination compound rather than the structure of the trapping capsule type molecule is thought to be that the size of the sulfate ion is larger than the size of the perchlorate ion.
  • the capsule skeleton since the size of the molecule that can be encapsulated by the capsule skeleton consisting of the bit4 molecule and two metal ions does not match the size of the sulfate ion, the capsule skeleton is not formed, and the coordination compound is formed.
  • FIGS. 5 to 7 show the structures of the coordination compounds that have been clarified from the results of elemental analysis and single crystal structure analysis.
  • the ionic species having six bonds represents a copper (II) ion, and one six-membered ring and two five-membered rings (heterocycles) arranged between two copper (II) ions.
  • bitb is coordinated to one copper (II) ion at the nitrogen atom in one heterocyclic ring, and coordinated to the other copper (II) ion at the nitrogen atom in the other heterocyclic ring. is doing.
  • the coordination compound has a structure spread in an infinite chain, in FIGS.
  • the structure of the coordination compound is a three-dimensional structure in which two types of two-dimensional sheet-type structures (A layer shown in FIG. 5 and B layer shown in FIG. 6) are alternately stacked ( FIG. 7). Details of each structure will be described below.
  • the A layer shown in FIG. 5 is a two-dimensional sheet-type structure that is formed by coordinating four molecules of bitb to one copper (II) ion and spreads in an infinite two-dimensional manner. More specifically, the A layer has a negatively charged two-dimensional sheet structure [Cu (bitb) 2 (SO 4 ) 2 in which two molecules of sulfate ions are coordinated with the copper (II) ion. ] ⁇ .
  • arrows a and b represent axes parallel to the two-dimensional plane of the A layer (hereinafter also referred to as “a axis” and “b axis”).
  • the B layer shown in FIG. 6 is also a two-dimensional sheet-type structure that is formed by coordinating four molecules of bitb to one copper (II) ion and spreads in an infinite two-dimensional manner. More specifically, the B layer is a positively charged two-dimensional sheet structure [Cu (bitb) 2 (H 2 O) in which two molecules of water are coordinated with the copper (II) ion. 2 ] ⁇ .
  • arrows a and b represent axes parallel to the two-dimensional plane of the B layer (hereinafter also referred to as “a axis” and “b axis”).
  • the three-dimensional structure shown in FIG. 7 is a structure in which the A layer and the B layer are alternately stacked.
  • an arrow c represents an axis that is not parallel to the two-dimensional plane of the A layer and the B layer.
  • the A layer and the B layer are respectively arranged on the ab plane, and have a structure in which they are alternately stacked along the c-axis.
  • Example 1 ⁇ Experiment on removal of perchlorate ion> ⁇ Sample 1 (blank) ⁇ Sodium perchlorate was dissolved in distilled water to prepare Sample 1 (30 ml) containing 100 ppm of perchlorate ions. About the obtained sample 1 (blank), the density
  • the measurement was performed using an ion chromatograph IC 861 manufactured by Metrohm. The measurement was performed by a CO 2 differential presser method, and anions were detected by an electric conductivity detector. The measurement was performed at room temperature of 23 ° C., and the sample used for the measurement was filtered through a membrane filter, and the aqueous solution used for the measurement was purified with an ultrapure water production apparatus Direct-Q manufactured by Millipore.
  • Sample 2 The sample 1 is represented by the coordination compound ( ⁇ [Cu (bitb) 2 (H 2 O) 2 ] ⁇ [Cu (bitb) 2 (SO 4 ) 2 ] ⁇ ⁇ ) obtained in Reference Example 3.
  • a polymer complex hereinafter referred to as “Cu-bitb polymer” (46 mg) was added (treatment A), and allowed to stand for 24 hours to obtain a sample 2. About the obtained sample 2, the same measurement as the sample 1 was performed.
  • Sample 3 Sample 3 ⁇ Sample 1 above includes 50 mg of activated carbon (activated carbon manufactured by Wako Pure Chemicals, crushed 0.2 mm to 1 mm), 50 mg of ion exchange resin (weakly basic anion exchange resin WA-30 manufactured by Mitsubishi Chemical Corporation), or zeolite (Union Showa) 50 mg of Molecular Sieve 13X (manufactured by Co., Ltd.) was added (Processing B) and allowed to stand for 24 hours to obtain Sample 3, Sample 6, or Sample 9. With respect to the obtained sample 3, sample 6, or sample 9, the same measurement as that of sample 1 was performed.
  • activated carbon activated carbon manufactured by Wako Pure Chemicals, crushed 0.2 mm to 1 mm
  • ion exchange resin weakly basic anion exchange resin WA-30 manufactured by Mitsubishi Chemical Corporation
  • zeolite Union Showa
  • Sample 4 Sample 4, Sample 7, Sample 10 ⁇
  • AB simultaneous this treatment is referred to as “AB simultaneous”
  • the sample was allowed to stand for 24 hours to obtain Sample 4, Sample 7, or Sample 10.
  • sample 7, or sample 10 the same measurement as that of sample 1 was performed.
  • Example 2 ⁇ Comparison of copper ion concentration> Next, with respect to Sample 4, Sample 5, Sample 7, Sample 8, Sample 10, and Sample 11 in Example 1, the concentration of copper ions was measured under the following conditions.
  • Multi-type ICP emission spectrometer After adding nitric acid (1%) to 20 ml of sample and thermally decomposing it, the sample is made up to 20 ml and the concentration of copper ions contained in the aqueous solution is determined using a multi-type ICP emission spectrometer (ICP (VISTA-MPX manufactured by Varian). )).
  • ICP VISTA-MPX manufactured by Varian.
  • Example 3 ⁇ Experiment on Removal of Tetrafluoroborate Ion (BF 4 ⁇ )> Sample 101 (30 ml) containing 100 ppm of tetrafluoroborate ions was prepared by dissolving sodium tetrafluoroborate in distilled water. In addition, the concentration (100 ppm) of tetrafluoroborate ions in the sample 101 (blank) is a value measured under the above-described conditions by ion chromatography.
  • sample 101 46 mg of Cu-bitb polymer, 50 mg of activated carbon (activated carbon made by Wako Pure Chemicals, crushed 0.2 mm to 1 mm), 50 mg of ion exchange resin (WA-30), or 50 mg of zeolite (13X)
  • activated carbon activated carbon made by Wako Pure Chemicals, crushed 0.2 mm to 1 mm
  • ion exchange resin WA-30
  • zeolite 13X
  • this treatment is referred to as “AB simultaneous”
  • the sample was allowed to stand for 24 hours to obtain Sample 102, Sample 104, or Sample 106.
  • the obtained sample 102, sample 104, or sample 106 was measured in the same manner as the sample 101.

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JP2012026981A (ja) * 2010-07-27 2012-02-09 Maezawa Ind Inc テトラフルオロホウ酸イオン検出剤、テトラフルオロホウ酸イオン検出キット、及びテトラフルオロホウ酸イオン検出方法
CN103979664A (zh) * 2014-06-03 2014-08-13 武汉纺织大学 一种oms-2活化过硫酸盐降解有机废水的方法
JP5954829B2 (ja) * 2011-01-28 2016-07-20 国立大学法人静岡大学 カプセル型化合物、陰イオン除去剤、及び陰イオン除去方法

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JP5842943B2 (ja) * 2014-02-19 2016-01-13 三浦工業株式会社 水処理方法及び水処理システム
FR3082525B1 (fr) * 2018-06-18 2022-04-01 Commissariat Energie Atomique Procede d'extraction du cobalt d'une solution comprenant, outre le cobalt, un ou plusieurs autres elements metalliques

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JP2012026981A (ja) * 2010-07-27 2012-02-09 Maezawa Ind Inc テトラフルオロホウ酸イオン検出剤、テトラフルオロホウ酸イオン検出キット、及びテトラフルオロホウ酸イオン検出方法
JP5954829B2 (ja) * 2011-01-28 2016-07-20 国立大学法人静岡大学 カプセル型化合物、陰イオン除去剤、及び陰イオン除去方法
CN103979664A (zh) * 2014-06-03 2014-08-13 武汉纺织大学 一种oms-2活化过硫酸盐降解有机废水的方法
CN103979664B (zh) * 2014-06-03 2016-01-06 武汉纺织大学 一种oms-2活化过硫酸盐降解有机废水的方法

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