WO2023063339A1 - 被処理液の精製方法 - Google Patents

被処理液の精製方法 Download PDF

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Publication number
WO2023063339A1
WO2023063339A1 PCT/JP2022/037992 JP2022037992W WO2023063339A1 WO 2023063339 A1 WO2023063339 A1 WO 2023063339A1 JP 2022037992 W JP2022037992 W JP 2022037992W WO 2023063339 A1 WO2023063339 A1 WO 2023063339A1
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Prior art keywords
liquid
group
treated
resin
purifying
Prior art date
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Ceased
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PCT/JP2022/037992
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English (en)
French (fr)
Japanese (ja)
Inventor
岳史 塩野
丈嗣 平居
祐子 蟻浪
佳奈 田辺
圭 石塚
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AGC Inc
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Asahi Glass Co Ltd
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Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to CN202280068947.9A priority Critical patent/CN118176168A/zh
Priority to KR1020247008175A priority patent/KR20240087681A/ko
Priority to EP22881034.7A priority patent/EP4417582A4/en
Priority to JP2023554558A priority patent/JPWO2023063339A1/ja
Publication of WO2023063339A1 publication Critical patent/WO2023063339A1/ja
Priority to US18/632,721 priority patent/US20240291009A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0693—Treatment of the electrolyte residue, e.g. reconcentrating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/05—Processes using organic exchangers in the strongly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/04—Processes using organic exchangers
    • B01J41/07—Processes using organic exchangers in the weakly basic form
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0239—Organic resins; Organic polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04007—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids related to heat exchange
    • H01M8/04044—Purification of heat exchange media
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • 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
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/36—Organic compounds containing halogen
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a method for purifying a liquid to be treated.
  • a fuel cell includes an electrolyte membrane and an anode and a cathode separated by the electrolyte membrane, for example, by supplying a gas containing oxygen to the cathode and a gas containing hydrogen to the anode, Generate electricity.
  • a quaternary ammonium base is used to remove contaminants contained in unreacted fuel discharged from a fuel cell and impurities contained in a coolant fluid used in the cooling system of the fuel cell.
  • an ion exchange filter comprising a resin having
  • the water electrolyzer includes an electrolyte membrane, and an anode and a cathode separated by the electrolyte membrane.
  • water is supplied to the anode, and a voltage is applied between the anode and the cathode to electrolyze the water and Oxygen generated at the cathode and hydrogen generated at the cathode are recovered.
  • Excess water is recovered together with oxygen on the anode side, and water that has passed through the electrolyte membrane is recovered together with hydrogen on the cathode side.
  • the recovered hydrogen and oxygen are separated into gas and water by gas-liquid separation, and the separated water is reused for the anode of the water electrolysis device.
  • liquid produced by the electrochemical reaction of the fuel cell containing the fluoropolymer having ion-exchange groups may be discharged.
  • the liquid discharged in this way contains a compound containing an ionic group and a fluorine atom and having an aliphatic hydrocarbon group, which is produced by chemically degrading a fluorine-containing polymer having an ion-exchange group.
  • ionic groups generated by chemical deterioration of the fluorine-containing polymer having an ion-exchange group may be present in surplus water on the anode side or permeated water on the cathode side.
  • Patent Document 1 a resin having a quaternary ammonium base as described in Patent Document 1 to evaluate the removability of the compound having an aliphatic hydrocarbon group, and found that there was room for improvement. I found something.
  • the present invention has been made in view of the above problems, and an object thereof is to provide a method for purifying a liquid to be treated, which contains an ionic group and a fluorine atom and is excellent in removability of a compound having an aliphatic hydrocarbon group.
  • a method for purifying a liquid to be treated. [8] The liquid to be treated is a liquid generated by an electrochemical reaction in a fuel cell or water electrolyzer containing a fluoropolymer having an ion-exchange group, and discharged out of the fuel cell or water electrolyzer system.
  • the tertiary amino group is a group represented by -NR N1 R N2 (wherein R N1 and R N2 are each independently a monovalent substituent) [1]-
  • the monovalent substituents in R N1 and R N2 may contain an etheric oxygen atom or a hydroxy group, an alkyl group, an alkenyl group, an aryl group, an acetyl group, a benzoyl group, a benzenesulfonyl group, or The method for purifying a liquid to be treated according to [9], which is a tert-butoxycarbonyl group.
  • the purification method is a method in which the liquid to be treated is passed through a container filled with the resin having a tertiary amino group, and the treatment rate of the liquid to be treated is represented by the following formula SV is 1 Hr ⁇ 1 or more and 400 Hr ⁇ 1 or less, the method for purifying a liquid to be treated according to any one of [1] to [12].
  • SV (Hr -1 ) flow rate (mL Hr -1 )/resin volume (mL) [14]
  • BV Total amount of liquid passed (mL) / Resin volume (mL)
  • the present invention it is possible to provide a method for purifying a liquid to be treated that contains an ionic group and a fluorine atom and is excellent in removability of a compound having an aliphatic hydrocarbon group.
  • FIG. 1 is a cross-sectional view schematically showing an example of a membrane electrode assembly used in a fuel cell or water electrolysis device
  • An "ion-exchange group” is a group capable of exchanging at least part of the ions contained in this group with other ions, and examples thereof include the following sulfonic acid-type functional groups and carboxylic acid-type functional groups.
  • “Sulfonic acid-type functional group” means a sulfonic acid group ( -SO3H ) or a sulfonate group ( -SO3M2 , where M2 is an alkali metal or quaternary ammonium cation) . do.
  • Carboxylic acid-type functional group means a carboxylic acid group (—COOH) or a carboxylic acid group (—COOM 1 , where M 1 is an alkali metal or quaternary ammonium cation).
  • An "aliphatic hydrocarbon group” is an aliphatic group composed of carbon atoms and hydrogen atoms, and means, for example, an alkyl group, an alkylene group, an alkenyl group, an alkynyl group, and the like.
  • a "unit" in a polymer means an atomic group derived from one molecule of a monomer formed by polymerizing the monomer.
  • the unit may be an atomic group directly formed by the polymerization reaction, or may be an atomic group in which a part of the atomic group is converted to another structure by treating the polymer obtained by the polymerization reaction. good.
  • a numerical range represented using “to” means a range including the numerical values described before and after “to” as lower and upper limits.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described stepwise.
  • the upper limit or lower limit described in a certain numerical range may be replaced with the values shown in the examples.
  • the amount of each component in the liquid to be treated is the total amount of the multiple substances present in the liquid to be treated unless otherwise specified. means.
  • ppm means “mg/L”
  • ppb means “ ⁇ g/L”
  • ppt means "ng/L”, as units indicating the concentration in the liquid.
  • the method for purifying a liquid to be treated of the present invention comprises at least one ionic group selected from the group consisting of a carboxylic acid group and a sulfonic acid group, and a fluorine atom.
  • a compound having an aliphatic hydrocarbon group (hereinafter also referred to as a "fluorine-containing aliphatic hydrocarbon compound containing an ionic group"), which may contain an oxygen atom, and HF and H 2 SO 4
  • specific acid an acid selected from the group
  • specific resin tertiary amino group
  • the liquid to be treated used for purification in this purification method contains a specific acid. This lowers the pH of the liquid to be treated, promotes protonation of the tertiary amino group of the specific resin, and forms an ion pair with the specific acid as an anion, thereby enhancing the anion exchange ability of the specific resin. presumed to have improved.
  • the liquid to be treated used for purification in the present purification method contains a fluorine-containing aliphatic hydrocarbon compound containing an ionic group, a specific acid, and water.
  • the fluorine-containing aliphatic hydrocarbon compound containing an ionic group includes at least one ionic group selected from the group consisting of a carboxylic acid group and a sulfonic acid group, a fluorine atom, and an oxygen atom.
  • a compound having an aliphatic hydrocarbon group which may contain
  • the fluorine-containing aliphatic hydrocarbon compound containing an ionic group is preferably a compound represented by formula (X), since it is more easily removed in the purification step.
  • Formula (X) (HOOC) m -L-(SO 3 H) n
  • L is an m+n-valent aliphatic hydrocarbon group containing a fluorine atom which may contain an oxygen atom, preferably an m+n-valent aliphatic hydrocarbon group containing an oxygen atom and a fluorine atom.
  • the aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, preferably a saturated hydrocarbon group.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic, but preferably linear or branched.
  • the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 or more, more preferably 2 or more, still more preferably 5 or more, and preferably 20 or less, more preferably 18 or less, and still more preferably 14 or less. At least one hydrogen atom in the aliphatic hydrocarbon group may be substituted with a fluorine atom, and all hydrogen atoms in the aliphatic hydrocarbon group may be substituted with fluorine atoms.
  • the number of etheric oxygen atoms may be 1 or 2 or more, preferably 4 or less.
  • Etheric oxygen atoms are preferably located between carbon atoms of the aliphatic hydrocarbon group.
  • n is an integer of 0 to 2, preferably 1 or 2.
  • m is an integer of 0-3.
  • the sum of m and n is 1 or more.
  • the compound represented by the formula (X) is preferably a compound in which m is 1 and n is 1 in that it is more easily removed in the purification step.
  • Compounds represented by the formula (X) are also preferably compounds in which m is 0 and n is 1.
  • Compounds represented by formula (X) are also preferably compounds in which m is 1 and n is 2.
  • fluorine-containing aliphatic hydrocarbon compounds containing ionic groups are shown below.
  • the fluorine-containing aliphatic hydrocarbon compound containing an ionic group may be contained singly or in combination of two or more.
  • the concentration of the fluorine-containing aliphatic hydrocarbon compound containing an ionic group in the liquid to be treated is preferably 0.2 ppb or more, more preferably 0.3 ppb or more, still more preferably 0.5 ppb or more, and preferably 1000 ppb or less. , is more preferably 100 ppb or less, and even more preferably 10 ppb or less.
  • the specific acid is at least one acid selected from the group consisting of HF and H2SO4 .
  • the liquid to be treated contains either one of HF and H 2 SO 4 , and may contain both. It is preferred to include both.
  • the specific acid may be ionized in the liquid to be treated and exist in the form of ions.
  • the concentration of the specific acid in the liquid to be treated is preferably 0.1 ppb or more, more preferably 1 ppb or more, and even more preferably 5 ppb or more, in terms of better removability of the fluorine-containing aliphatic hydrocarbon compound containing an ionic group.
  • F 2 - and SO 4 2- it is preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less, because it is excellent in suppressing competition for adsorption by 2-, F 2 - and SO 4 2-.
  • the concentration of water in the liquid to be treated is preferably 900 g/L or more, more preferably 990 g/L or more, still more preferably 999 g/L or more, and preferably less than 1000 g/L.
  • the liquid to be treated may contain components other than the fluorine-containing aliphatic hydrocarbon compound containing an ionic group, the specific acid and water. Specific examples of other components include metal ions and chloride ions.
  • the concentration of the other components in the liquid to be treated is preferably 100000 ppm or less, more preferably 10000 ppm or less, and even more preferably 1000 ppm or less.
  • the pH of the liquid to be treated is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably less than 7.
  • the liquid to be treated may be a liquid obtained by mixing the components described above, or may be a liquid generated by an electrochemical reaction in a fuel cell or water electrolysis device containing a fluorine-containing polymer having an ion exchange group.
  • the liquid to be treated is a liquid generated by an electrochemical reaction in a fuel cell or a water electrolysis device containing a fluorine-containing polymer having an ion-exchange group
  • the liquid to be treated is, for example, an electrochemical reaction of the fuel cell.
  • a fluorine-containing aliphatic hydrocarbon compound containing an ionic group and a specific acid are dissolved in the water generated by the reaction.
  • the fluorine-containing aliphatic hydrocarbon compound and specific acid containing an ionic group are decomposed products or extractables of a fluorine-containing polymer having an ion-exchange group contained in materials constituting a fuel cell or a water electrolysis device. It is speculated that When the liquid to be treated is a liquid generated by an electrochemical reaction in a fuel cell or water electrolyzer containing a fluorine-containing polymer having an ion-exchange group, the liquid to be treated is subjected to a refining process and then recharged to the fuel cell or water electrolyzer. It may be reused in the system or may be discharged outside the system, but it is preferable to discharge it outside the system in terms of simplicity of the system.
  • the fuel cell system refers to the cell stack, anode gas and cathode gas supply units, circulation unit and humidity control unit, and stack cooling medium supply unit and circulation unit. It also includes a fuel reformer when using hydrogen produced by reforming.
  • the system of the water electrolyzer consists of a cell stack, a fluid supply section to the cell stack and a humidity adjustment section, a stack cooling medium supply section and circulation section, a recovery section for the fluid discharged from the cell stack, and a liquid discharge section for the cell stack. It refers to the circulating part of the collected water to the cell stack.
  • the specific resin is a resin having a tertiary amino group as described above, and is an anion exchange resin used for removing a fluorine-containing aliphatic hydrocarbon compound containing an ionic group from the liquid to be treated in the purification step.
  • a tertiary amino group is a disubstituted amino group represented by —NR N1 R N2 (wherein R N1 and R N2 are each independently a monovalent substituent).
  • R N1 and R N2 include alkyl groups, alkenyl groups, aryl groups, acetyl groups, benzoyl groups, benzenesulfonyl groups, and tert-butoxycarbonyl groups which may contain an etheric oxygen atom or a hydroxy group.
  • An alkyl group and an alkenyl group are preferred, and an alkyl group is more preferred.
  • the number of carbon atoms in R N1 and R N2 is each independently preferably 1 or more, preferably 10 or less, more preferably 6 or less, and even more preferably 5 or less.
  • tertiary amino groups include dimethylamino, diethylamino, dipropylamino, dibutylamino, ethylmethylamino, diphenylamino and methylphenylamino groups.
  • Examples of the base resin in the specific resin include styrene-based resins and (meth)acrylic-based resins, and mixed resins of these may be used.
  • Styrene-based resins include cross-linked copolymers of styrene-based monomers such as styrene, ethylstyrene and methylstyrene, and cross-linking agents such as divinylbenzene and trivinylbenzene. Polymers are preferred.
  • (Meth)acrylic resins include monomers ((meth)acrylic acid esters) having (meth)acryloyl groups such as ethyl acrylate, methyl (meth)acrylate and glycidyl (meth)acrylate, and ethylene glycol di(meth) ) acrylates, polyethylene glycol di(meth)acrylates, divinylbenzene, trivinylbenzene, and other cross-linking copolymers with cross-linking agents, and cross-linking copolymers of acrylic acid esters and divinylbenzene are preferred.
  • monomers ((meth)acrylic acid esters) having (meth)acryloyl groups such as ethyl acrylate, methyl (meth)acrylate and glycidyl (meth)acrylate, and ethylene glycol di(meth) ) acrylates, polyethylene glycol di(meth)acrylates, divinylbenzene, trivinylbenzene, and other cross-
  • the shape of the specific resin is not particularly limited, it may be bead-like, fibrous, granular, film-like, or hollow-fiber-like.
  • the shape of the specific resin is preferably a bead shape from the viewpoint of cost and excellent workability at the time of replacement.
  • the structure of the specific resin is not particularly limited, examples thereof include gel type, porous type, and highly porous type.
  • the structure of the specific resin is preferably gel-type or porous-type from the viewpoint of excellent mechanical strength and removal efficiency.
  • Specific resins may be commercially available products such as Diaion (registered trademark) WA30, WA10 (all manufactured by Mitsubishi Chemical Corporation), Amberlite (registered trademark) IRA478RF, IRA67, IRA96SB, IRA98, XE583 (all manufactured by Organo Co., Ltd.).
  • the purification step is a step of contacting a liquid to be treated with a specific resin to remove a fluorine-containing aliphatic hydrocarbon compound containing an ionic group from the liquid to be treated.
  • Specific examples of the method of contacting the liquid to be treated with the specific resin include a method of mixing and stirring the specific resin and the liquid to be treated, and passing the liquid to be treated through a container (column, etc.) filled with the specific resin.
  • the latter method is preferred in terms of excellent purification efficiency.
  • a purification process using a column filled with a specific resin will be described as an example.
  • the processing speed SV of the liquid to be treated can increase the processing speed relative to the amount of the specific resin used.
  • the amount of the specific resin used it is preferably 1 Hr -1 or more, more preferably 10 Hr -1 or more, and still more preferably 100 Hr -1 or more, and a fluorine-containing aliphatic hydrocarbon compound containing an ionic group. is preferably 400 Hr -1 or less, more preferably 300 Hr -1 or less, and even more preferably 200 Hr -1 or less, from the viewpoint of better performance in removing .
  • the resin volume refers to the volume of a specific resin and water at 23°C placed in a graduated cylinder, soaked for 12 hours or more, and then vibrating the graduated cylinder to prevent the height of the resin layer from changing. refers to the volume at
  • the temperature of the liquid to be treated when passing through the column is preferably 0° C. or higher, more preferably 10° C. or higher, from the viewpoint of better performance in removing fluorine-containing aliphatic hydrocarbon compounds containing ionic groups. C. or higher is more preferable, and from the heat resistance point of the specific resin, it is preferably 130.degree. C. or lower, more preferably 120.degree.
  • the packing length of the specific resin in the column is preferably 3 cm or more, more preferably 5 cm or more, and still more preferably 10 cm or more, from the viewpoint of better performance in removing fluorine-containing aliphatic hydrocarbon compounds containing ionic groups. , from the point that the volume occupied by the column can be reduced, it is preferably 1000 cm or less, more preferably 500 cm or less, and even more preferably 100 cm or less.
  • the column may be straight or curved.
  • a linear shape is preferable from the viewpoint that the liquid flows uniformly in the column, but the volume occupied by the column can be reduced, and the ability to remove fluorine-containing alkyl compounds containing ionic groups can be increased with respect to the amount of the specific resin used. From the point of view, a curved shape is preferable.
  • Materials for the inner wall of the column include metal, glass, hydrocarbon resin, and fluororesin.
  • a hydrocarbon resin or a fluororesin is preferred from the viewpoint of excellent corrosion resistance, and polyethylene, polypropylene, and PFA (a copolymer of tetrafluoroethylene and perfluoroalkoxyethylene) are preferred.
  • Metal is preferred when weather resistance and mechanical strength are important, and among metals, stainless steel (SUS304, SUS316, etc.) is preferred in terms of cost.
  • purification is preferably carried out until the concentration of the fluorine-containing aliphatic hydrocarbon compound containing an ionic group in the liquid to be treated after the purification step (hereinafter also referred to as "purification liquid") is 100 ppt or less. , more preferably 70 ppt or less, more preferably 50 ppt or less.
  • the purification step not only the fluorine-containing aliphatic hydrocarbon compound containing the ionic group is removed, but also the anions in the specific acid are removed.
  • purification is preferably performed until the concentration of anions in the specific acid in the purification solution is 20 ppb or less, more preferably 10 ppb or less, and 5 ppb or less. is more preferred.
  • the purification process may be performed only once, or may be performed multiple times.
  • Implementation only once refers to contacting the liquid to be treated with the specific resin only once.
  • Multiple implementation refers to contacting the liquid to be treated after performing the purification step once with the same or another specific resin one or more times.
  • the liquid to be treated is circulated by means of a pump, pressure, or the like in a circulating apparatus comprising a tank for temporarily storing the liquid to be treated and a pipe connecting the two in a circular manner, thereby repeating the refining process.
  • the number of times of the purification process is preferably only once because the equipment required for purification is simple, and the liquid to be treated is passed only once through a container (column, etc.) filled with a specific resin. method is more preferred.
  • the fluorine-containing aliphatic hydrocarbon compound containing an ionic group in the liquid to be treated is in the form of a metal salt, which prevents the purification process from being identified.
  • the ability of the resin to remove a fluorine-containing aliphatic hydrocarbon compound containing an ionic group may decrease. Therefore, it is preferable to remove the metal ions in the liquid to be treated.
  • Methods for removing metal ions in the liquid to be treated include, for example, a method in which the liquid to be treated is brought into contact with a cation exchange resin and then subjected to a purification process, and a mixed resin in which a cation exchange resin and a specific resin are mixed in the purification process. and a method of bringing the liquid to be treated into contact with the mixed resin.
  • the former method is preferred from the viewpoint of excellent performance in removing a fluorine-containing aliphatic hydrocarbon compound containing an ionic group, and the latter method is preferred from the viewpoint of simplicity of the equipment required for purification.
  • the purification method of the treatment liquid may include steps other than the purification step.
  • steps include a step of contacting the specific resin with water (for example, pure water or ion-exchanged water) to wash the specific resin prior to the purification step, and a step of replacing the gas contained in the specific resin with water.
  • Degassing process for example, degassing by using a vacuum pump while immersed in water, degassing by applying vibration while immersed in water
  • pretreatment process By performing the pretreatment step, the removability of the fluorine-containing aliphatic hydrocarbon compound containing an ionic group by the specific resin is further improved.
  • the liquid to be treated is a liquid produced by an electrochemical reaction in a fuel cell or water electrolysis device containing a fluoropolymer having ion exchange groups (hereinafter also referred to as "fluoropolymer (I)").
  • fluoropolymer (I) may be a polymer contained in an electrolyte membrane in a fuel cell or water electrolysis device, or a polymer contained in an electrode (anode or cathode).
  • fluoropolymer (S) Specific examples of the ion exchange groups in the fluoropolymer (I) include sulfonic acid-type functional groups and carboxylic acid-type functional groups, with sulfonic acid-type functional groups being preferred.
  • fluoropolymer (S) embodiments of the fluoropolymer having a sulfonic acid-type functional group
  • the fluorine-containing polymer (S) preferably contains units based on a fluorine-containing olefin and units based on an olefin having a sulfonic acid type functional group and a fluorine atom.
  • fluorine-containing olefins include fluoroolefins having 2 to 3 carbon atoms and having one or more fluorine atoms in the molecule.
  • Specific examples of fluoroolefins include tetrafluoroethylene (hereinafter also referred to as “TFE”), chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and hexafluoropropylene.
  • TFE is preferable from the viewpoint of the production cost of the monomer, the reactivity with other monomers, and the excellent properties of the obtained fluoropolymer (S).
  • a fluorine-containing olefin may be used individually by 1 type, and may be used in combination of 2 or more type.
  • olefin-based unit having a sulfonic acid-type functional group and a fluorine atom a unit represented by formula (1) is preferable.
  • L 1 is an n+1 valent perfluorohydrocarbon group which may contain an etheric oxygen atom.
  • the etheric oxygen atoms may be located terminally or between carbon atoms in the perfluorohydrocarbon group.
  • the number of carbon atoms in the n+1-valent perfluorohydrocarbon group is preferably 1 or more, more preferably 2 or more, preferably 20 or less, and more preferably 10 or less.
  • the divalent perfluoroalkylene group may be linear or branched.
  • M is a hydrogen atom, an alkali metal or a quaternary ammonium cation.
  • n is 1 or 2;
  • the unit represented by formula (1) includes a unit represented by formula (1-1), a unit represented by formula (1-2), a unit represented by formula (1-3), or a unit represented by formula ( Units represented by 1-4) are preferred.
  • Formula (1-1) -[CF 2 -CF(-OR f1 -SO 3 M)]-
  • Formula (1-2) -[CF 2 -CF(-R f1 -SO 3 M)]-
  • R f1 is a perfluoroalkylene group optionally containing an etheric oxygen atom.
  • the number of carbon atoms in the perfluoroalkylene group is preferably 1 or more, more preferably 2 or more, preferably 20 or less, and more preferably 10 or less.
  • R f2 is a perfluoroalkylene group which may contain a single bond or an etheric oxygen atom.
  • the number of carbon atoms in the perfluoroalkylene group is preferably 1 or more, more preferably 2 or more, preferably 20 or less, and more preferably 10 or less.
  • R f3 is a single bond or a perfluoroalkylene group optionally containing an etheric oxygen atom.
  • the number of carbon atoms in the perfluoroalkylene group is preferably 1 or more, more preferably 2 or more, preferably 20 or less, and more preferably 10 or less.
  • the unit represented by formula (1-5) is more preferable.
  • Formula (1-5) -[CF 2 -CF(-(CF 2 ) x -(OCF 2 CFY) y -O-(CF 2 ) z -SO 3 M)]- x is 0 or 1
  • y is an integer from 0 to 2
  • z is an integer from 1 to 4
  • Y is F or CF3 .
  • M is as described above.
  • units represented by formula (1-1) include the following units.
  • w in the formula is an integer of 1-8, and x is an integer of 1-5.
  • M in the formula is as described above.
  • More specific examples of units represented by formula (1-1) include the following units.
  • units represented by formula (1-2) include the following units.
  • w in the formula is an integer of 1-8.
  • M in the formula is as described above.
  • Units represented by formula (1-3) are preferably units represented by formula (1-3-1).
  • the definition of M in the formula is as described above.
  • R f4 is a straight chain perfluoroalkylene group having 1 to 6 carbon atoms
  • R f5 is a straight chain perfluoroalkylene group having 1 to 6 carbon atoms which may contain a single bond or an etheric oxygen atom.
  • the definitions of r and M are as described above.
  • a unit represented by formula (1-4-1) is preferable.
  • the definitions of R f1 , R f2 and M in the formula are as described above.
  • the olefin-based units having a sulfonic acid-type functional group and a fluorine atom may be used singly or in combination of two or more.
  • the fluorine-containing polymer (I) may contain units based on other monomers other than units based on a fluorine-containing olefin and units based on an olefin having a sulfonic acid type functional group and a fluorine atom.
  • the fluoropolymer (I) contains one or more metals, metal compounds or metal ions selected from the group consisting of cerium and manganese in order to improve the durability under the operating environment of the fuel cell or water electrolysis device. You can stay. Cerium and manganese are believed to decompose hydrogen peroxide or hydroxyl radicals and hydroperoxyl radicals, which are causative substances that cause deterioration of the fluoropolymer (I).
  • One or more metals, metal compounds, or metal ions selected from the group consisting of cerium and manganese are included in fuel cell components such as catalyst layers, catalysts or catalyst carriers, microporous layers, and separators. good too.
  • the fluorine-containing polymer (I) is used as a water retention agent to prevent drying in the operating environment of the fuel cell or the water electrolysis device and to suppress chemical deterioration. tungstic acid). It is known that the use of the fluoropolymer (I) described in this item can greatly suppress the production of fluoroaliphatic hydrocarbon compounds containing ionic groups from fuel cells or water electrolyzers. is difficult to suppress. Therefore, the object of the present invention can be achieved more effectively by combining the present invention with a fuel cell or water electrolyzer containing the fluoropolymer (I) described in this section.
  • the membrane electrode assembly described later includes an anode having a catalyst layer containing a catalyst and a polymer having an ion-exchange group, a cathode having a catalyst layer containing a catalyst and a polymer having an ion-exchange group, and between the anode and the cathode and a solid polymer electrolyte membrane comprising a polymer having ion-exchange groups arranged in.
  • At least one of the polymer having ion-exchange groups contained in the anode, the polymer having ion-exchange groups contained in the cathode, and the polymer having ion-exchange groups contained in the solid polymer electrolyte membrane contains fluorine-containing groups having ion-exchange groups. is a polymer.
  • FIG. 1 is a cross-sectional view showing an example of a membrane electrode assembly.
  • the membrane electrode assembly 10 includes an anode 13 having a catalyst layer 11 and a gas diffusion layer 12, a cathode 14 having a catalyst layer 11 and a gas diffusion layer 12, and a catalyst layer 11 between the anode 13 and the cathode 14. and a solid polymer electrolyte membrane 15 arranged in a folded state.
  • the catalyst contained in the catalyst layer 11 include a supported catalyst in which a catalyst containing platinum, a platinum alloy, or platinum having a core-shell structure is supported on a carbon support, an iridium oxide catalyst, an alloy containing iridium oxide, and a core-shell structure.
  • Catalysts containing iridium oxide having Examples of carbon supports include carbon black powder.
  • the polymer having an ion exchange group contained in the catalyst layer 11 includes a fluoropolymer having an ion exchange group, and the fluoropolymer (S) described above is preferably used.
  • the gas diffusion layer 12 has a function of diffusing gas uniformly in the catalyst layer and a function of a current collector.
  • the gas diffusion layer include carbon paper, carbon cloth, carbon felt, and porous bodies made of titanium (specifically, sintered bodies of titanium particles or fibers, etc.).
  • the gas diffusion layer may be treated with PTFE or the like to make it water-repellent or hydrophilic, or may be made hydrophilic with a polymer having an ion-exchange group.
  • the gas diffusion layer 12 is included in the membrane electrode assembly of FIG. 1, the gas diffusion layer is an arbitrary member and may not be included in the membrane electrode assembly.
  • the polymer having ion exchange groups contained in the solid polymer electrolyte membrane 15 is preferably the fluorine-containing polymer (S) described above.
  • the anode 13 and cathode 14 may have other members than those mentioned above.
  • a specific example of the other member is a carbon layer (not shown) provided between the catalyst layer 11 and the gas diffusion layer 12 .
  • the carbon layer contains, for example, carbon and nonionic fluorine-containing polymer.
  • carbon nanofibers having a fiber diameter of 1 to 1000 nm and a fiber length of 1000 ⁇ m or less are preferable.
  • nonionic fluoropolymers include PTFE.
  • Methods for producing a membrane electrode assembly include, for example, a method in which a catalyst layer is formed on a solid polymer electrolyte membrane and the resulting assembly is further sandwiched between gas diffusion layers, and a method in which a catalyst layer is formed on the gas diffusion layer.
  • a method of forming electrodes (anode, cathode) and sandwiching a solid polymer electrolyte membrane between the electrodes can be mentioned.
  • examples of the method for producing the catalyst layer include a method in which the coating solution for forming the catalyst layer is applied to a predetermined position and dried as necessary.
  • the catalyst layer-forming coating liquid is a liquid in which a polymer having an ion-exchange group and a catalyst are dispersed in a dispersion medium.
  • Examples 1, 5 and 6 are examples, and examples 2 to 4 are comparative examples. However, the present invention is not limited to these examples.
  • a tube (tube material: PFA or PharMed (registered trademark) BPT manufactured by Saint-Gobain) is connected to a column packed with a resin (ion exchange resin), and a tube pump (manufactured by EYELA, NRP-3000) is used to perform the following was passed through at room temperature (23° C.).
  • a tertiary amine type resin resin having a tertiary amino group
  • ultrapure water was passed through for washing.
  • 1N-NaOH manufactured by Kanto Kagaku Co., Ltd., for pharmaceutical testing
  • 1N-NaOH manufactured by Kanto Kagaku Co., Ltd., for pharmaceutical testing
  • the filtrate was dried to remove chloroform and acetonitrile to give a white solid consisting of HOOC-CF(CF 3 )-O-CF 2 -CF 2 -SO 3 H.
  • the solid obtained was very hygroscopic. This solid was diluted with ultrapure water to prepare an aqueous solution consisting of HOOC--CF(CF 3 )--O--CF 2 --CF 2 --SO 3 H and water.
  • ion exchange resin DOWEX MONOSPHERE (registered trademark) 650C (H) Cation Exchange Resin
  • the height of the resin layer was set to 38 cm
  • An aqueous solution consisting of 2 -SO 3 H and water was obtained.
  • HFIP (1,1,1,3,3,3-hexafluoro-2-propanol) peak appearing at ⁇ 75.1 ppm in 19 F-NMR and a peak appearing at ⁇ 79.7 ppm from comparison of integral values .
  • HOOC-CF(CF 2 -O-CF 2 -CF 2 -SO 3 H)-O-CF 2 -CF 2 -SO 3 H is hereinafter referred to as compound 2 to be treated.
  • a predetermined amount of the aqueous solution of the compound to be treated was diluted with ultrapure water to prepare an aqueous solution having a predetermined concentration.
  • the aqueous solution after preparation is degassed under reduced pressure with a vacuum pump while performing ultrasonic treatment, and then HF (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., reagent special grade, 47% by mass) and H 2 SO 4 (manufactured by Junsei Chemical Co., Ltd., reagent Special grade, 95% by mass) was added so that each was 1 ppm, and a tube pump (manufactured by EYELA, NRP-3000, tube material: PharMed (registered trademark) BPT manufactured by Saint-Gobain) was used to circulate and mix the liquid in the container. After that, it was used as a liquid to be treated.
  • Quantification of the compound to be treated in the liquid to be treated and the purified liquid was performed using liquid chromatography/mass spectrometry (LC/MS/MS).
  • LC/MS/MS liquid chromatography/mass spectrometry
  • the compound to be treated is Compound 2 to be treated (HOOC-CF( CF2 -O- CF2 - CF2 - SO3H )-O- CF2- CF2- SO3H ), the following conditions was quantified.
  • the compound to be treated is Compound 2 to be treated (HOOC-CF(CF 2 -O-CF 2 -CF 2 -SO 3 H)-O-CF 2 -CF 2 -SO 3 H)
  • the following method was quantified.
  • Example 1 7.7 mL of a tertiary amine resin (Mitsubishi Chemical Co., Ltd., Diaion WA30) was packed in a PFA column (Flon Kogyo Co., Ltd., TKB-830, inner diameter 8 mm, height 30 cm). At this time, the height of the resin layer (height of resin filling) was 15.0 cm.
  • HF manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade, 47% by mass
  • H 2 SO 4 Japanesesei Chemical Co., Ltd.
  • This liquid to be treated 1-1 was passed through the column at room temperature (23° C.). The concentration of the compound 1 to be treated in the obtained purified liquid was 29 ppt.
  • Example 2 A purified liquid in Example 2 was obtained in the same manner as in Example 1, except that HF and H 2 SO 4 were not added during the preparation of liquid 1-1 to be treated.
  • the concentration of the compound 1 to be treated in the purified liquid in Example 2 was 223 ppt.
  • Example 3 A purified liquid in Example 3 was obtained in the same manner as in Example 1, except that the tertiary amine type resin was changed to a quaternary ammonium ion type resin (manufactured by Organo Co., Ltd., Amberlite IRA900J Cl). The concentration of the compound 1 to be treated in the purified liquid in Example 3 was 206 ppt.
  • Example 4 A purified liquid in Example 4 was obtained in the same manner as in Example 3, except that HF and H 2 SO 4 were not added during the preparation of liquid 1-1 to be treated.
  • the concentration of the compound 1 to be treated in the purified liquid in Example 4 was 175 ppt.
  • Example 5 7.7 mL of a tertiary amine resin (Mitsubishi Chemical Co., Ltd., Diaion WA30) was packed in a PFA column (Flon Kogyo Co., Ltd., TKB-830, inner diameter 8 mm, height 30 cm). At this time, the height of the resin layer (height of resin filling) was 15.0 cm.
  • HF manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., special reagent grade, 47% by mass
  • H 2 SO 4 Japanesesei Chemical Co., Ltd.
  • This processed liquid 2-1 was passed through the column at room temperature (23° C.). The concentration of the compound 2 to be treated in the resulting purified liquid was 100 ppt or less.
  • a membrane electrode assembly containing a polymer consisting of TFE units and units of -[CF 2 -CF(-O-CF 2 CF(CF 3 )-O-(CF 2 ) 2 -SO 3 H)]- was prepared.
  • the membrane electrode assembly is incorporated into a power generation cell, and the following open circuit test (OCV test) is performed.
  • Hydrogen (50% utilization) and air (50% utilization) corresponding to a current density of 0.2 A/cm 2 are supplied at normal pressure to the anode and cathode, respectively.
  • the cell temperature is 90°C
  • the anode gas dew point is 61°C
  • the cathode gas dew point is 61°C.
  • the discharged gas and liquid are trapped in a 0.1 mol/L potassium hydroxide aqueous solution for 24 hours.
  • the aqueous potassium hydroxide solution after trapping is passed through a cation exchange resin filter to obtain a filtrate.
  • This filtrate contains F ⁇ , SO 4 2 ⁇ , and compound 1 to be treated.
  • This filtrate is referred to as the liquid 6 to be treated.
  • 7.7 mL of a tertiary amine type resin Mitsubishi Chemical Co., Ltd., Diaion WA30
  • a PFA column Flon Kogyo Co., Ltd., TKB-830, inner diameter 8 mm, height 30 cm).
  • the height of the resin layer (height of resin filling) is 15.0 cm.
  • the liquid 6 to be treated is passed through the column at room temperature (23° C.).
  • the concentration of the compound 1 to be treated in the resulting purified liquid is reduced to 100 ppt or less.
  • Example 1 when HF and H 2 SO 4 were allowed to coexist in an aqueous solution consisting of the compound to be treated 1 and water, and purification was performed using a tertiary amine ion exchange resin (Example 1), The concentration of the compound 1 to be treated can be reduced to 100 ppt or less, indicating that the removability of the compound 1 to be treated is excellent.
  • Example 5 when HF and H 2 SO 4 were allowed to coexist in an aqueous solution consisting of compound 2 to be treated and water, and purification was performed using a tertiary amine type ion exchange resin, the concentration of compound 2 to be treated in the purified liquid was can be reduced to 100 ppt or less.

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