WO2017141709A1 - Procédé et dispositif de production d'une membrane fonctionnelle conductrice d'ions - Google Patents

Procédé et dispositif de production d'une membrane fonctionnelle conductrice d'ions Download PDF

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WO2017141709A1
WO2017141709A1 PCT/JP2017/003627 JP2017003627W WO2017141709A1 WO 2017141709 A1 WO2017141709 A1 WO 2017141709A1 JP 2017003627 W JP2017003627 W JP 2017003627W WO 2017141709 A1 WO2017141709 A1 WO 2017141709A1
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liquid
ion conductive
precursor film
conductive functional
producing
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PCT/JP2017/003627
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English (en)
Japanese (ja)
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福田誠司
藪内友子
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東レ株式会社
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Priority to JP2017510701A priority Critical patent/JP6962190B2/ja
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • 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
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method and an apparatus for manufacturing an ion conductive functional film.
  • An ion conductive functional membrane represented by an ion exchange membrane or a polymer electrolyte membrane is a functional membrane having ion conductivity and electronic insulation.
  • the ion exchange membrane includes a cation exchange membrane having cation (cation) conductivity and an anion exchange membrane having anion (anion) conductivity.
  • Cation exchange membranes and anion exchange membranes are widely used in the field of electrolysis industry in combination with their respective characteristics, and have also begun to be used in applications requiring high quality such as pharmaceutical production.
  • the polymer electrolyte membrane is a solid polymer type that converts hydrogen and hydrocarbons into electrical energy as a catalyst-attached electrolyte membrane with a catalyst applied or transferred, or as a membrane-electrode complex in which an electrode is further attached to the catalyst-attached electrolyte membrane.
  • Used in fuel cells hydrogen production devices that produce hydrogen from water, electrochemical hydrogen compression devices, and the like. In order to promote the popularization of fuel cells and the utilization of hydrogen energy, not only high quality but also low-cost mass production methods and production equipment are required.
  • An ion exchange membrane or polymer electrolyte membrane that is an ion conductive functional membrane usually contains a polymer having an ionic group.
  • the method of introducing an ionic group into a polymer can be roughly divided into a method of polymerizing a polymer using a monomer having an ionic group, a method of introducing an ionic group into a polymer by a polymer reaction, and a film formation of the polymer. After that, there is also a method of introducing an ionic group into a film-shaped polymer by a polymer reaction.
  • the ionic group forms a counter ion (counter ion) and a salt (ion pair (ion pair)) such as a metal ion or a halogen ion in the course of the synthesis reaction. It is necessary to obtain an ion conductive functional film that exhibits a function by exchanging metal ions with hydrogen ions or exchanging halogen ions with hydroxide ions by alkali treatment.
  • an ionic group includes a polymer in which a salt is formed with a counter ion such as a metal ion or a halogen ion, and an ion conductive functional membrane is obtained by a liquid treatment such as an acid solution or an alkali solution.
  • a film in a state before becoming is called a “precursor film”.
  • Patent Document 1 describes that a method for producing a polymer electrolyte membrane in which a precursor membrane is immersed in an acid solution in a plurality of times in acid treatment, the acidic solution is satisfied.
  • a liquid processing method for a hydrocarbon-based polymer electrolyte membrane is disclosed in which a film is conveyed in cascade to a plurality of dipping baths and an acidic solution is continuously supplied while overflowing in a cascade manner in the direction opposite to the film conveying direction.
  • An object of the present invention is to provide an ion conductive functional membrane manufacturing method and a manufacturing apparatus capable of manufacturing an ion conductive functional membrane at a low cost by reducing the amount of treatment solution used.
  • the present invention for solving the above problems is as follows. That is, The method for producing an ion conductive functional membrane of the present invention is a method for producing an ion conductive functional membrane containing a polymer having an ionic group, wherein the polymer in a state where the ionic group forms a salt with impurity ions. While having a liquid treatment step for contacting the precursor film containing the acid treatment solution or the alkali treatment solution multiple times and moving from one liquid treatment step of the plurality of liquid treatment steps to the next liquid treatment step, A droplet removing operation for removing the acid treatment solution or the alkali treatment solution attached to the surface of the precursor film is performed at least once.
  • the apparatus for producing an ion conductive functional membrane of the present invention is an apparatus for producing an ion conductive functional membrane containing a polymer having an ionic group, wherein the ionic group forms a salt with impurity ions.
  • a plurality of liquid treatment tanks that contact the acid treatment solution or the alkali treatment solution, and the precursor film is disposed between one liquid treatment tank and the next liquid treatment tank among the plurality of liquid treatment tanks.
  • the amount of treatment solution used can be reduced and the ion conductive functional membrane can be produced at a low cost.
  • the method for producing an ion conductive functional membrane of the present invention is a method for producing an ion conductive functional membrane containing a polymer having an ionic group, wherein the polymer in a state where the ionic group forms a salt with impurity ions. While having a liquid treatment step for contacting the precursor film containing the acid treatment solution or the alkali treatment solution multiple times and moving from one liquid treatment step of the plurality of liquid treatment steps to the next liquid treatment step, A droplet removing operation for removing the acid treatment solution or the alkali treatment solution attached to the surface of the precursor film is performed at least once.
  • the precursor film becomes an ion conductive functional film at any stage of a plurality of times of the liquid treatment process.
  • the film before the completion of all of the plurality of times of the liquid treatment process is used as the precursor.
  • the film and the film after all of the liquid treatment steps are called an ion conductive functional film.
  • the production method of the present invention a method for producing an ion conductive functional membrane of the present invention (hereinafter, simply referred to as “the production method of the present invention”) will be described with reference to the embodiments of the production apparatus shown in FIGS. However, these embodiments of the manufacturing apparatus do not limit the present invention.
  • the basic skeleton of the polymer contained in the ion conductive functional membrane produced according to the present invention is not particularly limited, but preferred examples include fluorine-based polymers such as perfluoroalkylene, polyphenylene oxide, polyether ketone, and polyether.
  • Aromatic hydrocarbon skeletons such as ether ketone, polyether sulfone, polyether ether sulfone, polyether phosphine oxide, polyether ether phosphine oxide, polyphenylene sulfide, polyamide, polyimide, polyetherimide, polyimidazole, polyoxazole, polyphenylene, etc.
  • the polymer which has is mentioned.
  • polymerizing styrene, ethyl styrene, vinyl pyridine, vinyl pyrazine, divinyl benzene, divinyl toluene, divinyl xylene, trivinyl benzene etc. is also mentioned.
  • the polymer having an ionic group is a polymer in which an ionic group is bonded to such a basic skeleton.
  • Ionic groups are roughly divided into cationic groups and anionic groups.
  • a polymer having an anionic group is used, and the anionic group and the cation form an ion pair to have a cation exchange ability.
  • a polymer having a cationic group is used, and the cationic group and the anion form an ion pair, thereby having anion exchange ability.
  • the anionic group of the polymer having an anionic group is not particularly limited as long as it has a cation exchange ability and exhibits cation conductivity.
  • Preferred examples of the anionic group include a sulfonic acid group (—SO 2 (OH)), a sulfuric acid group (—OSO 2 (OH)), and a sulfonimide group (—SO 2 NHSO 2 R (R represents an organic group). )), Phosphonic acid groups (—PO (OH) 2 ), phosphoric acid groups (—OPO (OH) 2 ), carboxylic acid groups (—CO (OH)), perfluorosulfonic acid groups (—O— (CF 2) n SO 2 (OH) ) can be exemplified.
  • the polymer having an anionic group may have two or more of these groups. Since the polymer having an anionic group has a high hydrogen ion conductivity, it is more preferable to have a perfluorosulfonic acid group, a sulfonic acid group, a sulfonimide group, a sulfuric acid group, or a phosphonic acid group. Most preferably, it has a perfluorosulfonic acid group or a sulfonic acid group from the viewpoint of degradability.
  • the cationic group of the polymer having a cationic group is not particularly limited as long as it has anion exchange ability and exhibits anion conductivity.
  • the cationic group include a tertiary amino group, a quaternary ammonium group, a tertiary phosphonium group, and a quaternary phosphonium group.
  • the polymer having a cationic group may have two or more of these groups.
  • the polymer having a cationic group preferably has either a quaternary ammonium group or a quaternary phosphonium group because of its high hydroxide ion conductivity.
  • ion conductive functional membrane In general, in the production of an ion conductive functional membrane, most of the ionic groups of the precursor membrane exist in the form of a salt ion-bonded to the impurity ions, and the impurity ions are finally processed by acid treatment or alkali treatment. It is removed to obtain an ion conductive functional membrane.
  • a metal cation is used as a catalyst.
  • metal cations include Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, and W cations.
  • alkali metal or alkaline earth metal cations are often used.
  • cations of Li, Na, K, Ca, Sr, and Ba are preferably used, and cations of Li, Na, and K are most preferably used.
  • an anion (anion) which is a counter ion of a metal cation used as a reaction catalyst and a cationic group in the polymer form an ionic bond
  • Anions remain as impurity ions in the precursor film.
  • examples of such anions include sulfate ions, nitrate ions, halogen ions, carbonate ions, and bicarbonate ions.
  • a cationic group is introduced into a polymer by a polymer reaction, a halogenoalkyl group is often used as a functional group that exchanges with the cationic group.
  • halogen ions such as chloride ions and fluoride ions are used in the polymer.
  • An ionic bond is formed with the cationic group therein and remains as impurity ions in the precursor film.
  • the precursor film typically, in the precursor film, 50% or more of the ion exchange capacity of the ion conductive functional film is present in a state of being bonded to impurity ions.
  • the production method of the present invention has a liquid treatment step of bringing the precursor film into contact with an acid treatment solution or an alkali treatment solution (hereinafter sometimes simply referred to as “treatment solution”) a plurality of times.
  • treatment solution an alkali treatment solution
  • impurity ions contained in the precursor film are removed by ion exchange.
  • a precursor film having an anionic group is liquid-treated with an acidic solution and ion-exchanged with hydrogen ions to form a cation exchange film, and a precursor film having a cationic group is liquid in an alkaline solution. It is processed and ion exchanged with hydroxide ions to form an anion exchange membrane.
  • a precursor film having a cationic group can be liquid-treated with a weak acid solution such as carbonic acid, and ion-exchanged to carbonate ions or hydrogen carbonate ions to form an anion exchange membrane.
  • a weak acid solution such as carbonic acid
  • ionic groups present in a salt state are ion-exchanged in the ion conductive functional membrane. It is preferable to perform ion exchange so that the capacity is 0.1% or less.
  • the method of bringing the precursor film into contact with the treatment solution is not particularly limited, but a method of immersing the elongated precursor film in a treatment solution tank, that is, a liquid treatment tank, is preferable.
  • a treatment solution tank that is, a liquid treatment tank
  • the elongated precursor film wound in a roll shape is continuously transported to the first liquid treatment tank and the second liquid treatment tank and immersed in the treatment solution.
  • membrane into a single wafer and immersing in a liquid processing tank by a batch type can also be used, the method of carrying out continuously conveying from a viewpoint of productivity is preferable.
  • the precursor film that is continuously transported may be a single film, or may be in a state of being stuck on a transport film for the purpose of facilitating handling or when the strength is insufficient.
  • it may be a porous membrane or a precursor membrane reinforced with a filler.
  • the acid treatment solution for the cation exchange membrane is not particularly limited as long as it is a strong acid treatment solution, but an aqueous solution of an inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid is preferable, and sulfuric acid is particularly preferred from the viewpoint of productivity and workability. Is preferred.
  • such a liquid treatment process is performed a plurality of times.
  • the unwound precursor film is subjected to a liquid treatment process twice in two liquid treatment tanks, a first liquid treatment tank and a second liquid treatment tank.
  • the precursor film is further subjected to liquid treatment in a third liquid treatment tank, and is subjected to a total of three liquid treatment steps.
  • the contact time in which the precursor film is immersed in the treatment solution is in contact with the first time because most of the impurity ions have already been ion-exchanged in the first liquid treatment step. It is possible to make it shorter than the contact time.
  • the contact time after the second time is 50% or less. As a result, the second and subsequent liquid treatment steps can be shortened, and the mass production efficiency can be increased.
  • the production method of the present invention removes the acid treatment solution or the alkali treatment solution adhering to the surface of the precursor film during the transition from one liquid treatment step to the next liquid treatment step among a plurality of liquid treatment steps.
  • the droplet removing operation is performed at least once.
  • the droplet removing operation is not particularly limited as long as it is a method that can remove the attached droplets.
  • the droplet removing operation involves blowing a gas onto the surface of the precursor film, or the droplet removing member is physically applied to the surface of the precursor film. It is preferable to employ a droplet removing operation that makes contact with each other.
  • a droplet removing unit is provided between the first liquid processing tank and the second liquid processing tank.
  • the first liquid droplet removing unit is provided between the first liquid processing tank and the second liquid processing tank
  • the second liquid is provided between the second liquid processing tank and the third liquid processing tank.
  • Droplet removal units are provided. In these droplet removal units, the precursor film is subjected to a droplet removal operation. By performing the droplet removal operation, the impurity ions concentrated during mass production in the droplets of the processing solution brought out from one liquid treatment process have the effect of deteriorating the impurity ion removal efficiency in the next liquid treatment process. Can be reduced.
  • Such a droplet removing operation is preferably performed between all the liquid treatment steps, that is, it is preferably performed between one liquid treatment step and the next liquid treatment step.
  • the number of times of the liquid treatment step is not particularly limited, but it is preferably performed 2 to 3 times. That is, when the liquid treatment process is performed twice, the droplet removal operation is performed at least once during the transition from the first liquid treatment process to the second liquid treatment process, and when the liquid treatment process is performed three times. It is preferable to perform the droplet removing operation at least twice in total during the transition from the first liquid treatment process to the second liquid treatment process and during the transition from the second liquid treatment process to the third liquid treatment process.
  • the treatment solution adhered to the surface of the precursor film by the droplet removing operation is 2 ml or less per square meter.
  • the treatment solution adhering to the surface refers to the total amount of the treatment solution adhering to both surfaces of the precursor film, and does not include the amount of treatment liquid absorbed by the precursor film.
  • the treatment solution is an acid treatment solution or an alkali treatment solution.
  • 2 milliliters or less per square meter is the amount of the treatment solution remaining on the surface obtained per the area of the precursor film after the amount of treatment solution remaining on the surface after the droplet removal operation. Corresponds to micrometer / 2 plane.
  • a wide area is used as a standard. For example, when the width of the transport substrate is wider than that of the precursor film, the amount of the treatment solution remaining on the surface per area of the transport substrate.
  • the amount of the processing solution adhering to the surface of the precursor film is usually 10 to 30 ml per square meter, and it can be said that droplets are removed if it is 5 ml or less per square meter, but it is 2 ml or less per square meter.
  • Measurement of the amount of the treatment solution attached to the surface of the precursor film is performed by adhering the filter paper for chemical analysis to both sides of the precursor film and adsorbing the treatment solution on the surface, and then adsorbing the filter solution for chemical analysis. This is done by quantitative analysis.
  • a thin cellulose filter paper having a low ash content which is defined as five types in JIS standard P3801 (1995), is used for quantitative analysis.
  • the transport of the precursor film from which the droplets have been removed is temporarily stopped, and the filter paper for chemical analysis is evenly attached to both sides of the precursor film within 1 minute from the temporary stop of the transport. Press and hold for more than a second.
  • a chemical analysis filter paper adsorbed with a treatment solution is immersed and extracted with deionized water as an extract, and the pH of the extract is measured to determine whether the pH of the extract varies. Quantitative analysis can be easily carried out for both treatment solutions.
  • the amount of impurity ions extracted by immersing the filter paper for chemical analysis using the new treatment solution as the extract is used.
  • a method may be used in which quantitative measurement is performed and the amount of the treatment solution attached is determined based on the impurity ion concentration in the treatment solution tank.
  • the quantitative measurement method for the amount of impurity ions in the acidic treatment solution include induction plasma emission analysis and induction plasma mass spectrometry, which are known as quantitative analysis methods for metal cations.
  • the quantitative measurement method for the amount of impurity ions in the alkaline treatment solution include an ion chromatography method known as a quantitative analysis method for anions.
  • the method for producing an ion conductive functional film of the present invention it is preferable to perform an operation of blowing a gas on the surface of the precursor film as the droplet removing operation. This is because the surface droplets can be quickly removed by performing such an operation.
  • the method for producing an ion conductive functional membrane of the present invention it is preferable to perform the operation of blowing the gas with an air knife. This is because high-pressure gas can be sprayed evenly over the entire film surface, and it is possible to effectively remove droplets on the surface and to prevent the adhesion of falling foreign substances.
  • the gas to spray removes a foreign material with a filter. This is because foreign matters can be easily removed from the precursor film by removing foreign matters using a filter.
  • the air knives 2 are installed on both sides of the precursor film M, and are configured to blow air on both sides of the precursor film after each liquid treatment step.
  • the droplet removing member is physically brought into contact with the surface of the precursor film as the droplet removing operation. This is because by performing such an operation, even when a large number of droplets adhere to the surface of the precursor film to form a liquid film, it can be effectively removed.
  • an operation of bringing the droplet removing member into physical contact with the surface of the precursor film an operation of squeezing the droplet using a squeezing roll installed so as to contact the precursor film, a liquid using a sponge roll For example, an operation of absorbing a droplet, and an operation of scraping the droplet using a scraper.
  • the method for producing an ion conductive functional membrane of the present invention is a pressing roll installed so that the droplet removing member is in contact with the precursor membrane.
  • the production method of the present invention is more preferably to perform an operation of squeezing the droplets with squeezing rolls installed on both sides of the precursor film, The operation of squeezing the droplets with a squeeze roll arranged so as to face both sides of the precursor film or a squeeze roll arranged so that the precursor film is conveyed in an S shape is particularly preferable.
  • 3B shows an example in the case of performing an operation of squeezing the droplets with the squeezing rolls (opposing arrangement) 3 arranged so as to face both sides of the precursor film M.
  • membrane M may be conveyed by S shape is shown.
  • positioning positioned so that the precursor film
  • the method for producing an ion conductive functional film of the present invention is a sponge roll in which the droplet removing member is installed so as to contact the precursor film. It is preferable. This is because a soft sponge roll does not apply excessive pressure to the precursor film.
  • the droplet removing member has a suction means for sucking a droplet on the surface of the precursor film.
  • a droplet removing member for example, a droplet removing roll such as a squeeze roll or a sponge roll, has suction means for sucking droplets on the surface of the precursor film, the removed droplets are less likely to stay. It is. More specifically, for example, it is one of preferred embodiments to use a suction roll as a roll constituting a squeeze roll or a sponge roll.
  • the deionized water used in the present invention is preferably purified water, distilled water, or deionized water that is deionized using ion exchange resin using raw water as RO water. This is because the amount of ion exchange resin used can be reduced by using purified water, distilled water, and RO water as raw water. Furthermore, it is because impurity ions can be efficiently removed by deionization using an ion exchange resin.
  • the method for producing an ion conductive functional film of the present invention is a method of showering deionized water on the precursor film as an operation of washing with the deionized water. It is preferable to perform an operation of pouring water.
  • the method for producing an ion conductive functional film of the present invention is filled with deionized water as an operation for cleaning with the deionized water. It is preferable to perform an operation of immersing the precursor film in a cleaning tank. By performing such an operation, the precursor film can be more easily cleaned.
  • the method for producing an ion conductive functional film of the present invention more preferably performs an operation of immersing the precursor film in a plurality of cleaning tanks filled with deionized water.
  • FIG. 3D shows an example of the operation of immersing the precursor film M in the cleaning tank 1 filled with deionized water.
  • the method for producing an ion conductive functional film of the present invention continuously performs the plurality of liquid treatment steps and the droplet removal operation in the production line. That is, it is preferable to continuously perform a plurality of liquid treatment steps and a droplet removal operation, that is, the flow from one liquid treatment step to the droplet removal operation and the next liquid treatment step continuously in the production line.
  • the present invention is not necessarily limited to the application only when producing an ion conductive functional film while continuously transporting, and after performing a droplet removing operation on the precursor film after one liquid treatment step, You may make it transfer to the following liquid processing process, after drying.
  • the ion conductive functional membrane obtained through the liquid treatment step is washed to reduce the residual treatment solution in the membrane. It is preferable to have a process.
  • the ion conductive functional film that has undergone two or three liquid treatment steps is subsequently transported to the cleaning section and subjected to the cleaning step.
  • the washing step is preferably performed by immersing the ion conductive functional membrane in washing water.
  • the washing water is preferably performed using deionized water. By using deionized water, it is possible to prevent the impurity ions contained in the wash water from penetrating into the membrane. Moreover, it is also preferable to perform an operation of showering deionized water onto the ion conductive functional membrane during the cleaning process.
  • the method for producing an ion conductive functional membrane of the present invention preferably further includes a drying step of drying the ion conductive functional membrane after the cleaning step.
  • a drying step of drying the ion conductive functional membrane after the cleaning step is transported to the drying section and used in the drying process.
  • the drying method in a drying process is not specifically limited, Generally, it is preferable to perform warm air drying.
  • the ion conductive functional film that has passed through the drying section is wound into a roll by a winding roller, and the entire process is completed.
  • the winding is preferably carried out by controlling the winding tension in order to maintain a good roll shape.
  • the processing solution supply unit is configured to independently supply a new processing solution to the first liquid processing tank and the second liquid processing tank. And the used processing solution (waste liquid) discharged
  • the treatment solution supply unit continuously supplies the treatment solution and the waste liquid continuously from the first liquid treatment tank.
  • the waste liquid treatment unit may be transferred to the waste liquid treatment unit, or each time the production of the continuous ion conductive functional membrane is completed, the liquid waste in the liquid treatment tank is transferred to the waste liquid treatment unit, and each liquid is supplied from the treatment solution supply unit.
  • a new processing solution may be supplied to fill the processing tank.
  • a common treatment solution supply and a waste liquid treatment tank may be provided for two or more liquid treatment tanks, or a separate waste liquid treatment tank may be provided in each liquid treatment tank.
  • the processing solution supply unit first supplies a new processing solution to the third liquid processing tank.
  • the processing solution used in the third liquid processing tank is then transferred to the second liquid processing tank, the processing solution used in the second liquid processing tank is then transferred to the first liquid processing tank, and the The waste liquid used in the one-liquid treatment tank is configured to be transferred to the waste liquid treatment unit.
  • the treatment solution supply unit continuously supplies the treatment solution, and the first solution treatment unit The waste liquid is continuously transferred from the liquid treatment tank to the waste liquid treatment unit.
  • the processing solution may be supplied independently and continuously from the processing solution supply unit to the first to third liquid processing tanks.
  • An apparatus for producing an ion conductive functional membrane according to the present invention is an apparatus for producing an ion conductive functional membrane containing a polymer having an ionic group, the polymer containing the ionic group forming a salt with impurity ions.
  • a droplet removing unit for removing the acid treatment solution or the alkali treatment solution adhering to the surface With such a production apparatus, an ion conductive functional membrane can be produced by the production method of the present invention.
  • At least one of the plurality of liquid treatment tanks includes an adjacent liquid supply tank, and the treatment sent from the liquid supply tank to the liquid treatment tank. It is preferable to provide a liquid circulation mechanism in which the solution overflows from the liquid treatment tank and returns to the liquid supply tank. When the processing solution overflows, a flow of the processing solution is generated on the surface of the liquid processing tank, and the suspended foreign matter moves to the liquid supply tank together with the overflowing processing solution, and is quickly removed from the liquid processing tank.
  • Such a liquid circulation mechanism may be provided in at least one liquid treatment tank, but it is preferable that all of the plurality of liquid treatment tanks are provided.
  • all of the plurality of liquid treatment tanks are provided with a liquid circulation mechanism, there is a drawback that the equipment is enlarged, but it is preferable that the liquid treatment efficiency is improved. If the liquid processing efficiency is improved and the amount of new processing solution supplied is reduced, the prior art has a drawback that the floating foreign matter removing ability is lowered because the overflow amount is also reduced.
  • the liquid circulation mechanism as described above, it is possible to change the supply amount of the processing solution while maintaining the total liquid supply amount from the liquid supply tank, so that the floating foreign matter removing ability does not deteriorate.
  • the liquid circulation mechanism preferably includes a mechanism for individually controlling the liquid feeding speed from the liquid supply tank to the liquid processing tank. This is because by providing such a mechanism, even if supply of a new processing solution is interrupted, it is possible to maintain the ability to remove floating foreign matters unless the processing solution is stopped from circulating.
  • the direction in which the processing solution overflows from the liquid processing tank is a direction parallel to the film surface of the precursor film.
  • the overflow direction refers to the direction in which the processing solution overflows when the liquid processing tank is viewed from directly above.
  • the direction parallel to the film surface of the precursor film is the surface of the precursor film when intersecting the surface of the processing solution, that is, the film of the precursor film when being immersed in the processing solution and when being removed from the processing solution.
  • the direction parallel to the surface Therefore, the direction in which the processing solution overflows from the liquid processing tank is a direction parallel to the film surface.
  • the direction in which the processing solution overflows from the liquid processing tank is approximately the rotational axis of the transport roller that transports the precursor film. Indicates that they are parallel. Since the direction in which the processing solution overflows is parallel to the film surface, the flow on the surface of the processing solution becomes substantially parallel to the film surface, and the suspended foreign matter also moves in the direction parallel to the film surface. If it does so, since the film surface of a precursor film becomes difficult to prevent the movement of a floating foreign material, a floating foreign material is removed from a liquid processing tank more rapidly.
  • FIG. 4 shows an example of the embodiment of the liquid circulation mechanism as described above.
  • the embodiments shown in FIGS. 4A and 4B are two embodiments in which the treatment solution overflows in a direction parallel to the film surface.
  • the transport direction of the precursor film is a direction from the front side to the back side of the sheet.
  • a processing solution is supplied from the liquid supply tank 6 to the liquid processing tank 5 using a liquid feed pump 7, and is parallel to the film surface of the precursor film M that is transported by a transport roller (in liquid) 8 and a transport roller (upper part) 9.
  • the suspended foreign matter also moves parallel to the film surface of the precursor film M, and is quickly removed from the liquid processing tank.
  • the overflow direction 11 is the right side of the page. Even when multiple liquid treatment tanks and multiple liquid supply tanks are provided, liquids are supplied so that the treatment solution overflows from all the liquid treatment tanks in the direction parallel to the film surface by arranging them in the film transport direction. It is possible to arrange a tank.
  • membrane is a direction in which a precursor film
  • FIG. 4C shows an embodiment in which the liquid treatment tank and the liquid supply tank are viewed from above.
  • the precursor film M Since the precursor film M is submerged in the four transport rollers (upper part) 9 and the processing liquid, the precursor film M is transported while being sequentially liquid-treated in the three liquid treatment tanks 5 by a transport roller (in the liquid) (not shown). .
  • the precursor film surface when the precursor film is immersed in the processing solution and when it is removed from the processing solution and the direction 11 in which the processing solution overflows are in a parallel relationship. Furthermore, the film surface is parallel to the rotation axis direction 13 of the transport roller (upper part) 9.
  • the direction 11 in which the processing solution overflows from the liquid processing tank 5 to the liquid supply tank 6 is a direction parallel to the film surface, the flow 15 on the surface of the processing solution becomes a flow in substantially the same direction, and the floating foreign matter is rapidly immersed in the liquid. It becomes possible to exclude from the tank 5 to the liquid supply tank 6.
  • FIG. 4B is an embodiment in which a spray shower nozzle (both sides) 10 is attached to both sides of the precursor film in the embodiment of FIG.
  • the production apparatus of the present invention removes the acid treatment solution or the alkali treatment solution adhering to the surface of the precursor film between one liquid treatment tank and the next liquid treatment tank among the plurality of liquid treatment tanks.
  • the droplet removing unit physically operates a droplet removing member on the surface of the precursor film, or a mechanism for performing a gas blowing operation on the surface of the precursor film. It is preferable to provide a mechanism for performing an operation of bringing the element into contact. A more preferable aspect of the droplet removing unit is the same as that in the above-described droplet removing operation.
  • the manufacturing apparatus of the present invention may be provided with a portion for performing an operation of washing the precursor film with deionized water between the droplet removing unit and the next liquid treatment step.
  • the more preferable aspect of the said part is the same as that of the case of operation wash
  • a cleaning unit for cleaning the ion conductive functional film in which the precursor film has been liquid processed, and the cleaned ion conductive functional film are dried. It is preferable that a drying unit and a winding unit for winding the dried ion conductive functional film are provided.
  • the unwound precursor film is subjected to liquid treatment in a liquid treatment tank, and is transferred to a cleaning unit as an ion conductive functional film.
  • the cleaning unit includes a mechanism for performing shower cleaning in multiple stages with deionized water.
  • the cleaning unit preferably includes a mechanism for immersing and cleaning in deionized water in multiple stages and a mechanism for performing shower cleaning in multiple stages. This is because, by providing these mechanisms, when the surface floating foreign matter in the cleaning tank adheres to the film, it can be quickly removed.
  • the drying mechanism is not particularly limited, but it is generally preferable to include a mechanism for performing hot air drying.
  • the ion conductive functional film production apparatus of the present invention preferably includes a mechanism in which a suction conveyance roll having a porous material at least on the roll surface is connected to a decompression device. By providing such a mechanism, it becomes easier to remove the washing water.
  • the ion conductive functional film that has passed through the drying unit is transported to the winding unit, wound up in a roll shape by a winding roller, and the whole process is completed.
  • the winding unit has a winding mechanism that controls the winding tension to be constant.
  • the winding tension is constant means that the accuracy is at least ⁇ 20% with respect to the set tension.
  • Precursor film 1 Cleaning tank 2: Air knife 3: Squeeze roll (opposite arrangement) 4: Squeeze roll (S-shaped arrangement) 5: Liquid treatment tank 6: Liquid supply tank 7: Liquid feed pump 8: Conveyance roller (in liquid) 9: Transport roller (upper part) 10: Spray shower nozzle (both sides) 11: Overflow direction 12: Transport direction of precursor film 13: Direction of rotation axis 14: Overflow 15: Flow of processing solution surface

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  • Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention se donne pour objectif de proposer un procédé et un dispositif de production d'une membrane fonctionnelle conductrice d'ions permettant de réduire la quantité de solution de traitement utilisée et de réduire le coût de production de ladite membrane. Pour atteindre ce but, le procédé de production a la configuration suivante. Pour produire une membrane fonctionnelle conductrice d'ions qui contient un polymère ayant un groupe ionique, le procédé implique plusieurs étapes au cours desquelles une membrane précurseur est mise en contact avec une solution de traitement acide ou une solution de traitement alcalin, ladite membrane précurseur contenant un polymère dans un état dans lequel ledit groupe ionique forme un sel d'une impureté ionique où, pendant l'intervalle de transition d'une étape de traitement de liquides à l'étape de traitement de liquides suivante, au moins une opération d'élimination de gouttelettes est nécessaire pour retirer ladite solution de traitement acide ou solution de traitement alcalin collée à la surface de ladite membrane précurseur.
PCT/JP2017/003627 2016-02-15 2017-02-01 Procédé et dispositif de production d'une membrane fonctionnelle conductrice d'ions WO2017141709A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008204951A (ja) * 2007-01-24 2008-09-04 Fujifilm Corp 固体電解質フィルム及びその製造方法、並びにこの固体電解質フィルムを用いた電極膜複合体、燃料電池
JP2008204952A (ja) * 2007-01-24 2008-09-04 Fujifilm Corp 固体電解質フィルム及びその製造方法、並びに、この固体電解質フィルムを用いた電極膜複合体、燃料電池
JP2011194593A (ja) * 2010-03-17 2011-10-06 Toray Ind Inc フィルム処理装置
JP2013218868A (ja) * 2012-04-09 2013-10-24 Toyobo Co Ltd イオン交換膜およびその製造方法、レドックスフロー電池、燃料電池

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5044132B2 (ja) * 2005-07-07 2012-10-10 富士フイルム株式会社 固体電解質フィルムの製造方法及び製造設備

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008204951A (ja) * 2007-01-24 2008-09-04 Fujifilm Corp 固体電解質フィルム及びその製造方法、並びにこの固体電解質フィルムを用いた電極膜複合体、燃料電池
JP2008204952A (ja) * 2007-01-24 2008-09-04 Fujifilm Corp 固体電解質フィルム及びその製造方法、並びに、この固体電解質フィルムを用いた電極膜複合体、燃料電池
JP2011194593A (ja) * 2010-03-17 2011-10-06 Toray Ind Inc フィルム処理装置
JP2013218868A (ja) * 2012-04-09 2013-10-24 Toyobo Co Ltd イオン交換膜およびその製造方法、レドックスフロー電池、燃料電池

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