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WO2018164143A1 - Appareil d'électrodialyse et appareil d'électrodialyse inverse - Google Patents

Appareil d'électrodialyse et appareil d'électrodialyse inverse Download PDF

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Publication number
WO2018164143A1
WO2018164143A1 PCT/JP2018/008634 JP2018008634W WO2018164143A1 WO 2018164143 A1 WO2018164143 A1 WO 2018164143A1 JP 2018008634 W JP2018008634 W JP 2018008634W WO 2018164143 A1 WO2018164143 A1 WO 2018164143A1
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Prior art keywords
ion exchange
chamber
exchange membrane
electrodialysis apparatus
electrodialysis
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PCT/JP2018/008634
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English (en)
Japanese (ja)
Inventor
剛之 岸野
福田　憲二
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株式会社アストム
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Application filed by 株式会社アストム filed Critical 株式会社アストム
Priority to JP2019504616A priority Critical patent/JP6958937B2/ja
Publication of WO2018164143A1 publication Critical patent/WO2018164143A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
    • B01D61/44—Ion-selective electrodialysis
    • B01D61/46—Apparatus therefor
    • B01D61/463—Apparatus therefor comprising the membrane sequence AC or CA, where C is a cation exchange membrane
    • 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
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods

Definitions

  • the present invention relates to an electrodialysis apparatus and a reverse electrodialysis apparatus, and more particularly to an electrodialysis apparatus and a reverse electrodialysis apparatus using an asymmetric ion exchange membrane.
  • Ion exchange membranes such as anion exchange membranes and cation exchange membranes are used for electrodialysis and reverse electrodialysis.
  • electrodialysis an anion exchange membrane and a cation exchange membrane are alternately arranged to constitute a desalting chamber and a concentration chamber.
  • electrodialysis includes salt production from seawater, desalination in the food sector such as soy sauce and oligosaccharides, desalting and concentration of leachate from the final disposal site, desalting and concentration of process wastewater, recovery of aluminum sash pickling wastewater, alkaline This technology is used for collecting waste liquid.
  • anion exchange membranes and cation exchange membranes are arranged alternately as in electrodialysis to form a dilute chamber and a thick chamber, with a low concentration electrolyte solution in the dilute chamber and a high concentration in the rich chamber.
  • This is a technology that converts concentration difference energy into electric power through an ion exchange membrane by supplying an electrolyte solution.
  • Reverse electrodialysis can be used for power generation using, for example, fresh water collected from a river and sea water collected from the sea.
  • seawater and concentrated seawater having a higher concentration than seawater discharged from a seawater desalination facility using a distillation method or reverse osmosis method can also be used.
  • Patent Document 1 discloses an asymmetric ion exchange membrane in which a predetermined nonwoven fabric sheet is used and an ion exchange resin layer is provided on one surface of the nonwoven fabric sheet.
  • the asymmetric ion exchange membrane of Patent Document 1 is excellent in strength, dimensional / shape stability, and the like. Furthermore, since the ion exchange resin is firmly fixed to the nonwoven fabric sheet and the thickness of the ion exchange resin layer on the nonwoven fabric sheet is thin and uniform, there is no variation in membrane characteristics and a reduction in membrane resistance is realized. .
  • an object of the present invention is to provide an electrodialysis apparatus and a reverse electrodialysis apparatus that can stably perform electrodialysis or reverse electrodialysis with high efficiency.
  • the present inventors conducted extensive research on the characteristics of the asymmetric ion exchange membrane.When the asymmetric ion exchange membrane is sandwiched between electrolyte solutions having different electrical conductivities, depending on the direction of the thickness direction of the membrane, In other words, it was discovered that there is a difference in electrical resistance depending on whether the surface on which the ion exchange resin layer is formed is in contact with an electrolyte solution with a high electrical conductivity or an electrolyte solution with a low electrical conductivity. The present invention has been reached.
  • the ion exchange membrane in the electrodialysis apparatus in which an ion exchange membrane is disposed in a space between the cathode and the anode, and further, a desalination chamber and a concentration chamber are formed by the ion exchange membrane, the ion exchange membrane includes: An asymmetric ion exchange membrane having an ion exchange resin layer formed on one surface of a porous substrate, and the surface on which the ion exchange resin layer is formed is the desalination chamber side of the asymmetric ion exchange membrane.
  • the porous substrate is a nonwoven fabric;
  • a cation exchange membrane and an anion exchange membrane are alternately arranged in the space between the cathode plate and the anode plate, and the anion exchange membrane on the anode plate side and the cation exchange membrane on the cathode plate side A demineralization chamber is formed between them, and a concentration chamber is formed between the cation exchange membrane on the anode plate side and the anion exchange membrane on the cathode plate side, (3) All ion exchange membranes forming the desalination chamber and the concentration chamber are asymmetric ion exchange membranes, and the surface on which the ion exchange resin layer is formed is placed on the desalination chamber side. is being done, Is preferred.
  • the electrodialysis apparatus is used to supply an electrolyte solution to the desalting chamber, and an electrolyte solution having a higher concentration than the electrolyte solution supplied to the desalting chamber is supplied to the concentration chamber.
  • a dialysis method is also provided.
  • the electrolyte solution supplied to the desalting chamber preferably has an electric conductivity (25 ° C.) of 0.05 to 100 mS / cm.
  • the ion exchange membrane Is an asymmetric ion exchange membrane in which an ion exchange resin layer is formed on one surface of a porous substrate, and the surface on which the ion exchange resin layer is formed is on the lean chamber side.
  • the porous substrate is a nonwoven fabric;
  • a cation exchange membrane and an anion exchange membrane are alternately arranged in the space between the negative electrode plate and the positive electrode plate, and between the anion exchange membrane on the positive electrode plate side and the cation exchange membrane on the negative electrode plate side.
  • a lean chamber is formed, and a thick chamber is formed between the cation exchange membrane on the positive electrode plate side and the anion exchange membrane on the negative electrode plate side, (3) All the ion exchange membranes forming the lean chamber and the rich chamber are asymmetric ion exchange membranes, and the surface on which the ion exchange resin layer is formed is placed on the lean chamber side. Being Is preferred.
  • an electrolyte solution is supplied to the lean chamber, and an electrolyte solution having a higher concentration than the electrolyte solution supplied to the lean chamber is supplied to the rich chamber.
  • a dialysis method is provided.
  • the electrolyte solution supplied to the lean chamber preferably has an electrical conductivity (25 ° C.) of 0.005 to 1 mS / cm.
  • the asymmetric ion exchange membrane is installed so that the ion exchange resin layer side faces the desalting chamber.
  • the electrodialysis apparatus of this invention can exhibit the processing efficiency (desalting ability) at the time of flowing a fixed electric current to the maximum and stably.
  • the ion exchange resin layer side of the asymmetric ion exchange membrane is installed so as to face the lean chamber.
  • the electrodialyzer and reverse electrodialyzer of the present invention ⁇ hereinafter, sometimes referred to as (reverse) electrodialyzer.
  • ⁇ Is very high, and the reason why the variation of each device is effectively suppressed is not clear, but the present inventors presume as follows. That is, until now, the direction of the asymmetric ion exchange membrane has not been conscious, and in the case of electrodialysis, the surface of the asymmetric ion exchange membrane on the ion exchange resin layer side faces the desalting chamber, or the surface of the porous substrate side faces It turned out to be suitable for the desalination room.
  • a plurality of ion exchange membranes are usually used to provide a plurality of desalting chambers / concentration chambers, so that the asymmetric ion exchange is arranged with the porous substrate side facing the desalting chamber.
  • the greater the number of membranes the greater the electrical resistance and the lower the processing efficiency of the entire device.
  • the number of asymmetric ion exchange membranes in which the porous substrate side faces the desalting chamber varies, the processing efficiency varies from device to device, resulting in performance variations.
  • the asymmetric ion exchange membrane is installed so that the ion exchange resin layer side is the desalination chamber side and the porous substrate side is the concentration chamber side, the high electrical resistance of the ion exchange membrane Therefore, variation in processing efficiency for each apparatus is suppressed.
  • the reverse electrodialysis apparatus usually uses a plurality of ion exchange membranes to form a plurality of lean chambers.
  • the thick chamber is provided, the larger the number of asymmetric ion exchange membranes arranged with the porous substrate side facing the lean chamber, the lower the power generation efficiency of the entire apparatus. Also, if the number of asymmetric ion exchange membranes with the porous substrate side facing the lean chamber is different, the power generation efficiency of each device will also be different.
  • the reverse electrodialysis apparatus of the present invention since the asymmetric ion exchange membrane is installed so that the ion exchange resin layer side is the lean chamber side and the porous substrate side is the rich chamber side, the high electrical resistance of the ion exchange membrane This has been avoided, and variations in power generation efficiency among devices have been suppressed. Such an effect becomes more prominent in the reverse electrodialysis apparatus. This is because, in order to increase the power generation output, the electrolyte concentration in the lean chamber of the reverse electrodialysis apparatus is generally lower than the electrolyte concentration in the desalination chamber of the electrodialysis apparatus.
  • the present invention relates to an electrodialysis apparatus and a reverse electrodialysis apparatus.
  • an asymmetric ion exchange membrane is used in the (reverse) electrodialysis apparatus of the present invention.
  • An asymmetric ion exchange membrane is an anion exchange membrane having a structure in which an ion exchange resin layer is formed on one surface of a porous substrate by impregnating one surface of the porous substrate with an ion exchange resin. It is a cation exchange membrane. The other surface of the asymmetric ion exchange membrane is in a state where the porous substrate is exposed.
  • a known asymmetric ion exchange membrane can be used without any limitation.
  • porous substrate a known porous film, net, knitted fabric, woven fabric, non-woven fabric, or the like can be used.
  • porous films, nets, knitted fabrics, woven fabrics, and nonwoven fabrics made of resins such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol, polyvinylidene chloride, and styrene-divinylbenzene copolymer can be used.
  • resins such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl alcohol, polyvinylidene chloride, and styrene-divinylbenzene copolymer
  • a nonwoven fabric is preferred. Since the fibers are closely entangled in the nonwoven fabric, the ion exchange resin layer can be firmly adhered, and the nonwoven fabric is inexpensive.
  • the nonwoven fabric is highly porous, the amount of the low-concentration electrolyte solution infiltrated into the nonwoven fabric increases, and the effect of increasing the electrical resistance of the nonwoven fabric due to the difference in the arrangement direction of the asymmetric ion-exchange membrane appears significantly.
  • the porosity of the porous substrate can be measured by the air permeability measured by the air permeability test of JIS L1913, and is preferably in the range of 1.0 to 1000 cm 3 / cm 2 ⁇ sec, particularly 5.0 to The range is preferably 500 cm 3 / cm 2 ⁇ sec. If the air permeability is too high, the strength of the resulting ion exchange membrane will decrease, and if it is too low, the resistance of the ion exchange membrane will increase.
  • the nonwoven fabric is preferably formed from fibers having a fiber diameter of 1 to 30 ⁇ m, particularly 3 to 20 ⁇ m.
  • the fiber diameter is too large, the smoothness of the surface of the nonwoven fabric is impaired and the anchor effect cannot be sufficiently exhibited, and the ion exchange resin layer may not be firmly held. If the fiber diameter is too small, the strength of the nonwoven fabric may be reduced.
  • the basis weight of the nonwoven fabric from the viewpoint of impregnating an appropriate amount of ion exchange resin to the nonwoven fabric is preferably 1 ⁇ 100g / m 2, particularly preferably 5 ⁇ 50g / m 2.
  • the thickness of the nonwoven fabric is preferably 5 to 200 ⁇ m, particularly preferably 10 to 100 ⁇ m.
  • the nonwoven fabric may have a single layer structure or a laminated structure.
  • the above-described ion exchange resin layer formed on the porous substrate is formed of an ion exchange resin that can be dissolved in an organic solvent and molded by coating.
  • an ion exchange resin that can be dissolved in an organic solvent and molded by coating.
  • a polymer obtained by polymerizing a monomer having an ethylenically unsaturated double bond such as vinyl, styrene or acrylic, or polysulfone, polyphenylene sulfide, polyether ketone, polyether ether ketone, polyether Polymers containing an aromatic ring in the main chain such as imide, polyphenylene oxide, polyethersulfone, polybenzimidazole, polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer, polystyrene-poly (ethylene-propylene) ) -Polystyrene triblock copolymer, polystyrene-polyisopre
  • the ion exchange group is a functional group that can be negatively or positively charged in an aqueous solution.
  • a cation exchange group examples thereof include a sulfonic acid group, a carboxylic acid group, and a phosphonic acid group.
  • the group sulfonic acid group is preferred.
  • anion exchange groups include primary to tertiary amino groups, quaternary ammonium groups, pyridyl groups, imidazole groups, and quaternary pyridinium groups. Generally, quaternary ammonium groups that are strongly basic are used. And quaternary pyridinium groups are preferred.
  • the cation exchange resin include sulfonic acid monomers such as ⁇ -halogenated vinyl sulfonic acid, styrene sulfonic acid, and vinyl sulfonic acid, and carboxylic acid resins such as methacrylic acid, acrylic acid, and maleic anhydride.
  • examples thereof include polymers obtained by polymerizing monomers, phosphonic acid monomers such as vinyl phosphoric acid, and salts or esters thereof.
  • transduced cation exchange groups, such as a sulfonic acid group, to the polymer which contains an aromatic ring in the principal chain mentioned above, and a styrene-type elastomer are mentioned. From the viewpoint of easy control of the amount of cation exchange groups and excellent moldability from an organic solvent, a polymer in which a cation exchange group is introduced into a polymer containing an aromatic ring in the main chain is more preferable.
  • anion exchange resins include amine monomers such as vinylbenzyltrimethylamine and vinylbenzyltriethylamine, nitrogen-containing heterocyclic monomers such as vinylpyridine and vinylimidazole, salts and esters thereof.
  • the polymer obtained by polymerizing can be mentioned. These can be used after amination or methylation before and after polymerization of the monomer.
  • a halogenoalkyl group such as a chloromethyl group or a bromobutyl group is introduced into the above-mentioned polymer or styrene elastomer containing an aromatic ring in the main chain, and then the quaternary amination of the halogenoalkyl group results in an anion exchange group.
  • polymers are listed. From the viewpoint of easy control of the amount of anion exchange groups and excellent moldability from an organic solvent, a polymer containing an aromatic ring in the main chain or a polymer having an anion exchange group introduced into a styrene elastomer is more preferred.
  • ion exchange resins may be introduced with a crosslinked structure as long as a solution dissolved in an organic solvent can be prepared.
  • divinylbenzene divinylsulfone, butadiene, chloroprene, divinylbiphenyl, trivinylbenzene.
  • it may be cross-linked by a polyfunctional monomer typified by a divinyl compound such as divinyl naphthalene, diallylamine, or divinylpyridine. It may be a copolymer in which other monomers such as styrene, acrylonitrile, methylstyrene, acrolein, methyl vinyl ketone, vinyl biphenyl and the like are copolymerized.
  • these ion exchange resin layers can be formed on the porous substrate, and then a crosslinked structure can be introduced by, for example, a method of thermally crosslinking sulfonic acid groups.
  • the ion exchange resin as described above has an ion exchange capacity of 0.5 to 3.0 meq / g, particularly from the viewpoint of reducing membrane resistance, preventing dissolution in an electrolyte solution, and suppressing swelling. It is preferably in the range of 8 to 2.0 meq / g. Therefore, it is preferable that a cation exchange group or an anion exchange group is introduced so as to have such an ion exchange capacity.
  • the asymmetric ion exchange membrane is manufactured by forming an ion exchange resin layer on the surface of the porous substrate described above by a coating method.
  • the organic solvent solution of the ion exchange resin described above is used, but an organic solvent solution of the ion exchange resin precursor can also be used instead.
  • the ion exchange resin precursor is a polymer having a functional group into which an ion exchange group can be introduced.
  • polystyrene examples include those obtained by polymerizing monomers such as styrene, vinyl toluene, vinyl xylene, ⁇ -methyl styrene, vinyl naphthalene, ⁇ -halogenated styrenes. Can be mentioned. Also, styrene such as polystyrene-poly (ethylene-butylene) -polystyrene triblock copolymer, polystyrene-poly (ethylene-propylene) -polystyrene triblock copolymer, polystyrene-polyisoprene block copolymer and hydrogenated products thereof.
  • the system elastomer is also exemplified as a polymer having a functional group capable of introducing a cation exchange group.
  • polymers having functional groups for introducing anion exchange groups include those obtained by polymerizing monomers such as styrene, vinyl toluene, chloromethyl styrene, vinyl pyridine, vinyl imidazole, ⁇ -methyl styrene, vinyl naphthalene. Can be mentioned.
  • polymers containing an aromatic ring in the main chain such as polysulfone, polyphenylene sulfide, polyether ketone, polyether ether ketone, polyether imide, polyphenylene oxide, polyether sulfone, and polybenzimidazole, polystyrene-poly ( Styrene elastomers such as ethylene-butylene) -polystyrene triblock copolymers, polystyrene-poly (ethylene-propylene) -polystyrene triblock copolymers, polystyrene-polyisoprene block copolymers and hydrogenated products thereof are also anion-exchange groups.
  • a polymer having a functional group capable of introducing As a polymer having a functional group capable of introducing.
  • a crosslinked structure may be introduced by copolymerizing a polyfunctional monomer such as the aforementioned divinyl compound. If necessary, other monomers may be copolymerized.
  • the ion exchange group introduction agent is usually contained in the solution, and the ion exchange group is introduced in parallel with the formation of the resin layer.
  • the examples of the ion exchange group introducing agent include polyalkylbenzenesulfonic acid (for example, 1,3,5-trimethylbenzene-2-sulfonic acid, 1,2,4,5-tetramethylbenzene-3-sulfonic acid, 1, 2,3,4,5-pentamethylbenzene-6-sulfonic acid, etc.), N, N, N ′, N′-tetramethyl-1,6-hexanediamine, N, N, N ′, N′-tetra And methyl-1,6-octanediamine, N, N, N ′, N′-tetraethyl-1,6-hexanediamine, and the like.
  • transduction agent for example, 1,3,5-trimethylbenzene-2-sulfonic acid, 1,2,4,5-tetramethylbenzene-3-sulfonic acid, 1,
  • the organic solvent used for preparing the organic solvent solution of the ion exchange resin or ion exchange resin precursor is not particularly limited as long as it can dissolve the above-described polymer. From the viewpoint that it can be easily removed by drying, ethylene chloride, chloroform, tetrahydrofuran, dimethylformamide, N-methylpyrrolidone, methyl alcohol, butyl acetate, ethyl acetate, toluene, methyl ethyl ketone, etc. are used alone or in combination of two or more. It is preferably used in a mixed state.
  • the amount of the organic solvent used should be in a range suitable for application by means described later.
  • the viscosity (25 ° C.) of the organic solvent solution is 0.5 to 80 dPa ⁇ s, particularly 1.0 to 60 dPa ⁇ s. It is preferable to use the organic solvent in an amount that falls within the range. If the viscosity is too high, the penetration is slow when applied to or superimposed on the porous substrate, and it takes time to obtain sufficient adhesion. If the viscosity is too low, the resin solution tends to penetrate into the nonwoven fabric excessively, and the surface ion exchange resin layer cannot be formed.
  • the ion exchange resin layer can be formed on the porous substrate by directly applying an organic solvent solution of the ion exchange resin or ion exchange resin precursor prepared as described above onto the porous substrate.
  • the following method is preferable in that an asymmetric structure can be obtained stably.
  • a release film is prepared, and the organic solvent solution for film formation prepared above is applied on the release film to form a coating layer of the organic solvent solution.
  • this coating layer is transferred to the surface of one side of the porous substrate to form an ion exchange resin layer.
  • the release film is such that it does not adhere to the finally formed ion exchange resin layer and does not dissolve in the organic solvent in the coating layer and can be easily peeled off at the end, its type Although it does not ask
  • Application of the organic solvent solution onto the release film can be performed by a known means, for example, doctor blade coating, knife coating, roll coating, bar coating, or the like.
  • the porous substrate After forming the coating layer, before completely drying, the porous substrate is superposed on the surface of the coating layer and held. Superposition may be performed under pressure as appropriate in order to promote penetration of the organic solvent solution into the porous substrate.
  • the pressurization can be performed by a roller press or the like, and the pressurization pressure is generally set in a range in which the coating layer is not excessively compressed.
  • the coating layer After overlapping the porous substrate as described above and allowing the coating layer to penetrate into the porous substrate, the coating layer is dried to remove the organic solvent and solidify the coating layer.
  • an organic solvent solution of an ion exchange resin is used, an ion exchange resin layer is thereby formed. Drying can be performed by heat drying at a temperature at which the porous substrate or the like does not melt and form a film, vacuum drying, air blowing drying, or the like.
  • the introduction of the ion exchange group is completed by the heat drying.
  • the coating layer is formed using an organic solvent solution of an ion exchange resin precursor that does not contain an ion exchange group introducing agent
  • the layer obtained by the above drying is a layer of an ion exchange resin precursor. It is necessary to introduce an exchange group.
  • the introduction of the ion exchange group is carried out by a method known per se. For example, when producing a cation exchange membrane, it is carried out by a treatment such as sulfonation, phosphoniumation, hydrolysis and the like. When producing an anion exchange membrane, it is carried out by treatment such as amination or alkylation. That is, the solution of the treatment agent for performing the above treatment is brought into contact with the coating layer of the ion exchange resin precursor obtained by drying to carry out exchange group introduction reaction, and then washed and dried to perform ion exchange. A resin layer can be formed.
  • a crosslinked structure can be introduced as necessary.
  • the crosslinked structure can be introduced by a method known per se.
  • a method known per se for example, in the case of a cation exchange membrane, it can be introduced by thermal crosslinking of sulfonic acid groups.
  • an anion exchange membrane a method in which a diamine compound such as N, N, N ′, N′-tetramethyl-1,6-hexanediamine is allowed to act on an ion exchange resin precursor layer containing a chloromethyl group is exemplified.
  • the introduction of the cross-linked structure can also be performed after the peeling film is peeled off.
  • the release film is peeled off, whereby the target asymmetric ion exchange membrane can be obtained.
  • the asymmetric ion exchange membrane obtained as described above has an ion exchange capacity of usually 0.1 to 2.0 meq / g-dry membrane, although it varies depending on the properties of the porous substrate and ion exchange resin used. Preferably, it is formed to be 0.2 to 1.5 meq / g-dry film.
  • the transport number is usually 0.9 to 0.99, preferably 0.93 to 0.98, and the membrane resistance is usually 0.1 to 3.0 ⁇ ⁇ cm 2 , preferably 0.00. It is 2 to 2.0 ⁇ ⁇ cm 2 , and the burst strength is usually 50 to 1000 kPa, preferably 100 to 800 kPa.
  • the ion exchange resin bites into the inside (void) of a porous substrate such as a nonwoven fabric.
  • the thickness of the porous substrate is in the range of 1 to 10 ⁇ m, particularly 2 to 5 ⁇ m, from the viewpoint of adhesion between the ion exchange resin layer and the porous substrate.
  • the thickness of the ion exchange resin layer is in the range of 1 to 50 ⁇ m, particularly 2 to 10 ⁇ m from the viewpoint of the balance between ion selectivity and resistance. Preferably there is.
  • the electrodialysis apparatus of the present invention using the asymmetric ion exchange membrane described above will be described.
  • the principle of electrodialysis will be described with reference to FIG.
  • the cation exchange membrane C and the anion exchange membrane A are alternately arranged in the space between the cathode 10 and the anode 11, and the ion exchange chamber is provided between these ion exchange membranes. Is formed.
  • the ion exchange chamber includes a desalting chamber 13 and a concentration chamber 15.
  • the desalting chamber 13 includes a cation exchange membrane C and an anion exchange membrane A positioned on the anode 11 side with respect to the cation exchange membrane C.
  • the concentration chamber 15 includes an anion exchange membrane A and a cation exchange membrane C positioned on the anode 11 side with respect to the anion exchange membrane A. Accordingly, a plurality of desalting chambers 13 and concentration chambers 15 are alternately arranged.
  • the ion exchange membrane is referred to as an electrode diaphragm 17.
  • the treatment liquid 19 containing a salt such as NaCl is circulated and supplied to the desalting chamber 13, and the concentration chamber 15 is supplied.
  • the electrolyte solution 21 is supplied while being circulated, the cation (Na + in FIG. 1) in the treatment liquid 19 passes through the cation exchange membrane C and enters the concentration chamber 15 adjacent to the cathode 10 side. Transition.
  • the anion (Cl ⁇ in FIG. 1) in the treatment liquid passes through the anion exchange membrane A and moves to the concentration chamber 15 adjacent to the anode 11 side.
  • the electrodialysis apparatus of the present invention for performing electrodialysis as described above is only required to have a known structure, and as shown in FIG.
  • the cation exchange membrane C and the anion exchange membrane A are alternately sandwiched between the gasket spacers 30 so as to have the structure shown in FIG. In FIG. 2, the net of the gasket spacer is omitted.
  • the space in each gasket spacer 30 (the space surrounded by the gasket frame 31) is the above-described ion exchange chamber (desalting chamber 13 or concentration chamber 15).
  • the gasket frame 31 of the gasket spacer having a space serving as the desalting chamber 13 is formed with a flow distribution portion 37 that connects the communication hole 33 and the space serving as the desalting chamber 13.
  • a flow distribution portion 39 that connects the communication hole 35 and the space serving as the concentrating chamber 15 is formed in the gasket frame 31 of the gasket spacer having a space serving as the concentrating chamber 15. That is, a liquid is supplied from these communication holes 33 and 35 to the desalting chamber 13 or the concentrating chamber 15 via the distributing portions 37 and 39, and the liquid supplied to the desalting chamber 13 or the concentrating chamber 15 is further supplied to the distributing portion. It is structured to be discharged to the communication hole 33 or 35 through 37 or 39.
  • an ion exchange membrane is sandwiched between gasket spacers 30, and contact between adjacent ion exchange membranes is effectively prevented by this gasket spacer 30. Further, openings 33 'and 35' are formed in the ion exchange membrane sandwiched between the gasket spacers 30 so as to allow the liquid to flow through the communication holes 33 and 35 (FIG. 2). reference). That is, by supplying electricity while circulating the treatment liquid and the electrolyte solution through the communication holes 33 and 35, desalting is performed in the desalting chamber 13, and the salt concentration of the liquid flowing through the concentration chamber 15 gradually increases. Will go.
  • the installation direction of the cation exchange membrane C and the anion exchange membrane A which are asymmetric ion exchange membranes, greatly affects the treatment efficiency in electrodialysis.
  • New knowledge was obtained. Therefore, in the present invention, as shown in FIG. 1, the asymmetric ion exchange membrane to be used is installed such that the surface on which the ion exchange resin layer 40 is formed is on the desalting chamber 13 side. The processing efficiency is fully demonstrated.
  • the electrodialysis apparatus of the present invention it is preferable to use at least 4 ion exchange membranes including an electrode diaphragm, and it is particularly preferable to use 10 or more ion exchange membranes for the following reasons.
  • the treatment capacity can be increased, and further, the treatment efficiency varies significantly depending on the orientation of the asymmetric ion exchange membrane.
  • the ion exchange membrane only an asymmetric ion exchange membrane may be used, but an asymmetric ion exchange membrane and a symmetric ion exchange membrane may be used in combination. What is necessary is just to use a well-known thing as a symmetrical ion exchange membrane. It is preferable that 50% or more of the ion exchange membranes forming the desalting chamber 13 and the concentration chamber 15 are asymmetric ion exchange membranes, and all the asymmetric ion exchange membranes are particularly preferable for the following reasons.
  • the electrodialysis apparatus can exhibit the processing efficiency to the maximum, and when the apparatus is mass-produced, variation in the processing efficiency of each apparatus can be effectively suppressed.
  • the electrodialysis apparatus of the present invention having such a structure is used by supplying an electrolyte solution containing a halide such as sodium or lithium.
  • the solvent of the electrolyte solution is generally water, and an organic solvent may be included.
  • the electrolyte solution includes a treatment solution that is a desalting target.
  • seawater may be supplied to the desalting chamber and the concentrating chamber.
  • a treatment solution may be supplied to the desalting chamber and an electrolyte solution different from the treatment solution may be supplied to the concentration chamber.
  • the electrolyte solution supplied to the desalting chamber preferably has an electric conductivity of 0.05 to 100 mS / cm (25 ° C.), and has an electric conductivity of 0.1 to 50 mS / cm (25 ° C.). Are more preferable, and those having an electric conductivity (25 ° C.) of 0.2 to 10 mS / cm are particularly preferable.
  • the effect of the present invention is more remarkable when the concentration of the electrolyte solution supplied to the desalting chamber is lower.
  • the high concentration electrolyte solution supplied to the concentrating chamber preferably has an electrical conductivity of 1 to 1000 mS / cm (25 ° C.), and particularly preferably has an electrical conductivity of 2 to 500 mS / cm (25 ° C.). preferable.
  • the electrical conductivity is measured by a method based on JIS K 0130: 2008.
  • the concentration of the electrolyte solution is appropriately determined so that the electric conductivity is within the above range.
  • the reverse electrodialysis apparatus of the present invention using the asymmetric ion exchange membrane described above will be described with reference to FIG.
  • the cation exchange membrane C and the anion exchange membrane A are alternately arranged between the negative electrode 51 and the positive electrode 53.
  • the lean chamber 55 and the rich chamber 57 are formed.
  • the lean chamber 55 includes a cation exchange membrane C and an anion exchange membrane A positioned on the positive electrode side with respect to the cation exchange membrane C.
  • the thick chamber 57 includes an anion exchange membrane A and a cation exchange membrane C positioned on the positive electrode side with respect to the anion exchange membrane A. As a result, a plurality of lean chambers 55 and rich chambers 57 are alternately arranged.
  • a low-concentration electrolyte solution 59 (for example, river water or sewage treatment water) is supplied to the dilute chamber 55, and a high-concentration electrolyte solution 61 (for example, the high-concentration chamber 57).
  • a membrane potential is generated between the lean chamber 55 and the rich chamber 57, and a current flows using this membrane potential as a driving force to generate power. be able to.
  • the cation Na + in FIG.
  • the reverse electrodialysis apparatus of the present invention can have a known structure as long as it is based on such a principle.
  • an apparatus having the same structure as the filter press type electrodialysis apparatus shown in FIG. 2 can be used as the reverse electrodialysis apparatus. That is, a chamber corresponding to a desalting chamber is a lean chamber, a chamber corresponding to a concentration chamber is a thick chamber, and a positive electrode (anode in FIG. 2) and a negative electrode (cathode in FIG. 2) are connected to electrical equipment or the like. Electricity can be generated by passing the liquid.
  • the reverse electrodialysis apparatus of the present invention as in the electrodialysis apparatus, it is important to install the asymmetric ion exchange membrane to be used so that the surface on which the ion exchange resin layer is formed is on the lean chamber side. .
  • the reverse electrodialysis apparatus of the present invention it is preferable to use at least 4 ion exchange membranes including the electrode diaphragm, and it is particularly preferable to use 10 or more ion exchange membranes for the following reason.
  • a large-scale reverse electrodialysis apparatus using a large number of ion exchange membranes can obtain a larger output, and moreover, fluctuations in power generation efficiency due to the orientation of the asymmetric ion exchange membrane are noticeable.
  • the ion exchange membrane only an asymmetric ion exchange membrane may be used, but an asymmetric ion exchange membrane and a symmetric ion exchange membrane may be used in combination. What is necessary is just to use a well-known thing as a symmetrical ion exchange membrane.
  • 50% or more are preferably asymmetric ion exchange membranes, and all are preferably asymmetric ion exchange membranes for the following reasons. Maximum power generation efficiency can be realized, and variation in power generation efficiency between devices can be effectively suppressed when the devices are mass-produced.
  • the reverse electrodialysis apparatus of the present invention having such a structure may be supplied with a desired electrolyte solution to generate electric power.
  • the lean chamber 55 may be supplied with an electrolyte solution such as river water or sewage treated water.
  • the concentrated chamber 57 may be supplied with an electrolyte solution having a higher concentration than the electrolyte solution supplied to the lean chamber, such as seawater and concentrated seawater.
  • an electrolyte solution having an electric conductivity of 0.005 to 1 mS / cm, particularly 0.01 to 0.8 mS / cm is supplied to the lean chamber 55.
  • an electrolytic solution having an electric conductivity of 0.05 to 200 mS / cm, particularly 0.1 to 150 mS / cm is supplied to the thick chamber 57. Since the voltage of reverse electrodialysis increases in proportion to the concentration ratio between the lean chamber and the rich chamber, it is advantageous to reduce the concentration of the lean chamber to increase the output.
  • the rich chamber is generally supplied with seawater or concentrated seawater that is about two to three times as much as seawater. Due to such restriction of the concentration chamber concentration, the concentration of the lean chamber in reverse electrodialysis is generally set lower than the concentration of the dilution chamber in electrodialysis.
  • the effect of the present invention is remarkably achieved in reverse electrodialysis using a low concentration electrolyte solution. Demonstrated.
  • the concentration of the electrolyte solution is appropriately determined so that the electric conductivity is within the above range.
  • the design of the (reverse) electrodialysis apparatus of the present invention may be changed as appropriate as long as the essence of the invention is not changed.
  • a symmetrical ion exchange membrane is used as an electrode diaphragm separating the most ion exchange chamber from the electrode, from the viewpoint of strength and melting point, and from the viewpoint of the influence of substances generated by the electrode on the membrane. Also good.
  • an asymmetric or symmetric ion exchange membrane may be used alone, or a plurality of electrodes may be used.
  • Electrode resistance measurement An ion exchange membrane is sandwiched in a two-chamber cell having a platinum black electrode plate, 0.5 mol / l sodium chloride aqueous solution is filled on both sides of the ion exchange membrane, and an electrode at 25 ° C. is applied by an AC bridge (frequency 1000 cycles / second). The resistance between was measured. The difference between the interelectrode resistance at this time and the interelectrode resistance measured when no ion exchange membrane was installed was taken as the membrane resistance. In addition, as an ion exchange membrane used for the said measurement, what was previously equilibrated in 0.5 mol / l sodium chloride aqueous solution was used.
  • V M is the membrane potential
  • t + is the cation transport number
  • t ⁇ is the anion transport number
  • R is the gas constant (8.314 J / mol ⁇ K)
  • T is the thermodynamic temperature
  • F is Faraday.
  • a ⁇ 1 is the activity of 0.1 mol / L-potassium chloride aqueous solution
  • a ⁇ 2 is the activity of 0.5 mol / L-potassium chloride aqueous solution.
  • the ion exchange membrane was immersed in a 1 mol / L-HCl aqueous solution for 10 hours or more. Thereafter, in the case of a cation exchange membrane, the counter ion of the ion exchange group is replaced with a sodium ion from a hydrogen ion with a 1 mol / L-NaCl aqueous solution, and the liberated hydrogen ion is converted into a potentiometric titrator (COMMITITE) using an aqueous sodium hydroxide solution. -900, manufactured by Hiranuma Sangyo Co., Ltd.) (Amol).
  • COMMITITE potentiometric titrator
  • burst strength measurement For the ion exchange membrane in a wet state, the burst strength of the ion exchange membrane was measured using a Mullen type burst strength meter (manufactured by Toyo Seiki Seisakusho).
  • the asymmetric ion exchange membrane was cut with a microtome (ESM-150S manufactured by Kuruma Sales Co., Ltd.) to form a measurement cross section.
  • ESM-150S manufactured by Kuruma Sales Co., Ltd.
  • VK-8700 manufactured by Keyence Corporation
  • the cross section of the film sample was observed with a 50 ⁇ objective lens, and the thickness of the ion exchange resin layer (portion existing on the nonwoven fabric) was determined from the observed image.
  • the thickness of the non-woven fabric void layer portion where no ion exchange resin was present was measured.
  • the total thickness of the ion exchange membrane was measured using a micrometer MED-25PJ (manufactured by Mitutoyo Corporation).
  • ⁇ Membrane formation of asymmetric cation exchange membrane> Preparation of polymer solution; Polyphenylene oxide was dissolved in chloroform, chlorosulfonic acid was added to the solution, and polyphenylene oxide was reacted with chlorosulfonic acid. Next, sodium hydroxide was added for neutralization, and the solvent was removed to obtain a sulfonated polyphenylene oxide (cation exchange resin) having an ion exchange capacity of 1.6 meq / g. Next, the sulfonated polyphenylene oxide was dissolved in N, N-dimethylformamide so as to be 28% by mass to prepare a sulfonated polyphenylene oxide solution. The solution viscosity was 20 dPa ⁇ s.
  • Non-woven sheet Novatexx 2442 manufactured by Freudenberg (25 g / m 2 basis weight, thickness 0.06 mm, air permeability 180 cm 3 / cm 2 ⁇ sec), or PY120-19 manufactured by Awa Paper Co., Ltd. (14 g / m 2 basis weight, thickness 0.02 mm, An air permeability of 82 cm 3 / cm 2 ⁇ sec) was used.
  • the polymer solution prepared above was applied to a PET film so as to have a thickness of 50 ⁇ m using a bar coater to form a coating layer (cast layer).
  • the PET film on which the coating layer has been formed is dried at 50 ° C. for 5 minutes, and then the above nonwoven sheet is overlaid and laminated by roller pressurization to form an ion exchange resin coating layer on one side of the nonwoven sheet. I let you.
  • the coating layer was solidified by heating at 60 ° C., and then the PET film was peeled to obtain an asymmetric cation exchange membrane.
  • Table 1 The physical properties of the resulting cation exchange membrane are shown in Table 1.
  • ⁇ Making an asymmetric anion exchange membrane> Preparation of polymer solution; 100 g of a copolymer consisting of a segment of polystyrene (65% by weight) and a hydrogenated segment of polyisoprene (35% by weight) is dissolved in 1000 g of chloroform, and 100 g of chloromethyl methyl ether and 10 g of tin chloride are added. The reaction was carried out at 0 ° C. for 15 hours. Subsequently, the precipitate was washed in methanol, washed, and then dried to obtain a chloromethylated styrene block copolymer.
  • chloromethylated polystyrene having a molecular weight of 5000 was mixed with the above chloromethylated styrene block copolymer to prepare a chloromethylated polystyrene ratio of 40% by mass.
  • the chloromethylated polymer mixture thus obtained was dissolved in tetrahydrofuran to obtain a 25% by mass solution, and N, N, N ′, N′-tetramethyl-1,6-hexanediamine was added to this solution.
  • a polymer solution for forming an anion exchange membrane containing an anion exchange resin precursor and an anion exchange group introducing agent was prepared.
  • the viscosity of the polymer solution was 5 dPa ⁇ s.
  • the polymer solution prepared above was applied to a PET film so as to have a liquid thickness of 50 ⁇ m using a bar coater to form a coating (cast) layer.
  • the PET film on which the coating layer is formed is dried at 30 ° C. for 0.5 minutes, and then the same non-woven fabric sheet used in the production of the asymmetric cation exchange membrane is overlaid on the coating layer and laminated by pressing with a roller.
  • an ion exchange resin coating layer was formed on one side of the nonwoven fabric sheet.
  • it heat-dried at 40 degreeC the coating layer was solidified, and the PET film was peeled after this and the asymmetric anion exchange membrane was obtained.
  • Table 1 shows the physical properties of the obtained asymmetric anion exchange membrane.
  • a cation exchange membrane 1 and an anion exchange membrane 1 are alternately arranged between a pair of cathode (Ti—Pt coat) and anode (Ti—Pt coat).
  • Filter press type electrodialyzer A3 type S3 with 11 and 10 plates Effective membrane areas of cation exchange membrane and anion exchange membrane are both 0.55 dm 2 / sheet). (Astom Co., Ltd.) was used.
  • the cation exchange membrane 1 and the anion exchange membrane 1 were all installed such that the ion exchange resin layer surface faces the desalting chamber.
  • the processing time (operation time) required was measured, and the processing capacity (desalting capacity) was calculated according to the following formula from the amount of the desalted liquid charged therein.
  • the effective membrane area is 5.5 dm 2 (0.55 dm 2 ⁇ 10 pairs). The results are shown in Table 3.
  • Electrodialysis was performed in the same manner as in Example 1 except that 500 ml was added. The treatment time until the electrical conductivity of the desalted solution reached 0.3 mS / cm (about 2.0 mmol / L) was measured, and the desalting ability was calculated in the same manner as in electrodialysis Example 1. The results are shown in Table 3.
  • cation exchange membrane 1 and anion exchange membrane 1 are alternately 11 sheets, 10 sheets (cation exchange membrane, An anion exchange membrane has an effective membrane area of 0.55 dm 2 / sheet), and a filter press type reverse electrodialysis apparatus (made by Astom Co., Ltd., gasket thickness 0.2 mm) equipped with a thick chamber and a lean chamber. It was constructed. The cation exchange membrane 1 and the anion exchange membrane 1 were all installed so that the surface of the ion exchange resin layer faces the lean chamber.
  • ⁇ Reverse electrodialysis example 2 Reverse electrodialysis except that 1.0 mol / L sodium chloride aqueous solution (85.8 mS / cm) was used in the thick chamber and 0.005 mol / L sodium chloride aqueous solution (0.6 mS / cm) was used in the dilute chamber. The measurement was performed under the same conditions as in Example 1, and the results are shown in Table 5.
  • Electrode diaphragm 19 Low concentration processing solution, 21 high concentration electrolyte solution, 30 gasket spacer, 31 gasket frame, 33, 33 'communication hole for processing liquid, 35, 35 'communicating holes for the electrolyte solution, 37 Distributor for processing liquid, 39 Distributor for electrolyte solution, 40 ion exchange resin layer, 50 reverse electrodialysis machine, 51 negative electrode, 53 positive electrode, 55 Sparse room, 57 Thick room 59 low concentration electrolyte solution, 61 high concentration electrolyte solution, 63 Electrical equipment

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Abstract

L'invention concerne un appareil d'électrodialyse comprenant une membrane échangeuse d'ions disposée dans l'espace entre une électrode négative et une électrode positive, une chambre de déminéralisation et une chambre de concentration étant formées par la membrane échangeuse d'ions, la membrane échangeuse d'ions étant une membrane échangeuse d'ions asymétrique comportant une couche de résine échangeuse d'ions formée sur une surface d'un substrat poreux, la membrane échangeuse d'ions asymétrique étant installée de sorte que la surface comportant la couche de résine échangeuse d'ions soit du côté chambre de déminéralisation. L'appareil d'électrodialyse peut effectuer une électrodialyse de manière stable, à une capacité de dessalement élevée. De plus, l'invention concerne un appareil d'électrodialyse inverse pouvant effectuer une électrodialyse inverse stable à haut rendement.
PCT/JP2018/008634 2017-03-10 2018-03-06 Appareil d'électrodialyse et appareil d'électrodialyse inverse WO2018164143A1 (fr)

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CN110813386A (zh) * 2019-09-11 2020-02-21 浙江工业大学 一种改性阳离子交换膜的制备方法
WO2020166536A1 (fr) * 2019-02-12 2020-08-20 日立化成株式会社 Stratifié
CN112897652A (zh) * 2021-01-28 2021-06-04 烟台大学 一种电渗析脱盐装置
JP2022551402A (ja) * 2019-09-19 2022-12-09 ラッペーンランナン－ラハデン テクニッリネン ユリオピスト ルト 電気化学的プロセスのためのシステム及び方法
JP2023544307A (ja) * 2020-09-30 2023-10-23 フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ 化合物、組成物、およびポリマーフィルム
WO2024135590A1 (fr) * 2022-12-22 2024-06-27 Ａｇｃエンジニアリング株式会社 Membrane échangeuse d'ions et son procédé de production
WO2025013725A1 (fr) * 2023-07-07 2025-01-16 Ａｇｃエンジニアリング株式会社 Membrane échangeuse d'anions, son procédé de production, et dispositif d'électrodialyse à récupération d'acide

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JP2000218270A (ja) * 1998-11-25 2000-08-08 Matsushita Electric Works Ltd 電解水生成装置
JP2006021193A (ja) * 2004-06-07 2006-01-26 Dainichiseika Color & Chem Mfg Co Ltd イオン交換複合膜体および電気透析装置
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WO2020166536A1 (fr) * 2019-02-12 2020-08-20 日立化成株式会社 Stratifié
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CN110813386A (zh) * 2019-09-11 2020-02-21 浙江工业大学 一种改性阳离子交换膜的制备方法
CN110813386B (zh) * 2019-09-11 2022-04-19 浙江工业大学 一种改性阳离子交换膜的制备方法
JP2022551402A (ja) * 2019-09-19 2022-12-09 ラッペーンランナン－ラハデン テクニッリネン ユリオピスト ルト 電気化学的プロセスのためのシステム及び方法
JP2023544307A (ja) * 2020-09-30 2023-10-23 フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ 化合物、組成物、およびポリマーフィルム
JP7725573B2 (ja) 2020-09-30 2025-08-19 フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ 化合物、組成物、およびポリマーフィルム
CN112897652A (zh) * 2021-01-28 2021-06-04 烟台大学 一种电渗析脱盐装置
WO2024135590A1 (fr) * 2022-12-22 2024-06-27 Ａｇｃエンジニアリング株式会社 Membrane échangeuse d'ions et son procédé de production
WO2025013725A1 (fr) * 2023-07-07 2025-01-16 Ａｇｃエンジニアリング株式会社 Membrane échangeuse d'anions, son procédé de production, et dispositif d'électrodialyse à récupération d'acide

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