WO2013108597A1 - Condensateur à flux traversant, dispositif de fabrication de liquide déionisé, et procédé de fabrication de liquide déionisé - Google Patents

Condensateur à flux traversant, dispositif de fabrication de liquide déionisé, et procédé de fabrication de liquide déionisé Download PDF

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Publication number
WO2013108597A1
WO2013108597A1 PCT/JP2013/000057 JP2013000057W WO2013108597A1 WO 2013108597 A1 WO2013108597 A1 WO 2013108597A1 JP 2013000057 W JP2013000057 W JP 2013000057W WO 2013108597 A1 WO2013108597 A1 WO 2013108597A1
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Prior art keywords
liquid
electrode
sheet
capacitor
current collector
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PCT/JP2013/000057
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English (en)
Japanese (ja)
Inventor
石田　修一
修治 川▲崎▼
山田　隆之
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クラレケミカル株式会社
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Priority to KR1020147018369A priority Critical patent/KR101479457B1/ko
Priority to JP2013554241A priority patent/JP5798201B2/ja
Priority to CN201380005656.6A priority patent/CN104185609B/zh
Publication of WO2013108597A1 publication Critical patent/WO2013108597A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
    • C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
    • C02F1/4691—Capacitive deionisation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/008—Terminals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/02—Diaphragms; Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/26—Structural combinations of electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices with each other
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Definitions

  • the present invention relates to a liquid-passing capacitor, a deionized liquid production apparatus, and a method for producing a deionized liquid for adsorbing and removing ions in the liquid for desalting.
  • Liquid passing type capacitors for removing ions in liquid using electrostatic force are known.
  • the desalting method using a flow-through capacitor is a desalting method that is excellent in energy efficiency because electrical energy supplied during ion adsorption can be stored in the capacitor, and electrical energy can be recovered during ion desorption. Further, the liquid passing type capacitor can be operated even at a low voltage. Furthermore, in a liquid-flowing type capacitor, since the polarity is switched between when ions are adsorbed and when they are desorbed, it is difficult for scale to be generated inside the apparatus. From these points, the liquid-pass capacitor is a desalting method with high equipment merit.
  • Patent Document 1 discloses a liquid-permeable capacitor in which at least one ion adsorption electrode is a porous metal foil.
  • Patent Document 2 includes a rechargeable electrode that includes a porous material and is configured to adsorb ions of opposite charges, and an ion exchange material that is in contact with the porous material of the rechargeable electrode.
  • An electrode assembly is disclosed. In this electrode assembly, the ion exchange material is charged the same as the rechargeable electrode, and the ion exchange material is permeable to ions of opposite charge and at least partially to ions of the same charge. It is disclosed that it is impermeable.
  • FIG. 9 is a partially exploded schematic view for explaining the cell structure of the liquid-permeable capacitor 110.
  • FIG. 10 is a schematic view of the XX ′ cross section of FIG. 9 when each cell of the liquid-passing capacitor 110 is assembled.
  • the liquid-flowing capacitor 110 includes two electrodes 101 and 102 for adsorbing ions in the liquid, and a separator 3 interposed between the electrodes 101 and 102.
  • a plurality of cells 120 are stacked.
  • Each electrode 101 includes a current collector 1a (1a ′) and a porous carbon sheet 1b (1b ′) laminated on the current collector 1a (1a ′).
  • Each electrode 102 includes a current collector 2a and a porous carbon sheet 2b laminated on the current collector 2a.
  • the electrodes 101 and 102 are counter electrodes.
  • the laminated body formed by accumulating the cell 120 several cells is fastened with the metal fastening bolts 5a and 5b, for example.
  • the fastening bolt 5a electrically connects the tab portions 1d provided on the current collector 1a so as not to face the porous carbon sheet 1b (1b ′).
  • the fastening bolt 5b electrically connects the tab portion 2d provided on the current collector 2a so as not to face the porous carbon sheet 2b in each cell 120.
  • the plurality of current collectors 1a or the plurality of current collectors 2a are electrically connected to each other by the tab portion 1d or the tab portion 2d fastened by the fastening bolt 5a or the fastening bolt 5b.
  • the liquid to be processed is passed in the direction as indicated by the white arrow in FIG.
  • a voltage is applied between the electrode 101 and the electrode 102 by an external power supply (not shown) and a liquid is passed between the capacitors formed by the electrode 101 and the electrode 102, ions in the passed liquid are porous carbon. Adsorbed to the sheet 1b (1b ') and the porous carbon sheet 2b. Then, the processing liquid after the ions are adsorbed and removed by the capacitor reaches the liquid passage hole 8 provided in the center of each cell, and is discharged to the outside through the liquid passage hole 8.
  • the current collectors 1a having the same polarity and the current collectors 2a are connected to each other by the metal fastening bolts 5a and 5b. It was electrically connected by fastening. Only by fastening with such fastening bolts, if the liquid to be treated contains a high concentration of ions, or if the liquid to be treated is processed at a high flow rate, the conductivity is insufficient and the removal of ions is performed. The rate may decline. In particular, when a material having a high electrical conductivity anisotropy, such as a graphite (graphite) sheet, having a high electrical conductivity in the surface direction of the sheet and low in the vertical direction is used as a current collector. In some cases, the ion removal rate may be reduced due to lack of electrical conductivity in the vertical direction.
  • a material having a high electrical conductivity anisotropy such as a graphite (graphite) sheet, having a high electrical conductivity in the surface direction of the sheet and low in the vertical direction is used
  • One aspect of the present invention is a liquid-permeable capacitor formed by stacking a plurality of cells, and the cell includes a first electrode, a second electrode, a separator interposed between the first electrode and the second electrode.
  • a first current collector sheet made of a graphite sheet; a first porous carbon sheet laminated on the first current collector sheet; and a cation exchange membrane laminated on the first porous carbon sheet.
  • a second current collector sheet made of a graphite sheet, a second porous carbon sheet laminated on the second current collector sheet, and an anion laminated on the second porous carbon sheet
  • the cation exchange membrane and the anion exchange membrane are disposed so as to face each other with a separator interposed therebetween, and at least one of the first current collector sheet and the second current collector sheet is made of each porous carbon.
  • At least two tabs that do not face the sheet Tab portions of the above are flow-through capacitor that is electrically connected with placed conductive sheets to contact the surface of the tab portion.
  • another aspect of the present invention includes a liquid-permeable capacitor as described above, a DC power supply, and a container that stores the liquid-flowing capacitor, and the DC power supply has a positive polarity and a negative polarity that are mutually opposite.
  • the container is connected to the first electrode and the second electrode in a replaceable manner, and the container is processed from the liquid supply port for supplying a liquid containing an ionic substance to the liquid-flowing capacitor, and the liquid-passing capacitor. It is a deionized liquid manufacturing apparatus provided with the drainage port for discharging
  • another aspect is a method for producing a deionized liquid using the deionized liquid production apparatus as described above, wherein ions are supplied from a liquid supply port while applying a voltage to the first electrode and the second electrode by a DC power source.
  • the present invention it is possible to provide a liquid-passing capacitor, a deionized liquid manufacturing method, and a deionized liquid manufacturing apparatus that have a higher ability to remove ionic substances than conventional liquid-flowing capacitors.
  • FIG. 2A is a schematic top view of the liquid-permeable capacitor 100.
  • FIG. 2B is a schematic front view of the liquid-permeable capacitor 100.
  • FIG. 3A is a schematic diagram for explaining an example of an arrangement pattern of conductive sheets of a liquid-permeable capacitor.
  • FIG. 3B is a schematic diagram for explaining an example of an arrangement pattern of conductive sheets of a liquid-permeable capacitor.
  • FIG. 4 is a schematic explanatory diagram for explaining a configuration of a deionized liquid manufacturing apparatus 200 including the liquid-permeable capacitor 100 according to the first embodiment.
  • FIG. 1 is a schematic top view of the liquid-permeable capacitor 100.
  • FIG. 2B is a schematic front view of the liquid-permeable capacitor 100.
  • FIG. 3A is a schematic diagram for explaining an example of an arrangement pattern of conductive sheets of a liquid-permeable capacitor.
  • FIG. 3B is a schematic diagram for explaining an example of an arrangement pattern of conductive sheets of a
  • FIG. 5A is an explanatory diagram for explaining a first stage of the operation of the capacitor structure in the liquid-flowing capacitor 100.
  • FIG. 5B is an explanatory diagram for explaining a second stage of the action of the capacitor structure in the liquid-permeable capacitor 100.
  • FIG. 5C is an explanatory diagram for explaining a third stage of the action of the capacitor structure in the liquid-permeable capacitor 100.
  • 3 is a graph plotting changes in current and voltage with respect to time (seconds) during operation of the liquid-flowing capacitor of Example 1.
  • FIG. 6 is a graph plotting changes in electrical conductivity with respect to time (seconds) during operation of the liquid-pass capacitor of Example 1.
  • FIG. 10 is a schematic view of the vicinity of the XX ′ cross section of FIG.
  • FIG. 1 is a partially exploded perspective schematic view for explaining a main part of the configuration of the liquid-permeable capacitor 100 of the present embodiment
  • FIG. 2A is a schematic top view of the liquid-permeable capacitor 100
  • FIG. 2B is a schematic front view thereof. is there.
  • the liquid passing type capacitor 100 of the present embodiment has a capacitor structure formed by stacking a plurality of cells 10 as shown in FIG.
  • Each cell 10 includes a first electrode 1, a second electrode 2, and a separator 3 interposed between the first electrode 1 and the second electrode 2.
  • FIG. 1 for convenience of explanation, a state in which a part of a layer is disassembled so as to develop a laminated structure is schematically illustrated.
  • the first electrode 1 includes a first current collector sheet 1a or a first current collector sheet 1a ′ and a first porous carbon sheet 1b (1b ′) laminated on the first current collector sheet 1a (1a ′). And a cation exchange membrane 1c (1c ′) laminated on the first porous carbon sheet 1b (1b ′).
  • the second electrode 2 includes a second current collector sheet 2a, a second porous carbon sheet 2b laminated on the second current collector sheet 2a, and an anion exchange membrane 2c laminated on the second porous carbon sheet 2b. With.
  • the cation exchange membrane 1c (1c ′) and the anion exchange membrane 2c are arranged to face each other with the separator 3 interposed therebetween.
  • the first current collector sheet 1a and the first porous carbon sheet 1b, the second current collector sheet 2a and the second porous carbon sheet 2b, the cation exchange membrane 1c and the anion exchange membrane 2c are substantially in the center.
  • the liquid passage hole 8 for passing the liquid deionized by the cell 10 is provided.
  • the first current collector sheet 1a ′ and the first porous carbon sheet 1b ′ cation exchange membrane 1c ′ do not have the liquid passage hole 8 in order to regulate the liquid passage direction, and form the uppermost cell.
  • the first current collector sheet 1a, 1a ' has a tab portion 1d that does not face the first porous carbon sheet 1b, 1b', and the second current collector sheet 2a faces the second porous carbon sheet 2b.
  • the tab portion 2d is not provided.
  • the plurality of tab portions 1d and the plurality of tab portions 2d are fastened by conductive fastening bolts 5a and 5b, respectively. Such fastening bolts 5a and 5b are electrically connected by bringing the tab portions 1d or the tab portions 2d into contact with each other on the surface.
  • the fastening bolt 5a for fastening the plurality of tab portions 1d and the fastening bolt 5b for fastening the plurality of tab portions 2d are respectively connected to one electrode side and the other electrode side of the DC power supply, as will be described later. Then, the plurality of first current collector sheets 1a or the plurality of second current collector sheets 2a are made equipotential.
  • the plurality of tab portions 1d are one conductive sheet 6a arranged so as to contact the surface of each tab portion 1d. Electrically connected. Similarly, the plurality of tab portions 2d are electrically connected by one conductive sheet 6b arranged so as to be in contact with the surface of each tab portion 2d. Thus, by connecting the plurality of tab portions 1d or the plurality of tab portions 2d via the conductive sheet 6a or the conductive sheet 6b, the plurality of first current collector sheets 1a or the plurality of second current collector sheets 1a are connected to each other. The current collector sheets 2a are electrically connected in a direction parallel to the sheet surface.
  • the electrical conductivity is high in the surface direction of the sheet like a graphite sheet. Even when a sheet material having high anisotropy in electrical conductivity, such as low in the vertical direction, is used, sufficient conductivity can be obtained. Thereby, even when a high concentration ionic substance is contained in the liquid to be processed or when the liquid is processed at a high flow rate, a high ion removal rate can be maintained.
  • the tab of one current collector sheet is provided.
  • the number of parts is not particularly limited, and may be one place or three or more places.
  • position a conductive sheet so that a tab part may contact directly so that the tab parts of several collector sheet of the same polarity may mutually conduct.
  • FIGS. 3A and 3B An example of the arrangement pattern of the conductive sheet is shown in FIGS. 3A and 3B. As the arrangement pattern, even if the conductive sheet C is arranged so as to sew the tab portions D one by one as in the arrangement pattern shown in FIG. 3A, the plurality of tab portions D are stacked as shown in FIG. 3B.
  • the conductive sheet C may be arranged so as to sew the body.
  • any conductive sheet having high corrosion resistance can be used without particular limitation.
  • a conductive sheet include, for example, a titanium metal made of titanium or a titanium alloy, a metal foil made of gold, platinum, silver, or a composite material thereof, or a graphite sheet.
  • the titanium foil formed from the titanium-type metal from the point which is excellent in the balance of corrosion resistance, electroconductivity, and low cost is used preferably.
  • the thickness of the conductive sheet is preferably 20 to 200 ⁇ m, more preferably 30 to 100 ⁇ m, from the viewpoint that it is not necessary to secure an excessive space while maintaining high conductivity.
  • the fastening bolt it is preferable to use a fastening means of a bolt / nut structure using a conductive bolt and a nut such as a metal bolt.
  • a fastening means of a bolt / nut structure using a conductive bolt and a nut such as a metal bolt.
  • the liquid passing type capacitor is used for desalting the liquid to be treated, it is particularly preferable to use a metal bolt having high corrosion resistance such as a titanium bolt made of titanium or a titanium alloy.
  • the fastening means is not limited to the bolt structure, and means such as clamping with a clip-like structure may be used.
  • the current collector sheet or conductive sheet may be damaged by the fastening pressure.
  • a metal plate 4 having excellent corrosion resistance and conductivity such as a titanium plate as shown in FIG. 1 is interposed between the bolt head of the fastening bolt and the conductive sheet. It is preferable to disperse the pressure.
  • the thickness of the metal plate 4 is not particularly limited, but is preferably about 0.5 to 5 mm. In this case, the metal plate, the fastening bolt, the current collector sheet, and the conductive sheet are electrically connected, so that they are electrically connected.
  • One cell consists of two electrodes with a separator in between.
  • the number of cells approximately matches the number of separators.
  • the number of cells of the liquid-permeable capacitor of this embodiment is not particularly limited, but specifically, it is preferably about 3 to 100, and more preferably about 5 to 50.
  • a graphite sheet As the first current collector sheet and the second current collector sheet, a graphite sheet is used.
  • the graphite sheet include a graphite sheet formed from expanded graphite.
  • the graphite sheet has an excellent balance of corrosion resistance, high conductivity, and low cost.
  • the graphite sheet is characterized in that the electrical conductivity is lower in the thickness direction than in the surface direction of the sheet.
  • the conductive sheet is disposed so as to contact the tab portion of the graphite sheet, and the plurality of tab portions are electrically connected to each other, thereby increasing the height in the surface direction of the graphite sheet.
  • the conductivity can be fully utilized.
  • the thickness of the graphite sheet is preferably 100 to 500 ⁇ m.
  • Examples of the first porous carbon sheet and the second porous carbon sheet include molded sheets obtained by binding porous carbon particles such as activated carbon particles with a binder.
  • the activated carbon particles include plant activated carbon particles such as wood, sawdust, charcoal, fruit shells such as coconut husk and walnut shell, fruit seeds, pulp production by-products, lignin, and molasses; peat, grass charcoal, lignite , Mineral activated carbon particles obtained by carbonizing and activating lignite, lemon blue, anthracite, coke, coal tar, coal pitch, petroleum distillation residue, petroleum pitch, etc .; carbonizing and activating phenol, saran, acrylic resin, etc. Synthetic resin-based activated carbon particles obtained by natural carbon; natural fiber-based activated carbon particles obtained by carbonizing and activating regenerated fibers (rayon) and the like. Among these, coconut shell activated carbon particles are particularly preferable from the viewpoint of excellent adsorption performance.
  • the central particle diameter of the activated carbon particles is preferably 1 to 100 ⁇ m, more preferably 2 to 50 ⁇ m, and particularly preferably 3 to 30 ⁇ m.
  • the central particle diameter is the particle diameter when the integrated value of the mass of all particles is 50% in the particle size distribution.
  • Such a center particle diameter can be measured, for example, using a Nikkiso Co., Ltd. Microtrac particle size distribution measuring device (MT3300).
  • MT3300 Microtrac particle size distribution measuring device
  • the specific surface area of the activated carbon particles is preferably 700 to 2500 m 2 / g, more preferably 1500 to 2000 m 2 / g.
  • the specific surface area can be measured, for example, by the following method.
  • the pore volume of the activated carbon particles is preferably 0.5 to 1.2 mL / g, more preferably 0.7 to 1.0 mL / g. If the pore volume is too small, ions tend to be difficult to desorb when the polarity of the electrode is reversed and ions adsorbed on the surface of the activated carbon sheet are desorbed. Moreover, when the pore volume is too large, the performance per volume tends to decrease.
  • the pore volume can be measured, for example, by the following method. The nitrogen adsorption isotherm of activated carbon at 77K is measured using BELSORP-mini or the like.
  • the average pore diameter of the activated carbon particles is preferably 1.5 to 2.4 nm, more preferably 1.6 to 2.2 nm. If the average pore diameter is too small, ions tend to be difficult to desorb when the polarity of the electrode is reversed and ions adsorbed on the surface of the activated carbon sheet are desorbed. Moreover, when the average pore diameter is too large, the performance per volume tends to decrease.
  • the surface functional group amount of the activated carbon particles is preferably 0.1 to 0.8 meq / g, more preferably 0.2 to 0.5 meq / g.
  • the amount of surface functional groups can be measured, for example, by the following method. After vacuum drying for 8 to 10 hours in a constant temperature dryer adjusted to 120 ° C., it is allowed to cool in a desiccator containing silica gel as a desiccant.
  • the activated carbon sheet is obtained by forming a mixture containing activated carbon particles and a binder into a sheet shape.
  • a binder when using for water purification, it is preferable to use the binder which is not harmful to living organisms.
  • the ratio of the activated carbon particles contained in the activated carbon sheet is preferably 50 to 99% by mass, more preferably 80 to 95% by mass. When the ratio of the activated carbon particles contained in the activated carbon sheet is too low, the performance tends to decrease.
  • binder examples include, for example, polytetrafluoroethylene, polyvinylidene fluoride, fluoroethylene-perfluoroalkoxyethylene copolymer, ethylene-tetrafluoroethylene copolymer, styrene-butadiene copolymer, polyethylene, polypropylene, polystyrene Ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyacrylonitrile, polyamide and the like.
  • polytetrafluoroethylene is preferable from the viewpoints of binding properties and stability.
  • the activated carbon sheet may further contain a conductive material.
  • a conductive material By blending the conductive material, excellent conductivity can be imparted to the activated carbon sheet.
  • a conductive material include, for example, carbon-based materials such as acetylene black, ketjen black, and graphite; noble metals such as gold, platinum, and silver; titanium nitride, titanium silicon carbide, titanium carbide, titanium boride, And highly conductive ceramics such as zirconium boride.
  • a carbon-based material is preferable because it is excellent in cost and workability.
  • the thickness of the activated carbon sheet is not particularly limited, but is preferably about 200 to 500 ⁇ m from the viewpoint that the electric resistance does not become too high.
  • the separator include, for example, a synthetic fiber resin net, a woven fabric, a paper-like aggregate, a nonwoven fabric in which synthetic fibers or recycled fibers are integrated.
  • resin nets and nonwoven fabrics, particularly resin nets are preferable from the viewpoint of excellent liquid permeability and economic efficiency.
  • Examples of the material of the separator include polyethylene terephthalate, polypropylene, polyamide, polytetrafluoroethylene, ethylene-tetrafluoroethylene copolymer, polyether ether ketone, and the like.
  • polyethylene terephthalate and polypropylene, particularly polyethylene terephthalate are preferable from the viewpoint of low cost and processability.
  • the thickness of the separator is preferably 50 to 250 ⁇ m, more preferably 70 to 150 ⁇ m.
  • the thickness of the separator is too thick, the ion trapping ability tends to decrease due to an increase in electrical resistance between cells during energization.
  • the ion trapping ability tends to decrease due to an increase in electrical resistance between cells during energization.
  • the aperture ratio of the separator is preferably 20 to 80%, more preferably 30 to 70%. If the opening rate of the separator is too small, the liquid flow resistance may be too large, and liquid flow may be difficult. Moreover, when too large, there exists a possibility that it may become unable to express the performance as a liquid-permeable type capacitor by carrying out an internal short circuit in an opening part.
  • the anion exchange membrane is not particularly limited, and specific examples include a membrane containing an anion exchange group such as a quaternary amino group and containing an ion exchange resin such as a styrene resin, an acrylic resin, or a fluorine resin. It is done.
  • the cation exchange membrane is not particularly limited, specifically, for example, a membrane containing an ion exchange resin such as a styrene resin, an acrylic resin, or a fluorine resin having a cation exchange group such as a sulfone group or a carboxyl group. Can be mentioned.
  • FIG. 4 is a schematic explanatory diagram for explaining a configuration of a deionized liquid manufacturing apparatus 200 including the liquid-passing capacitor 100 according to the first embodiment.
  • the operation of the deionized liquid manufacturing apparatus 200 provided with the liquid flow type capacitor 100 will be described with reference to FIG.
  • the deionized liquid manufacturing apparatus 200 includes a liquid passing capacitor 100, a DC power supply 20, and a container 30 that houses the liquid passing capacitor 100.
  • the DC power supply 20 is connected to fastening bolts 5a and 5b for fastening the first electrode 1 or the second electrode 2 of the liquid-flowing capacitor 100 by wires 20a and 20b so that the positive electrode side and the negative electrode side can be exchanged with each other.
  • the container 30 includes a liquid supply port 31 for supplying a liquid to be processed containing an ionic substance to the liquid flow type capacitor 100, and a liquid discharge port 32 for discharging the processing liquid processed by the liquid flow type capacitor 100. Is provided.
  • the container 30 also includes terminals 15a and 15b for energizing the fastening bolts 5a and 5b.
  • the liquid to be treated W1 such as water containing the ionic substance in the container 30 from the liquid supply port 31.
  • Supply liquid The liquid W1 to be treated is passed through the container 30 along the flow path indicated by the arrow in FIG.
  • the liquid to be treated W1 is discharged from the liquid discharge port 32 through the liquid passage hole 8 provided in the central portion of the liquid passage type capacitor 100.
  • a voltage is applied from the DC power supply 20 to the liquid-flowing capacitor 100 via the terminals 15a and 15b connected to the fastening bolts 5a and 5b, respectively.
  • deionized liquid is discharged
  • Ions contained in the liquid W1 to be treated are electrostatically adsorbed to the first porous carbon sheet 1b and the second porous carbon sheet 2b when passing between the first electrode 1 and the second electrode 2.
  • the valve V1 is opened and the valve V2 is closed to switch to the ion concentrate recovery path.
  • the concentrated ions can be recovered by reversing the polarity of the electrodes. In this way, the adsorption capacity of the first porous carbon sheet and the second porous carbon sheet can be regenerated.
  • the cycle for switching the electrodes is not particularly limited, but the adsorption process and the desorption process are performed so that the time of the adsorption process / the time of the desorption process is 1 to 5, and further 1.5 to 4.5. It is preferable to switch repeatedly.
  • the anion ( ⁇ ) and cation (+) in the liquid are not added even if the liquid to be treated W1 is passed through each cell 10.
  • the first electrode 1 and the second electrode 2 are not captured and pass between both electrodes.
  • FIG. 5B when a voltage is applied between both electrodes by connecting the negative electrode side of the DC power source to the first electrode 1 and the positive electrode side of the DC power source to the second electrode 2, the cations are on the surface of the first electrode 1.
  • the positive electrode side of the DC power source is connected to the first electrode 1 and the negative electrode side of the DC power source is connected to the second electrode 2, and a voltage opposite to that at the time of adsorption is applied between the two electrodes.
  • the cation adsorbed on the first electrode 1 and the anion adsorbed on the second electrode 2 are desorbed and released into the liquid to be passed.
  • the released cations cannot pass through the anion exchange membrane 2 c disposed on the surface of the second electrode 2, they are not adsorbed on the second electrode 2.
  • the released anion cannot pass through the cation exchange membrane 1c disposed on the surface of the first electrode 1, it is not adsorbed on the first electrode 1.
  • the high concentration ion contains in the liquid passed at this time. Therefore, by periodically discharging the liquid containing this high concentration of ions, the ions in the liquid can be efficiently removed.
  • liquid passing method for removing ions in the liquid using the liquid passing type capacitor 100 either a total filtration method for filtering the whole amount of the stock solution to be treated may be adopted, or a circulation filtration method may be adopted.
  • the conditions for passing the liquid are not particularly limited, but it is preferable to carry out at a space velocity (SV) of 5 to 100 hr ⁇ 1 because the pressure loss does not become too high.
  • the state of the ion removal capability can be monitored by plotting the relationship between the electric conductivity of the discharged liquid and the amount of liquid flowing from the start of liquid flow in a two-dimensional manner.
  • the ion removal rate can be calculated by measuring the electric conductivity of the liquid before and after the deionization process. .
  • the ion concentration in the liquid can also be measured by a method such as ion chromatography.
  • the type of the DC power supply 20 that supplies power to the deionized liquid manufacturing apparatus 200 is not particularly limited.
  • the voltage may be adjusted from a 100 V household power supply and used as a direct current, or power may be supplied using a battery or a storage battery.
  • independent power supplies such as a solar cell, a wind power generator, a fuel cell, and a cogenerator.
  • the liquid-flowing capacitor itself has a power storage capability, a plurality of liquid-flowing capacitors may be connected and the power stored in each other may be alternately used as a power source.
  • the voltage of the DC power supply is not particularly limited, but when the liquid-flowing capacitor 100 of the present embodiment is used, it can be operated even at a low voltage of 1.5 to 2V.
  • the liquid-permeable type capacitor and deionized liquid production apparatus of the present invention described above are independent of other water treatment means such as known water purification means, even if used alone for deionization treatment of water containing ionic substances. You may use it in combination.
  • Specific examples of known water treatment means include, for example, water treatment means including various adsorbents such as nonwoven fabric filters, ceramic filters, activated carbon, mineral additives, ceramic filter media, hollow fiber membrane filter materials, ion adsorbent materials, and the like. Can be mentioned.
  • Example 1 As a porous carbon sheet, activated carbon particles (coconut shells having a center particle diameter of 6 ⁇ m, a specific surface area of 1700 m 2 / g, a pore volume of 0.73 mL / g, an average pore diameter of 1.7 nm, and a surface functional group amount of 0.33 meq / g)
  • the activated carbon sheet A1 containing 10 parts by mass of a polytetrafluoroethylene binder was used with respect to 100 parts by mass of the activated carbon particles used as a raw material, GW-H manufactured by Kuraray Chemical Co., Ltd.
  • the activated carbon sheet A1 had a thickness of 250 ⁇ m and was cut into a length of 60 mm and a width of 60 mm.
  • a 250 ⁇ m thick graphite sheet (SIGRAFLEX S GRAFHITE FOIL manufactured by SGL Carbon Japan Co., Ltd.) formed by compression molding expanded graphite is 60 mm long, 60 mm wide, and the center of one side. Were cut into a shape having two tab portions of 50 mm in length and 20 mm in width. Furthermore, the tab part was provided with a hole with a diameter of 6.5 mm through which a bolt for fastening the laminated body can pass.
  • a polyester resin net (PETEX07-80 / 32 manufactured by Sefar AG) having a thickness of 90 ⁇ m, a wire diameter of 62 ⁇ m, an aperture of 80 ⁇ m, and an aperture ratio of 32% was cut into 68 mm length and 68 mm width. .
  • anion exchange membrane a 130 ⁇ m-thick Selemion AMV manufactured by Asahi Glass Co., Ltd.
  • a cation exchange membrane a 130 ⁇ m-thick Selemion CMV manufactured by Asahi Glass Co., Ltd. cut into a length of 64 mm and a width of 64 mm were used.
  • the above-mentioned activated carbon sheet, current collector sheet, separator, anion exchange membrane, and cation exchange membrane were laminated to form a laminate.
  • a laminated body having a 10-cell capacitor structure was formed.
  • a diameter of 9 mm for passing a deionized liquid to be treated is passed through the central portions of the current collector sheet, separator, anion exchange membrane, and cation exchange membrane, which form each layer except the uppermost layer.
  • the liquid passage hole was formed.
  • a plurality of tabs overlapping in each direction of the laminate are fastened with two titanium bolts (four in total) and nuts, respectively. Fixed.
  • a single band-shaped titanium foil having a width of 20 mm and a thickness of 100 ⁇ m is overlapped on the sheet surface as shown in FIG. 1 so as to be folded through the tab portions.
  • a titanium plate having a thickness of 2 mm and a width of 15 mm is disposed between the uppermost layer and the lowermost layer of the laminate and the bolt head, respectively. did.
  • the laminated body which is a liquid-permeable type capacitor was fastened and fixed.
  • the container had a substantially rectangular parallelepiped shape with an inner shape of 170 mm in length, 70 mm in width, and 50 mm in height, and was provided with a liquid supply path having a diameter of 9 mm and a drainage path having a diameter of 9 mm.
  • bolt of the liquid-permeable type capacitor accommodated in the container was distribute
  • a deionized liquid production apparatus was manufactured by enclosing a liquid-flowing type capacitor in a container. Then, the negative electrode side and the positive electrode side of the DC power source were respectively connected to the terminals exposed to the outside.
  • the electrical conductivity of the treated water discharged from the deionized liquid production device was measured for each predetermined amount of water flow, and the ion removal rate was calculated from the electrical conductivity of the saline solution of the raw water and the electrical conductivity of the treated water. .
  • the electrical conductivity ( ⁇ S / cm) of the water supplied to the deionized liquid production apparatus and the electrical conductivity ( ⁇ S / cm) of the water discharged from the deionized liquid production apparatus are measured, was used to calculate the ion removal rate.
  • Ion removal rate (%) (Electric conductivity of feed water ⁇ Electric conductivity of discharged water) / Electric conductivity of discharged water ⁇ 100
  • the adsorption amount at the 10th cycle in which the balance between adsorption and desorption was stable was treated as the adsorption amount of the cell.
  • the change in electrical conductivity plotted against time (seconds) is shown in the graph of FIG.
  • Example 2 to 4 The characteristics of the deionized liquid production apparatus were evaluated in the same manner as in Example 1 except that water was passed at a flow rate of 250 ml / min, 400 ml / min, or 1000 ml / min instead of water flow at a flow rate of 100 ml / min. The results are shown in Table 1.
  • Examples 5 to 8 Instead of forming a laminated body having a 10-cell capacitor structure, a laminated body having a 20-cell capacitor structure in which the respective layers are laminated in the same order is formed, and a liquid passing type capacitor and a deionized liquid manufacturing apparatus are produced. Evaluated the characteristics of the deionized liquid production apparatus in the same manner as in Examples 1 to 4. The results are shown in Table 1.
  • the liquid-passing capacitor and deionized liquid production apparatus of the present invention are used for various applications that require desalting treatment. Specifically, for example, it can be applied to a wide range of uses such as desalination treatment of tap water and industrial water, seawater desalination equipment, and groundwater beverage application water equipment.
  • the liquid-flowing capacitor and the deionized water production apparatus of the present invention have a high ion adsorption capacity and can be operated with a small amount of electric power. Therefore, for example, various water purifiers for treating water from household water supply, more specifically, the removal of washing water provided in local water purifiers, water purifiers, local washing devices provided in toilet seats, etc. It can be preferably used as a salt device.

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Hydrology & Water Resources (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Electrochemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)

Abstract

L'invention concerne un condensateur à flux traversant dans lequel une pluralité de cellules sont stratifiées, et dans lequel : les cellules comprennent une première électrode, une seconde électrode, et un séparateur interposé entre la première électrode et la seconde électrode ; la première électrode comprend une première feuille de collecteur faite d'une feuille de graphite, une première feuille de carbone poreux stratifié sur la première feuille de collecteur, et un film échangeur de cations stratifié sur la première feuille de carbone poreux ; la seconde électrode comprend une seconde feuille de collecteur faite d'une feuille de graphite, une seconde feuille de carbone poreux stratifié sur la seconde feuille de collecteur, et un film échangeur d'anions stratifié sur la seconde feuille de carbone poreux ; le film échangeur de cations et le film échangeur d'anions sont disposés de façon à se faire face l'un à l'autre, le séparateur étant interposé entre ceux-ci ; au moins une parmi la première feuille de collecteur et la seconde feuille de collecteur a une section de languette qui ne fait pas face à une feuille de carbone poreux ; et au moins deux sections de languette sont connectées l'une à l'autre par une feuille électroconductrice disposée de façon à être en contact avec la section de languette.
PCT/JP2013/000057 2012-01-16 2013-01-10 Condensateur à flux traversant, dispositif de fabrication de liquide déionisé, et procédé de fabrication de liquide déionisé WO2013108597A1 (fr)

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JP2013554241A JP5798201B2 (ja) 2012-01-16 2013-01-10 通液型キャパシタ、脱イオン液製造装置、及び脱イオン液の製造方法
CN201380005656.6A CN104185609B (zh) 2012-01-16 2013-01-10 通液型电容器、去离子液制造装置、及去离子液制造方法

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CN104944647A (zh) * 2015-06-19 2015-09-30 北京共创富来水处理设备有限公司 基于直流电场作用下电容式污水和废水处理设备和方法
KR102247227B1 (ko) * 2018-01-25 2021-05-03 엘지전자 주식회사 수처리 장치용 필터 및 이를 포함하는 수처리 장치
KR102089763B1 (ko) * 2018-05-23 2020-03-17 두산중공업 주식회사 축전식 탈염전극 및 이를 포함하는 축전식 탈염장치
KR20210021836A (ko) * 2019-08-19 2021-03-02 엘지전자 주식회사 수처리 장치용 필터
KR102358988B1 (ko) 2021-04-30 2022-02-08 두산중공업 주식회사 회전형 전기흡착식 탈염장치

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KR20140098241A (ko) 2014-08-07
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CN104185609B (zh) 2016-02-10
CN104185609A (zh) 2014-12-03

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