WO2010150534A1 - Condensateur continu, procédé de production d'eau désionisée, et dispositif de production d'eau déionisée - Google Patents

Condensateur continu, procédé de production d'eau désionisée, et dispositif de production d'eau déionisée Download PDF

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WO2010150534A1
WO2010150534A1 PCT/JP2010/004171 JP2010004171W WO2010150534A1 WO 2010150534 A1 WO2010150534 A1 WO 2010150534A1 JP 2010004171 W JP2010004171 W JP 2010004171W WO 2010150534 A1 WO2010150534 A1 WO 2010150534A1
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Prior art keywords
liquid
activated carbon
fiber
sheet
capacitor according
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PCT/JP2010/004171
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English (en)
Japanese (ja)
Inventor
大塚清人
川崎修治
石田修一
岩崎秀治
西山正一
藤原直樹
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クラレケミカル株式会社
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Priority to JP2011519599A priority Critical patent/JP5687620B2/ja
Publication of WO2010150534A1 publication Critical patent/WO2010150534A1/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 OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/38—Carbon pastes or blends; Binders or additives therein
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • 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
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C02F1/46104—Devices therefor; Their operating or servicing
    • C02F1/46109—Electrodes
    • C02F2001/46152—Electrodes characterised by the shape or form
    • C02F2001/46157—Perforated or foraminous electrodes
    • C02F2001/46161—Porous electrodes
    • 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 flow-through capacitor, a method for producing deionized water, and a deionized water production apparatus.
  • the ionic substances containing nitrate nitrogen contained in tap water are said to be caused by contaminated rivers, groundwater, lakes, etc., with fertilizer, livestock excrement and domestic wastewater.
  • ionic substances containing fluorine, boron, cyanide and various heavy metals contained in tap water are caused by the fact that the rivers taken in are contaminated by factory wastewater. Therefore, it is preferable that various wastewaters are discharged into rivers after being deionized.
  • the ionic substance can be removed by using, for example, a reverse osmosis membrane.
  • a reverse osmosis membrane since the reverse osmosis membrane has a high pressure loss when water is passed through, there is a problem that the amount of treatment that can be treated in a certain time is small. Further, the reverse osmosis membrane type water purifier has a problem that the operation cost becomes high because it is necessary to increase the water pressure with a booster pump. Therefore, there has been a demand for a method for deionizing water at a low cost without using a reverse osmosis membrane.
  • Patent Document 1 discloses a nitrate nitrogen removing device in which a filter medium containing an anion exchange resin and calcium carbonate is arranged on a flow path.
  • a nitrate nitrogen removing device is intended to effectively remove nitrate nitrogen and the like in water by adjusting pH by combining an anion exchange resin and calcium carbonate.
  • such a nitrate nitrogen removing apparatus has a problem that the production cost is high because the anion exchange resin is expensive.
  • a method of removing ionic substances in water using an electrostatic force has been proposed.
  • Patent Document 2 is a liquid-electricity type in which two activated carbon layers mainly made of activated carbon with a high specific surface area are arranged with a separator in between, and a collector electrode is laminated on the outside of the two activated carbon layers.
  • a double layer capacitor is disclosed.
  • Patent Document 3 discloses a liquid-flowing capacitor including a conductive layer including a stacked capacitor activated carbon in which an activated carbon layer is disposed with a separator interposed therebetween and a collector electrode is disposed on the outer side of the stacked capacitor activated carbon. .
  • patent document 4 removes an ionic substance by laminating
  • a liquid-permeable capacitor is disclosed. According to the flow-through capacitors disclosed in Patent Documents 2 to 4, it is possible to purify water containing ionic substances that dissociate in water, such as metal salts, amine salts, inorganic acids, and organic acids. Is described.
  • nitrate ions and fluorine ions that could not be removed by the conventional water purifier using the activated carbon adsorption function are removed without using a water purifier using a reverse osmosis membrane, which has a high operating cost. be able to.
  • the ion removal processing capacity of the conventional liquid-pass capacitor has not been sufficient.
  • the present invention relates to a liquid-permeable capacitor having a higher ability to remove ionic substances than conventional liquid-permeable capacitors, a method for producing deionized water using such a liquid-permeable capacitor, and deionized water production.
  • An object is to provide an apparatus.
  • One aspect of the present invention includes a laminate in which a plurality of electrodes capable of passing liquids and a plurality of separators capable of passing liquids are alternately stacked, and the electrodes include a liquid-permeable activated carbon sheet containing activated carbon powder and a binder.
  • the activated carbon powder has a central particle diameter of 10 to 500 ⁇ m
  • the binder is a liquid passing type capacitor containing at least one selected from fibrillated fibers and thermoplastic binder particles.
  • Another aspect of the present invention is a method for producing deionized water using the liquid-pass capacitor, wherein a plurality of electrodes stacked in the thickness direction of the multilayer body are connected to a positive electrode side and a negative electrode of a DC power source.
  • Another aspect of the present invention includes the above-described liquid-flowing capacitor, a DC power supply, and a container that stores the liquid-flowing capacitor, and the plurality of electrodes stacked in the laminate are positive electrodes of the DC power supply.
  • the container is connected alternately to the negative electrode side in the thickness direction, and the container has a water supply port for supplying water containing an ionic substance to the first main surface of the laminate, and the first main surface of the laminate It is a deionized water manufacturing apparatus provided with the drain outlet for draining the deionized water from the 2nd main surface which opposes.
  • a liquid-permeable capacitor having a higher ability to remove ionic substances than a conventional liquid-permeable capacitor, a method for producing deionized water using such a liquid-permeable capacitor, and deionized water A manufacturing apparatus can be provided.
  • FIG. 1 is a schematic explanatory view of a deionized water production apparatus 110 provided with a liquid-permeable capacitor 10 of the present embodiment.
  • the liquid-passing capacitor 10 is shown in a longitudinal sectional view.
  • the liquid-permeable capacitor 10 includes a plurality of activated carbon sheets 2 (2a, 2b, 2c, 2d, 2e, 2f) and a separator 1 (1a, 1b, 1c, 1d, 1e, 1f) having insulating properties and liquid permeability. And a laminate 11 formed by alternately laminating and.
  • the multilayer body 11 is accommodated in the capacitor container 4.
  • the capacitor container 4 includes a water supply port 7 for supplying water containing an ionic substance and a drain port 8 for draining deionized water.
  • the capacitor container 4 is preferably formed from a synthetic resin molded body from the viewpoint of suppressing water leakage and leakage.
  • the drainage port 8 is further connected to two paths of a deionized water recovery pipe 15 and an ion concentrated water recovery pipe 16. In these paths, the flow paths are switched by opening and closing the valves v1 and v2.
  • the activated carbon sheets 2a to 2f have tabs t led out of the capacitor container 4.
  • the tabs provided on the activated carbon sheets 2a to 2f are electrically connected to the electrode terminals 3a to 3f, respectively.
  • the electrode terminals 3a, 3c, and 3e are connected in parallel to the negative electrode side of the DC power supply 5, and the electrode terminals 3b, 3d, and 3f are connected in parallel to the positive electrode side of the DC power supply 5, respectively.
  • the multilayer body 11 is tightly fixed by a punched resin plate 13 in the capacitor container 4.
  • the activated carbon sheet 2 used in the present embodiment can be passed through a molded sheet comprising activated carbon powder having a center particle diameter of 10 to 500 ⁇ m and at least one binder selected from fibrillated fibers and thermoplastic binder particles. It is a sheet.
  • the activated carbon powder include, for example, wood, sawdust, charcoal, fruit husks such as coconut husk and walnut husk, fruit seeds, pulp production by-products, lignin, molasses, etc .; Mineral activated carbon powder obtained by carbonizing and activating lignite, lignite, anthracite, coke, coal tar, coal pitch, petroleum distillation residue, petroleum pitch, etc .; carbonizing and activating phenol, saran, acrylic resin, etc. And synthetic resin-based activated carbon powder obtained by carbonization; natural fiber-based activated carbon powder obtained by carbonizing and activating regenerated fiber (rayon) and the like. Among these, coconut shell activated carbon powder is particularly preferable because of its excellent adsorption performance.
  • impurities are removed from the activated carbon powder as much as possible.
  • the impurities include metals such as alkali metals, alkaline earth metals, nickel, and iron. Such a metal is removed by washing with water or an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid. The cleaning may be performed with one type of cleaning liquid or may be repeatedly performed by combining two or more types of cleaning liquids.
  • the washed activated carbon is heat-treated in an inert gas or oxidizing gas to remove metal salts adsorbed when washed with inorganic acids and inorganic acid ions such as hydrochloric acid ions, sulfate ions, and phosphate ions.
  • inorganic acids and inorganic acid ions such as hydrochloric acid ions, sulfate ions, and phosphate ions.
  • the oxidizing gas include combustion gas obtained by burning oxygen, water vapor, carbon dioxide, kerosene and propane.
  • the heat treatment temperature is preferably 500 to 1000 ° C., more preferably 650 to 900 ° C. If the heat treatment temperature is too low, a sufficient heat treatment effect cannot be obtained.
  • the heat treatment temperature when the heat treatment temperature is too high, the adjusted pore structure tends to change due to a rapid activation reaction. In addition, when the heat treatment temperature in the inert gas is too high, the pore structure adjusted by heat shrinkage tends to change.
  • the heat treatment time depends on the heat treatment temperature, it is usually preferably about 30 minutes to 3 hours.
  • the activated carbon powder used in the present embodiment is, for example, activated carbon powder having a central particle diameter of 10 to 500 ⁇ m obtained by pulverizing, finely pulverizing, or classifying granular activated carbon.
  • the central particle size of the activated carbon powder used in this embodiment is 10 to 500 ⁇ m, preferably 50 to 400 ⁇ m, more preferably 100 to 300 ⁇ 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).
  • the center particle diameter of the activated carbon powder When the center particle diameter of the activated carbon powder is less than 10 ⁇ m, the obtained activated carbon sheet becomes too dense, the water resistance increases, and the ion trapping ability unexpectedly decreases.
  • the reason why the ion capturing ability of the activated carbon sheet decreases when the center particle diameter is less than 10 ⁇ m is not well understood.
  • the present inventors consider as follows. That is, when activated carbon powder having a center particle diameter of less than 10 ⁇ m is used, the surface area covered with the binder is increased, and the contact resistance between the particles is increased, thereby lowering the conductivity. Yes.
  • the center particle diameter is too small, the activated carbon powder is easily dropped from the activated carbon sheet, and there is a problem that the activated carbon particles are easily mixed into the deionized water.
  • the specific surface area of the activated carbon powder is preferably 700 to 2500 m 2 / g, more preferably 1000 to 1800 m 2 / g, and particularly preferably 1100 to 1500 m 2 / g. If the specific surface area is too small, the deionization ability is lowered, and the ions are less likely to be desorbed when the polarities of the electrodes are reversed and desorbed concentrated ions adsorbed on the surface of the activated carbon sheet. There is. Further, when the specific surface area is too large, not only the performance per volume is lowered, but also fine powder is likely to be generated, and the fine powder tends to be mixed into deionized water.
  • the activated carbon sheet is obtained by molding a mixture containing activated carbon powder and fibrillated fibers and / or thermoplastic binder particles into a sheet.
  • a binder it is preferable to use a binder with no biological harm from a viewpoint used for water purification.
  • the ratio of the activated carbon powder contained in the activated carbon sheet is preferably in the range of 50 to 99% by weight, more preferably 80 to 95% by weight. When the ratio of the activated carbon powder contained in the activated carbon sheet is too low, the treatment amount tends to decrease.
  • fibrillated fiber When fibrillated fiber is used as the binder, it is preferably formed by wet molding.
  • the fibrillated fiber is obtained by fibrillating a fiber that can be fibrillated using a high-pressure homogenizer, a high-speed disaggregator, or the like.
  • the average fiber diameter is about 0.1 to 50 ⁇ m, and further 1 to 20 ⁇ m. It is a pulp-like fiber.
  • Such fibrillated fibers are intertwined by paper making to form a sheet.
  • the average fiber length of the fibrillated fibers is, for example, preferably about 0.5 to 4 mm, and more preferably about 1 to 2 mm.
  • fibers forming such fibrillated fibers include acrylic fibers, polyethylene fibers, polypropylene fibers, polyacrylonitrile fibers, cellulose fibers, nylon fibers, aramid fibers, and the like.
  • acrylic fibers and cellulose fibers are particularly preferable because they are easily fibrillated and have a high effect of restraining the activated carbon powder.
  • Bi-PUL which is a homoacrylic pulp manufactured by Nippon Exlan Co., Ltd., is available.
  • Examples of a method for wet-molding an activated carbon sheet using fibrillated fibers include the following methods. First, activated carbon powder and fibrillated fiber are mixed and then dispersed in water to prepare a slurry having a solid concentration of 1 to 5% by weight. Next, the slurry is poured into a water-permeable box-type container formed of, for example, a stainless steel wire net, and the moisture is cut and dried. An activated carbon sheet is obtained by such a method.
  • the above-described slurry is filled into a mold cavity having a sheet-like cavity having a predetermined shape and a large number of through holes for decompressing the inside of the cavity. And the water
  • An activated carbon sheet can also be obtained by such a method.
  • the mixing ratio of the fibrillated fibers to 100 parts by weight of the activated carbon powder is preferably 3 to 8 parts by weight from the viewpoint of excellent balance of conductivity, deionization, moldability and the like.
  • thermoplastic binder particles When using thermoplastic binder particles as the binder, dry molding is preferred.
  • the polymer forming the thermoplastic binder particles include polyethylene, polypropylene, polystyrene, polyacrylonitrile, ethylene vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate.
  • polyethylene, polypropylene, polystyrene, ethylene vinyl acetate copolymer, polyethylene terephthalate, polybutylene terephthalate, and polymethyl methacrylate and particularly polyethylene is preferable from the viewpoint of binding properties.
  • the average particle diameter of the thermoplastic binder particles is preferably about 0.1 to 200 ⁇ m, more preferably about 1.0 to 50 ⁇ m from the viewpoint of excellent sheet strength and conductivity.
  • Examples of the method for dry-molding the activated carbon sheet using the thermoplastic binder particles include the following methods. First, the activated carbon powder and the thermoplastic binder particles are weighed at a desired ratio, and the mixture is obtained by stirring using a mixer such as a Henschel mixer. Then, the obtained mixture is filled into a mold having a sheet-like cavity. Then, the mold is melted or softened by heating to a temperature equal to or higher than the melting point of the thermoplastic binder particles, and then the thermoplastic binder particles are solidified by cooling. And an activated carbon sheet is obtained by releasing from a metal mold
  • the mixing ratio of the thermoplastic binder particles to 100 parts by weight of the activated carbon powder is preferably 5 to 50 parts by weight, more preferably 7 to 20 parts by weight from the viewpoint of excellent sheet strength and conductivity.
  • 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 graphite, carbon, and graphite; noble metals such as gold, platinum, and silver; titanium nitride, titanium silicon carbide, titanium carbide, titanium boride, and zirconium boride. And the like.
  • a carbon-based material is preferable because it is excellent in cost and workability.
  • the shape of the conductive material is not particularly limited, and specific examples include powder, short fibers, whiskers, and the like. Among these, short fibers are preferable from the viewpoint of excellent balance of conductivity, water permeability, mechanical properties, flexibility of the obtained activated carbon sheet, and the like.
  • the average fiber diameter of such short fibers is preferably 1 to 50 ⁇ m, more preferably 3 to 20 ⁇ m, and particularly preferably 5 to 10 ⁇ m. If the average fiber diameter is too small, the flexibility of the activated carbon sheet tends to decrease, although it depends on the amount added. In addition, when the softness
  • the average fiber length of the short fibers is preferably 5 to 12000 ⁇ m, more preferably 100 to 6000 ⁇ m, and particularly preferably 1000 to 3000 ⁇ m.
  • the average fiber length is too short, it becomes difficult to get entangled with the activated carbon powder, so that it becomes difficult to obtain the effect of improving conductivity, and the water permeability tends to decrease. Further, when the average fiber length is too long, the dispersibility is lowered, and thus the deionization effect in the surface of the activated carbon sheet tends to be non-uniform.
  • the density of the short fibers is preferably 1 to 2.3 g / cm 3 , more preferably 1.5 to 2.0 g / cm 3 , and particularly preferably 1.6 to 1.9 g / cm 3 .
  • the addition ratio is preferably 1 to 40% by weight, more preferably 2 to 25% by weight, particularly 5 to 15% by weight, based on the total weight of the activated carbon sheet.
  • the addition ratio of the conductive material is too low, the effect of improving the conductivity tends not to be obtained sufficiently.
  • the addition ratio of the conductive material is too high, the deionization capacity per unit volume of the activated carbon sheet tends to decrease due to the relatively decreased content ratio of the activated carbon powder contained in the activated carbon sheet. .
  • the activated carbon sheet may contain other additives as necessary as long as the effects of the present invention are not impaired.
  • additives include granular or fibrous activated carbon capable of adsorbing and removing residual chlorine and trihalomethane, zeolite capable of adsorbing and removing soluble lead, and silver ions and silver compounds having antibacterial properties. Examples include adsorbents.
  • the thickness of the activated carbon sheet is not particularly limited, but is preferably about 0.1 to 3 mm, more preferably about 0.2 to 2 mm from the viewpoint that the electric resistance between the activated carbon sheets does not become too high.
  • the activated carbon sheet is used by cutting into a desired shape. Specifically, for example, a shape in which a tab t serving as a terminal (power receiving unit) as shown in FIG.
  • a tab t serving as a terminal (power receiving unit) as shown in FIG.
  • the tabs formed on each activated carbon sheet are led out from the capacitor container and alternately placed on the positive or negative side of the DC power supply.
  • a plurality of tabs having the same polarity may be connected together with a conductive adhesive, a metal tape, a metal bolt, or the like.
  • the separator 1 used in this embodiment will be described.
  • the separator include, for example, a nonwoven fabric in which synthetic fibers or recycled fibers are integrated, a resin net made of a synthetic resin, a woven fabric, a knitted fabric, a paper-like aggregate, and the like.
  • non-woven fabrics and resin nets, particularly non-woven fabrics are preferable from the viewpoint of excellent liquid permeability and economy.
  • the fiber constituting the nonwoven fabric is not particularly limited. Specific examples include polyethylene fiber, polypropylene fiber, polyethylene terephthalate fiber, polyacrylonitrile fiber, cellulose fiber, nylon fiber, and aramid fiber. These may be used alone or in combination of two or more. Further, a core-sheath type composite fiber including two or more of these fibers may be used.
  • the core-sheath type composite fiber a composite fiber in which the melting point or softening temperature of the sheath component fiber is lower than that of the core component fiber is preferably used.
  • the composite fiber comprising such a combination of the core component and the sheath component include core component polyethylene / sheath component polyethylene terephthalate, core component polyethylene / sheath component polypropylene, core component polypropylene / sheath component polyethylene terephthalate, core component polyethylene.
  • the basis weight of the nonwoven fabric is preferably 5 to 100 g / m 2 , more preferably 10 to 50 g / m 2 .
  • the basis weight of the nonwoven fabric is too large, the processing ability tends to decrease due to the decrease in water permeability.
  • the thickness of the nonwoven fabric is preferably 0.01 to 1 mm, more preferably 0.1 to 0.5 mm.
  • the ion trapping performance tends to decrease due to the increase in electrical resistance between cells during energization.
  • the activated carbon particles may be short-circuited during energization due to exposure or dropping of the activated carbon particles from the activated carbon sheet, and the performance as a capacitor may not be exhibited.
  • the average fiber diameter of the fibers constituting the nonwoven fabric is preferably 3 to 40 ⁇ m, more preferably 6 to 30 ⁇ m.
  • the average fiber diameter is too small, the nonwoven fabric becomes too dense and the water flow resistance tends to increase, or the fibers tend to fall off.
  • the average fiber diameter is too large, the bulkiness is increased, which makes it difficult to fill the capacitor container.
  • the nonwoven fabric When the nonwoven fabric is continuously laminated as a separator in the liquid-permeable capacitor, it may be a single layer or a laminate of two or more layers.
  • the number of stacked layers is not limited, but considering workability and bulkiness, it is desirable to have one layer, two layers or three layers.
  • the method for producing a nonwoven fabric is not particularly limited, and a conventionally known method for producing a nonwoven fabric can be used without any particular limitation.
  • Specific examples include a spun bond method, a melt blow method, a water entanglement method, a thermal bond method, and a chemical bond method.
  • the spun bond method, the hydroentanglement method, and the thermal bond method are preferable from the viewpoint of easy adjustment of the basis weight, thickness, and fiber diameter.
  • the ionic substance contained in the water W1 is electrostatically trapped as ions in the activated carbon sheets 2a to 2f.
  • the electrical conductivity of water is increased.
  • the valve v1 is opened and the valve v2 is closed, after switching to the path of the ion concentrated water recovery pipe 16, the polarity of the electrode is reversed so that the concentrated ions adsorbed on the activated carbon sheets 2a to 2f are obtained. Can be removed. Then, the purification ability of the activated carbon sheets 2a to 2f can be regenerated.
  • the ion concentrate can be recovered through the ion concentrated water recovery pipe 16.
  • a water flow method for removing ions in water using the liquid flow type capacitor 10 either a total filtration method for filtering the whole raw water or a circulation filtration method may be employed.
  • the water flow conditions are not particularly limited, but it is preferable to carry out at a space velocity (SV) of 10 to 100 hr ⁇ 1 because the pressure loss does not become too high.
  • the state of ion removal capability can be monitored by plotting the relationship between the electrical conductivity of the discharged water and the amount of water flowed from the start of water flow in two dimensions. Further, since the ion concentration in water has a correlation with the electrical conductivity of water, the ion removal rate can be calculated by measuring the electrical conductivity of water before and after the deionization treatment. The ion concentration in water can also be measured by a method such as ion chromatography.
  • the type of the DC power supply 5 that supplies power to the liquid-flow capacitor 10 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.
  • an independent power source such as a solar cell, a wind power generator, a fuel cell, or a co-generator may be used. From the viewpoint of energy saving, low carbon energy, and power generation efficiency, it is preferable to use a solar cell.
  • FIG. 2 is a schematic explanatory view of a deionized water production apparatus 120 provided with the liquid-permeable capacitor 20 of the present embodiment.
  • the configuration of the liquid-passing capacitor 20 is shown in a longitudinal sectional view.
  • symbol is shown about the element similar to what was demonstrated in 1st Embodiment.
  • the liquid-permeable capacitor 20 includes a plurality of electrodes 9 (9a to 9f) formed by sandwiching both surfaces of a liquid-permeable conductive sheet 6 (6a to 6f) between the activated carbon sheets 2 and the electrodes 9 (9a to 9f). 9f) is provided with a laminate 12 composed of a plurality of separators 1 disposed between them.
  • the multilayer body 12 is accommodated in the capacitor container 4.
  • the conductive sheets 6 (6a to 6f) are electrically connected to the electrode terminals 3 (3a to 3f), respectively.
  • the electrode terminals 3a to 3f are led out of the capacitor container 4.
  • a part of the conductive sheet 6 may be used as the electrode terminal 3.
  • the electrode terminals 3a, 3c, 3e are connected in parallel to the negative electrode side of each DC power source 5, the electrode terminals 3b, 3d, 3f are connected in parallel to the positive electrode side of each DC power source 5.
  • the multilayer body 12 is tightly fixed by a punched resin plate 13 in the capacitor container 4.
  • liquid-flow type capacitor 20 it is possible to apply a voltage to the activated carbon sheet 2 with low resistance due to the high conductivity of the conductive sheet 6 than when the DC power supply 5 is directly connected to the activated carbon sheet 2.
  • the material for forming the conductive sheet 6 is not particularly limited as long as it is a conductive sheet capable of passing liquid. Specific examples include iron punching metal with nickel coating, titanium lath net with platinum coating on the surface, aluminum punching metal with surface anodized by anodization, and graphite particles as binder. And a carbon fiber base material such as a graphite sheet having a void bound by woven fabric and a woven carbon fiber.
  • the nickel coat and the platinum coat are for preventing electric corrosion of the metal electrode, and are surface-treated by plating or sintering lamination. In these, a carbon fiber base material is especially preferable from the point by which electrocorrosion is suppressed.
  • the thickness of the conductive sheet 6 is preferably about 0.1 to 2 mm, more preferably about 0.2 to 1.0 mm from the viewpoint of excellent conductivity.
  • the conductive sheet 6 and the activated carbon sheet 2 need only be in electrical contact, but are adhered and fixed by bonding with a conductive adhesive or by integrally forming the conductive sheet 6 and the activated carbon sheet 2. You may let them.
  • Specific examples of the conductive adhesive include, for example, a silver paste conductive adhesive, a graphite paste conductive adhesive, a silver graphite mixed paste conductive adhesive, a titanium paste conductive adhesive, and an aluminum paste conductive. Adhesives and the like. Even if the conductive adhesive is directly applied to the conductive sheet 6 or the activated carbon sheet 2, it is partially applied in a grid, stripe, dot or the like by a method such as a screen printing machine, an offset printing machine, or a spray. May be.
  • the conductivity of the electrode can be improved by simply applying the conductive adhesive to the surface of the activated carbon sheet 2 without using the conductive sheet 6.
  • the conductive sheet 6 and the activated carbon sheet 2 are integrally formed, the conductive sheet 6 can be integrally formed with the activated carbon sheet 2 using the support as a support.
  • the resistance at the interface between the conductive sheet 6 and the activated carbon sheet 2 can be reduced. Thereby, the high electroconductivity to the activated carbon sheet 2 is acquired, and high ion capture property is acquired.
  • liquid-permeable type capacitor and deionized water production apparatus of the present invention explained by taking the first embodiment and the second embodiment as examples are used alone for deionization treatment of water containing an ionic substance, It may be used in combination with other known water treatment means such as water purification means.
  • 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 adsorbents, and the like.
  • the liquid-passing capacitor and deionized water production apparatus of the present invention may be used in combination with other known ion adsorbent filters. Further, it may be used in combination with a hollow fiber membrane separation device for physically removing turbidity and fine substances.
  • the present invention will be described more specifically with reference to examples. The scope of the present invention is not limited by the contents of the following examples.
  • Example 1 100 parts by weight of activated carbon powder having a center particle size of 120 ⁇ m and a specific surface area of 1200 m 2 / g (activated carbon powder using coconut shell as raw material, PGW-120MP manufactured by Kuraray Chemical Co., Ltd.) and fibrillated acrylic fiber (Nippon Exlan Industrial Co., Ltd.) A slurry was prepared by mixing 6 parts by weight of manufactured Bi-PUL / F) in water.
  • the slurry was filled into a mold having a cavity having a length of 220 mm, a width of 220 mm, and a thickness of 1 mm and a suction hole, and then the mold was clamped, and the inside of the mold was decompressed to 20 mmHg to form a sheet.
  • the obtained sheet was a square having a length of 215 mm, a width of 215 mm, and a thickness of 1 mm. From this sheet, an activated carbon sheet A1 having a length of 100 mm and a width of 100 mm and having a tab of 50 mm length and 10 mm width at the center of one side was cut out.
  • a separator B1 was prepared by cutting a non-woven fabric having a thickness of 0.1 mm and a basis weight of 40 g / m 2 (9540F manufactured by Shinwa Co., Ltd. including polyethylene fibers and polypropylene fibers) into a length of 100 mm and a width of 100 mm.
  • the activated carbon sheet A1 and the separator B1 were laminated
  • the obtained laminated body was accommodated in the resin-made capacitor containers 4 as shown in FIG.
  • the laminated body was fixed to the inner wall of the capacitor container 4 by placing a frame made of silicon rubber on each of the upper part and the lower part.
  • the tab provided in each activated carbon sheet A1 was each pulled out from the through-hole provided in the outer wall of the capacitor container 4. In this way, a liquid passing type capacitor was manufactured.
  • the electrode terminal was connected to each tab exposed to the exterior of the obtained liquid-permeable capacitor, and each electrode terminal was alternately connected to the negative electrode side and positive electrode side of the power supply.
  • Example 2 An activated carbon sheet A2 was produced in the same manner as in the production of the activated carbon sheet A1 of Example 1 except that no tab was provided.
  • a punched metal made of nickel-coated iron with a thickness of 0.1 mm having a tab of 50 mm length and 10 mm width at the center of one side of a square of 100 mm length and 100 mm width (aperture ratio 57.9%) Prepared.
  • region of the punching metal electrode was pinched
  • the laminated body was fixed in close contact with the inner wall of the capacitor container 4 by placing a frame made of silicon rubber on each of the upper part and the lower part. Further, each of the tabs provided on the punching metal electrode was drawn out from a through hole provided on the outer wall of the capacitor container 4. In this way, a liquid passing type capacitor was manufactured. And the electrode terminal was connected to each tab exposed to the exterior of the obtained liquid-permeable capacitor, and each electrode terminal was alternately connected to the negative electrode side and positive electrode side of the power supply. Then, evaluation was performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 3 A liquid-permeable capacitor was prepared and evaluated in the same manner as in Example 2 except that a carbon fiber cloth having a thickness of 0.11 mm (trade name: Torayca cloth CO6151B manufactured by Toray Industries, Inc.) was used instead of the punching metal. did. The results are shown in Table 1.
  • Examples 4 to 7 instead of the activated carbon sheet A2, a liquid-permeable capacitor was prepared in the same manner as in Example 2 except that activated carbon sheets A3 to A6 using activated carbon powder having a particle size and specific surface area as shown in Table 1 were used. evaluated. The results are shown in Table 1.
  • Example 8 instead of the activated carbon sheet A2 using the fibrillated acrylic fiber as the binder, the same procedure as in Example 2 was used except that the activated carbon sheet A7 using the fine powder polyethylene particles produced by the following method as the binder was used. A liquid capacitor was created and evaluated. The results are shown in Table 1.
  • Manufacture of activated carbon sheet A7) A mixture obtained by mixing 80 parts by weight of activated carbon powder having a central particle diameter of 120 ⁇ m and a specific surface area of 1200 m 2 / g and 10 parts by weight of finely powdered polyethylene having an average particle diameter (D 50 ) of 20 ⁇ m was obtained.
  • the fine powder polyethylene used was Sumitomo Seika Co., Ltd.
  • seat of length 215mm, width 215mm, and thickness 1mm was obtained by heat-molding the obtained mixture using the metal mold
  • the activated carbon sheet A7 was obtained by cut
  • Example 9 10 parts by weight of conductive short fiber having an average fiber length of 3 mm (Torayca Cut Fiber T010-003 (carbon fiber having an average fiber diameter of 7 ⁇ m and a density of 1.76 g / cm 3 ) manufactured by Toray Industries, Inc. with respect to 100 parts by weight of the activated carbon powder.
  • the activated carbon sheet A8 was obtained in the same manner as in the production of the activated carbon sheet A2 in Example 2.
  • the liquid-permeable type was obtained in the same manner as in Example 2 except that the activated carbon sheet A8 was used instead of the activated carbon sheet A2.
  • Capacitors were created and evaluated, and the results are shown in Table 1.
  • Example 10 to 12 As shown in Table 1, a liquid-permeable capacitor was prepared and evaluated in the same manner as in Example 9 except that the blending ratio of the conductive short fibers in the activated carbon sheet or the basis weight and thickness of the nonwoven fabric (separator) was changed. The results are shown in Table 1.
  • Example 13 The separator was used in the same manner as in Example 9 except that a non-woven fabric having a thickness of 0.1 mm and a basis weight of 18 g / m 2 (9718-5-0-F manufactured by Shinwa Co., Ltd. including polyethylene fiber and polypropylene fiber) was used. A liquid capacitor was created and evaluated. The results are shown in Table 1.
  • Example 14 A liquid-permeable capacitor was prepared and evaluated in the same manner as in Example 9 except that the basis weight and thickness of the separator were changed. The results are shown in Table 1.
  • Example 1 In place of the activated carbon sheet, a liquid-permeable capacitor was prepared in the same manner as in Example 2 except that an activated carbon fiber sheet CH700-25 (thickness 0.5 mm, specific surface area 2000 m 2 / g) manufactured by Kuraray Chemical Co., Ltd. was used. Created and evaluated. The results are shown in Table 1.
  • Example 2 A liquid-permeable capacitor was prepared and evaluated in the same manner as in Example 2 except that the activated carbon powder having the center particle diameter and specific surface area shown in Table 1 was used. The results are shown in Table 1.
  • the liquid-passing capacitor of Comparative Example 3 having a small center particle diameter of activated carbon had too high a water flow resistance, so that water could not flow smoothly, and ion removal treatment could not be performed.
  • the ion removal capacity when using the liquid-pass capacitors of Comparative Examples 1 to 3 was 2 L or less, whereas the liquid-pass capacitors of Examples 1 to 15 according to the present invention were used.
  • the ion removal capacity was 3 L or more.
  • the liquid passing type capacitor of Example 2 connected to the DC power source through the conductive sheet had a larger ion removal capacity than the liquid passing type capacitor of Example 1 in which the DC power source was directly connected to the activated carbon sheet.
  • Examples 9 to 11, 13, and 14 in which the conductive material was blended with the activated carbon sheet had a very large ion removal capacity.
  • the liquid-passing capacitor of the present invention is excellent in removing ions in water, and can efficiently remove nitrate ions and fluorine ions, which may cause health problems, so a water purifier, a seawater desalination device, a water softener, It can be used for drinking water equipment for groundwater, pure water equipment, wastewater treatment equipment, etc. Further, when a general water purifier is assumed, a processing amount of about 2.0 L or more per 10 minutes is preferable, but such a processing amount can be realized according to the liquid passing type capacitor of the present invention.

Abstract

Le condensateur continu ci-décrit comprend un corps de type empilement constitué d'une pluralité d'électrodes perméables aux liquides et d'une pluralité de séparateurs perméables aux liquides en alternance, les électrodes étant pourvues d'une feuille de charbon actif perméable aux liquides qui contient une poudre de charbon actif et un liant, la poudre de charbon actif ayant un diamètre de particule moyen de 10 à 500 µm, et le liant contenant au moins un type choisi dans la liste constituée par les fibres fibrillées et les particules de liant thermoplastiques. L'utilisation de ce condensateur continu permet d'éliminer plus efficacement les substances ioniques de l'eau que les précédents condensateurs continus.
PCT/JP2010/004171 2009-06-23 2010-06-23 Condensateur continu, procédé de production d'eau désionisée, et dispositif de production d'eau déionisée WO2010150534A1 (fr)

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JP2019506292A (ja) * 2016-01-22 2019-03-07 同▲済▼大学 汚水の脱塩回収に適用する複合膜分離方法
JPWO2020039676A1 (ja) * 2018-08-23 2021-08-12 株式会社寿ホールディングス 水処理装置及びイオン濃度調整水の製造方法
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