Classifications

• • 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
  • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
• • 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
  • B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
• • 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
  • B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
  • B01D61/485—Specific features relating to the ion-exchange material
• • 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
  • B01D61/50—Stacks of the plate-and-frame type
• • 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
  • C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
  • C02F1/4695—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis electrodeionisation
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2101/00—Nature of the contaminant
  • C02F2101/10—Inorganic compounds
  • C02F2101/12—Halogens or halogen-containing compounds
  • C02F2101/14—Fluorine or fluorine-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2201/00—Apparatus for treatment of water, waste water or sewage
  • C02F2201/46—Apparatus for electrochemical processes
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2201/00—Apparatus for treatment of water, waste water or sewage
  • C02F2201/46—Apparatus for electrochemical processes
  • C02F2201/461—Electrolysis apparatus
  • C02F2201/46105—Details relating to the electrolytic devices
  • C02F2201/4618—Supplying or removing reactants or electrolyte
• • 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
  • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
  • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
  • Y02A20/124—Water desalination

Definitions

• Electrodialysis apparatus water treatment method, and fluorine treatment system
• the present invention relates to an electrodialysis apparatus, and in particular, a liquid containing fluorine, for example, (1) drainage from an apparatus relating to semiconductor manufacturing, liquid crystal manufacturing or electronic component manufacturing, or drainage pretreated with the drainage, (2) semiconductor Waste water generated by cleaning PFC gas used for manufacturing, liquid crystal production or electronic parts production with abatement device with water or alkaline water, or the waste water pretreated Wastewater, (3) CFCs destroyers The gas produced by decomposing fauc
• An electrodialysis apparatus for treating waste water that is treated water of a fluorine recycling apparatus that recovers fluorine in a zk solution as calcium fluoride (C a F 2 ) or waste water prepared by treating the waste water, etc. It is about
• the present invention also relates to a method of treating wastewater using such an electrodialysis apparatus. Furthermore, the present invention relates to a fluorine treatment system for treating fluorine using such an electrodialysis apparatus.
• C a is Shasui or precipitated gluteal form a hydroxide in reacting with fluorine insoluble or precipitated to form calcium fluoride (Ca F 2) of, or alkaline aqueous solution. For this reason, it has been difficult to separate or concentrate the fluorine contained in the waste water.
• evaporative concentration is an effective method when trying to further concentrate concentrated wastewater of about 10 000 Omg ZL or more, but even if it is applied to dilute wastewater, energy consumption related to water evaporation is large. And there is a problem that it is difficult to apply.
• the carryover of fluorine ions in distilled water is also high, and the fluorine concentration of distilled water is high, and there is also a disadvantage that it is difficult to reuse as it is.
• electrodialysis is an excellent method for concentrating or desalting waste water with an ion concentration of 1, OO Omg ZL, or a concentration of about 8,000 Omg / L, and from drinking water to drinking water It is put to practical use as a water production, acid recovery, and salt concentration technology.
• electrodialysis can not be highly desalted, a large amount of ion remains in the treated water, so if it is applied to wastewater treatment, secondary treatment of the treated water may be required.
• -Also when applying the electrodialysis method to the treatment of acid drainage containing metal ions that form metal hydroxides, it is necessary to take measures to prevent the formation of metal hydroxides in the electrodialysis tank.
• the electrodes of the electrodialysis tank are corroded by the fluorine.
• fluoride ion is a harmful substance that may cause damage related to human health, and is a substance subject to drainage regulations. In Japan, it is emitted to public waters outside the sea area, and it is 8mg / L or less. 15mg ZL or less is defined as uniform drainage standard. In addition, an environmental standard for the purpose of protecting human health is defined as 0.8 mg L, and it is necessary to use fluorine in treated water treated with fluorine-containing wastewater. The concentration not only meets the uniform drainage standard, but it is desirable to bring it as close as possible to the environmental standard.
• the fluorine concentration be reduced, preferably to 1 mg ZL or less. desirable. This is because when the fluorine concentration exceeds 1 mg ZL, for example, when it is mixed with Ca-containing water such as ground water or tap water to make pure water for production, the pure water production process Separation of impurities: Calcium fluoride is generated during the concentration operation, which may block the pure water production apparatus. Examples of conventional techniques for treating fluorine-containing wastewater and the like using electrodialysis technology include the following.
• Japanese Patent Laid-Open Publication No. 54-2006 discloses a method using fluoride ion (F-) and calcium ion (C a 2+ ) in an electrodialysis tank using a cation exchange membrane and an anion exchange membrane.
• an electrodialysis tank in which demineralization compartments and concentration compartments are alternately arranged is used to operate at a current density of 1/2 or less of the limiting current density, and moves through the anion exchange membrane compared with other anions. It is desalted by leaving difficult fluoride ions in the desalting chamber and suppressing the precipitation of C a F 2 scale in the concentration chamber.
• a bipolar is known from an aqueous solution of a mixed salt containing at least two different kinds of anions containing fluoride ion and at least two kinds of salts (stainless steel acid washing waste liquid).
• a method of recovering mixed acid by using a three-chamber electrodialysis water dissociation apparatus using a membrane is disclosed.
• a waste solution containing heavy metal ions is precipitated by adding an alkaline solution (preferably KO H) in advance, and the resulting suspension is filtered through a filter system to obtain a soluble mixed salt.
• the mixed acid is recovered by forming a solution and supplying the solution of the soluble mixed salt to the desalting chamber of the electrodialytic water dissociation unit.
• Japanese Patent Publication No. 7-12525 discloses a method of regenerating the metal ion-containing nitric acid hydrofluoric acid waste solution.
• a hydrofluoric acid is added to the nitric acid hydrofluoric acid waste liquid containing metal ions to increase the nitric acid recovery efficiency in the electrodialysis operation to make the waste liquid having a one-to-one molar ratio of F 1 to Z N O 3
• Deacidification treatment nitric acid recovery
• metal ions contained in the treated water are alkaline Is precipitated out as hydroxide and removed.
• the ion exchange membrane electrodialysis apparatus which is a combination of a bipolar membrane and an anion exchange membrane, is separated into nitric acid hydrofluoric acid and alkaline water and recovered.
• Japanese Patent Publication No. 7-121559 discloses a method of treating alkaline fluoride waste liquid containing metal ions and oils.
• an alkaline fluoride waste solution containing metal ions and oils is neutralized by the addition of hydrofluoric acid to remove oils, and then a metal ion is adsorbed and removed by a chelating resin, Then, the membrane is separated into aluminum hydroxide and hydrofluoric acid by an ion exchange membrane electrodialysis apparatus comprising a combination of a bipolar membrane and an anion exchange membrane, and then recovered and recovered.
• Japanese Patent No. 3 6 4 3 0 8 discloses a method of treating wastewater containing fluorine.
• treated water from which fluorine is removed from the wastewater containing fluorine is generated using a fluorine adsorbent, and a solution in which fluorine is eluted from the fluorine adsorbent is separated electrically into fluorine-concentrated water and fluorine-diluted water.
• the treated water from which the fluorine has been removed again by the fluorine adsorbent is produced from the obtained fluorine-diluted water.
• fluorine is obtained by separating fluorine from an aqueous solution containing fluorine and ammonia such as BHF solution mainly discharged from a semiconductor factory.
• a method of recovering fluorine by reacting with calcium carbonate In this method, drainage and mineral acid are alternately supplied every other chamber using an electrodialysis tank in which fluorine- and ammonium-containing drainage is alternately arranged with anion exchange membranes and cation exchange membranes.
• fluoride ion is recovered as a solution concentrated to a concentration suitable for treatment with calcium carbonate particles
• ammonium ion is recovered in the form of a salt of mineral acid
• treated water is both fluoride ion and ammonium ion. It is reduced to a concentration range that can be used for secondary treatment processes such as resin adsorption and so on.
• Japanese Patent No. 3 5 5 5 7 2 discloses a method for treating dilute mixed acid waste water containing hydrofluoric acid and mineral acid generated in the process of manufacturing semiconductor devices with an electrodeionization apparatus. It is done.
• dilute acid water containing mineral acid and hydrofluoric acid is added with alkaline water to a pH value at which the weak electrolyte hydrofluoric acid dissociates, ion exchange materials such as ion exchange resin, ion exchange fiber, etc.
• the treated water from which the hydrofluoric acid has been removed is obtained by treatment with an electrodeionization device (EDI) having a desalting chamber filled with and a concentration chamber partitioned via an ion exchange membrane.
• EDI electrodeionization device
• concentrated water with concentrated salts is obtained.
• Japanese Patent Application Laid-Open No. 200-17047 discloses a waste liquid treatment apparatus for treating waste liquid generated at the time of semiconductor production in a semiconductor manufacturing plant.
• waste liquid generated at the time of semiconductor production is ion-exchanged into the waste liquid chamber of the electrodialysis apparatus.
• the fluorine in the waste liquid is recovered as hydrogen fluoride using an electrodialysis apparatus filled with a resin.
• metal ions are collected in the cathode chamber.
• the metal ion component permeates from the waste liquid chamber to the cathode side electrode liquid chamber through the cation exchange membrane, and the metal deposited on the cathode side electrode is deposited on the cathode side electrode by reversing the polarity of the electrode for a short period of time. These metals are ionized again, transferred to the cathode side electrode liquid tank, concentrated, and precipitated as hydroxides, thereby recovering the metal component.
• Japanese Patent Application Laid-Open No. 2000-229289 discloses a method of treating fluorine-containing water with an electrodeionization apparatus. This method restricts the relationship between the concentration product of the calcium concentration of the water supplied to the electrodeionization unit and the fluorine concentration and the water recovery rate of the electrodeionization unit, so that the calcium fluoride scale in the concentration chamber can be reduced. To prevent the formation of
• JP 2001-121152A discloses an electrodialysis apparatus for recovery and reuse of dilute acidic wastewater containing hydrofluoric acid.
• a deionization chamber and a concentration chamber are formed by arranging a cation exchange membrane and an anion exchange membrane at least partially alternately between positive and negative electrodes, and at least The electrode chamber is filled with an ion exchanger.
• the solution reduced in hydrofluoric acid is supplied to the electrode room, so it is possible to carry out the desalting treatment without corroding the electrode.
• this Japanese Patent Application Laid-Open No. 2001-121152 describes that the used electrode solution is returned to the raw water tank and mixed with the water to be treated.
• Japanese Patent Application Laid-Open No. 2001-145819 discloses a method of treating exhaust gas that renders harmful gas harmless.
• acid gas containing hydrogen fluoride is decomposed by gas-liquid contact with an absorbing solution (of alkaline aqueous solution) and a wet scrubber, and the generated effluent is sent to an electrodialysis apparatus having a anion selective permeation membrane.
• the dialyzed treatment is carried out and a part or all of the absorbed anions are discharged out of the system, and the obtained (alkaline aqueous solution) treatment solution is again sent as an absorption solution to a wet scrubber and circulated.
• Japanese Patent Application Laid-Open No. 2002-119974 discloses a method of producing deionized water by deionizing fluorine ion-containing water with an electrodeionization apparatus.
• the concentrated water of the electric regenerative demineralizer is treated with anion exchange resin and water with a fluoride ion concentration of 1 mg L or less, and if necessary, an aqueous salt solution is added, the electric conductivity is 10 ⁇ Sz cm or more.
• water or water of which the inlet of the anode chamber has a pH of 8 or more, The corrosion of the electrode is prevented by passing it as an electrolyte.
• Japanese Patent Application Laid-Open No. 2003-126863 discloses an apparatus for performing deionization treatment with an electrodeionization apparatus without causing corrosion to electrodes even if the water to be treated contains corrosion 1 ′ ′ strong ions such as fluorine ions.
• corrosion by hydrofluoric acid is prevented by using an anode plate and a cathode plate on which a boron-doped CVD diamond thin film is formed on the surface of a conductive substrate.
• Japanese Patent Application Laid-Open No. 2003-159593 discloses a method of treating a waste liquid containing a metal and a fluorine ion, such as a waste liquid used for pickling stainless steel.
• the waste solution containing metal and fluoride ion is neutralized with an alkali solution and then filtered to separate it into fluoride ion-free metal hydroxide sludge and fluoride ion-containing middle fluid, and then fluoride ion
• the neutralized solution is separated by bipolar membrane electrodialysis to separate it into an acid solution containing fluorine ion and an acid solution, and then the solution containing fluorine ion is added to a multistage steam rectification column to use fluorine ion.
• the fluorine ion concentration of a fluorine ion-containing acid solution separated and concentrated by a bipolar electrodialyzer is, for example, 20 g ZL (2%), and further concentrated in a multistage steam rectification column. It is described that the concentration of fluoride ions in the reusable fluoride ion-containing concentrate is about 130 g / L (13%).
• Japanese Patent Application Laid-Open No. 2004-17439 discloses a method for treating fluorine-containing wastewater.
• This method comprises an electrodialysis step of desalting and concentrating the fluorine-containing wastewater, regenerating the desalted solution as make-up water to the source of the fluorine-containing wastewater, and the hydrofluoric acid concentrate having an available concentration of fluorine Electrodialysis to the extent that it is regenerated as an acid solution.
• an electrodialysis means provided with a negative electrode part and a positive electrode part arranged in an opposite manner is used.
• cation exchange membranes and anion exchange rods are alternately arranged, and in the vicinity of the positive electrode part, a plurality of cation exchange membranes are continuously arranged.
• the electrode circulating fluid and blocking solution are supplied by supplying desalted water to the negative electrode part and the positive electrode part and also supplying the desalted solution to the cation exchange membrane arrangement site (blocking chamber) in the vicinity of the positive electrode part.
• the concentration of hydrofluoric acid is kept low to prevent corrosion of the positive electrode.
• a part of the water to be treated becomes a concentrated solution, and the concentration ratio is increased by circulating the concentrated solution. Also, measure the fluoride ion concentration and the concentration of Z or electrolyte in the hydrofluoric acid concentrate, and control the concentration ratio according to the fluctuation of this concentration.
• the fluorine ion of the ion exchange membrane is high, so that the fluorine ions flow into the electrode chamber to corrode the electrode, so the stable operation continues. There was a problem that it was impossible.
• the fluorine ion of the ion exchange membrane is high, so that the fluorine ions flow into the electrode chamber to corrode the electrode, so the stable operation continues.
• the stable operation continues.
• it was impossible in the case of treating dilute hydrofluoric acid wastewater containing calcium, there is a problem that stable operation can not be continued because calcium fluoride precipitates in the concentration chamber.
• fluorine-containing wastewater containing ammonium ions was difficult to recycle fluorine.
• the fluorine concentration in the concentrated water is reduced until it can be supplied to the fluorine recycling device at the same time as the fluorine concentration containing less than 1 mg ZL is obtained from dilute fluorine-containing wastewater.
• the fluorine concentration containing less than 1 mg ZL is obtained from dilute fluorine-containing wastewater.
• Japanese Examined Patent Publication No. 7-121559 is directed to a specific waste liquid, which is an alkaline fluoride waste liquid containing an oil component generated from an organic chemical plant.
• a specific waste liquid which is an alkaline fluoride waste liquid containing an oil component generated from an organic chemical plant.
• metal ions are removed with a chelate resin, and then hydrofluoric acid and alkali are recovered with an electrodialysis apparatus using a bipolar membrane method.
• the Japanese Patent Publication No. 7-12599 does not disclose a method for avoiding the corrosion of the electrode due to fluorine.
• JP-A-9-1262658 uses an electrodialysis tank to The concentration is lowered to increase the concentration of fluorine, and the concentrated water is recovered as a solution suitable for the concentration by calcium carbonate particles for fluorine recovery, but the concentration of fluorine in treated water is high and it is possible to reuse it as it is. As it can not be done, secondary treatment of treated water with resin is required. Further, this Japanese Patent Application Laid-Open No. 9-262588 does not disclose a method for avoiding corrosion of the electrode due to fluorine.
• the method described in Japanese Patent No. 3555732 is a method of obtaining treated water from which hydrofluoric acid has been removed by adding alkaline water to mixed acid water containing hydrofluoric acid and treating it with an electrodeionization apparatus.
• fluorine is concentrated in the form of salt, it is not suitable for recovery or reuse of hydrofluoric acid or fluorine.
• concentrated water is supplied to the electrode chamber, there is a problem that corrosion of the electrode can not be avoided due to fluorine.
• the device described in Japanese Patent Application Laid-Open No. 2003-126863 has a problem that an expensive large-sized C V D device is required to manufacture an electrode.
• JP-A-2004-1749 is a method for preventing corrosion of an electrode by introducing electrodialyzed desalted water into a blocking chamber and an electrode chamber.
• the operating voltage becomes high because no measures have been taken to suppress the rise in voltage that accompanies the supply of
• fluorine leaks into the blocking chamber adjacent to the high concentration concentrated concentrating chamber, the blocking chamber circulating fluid becomes water containing fluorine, and it is necessary to post-process to remove or recover the fluorine.
• the present invention has been made in view of the problems of the prior art as described above, and it is an object of the present invention to provide an electrodialysis apparatus which can electrodialyze fluorine-containing wastewater stably without electrode corrosion.
• Another object of the present invention is to provide an electrodialysis apparatus capable of reusing the treated water, as the fluorine concentration of the treated water after electrodialysis of the fluorine-containing waste water is as low as less than 1 m g Z L.
• Another object of the present invention is to provide an electrodialysis apparatus capable of obtaining fluorine-concentrated water from which ammonium ions have been separated by electrodialysis of fluorine-containing wastewater containing ammonium ions.
• the fourth objective is to provide an electrodialysis apparatus.
• Another object of the present invention is to provide an electrodialysis apparatus capable of recovering calcium fluoride (C a F 2 ) by supplying fluorine-concentrated water obtained by electrodialysis of fluorine-containing wastewater to a fluorine recycling apparatus.
• the purpose of 5 calcium fluoride (C a F) can be provided by separating the ammonium ions from the fluorine-containing wastewater containing ammonium ions to facilitate the fluorine recycling, and supplying hydrofluoric acid-concentrated water to the fluorine recycling device.
• the sixth purpose is to make an electrodiaphragm that can be recovered as 2 ).
• a seventh object is to provide a fluorine treatment system that effectively treats fluorine using the above-described electrodialysis apparatus.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the electrodialysis apparatus comprises: a desalting chamber for removing the supplied treated water, target ions and the like to generate treated water having a reduced concentration of the target ions; And a concentration chamber for concentrating a target ion in water to generate a concentrated water in which the concentration of the target ion is increased.
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the outflowing water from the anode chamber to the concentration chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the electrodialysis apparatus includes a desalting chamber for removing target ions from the supplied treated water to generate treated water having a reduced concentration of the target ions, and the treated water transferred from the desalting chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the electrodialysis apparatus includes: a desalting chamber for removing a supplied target water such as target water to generate treated water having a reduced concentration of the target ion; A concentration chamber for concentrating a target ion in water to generate concentrated water in which the concentration of the target ion is increased, and blocking so that a target ion in the water to be treated does not directly flow from the concentration chamber to the anode chamber It has a buffer room and
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the effluent water from the anode chamber to the buffer chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the electrodialysis apparatus Force ⁇ A desalting chamber for removing treated ions to generate treated water having a reduced concentration of the targeted ions, and a concentration of the targeted ions in the treated water in the treated water transferred from the desalting chamber And a buffer chamber for blocking the target ions in the treated water not to flow directly from the concentration chamber to the anode chamber.
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the effluent water from the anode chamber to the concentration chamber through the buffer chamber. doing.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the electrodialysis apparatus removes the first target ion and the second target ion from the supplied treated water to reduce the concentration of the first target ion and the second target ion.
• a desalting chamber for producing treated water, and a first target ion in the water to be treated transferred from the desalting chamber is concentrated to produce a first concentrated water in which the concentration of the first target ion is increased
• concentrating the second target ion in the treated water transferred from the desalting chamber to produce a second concentrated water in which the concentration of the second target ion is increased.
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the effluent water from the anode chamber to the first concentration chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• This electrodialysis apparatus is a process in which the concentration of the first target ion and the second target ion is reduced by removing the first target ion and the second target ion from the supplied treated water.
• a first deionization chamber for producing water, and a first target ion in the treated water transferred from the demineralization chamber are concentrated to generate a first concentrated water in which the concentration of the first target ion is increased.
• the electrodialysis apparatus concentrates the second target ion in the treated water transferred from the desalting chamber to generate a second concentrated water in which the concentration of the second target ion is increased.
• a ion supply chamber for supplying an ion having a polarity opposite to that of the second target ion in the water to be treated to the second concentration chamber.
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the effluent water from the anode chamber to the buffer chamber. ,.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• This electrodialysis apparatus is a process in which the concentration of the first target ion and the second target ion is reduced by removing the first target ion and the second target ion from the supplied treated water.
• a desalting chamber for producing water, and a first target ion in the treated water transferred from the desalting chamber is concentrated to produce a first concentrated water in which the concentration of the first target ion is increased.
• the electrodialysis apparatus concentrates the second target ion in the treated water moved from the desalting chamber to generate a second concentrated water in which the concentration of the second target ion is increased.
• a ion supply chamber for supplying an ion having a polarity opposite to that of the second target ion in the water to be treated to the second concentration chamber.
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the outflowing water from the anode chamber to the first concentration chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• This electrodialysis apparatus is a process in which the concentration of the first target ion and the second target ion is reduced by removing the first target ion and the second target ion from the supplied treated water.
• a desalting chamber for producing water, and a first target ion in the treated water transferred from the desalting chamber is concentrated to produce a first concentrated water in which the concentration of the first target ion is increased.
• the electrodialysis apparatus concentrates a second target ion in the treated water transferred from the desalting chamber to generate a second concentrated water in which the concentration of the second target ion is increased.
• a ion supply chamber for supplying an ion having a polarity opposite to that of the second target ion in the water to be treated to the second concentration chamber.
• the electrodialysis apparatus further comprises: a path for supplying pure water to the anode chamber; and a path for supplying at least a part of the effluent water from the anode chamber to the first concentration chamber via the buffer chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the concentration of the first target ion and the second target ion is reduced by removing the first target ion and the second target ion from the supplied treated water.
• a first concentration chamber for producing a first concentrated water having an increased concentration of ions, and a second target ion in the water to be treated transferred from the desalting chamber is concentrated to form a second target ion.
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the effluent water from the anode chamber to the first concentration chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the electrodialysis apparatus removes treated target water and second target ions from the supplied treated water to reduce the concentration of the first target ions and the second target ions.
• a desalting chamber for producing the first target water in the treated water transferred from the desalting chamber to form a first concentrated water in which the concentration of the first target ion is increased.
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the outflowing water from the anode chamber to the buffer chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the electrodialysis apparatus comprises: treated water in which a first target ion and a second target ion are removed from supplied treated water to reduce the concentration of the first target ion and the second target ion.
• a desalting chamber for producing the first target water in the treated water transferred from the desalting chamber to form a first concentrated water in which the concentration of the first target ion is increased.
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the outflowing water from the anode chamber to the first condensing chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode. This electrodialysis apparatus removes treated target water and second target ions from the supplied treated water, thereby reducing the concentration of the first target ions and the second target ions.
• Demineralization chamber to produce A first concentration chamber for concentrating a first target ion in the treated water transferred from the desalting chamber to generate a first concentrated water having an increased concentration of the first target ion; A buffer chamber for blocking the first target ions in the treated water not to directly flow into the anode chamber from the first concentration chamber; and a second target ion in the treated water moved from the desalting chamber And a second concentration chamber for producing a second concentrated water in which the concentration of the second target ion is increased.
• a path for supplying pure water to the anode chamber, and a path for supplying at least a part of the effluent water from the anode chamber to the first concentration chamber through the buffer chamber have.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the electrodialysis apparatus comprises: a demineralization chamber for removing a target ion from the supplied treated water to generate treated water having a reduced concentration of the target ion; and in the treated water moved from the deionization chamber.
• the electrodialysis apparatus has a path for supplying pure water to the buffer chamber, and a path for supplying at least a part of the outflowing water from the buffer chamber to the concentration chamber.
• the electrodialysis apparatus may further include a path for mixing at least a part of the effluent water from the buffer chamber with the treated water or the treated water.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• This electrodialysis apparatus removes treated target water and second target ions from the supplied treated water, thereby reducing the concentration of the first target ions and the second target ions.
• desalting chamber for producing the first target ion in the treated water transferred from the desalting chamber to form a first concentrated water in which the concentration of the first target ion is increased.
• a buffer chamber for blocking the first target ions in the treated water from directly flowing into the anode chamber from the first concentration chamber.
• the electrodialysis apparatus further includes: a second concentrated water in which the concentration of the second target ion is increased by concentrating the second target ion in the treated water moved from the salt removal chamber; It has 2 concentration rooms.
• the electrodialysis apparatus comprises: a first cation exchange membrane provided between the anode chamber and the buffer chamber; a first cation exchange membrane provided between the cathode chamber and the second concentration chamber; A cation exchange membrane, a second force exchange membrane provided between the buffer chamber and the first concentration chamber, and a second ion exchange membrane provided between the first concentration chamber and the desalting chamber.
• the second one r And a third cation exchange membrane provided between the deionization chamber and the second concentration chamber.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• This electrodialysis apparatus is a treatment in which the concentration of the first target ion and the second target ion is reduced by removing the first target ion and the second target ion from the supplied treated water.
• a buffer chamber for blocking the first target ions in the treated water not to flow directly from the first concentration chamber into the anode chamber.
• the electrodialysis apparatus concentrates the second target ion in the treated water moved from the desalting chamber to generate a second concentrated water in which the concentration of the second target ion is increased.
• a ion supply chamber for supplying ions having the opposite polarity to the second target ion in the treated water to the second concentration chamber.
• the electrodialysis apparatus comprises: a first cation exchange membrane provided between the anode chamber and the buffer 5 chamber; a first anion exchange membrane provided between the cathode chamber and the ion supply chamber A membrane, a second cation exchange membrane provided between the buffer chamber and the first concentration chamber, and a second anion ion provided between the first concentration chamber and the desalting chamber An exchange membrane, a third cation exchange membrane provided between the desalting chamber and the second concentration chamber, a second cation chamber provided between the second concentration chamber and the ion supply chamber 0, and It has three ion exchange membranes.
• an electrodialysis apparatus comprising: an anode chamber having an anode; and a cathode chamber having a cathode.
• the electrodialysis apparatus comprises: a plurality of chamber structures comprising a plurality of chambers; at least one bipolar chamber having an electrode; a first cation exchange membrane provided between the anode chamber and the chamber structure; A first anode exchange membrane provided between the cathode chamber and the chamber structure, a second ion exchange membrane disposed on the anode side of the bipolar chamber, and a cathode exchange membrane of the bipolar chamber. And a second cation exchange membrane provided on the cathode side.
• the bipolar chamber is disposed between the plurality of chamber structures, and is filled with ion exchange material.
• the chamber structure is a treated water in which the concentration of the first target ion and the second target ion is reduced by removing the first target ion and the second target ion from the supplied treated water.
• a desalting chamber for producing the first concentrated ion in which the concentration of the first target ion is increased by concentrating the first target ion in the for-treatment water transferred from the desalting chamber. 1 and the first target ion in the water to be treated does not directly flow from the first concentration chamber to the anode chamber or the bipolar chamber.
• a buffer chamber to shut off.
• the room structure is configured such that the second target ion in the treated water moved from the demineralization chamber is concentrated to generate a second concentrated water in which the concentration of the second target ion is increased.
• a ion supply chamber for supplying ions having the opposite polarity to the second target ion in the treated water to the second concentration chamber.
• the electrodialysis apparatus has a path for supplying pure water to the anode chamber and the bipolar chamber.
• a chamber structure is provided by: a third cation exchange membrane provided between the buffer chamber and the first concentration chamber; a third cation exchange membrane provided between the first concentration chamber and the salt removal chamber And a fourth cation exchange membrane provided between the deionization chamber and the second concentration chamber, and a third exchange chamber provided between the second concentration chamber and the ion supply chamber. And a fourth anion exchange membrane.
• the said to-be-processed water is waste water containing a fluorine.
• each chamber is preferably filled with a cation exchange material in contact with the cation exchange membrane or an anion exchange fiber material in contact with the cation exchange membrane.
• a waste water treatment method in which waste water containing at least ammonium ions and fluorine is treated by an electrodialysis apparatus.
• ammonium ions and fluorine are removed from the above-mentioned waste water to produce treated water having a reduced concentration of ammonium and fluorine, and the first concentrated water having a higher concentration of fluorine and -Produce a second concentrated water with an increased concentration of mumion. ..
• a waste water treatment method for treating waste water containing at least metal hydroxide sludge and metal ions by an electrodialysis apparatus.
• the metal ions and fluorine are removed from the waste water to generate treated water having a reduced concentration of the metal ions and fluorine, and the concentration of the first concentrated water and the concentration of the metal ions increased.
• waste water containing at least hydrogen peroxide and fluorine may be subjected to hydrogen peroxide decomposition treatment, and the waste water subjected to the hydrogen peroxide decomposition treatment may be supplied to the electrodialysis apparatus.
• the fluorine concentration of the above waste water is more than l mg ZL and less than 10 0 0 O mg / L. Is preferred.
• the fluorine concentration of the treated water is preferably less than 1 mg ZL.
• at least a part of the first concentrated water can be supplied to a fluorine recycling apparatus to recover fluorine in the waste water as calcium fluoride (C a F 2 ).
• the fluorine concentration of the treated water may be 1 mg / L or more. If the treated water is to be discharged to the outside without being reused, it may be 8 mg / L or less of the discharge standard. Therefore, it is possible to maintain the fluorine concentration of treated water at around 5 mg ZL by adjusting the operating current of the electrodialysis tank, and it is better than operating with the fluorine concentration maintained at less than 1 mg ZL. It is an energy saving 51 $ method.
• the fluorine concentrated water may not be supplied to the fluorine recycling apparatus, but may be supplied to the conventional coagulation precipitation equipment. Even in this case, the amount of chemicals necessary for the coagulation sedimentation treatment is reduced, and the amount of generated sludge is reduced, as compared to the case where the fluorine-containing wastewater, which is the water to be treated, is coagulated and settled as it is. Will occur. In addition, the concentration reduces the volume of wastewater to be treated, which has the advantage of requiring a smaller wastewater treatment facility.
• concentration of 1 O mg / L of fluorine-containing wastewater to 100 O mg ZL results in a 100-fold decrease in the amount of drainage, and the necessary flocculant necessary for coagulation sedimentation to be injected according to the amount of drainage.
• the amount is about 1/100 and the amount of sludge generated as a result can be significantly reduced.
• fluorine-concentrated water in which both ammonium ions and fluorine ions are concentrated in the same liquid may be obtained from fluorine-containing water containing ammonium ions.
• fluorine-containing water containing ammonium ions may be obtained from fluorine-containing water containing ammonium ions.
• fluorine-concentrated water when fluorine is recycled, including ammonium ions in the fluorine-concentrated water inhibits the reaction for fluorine recycling and reduces the reaction efficiency. This is because the presence of ammonium ions does not affect the reaction efficiency when coagulating and settling water.
• a fluorine treatment system comprising: the above-mentioned electrodialysis apparatus; and a fluorine recycling apparatus for recovering the fluorine-concentrated water obtained from the above-mentioned electric dialysis apparatus as calcium fluoride. It will be 3 ⁇ 4 ⁇ .
• a fluorine including: the above-mentioned electrodialysis apparatus; and a coagulation / sedimentation apparatus for carrying out coagulation / sedimentation processing of water containing at least a part of the fluorine-concentrated water obtained by the above electrodialysis apparatus.
• a processing system is provided.
• an electrodialysis apparatus as described above; And a pure water producing apparatus for producing pure water using raw water obtained from the treated water as raw water.
• an electrodialysis apparatus as described above, an abatement apparatus, a path for supplying drainage of the abatement apparatus to the electrodialysis apparatus, and a process obtained by the electrodialysis apparatus.
• a water recycling system comprising a path for supplying a part of water to the abatement device.
• an electrodialysis apparatus as described above, solid-liquid separation means for solid-liquid separation of waste water containing at least fluorine, and waste water separated by the solid-liquid separation means.
• the fluorine treatment system is provided with a route for supplying the above-mentioned electrodialysis apparatus to the above-mentioned electrodialysis apparatus.
• the above-mentioned electrodialysis apparatus organic matter separation means for separating organic matter of at least fluorine-containing waste water, and waste water separated by organic matter separation means by the above organic matter separation means are mentioned above.
• a fluorine processing system comprising a path for supplying an electrodialysis device.
• FIG. 1 is a schematic view showing the configuration of the electrodialysis apparatus in the first embodiment of the present invention. '
• FIG. 2 is a schematic view showing the electrodialysis tank of FIG.
• FIG. 3 is a schematic view showing a configuration of an electrodialysis apparatus according to a second embodiment of the present invention. ..
• FIG. 4 is a schematic view showing the configuration of an electrodialysis apparatus according to a third embodiment of the present invention.
• FIG. 5 is a schematic view showing a configuration of an electrodialysis apparatus according to a fourth embodiment of the present invention.
• FIG. 6 is a schematic view showing the electrodialysis tank of FIG.
• FIG. 7 is a schematic view showing a configuration of an electrodialysis apparatus according to a fifth embodiment of the present invention.
• FIG. 8 is a schematic view showing the electrodialysis tank of FIG. .
• FIG. 9 is a schematic view showing the configuration of the electrodialysis apparatus in the sixth embodiment of the present invention. is there.
• FIG. 10 is a schematic view showing the electrodialysis tank of FIG.
• FIG. 11 is a schematic view showing a configuration of an electrodialysis apparatus according to a seventh embodiment of the present invention.
• Figure 12 is a schematic view showing the electrodialysis tank of Figure 11.
• FIG. 13 is a schematic view showing an electrodialysis tank of the electrodialysis apparatus in the eighth embodiment of the present invention.
• FIG. 14 is a conceptual view showing an example of a fluorine treatment system combining an electrodialysis apparatus according to the present invention and a fluorine recycling apparatus.
• FIG. 15 is a conceptual view showing an example of a fluorine processing system in which an electrodialysis apparatus according to the present invention and a C a F 2 substitution apparatus are combined.
• FIG. 16 is a conceptual view showing an example of a fluorine treatment system in which an electrodialysis apparatus according to the present invention and a C a F 2 crystallizer are combined.
• FIG. 17 is a conceptual view showing an example of a fluorine 5 treatment system in which an electrodialysis apparatus according to the present invention and a coagulation precipitation apparatus are combined.
• FIG. 18 is a conceptual view showing an example of a fluorine treatment system in which the electrodialysis apparatus and the harm removal apparatus according to the present invention are combined.
• FIG. 19 is a conceptual view showing an example of a fluorine treatment system in which an electrodialysis apparatus according to the present invention and an activated carbon adsorption layer are combined.
• FIG. 20 is a conceptual view showing an example of a fluorine treatment system in which an electrodialysis apparatus according to the present invention and a vacuum distillation apparatus are combined.
• FIG. 1 to FIG. 20 the same or corresponding components are given the same reference numerals, and duplicate explanations are omitted.
• FIG. 1 is a schematic view showing the configuration of the electrodialysis apparatus in the first embodiment of the present invention.
• the electrodialysis apparatus has an anode chamber 10, a buffer chamber 20, a concentration chamber 30, a desalting chamber 40, a concentration chamber 21 and a cathode chamber 50. It is equipped with 0.
• the electrodialysis apparatus also includes an electrode tank 71 for supplying pure water to the anode chamber 10 and the cathode chamber 50 through the pump 70, and a buffer chamber 20 through which the buffer water is supplied through the pump 72. And a buffer water tank 73 supplied to the concentration chamber 21 and a concentrated water tank 75 supplying the concentrated water to the concentration chamber 30 via the pump 74.
• FIG. 2 is a schematic view showing the electrodialysis tank 1 of FIG. As shown in FIG.
• the anode chamber 10 and the buffer chamber 20 are separated by a cation exchange membrane CM 1 which is a type of ion exchange membrane, and the buffer chamber 20 and the concentration chamber 30 are ion exchange membranes. It is separated by the CM 2 which is a kind of cation exchange membrane.
• the concentration chamber 30 and the desalting chamber 40 are separated by an anion exchange membrane AMI, which is a type of ion exchange membrane, and the concentration chamber 21 and the desalting chamber 40 are a type of ion exchange membrane. It is partitioned by a cation exchange membrane CM 3.
• the cathode chamber 50 and the concentration chamber 21 are separated by an anion exchange membrane AM 2 which is a type of ion exchange membrane.
• FIG. 2 the illustration of the patterning located on both sides of the ion exchange membrane is omitted.
• the anode chamber 10 is filled with a cation exchange non-woven fabric C F 1 which is a type of ion exchanger.
• a cation exchange non-woven fabric CF 2 which is a kind of ion exchanger
• a cation exchange spacer CS 1 which is a kind of ion exchanger
• a cation exchange non-woven fabric CF 3 which is a kind of ion exchanger Is filled.
• Ion exchange non-woven fabric is a non-woven fabric type ion exchanger which is densely composed of fine fibers with large surface area, so it has high ion capturing ability and conductivity, but it has a large pressure loss when packed in an electrodialysis tank.
• ion exchange spacers are those in which an ion exchange function is introduced to the surface of a reticulated spacer that is commonly used in conventional electrodialysis cells. It has excellent water dispersibility and low pressure loss, but it does not There is a problem that the capture ability is low.
• the electrodialysis tank 1 in the present embodiment by combining and packing the ion exchange non-woven fabric and the ion exchange spacer, it is possible to reduce the pressure loss while keeping the ion capturing ability and the conduction ability high.
• a cation exchange non-woven fabric CF4 which is a kind of ion exchanger
• a cation exchange spacer CS2 which is a kind of ion exchange
• anion exchange non-woven fabric AF1 which is a kind of ion exchange It is filled.
• the deionization chamber 40 is filled with anion exchange nonwoven fabric AF 2 which is a kind of ion exchanger, anion exchange spacer AS 1 which is a kind of ion exchanger, and a cation exchange nonwoven fabric CF 5 which is a kind of ion exchanger. It is being done. .
• cation exchange non-woven fabric CF 6 which is a kind of ion exchanger
• cation exchange spacer CS 3 which is a kind of ion exchanger
• anion exchange non-woven fabric AF 3 which is a kind of ion exchanger. It is filled.
• the cathode chamber 50 is filled with an anion exchange non-woven fabric AF 4 which is a type of ion exchanger.
• Pure water as an electrode liquid is supplied from the electrode liquid tank 71 to the anode chamber 10 and the cathode chamber 50. Since the effluent water from the anode chamber 10 has a fluoride ion concentration higher than that of pure water, in the present embodiment, the entire amount is supplied to the buffer water tank 73 without being circulated to the electrode liquid tank 71. It has become. In the present embodiment, it is experimentally confirmed that the effluent water that has exited from the cathode chamber 50 usually has an extremely dilute fluorine ion concentration and a concentration level substantially the same as that of pure water. In order to replenish the polar solution, it is circulated to the polar solution tank 71.
• the effluent water from the anode chamber 1 ⁇ may be supplied to the concentrated water tank 75.
• the buffer water from the buffer water tank 73 may be a buffer chamber 20 and a concentration chamber 21 1
• the effluent water from the buffer chamber 20 and the concentration chamber 21 is supplied to the buffer water tank 73 and the concentrated water tank 75.
• the buffer chamber 20 and the concentration chamber 21 are left.
• concentrated water is supplied to the concentration chamber 30 from the concentrated water tank 75. Effluent water from the concentration chamber 30 is taken out as concentrated water, and a part is supplied to the concentrated water tank 75.
• Raw water is supplied to the desalination chamber 40, and the effluent water from the desalination chamber 40 is taken out as treated water.
• hydrogen ions generated by the electrolysis reaction of water in the anode chamber 10 are formed on the cation exchangers CF 1, CM 1, CF 2, CS 1, CF 3, CM 2, CF 4, CS 2. Can be conducted to the concentration chamber 30 via the buffer chamber 20. Therefore, the voltage applied to the anode chamber 10 and the buffer chamber 20 can be maintained low independently of the ion concentration of the anolyte and buffer water.
• the anions in the raw water are concentrated in the concentrated water.
• the concentration target is fluorine ions
• a part of the fluorine ions in the concentrated water permeates through the cation exchange membrane CM 2 separating the concentration chamber 30 and the buffer chamber 20, and the concentration chamber 30
• a phenomenon may occur in which the buffer chamber 20 located on the anode 2 side and eventually the anode chamber 10 are reached.
• pure water is always supplied to the anode chamber 10, and fluorine ions leaking from the buffer chamber 20 to the anode chamber 10 are released to the outside of the anode chamber 10. It is possible to discharge and maintain the fluorine concentration in the anode chamber 10 at an extremely low value. In addition, electrode corrosion due to fluorine can be suppressed.
• the concentration of fluorine in the 2 ⁇ room in the knocker chamber was also changed from the concentration chamber 30 to the buffer chamber 20 because the buffer water in the buffer water tank 73 was replenished with the outflow water from the anode chamber 10
• the leaked fluorine ions can be discharged to the outside of the buffer chamber 20.
• the concentration is slightly higher than that of the anode chamber 10
• the fluorine concentration of the buffer chamber 20 can be maintained at a low value.
• the concentrated water is replenished by the effluent water from the buffer chamber 20 and the concentration chamber 21, the amount of replenished pure water to be added to the concentrated water tank 75 can be reduced.
• the fluorine concentration in the replenishing water does not fluctuate or increase depending on the operating conditions. Therefore, regardless of the operating conditions, the fluorine concentration in the anode chamber 10 can always be maintained at an extremely low value. Also, corrosion of the anode 2 can be more reliably prevented.
• treated water can be used instead of pure water, such as when the quality of treated water of the electrodialysis apparatus is comparable to pure water, treated water may be used instead of pure water.
• the buffer water is replenished by the outflow water from the anode chamber 10, the amount of water discharged from the anode chamber 10 to the outside of the apparatus and the amount of replenished pure water to be added to the puffer water is small. can do.
• the total amount of effluent water from the anode chamber 10 is supplied to the buffer water tank 73, the amount of water discharged from the anode chamber 10 to the outside of the apparatus and the amount of makeup pure water added to puffer water. The quantity can be zero.
• the amount of the replenishment pure water to be added to the concentrated water and the buffer chamber 20 and the concentration chamber 21 to the outside of the apparatus can be reduced.
• the amount of makeup pure water added to the concentrated water and the buffer chamber 20 and the concentration chamber 21 to the outside of the apparatus can be zero.
• the types of drainage discharged from the electrodialysis tank 1 include the anode chamber 10 and the outside of the device. If the amount of water discharged to the water and the amount of water discharged from the buffer chamber 20 and the concentration chamber 21 to the outside of the device is zero, only two lines of treated water and concentrated water are needed, and the piping system is complicated. It never happens.
• the equilibrium fluorine concentration in the anode chamber 10, buffer chamber 20 and concentration chamber 21 is supplied to the amount of electrolyte supplied to the anode chamber 10 and the cathode chamber 5 G and to the buffer chamber 20 and the concentration chamber 21. It can be adjusted arbitrarily by adjusting the amount of buffer water to be In the embodiment shown in FIG. 1, at least a part of the polar solution Z or the buffer water may be mixed with the raw water or the treated water.
• FIG. 3 is a schematic view showing a configuration of an electrodialysis apparatus according to a second embodiment of the present invention.
• the electrodialysis apparatus according to this embodiment has basically the same configuration as the electrodialysis apparatus according to the first embodiment, but differs from the electrodialysis apparatus according to the first embodiment in the following points. There is.
• Buffer water is supplied only to the buffer chamber 20 from the buffer water tank 73, and is not supplied to the concentration chamber 21. Instead, the effluent water from the cathode chamber 50 is supplied to the concentration chamber 21. Further, the effluent water from the concentration chamber 21 is supplied to the polar fluid tank 71 in order to replenish the polar fluid.
• Cations present in the raw water are concentrated in the concentration chamber 21 adjacent to the cathode chamber 50. If it is determined that the concentrated cations do not adversely affect the processing performance of the electrodialysis apparatus, as shown in FIG.
• the configuration as shown can be used. It goes without saying that the effluent water from the concentration chamber 21 may be supplied to the buffer water tank 73. Even with such a configuration, the effects of the present invention can be exhibited.
• FIG. 4 is a schematic view showing the configuration of an electrodialysis apparatus according to a third embodiment of the present invention.
• the electrodialysis apparatus according to this embodiment has basically the same configuration as the electrodialysis apparatus according to the first embodiment, but differs from the electrodialysis apparatus according to the first embodiment in the following points. There is.
• Buffer water is supplied only to the buffer chamber 20 from the buffer water tank 73, and is not supplied to the concentration chamber 21. Instead, pure water as the polar solution is supplied from the polar solution tank 1 to the anode chamber 10 and the concentration chamber 21. Further, the effluent water from the concentration chamber 21 is supplied to the cathode chamber 50 adjacent to the concentration chamber 21. Even with such a configuration, the effects of the present invention can be exhibited.
• FIG. 5 is a schematic view showing the configuration of an electrodialysis apparatus according to a fourth embodiment of the present invention
• FIG. 6 is a schematic view showing the electrodialysis tank 101 a of FIG.
• the electrodialysis apparatus in the present embodiment has basically the same configuration as the electrodialysis apparatus in the first embodiment, but adjacent to the cathode chamber 50, buffered water (FIG. 1), polar fluid (FIG. 1) 3 and the concentration chamber 21 supplied with pure water (FIG. 4) is used as the concentration chamber 31 supplied with concentrated water in FIG. It is different.
• the effects of the present invention can be achieved also by such a configuration.
• FIG. 7 is a schematic view showing the configuration of the electrodialysis apparatus in the fifth embodiment of the present invention
• FIG. 8 is a schematic view showing the electrodialysis tank 101 b of FIG.
• the electrodialysis apparatus in the present embodiment has basically the same configuration as the electrodialysis apparatus in the first embodiment, but between the desalting chamber 40 and the concentration chamber 30 in FIG. It differs from the electrodialysis apparatus in the first embodiment in that a concentration chamber 30 and a desalting chamber 40 are further added.
• concentrated water may be supplied to the concentration chamber 31 by using the concentration chamber 21 adjacent to the cathode chamber 50 as the concentration chamber 31.
• FIG. 9 is a schematic view showing a configuration of an electrodialysis apparatus according to a sixth embodiment of the present invention. Similar to the electrodialysis apparatus shown in FIG. 1, this electrodialysis apparatus has the effect of preventing the corrosion of the anode, and also in the case of hydrofluoric acid waste water containing metal ions, it is possible to use hydrofluoric acid and metal ions. Can be concentrated individually. Moreover, since the metal ions are separated and concentrated as soluble chlorides, not as precipitated hydroxides, problems such as precipitation in the electrodialysis tank can be avoided.
• the electrodialysis apparatus comprises an anode chamber 210, a buffer chamber 220, an acid concentration chamber 230, a desalting chamber 240, an acid concentration chamber 231 and an acid supply unit.
• An electrodialysis tank 201 having an acid supply chamber (ion supply chamber) 260 and a cathode chamber 250 is provided.
• the bipolar chamber 261 is interposed between the knocker chamber 220, the acid concentration chamber 230, the salt removal chamber 240, and the force concentration chamber on both sides.
• An acid supply chamber 260 is provided.
• the electrodialysis apparatus includes an electrode tank 2 71 for supplying pure water to the anode chamber 210 and the cathode chamber 250 via a pump 270, and a pump 2 72 Buffer water tank that supplies buffer water to the buffer chamber 220 through the buffer tank 2 73, and acid concentrated water tank that supplies acid concentrated water to the acid concentration chamber 230 through the pump 2 74 5, Alkali concentrated water tank 2 7 1 which supplies alkali concentrated water to alkali concentration chamber 2 3 1 through pump 2 7 6 and acid supply chamber 2 6 7 To 0 It has an acid supply water tank 2 7 9 to supply.
• the electrodialysis apparatus comprises an acid stock solution tank 2 8 1 for supplying an acid stock solution such as HC 1 to an acid feed water tank 2 7 9 through a pump 2 8 0, and an acid feed water tank 2 7 9 pH It has a p H monitor 2 8 2 to be measured.
• the electrodialysis apparatus comprises a raw water tank 2 8 4 for supplying raw water to the deionization chamber 2 40 via a pump 2 8 3 and activated carbon 2 8 for abatement waste water (water to be treated containing fluorine). And a pump 2 8 7 for supplying the raw water tank 2 8 4 through the cartridge filter 2 8 6.
• An anode 202 is disposed inside the anode chamber 210, and a cathode 203 is disposed inside the cathode chamber 250. Further, an electrode 204 is disposed inside the bipolar chamber 2 61.
• the demineralization chamber 240 removes fluorine ions (first target ion) and calcium ions (second target ion) from raw water (water to be treated) to reduce fluorine concentration and calcium ion concentration. Produce treated water.
• the knocker chamber 220 blocks so that the fluorine ions in the raw water do not flow directly from the acid concentration chamber 230 into the anode chamber 120.
• the acid concentration chamber 230 condenses the fluorine ions in the raw water transferred from the desalting chamber 240 to generate a (first) concentrated water in which the fluoride ion concentration is increased.
• the alkali concentration chamber 21 concentrates the calcium ions in the raw water transferred from the desalting chamber 240 to generate a (second) concentrated water in which the calcium ion concentration is increased.
• the acid supply chamber 260 supplies ions having the opposite polarity to the calcium ions in the waste water to the alkali concentration chamber 231.
• FIG. 10 is a schematic view showing the electrodialysis tank 201 of FIG. As shown in Fig. 10, the anode chamber 210 and the buffer chamber 220 are separated by a cation exchange membrane CM11, which is a type of ion exchange membrane, and the buffer chamber 220 and the acid concentration chamber 2 3 0 is partitioned by a cation exchange membrane CM12, which is a type of ion exchange membrane.
• CM11 which is a type of ion exchange membrane
• CM12 which is a type of ion exchange membrane
• the acid concentration chamber 230 and the desalting chamber 240 are separated by an ion exchange membrane AM11, which is a type of ion exchange membrane, and the desalting chamber 240 and the alkali concentration chamber 231 are: It is partitioned by a cation exchange membrane CM13, which is a type of ion exchange membrane.
• Anion exchange membrane AMI 2 which is a type of ion exchange membrane, is divided between the alkali concentration chamber 21 and the acid supply chamber 260, and the acid supply chamber 260 and the bipolar chamber 26 1 are separated.
• the space is partitioned by an anion exchange membrane AM 13 which is a type of ion exchange membrane.
• FIG. 10 the illustration of the packing located on both sides of the ion exchange membrane is omitted.
• the anode chamber 120 is filled with a cation exchange non-woven fabric CF 11 which is a type of ion exchanger.
• a cation exchange non-woven fabric CF 1 2 which is a type of ion exchanger
• a cation exchange spacer CS 1 1 which is a type of ion exchanger
• a cation exchange non-woven fabric CF13 which is a kind of ion exchanger, is filled.
• cation exchange non-woven fabric CF 1 4 which is a type of ion exchanger
• cation exchange spacer CS 1 2 which is a type of ion exchanger
• a-on exchange which is a type of ion exchanger.
• Non-woven fabric AF 1 1 is filled.
• an ion exchange non-woven fabric AF12 which is a type of ion exchange material, an ion exchange material, an ion exchange spacer AS11, an ion exchange material Cation exchange non-woven fabric which is a kind
• a cation exchange non-woven fabric C which is a kind of ion exchanger
• anion exchange non-woven fabric AF 14 which is a type of ion exchanger
• an-on exchange spacer AS 12 which is a type of ion exchanger
• Non-woven fabric AF 15 is filled.
• Anion exchange non-woven fabric A F 16 5 and cation exchange non-woven fabric C F 1 1 which are kinds of ion exchangers are filled in the bipolar chamber 26 1.
• the structure from the electrode 2 0 4 of the bipolar chamber 2 6 1 to the cathode 2 0 3 of the cathode chamber 2 5 0 is the cation exchange non-woven fabric C F described above
• the structure is the same as the structure from 1 to 1 and the non-woven fabric A F 16 and thus the description is omitted here.
• the pure water as the pole solution is supplied from the pole solution tank 271 to the anode chamber 210, the bipolar chamber 261, the cathode chamber 250 and the cathode chamber 250.
• Effluent water from anode chamber 210, bipolar chamber 261, and cathode chamber 250 is circulated to polar fluid tank 271 to capture polar fluid.
• buffer water is supplied to the buffer chamber 220 from the buffer water tank 23.
• the effluent water from the buffer chamber 220 is supplied to the buffer water tank 5 2 3 3 and the raw water tank 2 8 4.
• a part of the outflowing water from the anode chamber 210, the bipolar chamber 261, and the cathode chamber 250 is mixed with the outflowing water from the buffer chamber 220.
• acid concentrated water is supplied from the acid concentrated water tank 25 to the acid concentration chamber 230.
• the effluent water from the acid concentration chamber 230 is supplied to the acid concentrated water tank 25 as well as 0 which is taken out as concentrated water.
• alkali concentrated water is supplied from the alkali concentrated water tank 277 to the alkali concentration chamber 2 3 1.
• Effluent water from the alkaline concentration chamber 2 31 is supplied to the alkaline concentrated water tank 2 7 7. .
• Raw water is supplied to the desalination chamber 240 from the raw water tank (284). Effluent water from demineralization chamber 240 is taken out as treated water.
• the bipolar chamber 26 Pure water is supplied to 1 in the same manner as in 5 anode chamber 2 10.
• the effluent water from the bipolar chamber 2 61 is also used as a feed water supply for the buffer water tank 2 3 3 similarly to the effluent water from the anode chamber 2 1 0.
• FIG. 11 is a schematic view showing a configuration of an electrodialysis apparatus according to a seventh embodiment of the present invention
• FIG. 12 is a schematic view showing an electrodialysis tank 301 of FIG.
• the electrodialysis tank 3 0 15 is obtained by omitting the acid supply chamber 2 6 0 provided on the cathode 2 0 0 3 side of the alkaline concentration chamber 2 3 1 in the electrodialysis tank according to the sixth embodiment described above. is there.
• Such a configuration can be used when concentrating cations such as ammonium ions which do not precipitate even with alkaline properties.
• FIG. 13 is a schematic view showing an electrodialysis tank 4010 of the electrodialysis apparatus according to the eighth embodiment of the present invention.
• the electrodialysis tank 401 has an anode chamber 201, a buffer chamber 220, an acid concentration chamber 230, a desalting chamber 240 and an alkali concentration chamber 231.
• the electrodialysis apparatus preferably performs constant current operation or constant voltage operation, and the current density is preferably 10 AZ dm 2 or less, and more preferably 3 AZ dm 2 or less.
• the thickness of the demineralization compartment and the concentration compartment is 1 to 10 mm, preferably 2 to 4 mm.
• the number and type of filling in each chamber can be set arbitrarily.
• the solution is supplied to each chamber such that the fluorine concentration in the anode chamber is less than 1 mg ZL and the fluorine concentration in the buffer chamber is less than 10 mg L.
• the material of the electrode white glaze, tantalum, niobium, diamond, SUS etc. It can be used.
• a base material such as titanium, nickel, monel, hastelloy, or inconel, in which platinum, gold, iridium oxide, or the like is plated can be used as an electrode.
• the shape of the electrode may be flat, or water-permeable and gas-permeable lath-net-like.
• the concentration of ions in the concentrated water is not particularly limited, but the concentration of the cation or anion is preferably in the range of 100 to 100 O mg / L.
• the concentration of the raw water is not particularly limited, but it is preferable that the concentration of the cation or anion is in the range of 5 to 50 mg / L.
• the concentration of treated water obtained in this case can be adjusted to a desired value by setting operating conditions such as the current value. For example, treated water having a cation or anion concentration in the range of 0.01 to 10 mg ZL can be obtained.
• the pure water supplied to the anode chamber, the cathode chamber and the bipolar chamber is not particularly limited, and any pure water produced by the method for producing pure water usually used by those skilled in the art can be used.
• pure water manufactured by a known technique such as RO (reverse osmosis membrane), ion exchange method, distillation method, electric desalting method or a combination thereof or ultrapure water obtained by further increasing the purity of the pure water is used can do.
• the amount of pure water supplied to the anode chamber is most preferably set so that the fluorine concentration in the anode chamber is less than 1 mg / L.
• thermoplastic resin base material may be a polyolefin-based polymer, for example, a kind of single fiber such as polyethylene or polypropylene, and the core and the sheath are composed of different polymers. It may be a composite fiber.
• a composite of core-sheath structure in which a core component is a core component, for example, a polymer other than that used as a sheath component and a liolefin polymer such as polyethylene as a sheath component Fiber is mentioned.
• An ion-exchange fiber material used for the above-mentioned purpose is excellent in ion-exchange capacity and can be produced with a uniform thickness since the composite fiber material to which the ion exchange group is introduced using radiation graft polymerization is excellent in ion exchange capacity and can be produced in uniform thickness.
• Examples of the form of the ion exchange »material include woven cloth and non-woven cloth.
• an ion exchanger in the form of a spacer member such as an oblique mesh it is possible to use a polyolefin-based polymer resin, for example, a polyethylene oblique mesh (net) widely used in an electrodialysis tank.
• a polyolefin-based polymer resin for example, a polyethylene oblique mesh (net) widely used in an electrodialysis tank.
• the ion exchange function is added to this using radiation graft polymerization method.
• the ion exchange capacity is excellent and the dispersibility of the water to be treated is high. It is preferable because it is excellent.
• the radiation graft polymerization method is a technique in which a polymer base material is irradiated with radiation to form a radical, and this is reacted with the monomer to introduce the monomer into the base material.
• radiation which can be used in the radiation graft polymerization method include radiation, radiation, radiation such as ⁇ -ray, ⁇ -ray, electron beam and ultraviolet ray, with preference given to gamma-ray and electron beam.
• a graft substrate is irradiated with radiation in advance, and then a pre-irradiation graft polymerization method in which a graft monomer is brought into contact and reacted, and a simultaneous irradiation graft in which radiation is irradiated in the coexistence of the substrate and the monomer.
• a polymerization method but any method can be used.
• a liquid phase graft polymerization method in which the polymerization is carried out while the substrate is immersed in the monomer solution by a method of contacting the monomer with the substrate
• a vapor phase graft polymerization method in which the substrate is brought into contact with the vapor of the monomer
• the substrate may be immersed in a monomer solution and then taken out of the monomer solution to carry out the reaction in the gas phase, such as an impregnated gas-phase polymerization method, but any method may be used.
• cation exchange groups or anion exchange groups can be used without particular limitation.
• cation exchange groups strongly acidic cation exchange groups such as sulfone groups, middle acid cation exchange groups such as phosphoric acid groups, weak acidity such as carboxyl groups, thione exchange groups, and anion exchange groups
• a weakly basic anion exchange group such as a tertiary amino group and a strongly basic anion exchange group such as a quaternary ammonium group can be used.
• an ion exchanger having both the above cation exchange group and anion exchange group can also be used.
• a functional group derived from sodium salt of iminodiacetic acid and its salt various amino acids such as, for example, a functional group derived from pheninolealanine, lysine, leucine, valine and proline and its sodium salt, An ion exchanger having a functional group derived from iminodiethanol or the like may be used.
• acrylic acid (AA c), methacrylic acid, sodium styrene sulfonate (SSS), sodium methallyl sulfonate, sodium aryl sulfonate, sodium vinyl sulfonate
• acrylic acid methacrylic acid
• SSS sodium styrene sulfonate
• VTAC butylbenzyltrimethyl ammonium chloride
• jetylaminoethyl methacrylate dimethylaminopropyl acrylamide and the like.
• a radiation graph using styrene styrene oleate as a monomer By carrying out polymerization, it is possible to introduce a sulfone group, which is a strongly acidic cation exchange group, directly into the substrate, and radiation graft polymerization is carried out using butylbenzyltrimethyl ammonium chloride as a monomer. Thus, it is possible to directly introduce a quaternary ammonium group which is a strongly basic anion exchange group into the base material.
• a monomer having a group convertible to an ion exchange group there may be mentioned Atari porto linole, acacrolein, bininole pyridine, styrene, chloromethinole styrene, glycidyl methacrylate (GMA) and the like.
• glycidyl methacrylate is introduced into a substrate by radiation graft polymerization, and then a sulfone group which is a strongly acidic thione exchange group is introduced into the substrate by reacting a sulfonating agent such as sodium sulfite, or After graft polymerization of chloromethylstyrene, the base material is immersed in a trimethylamine aqueous solution to carry out quaternary ammoniumization to introduce a quaternary ammonium group which is a strongly basic ban exchange group into the base material. can do.
• chloromethylstyrene is graft-polymerized to the base material
• a sulfide is reacted to form a sulfo-hum salt
• iminodiacetic acid sodium is reacted to introduce an iminodiacetic acid natrium group as a functional group to the material.
• chloromethylstyrene is graft-polymerized to the base material, and then the crocodile group is replaced with iodine, and then the iminodiacetic acid jetty ester is reacted to replace iodine with the iminodiacetic acid jetty ester group.
• sodium hydroxide to convert the ester group to a sodium salt
• a iminodiacetic acid sodium group can be introduced into the substrate as a functional group.
• ion exchange fiber materials in the form of non-woven fabrics or woven fabrics are particularly preferred.
• Fiber materials such as woven and non-woven fabrics have a very large surface area as compared to materials in the form of resin beads and crosslinks, so the amount of ion exchange groups introduced is large, and micropores inside beads like resin beads Or, since there are no ion exchange groups in the macropores and all ion exchange groups are disposed on the surface of the fiber, metal ions in the treated water are easily diffused in the vicinity of the ion exchange groups, It is adsorbed by ion exchange. Therefore, the ion exchange fiber material can further improve the metal ion removal and recovery efficiency.
• ion exchange resin beads can also be used.
• beads obtained by crosslinking polystyrene with divininolebenzene are used as a base resin, which is treated with a sulfonating agent such as sulfuric acid or chlorosulfonic acid to conduct sulfonation to introduce a sulfone group into the base material.
• a sulfonating agent such as sulfuric acid or chlorosulfonic acid
• Such production methods are well known, and examples of force-ion exchange resin beads produced by such a method include those commercially available under various trade names.
• a functional group a functional group derived from iminodiacetic acid and its sodium salt, a variety of amino acids, for example, a functional group derived from various amino acids, for example, fe / lealanine, lysine, leucine, parin and proline and its sodium salt, iminodiethanol
• resin beads having a functional group or the like may be used.
• ammonium ions and fluorine are removed from the wastewater to reduce the concentration of ammonium ions and fluorine. While producing treated water, it is possible to produce a first concentrated water with an increased concentration of fluorine and a second concentrated water with an increased concentration of ammonium ions.
• the waste water containing at least metal ions and fluorine is formed by the electrodialysis apparatus in each embodiment described above, the metal ions and fluorine are removed from the waste water to process the metal ions.
• a treated water having a reduced concentration of fluorine it is possible to produce a first concentrated water having an increased concentration of fluorine and a second concentrated water having an increased concentration of metal ions.
• the waste water may be decomposed by hydrogen peroxide and then supplied to the electrodialysis apparatus.
• the fluorine concentration of the waste water is preferably more than 1 mgzL and not more than 10, 00 O mg / L, and the fluorine concentration of the treated water is preferably less than 1 mgzL.
• the above-described electrodialysis apparatus can be combined with a fluorine recycling apparatus to constitute a fluorine treatment system.
• the fluorine-containing wastewater is treated with the above-mentioned electrodialysis apparatus, and the fluorine-concentrated water obtained by the electrodialysis apparatus is supplied to the fluorine recycling apparatus 500 and the wastewater is discharged.
• Fluorine can be recovered as crystals of calcium fluoride (C a F 2 ).
• a fluorine concentration measuring means for measuring the fluorine concentration of treated water, fluorine-concentrated water, or raw water, which is obtained by the electrodialysis apparatus according to the present invention for example, a conductivity meter for measuring the conductivity or the fluorine concentration Processing performance can be monitored by providing a fluorometer to measure. Also, by installing a flow meter on the raw water line or the treated water line, monitoring of the fluorine load Is possible.
• a fluorine concentration control means for controlling the fluorine concentration of treated water
• the fluorine concentration control means may be selected from raw water, treated water or concentrated water fluorine concentration, fluorine load or monitoring value of treatment performance. It is preferable to automatically adjust the amount of electrification 5 to the electrodialysis device, or to automatically adjust the flow rate of raw water by means of a flow adjustment valve. This enables automatic control of the fluorine concentration of treated water.
• water may be automatically supplied to the ion exchange resin layer. In this case, the stability of treated water quality can be further improved.
• the fluorine concentration measuring means may be detected by the fluorine concentration measuring means that the concentration of the fluorine-concentrated water is reduced to less than a predetermined value or that the concentration of the treated water is increased to a predetermined value or more.
• secondary treatment means for fluorine-concentrated water for example, a fluorine recycling apparatus (C a F 2 crystallizer, C a F 2 substitution apparatus for reacting fluorine with calcium carbonate to recover fluorine), Regardless of the type of coagulation / sedimentation apparatus and vacuum distillation apparatus), the performance of the apparatus for performing these secondary treatments can be stabilized by supplying the fluorine concentration of the fluorine-concentrated water as a stable concentration. it can.
• a line of fluorine-concentrated water based on the measurement value of a fluorine concentration measuring means such as a conductivity meter or a fluorine concentration meter attached to the line where the fluorine-concentrated water flows Or the amount of fluorine concentrated water withdrawn from the concentrated water tank (the amount of water supplied to the equipment for secondary treatment) or the amount of water supplied to the line of concentrated fluorine water or the concentrated water tank Good.
• the amount of electrification in the electrodialysis apparatus or the flow rate of the raw water may be automatically adjusted.
• the electrodialysis apparatus may be combined with a C a F 2 displacement apparatus 501 as a fluorine recycling apparatus to combine fluorine in waste water with C a F 2
• a fluorination system that recovers as crystals.
• a means for measuring the PH value or peak value (acidity value) of the fluorine-concentrated water obtained by the above-mentioned electrodialysis apparatus is provided, and it is adjusted by injecting an acid or alkaline so that this value becomes appropriate. It is preferable to provide p H value or a value adjustment means 5 0 2. This makes it possible to prevent the dissolution of the calcium carbonate particles used in the CaF 2 displacement device 51. In addition, the purity of the obtained C a F 2 crystal is increased.
• the abatement waste water contains hydrochloric acid, sulfuric acid, nitric acid, etc. in addition to hydrofluoric acid.
• Acids other than hydrofluoric acid have the property of dissolving calcium carbonate.
• these acids may be concentrated together with hydrofluoric acid. Therefore, for example, even in the case of fluorine-concentrated water of abatement system waste water (abatement waste water), the pH value is increased by the above-mentioned pH value or ⁇ value adjustment means 502, or acidity is increased. It is possible to prevent the dissolution of calcium carbonate by lowering the The fluorine contained in the residual liquid discharged from the C a F 2 displacement device 501 should be separated and removed as sludge by the coagulation and sedimentation device 54.
• the electrodialysis apparatus can set the operating conditions so that the fluorine concentration of the treated water falls below the effluent standard value of 8 mg-FZ L, it is necessary to further coagulate and precipitate the treated water. Absent. Therefore, it is possible to discharge or reuse water without the need for a large-scale flocculation treatment facility. For example, as shown in Figure 15, by reusing the treated water discharged from the electrodialysis apparatus as raw water for the pure water production system 505, the amount of water used in the facility (the amount of water purchased) can be reduced. It becomes possible.
• the fluorine in the waste water can be reduced to C a F by combining the electrodialysis device according to the present invention with a C a F 2 crystallizer as a fluorine reclamation device. It is possible to construct a fluorine treatment system which is recovered as two crystals. In this case, the fluorine-enriched water can be adjusted to ⁇ or acidity suitable for crystallization by ⁇ > H value or ⁇ value adjustment means 502.
• a calcium compound addition amount adjustment step for adjusting the addition amount of the calcium compound (for example, calcium chloride and calcium hydroxide) to be added in the CaF 2 crystallization apparatus 506 is provided,
• the addition amount of the calcium compound can be adjusted to be appropriate according to the measurement value obtained by the fluorine concentration measurement means of water. By this, even when fluctuation of fluorine concentration in the fluorine-concentrated water occurs, the addition amount of the cal and hum compounds can be adjusted, and the purity and grain size of the obtained C a F 2 crystal can be adjusted. It is possible to make the diameter as desired.
• the fluorine contained in the residual liquid discharged from the CaF 2 crystallizer 506 should be separated and removed as sludge by the coagulating and settling unit 504.
• the electrodialysis apparatus is combined with a coagulation / sedimentation treatment apparatus 500 for carrying out the coagulation / sedimentation treatment of water containing at least a part of the fluorine-concentrated water.
• Fluorine in concentrated water can also be separated and removed as C a F 2 containing sludge.
• the concentration of fluorine can be increased to a concentration suitable for the aggregation and precipitation treatment, and
• the amount of fluorine-concentrated water is greater than the amount of drainage water Since the amount is small, the amount of flocculant added (for example, the amount used per day) can be reduced as compared to the case of coagulating and settling fluorine-containing wastewater as it is, and solid-liquid treatment in a small-scale treatment facility It becomes possible to separate. For example, in the case of concentrating the fluorine in the fluorine-containing wastewater 10 times, it is possible to reduce the amount of treated water of the coagulation / sedimentation treatment apparatus 500 to 10: 1.
• the fluorine-containing wastewater contains solids such as suspended matter and powder
• An example of such drainage is abatement drainage.
• a silica-containing gas is also introduced in addition to the PFC gas, so a large amount of silica powder is generated after the gas decomposition process by the abatement system, and this is mixed into the waste water.
• abatement devices include those that generate waste water at the time of operation, such as combustion type and calorific type.
• a fluorine-containing wastewater is introduced into the electrodialysis apparatus through solid-liquid separation means such as sedimentation separation tank 550. Fluorination systems are preferred.
• the solids contained in the drainage are settled 5 and separated as sludge layer 52.
• the supernatant water 54 has been introduced into the electrodialysis unit. In this case, since the supernatant water 54 may contain suspended solids in a small amount, it may be further introduced into the electrodialysis apparatus through a security filter.
• any known means for example, a known membrane (filter) separation means, centrifugal separation means, etc. can be used in addition to the sedimentation separation tank 550.
• a sedimentation tank 550 it is preferable to use a sedimentation tank 550 as a solid-liquid separation means.
• a plurality of partition plates 5 5 6 are installed for the purpose of preventing the outflow of the sludge 5 5 2 to the rear stage of the sludge 5 2 and for detouring the water flow.
• the means for separating the solid substance of coarse particles for example, a solid-liquid separation tank or a filter
• the solid-liquid separation means may be provided on the latter stage side. It is desirable to provide separately.
• the treated water of the electrodialysis apparatus can be circulated as the feed water of the abatement system 0 5 5 8 because the fluorine concentration is sufficiently reduced, and the water consumption can also be reduced.
• drainage of part of the electrodialysis system's treated water also makes it possible to prevent accumulation of trace substances in the system.
• the fluorine-containing wastewater contains organic substances such as surfactants, these organic substances should be Separation and concentration makes it possible to separate and concentrate fluorine from such waste water.
• waste water include waste water derived from hydrofluoric acid or purified hydrofluoric acid (NH 4 F) containing a surfactant, and an abatement device to which industrial water containing a trace amount of organic matter is supplied. Drainage can be mentioned.
• a fluorine treatment system in which fluorine-containing wastewater is introduced into the electrodialysis apparatus through the organic substance separation means such as the activated carbon adsorption layer 560 is preferable.
• the organic matter separation means in addition to the activated carbon adsorption layer, known organic matter separation means such as membrane separation means can be used. It goes without saying that known organic matter decomposition means can also be used.
• the concentration of fluorine can be further easily increased to 1 to 10% or more even when the concentration of fluorine-concentrated water is 10000 to L 1000 O mg ZL. It can be used for stainless steel pickling applications in Japan, etc., and its reuse applications will be expanded.
• Cation exchange non-woven fabric The base material is polyethylene non-woven fabric.
• the functional group is a sulfone group. Created by graft polymerization.
• the base material is a polyethylene nonwoven fabric.
• Functional group is quaternary ammonium group. Created by graft polymerization.
• 'Cation exchange spacer base material made of polyethylene diagonal mesh.
• the functional group is a sulfone group. Created by graft polymerization.
• Anion replacement spacer The base material is a polyethylene diagonal mesh. Functional group is quaternary ammonium group. Created by graft polymerization.
• the operating conditions of the electrodialysis apparatus are as follows.
• the fluorine concentration in the concentration chamber is as high as 120 Omg-FZL
• the concentration in the buffer chamber is 5 to 1 Omg-FZL
• the concentration in the anode chamber is less than lmg-FZL
• the fluorine concentration in the anode chamber is It was maintained at a very low value. No corrosion of the anode was observed.
• the fluorine concentration in the cathode chamber was also less than 1 mg-F / L, and was very low. No corrosion of the cathode was also observed.
• the voltage between contacts was about 1 OV.
• a fluorine concentration test was conducted for fluorine-containing wastewater (60 mg-FZ L) using the electrodialysis apparatus shown in FIGS. 3 to 5.
• the specifications of the electrodialysis device are as follows.
• Anion exchange membrane Astomune ⁇ 3 ⁇ 4 Neosepta AHA
• the base material is polyethylene non-woven fabric.
• the functional group is a sulfone group. Created by graft polymerization.
• Ayuon exchange non-woven fabric The base material is polyethylene non-woven fabric. Functional group is quaternary ammonium group. Created by graft polymerization.
• Cation exchange spacer The base material is a polyethylene diagonal mesh.
• the functional group is a sulfone group. Created by graft polymerization.
• the base material is a polyethylene diagonal mesh.
• Functional group is quaternary ammonium group. Created by graft polymerization.
• Anode Titanium plated with platinum. Las net shape.
• the operating conditions of the electrodialysis apparatus are as follows.
• the concentration of fluorine in the concentration chamber is as high as about 120 Omg-F / L
• the concentration in the buffer chamber is 5 to 1 Omg-FZL
• the concentration in the anode chamber is less than 1 mg-F / L.
• the fluorine concentration in the chamber was maintained at a very low value.
• the fluorine concentration in the cathode chamber was less than lmg-FZL in any of the electrodialysis devices, and was extremely low. No corrosion of the anode was observed, nor corrosion of the cathode.
• a fluorine concentration test was conducted for abated drainage (6 Omg-F / L) containing 1 Omg ZL of calcium ion and 3 mg / L of organic matter (as total organic carbon).
• the abatement system was configured to abate the Si-containing gas and the PFC gas by the combustion process.
• the abatement waste water in this example used supernatant water after settling and separating solid contained in the abatement waste water by a settling separation tank.
• calcium ions are concentrated as hydrochlorides in a room (alkali-concentrated room) other than hydrofluoric acid.
• two electrodialysis cells are combined between one set of pressure plates, and a bipolar chamber is provided at the boundary. Similar to the anode chamber, pure water is supplied to the bipolar chamber, and the effluent water from the bipolar chamber is used as buffer water. A portion of the effluent from the buffer chamber is mixed with the raw water.
• the specifications of the electrodialysis device are as follows.
• Neosepta CMB made by Astom Co., Ltd.
• the base material is polyethylene non-woven fabric.
• the functional group is a sulfone group. Created by graft polymerization.
• Anion exchange nonwoven fabric The base material is a polyethylene nonwoven fabric. Functional group is quaternary ammonium group. Created by graft polymerization.
• Cation exchange spacer The base material is a polyethylene diagonal mesh.
• the functional group is a sulfone group. Created by graft polymerization.
• the base material is a polyethylene diagonal mesh.
• Functional group is quaternary ammonium group. Created by graft polymerization.
• Activated carbon granular activated carbon packed bed
• the operating conditions of the electrodialysis apparatus are as follows.
• the fluorine concentration in the acid concentration chamber was as high as about 120 Omg-F / L
• the concentration in the buffer chamber was as low as 5 to 1 Omg-FZL.
• the concentration in the anode chamber and the bipolar chamber was less than lmg-FZL, and the fluorine concentration in the anode chamber and the bipolar chamber was maintained at a very low value.
• the fluorine concentration in the cathode chamber was less than 1 mg-FZL, and was extremely low. No corrosion was found in the anode and the electrodes in the bipolar chamber, and no corrosion was found in the cathode.
• a fluorine concentration test was conducted for fluorine-containing wastewater (6 Omg-F / L) containing 4 Omg ZL of ammonium ions.
• ammonium ions are concentrated in a room (alkaline enrichment room) separate from hydrofluoric acid.
• two electrodialysis cells are combined between one set of pressure plates, and a bipolar chamber is provided at the boundary. Pure water is supplied to the bipolar chamber in the same way as the anode chamber, and the effluent water from the bipolar chamber is used as buffer water. A portion of the effluent from the puff chamber is supplied to the acid concentration tank.
• the specifications of the electrodialysis apparatus are as follows.
• Anion exchange membrane Astom Neosepta AHA
• the base material is a polyethylene nonwoven fabric.
• the functional group is a sulfone group. Created by graft polymerization.
• Anion exchange non-woven fabric The base material is polyethylene non-woven fabric.
• Functional group is quaternary ammonium group. Created by graft polymerization.
• the base material is a polyethylene diagonal hole network.
• the functional group is a sulfone group. Created by graft polymerization.
• the base material is a polyethylene diagonal mesh.
• Functional group is quaternary ammonium group. Created by graft polymerization.
• the conditions of the electrodialysis apparatus are as follows.
• Circulating water volume of acid or alkali concentrated water 500 ml / min
• fluorine ions were concentrated as hydrofluoric acid, and although the fluorine concentration was as high as about 1 200 mg-FZL, the concentration in the buffer chamber was as low as 5 to 1 Omg-FZL. Also, the concentration in the anode chamber and the bipolar chamber was less than 1 mg-FZL, and the fluorine concentration in the anode chamber and the bipolar chamber was maintained at a very low value. Also, the fluorine concentration in the cathode chamber was less than 1 mg ⁇ F / L, which was extremely low. In the alkaline concentration chamber, ammonium ions were concentrated as ammonia water at a concentration of about 100 Omg ZL ( Ammonium ions and fluoride ions could be separately concentrated. Corrosion of the electrode of the anode and the bipolar chamber was also recognized. And no corrosion of the cathode was observed.
• fluorine-containing wastewater can be electrodeposited stably without electrode corrosion.
• the fluorine concentration of treated water after electrodialysis of fluorine-containing waste water is as low as less than 1 mg ZL, and the treated water can be reused.
• metal hydroxide sludge Fluorine-enriched water from which metal ions are separated can be obtained without forming
• calcium fluoride (C a F 2 ) can be recovered by supplying fluorine-concentrated water obtained by electrodialysis of fluorine-containing waste water to a fluorine recycling device.
• calcium fluoride (C a) can be obtained by supplying fluorine-enriched water in which ammonium ions are separated from fluorine-containing wastewater containing ammonium ions to facilitate fluorine recycling to a fluorine recycling device. It can be recovered as F 2 ).
• the electrodialysis according to the present invention is to treat waste water which is treated water of a fluorine recycling apparatus which recovers fluorine in an aqueous solution as calcium fluoride (C a F 2 ) or waste water prepared by treating the waste water.
• the fluorine recycling rate of the fluorine recycling apparatus that is, the recovery rate as calcium fluoride crystals can be improved. This is because, in the fluorine recycling apparatus, about 10 to 20% of the received fluorine is discharged as dilute hydrofluoric acid drainage, but the fluorine contained in this is used in the electrodialysis apparatus according to the present invention. By concentrating it, it can be used again as raw water for fluorine recycling equipment.
• the fluorine recycling device In the case of dilute hydrofluoric acid wastewater, the fluorine recycling device is difficult to recycle, that is, it is difficult to recover calcium fluoride crystals, and in the case of concentrated hydrofluoric acid wastewater, sufficient performance is obtained. It is because it has the property of exerting Industrial applicability
• the present invention is suitably used for an electrodialysis apparatus for treating a liquid containing fluorine or the like.

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• 2005
  • 2005-06-16 JP JP2005176073A patent/JP2007014827A/ja active Pending
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