WO2003097536A1 - Demineralisateur electrique - Google Patents
Demineralisateur electrique Download PDFInfo
- Publication number
- WO2003097536A1 WO2003097536A1 PCT/JP2003/006065 JP0306065W WO03097536A1 WO 2003097536 A1 WO2003097536 A1 WO 2003097536A1 JP 0306065 W JP0306065 W JP 0306065W WO 03097536 A1 WO03097536 A1 WO 03097536A1
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- WIPO (PCT)
- Prior art keywords
- chamber
- anion
- cation
- exchange membrane
- desalination
- Prior art date
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Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—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
-
- 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
-
- 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
- B01D61/52—Accessories; Auxiliary operation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/08—Prevention of membrane fouling or of concentration polarisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/02—Column or bed processes
- B01J47/06—Column or bed processes during which the ion-exchange material is subjected to a physical treatment, e.g. heat, electric current, irradiation or vibration
- B01J47/08—Column or bed processes during which the ion-exchange material is subjected to a physical treatment, e.g. heat, electric current, irradiation or vibration subjected to a direct electric current
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2321/00—Details relating to membrane cleaning, regeneration, sterilization or to the prevention of fouling
- B01D2321/16—Use of chemical agents
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F2201/46115—Electrolytic cell with membranes or diaphragms
-
- 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
- C02F2201/46185—Recycling the cathodic or anodic feed
Definitions
- the present invention relates to an improvement relating to a so-called electric desalination apparatus, and relates to an electric desalination apparatus having a completely arranged structure, a new structure, and a chamber arrangement structure.
- an apparatus in which an ion exchange membrane is arranged between electrodes to constitute a plurality of chambers is called an “electrodialyzer”, and each chamber formed by filling an ion exchanger is called an “electrodialyzer”.
- the term “electrical disassembly” is used in the sense including the concept of the “electrodialysis device” described above. Background art
- the electric ⁇ m position means that a cation exchange membrane and an anion exchange membrane are arranged between the positive and negative electrodes to form a concentration / desalination chamber, and a potential gradient is used as a driving source in the liquid to be treated in the desalination chamber.
- the ion components in the liquid are removed by moving and separating the ions through the ion exchange membrane into the concentration chamber.
- Fig. 1 shows the concept of a conventional typical electric desalination unit.
- the anion exchange membrane A and the cation exchange membrane c are alternately arranged between m (1) and the anode (+), and the desalination chamber and the concentration chamber are alternately arranged. Is formed.
- the desalting chamber and the concentrating chamber are filled with an ion exchanger, which promotes the movement of ions in the chamber.
- the sections in contact with the anode and the cathode at both ends are generally called an anode chamber and a cathode chamber, and perform a function of transmitting and receiving electrons of a current applied by a DC current.
- water is generally supplied to the desalination room, such as a water bath (3 ⁇ 4 J sickle) to be treated, and also to the enrichment room and the bipolar room.
- the water supplied to the concentrating chamber is referred to as concentrated water
- the saltwater supplied to the desalting chamber is referred to as treated water.
- a cation exchange material such as a nonwoven fabric
- an Ayuon exchange material is placed facing the anion exchange membrane side in the desalting chamber.
- a spacer or an ion conductive spacer provided with ionic conductivity between these ion exchange materials, or an ion conductive space provided with a spacer or ion conductive material in the enrichment chamber A method of filling the substrate has also been proposed (see PCT / JP99 / 01391 International Publication W099 / 48820).
- H + ions and OH- ions generated by the hydrolysis are used for regeneration only in the desalination chamber where these ions are generated.
- Most of the H + and 9H ions, which are considered to be about 90%, are not used for the regeneration of the ion exchanger but move through the ion exchange membrane into the adjacent enrichment chamber (Fig. 1).
- recombination occurred in the enrichment chamber with H + and OH-ions that had moved from the desalination chambers on both sides.
- a large amount of energy is required to generate water lysis, and despite the fact that this is one of the factors that increase the operating miE of electric equipment, most of the energy used for the ⁇ solution is concentrated. At present, it was wasted simply because it was converted to heat generated by the recombination of ⁇ + ions and ⁇ ions in the room.
- the desalting chamber and the concentration chamber are alternately arranged, for example, calcium ions and carbonate ions react in the concentration chamber to generate calcium carbonate, which is deposited on the scale. That was the cause.
- the desalination chamber is «(heterogeneous ion exchanger In ⁇ ⁇ , water decomposition and recombination (recombination of H + ions and OH- ions) occurred in each part of the desalting chamber, and heat was generated.
- Increasing the thickness and number of the chambers increases the probability of hydrolysis and recombination, which may be due to the fact that much of the electrical energy was converted to heat.
- hydrolysis generation ⁇ can be defined as a potential difference between a cation exchanger and an aion exchanger in a desalting chamber. That is, in the conventional multi-pass structure (a system in which the water to be treated is supplied in series to each desalting chamber), the tendency of the occurrence of water decomposition increases, and the desalination in which the treated water is supplied first It was found that the occurrence of water lysis in the room (first desalination room) was the highest. this is,
- the present inventors have studied various factors that affect the conviction of electricity, and found that the ratio of ⁇ E required to generate a 7_k solution and the 3 ⁇ 4E required to conduct ions (de-) Focusing on the fact that the ratio of mi £ in the salt room) is about 20: 1, and that the effective utilization of H + and OH— in the current electrical system is only about 10%.
- H + ions and OH- ions generated by the hydrolysis effectively without recombining them immediately the whole electric device could be used.
- the inventors of the present invention have found that the configuration of a new electric arrangement having a powerful room, which has never been considered in the conventional electric equipment, can greatly increase the operation mi £. It has led to it.
- one embodiment of the present invention is an electric device in which a plurality of chambers are formed by arranging a cation exchange membrane and an ion-exchange membrane between an anode and a cathode;
- a water decomposition chamber is defined by the membrane and the cation exchange membrane on the cathode side.
- An anion desalination chamber sandwiched by an aion exchange membrane is disposed on the anode side of the water decomposition chamber, and a cation is disposed on the cathode side of the water decomposition chamber.
- a cation desalting chamber sandwiched between exchange membranes, wherein the electricity is characterized by: BRIEF DESCRIPTION OF THE FIGURES
- FIG. 1 is a schematic explanatory view of a conventional electric desalination apparatus.
- FIG. 2 is a schematic explanatory view of an electric disconnection device according to one embodiment of the present invention.
- FIG. 3 is a schematic explanatory diagram of an electric device according to another embodiment of the present invention.
- FIG. 4 is a schematic explanatory view of an electric detachment device according to still another embodiment of the present invention.
- FIG. 5 is a schematic explanatory view of an electric disconnection device according to still another embodiment of the present invention.
- FIG. 6 is a cell configuration diagram of an electric m-type device according to one embodiment of the present invention.
- FIG. 5 is a schematic explanatory view of a conventional multi-pass type electric desalination apparatus used in the comparative example.
- FIG. 2 is a conceptual diagram illustrating a configuration example of an electric device according to one embodiment of the present invention.
- a water dissolution chamber defined by an anion exchange membrane on the anode side and a cation exchange membrane on the cathode side.
- an aion desalination chamber sandwiched by anion exchange membranes
- a cation desalination chamber sandwiched by cation exchange membranes.
- the chamber outside the desalination chamber functions as a concentrating chamber that receives ions coming through the ion exchange membrane.
- each of the ⁇ dissolution chamber, the desalination chamber and the concentration chamber is filled with an ion exchanger. 7 As shown in Fig. 2, it is preferable to fill the cation exchange membrane with a cation exchanger and the anion exchange membrane with an anion exchanger, as shown in Fig. 2! / ⁇ . It is preferable that the anion desalting chamber is filled with an anion exchanger and the cation desalting chamber is filled with a cation exchanger.
- the anion exchange membrane is filled with an anion exchanger, and in contact with the anode, the cation exchanger is filled.
- the cation exchange membrane is preferably filled. It is preferable that the cation exchanger is filled with the cation exchanger and the cation exchanger is filled with the cathode. However, for example, even if a small amount of a cation exchanger is mixed in the anion exchanger filled in the anion desalting chamber, or a small amount of anion exchanger is mixed in the force thione exchanger packed in the cation desalting chamber. Good.
- water is introduced into the enrichment room, and STK to be treated is introduced into the aeon demineralization room.
- RO treatment «substantial impurities are low! / ⁇
- water V ⁇ It is preferable to introduce water V ⁇ .
- the water that has passed through the Anion desalination chamber is then introduced into the Kachion desalination chamber, and finally into the water splitting chamber. Also, the water discharged from the enrichment chamber
- the processing 11 the first Anion desalting, ⁇ in solution - one (e.g., S 0 4 2 -, C 1- etc.) is adsorbed more solid phase ion exchange, the solid unto bow I to the anode It moves through the phase and passes through the aeon exchange membrane to the adjacent concentrator.
- ⁇ in solution - one e.g., S 0 4 2 -, C 1- etc.
- the processing azK is introduced into the cation depletion chamber, cation (e.g., C a 2 +, N a + , etc.) of the dissolved solution is adsorbed to the solid phase by force S ion exchange, bows I to Fu ⁇ To move through the solid phase and pass through the cation exchange membrane to the adjacent concentrating chamber.
- cation e.g., C a 2 +, N a + , etc.
- the effluent from which the impurity ions have been removed is finally introduced into the sewage treatment chamber to further remove the impurity ions remaining in the sewage (that is, the sewage treatment chamber also functions as a final desalination chamber).
- water dissociation occurs in the fibers of the different ion exchangers, and H + and OH— are generated.
- the generated H + and OH-1 regenerate the ion exchanger in the water decomposition chamber, and the remaining H + and OH-1 that are not used for the regeneration of the ion exchanger in the water decomposition chamber are used to define the 7j decomposition chamber.
- the thione exchange membrane or ⁇ The deionization chamber is moved to a deionization chamber or anion deionization chamber, and the ion exchanger in each deionization chamber is regenerated.
- the H + and OH that have not been consumed in each demineralization chamber further move through the ion exchange membrane to the outer chamber (concentration chamber in the structure shown in Fig. 2 ).
- H + and OH-1 generated in the water splitting chamber move to the adjacent desalination chamber and regenerate the ion exchanger inside the chamber without being limited to the water splitting chamber alone, so the effective use of H + and OH— I can do it.
- FIG. 2 shows an embodiment in which the target is first supplied to the anion desalination chamber and then to the cation desalination chamber.
- the cation desalination is performed according to the water quality of the target a *.
- the anion desalination chamber For example, if the treated water contains a relatively large amount of calcium and the precipitation of calcium scale in the room or piping may be a problem, the treated material should be decatated first. It is preferred to feed the salt room to remove calcium ions in the treatment 37.
- a plurality of ayuon desalting chambers and a plurality of cation desalting chambers can be continuously arranged.
- Fig. 3 shows the concept of electric hardening in a powerful mode.
- the water separation chamber is defined by the anion-exchange membrane A on the anode side and the cation-exchange membrane C on the jelly side, and the anion exchange membrane is defined on the positive side of the K-separation chamber.
- a plurality of cation exchange membranes are arranged continuously by arranging a plurality of cation exchange membranes continuously on the cathode side of the water decomposition chamber.
- the outermost chamber functions as a concentrating chamber that receives ions moving from the adjacent desalting chamber.
- the anion exchanger In the water dissolution chamber, it is preferable to fill the anion exchanger with the anion exchanger and the thione exchanger with the force thione exchanger.
- the anion desalting chamber is filled with an anion exchanger and the cation desalting chamber is filled with a cation exchanger.
- the concentration chamber on the anode side it is preferable to fill the aion exchanger in contact with the anion exchange membrane, and to fill the cation exchanger in contact with the anode, preferably in the concentration chamber on the cathode side.
- the cation exchange membrane is filled with a force thione exchanger and the cathode is filled with an anion exchanger.
- the STR to be treated is supplied in series from the outer (ie, the side close to the electrode) desalination chamber, and finally the STR is supplied. Preferably, it is supplied to the chamber.
- the treatment is first supplied to the ion-desalting chamber (1), and then to the cation desalination chamber (1).
- anions such as so 4 2 — and C 1 — in the water to be treated reach the solid phase by ion exchange, are pulled by the anode, and move in the solid phase, and the anion 3 ⁇ 4m After passing through the membrane, they move one after another into the anion desalination chamber, and are finally introduced into the concentration chamber on the anode side and discharged as concentrated water.
- each cation depletion chamber C a 2 + in the processing ®, N a + a which cations are adsorbed to the solid phase by ion exchange, to move the solid phase medium is attracted to the cathode, a cation exchange membrane After passing through, it moves to the adjacent cation desalination chamber one after another, and finally is introduced into the enrichment chamber on the syrup side, and is discharged as concentrated water.
- water with extremely low residual ion concentration in the water passing through each desalting chamber is supplied to the 7 demolition chamber, and a small amount of remaining ions is removed (function as the final desalting chamber).
- Heterogeneous Water dissociation occurs in the parasite between the heat exchangers, and H + and OH— are generated.
- the H + and OH— generated in the water decomposition chamber move to the adjacent desalination chamber through the force cation exchange membrane and the aion exchange membrane, respectively, and regenerate the ion exchanger in each desalination chamber, Excess H + and OH— that were not used for regeneration move one after another to the desalination chamber.
- a plurality of anion desalination chambers and a cation desalination chamber are provided in a water digestion chamber that is a water splitting generation site. Since water containing extremely few impurity ions is supplied through the chamber, ions are adsorbed on the functional groups to form a salt form, and an increase in the voltage of water decomposition due to adsorption of humic substances can be suppressed. .
- H + and OH ⁇ generated in the water disintegration chamber are not limited to the water disintegration chamber but move one after another to the adjacent ffi room and regenerate the ion exchanger in the room. And OH— can be used very effectively for the regeneration of ion exchangers without recombination.
- a liquid in which the SK to be treated is first supplied to the Ayuon desalination chamber and then supplied to the cation desalination chamber.
- a distribution method in which the water to be treated is first supplied to the cation desalination chamber and then supplied to the anion deionization chamber may be adopted according to the quality of the water to be treated.
- the concentrated water recovered from each enrichment chamber is directly discharged outside the system.For example, the concentrated water discharged from the enrichment chamber on the anode side is concentrated on the It can also be introduced into the room. Independently flowing the wastewater from each concentrator has the advantage of suppressing the generation of calcium carbonate and preventing the generation of scale.
- the names of the chambers are, from the anode side, the anion desalination chamber (1), the anion desalination chamber (2), the water decomposition chamber, the cation desalination chamber (2), and the cation desalination chamber (1)).
- the treated water is supplied in the order of the cation desalination chamber (1) ⁇ the cation desalination chamber (2) ⁇ the water angle early chamber ⁇ ⁇ the ayuon desalination chamber (2) ⁇ the anion desalination chamber (1), or Conversely, it can flow in the order of Anion desalination room (1) ⁇ Aion desalination room (2) ⁇ Water dissolution room ⁇ Cation desalination room (2) ⁇ Cation desalination room (1).
- A-on desalination room (1) ⁇ Cation desalination room (1) ⁇ Water decomposition room ⁇ Agion desalination room (2) ⁇ Cation desalination room (2); Cation desalination room (1) ⁇ A -On desalination room (1) ⁇ 7_k dissolution room ⁇ cation desalination room (2) ⁇ anion desalination room (2);
- a cation exchange membrane is arranged on the most anode side, and an ion exchange membrane is arranged on the most cathode side.
- An anode compartment defined by: an aion enrichment compartment, adjacent to the anode compartment, defined by a cation exchange membrane on the anode side and a rion-exchange membrane on the injection side; A cathode compartment defined by a membrane; and a cation enrichment compartment defined by a cation exchange membrane on the positive side and an anion exchange membrane on the negative side adjacent to the Pt® chamber.
- pole chambers are formed outside (more electrode side) of the enrichment chamber, and Water is supplied to prevent precipitation components from flowing into the electrode chamber and suppress the accumulation of scale ions on the electrodes due to the accumulation of high-concentration ions in the section in contact with the electrodes. can do.
- the pole chamber can be formed only on one electrode side, and a strong form is also included in the present invention.
- FIG. 4 a force is shown to supply the polar water that has passed through the polar chamber to the adjacent concentrating chamber.
- the polar water that has passed through the anode chamber is then supplied to the cathode chamber, and
- the RO treatment Szk may be supplied to the enrichment chamber on the side, and the concentrated water that has passed through the enrichment chamber may be then supplied to the enrichment chamber on the cathode side.
- a plurality of 7 solution chambers are formed, and anion desalination sandwiched between the anode side by an ion exchange membrane is formed adjacent to each of the water chambers.
- At least one or more cation desalting chambers sandwiched between a cation exchange membrane on the chamber and the cathode side can be arranged, and such a configuration is also included in the scope of the present invention.
- FIG. 5 shows a specific example of such an electric arrangement.
- the electric desalination apparatus shown in Fig. 5 has two water digestion chambers (final desalination chambers) defined by an anion exchange membrane on the anode side and a cation exchange membrane on the cathode side.
- Examples of the ion exchange membrane used to constitute the electric de-wooling device according to the present invention include, for example, NEOSEPTA CMX (Tokuyama) as a cation exchange membrane, and NEOSEPTA AMX (Tokuyama) as an anion exchange membrane. ) Can be used.
- NEOSEPTA CMX Tokuyama
- NEOSEPTA AMX Tokuyama
- the electric deocclusion apparatus in the zk dissolution chamber, the desalination chamber, the concentration chamber, and in the apparatus of the embodiment shown in FIG. Prefer to place! ⁇ .
- an anion exchanger and a cation exchanger can be mixed and filled in the thawing chamber (“filling”).
- the movement of ions in these chambers can be promoted.
- desalination is performed only on one of anion and cation.
- the anion exchanger is charged into the cation desalting chamber, the cation exchanger is preferably charged.
- the anion exchange membrane is filled with an anion exchanger and the cation exchange membrane is filled with a cation exchanger.
- the electric water heater having a configuration as shown in FIG. 4 by filling the pole room with an ion exchanger, pure water having a very low ion concentration can be introduced into the pole room as This is advantageous for prevention of scale.
- the ion chamber with the ion exchanger it is preferable to fill the anode chamber with a cation exchanger and the cathode chamber with an ion exchanger.
- examples of the ion exchanger that can be filled in at least one of the dissolving chamber, the desalting chamber, the concentrating chamber, and the polar chamber include ion exchange! ⁇ Fat beads can be used.
- the ion-exchange beads that can be used for such a purpose beads known in the art, such as beads obtained by cross-linking polystyrene with divininolene benzene, are used as the base resin! Can be used.
- the above base resin may be made of sulfuric acid such as sulfuric acid.
- a strongly acidic cation exchange resin is obtained.
- a strongly basic anion exchange resin having a quaternary ammonium group In tj ⁇ , a tertiary amine such as trimethinoleamine is reacted after the methylated resin is subjected to a co-methylation treatment. Then, the quaternary ammonium is obtained to obtain a strong: ⁇ S-anion.
- ion-exchange beads produced by such a method include, for example, Dowex M0N0SPHERE 650C (Dow Kemi Canole), Amberlite IR-120B (Rohm & Haas), Dowex M0N0SPHERE 550A (Dow Kemikanore),
- a cation exchange pheasant material and an anion exchange maintenance material can be used as an ion exchanger to be filled in at least one of the seven deionization chambers, the desalination chamber, and the pole chamber.
- the ion exchange material used for such a purpose a material obtained by introducing an ion exchange group into a polymer fiber base material by a graft polymerization method is preferably used.
- the graft made of a polymer fiber may be a polyolefin-based polymer, for example, a type of single fiber such as polyethylene-polypropylene, or a polymer whose shaft core and sheath are different.
- composites that can be used »Examples of uru are polyolefin-based polymers, for example, a composite of a core-sheath structure using polyethylene as a sheath component and a polymer other than those used as the sheath component, such as polypropylene as a core component.
- An ion-exchange group used in the present invention is obtained by introducing an ion-exchange group into such a composite fiber material by using a radiation graft polymerization method, since the ion-exchange group is excellent in ion-exchange ability and can be manufactured to have a uniform thickness. Is preferred.
- Examples of the form of the ion exchange fiber material include a woven fabric and a nonwoven fabric.
- At least one of the water decomposition chamber, the desalination chamber, and the pole chamber is filled with the ion-exchange fiber material: ⁇ is a combination of the ion-exchange fiber material and the spacer. It is preferable to secure the flow path of the treatment target 3 or @ _ ⁇ by filling.
- the ion exchange material is combined with an ion-conducting spacer having an ion-gripping ability to fill at least one of a water dissolution chamber, a desalination chamber, and an electrode chamber.
- the cation exchange membrane side is filled with the cation exchange fiber material
- the anion exchange membrane side is filled with the anion exchange fiber TOP material
- the cation exchange fiber material side is interposed between the two materials. It is preferable to fill a cation conductive spacer, and to use an anion-conducting spacer for the ⁇ -ion exchange ⁇ material K rule.
- an anion conductive spacer with anion exchange function is sandwiched between two pieces of anion exchange material, and filled in the force-ion desalination chamber.
- the anion exchange membrane side is preferably used in the cathode chamber. It is preferable to fill the side with anion exchange material and the cathode side with an anion conductive spacer.
- the anion exchange membrane side is filled with an anion conductive spacer and the anode side is filled with a cation conductive spacer in the enrichment chamber on the anode side.
- the cation exchange membrane side is filled with the cation conductive spacer and the cathode side with the anion conductive spacer so as to face each other.
- an anion conductive spacer is provided on the anion exchange membrane side, and a cation conductive spacer is provided on the cation exchange membrane side. It is preferable to fill the cells facing each other! / ,.
- the filling form of the ion exchanger in the water dissolution chamber is as follows: (1) The cation exchange fiber material is filled in contact with both ion exchange membranes, and two cation conductive spacers are filled between both cation exchange materials; (2) Anion-exchange fiber material is filled on the cation-exchange membrane side, and cation-exchange fiber material is filled on the cation-exchange membrane side, and two anion-conductive spacers are filled between them; (3) Anion-exchange membrane Side is filled with anion-exchange fiber material, and the cation-exchange membrane side is filled with cation-exchange fiber material, during which two cation conductive spacers are filled; (4) Anion-exchange fiber material is in contact with both ion-exchange membranes And filling two anion conductive spacers between both anion exchange materials.
- a configuration such as (1) or (4) above is adopted, the membrane and fiber Since a water dissolution field is formed at the point of contact
- the ion exchanger is filled with a combination of the ion-exchange fiber material and the ion-conductive spacer provided with the ion function. Then, the STR is dispersed and made easy to flow, so that the pressure loss can be reduced and at the same time, the desalination rate is remarkably improved by the spacer ion trapping function, and the carbonic acid component, silica component, and organic carbon component (T0C) can also be removed satisfactorily.
- Ion conductive spacers that can be used for the above purposes are based on polyolefin-based polymer resins, such as the polyethylene oblique net used in conventional electrodialysis tanks.
- a material obtained by imparting ion repetition ability using a radiation graft polymerization method is preferable because of excellent ion conductivity and excellent dispersibility of S to be treated.
- the radiation graft polymerization method is a technique of irradiating a polymer substrate with radiation to form radicals, and reacting the monomers with the radicals to introduce the monomers into the radicals.
- Radiation that can be used in the ray graft polymerization method includes ⁇ -rays,
- the radiation graft polymerization method includes a pre-irradiation graft polymerization method in which the graft base material is irradiated with radiation in advance, and then is reacted with the graft monomer by inverting it. Although there is a legal method, any method can be used in the present invention.
- liquid-phase graft polymerization method in which polymerization is carried out with the ## immersed in the monomer at an intense night by the fiber method with the monomer
- Immersion gas-phase graft polymerization in which a substrate is immersed in a monomer solution, taken out of the monomer solution, and reacted in a gas phase, and any of these methods can be used in the present invention. V, you can.
- cation exchange groups include strong acid 1-cation exchange groups such as sulfone groups, medium acid 14 cation exchange groups such as phosphate groups, and weak acid cation exchange groups such as lipoxyl groups!
- Raw cation exchange groups and anion exchange groups include a weak base such as primary to tertiary tertiary amino groups, a strong base such as a quaternary ammonium exchange group, and a raw anion exchange group such as a quaternary ammonium group.
- an ion exchanger having both an anion exchange group and an anion exchange group.
- these various ion-exchange groups can be used for graft polymerization, preferably radiation graft polymerization using a monomer having these ion-exchange groups, or polymerizable monomers having groups convertible to these ion-exchange groups.
- the group After carrying out the graft polymerization using the compound, the group can be converted to an ion-exchange group, thereby introducing the compound into a genuine gel or a spacer.
- Monomers having an ion-exchange group that can be used for this purpose include acrylic acid (AA c), methacrylic acid, sodium styrenesnolephonate (SSS), sodium methallylsulfonate, sodium arylsulfonate, and sodium vinylsulfonate And benzylbenzyltrimethylammonium chloride (VBTAC), acetylaminoethyl methacrylate, dimethinorea aminopropylacrylamide, and the like.
- ⁇ f-ray graft polymerization using sodium styrene snorephonate as a monomer, it is possible to directly introduce a strong acid [“a sulfone group that is a viable thione exchange group” into vinyl benzyl.
- a strong acid “a sulfone group that is a viable thione exchange group”
- trimethylammonium chloride as a monomer, it is possible to directly introduce a quaternary ammonium group, which is a strong salt-produced anion exchange group, into the ion exchange group.
- Examples of the monomer having a convertible group include acrylonitrile, acrolein, vinyl pyridine, styrene, chloromethinolestyrene, glycidyl methacrylate (GMA), etc.
- glycidyl methacrylate is obtained by radiation graft polymerization.
- sulfone such as sodium sulfite
- the sulfonate which is a strongly acidic thione exchange group, is introduced into the coagulant by reacting the agent, or after darafft polymerization of chloromethy / restyrene, the £ f is soaked in trimethylamine water / firewood night.
- the quaternary ammonium group which is a strong anion-exchange group, can be introduced by crushing the quaternary ammonium.
- the water dissolving chamber performs the function of dissociating water
- at least one of the cation exchanger and the anion exchanger charged into the water dissolving chamber is a strong acid! Exchanger or strong: It is preferably a sex aion exchanger, and particularly preferably a combination of a strongly acidic cation exchanger and a strongly basic anion exchanger. This is because the dissociation of water generated at the withdrawal between the cation exchanger and the anion exchanger is better due to the generation of a strong electric field between the strongly acidic thione exchange group and the strong anion exchange group. This is because
- a cell plate having a space for forming a chamber in the center, and a hole for forming a liquid flow path formed above and below the cell plate is sandwiched by an ion exchange membrane. It can be formed by appropriately filling the space of the plate with an ion exchanger.
- Fig. 6 shows an example of the configuration of an electrosalinizer with a five-chamber structure (a water dissolution chamber, two cation desalination chambers on the cathode side, and two anion deionization chambers on the anode side). Show. In each cell plate shown in Fig.
- a space for forming a chamber is formed at the center, holes for forming a liquid flow passage are formed at the upper and lower parts, and one hole at the top and one at the bottom communicate with the center space. It is supposed to.
- Each cell plate as shown in Fig. 6a is sandwiched in this order by an ion exchange membrane and packing to prevent water leakage between cells, and a 5-chamber electrical structure as shown in Fig. 6b is inserted between the anode and cathode. Configure the 3 ⁇ 4m unit.
- Each chamber is appropriately filled with an ion exchanger.
- the cell plates constituting the concentration chamber and the electrode chamber are omitted.
- the SzK to be treated becomes the desalination chamber (D a 1). After passing through the inside, it is discharged from the right line of the lower liquid flow path (Fig. 6a). Thereafter, the treated ffi R circulates in the order of the cation desalting chamber (D el), the fermentation desalting chamber (D a 2), the cation desalting chamber (D c 2), and the 7 demolition chamber (D w). The liquid is recovered as R through the left line of the lower liquid flow path of the decomposing chamber (Dw).
- solid arrows indicate the flow of the liquid through the liquid flow passages
- dotted arrows indicate the flow of the liquid passing through each chamber.
- K indicates the pole room and C indicates the concentration room.
- the generation site of the seven solutions is limited to the water dissolution chamber only, and H + ions and OH ⁇ ions generated by the water decomposition are removed by the conventional electric deionization. It can be effectively used to regenerate ion exchangers in each desalination chamber without being recombined in adjacent concentrating chambers as in difficult storage, so extremely high efficiency while keeping the operating ME low A desalination treatment can be performed.
- the electrolyzing apparatus of the present invention for example, if water equivalent to RO treatment is supplied as STK to be treated, the apparatus having an electrode area of 100 cm 2 is continuously used for 100 hours. 2 Operate at a low voltage of about 5 V! / Operating voltage (current 100, processing amount 5 L / h), and obtain ultrapure water with electric conductivity 1 7. YMQcnf 1 as processing 7 It is possible.
- a polyethylene tangle with a thickness of 1.2 thighs and a pitch of 3 thighs is used, and vinyl benzoyl trimethyl ammonium chloride having a quaternary ammonium group as a graft monomer ( VB TAC) and N, N-dimethylacrylamide (DMAA) having nonionic functional groups were used.
- a polyethylene oblique net was irradiated with gamma rays (15 OkGy) in a nitrogen atmosphere.
- the irradiated oblique net was immersed in a mixed monomer solution of VB TAC and DMAA and reacted at 50 ° C for 3 hours to obtain an oblique net grafted with the mixed monomer solution of VB TAC and DMAA.
- the material was obtained.
- the obtained graft oblique net was dried, and the dry weight was measured to calculate the graft ratio (jugage ratio), which was 156%.
- the neutral salt ⁇ capacity of the obtained graft oblique net was 198 meq / m 2 . This was designated as an anion conduction spacer (1).
- the nonwoven substrate was irradiated with an electron beam (15 OkGy) under a nitrogen atmosphere.
- the irradiated nonwoven fabric substrate was immersed in a 10% methanol solution of glycidyl methacrylate, and reacted at 45 for 4 hours.
- the non-woven fabric after the reaction was immersed in a dimethylformamide solution at 60 ° C for 5 hours to remove the homopolymer, thereby obtaining a non-woven fabric material (graft ratio 131%) onto which glycidyl methacrylate was grafted. .
- the same nonwoven fabric as in Production Example 4 was irradiated with an electron beam (15 OkGy) under a nitrogen atmosphere.
- Chloromethinolestyrene manufactured by Seimi Chemical Co., Ltd., trade name: CMS-AM
- CMS-AM chloromethinolestyrene
- the non-woven fabric was taken out from the chloromethylstyrene firewood night, immersed in Tonolen for 3 hours to remove the homopolymer, and a non-woven fabric material grafted with chloromethinostyrene (graft ratio: 161%) was obtained.
- the grafted nonwoven fabric after quaternary Anmoeumu reduction in Torimechiruamin solution (1 0 wt 0/0), and reproduction processing with hydroxide Natoriumu, strongly basic with quaternary Anmoniumu group Anio-exchange non » (Neutral salt ⁇ capacity 35 Omeq / m 2 ) was obtained.
- Fig. 4 shows the assembled electric desalination apparatus.
- the cation exchange membrane C manufactured by Tokuyama: NEOSEPTA CMB
- the ion-exchange membrane A manufactured by Tokuyama: E0SEPTA AHA
- An array of electric ⁇ m salt devices was constructed. The thickness of each chamber was 5 mm, and the area of the pole was 10 O cm 2 .
- each of the anion deionization chambers one piece of the above-prepared anion cloth was placed on the surface of the anion exchange membrane, and between the two pieces of the anion exchange cloth, the anion conductive spacer manufactured above was placed. Two sheets of (2) were filled.
- the cation desalting chamber one piece of the above-prepared cation-woven fabric is placed on the cation-exchange membrane, and two pieces of the above-mentioned cation-conductive spacer are placed between both cation-exchange fabrics. Filled.
- the anion-exchange nonwoven fabric prepared above is placed on the anion-exchange membrane surface, and the cation-exchange fabric produced above is placed on the cation-exchange membrane surface.
- the woven fabric surface was filled with the arn conductive spacer (2) produced above, and the cation-exchanged nonwoven fabric surface was filled with the cation conductive spacer produced above, one by one.
- Each of the concentrating chambers was filled with one piece of the above-mentioned anion-conducting spacer on the anion-exchange membrane surface and one piece of the above-mentioned cation-conducting spacer on the cation exchange membrane surface.
- one cation exchange fabric prepared above was placed on the cation exchange membrane surface, and three cation conductive spacers produced above were filled on the cation exchange fabric surface.
- one piece of the above-prepared anion exchange spacer was placed on the surface of the ion-exchange membrane, and three pieces of the above-mentioned aeon conductive spacer (1) were filled on the surface of the anion exchange membrane.
- a 0.1 A DC current is applied between both electrodes, and 0.2 ⁇ RO treated water (reverse osmosis membrane treatment «: silica concentration 0.1 ⁇ 0.3ppm, water temperature 14 ⁇ 20 ° C)
- RO treated water reverse osmosis membrane treatment «: silica concentration 0.1 ⁇ 0.3ppm, water temperature 14 ⁇ 20 ° C
- water is passed through the aion deionization chamber (1), and the recovered water from the anion deionization chamber (1) is collected in the following order: the cation deionization chamber (1), the anion deionization chamber (2) )
- the water was passed through the cation desalination chamber (2) and the water dissolution chamber in this order.
- the same RO treatment was passed through the pole room and the concentrating room in the following order: the anode room, the concentrating room on the positive electrode side, and the cathode room, the concentrating room on the cathode side (flow rate 5 L / h).
- the operating voltage was 25 V, and the water quality of 17.7 ⁇ could be supplied stably.
- no scale was observed in any room.
- Example 2 A known type of electrical equipment with five rooms was assembled. The same ion exchange membrane as in Example 1 was used. In each of the desalting chambers, the anion exchange woven fabric produced above was applied to the aeon exchange membrane surface, and the cation exchange nonwoven fabric produced above was applied to the cation exchange membrane surface. One piece of cloth was placed, and two pieces of the above-described anion conductive spacer (2) were filled between the two nonwoven fabrics. In each of the concentrating chambers, the anion exchange membrane surface was filled with the anion conduction spacer (1) produced above, and the cation exchange membrane surface was filled with one of the cation conduction spacers produced above. The anode compartment was filled with four force conduction conductive spacers produced above, and the cathode compartment was filled with four anion conduction spacers (1) produced above.
- a 0.1 A direct current is applied between both electrodes, and 0.2 ⁇ RO treated water (reverse osmosis membrane treated water: silica concentration: 0.2 to 0.3 ppm, water temperature: 14 to 20 C)
- RO treated water reverse osmosis membrane treated water: silica concentration: 0.2 to 0.3 ppm, water temperature: 14 to 20 C
- the recovered water from the desalination room D 1 is as follows: desalination room D 2-desalination room D 3-desalination room Water was passed in the order of the salt room D4, and the water was obtained from the desalination room D4.
- the water recovered from the enrichment room C1 was passed through the enrichment room C2—the enrichment room C3—the enrichment room C4—the enrichment room C5 in the following order.
- the same RO treatment 7 was passed through the bipolar chamber at a flow rate of 5 L / h.
- the water quality of 17.5 ⁇ could be supplied stably for 1 000 hours, but the operating voltage after 1 000 hours of operation increased to 130V. Also, the equipment When observed visually, a scale was observed on the anion exchange membrane surface in the concentrating chamber next to the anode chamber.
- the operation can be performed at an extremely low operation ma as compared with a conventional electric device and even after a long operation.
- Stable desalination can be performed without causing a rise in water content.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2003231488A AU2003231488A1 (en) | 2002-05-17 | 2003-05-15 | Electric demineralizer |
US10/484,446 US20040188258A1 (en) | 2002-05-17 | 2003-05-15 | Electric demineralizer |
CA002454520A CA2454520A1 (en) | 2002-05-17 | 2003-05-15 | Electrical deionization apparatus |
JP2004505272A JP4343105B2 (ja) | 2002-05-17 | 2003-05-15 | 電気式脱塩装置 |
EP03725783A EP1506941A4 (en) | 2002-05-17 | 2003-05-15 | ELECTRIC DEMINERALIZER |
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JP2002142558 | 2002-05-17 | ||
JP2002-142558 | 2002-05-17 |
Publications (1)
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WO2003097536A1 true WO2003097536A1 (fr) | 2003-11-27 |
Family
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2003/006065 WO2003097536A1 (fr) | 2002-05-17 | 2003-05-15 | Demineralisateur electrique |
Country Status (7)
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US (1) | US20040188258A1 (ja) |
EP (1) | EP1506941A4 (ja) |
JP (1) | JP4343105B2 (ja) |
CN (1) | CN1537078A (ja) |
AU (1) | AU2003231488A1 (ja) |
CA (1) | CA2454520A1 (ja) |
WO (1) | WO2003097536A1 (ja) |
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- 2003-05-15 WO PCT/JP2003/006065 patent/WO2003097536A1/ja not_active Application Discontinuation
- 2003-05-15 CA CA002454520A patent/CA2454520A1/en not_active Abandoned
- 2003-05-15 US US10/484,446 patent/US20040188258A1/en not_active Abandoned
- 2003-05-15 EP EP03725783A patent/EP1506941A4/en not_active Withdrawn
- 2003-05-15 CN CNA038007231A patent/CN1537078A/zh active Pending
- 2003-05-15 JP JP2004505272A patent/JP4343105B2/ja not_active Expired - Fee Related
- 2003-05-15 AU AU2003231488A patent/AU2003231488A1/en not_active Abandoned
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2007090299A (ja) * | 2005-09-30 | 2007-04-12 | Japan Organo Co Ltd | 電気脱イオン装置およびそれを用いた加圧水型原子力発電所の2次系ライン水処理装置 |
JP2009226315A (ja) * | 2008-03-24 | 2009-10-08 | Japan Organo Co Ltd | 電気式脱イオン水製造装置及び脱イオン水の製造方法 |
JP2011000575A (ja) * | 2009-06-22 | 2011-01-06 | Japan Organo Co Ltd | 電気式脱イオン水製造装置及び脱イオン水の製造方法 |
JP2012096176A (ja) * | 2010-11-02 | 2012-05-24 | Japan Organo Co Ltd | 電気式脱イオン水製造装置 |
JP2013039510A (ja) * | 2011-08-12 | 2013-02-28 | Japan Organo Co Ltd | 電気式脱イオン水製造装置 |
JP2015509048A (ja) * | 2012-02-02 | 2015-03-26 | タンジェント カンパニー エルエルシー | 電気化学的再生水の脱イオン |
JP2012152740A (ja) * | 2012-03-22 | 2012-08-16 | Japan Organo Co Ltd | 電気式脱イオン水製造装置及び脱イオン水の製造方法 |
JP2015530238A (ja) * | 2012-08-27 | 2015-10-15 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングMerck Patent Gesellschaft mit beschraenkter Haftung | 改良型の電気脱イオンモジュールおよび装置 |
Also Published As
Publication number | Publication date |
---|---|
CN1537078A (zh) | 2004-10-13 |
US20040188258A1 (en) | 2004-09-30 |
CA2454520A1 (en) | 2003-11-27 |
JPWO2003097536A1 (ja) | 2005-09-15 |
AU2003231488A1 (en) | 2003-12-02 |
EP1506941A4 (en) | 2005-11-23 |
EP1506941A1 (en) | 2005-02-16 |
JP4343105B2 (ja) | 2009-10-14 |
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