WO2017056792A1 - 水処理装置および水処理方法 - Google Patents
水処理装置および水処理方法 Download PDFInfo
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- WO2017056792A1 WO2017056792A1 PCT/JP2016/074622 JP2016074622W WO2017056792A1 WO 2017056792 A1 WO2017056792 A1 WO 2017056792A1 JP 2016074622 W JP2016074622 W JP 2016074622W WO 2017056792 A1 WO2017056792 A1 WO 2017056792A1
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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
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
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- 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
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- 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
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates to a water treatment apparatus and a water treatment method, and more particularly to a water treatment apparatus and a water treatment method using an electric deionized water production apparatus.
- a deionized water production apparatus that performs deionization by ion exchange reaction by passing water to be treated through an ion exchanger such as an ion exchange resin is known.
- Such an apparatus needs to perform a process (regeneration process) of regenerating the ion exchanger with a chemical such as acid or alkali when the ion exchange group of the ion exchanger is saturated and the desalting performance is lowered.
- a regeneration process of regenerating the ion exchanger with a chemical such as acid or alkali when the ion exchange group of the ion exchanger is saturated and the desalting performance is lowered.
- cations (cations) and anions (anions) adsorbed on the ion exchanger are replaced with hydrogen ions (H + ) or hydroxide ions (OH ⁇ ) derived from acids or alkalis.
- This process restores the desalination performance of the exchanger.
- a deionized water production apparatus that requires a regeneration process with
- the EDI device is a device that combines electrophoresis and electrodialysis.
- the EDI apparatus includes a desalting chamber filled with an ion exchanger (anion exchanger and / or cation exchanger) between an anion exchange membrane that allows only anions to pass therethrough and a cation exchange membrane that allows only cations to pass through.
- a concentration chamber is disposed outside each of the anion exchange membrane and the cation exchange membrane as viewed from the desalting chamber.
- a desalination chamber and each concentration chamber are arrange
- an anion exchange membrane is disposed on the side close to the anode
- a cation exchange membrane is disposed on the side close to the cathode.
- the concentration chamber adjacent to the desalting chamber via the anion exchange membrane is adjacent to the anode chamber via the cation exchange membrane.
- the concentration chamber adjacent to the desalting chamber via the cation exchange membrane is adjacent to the cathode chamber via the anion exchange membrane.
- the treated water is passed through the desalting chamber in a state where a DC voltage is applied between the anode and the cathode. Then, the ionic component in the for-treatment water is adsorbed by the ion exchanger in the demineralization chamber and subjected to deionization (demineralization) treatment, and deionized water flows out from the demineralization chamber.
- an interface between different ion exchange materials for example, an anion exchanger and a cation exchanger, an anion exchanger and a cation exchange membrane, an anion exchange membrane, At the interface with the cation exchanger, a water dissociation reaction occurs as shown in the following formula, and hydrogen ions and hydroxide ions are generated.
- the ion component previously adsorbed on the ion exchanger in the desalting chamber is ion-exchanged and released from the ion exchanger.
- the anion is electrophoresed to the anion exchange membrane, electrodialyzed on the anion exchange membrane, and discharged to the concentrated water flowing through the concentration chamber on the anode side as viewed from the desalting chamber.
- cations out of the free ionic components are electrophoresed to the cation exchange membrane, electrodialyzed on the cation exchange membrane, and discharged to the concentrated water flowing through the cathode-side concentration chamber as viewed from the desalting chamber.
- the ion component in the for-treatment water supplied to the desalting chamber is transferred to the concentration chamber and discharged, and at the same time, the ion exchanger in the desalting chamber is also regenerated.
- Japanese Patent Application Laid-Open No. 2001-191080 describes an electrodeionization apparatus in which the demineralization chambers of two EDI apparatuses are connected in series.
- the first-stage demineralization chamber is filled with the anion exchanger alone or a mixture of the anion exchanger and the cation exchanger.
- the chamber is filled with a mixture of anion exchanger and cation exchanger.
- An object of the present invention is to provide a water treatment apparatus and a water treatment method capable of reducing the concentration of boron in treated water.
- the water treatment apparatus is a water treatment apparatus having a plurality of electric deionized water production apparatuses, wherein each of the plurality of electric deionized water production apparatuses is disposed between the anode and the cathode, on the anode side.
- a demineralization chamber partitioned by an anion exchange membrane positioned on the cathode side and filled with an ion exchanger, the demineralization chamber of each of the plurality of electric deionized water production apparatuses Are connected in series, and the plurality of demineralization chambers connected in series pass through the water to be treated to flow out the treated water, and the first stage through which the treated water is first passed.
- the most upstream portion of the desalting chamber and the most downstream portion of the final stage of the desalting chamber through which the treated water flows out are filled with an anion exchanger alone and are part of the plurality of desalting chambers. In the portion between the most upstream part of the first-stage desalting chamber and the most downstream part of the final-stage desalting chamber, Cation exchangers are filled even without.
- a desalting chamber partitioned between an anion exchange membrane located on the anode side and a cation exchange membrane located on the cathode side and filled with an ion exchanger is provided between an anode and a cathode.
- Each of the plurality of electric deionized water production apparatuses, the demineralization chambers of each of the plurality of electric deionized water production apparatuses are connected in series, and the plurality of demineralization chambers connected in series are The treated water is passed through and the treated water flows out, and the most upstream part of the first-stage desalination chamber through which the treated water is first passed, and the last stage where the treated water flows out.
- the most downstream portion of the desalting chamber is filled with an anion exchanger alone, and is a part of the plurality of desalting chambers, the most upstream portion of the first stage desalting chamber and the desalting of the last stage.
- Water treatment using a water treatment device in which at least a cation exchanger is filled in a portion between the most downstream part of the chamber The treatment water is treated by passing the treated water through the plurality of desalting chambers communicating in series while applying a DC voltage between the anode and the cathode. Run out of water.
- the demineralization chambers of the plurality of electric deionized water production apparatuses are communicated in series, and the most upstream portion of the first-stage demineralization chamber among the plural demineralization chambers communicating in series.
- the most downstream part of the desalting chamber in the final stage is filled with an anion exchanger alone, and at least the cation exchanger is filled between the parts.
- a water treatment apparatus in which the first-stage desalting chamber is filled with a mixture of an anion exchanger and a cation exchanger Compared with a water treatment apparatus in which a mixture of an anion exchanger and a cation exchanger is filled in the most downstream portion, it is possible to reduce the concentration of boron in the treated water.
- FIG. 1 is a diagram showing an EDI device 301.
- FIG. It is the figure which showed the water treatment apparatus of the comparative example 1. It is the figure which showed the water treatment apparatus of the comparative example 2. It is the figure which showed the water treatment apparatus of the comparative example 3.
- FIG. 6 is a diagram showing the measurement results of the boron concentration of treated water in Examples 1 to 8 and Comparative Examples 1 to 4. It is the figure which showed the measurement result of the boron concentration of the treated water in Examples 9-10. It is the figure which showed the measurement result of the boron concentration of the treated water in Examples 11-13. It is the figure which showed the measurement result of the boron concentration of the treated water in Example 14.
- Anode 12 Cathode 21 Anode chamber 22, 24 Concentration chamber 23a, 23b, 23c, 23d, 23e, 23f Desalination chamber 23d-1, 23e-1, 23f-1 First small desalination chamber 23d-2, 23e-2 23f-2 Second small desalination chamber 25 Cathode chamber 31, 33 Cation exchange membrane 32, 34 Anion exchange membrane 36 Intermediate ion exchange membrane CER, K Cation exchanger AER, A anion exchanger 101-106 EDI apparatus 201-208 Water treatment equipment
- the water treatment apparatus of the embodiment of the present invention has a plurality of EDI apparatuses (electric deionized water production apparatuses).
- the desalting chamber is filled with an ion exchanger, and ions captured by the ion exchange reaction travel along the ion exchanger and move to the ion exchange membrane. For this reason, ions can be efficiently removed.
- a current is passed at a current density that causes a water decomposition reaction.
- the minimum current at which water decomposition reaction occurs is called the limit current.
- a current exceeding the limit current flows.
- the six types of EDI apparatuses 101 to 106 used in the embodiment of the present invention will be described.
- the six types of EDI apparatuses differ from each other in the form of the desalination chamber.
- FIG. 1 is a diagram showing an EDI apparatus 101.
- a concentrating chamber 22, a desalting chamber 23 a, and a concentrating chamber 24 are provided in order from the anode chamber 21 side between an anode chamber 21 including the anode 11 and a cathode chamber 25 including the cathode 12. ing.
- the anode chamber 21 and the concentrating chamber 22 are adjacent to each other with a cation exchange membrane 31 therebetween, the concentrating chamber 22 and the desalting chamber 23a are adjacent to each other with an anion exchange membrane 32 therebetween, and the desalting chamber 23a and the concentrating chamber 24 are cation exchange membranes.
- the concentrating chamber 24 and the cathode chamber 25 are adjacent to each other with an anion exchange membrane 34 therebetween.
- the concentration chamber 24 is an example of a first concentration chamber
- the concentration chamber 22 is an example of a second concentration chamber.
- the desalting chamber 23 a is partitioned by an anion exchange membrane 32 and a cation exchange membrane 33.
- the desalting chamber 23a is filled with an anion exchanger AER in a single bed form.
- an anion exchanger AER for example, an anion exchange resin is used.
- the water to be treated is passed through the desalting chamber 23a.
- Supplied water is passed through the concentration chambers 22 and 24, the anode chamber 21 and the cathode chamber 25, respectively. Pure water or water to be treated is used as the supply water.
- the flow direction of the supply water to the concentration chambers 22 and 24 has a countercurrent relationship with the flow direction of the water to be treated to the desalination chamber 23a.
- the direction of water supply to the anode chamber 21 and the cathode chamber 25 has a countercurrent relationship with the direction of water to be treated to the desalting chamber 23a.
- the relationship of these water flow directions can be changed suitably.
- the electrode water discharged from the cathode chamber 25 is supplied to the anode chamber 21 as supply water. Note that the electrode water discharged from the anode chamber 21 may flow into the cathode chamber 25 as supply water.
- FIG. 2 is a diagram showing the EDI device 102.
- the EDI apparatus 102 is different from the EDI apparatus 101 shown in FIG. 1 in the ion exchanger filled in the desalting chamber.
- the region of the treated water inlet side 23b1 is filled with the anion exchanger AER alone, and the region of the outlet side 23b2 is filled solely with the cation exchanger CER.
- the cation exchanger CER for example, a cation exchange resin is used.
- FIG. 3 is a diagram showing the EDI device 103.
- the positions of the anion exchanger AER and the cation exchanger CER filled in the desalting chamber are reversed compared to the EDI apparatus 102 shown in FIG. That is, in the desalination chamber 23c of the EDI apparatus 103, the region of the treated water inlet side 23c1 is filled with the cation exchanger CER alone, and the region of the outlet side 23c2 is filled with the anion exchanger AER alone.
- FIG. 4 is a diagram showing the EDI device 104.
- an intermediate ion exchange membrane 36 is provided between the anion exchange membrane 32 and the cation exchange membrane 33, and the intermediate ion exchange membrane 36 makes the desalination chamber 23d into a small desalination chamber 23d-1.
- a small desalting chamber 23d-2 As the intermediate ion exchange membrane 36, any of an anion exchange membrane, a cation exchange membrane, and a composite membrane such as a bipolar membrane can be used.
- an anion exchange membrane is used as the intermediate ion exchange membrane 36.
- the small desalting chamber 23d-1 on the anode side is an example of a first small desalting chamber
- the small desalting chamber 23d-2 on the cathode side is an example of a second small desalting chamber.
- the small desalting chamber 23d-1 is filled with an anion exchanger AER in a single bed form, and the small desalting chamber 23d-2 is filled with a cation exchanger CER in a single bed form.
- the treated water is passed through the small desalting chamber 23d-1, and the water flowing out from the small desalting chamber 23d-1 flows into the small desalting chamber 23d-2 (see arrows 104a, 104b, and 104c). ),
- the small desalting chamber 23d-1 and the small desalting chamber 23d-2 are connected in series.
- the direction of water supply to the concentrating chambers 22 and 24 has a countercurrent relationship with the direction of water to be treated to the small desalting chambers 23d-1 and 23d-2.
- the direction of water supply to the anode chamber 21 and the cathode chamber 25 has a countercurrent relationship with the direction of water to be treated to the small desalting chambers 23d-1 and 23d-2.
- the relationship of these water flow directions can be changed suitably.
- the electrode water discharged from the cathode chamber 25 is supplied to the anode chamber 21 as supply water. Note that the electrode water discharged from the anode chamber 21 may flow into the cathode chamber 25 as supply water.
- FIG. 5 is a diagram showing the EDI device 105.
- the EDI apparatus 105 has a reverse order of water flow in the first small desalination chamber and the second small desalination chamber.
- water to be treated is supplied to the small desalting chamber 23e-2 and water flowing out from the small desalting chamber 23e-2 flows into the small desalting chamber 23e-1 (arrows 105a and 105b).
- the small desalting chamber 23e-1 and the small desalting chamber 23e-2 are connected in series.
- the direction of water supply to the concentrating chambers 22 and 24 has a countercurrent relationship with the direction of water to be treated to the small desalting chambers 23e-1 and 23e-2.
- the direction of water supply to the anode chamber 21 and the cathode chamber 25 has a countercurrent relationship with the direction of water to be treated to the small desalting chambers 23e-1 and 23e-2.
- the relationship of these water flow directions can be changed suitably.
- the electrode water discharged from the cathode chamber 25 is supplied to the anode chamber 21 as supply water. Note that the electrode water discharged from the anode chamber 21 may flow into the cathode chamber 25 as supply water.
- FIG. 6 is a diagram showing the EDI device 106.
- the EDI device 106 differs from the EDI device 104 shown in FIG. 4 in the ion exchanger filled in the small desalting chamber on the cathode side.
- the region on the inlet side 23f-21 of the water flowing out from the small desalting chamber 23f-1 is filled solely with the cation exchanger CER, and the region on the outlet side 23f-22 is filled with the anion exchanger.
- AER is filled alone.
- water to be treated is supplied to the small desalting chamber 23f-1 and water flowing out from the small desalting chamber 23f-1 flows into the small desalting chamber 23f-2 (arrow 106a, arrow 106b).
- the small desalting chamber 23f-1 and the small desalting chamber 23f-2 are connected in series.
- the flow direction of the water to be treated in the small desalting chamber 23f-1 and the small desalting chamber 23f-2 has a countercurrent relationship.
- An anion exchange membrane is used as the intermediate ion exchange membrane 36.
- the flow direction of the supply water to the concentration chambers 22 and 24 has a countercurrent relationship with the flow direction of the water to be treated to the desalination chamber 23f-2.
- the direction of water supply to the anode chamber 21 and the cathode chamber 25 is in a parallel flow relationship with the direction of water to be treated to the desalting chamber 23f-2.
- the relationship of these water flow directions can be changed suitably.
- the electrode water discharged from the cathode chamber 25 is supplied to the anode chamber 21 as supply water. Note that the electrode water discharged from the anode chamber 21 may flow into the cathode chamber 25 as supply water.
- FIG. 7 is a diagram showing the water treatment apparatus 201 according to the first embodiment of the present invention.
- the water treatment device 201 includes an EDI device 102 and an EDI device 103.
- the desalting chamber 23b of the EDI apparatus 102 and the desalting chamber 23c of the EDI apparatus 103 are connected in series in this order.
- the water flowing out from the outlet side 23b2 of the desalting chamber 23b flows into the desalting chamber 23c from the inlet side 23c1.
- the concentrating chamber is not connected in series, and supply water (pure water) is supplied separately.
- Supply water (pure water) is separately supplied to the electrode chamber (cathode chamber, anode chamber) of the EDI device 102 and the electrode chamber (cathode chamber, anode chamber) of the EDI device 103.
- the concentrating chamber may be connected in series between the EDI device 102 and the EDI device 103.
- common supply water may be supplied to the electrode chamber (cathode chamber, anode chamber) of the EDI device 102 and the electrode chamber (cathode chamber, anode chamber) of the EDI device 103.
- the upstream side in the flow direction of the water to be treated of the EDI apparatus in the preceding stage that is, the first stage of removal of the water to be treated first.
- the reverse osmosis membrane device 111 is preferably provided on the upstream side of the salt chamber in the direction in which the water to be treated flows.
- the reverse osmosis membrane device 111 can reduce the silica concentration of the water to be treated to, for example, 100 ⁇ g SiO 2 / L or less, and the boron concentration of the water to be treated, for example, to 100 ⁇ g B / L or less.
- the upstream EDI apparatus in the direction in which the water to be treated flows, that is, the upstream side in the direction in which the water to be treated flows in the first stage of the desalination chamber through which the water to be treated is first passed.
- a carbon dioxide film device 112 is preferably provided.
- the decarbonation film device 112 can reduce the carbonic acid concentration of the water to be treated to, for example, 5 mg CO 2 / L or less.
- Either the reverse osmosis membrane device 111 or the decarbonation membrane device 112 may be on the upstream side in the direction in which the water to be treated flows.
- desalting of the EDI device 102 is performed in a state where feed water is passed through the anode chamber 21, the concentration chambers 22 and 24, and the cathode chamber 25 and a DC voltage is applied between the anode 11 and the cathode 12. Water to be treated is passed from the inlet side 23b1 of the chamber 23b.
- the following processing is performed on the water to be treated.
- boron in the water to be treated touches the anion exchanger AER filled in the region on the inlet side 23b1 of the desalting chamber 23b, it dissociates as an anion and is adsorbed on the anion exchanger AER.
- a part of boron in the water to be treated remains in the water to be treated without being adsorbed by the anion exchanger AER.
- the water to be treated in which the boron remains flows into a portion (region) filled with the cation exchanger CER in the desalting chamber 23b.
- the desalting chamber 23b a dissociation reaction of water occurs due to an applied voltage between the anode 11 and the cathode 12, and hydrogen ions and hydroxide ions are generated. Then, the anion (boron) adsorbed on the anion exchanger AER in the desalting chamber 23b is ion-exchanged by the hydroxide ions and released from the anion exchanger AER. The liberated anion moves to the concentration chamber 22 through the anion exchange membrane 32 and is discharged from the concentration chamber 22 as concentrated water.
- the cations contained in the water to be treated are subjected to cation exchange. It is adsorbed by the body CER. Then, the cations adsorbed on the cation exchanger CER are ion-exchanged and released from the cation exchanger CER by hydrogen ions generated by the water dissociation reaction. The liberated cations move to the concentration chamber 24 through the cation exchange membrane 33 and are discharged from the concentration chamber 24 as concentrated water.
- the hydroxide ions in the water to be treated move to the concentration chamber 22 through the anion exchange membrane 32 and are discharged from the concentration chamber 22 as concentrated water.
- the hydroxide ions in the water to be treated react with hydrogen ions released by ion exchange from the cation exchanger CER and hydrogen ions generated by water dissociation to form water (H 2 O). For this reason, the density
- the hydroxide ion in to-be-processed water may adsorb
- the EDI apparatus 103 it is estimated that the following processing is performed.
- the to-be-treated water flowing out from the desalting chamber 23b flows into a region filled with the cation exchanger CER in the desalting chamber 23c, the region into which the cation exchanger CER in the desalting chamber 23b is filled with respect to the to-be-treated water
- region filled with the cation exchanger CER of the desalting chamber 23c becomes lower than the case where the cation exchanger CER does not exist in the desalting chamber 23c.
- the concentration of boron in the treated water is reduced by using a plurality of EDI apparatuses. For this reason, for example, the following effects can be obtained as compared with a case where a desalting chamber of one EDI apparatus is filled with ion exchangers in the order of “anion exchanger ⁇ cation exchanger ⁇ anion exchanger”.
- the current value can be easily controlled.
- the electrode plate tends to deteriorate as the current density increases.
- deterioration such as electric burning tends to occur. For example, it is considered that more stable operation can be performed by lowering the current value of the subsequent EDI apparatus in which the ion load is reduced.
- FIG. 8 is a diagram showing a water treatment apparatus 202 according to the second embodiment of the present invention.
- the water treatment device 202 includes an EDI device 101 and an EDI device 103.
- the desalting chamber 23a of the EDI apparatus 101 and the desalting chamber 23c of the EDI apparatus 103 are connected in series in this order.
- the treated water flows into the desalination chamber 23a.
- the water which flowed out from the desalting chamber 23a flows into the desalting chamber 23c from the inlet side 23c1.
- the concentrating chambers are not connected in series and supplied water is supplied separately. Supply water is separately supplied to the electrode chamber (cathode chamber and anode chamber) of the EDI device 101 and the electrode chamber (cathode chamber and anode chamber) of the EDI device 103.
- EDI devices 101 and 103 desalting of EDI device 101 is performed in a state where feed water is passed through anode chamber 21, concentration chambers 22 and 24, and cathode chamber 25, and a DC voltage is applied between anode 11 and cathode 12. Water to be treated is passed from the chamber 23a.
- the same process as that performed using the anion exchanger AER filled in the region on the inlet side 23b1 of the desalination chamber 23b in the first embodiment is performed.
- the treated water flowing out from the desalination chamber 23a of the EDI apparatus 101 flows into the desalination chamber 23c of the EDI apparatus 103 from the inlet side 23c1.
- the EDI apparatus 103 it is estimated that the same process as the process performed in the EDI apparatus 103 shown in the first embodiment is performed.
- the adsorption efficiency of boron (anions) by the anion exchanger AER filled in the region on the outlet side 23c2 of the desalting chamber 23c is improved. Therefore, it is possible to reduce the concentration of boron in the treated water flowing out from the desalting chamber 23c.
- FIG. 9 is a view showing a water treatment apparatus 203 according to the third embodiment of the present invention.
- the water treatment device 203 includes an EDI device 102 and an EDI device 101.
- the desalting chamber 23b of the EDI apparatus 102 and the desalting chamber 23a of the EDI apparatus 101 are communicated in series in this order.
- the water to be treated flows into the desalting chamber 23b from the inlet side 23b1.
- the water that has flowed out of the desalting chamber 23b flows into the desalting chamber 23a.
- the concentrating chambers are not connected in series, and supply water is supplied separately. Supply water is separately supplied to the electrode chamber (cathode chamber, anode chamber) of the EDI device 102 and the electrode chamber (cathode chamber, anode chamber) of the EDI device 101.
- the water treatment performed in the desalting chambers 23b and 23a of the water treatment apparatus 203 will be described.
- desalting of the EDI device 102 is performed in a state where feed water is passed through the anode chamber 21, the concentration chambers 22 and 24, and the cathode chamber 25 and a DC voltage is applied between the anode 11 and the cathode 12.
- Water to be treated is passed from the inlet side 23b1 of the chamber 23b.
- the EDI apparatus 102 it is estimated that the same process as the process performed in the EDI apparatus 102 shown in the first embodiment is performed.
- region of the exit side 23c2 of the desalination chamber 23c in 1st Embodiment is performed.
- the adsorption efficiency of boron (anions) by the anion exchanger AER filled in the desalting chamber 23a is improved, and the boron concentration in the treated water flowing out of the desalting chamber 23a is low. It becomes possible to plan.
- FIG. 10 is a view showing a water treatment apparatus 204 according to the fourth embodiment of the present invention.
- the water treatment device 204 includes an EDI device 104 and an EDI device 101.
- the desalting chamber 23d-1 of the EDI device 104, the desalting chamber 23d-2 of the EDI device 104, and the desalting chamber 23a of the EDI device 101 are communicated in series in this order.
- the water to be treated flows from the small desalting chamber 23d-1.
- the concentrating chambers are not connected in series, and supply water is supplied separately. Supply water is supplied separately to the electrode chamber (cathode chamber, anode chamber) of the EDI device 104 and the electrode chamber (cathode chamber, anode chamber) of the EDI device 101.
- the EDI device 104 can be removed from the anode chamber 21, the concentrating chambers 22 and 24, and the cathode chamber 25, while supplying the supply water and applying a DC voltage between the anode 11 and the cathode 12. Water to be treated is passed from the salt chamber 23d-1.
- the small desalting chamber 23d-1 of the EDI device 104 processing similar to that performed using the anion exchanger AER filled in the region on the inlet side 23b1 of the desalting chamber 23b in the first embodiment is performed. It is estimated to be.
- the treated water flowing out from the small desalting chamber 23d-1 flows into the small desalting chamber 23d-2.
- the small desalting chamber 23d-2 it is estimated that the same processing as that performed using the cation exchanger CER filled in the region on the outlet side 23b2 of the desalting chamber 23b in the first embodiment is performed. .
- the treated water flowing out from the small desalting chamber 23d-2 flows into the desalting chamber 23a of the EDI apparatus 101.
- the EDI apparatus 101 it is estimated that the same process as the process performed using the anion exchanger AER filled in the area
- the adsorption efficiency of boron (anions) by the anion exchanger AER filled in the desalting chamber 23a is improved, and the boron concentration in the treated water flowing out of the desalting chamber 23a is low. It becomes possible to plan.
- FIG. 11 is a view showing a water treatment device 205 according to the fifth embodiment of the present invention.
- the water treatment device 205 includes an EDI device 101 and an EDI device 105.
- the desalination chamber 23a of the EDI device 101, the small desalination chamber 23e-2 of the EDI device 105, and the small desalination chamber 23e-1 of the EDI device 105 are communicated in series in this order.
- the water to be treated flows from the desalting chamber 23a.
- the concentrating chambers are not connected in series, and supply water is supplied separately. Supply water is separately supplied to the electrode chamber (cathode chamber, anode chamber) of the EDI device 101 and the electrode chamber (cathode chamber, anode chamber) of the EDI device 105.
- EDI devices 101 and 105 desalting of EDI device 101 is performed in a state where feed water is passed through anode chamber 21, concentration chambers 22 and 24, and cathode chamber 25 and a DC voltage is applied between anode 11 and cathode 12. Water to be treated is passed from the chamber 23a.
- the same processing as that performed using the anion exchanger AER filled in the region on the inlet side 23b1 of the desalination chamber 23b in the first embodiment is performed.
- the treated water that flows out from the desalting chamber 23 a flows into the small desalting chamber 23 e-2 of the EDI apparatus 105.
- the same processing as that performed using the cation exchanger CER filled in the region on the inlet side 23c1 of the desalting chamber 23c in the first embodiment is performed.
- the treated water flowing out from the small desalting chamber 23e-2 flows into the small desalting chamber 23e-1.
- the same processing as that performed using the anion exchanger AER filled in the region on the outlet side 23c2 of the desalting chamber 23c in the first embodiment is performed. .
- the adsorption efficiency of boron (anions) by the anion exchanger AER filled in the small desalting chamber 23e-1 is improved. Therefore, it is possible to reduce the concentration of boron in the treated water flowing out from the small desalting chamber 23e-1.
- FIG. 12 is a view showing a water treatment device 206 according to the sixth embodiment of the present invention.
- the water treatment device 206 includes an EDI device 106 and an EDI device 101.
- the small desalting chamber 23f-1 of the EDI device 106, the small desalting chamber 23f-2 of the EDI device 106, and the desalting chamber 23a of the EDI device 101 are connected in series in this order.
- the water to be treated flows from the small desalting chamber 23f-1.
- the concentrating chambers are not connected in series and supplied water is supplied separately. Supply water is supplied separately to the electrode chamber (cathode chamber, anode chamber) of the EDI device 106 and the electrode chamber (cathode chamber, anode chamber) of the EDI device 101.
- the EDI device 106 is removed in a state where supply water is passed through the anode chamber 21, the concentration chambers 22 and 24, and the cathode chamber 25 and a DC voltage is applied between the anode 11 and the cathode 12. Water to be treated is passed from the salt chamber 23f-1.
- the small desalting chamber 23f-1 of the EDI apparatus 106 processing similar to that performed using the anion exchanger AER filled in the region on the inlet side 23b1 of the desalting chamber 23b in the first embodiment is performed. It is estimated to be.
- the treated water flowing out from the small desalting chamber 23f-1 passes through the small desalting chamber 23f-2 from the inlet side 23f-21 (portion filled with the cation exchanger CER) to the small desalting chamber 23f-2. Is done.
- the cation exchanger CER charged in the region on the outlet side 23b2 of the desalting chamber 23b in the first embodiment is used. It is presumed that the same processing as that performed using the processing is performed.
- the treated water that has passed through the region of the small desalting chamber 23f-2 filled with the cation exchanger CER is passed through the portion of the small desalting chamber 23f-2 filled with the anion exchanger AER.
- the treatment performed using the anion exchanger AER filled in the region on the outlet side 23c2 of the desalting chamber 23c in the first embodiment It is estimated that the same processing is performed.
- the treated water that has passed through the region filled with the anion exchanger AER in the small desalting chamber 23f-2 is passed through the desalting chamber 23a of the EDI apparatus 101.
- the desalting chamber 23a it is estimated that the same processing as that performed using the anion exchanger AER filled in the region on the outlet side 23c2 of the desalting chamber 23c in the first embodiment is performed.
- the adsorption efficiency of boron (anions) by the anion exchanger AER filled in the desalting chamber 23a is improved. Therefore, it is possible to reduce the concentration of boron in the treated water flowing out from the desalting chamber 23a.
- FIG. 13 is a view showing a water treatment device 207 according to the seventh embodiment of the present invention.
- the water treatment device 207 has two EDI devices 106.
- first stage EDI device 106-1 the EDI device 106 through which the water to be treated is first passed
- final stage EDI device 106- the EDI device 106 through which the water to be treated is finally passed. 2 ”.
- Small desalination chamber 23f-1 of the first stage EDI device 106-1; small desalination chamber 23f-2 of the first stage EDI device 106-1; and small desalination chamber 23f- of the last stage EDI device 106-2 1 and the small desalting chamber 23f-2 of the final stage EDI apparatus 106-2 are connected in series in this order.
- the water to be treated flows from the small desalting chamber 23f-1 of the first stage EDI device 106-1.
- the concentrating chambers are not connected in series, and supply water is supplied separately. Supply water is supplied separately to the electrode chamber (cathode chamber, anode chamber) of the first stage EDI device 106-1 and the electrode chamber (cathode chamber, anode chamber) of the last stage EDI device 106-2.
- water treatment performed in each desalting chamber of the water treatment device 207 will be described.
- supply water is passed through the anode chamber 21, the concentration chambers 22 and 24, and the cathode chamber 25, and a DC voltage is applied between the anode 11 and the cathode 12.
- water to be treated is passed from the small desalting chamber 23f-1 of the first stage EDI apparatus 106-1.
- the first stage EDI device 106-1 performs the same processing as the processing in the EDI device 106 (see FIG. 12) of the sixth embodiment.
- the treated water flowing out from the first stage EDI device 106-1 is passed through the small desalting chamber 23f-1 of the final stage EDI device 106-2.
- the same process as that in the EDI apparatus 106 of the sixth embodiment is performed on the water to be treated flowing out from the first stage EDI apparatus 106-1. It is estimated that
- the adsorption efficiency of boron (anions) by the anion exchanger AER filled in the region on the outlet side 23f-22 of the small desalination chamber 23f-2 of the final stage EDI apparatus 106-2 is improved, and the final stage EDI apparatus 106
- concentration of boron in the treated water flowing out from the small desalting chamber 23f-2 of -2 can be reduced.
- FIG. 14 is a view showing a water treatment device 208 according to the eighth embodiment of the present invention.
- the water treatment device 208 includes an EDI device 106 and an EDI device 105.
- a small desalination chamber 23f-1 of the EDI device 106, a small desalination chamber 23f-2 of the EDI device 106, a small desalination chamber 23e-2 of the EDI device 105, and a small desalination chamber 23e-1 of the EDI device 105 Are communicated in series in this order.
- the water to be treated flows from the small desalting chamber 23f-1.
- the concentrating chambers are not connected in series and supplied water is supplied separately. Supply water is supplied separately to the electrode chamber (cathode chamber, anode chamber) of the EDI device 106 and the electrode chamber (cathode chamber, anode chamber) of the EDI device 105.
- the EDI device 106 is removed in a state where supply water is passed through the anode chamber 21, the concentration chambers 22 and 24, and the cathode chamber 25 and a DC voltage is applied between the anode 11 and the cathode 12. Water to be treated is passed from the salt chamber 23f-1.
- the same processing as that in the EDI device 106 (see FIG. 12) of the sixth embodiment is performed.
- the treated water flowing out from the EDI device 106 passes through the small desalination chamber 23e-2 of the EDI device 105.
- the EDI apparatus 105 it is estimated that the same process as the process in the EDI apparatus 105 (see FIG. 11) of the fifth embodiment is performed.
- the adsorption efficiency of boron (anions) by the anion exchanger AER filled in the small desalting chamber 23e-1 of the EDI apparatus 105 is improved, and the boron concentration in the treated water discharged from the desalting chamber 23e-1 is low. It becomes possible to plan.
- the illustrated configuration is merely an example, and the present invention is not limited to the configuration.
- a water treatment apparatus using two EDI apparatuses is used.
- the anion exchanger is filled alone and is part of a plurality of desalting chambers communicating in series between the most upstream portion of the first-stage desalting chamber and the most downstream portion of the final-stage desalting chamber.
- the number of EDI apparatuses is not limited to two but may be three or more.
- the basic configuration comprising [concentration chamber (C)
- the processing capacity can be increased. Good.
- the anode chamber itself can function as a concentration chamber without interposing an independent concentration chamber between the anode chamber and the cathode chamber.
- the cathode chamber itself can also function as a concentrating chamber without interposing a concentrating chamber between it and the cathode chamber.
- at least one of the concentrating chamber, the anode chamber, and the cathode chamber may be filled with an ion exchanger to lower the electrical resistance of the EDI apparatus.
- pure water is used as the supply water flowing from the cathode chamber to the anode chamber.
- the supply water supplied to the cathode chamber and the anode chamber may not be pure water, for example, water to be treated.
- the cathode chamber and the anode chamber in the same EDI apparatus may not be connected but may be connected in parallel.
- pure water is supplied to each concentration chamber, but treated water output from the second-stage EDI apparatus may be supplied instead of pure water.
- the treated water output from the second stage EDI apparatus is supplied to each concentration chamber of the second stage EDI apparatus, and the water discharged from each concentration chamber of the second stage EDI apparatus is supplied to the first stage EDI apparatus.
- You may supply to each concentration chamber of an EDI apparatus.
- water to be treated may be supplied to each concentration chamber of the first stage EDI apparatus.
- a water treatment device having two EDI devices and having a desalination chamber of each EDI device communicated in series was used.
- the EDI apparatus through which the treated water is first passed is referred to as a “first stage EDI apparatus”, and the treated water flowing out from the first stage EDI apparatus is passed through.
- the apparatus (final stage EDI apparatus) is referred to as a “second stage EDI apparatus”.
- Examples 1 to 8 As the water treatment apparatuses of Examples 1 to 8, the water treatment apparatuses 201 to 208 (see FIG. 20) of the first to eighth embodiments shown in FIGS. 7 to 14 were used. Next, the EDI apparatus 301 used in the comparative example will be described.
- FIG. 15 is a diagram showing the EDI apparatus 301.
- the EDI apparatus 301 an EDI apparatus in which the desalting chamber 23g was filled with the anion exchanger A and the cation exchanger K in a mixed bed form was used.
- FIG. 16 to 19 are views showing water treatment apparatuses of Comparative Examples 1 to 4, respectively.
- the EDI apparatus 301 was used as the first stage EDI apparatus and the second stage EDI apparatus.
- Comparative Example 2 as shown in FIG. 17, the EDI device 301 was used as the first-stage EDI device, and the EDI device 103 was used as the second-stage EDI device.
- Comparative Example 3 as shown in FIG. 18, the EDI apparatus 301 was used as the first stage EDI apparatus, and the EDI apparatus 102 was used as the second stage EDI apparatus.
- the EDI apparatus 101 is used as the first stage EDI apparatus
- the EDI apparatus 301 is used as the second stage EDI apparatus.
- the operating conditions such as the specifications of the EDI apparatus, the water flow rate, the applied current, the quality of the water to be treated in Examples 1 to 8 and Comparative Examples 1 to 4 are as follows.
- An anion exchange resin [trade name: Amberjet (registered trademark) 4002 (strongly basic anion exchange resin 4002), manufactured by Dow Chemical Co., Ltd.] was used as the anion exchanger, and a cation exchange resin [commodity] Name: Amberjet (registered trademark) 1020 (strongly acidic cation exchange resin 1020) manufactured by Dow Chemical Co., Ltd.] was used.
- the volume ratio of the anion exchange resin and the cation exchange resin is set to 1. : 1.
- the volume of the cell was 100 mm ⁇ 100 mm ⁇ 10 mm.
- the number of cell pairs in the desalination chamber was 1 cell pair.
- FIG. 20 is a diagram showing the measurement results of the boron concentration (unit: ngB / L) of treated water in Examples 1 to 8 and Comparative Examples 1 to 4.
- FIG. 20 schematically shows the state of the desalination chamber of each EDI device (filled form of anion exchange resin or cation exchange resin).
- the anion exchange resin layer is indicated by “A”
- the cation exchange resin layer is indicated by “K”
- the mixed layer of the anion exchange resin and the cation exchange resin is indicated by “MB”.
- the boron concentration in the treated water of Examples 1 to 8 and Comparative Examples 1 to 4 is reduced to 50 ng B / L or less simply by connecting the desalting chambers of the two EDI devices in series. I could't. Note that it is desirable that the boron concentration be 50 ng B / L or less, for example, in pure water used in a semiconductor process.
- the region of the most upstream part of the desalination chamber of the first stage EDI apparatus is filled with anion exchange resin alone, and the desalination chamber of the second stage (final stage) EDI apparatus
- the boron concentration could be reduced to 50 ng B / L or less by filling the most downstream region with the anion exchange resin alone and filling the portion between them with the cation exchange resin.
- the desalination chamber of the first-stage EDI apparatus is filled with an anion exchange resin in a single bed form, or
- the boron concentration of the treated water could be further reduced by filling the desalting chamber of the second stage EDI apparatus with the anion exchange resin in a single bed form.
- At least one of the desalting chambers communicating in series includes an intermediate ion exchange membrane, a first small desalting chamber, and a second small desalting chamber.
- D2 desalting chamber By having the desalting chamber (hereinafter referred to as “D2 desalting chamber”), the boron concentration of the treated water could be further reduced. However, if the D2 desalting chambers are connected in series, there is a concern that the water flow differential pressure will increase.
- the concentration of boron in the treated water can be reduced to a target value (for example, 50 ngB / L) or less without increasing the number of D2 desalination chambers more than necessary as in Examples 4 to 6, in terms of water flow differential pressure.
- Example 7 the boron concentration of the treated water is filled by filling the demineralization chamber in the most downstream part of the final stage (second stage) EDI apparatus with an anion exchange resin in a single bed form. Was further reduced.
- cation exchange resin: anion exchange resin 9: 1 in Example 1.
- FIG. 21 is a diagram showing the measurement results of the boron concentration of treated water in Examples 9 to 10.
- the state of the desalination chamber of each EDI apparatus filling form of anion exchange resin or cation exchange resin
- the anion exchange resin is indicated by “A” or “AER”
- the cation exchange resin Is indicated by “K”.
- Example 9 a water flow test was performed under the same water supply load conditions as in Examples 1 to 8 and Comparative Examples 1 to 4 (for example, using two-stage RO permeated water as the treated water, one stage The boron concentration of the water to be treated passed through the desalting chamber of the eye EDI apparatus was 90-100 ⁇ g B / L.)
- the ratio of the anion exchange resin was 50% or more, it was confirmed that the effect of reducing the boron concentration of the treated water was greater than when the ratio was 10 to less than 50%.
- This is the ratio of the volume of the anion exchanger singly packed in the uppermost stream of the first stage desalting chamber to the volume of the first stage desalting chamber, and the final volume relative to the volume of the final stage desalting chamber.
- the ratio of the volume of the anion exchanger packed alone in the most downstream portion of the stage desalting chamber is 50% or more, it means that the degree of decrease in the boron concentration of the treated water is further significantly increased. .
- Example 11 water treatment apparatuses according to Examples 11 to 13 will be described with reference to FIG.
- the concentration of silica and boron is constant at about 100 micrograms per liter with respect to the water to be treated that passes through the desalination chamber of the first stage EDI device (Silica: 98 ⁇ g S i O 2 / This is an example in which the concentration of carbonic acid (mgCO 2 / L) was changed in the state of L, boron: 97 ⁇ g B / L.
- Example 12 the concentration of boron and carbonic acid is constant (boron: 97 ⁇ g B / L, carbonic acid: 5 mg CO 2 / L) with respect to the water to be treated that passes through the desalination chamber of the first-stage EDI apparatus in Example 1. In this state, the silica concentration ( ⁇ g S i O 2 / L) was changed.
- Example 13 in Example 1, with respect to the treatment water to be passed through the desalting compartments of the first stage EDI apparatus, constant concentration of silica and carbonate (silica: 98 ⁇ gS i O 2 / L, carbonate: 5mgCO 2 / This is an example in which the boron concentration ( ⁇ g B / L) is changed in the state of L).
- FIG. 22 is a graph showing the measurement results of the boron concentration of treated water in Examples 11 to 13.
- the anion exchange resin is indicated by “A” and the cation exchange resin is indicated by “K”.
- the carbonic acid concentration is 5 mg CO 2 / L or less
- the silica concentration is 100 ⁇ g S i O 2 / L or less
- the boron concentration is 100 ⁇ g B. It can be confirmed that the boron concentration of the treated water can be reduced to 50 ng B / L or less when / L or less.
- Example 13 when the boron concentration of the water to be treated flowing into the desalination chamber of the first stage EDI apparatus is approximately 200 (198) ⁇ g B / L, the current flowing between the anode and the cathode is 0. When tested as 8A, the boron concentration of the treated water could not be reduced to 50 ng B / L or less. For this reason, it was confirmed that the boron concentration of the treated water cannot be reduced to 50 ng B / L or less simply by increasing the current value.
- Example 14 Next, the water treatment apparatus of Example 14 will be described with reference to FIG.
- the concentration of silica and carbonic acid is constant for silica to be treated which is passed through the small desalination chamber 23f-1 of the first-stage EDI apparatus in Example 8 (silica: 101 ⁇ g S i O 2 / L, carbonic acid : 5 mg CO 2 / L)
- FIG. 23 is a view showing the measurement results of the boron concentration of treated water in Example 14.
- the anion exchange resin is indicated by “A”
- the cation exchange resin is indicated by “K”.
- the boron concentration of the treated water is 50 ng B / L or less. It has been found that the boron concentration of the water to be treated that is passed through the first stage EDI apparatus should be about 100 ⁇ g B / L or less.
- Example 14 the boron concentration of the water to be treated passing through the first-stage EDI apparatus was approximately 300 (298) ⁇ g B / L, which is higher than the boron concentration of the water to be treated in Example 13. However, it was confirmed that the boron concentration of the treated water could be 50 ng B / L or less.
- the reason why the anion exchange resin is filled alone in the most downstream part of the desalting chamber communicated in series and at least the cation exchange resin is filled between the most upstream part and the most downstream part will be described. It is better to remove the cation component in the water to be treated using the cation exchange resin and then pass the water to be treated through the anion exchange resin at the most downstream part without removing the cation component using the cation exchange resin. Compared with the case where the treated water is passed through the anion exchange resin in the most downstream portion, the concentration of hydroxide ions present in the treated water passed through the anion exchange resin in the most downstream portion can be reduced, and the anion exchange is performed. The removal efficiency of boron using resin is improved.
- Example 7 in the final second small desalination chamber, the ion exchange resin is in a double bed form (a form in which both anion exchange resin and cation exchange resin are separately filled), A drift occurs in the current flowing through the second small desalting chamber. This drift is caused by a difference in electrical resistance between the anion exchange resin and the cation exchange resin, and is a phenomenon in which a large amount of current flows through the lower one of the anion exchange resin and the cation exchange resin. . On the other hand, since the second small desalting chamber in the final stage of Example 8 is filled with the anion exchange resin in a single-bed form, drift is less likely to occur than in Example 7, and boron removal efficiency is reduced. Will be better.
- the most upstream part of the desalting chamber refers to a (fixed) part through which treated water flows first when flowing into the desalting chamber
- the most downstream part of the desalting chamber refers to the part (fixed) through which treated water finally passes when it flows out of the desalting chamber.
- the most upstream part of the desalination chamber and “the most downstream part of the desalination chamber” do not necessarily indicate a physical vertical relationship.
- the water to be treated flows from the upper side surface of the desalination chamber and is dehydrated. The case where it flows out from the lower side of the salt chamber is also included.
Abstract
Description
EDI装置は、電気泳動と電気透析とを組み合わせた装置である。EDI装置は、アニオンのみを透過させるアニオン交換膜とカチオンのみを透過させるカチオン交換膜との間にイオン交換体(アニオン交換体および/またはカチオン交換体)が充填された脱塩室を備える。EDI装置では、脱塩室から見てアニオン交換膜およびカチオン交換膜の各々の外側に濃縮室が配置される。そして、脱塩室と各濃縮室が、陽極を備える陽極室と陰極を備える陰極室との間に配置される。脱塩室では、陽極に近い側にアニオン交換膜が配置され、陰極に近い側にカチオン交換膜が配置される。脱塩室とアニオン交換膜を介して隣接する濃縮室は、カチオン交換膜を介して陽極室と隣接する。脱塩室とカチオン交換膜を介して隣接する濃縮室は、アニオン交換膜を介して陰極室と隣接する。
H2O → H++OH-
本発明の目的は、処理水におけるホウ素の低濃度化が可能な水処理装置および水処理方法を提供することである。
12 陰極
21 陽極室
22、24 濃縮室
23a、23b、23c、23d、23e、23f 脱塩室
23d-1、23e-1、23f-1 第1小脱塩室
23d-2、23e-2、23f-2 第2小脱塩室
25 陰極室
31、33 カチオン交換膜
32、34 アニオン交換膜
36 中間イオン交換膜
CER、K カチオン交換体
AER、A アニオン交換体
101~106 EDI装置
201~208 水処理装置
図1は、EDI装置101を示した図である。
EDI装置101では、陽極11を備えた陽極室21と、陰極12を備えた陰極室25との間に、陽極室21側から順に、濃縮室22、脱塩室23aおよび濃縮室24が設けられている。
図2は、EDI装置102を示した図である。EDI装置102は、図1に示したEDI装置101と比べて、脱塩室に充填されているイオン交換体が異なる。EDI装置102の脱塩室23bでは、被処理水の入口側23b1の領域にアニオン交換体AERが単独で充填され、出口側23b2の領域にカチオン交換体CERが単独で充填されている。カチオン交換体CERとしては、例えばカチオン交換樹脂が使用される。
図3は、EDI装置103を示した図である。EDI装置103は、図2に示したEDI装置102と比べて、脱塩室に充填されているアニオン交換体AERとカチオン交換体CERの位置が逆になっている。つまり、EDI装置103の脱塩室23cでは、被処理水の入口側23c1の領域にカチオン交換体CERが単独で充填され、出口側23c2の領域にアニオン交換体AERが単独で充填されている。
図4は、EDI装置104を示した図である。
EDI装置104の脱塩室23dでは、アニオン交換膜32とカチオン交換膜33との間に中間イオン交換膜36が設けられ、中間イオン交換膜36によって脱塩室23dが小脱塩室23d-1と小脱塩室23d-2に区画されている。中間イオン交換膜36としては、アニオン交換膜、カチオン交換膜、および、バイポーラ膜などの複合膜のいずれも使用できる。EDI装置104では、中間イオン交換膜36として、アニオン交換膜が用いられる。陽極側の小脱塩室23d-1は第1小脱塩室の一例であり、陰極側の小脱塩室23d-2は第2小脱塩室の一例である。
図5は、EDI装置105を示した図である。
EDI装置105は、図4に示したEDI装置104と比べて、第1小脱塩室と第2小脱塩室における被処理水の通水の順番が逆になっている。EDI装置105では、小脱塩室23e-2に被処理水が供給されて小脱塩室23e-2から流出する水が小脱塩室23e-1に流入するように(矢印105a、矢印105b、矢印105c参照)、小脱塩室23e-1と小脱塩室23e-2は直列に連通されている。
図6は、EDI装置106を示した図である。
EDI装置106は、図4に示したEDI装置104と比べて、陰極側の小脱塩室に充填されているイオン交換体が異なっている。小脱塩室23f-2では、小脱塩室23f-1から流出する水の入口側23f-21の領域にカチオン交換体CERが単独で充填され、出口側23f-22の領域にアニオン交換体AERが単独で充填されている。EDI装置106では、小脱塩室23f-1に被処理水が供給されて小脱塩室23f-1から流出する水が小脱塩室23f-2に流入するように(矢印106a、矢印106b、矢印106c参照)、小脱塩室23f-1と小脱塩室23f-2は直列に連通されている。小脱塩室23f-1と小脱塩室23f-2における被処理水の通水方向は向流の関係となっている。また、中間イオン交換膜36として、アニオン交換膜が用いられる。
図7は、本発明の第1の実施形態の水処理装置201を示した図である。
水処理装置201は、EDI装置102とEDI装置103とを有する。EDI装置102の脱塩室23bとEDI装置103の脱塩室23cは、この順に直列に連通している。脱塩室23bの出口側23b2から流出した水は、脱塩室23cに入口側23c1から流入する。EDI装置102とEDI装置103の間では、濃縮室は直列に連通しておらず別々に供給水(純水)が供給される。EDI装置102の電極室(陰極室、陽極室)と、EDI装置103の電極室(陰極室、陽極室)には、別々に供給水(純水)が供給される。なお、EDI装置102とEDI装置103の間で、濃縮室が直列に連通されてもよい。また、EDI装置102の電極室(陰極室、陽極室)と、EDI装置103の電極室(陰極室、陽極室)に、共通の供給水が供給されてもよい。
被処理水内のホウ素は、脱塩室23bの入口側23b1の領域に充填されたアニオン交換体AERに触れると、アニオンとして解離してアニオン交換体AERに吸着される。なお、被処理水内のホウ素の一部は、アニオン交換体AERに吸着されずに被処理水の中に残る。ホウ素が残った被処理水は、脱塩室23b内のカチオン交換体CERが充填された部分(領域)に流れる。
脱塩室23bから流れ出た被処理水が、脱塩室23cのカチオン交換体CERが充填された領域に流れ込むと、被処理水に対して脱塩室23bのカチオン交換体CERが充填された領域で行われた処理と同様の処理が行われる。このため、脱塩室23cのカチオン交換体CERが充填された領域から流れ出る被処理水での水酸化物イオンの濃度は、脱塩室23cにカチオン交換体CERが存在しない場合よりも低くなる。
例えば、1台のEDI装置の脱塩室に「アニオン交換体→カチオン交換体→アニオン交換体」の順にイオン交換体が充填された場合、アニオン交換体とカチオン交換体との間での電気抵抗が異なるため、その電気抵抗の差異に応じて電流の偏流が生じてしまう。
これに対して、複数のEDI装置を用いた場合、1台のEDI装置を用いた場合に比べて、1つの脱塩室に充填するイオン交換体の種類を減らすことができ、イオン交換体の電気抵抗の差異に応じた電流の偏流を低減できる。
電極板は電流密度が高くなると、劣化しやすくなる。また、EDI装置を構成するイオン交換膜やイオン交換樹脂もイオン負荷が少ない状態にて高い電流値で運転すると電気的な焼けなどの劣化が発生する傾向がある。例えば、イオン負荷が少なくなる後段のEDI装置の電流値を低くすることでより安定した運転を行うことも可能になると考えられる。
後段のEDI装置は、その前段のEDI装置で処理された処理水を処理するため、全く処理されていない被処理水を処理する場合に比べて、処理の負荷が低くなる。そのため、後段のEDI装置は前段のEDI装置よりも劣化の進行度合いも少なく、より長い期間使用できることが想定される。後段のEDI装置は前段のEDI装置よりも交換頻度を少なくできることが考えられる。
図8は、本発明の第2の実施形態の水処理装置202を示した図である。
水処理装置202は、EDI装置101とEDI装置103とを有する。EDI装置101の脱塩室23aとEDI装置103の脱塩室23cは、この順に直列に連通している。被処理水は、脱塩室23aに流入する。そして、脱塩室23aから流出した水は、脱塩室23cに入口側23c1から流入する。EDI装置101とEDI装置103の間では、濃縮室は直列に連通しておらず別々に供給水が供給される。EDI装置101の電極室(陰極室、陽極室)と、EDI装置103の電極室(陰極室、陽極室)には別々に供給水が供給される。
EDI装置101および103において、陽極室21と濃縮室22および24と陰極室25に供給水を通水し陽極11と陰極12との間に直流電圧を印加した状態で、EDI装置101の脱塩室23aから被処理水を通水する。
図9は、本発明の第3の実施形態の水処理装置203を示した図である。
水処理装置203は、EDI装置102とEDI装置101とを有する。EDI装置102の脱塩室23bとEDI装置101の脱塩室23aは、この順に直列に連通している。被処理水は、脱塩室23bに入口側23b1から流入する。脱塩室23bから流出した水は、脱塩室23aに流入する。EDI装置102とEDI装置101の間では、濃縮室は直列に連通しておらず別々に供給水が供給される。EDI装置102の電極室(陰極室、陽極室)と、EDI装置101の電極室(陰極室、陽極室)には別々に供給水が供給される。
EDI装置102および101において、陽極室21と濃縮室22および24と陰極室25に供給水を通水し陽極11と陰極12との間に直流電圧を印加した状態で、EDI装置102の脱塩室23bの入口側23b1から被処理水を通水する。
EDI装置102では、第1の実施形態に示したEDI装置102にて行われる処理と同様の処理が行われると推定される。EDI装置102の脱塩室23bの出口側23b2から流れ出た被処理水は、EDI装置101の脱塩室23aに流入する。EDI装置101では、第1の実施形態における脱塩室23cの出口側23c2の領域に充填されたアニオン交換体AERを用いて行われる処理と同様の処理が行われると推定される。
図10は、本発明の第4の実施形態の水処理装置204を示した図である。
水処理装置204は、EDI装置104とEDI装置101とを有する。EDI装置104の脱塩室23d-1と、EDI装置104の脱塩室23d-2と、EDI装置101の脱塩室23aは、この順に直列に連通している。被処理水は、小脱塩室23d-1から流入する。EDI装置104とEDI装置101の間では、濃縮室は直列に連通しておらず別々に供給水が供給される。EDI装置104の電極室(陰極室、陽極室)と、EDI装置101の電極室(陰極室、陽極室)には別々に供給水が供給される。
EDI装置104および101において、陽極室21と濃縮室22および24と陰極室25に供給水を通水し陽極11と陰極12との間に直流電圧を印加した状態で、EDI装置104の小脱塩室23d-1から被処理水を通水する。
図11は、本発明の第5の実施形態の水処理装置205を示した図である。
水処理装置205は、EDI装置101とEDI装置105とを有する。EDI装置101の脱塩室23aと、EDI装置105の小脱塩室23e-2と、EDI装置105の小脱塩室23e-1は、この順に直列に連通している。被処理水は、脱塩室23aから流入する。EDI装置101とEDI装置105の間では、濃縮室は直列に連通しておらず別々に供給水が供給される。EDI装置101の電極室(陰極室、陽極室)と、EDI装置105の電極室(陰極室、陽極室)には別々に供給水が供給される。
EDI装置101および105において、陽極室21と濃縮室22および24と陰極室25に供給水を通水し陽極11と陰極12との間に直流電圧を印加した状態で、EDI装置101の脱塩室23aから被処理水を通水する。
図12は、本発明の第6の実施形態の水処理装置206を示した図である。
水処理装置206は、EDI装置106とEDI装置101とを有する。EDI装置106の小脱塩室23f-1と、EDI装置106の小脱塩室23f-2と、EDI装置101の脱塩室23aは、この順に直列に連通している。被処理水は、小脱塩室23f-1から流入する。EDI装置106とEDI装置101の間では、濃縮室は直列に連通しておらず別々に供給水が供給される。EDI装置106の電極室(陰極室、陽極室)と、EDI装置101の電極室(陰極室、陽極室)には別々に供給水が供給される。
EDI装置106および101において、陽極室21と濃縮室22および24と陰極室25に供給水を通水し陽極11と陰極12との間に直流電圧を印加した状態で、EDI装置106の小脱塩室23f-1から被処理水を通水する。
図13は、本発明の第7の実施形態の水処理装置207を示した図である。
水処理装置207は、2台のEDI装置106を有する。以下、最初に被処理水が通水されるEDI装置106を「1段目EDI装置106-1」と称し、最後に被処理水が通水されるEDI装置106を「最終段EDI装置106-2」と称する。
1段目EDI装置106-1と最終段EDI装置106-2において、陽極室21と濃縮室22および24と陰極室25に供給水を通水し陽極11と陰極12との間に直流電圧を印加した状態で、1段目EDI装置106-1の小脱塩室23f-1から被処理水を通水する。
図14は、本発明の第8の実施形態の水処理装置208を示した図である。
水処理装置208は、EDI装置106とEDI装置105とを有する。EDI装置106の小脱塩室23f-1と、EDI装置106の小脱塩室23f-2と、EDI装置105の小脱塩室23e-2と、EDI装置105の小脱塩室23e-1とは、この順に直列に連通している。被処理水は、小脱塩室23f-1から流入する。EDI装置106とEDI装置105の間では、濃縮室は直列に連通しておらず別々に供給水が供給される。EDI装置106の電極室(陰極室、陽極室)と、EDI装置105の電極室(陰極室、陽極室)には別々に供給水が供給される。
EDI装置106および105において、陽極室21と濃縮室22および24と陰極室25に供給水を通水し陽極11と陰極12との間に直流電圧を印加した状態で、EDI装置106の小脱塩室23f-1から被処理水を通水する。
例えば、上述した各実施形態では、2台のEDI装置を用いた水処理装置が使用されている。しかしながら、複数の脱塩室のうち、被処理水が最初に通水される1段目の脱塩室の最上流部と、処理水を出力する最終段の脱塩室の最下流部に、アニオン交換体が単独で充填され、直列に連通する複数の脱塩室の一部であって1段目の脱塩室の最上流部と最終段の脱塩室の最下流部との間の部分に、少なくともカチオン交換体が充填されていれば、EDI装置の数は2台に限らず3台以上でもよい。
実施例および比較例として、2台のEDI装置を有し各EDI装置の脱塩室が直列に連通された水処理装置を用いた。以下、2台のEDI装置のうち、被処理水が最初に通水されるEDI装置を「1段目EDI装置」と称し、1段目EDI装置から流れ出た被処理水が通水されるEDI装置(最終段EDI装置)を「2段目EDI装置」と称する。
実施例1~8の水処理装置として、図7~図14に示した第1~第8の実施形態の水処理装置201~208(図20参照)を用いた。
次に、比較例で用いたEDI装置301について説明する。
図15は、EDI装置301を示した図である。EDI装置301としては、脱塩室23gにアニオン交換体Aとカチオン交換体Kとを混床形態で充填したEDI装置を用いた。
図16~図19は、それぞれ、比較例1~4の水処理装置を示した図である。
比較例1では、図16に示したように1段目EDI装置および2段目EDI装置としてEDI装置301を用いた。比較例2では、図17に示したように1段目EDI装置としてEDI装置301を用い2段目EDI装置としてEDI装置103を用いた。比較例3では、図18に示したように1段目EDI装置としてEDI装置301を用い2段目EDI装置としてEDI装置102を用いた。比較例4では、図19に示したように1段目EDI装置としてEDI装置101を用い2段目EDI装置としてEDI装置301を用いた。
・アニオン交換体として、アニオン交換樹脂[商品名:アンバージェット(登録商標)4002(強塩基性陰イオン交換樹脂4002)、ダウ・ケミカル社製]を用い、カチオン交換体として、カチオン交換樹脂[商品名:アンバージェット(登録商標)1020(強酸性陽イオン交換樹脂1020)、ダウ・ケミカル社製]を用いた。
・アニオン交換樹脂とカチオン交換樹脂の両方が充填されている脱塩室23b、23c、小脱塩室23f-2、脱塩室23gでは、アニオン交換樹脂とカチオン交換樹脂との体積の割合を1:1にした。
・セル(脱塩室、濃縮室、陽極室、陰極室)の容積を、100mm×100mm×10mmとした。
・脱塩室セルペア数を、1セルペアとした。
・1段目EDI装置に通水される被処理水として、2段RO(逆浸透膜)処理水(導電率:3~4μS/cm、ホウ素濃度:90~100μgB/L)を用いた。
・被処理水流量を、20L/hとした。
・陽極と陰極との間を流れる電流の値を、0.4Aとした。
・濃縮室へ供給する供給水として、別系統からの純水を用いた。
・濃縮室への供給水流量を、5L/hとした。
・陽極室へ供給する供給水および陰極室へ供給する供給水として、別系統からの純水を用いた。
・陽極室へ供給する供給水流量および陰極室への供給水流量を、5L/hとした。
次に、図21を参照して実施例9~10の水処理装置を説明する。
実施例9は、実施例1において、2段目EDI装置の脱塩室におけるカチオン交換樹脂とアニオン交換樹脂との体積比を一定(カチオン交換樹脂:アニオン交換樹脂=9:1)にした状態で、1段目EDI装置の脱塩室におけるアニオン交換樹脂とカチオン交換樹脂の体積比を変更(アニオン交換樹脂の体積比を5%~100%の間で変更)した例である。
次に、図22を参照して実施例11~13の水処理装置を説明する。
実施例11は、実施例1において、1段目EDI装置の脱塩室に通水する被処理水に関して、シリカとホウ素の濃度を100マイクログラムパーリッター程度で一定(シリカ:98μgSiO2/L、ホウ素:97μgB/L)にした状態で炭酸の濃度(mgCO2/L)を変更した例である。
次に、図23を参照して実施例14の水処理装置を説明する。
実施例14は、実施例8において、1段目EDI装置の小脱塩室23f-1に通水する被処理水について、シリカと炭酸の濃度を一定(シリカ:101μgSiO2/L、炭酸:5mgCO2/L)にした状態でホウ素の濃度(μgB/L)を変更した例である。
Claims (14)
- 複数の電気式脱イオン水製造装置を有する水処理装置において、
前記複数の電気式脱イオン水製造装置の各々は、陽極と陰極との間に、前記陽極側に位置するアニオン交換膜と前記陰極側に位置するカチオン交換膜とで区画されイオン交換体が充填された脱塩室を有し、
前記複数の電気式脱イオン水製造装置の各々の前記脱塩室は、直列に連通しており、
前記直列に連通する複数の脱塩室は、被処理水を通水して処理水を流出し、
前記被処理水が最初に通水される1段目の前記脱塩室の最上流部と、前記処理水を流出する最終段の前記脱塩室の最下流部には、アニオン交換体が単独で充填され、
前記複数の脱塩室の一部であって前記1段目の脱塩室の最上流部と前記最終段の脱塩室の最下流部との間の部分に、少なくともカチオン交換体が充填されていることを特徴とする水処理装置。 - 前記1段目の脱塩室の体積に対する前記1段目の脱塩室の最上流部に単独で充填されたアニオン交換体の体積の比、および、前記最終段の脱塩室の体積に対する前記最終段の脱塩室の最下流部に単独で充填されたアニオン交換体の体積の比は、10%以上である、請求項1に記載の水処理装置。
- 前記1段目の脱塩室または前記最終段の脱塩室には、アニオン交換体が単床形態で充填されている、請求項1または2に記載の水処理装置。
- 前記複数の脱塩室の少なくとも1つは、
前記アニオン交換膜と前記カチオン交換膜との間に位置する中間イオン交換膜と、
前記アニオン交換膜と前記中間イオン交換膜とで区画された第1小脱塩室と、
前記カチオン交換膜と前記中間イオン交換膜とで区画された第2小脱塩室と、を有し、
前記第1小脱塩室と前記第2小脱塩室とが直列に連通している、請求項1から3のいずれか1項に記載の水処理装置。 - 前記1段目の脱塩室は、前記中間イオン交換膜と前記第1小脱塩室と前記第2小脱塩室とを有し、
前記1段目の脱塩室では、前記第1小脱塩室が前記第2小脱塩室より上流側に位置し、当該第1小脱塩室にアニオン交換体が単床形態で充填されている、請求項4に記載の水処理装置。 - 前記最終段の脱塩室は、前記中間イオン交換膜と前記第1小脱塩室と前記第2小脱塩室とを有し、
前記最終段の脱塩室では、前記第1小脱塩室が前記第2小脱塩室より下流側に位置し、当該第1小脱塩室にアニオン交換体が単床形態で充填されている、請求項4または5に記載の水処理装置。 - 2つ以上の前記電気式脱イオン水製造装置が設けられ、
前記1段目および前記最終段の脱塩室は、それぞれ、前記中間イオン交換膜と前記第1小脱塩室と前記第2小脱塩室とを有し、
前記1段目および前記最終段の脱塩室では、前記第1小脱塩室が前記第2小脱塩室より上流側に位置し、当該第1小脱塩室にアニオン交換体が単床形態で充填され、前記第2小脱塩室における最上流部にカチオン交換体が単独で充填され、当該第2小脱塩室における前記最上流部以外の部分にアニオン交換体が単独で充填されている、請求項4または5に記載の水処理装置。 - 2つ以上の前記電気式脱イオン水製造装置が設けられ、
前記1段目および前記最終段の脱塩室は、それぞれ、前記中間イオン交換膜と前記第1小脱塩室と前記第2小脱塩室とを有し、
前記1段目の脱塩室では、前記第1小脱塩室が前記第2小脱塩室より上流側に位置し、当該第1小脱塩室にアニオン交換体が単床形態で充填され、前記第2小脱塩室における最上流部にカチオン交換体が単独で充填され、当該第2小脱塩室における前記最上流部以外の部分にアニオン交換体が単独で充填され、
前記最終段の脱塩室では、前記第1小脱塩室が前記第2小脱塩室より下流側に位置し、前記第1小脱塩室にアニオン交換体が単床形態で充填され、前記第2小脱塩室にカチオン交換体が単床形態で充填されている、請求項4から6のいずれか1項に記載の水処理装置。 - 前記1段目の脱塩室の上流側に逆浸透膜装置が設けられている、請求項1から8のいずれか1項に記載の水処理装置。
- 前記1段目の脱塩室の上流側に脱炭酸膜装置が設けられている、請求項1から9のいずれか1項に記載の水処理装置。
- 陽極と陰極との間に、前記陽極側に位置するアニオン交換膜と前記陰極側に位置するカチオン交換膜とで区画されイオン交換体が充填された脱塩室を有する複数の電気式脱イオン水製造装置を備え、前記複数の電気式脱イオン水製造装置の各々の前記脱塩室は、直列に連通しており、前記直列に連通する複数の脱塩室は、被処理水を通水して処理水を流出し、前記被処理水が最初に通水される1段目の前記脱塩室の最上流部と、前記処理水を流出する最終段の前記脱塩室の最下流部には、アニオン交換体が単独で充填され、前記複数の脱塩室の一部であって前記1段目の脱塩室の最上流部と前記最終段の脱塩室の最下流部との間の部分に、少なくともカチオン交換体が充填されている水処理装置を用いた水処理方法であって、
前記陽極と前記陰極との間に直流電圧を印加しつつ前記直列に連通する複数の脱塩室に前記被処理水を通水して前記被処理水を処理して前記処理水を流出する水処理方法。 - 前記1段目の電気式脱イオン水製造装置に通水する被処理水のシリカ濃度が100μgSiO2/L以下である請求項11に記載の水処理方法。
- 前記1段目の電気式脱イオン水製造装置に通水する被処理水のホウ素濃度が100μgB/L以下である請求項11または12に記載の水処理方法。
- 前記1段目の電気式脱イオン水製造装置に通水する被処理水の炭酸濃度が5mgCO2/L以下である請求項11から13のいずれか1項に記載の水処理方法。
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