WO2022190727A1 - 水処理方法及び水処理装置 - Google Patents
水処理方法及び水処理装置 Download PDFInfo
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- WO2022190727A1 WO2022190727A1 PCT/JP2022/004236 JP2022004236W WO2022190727A1 WO 2022190727 A1 WO2022190727 A1 WO 2022190727A1 JP 2022004236 W JP2022004236 W JP 2022004236W WO 2022190727 A1 WO2022190727 A1 WO 2022190727A1
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- water
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- dissolved oxygen
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 406
- 238000000034 method Methods 0.000 title claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 226
- 239000001301 oxygen Substances 0.000 claims abstract description 226
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 226
- 239000001257 hydrogen Substances 0.000 claims abstract description 61
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 61
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 150000002500 ions Chemical class 0.000 claims abstract description 46
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 38
- 238000011033 desalting Methods 0.000 claims description 23
- 150000001450 anions Chemical group 0.000 claims description 17
- 239000003014 ion exchange membrane Substances 0.000 claims description 17
- 239000003011 anion exchange membrane Substances 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 15
- 238000005192 partition Methods 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 239000003957 anion exchange resin Substances 0.000 abstract description 73
- 239000012528 membrane Substances 0.000 description 41
- 238000009296 electrodeionization Methods 0.000 description 38
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 35
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 25
- 238000005115 demineralization Methods 0.000 description 20
- 230000002328 demineralizing effect Effects 0.000 description 20
- 239000003729 cation exchange resin Substances 0.000 description 19
- 238000005341 cation exchange Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052763 palladium Inorganic materials 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002242 deionisation method Methods 0.000 description 8
- 238000010612 desalination reaction Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000001223 reverse osmosis Methods 0.000 description 8
- 238000007872 degassing Methods 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000003456 ion exchange resin Substances 0.000 description 6
- 229920003303 ion-exchange polymer Polymers 0.000 description 6
- 230000001172 regenerating effect Effects 0.000 description 6
- 239000008400 supply water Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 238000010349 cathodic reaction Methods 0.000 description 5
- -1 for example Chemical compound 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000008235 industrial water Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 1
- 229910001260 Pt alloy Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000006114 decarboxylation reaction Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 150000002739 metals Chemical class 0.000 description 1
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- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- B01D61/463—Apparatus therefor comprising the membrane sequence AC or CA, where C is a cation exchange membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
- B01D61/485—Specific features relating to the ion-exchange material
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- 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
-
- 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
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
Definitions
- the present invention relates to a water treatment device and a water treatment method capable of removing dissolved oxygen in water.
- a membrane degassing method using a degassing membrane is well known as a method for removing dissolved oxygen in the water to be treated to produce pure water.
- it is necessary to maintain the degree of vacuum on the gas phase side opposite to the water to be treated with the degassing membrane interposed therebetween. Therefore, after adding a reducing agent such as hydrogen or hydrazine to the water to be treated, it is brought into contact with a deoxidizing catalyst supporting palladium or the like to proceed with the reaction to generate water from dissolved oxygen and hydrogen (or hydrazine).
- a reducing agent such as hydrogen or hydrazine
- Patent document 2 uses an electrolytic cell in which a cathode chamber and an anode chamber are separated by a solid polymer electrode film, and electrolysis of water is advanced while water to be treated is supplied to the cathode chamber, and a cathode reaction is performed in the cathode chamber. Dissolved oxygen is reduced and removed by , and the dissolved oxygen that could not be removed is brought into contact with a deoxidizing catalyst together with hydrogen generated by electrolysis to remove the dissolved oxygen.
- an EDI device is a device that combines electrophoresis and electrodialysis, and at least its desalting chamber is filled with an ion exchange resin.
- the EDI device has the advantage of not requiring treatment to regenerate the ion exchange resin with chemicals.
- an anion exchange resin and a cation exchange resin are mixed and filled in a deionization chamber of an EDI device, and a part of the anion exchange resin is a catalyst resin supporting copper or palladium.
- Patent Document 4 discloses that hydrogen peroxide in the water to be treated can be decomposed and removed by bringing it into contact with an anion exchange resin supporting platinum, palladium, or the like.
- Patent Document 3 has room for improving the removal rate of dissolved oxygen in the water to be treated. Further, the technology disclosed in Patent Document 3 is a technology capable of removing dissolved oxygen in the water to be treated while performing desalination without requiring a vacuum pump or the like. A mechanism for this is required separately. Adding cathodic water to the water to be treated also requires a pump for pressurizing the cathodic water, since the pressure at the outlet of the cathode chamber is generally lower than the pressure at the inlet of the demineralization chamber.
- An object of the present invention is to provide a water treatment method and a water treatment apparatus capable of efficiently removing dissolved oxygen and the like in water to be treated with a simple configuration.
- part of the anion exchange resin filled in the deionization chamber is a catalyst resin supporting copper or palladium, and the catalyst resin is mixed with a cation exchange resin that is not a catalyst resin.
- the demineralization compartments are filled in a mixed bed configuration.
- the catalyst resin in at least a part of the deionization chamber is more concentrated than when the catalyst resin is filled in the deionization chamber in a mixed bed. The dissolved oxygen removal rate was improved and the power consumption was reduced when the was packed in a single bed form.
- the present inventors focused on the cathode chamber, which was not effectively used for desalination in the conventional EDI apparatus, and reacted the hydrogen generated by the cathode reaction in the cathode chamber with dissolved oxygen in the cathode chamber. It was also found that dissolved oxygen in the water to be treated can be removed by this. In this case, since the purpose is to remove dissolved oxygen, it is not necessary to provide a desalting chamber as an EDI device.
- a water treatment method is a water treatment method for removing at least dissolved oxygen contained in water to be treated, the step of applying a direct current between an anode and a cathode; a step of passing the water to be treated through a dissolved oxygen removal chamber disposed between the anode and the cathode and filled with an ion exchanger, wherein the ion exchanger filled in the dissolved oxygen removal chamber. At least part of it is an ion exchanger supporting a metal catalyst, and the ion exchanger supporting a metal catalyst is packed in a single bed form in at least a part of the dissolved oxygen removal chamber.
- the step of applying a direct current between the anode and the cathode and the step of passing the water to be treated through the dissolved oxygen removal chamber may be performed simultaneously or separately.
- the water treatment apparatus for carrying out the above method is a water treatment apparatus for removing at least dissolved oxygen contained in the water to be treated, comprising an anode and a cathode, and an ion exchanger disposed between the anode and the cathode and filled with an ion exchanger. and a dissolved oxygen removing chamber through which the water to be treated flows, and at least part of the ion exchanger filled in the dissolved oxygen removing chamber is an ion exchanger carrying a metal catalyst, and the metal catalyst is packed in a single bed form in at least part of the dissolved oxygen removal chamber, and a direct current is applied between the anode and the cathode.
- the reason why dissolved oxygen can be removed in the dissolved oxygen removing chamber in the first aspect is that dissolved oxygen reacts with hydrogen to form water in the presence of a metal catalyst. Therefore, unless the water to be treated originally contains hydrogen, hydrogen must be generated in the dissolved oxygen removing chamber or hydrogen must be added to the water to be treated upstream of the dissolved oxygen removing chamber.
- the water treatment device in the first aspect basically has the same configuration as a general EDI device, except that it is configured to remove dissolved oxygen. In the cathode chamber of the EDI apparatus, hydrogen is generated by a cathodic reaction on the surface of the cathode.
- the water to be treated is first supplied to the cathode chamber, and the outlet water of the cathode chamber, that is, the cathode chamber
- the water to be treated containing hydrogen can be supplied to the dissolved oxygen removal chamber.
- the cathode chamber itself can be used as the dissolved oxygen removal chamber.
- the outlet water of the cathode chamber is added to the water to be treated which is supplied to the demineralization chamber functioning as the dissolved oxygen removal chamber. Since the pressure of the outlet water of the cathode water is generally much lower than the pressure of the treated water, a pump is required to raise the pressure of the outlet water of the cathode chamber. When the pressure is increased by the pump, so-called air entrapment of the pump may be caused by hydrogen bubbles contained in the outlet water of the cathode chamber. In order to prevent air entrapment, etc., it is conceivable to receive the outlet water from the cathode chamber in a tank and then supply the water with a pump. Hydrogen utilization efficiency decreases.
- the outlet water of the cathode chamber is directly used as the inlet water to the dissolved oxygen removal chamber. That is, the dissolved oxygen removal chamber is connected in series with the cathode chamber with respect to the flow of the water to be treated.
- a boosting pump is not required, and hydrogen generated in the cathode chamber does not dissipate, so that the utilization efficiency of hydrogen can be improved. If the amount of hydrogen contained in the outlet water of the cathode chamber is insufficient to remove dissolved oxygen, for example, hydrogen can be injected into the line connecting the outlet of the cathode chamber and the inlet of the dissolved oxygen removal chamber. .
- the water to be treated containing hydrogen can be removed. can be supplied to the dissolved oxygen removal chamber.
- the mass of hydrogen that stoichiometrically reacts with oxygen is one-eighth the mass of oxygen, or 0.125 times.
- the dissolved oxygen load of the object to be treated in the water to be treated is The amount of hydrogen contained in the water to be treated supplied to the dissolved oxygen removal chamber can be adjusted so that the mass ratio of the amount of hydrogen supplied to the dissolved oxygen removal chamber is 0.1 or more and 0.4 or less. preferable.
- the water treatment device in the first aspect is typically designed so that dissolved oxygen can also be removed in the demineralization chamber of the EDI device. Therefore, it is preferable that the dissolved oxygen removal chamber is partitioned by an ion exchange membrane. By partitioning with an ion exchange membrane, the water to be treated can be efficiently desalted in the dissolved oxygen removal chamber. become.
- the anode chamber or the cathode chamber in the EDI apparatus can be used as the dissolved oxygen removal chamber, in which case the dissolved oxygen removal chamber will be partitioned by the electrode plate that is the anode or the electrode plate that is the cathode.
- a water treatment method is a water treatment method for removing at least dissolved oxygen contained in water to be treated, wherein an anode provided in an anode chamber and an ion exchanger are filled. and a step of passing water to be treated through the cathode chamber, wherein at least one of the ion exchangers filled in the cathode chamber.
- Part is an ion exchanger carrying a metal catalyst.
- the step of applying a direct current between the anode and the cathode and the step of passing the water to be treated through the cathode chamber may be performed simultaneously or separately. good.
- a water treatment apparatus for carrying out the water treatment method of the second aspect has an anode chamber provided with an anode, and a cathode chamber provided with a cathode, filled with an ion exchanger, and supplied with water to be treated. At least a part of the ion exchangers filled in is an ion exchanger carrying a metal catalyst, and a direct current is applied between the anode and the cathode.
- the cathode chamber is preferably partitioned by an ion exchange membrane on the anode chamber side. If it is partitioned by the ion exchange membrane, it becomes possible to move the ions captured by the ion exchanger in the cathode chamber to the outside of the cathode chamber through the ion exchange membrane, and the ion exchanger in the cathode chamber is regenerated. Therefore, the dissolved oxygen removal performance can be maintained for a long period of time. More specifically, it is preferable to use an anion exchanger such as an anion exchange resin as the ion exchanger with which the cathode chamber is filled, and an anion exchange membrane as the ion exchange membrane that partitions the cathode chamber.
- an anion exchanger such as an anion exchange resin as the ion exchanger with which the cathode chamber is filled
- an anion exchange membrane as the ion exchange membrane that partitions the cathode chamber.
- anions in the water to be treated such as carbonate ions and hydrogen carbonate ions
- anion exchanger subsequently anion exchange is performed with hydroxide ions produced by the electrolysis reaction of water proceeding at the cathode.
- Anions liberated by body regeneration migrate to the outside of the cathode chamber through the anion exchange membrane.
- the water to be treated is desalted with respect to anions such as carbonate ions and hydrogen carbonate ions in the cathode chamber. That is, in the cathode chamber, not only the dissolved oxygen removal treatment but also the decarboxylation treatment of the water to be treated is performed.
- the water treatment apparatus in the second aspect can be easily realized by using an existing EDI apparatus and using an ion exchanger supporting a metal catalyst as an ion exchanger packed in the cathode chamber. can.
- the water to be treated other than the water to be treated from which the dissolved oxygen is to be removed can be passed through the demineralization chamber of the EDI apparatus.
- the water to be treated from which dissolved oxygen has been removed by passing through the cathode chamber may be passed through the desalting chambers to desalinate the water to be treated.
- Both the metal catalyst supported on the ion exchanger packed in the dissolved oxygen removal chamber in the first aspect and the metal catalyst packed in the cathode chamber in the second aspect are composed of hydrogen and oxygen.
- Any catalyst can be used as long as it promotes the reaction that produces water.
- metal catalysts include iron, copper, manganese, palladium, platinum and the like.
- the platinum group metal catalyst not only promotes the reduction reaction of oxygen, but also has high catalytic activity for decomposing hydrogen peroxide. Therefore, it can be suitably used when the water to be treated contains hydrogen peroxide.
- a platinum group metal catalyst is a catalyst containing one or more metals selected from ruthenium, rhodium, palladium, osmium, iridium and platinum.
- the platinum group metal catalyst may contain any one of these metal elements alone, or may contain two or more of these metal elements in combination.
- platinum, palladium, and platinum/palladium alloys have high catalytic activity and are suitably used as platinum group metal catalysts.
- FIG. 2 shows a water treatment device according to a second embodiment; It is a figure which shows another example of a water treatment apparatus. It is a figure which shows the water treatment apparatus comprised as an EDI apparatus. It is a figure which shows another example of the water treatment apparatus comprised as an EDI apparatus. It is a figure which shows another example of the water treatment apparatus comprised as an EDI apparatus. It is a flow sheet which shows an example of the water treatment system provided with a water treatment apparatus. 4 is a flowsheet showing another example of a water treatment system that includes a water treatment device; 4 is a flowsheet showing another example of a water treatment system that includes a water treatment device; It is a figure which shows the water treatment apparatus of the comparative example 1.
- 4 is a graph showing the relationship between current density and dissolved oxygen removal rate. It is a graph which shows the relationship between power consumption and a dissolved oxygen removal rate. 4 is a graph showing the relationship between current per dissolved oxygen load and dissolved oxygen removal rate. 4 is a graph showing the relationship between space velocity and dissolved oxygen removal rate in a Pd-supporting anion exchange resin.
- FIG. 1 shows the basic configuration of a water treatment device according to a first embodiment of the invention.
- the water treatment apparatus shown in FIG. 1 removes oxygen dissolved in the water to be treated and also desalinates it.
- a concentration chamber 22 and between the anode chamber 21 and the cathode chamber 25, a concentration chamber 22, a dissolved oxygen removal chamber 23 and a concentration chamber 24 are provided in order from the anode chamber 21 side.
- a cation exchange membrane 31 separates the space between the anode compartment 21 and the concentration compartment 22, an anion exchange membrane 32 separates the space between the concentration compartment 22 and the dissolved oxygen removal compartment 23, and a space between the dissolved oxygen removal compartment 23 and the concentration compartment 24.
- a cation exchange membrane 33 separates them, and an anion exchange membrane 34 separates the concentrating compartment 24 from the cathode compartment 25 .
- the anode compartment 21 is filled with a cation exchange resin (CER), which is a cation exchanger, and the concentration compartments 22, 24 and the cathode compartment 25 are filled with anion exchange resin (AER), which is an anion exchanger.
- CER cation exchange resin
- AER anion exchange resin
- the dissolved oxygen removal chamber 23 is filled with an ion exchanger carrying a metal catalyst on its surface in the form of a single bed.
- the dissolved oxygen removal chamber 23 is filled with an anion exchange resin having palladium (Pd) supported on its surface in a single bed form.
- Pd AER an anion exchange resin carrying palladium (Pd) on its surface
- the water to be treated is supplied to the cathode chamber 25, and the outlet water of the cathode chamber 25 is directly supplied to the entrance of the dissolved oxygen removal chamber 23. From the dissolved oxygen removal chamber 23, treated water from which dissolved oxygen has been removed and desalted is discharged. Feed water is supplied to the concentration compartments 22, 24, the outlet water of the concentration compartments 22, 24 is supplied to the anode compartment 21, and the outlet water of the anode compartment 21 is discharged to the outside of the water treatment apparatus.
- the supplied water is not particularly limited, and may be, for example, water obtained by removing turbidity and oxidizing substances from city water, industrial water, groundwater, etc., and then treating it with a reverse osmosis membrane device. .
- feed water may flow directly into the anode chamber 21 instead of the outlet water of the concentration chambers 22 and 24, ie, the concentrated water.
- the water to be treated may be supplied to the dissolved oxygen removal chamber 23 from a line different from the outlet water of the cathode chamber 25 .
- a DC current is applied between the anode 11 and the cathode 12 , and the water to be treated is supplied to the cathode chamber 25 while supplying the supply water to the concentration chambers 22 and 24 .
- a cathodic reaction proceeds on the surface of the cathode 12 due to the direct current to generate hydrogen, so the water to be treated discharged from the cathode chamber 25 as outlet water contains hydrogen.
- This hydrogen may not only be dissolved in the water to be treated, but may also be dispersed in the water to be treated as fine bubbles.
- the water to be treated containing hydrogen in this way flows into the dissolved oxygen removal chamber 23 as it is.
- dissolved oxygen and hydrogen in the water to be treated react to produce water.
- Dissolved oxygen in the water to be treated decreases by the amount of reaction with hydrogen. Since the reaction rate of hydrogen and oxygen is high in the presence of palladium, which is a metal catalyst, if a sufficient amount of hydrogen is contained in the water to be treated, dissolved oxygen is sufficiently removed from the cathode chamber 25. water is discharged. If there is hydrogen in the dissolved oxygen removal chamber 23, the dissolved oxygen is removed. Dissolved oxygen can also be removed by intermittently applying a direct current. Furthermore, the water to be treated may be intermittently supplied to the dissolved oxygen removing chamber 23 while applying the DC current continuously or intermittently.
- the dissolved oxygen removal chamber 23 filled with the Pd-supporting anion exchange resin functions in the same manner as the demineralization chamber in a general EDI device. Then, desalting treatment for the water to be treated also progresses. For example, anions such as carbonate ions (CO 3 2 ⁇ ) and hydrogen carbonate ions (HCO 3 ⁇ ) in the water to be treated are captured by the Pd-supporting anion exchange resin. Hydroxide ions (OH ⁇ ) are also generated by dissociation of water on the surface of the cation exchange membrane 33 on the side of the dissolved oxygen removal chamber 23 .
- the anions that have moved to the concentration chamber 22 are carried by the flow of the supply water in the concentration chamber 22 and discharged to the outside of the apparatus through the anode chamber 21 .
- the water treatment apparatus of this embodiment can also remove hydrogen peroxide from the water to be treated.
- the decomposition products are hydrogen and oxygen. Since the generated oxygen reacts with hydrogen in the presence of the Pd-supporting anion exchange resin to form water, the dissolved oxygen concentration does not increase even if the hydrogen peroxide is decomposed and removed.
- FIG. 2 shows another example of the water treatment device in the first embodiment.
- the water treatment apparatus shown in FIG. 2 is similar to the water treatment apparatus shown in FIG. It differs from that shown in FIG. 1 in that it is provided only on the upstream side of the flow at 23 .
- the downstream side of the dissolved oxygen removal chamber 23 is filled with an anion exchange resin (AER) that does not carry a metal catalyst. Since the reaction rate between hydrogen and oxygen in the presence of the Pd-supporting anion exchange resin is sufficiently high, even if the Pd-supporting anion exchange resin is filled in a double bed form so as to be arranged in a part of the dissolved oxygen removal chamber 23, , the dissolved oxygen in the water to be treated can be sufficiently removed.
- AER anion exchange resin
- the region where the Pd-supporting anion exchange resin is arranged is in a form in which nothing other than the Pd-supporting anion exchange resin exists (that is, a single bed form). ), a layer of Pd-supporting anion exchange resin may be filled at any position in the dissolved oxygen removal chamber 23 . In that case, naturally, it is necessary to prevent the water to be treated from flowing through the dissolved oxygen removing chamber 23 without passing through the layer of the Pd-supporting anion exchange resin. With the configuration shown in FIG. 2, the amount of the expensive palladium catalyst used can be reduced, so costs can be reduced.
- Fig. 3 shows yet another example of water treatment equipment.
- the water treatment apparatus shown in FIG. 3 is similar to the water treatment apparatus shown in FIG. However, it differs from that shown in FIG. 2 in that it is a cation exchange resin (CER) that does not support a metal catalyst, rather than an anion exchange resin that does not support a metal catalyst.
- CER cation exchange resin
- Fig. 4 shows yet another example of water treatment equipment.
- the water treatment apparatus shown in FIG. 4 is similar to the water treatment apparatus shown in FIG. 2 in that the anion exchange resin without the catalyst and the cation exchange resin without the metal catalyst are packed in a mixed bed configuration (MB).
- MB mixed bed configuration
- the dissolved oxygen removal chamber 23 is placed adjacent to the cathode side or the anode side of the dissolved oxygen removal chamber 23 via an intermediate ion exchange membrane.
- a desalting chamber is provided, and the outlet water from the dissolved oxygen removing chamber 23 is passed through the desalting chamber, or the outlet water of the cathode chamber 25 is passed through the desalting chamber and then supplied to the dissolved oxygen removing chamber 23.
- the desalting compartment is filled with an ion exchanger.
- the intermediate ion exchange membrane may be an anion exchange membrane, a cation exchange membrane, or a composite membrane such as a bipolar membrane.
- FIG. 5A shows an example of a water treatment apparatus in which a demineralization chamber is provided adjacent to the dissolved oxygen removal chamber 23 as such.
- the water treatment apparatus shown in FIG. 5A has a demineralization chamber 26 arranged between the dissolved oxygen removal chamber 23 and the concentration chamber 24 in the water treatment apparatus shown in FIG.
- the dissolved oxygen removal compartment 23 and the deionization compartment 26 are separated by a cation exchange membrane 35, which is an intermediate ion exchange membrane, and the deionization compartment 26 and the concentration compartment 24 are separated by a cation exchange membrane 33.
- the desalting chamber 26 is filled with a cation exchange resin.
- the outlet water of the cathode chamber 25 is first supplied to the dissolved oxygen removal chamber 23, the outlet water of the dissolved oxygen removal chamber 23 is supplied to the demineralization chamber 26, and the dissolved oxygen is removed from the demineralization chamber 26, followed by desalination. treated water flows out.
- the water treatment apparatus shown in FIG. 5B is the same as the water treatment apparatus shown in FIG. Further, the water to be treated supplied from a line different from the water to be treated supplied to the cathode chamber 25 is supplied to the dissolved oxygen removal chamber 23 together with the outlet water of the cathode chamber 25. . By supplying the water to be treated from another line to the dissolved oxygen removal chamber 23, the treatment capacity of the water to be treated as a whole of the water treatment apparatus is improved. Electrode water is discharged from the anode chamber 21 and concentrated water is discharged from the concentration chambers 22 and 24 .
- the ion exchange membrane that can be used as an intermediate ion exchange membrane that separates the dissolved oxygen removal chamber 23 and the demineralization chamber 26 is not limited to a cation exchange membrane.
- the water treatment apparatus shown in FIG. 5C is similar to the water treatment apparatus shown in FIG. It has a double-floor structure.
- the inlet side is filled with a cation exchange resin (CER) that does not support a metal catalyst
- the outlet side is filled with an anion exchange resin (AER) that does not support a metal catalyst. .
- the water treatment apparatus shown in FIGS. 1, 2, 3, 4, 5A, 5B, and 5C has a demineralization chamber as a dissolved oxygen removal chamber, in which not only desalination treatment but also dissolved oxygen removal is performed in the dissolved oxygen removal chamber. It has the same configuration as a general EDI device except that it can also remove . In a typical EDI apparatus, multiple demineralization compartments can be arranged between the anode and cathode. 1, 2, 3, 4, 5A, 5B and 5C also have a configuration consisting of an anion exchange membrane 32, a dissolved oxygen removal chamber 23, a cation exchange membrane 33 and a concentration chamber 24.
- a stripping chamber 23 is a repeating unit, and a plurality of repeating units are arranged between the anion exchange membrane 34 that partitions the concentration chamber 22 adjacent to the anode chamber 21 and the cathode chamber 25, so that a plurality of dissolved oxygen A stripping chamber 23 can be arranged.
- the water treatment apparatus shown in FIG. 6A has a plurality of dissolved oxygen removal chambers 23 arranged in the water treatment apparatus shown in FIG. is distributed to and water is passed through. From each dissolved oxygen removing chamber 23, desalted water from which dissolved oxygen has been removed and which has undergone desalting treatment is discharged.
- the water treatment apparatus shown in FIG. 6B is the same as the water treatment apparatus shown in FIG. Further, the water to be treated supplied from a line different from the water to be treated supplied to the cathode chamber 25 is supplied to the dissolved oxygen removal chamber 23 together with the outlet water of the cathode chamber 25. . Electrode water is discharged from the anode chamber 21 and concentrated water is discharged from the concentration chambers 22 and 24 .
- FIG. 7 shows the basic configuration of a water treatment device according to a second embodiment of the invention.
- the water treatment apparatus shown in FIG. 7 includes an anode chamber 21 provided with an anode 11, a concentration chamber 24 separated from the anode chamber 21 by a cation exchange membrane 31, and a cathode 12 provided with an anion exchange membrane 34 for concentration. and a cathode chamber 25 which is separated from chamber 24 .
- the anode chamber 21 is filled with a cation exchange resin (CER) as a cation exchanger
- the concentration chamber 24 is filled with an anion exchange resin (AER) as an anion exchanger.
- the cathode chamber 25 is filled with an ion exchanger carrying a metal catalyst on its surface. Specifically, the cathode chamber 25 is filled with a single bed of Pd-supporting anion exchange resin.
- Water to be treated containing dissolved oxygen is supplied to the cathode chamber 25 , and the water to be treated passes through the cathode chamber 25 .
- Supply water is supplied to the concentration chamber 24, and the outlet water of the concentration chamber 24 is supplied to the anode chamber 21 as it is.
- the supply water that has passed through the anode chamber 21 is discharged from the anode chamber 21 as waste water.
- the supplied water is not particularly limited. For example, after removing turbidity and oxidizing substances from city water, industrial water, groundwater, etc., even if it is water obtained by processing with a reverse osmosis membrane device. good.
- a DC current is applied between the anode 11 and the cathode 12, and water to be treated is supplied to the cathode chamber 25 while supplying water to the concentration chamber 24.
- a cathodic reaction proceeds on the surface of the cathode 12 due to the direct current to generate hydrogen.
- This hydrogen reacts with dissolved oxygen in the water to be treated on the surface of the Pd-supported anion exchange resin (Pd AER), resulting in the formation of water.
- Dissolved oxygen in the water to be treated decreases by the amount of reaction with hydrogen.
- the reaction rate of hydrogen and oxygen is high in the presence of palladium, which is a metal catalyst, if a sufficient amount of hydrogen is generated, treated water from which dissolved oxygen is sufficiently removed is discharged from the cathode chamber 25 . be. As a result, treated water from which dissolved oxygen has been sufficiently removed is discharged from the cathode chamber 25 . If there is hydrogen in the cathode chamber 25, dissolved oxygen is removed. Therefore, considering the residence time of the water to be treated in the cathode chamber 25, the direct current is intermittently applied between the anode 11 and the cathode 12. You can also go to Furthermore, the water to be treated may be intermittently supplied to the dissolved oxygen removing chamber 23 while applying the DC current continuously or intermittently.
- the Pd-supporting anion exchange resin is an anion exchanger
- anions such as carbonate ions (CO 3 2 ⁇ ) and hydrogen carbonate ions (HCO 3 ⁇ ) in the water to be treated in the cathode chamber 25 are It is trapped on a Pd-supported anion exchange resin.
- the cathodic reaction at the cathode 12 also generates hydroxide ions (OH ⁇ )
- the anions captured by the Pd-supporting anion exchange resin are ion-exchanged by the hydroxide ions to be liberated, and are released between the anode 11 and the cathode 12. , and moves through the anion exchange membrane 34 to the concentration compartment 24 .
- the anions that have moved to the concentration chamber 24 are discharged outside the apparatus through the anode chamber 21 along with the flow of the supply water in the concentration chamber 24 . That is, in the water treatment apparatus shown in FIG. 7, in the cathode chamber 25, desalting treatment for anions is also performed. In addition, since the Pd-supporting anion exchange resin can also decompose hydrogen peroxide, this water treatment apparatus also removes hydrogen peroxide in the water to be treated in the same manner as the water treatment apparatus shown in FIGS. be able to.
- the water treatment apparatus of this embodiment can also remove hydrogen peroxide in the water to be treated.
- the Pd-supported anion exchange resin decomposes hydrogen peroxide
- the decomposition products are hydrogen and oxygen. Since the generated oxygen reacts with hydrogen in the presence of the Pd-supporting anion exchange resin to form water, the dissolved oxygen concentration does not increase even if the hydrogen peroxide is decomposed and removed.
- the anode chamber 21 may function as the concentration chamber 24 as well. In that case, the cation exchange membrane 31 may be removed and the anode chamber 21 and the concentration chamber 24 may be integrated.
- FIG. 8 shows another example of the water treatment device in the second embodiment.
- the water treatment apparatus shown in FIG. 8 is similar to the water treatment apparatus shown in FIG. It differs from that shown in FIG. 7 in that it is provided only on the downstream side.
- the upstream side of the cathode chamber 25 is filled with an anion exchange resin (AER) that does not carry a metal catalyst.
- AER anion exchange resin
- the cathodic reaction in the cathode chamber 25 proceeds over the entire surface of the cathode 12, and the reaction rate between hydrogen and oxygen in the presence of the Pd-supporting anion exchange resin is sufficiently high. Dissolved oxygen in the water to be treated can be sufficiently removed even if the exchange resin is arranged.
- the amount of the expensive palladium catalyst used can be reduced, so costs can be reduced.
- FIGS. 7 and 8 has a configuration in which the desalting chamber is removed from the general EDI apparatus. With the same configuration as a typical EDI apparatus, it is possible to perform desalination processing in the desalting chamber and to perform dissolved oxygen removal processing in the cathode chamber.
- FIG. 9 shows a second embodiment of a water treatment system configured as an EDI system.
- the water treatment apparatus shown in FIG. 9 is the same as the water treatment apparatus shown in FIG. 7, except that a concentration chamber 22 and a demineralization chamber 26 are provided in this order from the anode chamber 21 side between the anode chamber 21 and the concentration chamber 24. It is.
- the anode compartment 21 and the concentration compartment 22 are partitioned by a cation exchange membrane 31, the concentration compartment 22 and the deionization compartment 26 are partitioned by an anion exchange membrane 32, and the deionization compartment 26 and the concentration compartment 24 are separated by cation exchange membranes. It is separated by an exchange membrane 33 .
- the concentration compartment 22 is packed with an anion exchange resin (AER), and the demineralization compartment 26 is packed with a mixed bed (MB) of cation exchange resin and anion exchange resin.
- the demineralization chamber 26 is supplied with water to be treated that is different from the water to be treated from which dissolved oxygen is to be removed. Supply water is supplied to the anode chamber 21 and the concentration chambers 22 and 24 , electrode water is discharged from the anode chamber 21 and concentrated water is discharged from the concentration chambers 22 and 24 .
- the water to be treated is desalinated in the desalting chamber 26, as in the desalting chamber in a general EDI apparatus. is performed, and desalted water is discharged from the desalting chamber 26 .
- the cathode chamber 25 as in the case of the water treatment apparatus shown in FIG. is discharged. At this time, as described above, hydrogen peroxide contained in the water to be treated is also removed.
- FIG. 10 shows another example of the water treatment device of the second embodiment configured as an EDI device.
- the treated water discharged from the cathode chamber 25 of the water treatment apparatus shown in FIG. Therefore, according to the water treatment apparatus shown in FIG. 10, desalted water from which dissolved oxygen is removed and hydrogen peroxide is also removed can be obtained.
- the anode chamber 21 is provided with a structure consisting of an anion exchange membrane 32, a demineralization chamber 26, a cation exchange membrane 33, and a concentration chamber 24 as a repeating unit.
- a plurality of desalting compartments 26 can be arranged between the anode 11 and the cathode 12 .
- the water treatment apparatus shown in FIG. 11 has a plurality of desalting chambers 26 arranged in the water treatment apparatus shown in FIG. Water is distributed in parallel. From each desalting chamber 26, desalted water from which dissolved oxygen has been removed and desalted is discharged.
- Water treatment apparatuses can be incorporated into a water treatment system that produces pure water or ultrapure water.
- Water treatment systems that produce pure water or ultrapure water include, for example, activated carbon equipment (AC), reverse osmosis membrane equipment (RO), ultraviolet irradiation equipment (UV), ion exchange resin equipment (IER), membrane degassing equipment ( MD), an EDI device, a non-regenerative ion exchange device (CP), various filters, etc. are combined.
- FIG. 12 shows an example of a water treatment system incorporating a water treatment device according to the invention.
- the water treatment system shown in FIG. 12 is a system that generates ultrapure water from raw water such as city water, and includes a primary pure water system that generates primary pure water from raw water and a primary pure water system that generates ultrapure water from primary pure water. It consists of subsystems.
- Reference numeral 100 in the figure denotes any of the water treatment devices described with reference to FIGS. 1 to 11.
- FIG. In the primary pure water system, the raw water tank 41, the first reverse osmosis membrane device 51, the second reverse osmosis membrane device 52, the reverse osmosis membrane treated water tank 42, the ultraviolet irradiation device (UV) 55, and the water treatment device 100 are The raw water is treated in this order, as a result of which primary pure water is produced.
- the water treatment device 100 based on the present invention is not used, an ion exchange resin device, an EDI device, or a non-regenerative ion exchange device is provided instead of the water treatment device 100, and a membrane degassing device is provided. become.
- the produced primary pure water is circulated to the reverse osmosis membrane-treated water tank 42 when the downstream equipment to which the pure water is supplied is full.
- a pure water tank 45 for storing primary pure water from the primary pure water system is provided.
- ) 63, a membrane deaerator (MD) 65, and an ultrafiltration membrane (UF) 67 are arranged in this order to treat primary pure water in this order to produce ultrapure water.
- a part of the produced ultrapure water is circulated to the pure water tank 45 .
- a microfiltration membrane may be used instead of the ultrafiltration membrane (UF) 67 .
- a water treatment device based on the present invention may be provided. or may be provided at a later stage.
- the removal rate of dissolved oxygen as a whole may be increased by providing a plurality of membrane deaerators in series. It is also possible to replace some of the membrane deaerators with the water treatment system according to the invention when the membrane deaerators are installed in series.
- FIG. 13 shows another example of a water treatment system incorporating a water treatment device according to the present invention.
- the water treatment system shown in FIG. 13 is the same as the water treatment system shown in FIG. Alternatively, a processing device (IER/EDI) 56, which is an EDI device, is arranged.
- IER/EDI processing device
- the water in the reverse osmosis membrane treated water tank 42 is passed through the water treatment device 100 based on the present invention, the ultraviolet irradiation device 55 and the treatment device 56 in this order, and the water from the treatment device 56, which is an ion exchange resin device or an EDI device, is firstly Pure water is discharged.
- Fig. 14 shows yet another example of a water treatment system incorporating a water treatment device according to the present invention.
- a water treatment apparatus based on the present invention is also placed between the outlet of the ultraviolet irradiation device 61 and the inlet of the non-regenerative ion exchange device 63 of the subsystem. 100 are arranged.
- organic matter in water is decomposed and removed by ultraviolet irradiation, carbonate ions, hydrogen carbonate ions, etc. are generated.
- the water treatment device 100 it is possible to reduce the processing load in the non-regenerative ion exchange device 63 in the latter stage and improve the impurity removal performance.
- Example 1 As Example 1, the water treatment apparatus shown in FIG. 1 was assembled. The dimensions of the anode compartment 21, the concentration compartments 22, 24 and the cathode compartment 25 were all 105 mm x 105 mm x 9.5 mm, and the dimensions of the dissolved oxygen removal compartment 23 were 105 mm x 105 mm x 19.5 mm. In Example 1, the dissolved oxygen removal chamber 23 was packed with a single bed of Pd-supported anion exchange resin (Pd AER). The size of the anode 11 and cathode 12 is 105 mm ⁇ 105 mm, and the current density can be calculated by dividing the applied current by the area of these electrodes.
- Pd AER Pd-supported anion exchange resin
- Example 2 As Example 2, the water treatment apparatus shown in FIG. 3 was assembled. This water treatment apparatus has the same structure and dimensions as those of Example 1, but is different from that of Example 1 in that the dissolved oxygen removal chamber 23 is filled with Pd-supported anion exchange resin (Pd AER) in multiple beds. is different from Specifically, in the dissolved oxygen removal chamber 23 of Example 2, a layer of Pd-supporting anion exchange resin (Pd AER) is arranged on the inlet side of the water to be treated, and a metal catalyst is supported on the outlet side of the water to be treated. A layer of free cation exchange resin (CER) is disposed. The ratio of the channel length in the layer of Pd-supporting anion exchange resin to the channel length in the layer of cation exchange resin not supporting a metal catalyst was 1:1.
- Pd AER Pd-supported anion exchange resin
- Comparative Example 1 As Comparative Example 1, the water treatment apparatus shown in FIG. 15 was assembled. This water treatment apparatus has the same configuration and dimensions as those of Example 1, but the dissolved oxygen removal chamber 23 is filled with a Pd-supporting anion exchange resin and a cation exchange resin not supporting a metal catalyst in a mixed bed form. It is different from that of Example 1 in that Specifically, in Comparative Example 1, a Pd-supporting anion exchange resin and a cation exchange resin not supporting a metal catalyst were mixed at a volume volume of 1:1, and dissolved in a mixed state (Pd AER MB). The oxygen removal chamber 23 was filled.
- the water to be treated was passed through each of the water treatment apparatuses of Examples 1 and 2 and Comparative Example 1 at a flow rate of 50 L/h while changing the applied current in the range of 0.5 A to 2.5 A. These water treatment units were operated by passing the feed water at a flow rate of h. From the dissolved oxygen concentration of the water to be treated at the inlet of the cathode chamber 25 and the dissolved oxygen concentration of the treated water discharged from the dissolved oxygen removal chamber 23, changes in dissolved oxygen concentration according to current density were examined. The results are shown in FIG. From FIG. From FIG.
- Example 16 in Comparative Example 1 in which the packing form of the Pd-supporting anion exchange resin was a mixed bed form, the dissolved oxygen removal rate peaked out at about 70% even when the current density was increased, but it was a single bed form.
- Example 1 and Example 2 which has a double bed configuration, the dissolved oxygen removal rate could be increased to 80% or more by increasing the current density.
- the applied current between the anode 11 and the cathode 12 when the applied current between the anode 11 and the cathode 12 is changed, the applied voltage at that time also changes, and the power consumption, which is the product of the current and the voltage, changes more than the change in the applied current.
- the power consumption for each result shown in FIG. 16 was calculated and converted into power consumption per unit flow rate of the water to be treated, and the results are shown in FIG. In FIG. 17, the horizontal axis represents power consumption per unit flow rate of water to be treated. Since the applied current is the same in Examples 1 and 2 and Comparative Example 1, in Comparative Example 1 of the mixed bed form, the applied voltage is higher than in Examples 1 and 2, and the same dissolved oxygen removal rate is achieved. The power consumption required to obtain this is increasing.
- the power consumption per unit flow rate of the water to be treated is preferably 0.06 W h / L or more and 0.70 W h / L or less, and 0.17 W ⁇ It is more preferable that it is more than h/L and below 0.50 W ⁇ h/L.
- the current value per dissolved oxygen load is preferably 2 mA ⁇ h/mg or more and 8 mA ⁇ h/mg or less, more preferably 4 mA ⁇ h/mg or more and 8 mA ⁇ h/mg or less.
- the water treatment apparatuses of Examples 1 and 2 and Comparative Example 1 were operated with the applied current fixed at 2 A, and changes in the dissolved oxygen removal rate were investigated when the flow rate of the water to be treated was changed.
- the results are shown in FIG. 19 as changes in the dissolved oxygen removal rate with respect to the space velocity based on the volume of the Pd-supporting anion exchange resin in the dissolved oxygen removal chamber 23 .
- the dissolved oxygen removal rate decreases as the flow rate of the water to be treated increases.
- the quotient obtained by dividing the flow rate of the water to be treated by the volume of the Pd-supporting anion exchange resin was 500 h ⁇ 1
- the dissolved oxygen removal rate decreased to 50%.
- the flow rate of the water to be treated is increased, it is thought that the dissolved oxygen removal rate will decrease.
- Example 3 Water treatment of Example 1 in which the water to be treated has a dissolved oxygen concentration of 7.9 mg / L and a carbonic acid concentration of 3.2 mg / L, and the water to be treated is in a single bed form at a flow rate of 50 L / h.
- the water treatment equipment was operated with an applied current of 1.0 A. Then, the dissolved oxygen concentration and the carbonic acid concentration in the treated water discharged from the dissolved oxygen removal chamber 23 were measured to determine the respective removal rates.
- Table 1 shows the results. Table 1 shows that the water treatment apparatus according to the present invention can remove not only dissolved oxygen but also carbonic acid in the water to be treated.
- the water to be treated has a dissolved oxygen concentration of 7.8 mg / L to 8.2 mg / L, and the water to be treated is flowed at a flow rate of 50 L / h. , and each water treatment apparatus was operated with an applied current of 1.5 A.
- the hydrogen concentration in the outlet water of the cathode chamber 25 and the dissolved oxygen concentration in the treated water discharged from the dissolved oxygen removing chamber 23 were measured.
- the amount of oxygen removed in the dissolved oxygen removal chamber 23 was calculated from the dissolved oxygen concentration of the treated water, and the utilization efficiency of hydrogen produced in the cathode chamber 25 was calculated from this and the hydrogen concentration in the cathode chamber outlet water. For the calculation, it was assumed that 1 mol of hydrogen (H 2 ) would react with 0.5 mol of oxygen (O 2 ). Table 2 shows the results.
- Example 2 of the double-bed form Comparative Example 1 of the mixed-bed form, it can be seen that although the amount of Pd-supporting anion exchange resin filled in the dissolved oxygen removal chamber 23 is the same, the mixed-bed form of the comparative example 1 had lower hydrogen utilization efficiency.
- Example 2 of the double-bed configuration when comparing Example 2 of the double-bed configuration with Example 1 of the single-bed configuration, the amount of Pd-supporting anion exchange resin packed in the dissolved oxygen removal chamber 23 in Example 1 was twice that in Example 2. Despite this, there was no significant difference in hydrogen utilization efficiency. In Examples 1 and 2, almost all of the hydrogen generated in the cathode chamber 25 is used to remove dissolved oxygen.
- Example 5 A water treatment apparatus shown in FIG. 7 was assembled. The dimensions of the anode compartment 21, concentration compartment 24 and cathode compartment 25 were all 105 mm x 105 mm x 9.5 mm. Water having a dissolved oxygen concentration of 8.2 mg/L was prepared, and this water was passed through the cathode chamber 25 at 50 L/h as water to be treated, and passed through the concentration chamber 24 at 5 L/h as feed water. The water treatment apparatus was operated while changing the value of the current flowing between the anode 11 and the cathode 12 in the range of 0.5 A to 2.5 A, and the dissolved oxygen concentration of the treated water discharged from the cathode chamber 25 was measured. The dissolved oxygen removal rate was determined. The results are shown in FIG.
- Example 6 Using the same apparatus as in Example 5, hydrogen peroxide was added to the water to be treated, and the experiment was performed in the same manner as in Example 1 except that the current setting during operation was set to 1.5 A. was measured to determine the removal rate of hydrogen peroxide. Table 3 shows the results.
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Abstract
Description
実施例1として、図1に示した水処理装置を組み立てた。陽極室21、濃縮室22,24及び陰極室25の寸法は、いずれも105mm×105mm×9.5mmであり、溶存酸素除去室23の寸法は105mm×105mm×19.5mmであった。実施例1では、溶存酸素除去室23にPd担持アニオン交換樹脂(Pd AER)を単床で充填した。陽極11及び陰極12の大きさは105mm×105mmであり、印加電流をこれらの電極の面積で除することによって電流密度を算出できる。
実施例2として、図3に示した水処理装置を組み立てた。この水処理装置は、構成や寸法では実施例1のものと同じであるが、溶存酸素除去室23において複床でPd担持アニオン交換樹脂(Pd AER)が充填されている点で実施例1のものと異なっている。具体的には、実施例2の溶存酸素除去室23では、被処理水の入口側にPd担持アニオン交換樹脂(Pd AER)の層が配置し、被処理水の出口側に、金属触媒を担持していないカチオン交換樹脂(CER)の層が配置している。Pd担持アニオン交換樹脂の層での流路長と金属触媒を担持していないカチオン交換樹脂の層での流路長の比は1:1であった。
比較例1として、図15に示した水処理装置を組み立てた。この水処理装置は、構成や寸法では実施例1のものと同じであるが、溶存酸素除去室23において混床形態でPd担持アニオン交換樹脂と金属触媒を担持していないカチオン交換樹脂とが充填されている点で実施例1のものと異なっている。具体的には比較例1では、Pd担持アニオン交換樹脂と金属触媒を担持していないカチオン交換樹脂とを嵩体積で1:1で混合し、これらが混じり合った状態(Pd AER MB)で溶存酸素除去室23に充填した。
被処理水として溶存酸素濃度が7.9mg/L、炭酸濃度が3.2mg/Lであるものを使用してこの被処理水を流量50L/hで単床形態である実施例1の水処理装置に供給し、印加電流を1.0Aとして水処理装置を運転した。そして、溶存酸素除去室23から排出される処理水における溶存酸素濃度と炭酸濃度とを測定してそれぞれの除去率を求めた。結果を表1に示す。表1より、本発明に基づく水処理装置によれば、被処理水中の溶存酸素だけでなく炭酸も除去できることが分かった。
被処理水として溶存酸素濃度が7.8mg/L~8.2mg/Lであるものを使用してこの被処理水を流量50L/hで、実施例1,2及び比較例1の水処理装置に供給し、印加電流を1.5Aとしてそれぞれの水処理装置を運転した。陰極室25の出口水における水素濃度と、溶存酸素除去室23から排出される処理水の溶存酸素濃度を測定した。処理水の溶存酸素濃度から、溶存酸素除去室23で除去された酸素量を算出し、これと陰極室出口水での水素濃度から、陰極室25で生成した水素の利用効率を算出した。算出に際しては、水素(H2)の1モルが酸素(O2)の0.5モルと反応するものとした。結果を表2に示す。
図7に示す水処理装置を組み立てた。陽極室21、濃縮室24及び陰極室25の寸法は、いずれも、105mm×105mm×9.5mmであった。溶存酸素濃度が8.2mg/Lの水を用意し、この水を被処理水として50L/hで陰極室25に通水し、濃縮室24には供給水として5L/hで通水した。陽極11と陰極12の間に流す電流の値を0.5Aから2.5Aの範囲で変化させて水処理装置を運転し、陰極室25から排出される処理水の溶存酸素濃度を測定して溶存酸素除去率を求めた。結果を図20に示す。図20から、電流値と溶存酸素除去率との間には相関があり、電流密度を大きくすることによって溶存酸素除去率を向上できることが分かった。このことは、陰極室25内で発生した水素を有効に利用して溶存酸素の除去を行なえたことを意味する。
実施例5と同じ装置を用い、被処理水に過酸化水素を添加し、運転時の電流設定を1.5Aとしたほかは実施例1と同様に実験を行い、処理水中の過酸化水素濃度を測定して、過酸化水素の除去率を求めた。結果を表3に示す。
12 陰極
21 陽極室
22,24 濃縮室
23 溶存酸素除去室
25 陰極室
26 脱塩室
31,33,35 カチオン交換膜
32,34,36 アニオン交換膜
100 水処理装置
Claims (19)
- 被処理水に含まれる少なくとも溶存酸素を除去する水処理方法であって、
陽極と陰極との間に直流電流を印加する工程と、
前記陽極と前記陰極との間に配置されてイオン交換体が充填されている溶存酸素除去室に前記被処理水を通水する工程と、
を有し、
前記溶存酸素除去室に充填されている前記イオン交換体の少なくとも一部は金属触媒が担持されたイオン交換体であり、
前記金属触媒が担持されたイオン交換体は、前記溶存酸素除去室の少なくとも一部において単床形態で充填されている、水処理方法。 - 前記被処理水を前記陰極が設けられている陰極室に供給し、前記陰極室を通過した後の前記被処理水を溶存酸素除去室に通水させる、請求項1に記載の水処理方法。
- 被処理水に含まれる少なくとも溶存酸素を除去する水処理方法であって、
陽極室に設けられた陽極とイオン交換体が充填されている陰極室に設けられた陰極との間に直流電流を印加する工程と、
前記陰極室に前記被処理水を通水する工程と、
を有し、
前記陰極室に充填されている前記イオン交換体の少なくとも一部は金属触媒が担持されているイオン交換体である、水処理方法。 - 前記陰極室が、前記陽極室の側においてイオン交換膜によって区画されている、請求項3に記載の水処理方法。
- 前記陰極室を区画する前記イオン交換膜がアニオン交換膜であり、前記陰極室に充填されるイオン交換体がアニオン交換体である、請求項4に記載の水処理方法。
- 前記陽極室と前記陰極室の間においてイオン交換膜によって区画されてイオン交換体が充填されている脱塩室に対し、前記陰極室を通過した後の前記被処理水を通水させて前記被処理水の脱塩を行う工程をさらに有する、請求項3乃至5のいずれか1項に記載の水処理方法。
- 前記金属触媒は白金族金属触媒であり、前記被処理水中の溶存酸素に加えて過酸化水素を除去する、請求項1乃至6のいずれか1項に記載の水処理方法。
- 被処理水に含まれる少なくとも溶存酸素を除去する水処理装置であって、
陽極及び陰極と、
前記陽極と前記陰極との間に配置されてイオン交換体が充填され、前記被処理水が通水する溶存酸素除去室と、
を有し、
前記溶存酸素除去室に充填されている前記イオン交換体の少なくとも一部は金属触媒が担持されたイオン交換体であり、
前記金属触媒が担持されたイオン交換体は、前記溶存酸素除去室の少なくとも一部において単床形態で充填されており、
前記陽極と前記陰極の間に直流電流が印加される水処理装置。 - 前記溶存酸素除去室は、前記陽極である電極板、前記陰極である電極板、及びイオン交換膜のいずれか1つ以上で区画されている、請求項8に記載の水処理装置。
- 前記溶存酸素除去室は、前記陰極を備える陰極室であるか、あるいは前記被処理水の流れに関して前記陰極室に直列に接続されている、請求項8または9に記載の水処理装置。
- 前記溶存酸素除去室の上流に、前記被処理水に対して水素を供給する手段が設けられている、請求項8乃至10のいずれか1項に記載の水処理装置。
- 前記被処理水中の処理対象の溶存酸素負荷量に対する前記直流電流の電流値が2mA・h/mg以上8mA・h/mgに設定される、請求項8乃至11のいずれか1項に記載の水処理装置。
- 前記溶存酸素除去室に充填された前記金属触媒が担持されたイオン交換体の体積を基準とする前記被処理水の空間速度が1000h-1以下に設定される、請求項8乃至12のいずれか1項に記載の水処理装置。
- 前記被処理水中の処理対象の溶存酸素負荷量に対する単位時間あたりに前記溶存酸素除去室に供給される水素の量の質量比が0.1以上0.4以下となるように、前記溶存酸素除去室に供給される前記被処理水に含まれる水素の量が調整される、請求項8乃至13のいずれか1項に記載の水処理装置。
- 前記溶存酸素除去室における電流密度が0.45A/dm2以上2.3A/dm2以下である、請求項8乃至14のいずれか1項に記載の水処理装置。
- 前記溶存酸素除去室での前記被処理水の流量あたりの消費電力が0.06W・h/L以上0.70W・h/L以下である、請求項8乃至15のいずれか1項に記載の水処理装置。
- 陽極を備える陽極室と、
陰極を備えてイオン交換体が充填され被処理水が供給される陰極室と、
を有し、
前記陰極室に充填されている前記イオン交換体の少なくとも一部は、金属触媒が担持されているイオン交換体であり、
前記陽極と前記陰極の間に直流電流が印加される水処理装置。 - 前記陰極室が、前記陽極室の側においてイオン交換膜によって区画されている、請求項17に記載の水処理装置。
- 前記陰極室を区画するイオン交換膜がアニオン交換膜であり、前記陰極室に充填されるイオン交換体がアニオン交換体である、請求項18に記載の水処理装置。
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JPH06320165A (ja) * | 1993-05-19 | 1994-11-22 | Tookemi:Kk | 水処理の方法 |
JPH10272474A (ja) * | 1997-03-28 | 1998-10-13 | Kurita Water Ind Ltd | 電気式脱イオン装置 |
JP2003094064A (ja) * | 2001-09-27 | 2003-04-02 | Kurita Water Ind Ltd | 電気脱イオン装置 |
JP2003190961A (ja) * | 2001-12-28 | 2003-07-08 | Ebara Corp | 電気式脱塩装置 |
JP2007185587A (ja) * | 2006-01-12 | 2007-07-26 | Kurita Water Ind Ltd | 過酸化水素の除去方法及び除去装置 |
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JPH0596283A (ja) | 1991-10-03 | 1993-04-20 | Japan Organo Co Ltd | 溶存酸素除去装置 |
JPH07241569A (ja) | 1994-03-01 | 1995-09-19 | Tookemi:Kk | 水の溶存酸素除去方法およびその装置 |
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JPH10272474A (ja) * | 1997-03-28 | 1998-10-13 | Kurita Water Ind Ltd | 電気式脱イオン装置 |
JP2003094064A (ja) * | 2001-09-27 | 2003-04-02 | Kurita Water Ind Ltd | 電気脱イオン装置 |
JP2003190961A (ja) * | 2001-12-28 | 2003-07-08 | Ebara Corp | 電気式脱塩装置 |
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