WO2022249519A1 - Cellule d'électrolyse et générateur d'eau électrolysée - Google Patents

Cellule d'électrolyse et générateur d'eau électrolysée Download PDF

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WO2022249519A1
WO2022249519A1 PCT/JP2021/045508 JP2021045508W WO2022249519A1 WO 2022249519 A1 WO2022249519 A1 WO 2022249519A1 JP 2021045508 W JP2021045508 W JP 2021045508W WO 2022249519 A1 WO2022249519 A1 WO 2022249519A1
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chamber
cathode
water
electrolyte
diaphragm
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PCT/JP2021/045508
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English (en)
Japanese (ja)
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勝 二階堂
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森永乳業株式会社
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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
    • C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features

Definitions

  • the present invention relates to an electrolytic cell and an electrolytic water generator.
  • electrolyzed water which is obtained by electrolyzing water to give it various functions
  • an electrolyzed water generator that generates electrolyzed water (hypochlorous acid water) that has a function of sterilization and deodorization
  • an electrolyzed water generator that generates electrolyzed water (alkaline ion water) that has a function of drinking and washing and rust prevention.
  • An electrolyzed water generator electrolyzes an electrolyte in an electrolytic solution or water to obtain an electrolytic product, thereby generating electrolyzed water to which various functions are added.
  • Electrolytes include artificially added chlorides, oxides, alkali salts, carbonates, organic acids, etc., in addition to ion components contained in water.
  • An electrolyzed water generator that generates hypochlorous acid water for example, is provided with two diaphragms between a pair of electrodes, and an electrolyte chamber separated by two diaphragms between an anode chamber and a cathode chamber.
  • an electrolytic solution containing chloride ions is supplied only to the central electrolytic solution chamber, and water is circulated to the anode chamber and the cathode chamber, respectively.
  • Anode-produced water is produced from the anode chamber and cathode-produced water is produced from the cathode chamber in a form in which the anode and cathode products are separated from the electrolyte.
  • the generated anode-generated water (hypochlorous acid water) is basically acidic. However, hypochlorous acid water is more likely to generate chlorine gas as its acidity is stronger and its salt content (residual chlorine ion concentration) is higher. On the other hand, when the hypochlorous acid water is alkaline over pH 8, the hypochlorous acid changes to hypochlorous acid ions, and the sterilization ability is lowered.
  • the hydroxide ions OH - contained in the cathode-generated water neutralize the hydrogen ions H + contained in the anode-generated water.
  • a method of controlling the pH of the mixed water near neutral has been proposed.
  • a second cathode is provided in the electrolyte chamber as a method for accurately controlling the amount of hydroxide ions OH ⁇ contained in the cathode-generated water following fluctuations in hardness and pH of water flowing through the anode chamber and the cathode chamber. Therefore, a method has been proposed in which electrolysis is performed while switching the first cathode in the cathode chamber.
  • An object of the present invention is to obtain an electrolysis cell that can be used for a long period of time, and an electrolyzed water generator provided with the electrolysis cell.
  • an electrolyte chamber containing an electrolyte, an anode chamber partitioned from the electrolyte chamber by a first diaphragm, and an anode chamber partitioned from the electrolyte chamber by a second diaphragm an anode provided in the anode chamber facing the first diaphragm; a first cathode provided in the cathode chamber facing the second diaphragm; and a cathode provided in the electrolyte chamber.
  • a second cathode facing the anode with the first diaphragm interposed therebetween; and a first electrolyte chamber provided between the second cathode and the first diaphragm, the inside of the electrolyte chamber being located on the side of the anode chamber. and a third diaphragm separating a second electrolyte chamber on the cathode chamber side.
  • an electrolyte chamber containing an electrolyte, an anode chamber partitioned from the electrolyte chamber by a first diaphragm, and an anode chamber partitioned from the electrolyte chamber by a second diaphragm an anode provided in the anode chamber facing the first diaphragm; a first cathode provided in the cathode chamber facing the second diaphragm; a cathode provided in the electrolyte chamber; a second cathode facing the anode via a diaphragm; a first electrolyte chamber provided between the second cathode and the first diaphragm; a first electrolysis cell comprising a third diaphragm separating a chamber-side second electrolyte chamber; a first power supply unit that supplies power to the anode, the first cathode, and the second cathode; a switch for energizing the first cathode
  • FIG. 1 is a schematic representation of an electrolysis cell that can be used in the first embodiment.
  • FIG. 2 is a diagram schematically showing a running-water electrolyzed water generator according to the first embodiment.
  • FIG. 3 is a timing chart showing an example of switching between the first cathode and the second cathode used in the first embodiment.
  • FIG. 4 is a graph showing the results of a water quality change test according to the energization ratio in the first embodiment.
  • FIG. 5 is a graph showing the continuous operation test results of the electrolyzed water generator according to the first embodiment.
  • FIG. 6 is a schematic diagram showing an application example of the electrolyzed water generator according to the first embodiment.
  • FIG. 7 is a diagram schematically showing a running-water electrolyzed water generator according to the second embodiment.
  • FIG. 8 is a graph showing the results of a water quality change test according to the energization ratio in the second embodiment.
  • FIG. 9 is a diagram schematically showing a running-water electrolyzed water generator according to the third embodiment.
  • FIG. 10 is a graph showing the results of a water quality change test according to the energization ratio in the third embodiment.
  • FIG. 11 is a diagram schematically showing a running-water electrolyzed water generator according to the fourth embodiment.
  • FIG. 12 is a schematic diagram of an electrolytic cell used in the fifth embodiment.
  • FIG. 13 is a diagram schematically showing a storage-type electrolyzed water generator according to the fifth embodiment.
  • FIG. 14 is a graph showing the results of a water quality change test according to the energization ratio in the fifth embodiment.
  • FIG. 15 is a graph showing continuous operation test results in the fifth embodiment.
  • FIG. 16 is a diagram schematically showing an application example of the storage-type electrolyzed water generator according to the fifth embodiment.
  • FIG. 17 is a diagram schematically showing a storage-type electrolyzed water generator according to the sixth embodiment.
  • FIG. 1 shows a schematic diagram of an electrolysis cell that can be used in the first embodiment.
  • this electrolytic cell 2′ is a so-called three-chamber type electrolytic cell, in which a first diaphragm 3a made of an anion exchange membrane as a diaphragm on the anode side and a cathode as a diaphragm on the cathode side are provided. It has a second diaphragm 4a made of an ion exchange membrane.
  • an electrolyte chamber 5 functioning as an intermediate chamber defined between the diaphragms
  • An anode 3b is provided inside the anode chamber 3 so as to closely face the first diaphragm 3a
  • a first cathode 4b is provided inside the cathode chamber 4 so as to closely face the second diaphragm 4a.
  • proximity means adjoining, contacting, or being in close contact with the other.
  • the term "adjacent” refers to a state in which one is opposed to the other at a constant distance, and the distance between them is 0.3 mm or less, preferably 0.2 mm or less.
  • the anode 3b and the first cathode 4b are formed in rectangular shapes of substantially the same size, and face each other with the electrolyte chamber 5 and the first and second diaphragms 3a and 4a interposed therebetween.
  • the electrolytic solution chamber 5 has a third diaphragm 5a made of a neutral membrane having fine pores that do not have ion permeation selectivity and allow passage of cations and anions.
  • the electrolyte chamber 5 is partitioned by the third diaphragm 5a into a first electrolyte chamber 5c on the anode chamber 3 side and a second electrolyte chamber 5d on the cathode chamber 4 side.
  • the neutral membrane preferably has no ion selectivity, and for example, an electrolytic diaphragm for plating (manufactured by Yuasa Membrane Systems Co., Ltd.) can be used.
  • a second cathode 5b is provided in the second electrolytic solution chamber 5d so as to closely face the third diaphragm 5a.
  • the second cathode 5b like the anode 3b and the first cathode 4b, is formed in a rectangular shape having approximately the same size as the anode 3b and the first cathode 4b.
  • a titanium (Ti) metal plate having a large number of through holes can be used for the second cathode 5b.
  • a so-called insoluble electrode may be used in which a metal plate made of Ti and having a large number of through holes is coated with a catalyst such as Ir or Pt.
  • the third diaphragm 5a is provided between the second cathode 5b and the first diaphragm 3a, and the electrolyte chamber 5 is filled with the first electrolyte on the anode chamber 3 side. It is separated into a chamber 5c and a second electrolyte chamber 5d on the cathode chamber 4 side.
  • the flow of the electrolyte in the electrolyte chamber 5 is divided into two flows, that is, the flow of the first electrolyte in the first electrolyte chamber 5c and the flow of the second electrolyte in the second electrolyte chamber 5d. can be done.
  • the pH of the electrolyte in the second electrolyte chamber 5d shifts to the alkaline side.
  • the pH of the first electrolytic solution chamber 5c is closer to neutral than the pH of the second electrolytic solution chamber 5d. can be maintained at Therefore, the first diaphragm 3a that separates the first electrolytic solution chamber 5c and the anode chamber 3 is less likely to deteriorate, and an electrolytic cell that can be used for a long period of time can be obtained.
  • Electrodes such as the anode 3b, the first cathode 4b, and the second cathode 5b used in the embodiment for example, a metal plate substrate made of Ti in which a large number of through holes are formed and a metal plate substrate made of Ti An insoluble electrode with a catalyst layer formed on the surface can be used. Electrodes such as the first cathode 4b and the second cathode 5b do not have to be provided with a catalyst layer. As the electrode, a metal plate or a metal plate provided with a catalyst layer on its surface can be used. However, metal materials and catalyst materials that can be used in electrolyzed water generators that generate hypochlorous acid water are limited to those described in JIS B8701.
  • Ti of 1 to 13 species specified in JIS H 4650 can be used as the metal plate material.
  • the catalyst for example, a noble metal catalyst containing Pt and/or Ir, or an oxide catalyst containing iridium oxide as a main component and a stabilizing substance such as tantalum pentoxide, or the like can be used.
  • an oxide catalyst based on iridium oxide can be used.
  • the catalyst layer is formed by plating the noble metal catalyst in a plating solution for a predetermined period of time, and the oxide catalyst by repeatedly applying and drying a coating solution containing the catalyst on the surface of the metal plate material, followed by firing. can be done.
  • a commercially available insoluble electrode for generating chlorine can be used as the anode 3b.
  • Commercially available insoluble electrodes for generating chlorine include those provided by coating a Ti plate with a catalyst layer of Pt and/or Ir and those provided with a catalyst layer mainly composed of iridium oxide.
  • a Ti plate for example, a Ti plate having a large number of through holes can be used.
  • a Ti plate or a commercially available insoluble electrode for generating chlorine can be used.
  • Commercially available insoluble electrodes for generating chlorine include, for example, a Ti plate provided with a catalyst layer of Pt and/or Ir, or a catalyst layer mainly composed of iridium oxide.
  • a Ti plate having a large number of through holes can be used.
  • an anion exchange membrane in which a cation group is fixed to a porous polymer made of a hydrocarbon polymer or the like, positively charged, and only anions can pass through is used.
  • an anion exchange membrane for example, Neosepta AMX (manufactured by Astom) can be used.
  • a cation exchange membrane is used in which anion groups are fixed to a porous polymer made of, for example, a hydrocarbon-based polymer, a fluorine-based polymer, etc., and negatively charged so that only cations can pass through. can do.
  • a cation exchange membrane for example, Nafion (registered trademark) (manufactured by DuPont), which is a cation exchange membrane of a fluororesin copolymer, can be used.
  • a non-woven fabric or a porous diaphragm having a coating layer containing, for example, aluminum oxide on a porous base material such as a glass cloth and having no ion selective permeability can be used.
  • the porous diaphragm can be formed, for example, by impregnating a porous substrate such as non-woven fabric or glass cloth with aluminum oxide and drying.
  • the electrolysis cell of FIG. 1 can be incorporated into an electrolyzed water generator.
  • FIG. 2 shows a schematic diagram of a running-water electrolyzed water generator according to the first embodiment.
  • the electrolyzed water generator 1 includes an electrolysis cell 2 .
  • the electrolysis cell 2 uses an electrolysis cell having the same configuration as the electrolysis cell 2' shown in FIG.
  • a first electrolytic solution supply port 5f for supplying an electrolytic solution is provided below the first electrolytic solution chamber 5c.
  • a first electrolytic solution discharge port 5h for discharging the electrolytic solution that has flowed through the first electrolytic solution chamber 5c is provided in the upper portion of the first electrolytic solution chamber 5c.
  • a second electrolytic solution supply port 5g for supplying an electrolytic solution is provided in the lower portion of the second electrolytic solution chamber 5d.
  • a second electrolytic solution discharge port 5i for draining the electrolytic solution that has flowed through the second electrolytic solution chamber 5d is provided in the upper portion of the second electrolytic solution chamber 5d.
  • a first water supply port 3 f for supplying water is provided in the lower portion of the anode chamber 3 .
  • a first drain port 3 h for draining water that has flowed through the anode chamber 3 is provided in the upper portion of the anode chamber 3 .
  • a second water supply port 4 f for supplying water is provided in the lower portion of the cathode chamber 4 .
  • a second drain port 4 h for draining water that has flowed through the cathode chamber 4 is provided in the upper portion of the cathode chamber 4 .
  • a first electrolytic solution supply port 5f and a first electrolytic solution outlet 5h are provided in the first electrolytic solution chamber 5c, and a second electrolytic solution supply port 5g and a second electrolytic solution outlet 5i are provided in the second electrolytic solution chamber 5d. is provided.
  • the electrolyzed water generator 1 includes an electrolytic solution supply unit 8 that supplies an electrolytic solution containing chloride ions, such as salt water, to the electrolytic solution chamber 5 of the electrolytic cell 2 .
  • anode chamber 3 and the cathode chamber 4 are provided with a water supply unit 21 for supplying electrolyzed raw water, for example, water.
  • a power supply unit 7 having a power source 7a for applying a positive voltage to the anode 3b and a negative voltage to the first cathode 4b and/or the second cathode 5b is provided.
  • the power supply unit 7 includes a power source 7a that supplies a current necessary for electrolysis, a switch 7b that energizes the first cathode 4b and/or the second cathode 5b from the power source 7a, and a control unit 7c that controls the power source 7a and the switch 7b.
  • a switch 7b a selector switch for switching power supply to the first cathode 4b or the second cathode 5b is used.
  • a constant current power supply is desirable as the power supply 7a.
  • the positive electrode of the power supply 7a is connected to the anode 3b of the electrolytic cell 2 via wiring.
  • the negative electrode of the power supply 7a is connected to the first cathode 4b and the second cathode 5b via the switch 7b and two wires.
  • a negative voltage can be selectively applied to the first cathode 4b and the second cathode 5b.
  • the switch 7b for example, the current supplied to the first cathode 4b and the second cathode 5b is fixed, and the energization to the first cathode 4b or the second cathode 5b is switched over time, whereby the first cathode 4b and the second cathode 5b are switched.
  • the energization ratio of the two cathodes 5b can be adjusted.
  • a switch for energizing the first cathode 4b and/or the second cathode 5b for example, various values of current output can be obtained from the power supply 7a for the first cathode 4b and the second cathode 5b, respectively.
  • a switch device having a plurality of negative terminals connected to each other can be used.
  • ON/OFF switches are arranged between the first cathode 4b and the second cathode 5b and a plurality of negative terminals. By selectively turning ON/OFF these ON/OFF switches by the control unit 7c, it is possible to arbitrarily change the energization ratio as the current amount ratio of the first cathode 4b and the second cathode 5b.
  • the electrolyte supply unit 8 includes a salt water tank (electrolyte tank) 25 that stores an electrolyte 25a (for example, a 20% by mass sodium chloride aqueous solution (salt water)), and a supply that guides the salt water from the salt water tank 25 to the lower part of the electrolyte chamber 5.
  • a pipe 8a, a liquid feed pump 29 provided in the supply pipe 8a, and a drain pipe 8f for discharging salt water from above the electrolytic solution chamber 5 are provided.
  • the supply pipe 8a is connected to a first electrolytic solution supply port 5f provided in the lower part of the first electrolytic solution chamber 5c of the electrolytic solution chamber 5, and functions as a first electrolytic solution supply line for supplying the electrolytic solution. and a supply pipe 8c functioning as a second electrolyte supply line for supplying the electrolyte by connecting to the second electrolyte supply port 5g provided in the lower part of the second electrolyte chamber 5d of the electrolyte chamber 5; branched. Thereby, the electrolyte is separately supplied to the first electrolyte chamber 5c and the second electrolyte chamber 5d.
  • a drain pipe 8d is connected to the first electrolyte drain port 5h and functions as a first electrolyte drain line for draining the electrolyte that has flowed through the first electrolyte chamber 5c. is provided.
  • a drain pipe 8e is connected to the second electrolyte drain port 5i and functions as a second electrolyte drain line for draining the electrolyte that has flowed through the second electrolyte chamber 5d. is provided.
  • the first electrolytic solution (salt water) flows in the first electrolytic solution chamber 5c separated by providing the third diaphragm 5a in the electrolytic solution chamber 5, and the second electrolytic solution (salt water) flows in the second electrolytic solution chamber 5d. ) flow.
  • the drain pipe 8d and the drain pipe 8e are merged to form the drain pipe 8f, and the electrolytic solutions in the drain pipe 8d and the drain pipe 8e are mixed and discharged.
  • the drain pipe 8d and the drain pipe 8e may not be merged and discharged as they are.
  • the water supply unit 21 includes a water supply source 9 that supplies water, an opening/closing valve 28 provided near the outlet of the water supply source 9, and a first water supply pipe that guides water from the water supply source 9 to the lower portions of the anode chamber 3 and the cathode chamber 4. 21a and.
  • the electrolyzed water generator 1 also includes a first drain pipe 21b connected to the first drain port 3h and functioning as a first drain line for discharging the water that has flowed through the anode chamber 3 from the upper portion of the anode chamber 3; A second drain pipe 21c that is connected to the drain port 4h and functions as a second drain line for discharging the water that has flowed through the cathode chamber 4 from the upper portion of the cathode chamber 4 is provided.
  • the first water supply pipe 21a branches into a second water supply pipe 21e functioning as a first water supply line and a third water supply pipe 21f functioning as a second water supply line.
  • the second water supply pipe 21 e is connected to the first water supply port 3 f to supply water to the anode chamber 3 .
  • the third water supply pipe 21f is connected to the second water supply port 4f to supply water to the cathode chamber 4.
  • the first drain pipe 21b is connected to the middle part of the second drain pipe 21c and constitutes the first generated water mixing section 10 .
  • the anode-generated water discharged from the first drainage pipe 21b and the cathode-generated water discharged from the second drainage pipe 21c are mixed and discharged as mixed water (first mixed water).
  • the mixed water to be discharged is hypochlorous acid water whose pH is controlled to be slightly acidic/neutral.
  • each pipe may be provided with an on-off valve or a flow control valve.
  • the electrolyzed water generator configured as described above actually electrolyzes salt water to produce acidic water (anode-generated water) containing hypochlorous acid water, which is an acidic component, and sodium hydroxide, which is an alkaline substance.
  • acidic water anode-generated water
  • sodium hydroxide sodium hydroxide
  • alkaline water anode-generated water
  • the anode-generated water used here is hypochlorous acid water, which is acidic electrolyzed water, and is hereinafter sometimes referred to as acidic water.
  • the cathode-generated water is strongly alkaline electrolyzed water, and is hereinafter sometimes referred to as alkaline water. As shown in FIG.
  • the liquid feed pump 29 is operated to supply salt water from the salt water tank 25 to the first electrolyte chamber 5 c and the second electrolyte chamber 5 d of the electrolyte chamber 5 of the electrolytic cell 2 . Also, water is supplied from the water supply source 9 to the anode chamber 3 and the cathode chamber 4 .
  • power is supplied by switching the switch 7b to the first cathode 4b, positive and negative voltages are applied from the power supply 7a to the anode 3b and the first cathode 4b, respectively.
  • the sodium ions ionized in the salt water flowing into the first electrolyte chamber 5c and the second electrolyte chamber 5d are attracted to the first cathode 4b, pass through the second diaphragm 4a, and reach the first cathode 4b. do. Since the third diaphragm 5a is a neutral membrane that does not selectively permeate ions, it is permeable to sodium ions.
  • Chlorine ions ionized in the salt water in the first electrolyte chamber 5c and the second electrolyte chamber 5d are attracted to the anode 3b, pass through the first diaphragm 3a, and reach the anode 3b. Then, as shown in the following formula (2), the chlorine ions are oxidized at the anode 3b to generate chlorine gas. 2Cl ⁇ ⁇ Cl 2 +2e ⁇ (2) After that, the chlorine gas immediately reacts with water in the anode chamber 3 to produce hypochlorous acid and hydrochloric acid as shown in the following formula (3).
  • the acidic water (hypochlorous acid water) thus generated flows out from the anode chamber 3 to the first drain pipe 21b.
  • the alkaline water flowing out to the second drainage pipe 21c and the acidic water flowing out to the first drainage pipe 21b are mixed in the first generated water mixing section 10 to form mixed generated water. Then, the pH-adjusted hypochlorous acid water is discharged as the mixed product water.
  • a positive voltage and a negative voltage are applied from the power supply 7a to the anode 3b and the second cathode 5b, respectively.
  • the sodium ions ionized in the salt water flowing into the first electrolyte chamber 5c and the second electrolyte chamber 5d are attracted to the second cathode 5b.
  • the sodium ions ionized in the salt water in the first electrolyte chamber 5c can pass through the third diaphragm 5a and reach the second cathode 5b.
  • a sodium hydroxide aqueous solution containing hydrogen gas is produced in the second electrolyte chamber 5d by the electrolysis of salt water in the second cathode 5b.
  • the inside of the second electrolytic solution chamber 5d shifts to the strong alkaline side.
  • Alkaline water aqueous sodium hydroxide solution containing hydrogen gas
  • the alkaline water generated in the second electrolyte chamber 5d is separated from the cathode. Almost no liquid flows into the chamber 4 and the first electrolyte chamber 5c. As a result, the first electrolyte chamber 5c does not shift to the alkaline side. Therefore, the first diaphragm 3a in the first electrolytic solution chamber 5c is not exposed to strong alkali and is less likely to deteriorate. Moreover, the cathode-generated water discharged from the cathode chamber 4 at this time is the water supplied from the water supply source 9 itself.
  • Chlorine ions ionized in the salt water in the first electrolyte chamber 5c and the second electrolyte chamber 5d are attracted to the anode 3b. At this time, chlorine ions ionized in the salt water in the second electrolyte chamber 5d can pass through the first diaphragm 3a and reach the anode 3b. Chlorine ions are oxidized at the anode 3b to generate chlorine gas. After that, the chlorine gas immediately reacts with water in the anode chamber 3 to produce hypochlorous acid and hydrochloric acid. The acidic water (hypochlorous acid water) thus generated flows out from the anode chamber 3 through the first drain pipe 21b.
  • the acidic water is mixed with the waste water from the second drainage pipe 21c, but alkaline water is not mixed with the waste water from the second drainage pipe 21c. Therefore, the pH of the hypochlorous acid water obtained as mixed product water when power is supplied to the second cathode 5b is lower than the pH of the hypochlorous acid water obtained as mixed product water when power is supplied to the first cathode 4b. also lower.
  • the water used as raw water contains different impurities depending on the region and location, and especially the carbonic acid component has an interference effect toward weak alkalinity. Therefore, depending on the water used, the pH adjustment point may not match and may shift slightly.
  • the electrolyte chamber 5 is provided with the second cathode 5b, and the switch 7b is switched to the first cathode 4b or the second cathode 5b to supply power.
  • the first cathode 4b in the cathode chamber 4 and the second cathode 5b in the second electrolyte chamber 5d are selectively switched and energized to shift the cathode-generated water to the alkaline side or the neutral side. and the anode-generated water, the pH of the generated water can be adjusted.
  • the pH of the mixed product water can be adjusted at any time, and the pH of the hypochlorous acid water obtained as the mixed product water can be controlled to be slightly acidic or near neutral. Become. Further, when the energization from the power supply portion 7 is switched to the second cathode 5b, the pH of the electrolyte in the second electrolyte chamber 5d shifts to the alkaline side.
  • a third diaphragm 5a is provided between the second cathode 5b and the first diaphragm 3a, and the electrolyte chamber 5 is divided into a first electrolyte chamber 5c on the anode chamber 3 side and a second electrolyte chamber on the cathode chamber 4 side.
  • the alkaline substance is discharged by the flow of the second electrolyte and is hardly mixed into the flow of the first electrolyte. Therefore, since the pH of the first electrolyte chamber 5c can be maintained closer to neutral than the pH of the second electrolyte chamber 5d, the first diaphragm 3a of the first electrolyte chamber 5c is resistant to deterioration and has good durability. Become. Therefore, according to the embodiment, an electrolyzed water generator that can be used for a long period of time is obtained.
  • FIG. 3 shows a timing chart showing an example of switching of the current application path in the power feeding section 7.
  • This fixed the electrolysis current to 2 A, set the current application path to the first cathode 4b and the second cathode 5b with 1 cycle of 10 seconds, applied the first cathode 4b for 4 seconds, and applied the current to the second cathode 5b.
  • a pulse waveform 101 represents the relationship between the energization time to the first cathode 4b and the voltage at this time
  • a pulse waveform 102 represents the relationship between the energization time to the second cathode 5b and the voltage.
  • the electrolysis current, cycle, energization ratio at the first and second cathodes are configured to be user-manipulable.
  • the application time to the first cathode 4b is set to 10 seconds and the application time to the second cathode 5b is set to 0 seconds
  • normal three-chamber operation is performed.
  • the acid water and alkaline water generated at this time are mixed, mixed water having a pH of around 8.5 is obtained.
  • the application time to the first cathode 4b was set to 0 seconds and the application time to the second cathode 5b was set to 10 seconds
  • the electrolytic reaction did not occur in the cathode chamber 4, and the cathode chamber 4 was supplied to the electrolytic cell. Only raw water flows.
  • FIG. 4 is a graph showing the relationship between the energization ratio (duty ratio) of the second cathode 5b and the water quality (pH and effective chlorine concentration) of the mixed water in the electrolyzed water generator according to the first embodiment.
  • a characteristic line 104 is a graph representing the pH of the mixed product water with respect to the electrification ratio of the second cathode 5b.
  • a characteristic line 103 indicates the effective chlorine concentration of the mixed product water with respect to the energization ratio of the second cathode 5b.
  • the energization ratio of the second cathode 5b is the ratio of the energization time of the second cathode 5b to the time of one cycle. That is, the energization ratio of the second cathode 5b indicates the ratio of the amount of energization to the second cathode 5b to the total amount of current. In the energization ratio of the second cathode 5b, 0% indicates energization of only the first cathode 4b, and 100% indicates energization of only the second cathode 5b.
  • the energization ratio of 50% of the second cathode 5b means repeating the energization time of 5 seconds to the first cathode 4b and the energization time of 5 seconds to the second cathode 5b.
  • the water quality (pH and effective chlorine concentration) of the mixed product water was measured by sampling the mixed product water for a time sufficiently longer than the cycle time so that the difference in water quality due to switching the power supply was not sufficiently accumulated and affected. .
  • 3 mL/min of a 20% sodium chloride aqueous solution was supplied to each of the first electrolyte chamber 5c and the second electrolyte chamber 5d.
  • the mixed product water is alkaline. This is because all the alkaline substances generated at the first cathode 4b are mixed with the generated water.
  • the energization ratio of the second cathode 5b is increased from 0, as shown in the characteristic line 103, the effective chlorine concentration of the mixed product water is almost constant, but as shown in the characteristic line 104, the pH becomes acidic. become. This is because the alkaline substance produced at the second cathode 5b is released only into the second electrolyte chamber 5d and is not mixed with the mixed product water.
  • the pH fluctuates greatly from around 55% of the energization ratio of the second cathode, and the raw water is acidified.
  • the acidic water (hypochlorous acid chloric acid water) can be obtained.
  • the energization ratio of the second cathode 5b is increased and only the second cathode 5b is used without using the first cathode 4b (100% energization ratio)
  • the mixed product water is weakly acidic to strongly acidic. This is because no alkaline material is produced at the first cathode.
  • the raw water is mixed with the acid water as it is in the mixed product water, and the water quality of the acid water produced in the anode chamber 3 appears as it is.
  • tap water with a Ca hardness of 55 g/L was used as raw water.
  • the energization ratio of the second cathode 5b showing a slightly acidic region shifts to a smaller side
  • harder water is used, the energizing ratio of the second cathode 5b showing a slightly acidic region shifts to a larger side.
  • Continuous operation test The following continuous operation test was performed using the electrolyzed water generator 1 according to the first embodiment.
  • a 20% sodium chloride aqueous solution was supplied to each of the first electrolyte chamber 5c and the second electrolyte chamber 5d at 3 mL/min.
  • the electrolysis current is fixed at 2 A, one cycle is 10 seconds, and the electrification ratio of the second cathode is 60% (energization time to the first cathode 4b is 4 seconds, the second The energization time of the cathode 5b was set to 6 seconds).
  • the electrolyzed water generator 1 was operated for about 700 hours to continuously obtain mixed water.
  • the pH and effective chlorine concentration of the resulting mixed product water were initially measured every 24 hours, and then every week.
  • electrolyzed water generators having the same configuration as that of the first embodiment except that the third diaphragm 5a was not provided in the electrolyte chamber 5 of the electrolytic cell 2 were prepared.
  • the electrolyzed water generator was operated for about 700 hours under the same conditions to obtain mixed water.
  • the pH and effective chlorine concentration were similarly measured as changes in the water quality of the mixed product water obtained.
  • FIG. 5 shows a graph showing the continuous operation test results of the electrolyzed water generator according to the first embodiment.
  • the horizontal axis is the operating time.
  • Characteristic line 110 indicates the pH of the resulting mixed product water.
  • a characteristic line 105 indicates the effective chlorine concentration of the obtained mixed product water.
  • Characteristic lines 106 and 107 indicate the effective chlorine concentration of Comparative Examples 1 and 2
  • characteristic lines 108 and 109 indicate the pH of Comparative Examples 1 and 2.
  • Comparative Example 1 after 48 hours, a phenomenon was confirmed in which the pH increased as indicated by characteristic line 108 and the available chlorine concentration decreased as indicated by characteristic line 106 .
  • Comparative Example 2 After 168 hours, a phenomenon was confirmed in which the pH increased as indicated by characteristic line 109 and the effective chlorine concentration decreased as indicated by characteristic line 107 .
  • the electrolytic cells of Comparative Examples 1 and 2 were disassembled and investigated, it was confirmed that the first diaphragm in the anode chamber became cloudy and the membrane was broken in places. From this, it is considered that the electrolytic solution chamber was alkalinized by the alkaline substance generated at the second cathode, and the first diaphragm in contact with the electrolytic solution chamber was degraded and fractured.
  • the effective chlorine concentration and pH are constant even if it is operated for a long time, and the water quality of the mixed water does not change. unacceptable.
  • the electrolyte chamber 5 is divided into the first electrolyte chamber 5c on the side of the anode chamber 3 and the second electrolyte chamber 5d on the side of the cathode chamber 4 by the third diaphragm 5a made of a neutral membrane having no ion permeation selectivity. This is because the second cathode 5b is provided in the second electrolyte chamber 5d so as to closely face the third diaphragm 5a.
  • the alkaline substance produced at the second cathode 5b is produced and discharged only from the second electrolyte chamber 5d, which is not in contact with the first diaphragm 3a, and the action of the alkaline substance on the first diaphragm 3a is suppressed. It is believed that there is.
  • the electrolyte chamber 5 is divided into the first electrolyte chamber 5c on the anode chamber 3 side and the second electrolyte chamber 5d on the cathode chamber 4 side by the third diaphragm 5a made of a neutral membrane having no ion permeation selectivity.
  • a second cathode 5b is provided in the second electrolyte chamber 5d so as to be closely opposed to the third diaphragm 5a.
  • FIG. 6 shows a schematic diagram showing an application example of the electrolyzed water generator according to the first embodiment.
  • the mixed generated water 41 is accommodated in the rear stage of the first generated water mixing section 10 of the electrolysis cell 2, and the bottom portion 11a and the side wall 11b are accommodated.
  • a water reservoir 11 having a is further provided.
  • an online pH meter 12 functioning as a pH measuring section and a third drainage pipe 21d for discharging the mixed water from the water storage section 11 are installed.
  • the online pH meter 12 is connected to the controller 7c.
  • the water storage unit 11 can have a capacity to store the mixed product water for a time sufficiently longer than the cycle time so that the difference in water quality due to the power switching is sufficiently integrated and does not affect the water quality.
  • Other configurations of the electrolyzed water generator 1-1 are the same as those of the electrolyzed water generator 1 shown in FIG.
  • the mixed product water 41 from the first product water mixing unit 10 is introduced into the water storage unit 11, and the pH of the mixed product water 41 is measured at any time by the online pH meter 12, and the mixed product is produced. Water 41 is discharged from the third drain pipe 21d.
  • the pH measurement signal from the online pH meter 12 is calculated by the control unit 7c, and the second An algorithm is constructed to automatically change the energization ratio of the cathode 5b. This allows automatic pH control of the mixed product water. In addition, it has the same effects as those of the electrolyzed water generator 1 .
  • the online pH meter 12 that can automatically measure the pH of the mixed water 41 in the water reservoir 11 is used, but the operator manually measures the pH of the mixed water 41 in the water reservoir 11 at any time.
  • the value is input to the control unit 7c, and the control unit 7c calculates based on the value to create an algorithm for automatically changing the energization ratio of the second cathode 5b.
  • FIG. 7 is a diagram schematically showing a running-water electrolyzed water generator according to the second embodiment.
  • the electrolyzed water generator 1-2 uses a so-called three-chamber type electrolyzer (electrolytic cell) 2-2.
  • the interior thereof is provided with a first diaphragm (anode side diaphragm, anion exchange membrane) 3a and a second diaphragm (cathode side diaphragm, cation exchange membrane) 4a, thereby forming an electrolyte chamber defined between the diaphragms. 5 , and an anode chamber 3 and a cathode chamber 4 located on both sides of the electrolyte chamber 5 .
  • An anode 3b is provided in the anode chamber 3, and is closely opposed to the first diaphragm 3a.
  • a first cathode 4b is provided in the cathode chamber 4 and closely faces the second diaphragm 4a.
  • the anode 3b and the cathode 4b are formed in the shape of rectangular plates of approximately the same size, and face each other with the electrolyte chamber 5 and the first and second diaphragms 3a and 4a interposed therebetween.
  • the electrolytic solution chamber 5 is a third diaphragm 5a made of a neutral membrane having no selectivity of ion permeation and allowing the passage of cations and anions. is partitioned into a second electrolyte chamber 5d.
  • a second cathode 5b is provided in the second electrolytic solution chamber 5d so as to closely face the third diaphragm 5a.
  • the second cathode 5b like the anode 3b and the first cathode 4b, is formed in a rectangular shape having approximately the same size as the anode 3b and the first cathode 4b.
  • a porous member 5e is provided in at least a part of the first electrolytic solution chamber 5c on the anode chamber 3 side as a "water-permeable diffusion suppressing member" for controlling diffusion of alkaline substances.
  • the diffusion suppressing member is water permeable. That is, when the electrolytic solution is supplied from the first electrolytic solution supply port 5f through the supply pipe 8b, the electrolytic solution needs to pass through the diffusion suppressing member. Therefore, the diffusion suppressing member has water permeability. When the positive and negative electrodes are energized while the electrolyte is flowing inside, the sodium ions and chloride ions in the electrolyte move toward the electrodes due to the electrical force. However, no electric force is generated when the current is stopped.
  • the diffusion suppressing member has a function of making such diffusion difficult, that is, a function of suppressing natural movement of substances not caused by electrical force.
  • the action of the water-permeable diffusion suppressing member as described above is as follows. First, when the electrolyzed water generator 1-2 is in operation, the diffusion suppressing member is water permeable, so the electrolytic solution passes through the inside of the diffusion suppressing member, and electrolyzed water is generated by energizing both the positive and negative electrodes. . On the other hand, when the electrolyzed water generator 1-2 is stopped, an alkaline substance may flow into the first electrolyte chamber 5c from the second electrolyte chamber 5d side due to diffusion. In this case, if the diffusion suppressing member is installed, it is possible to suppress the inflow of the alkaline substance into the first electrolytic solution chamber 5c. This makes the first diaphragm 3a more difficult to deteriorate.
  • the porous member 5e examples include a sintered plastic porous material (manufactured by Fuji Chemical Co., Ltd.), a sintered ceramic porous material, and the like.
  • the power supply unit 7 has a power supply 7a, a control unit 7c that controls the power supply 7a, and a switch 7b (changeover switch) that switches power supply to the first cathode 4b and the second cathode 5b.
  • the positive electrode of the power supply 7a is connected to the anode 3b via wiring.
  • the negative electrode of the power supply 7a is connected to the first cathode 4b and the second cathode 5b via the switch 7b and two wires. That is, by switching the switch 7b, a negative voltage can be selectively applied to the first cathode 4b or the second cathode 5b.
  • the switch 7b is configured to be operable by a user.
  • the electrolyzed water generator 1-2 includes an electrolytic solution supply unit 8 that supplies an electrolytic solution (for example, salt water) to the first and second electrolytic solution chambers 5c and 5d of the electrolytic cell 2-2, the anode chamber 3 and It has a water supply unit 21 that supplies water to the cathode chamber 4 and a first generated water mixing unit 10, and is configured in the same manner as the electrolyzed water generator 1 according to the first embodiment described above.
  • the mixed water discharged from the electrolyzed water generator 1-2 is hypochlorous acid water whose pH is controlled to be slightly acidic/neutral.
  • a positive voltage is selectively applied to the anode 3b and a negative voltage is selectively applied to the first cathode 4b or the second cathode 5b.
  • the switch 7b changeover switch
  • the switch 7b changeover switch
  • the alkaline substance generated in the second electrolyte chamber 5d permeates the third diaphragm 5a to the first electrolyte chamber 5c and the first electrolyte chamber 5c. Diffusion to the first diaphragm 3a in contact with the first electrolyte chamber 5c can be suppressed.
  • the pH of the mixed product water can be adjusted at any time. It is possible to control the pH of the hypochlorous acid water obtained as a slightly acidic / neutral. Further, when the energization from the power supply portion 7 is switched to the second cathode 5b, the pH of the electrolyte in the second electrolyte chamber 5d shifts to the alkaline side.
  • the alkaline substance is discharged by the flow of the second electrolyte, and the flow of the first electrolyte hardly mixed with Therefore, the first diaphragm 3a of the first electrolytic solution chamber 5c is less likely to deteriorate and has good durability. Therefore, according to the second embodiment, it is possible to obtain an electrolyzed water generator that can be used for a long period of time.
  • a water quality change test and a continuous operation test were conducted as follows.
  • Water quality change test by energization ratio Using the electrolyzed water generator 1-2, pure water was flowed as raw water at 0.5 L/min, the electrolysis current was fixed at 2 A, and one cycle was 10 seconds. The energization of the first cathode and the second cathode in one cycle was switched to variously change the ratio of the energization time, and the water quality change (pH and effective chlorine concentration) of the mixed product water was measured.
  • FIG. 8 is a graph showing the relationship between the energization ratio (duty ratio) of the second cathode 5b and the water quality of the mixed water in the electrolyzed water generator 1-2 according to the second embodiment.
  • a characteristic line 112 indicates the change in pH with respect to the energization ratio of the second cathode 5b
  • a characteristic line 111 indicates the change in effective chlorine concentration with respect to the energization ratio of the second cathode 5b.
  • the energization ratio of the second cathode 5b is the ratio of the energization time of the second cathode 5b to the time of one cycle, as in the first embodiment.
  • the water quality (pH and effective chlorine concentration) of the mixed product water was measured by sampling the mixed product water for a time sufficiently longer than the cycle time so that the difference in water quality due to switching the power supply was not sufficiently integrated and affected. .
  • 3 mL/min of a 20% sodium chloride aqueous solution was supplied to each of the first electrolyte chamber 5c and the second electrolyte chamber 5d.
  • the acidic water (pH 5 to 6.5) is in a slightly acidic region (pH 5 to 6.5) with a high abundance ratio of the active ingredient HClO and is less affected by corrosion ( Hypochlorous acid water) can be obtained.
  • the effective chlorine concentration of the mixed product water is almost constant.
  • the pH of the mixed product water can be sufficiently controlled by the energization ratio of the second cathode 5b.
  • the porous member 5e is provided in the first electrolyte chamber 5c, diffusion of the alkaline substance into the first electrolyte chamber 5c is suppressed while the electrolysis cell is stopped.
  • the first diaphragm 3a deteriorates, the first diaphragm 3a is mechanically sandwiched between the porous member 5e and the anode 3b.
  • porous member 5e when the porous member 5e is provided in the first electrolytic solution chamber 5c, the porous member 5e also acts as a flow path resistance, and the flow rate of the electrolytic solution flowing into the first electrolytic solution chamber 5c is higher than the flow rate of the electrolytic solution. In some cases, the flow rate of the electrolyte flowing into the second electrolyte chamber 5d is greater. In that case, there is an advantage that the alkaline water generated in the second electrolyte chamber 5d can be efficiently discharged.
  • a flow control valve may be provided in the supply pipe 8b and/or the supply pipe 8c.
  • FIG. 9 is a diagram schematically showing a running-water electrolyzed water generator according to the third embodiment.
  • the electrolyzed water generator 1-3 according to the third embodiment connects at least two electrolysis cells 2, 2-1 in series, and for example, the first electrolysis cell 2 is used as raw water to be supplied to the second electrolysis cell 2-1.
  • the pH is adjusted stepwise using the first mixed product water.
  • the electrolyzed water generator 1-3 uses a so-called three-chamber type first electrolysis cell 2 and second electrolysis cell 2-1.
  • the inside of the first electrolytic cell 2 includes a first diaphragm (anode side diaphragm, anion exchange membrane) 3a and a second diaphragm (cathode side diaphragm, cation exchange membrane) 4a.
  • the electrolyte chamber 5 defined between the diaphragms is partitioned into three chambers, an anode chamber 3 and a cathode chamber 4 located on both sides of the electrolyte chamber 5 .
  • An anode 3b is provided in the anode chamber 3, and is closely opposed to the first diaphragm 3a.
  • a first cathode 4b is provided in the cathode chamber 4 and closely faces the second diaphragm 4a.
  • the anode 3b and the first cathode 4b are formed in the shape of rectangular plates of substantially the same size, and face each other with the electrolyte chamber 5 and the first and second diaphragms 3a and 4a interposed therebetween.
  • the electrolytic solution chamber 5 is a third diaphragm 5a made of a neutral membrane having no selectivity of ion permeation and allowing the passage of cations and anions. is partitioned into a second electrolyte chamber 5d.
  • a second cathode 5b is provided in the second electrolytic solution chamber 5d so as to closely face the third diaphragm 5a.
  • the second cathode 5b like the anode 3b and the first cathode 4b, is formed in a rectangular shape having approximately the same size as the anode 3b and the first cathode 4b.
  • the power supply unit 7 connected to the first electrolysis cell 2 includes a power supply 7a that supplies current necessary for electrolysis, a switch 7b that supplies current to the first cathode 4b and/or the second cathode 5b, the power supply 7a and the switch 7b. and a control unit 7c for controlling.
  • a switch 7b a changeover switch for switching power supply to the first cathode 4b and the second cathode 5b is used.
  • a constant current power supply is desirable as the power supply 7a.
  • the positive electrode of the power supply 7a is connected to the anode 3b of the first electrolytic cell 2 via wiring.
  • the negative electrode of the power supply 7a is connected to the first cathode 4b and the second cathode 5b via the switch 7b and two wires. By switching the switch 7b, a negative voltage can be selectively applied to the first cathode 4b and the second cathode 5b.
  • the switch 7b is configured to be operable by a user.
  • the second electrolysis cell 2-1 is connected to the first electrolysis cell 2 and the first product water mixing unit 10-1 used in the mixed product water supply line 10s, and is provided downstream of the first electrolysis cell 2. , has almost the same configuration as the first electrolytic cell 2 .
  • the interior of the second electrolytic cell 2-1 includes a first diaphragm (anode side diaphragm, anion exchange membrane) 3-1a and a second diaphragm (cathode side diaphragm, cation exchange membrane) 4-1a.
  • the electrolyte chamber 5-1 defined between the diaphragms is partitioned into three chambers, an anode chamber 3-1 and a cathode chamber 4-1 located on both sides of the electrolyte chamber 5-1.
  • An anode 3-1b is provided in the anode chamber 3-1 and faces the first diaphragm 3-1a.
  • a first cathode 4-1b is provided in the cathode chamber 4-1 and faces the second diaphragm 4-1a.
  • the anode 3-1b and the first cathode 4-1b are formed in the shape of rectangular plates of approximately the same size, sandwiching the electrolyte chamber 5-1 and the first and second diaphragms 3-1a and 4-1a. , facing each other.
  • the electrolyte chamber 5-1 is a third diaphragm 5-1a made of a neutral membrane that has no selectivity in ion permeation and allows passage of cations and anions, and a first electrolyte chamber 5-1c on the anode chamber 3 side. and a second electrolyte chamber 5-1d on the cathode chamber 4 side.
  • a second cathode 5-1b is provided in the second electrolyte chamber 5-1d so as to closely face the third diaphragm 5-1a.
  • the second cathode 5-1b is formed in a rectangular shape having approximately the same size as the anode 3-1b and the first cathode 4-1b.
  • Anode 3-1b has the same configuration as anode 3b.
  • the first cathode 4-1b has the same configuration as the first cathode 4b.
  • the second cathode 5-1b has the same configuration as the second cathode 5b.
  • the power supply unit 7-1 connected to the second electrolysis cell 2-1 includes a power supply 7-1a, a control unit 7-1c for controlling the power supply 7-1a, a first cathode 4-1b and a second cathode 5-1. It has a switch 7-1b (changeover switch) for switching power supply to 1b.
  • the positive electrode of the power supply 7-1a is connected to the anode 3-1b via wiring.
  • the negative electrode of the power supply 7-1a is connected to the first cathode 4-1b and the second cathode 5-1b via the switch 7-1b and two wires. That is, by switching the switch 7-1b, a negative voltage can be selectively applied to the first cathode 4-1b or the second cathode 5-1b.
  • the switch 7-1b is configured to be operable by the user.
  • the electrolyzed water generator 1-3 includes first and second electrolyte chambers 5c and 5d of the first electrolysis cell 2, and first and second electrolyte chambers 5-1c of the second electrolysis cell 2-1, 5-1d is provided with an electrolytic solution supply unit 8-1 for supplying an electrolytic solution (eg, salt water).
  • the water supply part 21 which supplies water to the anode chamber 3 and the cathode chamber 4 of the 1st electrolysis cell 2 is provided.
  • the first mixed product water obtained by mixing the anode-generated water and the cathode-generated water discharged from the anode chamber 3 and the cathode chamber 4 is added to the anode chamber 3-1 and the cathode chamber 4 of the second electrolytic cell 2-1.
  • -1 is provided with a first generated water mixing unit 10-1.
  • the first generated water mixing section 10-1 is used as a mixed generated water supply line 10s.
  • the electrolyte supply unit 8-1 has a salt water tank (electrolyte tank) 25 that stores an electrolyte 25a (eg, 20% sodium chloride aqueous solution). It also has a supply pipe 8a for guiding salt water from the salt water tank 25 to below the first and second electrolyte chambers 5c and 5d of the first electrolytic cell 2, and a liquid feed pump 29 provided in the supply pipe 8a. Furthermore, it has a drainage pipe 8f for discharging salt water from above the first and second electrolyte chambers 5c and 5d of the first electrolytic cell 2. As shown in FIG.
  • a supply pipe 8-1a branches from the supply pipe 8a in the vicinity of the outlet of the salt water tank 25, and guides the salt water below the first and second electrolyte chambers 5-1c and 5-1d.
  • a liquid transfer pump 29-1 is provided in the supply pipe 8-1a.
  • the supply pipe 8a is connected to a first electrolytic solution supply port 5f provided in the lower part of the first electrolytic solution chamber 5c of the electrolytic solution chamber 5, and functions as a first electrolytic solution supply line for supplying salt water.
  • 8b and a supply pipe 8c functioning as a second electrolyte supply line for supplying salt water by connecting to a second electrolyte supply port 5g provided in the lower portion of the second electrolyte chamber 5d of the electrolyte chamber 5. .
  • Electrolyzed water is thereby separately supplied to the first electrolyte chamber 5c and the second electrolyte chamber 5d.
  • a drain pipe 8d is connected to the first electrolyte drain port 5h and functions as a first electrolyte drain line for draining the electrolyte that has flowed through the first electrolyte chamber 5c.
  • a drain pipe 8e is connected to the second electrolyte drain port 5i and functions as a second electrolyte drain line for draining the electrolyte that has flowed through the second electrolyte chamber 5d. is provided.
  • the flow of salt water in the first electrolyte chamber 5c is separate from the flow of salt water in the second electrolyte chamber 5d.
  • the drain pipe 8d and the drain pipe 8e are merged to form the drain pipe 8f, and the electrolytic solutions in the drain pipe 8d and the drain pipe 8e are mixed and discharged.
  • the supply pipe 8-1a is connected to a first electrolyte supply port 5-1f provided in the lower portion of the first electrolyte chamber 5-1c of the electrolyte chamber 5-1 to supply salt water.
  • a supply pipe 8-1b functioning as a line is connected to a second electrolytic solution supply port 5-1g provided in the lower part of the second electrolytic solution chamber 5-1d of the electrolytic solution chamber 5-1 to supply salt water.
  • a supply pipe 8-1c functioning as an electrolyte solution supply line.
  • first electrolyte chamber 5-1c Above the first electrolyte chamber 5-1c, it is connected to the first electrolyte discharge port 5-1h and serves as a first electrolyte discharge line for draining the electrolyte that has flowed through the first electrolyte chamber 5-1c.
  • a functioning drain pipe 8-1d is connected.
  • a second electrolyte discharge line Above the second electrolyte chamber 5-1d, a second electrolyte discharge line is connected to the second electrolyte discharge port 5-1i and serves as a second electrolyte discharge line for draining the electrolyte that has flowed through the second electrolyte chamber 5-1d.
  • a functioning drain pipe 8-1e is connected.
  • the flow of salt water in the first electrolyte chamber 5-1c is separate from the flow of salt water in the second electrolyte chamber 5-1d.
  • the drain pipe 8-1d and the drain pipe 8-1e are merged to form the drain pipe 8-1f, and the electrolytic solutions in the drain pipe 8-1d and the drain pipe 8-1e are mixed and discharged.
  • the water supply unit 21 includes a water supply source 9 that supplies water, an opening/closing valve 28 provided near the outlet of the water supply source 9, and a first water supply pipe that guides water from the water supply source 9 to the lower portions of the anode chamber 3 and the cathode chamber 4. 21a.
  • the first electrolytic cell 2 also includes a first drain pipe 21b connected to a first drain port 3h and functioning as a first drain line for discharging water that has flowed through the anode chamber 3 from the upper portion of the anode chamber 3;
  • a second drain pipe 21c that is connected to the drain port 4h and functions as a second drain line for discharging the water that has flowed through the cathode chamber 4 from the upper portion of the cathode chamber 4 is provided.
  • the first water supply pipe 21a branches into a second water supply pipe 21e functioning as a first water supply line and a third water supply pipe 21f functioning as a second water supply line.
  • the second water supply pipe 21 e is connected to the first water supply port 3 f to supply water to the anode chamber 3 .
  • the third water supply pipe 21f is connected to the second water supply port 4f to supply water to the cathode chamber 4.
  • the first drain pipe 21b is connected to the middle portion of the second drain pipe 21c, and constitutes the first generated water mixing section 10-1 used as the mixed generated water supply line 10s.
  • the first mixed product water is hypochlorous acid water whose pH is controlled from a weak alkaline acid to a neutral range.
  • the first mixed product water obtained from the first electrolytic cell 2 is sent to the second electrolytic cell 2-1 by the first product water mixing section 10-1.
  • the downstream of the first generated water mixing section 10-1 is connected to the first water supply port 3-1f provided in the lower part of the anode chamber 3-1, and the third drainage pipe 10-1a for supplying the first mixed generated water.
  • a fourth drain pipe 10-1b connected to a second water supply port 4-1f provided in the lower part of the cathode chamber 4-1 to supply the first mixed product water.
  • the first generated water mixing unit 10-1, the third drain pipe 10-1a, and the fourth drain pipe 10-1b are connected to the anode chamber 3-1 and the cathode chamber 4-1. It can be used as the mixed product water supply line 10s for supplying the first mixed product water.
  • a fifth drain pipe 10-1c for draining the anode-generated water flowing through the anode chamber 3-1 is connected to the first drain port 3-1h provided in the upper part of the anode chamber 3-1.
  • a sixth drain pipe 10-1d for draining cathode-generated water flowing through the cathode chamber 4-1 is connected to a second outlet 4-1h provided in the upper portion of the cathode chamber 4-1.
  • the sixth drain pipe 10-1d is connected to the middle portion of the fifth drain pipe 10-1c, and mixes the anode-generated water and the cathode-generated water of the second electrolysis cell 2-1 to obtain second mixed generated water. It constitutes the second water mixing section 10-1e.
  • the second mixed product water is hypochlorous acid water whose pH is controlled to be slightly acidic or near neutral by the second electrolytic cell 2-1.
  • each pipe may be provided with an on-off valve or a flow control valve.
  • the electrolyzed water generator according to the third embodiment, mixed production of the first electrolysis cell 2 as raw water to be supplied to the anode chamber 3-1 and the cathode chamber 4-1 of the second electrolysis cell 2-1
  • water first mixed product water
  • the pH of the generated water is adjusted step by step in the first electrolytic cell 2 and the second electrolytic cell 2-1, and the final mixed product water (second mixed product water) can be obtained.
  • the electrolytic cell it is possible to use the electrolytic cell 2 or 2-2 used in the first embodiment or the second embodiment.
  • the electrolytic cell 2 used in the first embodiment is used.
  • the first electrolysis cell 2 and the second electrolysis cell 2-1 have the same configuration in material, shape, size, etc., but may have different configurations.
  • the electrolytic solution supply unit 8 shares the electrolytic solution supply unit for the first electrolytic cell 2 and the second electrolytic cell 2-1, but may be separate.
  • the pH of the mixed product water can be adjusted at any time. It is possible to control the pH of hypochlorous acid water obtained as water to be slightly acidic or near neutral. Further, when the current supply from the power supply portion 7 is switched to the second cathodes 5b and 5-1b, the pH of the electrolyte in the second electrolyte chambers 5d and 5-1d shifts to the alkaline side.
  • the third diaphragms 5a, 5-1a by separating the electrolyte chambers 5, 5-1 into the first electrolyte chambers 5c, 5-1c and the second electrolyte chambers 5d, 5-1d by the third diaphragms 5a, 5-1a, alkaline substances can be It is discharged by the flow of the second electrolytic solution and hardly mixed into the flow of the first electrolytic solution. Therefore, the first diaphragms 3a and 3-1a of the first electrolytic solution chambers 5c and 5-1c are less likely to deteriorate and have good durability. In addition to this, the alkalinity of the second electrolytic solution chambers 5d and 5-1d can be suppressed by performing stepwise pH adjustment in the first electrolytic cell 2 and the second electrolytic cell 2-1. Therefore, according to the third embodiment, it is possible to obtain an electrolyzed water generator that can be used for a longer period of time than the first and second embodiments.
  • the electrolysis current of the second electrolysis cell 2-1 was fixed at 1.0 A, and one cycle was 10 seconds.
  • the water quality (pH and effective chlorine concentration) of the mixed water produced in the second electrolysis cell 2-1 is measured. did.
  • FIG. 10 is a graph showing the relationship between the energization ratio (duty ratio) of the second cathode 5-1b of the second electrolysis cell 2-1 and the quality of the mixed product water in the electrolyzed water generator according to the third embodiment.
  • the characteristic line 113 is the effective chlorine concentration with respect to the energization ratio of the second cathode 5-1b of the second electrolytic cell 2-1
  • the characteristic line 114 is the energization ratio of the second cathode 5-1b of the second electrolytic cell 2-1. pH is shown respectively.
  • the energization ratio of the second cathode is the ratio of the energization time of the second cathode 5-1b to the time of one cycle.
  • the water quality (pH and effective chlorine concentration) of the mixed product water in the second electrolysis cell 2-1 is measured in a time sufficiently longer than the cycle time so that the difference in water quality due to the switching of the power supply is not sufficiently integrated and affected. I collected water. During the production of electrolyzed water, 3 mL/mL of 20% sodium chloride aqueous solution was added to each of the first electrolyte chamber 5c, the second electrolyte chamber 5d, the first electrolyte chamber 5-1c, and the second electrolyte chamber 5-1d. Separately fed.
  • the electrolysis current of the first electrolysis cell 2 was fixed at 1.0 A, the energization time of the first cathode 4b was set to 7 seconds and the energization time of the second cathode 5b was set to 3 seconds, and the pH was 6.9 and the effective chlorine concentration was 48 mg / L.
  • a mixed product water was obtained. When this mixed product water is used as the raw water to be supplied to the second electrolysis cell 2-1, as shown by the characteristic line 114, the pH fluctuates greatly from the second cathode 5-1b energization ratio of around 40%, and becomes acidic.
  • the acidic water (pH 5 to 6.5) is in a slightly acidic region (pH 5 to 6.5) with a high abundance ratio of the active ingredient HClO and is less affected by corrosion ( Hypochlorous acid water) can be obtained.
  • Hypochlorous acid water Hypochlorous acid water
  • At least two electrolytic cells 2 and 2-1 are connected in series using the electrolyzed water generator 1-3 according to the third embodiment. Then, the mixed product water of the first electrolytic cell 2 is used as the raw water to be supplied to the second electrolytic cell 2-1, and the pH is adjusted step by step. As a result, acidic water (next chlorous acid water) can be obtained. In addition, the amount of alkaline substances generated per electrolytic cell is suppressed, the abundance ratio of the active ingredient HClO is higher, and acidic water (hypochlorous acid water) in a slightly acidic range (pH 5 to 6.5) is produced. Obtainable. As a result, the influence of corrosion and the like is small, and it is possible to operate for a longer period of time.
  • FIG. 11 is a diagram schematically showing a running-water electrolyzed water generator according to the fourth embodiment.
  • the electrolyzed water generator according to the fourth embodiment two or more electrolyzed cells are connected in parallel to increase the amount of electrolyzed water generated.
  • the electrolyzed water generator 1-4 uses a so-called three-chamber type first electrolysis cell 2 and second electrolysis cell 2-1. Since the configurations of the first electrolytic cell 2 and the second electrolytic cell 2-1 are the same as those of the electrolytic cell shown in FIG. 9, description thereof is omitted here.
  • the electrolyzed water generator 1-4 includes first and second electrolyte chambers 5c and 5d of the first electrolysis cell 2, and first and second electrolyte chambers 5-1c of the second electrolysis cell 2-1, 5-1d is provided with an electrolytic solution supply unit 8-1 for supplying an electrolytic solution (eg, salt water). Further, a water supply unit 21 for supplying water to the anode chamber 3 and cathode chamber 4 of the first electrolysis cell 2 and the anode chamber 3-1 and cathode chamber 4-1 of the second electrolysis cell 2-1 is provided.
  • an electrolytic solution eg, salt water
  • a first water mixing unit 10 for mixing the anode-generated water and the cathode-generated water discharged from the anode chamber 3 and the cathode chamber 4, and the anode-generated water discharged from the anode chamber 3-1 and the cathode chamber 4-1. and a third generated water mixing unit 10-2 that mixes the cathode generated water, a fourth generated water mixing unit 10-2a that further mixes the first generated water mixing unit 10 and the third generated water mixing unit 10-2, Prepare.
  • the electrolytic solution supply unit 8-1 has the same configuration as the electrolytic solution supply unit shown in FIG.
  • the water supply unit 21 includes a water supply source 9 that supplies water, an opening/closing valve 28 provided near the outlet of the water supply source 9, and a first water supply pipe that guides water from the water supply source 9 to the lower portions of the anode chamber 3 and the cathode chamber 4. 21a and.
  • the electrolyzed water generator 1-4 also includes a first drain pipe 21b connected to the first drain port 3h and functioning as a first drain line for discharging the water that has flowed through the anode chamber 3 from the upper portion of the anode chamber 3;
  • a second drain pipe 21c is provided, which is connected to the second drain port 4h and functions as a second drain line for discharging the water that has flowed through the cathode chamber 4 from the upper portion of the cathode chamber 4.
  • the first water supply pipe 21a branches into a second water supply pipe 21e functioning as a first water supply line and a third water supply pipe 21f functioning as a second water supply line.
  • the second water supply pipe 21 e is connected to the first water supply port 3 f to supply water to the anode chamber 3 .
  • the third water supply pipe 21f is connected to the second water supply port 4f to supply water to the cathode chamber 4. As shown in FIG.
  • the water supply unit 21 further includes a fourth water supply pipe 21-1a that branches off from the first water supply pipe 21a downstream of the on-off valve 28 and guides water to the anode chamber 3-1 and the cathode chamber 4-1. It also has a fifth drain pipe 21-1b for discharging the water that has flowed through the anode chamber 3-1 from above the anode chamber 3-1. Further, a sixth drain pipe 21-1c for discharging water flowing through the cathode chamber 4 from the upper portion of the cathode chamber 4-1 is provided.
  • the first water supply pipe 21-1a branches into a second water supply pipe 21-1e functioning as a first water supply line and a third water supply pipe 21-1f functioning as a second water supply line.
  • the second water supply pipe 21-1e is connected to the first water supply port 3-1f to supply water to the anode chamber 3-1.
  • the third water supply pipe 21-1f is connected to the second water supply port 4-1f to supply water to the cathode chamber 4-1.
  • the first drainage pipe 21b is connected to the middle portion of the second drainage pipe 21c and constitutes the first generated water mixing section 10. As a result, the anode-generated water discharged from the first drainage pipe 21b and the cathode-generated water discharged from the second drainage pipe 21c are mixed to form the first mixed water. Also, the fifth drain pipe 21-1b is connected to the middle portion of the sixth drain pipe 21-1c to constitute the third generated water mixing section 10-2. As a result, the anode-generated water drained from the fifth drain pipe 21-1b and the cathode-generated water drained from the sixth drain pipe 21-1c are mixed to form the third mixed water.
  • the second drainage pipe 21c and the sixth drainage piping 21-1c join to form the fourth generated water mixing section 10-2a.
  • the fourth generated water mixing section 10-2a the first mixed generated water of the first generated water mixing section 10 and the third mixed generated water of the third generated water mixing section 10-2 are mixed to form the fourth mixed generated water.
  • the mixed product water is hypochlorous acid water whose pH is controlled near neutral.
  • the electrolyzed water generator 1-4 according to the fourth embodiment, at least two electrolysis cells are connected in parallel. As a result, it is possible to increase the amount of electrolyzed water generated. Further, it is possible to shift the switching timing of the first cathode and the second cathode of the two electrolytic cells, so that more precise mixing in the fourth water mixing section 10-2a is possible. Therefore, it is possible to operate without providing a water storage section in the rear stage of the fourth generated water mixing section 10-2a.
  • the electrolyzed water generator 1-4 according to the fourth embodiment is used, similarly to the first embodiment, even if the quality of the raw water fluctuates, the pH of the mixed product water can be adjusted at any time. Therefore, it is possible to control the pH of the hypochlorous acid water obtained as the mixed product water to be slightly acidic or near neutral. Further, when the current supply from the power supply portion 7 is switched to the second cathodes 5b and 5-1b, the pH of the electrolyte in the second electrolyte chambers 5d and 5-1d shifts to the alkaline side.
  • the electrolytic cell it is possible to use the electrolytic cell 2 or 1-2 used in the first embodiment or the second embodiment.
  • the first electrolytic cell and the second electrolytic cell can also have different configurations.
  • the electrolytic solution supply unit 8 shares the electrolytic solution supply unit for the first electrolytic cell 2 and the second electrolytic cell 2-1, but may be separate.
  • FIG. 12 shows a diagram schematically representing an electrolytic cell used in the fifth embodiment.
  • this electrolytic cell 2-3' is a so-called three-chamber type electrolytic cell.
  • a first diaphragm 3-2a made of an anion-exchange membrane as a diaphragm on the anode side
  • a second diaphragm 4-2a made of a cation-exchange membrane as a diaphragm on the cathode side are provided.
  • the electrolyte chamber 5-2 defined between the diaphragms is partitioned into three chambers, an anode chamber 3-2 and a cathode chamber 4-2 located on both sides of the electrolyte chamber.
  • An anode 3-2b is provided inside the anode chamber 3-2 so as to closely face the first diaphragm 3-2a. -2b is provided.
  • the anode 3-2b and the first cathode 4-2b are formed in rectangular shapes of approximately the same size, sandwiching the electrolytic solution chamber 5-2 and the first and second diaphragms 3-2a and 4-2a. facing each other.
  • the anode 3-2b has the same configuration as the anode 3b in FIG.
  • the first cathode 4-2b has the same configuration as the first cathode 4b in FIG.
  • a part of the cell 31a that defines the anode chamber 3-2 is open.
  • a part of the cell 31b that defines the cathode chamber 4-2 is opened.
  • a resin excellent in acid resistance and alkali resistance such as vinyl chloride, polypropylene, or polyethylene, can be used.
  • the electrolyte chamber 5-2 is a third diaphragm 5-2a made of a neutral membrane that has no selectivity for ion permeation and allows cations and anions to pass through, and is located on the side of the first electrolyte chamber 5 on the anode chamber 3-2 side.
  • a second cathode 5-2b is provided in the second electrolyte chamber 5-2d so as to closely face the third diaphragm 5-2a.
  • the second cathode 5-2b like the first cathode 4-2b, is formed in a rectangular shape having approximately the same size as the first cathode 4-2b.
  • the second cathode 5-2b has the same configuration as the second cathode 5b in FIG.
  • the third diaphragm 5-2a is provided between the second cathode 5-2b and the first diaphragm 3-2a, and the electrolyte chamber 5-2 are separated into a first electrolyte chamber 5-2c on the anode chamber 3-2 side and a second electrolyte chamber 5-2d on the cathode chamber 4-2 side.
  • the pH of the electrolyte in the second electrolyte chamber 5-2d shifts to the alkaline side, but alkaline substances are discharged by the flow of the second electrolyte, and the first Almost no entrainment in the electrolyte flow. Therefore, the pH of the first electrolyte chamber 5-2c can be maintained closer to neutral than the pH of the second electrolyte chamber 5-2d. Therefore, the first diaphragm 3-2a of the first electrolyte chamber 5-2c is less likely to deteriorate. Thereby, an electrolytic cell that can be used for a long period of time is obtained.
  • FIG. 13 schematically shows a storage-type electrolyzed water generator 1-5 according to a fifth embodiment using the example of the electrolysis cell of FIG.
  • the electrolysis cell 2-3 used in this embodiment has the same configuration as the electrolysis cell 2-3' shown in FIG. is provided with a first electrolytic solution supply port 5-2f.
  • a first electrolytic solution discharge port 5-2h for discharging the electrolytic solution that has flowed through the first electrolytic solution chamber 5-2c is provided in the upper portion of the first electrolytic solution chamber 5-2c.
  • a second electrolytic solution supply port 5-2g for supplying an electrolytic solution is provided in the lower portion of the second electrolytic solution chamber 5-2d.
  • a second electrolytic solution discharge port 5-2i for draining the electrolytic solution that has flowed through the second electrolytic solution chamber 5-2d is provided in the upper portion of the second electrolytic solution chamber 5-2d.
  • the electrolyzed water generator 1-5 includes an electrolyte supply unit 8 that supplies electrolyte (eg, salt water) to the electrolyte chamber 5-2 of the electrolytic cell 2-3. Further, a water tank 32 is provided for storing together water as raw water to be supplied to the anode chamber 3-2 and the cathode chamber 4-2, the anode generated water, and the cathode generated water. Further, a power supply unit 7 having a power source 7a for applying a positive voltage to the anode 3-2b and a negative voltage to the first cathode 4-2b and/or the second cathode 5-2b is provided.
  • electrolyte eg, salt water
  • the power supply unit 7 includes a power source 7a that supplies a current necessary for electrolysis, a switch 7b that energizes the first cathode 4-2b and/or the second cathode 5-2b, and a control unit 7c that controls the power source 7a and the switch 7b. and
  • a switch 7b a selector switch for switching power supply to the first cathode 4-2b and the second cathode 5-2b is used.
  • a constant current power supply is desirable as the power supply 7a.
  • the positive electrode of the power supply 7a is connected to the anode 3-2b of the electrolytic cell 2-3 via wiring.
  • the negative electrode of the power supply 7a is connected to the first cathode 4-2b and the second cathode 5-2b via a switch 7b and two wires. A negative voltage can be selectively applied to the two cathodes 5-2b.
  • the electrolyte supply unit 8 includes a salt water tank (electrolyte tank) 25 storing an electrolyte 25a (for example, a 20% sodium chloride aqueous solution (salt water)), and leads the salt water from the salt water tank 25 to the lower part of the electrolyte chamber 5-2. It has a supply pipe 8a, a liquid feed pump 29 provided in the supply pipe 8a, and a drain pipe 8f for discharging salt water from above the electrolytic solution chamber 5-2.
  • the supply pipe 8a is connected to a first electrolyte supply port 5-2f provided in the lower part of the first electrolyte chamber 5-2c of the electrolyte chamber 5-2, and supplies salt water.
  • a second electrolyte supply port 5-2g provided in the lower part of the second electrolyte chamber 5-2d of the chamber 5-2 and branches to a supply pipe 8c for supplying salt water.
  • the electrolyte is separately supplied to the first electrolyte chamber 5-2c and the second electrolyte chamber 5-2d.
  • the supply pipe 8b and the supply pipe 8c from the salt water tank 25 are passed through the through holes 32b and 32c provided in the bottom of the water tank 32, the lower part of the first electrolytic solution chamber 5-2c and the second electrolytic solution chamber. It connects to the bottom of 5-2d.
  • first electrolyte chamber 5-2c Above the first electrolyte chamber 5-2c, it is connected to the first electrolyte discharge port 5-2h and serves as a first electrolyte discharge line for draining the electrolyte that has flowed through the first electrolyte chamber 5-2c.
  • a functioning drain pipe 8d is connected.
  • a second electrolyte discharge port 5-2i is connected to the upper portion of the second electrolyte chamber 5-2d, and a second electrolyte discharge port 5-2i drains the electrolyte that has flowed through the second electrolyte chamber 5-2d.
  • a drain pipe 8e that functions as a line is connected. Therefore, the flow of salt water in the first electrolyte chamber 5-2c is separate from the flow of salt water in the second electrolyte chamber 5-2d.
  • the drain pipe 8d and the drain pipe 8e are merged to form the drain pipe 8f, and the electrolytic solutions in the drain pipe 8d and the drain pipe 8e are mixed and discharged.
  • the water storage area 10-3 includes a water supply source, a first water supply line that supplies water to the anode chamber, a second water supply line that supplies water to the cathode chamber, and a mixture of the water produced by the anode and the water produced by the cathode. It also has a function of functioning as a first generated water mixing section that prepares generated water (first mixed generated water).
  • the mixed product water obtained in the water tank 32 is hypochlorous acid water whose pH is controlled to be slightly acidic/neutral.
  • a stirrer (not shown) can be installed in the water tank 32 as needed.
  • each pipe may be provided with an on-off valve or a flow control valve.
  • the electrolyzed water generator 1-5 configured as described above actually electrolyzes salt water to generate acidic water (hypochlorous acid and hydrochloric acid) and alkaline water (sodium hydroxide) to obtain mixed generated water. Operation will be explained. As shown in FIG. 13, the liquid feed pump 29 is operated to supply salt water from the salt water tank 25 to the first electrolyte chamber 5-2c and the second electrolyte chamber 5-2d of the electrolytic cell 2-3. The anode chamber 3-2 and the cathode chamber 4-2 are filled with water in the water storage area 10-3.
  • water is electrolyzed at the first cathode 4-2b to produce hydrogen gas and sodium hydroxide in the cathode chamber 4-2.
  • the generated sodium hydroxide aqueous solution and hydrogen gas are mixed into the raw water in the water storage tank 32 from the cathode chamber 4-2.
  • Chlorine ions ionized in the salt water of the first electrolyte chamber 5-2c and the second electrolyte chamber 5-2d are attracted to the anode 3-2b, pass through the first diaphragm 3-2a, and flow into the anode chamber. Flow into 3-2. Then, the chlorine is oxidized at the anode 3-2b to generate chlorine gas. Immediately thereafter, chlorine gas reacts with water to produce hypochlorous acid and hydrochloric acid. Hypochlorous acid and hydrochloric acid generated in the anode chamber 3 mix with raw water in the water tank 32 . In this manner, hypochlorous acid water having a pH adjusted is obtained as mixed product water in the water tank 32 .
  • a positive voltage and a negative voltage are applied from the power supply 7a to the anode 3-2b and the second cathode 5-2b, respectively.
  • the sodium ions ionized in the salt water in the first electrolyte chamber 5-2c and the second electrolyte chamber 5-2d are attracted to the second cathode 5-2b.
  • Sodium ions in the first electrolyte chamber 5-2c can pass through the third diaphragm 5-2a and reach the second cathode 5-2b in the second electrolyte chamber 5-2d.
  • Electrolysis of salt water at the second cathode 5-2b produces hydrogen gas and an aqueous sodium hydroxide solution in the second electrolyte chamber 5-2d.
  • the inside of the second electrolytic solution chamber 5-2d shifts to the alkaline side.
  • the generated alkaline water (sodium hydroxide aqueous solution) and hydrogen gas flow out from the second electrolyte chamber 5-2d to the drain pipe 8e due to the flow of salt water in the second electrolyte chamber 5-2d, and then to the drain pipe 8d. It mixes with the electrolytic solution and is discharged to the outside through the drain pipe 8f.
  • the alkaline water generated in the second electrolyte chamber 5-2d is discharged from the second electrolyte chamber 5-2d without flowing into the cathode chamber 4-2 and the first electrolyte chamber 5-2c. . Therefore, the cathode chamber 4-2 and the first electrolyte chamber 5-2c do not shift to the alkaline side. Therefore, the first diaphragm 3-2a in the first electrolyte chamber 5-2c is not exposed to the strong alkali and is less likely to deteriorate. Further, in the cathode chamber 4-2, the water in the water tank 32 is hardly mixed with hydrogen gas and sodium hydroxide aqueous solution as alkaline water.
  • Chlorine ions ionized in the salt water in the first electrolyte chamber 5-2c and the second electrolyte chamber 5-2d are attracted to the anode 3-2b, pass through the first diaphragm 3-2a, It flows into chamber 3-2. At this time, the chlorine ions in the first electrolyte chamber 5-2c can permeate the third diaphragm 5-2a. Chlorine ions are oxidized at the anode 3-2b to generate chlorine gas. After that, the chlorine gas reacts with water in the anode chamber 3-2 to produce hypochlorous acid and hydrochloric acid. The generated hypochlorous acid and hydrochloric acid are mixed into the water in the water tank 32 from the anode chamber 3-2.
  • the alkaline water produced in the second electrolyte chamber 5-2d is discharged outside, and almost no alkaline water is mixed in the cathode chamber 4-2. Therefore, regarding the pH of the hypochlorous acid water obtained as the mixed product water in the water tank 32, the pH when power is supplied to the second cathode 5-2b is the pH when power is supplied to the first cathode 4-2b. lower than
  • the water used as raw water contains different impurities depending on the region and location, and especially the carbonic acid component has an interference effect toward weak alkalinity. Therefore, depending on the water used, the pH adjustment point may not match and may shift slightly.
  • the second cathode 5-2b is provided in the electrolyte chamber 5-2, and the switch 7b is set to the first cathode 4-2b or the second cathode 5.
  • Power can be supplied by switching to -2b.
  • the first cathode 4-2b in the cathode chamber 4-2 and the second cathode 5-2b in the second electrolyte chamber 5-2d are selectively switched to energize the sodium hydroxide in the cathode chamber 4-2.
  • the pH of the hypochlorous acid water obtained as mixed water in the water reservoir 32 can be adjusted.
  • the pH of the mixed product water can be adjusted at any time, and the pH of the hypochlorous acid water obtained as the mixed product water can be controlled to be slightly acidic or near neutral.
  • a third diaphragm 5-2a is provided between the second cathode 5-2b and the first diaphragm 3-2a, and the electrolyte chamber 5-2 is replaced with the first electrolyte chamber 5- on the side of the anode chamber 3-2. 2c and a second electrolyte chamber 5-2d on the side of the cathode chamber 4-2.
  • the pH of the electrolyte in the second electrolyte chamber 5-2d shifts to the alkaline side, but alkaline substances are discharged by the flow of the second electrolyte.
  • the pH of the first electrolyte chamber 5-2c can be maintained closer to neutral than the pH of the second electrolyte chamber 5-2d. Therefore, the first diaphragm 3-2a of the first electrolyte chamber 5-2c is less likely to deteriorate and has good durability.
  • an electrolyzed water generator that can be used for a long period of time is obtained.
  • the anode chamber 3-2 and the cathode chamber 4-2 are respectively a region with a high concentration of acidic water and a region with a high concentration of alkaline water.
  • a stirrer (not shown) in the water tank 32, it is possible to bring the pH of the water close to slightly acidic/neutral to make the water quality uniform.
  • a water quality change test and a continuous operation test were conducted as follows.
  • FIG. 14 is a graph showing the relationship between the energization ratio (duty ratio) of the second cathode 5-2b and the water quality of the mixed water in the electrolyzed water generator according to the fifth embodiment 1-5.
  • a characteristic line 115 indicates the change in pH with respect to the energization ratio of the second cathode 5-2b
  • a characteristic line 116 indicates the change in effective chlorine concentration with respect to the energization ratio of the second cathode 5-2b.
  • the energization ratio of the second cathode is the ratio of the energization time of the second cathode 5-2b to the time of one cycle.
  • the water quality (pH and effective chlorine concentration) of the mixed water was measured after the mixed water was sold sufficiently so that the difference in water quality due to the power switching was not sufficiently accumulated and affected.
  • the effective chlorine concentration of the mixed product water is almost constant as shown by the characteristic line 116, but the pH becomes acidic as shown by the characteristic line 115. become. This is because the alkaline substance produced at the second cathode 5-2b is released only into the second electrolyte chamber 5-2d and is not mixed with the mixed product water.
  • the pH fluctuates greatly from around 20% of the electrification ratio of the second cathode 5-2b, and the raw water is acidified.
  • the acidic water (pH 5 to 6.5) is in a slightly acidic region (pH 5 to 6.5) with a high abundance ratio of the active ingredient HClO and is less affected by corrosion ( Hypochlorous acid water) can be obtained. Furthermore, when the energization ratio of the second cathode 5-2b is increased and only the second cathode 5-2b is used without using the first cathode 4-2b (100% energization ratio), the mixed product water is strongly acidic. I understand.
  • pure water is used as raw water. From this, when hard water is used, the energization ratio of the second cathode 5-2b, which indicates a slightly acidic region, shifts to a higher side.
  • Continuous operation test Using the electrolyzed water generator 1-5, a continuous operation test was performed as follows. As raw water, 20 L of pure water was stored in the water tank 32 . During the production of electrolyzed water, a 20% sodium chloride aqueous solution was supplied to the first electrolyte chamber 5-2c and the second electrolyte chamber 5-2d at 3 mL/min.
  • the electrolysis current is fixed at 2 A, one cycle is 10 seconds, and the electrification ratio of the second cathode 5-2b is 60% (the electrification time to the first cathode 4-2b is Electrolysis was carried out for 60 minutes with the setting of 4 seconds, and the energization time of the second cathode 5-2b of 6 seconds). While replacing the water in the water tank every 60 minutes, the electrolyzed water generator is operated for about 700 hours, and the pH and effective chlorine concentration of the first mixed product water obtained are measured every 24 hours at the beginning and every week thereafter. measured to
  • Comparative Example 3 an electrolyzed water generator having the same configuration as that of the fifth embodiment except that the third diaphragm 5-2a was not provided in the electrolyte chamber 5-2 of the electrolysis cell 2-3 was prepared.
  • the electrolyzed water generator was operated for about 700 hours under the same conditions.
  • the pH and available chlorine concentration were measured in the same manner as in the fifth embodiment as changes in the quality of the resulting mixed product water.
  • FIG. 15 shows a graph showing the continuous operation test results of the electrolyzed water generator 1-5 according to the fifth embodiment. In the figure, the horizontal axis is the operating time.
  • a characteristic line 117 indicates the change in pH of the mixed product water obtained by the electrolyzed water generator 1-5.
  • a characteristic line 118 indicates changes in the effective chlorine concentration of the mixed water produced by the electrolyzed water generator 1-5.
  • a characteristic line 120 indicates the effective chlorine concentration of Comparative Example 3, and a characteristic line 119 indicates the pH of Comparative Example 3, respectively.
  • Comparative Example 3 after 48 hours, the pH increased as indicated by characteristic line 119 and the effective chlorine concentration decreased as indicated by characteristic line 120.
  • the electrolytic cell of Comparative Example 3 was disassembled and investigated, it was confirmed that the first diaphragm in the anode chamber became cloudy and the membrane was torn in places. From this, it is considered that the electrolyte chamber was alkalinized by the alkaline substance generated at the second cathode, and the first diaphragm in contact with the electrolyte chamber was degraded and fractured.
  • the electrolyzed water generator 1-5 even if it operates for a long time, as shown in characteristic lines 118 and 117, the effective chlorine concentration and pH are constant, and the quality of the mixed water is change is not allowed.
  • the electrolyte chamber 5-2 is separated from the first electrolyte chamber 5-2c on the side of the anode chamber 3-2 and the cathode chamber 4- by the third diaphragm 5-2a made of a neutral membrane having no ion permeation selectivity.
  • the second electrolyte chamber 5-2d is divided into the second electrolyte chamber 5-2d, and the second cathode 5-2b is provided in the second electrolyte chamber 5-2d so as to closely face the third diaphragm 5-2a. That is, the alkaline substance produced at the second cathode 5-2b is produced only in the second electrolyte chamber 5-2d, immediately discharged from the second electrolyte chamber 5-2d, and transferred to the first diaphragm 3-2a. This is probably because the action on alkaline substances was suppressed.
  • the electrolyte chamber 5-2 is separated from the first electrolyte chamber 5-2c on the side of the anode chamber 3-2 and the cathode chamber 4 by the third diaphragm 5-2a made of a neutral membrane having no ion permeation selectivity.
  • a second electrolyte chamber 5-2d on the -2 side is partitioned, and a second cathode 5-2b is provided in the second electrolyte chamber 5-2d so as to be closely opposed to the third diaphragm 5-2a.
  • FIG. 16 shows a diagram schematically showing an application example of the storage-type electrolyzed water generator according to the fifth embodiment.
  • the electrolyzed water generator 1-6 shown in FIG. 16 has a supply pipe 8a and a supply pipe 8b from a salt water tank (electrolyte tank) 25 connected to the lower portion of the first electrolytic solution chamber 5-2c and the second electrolytic solution chamber 5.
  • the electrolyzed water generator 1-5 of FIG. different. Other than that, it has the same configuration as the electrolyzed water generator shown in FIG. 13, and has the same effects.
  • any water storage container 32-1 that can secure the water storage area 10-3 can be used, and the electrolytic cell 2-3 can be used as the water storage tank. 32 does not have to be installed. In other words, it can be used simply by putting the electrolysis cell 2-3 into an arbitrary water storage container 32-1, so that the cost is low.
  • Such a configuration is more suitable when the electrolytic cell 2-3 is made more compact.
  • the supply pipe 8a and the drain pipe 8f are made of a flexible material so that the electrolytic cell 2-3 can be easily handled.
  • FIG. 17 is a diagram schematically showing a storage-type electrolyzed water generator according to the sixth embodiment.
  • the electrolyzed water generator 1-7 uses a so-called three-chamber type electrolysis tank (electrolysis cell) 2-4.
  • the inside of the electrolytic cell 2-4 is equipped with a first diaphragm (anode side diaphragm, anion exchange membrane) 3-2a and a second diaphragm (cathode side diaphragm, cation exchange membrane) 4-2a.
  • the electrolyte chamber 5-2 defined between the diaphragms is partitioned into three chambers, an anode chamber 3-2 and a cathode chamber 4-2 located on both sides of the electrolyte chamber 5-2.
  • An anode 3-2b is provided in the anode chamber 3-2 and faces the first diaphragm 3-2a.
  • a cathode 4-2b is provided in the cathode chamber 4-2 and faces the second diaphragm 4-2a.
  • the anode 3-2b and the cathode 4-2b are formed in the shape of rectangular plates of approximately the same size, and are separated from each other with the electrolytic solution chamber 5-2 and the first and second diaphragms 3-2a and 4-2a interposed therebetween. facing each other.
  • the electrolyte chamber 5-2 is a third diaphragm 5-2a made of a neutral membrane having no selectivity of ion permeation and allowing the passage of cations and anions.
  • a second cathode 5-2b is provided in the second electrolyte chamber 5-2d so as to closely face the third diaphragm 5-2a.
  • the second cathode 5-2b like the anode 3-2b and the first cathode 4-2b, is formed in a rectangular shape having approximately the same size as the anode 3-2b and the first cathode 4-2b.
  • the second cathode 5-2b is a so-called insoluble electrode obtained by applying a catalyst such as Ir or Pt to a metal plate having a large number of through holes formed in Ti, or a metal plate made of Ti having a large number of through holes formed therein.
  • a catalyst such as Ir or Pt
  • a metal plate having a large number of through holes formed in Ti or a metal plate made of Ti having a large number of through holes formed therein.
  • this electrolytic cell 2-4 a part of the cell 31a that defines the anode chamber 3-2 is open. Similarly, a part of the cell 31b that defines the cathode chamber 4-2 is opened.
  • at least part of the first electrolyte chamber 5-2c on the anode chamber 3-2 side is provided with a porous member 5-2e, which is a water-permeable diffusion suppressing member for controlling the diffusion of alkaline substances.
  • a sintered plastic porous body (manufactured by Fuji Chemical Co.
  • the power supply unit 7 has a power supply 7a, a control unit 7c for controlling the power supply 7a, and a switch 7b for switching power supply to the first cathode 4-2b and the second cathode 5-2b.
  • the positive electrode of the power supply 7a is connected to the anode 3-2b via wiring.
  • the negative electrode of the power supply 7a is connected to the first cathode 4-2b and the second cathode 5-2b via the switch 7b and two wires. That is, by switching the switch 7b, a negative voltage can be selectively applied to the first cathode 4-2b or the second cathode 5-2b.
  • the switch 7b is configured to be operable by a user.
  • the electrolyzed water generator 1-7 includes an electrolyte supply unit 8 that supplies an electrolyte, such as salt water, to the first and second electrolyte chambers 5-2c and 5-2d of the electrolytic cell 2-4, It is configured in the same manner as the electrolyzed water generator 1-5 according to the fifth embodiment described above.
  • an electrolyte supply unit 8 that supplies an electrolyte, such as salt water, to the first and second electrolyte chambers 5-2c and 5-2d of the electrolytic cell 2-4, It is configured in the same manner as the electrolyzed water generator 1-5 according to the fifth embodiment described above.
  • the mixed water discharged from the electrolyzed water generator 1-7 is hypochlorous acid water whose pH is controlled to near neutral. That is, in a normal generating operation, a positive voltage is applied to the anode 3-2b and a negative voltage is selectively applied to the first cathode 4-2b or the second cathode 5-2b.
  • a positive voltage is applied to the anode 3-2b and a negative voltage is selectively applied to the first cathode 4-2b or the second cathode 5-2b.
  • the switch 7b and applying a voltage to the second cathode 5-2b it is possible to further adjust the pH according to the connection duty.
  • the porous member 5-2e the alkaline substance generated in the second electrolytic solution chamber 5-2d is released into the first electrolytic solution chamber 5-2c when the electrolyzed water generator 1-7 is stopped. And diffusion to the first diaphragm 3-2a in contact with the first electrolyte chamber 5-2c can be suppressed.
  • the pH of the mixed product water can be adjusted at any time even if the quality of the raw water fluctuates. It is possible to control the pH of the hypochlorous acid water obtained as a slightly acidic / neutral. Further, when the power supply from the power supply portion 7 is switched to the second cathode 5-2b, the pH of the electrolyte in the second electrolyte chamber 5-2d shifts to the alkaline side.
  • the alkaline substance is discharged by the flow of the second electrolyte. and is hardly mixed into the flow of the first electrolytic solution. Therefore, the first diaphragm 3-2a of the first electrolytic solution chamber 5-2c is less likely to deteriorate and has good durability. Therefore, according to the sixth embodiment, it is possible to obtain an electrolyzed water generator that can be used for a long period of time.
  • the present invention can be used as a commercial electrolyzed water generator and a compact electrolyzed water generator for home use.
  • Second cathode 5c, 5-1c, 5-2c... first electrolyte Chamber 5d, 5-1d, 5-2d Second electrolytic solution chamber 5e, 5-2e
  • Diffusion suppressing member 7 Feeder 7-1 Feeder (second feeder) , 7b... switch, 7-1b... switch (second switch), 7c, 7-1c... control section, 8a, 8-1a... supply pipe, 8b, 8-1b... supply pipe (first electrolytic solution supply line) , 8c, 8-1c... Supply pipe (second electrolytic solution supply line), 10... First generated water mixing portion, 10-1... First generated water mixing portion, 10-1e... Second generated water mixing portion, 10 -2... Third generated water mixing unit 10-2a... Fourth generated water mixing unit 10-3... Water storage area 10s... Mixed generated water supply line 12... Online pH meter (pH measurement unit)

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

Un générateur d'eau électrolysée selon un mode de réalisation de l'invention est pourvu des éléments suivants : une première cellule d'électrolyse qui est dotée d'une chambre de solution d'électrolyte, d'une chambre d'électrode positive qui est séparée de la chambre de solution d'électrolyte au moyen d'un premier diaphragme, d'une chambre d'électrode négative qui est séparée de la chambre de solution d'électrolyte au moyen d'un deuxième diaphragme, d'une électrode positive qui est disposée dans la chambre d'électrode positive de manière à faire face au premier diaphragme, d'une première électrode négative qui est disposée dans la chambre d'électrode négative de manière à faire face au deuxième diaphragme, une seconde électrode négative qui est disposée dans la chambre de solution d'électrolyte de manière à faire face à l'électrode positive, le premier diaphragme étant interposé entre eux, et un troisième diaphragme qui est disposé entre la seconde électrode négative et le premier diaphragme de manière à diviser l'intérieur de la chambre de solution d'électrolyte en une première chambre de solution d'électrolyte qui se trouve du côté de la chambre d'électrode positive et une seconde chambre de solution d'électrolyte qui se trouve du côté de la chambre d'électrode négative ; une première unité d'alimentation qui alimente en énergie l'électrode positive, la première électrode négative et la seconde électrode négative ; un commutateur qui applique un courant de l'unité d'alimentation à la première électrode négative et/ou à la seconde électrode négative ; et une première unité de mélange d'eau de produit qui forme une première eau de produit mélangée en mélangeant l'une avec l'autre l'eau de produit à l'électrode positive et l'eau de produit à l'électrode négative, lesdites eaux de produit étant obtenues par électrolyse d'une solution d'électrolyte dans la première cellule d'électrolyse.
PCT/JP2021/045508 2021-05-26 2021-12-10 Cellule d'électrolyse et générateur d'eau électrolysée WO2022249519A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017141284A1 (fr) * 2016-02-15 2017-08-24 株式会社 ゴーダ水処理技研 Dispositif de génération d'eau électrolysée
WO2018034317A1 (fr) * 2016-08-19 2018-02-22 株式会社 ゴーダ水処理技研 Eau hydrogénocarbonatée et procédé de nettoyage l'utilisant
JP2019076800A (ja) * 2017-10-19 2019-05-23 パナソニックＩｐマネジメント株式会社 機能水生成装置
JP2021080508A (ja) * 2019-11-15 2021-05-27 パナソニックＩｐマネジメント株式会社 電解水生成装置

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017170421A (ja) * 2016-03-22 2017-09-28 株式会社東芝 電解水生成装置および電解水生成方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017141284A1 (fr) * 2016-02-15 2017-08-24 株式会社 ゴーダ水処理技研 Dispositif de génération d'eau électrolysée
WO2018034317A1 (fr) * 2016-08-19 2018-02-22 株式会社 ゴーダ水処理技研 Eau hydrogénocarbonatée et procédé de nettoyage l'utilisant
JP2019076800A (ja) * 2017-10-19 2019-05-23 パナソニックＩｐマネジメント株式会社 機能水生成装置
JP2021080508A (ja) * 2019-11-15 2021-05-27 パナソニックＩｐマネジメント株式会社 電解水生成装置

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