JP7052121B1 - Electrolyzed cell and electrolyzed water generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an electrolyzed water generator provided with an electrolytic cell which can be used for a long period of time. An electrolytic water generator according to an embodiment includes an electrolytic solution chamber, an anode chamber partitioned from the electrolytic solution chamber by a first diaphragm, and a cathode chamber partitioned from the electrolytic solution chamber by a second diaphragm. The anode provided in the anode chamber facing the first diaphragm, the first cathode provided in the cathode chamber facing the second diaphragm, and the second cathode provided in the electrolytic solution chamber facing the anode via the first diaphragm. A third diaphragm provided between the two cathodes and the second cathode and the first diaphragm and separating the electrolyte chamber into the first electrolyte chamber on the anode chamber side and the second electrolyte chamber on the cathode chamber side. A first electrolytic cell provided, a first power feeding unit that supplies power to the anode, the first cathode, and the second cathode, a switch that energizes the first cathode and / or the second cathode from the feeding unit, and electrolysis in the first electrolytic cell. It is provided with a first generated water mixing unit for producing a first mixed produced water by mixing an anode-generated water obtained by electrolyzing the liquid and a cathode-generated water. [Selection diagram] Fig. 2

Description

The present invention relates to an electrolytic cell and an electrolyzed water generator.

In recent years, electrolyzed water obtained by electrolyzing water to give various functions is known. For example, an electrolyzed water generator that produces hypochlorite water as electrolyzed water having a sterilizing and deodorizing function, and an electrolyzed water generator that produces alkaline ionized water as electrolyzed water having a function of drinking and cleaning rust prevention. Proposed.
The electrolyzed water generator produces electrolyzed water having various functions by using an electrolyzed product obtained by electrolyzing an electrolyte in an electrolytic solution or water. Examples of the electrolyte include chlorides, oxides, alkaline salts, carbonates, organic acids and the like artificially added in addition to the ionic components contained in water.

The electrolyzed water generator that generates hypochlorite water is provided with, for example, two diaphragms between a pair of electrodes and an electrolytic cell chamber separated by two diaphragms between the anode chamber and the cathode chamber. There is one that uses a three-chamber type electrolytic cell. In the three-chamber type electrolytic cell that produces hypochlorite water, the electrolytic solution containing chlorine ions is supplied only to the central electrolytic cell chamber, and water is circulated to the anode chamber and the cathode chamber, respectively. In the form of separating the anode product and the cathode product from the electrolytic solution, the anode-generated water is generated from the anode chamber, and the cathode-generated water is generated from the cathode chamber.
The generated anode-generated water (hypochlorite water) is basically acidic. However, the stronger the acidity of the hypochlorite water and the higher the salt content (residual chlorine ion concentration), the more easily chlorine gas is generated. On the other hand, if the pH is more alkaline than 8, hypochlorous acid is changed to hypochlorite ion, and the bactericidal ability is lowered.

Japanese Unexamined Patent Publication No. 2018-30041 Japanese Unexamined Patent Publication No. 2018-30043 Japanese Unexamined Patent Publication No. 2018-30044 Japanese Unexamined Patent Publication No. 2018-30045 Japanese Unexamined Patent Publication No. 2019-162607

By mixing the cathode-generated water and the anode-generated water generated by the three-chamber electrolyzed water generator, the hydroxide ion OH ^- contained in the cathode-generated water neutralizes the hydrogen ion H ⁺ contained in the anode-generated water. However, a method of controlling the pH of the mixed water to near neutrality has been proposed. A second cathode is provided in the electrolytic solution chamber as a method of accurately controlling the amount of hydroxide ion OH ^- contained in the cathode-generated water in accordance with fluctuations in the hardness and pH of the water flowing in the anode chamber and the cathode chamber. Therefore, a method of performing electrolysis while switching to the first cathode of the cathode chamber has been proposed. However, in the case of such a configuration, the electrolytic cell becomes a strong alkali, and the diaphragm provided in contact with the anode deteriorates with use and breaks, so that the electrolytic cell cannot withstand long-term practical use. There is.
An object of the present invention is to obtain an electrolytic cell that can be used for a long period of time and an electrolyzed water generator provided with the electrolytic cell.

According to the embodiment of the present invention, the electrolytic solution chamber containing the electrolytic solution, the anode chamber partitioned from the electrolytic solution chamber by the first diaphragm, and the electrolytic solution chamber partitioned by the second diaphragm. In the cathode chamber, the anode provided in the anode chamber in close opposition to the first diaphragm, the first cathode provided in the cathode chamber in close opposition to the second diaphragm, and the electrolyte chamber. A second cathode that is provided and faces the anode via the first diaphragm, and is provided between the second cathode and the first diaphragm, and the electrolytic solution chamber is subjected to the first electrolysis on the anode chamber side. A liquid chamber and a third diaphragm separated into a second electrolytic solution chamber on the cathode chamber side are provided .
The second electrolytic cell chamber is provided with an electrolytic cell in which the second cathode is provided so as to be close to the third diaphragm and face the third diaphragm .

Further, according to the embodiment of the present invention, the electrolytic solution chamber containing the electrolytic solution, the anode chamber partitioned from the electrolytic solution chamber by the first diaphragm, and the electrolytic solution chamber partitioned by the second diaphragm. The cathode chamber, the anode provided in the anode chamber in close opposition to the first diaphragm, the first cathode provided in the cathode chamber in close opposition to the second diaphragm, and the electrolyte chamber. The second cathode facing the anode via the first diaphragm, the electrolytic solution chamber provided between the second cathode and the first diaphragm, the electrolytic solution chamber, the first electrolyte chamber on the anode chamber side, and. A third diaphragm, which is separated into a second electrolyte chamber on the cathode chamber side, is provided .
In the second electrolytic cell, a first electrolytic cell in which the second cathode is provided so as to be close to the third diaphragm and opposed to the third diaphragm is provided .
A first feeding unit that feeds the anode, the first cathode, and the second cathode,
A switch that energizes the first cathode and / or the second cathode from the first feeding unit,
An electrolyzed water generator including a first generated water mixing unit for producing a first mixed produced water by mixing an anode generated water obtained by electrolyzing the electrolytic solution and a cathode generated water in the first electrolytic cell. Provided.

According to the present invention, it is possible to obtain an electrolytic cell and an electrolyzed water generator that can be used for a long period of time.

It is a figure which shows schematically the electrolytic cell which can be used in 1st Embodiment. It is a figure which shows schematically the running water type electrolyzed water generator which concerns on 1st Embodiment. It is a timing chart which shows an example of switching of a 1st cathode and a 2nd cathode used in 1st Embodiment. It is a graph which shows the result of the water quality change test by the energization ratio in 1st Embodiment. It is a graph which shows the continuous operation test result of the electrolyzed water generation apparatus which concerns on 1st Embodiment. It is a schematic diagram which shows the application example of the electrolyzed water generation apparatus which concerns on 1st Embodiment. It is a figure which shows schematically the running water type electrolyzed water generator which concerns on 2nd Embodiment. It is a graph which shows the result of the water quality change test by the energization ratio in 2nd Embodiment. It is a figure which shows schematically the running water type electrolyzed water generator which concerns on 3rd Embodiment. It is a graph which shows the result of the water quality change test by the energization ratio in 3rd Embodiment. It is a figure which shows schematically the running water type electrolyzed water generator which concerns on 4th Embodiment. It is a figure which shows schematically the electrolytic cell used in 5th Embodiment. It is a figure which shows schematically the water storage type electrolyzed water generation apparatus which concerns on 5th Embodiment. It is a graph which shows the result of the water quality change test by the energization ratio in 5th Embodiment. It is a graph which shows the continuous operation test result in 5th Embodiment. It is a figure which shows the application example of the water storage type electrolyzed water generator which concerns on 5th Embodiment schematically. It is a figure which shows schematically the water storage type electrolyzed water generation apparatus which concerns on 6th Embodiment.

Hereinafter, embodiments will be described with reference to the drawings.
It should be noted that the same reference numerals are given to the common configurations throughout the embodiments, and duplicate description may be omitted.
(First Embodiment)
FIG. 1 shows a diagram schematically showing an electrolytic cell that can be used in the first embodiment.
As shown in the figure, this electrolytic cell 2'is a so-called three-chamber type electrolytic cell, and the inside thereof is a first diaphragm 3a made of an anion exchange membrane as a anode-side diaphragm and a cation as a cathode-side diaphragm. The second diaphragm 4a made of an exchange membrane divides the electrolyte chamber 5 as an intermediate chamber defined between the diaphragms into three chambers, an anode chamber 3 and a cathode chamber 4 located on both sides of the electrolyte chamber. .. An anode 3b is provided inside the anode chamber 3 in close opposition to the first diaphragm 3a, and a first cathode 4b is provided in the cathode chamber 4 in close opposition to the second diaphragm 4a. Here, the term "proximity" means that one is adjacent to, is in contact with, or is in close contact with the other. Further, the term "adjacent" means a state in which one of them faces the other while maintaining a certain 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 a rectangular shape having substantially the same size, and face each other with the electrolytic solution chamber 5, the first diaphragm 3a, and the second diaphragm 4a interposed therebetween.

The electrolytic solution chamber 5 is a third diaphragm 5a made of a neutral film having fine pores through which cations and anions can pass without selectivity of ion permeation, and is a first electrolytic solution chamber 5c on the anode chamber 3 side and a cathode. It is partitioned into a second electrolyte chamber 5d on the chamber 4 side. The neutral membrane is preferably one that does not have ion selectivity, and for example, an electrolytic diaphragm for plating (manufactured by Yuasa Membrane System Co., Ltd.) can be used. The second electrolyte chamber 5d is provided with a second cathode 5b so as to face the third diaphragm 5a in close proximity to the third diaphragm 5a. Like the anode 3b and the first cathode 4b, the second cathode 5b is formed in a rectangular shape having substantially the same size as the anode 3b and the first cathode 4b. Further, as the second cathode 5b, for example, a titanium (Ti) metal plate having a large number of through holes can be used, but for example, Ir, Pt, etc. can be used on the metal plate made of Ti having a large number of through holes. A so-called insoluble electrode coated with the catalyst of the above may be used.
According to the electrolytic cell 2'according to the first embodiment, a third diaphragm 5a is provided between the second cathode 5b and the first diaphragm 3a, and the inside of the electrolytic solution chamber 5 is filled with the first electrolytic solution on the anode chamber 3 side. By separating the chamber 5c and the second electrolytic solution chamber 5d on the cathode chamber 4 side, the flow of the electrolytic solution in the electrolytic solution chamber 5 is separated from the flow of the first electrolytic solution in the first electrolytic solution chamber 5c and the second electrolysis. It can be divided into two flows of the second electrolytic solution in the liquid chamber 5d. When the second cathode 5b is energized, the pH of the electrolytic solution in the second electrolytic solution chamber 5d shifts to the alkaline side, but the alkaline substance is discharged by the flow of the second electrolytic solution, and most of the flow of the first electrolytic solution is carried out. Since it does not mix, the pH of the first electrolytic solution chamber 5c can be maintained closer to neutral than the pH of the second electrolytic solution chamber 5d. Therefore, the first diaphragm 3a that separates the first electrolytic cell 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.

As electrodes such as the anode 3b, the first cathode 4b, and the second cathode 5b used in the embodiment, for example, a metal plate base material made of Ti having a large number of through holes and a metal plate base material made of Ti. An insoluble electrode having a catalyst layer formed in the above can be used, but electrodes such as the first cathode 4b and the second cathode 5b may not be provided with the catalyst layer.
As the electrode, a metal plate or one having a catalyst layer provided on the surface of the metal plate can be used, but the metal material and the catalyst material that can be used in the electrolyzed water generator that produces hypochlorite water can be used. Limited to those described in JIS B 8701. That is, as the metal plate material, 1 to 13 types of Ti specified in JIS H4650 can be used.
As 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 further containing a stabilizing substance such as tantalum pentoxide can be used. Preferably, an oxide catalyst containing iridium oxide as a main component can be used. The catalyst layer is formed by plating the noble metal catalyst in the plating solution for a predetermined time, and repeatedly applying and drying the coating solution containing the catalyst on the surface of the metal plate material, and then firing. Can be done.

As the anode 3b, a commercially available insoluble electrode for chlorine generation can be used. Examples of commercially available insoluble electrodes for chlorine generation 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. As the Ti plate, for example, a Ti plate having a large number of through holes can be used.
As the first cathode 4b and the second cathode 5b, a Ti plate or a commercially available insoluble electrode for chlorine generation can be used. Examples of commercially available insoluble electrodes for chlorine generation include those provided with a catalyst layer of Pt and / or Ir or a catalyst layer mainly composed of iridium oxide on a Ti plate. As the Ti plate, for example, a Ti plate having a large number of through holes can be used.

As the first diaphragm 3a used in the embodiment, an anion exchange membrane in which a cation group is fixed to a porous polymer made of, for example, a hydrocarbon polymer and positively charged so that only anions can pass through is used. Can be used. As such an anion exchange membrane, for example, Neocepta AMX (manufactured by Astom) can be used.
Further, as the second diaphragm 4a, a cation exchange membrane in which an anion group is fixed to a porous polymer composed of, for example, a hydrocarbon polymer or a fluoropolymer and negatively charged so that only cations can pass through is used. can do. As such a cation exchange membrane, for example, Nafion (registered trademark) (manufactured by DuPont), which is a cation exchange membrane of a copolymer of a fluororesin, can be used.
Further, as the third diaphragm 5a, a non-woven fabric or a porous diaphragm having a coating layer containing, for example, an aluminum oxide on a porous substrate such as a glass cloth and having no selective passage of ions can be used. The porous diaphragm can be formed by impregnating a porous substrate such as a non-woven fabric or a glass cloth with an aluminum oxide and drying it.
The electrolytic cell of FIG. 1 can be incorporated into an electrolyzed water generator.

FIG. 2 shows a diagram schematically showing a running water type electrolyzed water generator according to the first embodiment.
As shown in the figure, the electrolyzed water generator 1 includes an electrolyzed cell 2. In one example, the electrolytic cell 2 uses an electrolytic cell having the same configuration as the electrolytic cell 2'shown in FIG. 1. In the electrolytic water generator 1, the lower part of the first electrolytic solution chamber 5c is the first electrolytic solution supply port 5f for supplying the electrolytic solution, and the upper part thereof is the electrolytic solution flowing through the first electrolytic solution chamber 5c. The first electrolytic solution discharge port 5h for discharging, the second electrolytic solution supply port 5g for supplying the electrolytic solution at the lower part of the second electrolytic solution chamber 5d, and the second electrolytic solution chamber 5d at the upper part thereof. A second electrolytic solution discharge port 5i for draining the flowing electrolytic solution is provided. Further, the lower part of the anode chamber 3 is the first water supply port 3f for supplying water, the upper part thereof is the first drainage port 3h for draining the water flowing through the anode chamber 3, and the lower part of the cathode chamber 4. Is provided with a second water supply port 4f for supplying water, and a second drainage port 4h for draining the water flowing through the cathode chamber 4 above the second water supply port 4f.

The first electrolytic solution chamber 5c is provided with a first electrolytic solution supply port 5f and a first electrolytic solution discharge port 5h, and in the second electrolytic solution chamber 5d, a second electrolytic solution supply port 5g and a second electrolytic solution discharge port 5i. Is provided, it is possible to supply and discharge the electrolytic solution to both chambers independently. Therefore, there is an advantage that the supply amount of the electrolytic solution to both chambers can be controlled separately.
The electrolytic water generator 1 supplies the electrolytic solution chamber 5 of the electrolytic cell 2, an electrolyte containing chlorine ions as an electrolytic solution, for example, salt water, and the electrolytic solution raw water to the anode chamber 3 and the cathode chamber 4. For example, a water supply unit 21 for supplying water and a power supply unit 7 having a power supply 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 are provided.

The power feeding unit 7 includes a power source 7a that supplies the current required 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. Has. Here, as the switch 7b, a changeover switch for switching the 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, and by switching the switch 7b, the first cathode 4b and the second cathode 5b are selectively selected. A negative voltage can be applied to. When the switch 7b is used, for example, the current supplied to the first cathode 4b and the second cathode 5b is fixed, and the energization of the first cathode 4b or the second cathode 5b is temporally switched to cause the first cathode 4b and the second cathode 5b. The energization ratio of the two cathodes 5b can be adjusted.

Further, as another example of a switch that energizes the first cathode 4b and / or the second cathode 5b, for example, for each of the first cathode 4b and the second cathode 5b, various values of current output can be obtained from the power supply 7a. A switch device having a plurality of negative terminals can be used. In this switch device, an ON / OFF switch is arranged between the first cathode 4b and the second cathode 5b and the plurality of negative terminals, respectively. By selectively turning on / off these ON / OFF switches by the control unit 7c, the energization ratio as the current amount ratio of the first cathode 4b and the second cathode 5b can be arbitrarily changed.
The electrolytic solution supply unit 8 includes, for example, a salt water tank (electrolyte solution tank) 25 that stores a 20 mass% sodium chloride aqueous solution (salt water) as the electrolytic solution 25a, and a supply pipe that guides salt water from the salt water tank 25 to the lower part of the electrolytic solution chamber 5. 8a, a liquid feed pump 29 provided in the supply pipe 8a, and a drainage pipe 8f for discharging salt water from above the electrolytic solution chamber 5 are provided.

The supply pipe 8a is connected to the first electrolytic solution supply port 5f provided at the lower part of the first electrolytic solution chamber 5c of the electrolytic solution chamber 5, and is connected to the supply pipe 8b as the first electrolytic solution supply line for supplying the electrolytic solution. , It is branched to a supply pipe 8c as a second electrolytic solution supply line connected to a second electrolytic solution supply port 5g provided at the lower part of the second electrolytic solution chamber 5d of the electrolytic solution chamber 5 to supply the electrolytic solution. , The electrolytic solution is separately supplied to the first electrolytic solution chamber 5c and the second electrolytic solution chamber 5d. The upper part of the first electrolytic solution chamber 5c is a drain pipe 8d, which is connected to the first electrolytic solution discharge port 5h and serves as a first electrolytic solution discharge line for draining the electrolytic solution flowing in the first electrolytic solution chamber 5c. At the upper part of the 2 electrolytic solution chamber 5d, drainage pipes 8e connected to the 2nd electrolytic solution discharge port 5i and used as a second electrolytic solution discharge line for draining the electrolytic solution flowing in the 2nd electrolytic solution chamber 5d are provided. Has been done. Therefore, the flow of the first electrolytic solution (salt water) 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) in the second electrolytic solution chamber 5d. ) Is separate from the flow. The drainage pipe 8d and the drainage pipe 8e are merged into the drainage pipe 8f, and the electrolytic solution of the drainage pipe 8d and the drainage pipe 8e is mixed and discharged. The drainage pipe 8d and the drainage pipe 8e may not be merged and may be discharged as they are, but the alkalinity of the electrolytic solution flowing through the drainage pipe 8f can be lowered by merging and discharging.

In the first electrolytic solution chamber 5c and the second electrolytic solution chamber 5d, the electrolytic solutions can be independently and independently supplied to both chambers by the first electrolytic solution supply line and the second electrolytic solution supply line. Therefore, there is an advantage that the supply amount of the electrolytic solution to both chambers can be controlled separately.
The water supply unit 21 includes a water supply source 9 for supplying water, an on-off valve 28 provided near the outlet of the water supply source 9, and a first water supply pipe for guiding water from the water supply source 9 to the lower parts of the anode chamber 3 and the cathode chamber 4. The 21a is connected to the first drainage port 3h, and is connected to the first drainage pipe 21b as the first drainage line for discharging the water flowing through the anode chamber 3 from the upper part of the anode chamber 3 and the second drainage port 4h. It is provided with a second drainage pipe 21c as a second drainage line for discharging the water flowing through the cathode chamber 4 from the upper part of the cathode chamber 4. The first water supply pipe 21a is branched into a second water supply pipe 21e as a first water supply line and a third water supply pipe 21f as a second water supply line. The second water supply pipe 21e is connected to the first water supply port 3f 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 drainage pipe 21b is connected to the middle part of the second drainage pipe 21c and constitutes the first generated water mixing part 10. As a result, the anode-generated water drained from the first drainage pipe 21b and the cathode-generated water drained from the second drainage pipe 21c are mixed and drained as mixed-generated water (first mixed-generated water). The mixed water to be drained is hypochlorite water whose pH is controlled near slightly acidic and neutral.
In addition, an on-off valve or a flow rate adjusting valve may be provided in each pipe.

The electrolyzed water generator configured as described above actually electrolyzes salt water to contain acidic water (anodized water) containing hypochlorite water, which is an acidic component, and alkaline containing sodium hydroxide, which is an alkaline substance. The operation of producing water (catalyst-generated water) and obtaining mixed-generated water will be described.
The anode-generated water used here is hypochlorite water of acidic electrolyzed water, and may be hereinafter referred to as acidic water. Further, the cathode-generated water is strongly alkaline electrolyzed water, and may be hereinafter referred to as alkaline water.
As shown in FIG. 2, the liquid feed pump 29 is operated to supply salt water from the salt water tank 25 to the first electrolytic solution chamber 5c and the second electrolytic solution chamber 5d of the electrolytic solution chamber 5 of the electrolytic cell 2. Further, water is supplied from the water supply source 9 to the anode chamber 3 and the cathode chamber 4.
When the switch 7b is switched to the first cathode 4b to supply power, a positive voltage and a negative voltage are applied from the power source 7a to the anode 3b and the first cathode 4b, respectively. Sodium ions ionized in the salt water flowing into the first electrolytic solution chamber 5c and the second electrolytic solution 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 having no selective permeability of ions, sodium ions can permeate.

After that, electrolysis of water corresponding to the amount of passing sodium ions occurs in the first cathode 4b, and hydrogen gas is generated in the cathode chamber 4. Sodium ions remain in the cathode chamber 4 as sodium hydroxide. The total reaction equation in the cathode chamber 4 is shown in the following equation (1).
2H ₂ O + 2Na ⁺ → 2e ⁻ + H ₂ + 2NaOH… (1)
As a result, the pH of the cathode chamber 4 shifts to the alkaline side. The generated sodium hydroxide aqueous solution and hydrogen gas containing hydrogen gas as alkaline water flow out from the cathode chamber 4 to the second drain pipe 21c.

Chloride ions ionized in the salt water of the first electrolytic solution chamber 5c and the second electrolytic solution 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), chlorine ions are oxidized at the anode 3b to generate chlorine gas.
2Cl- → Cl ₂ + 2e-... ⁽ 2 ⁾
Then, as shown in the following formula (3), the chlorine gas immediately reacts with water in the anode chamber 3 to produce hypochlorous acid and hydrochloric acid.
Cl ₂ + H ₂ O → HClO + HCl… (3)
The acidic water (hypochlorite water) thus generated flows out from the anode chamber 3 to the first drainage pipe 21b. The alkaline water that has flowed out to the second drainage pipe 21c and the acidic water that has flowed out to the first drainage pipe 21b are mixed in the first generated water mixing unit 10, and hypochlorite water whose pH has been adjusted is used as the mixed generated water. It is drained.

Further, when the switch 7b is switched to the second cathode 5b to supply power, the positive voltage and the negative voltage are applied from the power source 7a to the anode 3b and the second cathode 5b, respectively. The sodium ions ionized in the salt water flowing into the first electrolytic solution chamber 5c and the second electrolytic solution chamber 5d are attracted to the second cathode 5b. At this time, the sodium ions ionized in the salt water of the first electrolytic solution chamber 5c can pass through the third diaphragm 5a and reach the second cathode 5b. The electrolysis of the salt water in the second cathode 5b produces an aqueous sodium hydroxide solution containing hydrogen gas in the second electrolyte chamber 5d. As a result, the inside of the second electrolytic solution chamber 5d shifts to the strong alkaline side. The sodium hydroxide aqueous solution containing hydrogen gas as alkaline water flows out from the second electrolytic solution chamber 5d to the drain pipe 8e due to the flow of the second electrolytic solution (salt water) in the second electrolytic solution chamber 5d supplied from the supply pipe 8c. After that, it is mixed with the electrolytic solution of the drainage pipe 8d and discharged to the outside by the drainage pipe 8f. Since the flow of salt water in the first electrolytic solution chamber 5c and the flow of salt water in the second electrolytic solution chamber 5d are separated by the third diaphragm 5a, the alkaline water generated in the second electrolytic solution chamber 5d is a cathode. It hardly flows into the chamber 4 and the first electrolytic solution chamber 5c, and the first electrolytic solution 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 the strong alkali and is less likely to deteriorate. Further, the cathode-generated water discharged from the cathode chamber 4 at this time is the water itself supplied from the water supply source 9.

Chloride ions ionized in the salt water in the first electrolytic solution chamber 5c and the second electrolytic solution chamber 5d are attracted to the anode 3b. At this time, the chlorine ions ionized in the salt water in the second electrolytic solution chamber 5d can pass through the first diaphragm 3a and reach the anode 3b. Then, 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 (hypochlorite water) thus generated flows out from the anode chamber 3 through the first drainage pipe 21b. In the first generated water mixing unit 10, the acidic water is mixed with the drainage from the second drainage pipe 21c, but the alkaline water is not mixed in the drainage from the second drainage pipe 21c. Therefore, the pH of the hypochlorite water obtained as the mixed product water when feeding the second cathode 5b is higher than the pH of the hypochlorite water obtained as the mixed product water when the first cathode 4b is fed. Will also be low.
Impurities contained in water used as raw water differ depending on the region and location, and in particular, the carbonic acid component has an interference effect toward weak alkalinity. Therefore, depending on the water used, the pH adjustment points may not match and may deviate slightly. In general, carbonate ions are dissolved in water as counter ions of alkaline components, so that hard water tends to shift to the alkaline side, and soft water (ultimately pure water) tends to shift to the acid side.

On the other hand, when the electrolytic water generator 1 according to the embodiment is used, a second cathode 5b is provided in the electrolytic solution chamber 5, 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 cathode-generated water and the cathode-generated water are generated. The pH of the mixed product water with water can be adjusted. As a result, the pH of the mixed product water can be adjusted at any time even if the water quality of the raw water fluctuates, and the pH of the hypochlorite water obtained as the mixed product water can be controlled to be slightly acidic or near neutral. Become. Further, a third diaphragm 5a is provided between the second cathode 5b and the first diaphragm 3a, and the electrolytic solution chamber 5 is provided in the first electrolytic solution chamber 5c on the anode chamber 3 side and the second electrolytic solution chamber on the cathode chamber 4 side. By separating into 5d, when the energization from the feeding unit 7 is switched to the second cathode 5b, the electrolytic solution pH of the second electrolytic solution chamber 5d shifts to the alkaline side, but the alkaline substance flows through the second electrolytic solution. Since the pH of the first electrolytic solution chamber 5c can be maintained closer to neutral than the pH of the second electrolytic solution chamber 5d, the pH of the first electrolytic solution chamber 5c can be maintained closer to neutral than the pH of the second electrolytic solution chamber 5d. The first diaphragm 3a of 5c is less likely to deteriorate and has good durability. Therefore, according to the embodiment, an electrolyzed water generator that can be used for a long period of time can be obtained.

FIG. 3 shows a timing chart showing an example of switching the current application path in the feeding unit 7.
This is because the electrolytic current is fixed at 2A, the current application path to the first cathode 4b and the second cathode 5b is 10 seconds per cycle, the application is applied to the first cathode 4b for 4 seconds, and the second cathode 5b. This is a control example in which application for 6 seconds is switched. The pulse waveform 101 represents the relationship between the energization time of the first cathode 4b and the voltage at this time, and the pulse waveform 102 represents the relationship between the energization time of the second cathode 5b and the voltage. Even though the electrolytic current is fixed at the same 2A, the voltage when applied to the first cathode 4b and the voltage when applied to the second cathode 5b are different because the distance from the anode 3b is different.

The electrolytic current, cycle, and energization ratio at the first cathode and the second cathode are configured to be operable by the user. In the case of this example, if 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, the normal three-chamber operation is performed, and the acidic water and alkalinity generated at this time are obtained. When water is mixed, it becomes mixed water with a pH of around 8.5. On the contrary, when 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, and when mixed with the acidic water generated at this time, it changes from strongly acidic to weakly acidic mixed water.
Using the electrolyzed water generator 1 according to the first embodiment, a water quality change test based on the energization ratio and a continuous operation test were performed as follows.

Water quality change test based on energization ratio Using the electrolyzed water generator 1, tap water with a Ca hardness of 55 mg / L, which is standard in Japan, is used as raw water at 0.5 L / min, and the electrolytic current is fixed at 2 A. The cycle was set to 10 seconds, the ratio of the energization time to the first cathode 4b and the second cathode 5b in one cycle was variously changed, and the water quality change (pH and effective chlorine concentration) of the mixed water was measured.
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 produced water in the electrolyzed water generator according to the first embodiment.
In the figure, the characteristic line 104 is a graph showing the pH of the mixed product water with respect to the energization ratio of the second cathode 5b. The characteristic line 103 shows 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 energization amount to the second cathode 5b to the total current amount. An energization ratio of 0% for the second cathode 5b indicates energization of only the first cathode 4b, 100% indicates energization of only the second cathode 5b, and an energization ratio of 50% for the second cathode 5b indicates energization of the first cathode 4b. It means that the time of 5 seconds and the energization time of the second cathode 5b for 5 seconds were repeated. The measurement of the water quality (pH and effective chlorine concentration) of the mixed product water was carried out by collecting the mixed product water for a time sufficiently longer than the cycle time so that the water quality difference due to the energization switching would not be sufficiently integrated and affected. .. Further, during the generation of the electrolyzed water, a 20% sodium chloride aqueous solution was sent to the first electrolytic solution chamber 5c and the second electrolytic solution chamber 5d, respectively, at 3 mL / min.
As shown in the characteristic line 104, it can be seen that the mixed product water is alkaline when the second cathode 5b is not used (energization ratio 0%). This is because all the alkaline substances produced by the first cathode 4b are mixed with the produced water.

On the other hand, when the energization ratio of the second cathode 5b is increased from 0, the effective chlorine concentration of the mixed product water is almost constant as shown in the characteristic line 103, but the pH is acidic as shown in the characteristic line 104. It will become. This is because the alkaline substance generated at the second cathode 5b is released only into the second electrolytic solution chamber 5d and is not mixed with the mixed product water. In the case of the raw water used in the first embodiment, the pH of the second cathode varies greatly from around 55% and is acidified. When the energization ratio of the second cathode 5b is set from 55% to 60%, the influence of corrosion and the like is small, and the acid water (hypochlorous acid) in the slightly acidic region (pH 5 to 6.5) in which the abundance ratio of the active ingredient HClO is high is low. Chloric acid water) can be obtained. Further, when the energization ratio of the second cathode 5b is increased and only the second cathode 5b is used without using the first cathode 4b (energization ratio 100%), it can be seen that the mixed water is weakly acidic to strongly acidic. This is because no alkaline substance is generated at the first cathode, the raw water is mixed with the acidic water as it is, and the water quality of the acidic water generated in the anode chamber 3 appears as it is.
In this embodiment, tap water having a Ca hardness of 55 g / L was used as raw water. When soft water is used, the energization ratio of the second cathode 5b, which indicates a slightly acidic region, shifts to a smaller one, and when hard water is used, the energization ratio of the second cathode 5b, which indicates a slightly acidic region, shifts to a larger one.

Continuous operation test
The following continuous operation test was performed using the electrolyzed water generator 1 according to the first embodiment.
In Japan, tap water having a standard Ca hardness of 55 mg / L was used as raw water and flowed at 0.5 L / min. During the generation of the electrolyzed water, a 20% sodium chloride aqueous solution was sent to the first electrolytic solution chamber 5c and the second electrolytic solution chamber 5d at 3 mL / min, respectively. The electrolysis current is fixed at 2 A, one cycle is set to 10 seconds, and the energization ratio of the second cathode is 60% so that the pH of the mixed product water is 6 (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 generated water. The pH and effective chlorine concentration of the obtained mixed product water were initially measured every 24 hours, and then every week thereafter.
Further, as Comparative Example 1 and Comparative Example 2, an electrolyzed water generator having the same configuration as that of the first embodiment is prepared except that the electrolytic cell 5a of the electrolytic cell 2 is not provided with the third diaphragm 5a. The electrolyzed water generator was operated for about 700 hours under the same conditions to obtain mixed generated water. The pH and effective chlorine concentration were similarly measured as changes in the water quality of the obtained mixed product water.

FIG. 5 shows a graph showing the results of a continuous operation test of the electrolyzed water generator according to the first embodiment.
In the figure, the horizontal axis is the operating time. The characteristic line 110 indicates the pH of the obtained mixed product water. Further, the characteristic line 105 shows the effective chlorine concentration of the obtained mixed product water. The characteristic lines 106 and 107 indicate the effective chlorine concentrations of Comparative Examples 1 and 2, and the characteristic lines 108 and 109 indicate the pHs of Comparative Examples 1 and 2.
In Comparative Example 1, it was confirmed that the pH increased as shown in the characteristic line 108 and the effective chlorine concentration decreased as shown in the characteristic line 106 from the place where the time exceeded 48 hours. Further, in Comparative Example 2, it was confirmed that the pH increased as shown in the characteristic line 109 and the effective chlorine concentration decreased as shown in the characteristic line 107 from the place where the time exceeded 168 hours. When the electrolytic cells of Comparative Example 1 and Comparative Example 2 were disassembled and investigated, it was confirmed that the first diaphragm of the anode chamber became cloudy and the membrane was torn in some places. From this, it is considered that the alkaline substance generated at the second cathode alkalizes the electrolytic solution chamber, and the first diaphragm in contact with the electrolytic solution chamber is denatured, resulting in fracture. On the other hand, in the electrolyzed water generator 1 according to the first embodiment, as shown in the characteristic lines 110 and 105, the effective chlorine concentration and pH are constant even after long-term operation, and the water quality of the mixed generated water changes. unacceptable. In this method, the electrolytic solution chamber 5 is divided into a first electrolytic solution chamber 5c on the anode chamber 3 side and a second electrolytic solution chamber 5d on the cathode chamber 4 side by a third diaphragm 5a made of a neutral film having no ion permeation selectivity. By providing the second cathode 5b in the second electrolytic solution chamber 5d so as to be in close contact with the third diaphragm 5a, the alkaline substance generated by the second cathode 5b does not come into contact with the first diaphragm 3a. It is considered that this is because it was generated and discharged only in the liquid chamber 5d, and the action on the alkaline substance on the first diaphragm 3a was suppressed.

In this way, the electrolyte chamber 5 is a third diaphragm 5a made of a neutral film having no ion permeation selectivity, and the first electrolyte chamber 5c on the anode chamber 3 side and the second electrolyte chamber 5d on the cathode chamber 4 side. By providing the second cathode 5b in the second electrolyte chamber 5d in close proximity to the third diaphragm 5a, the energization ratio of the second cathode 5b can be changed even if raw water having different Ca hardness is used. As a result, it is possible to generate a slightly acidic mixed product water, and it is possible to stably generate a slightly acidic mixed product water even after long-term operation. In addition, when the water quality of the raw water fluctuates due to seasonal fluctuations and the pH of the mixed product water deviates from the slightly acidic range, it can be easily adjusted to the slightly acidic range by changing the energization ratio of the second cathode 5b. ..

Application example of electrolyzed water generator
The energization ratio of the second cathode 5b can be automatically changed according to the pH measurement value of the mixed product water.
FIG. 6 shows a schematic view showing an application example of the electrolyzed water generator according to the first embodiment.
As shown in the figure, the electrolyzed water generator 1-1 according to the application example of the first embodiment accommodates the mixed generated water 41 in the subsequent stage of the first produced water mixing unit 10 of the electrolytic cell 2, and has the bottom portion 11a and the side wall 11b. A water storage unit 11 is further provided, and an online pH meter 12 as a pH measuring unit and a third drainage pipe 21d for discharging mixed generated water from the water storage unit 11 are installed in the water storage unit 11. The online pH meter 12 is connected to the control unit 7c. The water storage unit 11 can have a capacity capable of storing the mixed water in a time sufficiently longer than the cycle time so that the difference in water quality due to the energization switching is sufficiently integrated and does not affect the water storage unit 11. The other configuration of the electrolyzed water generator 1-1 is the same as that of the electrolyzed water generator 1 shown in FIG.

In the electrolyzed water generator 1-1, the mixed generated water 41 from the first generated water mixing unit 10 is introduced into the water storage unit 11, the pH is measured at any time by the online pH meter 12, and the water is discharged from the third drain pipe 21d. do. When the water quality of the raw water fluctuates due to seasonal fluctuations and the pH measurement value of the mixed product water 41 deviates from the slightly acidic range, the pH measurement signal from the online pH meter 12 is calculated by the control unit 7c, and the second By building an algorithm that automatically changes the energization ratio of the cathode 5b, it is possible to automatically control the pH of the mixed product water. In addition, it has the same effect as the electrolyzed water generator 1. In this application example, an online pH meter 12 that can automatically measure the pH of the mixed generated water 41 of the water storage unit 11 is used, but the operator manually measures the pH of the mixed generated water 41 of the water storage unit 11 at any time. It is also possible to construct an algorithm that automatically changes the energization ratio of the second cathode 5b by inputting the value to the control unit 7c and calculating the value in the control unit 7c based on the value.

(Second Embodiment)
FIG. 7 is a diagram schematically showing a running water type electrolyzed water generator according to the second embodiment.
As shown in the figure, the electrolyzed water generator 1-2 uses a so-called three-chamber type electrolytic cell (electrolyzed cell) 2-2. Inside, the electrolyte chamber 5 and the electrolyte chamber defined between the diaphragms by the first diaphragm (anode side membrane, anion exchange membrane) 3a and the second diaphragm (cathode side membrane, cation exchange membrane) 4a. It is divided into three chambers, an anode chamber 3 and a cathode chamber 4 located on both sides of 5. An anode 3b is provided in the anode chamber 3 and is in close proximity to the first diaphragm 3a. The first cathode 4b is provided in the cathode chamber 4 and is in close proximity to the second diaphragm 4a. The anode 3b and the cathode 4b are formed in the shape of a rectangular plate having 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 film capable of passing cations and anions without selectivity of ion permeation, and is a first electrolytic solution chamber 5c on the anode chamber 3 side and a cathode chamber 4 side. It is partitioned into a second electrolyte chamber 5d. The second electrolyte chamber 5d is provided with a second cathode 5b so as to face the third diaphragm 5a in close proximity to the third diaphragm 5a. Like the anode 3b and the first cathode 4b, the second cathode 5b is formed in a rectangular shape having substantially the same size as the anode 3b and the first cathode 4b.

Further, a porous member 5e is provided as a "water-permeable diffusion suppressing member" for controlling the diffusion of an alkaline substance in at least a part of the first electrolytic solution chamber 5c on the anode chamber 3 side.
The diffusion suppressing member is water permeable. That is, when the electrolytic solution is supplied from the first electrolytic solution supply port 5f via the supply pipe 8b, the electrolytic solution needs to pass through the inside of the diffusion suppressing member. Therefore, the diffusion suppressing member has water permeability.
In such a diffusion suppressing member, when the yin and yang poles are energized with the electrolytic solution passing through the inside, sodium ions and chloride ions in the electrolytic solution move toward the electrode by an electric force. However, no electrical force is generated when the energization is stopped. Even in this case, the substance may move naturally inside the electrolytic cell 2-2 due to, for example, a concentration gradient. Such movement of natural substances without electrical force is called "diffusion". The diffusion suppressing member has a function of making such diffusion less likely to occur, that is, a function of suppressing the movement of natural substances not due to 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 operating, since the diffusion suppressing member is water permeable, the electrolytic solution passes through the inside of the diffusion suppressing member, and the electrolyzed water is generated by energizing both the yin and yang poles. .. On the other hand, when the electrolyzed water generator 1-2 is stopped, an alkaline substance may flow into the first electrolytic solution chamber 5c from the second electrolytic solution chamber 5d side due to diffusion. In this case, if the diffusion suppressing member is installed, the inflow of the alkaline substance into the first electrolytic solution chamber 5c can be suppressed. As a result, the first diaphragm 3a is less likely to deteriorate.

Examples of the porous member 5e that can be used in the second embodiment include a plastic sintered porous body (manufactured by Fuji Chemical Co., Ltd.), a ceramic sintered porous body, and the like.
The power feeding unit 7 has a power supply 7a, a control unit 7c for controlling the power supply 7a, and a switch 7b (changeover switch) for switching the power supply to the first cathode 4b and the second cathode 5b. The positive electrode of the power source 7a is connected to the anode 3b via wiring. The negative electrode of the power source 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 the user.

In addition, the electrolyzed water generator 1-2 includes an electrolytic solution supply unit 8 for supplying an electrolytic solution, for example, salt water to the first and second electrolytic solution chambers 5c and 5d of the electrolytic cell 2-2, an anode chamber 3 and a cathode. A water supply unit 21 for supplying water to the chamber 4 and a first generated water mixing unit 10 are provided, and are configured in the same manner as the electrolyzed water generation device 1 according to the first embodiment described above.
In the second embodiment, the mixed generated water drained from the electrolyzed water generator 1-2 is hypochlorite water whose pH is controlled to be near slightly acidic / neutral. That is, in the normal generation operation, 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. According to the present embodiment, by switching the switch 7b (changeover switch) and applying a voltage to the second cathode 5b, it is possible to further adjust the pH by the connection duty. Further, by providing the porous member 5e, the alkaline substance generated in the second electrolytic solution chamber 5d permeates through the third diaphragm 5a and the first electrolytic solution chamber 5c and when the electrolytic water generator is stopped. It is possible to suppress diffusion to the first diaphragm 3a in contact with the first electrolyte chamber 5c.

Further, when the electrolyzed water generator 1-2 according to the second embodiment is used, the pH of the mixed generated water can be adjusted at any time even if the quality of the raw water fluctuates, as in the first embodiment, and the mixed produced water can be adjusted at any time. It is possible to control the pH of the hypochlorite water obtained as a medium acid to near neutrality. Further, by separating the electrolytic solution chamber 5 into the first electrolytic solution chamber 5c and the second electrolytic solution chamber 5d by the third diaphragm 5a, when the energization from the feeding unit 7 is switched to the second cathode 5b, the second electrolysis The electrolytic solution pH of the liquid chamber 5d shifts to the alkaline side, but the alkaline substance is discharged by the flow of the second electrolytic solution and hardly mixes with the flow of the first electrolytic solution. The diaphragm 3a is less likely to deteriorate and has good durability. Therefore, according to the second embodiment, an electrolyzed water generator that can be used for a long period of time can be obtained.

Using the electrolyzed water generator 1-2 according to the second embodiment, a water quality change test based on the energization ratio and a continuous operation test were performed 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 electrolytic current was fixed at 2 A, one cycle was set to 10 seconds, and the first cathode and the second cathode in one cycle were used. The energization was switched and the ratio of the energization time was changed in various ways, and the water quality change (pH and effective chlorine concentration) of the mixed water was measured.

FIG. 8 is a graph showing the relationship between the energization ratio (duty ratio) of the second cathode 5b in the electrolyzed water generator 1-2 according to the second embodiment and the water quality of the mixed generated water.
The characteristic line 112 shows the change in pH with respect to the energization ratio of the second cathode 5b, and the characteristic line 111 shows the change in the 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 measurement of the water quality (pH and effective chlorine concentration) of the mixed product water was carried out by collecting the mixed product water for a time sufficiently longer than the cycle time so that the water quality difference due to the energization switching would not be sufficiently integrated and affected. .. Further, during the generation of the electrolyzed water, a 20% sodium chloride aqueous solution was sent to the first electrolytic solution chamber 5c and the second electrolytic solution chamber 5d, respectively, at 3 mL / min.

When pure water is used as raw water, as shown in the characteristic line 112, the pH of the second cathode 5b fluctuates greatly from around 25%, and acidification occurs. Further, when the energization ratio of the second cathode 5b is set from 25% to 30%, the influence of corrosion and the like is small, and the acidic water (pH 5 to 6.5) in the slightly acidic region (pH 5 to 6.5) in which the abundance ratio of the active ingredient HClO is high is low. Hypochlorous acid water) can be obtained. On the other hand, as shown in the characteristic line 111, the effective chlorine concentration of the mixed product water is almost constant. As described above, in the electrolyzed water generator 1-2 in the second embodiment, even when the porous member 5e for suppressing the diffusion of the alkaline substance into the first diaphragm 3a is provided in the first electrolytic solution chamber 5c. It was found that the pH of the mixed product water can be sufficiently controlled by the energization ratio of the second cathode 5b. When the porous member 5e is provided in the first electrolytic cell 5c, not only the diffusion of the alkaline substance into the first electrolytic cell 5c while the electrolytic cell is stopped is suppressed, but also the first diaphragm 3a is deteriorated. However, since the structure is such that the first diaphragm 3a is mechanically sandwiched between the porous member 5e and the anode 3b, it is possible to prevent the progress of breakage of the first diaphragm 3a.
Further, 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 that of the flow rate. 2 The flow rate of the electrolytic solution flowing into the electrolytic solution chamber 5d may be larger. In that case, there is an advantage that the alkaline water generated in the second electrolytic solution chamber 5d can be efficiently discharged. A flow rate control valve may be provided in the supply pipe 8b and / or the supply pipe 8c.

(Third Embodiment)
FIG. 9 is a diagram schematically showing a running water type electrolyzed water generator according to a third embodiment.
In the electrolytic water generator 1-3 according to the third embodiment, at least two electrolytic cells 2 and 2-1 are connected in series, and for example, the first electrolytic cell 2 is used as raw water to be supplied to the second electrolytic cell 2-1. The pH was adjusted step by step using the first mixed water produced in the above.
As shown in the figure, the electrolyzed water generator 1-3 uses a so-called three-chamber type first electrolytic cell 2 and a second electrolytic cell 2-1.
The inside of the first electrolytic cell 2 is an electrolytic cell 5 defined between the diaphragms by a first diaphragm (anode side diaphragm, anion exchange membrane) 3a and a second diaphragm (cathode side diaphragm, cation exchange membrane) 4a. It is divided into three chambers, an anode chamber 3 and a cathode chamber 4 located on both sides of the electrolytic cell chamber 5. An anode 3b is provided in the anode chamber 3 and is in close proximity to the first diaphragm 3a. The first cathode 4b is provided in the cathode chamber 4 and is in close proximity to the second diaphragm 4a. The anode 3b and the first cathode 4b are formed in the shape of a rectangular plate having 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 film capable of passing cations and anions without selectivity of ion permeation, and is a first electrolytic solution chamber 5c on the anode chamber 3 side and a cathode chamber 4 side. It is partitioned into a second electrolyte chamber 5d. The second electrolyte chamber 5d is provided with a second cathode 5b so as to face the third diaphragm 5a in close proximity to the third diaphragm 5a. Like the anode 3b and the first cathode 4b, the second cathode 5b is formed in a rectangular shape having substantially the same size as the anode 3b and the first cathode 4b.
The power feeding unit 7 connected to the first electrolytic cell 2 has a power supply 7a that supplies a current required for electrolysis, a switch 7b that energizes the first cathode 4b and / or the second cathode 5b, and a power supply 7a and a switch 7b. It has a control unit 7c to control. Here, as the switch 7b, a changeover switch for switching the 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, and by switching the switch 7b, the first cathode 4b and the second cathode 5b are selectively selected. A negative voltage can be applied to. The switch 7b is configured to be operable by the user.

When a changeover switch such as a switch 7b is used as a switch for energizing the first cathode 4b and / or the second cathode 5b, the voltage applied to the first cathode 4b and the second cathode 5b is fixed, and the first cathode 4b and The energization ratio can be adjusted by temporally switching the energization of the second cathode 5b.
The second electrolytic cell 2-1 is connected to the first electrolytic cell 2 and the first generated water mixing unit 10-1 used in the mixed generated water supply line 10s, and is provided after the first electrolytic cell 2. , Has almost the same configuration as the first electrolytic cell 2.
The inside of the second electrolytic cell 2-1 is defined between the diaphragms by the first diaphragm (anode side diaphragm, anion exchange membrane) 3-1a and the second diaphragm (cathode side diaphragm, cation exchange membrane) 4-1a. It is divided into three chambers, that is, an electrolytic cell chamber 5-1 and an anode chamber 3-1 and a cathode chamber 4-1 located on both sides of the electrolytic cell chamber 5-1. An anode 3-1b is provided in the anode chamber 3-1 and faces the first diaphragm 3-1a. The 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 a rectangular plate having substantially the same size, and sandwich the electrolytic solution chamber 5-1 and the first and second diaphragms 3-1a and 4-1a in between. , Facing each other.

The electrolytic solution chamber 5-1 is a third diaphragm 5-1a made of a neutral film capable of passing cations and anions without selectivity of ion permeation, and is a first electrolytic solution chamber 5-1c on the anode chamber 3 side. It is partitioned into a second electrolyte chamber 5-1d on the cathode chamber 4 side. The second electrolyte chamber 5-1d is provided with a second cathode 5-1b so as to face the third diaphragm 5-1a in close proximity to the third diaphragm 5-1a. The second cathode 5-1b is formed in a rectangular shape having substantially the same size as the anode 3-1b and the first cathode 4-1b in the same manner as the anode 3-1b and the first cathode 4-1b.
The anode 3-1b has the same configuration as the 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 feeding unit 7-1 connected to the second electrolytic cell 2-1 includes a power supply 7-1a, a control unit 7-1c for controlling the power supply 7-1a, and a first cathode 4-1b and a second cathode 5-. It has a switch 7-1b (changeover switch) for switching the 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.

Further, the electrolytic water generator 1-3 includes the first and second electrolytic solution chambers 5c and 5d of the first electrolytic cell 2, and the first and second electrolytic solution chambers 5-1c of the second electrolytic cell 2-1. The 5-1d is provided with an electrolytic solution supply unit 8-1 for supplying an electrolytic solution, for example, salt water, and a water supply unit 21 for supplying water to the anode chamber 3 and the cathode chamber 4 of the first electrolytic cell 2, and also having an anode chamber. The first mixed generated water obtained by mixing the anode-generated water and the cathode-generated water discharged from 3 and the cathode chamber 4 is supplied to the anode chamber 3-1 and the cathode chamber 4-1 of the second electrolytic cell 2-1. The first generated water mixing unit 10-1 is provided. The first generated water mixing unit 10-1 is used as the mixed generated water supply line 10s.

The electrolytic solution supply unit 8-1 includes a salt water tank (electrolyte solution tank) 25 in which, for example, a 20% sodium chloride aqueous solution is stored as the electrolytic solution 25a, and the first and second electrolytic solution chambers of the first electrolytic cell 2 from the salt water tank 25. A supply pipe 8a for guiding salt water below 5c and 5d, a liquid feed pump 29 provided in the supply pipe 8a, and salt water from above the first and second electrolytic solution chambers 5c and 5d of the first electrolytic cell 2 It has a drainage pipe 8f for discharging. In the vicinity of the outlet of the salt water tank 25, the supply pipe 8-1a branches from the supply pipe 8a and guides the salt water below the first and second electrolytic solution chambers 5-1c and 5-1d. A liquid feed pump 29-1 is provided in the supply pipe 8-1a.
Further, the supply pipe 8a is connected to the 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 is connected to the supply pipe 8b as a first electrolytic solution supply line for supplying salt water. And branch to the supply pipe 8c as the second electrolytic solution supply line which is connected to the second electrolytic solution supply port 5g provided at the lower part of the second electrolytic solution chamber 5d of the electrolytic solution chamber 5 to supply salt water. Electrolyzed water is separately supplied to the 1 electrolytic solution chamber 5c and the 2nd electrolytic solution chamber 5d. At the upper part of the first electrolytic solution chamber 5c, a drain pipe 8d is connected to the first electrolytic solution discharge port 5h and as a first electrolytic solution discharge line for draining the electrolytic solution flowing in the first electrolytic solution chamber 5c. A drain pipe 8e is connected to the second electrolytic solution discharge port 5i at the upper part of the second electrolytic solution chamber 5d and serves as a second electrolytic solution discharge line for draining the electrolytic solution flowing in the second electrolytic solution chamber 5d. Are provided respectively. Therefore, the flow of salt water in the first electrolytic solution chamber 5c is different from the flow of salt water in the second electrolytic solution chamber 5d. The drainage pipe 8d and the drainage pipe 8e are merged into the drainage pipe 8f, and the electrolytic solution of the drainage pipe 8d and the drainage pipe 8e is mixed and discharged.

The supply pipe 8-1a is connected to the first electrolytic solution supply port 5-1f provided at the lower part of the first electrolytic solution chamber 5-1c of the electrolytic solution chamber 5-1 to supply the first electrolytic solution to supply salt water. A second supply pipe 8-1b as a line and a second electrolyte supply port 5-1g provided at the bottom of the second electrolytic solution chamber 5-1d of the electrolytic solution chamber 5-1 are connected to supply salt water. It is branched into a supply pipe 8-1c as an electrolytic solution supply line, and the electrolytic solution is separately supplied to the first electrolytic solution chamber 5-1c and the second electrolytic solution chamber 5-1d. The upper part of the first electrolytic solution chamber 5-1c is connected to the first electrolytic solution discharge port 5-1h and serves as a first electrolytic solution discharge line for draining the electrolytic solution flowing in the first electrolytic solution chamber 5-1c. The drainage pipe 8-1d of the above is connected, and the electrolytic solution that is connected to the second electrolytic solution discharge port 5-1i at the upper part of the second electrolytic solution chamber 5-1d and flows in the second electrolytic solution chamber 5-1d. The drainage pipe 8-1e as the second electrolytic solution discharge line for draining the water is connected. Therefore, the flow of salt water in the first electrolytic solution chamber 5-1c is different from the flow of salt water in the second electrolytic solution chamber 5-1d. The drainage pipe 8-1d and the drainage pipe 8-1e are merged into the drainage pipe 8-1f, and the electrolytic solution of the drainage pipe 8-1d and the drainage pipe 8-1e is mixed and discharged.

The water supply unit 21 includes a water supply source 9 for supplying water, an on-off valve 28 provided near the outlet of the water supply source 9, and a first water supply pipe for guiding water from the water supply source 9 to the lower parts of the anode chamber 3 and the cathode chamber 4. The 21a is connected to the first drainage port 3h, and is connected to the first drainage pipe 21b as the first drainage line for discharging the water flowing through the anode chamber 3 from the upper part of the anode chamber 3 and the second drainage port 4h. It is provided with a second drainage pipe 21c as a second drainage line for discharging the water flowing through the cathode chamber 4 from the upper part of the cathode chamber 4. The first water supply pipe 21a is branched into a second water supply pipe 21e as a first water supply line and a third water supply pipe 21f as a second water supply line. The second water supply pipe 21e is connected to the first water supply port 3f 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 drainage pipe 21b is connected to the middle part of the second drainage pipe 21c and constitutes the first generated water mixing unit 10-1 used as the mixed generated water supply line 10s. As a result, the anode-generated water drained from the first drainage pipe 21b and the cathode-generated water drained from the second drainage pipe 21c are mixed to form the first mixed-generated water. The first mixed product water is hypochlorite water whose pH is controlled in the neutral range from a weak alkaline acid.

The first mixed generated water obtained from the first electrolytic cell 2 is sent to the second electrolytic cell 2-1 by the first generated water mixing unit 10-1. The downstream of the first generated water mixing section 10-1 is connected to the first water supply port 3-1f provided at the lower part of the anode chamber 3-1 and the third drainage pipe 10-1a for supplying the first mixed generated water. It is connected to the second water supply port 4-1f provided at the lower part of the cathode chamber 4-1 and branches to the fourth drainage pipe 10-1b for supplying the first mixed generated water. In this electrolyzed water generator 1-3, the first generated water mixing section 10-1, the third drainage pipe 10-1a, and the fourth drainage pipe 10-1b are in the anode chamber 3-1 and the cathode chamber 4-1. It can be used as a mixed generated water supply line 10s for supplying the first mixed produced water.

A fifth drainage pipe 10-1c for draining the anode-generated water flowing through the anode chamber 3-1 is connected to the first drainage port 3-1h provided in the upper part of the anode chamber 3-1. A sixth drainage pipe 10-1d for draining the cathode-generated water flowing through the cathode chamber 4-1 is connected to the second discharge port 4-1h provided in the upper part of the cathode chamber 4-1. -1d is connected to the middle part of the fifth drainage pipe 10-1c, and the anodized water and the cathode generated water of the second electrolytic cell 2-1 are mixed to form the second mixed generated water. It constitutes a part 10-1e. The second mixed product water is hypochlorite water whose pH is further controlled to be slightly acidic and near neutral by the second electrolytic cell 2-1.
In addition, an on-off valve or a flow rate adjusting valve may be provided in each pipe.

As described above, according to the electrolyzed water generator according to the third embodiment, the first electrolytic cell 2 is mixed and generated as the raw water to be supplied to the anode chamber 3-1 and the cathode chamber 4-1 of the second electrolytic cell 2-1. By using water (first mixed generated water), the pH of the produced water is adjusted stepwise in the first electrolytic cell 2 and the second electrolytic cell 2-1 to make the final mixed generated water (second mixed generated water). Water) can be obtained.
As the electrolytic cell, the electrolytic cell 2 or 2-2 used in the first embodiment or the second embodiment can be used. Here, the electrolytic cell 2 used in the first embodiment is used. Here, the first electrolytic cell 2 and the second electrolytic cell 2-1 have the same structure in terms of material, shape, size, and the like, but they may have different configurations. In FIG. 9, the electrolytic solution supply unit 8 shares the electrolytic solution supply unit of the first electrolytic cell 2 and the second electrolytic cell 2-1 but may be separate.

Further, when the electrolyzed water generator 1-3 according to the third embodiment is used, the pH of the mixed generated water can be adjusted at any time even if the quality of the raw water fluctuates, as in the first embodiment, and the mixed produced water can be adjusted at any time. It is possible to control the pH of the hypochlorite water obtained as a medium acid to near neutrality. Further, by separating the electrolytic solution chambers 5 and 5-1 into the first electrolytic solution chambers 5c and 5-1c and the second electrolytic solution chambers 5d and 5-1d by the third diaphragm 5a and 5-1a, the feeding unit 7 When the energization from the second cathode 5b and 5-1b is switched to, the electrolytic solution pH of the second electrolytic solution chambers 5d and 5-1d shifts to the alkaline side, but the alkaline substance is discharged by the flow of the second electrolytic solution. Since it is hardly mixed in the flow of the first electrolytic solution, the first diaphragms 3a and 3-1a of the first electrolytic solution chambers 5c and 5-1c are less likely to deteriorate and the durability is improved. In addition to this, the alkalinity of the second electrolytic cell chambers 5d and 5-1d can be suppressed by adjusting the pH stepwise in the first electrolytic cell 2 and the second electrolytic cell 2-1. Therefore, according to the third embodiment, an electrolyzed water generator that can be used for a longer period of time than the first embodiment and the second embodiment can be obtained.

Water quality change test by energization ratio
Using the electrolyzed water generator 1-3, tap water having a Ca hardness of 45 g / L was flowed as raw water of the first electrolytic cell 2 at 0.5 mL / min, and the electrolytic current of the first electrolytic cell 2 was set to 1.0 A. It was fixed, one cycle was set to 10 seconds, 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 mixed generated water having a pH of 6.9 and an effective chlorine concentration of 48 mg / L was added. Obtained. Subsequently, this mixed generated water was used as the raw water of the second electrolytic cell 2-1 and the electrolytic current of the second electrolytic cell 2-1 was fixed at 1.0 A, one cycle was set to 10 seconds, and the first cathode 4 was used. The energization of -1b and the second cathode 5-1b was switched to change the ratio of the energization time in various ways, and the water quality (pH and effective chlorine concentration) of the mixed product water of the second electrolytic cell 2-1 was measured.

FIG. 10 is a graph showing the relationship between the energization ratio (duty ratio) of the second cathode 5-1b of the second electrolytic cell 2-1 and the water quality of the mixed generated water in the electrolyzed water generator according to the third embodiment. be.
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 and the characteristic line 114 is with respect to the energization ratio of the second cathode 5-1b of the second electrolytic cell 2-1. The 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 measurement of the water quality (pH and effective chlorine concentration) of the mixed water quality of the second electrolytic cell 2-1 is performed in a time sufficiently longer than the cycle time so that the water quality difference due to the energization switching is not sufficiently integrated and affected. Water was sampled. Further, during the generation of the electrolytic water, 3 mL / 3 mL of a 20% sodium chloride aqueous solution was added to each of the first electrolytic solution chamber 5c, the second electrolytic solution chamber 5d, the first electrolytic solution chamber 5-1c, and the second electrolytic solution chamber 5-1d. The liquid was dispensed.

The electrolytic current of the first electrolytic 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. The pH was 6.9 and the effective chlorine concentration was 48 mg. When the mixed generated water of / L is used as the raw water to be supplied to the second electrolytic cell 2-1 as shown in the characteristic line 114, the pH of the second cathode 5-1b energization ratio fluctuates greatly from around 40%. , Acidify. When the energization ratio of the second cathode 5-1b is set from 40% to 45%, the influence of corrosion and the like is small, and the acid water (pH 5 to 6.5) in the slightly acidic region (pH 5 to 6.5) in which the abundance ratio of the active ingredient HClO is high is low. Hypochlorous acid water) can be obtained. As shown in the characteristic line 113, the effective chlorine concentration of the mixed product water is almost constant.

As described above, at least two electrolytic cells 2 and 2-1 are connected in series by using the electrolytic water generator 1-3 according to the third embodiment, and the raw water supplied to the second electrolytic cell 2-1 is the first. 1 Compared to the electrolyzed water generators 1 and 1-2 according to the first and second embodiments using a single electrolytic cell by adjusting the pH step by step using the mixed generated water of the electrolytic cell 2. Under the condition that the electrolytic current is low, that is, the load on the electrode is small, the amount of alkaline substance produced per electrolytic cell is suppressed, the abundance ratio of the active ingredient HClO is higher, and the slightly acidic range (pH 5 to 6.5). ) Acidic water (hypochlorite water) can be obtained. As a result, the influence of corrosion and the like is small, and the operation for a longer time becomes possible.

(Fourth Embodiment)
FIG. 11 is a diagram schematically showing a running water type electrolyzed water generator according to a fourth embodiment.
In the electrolyzed water generating apparatus according to the fourth embodiment, two or more electrolytic cells are connected in parallel to increase the amount of electrolyzed water generated.
As shown in the figure, the electrolyzed water generator 1-4 uses a so-called three-chamber type first electrolytic cell 2 and a second electrolytic 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, the description thereof will be omitted here.
Further, the electrolyzed water generator 1-4 includes the first and second electrolytic solution chambers 5c and 5d of the first electrolytic cell 2, and the first and second electrolytic solution chambers 5-1c of the second electrolytic cell 2-1. An electrolytic solution supply unit 8-1 for supplying an electrolytic solution, for example, salt water, an anode chamber 3 and a cathode chamber 4 of the first electrolytic cell 2, an anode chamber 3-1 of the second electrolytic cell 2-1 and the 5-1d. The water supply unit 21 that supplies water to the cathode chamber 4-1, the first generated water mixing unit 10 that mixes the anodized water and the cathode generated water discharged from the anode chamber 3 and the cathode chamber 4, and the anode chamber 3-1. The third generated water mixing unit 10-2 for mixing the anodized water and the cathode generated water discharged from the cathode chamber 4-1 and the first generated water mixing unit 10 and the third generated water mixing unit 10-2 are further added. A fourth generated water mixing unit 10-2a to be mixed is provided.

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 for supplying water, an on-off valve 28 provided near the outlet of the water supply source 9, and a first water supply pipe for guiding water from the water supply source 9 to the lower parts of the anode chamber 3 and the cathode chamber 4. The 21a is connected to the first drainage port 3h, and is connected to the first drainage pipe 21b as the first drainage line for discharging the water flowing through the anode chamber 3 from the upper part of the anode chamber 3 and the second drainage port 4h. It is provided with a second drainage pipe 21c as a second drainage line for discharging the water flowing through the cathode chamber 4 from the upper part of the cathode chamber 4.
The first water supply pipe 21a is branched into a second water supply pipe 21e as a first water supply line and a third water supply pipe 21f as a second water supply line. The second water supply pipe 21e is connected to the first water supply port 3f 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 water supply unit 21 further branches from the first water supply pipe 21a downstream of the on-off valve 28 to guide water to the anode chamber 3-1 and the cathode chamber 4-1 and the fourth water supply pipe 21-1a and the anode chamber 3-. The fifth drainage pipe 21-1b that discharges the water flowing through 1 from the upper part of the anode chamber 3-1 and the sixth drainage pipe 21-1c that discharges the water flowing through the cathode chamber 4 from the upper part of the cathode chamber 4-1. And have.
The first water supply pipe 21-1a is branched into a second water supply pipe 21-1e as a first water supply line and a third water supply pipe 21-1f 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 part of the second drainage pipe 21c and constitutes the first generated water mixing part 10. As a result, the anode-generated water drained from the first drainage pipe 21b and the cathode-generated water drained from the second drainage pipe 21c are mixed to form the first mixed-generated water. Further, the fifth drainage pipe 21-1b is connected to the middle part of the sixth drainage pipe 21-1c and constitutes the third generated water mixing unit 10-2. As a result, the anode-generated water drained from the fifth drainage pipe 21-1b and the cathode-generated water drained from the sixth drainage pipe 21-1c are mixed to form the third mixed-generated water. Further, in the rear stage of the first generated water mixing section 10 and the third generated water mixing section 10-2, the second drainage pipe 21c and the sixth drainage pipe 21-1c merge to form the fourth generated water mixing section 10-2a. It is configured. In the 4th generated water mixing unit 10-2a, the 1st mixed generated water of the 1st generated water mixing unit 10 and the 3rd mixed generated water of the 3rd generated water mixing unit 10-2 are mixed and combined with the 4th mixed generated water. Become. The mixed product water is hypochlorite water whose pH is controlled near neutrality.

As described above, according to the electrolyzed water generating apparatus 1-4 according to the fourth embodiment, by connecting at least two electrolytic cells in parallel, it is possible to increase the amount of electrolyzed water generated and 2 It is possible to shift the timing of switching between the first cathode and the second cathode of the electrolytic cell of the table, and more precisely, the mixing in the fourth generated water mixing unit 10-2a becomes possible, and the fourth generated water mixing unit 10- It is possible to operate without providing a water storage unit after 2a.

Further, when the electrolyzed water generator 1-4 according to the fourth embodiment is used, the pH of the mixed generated water can be adjusted at any time even if the quality of the raw water fluctuates, as in the first embodiment, and the mixed produced water can be adjusted at any time. It is possible to control the pH of the hypochlorite water obtained as a medium acid to near neutrality. Further, by separating the electrolytic solution chambers 5, 5-1 into the first electrolytic solution chambers 5c, 5-1c and the second electrolytic solution chambers 5d, 5-1d by the third diaphragm 5, 5-1a, the feeding unit 7 When the energization from the second cathode 5b and 5-1b is switched to, the electrolytic solution pH of the second electrolytic solution chambers 5d and 5-1d shifts to the alkaline side, but the alkaline substance is discharged by the flow of the second electrolytic solution. Since it is hardly mixed in the flow of the first electrolytic solution, the first diaphragms 3a and 3-1a of the first electrolytic solution chambers 5c and 5-1c are less likely to deteriorate and the durability is improved. Therefore, according to the fourth embodiment, an electrolyzed water generator that can be used for a long period of time can be obtained.

As the electrolytic cell, the electrolytic cell 2 or 1-2 used in the first embodiment or the second embodiment can be used. The first electrolytic cell and the second electrolytic cell may have different configurations. Further, in FIG. 11, the electrolytic solution supply unit 8 shares the electrolytic solution supply unit of the first electrolytic cell 2 and the second electrolytic cell 2-1 but may be separate.

(Fifth Embodiment)
FIG. 12 shows a diagram schematically showing the electrolytic cell used in the fifth embodiment.
As shown in the figure, this electrolytic cell 2-3'is a so-called three-chamber type electrolytic cell, and the inside thereof is a first diaphragm 3-2a made of an anion exchange membrane as a anode side diaphragm, and a cathode side. The second diaphragm 4-2a, which is a cation exchange membrane as a diaphragm, defines the electrolyte chamber 5-2 between the diaphragms, and the anode chambers 3-2 and the cathode chambers 4-2 located on both sides of the electrolyte chamber. It is divided into 3 rooms. An anode 3-2b is provided inside the anode chamber 3-2 in close opposition to the first diaphragm 3-2a, and inside the cathode chamber 4-2, the first cathode 4 is in close opposition to the second diaphragm 4-2a. -2b is provided. The anode 3-2b and the first cathode 4-2b are formed in a rectangular shape having substantially the same size, and the electrolyte chamber 5-2 and the first and second diaphragms 3-2a and 4-2a are sandwiched between them. They are facing each other. Further, 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. Further, in the electrolytic cell 2-3', a part of the cell 31a that partitions the anode chamber 3-2 is open. Similarly, a part of the cell 31b that partitions the cathode chamber 4-2 is open. As the material of the cells 31a and 31b, a resin having excellent acid resistance and alkali resistance, for example, vinyl chloride, polypropylene, polyethylene or the like can be used.

The electrolytic solution chamber 5-2 is a third diaphragm 5-2a made of a neutral film capable of passing cations and anions without selectivity of ion permeation, and the first electrolytic solution chamber 5 on the anode chamber 3-2 side. It is partitioned into -2c and the second electrolyte chamber 5-2d on the cathode chamber 4-2 side. The second electrolyte chamber 5-2d is provided with a second cathode 5-2b so as to face the third diaphragm 5-2a in close proximity to the third diaphragm 5-2a. The second cathode 5-2b is formed in a rectangular shape having a size substantially equal to that of the first cathode 4-2b, similarly to the first cathode 4-2b. Further, the second cathode 5-2b has the same configuration as the second cathode 5b in FIG.
According to the electrolytic cell 2-3'used in the fifth embodiment, a third diaphragm 5-2a is provided between the second cathode 5-2b and the first diaphragm 3-2a, and the inside of the electrolytic solution chamber 5-2 is provided. When the second cathode 5-2b is energized by separating the first electrolytic solution chamber 5-2c on the anode chamber 3-2 side and the second electrolytic solution chamber 5-2d on the cathode chamber 4-2 side. The pH of the electrolytic solution in the second electrolytic solution chamber 5-2d shifts to the alkaline side, but the alkaline substance is discharged by the flow of the second electrolytic solution and hardly mixes with the flow of the first electrolytic solution, so that the first electrolytic solution is used. Since the pH of the liquid chamber 5-2c can be maintained closer to neutral than the pH of the second electrolytic solution chamber 5-2d, the first diaphragm 3-2a of the first electrolytic solution chamber 5-2c is less likely to deteriorate. As a result, an electrolytic cell that can be used for a long period of time can be obtained.

Further, in the electrolytic cell 2-3'which can be used in the fifth embodiment, a part of the cell 31a for partitioning the anode chamber 3-2 and a part of the cell 31b for partitioning the cathode chamber 4-2 are opened. It is suitable for a water storage type electrolyzed water generator.
The electrolytic cell of FIG. 12 can be incorporated into an electrolyzed water generator.
FIG. 13 shows a diagram schematically showing a water storage type electrolyzed water generator 1-5 according to a fifth embodiment using an example of the electrolytic cell of FIG. 12.
In addition to the same configuration as the electrolytic cell 2-3'shown in FIG. 12, the electrolytic cell 2-3 used in the present embodiment is for supplying an electrolytic solution to the lower part of the first electrolytic solution chamber 5-2c. 1st electrolytic solution supply port 5-2f, a first electrolytic solution discharge port 5-2h for discharging the electrolytic solution flowing through the first electrolytic solution chamber 5-2c, and a second electrolytic solution chamber 5 above the first electrolytic solution supply port 5-2f. The lower part of -2d is the second electrolytic solution supply port 5-2g for supplying the electrolytic solution, and the upper part thereof is the second electrolysis for draining the electrolytic solution flowing through the second electrolytic solution chamber 5-2d. A liquid discharge port 5-2i is provided.

The electrolytic water generator 1-5 is provided in the electrolytic solution supply unit 8 for supplying an electrolytic solution, for example, salt water, to the electrolytic solution chamber 5-2 of the electrolytic cell 2-3, and the anode chamber 3-2 and the cathode chamber 4-2. A water storage tank 32 that stores water as raw water to be supplied, anode-generated water, and cathode-generated water together, a positive voltage on the anode 3-2b, and a negative voltage on the first cathode 4-2b and / or the second cathode 5-2b. A feeding unit 7 having a power source 7a to which a voltage is applied is provided.
The feeding unit 7 is a power supply 7a that supplies the current required 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 supply 7a and the switch 7b. And have. Here, as the switch 7b, a changeover switch for switching the 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 source 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 the switch 7b and two wires, and by switching the changeover switch, the first cathode 4-2b and the first cathode 4-2b and the second cathode 4-2b are connected. 2 A negative voltage can be selectively applied to the cathode 5-2b.

The electrolytic solution supply unit 8 supplies, for example, a salt water tank (electrolyte solution tank) 25 that stores a 20% sodium chloride aqueous solution (salt water) as the electrolytic solution 25a, and supplies salt water from the salt water tank 25 to the lower part of the electrolytic solution chamber 5-2. It is provided with a pipe 8a, a liquid feed pump 29 provided in the supply pipe 8a, and a drainage pipe 8f for discharging salt water from above the electrolytic solution chamber 5-2.
The supply pipe 8a is connected to the first electrolytic solution supply port 5-2f provided at the lower part of the first electrolytic solution chamber 5-2c of the electrolytic solution chamber 5-2 to supply salt water, and the electrolytic solution. It is connected to the second electrolytic solution supply port 5-2g provided at the lower part of the second electrolytic solution chamber 5-2d of the chamber 5-2 and is branched into the supply pipe 8c for supplying salt water, and the electrolytic solution is the first. It is supplied separately to the electrolytic solution chamber 5-2c and the second electrolytic solution chamber 5-2d. Here, the supply pipe 8b from the salt water tank 25 and the supply pipe 8c are passed through the through holes 32b and 32c provided at the bottom of the water storage tank 32 to the lower part of the first electrolytic solution chamber 5-2c and the second electrolytic solution chamber. It is connected to the bottom of 5-2d.

The upper part of the first electrolytic solution chamber 5-2c is connected to the first electrolytic solution discharge port 5-2h and serves as a first electrolytic solution discharge line for draining the electrolytic solution flowing in the first electrolytic solution chamber 5-2c. The drainage pipe 8d of the above is connected, and the electrolytic solution flowing in the second electrolytic solution chamber 5-2d is drained by being connected to the second electrolytic solution discharge port 5-2i at the upper part of the second electrolytic solution chamber 5-2d. The drainage pipe 8e as the second electrolytic solution discharge line is connected. Therefore, the flow of salt water in the first electrolytic solution chamber 5-2c is different from the flow of salt water in the second electrolytic solution chamber 5-2d. The drainage pipe 8d and the drainage pipe 8e are merged into the drainage pipe 8f, and the electrolytic solution of the drainage pipe 8d and the drainage pipe 8e is mixed and discharged.

Electrolyzed raw water, for example, tap water is stored in the water storage area 10-3 in the water tank 32 in the initial state. When electrolysis is performed, the anode-generated water and the cathode-generated water are mixed with the electrolyzed raw water. In this way, the water storage area 10-3 is a mixture of the water supply source, the first water supply line for supplying water to the anode chamber, the second water supply line for supplying water to the cathode chamber, and the anode-generated water and the cathode-generated water. It also has a function as a first generated water mixing unit for producing generated water (first mixed produced water). The mixed water obtained by the water tank 32 is hypochlorite water whose pH is controlled to be near slightly acidic and neutral. A stirrer (not shown) can be installed in the water tank 32, if necessary. In addition, an on-off valve or a flow rate adjusting valve may be provided in each pipe.

The electrolyzed water generator 1-5 configured as described above actually electrolyzes salt water to generate acidic water (hypochloric acid and hydrochloric acid) and alkaline water (sodium hydroxide) to obtain mixed water. The operation will be described.
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 electrolytic cell chamber 5-2c and the second electrolytic cell 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 region 10-3.
When the switch 7b is switched to the first cathode 4-2b to supply power, the positive voltage and the negative voltage are applied from the power source 7a to the anode 3-2b and the first cathode 4-2b, respectively.
Sodium ions ionized in the salt water flowing into the first electrolytic solution chamber 5-2c and the second electrolytic solution chamber 5-2d are attracted to the first cathode 4-2b and pass through the second diaphragm 4-2a. Then, it flows into the cathode chamber 4-2. Since the third diaphragm 5-2a is a neutral membrane, sodium ions can sufficiently permeate. After that, water is electrolyzed at the first cathode 4-2b to generate 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 tank 32 from the cathode chamber 4-2.

Chloride 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 pass through the anode chamber. It flows into 3-2. Then, 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 are mixed with the raw water in the water tank 32. In this way, hypochlorite water whose pH has been adjusted can be obtained as mixed generated water in the water tank 32.

Further, when the switch 7b (changeover switch) is switched to the second cathode 5-2b to supply power, the positive voltage and the negative voltage are applied from the power source 7a to the anode 3-2b and the second cathode 5-2b, respectively. Sodium ions ionized in the salt water in the first electrolytic solution chamber 5-2c and the second electrolytic solution 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. The electrolysis of the salt water in the second cathode 5-2b produces hydrogen gas and an aqueous sodium hydroxide solution in the second electrolyte chamber 5-2d. As a result, the inside of the second electrolytic solution chamber 5-2d shifts to the alkaline side. The generated alkaline aqueous solution of sodium hydroxide 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 the drain pipe 8d. It is mixed with the electrolytic solution and discharged to the outside by the drain pipe 8f. As described above, the alkaline water generated in the second electrolytic solution chamber 5-2d is discharged from the second electrolytic solution chamber 5-2d without flowing into the cathode chamber 4-2 and the first electrolytic solution 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 electrolytic solution chamber 5-2c is not exposed to the strong alkali and is less likely to deteriorate. Further, in the cathode chamber 4-2, hydrogen gas as alkaline water and an aqueous solution of sodium hydroxide are hardly mixed in the water of the water storage tank 32.

Chloride 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, and pass through the anode 3-2a. It flows into room 3-2. At this time, the chlorine ions in the first electrolytic solution chamber 5-2c can permeate through the third diaphragm 5-2a. Then, chlorine ions are oxidized at the anode 3-2b to generate chlorine gas. After that, 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. At this time, the alkaline water generated in the second electrolytic solution chamber 5-2d is discharged to the outside, and the alkaline water is hardly mixed in the cathode chamber 4-2. Therefore, the pH of the hypochlorite water obtained as the mixed product water in the water storage tank 32 when the power is supplied to the second cathode 5-2b is the pH of the hypochlorite water obtained as the mixed product water in the water storage tank 32 when the power is supplied to the first cathode 4-2b. The pH of the hypochlorite water obtained as mixed water is lower than that of the water.
Impurities contained in water used as raw water differ depending on the region and location, and in particular, the carbonic acid component has an interference effect toward weak alkalinity. Therefore, depending on the water used, the pH adjustment points may not match and may deviate slightly. In general, carbonate ions are dissolved in water as counter ions of alkaline components, so that hard water tends to shift to the alkaline side, and soft water (ultimately pure water) tends to shift to the acid side.

On the other hand, when the electrolyzed water generator 1-5 according to the embodiment is used, the second cathode 5-2b is provided in the electrolytic solution chamber 5-2, and the switch 7b is set to the first cathode 4-2b or the second cathode 5. By switching to -2b and supplying power, 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 and energized to energize the cathode chamber. The pH of the hypochlorite water obtained as the mixed generated water in the water storage tank 32 can be adjusted by controlling the mixing of the sodium hydroxide aqueous solution and the hydrogen gas into the water storage portion in 4-2. As a result, the pH of the mixed product water can be adjusted at any time even if the water quality of the raw water fluctuates, and the pH of the hypochlorite water obtained as the mixed product water can be controlled to be slightly acidic or near neutral. Become. Further, a third diaphragm 5-2a is provided between the second cathode 5-2b and the first diaphragm 3-2a, and the electrolytic solution chamber 5-2 is provided with the electrolytic solution chamber 5-2 as the first electrolytic solution chamber 5- on the anode chamber 3-2 side. By separating into 2c and the second electrolytic solution chamber 5-2d on the cathode chamber 4-2 side, when the energization from the feeding unit 7 is switched to the second cathode 5-2b, the second electrolytic solution chamber 5-2d The pH of the electrolytic solution shifts to the alkaline side, but the alkaline substance is discharged by the flow of the second electrolytic solution and hardly mixes with the flow of the first electrolytic solution. Therefore, the pH of the first electrolytic solution chamber 5-2c is the second. Since the pH of the electrolytic solution chamber 5-2d can be maintained closer to neutral, the first diaphragm 3-2a of the first electrolytic solution chamber 5-2c is less likely to deteriorate and has good durability. As described above, according to the fifth embodiment, an electrolyzed water generator that can be used for a long period of time can be obtained.

When a voltage is applied to the anode 3-2b and the first cathode 4-2b, the anode chamber 3-2 and the cathode chamber 4-2 have a region having a high concentration of acidic water and a region having a high concentration of alkaline water, respectively. However, by providing a stirrer (not shown) in the water storage tank 32, it is possible to bring the pH of water closer to slightly acidic / neutral and make the water quality uniform.
Using the electrolyzed water generator according to the fifth embodiment, a water quality change test based on the energization ratio and a continuous operation test were performed as follows.

Water quality change test by energization ratio
Using the electrolyzed water generator 1-5, 20 L of pure water was stored in the water storage tank 32 as raw water, the electrolytic current was fixed at 2 A, one cycle was set to 10 seconds, and the first cathode 4-2b and the second in one cycle. The energization of the cathode 5-2b was switched and the ratio of the energization time was variously changed, and electrolysis was performed for 60 minutes at each energization ratio, and the water quality change (pH and effective chlorine concentration) of the mixed product water was measured.
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 generated water in the electrolyzed water generator according to the fifth embodiment 1-5.

The characteristic line 115 shows the change in pH with respect to the energization ratio of the second cathode 5-2b, and the characteristic line 116 shows the change in the 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 measurement of the water quality (pH and effective chlorine concentration) of the mixed product water was carried out after sufficiently expanding the sales of the mixed product water so that the difference in water quality due to the energization switching would not be sufficiently integrated and affected. Further, during the generation of the electrolyzed water, a 20% sodium chloride aqueous solution was sent to the first electrolytic solution chamber 5-2c and the second electrolytic solution chamber 5-2d, respectively, at 3 mL / min.
As shown in the characteristic line 115, it can be seen that the mixed product water is alkaline when the second cathode 5-2b is not used (energization ratio 0%). This is because all the alkaline substances produced by the first cathode 4-2b are mixed with the produced water.

On the other hand, when the energization ratio of the second cathode 5-2b is increased from 0, the effective chlorine concentration of the mixed product water is almost constant as shown in the characteristic line 116, but the pH is acidic as shown in the characteristic line 115. It will become. This is because the alkaline substance produced at the second cathode 5-2b is released only into the second electrolytic solution chamber 5-2d and is not mixed with the mixed product water. In the case of the raw water used in the fifth embodiment, the pH of the second cathode 5-2b fluctuates greatly from around 20% and is acidified. When the energization ratio of the second cathode 5-2b is set from 22% to 27%, the influence of corrosion and the like is small, and the acid water in the slightly acidic region (pH 5 to 6.5) in which the abundance ratio of the active ingredient HClO is high (pH 5 to 6.5). Hypochlorous acid water) can be obtained. Further, 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 (energization ratio 100%), the mixed water is strongly acidic. I understand. This is because no alkaline substance is generated at the first cathode 4-2b, the raw water is mixed with hypochlorous acid and hydrochloric acid as it is, and the water quality of the acidic water produced in the anode chamber 3-2 appears as it is.

In this embodiment, pure water was used as raw water. If hard water is used, the energization ratio of the second cathode 5-2b, which indicates a slightly acidic region, shifts to the larger one.
Continuous operation test Using the electrolyzed water generator 1-5, the continuous operation test was performed as follows.
As raw water, 20 L of pure water was stored in the water tank 32. During the generation of the electrolyzed water, a 20% sodium chloride aqueous solution was sent to the first electrolytic solution chamber 5-2c and the second electrolytic solution chamber 5-2d at 3 mL / min. The electrolysis current is fixed at 2A, one cycle is set to 10 seconds, and the energization ratio of the second cathode 5-2b is 60% so that the pH of the mixed product water is 6 (energization time to the first cathode 4-2b). The energization time of the second cathode 5-2b was set to 4 seconds (6 seconds), and electrolysis was performed for 60 minutes. The electrolyzed water generator was operated for about 700 hours while changing the water in the water tank every 60 minutes, and the pH and effective chlorine concentration of the obtained first mixed water were adjusted every 24 hours at the beginning and every week thereafter. Was measured.

Further, as Comparative Example 3, an electrolyzed water generator having the same configuration as that of the fifth embodiment is prepared except that the third diaphragm 5-2a is not provided in the electrolytic cell chamber 5-2 of the electrolytic cell 2-3. The electrolyzed water generator was operated for about 700 hours under the same conditions, and the pH and the effective chlorine concentration were similarly measured as changes in the water quality of the obtained mixed produced water.
The obtained results are shown in FIG.
FIG. 15 shows a graph showing the results of a continuous operation test of the electrolyzed water generator 1-5 according to the fifth embodiment.
In the figure, the horizontal axis is the operating time. The characteristic line 117 shows the change in pH of the mixed generated water obtained by the electrolyzed water generator 1-5. Further, the characteristic line 118 shows the change in the effective chlorine concentration of the mixed generated water obtained by the electrolyzed water generator 1-5. The characteristic line 120 shows the effective chlorine concentration of Comparative Example 3, and the characteristic line 119 shows the pH of Comparative Example 3.

In Comparative Example 3, it was confirmed that the pH increased as shown in the characteristic line 119 and the effective chlorine concentration decreased as shown in the characteristic line 120 from the point where the time exceeded 48 hours. When the electrolytic cell of Comparative Example 3 was disassembled and investigated, it was confirmed that the first diaphragm of the anode chamber became cloudy and the membrane was torn in some places. From this, it is considered that the alkaline substance generated at the second cathode alkalizes the electrolytic solution chamber, and the first diaphragm in contact with the electrolytic solution chamber is denatured, resulting in fracture. On the other hand, in the electrolyzed water generator 1-5 according to the fifth embodiment, the effective chlorine concentration and pH are constant as shown in the characteristic lines 118 and 117 even if the electrolyzed water generator 1-5 is operated for a long time, and the water quality of the mixed generated water is constant. No change is observed. This is because the electrolytic solution chamber 5-2 is a third diaphragm 5-2a made of a neutral film having no ion permeation selectivity, and the first electrolytic solution chamber 5-2c and the cathode chamber 4-on the side of the anode chamber 3-2. The second cathode is partitioned into the second electrolyte chamber 5-2d on the second side, and the second cathode 5-2b is provided in the second electrolyte chamber 5-2d in close proximity to the third diaphragm 5-2a. The alkaline substance generated in 5-2b is generated only in the second electrolytic solution chamber 5-2d, is immediately discharged from the second electrolytic solution chamber 5-2d, and acts on the alkaline substance on the first diaphragm 3-2a. Is thought to be due to the suppression.

In this way, the electrolyte chamber 5-2 is the first electrolyte chamber 5-2c and the cathode chamber 4 on the anode chamber 3-2 side with the third diaphragm 5-2a made of a neutral film having no ion permeation selectivity. The raw water was partitioned into the second electrolyte chamber 5-2d on the −2 side, and the second cathode 5-2b was provided in the second electrolyte chamber 5-2d in close proximity to the third diaphragm 5-2a. Even if raw water with different Ca hardness is used, it is possible to generate a slightly acidic mixed product water by changing the energization ratio of the second cathode 5-2b, and even if it is operated for a long time, it is stable and fine. It is possible to produce an acidic mixed-form water. In addition, if the quality of the raw water fluctuates due to seasonal fluctuations and the pH of the mixed product water deviates from the slightly acidic range, it can be easily adjusted to the slightly acidic range by changing the energization ratio of the second cathode 5-2b. Is.

Application example of the fifth embodiment
FIG. 16 shows a diagram schematically showing an application example of the water storage type electrolyzed water generator according to the fifth embodiment.
In the electrolyzed water generator 1-6 shown in FIG. 16, the supply pipe 8a and the supply pipe 8b from the salt water tank (electrolyzed water tank) 25 are provided in the lower part of the first electrolytic solution chamber 5-2c and the second electrolytic solution chamber 5. Unlike the electrolyzed water generator 1-5 of FIG. 13, the fact that it is directly connected to the lower part of -2d and put into a water storage container 32-1 that does not have through holes 32b and 32c is installed. Other than that, it has the same configuration as the electrolyzed water generator shown in FIG. 13 and has the same function and effect.
By using the electrolyzed water generator 1-6, it is possible to use an arbitrary water storage container 32-1 that can secure a water storage area 10-3 instead of the water storage tank 32, and the electrolytic cell 2-3 can be used as a water storage tank. It is low cost because it can be easily used by simply putting the electrolytic cell 2-3 into an arbitrary water storage container 32-1 without performing the work of installing it in 32. Such a configuration is more suitable when the electrolytic cell 2-3 is made smaller. In this case, it is preferable to configure the supply pipe 8a and the drainage pipe 8f with a flexible material because the electrolytic cells 2-3 can be easily handled.

(Sixth Embodiment)
FIG. 17 is a diagram schematically showing a water storage type electrolyzed water generator according to the sixth embodiment.
As shown in the figure, the electrolyzed water generator 1-7 uses a so-called three-chamber type electrolytic cell (electrolytic cell) 2-4. The inside of the electrolytic cell 2-4 was defined between the diaphragms by the first diaphragm (anode side diaphragm, anion exchange membrane) 3-2a and the second diaphragm (cathode side diaphragm, cation exchange membrane) 4-2a. The electrolyte chamber 5-2 is divided 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 a rectangular plate having substantially the same size, sandwiching the electrolyte chamber 5-2 and the first and second diaphragms 3-2a and 4-2a, and each other. They are facing each other.

The electrolytic solution chamber 5-2 is a third diaphragm 5-2a made of a neutral film capable of passing cations and anions without selectivity of ion permeation, and the first electrolytic solution chamber 5 on the anode chamber 3-2 side. It is partitioned into -2c and the second electrolyte chamber 5-2d on the cathode chamber 4-2 side. The second electrolyte chamber 5-2d is provided with a second cathode 5-2b so as to face the third diaphragm 5-2a in close proximity to the third diaphragm 5-2a. The second cathode 5-2b is formed in a rectangular shape having substantially the same size as the anode 3-2b and the first cathode 4-2b, similarly to 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. Can be configured.
In the electrolytic cell 2-4, a part of the cell 31a that partitions the anode chamber 3-2 is open. Similarly, a part of the cell 31b that partitions the cathode chamber 4-2 is open.
Further, at least a part of the first electrolytic solution 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 that controls the diffusion of alkaline substances. As the porous member 5-2e, a plastic sintered porous body (manufactured by Fuji Chemical Co., Ltd.) is provided.

The power feeding unit 7 has a power supply 7a, a control unit 7c for controlling the power supply 7a, and a switch 7b for switching the power supply to the first cathode 4-2b and the second cathode 5-2b. The positive electrode of the power source 7a is connected to the anode 3-2b via wiring. The negative electrode of the power source 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 the user.
In addition, the electrolyzed water generator 1-7 includes an electrolytic solution supply unit 8 for supplying an electrolytic solution, for example, salt water, to the first and second electrolytic solution chambers 5-2c and 5-2d of the electrolytic cell 2-4. It has the same configuration as the electrolyzed water generator 1-5 according to the fifth embodiment described above.

In the sixth embodiment, the mixed generated water drained from the electrolyzed water generator 1-7 is hypochlorite water whose pH is controlled near neutrality. That is, in the normal generation operation, a positive voltage is selectively 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. According to the present embodiment, by switching the switch 7b and applying a voltage to the second cathode 5-2b, it is possible to further adjust the pH by the connection duty. Further, by providing the porous member 5-2e, when the alkaline substance generated in the second electrolytic solution chamber 5-2d stops the electrolytic water generator 1-7, the first electrolytic solution chamber 5-2c And it is possible to suppress diffusion to the first diaphragm 3-2a which is in contact with the first electrolyte chamber 5-2c.

Further, when the electrolyzed water generator 1-7 according to the sixth embodiment is used, the pH of the mixed generated water can be adjusted at any time even if the quality of the raw water fluctuates, as in the first embodiment, and the mixed produced water can be adjusted at any time. It is possible to control the pH of the hypochlorite water obtained as a medium acid to near neutrality. Further, by separating the electrolytic solution chamber 5-2 into the first electrolytic solution chamber 5-2c and the second electrolytic solution chamber 5-2d by the third diaphragm 5-2a, the energization from the feeding unit 7 is supplied to the second cathode 5. When switching to -2b, the electrolytic solution pH in the second electrolytic solution chamber 5-2d shifts to the alkaline side, but the alkaline substance is discharged by the flow of the second electrolytic solution and is almost mixed in the flow of the first electrolytic solution. Therefore, the first diaphragm 3-2a of the first electrolyte chamber 5-2c is less likely to deteriorate and the durability is improved. Therefore, according to the sixth embodiment, an electrolyzed water generator that can be used for a long period of time can be obtained.

The present invention is not limited to the above-described embodiments and modifications described with reference to the drawings, and various other modifications can be considered within the technical scope thereof. Further, as long as it does not deviate from the gist of the present invention, it is possible to select the configurations described in each of the above-described embodiments and modifications, and to appropriately change to other configurations.

The present invention can be used as a commercial electrolyzed water generator and a miniaturized electrolyzed water generator for home use.

1, 1-1, 1-2, 1-3, 1-4, 1-5, 1-6, 1-7 ... Electrolyzed water generator, 2 2'2-1, 2-2, 2- 3, 2-3', 2-4 ... Electrolyzed cell, 3,3-1, 3-2 ... Anode chamber, 3a, 3-1a, 3-2a ... First diaphragm, 3b, 3-1b, 3-2b ... Anode, 4,4-1, 4-2 ... Cathode chamber, 4a, 4-1a, 4-2a ... Second diaphragm, 4b, 4-1b, 4-2b ... First cathode, 5,5-1, 5-2 ... Electrolyte chamber, 5a, 5-1a, 5-2a ... Third diaphragm, 5b, 5-1b, 5-2b ... Second cathode, 5c, 5-1c, 5-2c ... First electrolyte Room, 5d, 5-1d, 5-2d ... Second electrolyte chamber, 5e, 5-2e ... Diffusion suppressing member (porous member), 7 ... Feeding section, 7-1 ... Feeding section (second feeding section) , 7b ... Switch, 7-1b ... Switch (second switch), 7c, 7-1c ... Control unit, 8a, 8-1a ... Supply pipe, 8b, 8-1b ... Supply pipe (first electrolyte supply line) , 8c, 8-1c ... Supply pipe (second electrolytic solution supply line), 10 ... 1st generated water mixing section, 10-1 ... 1st generated water mixing section, 10-1e ... 2nd generated water mixing section, 10 -2 ... 3rd generated water mixing unit, 10-2a ... 4th generated water mixing unit, 10-3 ... water storage area, 10s ... mixed generated water supply line, 12 ... online pH meter (pH measuring unit)

Claims (13)

An electrolyte chamber that houses the electrolyte and
An anode chamber partitioned from the electrolyte chamber by the first diaphragm, and
A cathode chamber partitioned from the electrolyte chamber by a second diaphragm,
An anode provided in the anode chamber facing the first diaphragm in close proximity to the anode chamber.
A first cathode provided in the cathode chamber facing the second diaphragm in close proximity to the cathode chamber.
A second cathode provided in the electrolyte chamber and facing the anode via the first diaphragm,
A third diaphragm provided between the second cathode and the first diaphragm and separating the electrolyte chamber into a first electrolyte chamber on the anode chamber side and a second electrolyte chamber on the cathode chamber side. And, with
An electrolytic cell in which the second cathode is provided in the second electrolytic cell chamber so as to be close to the third diaphragm and face the third diaphragm . The electrolytic cell according to claim 1, further comprising a first electrolytic cell supply port provided in the first electrolytic cell chamber and a second electrolytic solution supply port provided in the second electrolytic cell chamber. The electrolytic cell according to claim 1 or 2, wherein the first diaphragm comprises an anion exchange membrane, the second diaphragm comprises a cation exchange membrane, and the third diaphragm comprises a neutral membrane. The electrolytic cell according to any one of claims 1 to 3, further comprising a water-permeable diffusion suppressing member in at least a part of the first electrolytic cell chamber. The electrolytic cell according to any one of claims 1 to 4, wherein a part of the anode chamber and a part of the cathode chamber are open. Electrolyte chamber for accommodating electrolyte,
An anode chamber partitioned from the electrolyte chamber by the first diaphragm,
A cathode chamber partitioned from the electrolyte chamber by a second diaphragm,
An anode provided in the anode chamber in close proximity to the first diaphragm,
A first cathode provided in the cathode chamber facing the second diaphragm in close proximity to the cathode chamber,
A second cathode provided in the electrolytic solution chamber and facing the anode via the first diaphragm, and provided between the second cathode and the first diaphragm, the electrolytic solution chamber is provided in the anode chamber. It is provided with a first electrolyte chamber on the side and a third diaphragm separated into a second electrolyte chamber on the cathode chamber side .
In the second electrolytic cell, a first electrolytic cell in which the second cathode is provided so as to be close to the third diaphragm and opposed to the third diaphragm is provided .
A first feeding unit that feeds the anode, the first cathode, and the second cathode,
A switch that energizes the first cathode and / or the second cathode from the first feeding unit,
An electrolyzed water generator comprising a first generated water mixing unit for producing the first mixed produced water by mixing the anode-generated water and the cathode-generated water obtained by electrolyzing the electrolytic solution in the first electrolytic cell. It is connected to the first electrolytic solution chamber of the first electrolytic cell and is connected to the first electrolytic solution supply line for supplying the electrolytic solution to the first electrolytic solution chamber and the second electrolytic solution chamber of the first electrolytic cell. The electrolytic water generator according to claim 6, further comprising a second electrolytic solution supply line for supplying the electrolytic solution to the second electrolytic solution chamber. A pH measuring unit that measures the pH of the first mixed water is connected to the pH measuring unit, and the first cathode and / or the second cathode is energized based on the pH measurement result of the first mixed water. The electrolyzed water generator according to claim 6 or 7, further comprising a control unit for controlling the switch. Electrolyte chamber for accommodating electrolyte,
An anode chamber partitioned from the electrolyte chamber by the first diaphragm,
A cathode chamber partitioned from the electrolyte chamber by a second diaphragm,
An anode provided in the anode chamber in close proximity to the first diaphragm,
A first cathode provided in the cathode chamber facing the second diaphragm in close proximity to the cathode chamber,
A second cathode provided in the electrolytic solution chamber and facing the anode via the first diaphragm, and provided between the second cathode and the first diaphragm, the electrolytic solution chamber is provided in the anode chamber. A first electrolyte chamber on the side and a third diaphragm separated into a second electrolyte chamber on the cathode chamber side are provided , and the second electrolyte chamber is in close proximity to the third diaphragm and the second. A second electrolytic cell provided with a cathode and provided after the first generated water mixing portion of the first electrolytic cell, and a second electrolytic cell.
A second feeding unit that feeds the anode, the first cathode, and the second cathode of the second electrolytic cell,
A second switch that energizes the first cathode and / or the second cathode from the feeding portion of the second electrolytic cell.
Further, a second generated water mixing unit, which is obtained by mixing the anode-generated water obtained by electrolyzing the electrolytic solution in the second electrolytic cell and the cathode-generated water to obtain the second mixed-generated water, is further provided.
The first generated water mixing unit is connected to the anode chamber and the cathode chamber of the second electrolytic cell, and is used as a mixed generated water supply line for supplying the first mixed produced water. The electrolyzed water generator according to any one of the following items. Electrolyte chamber for accommodating electrolyte,
An anode chamber partitioned from the electrolyte chamber by the first diaphragm,
A cathode chamber partitioned from the electrolyte chamber by a second diaphragm,
An anode provided in the anode chamber in close proximity to the first diaphragm,
A first cathode provided in the cathode chamber facing the second diaphragm in close proximity to the cathode chamber,
A second cathode provided in the electrolytic solution chamber and facing the anode via the first diaphragm, and provided between the second cathode and the first diaphragm, the electrolytic solution chamber is provided in the anode chamber. A first electrolyte chamber on the side and a third diaphragm separated into a second electrolyte chamber on the cathode chamber side are provided , and the second electrolyte chamber is in close proximity to the third diaphragm and the second. A second electrolytic cell provided with a cathode and arranged in parallel with the first electrolytic cell,
A second feeding unit that feeds the anode, the first cathode, and the second cathode of the second electrolytic cell.
Further, a second switch for energizing the first cathode and / or the second cathode from the feeding portion of the second electrolytic cell is provided.
The electrolysis according to any one of claims 6 to 8, wherein the first generated water mixing unit further mixes the anode-generated water and the cathode-generated water obtained by electrolyzing the electrolytic solution in the second electrolytic cell. Water generator. The electrolyzed water generation according to any one of claims 6 to 10, wherein the first diaphragm comprises an anion exchange membrane, the second diaphragm comprises a cation exchange membrane, and the third diaphragm comprises a neutral membrane. Device. The electrolyzed water generating apparatus according to any one of claims 6 to 11, further comprising a water-permeable diffusion suppressing member in at least a part of the first electrolytic solution chamber. The electrolyzed water generator according to any one of claims 6 to 12, wherein a part of the anode chamber and a part of the cathode chamber are open.

Images