JPH09299953A - Electrolytic water generator - Google Patents

Abstract

PROBLEM TO BE SOLVED: To generate an electrolytic water having an oxidationreduction property close to neutral by providing an electrolytic cell having a partition wall furnished with a hydrogen ion-conductive membrane partitioning a cathode compartment and an anode compartment, filling the cell with an electrolyte and impressing a DC voltage between the cathode and anode. SOLUTION: An electrolytic cell 12 is divided by a partition wall 18 formed with a hydrogen ion-conductive membrane 17 into an anode compartment 14 having an anode 13 and a cathode compartment 16 having a cathode 15. Both electrodes 13 and 15 are connected to a DC power source, and gaseous chlorine and gaseous oxygen are generated from the surface of the anode 13 as a current is applied to form hypochlorous acid and hypochlorite ion in electrolytic water 20. However, the chlorine ion is not increased, an excess of hydrogen ion is transferred to the cathode compartment 16 through the membrane 17, and the generation of strongly acidic water is suppressed. Meanwhile, since gaseous hydrogen is generated on the cathode 15 surface and hydroxyl ion is formed in an electrolyte 23, the change to alkali is retarded.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an apparatus for producing a sterilizing and cleaning treatment liquid produced by electrolyzing water for the purpose of sterilizing and cleaning various pollutants and surface treatment of industrial materials.

[0002]

2. Description of the Related Art Electrolysis of saline solution in an electrolytic cell having an anode chamber and a cathode chamber partitioned by a diaphragm, as illustrated in JP-A-6-237747,
Acidic product water is obtained from the anode chamber, and alkaline product water is obtained from the cathode chamber side. The water produced in this way has a high oxidation / reduction ability, and this oxidation / reduction ability of water affects the cleaning of medical equipment and kitchen equipment, surface treatment of industrial materials, disinfection of microorganisms, growth of plants, etc. Is known to give.

Contaminants to be washed and surface-treated include lipids such as proteins and body fluids in medical instruments, and cleaning liquids such as soil bacteria of fresh foods, slime such as water stains and seafood, and oil stains in kitchens. There is. Industrial materials are mainly ionic substances and reaction products on the semiconductor surface, and liquid and particulate contaminants.

Acidic water produced in the anode chamber lends a sterilizing action, and water produced in the alkaline cathode chamber acts to prevent the deterioration of the hue of fish and seafood and to prevent the occurrence of drip and the deterioration of the hue of vegetables. Have an effect. Therefore, each of these produced waters is used alone as a treatment liquid such as a resuscitation liquid for fresh plants.

Contaminated forms of ionic substances include adsorption by ion exchange found on the glass surface, adhesion by electrostatic attraction of ions found on the surface of semiconductors and metals, and adhesion to the surface layer of semiconductors, metals and ceramics. The thing called the penetration | invasion by the diffusion of an ion is mentioned. Such an ionic substance is generally washed with pure water or ultrapure water as a finish after chemical cleaning. For example, when cleaning a semiconductor, ultrapure water having an electric resistivity of about 18 MΩ / cm is used. Then, in order to remove the liquid or film-like contaminants adhering to the silicon wafer or the like, a method of oxidatively decomposing or dissolving this contaminant is applied, and as a drug used for oxidative decomposition, , A combination of sulfuric acid and hydrogen peroxide, a combination of ammonium hydroxide and hydrogen peroxide, etc. are utilized for the oxidizing power of hydrogen peroxide.

It is possible to use electrolyzed water produced by electrolyzing a saline solution in the production of these washing liquids that add oxidizing power. However, in order to smoothly perform electrolysis in the conventional diaphragm electrolysis, an electrolyte such as a salt solution is used. It was indispensable to add a few%. Therefore, the obtained electrolyzed water contains a considerable amount of electrolyte ions, and when it is used for cleaning, for example, the electrolyte ions remain and remain on the surface of the object to be cleaned. Then, a kind of problem occurs due to the residual ions. For example, corrosion and deterioration of metal materials, alteration of fresh foods, and when chlorides such as salt are used as electrolytes, a problem of offensive odor such as chlorine odor occurs.

As a method for solving the above-mentioned problems, an electrolytic solution 3 such as a saline solution partitioned by a cation type ion exchange membrane 1 and an anion type ion exchange type 2 is disclosed in Japanese Patent Laid-Open No. 7-75784 shown in FIG. An anode 7 is formed on the cation-type ion exchange membrane 1 in an electrolytic cell 9 which is composed of a cathode chamber 6 having a cathode 5 and an anode chamber 8 having an anode 7 with an intermediate chamber 4 interposed therebetween.
It has been devised that the cathode 5 is closely attached to the anion-ion exchange membrane 2 and a DC voltage is applied to both electrodes by a DC power supply 10 to perform electrolytic treatment.

The operation of the electrolytic treatment apparatus of the above publication will be described with reference to FIG. The aqueous solution to be injected into the cathode chamber 6 and the anode chamber 8 is pure water poured by using a pure water producing device (not shown), and the intermediate chamber 4 contains saline as the electrolytic solution 3. . When a DC voltage is applied to the anode 7 and the cathode 5 to perform electrolysis, sodium ions which are cations in the salt solution of the electrolytic solution 3 in the intermediate chamber 4 are attracted to the cathode 5 side and chlorine ions which are anion ions are attracted to the anode 7 side. To be
However, since the cation-type ion exchange membrane 1 is present on the anode 7 side, movement of chlorine ions is blocked, and hydrogen ions generated by water decomposition in the anode chamber 8 move from the anode chamber 8 side to the intermediate chamber 4 side. Further, since the anion-type ion exchange membrane 2 is interposed on the cathode 2 side, movement of sodium ions is blocked, and hydroxyl ions move from the cathode chamber 6 side to the intermediate chamber 4. That is, in the intermediate chamber 4, water is produced by the reaction of hydrogen ions and hydroxyl ions, and the saline solution is diluted with the produced water. Due to such movement of hydrogen ions and hydroxyl ions, an electric current flows between the cathode 5 and the anode 7, oxygen gas is generated from the anode 7 and hydrogen gas is generated from the cathode 5, and electrolysis of water is performed. Be done.

In this oxygen production reaction on the surface of the anode 7, oxidizing substances such as oxygen radicals, hydrogen peroxide and ozone are produced as intermediate products, and it is possible to produce electrolyzed water having an acid bacteria cleaning effect. That is.

[0010]

However, as described above, in the case where a salt solution is used as an electrolytic solution and electrolysis is performed via a cation type or anion type ion exchange membrane, when a DC voltage is not applied. Due to the effect of osmotic pressure due to the difference in concentration, cation ions such as sodium ions will flow into the anode chamber side, and anion ions such as chlorine ions will flow into the cathode side, filling the cathode chamber and anode chamber. Reduce the performance level of pure water.

Further, even during the electrolysis operation, the separation ability of the cation-type ion exchange membrane is not 100% perfect, and the current commercial product has an ability of about 90 to 95%, and the cathode side has several hundreds. % Of the cations, sodium ions, penetrate through the anion-type ion exchange membrane, and a few% of the anion ions, chloride ions, enter the anode chamber side with the anode.

Due to the chlorine ions thus penetrating, the cathode chamber becomes strongly acidic, and the chlorine ions change as chlorine gas when electrons are deprived from the anode. In addition, chlorine gas dissolves in water and changes as hypochlorous acid, which has a bactericidal effect, but it produces a bad odor as chlorine odor, forms salts with sodium ions, and forms corrosive and electronic substances as residues on the object to be treated. This will have an adverse effect on parts and the like.

Further, although strongly acidic water and strongly alkaline water have some bactericidal effects, on the other hand, they cause irritation to the human body and destruction of cell membranes due to permeability,
If you use it for a long time, it may damage the human body,
Handle with care.

Furthermore, acidic water and alkaline water are one of the causes of pollution problems, and there is also a problem that wastewater treatment takes time, such as requiring a neutralization step in wastewater.

[0015]

The present invention is characterized in that a cathode chamber having a cathode, an anode chamber having an anode, and a partition wall for partitioning the cathode chamber and the anode chamber are made of a hydrogen ion conductive type membrane. In the electrolytic bath, the electrolytic bath is filled with an electrolytic solution or purified water, ion-exchanged water, distilled water, pure, and an electrolytic water generator for treating the electrolytic solution by applying a DC voltage to the cathode and the anode. It has the characteristic of producing electrolyzed water having a near-oxidative / reducing property.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The invention according to claim 1 of the present invention comprises a cathode chamber having a cathode, an anode chamber having an anode, and a hydrogen ion conductive type membrane for partitioning the cathode chamber and the anode chamber. In an electrolytic cell having a partition, an electrolytic water generator for filling the electrolytic cell with an electrolytic solution such as saline solution and applying a DC voltage to the cathode and the anode, and the hydrogen ion conductive type membrane has a property of passing only hydrogen ions. As a result, chlorine gas and oxygen gas are generated at the anode, and hydrogen ions are generated by the decomposition of water, and at the cathode, electrons are donated to the hydrogen ions generated by the decomposition of water to generate hydrogen gas. The transfer of hydrogen ions occurs between the two, and due to the transfer function of only hydrogen ions in the hydrogen-ion-conducting membrane, the cathode chamber does not become alkaline due to the increase of alkali metal, and the Even if the amount of chloride ion increases, it will not become acidic and will remain relatively neutral, and it will be possible to obtain strong reducing electrolyzed water and strong oxidizing electrolyzed water that is easy to drain and has little effect on the human body. .

According to a second aspect of the present invention, the cathode chamber having a cathode is filled with an electrolytic solution, the anode chamber having an anode is filled with purified water, ion-exchanged water, distilled water or pure water, and the anode has a mesh shape having a through hole. It is characterized by an electrolytic cell formed on the partition wall and adhered to the hydrogen ion conductive type membrane of the partition wall to ensure conductivity by adhering to the hydrogen ion conductive type membrane, and to prevent hydrogen ions generated by water decomposition. It efficiently transfers to the hydrogen ion conductive type membrane through the through hole of the anode, and the purified water in the anode chamber or ion-exchanged water or distilled water or pure water becomes electrolyzed water with a strong oxidizing property and very few impurities. Even if it is used for cleaning, etc., it is possible to use it without leaving any residue.

According to a third aspect of the present invention, the cathode chamber and the anode chamber are filled with purified water, ion-exchanged water, distilled water or pure water, and the cathode and the anode are formed in a mesh shape having a through hole, and the partition wall is a hydrogen ion conductive type. It comes in close contact with the membrane,
By ensuring that both electrodes are in close contact with the hydrogen ion conductive membrane, conductivity is ensured, and hydrogen ions generated by the decomposition of water on the anode side are efficiently transmitted to the hydrogen ion conductive membrane through the through holes.
In addition, the hydrogen gas generated at the cathode is generated in the cathode chamber through the hydrogen ion conductive membrane and the through hole, and the purified water or ion-exchanged water or distilled water or pure water in the anode chamber has a strong oxidizing property. Purified water, ion-exchanged water, distilled water, or pure water in the cathode chamber is for obtaining electrolyzed water having a strong reducing property, and both chambers are electrolyzed water having a sterilizing and cleaning power with very few impurities.

According to a fourth aspect of the present invention, a hydrogen ion conductive type membrane is interposed between an anode chamber filled with an electrolytic solution and having an anode immersed therein, and a mesh-shaped cathode having a through hole. The cathode is an electrolytic cell that is in close contact with the hydrogen ion conductive type membrane and is provided with an intake / exhaust mechanism for sequentially feeding a gas containing oxygen to the cathode surface, and in an electrolyzed water generator that applies a DC voltage to the cathode and the anode. Yes, the electrolyte in the anode chamber becomes neutral electrolyzed water for acid bacterium cleaning, and the cathode starts the oxygen and hydrogen ion conductive membranes sent by the intake / exhaust mechanism and the through holes and the hydrogen ions transmitted from the anode chamber. Water is generated by the reaction with electrons, the electrolyzed water that can be formed in the anode chamber is neutralized, safe, and oxidizing water that does not cause any problems in drainage, and oxygen is sent on the cathode side to generate water. But In which it is very structurally simplified because kill.

According to a fifth aspect of the present invention, the electrolytic solution is an aqueous solution of a conductive food additive such as sodium chloride, citric acid, boric acid, acetic acid, etc., so that when it is used for cleaning and sterilizing kitchen equipment, it comes into contact with food. Is a food hygiene condition that can be handled safely.

According to a sixth aspect of the present invention, a hydrogen ion conductive type membrane is interposed between an anode and a cathode immersed in an anode chamber filled with purified water, ion exchanged water, distilled water or pure water, and The cathode is formed in a mesh shape having through holes and is in close contact with the hydrogen ion conductive type membrane, and is an electrolytic cell provided with an intake / exhaust mechanism for sequentially feeding a gas containing oxygen to the cathode surface, and the cathode and the anode are provided. This is an electrolyzed water generator that applies a DC voltage, and ensures electrical conductivity by closely adhering to the hydrogen ion conductive type membrane, and efficiently transfers hydrogen ions generated by water decomposition to the hydrogen ion conductive type membrane through the through hole of the anode. The purified water in the anode chamber, ion-exchanged water, distilled water, or pure water becomes electrolyzed water that has strong oxidizing properties and very few impurities, and can be used without any residue for cleaning semiconductors. It is intended. Further, on the cathode side, oxygen is sent to generate water, which does not generate hydrogen gas, is safe, and can be structurally simplified.

According to a seventh aspect of the present invention, the cathode chamber and / or the anode chamber of the electrolytic cell are provided with an injection mechanism for sequentially feeding the electrolyte, purified water, ion-exchanged water, distilled water, or pure water and a discharge mechanism for sequentially discharging the circulation. By using the circulating water, it is possible to continuously secure the necessary electrolyzed water.

An embodiment of the present invention will be described below with reference to the drawings. (Embodiment 1) FIG. 1 shows a schematic view of an electrolyzed water producing apparatus 11 which is an embodiment of the present invention and a cross-sectional view of an electrolytic cell 12 part.

The electrolytic cell 12 is an anode chamber 1 having an anode 13.
4 and a cathode chamber 16 having a cathode 15. The anode chamber 14 and the cathode chamber 16 are partitioned by a partition wall 18 formed of a hydrogen ion conductive type membrane 17. The hydrogen ion conductive type membrane 17 is a film mainly composed of a Teflon-based resin having a sulfonic acid group, and the hydrogen ion conductive type membrane 17 is utilized by utilizing the property that hydrogen ions of the sulfonic acid group freely enter and leave.
It was developed as The hydrogen ion conductive film 17 is a resin having a property of transmitting only hydrogen ions, and does not conduct or transmit other ions. As the hydrogen ion conductive membrane 17 used this time, a polymer membrane sold under the name of Nafion membrane by DuPont was used.

Reference numeral 19 is a DC power source for applying a positive potential to the anode 13 and a negative potential to the cathode 15, and a signal from the oxidation potential measuring electrode 21 immersed in the electrolyte solution A20 in the anode chamber 14 is measured by an oxidation potential meter 22. The reduction potential meter 25 measures the signal of the reduction potential measuring electrode 24 immersed in the electrolytic solution B23 in the cathode chamber 16, and controls the operation and stop.
The material of the anode 13 and the cathode 15 was a titanium plate coated with platinum.

Reference numeral 26 is an injection mechanism A composed of an electrolytic source solution adjusting device A27 for adjusting the salt concentration to a predetermined concentration and an opening / closing valve A29 which is automatically opened / closed by a float switch A28. A certain electrolytic solution 20 is sequentially sent to the anode chamber 14.

Reference numeral 30 denotes an injection mechanism B for sequentially feeding the electrolytic solution 23 of electrolytic source water whose salt concentration has been adjusted to a predetermined level into the cathode chamber 16, and an opening / closing valve B33 which is opened / closed by an electrolytic source solution adjusting device B31 and a float switch B32. Composed.

Reference numeral 34 is a drainage mechanism A for sequentially discharging the electrolyzed water in the anode chamber 14, and 35 is a drainage mechanism B for similarly sequentially discharging the electrolyzed water in the cathode chamber 16.

Reference numeral 36 is an exhaust port A for oxygen gas or chlorine gas generated by electrolysis of the anode chamber 14, and 37 is an exhaust port B for discharging hydrogen gas generated by electrolysis of the cathode chamber 16.

The operation of the electrolyzed water producing apparatus 11 of the first embodiment and the scientific reaction in the electrolytic cell 12 will be described below.

First, the electrolytic source solution adjusting device A27 is operated to determine the concentration of saline solution. This time, we aimed to sterilize and wash water for kitchen equipment, and set the concentration to the same level as physiological saline of 0.9%. Next, the electrolytic solution A20 is injected into the anode chamber 14 by opening the opening / closing valve A29. The on-off valve A29 is open until the float switch A28 detects full water, and is automatically closed when the anode chamber 14 is filled with electrolyte.

Similarly, in the cathode chamber 16, the electrolytic source solution adjusting device B31 was operated to set the adjusted source solution to a concentration equivalent to 0.9% physiological saline. Next, the electrolytic solution B23 is injected into the cathode chamber 16 by opening the opening / closing valve B33. The open / close valve B33 is open until the float switch B28 detects full water, and is automatically closed when the cathode chamber 14 is full.

Next, the main body power supply terminal 38 of the DC power supply 19 is connected to a commercial power supply to start the electrolysis operation. This time, the anode 13 has a positive potential and the cathode 15 has a negative potential, and a DC voltage of 3 V is applied between the anode 13 and the cathode 15.

The surface material of the anode 13 and the cathode 15 is formed of platinum having a high corrosion potential, and the electrode material is hardly dissolved. On the surface of the anode 13, chlorine ions and water molecules in the electrolytic solution 20 are oxidized. , (Chemical formula 1) to (Chemical formula 4) are observed, and chlorine gas and oxygen gas are generated from the surface of the anode 13.
Further, hypochlorous acid or hypochlorous ion and hydrogen ion having a bactericidal effect are generated in the electrolyzed water.

[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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Here, since there is almost no increase in chlorine ions, which are counter ions of hydrogen ions, excess hydrogen ions move to the cathode chamber 16 through the ion conductive membrane 17. Therefore, no increase in hydrogen ion concentration is observed in the anode chamber 14, and strong acidic water is not obtained.

On the surface of the cathode 15, the chemical reaction of (Chemical Formula 5) occurs, hydrogen gas is generated, and hydroxyl ions are generated in the electrolytic solution 23. This hydroxyl ion is generated in the anode chamber 16 and becomes water by reacting with the excess hydrogen ion that has passed through the hydrogen ion conductive type membrane 17,
The neutralization also alleviates the change of the electrolyzed water 23 in the cathode chamber to alkaline. However, since a reducing agent such as hydrogen radicals is produced as an intermediate product in the process of generating hydrogen gas, electrolyzed water having sterilizing power can be obtained.

The oxidation potential measuring electrode 21 and the oxidation potential meter 2
The result of measuring the oxidation potential by 2 is the ambassador for the hydrogen electrode 12
When the result of measuring the reduction potential with the reduction potential measuring electrode 24 and the reduction potential meter at 00 mV or higher was -900 mV or lower, electrolysis was stopped.

By using the hydrogen ion conductive type membrane 17 as the partition wall 18 of the electrolytic cell 12 as described above, the movement of hydrogen ions only occurs, and the movement of sodium ions and chlorine ions contained in the saline is blocked. By doing
Electrolyzed water in the anode chamber 14 does not become strongly acidic water,
Further, since the electrolyzed water in the cathode chamber 16 does not become strong alkaline water, it is easy to handle, and it is possible to obtain electrolyzed water that does not require neutralization treatment for drainage. Since this electrolyzed water uses 0.9% physiological saline, it has a strong bactericidal effect due to chlorine, hypochlorous acid, and hypochlorite ion generated by electrolysis of sodium chloride. The electrolyzed water in the cathode chamber 16 also has a reducing ability by hydrogen radicals and has a sterilizing effect.

(Embodiment 2) FIG. 2 is a schematic view of an electrolyzed water producing apparatus 11 and an electrolyzer 1 according to another embodiment of the present invention.
It is a cross-sectional view of 2 parts. The description of the same components as in the first embodiment will be omitted.

The electrolytic cell 12 is composed of an anode chamber 14 and a cathode chamber 16 as in the first embodiment, and the anode chamber 14 and the cathode chamber 16 are partitioned by a partition wall 18 formed of a hydrogen ion conductive type membrane 17. ing. The anode 39 is made of a porous mesh titanium material having through holes and coated with platinum, and is attached in close contact with the hydrogen ion conduction type membrane 17. As the material for the anode 39, a titanium electrode such as punch metal coated with platinum can be used.

Reference numeral 40 denotes an injection mechanism C composed of a pure water producing device 41 for producing pure water and an opening / closing valve A29 which is automatically opened / closed by a float switch A28, and successively supplies pure water to the anode chamber 14. .

The cathode chamber 16 has the same structure as in the first embodiment. Next, the operation of the electrolyzed water producing apparatus 11 and the chemical reaction in the electrolytic cell 12 with such a configuration will be described, but the same parts as in Embodiment 1 are omitted.

This time is the production of electrolyzed water for the purpose of improving the oxidizing power of ultrapure water used for cleaning the surface of ceramics in the semiconductor production process. First, the pure production apparatus 41 is operated. Next, the electrolytic solution A20, which is pure water, is injected into the anode chamber 14 by opening the opening / closing valve A29. Open / close valve A2
9 is open until the float switch A28 detects full water, and is automatically closed when the anode chamber 14 is full of electrolyte.

Next, the main body power supply terminal 38 of the DC power supply 19 is connected to a commercial power supply to start the electrolysis operation. This time, the anode 39 was set to a positive potential and the cathode 15 was set to a negative potential, and a DC voltage of 3 V was applied between the anode 39 and the cathode 15.

The surface material of the anode 39 and the cathode 15 is formed of platinum having a high corrosion potential, the electrode material hardly dissolves, and water molecules are oxidized on the surface of the anode 39, and the chemical formulas The reaction 8) is observed, and oxygen gas is generated from the surface of the anode 39. In addition to hydrogen ions, oxygen radicals and hydroxyl radicals having bactericidal power, and hydrogen peroxide and ozone are generated in the electrolyzed water.

[0051]

[Chemical 6]

[0052]

[Chemical 7]

[0053]

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Since counter ions of hydrogen ions do not exist originally, excess hydrogen ions cannot exist in the anode chamber and move to the cathode chamber 16 through the hydrogen ion conduction type membrane 17. Therefore, no increase in hydrogen ion concentration is observed in the anode chamber 14, and strong acidic water is not obtained.

The anode 39 is made of a mesh-shaped material having through holes and is closely attached to the hydrogen ion conductive film 17, so that the pure water of the non-conductor is in contact with the electrolyzed water 20.
It is possible to smoothly transfer the hydrogen ions generated on the surface of the hydrogen ion conduction type membrane 17 to the hydrogen ion conduction type membrane 17. That is, when the anode 39 and the hydrogen ion conductive film 17 are separated from each other, the movement of hydrogen ions is hindered by the pure water layer of the non-conductive material and does not proceed smoothly. Since the anode 39 itself blocks the movement of hydrogen ions to the film 17, smooth movement of hydrogen ions cannot be performed.

Similar to the first embodiment, the chemical reaction of (Chemical Formula 5) occurs on the surface of the cathode 15 to generate hydrogen gas and hydroxyl ions in the electrolyzed water 23. This hydroxyl group ion is generated in the anode chamber 16 and becomes water by reacting with the excess hydrogen ion that has passed through the hydrogen ion conductive type membrane 17, and is neutralized, so that the electrolyzed water 23 in the cathode chamber is made alkaline. Changes are also eased. However, since a reducing agent such as hydrogen radicals is produced as an intermediate product in the process of generating hydrogen gas, electrolyzed water having sterilizing power can be obtained.

As described above, the anode 39 is made of a porous mesh titanium material having through holes and coated with platinum, and is adhered to the hydrogen ion conduction type membrane 17 so as to be a non-conductive body. By smoothly moving the hydrogen ions generated by electrolysis of pure water to the cathode 15 to enable electrolysis, pure water electrolyzed water that can utilize the oxidizing power of oxygen radicals and ozone generated during generation of oxygen can be manufactured. Further, since the electrolyzed water is neutral, the influence on the human body is small, and the problem of pollution in drainage does not occur.

(Embodiment 3) FIG. 3 is a schematic view of an electrolyzed water producing apparatus 11 and an electrolyzer 1 according to another embodiment of the present invention.
It is a cross-sectional view of 2 parts. The description of the same components as in the first or second embodiment will be omitted.

Like the first embodiment, the electrolytic cell 12 is made porous by the anode chamber 14 and the cathode chamber 16, and the anode chamber 14 and the cathode chamber 16 are partitioned by the partition wall 18 formed of the hydrogen ion conductive type membrane 17. Has been. Similarly to the anode 39, the cathode 42 is made of a porous mesh titanium material having through holes and coated with platinum, and is attached to the hydrogen ion conduction type membrane 17 in close contact.

Reference numeral 43 denotes an injection mechanism D composed of a pure production device 44 for producing pure water and an opening / closing valve B33 which is automatically opened / closed by a float switch B32, and successively sends pure water into the cathode chamber 16.

Next, the operation of the electrolyzed water producing apparatus 11 and the chemical reaction in the electrolytic cell 12 with such a configuration will be described, but the same parts as in Embodiment 1 or 2 will be omitted.

The purpose of the present invention is to produce electrolyzed water for the purpose of improving the oxidizing power and reducing power of ultrapure water used for cleaning the surface of ceramics in the semiconductor manufacturing process. Get up and running. Next, the electrolytic solution B23, which is pure water, is injected into the cathode chamber 16 by opening the open / close valve B33. The open / close valve B33 is open until the float switch B32 detects full water, and is automatically closed when the cathode chamber 16 is full of electrolytic solution.

The anode chamber 14 and the water injection mechanism C40 have the same structure as in the second embodiment.

Next, the main body power supply terminal 38 of the DC power supply 19 is connected to a commercial power supply to start the electrolysis operation. Anode 39
Is a positive potential, the cathode 42 is a negative potential, and the anode 39 and the cathode 42 are
And a DC voltage of 3 V was applied between and.

The surface material of the anode 39 and the cathode 42 is formed of platinum having a high corrosion potential, the electrode material is hardly dissolved, and the same reaction as in the second embodiment occurs on the surface of the anode 39. With respect to the cathode 42, the reaction of (Chemical Formula 5) occurs on the surface of the cathode, and in the course of the reaction in which hydrogen ions become hydrogen gas, reducing hydrogen radicals are produced as intermediate products to produce electrolyzed water having sterilizing power.

By using a mesh-shaped material having a through hole in the cathode 42 and adhering it to the hydrogen ion conduction type membrane 17, it is possible to smoothly react with the hydroxyl ions generated on the surface of the cathode 42 in contact with the electrolyzed water 23 which is pure water. Hydrogen ion conductive film 17
It is possible to react with hydrogen ions passing through. That is, when the cathode 42 and the hydrogen ion conductive type film 17 are separated from each other, the movement of hydroxyl ions or hydrogen ions is hindered by the pure water layer of the non-conductive member and does not go smoothly. Since the cathode 42 itself blocks the movement of the hydroxyl ions from the hydrogen ion conduction type membrane 17 to the hydrogen ion conductive type film 17, smooth movement of the hydroxyl ions and the hydrogen ions cannot be performed.

Similar to the second embodiment, on the surface of the anode 39, the chemical reactions (Formula 6) to (8) occur to generate oxygen gas and hydrogen ions in the electrolytic solution 20. The hydrogen ions pass through the hydrogen ion conductive type 17 and react with the hydroxyl ions generated in the cathode chamber 16 to become water, which is neutralized.
The change to alkalinity is moderated. However, since a reducing agent such as hydrogen radicals is produced as an intermediate product in the process of generating hydrogen gas, electrolyzed water having sterilizing power can be obtained.

As described above, as the cathode 42, a porous mesh-shaped titanium material having through holes coated with platinum is used, and it is a non-conductor when it is attached in close contact with the hydrogen ion conduction type membrane 17. Hydroxyl ions generated by electrolysis of pure water and hydrogen ions transferred from the anode chamber 14 can be smoothly neutralized, and the electrolysis of water can be performed. Therefore, when oxygen is generated in the anode chamber 14, Electrolyzed water of pure water having an oxidizing power of oxygen radicals or ozone or hydrogen peroxide generated can be produced, and electrolyzed water of pure water having reducing ability can be produced in the cathode chamber 16. Also, since this electrolyzed water is neutral, it has little effect on the human body,
Pollution problems in drainage will not occur.

(Embodiment 4) FIG. 4 is a schematic view of an electrolyzed water producing apparatus 11 and an electrolysis layer 1 according to another embodiment of the present invention.
It is a cross-sectional view of 2 parts. The description of the same components as in the first, second or third embodiment will be omitted.

The electrolytic cell 12 is composed of an anode chamber 14 and a cathode chamber 16 as in the first embodiment, and the anode chamber 14 and the cathode chamber 16 are partitioned by a partition wall 18 formed of a hydrogen ion conductive type membrane 17. ing. As the anode 13, a titanium plate coated with platinum is used, and as the cathode 42, a porous mesh having through holes is used, and a carbon having platinum ultrafine particles supported on the surface thereof is used to increase the reaction on the electrode surface. The cathode is attached to the hydrogen ion conduction type membrane 17 in close contact with it, using a porous gas diffusion electrode which is formed by pressure molding a mixture of powder and fluororesin powder to have appropriate water repellency.

Reference numeral 26 is an injection mechanism A composed of an electrolytic source solution adjusting device A27 similar to that of the first embodiment and an opening / closing valve A29 which is automatically opened / closed by a float switch A28. Are sequentially sent to the anode chamber 14.

Reference numeral 45 is an intake fan 48 for sucking the outside air through a filter 47 attached to the suction port 46, oxygen is introduced into the cathode chamber 16 comprising a balance duct 49 for uniformly introducing the gas to the cathode surface and an exhaust port 50. It is an intake / exhaust mechanism that sequentially sends gas containing

Electrolyzed water generator 11 having the following structure
The action and the chemical reaction in the electrolytic cell 12 will be described.
The same parts as in Embodiment 1, 2 or 3 are omitted.

First, the electrolytic source solution adjusting apparatus A27 is operated to determine a predetermined salt solution concentration. The operation and chemical reaction on the anode chamber 14 side are the same as those in the first embodiment, and the description thereof will be omitted. The main uses of this electrolyzed water are as sterilizing and washing water for kitchen and equipment, as water for revitalizing vegetables, and for washing and sterilizing dishes and cutting boards.

In this embodiment, the main body power supply terminal 38 of the DC power supply 19 is connected to the commercial power supply to start the electrolysis operation, but a DC voltage of 3 V is applied between the anode 13 and the cathode 42.
In addition, the DC power supply 19 measures the oxidation potential with the oxidation potential measuring electrode 21 and the oxidation potential meter 22 of the anode chamber 14,
The operation is controlled to stop when the oxidation potential of the electrolyzed water in the anode chamber 14 becomes 1200 mV or higher.

At the anode 13, the reactions of (Chemical formula 1) to (Chemical formula 4) occur, and chlorine produces hydrogen gas and oxygen gas, and also produces hypochlorite ion of chlorous acid when it has sterilizing power, and also hydrogen. Generates ions. Chlorine ions, which are counter ions of hydrogen ions, are not expected to increase in principle, and therefore excess hydrogen ions pass through the hydrogen ion conduction type membrane 17 and move to the cathode chamber 16 side.

On the surface of the cathode 42 of the cathode chamber 16, oxygen sent by the intake / exhaust mechanism 45 and the DC power source 19
Of electrons flowing as a negative potential of the hydrogen ions and hydrogen ions passing through the hydrogen ion conductive type membrane 17 from the anode chamber.
Two components collide with each other to generate water by causing the reaction of (Chemical Formula 9). The generated water is a hydrogen ion conduction type membrane 17
Is adsorbed on or becomes vapor and is discharged from the exhaust port 50.

[0078]

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Further, when hydrogen ions generated by electrolysis react with oxygen gas on the surface of the cathode 42 and are converted into water, it is assumed that unreacted hydrogen remains without sufficient reaction. A carbonaceous honeycomb current collector carrying a platinum catalyst may be pressure-bonded to the surface of 42 opposite to the hydrogen ion conductive membrane 17.

The cathode 42 is a porous mesh having through-holes, and a mixture of carbon powder carrying platinum ultrafine particles on its surface and fluororesin powder is pressure-molded to have an appropriate water-repellent property. By using the porous gas diffusion electrode and closely attaching it to the hydrogen ion conduction type membrane 17, the gas containing oxygen, the electrons carried to the cathode 42, and the hydrogen passing through the hydrogen ion conduction type membrane 17 are attached. It is possible to smoothly react with ions. That is, when the cathode 42 and the hydrogen ion conductive type film 17 are separated from each other, the movement of hydrogen ions is hindered by the gas layer of the non-conductive material, and the hydrogen ion conductive film 17 does not move smoothly if there is no through hole. Since the cathode 42 itself blocks the movement of oxygen to 17, the smooth reaction of the three components cannot be performed.

As described above, as the cathode 42, a porous mesh-shaped one having a through hole such as a porous gas diffusion electrode is used, and the hydrogen ion conduction type membrane 17 is closely attached to the cathode 42, whereby the intake / exhaust mechanism 45 is provided. The generation of moisture by the oxygen fed in, the hydrogen ions passing through the hydrogen ion conduction type membrane 17 from the anode material 14 and the electrons carried to the cathode eliminates the generation of hydrogen gas from the surface of the cathode 42. Escape from the danger of fire and explosion due to hydrogen gas. Further, since it is not necessary to control or adjust the concentration of the electrolytic solution, purified water, ion-exchanged water, distilled water, pure water, etc. in the cathode material 16, the structure of the electrolytic cell can be greatly simplified and the facility cost can be reduced.

Further, naturally, in the anode chamber 14, pure water electrolyzed water which can utilize the oxygen radicals generated during the generation of oxygen and the oxidizing power of ozone and hydrogen peroxide water can be produced, and this electrolyzed water is close to neutral. The impact on the human body is small and the problem of pollution in drainage will not occur.

(Embodiment 5) FIG. 5 is a schematic view of an electrolyzed water producing apparatus 11 and an electrolyzer 1 according to another embodiment of the present invention.
It is a cross-sectional view of 2 parts. In addition, Embodiment 1
The description of the same components as those in 4 will be omitted.

The electrolytic cell 12 is composed of an anode chamber 14 and a cathode chamber 16 as in the first embodiment, and the anode chamber 14 and the cathode chamber 16 are partitioned by a partition wall 18 formed of a hydrogen ion conductive type membrane 17. ing. The anode 39 is a porous mesh titanium material having a through hole coated with platinum, and the cathode 42 is a porous mesh material having a through hole and is a carbon powder having platinum ultrafine particles carried on the surface thereof. A porous gas diffusion electrode having a proper water-repellent property obtained by press-molding a mixture of fluorinated resin powder and is mixed, and both electrodes are attached in close contact with the hydrogen ion conduction type membrane 17.

The anode chamber 14 is the same as that of the second embodiment, the cathode chamber 16 is the same as that of the fourth embodiment, and these two forms are combined.

With the above combination, it is possible to manufacture a neutral sterilizing and cleaning material having an oxidizing property of oxygen radicals, hydrogen peroxide solution, and ozone generated by electrolysis of ultrapure water, and oxygen is stored in the cathode chamber 16. It is not necessary to control or adjust the concentration of the aqueous solution just by sending in a gas containing the gas, and it is possible to provide the electrolyzed water generation apparatus 11 in which the risk of fire or explosion is small because hydrogen is not generated.

Also, of course, in the anode chamber 14, pure water electrolyzed water can be produced which can utilize the oxygen radicals generated during the generation of oxygen and the oxidizing power of ozone and hydrogen peroxide, and the electrolyzed water is close to neutral. As a result, there is little impact on the human body, and pollution problems in wastewater do not occur.

Further, although the electrolytic solution introduced in the case of the present embodiment has been described mainly using a saline solution, the same effect can be obtained if the electrolytic solution generates chlorine gas and oxygen gas by electrolysis. However, from the viewpoint of food safety, it is desirable to use an aqueous solution of a conductive food additive such as salt, citric acid, boric acid or acetic acid as the electrolytic solution in order to use it as a germicidal detergent for the kitchen.

Further, as shown in FIG. 1, a drainage mechanism A34 and a drainage mechanism B capable of sequentially draining the electrolytic solution from the electrolytic cell 12.
As a result of 35, when electrolytic water is continuously used, the transition of the electrolytic solution 20 is lowered and the float switch 28 operates to automatically pour new electrolytic solution 20 from the electrolytic water supply device 27. Further, when the oxidation potential is lowered by the injection of new electrolyte solution 20, the oxidation potential meter 22 shows a decrease in the oxidation potential,
The stopped electrolysis will be automatically restarted. As described above, the electrolytic solution is efficiently generated by continuously circulating the electrolytic solution, the purified water, the ion-exchanged water, the distilled water, and the pure water by the injecting mechanism that sequentially sends the pure water and the discharging mechanism that sequentially discharges the pure water.

[0090]

As described above, in the electrolyzed water producing apparatus of the present invention, the cathode chamber having the cathode, the anode chamber having the anode, and the partition wall for partitioning the cathode chamber and the anode chamber are composed of the hydrogen ion conductive type membrane. In the electrolytic cell characterized by
An electrolyzed water generator that treats the electrolytic solution by filling the electrolytic cell with electrolytic solution or purified water, ion-exchanged water, distilled water, and pure water, and applying a DC voltage to the cathode and anode. It is possible to provide a device having a characteristic of generating electrolyzed water having a sterilizing property and a strong detergency having a reducing property.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of an electrolyzed water generator and an electrolyzer according to a first embodiment of the present invention.

FIG. 2 is a cross-sectional view of an electrolyzed water generator and an electrolyzer according to a second embodiment of the present invention.

FIG. 3 is a cross-sectional view of an electrolyzed water generator and an electrolyzer according to a third embodiment of the present invention.

FIG. 4 is a cross-sectional view of an electrolyzed water generator and an electrolyzer according to a fourth embodiment of the present invention.

FIG. 5 is a cross-sectional view of an electrolyzed water generator and an electrolyzer according to a fifth embodiment of the present invention.

FIG. 6 is a cross-sectional view of an electrolytic cell of an electrolyzed water generator according to a conventional embodiment.

[Explanation of symbols]

 11 Electrolyzed Water Generator 12 Electrolyzer 13,39 Anode 14 Anode Chamber 15,42 Cathode 16 Cathode Chamber 17 Hydrogen Ion Conductive Membrane 18 Partition Wall 20,23 Electrolyte 26, 30, 40, 43 Injection Mechanism 33, 34 Drainage Mechanism 45 Intake and exhaust mechanism

Claims (7)

[Claims] 1. An electrolytic cell having a cathode chamber having a cathode, an anode chamber having an anode, and a partition wall composed of a hydrogen ion conductive type membrane for partitioning the cathode chamber and the anode chamber,
An electrolyzed water generator for filling the electrolytic cell with an electrolytic solution and applying a DC voltage to the cathode and the anode. 2. A cathode chamber having a cathode is filled with an electrolytic solution, an anode chamber having an anode is filled with purified water, ion-exchanged water, distilled water or pure water, and the anode is formed in a mesh shape having a through hole to form hydrogen in a partition wall. The electrolyzed water producing apparatus according to claim 1, wherein the electrolyzed water producing apparatus is an electrolyzer which is in close contact with the ion conductive membrane. 3. The cathode chamber and the anode chamber are filled with purified water, ion-exchanged water, distilled water or pure water, and the cathode and the anode are formed in a mesh shape having a through hole and adhered to the hydrogen ion conductive type membrane of the partition wall. The electrolyzed water generator according to claim 1, wherein the electrolyzed water generator is an electrolyzer. 4. A hydrogen ion conductive type membrane is interposed between an anode chamber filled with an electrolytic solution, in which an anode is immersed, and a mesh-shaped cathode having a through hole, and the cathode is the hydrogen ion. An electrolyzed water producing apparatus for applying a DC voltage to the cathode and the anode in an electrolytic cell which is in close contact with the conductive type membrane and is provided with an intake / exhaust mechanism for sequentially feeding the gas containing oxygen on the cathode surface. 5. The electrolyzed water generator according to claim 1, 2 or 4, wherein the electrolytic solution is an aqueous solution of a conductive food additive such as salt, citric acid, boric acid or acetic acid. 6. A hydrogen ion conductive membrane is interposed between an anode and a cathode, which is immersed in an anode chamber filled with purified water, ion-exchanged water, distilled water or pure water, and the anode and the cathode have through holes. A DC voltage is applied to the cathode and the anode in an electrolytic cell that is formed in a mesh shape and is in close contact with the hydrogen ion conductive type membrane, and is provided with an intake / exhaust mechanism for sequentially feeding a gas containing oxygen to the cathode surface. Electrolyzed water generator. 7. The method according to claim 1, wherein the cathode chamber and / or the anode chamber of the electrolytic cell are provided with an injection mechanism for sequentially feeding an electrolytic solution, purified water, ion-exchanged water or pure water, and a drainage mechanism for sequentially discharging the electrolytic solution. 6. The electrolyzed water generator according to item 6.