JP6944152B2 - Sterilized water generator and water supply equipment - Google Patents

Sterilized water generator and water supply equipment Download PDF

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JP6944152B2
JP6944152B2 JP2017192121A JP2017192121A JP6944152B2 JP 6944152 B2 JP6944152 B2 JP 6944152B2 JP 2017192121 A JP2017192121 A JP 2017192121A JP 2017192121 A JP2017192121 A JP 2017192121A JP 6944152 B2 JP6944152 B2 JP 6944152B2
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JP2019065350A (en
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秋山　秀典
秀典 秋山
謙一 末松
謙一 末松
忠 甲田
忠 甲田
石川　隆久
隆久 石川
山本　剛之
剛之 山本
中島　泰仁
泰仁 中島
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Lixil Corp
Suematsu Electronics Co Ltd
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Suematsu Electronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/48—Treatment of water, waste water, or sewage with magnetic or electric fields
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/28—Per-compounds
    • C25B1/30—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/02—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
    • E—FIXED CONSTRUCTIONS
    • E03—WATER SUPPLY; SEWERAGE
    • E03D—WATER-CLOSETS OR URINALS WITH FLUSHING DEVICES; FLUSHING VALVES THEREFOR
    • E03D9/00—Sanitary or other accessories for lavatories ; Devices for cleaning or disinfecting the toilet room or the toilet bowl; Devices for eliminating smells
    • E03D9/02—Devices adding a disinfecting, deodorising, or cleaning agent to the water while flushing

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Automation & Control Theory (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Bidet-Like Cleaning Device And Other Flush Toilet Accessories (AREA)

Description

本発明は、除菌水を生成する除菌水生成装置及び除菌水生成装置が組み込まれた水回り機器に関する。 The present invention relates to a sterilized water generator for generating sterilized water and a water supply device incorporating the sterilized water generator.

従来、トイレ、浴室、キッチン、洗面台、洗濯機などの水回り機器に、除菌水を供給するためのさまざまな除菌水生成装置が提案されている。 Conventionally, various disinfectant water generators for supplying disinfectant water to water-related devices such as toilets, bathrooms, kitchens, wash basins, and washing machines have been proposed.

例えば、一対の電極間に電圧を印加して、水を電気分解し、殺菌力のある次亜塩素酸（ＨＣｌＯ）を生成する除菌水生成装置が提案されている（例えば特許文献１参照）。しかし、特許文献１に記載された技術では、次亜塩素酸の生成量が水に含まれる塩素の量に依存することになるので、水の成分に依らずに除菌水を供給することが難しい。 For example, a disinfectant water generator has been proposed in which a voltage is applied between a pair of electrodes to electrolyze water to generate bactericidal hypochlorous acid (HClO) (see, for example, Patent Document 1). .. However, in the technique described in Patent Document 1, since the amount of hypochlorous acid produced depends on the amount of chlorine contained in water, it is possible to supply sterilized water regardless of the water component. difficult.

水の成分に依らずに除菌水を供給するために、水に食塩水などの電解質を添加した溶液を電気分解し、殺菌力のある次亜塩素酸を生成する除菌水生成装置が提案されている（例えば特許文献２参照）。また、殺菌性金属である電極を用いて水を電気分解し、殺菌性イオンを水に溶出させる除菌水生成装置が提案されている（例えば特許文献３参照）。しかし、特許文献２に記載された技術では電解質を、特許文献３に記載された技術では殺菌性金属を、それぞれ定期的に供給しなければならない。 In order to supply sterilized water regardless of the composition of water, a sterilized water generator that electrolyzes a solution in which an electrolyte such as salt solution is added to water to generate bactericidal hypochlorous acid has been proposed. (See, for example, Patent Document 2). Further, a sterilizing water generator has been proposed in which water is electrolyzed using an electrode which is a bactericidal metal and sterilizing ions are eluted into the water (see, for example, Patent Document 3). However, in the technique described in Patent Document 2, an electrolyte must be supplied periodically, and in the technique described in Patent Document 3, a bactericidal metal must be supplied on a regular basis.

そこで、水中で放電を行うことで過酸化水素を生成し、過酸化水素によって水を除菌する技術が提案されている。例えば、汚染水を処理するための装置として、放電部間に高電圧パルスを印加して水を処理する水処理装置が提案されている（例えば特許文献４参照）。 Therefore, a technique has been proposed in which hydrogen peroxide is generated by discharging in water and the water is sterilized by hydrogen peroxide. For example, as an apparatus for treating contaminated water, a water treatment apparatus for treating water by applying a high voltage pulse between discharge portions has been proposed (see, for example, Patent Document 4).

特開２０００−２２０１９３号公報Japanese Unexamined Patent Publication No. 2000-220093 特開２００１−２９３０６号公報Japanese Unexamined Patent Publication No. 2001-29306 特開２００７−１４８５３号公報JP-A-2007-14853 特開２００４−１４３５１９号公報Japanese Unexamined Patent Publication No. 2004-143519

しかし、特許文献４に記載された技術では放電電極が針状であり、放電時間の経過にともなって電極が浸食劣化して放電プラズマが生成しなくなるため、除菌水中の過酸化水素濃度を、除菌に十分な濃度まで高めることが困難であった。 However, in the technique described in Patent Document 4, the discharge electrode is needle-shaped, and the electrode is eroded and deteriorated with the lapse of the discharge time, and discharge plasma is not generated. Therefore, the hydrogen peroxide concentration in the sterilized water is determined. It was difficult to increase the concentration to a level sufficient for eradication.

本発明は、長時間の放電プラズマの生成を可能にして除菌水中の過酸化水素濃度を高濃度にできる除菌水生成装置を提供することを目的とする。 An object of the present invention is to provide a disinfectant water generator capable of generating a discharge plasma for a long time and increasing the hydrogen peroxide concentration in the disinfectant water.

本発明は、水が介在する一対の電極を備えた除菌水生成装置であって、前記一対の電極は、少なくとも一方が陽極酸化皮膜で被覆された金属平板であり、前記一対の電極間に水中放電プラズマを生じさせることで除菌水を生成する除菌水生成装置に関する。 The present invention is a disinfectant water generator provided with a pair of electrodes in which water is interposed, and the pair of electrodes is a metal flat plate on which at least one is coated with an anodic oxide film, and between the pair of electrodes. The present invention relates to a sterilized water generator that generates sterilized water by generating an underwater discharge plasma.

また、前記陽極酸化皮膜は、アルマイト皮膜である請求項１に記載の除菌水生成装置が好ましい。 The sterilized water generator according to claim 1, which is an alumite film, is preferable as the anodic oxide film.

また、前記一対の電極間に高電圧パルスを印加し、水中放電プラズマを生じさせる高電圧パルス印加手段を更に備えることが好ましい。 Further, it is preferable to further provide a high voltage pulse applying means for applying a high voltage pulse between the pair of electrodes to generate an underwater discharge plasma.

また、前記高電圧パルス印加手段は、パルス電界が１〜２０ｋＶ／ｃｍとなるように前記一対の電極間に高電圧パルスを印加することが好ましい。 Further, the high voltage pulse applying means preferably applies a high voltage pulse between the pair of electrodes so that the pulse electric field is 1 to 20 kV / cm.

また、前記高電圧パルス印加手段は、パルス幅が２０ｎ秒以上となるように前記一対の電極間に高電圧パルスを印加することが好ましい。 Further, the high voltage pulse applying means preferably applies a high voltage pulse between the pair of electrodes so that the pulse width is 20 nsec or more.

また、前記高電圧パルス印加手段は、電流密度が０．１〜１０Ａ／ｃｍ２となるように前記一対の電極間に高電圧パルスを印加することが好ましい。 Further, the high voltage pulse applying means preferably applies a high voltage pulse between the pair of electrodes so that the current density is 0.1 to 10 A / cm 2.

また、前記水の温度を維持する保温手段を更に備えることが好ましい。 Further, it is preferable to further provide a heat retaining means for maintaining the temperature of the water.

また、上記除菌水生成装置が組み込まれた水回り機器に関する。 Further, the present invention relates to a water supply device incorporating the above-mentioned sterilized water generator.

本発明によれば、長時間の水中放電プラズマの生成を可能にし、除菌水中の過酸化水素濃度を高濃度にできる。 According to the present invention, it is possible to generate an underwater discharge plasma for a long time, and the hydrogen peroxide concentration in the sterilized water can be increased.

本発明の一実施形態に係る除菌水生成装置の模式図である。It is a schematic diagram of the disinfectant water generator which concerns on one Embodiment of this invention. 実施例１〜７及び比較例１〜５に係る除菌水生成装置の模式図である。It is a schematic diagram of the sterilized water generation apparatus which concerns on Examples 1-7 and Comparative Examples 1-5. 比較例６、７に係る除菌水生成装置の模式図である。It is a schematic diagram of the sterilized water generator which concerns on Comparative Examples 6 and 7. 本発明のパルス幅に関する説明図である。It is explanatory drawing about the pulse width of this invention.

以下、本発明の一実施形態について、図面を参照しながら説明する。なお、本発明は、以下の実施形態に限定されない。 Hereinafter, an embodiment of the present invention will be described with reference to the drawings. The present invention is not limited to the following embodiments.

図１は、本発明の一実施形態に係る除菌水生成装置の模式図である。図１に示すように、本実施形態に係る除菌水生成装置１は、高電圧パルス印加手段としての高電圧パルス印加装置２と、処理槽１３と、を備える。 FIG. 1 is a schematic view of a sterilized water generator according to an embodiment of the present invention. As shown in FIG. 1, the disinfectant water generation device 1 according to the present embodiment includes a high voltage pulse application device 2 as a high voltage pulse application means and a treatment tank 13.

除菌水生成装置１は、単独の装置として使用されてもよいが、本実施形態においては、コンパクトさが要求される水回り機器（不図示）に組み込まれる装置として使用される。水回り機器としては、特に限定されないが、トイレ、浴室、キッチン、洗面台、洗濯機やこれに付属する水栓金具等を挙げることができる。 The disinfectant water generation device 1 may be used as a single device, but in the present embodiment, it is used as a device incorporated in a water supply device (not shown) that requires compactness. The water supply device is not particularly limited, and examples thereof include a toilet, a bathroom, a kitchen, a wash basin, a washing machine, and a faucet fitting attached thereto.

高電圧パルス印加装置２は、処理槽１３内の一対の電極３間に高電圧パルスを印加し、高電圧パルス放電を生じさせることで、水中放電プラズマを生じさせる装置である。高電圧パルス印加装置２としては、特に限定されないが、株式会社末松電子製作所製のＭＰＣ３０１０Ｓ−５０ＳＰなどの市販品を挙げることができる。高電圧パルス印加装置２は、一対の電極３間に高電圧パルスを印加し、水中放電プラズマを生じさせる The high-voltage pulse application device 2 is a device that generates an underwater discharge plasma by applying a high-voltage pulse between a pair of electrodes 3 in the processing tank 13 to generate a high-voltage pulse discharge. The high voltage pulse application device 2 is not particularly limited, and examples thereof include commercially available products such as MPC3010S-50SP manufactured by Suematsu Denshi Seisakusho Co., Ltd. The high voltage pulse application device 2 applies a high voltage pulse between the pair of electrodes 3 to generate an underwater discharge plasma.

処理槽１３は、除菌水を生成する槽である。処理槽１３は、一対の電極３と、水８と、封止部材９と、保温手段としての保温材１１と、を収容する。 The treatment tank 13 is a tank that produces sterilized water. The treatment tank 13 houses a pair of electrodes 3, water 8, a sealing member 9, and a heat insulating material 11 as a heat insulating means.

一対の電極３は、高電圧パルス印加装置２と電気的に接続される。高電圧パルス印加装置２を作動させると、一対の電極３間に水中放電プラズマが生じる。 The pair of electrodes 3 are electrically connected to the high voltage pulse application device 2. When the high voltage pulse application device 2 is operated, an underwater discharge plasma is generated between the pair of electrodes 3.

一対の電極３は、陽極３ａと陰極３ｂとからなる。陽極３ａと、陰極３ｂとは、何れも平板状の金属材料（以下、金属平板ともいう）からなる。陽極３ａと、陰極３ｂとは、水８を介在して互いに対向して配置される。本実施形態においては、一対の電極３はアルミニウムからなり、陽極３ａ、陰極３ｂの少なくとも一方が陽極酸化膜からなるアルマイト皮膜で被覆される。 The pair of electrodes 3 includes an anode 3a and a cathode 3b. Both the anode 3a and the cathode 3b are made of a flat metal material (hereinafter, also referred to as a metal flat plate). The anode 3a and the cathode 3b are arranged so as to face each other with the water 8 interposed therebetween. In the present embodiment, the pair of electrodes 3 are made of aluminum, and at least one of the anode 3a and the cathode 3b is coated with an alumite film made of an anodized film.

なお、本明細書において、金属平板は、別工程の処理により、陽極酸化皮膜で予め被覆される。その後、一対の電極３の陽極３ａ、陰極３ｂの少なくとも一方に陽極酸化皮膜で被覆された金属平板が使用される。 In the present specification, the metal flat plate is pre-coated with an anodic oxide film by a treatment in a separate step. After that, a metal flat plate coated with an anode oxide film on at least one of the anode 3a and the cathode 3b of the pair of electrodes 3 is used.

一対の電極３をアルマイト皮膜で被覆する処理する方法としては、特に限定されず、従来公知の方法を用いることができる。例えば、アルミニウムを陽極にして電解処理することによってアルマイト皮膜を得ることができる。 The method for coating the pair of electrodes 3 with the alumite film is not particularly limited, and a conventionally known method can be used. For example, an alumite film can be obtained by electrolyzing aluminum as an anode.

なお、必ずしも陽極３ａ、陰極３ｂの両方が陽極酸化皮膜で被覆されていなくてもよい。陽極３ａ又は陰極３ｂの少なくともどちらかが陽極酸化皮膜で被覆されていれば、一対の電極３間に大電流は流れず、陽極酸化皮膜を施した電極表面で無数の水中放電プラズマが生じ、過酸化水素が生成される。なお、陽極３ａ、陰極３ｂの両方を陽極酸化皮膜で被覆した場合には、一定時間ごとに電極の陰陽を入れ替える極性変換が可能となり、電極表面への析出物の蓄積を抑制できる。 It should be noted that both the anode 3a and the cathode 3b do not necessarily have to be coated with the anodic oxide film. If at least one of the anode 3a and the cathode 3b is coated with an anodic oxide film, a large current does not flow between the pair of electrodes 3, and innumerable underwater discharge plasmas are generated on the electrode surface coated with the anodic oxide film. Hydrogen peroxide is produced. When both the anode 3a and the cathode 3b are coated with the anodic oxide film, it is possible to change the polarity by changing the yin and yang of the electrode at regular intervals, and it is possible to suppress the accumulation of precipitates on the electrode surface.

後述するように、陽極酸化皮膜は絶縁層として機能し、破壊電圧と耐摩耗性を向上させて、高寿命化するため、厚みが１０ｎｍ以上であるアルマイト皮膜とすることが好ましい。一方で、陽極酸化皮膜へ高電界を印加して水中放電プラズマ生成を容易にするため、厚みが１００μｍ以下であることが好ましい。
なお、陽極酸化皮膜の種類としては、ＪＩＳ Ｈ８６０３に規定された硬質陽極酸化被膜が耐久性に優れており、好ましい。 As will be described later, the anodized film functions as an insulating layer, improves the fracture voltage and wear resistance, and prolongs the service life. Therefore, it is preferable to use an alumite film having a thickness of 10 nm or more. On the other hand, in order to easily generate an underwater discharge plasma by applying a high electric field to the anodic oxide film, the thickness is preferably 100 μm or less.
As the type of anodic oxide film, the hard anodic oxide film specified in JIS H8603 is preferable because it has excellent durability.

水８は一対の電極３間に介在する。水８は、例えば水回り機器から供給され、水中放電プラズマによって過酸化水素が生成し、除菌水となって水回り機器に戻される。このようにして水回り機器の水は除菌される。水８は、水道法に規定された水質基準に適合した水が好適であるが、水道法に規定された水質基準に適合した水に限定されず、例えば、水回り機器に由来する成分（具体的には、洗剤、芳香剤、汚れ等の有機物又は無機物）を含む水や各種陽イオン、陰イオンを含む水でもよい。 Water 8 is interposed between the pair of electrodes 3. The water 8 is supplied from, for example, a water supply device, hydrogen peroxide is generated by an underwater discharge plasma, becomes sterilized water, and is returned to the water supply device. In this way, the water of the water supply device is sterilized. Water 8 is preferably water that conforms to the water quality standards stipulated in the Waterworks Law, but is not limited to water that conforms to the water quality standards stipulated in the Waterworks Law. Specifically, it may be water containing (organic or inorganic substances such as detergents, fragrances and stains) and water containing various cations and anions.

封止部材９は、一対の電極３の側面及び底面に配置される。本実施形態においては、封止部材９は樹脂によって構成される。封止部材９は、水８を一対の電極３間に封止する。封止部材９は複数の部品で構成され、封止部材９同士の間又は封止部材９と陽極３ａ及び陰極３ｂとの間に、図示していないパッキンや接着剤を介在させてもよい。 The sealing member 9 is arranged on the side surface and the bottom surface of the pair of electrodes 3. In the present embodiment, the sealing member 9 is made of resin. The sealing member 9 seals water 8 between the pair of electrodes 3. The sealing member 9 is composed of a plurality of parts, and a packing or an adhesive (not shown) may be interposed between the sealing members 9 or between the sealing member 9 and the anode 3a and the cathode 3b.

保温材１１は、水８の温度を保持する。本実施形態においては、保温材１１は断熱材である。保温材１１は、一対の電極３及び封止部材９の外部に配置される。一対の電極３間に水中放電プラズマが生じると、水８の温度が上昇する。保温材１１は、水８の温度が低下しにくいように水８を断熱する。 The heat insulating material 11 maintains the temperature of the water 8. In the present embodiment, the heat insulating material 11 is a heat insulating material. The heat insulating material 11 is arranged outside the pair of electrodes 3 and the sealing member 9. When an underwater discharge plasma is generated between the pair of electrodes 3, the temperature of the water 8 rises. The heat insulating material 11 insulates the water 8 so that the temperature of the water 8 does not easily drop.

続いて、水中放電プラズマについて説明する。
本実施形態に係る高電圧パルス印加装置２を作動させると、一対の電極３間で、パルス電界が生じる。陽極３ａと、陰極３ｂは、少なくとも一方が陽極酸化皮膜（例えばアルマイト皮膜）で被覆されているため、陽極酸化皮膜が絶縁層となり、一対の電極３間の通電が抑制されると共に、陽極酸化皮膜で被覆した電極にパルス高電界が印加され、陽極酸化皮膜の表面で水８が電離されて発光し、無数の水中放電プラズマが生成される。この水中放電プラズマによって、ヒドロキシルラジカルが生成され、過酸化水素が発生する。 Subsequently, the underwater discharge plasma will be described.
When the high voltage pulse application device 2 according to the present embodiment is operated, a pulse electric field is generated between the pair of electrodes 3. Since at least one of the anode 3a and the cathode 3b is coated with an anodic oxide film (for example, an alumite film), the anodic oxide film serves as an insulating layer, the energization between the pair of electrodes 3 is suppressed, and the anodic oxide film is suppressed. A pulsed high electric field is applied to the electrode coated with, and water 8 is ionized on the surface of the anodic oxide film to emit light, and innumerable underwater discharge plasmas are generated. Hydroxyl radicals are generated by this underwater discharge plasma to generate hydrogen peroxide.

ここで、水８の温度に依らず水中放電プラズマは生じるが、本実施形態においては、保温材１１が水８の温度を保持することにより、水中放電プラズマによって生成した除菌水から、過酸化水素は蒸発させずに水分が蒸発し、更に過酸化水素濃度を高くできる。これは、水分の沸点が１００℃であるのに対し、過酸化水素の沸点が１００℃以上であることを利用したものである。 Here, the underwater discharge plasma is generated regardless of the temperature of the water 8, but in the present embodiment, the heat insulating material 11 maintains the temperature of the water 8 so that the sterilized water generated by the underwater discharge plasma is peroxidized. Water evaporates without evaporating hydrogen, and the concentration of hydrogen peroxide can be further increased. This utilizes the fact that the boiling point of water is 100 ° C., whereas the boiling point of hydrogen peroxide is 100 ° C. or higher.

本実施形態においては、高電圧パルス放電におけるパルス電界が１〜２０ｋＶ／ｃｍとなり、パルス幅が２０ｎ秒以上となるように、又は電流密度が０．１〜１０Ａ／ｃｍ２となるように、高電圧パルス印加装置２は一対の電極３間に高電圧パルスを印加する。パルス電界が１ｋＶ／ｃｍ未満の場合、パルス幅が２０ｎ秒未満の場合、又は電流密度が０．１Ａ／ｃｍ２未満の場合には、水中放電プラズマが生じにくい。パルス電界が２０ｋＶ／ｃｍを超える場合、又は電流密度が１０Ａ／ｃｍ２を超える場合には、アーク放電が生じやすい。 In the present embodiment, the pulse electric field in the high voltage pulse discharge is as high as 1 to 20 kV / cm, the pulse width is as high as 20 nsec or more, or the current density is as high as 0.1 to 10 A / cm 2. The voltage pulse application device 2 applies a high voltage pulse between the pair of electrodes 3. When the pulse electric field is less than 1 kV / cm, the pulse width is less than 20 nsec, or the current density is less than 0.1 A / cm 2 , underwater discharge plasma is unlikely to occur. When the pulse electric field exceeds 20 kV / cm or the current density exceeds 10 A / cm 2 , arc discharge is likely to occur.

なお、アーク放電が生じても、アーク放電に転移する前に陽極酸化皮膜表面で無数の水中放電プラズマが発光し、過酸化水素も生成するが、一対の電極３の摩耗が激しくなり長時間の水中放電プラズマの生成は不可能であり、水８中の過酸化水素濃度は十分に高くならない。更に電気ノイズが生じ周囲の電気機器を誤作動させたりするため、十分な対策を施さないと大変危険である。 Even if an arc discharge occurs, innumerable underwater discharge plasmas emit light on the surface of the anodic oxide film before the transition to the arc discharge, and hydrogen peroxide is also generated, but the pair of electrodes 3 are severely worn for a long time. It is impossible to generate an underwater discharge plasma, and the concentration of hydrogen peroxide in the water 8 is not sufficiently high. Furthermore, electrical noise is generated and causes the surrounding electrical equipment to malfunction, which is extremely dangerous unless sufficient measures are taken.

本実施形態によれば、以下のような効果が奏される。
除菌水生成装置１は、水８が介在する一対の電極３を備えた除菌水生成装置１であって、一対の電極３は、少なくとも一方が陽極酸化皮膜で被覆された金属平板であり、一対の電極３間に水中放電プラズマを生じさせることで除菌水を生成する。これにより、除菌水中の過酸化水素濃度を高濃度にできる。 According to this embodiment, the following effects are achieved.
The disinfectant water generator 1 is a disinfectant water generator 1 provided with a pair of electrodes 3 intervening with water 8, and the pair of electrodes 3 is a metal flat plate having at least one coated with an anodic oxide film. , Disinfecting water is generated by generating an underwater discharge plasma between the pair of electrodes 3. As a result, the hydrogen peroxide concentration in the sterilized water can be increased.

また、陽極酸化皮膜はアルマイト皮膜が好ましい。つまり、一対の電極３は、少なくとも一方がアルマイト皮膜で被覆される。アルマイト皮膜では、皮膜１ｃｍ２あたり数百億の微細孔が生成し、この微細孔が水中放電プラズマの生成に有効に作用する。
なお、水中放電プラズマは陽極酸化皮膜を施した電極に生じるため、陽極３ａ、陰極３ｂの少なくとも一方が陽極酸化皮膜で被覆されていれば、水中放電プラズマが生じ、過酸化水素が生成する。 The anodized film is preferably an alumite film. That is, at least one of the pair of electrodes 3 is coated with an alumite film. In the alumite film, tens of billions of micropores are generated per 1 cm 2 of the film, and these micropores effectively act on the generation of underwater discharge plasma.
Since the underwater discharge plasma is generated on the electrode coated with the anodic oxide film, if at least one of the anode 3a and the cathode 3b is covered with the anodic oxide film, the underwater discharge plasma is generated and hydrogen peroxide is generated.

また、除菌水生成装置１は、一対の電極３間に高電圧パルスを印加し、水中放電プラズマを生じさせる高電圧パルス印加装置２を更に備える。高電圧パルス印加装置２は、パルス電界が１〜２０ｋＶ／ｃｍとなるように一対の電極３間に高電圧パルスを印加する。または、高電圧パルス印加装置２は、パルス幅が２０ｎ秒以上となるように一対の電極３間に高電圧パルスを印加する。または、高電圧パルス印加装置２は、電流密度が、０．１〜１０Ａ／ｃｍ２となるように一対の電極３間に高電圧パルスを印加する。そのため、高電圧パルス印加装置２を作動させると、処理槽１３内に水中放電プラズマが生じる。これにより、除菌水中の過酸化水素濃度を高濃度にできる。 Further, the disinfectant water generation device 1 further includes a high voltage pulse application device 2 that applies a high voltage pulse between the pair of electrodes 3 to generate an underwater discharge plasma. The high voltage pulse application device 2 applies a high voltage pulse between the pair of electrodes 3 so that the pulse electric field is 1 to 20 kV / cm. Alternatively, the high voltage pulse application device 2 applies a high voltage pulse between the pair of electrodes 3 so that the pulse width is 20 nsec or more. Alternatively, the high voltage pulse application device 2 applies a high voltage pulse between the pair of electrodes 3 so that the current density is 0.1 to 10 A / cm 2. Therefore, when the high voltage pulse application device 2 is operated, an underwater discharge plasma is generated in the processing tank 13. As a result, the hydrogen peroxide concentration in the sterilized water can be increased.

また、除菌水生成装置１は、水の温度を維持する保温手段を有する。水の温度を維持することにより、生成した除菌水からの水成分が蒸発し、過酸化水素濃度をより高めることができる。 In addition, the sterilized water generator 1 has a heat retaining means for maintaining the temperature of the water. By maintaining the temperature of the water, the water component from the generated sterilized water evaporates, and the hydrogen peroxide concentration can be further increased.

また、除菌水生成装置１は、水回り機器に組み込まれる。これにより水回り機器を流通する水の過酸化水素濃度を高濃度にできる。 Further, the sterilizing water generation device 1 is incorporated in the water supply device. As a result, the concentration of hydrogen peroxide in the water circulating in the water supply equipment can be increased.

なお、本発明は上記実施形態に限定されるものではなく、本発明の目的を達成できる範囲での変形、改良等は本発明に含まれる。 The present invention is not limited to the above-described embodiment, and modifications, improvements, and the like within the range in which the object of the present invention can be achieved are included in the present invention.

例えば、一対の電極３はアルミニウムからなり、アルマイト皮膜で被覆される例に説明したが、一対の電極３はアルミニウム以外の材料で構成されてもよく、アルマイト皮膜以外の酸化物で被覆されてもよい。 For example, although the pair of electrodes 3 are made of aluminum and coated with an alumite film, the pair of electrodes 3 may be made of a material other than aluminum or may be coated with an oxide other than the alumite film. good.

次に、本発明の実施例について図面を参照しながら説明するが、本発明はこれら実施例に限定されるものではない。 Next, examples of the present invention will be described with reference to the drawings, but the present invention is not limited to these examples.

図２は、実施例１〜７及び比較例１〜５に係る除菌水生成装置１の模式図である。図３は比較例６、７に係る除菌水生成装置１の模式図である。図２、３に示した除菌水生成装置１の各構成は以下の表に記載した通りである。 FIG. 2 is a schematic view of the sterilized water generator 1 according to Examples 1 to 7 and Comparative Examples 1 to 5. FIG. 3 is a schematic view of the sterilized water generator 1 according to Comparative Examples 6 and 7. Each configuration of the sterilized water generator 1 shown in FIGS. 2 and 3 is as described in the table below.

Figure 0006944152
Figure 0006944152

各実施例、比較例における電極の材質、形状は、以下の表２の通りである。 Table 2 below shows the materials and shapes of the electrodes in each of the examples and comparative examples.

Figure 0006944152
Figure 0006944152

図２、３に示されていない実験機器は以下の表３の通りである。 The experimental equipment not shown in FIGS. 2 and 3 is shown in Table 3 below.

Figure 0006944152
Figure 0006944152

＜評価試験＞
［実施例１〜７及び比較例１〜５］
実施例１〜７及び比較例１〜５では、図２に示したパルス電源装置２の電圧（ｋＶ）、パルス幅（ｎ秒）を、高電圧プローブ５、カレントモニター６及びオシロスコープ７によって、パルス電源装置２をＯＮにした時に１回のみ放電する単パルス放電にて測定し、パルス印加条件が表４に記載された条件になるように調整した。 <Evaluation test>
[Examples 1 to 7 and Comparative Examples 1 to 5]
In Examples 1 to 7 and Comparative Examples 1 to 5, the voltage (kV) and pulse width (n seconds) of the pulse power supply device 2 shown in FIG. 2 are pulsed by the high voltage probe 5, the current monitor 6, and the oscilloscope 7. The measurement was performed by a single pulse discharge that discharges only once when the power supply device 2 is turned on, and the pulse application conditions are adjusted so as to be the conditions shown in Table 4.

なお、パルス電界（ｋＶ／ｃｍ）とは、１対の電極間に印加して得られた電圧波形について、最大電圧Ｖｍａｘ（ｋＶ）を、電極間距離で割って得られる値である。また、電流密度（Ａ／ｃｍ２）は、パルス印加時に１対の電極間に、１回のパルス印加で流れた最大電流を電極面積で割って得られる値である。また、図４に示したように、本発明のパルス幅とは、得られた電圧波形について、最大電圧をＶｍａｘとした場合の、昇圧時の１／２Ｖｍａｘから降圧時の１／２Ｖｍａｘに至るまでの時間を指す。 The pulse electric field (kV / cm) is a value obtained by dividing the maximum voltage Vmax (kV) by the distance between the electrodes with respect to the voltage waveform obtained by applying the voltage waveform between the pair of electrodes. The current density (A / cm 2 ) is a value obtained by dividing the maximum current flowing by one pulse application between a pair of electrodes when a pulse is applied by the electrode area. Further, as shown in FIG. 4, the pulse width of the present invention refers to the obtained voltage waveform from 1 / 2Vmax at the time of boosting to 1 / 2Vmax at the time of depressing when the maximum voltage is Vmax. Refers to the time of.

その後、パルス電源装置２の放電設定を、ＯＮにした時に継続的にパルス放電する設定に切り替え、電源をＯＮにし、パルス放電を開始した。その後、パルス電源装置２に設置されたパルス数累積カウンターによって累積パルス数をカウントし、表４に示した累積パルス数になったところでパルス電源装置２の電源をＯＦＦにした。 After that, the discharge setting of the pulse power supply device 2 was switched to a setting of continuously pulse discharging when the power was turned on, the power was turned on, and pulse discharging was started. After that, the cumulative number of pulses was counted by the pulse number accumulation counter installed in the pulse power supply device 2, and when the cumulative pulse number shown in Table 4 was reached, the power supply of the pulse power supply device 2 was turned off.

［比較例６、７］
比較例６、７では、図３に示した除菌水生成装置１’を使用した。除菌水生成装置１’の構成は、処理槽１３を構成する電極の形状が実施例１〜７、比較例１〜５と異なるが、パルス電源装置２や高電圧プローブ５、カレントモニター６及びオシロスコープ７は同じものを使用し、パルス印加条件の調整方法も、実施例１〜７及び比較例１〜５と同じである。 [Comparative Examples 6 and 7]
In Comparative Examples 6 and 7, the sterilized water generator 1'shown in FIG. 3 was used. The configuration of the disinfectant water generator 1'is different from that of Examples 1 to 7 and Comparative Examples 1 to 5 in the shape of the electrodes constituting the treatment tank 13, but the pulse power supply device 2, the high voltage probe 5, the current monitor 6 and the current monitor 6 The same oscilloscope 7 is used, and the method of adjusting the pulse application conditions is the same as in Examples 1 to 7 and Comparative Examples 1 to 5.

「１秒間に何パルス印加するか」を表すパルス間隔は、パルス電源装置２に内蔵された、図示していないパルス間隔設定装置によって、１パルス／秒から、１０００パルス／秒まで変化させた。パルス間隔は、累積パルス数と過酸化水素濃度の関係には大きく変化を与えず、水の温度上昇に関係した。すなわち、パルス頻度を大きくすると水の温度上昇が早く、小さくすると水の放熱とバランスする温度で一定となった。 The pulse interval indicating "how many pulses are applied per second" was changed from 1 pulse / second to 1000 pulses / second by a pulse interval setting device (not shown) built in the pulse power supply device 2. The pulse interval did not significantly change the relationship between the cumulative number of pulses and the hydrogen peroxide concentration, but was related to the temperature rise of water. That is, when the pulse frequency was increased, the temperature of water rose quickly, and when it was decreased, the temperature balanced with the heat dissipation of water became constant.

パルス電源装置２をＯＦＦにした後、パルス電源装置２をＯＮにして水中放電プラズマの生成を継続していた間に生成した過酸化水素濃度を、硫酸チタン法により定量した。
硫酸チタン法とは、過酸化水素と硫酸チタン(ＩＶ)を混合すると、混合液が過酸化水素濃度に応じた濃さで発色することを利用したものである。事前に標準過酸化水素試薬を使用して、吸光度−過酸化水素濃度の検量線を作成した。なお、吸光度計測における測定波長は４１０ｎｍとした。 After turning off the pulse power supply device 2, the concentration of hydrogen peroxide generated while the pulse power supply device 2 was turned on and the generation of the underwater discharge plasma was continued was quantified by the titanium sulfate method.
The titanium sulfate method utilizes the fact that when hydrogen peroxide and titanium (IV) sulfate are mixed, the mixed solution develops a color with a concentration corresponding to the concentration of hydrogen peroxide. A calibration curve of absorbance-hydrogen peroxide concentration was prepared in advance using a standard hydrogen peroxide reagent. The measurement wavelength in the absorbance measurement was 410 nm.

除菌水を生成後、その一部を抜き出して適宜希釈し、硫酸チタン(ＩＶ)溶液と混合した。混合後、混合液の吸光度を吸光光度計で測定し、作製した検量線を利用して過酸化水素濃度を算出した。結果を表４に示した。 After producing sterilized water, a part thereof was extracted, diluted appropriately, and mixed with a titanium (IV) sulfate solution. After mixing, the absorbance of the mixed solution was measured with an absorptiometer, and the hydrogen peroxide concentration was calculated using the prepared calibration curve. The results are shown in Table 4.

Figure 0006944152
Figure 0006944152

＜考察＞
実施例１〜７においては、電極の損耗は認められず放電プラズマの生成を維持できており、放電を継続してパルス数をさらに追加することで、過酸化水素濃度を更に高められると考えられた。 <Discussion>
In Examples 1 to 7, no wear of the electrodes was observed and the generation of the discharge plasma could be maintained, and it is considered that the hydrogen peroxide concentration can be further increased by continuing the discharge and further adding the number of pulses. rice field.

比較例１においては、水中放電プラズマは生成されず、放電状態がアーク放電となったことから、放電を継続しなかった。これは電圧が２０ｋＶ／ｃｍを超えたことによるものと考えられた。
比較例２〜５においては、水中放電プラズマは生成されず、過酸化水素の生成が認められなかった。これは、電流密度が０．１未満であったこと（比較例２）、パルス幅が２０ｎ秒未満となったこと（比較例３）、一対の電極３のいずれもが陽極酸化皮膜で被覆されなかったこと（比較例４、５）によるものと考えられた。
比較例６、７においては、過酸化水素の生成は認められたものの、過酸化水素の生成量が少なかった。これは、陽極４ａが針状の電極であったために放電によって電極が浸食劣化し、次第にパルス放電しなくなったことによるものと考えられた。 In Comparative Example 1, no underwater discharge plasma was generated, and the discharge state was an arc discharge, so the discharge was not continued. It was considered that this was because the voltage exceeded 20 kV / cm.
In Comparative Examples 2 to 5, no underwater discharge plasma was generated, and no hydrogen peroxide was observed. This was because the current density was less than 0.1 (Comparative Example 2), the pulse width was less than 20 nsec (Comparative Example 3), and all of the pair of electrodes 3 were coated with the anodic oxide film. It was considered that this was due to the fact that there was no such thing (Comparative Examples 4 and 5).
In Comparative Examples 6 and 7, although the formation of hydrogen peroxide was observed, the amount of hydrogen peroxide produced was small. It is considered that this is because the anode 4a was a needle-shaped electrode, so that the electrode was eroded and deteriorated by the discharge, and the pulse discharge gradually stopped.

以上から、一対の電極３の陽極３ａ、陰極３ｂの少なくともいずれかが陽極酸化皮膜で被覆された金属平板を備えた除菌水生成装置１において、一対の電極３間にパルス高電圧を印加すると、陽極酸化皮膜表面に無数の水中放電プラズマが継続的に生じることによって、除菌水中の過酸化水素濃度を高濃度にできることが確認された。また、水中放電プラズマは、パルス電界が１〜２０ｋＶ／ｃｍとなる場合や、パルス幅が２０ｎ秒以上となる場合や、電流密度が０．１〜１０Ａ／ｃｍ２となる場合に生じることが確認された。 From the above, when a pulsed high voltage is applied between the pair of electrodes 3 in the disinfectant water generator 1 provided with a metal flat plate in which at least one of the anode 3a and the cathode 3b of the pair of electrodes 3 is coated with an anodic oxide film. It was confirmed that the concentration of hydrogen peroxide in the sterilized water can be increased by continuously generating innumerable underwater discharge plasmas on the surface of the anodic oxide film. It was also confirmed that underwater discharge plasma occurs when the pulse electric field is 1 to 20 kV / cm, the pulse width is 20 nsec or more, and the current density is 0.1 to 10 A / cm 2. Was done.

１ 除菌水生成装置
２ 高電圧パルス印加装置（高電圧パルス印加手段）
３ 一対の電極
８ 水 1 Sterilized water generator 2 High-voltage pulse application device (high-voltage pulse application means)
3 Pair of electrodes 8 Water

Claims (7)

水が介在する一対の電極を備えた除菌水生成装置であって、
前記一対の電極は、少なくとも一方が陽極酸化皮膜で被覆された金属平板であり、
前記陽極酸化皮膜は、アルマイト皮膜であり、
前記一対の電極間に水中放電プラズマを生じさせることで除菌水を生成する除菌水生成装置。 A disinfectant water generator equipped with a pair of electrodes with water intervening.
The pair of electrodes are metal flat plates on which at least one is coated with an anodic oxide film.
The anodized film is an alumite film and is an alumite film.
A sterilized water generator that generates sterilized water by generating an underwater discharge plasma between the pair of electrodes. 前記一対の電極間に高電圧パルスを印加し、水中放電プラズマを生じさせる高電圧パルス印加手段を更に備える請求項１に記載の除菌水生成装置。 The sterilized water generator according to claim 1 , further comprising a high voltage pulse applying means for applying a high voltage pulse between the pair of electrodes to generate an underwater discharge plasma. 前記高電圧パルス印加手段は、パルス電界が１〜２０ｋＶ／ｃｍとなるように前記一対の電極間に高電圧パルスを印加する請求項２に記載の除菌水生成装置。 The disinfectant water generator according to claim 2 , wherein the high voltage pulse applying means applies a high voltage pulse between the pair of electrodes so that the pulse electric field becomes 1 to 20 kV / cm. 前記高電圧パルス印加手段は、パルス幅が２０ｎ秒以上となるように前記一対の電極間に高電圧パルスを印加する請求項２又は３に記載の除菌水生成装置。 The disinfectant water generator according to claim 2 or 3 , wherein the high voltage pulse applying means applies a high voltage pulse between the pair of electrodes so that the pulse width is 20 nsec or more. 前記高電圧パルス印加手段は、電流密度が０．１〜１０Ａ／ｃｍ２となるように前記一対の電極間に高電圧パルスを印加する請求項２〜４のいずれかに記載の除菌水生成装置。 The sterilized water generation according to any one of claims 2 to 4 , wherein the high voltage pulse applying means applies a high voltage pulse between the pair of electrodes so that the current density is 0.1 to 10 A / cm 2. Device. 前記水の温度を維持する保温手段を更に備える請求項１〜５のいずれかに記載の除菌水生成装置。 The sterilized water generator according to any one of claims 1 to 5 , further comprising a heat retaining means for maintaining the temperature of the water. 請求項１〜６のいずれかに記載の除菌水生成装置が組み込まれた水回り機器。 A water supply device incorporating the sterilizing water generator according to any one of claims 1 to 6.
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