JP2014223607A - Treatment method of treatment target liquid based on electrochemical reaction - Google Patents

Treatment method of treatment target liquid based on electrochemical reaction Download PDF

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JP2014223607A
JP2014223607A JP2013245752A JP2013245752A JP2014223607A JP 2014223607 A JP2014223607 A JP 2014223607A JP 2013245752 A JP2013245752 A JP 2013245752A JP 2013245752 A JP2013245752 A JP 2013245752A JP 2014223607 A JP2014223607 A JP 2014223607A
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清 西山
Kiyoshi Nishiyama
清 西山
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Abstract

PROBLEM TO BE SOLVED: To provide a treatment method of a treatment target liquid based on an electrochemical reaction capable not only of realizing an excellent electrochemical reaction but also of improving the durability of a ceramic electrode.SOLUTION: In a treatment method of a treatment target liquid based on an electrochemical reaction using a ceramic electrode 10 including a titanium dioxide powder as a main ingredient and at least a manganese dioxide powder and a binder as additive ingredients and obtained by firing, within an oxidative atmosphere, a molding obtained by mixing and molding these ingredients in a desired shape, subsequently heating the fired molding within a reducing atmosphere, and then immersing the resulting molding within a treatment target liquid designated as a treatment target so as to treat the treatment target liquid on the basis of an electrochemical reaction by impressing a voltage on the ceramic electrode 10, the ceramic electrode 10 is used as both positive and negative electrodes, and a voltage abiding in a state where an AC voltage is coupled with a DC voltage is impressed in-between the positive and negative ceramic electrodes 10.

Description

この発明は、少なくとも二酸化チタン（ＴｉＯ２）粉末と二酸化マンガン（ＭｎＯ２）粉末及びバインダーを原料とし、これらの原料を混合して所要の形状に成型した成型物を、酸化性雰囲気中で焼成した後、還元性雰囲気中で熱処理して得られ、処理の対象となる被処理液に浸漬される電気化学反応による被処理液の処理方法に関する。 In this invention, at least titanium dioxide (TiO 2 ) powder, manganese dioxide (MnO 2 ) powder and a binder are used as raw materials, and a molded product formed by mixing these raw materials into a required shape is fired in an oxidizing atmosphere. Then, it is related with the processing method of the to-be-processed liquid by the electrochemical reaction obtained by heat-processing in a reducing atmosphere, and being immersed in the to-be-processed liquid used as a process target.

従来、ＴｉＯｘ（０＜ｘ＜２）からなる酸化チタン電極をアノード（陽極電極）に用いて被処理水を電気分解することによって、被処理水中の硬度成分（カルシウム、マグネシウムなどの成分）をカソード（陰極電極）側に析出させ、除去する方法が開示されている（特許文献１参照）。
しかしながら、この酸化チタン電極では、アノード電解を行うと電極表面が次第に白くなって電解電流が良好に流れなくなり、長時間の電解処理ができなくなるという課題が生じた。これは、電解処理により、ＴｉＯｘ（０＜ｘ＜２）が次第に酸化されて、電極表面に導電性の悪いＴｉＯ２膜が形成されるからと考えられる。 Conventionally, by using a titanium oxide electrode made of TiOx (0 <x <2) as an anode (anode electrode), the water to be treated is electrolyzed to remove hardness components (calcium, magnesium, etc.) in the water to be treated as a cathode. A method of depositing on the (cathode electrode) side and removing it is disclosed (see Patent Document 1).
However, with this titanium oxide electrode, when the anode electrolysis is performed, the electrode surface gradually becomes white and the electrolytic current does not flow well, and there is a problem that the electrolytic treatment cannot be performed for a long time. This is presumably because TiOx (0 <x <2) is gradually oxidized by the electrolytic treatment, and a TiO 2 film having poor conductivity is formed on the electrode surface.

これに対しては、先に、ＴｉＯ２の粉末とＭｎＯ２の粉末とバインダーとからなる原料を混合し、所要形状に成形し、この成形物を焼成して得られるＴｉＯｘ−ＭｎＯｘ混合電極（セラミックス電極）およびこれを用いた水処理方法（特許文献２参照）が提案されている。
このセラミックス電極によれば、ＴｉＯｘ−ＭｎＯｘの混合電極としたことにより、ミクロセル構造が形成され、ＴｉＯｘがカソード防食されることにより、長時間電解電流を持続させることができ、一定の範囲では耐久性が向上する。 For this, a TiOx-MnOx mixed electrode (ceramics) obtained by mixing raw materials composed of TiO 2 powder, MnO 2 powder and a binder, forming the mixture into a required shape, and firing the molded product. Electrode) and a water treatment method using the same (see Patent Document 2).
According to this ceramic electrode, by using a mixed electrode of TiOx-MnOx, a microcell structure is formed, and TiOx is cathodically protected, so that an electrolytic current can be maintained for a long time, and durability is maintained within a certain range. Will improve.

しかしながら、このセラミックス電極を、例えば陽極電極として一定の電流電圧を印加する状態で固定的に使用する場合、セラミックス電極自体が有する電気抵抗によるものと考えられるが、そのセラミックス電極での部分位置によって、電気化学反応の活性度に勾配が生じてしまう。すなわち、セラミックス電極の電源に接続された部位に近い部分であって、他方の電極に近接する部分においては、そのセラミックス電極の他の部分よりも、電気化学反応が活性化することになる。これによれば、そのセラミックス電極の電源に接続された部位に近い部分のみが、破損の原因となるように消耗・劣化しやすく、セラミックス電極の耐久性をより飛躍的に向上させることができなかった。   However, when this ceramic electrode is used, for example, as a positive electrode in a state where a constant current voltage is applied, it is considered to be due to the electric resistance of the ceramic electrode itself, but depending on the partial position of the ceramic electrode, A gradient occurs in the activity of the electrochemical reaction. That is, the electrochemical reaction is activated in the portion near the portion connected to the power source of the ceramic electrode and in the portion close to the other electrode as compared with the other portion of the ceramic electrode. According to this, only the portion of the ceramic electrode that is close to the portion connected to the power source is likely to be worn out and deteriorated so as to cause damage, and the durability of the ceramic electrode cannot be improved dramatically. It was.

特開２００１−１３７８５８号公報（第１頁）JP 2001-137858 A (first page) 特開２００５−２８１７５８号公報（第１頁など）Japanese Patent Laying-Open No. 2005-281758 (first page, etc.)

電気化学反応による被処理液の処理方法に関して解決しようとする問題点は、セラミックス電極（ＴｉＯｘ−ＭｎＯｘの混合電極）を用いて、より優れた電気化学反応を実現できると共にセラミックス電極の耐久性をより飛躍的に向上できる方法が提案されていないことにある。
そこで本発明の目的は、優れた電気化学反応を実現できると共にセラミックス電極の耐久性を向上できる電気化学反応による被処理液の処理方法を提供することにある。 The problem to be solved regarding the treatment method of the liquid to be treated by the electrochemical reaction is that a ceramic electrode (a mixed electrode of TiOx-MnOx) can be used to realize a more excellent electrochemical reaction and further improve the durability of the ceramic electrode. There is no proposal of a method that can dramatically improve.
Accordingly, an object of the present invention is to provide a method for treating a liquid to be treated by an electrochemical reaction capable of realizing an excellent electrochemical reaction and improving the durability of a ceramic electrode.

本発明は、上記目的を達成するために次の構成を備える。
本発明に係る電気化学反応による被処理液の処理方法の一形態によれば、二酸化チタン粉末を主原料として少なくとも二酸化マンガン粉末及びバインダーを添加原料とし、これらの原料を混合して所要の形状に成型した成型物を、酸化性雰囲気中で焼成した後、還元性雰囲気中で熱処理して得られ、処理の対象となる被処理液に浸漬されるセラミックス電極を用い、該セラミックス電極に電圧を印加することで電気化学反応によって被処理液を処理する電気化学反応による被処理液の処理方法であって、前記セラミックス電極を正負のどちらの電極としても用い、直流電圧に交流電圧をカップリングした状態の電圧を、正負の前記セラミックス電極の間に印加する。 The present invention has the following configuration in order to achieve the above object.
According to an embodiment of the method for treating a liquid to be treated by an electrochemical reaction according to the present invention, titanium dioxide powder is used as a main raw material, and at least manganese dioxide powder and a binder are used as additive raw materials. These raw materials are mixed into a required shape. The molded product is fired in an oxidizing atmosphere and then heat-treated in a reducing atmosphere. A ceramic electrode immersed in the liquid to be treated is applied to the ceramic electrode, and voltage is applied to the ceramic electrode. A method for treating a liquid to be treated by an electrochemical reaction in which the liquid to be treated is treated by an electrochemical reaction, wherein the ceramic electrode is used as either a positive or negative electrode and an AC voltage is coupled to a DC voltage. Is applied between the positive and negative ceramic electrodes.

また、本発明に係る電気化学反応による被処理液の処理方法の一形態によれば、前記直流電圧に交流電圧をカップリングした状態の電圧が、正負の前記セラミックス電極について整流器を並列に接続すると共にコンデンサを直列に接続することで構成される回路によって、一つの交流電源から得られるものであることを特徴とすることができる。   Moreover, according to one form of the processing method of the to-be-processed liquid by the electrochemical reaction which concerns on this invention, the voltage of the state which couple | bonded the alternating voltage with the said DC voltage connects a rectifier in parallel about the said ceramic electrode positive / negative In addition, it can be obtained from a single AC power supply by a circuit configured by connecting capacitors in series.

また、本発明に係る電気化学反応による被処理液の処理方法の一形態によれば、正極の前記セラミックス電極に二酸化マンガンのメッキがなされ、陰極の前記セラミックス電極に亜酸化銅のメッキがなされていることを特徴とすることができる。   Further, according to one embodiment of the method for treating a liquid to be treated by an electrochemical reaction according to the present invention, manganese dioxide is plated on the ceramic electrode of the positive electrode, and cuprous oxide is plated on the ceramic electrode of the cathode. It can be characterized by being.

また、本発明に係る電気化学反応による被処理液の処理方法の一形態によれば、正極の前記セラミックス電極になされた二酸化マンガンのメッキや、陰極の前記セラミックス電極になされた亜酸化銅のメッキが、直流電圧に交流電圧をカップリングした状態の電圧をメッキ溶液に浸漬された前記セラミックス電極に印加することでなされていることを特徴とすることができる。   Further, according to one embodiment of the method for treating a liquid to be treated by an electrochemical reaction according to the present invention, manganese dioxide plating made on the ceramic electrode of the positive electrode or cuprous oxide plating made on the ceramic electrode of the cathode However, it can be characterized by applying a voltage obtained by coupling an AC voltage to a DC voltage to the ceramic electrode immersed in the plating solution.

また、本発明に係る電気化学反応による被処理液の処理方法の一形態によれば、正負の前記セラミックス電極にかかる直流電圧の極性を反対にすることで、陰極の前記セラミックス電極に付いたスケールを前記亜酸化銅のメッキと共に落とすことを特徴とすることができる。   Further, according to one aspect of the method for treating a liquid to be treated by an electrochemical reaction according to the present invention, the scale attached to the ceramic electrode of the cathode is reversed by reversing the polarity of the DC voltage applied to the positive and negative ceramic electrodes. Is removed together with the cuprous oxide plating.

本発明に係る電気化学反応による被処理液の処理方法によれば、優れた電気化学反応を実現できると共にセラミックス電極の耐久性を向上できるという特別有利な効果を奏する。   According to the method for treating a liquid to be treated by an electrochemical reaction according to the present invention, an excellent electrochemical reaction can be realized and the durability of the ceramic electrode can be improved.

本発明に係る電気化学反応による被処理液の処理方法の形態例を説明する断面図である。It is sectional drawing explaining the example of the form of the processing method of the to-be-processed liquid by the electrochemical reaction based on this invention. 本発明に係る電気化学反応による被処理液の処理方法の他の形態例を説明する斜視図である。It is a perspective view explaining the other example of a processing method of the to-be-processed liquid by the electrochemical reaction which concerns on this invention. 本発明に係る電気化学反応による被処理液の処理方法に用いる電源回路の形態例を説明する回路図である。It is a circuit diagram explaining the example of the form of the power supply circuit used for the processing method of the to-be-processed liquid by the electrochemical reaction which concerns on this invention.

以下、本発明に係る電気化学反応による被処理液の処理方法の形態例を添付図面（図１及び２）に基づいて詳細に説明する。
電気化学反応による被処理液の処理方法は、少なくとも二酸化チタン（ＴｉＯ２）粉末と二酸化マンガン（ＭｎＯ２）粉末及びバインダーを原料とし、これらの原料を混合して所要の形状に成型した成型物を、酸化性雰囲気中で焼成した後、還元性雰囲気中で熱処理して得られ、処理の対象となる被処理液３１に浸漬されるセラミックス電極１０を用い、そのセラミックス電極に電圧を印加することで被処理液を処理するものである。 Hereinafter, an example of a method for treating a liquid to be treated by an electrochemical reaction according to the present invention will be described in detail with reference to the accompanying drawings (FIGS. 1 and 2).
The processing method of the liquid to be processed by electrochemical reaction is a method of using at least titanium dioxide (TiO 2 ) powder, manganese dioxide (MnO 2 ) powder and a binder as raw materials, and mixing these raw materials into a desired shape. By applying a voltage to the ceramic electrode, using the ceramic electrode 10 obtained by firing in an oxidizing atmosphere and then heat-treating in a reducing atmosphere and immersed in the liquid 31 to be processed. The liquid to be processed is processed.

そして、本発明によれば、セラミックス電極１０、１０を正負のどちらの電極としても用いるように二つ用い、直流電圧に交流電圧をカップリングした電圧を、その二つのセラミックス電極１０、１０の間に印加することを特徴とする。
図１及び２に示すように、本発明にかかる処理方法を実現する装置としては、正負のセラミックス電極１０、１０が、直流電圧に交流電圧をカップリングした電圧を印加できる電源装置２０に配線１１を介して接続されて設けられている。また、正負のセラミックス電極１０、１０が、絶縁体１２によって配線１１の各電極への接合部が被覆されて設けられ、液槽３０に貯留された被処理液３１に浸漬されように設けられている。なお、絶縁体１２としては、例えばエポキシ樹脂を用いて構成することができる。 According to the present invention, two ceramic electrodes 10 and 10 are used as both positive and negative electrodes, and a voltage obtained by coupling an AC voltage to a DC voltage is used between the two ceramic electrodes 10 and 10. It is characterized by applying to.
As shown in FIGS. 1 and 2, as an apparatus for realizing the processing method according to the present invention, the positive and negative ceramic electrodes 10, 10 are connected to a power supply apparatus 20 that can apply a voltage obtained by coupling an AC voltage to a DC voltage. It is provided via a connection. Further, the positive and negative ceramic electrodes 10 and 10 are provided so that the joints to the respective electrodes of the wiring 11 are covered with the insulator 12 and are provided so as to be immersed in the liquid 31 to be treated stored in the liquid tank 30. Yes. The insulator 12 can be configured using, for example, an epoxy resin.

なお、従来は、同一素材の電極を正負の両方に用いること自体が通常は行われていない。これは、電極素材の性質によって電極電位の特性が異なり、使用される極性によっては溶出・消耗するなど、通常はどちらか一方の電極とすることが、効果的であることによる。これに対して、本発明のセラミックス電極１０は、正極電極として用いられるだけでなく、負極電極としても溶出・消耗することがなく、どちらの電極としても好適に利用できるものである。また、このセラミックス電極１０は、安価な材料によって製造でき、使用による消耗・劣化も少なく、製造コストとランニングコストを大幅に低減できるものである。   Conventionally, the use of electrodes of the same material for both positive and negative is not usually performed. This is due to the fact that it is effective to use either one of the electrodes, such as the characteristics of the electrode potential differ depending on the properties of the electrode material, and elution and consumption depending on the polarity used. On the other hand, the ceramic electrode 10 of the present invention is not only used as a positive electrode, but also does not elute and wear out as a negative electrode, and can be suitably used as either electrode. Further, the ceramic electrode 10 can be manufactured from an inexpensive material, is less consumed and deteriorated by use, and can greatly reduce the manufacturing cost and the running cost.

また、直流電圧に交流電圧をカップリングする場合に、直流電圧による電圧の大きさが、交流電圧の変動する電圧の最大振れ幅の１／２よりも大きくするとよい。これによれば、正負のセラミックス電極１０、１０としてのそれぞれの電極の極性は変化しないため、電気化学反応を安定的且つ効果的に行うことに支障はない。つまり、両電極に負荷される電圧の大きさは変動するが、一方の電極と他方の電極との正負の関係（極性）は維持されるため、その両電極における電気化学反応は定性的に維持されることになる。   In addition, when the AC voltage is coupled to the DC voltage, the magnitude of the voltage due to the DC voltage is preferably larger than ½ of the maximum fluctuation width of the voltage where the AC voltage varies. According to this, since the polarity of each electrode as the positive and negative ceramic electrodes 10 and 10 does not change, there is no problem in performing the electrochemical reaction stably and effectively. In other words, the magnitude of the voltage applied to both electrodes varies, but the positive / negative relationship (polarity) between one electrode and the other is maintained, so the electrochemical reaction at both electrodes is maintained qualitatively. Will be.

このように、セラミックス電極１０、１０を用い、直流電圧に交流電圧をカップリングした電圧を印加すると、直流電圧のみを印加する場合に比べて、その寿命を１０倍程度も延長させることができた。
つまり、本発明者は、直流電圧に交流電圧をカップリングして印加する電圧の大きさを常態的に変化させることで、よりセラミックス電極１０を全面的に利用することができ、電気化学反応の効率を向上できると共にその寿命が長くなることを見出した。
従来の方法によって使用した場合のセラミックス電極１０の寿命が半年であるとすると、本発明の方法によって使用した場合のセラミックス電極１０の寿命は５年以上となっている。 Thus, when the ceramic electrodes 10 and 10 were used and a voltage obtained by coupling an AC voltage to a DC voltage was applied, the life could be extended by about 10 times compared to the case where only the DC voltage was applied. .
That is, the present inventor can utilize the ceramic electrode 10 more fully by coupling the AC voltage to the DC voltage and changing the magnitude of the applied voltage in a normal manner. It has been found that the efficiency can be improved and the lifetime is extended.
If the lifetime of the ceramic electrode 10 when used by the conventional method is half a year, the lifetime of the ceramic electrode 10 when used by the method of the present invention is 5 years or more.

これに対して、従来のように一定の直流電圧を印加する状態で固定的に使用すると、セラミックス電極の電源に接続された部位に近い部分のみが劣化し、セラミックス電極が損傷しやすかった。本発明によれば、この問題を、極めて簡易的且つ合理的に解消することができたことになる。   On the other hand, when fixedly used in a state where a constant DC voltage is applied as in the prior art, only the portion near the portion connected to the power source of the ceramic electrode is deteriorated, and the ceramic electrode is easily damaged. According to the present invention, this problem can be solved extremely simply and rationally.

これらの本願発明の作用効果について、従来の方法と比較してさらに説明する。
先ず、従来のセラミックス電極（ＴｉＯｘ−ＭｎＯｘの混合電極）に直流電圧のみを印加した場合は、電極の電源が最初に被処理液中に放出する場所から電極が破損してしまう。これは、金属酸化物電極であるセラミックス電極（ＴｉＯｘ−ＭｎＯｘの混合電極）は、電流の流れ出た表面のみ酸化被膜が生成され、他の所は均一な酸化被膜が生成されないため、酸化被膜が生成されない場所から破損してしまうことによる。
このように従来のセラミックス電極に直流電圧のみを印加した場合に、その一部分のみだけで電気化学反応が活性化していることは、酸素ガスや水素ガスが、セラミックス電極のある一部分から大きな泡となって発生することから確認できる。 These effects of the present invention will be further described in comparison with the conventional method.
First, when only a DC voltage is applied to a conventional ceramic electrode (a mixed electrode of TiOx-MnOx), the electrode is damaged from the place where the power source of the electrode is first discharged into the liquid to be treated. This is because the ceramic electrode (TiOx-MnOx mixed electrode), which is a metal oxide electrode, generates an oxide film only on the surface from which current flows, and a uniform oxide film is not generated elsewhere. By damaging from a place that is not.
In this way, when only a direct current voltage is applied to a conventional ceramic electrode, the electrochemical reaction is activated by only a part of it, and oxygen gas or hydrogen gas becomes a large bubble from a part of the ceramic electrode. Can be confirmed.

これに対して、本発明の被処理液の処理方法によれば、直流電圧に交流電圧をカップリングすることで、ＭｎＯ２被膜が均一に且つ均等厚で生成されることで、アノード電極やカソード電極の全体で電気化学反応が行われる。
すなわち、セラミックス電極（ＴｉＯｘ−ＭｎＯｘの混合電極）が、水溶液中で均一な反応電極として作用するため、電極反応（電気化学反応）が均一に行われる。このように 電極の全面を適切に活用できるため、電気化学反応とその反応に伴う触媒反応を効率的に行うことができる。
このことは、セラミックス電極の全面について、泡が生じていることで確認することができる。 On the other hand, according to the treatment method of the liquid to be treated according to the present invention, the MnO 2 coating is uniformly and uniformly formed by coupling the AC voltage to the DC voltage, so that the anode electrode and the cathode An electrochemical reaction takes place throughout the electrode.
That is, since the ceramic electrode (a mixed electrode of TiOx-MnOx) acts as a uniform reaction electrode in an aqueous solution, the electrode reaction (electrochemical reaction) is performed uniformly. As described above, since the entire surface of the electrode can be appropriately used, an electrochemical reaction and a catalytic reaction accompanying the reaction can be efficiently performed.
This can be confirmed by the occurrence of bubbles on the entire surface of the ceramic electrode.

また、本発明の被処理液の処理方法によれば、金属酸化物電極であるセラミックス電極に電圧が印加されるため、電気化学反応と触媒反応の両方が相乗効果的に作用する。これによれば、例えば、低濃度の塩素イオン溶液：２０〜３０ｍｇＣｌ−／ｌ（２０〜３０ｐｐｍ）においても、ＣｌＯ−（次亜塩素酸イオン）が２〜３ｍｇＣｌＯ−／ｌ（２〜３ｐｐｍ）生成できる。 Moreover, according to the processing method of the to-be-processed liquid of this invention, since a voltage is applied to the ceramic electrode which is a metal oxide electrode, both an electrochemical reaction and a catalytic reaction act synergistically. According to this, for example, even in a low concentration chlorine ion solution: 20 to 30 mg Cl − / l (20 to 30 ppm), ClO − (hypochlorite ion) is generated to 2 to 3 mg ClO − / l (2 to 3 ppm). it can.

さらに、本発明の被処理液の処理方法によれば、電極表面に酸化被膜が生成されているため、正負の電圧を反転しても破損することがない。これによれば、例えば、ＣａＣＯ３、ＭｇＣＯ３、ＳｉＯ２などがカソード電極（陰極電極）に析出すると電流が流れにくくなることを、電圧の極性を反転することで析出物を下に落とし、電流を初期値と同じにして流し続けることができる。 Furthermore, according to the processing method of the to-be-processed liquid of this invention, since the oxide film is produced | generated on the electrode surface, even if it reverses a positive / negative voltage, it will not be damaged. According to this, for example, when CaCO 3 , MgCO 3 , SiO 2, etc. are deposited on the cathode electrode (cathode electrode), the current hardly flows, and the precipitate is dropped down by reversing the polarity of the voltage, Can be kept the same as the initial value.

また、本発明の被処理液の処理方法によれば、正極にＭｎＯ２被膜が生成されると、酸素過電圧が高くなって酸素が発生しなくなり、負極の水素の泡が交流電圧を印加することで非常に細かくなり、ＣａＣＯ３、ＭｇＣＯ３、ＳｉＯ２や他の金属水酸化物が浮上し大きなフロックが生成すると凝集沈殿して下に溜まってくる。 Further, according to the treatment method of the liquid to be treated of the present invention, when the MnO 2 coating is formed on the positive electrode, the oxygen overvoltage becomes high and oxygen is not generated, and the hydrogen bubbles on the negative electrode apply an alternating voltage. When CaCO 3 , MgCO 3 , SiO 2 and other metal hydroxides float and large flocs are formed, they are agglomerated and settled.

次に、本発明の他の形態例について、その構成と効果について説明する。
本発明の形態例によれば、セラミックス電極１０にかかる直流電圧を、所要の時間的間隔で正負逆転させることができる。これによれば、セラミックス電極１０の極性が反転するため、そのセラミックス電極１０の表面に析出した物質を分離・落下させて、その表面を再生させることができる。再生されたセラミックス電極１０は、電気化学反応及び触媒作用の効果を高めることができ、被処理液の処理を効率良く行うことができる。 Next, the configuration and effects of another embodiment of the present invention will be described.
According to the embodiment of the present invention, the DC voltage applied to the ceramic electrode 10 can be reversed positive and negative at a required time interval. According to this, since the polarity of the ceramic electrode 10 is reversed, the substance deposited on the surface of the ceramic electrode 10 can be separated and dropped to regenerate the surface. The regenerated ceramic electrode 10 can enhance the effect of electrochemical reaction and catalysis, and can efficiently treat the liquid to be treated.

また、図２に示すように、本発明の形態例によれば、正負のセラミックス電極を、複数隣り合うように配設することができる。
これによれば、両端に配されたセラミックス電極を除き、セラミックス電極の両面を有効に利用できるため、被処理液の処理効率を向上させることができる。 As shown in FIG. 2, according to the embodiment of the present invention, a plurality of positive and negative ceramic electrodes can be arranged adjacent to each other.
According to this, since both surfaces of the ceramic electrode can be effectively used except for the ceramic electrodes arranged at both ends, the processing efficiency of the liquid to be processed can be improved.

また、本発明の形態例によれば、バインダーとしての材料をホウケイ酸ガラスとすることができる。このホウケイ酸ガラスは、安価な材料であり、適切にセラミックス電極１０を焼成・製造することができる。   Moreover, according to the embodiment of the present invention, the material as the binder can be borosilicate glass. This borosilicate glass is an inexpensive material, and the ceramic electrode 10 can be appropriately fired and manufactured.

次に、本発明によって有効になされる電気化学反応の事例について説明する。
本発明によれば、被処理液中に含まれる金属イオン（カルシウムイオン、マグネシウムイオン、鉄イオン、銅イオン、ニッケルイオン、マンガンイオン、亜鉛イオン等）を、カソード（負極電極）に水酸化物等として析出・除去できる。なお、水中に含まれるシリカ成分（ＳｉＯ２成分）も、本発明によれば、析出成分（炭酸カルシウム、炭酸マグネシウム）中に抱き込まれるようにして除去できる。また、塩素イオンも除去できる。
さらに、本発明によれば、水溶性の有機物など、被処理液に溶け込んだ有機物成分の分解・除去もできる。
また、本発明の被処理水の電解処理によって、水中にＮａＣｌＯを生成することもできる。このＮａＣｌＯは殺菌効果があり、微生物の繁殖を防止できる。
これによれば、天然水の硬度成分及び有機成分の除去や、クーリングタワーなどの熱交換器における冷却水中のスケール成分の除去及び殺菌効果など、被処理水の浄化を効率よく長時間連続的に行うことができる。 Next, an example of an electrochemical reaction effectively performed by the present invention will be described.
According to the present invention, metal ions (calcium ions, magnesium ions, iron ions, copper ions, nickel ions, manganese ions, zinc ions, etc.) contained in the liquid to be treated are used as hydroxides on the cathode (negative electrode). Can be deposited and removed. Incidentally, the silica component (SiO 2 component) contained in the water, according to the invention, deposition component (calcium carbonate, magnesium carbonate) can be to removed to be embraced in the. In addition, chlorine ions can be removed.
Furthermore, according to the present invention, it is possible to decompose and remove organic components dissolved in the liquid to be treated, such as water-soluble organic matters.
Moreover, NaClO can also be produced | generated in water by the electrolytic treatment of the to-be-processed water of this invention. This NaClO has a bactericidal effect and can prevent the growth of microorganisms.
According to this, purification of water to be treated is performed efficiently and continuously for a long time, such as removal of hardness components and organic components of natural water, removal of scale components in cooling water in a heat exchanger such as a cooling tower, and sterilization effect. be able to.

次に、正極のセラミックス電極１０に二酸化マンガン（ＭｎＯ２）のメッキがなされ、陰極のセラミックス電極１０に亜酸化銅（Ｃｕ２Ｏ）のメッキがなされている電気化学反応による被処理液の処理方法について説明する。なお、これらの電極のベースとなるセラミックス電極１０は、以上に説明したものと同様に設けられたものであって、二酸化チタン粉末を主原料として少なくとも二酸化マンガン粉末及びバインダーを添加原料とし、これらの原料を混合して所要の形状に成型した成型物を、酸化性雰囲気中で焼成した後、還元性雰囲気中で熱処理して得られる。 Next, a method for treating a liquid to be treated by an electrochemical reaction in which manganese dioxide (MnO 2 ) is plated on the positive electrode ceramic electrode 10 and cuprous oxide (Cu 2 O) is plated on the negative electrode ceramic electrode 10 Will be described. The ceramic electrode 10 serving as the base of these electrodes is provided in the same manner as described above, and the titanium dioxide powder is the main raw material and at least the manganese dioxide powder and the binder are the additional raw materials. A molded product formed by mixing raw materials into a desired shape is fired in an oxidizing atmosphere and then heat-treated in a reducing atmosphere.

この正極のセラミックス電極１０に二酸化マンガンのメッキがなされ、陰極のセラミックス電極１０に亜酸化銅のメッキがなされた電気化学反応装置において、前述の形態例と同様に、直流電圧に交流電圧をカップリングした状態の電圧を、正負のセラミックス電極１０、１０の間に印加した際の効果について、以下に、食塩（ＮａＣｌ）の水溶液から殺菌効果のある次亜塩素酸イオン（ＣｌＯ−）を生成させる電気化学反応を一例として、試験結果を説明する。 In the electrochemical reaction apparatus in which manganese dioxide is plated on the ceramic electrode 10 of the positive electrode and cuprous oxide is plated on the ceramic electrode 10 of the cathode, the AC voltage is coupled to the DC voltage as in the above-described embodiment. Regarding the effect when the voltage in the state is applied between the positive and negative ceramic electrodes 10, 10, electricity for generating hypochlorite ions (ClO − ) having a bactericidal effect from an aqueous solution of sodium chloride (NaCl) will be described below. The test results will be described using a chemical reaction as an example.

比較試験を行うため、電極の試料として、次の３点（イ）、（ロ）、（ハ）を用意した。
（イ）二酸化マンガンのメッキがなされた正極のセラミックス電極と、亜酸化銅のメッキがなされた陰極のセラミックス電極とから構成されるメッキ電極の試料。
（ロ）正極と陰極とがどちらもセラミックス電極から構成される対照試料１。
（ハ）セラミックス電極の正極と、チタン板の陰極とから構成される対照試料２。
試験条件は、１０リットルの水に食塩を添加して１００ｍｇＣｌ−／ｌの水溶液とし、その水溶液に電極を投入して、直流電圧に交流電圧をカップリングした状態の電圧（２５Ｖの一つの交流電源から図３に示す回路を介した電圧）を印加した。３点について、同一の条件下で、同時に試験を行った。
２３．５時間が経過した時点での、上記水溶液の１０リットルに生じた次亜塩素酸イオンの濃度であって、電流１アンペア（Ａ）当たりであって１時間（Ｈ）当たりに換算した次亜塩素酸イオンの濃度は、以下のようになった。
（イ）２５．６ｍｇＣｌＯ／Ａ・Ｈ
（ロ）１２．０ｍｇＣｌＯ／Ａ・Ｈ
（ハ）１１．６ｍｇＣｌＯ／Ａ・Ｈ
この試験結果によれば、メッキ電極の試料（イ）が、対照試料１（ロ）及び対照試料２（ハ）に比較して、倍以上の効率で、次亜塩素酸イオンを生成できることが分かった。 In order to perform a comparative test, the following three points (A), (B), and (C) were prepared as electrode samples.
(A) A sample of a plated electrode composed of a positive ceramic electrode plated with manganese dioxide and a negative ceramic electrode plated with cuprous oxide.
(B) A control sample 1 in which the positive electrode and the cathode are both ceramic electrodes.
(C) A control sample 2 composed of a positive electrode of a ceramic electrode and a negative electrode of a titanium plate.
The test condition is that a salt solution is added to 10 liters of water to make an aqueous solution of 100 mg Cl − / l, an electrode is inserted into the aqueous solution, and a voltage in which AC voltage is coupled to DC voltage (one AC power source of 25 V). To the voltage via the circuit shown in FIG. Three points were tested simultaneously under the same conditions.
The concentration of hypochlorite ions generated in 10 liters of the above aqueous solution at the time when 23.5 hours have elapsed, and is converted into current per ampere (A) and converted per hour (H). The concentration of chlorite ion was as follows.
(I) 25.6 mg ClO / A · H
(B) 12.0 mg ClO / A · H
(C) 11.6 mg ClO / A · H
According to this test result, it can be seen that the sample (b) of the plating electrode can generate hypochlorite ions with more than double the efficiency of the control sample 1 (b) and the control sample 2 (c). It was.

このように、次亜塩素酸イオンの生成を効率良く行うことができる要因、換言すれば電気化学反応が効率良く行われる要因は、半導体（二酸化マンガンのメッキがなされた正極がＮ型、亜酸化銅のメッキがなされた陰極がＰ型）として機能することによる効果、正負の両方の電極による電極電位が高いことによる効果であると考えられる。
また、各電極に上記のようにメッキが施されることで、電極のさらなる長寿命化を図ることができる。 Thus, the factor that can efficiently generate hypochlorite ions, in other words, the factor that the electrochemical reaction is efficiently performed, is that the semiconductor (the positive electrode plated with manganese dioxide is N-type, suboxide This is considered to be due to the fact that the cathode plated with copper functions as P-type) and the effect that the electrode potential by both positive and negative electrodes is high.
In addition, since the electrodes are plated as described above, the life of the electrodes can be further extended.

また、正極のセラミックス電極１０になされた二酸化マンガンのメッキや、陰極のセラミックス電極１０になされた亜酸化銅のメッキが、直流電圧に交流電圧をカップリングした状態の電圧をメッキ溶液に浸漬されたセラミックス電極１０に印加することでなされている。これによれば、通常の直流電流によるメッキ方法に比較して、特別な温度条件や電源制御を必要とせず、常温で均一且つ簡単に行うことができる。なお、二酸化マンガンのメッキをセラミックス電極１０に施すには、メッキ溶液として、硫酸マンガン溶液などを用いればよい。また、亜酸化銅のメッキをセラミックス電極１０に施すには、メッキ溶液として、硫酸銅溶液などを用いればよい。また、このメッキ方法の対象は、セラミックス電極１０に限らす、他の素材にメッキをする場合にも適用できる。例えば、チタン板に二酸化マンガンのメッキを好適に行うことができる。   Further, the manganese dioxide plating made on the positive electrode ceramic electrode 10 and the cuprous oxide plating made on the negative electrode ceramic electrode 10 were immersed in a plating solution with a voltage in a state where an AC voltage was coupled to a DC voltage. This is done by applying to the ceramic electrode 10. According to this, compared with the plating method by a normal direct current, special temperature conditions and power supply control are not required, and it can perform uniformly and easily at normal temperature. In order to apply manganese dioxide plating to the ceramic electrode 10, a manganese sulfate solution or the like may be used as a plating solution. In order to apply cuprous oxide plating to the ceramic electrode 10, a copper sulfate solution or the like may be used as a plating solution. Moreover, the object of this plating method is not limited to the ceramic electrode 10, but can be applied to the case of plating on other materials. For example, a titanium plate can be suitably plated with manganese dioxide.

また、直流電圧に交流電圧をカップリングした状態の電圧が、図３に示すように、正負のセラミックス電極１０、１０について整流器５１を並列に接続すると共にコンデンサを５２直列に接続することで構成される回路によって、一つの交流電源５０から得られるものである。これによれば、簡易な構成でありながら、本発明において好適に利用できる直流電圧に交流電圧をカップリングした状態の電圧を、好適に得ることができる。この正負のセラミックス電極１０、１０に印加される電圧によれば、前述したように、電極の全面を適切に活用できるため、電気化学反応とその反応に伴う触媒反応を効率的に行うことができる。なお、コンデンサ５２を接続していることで、電流を安定化できると共に、その静電容量以上に電流が流れることを防止できる。すなわち、コンデンサ５２によって最大電流を規制でき、電気伝導率が高い水溶液などの被処理液についても過剰な電流を流すことなく、電気化学反応を行うことができる。   Further, as shown in FIG. 3, the voltage in a state where the AC voltage is coupled to the DC voltage is configured by connecting the rectifier 51 in parallel and connecting the capacitors 52 in series with respect to the positive and negative ceramic electrodes 10 and 10. It is obtained from one AC power supply 50 by a circuit. According to this, although it is a simple structure, the voltage of the state which couple | bonded AC voltage with the DC voltage which can be utilized suitably in this invention can be obtained suitably. According to the voltage applied to the positive and negative ceramic electrodes 10 and 10, as described above, since the entire surface of the electrode can be appropriately utilized, the electrochemical reaction and the catalytic reaction accompanying the reaction can be efficiently performed. . In addition, by connecting the capacitor 52, the current can be stabilized and the current can be prevented from flowing beyond its electrostatic capacity. That is, the maximum current can be regulated by the capacitor 52, and an electrochemical reaction can be performed without flowing an excessive current even for a liquid to be treated such as an aqueous solution having high electrical conductivity.

また、正負のセラミックス電極１０にかかる直流電圧の極性を反対にすることで、陰極のセラミックス電極１０に付いたスケールを亜酸化銅のメッキと共に落とすことができる。これによれば、亜酸化銅のメッキがなされたセラミックス電極１０を陽極とすることで、亜酸化銅のメッキが溶解して消失することに伴って、セラミックス電極１０を完全に浄化することができる。再度利用するには、前述したようなメッキ方法で再度メッキをセラミックス電極１０に施せばよい。これによれば、定期的に管理することで、電気化学反応の効率を最良化することができる。   Further, by reversing the polarity of the DC voltage applied to the positive and negative ceramic electrodes 10, the scale attached to the cathode ceramic electrode 10 can be dropped together with the cuprous oxide plating. According to this, by using the ceramic electrode 10 plated with cuprous oxide as an anode, the ceramic electrode 10 can be completely purified as the cuprous oxide plating dissolves and disappears. . In order to use again, the ceramic electrode 10 may be plated again by the plating method as described above. According to this, the efficiency of an electrochemical reaction can be optimized by managing periodically.

以上、本発明につき好適な形態例を挙げて種々説明してきたが、本発明はこの形態例に限定されるものではなく、発明の精神を逸脱しない範囲内で多くの改変を施し得るのは勿論のことである。   As described above, the present invention has been described in various ways with preferred embodiments. However, the present invention is not limited to these embodiments, and many modifications can be made without departing from the spirit of the invention. That is.

１０ セラミックス電極
１１ 配線
１２ 絶縁体
２０ 電源装置
３０ 液槽
３１ 被処理液
５０ 一つの交流電源
５１ 整流器
５２ コンデンサ DESCRIPTION OF SYMBOLS 10 Ceramic electrode 11 Wiring 12 Insulator 20 Power supply device 30 Liquid tank 31 Liquid to be processed 50 One alternating current power supply 51 Rectifier 52 Capacitor

Claims (5)

二酸化チタン粉末を主原料として少なくとも二酸化マンガン粉末及びバインダーを添加原料とし、これらの原料を混合して所要の形状に成型した成型物を、酸化性雰囲気中で焼成した後、還元性雰囲気中で熱処理して得られ、処理の対象となる被処理液に浸漬されるセラミックス電極を用い、該セラミックス電極に電圧を印加することで電気化学反応によって被処理液を処理する電気化学反応による被処理液の処理方法であって、
前記セラミックス電極を正負のどちらの電極としても用い、直流電圧に交流電圧をカップリングした状態の電圧を、正負の前記セラミックス電極の間に印加することを特徴とする電気化学反応による被処理液の処理方法。 Titanium dioxide powder is the main raw material, and at least manganese dioxide powder and binder are added raw materials. After mixing these raw materials into a required shape, the molded product is baked in an oxidizing atmosphere and then heat-treated in a reducing atmosphere. Of the liquid to be processed by the electrochemical reaction obtained by using the ceramic electrode immersed in the liquid to be processed and applying a voltage to the ceramic electrode to treat the liquid to be processed by the electrochemical reaction. A processing method,
The ceramic electrode is used as either a positive or negative electrode, and a voltage in a state in which an AC voltage is coupled to a DC voltage is applied between the positive and negative ceramic electrodes. Processing method. 前記直流電圧に交流電圧をカップリングした状態の電圧が、正負の前記セラミックス電極について整流器を並列に接続すると共にコンデンサを直列に接続することで構成される回路によって、一つの交流電源から得られるものであることを特徴とする請求項１記載の電気化学反応による被処理液の処理方法。   A voltage obtained by coupling an AC voltage to the DC voltage is obtained from one AC power source by a circuit configured by connecting a rectifier in parallel and connecting a capacitor in series with respect to the positive and negative ceramic electrodes. The processing method of the to-be-processed liquid by the electrochemical reaction of Claim 1 characterized by the above-mentioned. 正極の前記セラミックス電極に二酸化マンガンのメッキがなされ、陰極の前記セラミックス電極に亜酸化銅のメッキがなされていることを特徴とする請求項１又は２記載の電気化学反応による被処理液の処理方法。   The method for treating a liquid to be treated by an electrochemical reaction according to claim 1 or 2, wherein the ceramic electrode of the positive electrode is plated with manganese dioxide, and the ceramic electrode of the cathode is plated with cuprous oxide. . 正極の前記セラミックス電極になされた二酸化マンガンのメッキや、陰極の前記セラミックス電極になされた亜酸化銅のメッキが、直流電圧に交流電圧をカップリングした状態の電圧をメッキ溶液に浸漬された前記セラミックス電極に印加することでなされていることを特徴とする請求項３記載の電気化学反応による被処理液の処理方法。   The ceramics in which the manganese dioxide plating formed on the ceramic electrode of the positive electrode or the cuprous oxide plating formed on the ceramic electrode of the cathode is immersed in a plating solution with a voltage in a state where an AC voltage is coupled to a DC voltage 4. The method for treating a liquid to be treated by an electrochemical reaction according to claim 3, wherein the treatment liquid is applied to an electrode. 正負の前記セラミックス電極にかかる直流電圧の極性を反対にすることで、陰極の前記セラミックス電極に付いたスケールを前記亜酸化銅のメッキと共に落とすことを特徴とする請求項３又は４に記載の電気化学反応による被処理液の処理方法。   5. The electricity according to claim 3 or 4, wherein the scale attached to the ceramic electrode of the cathode is dropped together with the plating of the cuprous oxide by reversing the polarity of the DC voltage applied to the positive and negative ceramic electrodes. A method for treating a liquid to be treated by chemical reaction.
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