JP2008272744A - Fungistatic apparatus for circulating water - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fungistatic apparatus for circulating water which can solve the problem of adverse effects of chlorine, oxygen, hydrogen or another gas electrochemically evolved from the surface of an electrode in the control of water quality of circulating water on organisms raised in a water tank in a fungistatic apparatus, for circulating water, adapted for compositive control of water quality of circulating water by inhibiting microorganism propagation and formation of a microorganism film (a biofilm or slime) in a circulating water system over a long period of time without the possibility of water contamination, preventing water in the water tank from being rendered turbid or causing bad odor, reducing the washing work of the water tank, and subjecting the water to adsorption, degradation, and denaturation of inorganic salts and an organic matter. <P>SOLUTION: The fungistatic apparatus for circulating water is characterized in that one or more electroconductive base materials disposed on each of both sides of an electroconductive base material, which is allowed to function as an anode, are allowed to function as a cathode, and an assembly of one or more electrode units, which can energize each of the electroconductive base materials, constitutes an electrode part so that the ratio of the sum of the surface area of the plurality of electroconductive base materials, which are allowed to function as the cathode, to the surface area of an electroconductive base material, which is allowed to function as the anode, is more than 1 and less than 3. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a circulating water sterilization apparatus that sterilizes circulating water organisms, controls water quality, and suppresses generation of chlorine, oxygen, hydrogen gas, or the like from an electrode by electrolysis.

Circulating water is water used in the industry, such as tap water, reprocessed water, and cooling water that is guided into equipment if it is seawater, and is used in general households such as bath water and aquarium water. Or water. Furthermore, it means the water in which the same water is circulated and controlled over a certain period.
Moreover, the whole including the circulation water used for this invention and flow paths, such as piping through which the circulation water flows, is called a circulation water system.
Circulating water contains a lot of microorganisms, and it uses the excrement of aquatic organisms as nutrients for breeding. Because of the turbidity of the circulating water and bad odor caused by the growth of microorganisms, purification of the circulating water by a physical means such as a filter or a chemical means such as administration of a chlorinated drug has been required. Furthermore, since microorganisms adhere to the wall surface in contact with the circulating water, the wall surface was washed at the same time when the circulating water was replaced, and a great deal of labor was spent.
In particular, in the case of a breeding aquarium using circulating water, the quality of the water needs to be stably maintained by the organisms being bred, so the water quality is checked. In this operation as well, as with the removal of dirt caused by microorganisms, such as drug administration and circulating water exchange, a great amount of cost and labor were spent.

In order to solve the above problems and maintain the water quality of the circulating water system, conventionally, as disclosed in JP-A-2003-52275, it decomposes nitrogen compounds harmful to living organisms and has bactericidal properties. Microorganisms caused by germicidal chlorine compounds generated by electrolysis of circulating water while generating chlorine chemicals to suppress the growth of microorganisms in the water tank or monitoring pH as disclosed in Japanese Patent Application Laid-Open No. 2003-97 Or restrained breeding.
However, these methods have concerns such as the effects on harmful organisms in the aquarium due to the generation of harmful substances. In the invention disclosed in Japanese Examined Patent Publication No. 63-38440, gas is generated at an electrode connected to a power source to forcibly precipitate calcium carbonate or the like in a short time to improve water quality. However, in this method, if the generated gas is excessive or collected at a certain location, it is dangerous. Moreover, water quality changes such as pH occur due to the generation of a large amount of gas, and there is a concern that the gas may be dissolved in an aqueous solution and adversely affect living organisms.
In order to suppress gas generation from the electrode, Japanese Patent Application Laid-Open No. 2007-7514 discloses that the electrode area ratio of the cathode to the anode is tripled or more. By making the electrode area ratio of the cathode to the anode 3 times or more, the current density at the cathode can be kept low, and the cathode potential can be kept below the gas generation potential. However, increasing the electrode area ratio of the cathode to the anode has a problem of increasing the electrode installation space and the entire apparatus.
JP 2003-52275 A Japanese Patent Laid-Open No. 2003-97 Japanese Examined Patent Publication No. 63-38440 JP 2007-7514 A

  In the circulating water control apparatus, there is no concern about water pollution, and microbial growth and microbial film (biofilm or slime) formation in the circulating water system is suppressed over a long period of time, and the water quality in the aquarium is turbid and bad odor. The water quality of the circulating water can be controlled in a complex manner by reducing these washing operations of the aquarium, and adsorbing, decomposing, and modifying the inorganic salt concentration and organic matter as water quality. Another object of the present invention is to provide a circulating water sterilization apparatus that controls chlorine, oxygen, hydrogen gas, etc. generated from the electrode surface and controls water quality changes such as pH. Another object of the present invention is to prevent the electrode installation space and the entire apparatus from becoming excessively large by setting the area ratio of the cathode to the anode to be greater than 1 and less than 3.

The present invention has an electrode portion formed by laminating a plurality of conductive base materials, energized between the anode and the cathode made of the conductive base material, and the anode by direct / indirect contact on the anode surface by an electrochemical reaction. A circulating water sterilization apparatus that sterilizes microorganisms existing in the vicinity of a surface and treats circulating water, and has at least one conductive element disposed on both sides of one conductive base material that acts as an anode. A circulating water control apparatus characterized in that an electrode unit is formed by one or more aggregates of electrode units that act as a cathode as a base material, and the electrode unit serves as an anode in the electrode unit. At least one or more conductive substrates arranged on both sides of one conductive substrate act as a cathode, and act as the cathode for the surface area of one conductive substrate that acts as the anode. Duplicate The circulating water-control bacterium according to claim 1, wherein each conductive substrate can be selectively energized so that the ratio of the sum of the surface areas of the conductive substrates exceeds 1 and is less than 3. 3. The apparatus according to claim 1, wherein the device is a second gist and the conductive base material that acts as at least the cathode in the electrode unit has a plurality of openings whose opening diameter is larger than the plate thickness. In the electrode unit, in the electrode unit, a part or all of a surface of the anode is at least platinum, ruthenium, rhodium, palladium, iridium, titanium, zirconium, niobium, tantalum, manganese, A conductive substrate comprising a single metal oxide selected from oxides of cobalt, tin and antimony or one selected from mixed metal oxides or composite metal oxides; and 2. The cathode according to claim 1, wherein a part or all of a surface of the cathode is a conductive substrate made of at least one of copper, zinc, tin, lead, nickel, titanium, titanium alloy, and stainless steel. The fourth aspect of the circulating water control apparatus according to any one of claims 1 to 3, wherein, in the plurality of conductive base materials constituting the electrode portion, the conductive base material that acts as an anode is changed at regular intervals and selectively energized. The circulating water control apparatus according to any one of claims 1 to 4, wherein the circulating water control apparatus according to claim 1 is a fifth aspect, wherein the plurality of conductive base materials constituting the electrode section are made to act as anodes. The current and voltage are measured, and when there is an abnormality, the energization is stopped and the energization can be selectively performed so that another conductive base material acts as an anode. The circulating water control apparatus according to 5 is a sixth aspect.

The circulating water sterilization apparatus according to the present invention includes an anode and a cathode made of a conductive base material so as not to short-circuit each other in at least a part of the circulating water path of the circulating water system, and between the anode and the cathode by a power source. By energizing, there is no water decomposition reaction at the anode and the cathode, and there is a sterilizing effect of microorganisms on the anode surface. Controls microorganisms and adjusts the water quality (adsorption / decomposition / denaturation of microorganisms) in the vicinity of each anode plate and cathode plate, suppresses the growth of microorganisms, and suppresses the formation of microorganism films (biofilm or slime) over the long term An effect is obtained. In addition, since no water splitting reaction occurs, the generation of oxygen gas and chlorine gas from the anode by electrolysis and the generation of hydrogen gas from the cathode are suppressed, and these gases may be generated excessively or at certain locations. It does not gather in the water or dissolve in the aqueous solution, so that it does not adversely affect the organisms being bred.
In addition, organic substances present in the circulating water path of the circulating water system can be oxidized and decomposed at the anode to prevent water turbidity and offensive odor, and the cleaning work in the circulating water path of the circulating water system can be reduced.
Furthermore, by setting the area ratio of the cathode to the anode to be greater than 1 and less than 3, the electrode installation space and the entire apparatus can be configured not to be excessively large.
In addition, when a malfunction occurs due to disconnection of some anodes, the user is informed of the malfunction status by means of information transmission by communication, etc., the malfunctioning anode is not used, and other anodes are used to circulate water. It is possible to maintain the antibacterial effect of the antibacterial device.

<Structure of electrode part>
The electrode part of the circulating water sterilization apparatus of the present invention in which a plurality of conductive base materials are laminated has at least one or more sheets not adjacent to at least other anodes on both sides of one conductive base material that acts as an anode. It is an aggregate of one or more electrode units having a conductive base material that acts as a cathode. In this configuration, if at least one or more cathode plates are not arranged on both sides of one anode plate, it is difficult for current to flow between the electrodes, and in order to pass a desired current, the electrode potential increases, There is a problem that the occurrence of.
Further, in one electrode unit, the ratio of the sum of the surface areas of a plurality of conductive substrates acting as cathodes to the surface area of one conductive substrate acting as an anode is more than 1 and less than 3 Or each conductive group so that the ratio of the sum of the surface areas of the plurality of conductive substrates acting as the cathode to the surface area of one conductive substrate acting as the anode is more than 1 and less than 3. The material can be selectively energized.
When the ratio of the sum of the energized surface areas is 1 or less, in order to flow a desired current, the current density of the conductive base material acting as a cathode increases, the electrode potential increases, and gas is generated. There is. On the other hand, when this ratio becomes too large, the surface area of the conductive base material that acts as an anode that develops the antibacterial effect becomes too small with respect to the volume of the entire electrode part, so The problem is that the performance of the antibacterial effect obtained in this way decreases.

In the electrode portion in which the conductive substrate serving as the anode and the conductive substrate serving as the cathode are alternately laminated, the conductive substrate serving as the plurality of anodes and the conductive substrate serving as the plurality of cathodes are the same. There is no need, and the surface area, shape, and material may be different for each conductive base material that forms the anode and each conductive base material that forms the cathode. It is also possible to energize with the conductive substrate serving as the anode as the cathode and the conductive substrate serving as the cathode as the anode.
Further, the distance between the electrodes when the conductive base material serving as the anode and the conductive base material serving as the cathode are not in contact with each other is required, and is 5 mm or less at the maximum, preferably 3 mm or less. If the distance between the anode and the cathode is 5 mm or more, depending on the specific resistance value of the circulating water, the output voltage generally increases when energization is performed to the extent that the antibacterial effect is exhibited. As a result, the anode surface potential becomes noble and the cathode surface potential becomes base, and gas generation associated with the electrochemical reaction is likely to occur.
For example, using an O-ring, a non-conductive porous body, etc. to such an extent that the water flow is not obstructed, or using a non-conductive organic or inorganic material and a dedicated fixing tool, It can laminate | stack so that the conductive base material made may not contact.

<Structure of electrode plate>
There are various shapes of conductive base materials that are suitable for applications as the electrode plate. There are various types such as a plate shape, a lattice shape, a honeycomb type having pores, a mesh type, a plate having a perforated shape (for example, a punching metal, an expanded metal or a lath plate), and a porous body. In some cases, there are composite shapes. The pore shape of the conductive substrate is not particularly limited, such as a mesh or a lattice. The size of the mesh, lattice or perforation is preferably 0.5 mm to 10 mm in the vertical dimension and 0.5 mm to 10 mm in the horizontal dimension. The opening ratio, which is the opening area relative to the substrate area, is preferably 10 to 60%.
In addition, when installing the electrode section so that the flow of the circulating water and the conductive base material that becomes the electrode plate are perpendicular, the electrode plate has a mesh shape, punching metal shape, honeycomb shape, fiber shape, porous shape. It is necessary to adopt a structure that allows circulating water to pass through.
The electrode plate using the conductive substrate of the above shape can be installed and passed vertically to the water flow, but also includes the shape, plate shape, corrugated plate shape, embossed uneven plate shape, etc. When an electrode plate having a shape that cannot be used is used as the anode, it is possible to install and pass the electrode plate in parallel with the water flow, and it is desirable to select appropriately considering the processing efficiency and the installation location.

In particular, a conductive base material that acts as a cathode has a plurality of openings whose opening diameter is larger than the plate thickness, so that not only the face facing the anode but also the opposite face (back face) can be substantially used as a cathode. The ratio of the sum of the surface areas of a plurality of conductive substrates that act as cathodes to the surface area of a single conductive substrate that acts as an anode without increasing the overall volume of the electrode part because it can be effectively acted on. This is effective in suppressing the generation of gas.
Further, when a plurality of cathode plates are arranged on both sides of one anode plate, a plurality of openings having an opening diameter larger than the sum of the interval between the plurality of cathode plates and the plate thickness are provided. In addition to the cathode plate facing the anode plate, the second and subsequent cathode plates can be made to act more effectively as the cathode, so that one conductive base material that acts as the anode. It is possible to increase the ratio of the sum of the surface areas of the plurality of conductive base materials that act as the cathode to the surface area of the gas, which is more effective in suppressing the generation of gas.

<Installation location of electrode part>
If it is in the circulation path | route of a circulating water system, the installation place of the electrode part of the circulating water control apparatus of this invention will not be specifically limited. In order to efficiently exhibit the bactericidal effect, it is preferable that each conductive base material of the electrode portion is in contact with the circulating water as much as possible. For example, the circulated water may be turbulent to increase the contact of the circulating water with the conductive substrate serving as the anode and the conductive substrate serving as the cathode. It is also appropriate to install the electrode unit of the present invention in a structure that causes turbulent flow to increase contact with the conductive base material that serves as an anode and the negative electrode through which circulating water passes. It is.
In the circulation path of the circulating water system, there are many foreign substances, dust, and excrement that affect water quality, and a filter is installed to filter them. At least a part of the filter may be a conductive base material, or a conductive base material may be installed on a part of the filter to serve as an electrode, or a part of the water channel may be installed in contact with circulating water. That's fine. Further, since the circulating water sterilization apparatus of the present invention uses an electrochemical reaction, it is possible to improve the uniformity of the reaction rate by installing the electrode part in a place where the flow rate of the circulating water is stable to some extent. It is preferable because it can comprehensively control desired microorganism control, decomposition and modification of organic matter, and the like.
Alternatively, a plurality of electrodes composed of single or stacked electrode units may be installed in parallel, and the circulating water may be branched and injected continuously into each electrode.

<Material of anode conductive substrate>
The conductive substrate used as the anode in the present invention has a part or all of the surface thereof made of at least platinum, ruthenium, rhodium, palladium, iridium, titanium, zirconium, niobium, tantalum, manganese, cobalt, tin, and antimony oxide. It is preferable that the conductive base material contains one selected from a selected single metal oxide, mixed metal oxide, or composite metal oxide.
Since these conductive base materials have a mild reaction activity, a sudden reaction is unlikely to occur when water containing impurities is used. For example, when tap water is used as water for ornamental organisms, it is generally used after chlorine that can be contained in tap water is changed to sodium chloride or hydrochloric acid with sodium thiosulfate to reduce toxicity. If this water is used immediately and placed in an electrode tank using a highly active conductive substrate, sodium chloride or hydrochloric acid may react on the electrode to form chlorine or hypochlorous acid. The conductive base material having a mild reaction activity is preferable because there is a concern that an object may be affected by objects.
The metal oxide is not particularly limited because two or more kinds of metals are included or a part of the oxide is included depending on the forming method, and two or more of these compounds are mixed. The metal oxide thin film may be a film having a thickness of 0.1 μm or more, and the maximum thickness is not particularly limited, but may be set as appropriate depending on the metal oxide formation method and purpose of use. Also, in the case of carrying the dispersion, the carrying amount selected as appropriate according to the environment to be used may be set. Furthermore, the base material made of titanium or titanium alloy used in the present invention is made of the above platinum group and / or metal oxide according to a commonly used method when producing an electrode for seawater electrolysis or an oxygen generating electrode. The selected single metal oxide, mixed metal oxide or composite metal oxide can be coated or laminated. When coating and laminating, it is necessary to consider such as improving the adhesion between a single metal oxide, mixed metal oxide or composite metal oxide selected from the above platinum group and / or metal oxide and the substrate. It is.
In forming a conductive film on the surface of the electrode substrate, a platinum group and / or metal oxide is formed on the substrate by adopting a method such as plating, thermal spraying, sputtering or ion plating, or by carrying it in a dispersed manner. It is also possible to intersperse a single metal oxide, mixed metal oxide or composite metal oxide selected from those.
In addition, the conductive substrate may be any material that can efficiently adsorb aquatic organisms and can directly or indirectly contact and impart a potential, and can have a plate shape, a perforated plate shape, a rod shape, or a plate network shape. It will not be specifically limited if it has the function to process and maintain a structure.

Among the conductive substrates described above, in particular, 35 to 65 mol% iridium oxide and 65 to 35 mol% oxidation based on metal conversion on the conductive titanium oxide layer provided on the electrode substrate surface made of titanium or a titanium alloy. A conductive base material carrying a mixed oxide with tantalum is effective. These conductive base materials can make the chlorine overvoltage a positive potential lower than the oxygen overvoltage even when the electrolyte is seawater, and can suppress the generation of chlorine.
As an example in the case of carrying in a dispersed manner, a part or all of the substrate surface has 25 to 90 mol% platinum based on metal conversion, 5 to 65 mol% iridium oxide based on metal conversion, and 5 to 5 based on metal conversion. There is a conductive substrate carrying a composite with 60 mol% tantalum oxide. Then, by adjusting the composition ratio of the complex of platinum, iridium oxide, and tantalum oxide, it is possible to sterilize aquatic organisms that directly or indirectly contact the anode surface, or to suppress growth by generating radicals. it can. When the electrolyte is seawater, the chlorine overvoltage is set to a positive potential lower than the oxygen overvoltage, and when the electrolyte is water not containing a chlorine compound, the oxygen overvoltage is set to a positive potential lower than the chlorine overvoltage. Thus, the composition ratio of the composite of platinum, iridium oxide, and tantalum oxide is adjusted.

You may add the specific compound which has the effect | action which accelerates | stimulates the electron transfer reaction of a biological cell and an electrode to said electroconductive base material. That is, aquatic organisms can be sterilized more efficiently by using an electron mediator that mediates electron transfer between a microorganism and an electrode together with a conductive material. Examples of electron mediators include ferrocene, ferrocene monocarboxylic acid, ferrocene dicarboxylic acid, or ferrocene such as [(trimethylamine) methyl] ferrocene and its derivatives, H ₄ Fe (CN) ₆ , K ₄ Fe (CN) ₆ , Na ferrocyanide such as ₄ Fe _{(CN) 6,} 2,6- dichlorophenol indole, phenanthryl methosulfate, benzoquinone, phthalocyanine, brilliant cresyl blue, Karoshianin, resorcinol, thionine, N, N-dimethyl - Soo Gandolfo native de・ Thionine, new methylene blue, tobucin blue O, safranin-O, 2,6-dichlorophenolindophenol, benzyl viologen, alizarin brilliant blue, phenocyanidinone, phenazine etsulfate, etc. And the like.
An example of the conductive substrate carrying such an electron mediator is a ferrocene modified electrode. By the way, when the oxidation peak current from the marine-adherent bacterium Vibrio arginolyticus was confirmed using the ferrocene-modified carbon electrode, it was 0.3 V vs. The peak current was confirmed by SCE, and 0.4V vs. Can be sterilized with SCE. In this way, since the sterilizing effect can be obtained at a lower voltage, it is effective in that the generation of chlorine gas can be suppressed.

Moreover, you may add the material which has antimicrobial property. Substances having antibacterial properties include those belonging to inorganic substances and those belonging to organic substances.
Examples of inorganic substances include metals such as silver, copper, nickel, zinc, lead, germanium, and oxides, oxyacid salts, chlorides, sulfates, nitrates, carbonates, and organic chelate compounds.
Examples of organic substances include 2- (4-thiazolyl) -benzimidazole, 4,5,6,7-tetrachloro-2-trifluoromethylbenzimidazole, 10,10′-oxysphenoxyarsine, trimethoxysilyl-propyloctadecylammonium Examples include chloride, 2-N-octyl-4-isothiazolin-3-one, and bis (2-pyridylthio-1-oxide) zinc.

<Material of cathode conductive substrate>
As the conductive substrate for the cathode, it is desirable to use a metal having a high hydrogen overvoltage electrochemically.
Examples of the metal having a large hydrogen overvoltage include copper, zinc, tin, lead, nickel, and titanium. These metals may be used alone, or a mixed or composite alloy such as a titanium alloy or stainless steel may be used.
Moreover, the control method which has an antibacterial effect can be considered when no current is applied or when no current is supplied. At this time, elution of a very small amount of the above metals can be considered. For example, according to the water standard for fisheries (2005 version) issued by the Japan Fisheries Resource Conservation Association, copper is 0.9 microgram / liter and zinc is detected as the concentration that may affect living organisms in freshwater. The standard is set at a very low concentration of 3 microgram / liter for lead and 4 microgram / liter for lead. From this, titanium, titanium alloy and stainless steel are less likely to be eluted even when no current is applied, and even when eluted, a metal material having extremely low influence on living organisms is preferable as the cathode material of the present apparatus.

Furthermore, when the substrate is an organic material or an inorganic material, the metal can be formed as a conductive film. Examples of organic materials include resin materials. Examples include acrylonitrile-butadiene-styrene copolymer, acrylonitrile-styrene copolymer, nylon, polyester, polystyrene, polycarbonate, polyethylene, polypropylene, vinyl chloride, polyethylene terephthalate, Examples include fiber reinforced plastic (FRP). Examples of the inorganic material include glass, alumina, zirconia, cement, carbon and the like.
In forming the conductive film on these substrates, methods such as thermal spraying, sputtering, ion plating and plating can be employed. Further, a conductive film may be formed by filling the binder resin with the metal. In the case of a porous body, for example, by using electroless plating, a metal film having a large hydrogen overvoltage can be formed not only on the substrate surface but also inside.

<Shape of electrode plate>
The shape of the conductive substrate for the anode and cathode is not particularly limited, and it can adsorb aquatic organisms efficiently and contact directly or indirectly, and can be energized by arbitrarily setting a constant current when energizing constant current Alternatively, any method can be used as long as it can apply a potential and can apply a potential that does not decompose water electrochemically.

<Power supply unit>
The power supply unit is a device that supplies a direct current between the anode and the cathode, and may be driven by an AC power supply or a DC power supply such as a battery.
The conductive substrate is electrically connected to the output terminal of the power supply unit by a lead wire or the like. The power supply unit controls the energization or stop by selecting a conductive base material, controls the output voltage so as to keep the current at the specified value by feedback, or the output value of voltage or current is specified in advance It is preferable to have a function of turning on / off according to the schedule or conditions, or changing with time.
Further, the power source may have a function of appropriately selecting the number of output terminals and which conductive base material is connected to which output terminal. In this case, when an abnormality was found in the output current or output voltage to the conductive substrate that is currently energized, the energization to the conductive substrate that was energized was stopped and the current was not energized. It is possible to continue control of circulating water control bacteria by switching to energization to another conductive substrate. When this abnormality is detected, the user may be notified by display of LED, liquid crystal, etc., by sound from a speaker, etc., or may be notified by e-mail etc. using a communication line. Is possible.
These functions combine CPU, A / D converter (analog / digital converter), D / A converter (digital / analog converter), amplifier, relay, communication interface, LED, speaker, etc. This can be realized by controlling with a program.
It is also preferable to provide means for detecting the flow rate of the liquid supplied to the conductive substrate. Instead of the detected liquid flow rate data or the liquid flow rate, the power output to the conductive substrate may be controlled based on the liquid flow rate or liquid pressure data. This control means, for example, that when the flow rate becomes small, it is judged that there is a high possibility that an abnormality has occurred in the pump or the flow path, and the energization is stopped. You may add measures that notify you.
It is also preferable to provide means for detecting a water quality change in contact with the conductive substrate using a pH sensor. When the amount of change in the detected pH data is abrupt, control of power output to the conductive substrate that is energized may be performed.

<Integration of circulating water system and power supply>
In the circulating water control electrode device, the power source and the circulating water system can be integrated. By integrating, it is possible to overcome problems such as the installation location of the power source and the handling of the lead wire that electrically connects the power source and the circulating water system when the power source is installed separately from the circulating water system. In addition, if a battery is used, it is possible to eliminate the connection from the power source to the outside and form an integrated structure. By using a battery as the power source, the problem of securing the power source can be overcome.
In the circulating water control electrode device, in order to integrate the power source and the circulating water system, a battery is used, and an output control board on which the power source is mounted is incorporated into an electrode made of each conductive base material for circulating water control. For this purpose, it is necessary to make the portion for housing the output control board and the battery waterproof. Since it is preferable that the battery can be replaced, it is better to install at least an opening portion with a lid having a waterproof structure in which the battery can be taken in and out. For example, rubber packing and screwing may be used in combination. The output control board may be housed in the same space, sealed using a sealing material, etc., opened like a battery so that it can be accessed, and replaced or touched. It may not be possible. It is necessary to electrically connect the battery and the output control board, and the output control board and the conductive base material by lead wires or the like.

<Reference electrode>
In addition to the above configuration, a reference electrode can be used as necessary.
The reference electrode is used as a standard when measuring the potential of a conductive member that undergoes an electrochemical reaction. The reference electrode measures the potential difference between the reference electrode and the conductive substrate, and properly adjusts the potential of the conductive substrate with the power supply. It is to correct.
Therefore, if the potential difference between the reference electrode and the conductive base material is measured in advance in an energized state, the energization conditions for adjusting the water quality can be known, so there is no need to install a reference electrode in the circulating water system. .
The reference electrode has a reversible electrode reaction on the surface of the reference electrode and responds according to the Nernst equilibrium potential equation with a certain chemical species in the electrolyte, and the potential is stable with respect to time. Returning to the above, a device that produces a constant potential when the temperature changes to a constant temperature is used. Examples thereof include a hydrogen electrode (NHE, RHE, platinum black electrode), a calomel electrode (SCE), a silver / silver chloride electrode (Ag / AgCl), a mercuric sulfate electrode, and a mercury oxide electrode.

<Circulating water>
Circulating water that can be used according to the present invention is not particularly limited. For example, seawater, river water, lake water, tap water, drinking water, aquatic aquarium water, or various buffer solutions may be used. In addition, the target organism is not particularly limited as long as it is an organism present in the water. Furthermore, there is no need for special limitation as long as it is present in water, such as organic matter released from the dead bodies of microorganisms and inorganic salts mixed in water.

<Control conditions>
Next, control conditions will be described. Constant current control can be performed on the electrode unit or the electrode unit that can be selectively energized.
The constant current control conditions are as follows.
In order to adjust the water quality with a constant current, it is preferable to appropriately adjust the current value according to the water quality. In addition, it is preferable to change the setting of the current value as appropriate in consideration of the material and shape of the conductive substrate and the maintenance of the conductive substrate. For example, in order to obtain a bactericidal effect in a 60-liter closed circulation water tank, generally, a current value of 50 mA to 1 A is effective as a total current value. Preferably, the total current value is preferably 80 mA or more and 800 mA or less when the water splitting reaction does not occur and when an antibacterial effect is expected. The energization time can be appropriately selected and controlled depending on the purpose.
In addition, when performing constant current control in a control mode in which current is applied between the conductive base material serving as the anode and the conductive base material serving as the cathode of the electrode part that is selected and energized from the power supply terminal, no current is applied. The conductive base material serving as the anode and the conductive base material serving as the cathode are kept in a state of natural potential so that microorganisms are easily attached.
Then, by switching the current between the conductive base material that is not energized every certain time and the conductive base material that is the cathode, and performing constant current control, sterilization of microorganisms attached in a state of natural potential is suppressed. Is possible.
In addition, by changing the conductive base material that acts as an anode every predetermined time and selectively energizing, the deterioration of the surface of the conductive base material due to the energization is suppressed, and the overall durability of the electrode part is improved. be able to.
In addition, when an abnormality occurs in the current between the conductive base material acting as the current-carrying anode and the conductive base material acting as the cathode, a voltage with a large potential difference is output. Nevertheless, when the total current value is very low, there may be a problem such as disconnection in the lead wire connecting between the output terminal of the power supply and the conductive base material of the energized electrode part. It ’s big. Therefore, it is also possible to continue the constant current control by switching the energization between a conductive base material serving as another anode that is not energized and a conductive base material serving as the cathode.

Further, the fluctuation value of the pH of the circulating water under the control conditions of the present invention is desirably ± 0.1 or less, and the fluctuation is preferably within this range within one month of the control period. It is believed that the variation between at least 3 hours needs to be within this range.

<Output control board>
As an output control board for a power source used for an electrode unit capable of selectively energizing a conductive base material, in the following, a relay and an amplifier are used to selectively flow an anode with a conductive base material as an anode or a cathode. An example of a configuration having a function capable of controlling the flow of a designated current by measuring a current value using an A / D converter and a CPU and outputting a voltage by feedback by disconnecting the output as non-connection However, a similar configuration that realizes the same function and other configurations that do not have a function of selecting a conductive substrate can be easily derived from this.
For example, description will be made with reference to the simplified configuration diagram shown in FIG. 1 of the present invention and the block diagram of the power source 7 shown in FIG. A circulating water tank 1 shown in FIG. 1 is a water tank containing circulating water 6. An antibacterial tank 4 is connected to the circulating water tank 1 through a pipe 3 having a pump 2 interposed therebetween. As shown in FIG. 1, the bacteriostatic tank 4 is provided with an electrode portion formed by laminating an arbitrary number of conductive substrates 201, 202, 203,. These conductive substrates 201, 202, 203,... May be made of the same material or different materials.
The output control board 37 includes analog units 101, 102, 103,... That output voltages to the conductive substrates 201, 202, 203,. That is, the CPU 12 controls the analog units 101, 102, 103,... To output voltages to the respective conductive substrates 201, 202, 203,. Or cut off the output.
First, the operation of the analog unit 101 connected to the conductive base material 201 of the output control board 37 will be described. 9, the internal block diagram is shown in detail only for the analog unit 101, but the analog units 102, 103,... Have the same configuration. When the conductive substrate 201 connected to the analog unit 101 is set to a natural potential, the CPU 12 turns off the FET 29 and does not drive the relay 28. Thereby, the output of the voltage to the electroconductive base material 201 will be in a disconnection state, and the electroconductive base material 201 can be made into a natural potential.
Further, in order to apply a voltage to the conductive base material 201 connected to the analog unit 101, the CPU 12 turns on the FET 29 and puts the relay 28 in a driving state. Thereby, the output of the voltage to the electroconductive base material 201 will be in an output state. Further, the CPU 12 sets data of the output voltage to the conductive base material 201 in the D / A converter 21, and an output voltage is generated from the amplifier 24 via the D / A converter 21, and the current detection resistor 27 and A voltage is output to the conductive substrate 201 via the relay 28.
Further, the CPU 12 inputs the output voltage via the amplifier 25 and the A / D converter 22 in order to monitor the voltage output from the amplifier 24 to the conductive base material 201. Similarly, the CPU 12 monitors the current flowing by the voltage applied to the conductive base material 201 from the amplifier 24. Therefore, the CPU 12 measures the voltage difference between both ends of the current detection resistor 27 by the amplifier 26, and the A / D converter The voltage difference data is input through the terminal 23. From the voltage difference data and the resistance value of the current detection resistor 27, the current value currently flowing through the conductive base material 201 can be measured.

The power supply 7 can be controlled by the CPU 12 controlling the FET 29 and the D / A converter 21 of the analog units 101, 102, 103,. The conductive substrate can be selectively anode, cathode, or disconnected. At this time, in each electrode unit, the power source 7 is arranged so that at least one conductive base material acting as a cathode is disposed on both sides of one conductive base material acting as an anode, and The conductive substrate 201 is configured such that the electrode unit is configured such that the ratio of the sum of the surface areas of the plurality of conductive substrates acting as the cathode to the conductive substrate acting as the anode is greater than 1 and less than 3. , 202, 203,... Are selectively anodes, cathodes, or disconnected. The configuration of this electrode unit and its assembly can be dynamically changed.
In constructing an assembly of electrode units from the conductive substrates 201, 202, 203,..., Various methods are conceivable. For example, you may comprise an electrode unit and its aggregate | assembly so that all the laminated | stacked electroconductive base materials 201, 202, 203, ... may be allocated to either an anode or a cathode. In this case, assuming that the surface areas of the conductive substrates 201, 202, 203,... Are all equal, for example, “cathode-anode-cathode” is an electrode unit, and the electrode unit is the conductive substrate 201, 202. , 203,... Can be considered from the end.
In this allocation method, when the total number of conductive substrates is not a multiple of 3, a conductive substrate that does not belong to any electrode unit is generated. This conductive substrate may be disconnected. Since the configuration of the electrode unit can be changed dynamically, the power source 7 reconfigures the electrode unit and its assembly after a predetermined time has passed, and removes the conductive base material that has been disconnected until then. It can be included in the electrode unit. At this time, naturally, since the conditions of the arrangement of the anode and the cathode and the ratio of the surface area are imposed, the conductive base material different from that is disconnected. In this case, the specific conductive substrate may be an anode or a cathode depending on the control. However, since there are conductive base materials that are not suitable for forming an anode or a cathode, it is necessary to consider the material and control conditions of the conductive base material.
Moreover, you may select as a structural method of an electrode unit so that only an arbitrary ratio of conductive base materials may become an anode or a cathode among the total number of conductive base materials. If a sufficient antibacterial effect can be obtained, for example, select about half of the number of conductive substrates, and configure an assembly of electrode units that satisfies the conditions of the anode and cathode arrangement and the surface area ratio. It is possible to suppress the deterioration of the conductive base material by dynamically reconfiguring them with the passage of time.
Further, among the conductive base materials 201, 202, 203,..., If the group of conductive base materials that simultaneously serve as anodes or the group of conductive base materials that simultaneously serve as cathodes is fixed, the analog unit 101, A configuration is also possible in which 102, 103,... Are reduced to the number of groups. For example, in the configuration shown in FIG. 2, the conductive substrate is divided into two groups A and B, which are anodes or disconnected, and three groups C, D, and E which are cathodes or disconnected, and voltage output to each group. A dynamic assembly of electrode units satisfying the conditions of the arrangement of the anode and the cathode and the ratio of the surface area is constituted by the combination of / no connection.

Next, a current control method will be described. When performing current control, first, a conductive base material that outputs voltage and serves as an anode, a conductive base material that outputs voltage and serves as a cathode, and a conductive material that produces a natural potential without outputting voltage. Decide whether it is one of the substrates. Next, based on the total current of the currents to be controlled, the current to be passed through the conductive substrate serving as the anode is determined according to the ratio of the surface area of the conductive substrate serving as the anode. Similarly, from the total current of the current to be controlled, the value of the current flowing through the conductive base material serving as the cathode is determined according to the ratio of the surface area of the conductive base material serving as the cathode. And with respect to each electroconductive base material, CPU12 controls an output voltage and performs electric current control. For simplicity, only the total current may be evaluated, and the same voltage may be output between all anodes and all cathodes.
The CPU 12 uses the timer 17 to output a voltage and output a conductive base material at regular intervals, a conductive base material that outputs a voltage and a negative electrode, and a natural output without outputting a voltage. It is also possible to change the method of outputting to the conductive substrate by changing the control with the conductive substrate to be a potential. And the information which made the time schedule the change of the electric current value which flows through the electroconductive base material used as the anode by the timer 17 and the output method is stored in the FLASH memory 15 in advance, and the CPU 12 may control according to this time schedule. Is possible. The CPU 12 can also measure the potential of the reference electrode 8 when the reference electrode 8 is installed in the circulating water tank 1, measure the pH when the pH sensor 10 is installed, and measure the liquid flow rate using the flow sensor 11. . Based on these measured contents, it is possible to correct the total current flowing through the conductive base material used as the anode. For example, if the potential difference between the conductive base material used as the anode and the reference electrode is too large, if the fluctuation in pH increases, or if the liquid flow rate decreases, the total current flowing through the conductive base material used as the anode It is also possible to correct the voltage output to the conductive substrate so as to reduce it. Similarly, if there is a difference between the total current of the conductive base material used as the anode and the total current of the conductive base material used as the cathode, the conductive current is reduced so that the total current flowing through the conductive base material used as the anode is reduced. It is also possible to correct the voltage output to the conductive substrate. Then, the CPU 12 displays the voltage and current information output to each conductive base material, the potential information of the reference electrode 2, the pH information of the pH sensor 10, the liquid flow rate information of the flow sensor 11, and the communication interface 13. It is also possible to transmit information to the data processing unit 14 via the network. In particular, in the case of abnormal information, the user can be notified by the speaker 18 or the LED 19.

  In the circulating water control apparatus of the present invention, the conductive substrate serving as the anode directly adsorbs and sterilizes microorganisms on the electrode surface by an electrochemical oxidation reaction, and the molecular charge of organic substances is negative. A substance is adsorbed and decomposed, microorganisms are indirectly sterilized near the anode surface by OH radicals generated from the anode, and organic substances are decomposed. In addition, the conductive base material that serves as the cathode is mainly responsible for the transmission and reception of ionic currents for causing reactions at the anode. At the cathode, the generation of hydrogen, the modification and decomposition of organic substances due to alkalinization, and calcium and magnesium Reactions such as adsorption and adhesion of inorganic substances such as ions do not occur.

Hereinafter, the present invention will be described in more detail with reference to examples.
In the embodiment, FIGS. 1 to 9 schematically represent a simple configuration so that the apparatus drawings are not complicated. The present invention is not limited to the following examples, and includes various modifications within the technical scope of the present invention. In each embodiment, the same reference numerals are assigned to the same components.
<Confirmation of gas generation from electrode (existence of electrolytic reaction)>
Example 1
One conductive substrate 5a (dimension φ40mm) made of metal oxide-coated titanium expanded metal (thickness 1mm, SW3mm, LW6mm) and copper mesh (thickness 1mm, SW3mm, LW6mm, (dimension φ40mm)) The electrode unit which consists of the two electroconductive base materials 5c created by (1) was created. The electrode unit has a conductive base material 5a in the middle and a conductive base material 5c at each end. Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 1 mm. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.
The conductive substrate 5a was subjected to the following treatment.

The titanium expanded metal was washed with alcohol, treated in an aqueous 8 wt% hydrogen fluoride solution at 20 ° C. for 2 minutes, and then treated in an aqueous 60 wt% sulfuric acid solution at 120 ° C. for 3 minutes. Subsequently, the titanium expanded metal was taken out from the sulfuric acid aqueous solution and rapidly cooled by spraying cold water in a nitrogen atmosphere. Further, it was immersed in a 0.3 wt% HF aqueous solution at 20 ° C. for 2 minutes and then washed with water.
After washing with water, Pt (NH ₃ ) ₂ (NO ₂ ) ₂ was dissolved in a sulfuric acid solution, and the platinum content was adjusted to about 5 mA / cm ² at a platinum content of 5 g / liter, pH of about 2, and 50 ° C. Pt was dispersed and deposited by plating for 50 seconds. The dispersion coating amount was 1 g / m ³ . At this time, the Pt coverage on the titanium substrate was about 40%.
In this way, the titanium substrate on which Pt was dispersedly coated was heat-treated in the atmosphere at 40 ° C. for 1 hour.
Then, an ethanol solution of tantalum chloride and butanol solution of chloroiridic acid were mixed, to prepare a coating liquid containing Ir13.0G / l and Ta50.0G / liter (in terms of metal), 1 cm ² per 2 with a micropipette. 7 microliters was weighed and applied onto a titanium substrate coated with Pt prepared as described above, followed by vacuum drying at room temperature for 30 minutes and further firing in air at 500 ° C. for 10 minutes. This process was repeated twice.
Finally, a butanol solution of chloroiridate and ethanol solution of tantalum chloride were mixed to prepare a coating solution containing Ir 50.0 g / liter and Ta 20.0 g / liter (in metal conversion), and then using this coating solution. The same process as described above was repeated 8 times.
Thus, a titanium base material (conductive base material 5a) having an oxide film interspersed with complex oxides such as tantalum and iridium was obtained.

The conductive base materials 5a and 5c thus produced were placed in a 500 ml beaker containing tap water and stirred, and connected to a potentiostat / galvanostat HA-151 manufactured by Hokuto Denko Corporation as a power source. The control conditions were as follows: the energization amount shown below was applied for 1 hour, and whether or not an electrolytic reaction occurred in this example was confirmed.
Control condition 1: 10 mA
Control condition 2: 20 mA

(Comparative Example 1)
Conductive base material 5a (dimension 40 mm) made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm), which is a conductive base material 5a having the same treatment as Example 1 on the anode, and a copper mesh (thickness) on the cathode An electrode unit using a thickness of 1 mm, SW 3 mm, LW 6 mm, (dimension φ 56 mm), and conductive base material 5c) was prepared. This configuration is composed of one conductive substrate 5a and one conductive substrate 5c. Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 1 mm. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.
With this configuration, tests were performed in the same manner as in Example 1 under other conditions.

Table 1 shows the results of Example 1 and Comparative Example 1.
From this result, Example 1 was of a level where no electrolysis reaction of water occurred.
On the other hand, in Comparative Example 1, generation of bubbles was confirmed on the surfaces of the conductive substrates 5a and 5c.
In the results of Example 1, the output voltage is 2.5 V or less, and the applied potential is 2.0 V vs. Ag / AgCl or less, in Comparative Example 1, the output voltage is 3.8 V or less, and the applied potential is 2.5 V vs. It was below Ag / AgCl.

(Example 2)
FIG. 2 shows a simple configuration of the present invention. The circulating water system tank 1 shown by FIG. 2 shows the tank in which the circulating water 6 (tap water) entered. An antibacterial tank 4 is connected to the circulating water tank 1 through a pipe 3 having a pump 2 interposed therebetween. In this sterilization tank 4, as shown in FIG. 3, one conductive base material 5a (dimension φ40 mm) made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm) treated in the same manner as in Example 1 was used. 10 electrode units composed of two conductive substrates 5c made of copper mesh (thickness 1 mm, SW 3 mm, LW 6 mm, (dimension 40 mm)) are installed. In the configuration of this set of electrode units, the conductive base material 5a is placed at both ends with the conductive base material 5a in the middle. Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 1 mm. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.

The conductive substrates 5a and 5c thus produced were installed in the antimicrobial tank 4. In FIG. 2, conductive base materials 5 a and 5 c and a reference electrode 8 (not shown) are arranged and connected to the power source 7. The circulating water system tank 1 is circulated with 2 liters of circulating water at a circulating water volume of 200 ml / min, and the conductive substrates 5a and 5c are energized for 1 hour under the control conditions shown below. confirmed.
Control condition 1: 100 mA
Control condition 2: 200 mA

(Example 3)
For the anode, one conductive base material 5a (size φ40 mm) made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm), which is the conductive base material 5a treated in the same manner as in Example 1, and a copper mesh Ten electrode units composed of two conductive base materials 5c made of (thickness 1 mm, SW 3 mm, LW 6 mm, (dimension 30 mm)) are installed. In the configuration of this set of electrode units, the conductive base material 5a is placed at both ends with the conductive base material 5a in the middle. Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 1 mm. At this time, the ratio of the surface area of the anode to the surface area of the cathode was set to 1: 1. The other conditions were the same as in Example 2.

Example 4
For the anode, one conductive base material 5a (size φ40 mm) made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm), which is the conductive base material 5a treated in the same manner as in Example 1, and a copper mesh Ten sets of electrode units composed of two conductive base materials 5c made of (thickness 1 mm, SW 3 mm, LW 6 mm, (dimension φ48 mm)) are installed. In the configuration of this set of electrode units, one conductive base material 5c is installed at each end with the conductive base material 5a in the middle. Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 1 mm. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1 to 2.9. The other conditions were the same as in Example 2.

(Example 5)
The conductive substrate 5c of Example 2 was replaced with a nickel expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension 40 mm)), and tests were performed in the same manner as in Example 2 except for the other conditions. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.

(Example 6)
The conductive base material 5c of Example 2 was replaced with a zinc expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension 40 mm)), and tests were performed in the same manner as in Example 2 except for the other conditions. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.

(Example 7)
The conductive base material 5c of Example 2 was replaced with a titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension 40 mm)), and tests were performed in the same manner as in Example 2 except for the other conditions. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.

(Example 8)
The conductive base material 5c of Example 2 was replaced with an expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension φ40 mm)) made of stainless steel (SUS304), and tests were performed in the same manner as Example 2 except for other conditions. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.

(Comparative Example 2)
For the anode, one conductive base material 5a (size φ40 mm) made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm), which is the conductive base material 5a treated in the same manner as in Example 1, and a copper mesh Ten electrode units composed of two conductive base materials 5c made of (thickness 1 mm, SW 3 mm, LW 6 mm, (dimension φ20 mm)) are installed. In the configuration of this set of electrode units, one conductive base material 5b is installed at each end with the conductive base material 5a in the middle. Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 1 mm. At this time, the ratio of the surface area of the anode to the surface area of the cathode was set to 1: 0.5. The other conditions were the same as in Example 2.

(Comparative Example 3)
For the anode, one conductive base material 5a (size φ40 mm) made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm), which is the conductive base material 5a treated in the same manner as in Example 1, and a copper mesh Ten sets of electrode units composed of two conductive base materials 5c made of (thickness 1 mm, SW 3 mm, LW 6 mm, (dimension φ28 mm)) are installed. In the configuration of this set of electrode units, one conductive base material 5c is installed at each end with the conductive base material 5a in the middle. Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 1 mm. In this case, the ratio of the surface area of the anode to the surface area of the cathode was set to 1: 1. The other conditions were the same as in Example 2.

Table 2 shows the results of Examples 2 to 8 and Comparative Examples 2 and 3.
From these results, Examples 2 to 8 were at a level where no electrolysis reaction of water occurred.
On the other hand, in Comparative Examples 2 and 3, generation of bubbles was confirmed on the surface of the conductive substrate 5b.
In the results of Examples 2 to 8, the output voltage is 3.0 V or less and the applied potential is 2.0 V vs. Ag / AgCl or less, in Comparative Examples 2 and 3, the output voltage is 3.8 V or less, and the applied potential is 2.5 V vs. It was below Ag / AgCl.

Example 9
FIG. 4 shows a simple configuration of this embodiment. A circulating water tank 1 shown in FIG. 4 is a water tank (capacity 60 liters) containing circulating water 6 (tap water). An antibacterial tank 4 is connected to the circulating water tank 1 through a pipe 3 having a pump 2 interposed therebetween. In this sterilization tank 4, conductive base materials 5a and 5b made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm, (dimension φ 40 mm)) treated in the same manner as in Example 1, copper mesh (thickness) 1 mm, SW 3 mm, LW 6 mm, (dimension φ40 mm)), the electrode part which laminated | stacked the electroconductive base materials 5c, 5d, and 5e was installed. Moreover, the reference electrode 8 and the pH sensor 10 were installed and connected to the power source 7 together with the conductive base materials 5a, 5b, 5c, 5d, and 5e.

In the bacteriostatic tank 4, as shown in FIG. 5, there are 10 conductive substrates 5a, 10 conductive substrates 5b, 19 conductive substrates 5c, and 1 conductive substrate 5d. The electrode which consists of 1 sheet and the electroconductive base material 5e is laminated | stacked and installed. In the lamination, two conductive substrates 5a and 5b are alternately arranged, and each of the 20 conductive substrates (5a and 5b) is disposed between the conductive substrates 5a and 5b (19 locations). A total of 19 materials 5c are arranged one by one, and further, the conductive substrate 5d is arranged on the upstream side and the conductive substrate 5e is arranged on the downstream side, respectively, on both ends of the 39 laminated conductive substrates. . These conductive substrates 5a and 5c, 5b and 5c, 5a and 5d, and 5b and 5e were installed so that the distance between them was 1 mm.
At this time, the ratio of the surface area of the conductive substrate serving as the current-carrying anode and the surface area of the conductive substrate serving as the current-carrying cathode was 1: 2. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of. By switching the energization of the anode serving as the conductive substrate every time, the conductive substrate serving as the anode is protected.

Circulating 2 liters of circulating water in the circulating water tank 1 at a circulating water volume of 200 ml / min, and energizing the conductive substrate 5a or 5b serving as the anode for 1 hour under the following control conditions, an electrolytic reaction occurs in this embodiment. The presence or absence was confirmed. In addition, the switching interval for energizing the conductive base materials 5a and 5b as the anode was 10 minutes.
Control condition 1: 100 mA
Control condition 2: 200 mA

(Example 10)
A total of 10 conductive base materials 5a and 10 conductive base materials 5b made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension 40 mm)) treated in the same manner as in Example 1 were used for the anode. 20 conductive substrates 5c made of copper mesh (thickness 1mm, SW 3mm, LW 6mm, (dimension φ30mm)), 19 conductive substrates 5d, 1 conductive substrate 5e A total of 21 electrodes are stacked and installed. The lamination method was the same as in Example 9.
At this time, the ratio of the surface area of the conductive base material serving as the current-carrying anode and the surface area of the conductive base material serving as the current-carrying cathode was 1: 1. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of. By switching the energization of the anode serving as the conductive substrate every time, the conductive substrate serving as the anode is protected. Other conditions were the same as in Example 9.

(Example 11)
A total of 10 conductive base materials 5a and 10 conductive base materials 5b made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension 40 mm)) treated in the same manner as in Example 1 were used for the anode. 20 conductive substrates 5c made of copper mesh (thickness 1mm, SW3mm, LW6mm, (dimension φ48mm)), 19 conductive substrates 5d, 1 conductive substrate 5e A total of 21 electrodes are stacked and installed. The lamination method was the same as in Example 9.
At this time, the ratio of the surface area of the conductive base material serving as the current-carrying anode and the surface area of the conductive base material serving as the current-carrying cathode was set to 1: 2.9. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of. By switching the energization of the anode serving as the conductive substrate every time, the conductive substrate serving as the anode is protected. Other conditions were the same as in Example 9.

(Example 12)
The conductive substrates 5c, 5d, and 5e of Example 9 were replaced with nickel expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension φ40 mm)), and tests were performed in the same manner as Example 9 except for other conditions. At this time, the ratio of the surface area of the conductive substrate serving as the current-carrying anode and the surface area of the conductive substrate serving as the current-carrying cathode was 1: 2. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of.

(Example 13)
The conductive substrates 5c, 5d, and 5e of Example 9 were replaced with zinc expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension φ40 mm)), and tests were performed in the same manner as Example 9 except for other conditions. At this time, the ratio of the surface area of the conductive substrate serving as the current-carrying anode and the surface area of the conductive substrate serving as the current-carrying cathode was 1: 2. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of.

(Example 14)
The conductive substrates 5c, 5d, and 5e of Example 9 were replaced with titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension φ40 mm)), and tests were performed in the same manner as Example 9 except for other conditions. At this time, the ratio of the surface area of the conductive substrate serving as the current-carrying anode and the surface area of the conductive substrate serving as the current-carrying cathode was 1: 2. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of.

(Example 15)
The conductive base materials 5c, 5d, and 5e of Example 9 were replaced with stainless steel (SUS304) expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension 40 mm)), and other conditions were tested in the same manner as in Example 9. Carried out. At this time, the ratio of the surface area of the conductive substrate serving as the current-carrying anode and the surface area of the conductive substrate serving as the current-carrying cathode was 1: 2. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of.

(Comparative Example 4)
10 conductive substrates 5a made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension 40 mm)) treated in the same manner as in Example 1 were used as the conductive substrate serving as the anode. 19 conductive substrates 5c made of copper mesh (thickness 1 mm, SW 3 mm, LW 6 mm, (dimension φ 20 mm)), 19 conductive substrates 5 d, and conductive substrate The electrode which consists of 21 sheets of 1 material 5e is laminated | stacked and installed. The lamination method was the same as in Example 9.
At this time, the ratio of the surface area of the conductive base material serving as the current-carrying anode and the surface area of the conductive base material serving as the current-carrying cathode was set to 1: 0.5. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of. Other conditions were the same as in Example 9.

(Comparative Example 5)
10 conductive substrates 5a made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm (dimension 40 mm)) treated in the same manner as in Example 1 were used as the conductive substrate serving as the anode. 19 conductive substrates 5c made of copper mesh (thickness 1mm, SW3mm, LW6mm, (dimension φ28mm)), 19 conductive substrates 5d, 1 conductive substrate The electrode which consists of 21 sheets of 1 material 5e is laminated | stacked and installed. The lamination method was the same as in Example 9.
At this time, the ratio of the surface area of the conductive base material serving as the current-carrying anode and the surface area of the conductive base material serving as the current-carrying cathode was 1: 1. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of. Other conditions were the same as in Example 9.

Table 3 shows the results of Examples 9 to 15 and Comparative Examples 4 and 5.
From these results, Examples 9 to 15 were at a level where no electrolysis reaction of water occurred.
On the other hand, in Comparative Examples 4 and 5, it was confirmed that bubbles were generated on the surface of the conductive substrate 5c, 5d, or 5e when the cathode was energized.
In the results of Examples 9 to 15, the output voltage of the conductive base material energized as the anode was 3.0 V or less, and the applied potential was 2.0 V vs. In Ag / AgCl or lower, in Comparative Examples 4 and 5, the output voltage of the conductive substrate energized as the anode is 3.8 V or lower, and the applied potential is 2.5 V vs. It was below Ag / AgCl.

<Effect on water quality 1 (confirm pH change)>
(Example 16)
Using the configuration of Example 2, the tap water of the circulating water 6 in the aquarium was changed to a buffer solution.
Six types of buffer solutions adjusted to pH 4 to 9 were used. In addition, pH 4 and 5 used 10 mM sodium acetate buffer, and pH 6 to 9 used 10 mM sodium phosphate buffer.
The test condition is that 2 liters of the buffer solution is circulated in the circulating water tank 1 at a circulating water amount of 200 ml / min, and the conductive substrates 5a and 5c are energized for 6 hours under the control conditions shown below. The presence or absence was confirmed.
Control condition 1: 100 mA
Control condition 2: 200 mA
Evaluation was performed in the same manner as in Example 2, and the pH was measured every hour until the end of the test, and the surface state of the conductive substrate during energization was confirmed visually.
As a result, the pH change from the start of the test to the end of the test was within ± 0.1 and there was almost no change. Moreover, generation | occurrence | production and the change of the gas from the electroconductive base material surface were not confirmed.

(Example 17)
The tap water of the circulating water 6 in the water tank was changed to a buffer solution using the configuration of Example 9.
Six types of buffer solutions adjusted to pH 4 to 9 were used. In addition, pH 4 and 5 used 10 mM sodium acetate buffer, and pH 6 to 9 used 10 mM sodium phosphate buffer.
The test conditions were as follows: 2 liters of buffer solution was circulated in the circulating water tank 1 at a circulating water volume of 200 ml / min, and the conductive substrate 5a or 5b serving as the anode was energized for 6 hours under the control conditions shown below. Whether or not a reaction occurred was confirmed. The switching interval for energizing the conductive substrate 5a or 5b as an anode was 10 minutes.
Control condition 1: 100 mA
Control condition 2: 200 mA
Evaluation was performed in the same manner as in Example 9, and the pH was measured every hour until the end of the test, and the surface state of the conductive substrate during energization was visually confirmed.
As a result, the pH change from the start of the test to the end of the test was within ± 0.1 and there was almost no change. Moreover, generation | occurrence | production and the change of the gas from the electroconductive base material surface were not confirmed.

<Effect on water quality 2 (confirmation based on differences in salt concentration)>
(Example 18)
Using the configuration of Example 2, the tap water of the circulating water 6 in the aquarium was changed to artificial seawater (Marine Art SF1 manufactured by Tomita Pharmaceutical Co., Ltd.).
The test conditions were the same as in Example 2. The pH was measured after the test was completed, the output voltage and the electrode potential were measured, and the surface state of the conductive substrate during energization was confirmed visually.
As a result, there was no change in pH (pH change was within ± 0.1). The output voltage is 1.5 V or less, and the electrode potential is 0.9 V vs. 0.9 for the conductive substrate 5a. Less than Ag / AgCl, the conductive substrate 5b is −0.6 V vs. It was below Ag / AgCl. Furthermore, there was no gas generation from the electrodes.
In addition, 50 ml of artificial seawater at the start and end of the test was collected and measured for confirmation of chlorine generation from the conductive substrate 5a. The measurement was performed using a residual chlorine electrode (97-70BN; manufactured by Orion Research). Ten milliliters of the collected artificial seawater was sampled, and 100 microliters of iodine reagent (manufactured by Orion Research) and acid reagent (manufactured by Orion Research) were added and stirred. After the solution was allowed to stand for 2 minutes, a multimeter (83 MULTITIMER; manufactured by FLUKE) was connected, the potential was measured with a residual chlorine electrode, and the chlorine concentration was determined using a calibration curve from the electrode potential difference from the standard sample. The chlorine measurement limit is 0.2 ppm. A standard sample was prepared by mixing 100 microliters of residual chlorine standard solution (manufactured by Orion Research), iodine reagent, and acid reagent, respectively, and stirring for 2 minutes, and then adding 9900 microliters of distilled water and stirring again.
As a result of the test, generation of chlorine was not confirmed from the collected artificial seawater at the start and end of the test.

(Example 19)
Using the configuration of Example 9, the tap water of the circulating water 6 in the aquarium was changed to artificial seawater (Marine Art SF1 manufactured by Tomita Pharmaceutical Co., Ltd.).
The test conditions were the same as in Example 9. The pH was measured after the test was completed, the output voltage and the electrode potential were measured, and the surface state of the conductive substrate during energization was confirmed visually.
As a result, there was no change in pH (pH change was within ± 0.1). In addition, the output voltage of the conductive substrate energized as the anode is 1.5 V or less, and the electrode potential is 0.9 V vs. 0.1 V when the conductive substrate 5 a or 5 b is energized as the anode. Less than Ag / AgCl, the conductive substrate 5c or 5d or 5e when being energized as a cathode is −0.6 V vs. It was below Ag / AgCl. Furthermore, there was no gas generation from the electrodes.
Further, 50 milliliters of artificial seawater at the start and end of the test was collected and measured for confirmation of chlorine generation from the conductive substrate 5a or 5b when the anode was energized. The measurement was performed in the same manner as in Example 18.
As a result of the test, generation of chlorine was not confirmed from the collected artificial seawater at the start and end of the test.

(Example 20)
FIG. 6 shows the configuration of the circulating water sterilization apparatus used for carrying out the examples of the present invention.
A circulating water tank 1 shown in FIG. 6 is a tank (capacity 60 liters) filled with fresh water containing aquatic organisms in the circulating water 6. A sterilization tank 4 is connected to the circulating water tank 1 through a pipe 3 having a pump 2 interposed therebetween. In this antibacterial tank 4, one conductive base material 5a (dimension 40 mm) made of a titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm) treated in the same manner as in Example 1, and a copper mesh (thickness) Ten electrode units composed of two conductive base materials 5c made with a thickness of 1 mm, SW 3 mm, LW 6 mm, (dimension 40 mm) are installed. In the configuration of this set of electrode units, one conductive base material 5b is installed at each end with the conductive base material 5a in the middle. Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 1 mm. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.
In FIG. 6, conductive base materials 5 a and 5 c and a reference electrode 8 are arranged and connected to a power source 7.
Circulating the circulating water in the circulating water system tank 1 of the circulating water control electrode unit at a circulating water volume of 5 liters / min, and keeping the conductive substrates 5a and 5c at 25 ° C. while energizing them under the control conditions shown below. A test was conducted for one month to confirm the effect of this example.
Control condition 1: 100 mA always energized Control condition 2: 200 mA always energized

(Example 21)
Using the same circulating water system tank 1 used in Example 20, a bacteriostatic tank 4 is connected to the circulating water system tank 1 through a pipe 3 having a pump 2 interposed therebetween. In this sterilization tank 4, one conductive base material 5a made of a titanium plate (thickness 1 mm, 50 mm × 300 mm) treated in the same manner as in Example 1, and a copper plate (t0.5 mm × 50 mm × 300 mm) 10) of electrode units composed of the two conductive base materials 5c prepared in (1) are stacked in parallel in the longitudinal direction so that the electrode plates are parallel to the direction of flow of the circulating water. In the configuration of this set of electrode units, one conductive substrate 5c is installed at each end with the conductive substrate 5a in the middle (FIG. 7). Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 0.5 mm. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.
In FIG. 6, conductive base materials 5 a and 5 c and a reference electrode 8 are arranged and connected to a power source 7.
Circulating the circulating water in the circulating water system tank 1 of the circulating water control electrode unit at a circulating water volume of 5 liters / min, and keeping the conductive substrates 5a and 5c at 25 ° C. while energizing them under the control conditions shown below. A test was conducted for one month to confirm the effect of this example.
Control condition 1: 100 mA always energized Control condition 2: 200 mA always energized

(Example 22)
Using the same circulating water system tank 1 used in Example 20, a bacteriostatic tank 4 is connected to the circulating water system tank 1 through a pipe 3 having a pump 2 interposed therebetween. The antibacterial tank 4 includes one conductive base material 5a (size φ40 mm) made of titanium expanded metal (thickness 1 mm, SW 3 mm, LW 6 mm) coated with metal oxide, and titanium expanded metal (thickness). 10 sets of electrode units composed of two conductive base materials 5c made with a thickness of 1 mm, SW 3 mm, and LW 6 mm are installed. In the configuration of this set of electrode units, the conductive base material 5a is placed at both ends with the conductive base material 5a in the middle. Furthermore, these conductive base materials 5a and 5c were installed so that the distance between them was 1 mm. At this time, the ratio of the surface area of the anode to the surface area of the cathode was 1: 2.
In addition, the conductive substrate 5a was subjected to the following metal oxide coating treatment.

The titanium expanded metal was degreased and washed with ethyl alcohol, and then treated for 1 minute in an aqueous solution containing 8% by weight hydrofluoric acid at 20 ° C. and 60% by weight sulfuric acid. The titanium expanded metal was taken out from the sulfuric acid solution and washed with water in the atmosphere. Moreover, the average roughness (Ra) of the titanium base material surface at this time was 0.3 micrometer. Next, heat treatment was performed in the atmosphere at 400 ° C. for 30 minutes to form a conductive titanium oxide layer. Then each dissolved chloroiridic acid _{(H 2 IrCl 6 · 6H 2} O) and tantalum ethoxide _{(Ta (OC 2 H 5)} 5) to butanol, 60 mol% of iridium oxide composition ratio is based on metal conversion And 40 mol% tantalum oxide, and a total amount of iridium (Ir) and tantalum (Ta) metal concentration of 50 g · dm ⁻³ is measured by 0.4 cm ³ per 1 dm ² with a measuring pipette. Then, it was coated on the titanium substrate, dried at room temperature for 20 minutes, and then baked in air at 530 ° C. for 10 minutes. Loading of iridium oxide and tantalum oxide each in terms of metal ^{0.020 g} · dm -2, was 0.014 g · ^{dm -2.} Through the above steps, a conductive titanium oxide layer was formed on the surface of the titanium substrate, and a mixed oxide of 60 mol% iridium oxide and 40 mol% tantalum oxide based on metal conversion was supported thereon.
In this way, a titanium plate (conductive substrate 5a) having an oxide film interspersed with complex oxides such as tantalum and iridium was obtained.

In FIG. 6, the conductive substrates 5 a and 5 c and the reference electrode 8 produced as described above are arranged and connected to the power source 7.
Circulating the circulating water in the circulating water system tank 1 of the circulating water control electrode unit at a circulating water volume of 5 liters / min, and keeping the conductive substrates 5a and 5c at 25 ° C. while energizing them under the control conditions shown below. A test was conducted for one month to confirm the effect of this example.
Control condition 1: 100 mA always energized Control condition 2: 200 mA always energized

(Example 23)
Using the configuration of Example 9, fresh water containing aquatic organisms was used as circulating water 6. Circulating the circulating water in the circulating water tank 1 at a circulating water volume of 5 liters / min, and conducting the test for one month in a greenhouse maintained at 25 ° C. while energizing the conductive substrate 5a or 5b serving as the anode under the control conditions shown below. The effect of this example was confirmed. The switching interval for energizing the conductive substrates 5a and 5b as anodes was 10 minutes.
Control condition 1: 100 mA always energized Control condition 2: 200 mA always energized

(Example 24)
Using the same circulating water system tank 1 used in Example 23, the bacteriostatic tank 4 was replaced with the one described below. As shown in FIG. 8, the antibacterial tank 4 includes 10 conductive base materials 5 a made of a titanium plate (thickness 1 mm, 50 mm × 300 mm) treated in the same manner as in Example 1. 19 pieces of the conductive base material 5c made of copper plate (t0.5 mm × 50 mm × 300 mm), 19 pieces of the conductive base material 5d, and 1 piece of the conductive base material 5e. A total of 21 electrodes are stacked and installed. The laminating method was the same as in Example 8. However, the conductive substrates 5a and 5c, 5b and 5c, each conductive substrate surface and the direction of the water flow in and out of the sterilization tank 4 were parallel to each other. Each interval between 5a and 5d, 5b and 5e was 0.5 mm.
At this time, the ratio of the surface area of the conductive substrate serving as the current-carrying anode and the surface area of the conductive substrate serving as the current-carrying cathode was 1: 2. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of.
Circulating the circulating water in the circulating water tank 1 at a circulating water volume of 5 liters / min, and conducting the test for one month in a greenhouse maintained at 25 ° C. while energizing the conductive substrate 5a or 5b serving as the anode under the control conditions shown below. The effect of this example was confirmed. In addition, the switching interval for energizing the conductive base materials 5a and 5b as the anode was 10 minutes.
Control condition 1: 100 mA always energized Control condition 2: 200 mA always energized

(Example 25)
Using the same circulating water system tank 1 used in Example 23, the bacteriostatic tank 4 was replaced with the one described below. As shown in FIG. 8, the antibacterial tank 4 includes 10 conductive base materials 5 a made of a titanium plate (thickness 1 mm, 50 mm × 300 mm) processed in the same manner as in Example 22. 19 conductive substrates 5c made of titanium plates (t0.5 mm × 50 mm × 300 mm), 19 conductive substrates 5d, and 1 conductive substrate 5e A total of 21 electrodes are stacked and installed. The laminating method was the same as in Example 9, except that the surface of each conductive substrate and the direction of the water flowing into and out of the sterilization tank 4 were parallel to each other, and the conductive substrates 5a and 5c, 5b and 5c, Each interval between 5a and 5d, 5b and 5e was 0.5 mm.
At this time, the ratio of the surface area of the conductive substrate serving as the current-carrying anode and the surface area of the conductive substrate serving as the current-carrying cathode was 1: 2. That is, when the conductive substrate 5a is energized with the anode as the anode, the conductive substrates 5c and 5d are energized as the cathode, and the conductive substrates 5b and 5e are set to the natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5a that is energized and conductive bases 5c and 5d that are arranged on both sides thereof, and the electrode portion is composed of 10 sets of electrode units. It is made up of. Further, when the conductive substrate 5b is energized with the anode as an anode, the conductive substrates 5c and 5e are energized with the cathode as a cathode, so that the conductive substrates 5a and 5d have a natural potential. The configuration of one set of electrode units at this time is composed of one conductive base 5b that is energized and conductive bases 5c and 5e disposed on both sides of the conductive base 5b. It is made up of.
Circulating the circulating water in the circulating water tank 1 at a circulating water volume of 5 liters / min, and conducting the test for one month in a greenhouse maintained at 25 ° C. while energizing the conductive substrate 5a or 5b serving as the anode under the control conditions shown below. The effect of this example was confirmed. In addition, the switching interval for energizing the conductive base materials 5a and 5b as the anode was 10 minutes.
Control condition 1: 100 mA always energized Control condition 2: 200 mA always energized

(Comparative Example 6)
Circulating water was circulated in the circulating water tank 1 of the same type used in Example 22 at a circulating water amount of 5 liters / min, and the conductive base materials 5a and 5c were not energized, and a test was conducted for one month.

(Comparative Example 7)
Circulating water is circulated at a circulating water volume of 5 liters / min in the same circulating water tank 1 used in Example 25, and the conductive base materials 5a, 5b, 5c, 5d, and 5e are not energized for one month. did.

The test results of Examples 20 to 25 and Comparative Examples 6 and 7 were confirmed as follows. The antibacterial effect was determined by visually judging the change in the color of water in the water tank. Furthermore, the circulating water of the circulating water system that was energized was collected during observation and the pH was measured. As a result, the circulating water sterilization apparatus of the present invention that was energized in Examples 20 to 25 had a sterilizing effect because there was no dirt on the inner wall of the aquarium due to the growth of microorganisms and no change in water color. Moreover, there was no fluctuation | variation of pH. Further, no alkaline white precipitate (mainly composed of magnesium and calcium) was confirmed on the cathode by visual observation. Further, gas generation from the conductive substrate was not confirmed during the test period.
On the other hand, in Comparative Examples 6 and 7, the stain on the inner wall of the water tank due to the growth of microorganisms was confirmed from the first week, and the entire inner surface was covered with microbial films, algae and the like after one month.

  In the embodiment, FIGS. 2 to 8 schematically represent a simple configuration so that the apparatus drawings are not complicated, and FIG. 9 represents a block diagram of a power source. The present invention is not limited to the following examples, and includes various modifications within the technical scope of the present invention. Moreover, in each Example, the same referential mark was attached | subjected about the same structure.

As mentioned above, the electroconductive base material used as the anode which has supplied electricity of the electrode part of the circulating water antimicrobial apparatus of this invention performs antimicrobial and oxidative decomposition of organic substance. In addition, there is no gas generation due to electrolysis in the conductive base material that becomes the energized cathode, that is, the function of the cathode contributes only to the electron transfer necessary for causing an electrochemical reaction at the anode.
Therefore, the circulating water sterilization apparatus of the present invention has a sterilizing effect while maintaining the initial water quality, and makes it possible to realize maintenance-free for contamination due to biological fouling.
In addition, the function of switching the conductive base material to be energized can be used to protect the deterioration rate of the conductive base material by switching the conductive base material being energized every time and If a problem such as disconnection occurs between the conductive base material and the power source, it can be used by switching to a conductive base material that can be energized, which contributes to extending the continuous operation time. .

Configuration diagram of the circulating water sterilization apparatus used in the examples of the present invention Configuration diagram of the circulating water sterilization apparatus used in the examples of the present invention The electrode part block diagram of the circulating water control apparatus used for the Example of this invention Configuration diagram of the circulating water sterilization apparatus used in the examples of the present invention The electrode part block diagram of the circulating water control apparatus used for the Example of this invention Configuration diagram of the circulating water sterilization apparatus used in the examples of the present invention The electrode part block diagram of the circulating water control apparatus used for the Example of this invention The electrode part block diagram of the circulating water control apparatus used for the Example of this invention The block diagram of the output control board in the power supply of the circulating water control apparatus used for the Example of this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Circulating water system tank 2 Pump 3 Piping 4 Antibacterial tank 5a, 5b, 5c, 5d, 5e Conductive base material 6 Circulating water (fresh water containing tap water, artificial seawater, buffer solution, aquatic organism)
7 Power supply 8 Reference electrode 9 Packing (O-ring)
10 pH sensor 11 Flow sensor 12 CPU
13 Communication Interface 14 Data Processing Unit 15 FLASH Memory 16 RAM
17 Timer 18 Speaker 19 LED
21 D / A converter 22, 23 A / D converter 24, 25, 26 Amplifier 27 Current detection resistor 28 Relay 29 FET
30, 31, 32 A / D converters 33, 34, 35 Amplifier 37 Output control boards 101, 102, 103, 104 Analog units 201, 202, 203, 204 Conductive base material

Claims (6)

It has an electrode part composed of a plurality of conductive base materials, and it is energized between the anode and the cathode made of the conductive base material, and exists near the anode surface by direct / indirect contact on the anode surface by electrochemical reaction. A circulating water sterilization apparatus for sterilizing microorganisms to be treated and treating circulating water, wherein at least one conductive substrate disposed on both sides of one conductive substrate to act as an anode is a cathode A circulating water control device characterized in that an electrode part is formed by one or more aggregates of electrode units that act as In the electrode unit, at least one conductive substrate disposed on both sides of one conductive substrate that acts as an anode acts as a cathode and one conductive group that acts as the anode Each conductive substrate can be selectively energized such that the ratio of the sum of the surface areas of the plurality of conductive substrates that act as the cathode to the surface area of the material is greater than 1 and less than 3. The circulating water control device according to claim 1. 3. The circulating water sterilization apparatus according to claim 1, wherein at least the conductive base material acting as the cathode in the electrode unit has a plurality of openings having an opening diameter larger than a plate thickness thereof. In the electrode unit, a part or all of the surface of the anode is selected from oxides of at least platinum, ruthenium, rhodium, palladium, iridium, titanium, zirconium, niobium, tantalum, manganese, cobalt, tin, and antimony. Comprising a conductive substrate comprising one selected from a single metal oxide or a mixed metal oxide or a composite metal oxide;
The cathode has a conductive substrate made of at least one of copper, zinc, tin, lead, nickel, titanium, titanium alloy, and stainless steel. The circulating water control apparatus according to 1 to 3. 5. The circulation according to claim 1, wherein, in the plurality of conductive base materials constituting the electrode portion, the conductive base material that acts as an anode is changed at regular intervals and can be selectively energized. Water control device. In the plurality of conductive base materials constituting the electrode part, the voltage and current to the conductive base material acting as the anode are measured, and when there is an abnormality, the energization is stopped and another conductive base material is used. The circulating water sterilization device according to claim 1, wherein the device can be selectively energized so as to act as an anode.

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