JPH1099863A - Method for sterilizing water and water-treating apparatus used therein - Google Patents

Abstract

PROBLEM TO BE SOLVED: To inexpensively and certainly kill a microorganism in water to sterilize water without being accompanied by danger from an aspect of work and generating harmful gas. SOLUTION: A plate anode 2 composed of a platinum plated titanium plate, a cathode 1 composed of a platinum plated titanium plate having polyaniline films 3 applied to both main surfaces thereof and a stirrer 5a rotationally driven by a motor 5 are immersed in water 6 housed in a container 7 and a current is supplied across the anode 2 and the cathode 1 while water 6 is stirred by the stirrer 5a. By this constitution, the polyaniline films 3 reduce dissolved oxygen in water 6 to form superoxide which in turn kills a microorganism in water 6. This superoxide also contributes to the reductive reaction of oxygen to reduce once oxidized polyanilin by the reducing current flowing to polyanline capable of again reducing oxygen in water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for disinfecting water and a water treatment apparatus used for the method, and more particularly to a method for dispensing any disinfectant from the outside without danger to the human body and at low cost. The present invention relates to a method for sterilizing water that can surely sterilize microorganisms in water and a water treatment apparatus used for the method.

[0002]

2. Description of the Related Art Sterilizing harmful microorganisms contained in so-called water, such as drinking water used in homes and offices, cooling water for heat exchangers in factories and buildings, hot water in public baths, and pool water. As a method for performing the method, a method of boiling water, a method of adding a bactericide such as chlorine or hydrogen peroxide to the water, and an electrolytic sterilization method are known.

[0003]

However, the above-mentioned conventional method for disinfecting water has the following problems.

[0004] For example, in the method of boiling service water, the energy consumed for boiling the service water is extremely large.
In addition, there is a problem that the management of the heat source for heating the water is complicated. In addition, since the properties of the water are changed by boiling the water, the water often cannot be used depending on the use of the water.

Also, the method of adding chlorine to service water is widely used as a method of sterilizing tap water, but this method requires a large amount of chlorine to be added, and chlorine odor remains in the water after sterilization. In addition, there is a problem that an organic chlorine compound (for example, trihalomethane) is generated from the residual chlorine, which may impair human health or cause environmental pollution. In addition, in the method of adding hydrogen peroxide to water, a relatively large amount of hydrogen peroxide needs to be added because the hydrogen peroxide is easily decomposed in water. Due to the intense intensity, there is a problem in that handling during transportation to the use site and during loading is dangerous.

In addition, the electrolytic sterilization method requires a relatively large amount of electric power to increase the cost, and if the voltage is reduced to reduce the amount of electric power, the sterilization of microorganisms becomes insufficient. If the voltage is increased to perform sufficient sterilization, there is a problem that water itself is decomposed and harmful gas is generated.

[0007] The present invention has been made in view of the above-mentioned circumstances, and it is inexpensive and surely sterilizes microorganisms in water without causing any danger to the work or generating harmful gas. It is an object of the present invention to provide a method for sterilizing water that can be used and a water treatment apparatus used for the method.

[0008]

Means for Solving the Problems To achieve the above object, a method for sterilizing water according to the present invention comprises disposing an anode and a cathode having polyaniline in contact with the surface of the water. Microorganisms contained in the water are sterilized by superoxide generated by the polyaniline reducing dissolved oxygen in the water while intermittently or continuously energizing. That is, when the present inventors bring polyaniline into contact with service water, it reduces dissolved oxygen (O ₂ ) in the service water to produce superoxide (· O ₂ ⁻ ) having an excellent bactericidal action. It has been found that the polyaniline once oxidized by the reduction is electrochemically reduced by a reduction current flowing to the electrode in the water and is regenerated again into a polyaniline capable of reducing oxygen in the water. The sterilization method was completed. In such a method for sterilizing service water of the present invention, polyaniline once oxidized by reaction with dissolved oxygen in service water is reduced by a reduction current flowing to a cathode in service water to regenerate polyaniline capable of reducing dissolved oxygen again. Therefore, the production of superoxide by polyaniline is performed without interruption, and even if a large amount of water is used, microorganisms in the water can be surely sterilized. Further, the reduction current density (absolute value) required to reduce the polyaniline oxidized by the reaction with the dissolved oxygen in the service water may be about 0.01 to 100 mA · cm ⁻² , so that the power consumption is small, and There is no problem that the water itself decomposes to generate harmful gas. In addition, the polyaniline itself has no toxicity, and no toxic gas is generated in the reduction reaction of oxygen by the polyaniline, and no dangerous phenomena occur, so that the operation can be performed safely.

[0009] In the method for sterilizing water according to the present invention,
It is preferable that the service water is stirred by a stirrer. With such a preferable configuration, the entire service water to be sterilized is efficiently brought into contact with polyaniline, and the dissolved oxygen in the service water is efficiently reduced to superoxide. Since the contact frequency between the oxide and the microorganisms in the service water can be effectively increased, the microorganisms in the service water can be efficiently sterilized.

In the method for sterilizing water according to the present invention, the cathode is a cloth-like, mesh-like or porous plate-like cathode having at least one main surface coated with a polyaniline film. Alternatively, it is preferable to make the fluid flow so as to pass through the porous plate-shaped cathode and the polyaniline membrane. With such a preferable configuration, even if the amount of the water to be sterilized is large, the entire water is surely brought into contact with the polyaniline. As a result, the dissolved oxygen in the service water is efficiently reduced to superoxide, and the microorganisms in the service water can be efficiently sterilized.

In the method for sterilizing service water according to the present invention, the service water is preferably caused to flow so as to repeatedly pass through a cloth-like, mesh-like or porous plate-like cathode and a polyaniline membrane. The entire service water contacts the polyaniline reliably and multiple times, and the dissolved oxygen in the service water is uniformly reduced to superoxide, and can be sterilized to the extent that microorganisms in the service water can be almost completely eliminated. .

In the method for disinfecting water according to the present invention, it is preferable that both the front and back main surfaces of the cloth-like, net-like or porous plate-like cathode are coated with a polyaniline film. By passing the water through the polyaniline membrane provided on the front and back main surfaces of the cathode,
The entire service water to be sterilized comes into contact with polyaniline efficiently, and the dissolved oxygen in the service water is reduced to superoxide in a short time, so that the sterilization time of the microorganism can be shortened.

Further, in the method for sterilizing water according to the present invention, the cathode is a cloth-like, mesh-like or porous plate-like cathode,
A block-shaped porous structure in which polyaniline is adhered to the surface of a block-shaped body having a porous structure made of a conductive material is arranged so as to be in contact with one main surface of the cloth-like, net-like or porous plate-like cathode. It is preferable to flow the water so as to pass through the cloth-like, mesh-like or porous plate-like cathode and the porous structure. With such a preferable configuration, the amount of the water to be sterilized is large. Even so, the entire service water reliably contacts the polyaniline, and the dissolved oxygen in the service water is efficiently reduced to superoxide, and the microorganisms in the service water can be efficiently killed.

In the method for sterilizing service water according to the present invention, the service water is preferably caused to flow so as to repeatedly pass through a cloth-like, mesh-like or porous plate-like cathode and a block-like porous structure. The preferred configuration ensures that the entire service water comes into contact with the polyaniline several times and the dissolved oxygen in the service water is uniformly reduced to superoxide, and to the extent that microorganisms in the service water can be almost completely eliminated. Can be sterilized.

[0015] In the method for sterilizing water according to the present invention, the plate-shaped anode and the plate-shaped cathode having at least one principal surface covered with a polyaniline film are opposed to each other so that the polyaniline film faces the anode. It is preferable to pass water through the gap between the cathode and the anode. With such a preferable configuration, when the water passes through the gap between the opposed plate-shaped cathode and the anode, the water is mainly used as the cathode. By contacting the polyaniline membrane covering the surface for a relatively long time, the dissolved oxygen in the service water is efficiently reduced to superoxide, and the microorganisms in the service water can be efficiently killed.

The first water treatment apparatus of the present invention comprises a water tank in which water to be sterilized is stored, an anode at least a part of which is immersed in the water, and a polyaniline film on the surface. A cathode, which is attached and arranged so that the polyaniline film is immersed in the water, and a current source for applying a current to the anode and the cathode. With such a configuration, the method for sterilizing service water of the present invention for sterilizing microorganisms in service water while regenerating polyaniline that is oxidized by the reaction with dissolved oxygen in service water to polyaniline that can reduce dissolved oxygen again is reasonable. It can be executed stably.

In the first water treatment apparatus of the present invention, it is preferable that a stirrer for stirring the water is provided. With such a preferable configuration, the water to be sterilized is efficiently brought into contact with the polyaniline. As a result, the dissolved oxygen in the service water can be efficiently reduced to superoxide, and the frequency of contact between the superoxide and the microorganisms in the service water can be increased, so that the sterilization efficiency of the microorganisms in the service water can be improved.

In the second water treatment apparatus of the present invention, a first opening for introducing water into the tank and a second opening for discharging water in the tank to the outside of the tank are formed in the tank body, and at least A cloth-like, mesh-like or porous plate-like cathode, one main surface of which is covered with a polyaniline film, is arranged on the first opening side, and a cloth-like, mesh-like, or porous plate-like cathode is arranged on the second opening side. And the water introduced into the tank from the first opening passes through the cloth-like, mesh-like or porous plate-like cathode and the polyaniline membrane,
Further, an electrolytic cell unit configured to pass through the cloth-like, mesh-like or porous plate-like anode and to be discharged from the second opening to the outside of the tank, and a current source that applies a current to the anode and the cathode, A water storage tank in which water to be sterilized is stored,
A pump for pumping water from the water storage tank and guiding the pumped water to the first opening of the electrolytic cell. With such a configuration, the present invention sterilizes microorganisms in the water by allowing the water to flow so as to pass through a cloth-like, net-like or porous plate-like cathode having at least one main surface covered with a polyaniline film. The sterilization method for water can be executed reasonably and stably. In addition, since the electrolytic cell is a unit, when the electrode material or polyaniline in the electrolytic cell deteriorates with time or when the electrode or polyaniline film is clogged, the electrolytic cell can be easily replaced with a new electrolytic cell. It can be easily maintained.

In the second water treatment apparatus of the present invention, it is preferable that a drain pipe for discharging the water discharged from the electrolytic cell unit into the water storage tank is provided. According to the configuration, the water to be sterilized can be easily and repeatedly passed through the electrolytic cell unit, so that the above-described water is used as a cloth-like, net-like or porous plate-like cathode coated with a polyaniline film on at least one main surface. The method for sterilizing service water of the present invention, in which microorganisms in service water are sterilized by flowing so as to repeatedly pass can be rationally and stably performed.

In the second water treatment apparatus of the present invention, a pair of opposite main surfaces of a cloth-like, mesh-like or porous plate-like cathode are coated with a polyaniline film. A cloth-like, net-like or porous plate-like cathode coated with a polyaniline film is disposed in the electrolytic cell so that water passes through the polyaniline film provided on the pair of main surfaces sequentially. With such a preferred configuration, the water to be sterilized comes into contact with the polyaniline efficiently, and the dissolved oxygen in the water is reduced to superoxide in a short time, thereby shortening the sterilization time of the microorganism. be able to.

In the third water treatment apparatus of the present invention, a first opening for introducing water into the tank and a second opening for discharging water in the tank to the outside of the tank are formed in the tank body. , Cloth,
A reticulated or porous plate-shaped cathode is disposed on the first opening side, and a cloth, reticulated or porous plate-shaped anode is disposed on the second opening side, and a conductive material is provided between the cathode and the anode. A block-shaped porous structure having polyaniline adhered to the surface of the block-shaped porous structure is disposed so as to be in contact with the cathode, and the water introduced into the tank from the first opening is filled with the cloth. After passing through a mesh-like or porous plate-like cathode and the porous structure having a relatively large thickness, further passing through a cloth-like, mesh-like or porous plate-like anode, and then discharged out of the tank through the second opening. Electrolyzer unit configured to be, a constant current source that provides a constant current to the anode and the cathode, a water storage tank in which the water to be sterilized is stored, and pumping water from the water storage tank, This to the first opening of the electrolytic cell unit It is obtained by a Ku pump. With such a configuration, the surface of a block-shaped porous structure made of a conductive material disposed so as to contact the above-mentioned water with a cloth-like, mesh-like or porous plate-like cathode and one main surface of the cathode is used. The water sterilization method of the present invention for sterilizing microorganisms in the water by circulating it through a block-shaped porous structure having polyaniline adhered thereto can be rationally and stably performed. In addition, since the electrolytic cell is a unit, the electrode tank and the porous structural material in the electrolytic cell may deteriorate over time, or the electrode or the porous structure may be clogged. It can be easily replaced with a new electrolytic cell, and has excellent maintainability.

In the third water treatment apparatus according to the present invention, a drain pipe is provided which is connected to the second opening of the electrolytic cell unit and discharges the water discharged from the electrolytic cell unit into the water storage tank. It is preferable that the water to be sterilized can be easily and repeatedly passed through the electrolytic cell unit by such a preferable configuration.
The water sterilization method of the present invention for sterilizing microorganisms in the water by allowing the above-mentioned water to flow so as to repeatedly pass through the cloth-like, mesh-like or porous plate-like cathode and the block-like porous structure is rational and effective. It can be executed stably.

[0023] In the third water treatment apparatus of the present invention, the electrolytic cell may include a block-shaped porous structure in which polyaniline is adhered to the surface of a block-shaped porous structure between a cathode and an anode. It is preferable that a plurality of conductive materials are arranged one on top of another via a cloth, mesh, or porous plate. In an electrolytic cell in which a single block-shaped porous structure is placed between the cathode and anode, the thickness of the single block-shaped porous structure is increased in order to increase the contact area between polyaniline and water. When it is large, water cannot pass smoothly through the porous structure, but the block-shaped porous structure with polyaniline adhered to the surface of the block-shaped porous structure of this configuration is made of conductive material. In an electrolytic cell in which a plurality of cloth-like, mesh-like, or porous plate-like materials are stacked one on another, even if the thickness of each block-like porous structure is reduced, the block-like porous structure By increasing the number of layers, the total thickness of the block-shaped porous structure between the cathode and the anode can be increased, so that the water is always used individually for the block-shaped porous structure and the block-shaped porous structure. Cloth made of a conductive material interposed between porous structure, a reticulated or porous plate-like material to pass through smoothly, water is able to pass through the entire electrolytic cell smoothly.

In the fourth water treatment apparatus of the present invention, a first opening for introducing water into the tank and a second opening for discharging water in the tank out of the tank are formed in the tank body. A plate-shaped anode and a plate-shaped cathode at least one main surface of which is covered with a polyaniline film accommodate an electrode-facing arrangement structure disposed so as to face the polyaniline film at a predetermined interval so as to face the anode side; Then, the water introduced into the tank from the first opening passes through a gap between the plate-shaped cathode and the plate-shaped anode in the electrode-facing arrangement structure, and is discharged out of the tank from the second opening. An electrolytic cell unit configured as described above, a constant current source for supplying a current between the anode and the cathode, and pumping up the water from a water storage tank in which the water to be sterilized is stored. A pump leading to the first opening, With such a configuration, the above-mentioned water is passed through the gap between the plate-shaped anode and the cathode and the anode, which are arranged so that the plate-shaped cathode whose one main surface is covered with the polyaniline film and the polyaniline film face the anode side. Thus, the method for disinfecting service water of the present invention for disinfecting microorganisms in service water can be rationally and stably performed. In addition, since the electrolytic cell is a unit, when the electrode material and the polyaniline film in the electrolytic cell deteriorate over time, the electrolytic cell can be easily replaced with a new electrolytic cell, and the maintenance property is excellent. .

[0025] In the fourth water treatment apparatus of the present invention, the electrolyzer unit accommodates the plurality of electrode-facing arrangement structures, and the water is connected to each of the plate-like cathodes in the plurality of electrode-facing arrangement structures. It is preferable that the electrolytic cell unit is configured to pass through the gap between the plate-shaped anode, and such a preferable configuration increases the contact period between the water to be sterilized and the polyaniline, thereby dissolving the water in the water. Oxygen can be efficiently reduced to superoxide,
The sterilization efficiency of microorganisms is improved.

In the first to fourth water treatment apparatuses of the present invention, it is preferable that a filter for removing unnecessary suspended matter in the water is provided before the second opening in the tank body of the electrolytic cell unit. With such a configuration, it is possible to filter out dirt and foreign matter in the water, or dead microorganisms,
Water can be made more sanitary.

In the first to fourth water treatment apparatuses of the present invention, it is preferable that a filter for removing unnecessary suspended matter in the water discharged from the second opening of the electrolytic cell unit is connected to the electrolytic cell unit. With such a configuration, dirt and foreign matter in the service water or dead bodies of microorganisms can be filtered, and the service water can be made more sanitary.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the present inventors have found that when polyaniline is brought into contact with service water, it reduces dissolved oxygen (O ₂ ) in the service water and superoxide (. O ₂ ⁻ ) is generated, and the polyaniline once oxidized by the oxygen reduction reaction is electrochemically reduced by the reduction current flowing to the electrode in the service water to be regenerated to polyaniline capable of reducing oxygen in the service water again. It was found that an electrode (cathode) was placed in service water with polyaniline in contact with it, and a reducing current was passed through the electrode (cathode) to reduce polyaniline, and dissolved oxygen was reduced by polyaniline to produce superoxide. The present invention has completed the method for sterilizing water for use of the present invention.
In such a method for sterilizing service water of the present invention, the reaction principle of the reaction between polyaniline and dissolved oxygen in service water and the reduction reaction of polyaniline on an electrode (cathode) is as shown in FIG. In the figures, n represents a natural number as the number of repeating units (degree of polymerization), x represents a natural number as the number of dimeric anilines (a) having a reduced structure constituting the repeating unit, and y represents a repeating number. It represents the number of aniline bimolecular (b) having an oxidized structure constituting a unit.

That is, the dissolved oxygen (O ₂ ) in the service water is brought into contact with the polyaniline to form superoxide (.
O ₂ ^-) is reduced to. Then, the dimer (a) of aniline having a reduced structure in the repeating unit in polyaniline that has contributed to the reduction of dissolved oxygen (O ₂ ) becomes a dimer (b) of aniline having an oxidized structure, Electrode (cathode)
, And is returned to the reduced structure (a) again. Therefore, by flowing a reduction current through the electrode (cathode), the polyaniline is converted to oxygen (O 2
₂ ) A state in which the reduction can be performed (aniline 2 having a reduced structure).
(Including molecular bodies), and the sterilization treatment of the water can be performed substantially semipermanently.

The polyaniline used in the present invention is a polymer containing at least one of the polyanilines represented by the following formulas (1) to (4).

[0031]

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[0032]

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[0033]

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[0034]

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In the above formulas (A) to (A), A represents a negative electrode such as sulfuric acid, perchloric acid, trifluoroacetic acid, boron trifluoride, polyacrylic acid, polystyrenesulfonic acid, cresolsulfonic acid, camphorsulfonic acid and the like. Is an ion,
n is an integer in the range of 2 to 5000, preferably 10 to 1000, and x and y are x + y = 1 and 0 ≦ y ≦ 0.
This is a number that satisfies 5 at the same time.

The water used in the present invention includes tap water, groundwater,
Industrial water, etc., for example, drinking water, cooling water for heat exchangers,
Examples include water for various washings, water used in pools, baths, and the like. Microorganisms in service water to be sterilized in the present invention include bacteria (bacteria), fungi, molds (fungi), Escherichia coli, yeast, deformed fungi, single-cell algae, protozoa, and viruses.

The electrodes used as the cathode and the anode in the present invention are made of a carbon material, a noble metal such as titanium, platinum-plated titanium or platinum, or a conductive material such as ferrite, and are in the form of a sheet, a plate, or a cloth. , A net, a porous plate, a porous block, or the like. In an embodiment in which the electrode is used such that water (water to be treated) is passed through the electrode, an electrode formed in a cloth, net, porous plate, porous block, or the like is used.
Among the above electrode materials, carbon materials are preferable because they are conductive, have no toxicity, do not generate ions or hydroxides, are relatively inexpensive, and do not have corrosive properties such as metals.

In the present invention, the polyaniline is preferably brought into contact with the entire surface of the cathode as much as possible.
Usually, a method is used in which a polyaniline film is adhered to the entire surface of the cathode, that is, the entire surface of the electrode material constituting the cathode by using a polymerization method known per se such as an electrolytic polymerization method. Further, the contact of the polyaniline with the cathode may be performed in such a manner that the polyaniline is attached to the surface of a support other than the cathode, and the support is brought into contact with the cathode.

When a polyaniline film is deposited on the surface of the cathode, the weight ratio of polyaniline to the cathode (polyaniline: cathode) is not particularly limited, but may be 0.001 to 0.1.
It is common to have a ratio of 3: 1. The thickness of the polyaniline film should be as thin as possible.However, if the thickness is too small, the absolute amount of polyaniline decreases, so that the amount of superoxide generated tends to decrease. The flow is hindered, and the regeneration efficiency of polyaniline tends to decrease, and the production cost increases. Therefore, the thickness of the polyaniline film is usually preferably in the range of 0.1 to 10 μm.

When the polyaniline is brought into contact with the cathode in such a manner that the polyaniline is adhered to the surface of a support other than the cathode and the support is brought into contact with the cathode, the support is made of a conductive material and has a certain thickness. It is preferably a block-shaped porous structure having This is because of the block-like porous structure with a certain thickness, not only the polyaniline attached to the outermost surface but also the wall surface surrounding a large number of internal holes, that is, water is applied not only to the polyaniline attached to the inner surface. In contact, the superoxide generation efficiency increases, and furthermore, due to the conductive property, the reduction current flowing to the cathode also flows to the support, and not only the polyaniline in contact with the cathode, but also the surface of the support. This is because the regeneration reaction of polyaniline is performed above, and the regeneration efficiency of polyaniline is improved. Examples of the block-shaped porous structure made of such a conductive material include felts and mats made of carbon fibers, and a three-dimensional molded product obtained by forming a carbon material into a block having a large number of continuous holes. it can. When attaching polyaniline to the surface of the block-shaped porous structure made of such a conductive material,
It is desirable that polyaniline be thinly and uniformly attached to the entire surface of the material as much as possible without losing porosity, but if it is too thin, the amount of superoxide tends to decrease because the absolute amount of polyaniline decreases. In addition, if it is too thick, the manufacturing cost increases, and
The flow of electric current becomes worse, or the gap of the porous three-dimensional molded product is narrowed, thereby obstructing the flow of water. For this reason, the thickness of the polyaniline film is usually in the range of 0.1 to 10 μm. The weight ratio between polyaniline and the block-shaped porous structure (polyaniline: porous structure) is not particularly limited, but is preferably in the range of 0.001: 1 to 0.3: 1.

In the present invention, the current flowing between the anode and the cathode may be a current as low as necessary for stably performing the polyaniline reduction reaction (regeneration reaction) at the cathode, and may be 0.01% in current density (absolute value). About 100 μA · cm ⁻² . With such a value, the reduction reaction (regeneration reaction) of polyaniline can be stably performed without generating harmful gas due to the electrolytic reaction of water itself.

In the sterilization treatment of the water, the water to be sterilized is stored in a fixed volume tank, and an anode and a cathode having a surface contacted with polyaniline are arranged in the water stored in the tank. A method based on batch processing performed by energizing between an anode and a cathode is generally used. In this case, it is preferable to stir the service water with a stirrer in order to efficiently contact the dissolved oxygen in the whole service water stored in the tank with the polyaniline.

Although it depends on the performance of the stirrer, the kind of microorganisms to be sterilized, etc., the above-mentioned treatment method, that is, the method of disinfecting the water contained in the fixed volume tank by batch treatment, should be sterilized. When the amount of water increases, the treatment time tends to be prolonged. For this reason, when sterilizing a relatively large amount of water, a water inlet and a drain were provided, and an electrode (cathode and anode) and a polyaniline arranged to be in contact with the cathode were accommodated in the tank. Using an electrolytic cell unit,
It is preferable to use a method in which service water to be sterilized is passed into the electrolytic cell unit while passing electricity between the cathode and the anode, and dissolved oxygen in the service water is brought into contact with polyaniline. In this case, although it depends on the contact efficiency between the polyaniline and the dissolved oxygen in the electrolytic cell unit, in order to further enhance the sterilizing effect (more efficiently generate superoxide), the electrolytic cell unit should be sterilized. It is preferable to pass water repeatedly. The cell body of the electrolytic cell unit is preferably made of an electrically insulating material that can withstand long-term use, and is generally made of a synthetic resin. Also,
The cathode and anode accommodated in the tank body are usually arranged at a predetermined interval, but a diaphragm may be provided between the two to prevent a short circuit between the two electrodes. As the diaphragm, for example, a glass cloth, a mesh made of an electrically insulating synthetic resin, a porous membrane made of an electrically insulating synthetic resin, or the like is used.
If a filter is placed in front of the outlet in the electrolytic cell unit to filter out dirt and foreign matter contained in the water or dead microorganisms generated in the electrolytic cell, the water can be made more sanitary. Can be something. Further, even if the filter is not integrated with the electrolytic cell unit, the same effect can be obtained even when the filter is connected to the outlet of the electrolytic cell unit when the electrolytic cell unit is used. The time during which the service water stays in the tank, that is, the time during which the service water and the polyaniline are substantially in contact, depends on the nature of the service water to be treated, the use of the service water after the treatment, the amount of the service water to be treated, and the It is appropriately determined in consideration of the size, form, and the like, but is generally in the range of 5 to 600 seconds. With this range, microorganisms can be sufficiently sterilized without lowering treatment efficiency.

[0044]

The present invention will be described in more detail with reference to the following examples. Example 1 A water treatment apparatus shown in FIG. 2 was prepared. In the figure, reference numeral 90 denotes a water treatment device, which is a polyethylene container 7 in which a polyaniline film 3 is adhered to both surfaces of a cathode 1 made of a platinum-plated titanium plate;
Anode 2 made of the same platinum-plated titanium plate as above
The glass cloth 4 is suspended at a predetermined interval, and the water 6 is stirred by a stirrer (stirring blade) 5a which is rotated by driving by a motor 5. The cathode 1 and the anode 2 are each connected to a constant current source (not shown) so that a reduction current for reducing polyaniline flows through the cathode 1. Here, the capacity of the polyethylene container 7 is 2 liters, the size of the platinum-plated titanium plate is 5 cm × 10 cm, and the thickness of the polyaniline film 3 is 2 μm.

A treated water solution was prepared by adding 0.2% by weight of factory wastewater containing a large amount of general bacteria to a saline solution obtained by adding 0.9% by weight of salt to distilled water. 1000 cc of this treated water stock solution 6 is put into the container 7 of the water treatment device 90,
The mixture was stirred with a stirrer (stirring blade) 5a. At the start of the treatment, that is, at the same time as the supply of the treated water solution 6, the current is passed between the cathode 1 and the anode 2 so that the current flowing through the cathode 1 is -3.0 mA (current density is -30.0 μA · cm ^-2 ). Set.

The treated water stock solution 6 was sampled at predetermined intervals, and the sampled treated water was cultured in petri dish agar, and the number of bacteria (the number of colonies:
(Number / number) was measured. Culture conditions were 36 ° C. for 24 hours. The results of the culture test are shown in Table 1 below. Also,
Comparative Example 1 in which the same culture test was performed without conducting electricity to the electrode, and Comparative Example 2 in which the same culture test was performed without applying polyaniline to the cathode and without conducting electricity to the electrode
Are also shown in Table 1.

[0047]

[Table 1]

From the above test results, the bactericidal effect of polyaniline can be confirmed, and if the polyaniline is attached (contacted) to the cathode and energized, general bacteria are almost sterilized in 1 hour treatment and completely germ-free within 3 hours. It was sterilized, and it was found that the sterilizing effect could be maintained for 48 hours or more. In addition, it was found that when no electricity was supplied, there was a sterilizing effect up to 5 hours, but the sterilizing effect was lost after 24 hours. This shows that polyaniline loses its activity in a few hours when electricity is not supplied, ie, the property of reducing oxygen in service water to superoxide, and is restored when electricity is supplied.

Example 2 A water treatment apparatus shown in FIG. 3 was prepared. In FIG. 3, reference numeral 100 denotes a water treatment apparatus, which is a polyethylene treated water tank 18 for accommodating treated water (water to be sterilized) 16 and an electrolytic cell unit 10.
0a, a pump 15 that sucks up the treated water 16 contained in the treated water tank 18 through the hose 51a, and guides the treated water 16 to the inlet 17a of the electrolytic cell unit 100a through the hose 51b, and is connected to the discharge port 17b of the electrolytic cell unit 100a. And a hose 52 for guiding the treated water 16 discharged from the electrolytic cell unit 100a to the treated water tank 18.

The electrolytic cell unit 100a has an inlet 17a
A cathode 11 made of a carbon fiber cloth having a polyaniline film 13 adhered to the surface thereof is placed on the inlet 17a side of a cylindrical tank body 17 made of an acrylic resin having an outlet 17b formed of polyvinyl chloride. An anode 12 made of a carbon fiber cloth is disposed on the discharge port 17b side, and a glass cloth 14 is disposed on the lower surface thereof.
The filter 19 is disposed in a state of being clamped at 0, and a filter 19 is disposed in front of the discharge port 17b. Here, the total area of the front and back main surfaces of the cathode 11 made of carbon fiber cloth is 47.5 cm ² , and the thickness of the polyaniline film 13 attached to each main surface is 3 μm. Further, the polyvinyl chloride porous plate 50 is fixed with its peripheral surface in contact with the inner wall surface of the tank body 17,
Thus, the cathode 11, the glass cloth 14, and the anode 12 are held at predetermined positions. The filter 19 is formed by laminating a wire mesh and filter paper, and is fixed to the inner wall surface of the tank body 17. The cathode 11 and the anode 12 are connected to a constant current source (not shown) outside the tank body 17. In this water treatment apparatus 100, the treated water 16 stored in the treated water tank 18 is sucked up from the tank 18 by the pump 15 through the hose 51a, and the pump 15 passes through the hose 51b to the inlet 1 of the electrolytic cell unit 100a.
After being introduced into the electrolytic cell unit 7a and passing through the inside of the electrolytic cell unit 100a, it is discharged out of the cell through the outlet 17b of the electrolytic cell unit 100a, and returned to the treated water tank 18 again through the hose 52. That is, the treated water 16 is circulated by the pump 15 so as to repeatedly pass through the electrolytic cell unit 100a, and the dissolved oxygen in the treated water 16 repeatedly contacts the polyaniline (the polyaniline film 13), so that the dissolved oxygen in the entire treated water 16 is surely increased. Comes into contact with polyaniline. Further, the cathode 11 and the anode 1 in the electrolytic cell unit 100a
2 and constituent members such as the polyaniline film 13 deteriorate with time, or the cathode 11, the anode 12, or the polyaniline film 13
When clogging occurs, the cell may be replaced with a new electrolytic cell unit.

Using this water treatment apparatus 100, a treated water stock 1500 obtained by adding 0.2% by weight of factory wastewater containing a large amount of general bacteria to a saline solution obtained by adding 0.9% by weight of sodium salt to distilled water.
The cc was placed in the treated water tank 18 and circulated at a flow rate of 2000 cc / min. Simultaneously with the start of this circulation, a current is passed between the cathode 11 and the anode 12 to form a cathode 11 made of carbon fiber cloth.
Is -3.0 mA (the current density is -63.2 [mu] m).
A · cm ^-2 ).

A stock solution of treated water coming out of the hose 52 is sampled at predetermined time intervals, and the sampled treated water is cultured in a Petri dish agar to determine the number of bacteria (the number of colonies: cells / cc) contained in the treated water after the culture. It was measured. Furthermore, 49 hours after the start of the treatment, 0.2% by weight of the used factory wastewater was used.
Was added again, and the treatment was continued. Culture conditions were 36
C. for 24 hours. The results of the culture test are shown in Table 2 below.

[0053]

[Table 2]

From the above test results, it was found that a cathode composed of a cloth-like electrode having polyaniline adhered to the main surface on the surface thereof and an anode composed of the cloth-like electrode were opposed to each other. When water is repeatedly passed through the electrolytic cell unit at an appropriate flow rate while performing appropriate energization between the anode and the anode, general bacteria in the water are almost sterilized by a treatment for 30 minutes, and completely sterilized within one hour. 48 sterilizing effects
It has been found that the time can be maintained for more than one hour, and even if bacteria are added, the activity of polyaniline is not lost, and sterilization treatment of water can be performed semipermanently. The sampled treated water had less dust and foreign matters as the sampling time was later, and the effect of removing unnecessary suspended matter in the treated water by the filter provided in the electrolytic cell unit could be confirmed.

Example 3 A water treatment apparatus shown in FIG. 4 was prepared. 4, the same reference numerals as those in FIG. 3 denote the same or corresponding parts, and reference numeral 200 denotes a water treatment apparatus.
In this embodiment, the electrolytic cell unit 100a of the water treatment apparatus 100 used in Example 2 is replaced with an electrolytic cell unit 200a.

The electrolytic cell unit 200a comprises a block-shaped porous structure 33 made by attaching a polyaniline polymer film on the surface of a carbon fiber mat, a glass cloth 14, a carbon fiber cloth, and a cathode 11 made of a carbon fiber cloth. Are arranged in this order, sandwiched from above and below by a polyvinyl chloride porous plate 50, and fixed in the tank main body 17 so that the cathode 11 is disposed on the inlet 17a side. is there. Here, the carbon fiber mat constituting the block-shaped porous structure 33 is a mat made of carbon fibers having a specific gravity of 1.65 and a diameter of 18 μm and weighing 7 g, and the thickness of the polyaniline film adhered to the surface of the carbon fiber mat. Is 3 μm, and the thickness of the block-shaped porous structure 33 is 70 mm.
It is. The cathode 11 and the anode 12 are connected to a constant current source (not shown) outside the tank body 17.

The operation of the water treatment apparatus 200 is basically the same as the operation of the water treatment apparatus 100. That is, the treated water 16 is circulated by the pump 15 so as to repeatedly pass through the electrolytic cell unit 200a.
The dissolved oxygen in 6 contacts the polyaniline in the porous structure 33 repeatedly. Also in the present water treatment apparatus 200, the cathode 11 and the anode 1 in the electrolytic cell unit 200a are used.
2. When the constituent members such as the block-shaped porous structure 33 and the like are deteriorated with time, or when the cathode 11, the anode 12, or the block-shaped porous structure 33 is clogged, replace with a new electrolytic cell unit. do it.

Using this water treatment apparatus 200, a treated water stock solution obtained by adding 0.2% by weight of factory wastewater containing a large amount of general bacteria to a saline solution obtained by adding 0.9% by weight of salt to distilled water 1500
cc into the treated water tank 18, 2000 cc / min
Circulating at a flow rate of At the same time as the start of this circulation, the cathode 11
And between the anode 12 and the current flowing through the cathode 11 is −5.
0 mA (the current density of the current flowing through the carbon fiber mat of the block-shaped porous structure 33 is -0.53 μA · cm ⁻² )
It was set to be.

The treated water stock solution coming out of the hose 52 is sampled every predetermined time, and the sampled treated water is cultured in a Petri dish agar to determine the number of bacteria (the number of colonies: number / number) contained in the treated water after the culture. It was measured. Culture conditions are
36 ° C., 24 hours. The results of the culture test are shown in Table 3 below. In addition, Comparative Example 3 in which the same culture test was performed as described above without energizing the electrode, and Comparative Example in which the same culture test was performed as described above without attaching polyaniline to the cathode and without energizing the electrode. The results of No. 4 are also shown in Table 3.

[0060]

[Table 3]

From the above test results, it was found that an electrolytic solution obtained by disposing a carbon fiber mat having a cathode composed of a cloth electrode and an anode composed of a cloth electrode in a tank and interposing a carbon fiber mat with polyaniline adhered between them. When using the tank unit and passing the water repeatedly at an appropriate flow rate through the electrolytic tank unit while applying an appropriate current between the cathode and the anode, the general bacteria in the water are almost sterilized in 1 hour, and within 5 hours It was completely sterilized, and it was found that this sterilizing effect could be maintained for 48 hours or more. In addition, it was found that when no electricity was supplied, there was a sterilizing effect up to 5 hours, but the sterilizing effect was lost after 24 hours. From this, even when the polyaniline is not attached to the cathode itself, and the block-shaped porous structure in which polyaniline is attached to the surface of the block-shaped porous structure made of a conductive material is brought into contact with the cathode, It was also found that the current flowing through the cathode also flows through the conductive material of the porous structure, so that the activity of the polyaniline, which once lost its activity, is regenerated on the surface of the porous structure.

Example 4 A water treatment apparatus shown in FIG. 5 was prepared. In FIG. 5, the same reference numerals as those in FIGS. 3 and 4 denote the same or corresponding parts, and reference numeral 300 denotes a water treatment apparatus which is the same as the electrolytic cell unit 100a of the water treatment apparatus 100 used in the second embodiment. 300a.

The electrolytic cell unit 300a is composed of a block-shaped porous structure 33a having a carbon fiber mat and a polyaniline polymer film adhered to the surface thereof on the cathode 11 made of a carbon fiber cloth, a carbon fiber cloth 53, and a carbon fiber mat. , A block-shaped porous structure 33b having a polyaniline polymer film adhered to the surface thereof, a carbon fiber cloth 53, a block-shaped porous structure 33c having a polyaniline polymer film adhered to the surface of a carbon fiber mat, glass cloth 14, And an anode 12 made of carbon fiber cloth stacked in this order, sandwiched by a polyvinyl chloride porous plate 50 from above and below, so that the cathode 11 is disposed in the tank body 17 on the inlet 17a side. It is stuck. Here, each of the block-shaped porous structures 33a to 33c has a specific gravity of 1.65 and a diameter of 1
It is obtained by adhering a 3 μm-thick polyaniline film to the surface of a 2 g carbon fiber mat made of 8 μm carbon fibers, each having a thickness of 20 mm. The cathode 11 and the anode 12 are connected to a constant current source (not shown) outside the tank body 17.

The operation of the water treatment apparatus 300 is basically the same as the operation of the water treatment apparatus 100 of the second embodiment. That is, the treated water 16 repeatedly passes through the electrolytic cell unit 300 a by the pump 15, and the dissolved oxygen in the treated water 16 repeatedly contacts the polyaniline (polyaniline) in the porous structure 33. Main water treatment device 300
Also in the cathode 11 in the electrolytic cell unit 300a,
Constituent members such as the anode 12, the carbon fiber cloth 53, and the block-shaped porous structures 33a to 33c deteriorate over time,
When the cathode 11, the anode 12, the carbon fiber cloth 53, or the block-shaped porous structures 33a to 33c are clogged, it may be replaced with a new electrolytic cell unit.

Using this water treatment apparatus 300, a treated water stock solution 1500 obtained by adding 0.2% by weight of factory wastewater containing a large amount of general bacteria to a saline solution obtained by adding 0.9% by weight of salt to distilled water.
cc into the treated water tank 18, 2000 cc / min
Circulating at a flow rate of At the same time as the start of this circulation, the cathode 11
And the anode 12 is energized, and the current of the cathode 11 is -5.0 mA
(The current density of the current flowing through the carbon fiber mats of the block-shaped porous structures 33a to 33c is -0.62 μA · cm.
^-2 ). The treated water stock solution coming out of the hose 52 was sampled every predetermined time, and the sampled treated water was cultured in petri dish agar, and the number of bacteria (the number of colonies: cells / cc) contained in the treated water after the culture was measured. Furthermore,
Forty-nine hours after the start of the treatment, 0.2% by weight of the used factory wastewater was added again, and the treatment was continued. Culture conditions are
36 ° C., 24 hours. The results of the culture test are shown in Table 4 below.

[0066]

[Table 4]

From the above test results, a carbon fiber mat and a carbon fiber cloth having a cathode composed of a cloth-like electrode and an anode composed of a cloth-like electrode were placed in a tank so as to face each other, and polyaniline was adhered to the surface between them. Using an electrolyzer unit filled with alternately stacked laminates, if water is repeatedly passed through the electrolyzer unit at an appropriate flow rate while applying appropriate current to the cathode and anode, the general bacteria in the water will be 30 minutes It was found that the treatment was almost sterilized, completely aerated in 1 hour, and the sterilizing effect could be maintained for 48 hours or more. In addition, it was found that even if bacteria were added, the activity of polyaniline was not lost, and sterilization of water could be performed semipermanently.
In addition, when compared with the result of Example 3, the flow of the treated water 16 in the electrolytic cell unit was good, and the sterilization treatment efficiency was slightly improved.

Example 5 A water treatment apparatus shown in FIG. 6 was prepared. FIG. 6 is a transparent perspective view. In the figure, the same reference numerals as those in FIG. 5 indicate the same or corresponding parts.
Reference numeral 400 denotes a water treatment apparatus, which is a polyethylene treated water tank 18 for accommodating treated water (water to be sterilized) 16, an electrolytic cell unit 400a, and a treated water tank 1
8 is sucked up through a hose 51a, and the electrolytic cell unit 400a is sucked up through a hose 51b.
Pump 15 leading to the inlet 60a of the cell and the electrolytic cell unit 4
And a discharge hose 65 connected to the discharge port 60b of the discharge port 00a.

The electrolytic cell unit 400a is a rectangular parallelepiped plastic container (120 × 70 ×) in which an inlet 60a and an outlet 60b are formed near the corners of the pair of large-area opposing surfaces that are farthest apart from each other. 8mm, Inner volume 23m
l) In 60, a cathode composed of a plate-like electrode plated with platinum on a titanium substrate and coated on both main surfaces with a polyaniline film (hereinafter referred to as cathode 61) is placed at the center.
On both sides of the plate-shaped cathode 61, an electrode facing arrangement structure 70 in which anodes 62a and 62b made of plate-shaped electrodes plated with platinum on a titanium substrate are arranged at predetermined intervals to face the plate-shaped cathode 61 is accommodated. And a cathode 61 and anodes 62a, 62
b is connected to a constant current source 63 outside the plastic container. Here, the area of the main surface of the cathode composed of the platinum-plated plate-like electrode is 84 cm ² (12 × 7).
The formation of the polyaniline film on both the front and back principal surfaces is performed by an electrolytic polymerization method (Coulomb number: 3.2 Coulomb).
To form a 2.7 μm thick film.

FIG. 7 is a sectional view of the electrolytic cell unit 400a as viewed from above. As shown in FIG.
a and 62b are joined to the inner wall of the container 60 at the other end than the ends 62c and 62d on one side (right side in the figure) of the longitudinal direction, and the cathode 61 is arranged on the other side (left side in the figure) in the longitudinal direction. The other end other than the end 61c is joined to the inner wall of the container 60, and the water 16 contacts the polyaniline films 61a, 61b on both main surfaces of the cathode 61 from the inlet 60a to the outlet 6
A flow path 64 flowing toward Ob is formed.

In this water treatment apparatus 400, the treated water 16 in the treated water tank 18 is sent into the electrolytic cell unit 400 a by the pump 15, and
As a result, the dissolved oxygen in the treated water 16 repeatedly contacts the polyaniline films formed on both main surfaces of the cathode 61.

Using this water treatment apparatus 400, the cathode 61
While flowing a current of −0.3 mA (while a current density of −17.8 μA · cm ⁻² is flowing through the cathode 61), 30 ml / mi of physiological saline in the electrolytic cell unit 400 a.
n at a flow rate of n. The amount of hydrogen peroxide contained in the physiological saline flowing out was determined to be 5 ppm, and it was confirmed that superoxide was effectively generated in the water by contact with polyaniline. Based on the principle that hydrogen peroxide is produced.) Further, the interfacial tension of the physiological saline was 70.6 dyne / cm before entering the electrolytic cell, but became 54.2 dyne / cm after exiting the electrolytic cell. This also confirmed that superoxide was effectively generated in the water.

Therefore, in the same manner as in the above embodiment, a treated water stock solution obtained by adding 0.2% by weight of factory wastewater containing a large amount of general bacteria to a saline solution obtained by adding 0.9% by weight of salt to distilled water was used. , At a flow rate of 30 cc / min.
When the solution was poured into the sample solution No. 00a and sterilized, the results were substantially the same as those in Examples 1 to 4. Although the treated water 16 is not circulated here, the treated water 16 discharged from the discharge hose 65 may be returned into the treated water tank 18 to circulate the treated water 16.

In each of the embodiments described above, the energization between the cathode and the anode is performed continuously. However, this is not always necessary. Can no longer do,
That is, the polyaniline has a reduced structure of aniline 2
The intermittent energization may be such that the energization is started again before the molecular body completely disappears.

[0075]

As described above, according to the method for sterilizing water according to the present invention, an anode and a cathode having a surface contacted with polyaniline are arranged in water, and intermittently or intermittently between the anode and the cathode. By sterilizing microorganisms contained in the water by superoxide generated by reducing the dissolved oxygen in the water while the polyaniline is continuously energized, without adding a drug, extremely low voltage with a small voltage It is possible to perform highly efficient sterilization treatment of water. Therefore, there are no safety issues related to the transport, handling, storage, etc. of the drug or any issues that cause environmental pollution,
In addition, there is an effect that an extremely useful sterilizing method for service water can be provided which can sterilize the service water at low cost with energy saving.

In the method for sterilizing service water according to the present invention, the service water to be sterilized is efficiently brought into contact with the polyaniline, and the dissolved oxygen in the service water is efficiently superposed. It is reduced to an oxide, and moreover, the frequency of contact between the superoxide and the microorganisms in the service water is effectively increased, and the effect of improving the sterilization efficiency is obtained.

In the method for sterilizing water according to the present invention, the cathode is a cloth-like, mesh-like or porous plate-like cathode having at least one principal surface covered with a polyaniline film. By the preferred embodiment of flowing so as to pass through the plate-shaped cathode and the polyaniline membrane, even if the entire service water to be sterilized is in contact with polyaniline, even if the amount of water to be sterilized is large,
The dissolved oxygen in the service water is efficiently reduced to superoxide, and the effect of efficiently sterilizing microorganisms in the service water is obtained.

In the method for sterilizing service water according to the present invention, the service water is flowed so as to repeatedly pass through a cloth-like, mesh-like or porous plate-like cathode and a polyaniline membrane, so that the entire service water is surely and plurally supplied. In contact with polyaniline, dissolved oxygen in service water is uniformly reduced to superoxide, so that even if the amount of service water to be sterilized is large, microorganisms in service water can be almost completely eliminated. The effect of being able to sterilize is obtained.

In the method for sterilizing water according to the present invention, the water is preferably applied to both the front and back surfaces of the cathode by forming a polyaniline film on both front and back main surfaces of the cloth-like, net-like or porous plate-like cathode. By passing through the polyaniline membrane provided on the surface, the entire service water to be sterilized comes into contact with the polyaniline efficiently, and the dissolved oxygen in the service water is reduced to superoxide in a short time,
The effect of shortening the time for sterilizing microorganisms can be obtained.

In the method for disinfecting water of the present invention, the cathode is a cloth-like, mesh-like or porous plate-like cathode,
A block-shaped porous structure in which polyaniline is adhered to the surface of a block-shaped body having a porous structure made of a conductive material is arranged so as to be in contact with one main surface of the cloth-like, net-like or porous plate-like cathode. Then, the preferred embodiment of flowing the water so as to pass through the cloth-like, mesh-like or porous plate-like cathode and the porous structure ensures that the entire water to be sterilized is in contact with the polyaniline, Is evenly reduced to superoxide, so that even if the amount of service water to be sterilized is large, the effect of efficiently sterilizing microorganisms in the service water can be obtained.

In the method for sterilizing service water according to the present invention, the service water is preferably made to flow so as to repeatedly pass through a cloth-like, mesh-like or porous plate-like cathode and a block-like porous structure. Contact with polyaniline reliably and multiple times to reduce the dissolved oxygen in the service water to superoxide evenly, so that even if the amount of service water to be sterilized is large, microorganisms in the service water can be almost completely eliminated. The effect is obtained that sterilization can be performed to such an extent that it can be eliminated.

Further, in the method for disinfecting water of the present invention, a plate-shaped anode and a plate-shaped cathode having at least one main surface covered with a polyaniline film are disposed so as to face each other so that the polyaniline film faces the anode. According to a preferred embodiment of passing water through the gap between the cathode and the anode, the polyaniline film covers the main surface of the cathode when the water passes through the gap between the opposed plate-shaped cathode and the anode. , The dissolved oxygen in the service water is efficiently reduced to superoxide, and the effect of efficiently killing microorganisms in the service water is obtained.

According to the first water treatment apparatus of the present invention, the water tank in which the water to be sterilized is stored, the anode disposed at least partially so as to be immersed in the water, A cathode having a polyaniline film attached thereto and arranged so that the polyaniline film is immersed in the service water, and a current source for applying a current to the anode and the cathode are provided, whereby dissolved oxygen in the service water is provided. Thus, there is obtained an effect that the method for sterilizing water of the present invention for sterilizing microorganisms in water can be performed rationally and stably while regenerating polyaniline which is oxidized by the reaction with polyaniline capable of reducing dissolved oxygen again.

Further, in the first water treatment apparatus of the present invention, the water to be sterilized is efficiently brought into contact with the polyaniline, and the water in the water is dissolved in a preferable mode in which a stirrer for stirring the water is provided. Oxygen is efficiently reduced to superoxide, and the frequency of contact between the superoxide and the microorganisms in the service water is increased, so that the effect of improving the sterilization efficiency of the microorganisms in the service water is obtained.

According to the second water treatment apparatus of the present invention, the first opening for introducing the water into the tank and the second opening for discharging the water in the tank to the outside of the tank are provided in the tank body. Formed,
At least one main surface is a cloth-like coated with a polyaniline film,
A mesh-shaped or porous plate-shaped cathode is arranged on the first opening side, and a cloth-shaped, mesh-shaped or porous plate-shaped anode is arranged on the second opening side, and introduced into the tank from the first opening. The water is passed through the cloth-like, mesh-like or porous plate-like cathode and the polyaniline membrane, and further passes through the cloth-like, mesh-like or porous plate-like anode, and is discharged from the second opening to the outside of the tank. An electrolytic cell unit, a constant current source for applying a constant current to the anode and the cathode, a water storage tank in which water to be sterilized is stored, and pumping water from the water storage tank. And a pump for guiding the water to the first opening of the tank so that the water passes through a cloth-like, net-like, or porous plate-like cathode whose at least one main surface is covered with a polyaniline film. To disinfect microorganisms in the water The method for sterilizing water of the present invention can be carried out rationally and stably, and when the electrode material or polyaniline in the electrolytic cell unit is deteriorated with time, or when the electrode or the polyaniline film is clogged, the electrolytic treatment is performed. There is an effect that the tank unit can be easily replaced with a new one.

In the second water treatment apparatus of the present invention, the drainage pipe connected to the second opening of the electrolytic cell unit for discharging the water discharged from the electrolytic cell unit into the water storage tank is provided. According to a preferred embodiment, the water to be sterilized can be easily and repeatedly passed through the electrolytic cell unit, and the water is cloth-like, net-like or porous having at least one main surface covered with a polyaniline film. An effect is obtained that the method for sterilizing service water of the present invention, which sterilizes microorganisms in service water by flowing so as to repeatedly pass through a plate-shaped cathode, can be performed rationally and stably.

Further, in the second water treatment apparatus of the present invention, the cloth-like, net-like or porous plate-like cathode is coated on both front and back main surfaces with a polyaniline film, and the polyaniline film is coated on both front and back main surfaces. According to a preferred embodiment, the coated cloth-like, mesh-like or porous plate-like cathode is disposed in the electrolytic cell so that the water sequentially passes through the polyaniline films provided on the front and back main surfaces, The water to be sterilized efficiently contacts the polyaniline, and the dissolved oxygen in the water is reduced to superoxide in a short time,
The effect of shortening the sterilization time of the microorganism is obtained.

According to the third water treatment apparatus of the present invention, the first opening for introducing the water into the tank and the second opening for discharging the water in the tank to the outside of the tank are provided in the tank body. Formed,
A cloth-like, mesh-like, or porous plate-like cathode is disposed on the first opening side, and a cloth-like, mesh-like, or porous plate-like anode is provided in the second opening side.
Arranged on the opening side, a block-shaped porous structure in which polyaniline is adhered to the surface of a block-shaped porous structure made of a conductive material between the cathode and the anode is arranged to be in contact with the cathode. The water introduced into the tank from the first opening passes through the cloth-like, mesh-like or porous plate-like cathode and the relatively thick porous structure, and
After passing through a mesh or porous plate-shaped anode, an electrolytic cell unit configured to be discharged out of the cell from the second opening, a constant current source that applies a constant current to the anode and the cathode,
By providing a service water storage tank in which service water to be sterilized is stored, and a pump for pumping service water from the service water storage tank and guiding the pump to the first opening of the electrolytic cell unit, A water-like, cloth-like, mesh-like or porous plate-like cathode and a block-like porous structure made of a conductive material placed in contact with one main surface of the cathode with a polyaniline attached to the surface of a block-like porous structure The method for sterilizing water of the present invention for sterilizing microorganisms in the water by flowing so as to pass through the porous structure can be rationally and stably performed, and furthermore, the electrode material in the electrolytic cell unit and When the constituent material of the porous structure deteriorates with time or when the electrode or the porous structure is clogged, the effect that the electrolytic cell unit can be easily replaced with a new one is obtained.

In the third water treatment apparatus of the present invention, a drain pipe is provided which is connected to the second opening of the electrolytic cell unit and discharges the water discharged from the electrolytic cell unit into the water storage tank. According to the preferred embodiment, the water to be sterilized can be easily and repeatedly passed through the electrolytic cell unit, and the water is used as a cloth-like, mesh-like or porous plate-like cathode, and one main surface of the cathode. Microorganisms in the water are sterilized by flowing the block-shaped porous structure made of conductive material placed in contact with the surface so that it repeatedly passes through the surface of the block-shaped porous structure with polyaniline attached to the surface. The present invention has an effect that the method for sterilizing water for use according to the present invention can be executed rationally and stably.

Further, in the third water treatment apparatus of the present invention, the electrolytic cell conducts the block-shaped porous structure in which polyaniline is adhered to the surface of the block-shaped porous structure between the cathode and the anode. Even if the thickness of each block-shaped porous structure is reduced, even if the thickness of each block-shaped porous structure is reduced, By increasing the number of stacked porous structures, the total thickness of the block-shaped porous structure between the cathode and the anode can be increased. Even if the thickness is increased, a cloth-like, net-like or porous plate made of a conductive material interposed between the block-shaped porous structure and the block-shaped porous structure is always used. Passed in over's, the effect is obtained that the entire electrolytic cell water passes smoothly.

According to the fourth water treatment apparatus of the present invention, the first opening for introducing the water into the tank and the second opening for discharging the water in the tank to the outside of the tank are provided in the tank body. Formed,
A plate-shaped anode and a plate-shaped cathode having at least one main surface covered with a polyaniline film accommodate an electrode-facing arrangement structure that is arranged at a predetermined interval so that the polyaniline film faces the anode side. After the water introduced into the tank from the first opening passes through the gap between the plate-shaped cathode and the plate-shaped anode in the electrode-facing arrangement structure, the water is discharged out of the tank from the second opening. Electrolyzer unit configured as described above, a constant current source for energizing between the anode and the cathode, and pumping up the water from a water storage tank in which water to be sterilized is stored, and this is used for the electrolytic cell. By providing a pump for guiding to the first opening, the water is opposed so that the plate-shaped anode, the plate-shaped cathode covered with a polyaniline film on one main surface, and the polyaniline film face the anode side. Between the arranged cathode and anode The sterilization method of the water of the present invention, which sterilizes microorganisms in the water by passing through it, can be executed reasonably and stably, and when the electrode material or the polyaniline film in the electrolytic cell unit deteriorates with time, etc. The effect is that the electrolytic cell unit can be easily replaced with a new one.

[0092] In the fourth water treatment apparatus of the present invention, the electrolyzer unit accommodates the plurality of electrode-facing arrangement structures, and the water is connected to each of the plate-like cathodes in the plurality of electrode-facing arrangement structures. By a preferred embodiment that is configured to pass through the gap with the plate-shaped anode,
Since the contact period between the service water to be sterilized and the polyaniline can be lengthened and the dissolved oxygen in the service water can be efficiently reduced to superoxide, the effect of improving the sterilization efficiency of microorganisms can be obtained.

In the first to fourth water treatment apparatuses of the present invention, a preferred embodiment is provided with a filter for removing unnecessary suspended matter in the water before the second opening in the tank body of the electrolytic cell unit. Accordingly, an effect is obtained that dirt, foreign matter, or dead bodies of microorganisms in the water are filtered during the sterilization treatment of the water, thereby making the water more sanitary.

Further, in the first to fourth water treatment apparatuses of the present invention, according to a preferred embodiment, a filter for removing unnecessary suspended matter in the water discharged from the second opening of the electrolytic cell unit is connected to the electrolytic cell unit. In addition, during the sterilization treatment of the water, dirt and foreign matters in the water, or dead bodies of microorganisms are filtered out, so that the effect of making the water more sanitary can be obtained.

[Brief description of the drawings]

FIG. 1 is a diagram for explaining the reaction principle of a reaction between polyaniline and dissolved oxygen in service water and a reduction reaction of polyaniline on an electrode (cathode).

FIG. 2 is a sectional view showing a configuration of a water treatment apparatus used in Embodiment 1 of the present invention.

FIG. 3 is a sectional view showing a configuration of a water treatment apparatus used in Embodiment 2 of the present invention.

FIG. 4 is a sectional view showing a configuration of a water treatment apparatus used in Embodiment 3 of the present invention.

FIG. 5 is a sectional view showing a configuration of a water treatment apparatus used in Embodiment 4 of the present invention.

FIG. 6 is a perspective view showing the configuration of a water treatment apparatus used in Embodiment 5 of the present invention.

FIG. 7 is a cross-sectional view showing a configuration of a water treatment apparatus used in Embodiment 5 of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cathode 2 Anode 3 Polyaniline film 4 Glass cloth 5 Motor 5a Stirrer 6 Water 7 Polyethylene container 90 Water treatment device

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C02F 1/50 550 C02F 1/50 550D 560 560F

Claims (20)

[Claims] 1. An anode and a cathode in which polyaniline is brought into contact with the surface are placed in service water, and the polyaniline reduces dissolved oxygen in the service water while intermittently or continuously energizing between the anode and the cathode. A method for disinfecting water for disinfecting microorganisms contained in the water with superoxide generated by the method. 2. The method for sterilizing service water according to claim 1, wherein the service water is stirred by a stirrer. 3. A cloth-like, mesh-like or porous plate-like cathode, wherein at least one principal surface of the cathode is coated with a polyaniline film, and water is applied to the cloth-like, mesh-like or porous plate-like cathode and a polyaniline film. The method for sterilizing water according to claim 1, wherein the water is flowed so as to pass through. 4. The method for sterilizing service water according to claim 3, wherein the service water is caused to flow so as to repeatedly pass through the cloth-like, mesh-like or porous plate-like cathode and the polyaniline membrane. 5. The method according to claim 3, wherein a polyaniline film is coated on both front and back main surfaces of the cloth-like, net-like, or porous plate-like cathode. 6. A block-shaped porous structure in which a cathode is a cloth-shaped, mesh-shaped or porous plate-shaped cathode, and polyaniline is adhered to a surface of a block-shaped porous structure made of a conductive material. A cloth-like, mesh-like or porous plate-shaped cathode is disposed so as to be in contact with one main surface, and water is passed through the cloth-like, mesh-like or porous plate-like cathode, and a block-like porous structure. The method for sterilizing water for use according to claim 1, wherein the water is fluidized. 7. The method for sterilizing water according to claim 6, wherein the water is flowed so as to repeatedly pass through the cloth-like, mesh-like or porous plate-like cathode and the block-like porous structure. 8. A plate-shaped anode and a plate-shaped cathode at least one principal surface of which is covered with a polyaniline film are opposed to each other such that the polyaniline film faces the anode, and a gap between the cathode and the anode is provided. The method for sterilizing water according to claim 1, wherein the water is passed. 9. A water treatment apparatus used in the method for sterilizing water according to claim 1, wherein a water tank in which water to be sterilized is stored, and at least a part of the water tank is immersed in the water. A water treatment apparatus, comprising: an anode disposed at a position; a cathode having a polyaniline film adhered to the surface thereof; and a cathode disposed so that the polyaniline film is immersed in the service water; and a current source for supplying a current to the anode and the cathode. 10. The water treatment apparatus according to claim 8, further comprising a stirrer for stirring the water. 11. A water treatment apparatus used in the method for sterilizing water according to claim 1, wherein the first opening for introducing the water into the tank and the water in the tank are moved out of the tank. A cloth-like, mesh-like, or porous plate-like cathode having a second opening for discharging and having at least one main surface covered with a polyaniline film is disposed on the first opening side, and is formed in a cloth-like, mesh-like, or porous state. A plate-shaped anode is disposed on the second opening side, and water introduced into the tank from the first opening passes through the cloth-like, net-like or porous plate-like cathode and the polyaniline film, and further, the cloth-like An electrolytic cell unit configured to pass through a mesh-like or porous plate-like anode and to be discharged out of the tank from the second opening; a current source for applying a current to the anode and the cathode; A water storage tank in which water is stored, and pumping water from the water storage tank. Raised, water treatment apparatus characterized by comprising a pump for directing it to said first opening of said electrolyzer unit. 12. A drainage pipe connected to the second opening of the electrolytic cell unit and configured to discharge the water discharged from the electrolytic cell unit into the water storage tank.
2. The water treatment apparatus according to 1. 13. A cloth-like, net-like or porous plate in which a polyaniline film is coated on both front and back main surfaces of a cloth-like, mesh-like or porous plate-like cathode, and the polyaniline film is coated on both front and back surfaces of the cathode. 13. The water treatment apparatus according to claim 11, wherein a cathode having a shape of a circle is disposed in the electrolytic cell unit such that water passes through the polyaniline films provided on the front and back main surfaces in order. 14. A water treatment apparatus used in the method for sterilizing water according to claim 1, wherein the first opening for introducing the water into the tank and the water in the tank are moved out of the tank. A second opening for discharging is formed, and a cloth-like, mesh-like or porous plate-like cathode is disposed on the first opening side, and a cloth-like, mesh-like or porous plate-like anode is provided on the second opening side. Disposed, a block-shaped porous structure in which polyaniline is adhered to the surface of a block-shaped porous structure made of a conductive material between the cathode and the anode is disposed so as to be in contact with the cathode; After the water introduced into the tank from one opening passes through the cloth-like, mesh-like or porous plate-like cathode and the porous structure, and further passes through the cloth-like, mesh-like or porous plate-like anode, An electrolytic cell unit configured to be discharged out of the cell from the second opening; A current source that supplies current to the anode and the cathode, a water storage tank in which water to be sterilized is stored, and a pump that pumps water from the water storage tank and guides it to the first opening of the electrolytic cell unit. A water treatment apparatus comprising: 15. A drain pipe connected to the second opening of the electrolytic cell unit for discharging the water discharged from the electrolytic cell unit into the water storage tank.
5. The water treatment apparatus according to 4. 16. An electrolytic cell comprising: a block-shaped porous structure in which polyaniline is adhered to the surface of a block-shaped porous structure between a cathode and an anode; The water treatment apparatus according to claim 14 or 15, wherein a plurality of the water treatment apparatuses are arranged with a plurality of plates interposed therebetween. 17. A water treatment apparatus used in the method for sterilizing water according to claim 1, wherein the first opening for introducing the water into the tank and the water in the tank are moved out of the tank. A second opening for discharging is formed, and a plate-shaped anode and a plate-shaped cathode having at least one main surface covered with a polyaniline film are opposed at a predetermined interval so that the polyaniline film faces the anode side. After receiving the disposed electrode-facing arrangement structure, the water introduced into the tank from the first opening passes through the gap between the plate-shaped cathode and the plate-shaped anode in the electrode-facing arrangement structure. An electrolytic cell unit configured to be discharged out of the cell from the second opening; a current source for applying current to the anode and the cathode; and pumping the water from a water storage tank in which water to be sterilized is stored. This is the A water treatment apparatus, comprising: a pump for leading to one opening. 18. An electrolytic cell unit for accommodating a plurality of electrode-facing arrangement structures such that water passes through gaps between respective plate-like cathodes and plate-like anodes in the plurality of electrode-facing arrangement structures. The water treatment apparatus according to claim 17, wherein the water treatment apparatus is configured. 19. The water treatment apparatus according to claim 9, further comprising a filter for removing unnecessary suspended matter in the water before the second opening in the tank body of the electrolytic cell unit. 20. The water treatment apparatus according to claim 9, wherein a filter for removing unnecessary suspended matter in the water discharged from the second opening of the electrolytic cell unit is connected to the electrolytic cell unit.