JP2016101579A - Apparatus for adjusting liquid quality of aqueous liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel apparatus for adjusting liquid quality of an aqueous liquid.SOLUTION: The disclosed apparatus is an apparatus for adjusting liquid quality of an aqueous liquid. The apparatus includes a container 10 in which the aqueous liquid is disposed, a separator 13 partitioning the container 10 into a first tank 11 and a second tank 12, a first electrode 21, a second electrode 22, and a power supply 23 for applying a voltage between the first electrode 21 and the second electrode 22. A first outflow passage 11b is connected above the first tank 11, and a second outflow passage 12b is connected above the second tank 12. The second tank 12 and the second outflow passage 12b constitute a part of a channel through which the aqueous liquid flows. The first outflow passage 11b and the second outflow passage 12b are connected.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an apparatus for adjusting the quality of an aqueous liquid.

  One of the physical properties of water is the dissolved hydrogen concentration. Water with a high dissolved hydrogen concentration is expected to have various applications due to its characteristics. For example, it is expected to be applied to health promotion, beauty, washing, sterilization, and the like.

  Conventionally, methods for preparing water having a high dissolved hydrogen concentration have been proposed. For example, a method is disclosed in which hydrogen gas is blown into water to increase the concentration of dissolved hydrogen in the liquid (for example, Japanese Patent Application Laid-Open No. 2007-230964). However, the method of blowing hydrogen gas from the outside requires a gas supply source, which is costly and troublesome.

  On the other hand, an apparatus for increasing the dissolved hydrogen concentration of water by dissolving hydrogen gas generated when water is electrolyzed in water is disclosed (International Publication WO2012 / 60078 pamphlet). In this apparatus, water is electrolyzed in the tank. The water level in the tank may vary depending on conditions. If the water level in the tank changes greatly, the water may overflow from the tank.

JP 2007-230964 A International Publication WO2012 / 60078 Pamphlet

  Under such circumstances, one of the objects of the present invention is to provide a novel apparatus for adjusting the quality of an aqueous liquid.

  To achieve the above object, the present invention provides an apparatus. The apparatus is an apparatus for adjusting the quality of an aqueous liquid, the container in which the aqueous liquid is disposed, a separator that partitions the container into a first tank and a second tank, and the first A first electrode disposed in the tank, a second electrode disposed in the second tank, and a power source for applying a voltage between the first electrode and the second electrode A first outflow path is connected above the first tank, a second outflow path is connected above the second tank, and the second tank and the second tank The second outflow path constitutes a part of the flow path through which the aqueous liquid flows, and the first outflow path and the second outflow path are connected.

  The present invention also provides other devices. The apparatus is an apparatus for adjusting the quality of an aqueous liquid, a container in which an aqueous liquid is disposed, a separator that partitions the container into a first tank and a second tank, and the first A first electrode disposed in the tank; a second electrode disposed in the second tank; and a power source for applying a voltage between the first electrode and the second electrode. An outlet channel is connected to the upper side of the second tank, and a cylindrical part capable of raising the aqueous liquid is connected to the upper side of the first tank, and is downstream of the second tank. In the channel on the side, there is an open portion that is open to the atmosphere.

  The present invention also provides other devices. The apparatus is an apparatus for adjusting the quality of an aqueous liquid, the container in which the aqueous liquid is disposed, a separator that partitions the container into a first tank and a second tank, and the first A first electrode disposed in the tank, a second electrode disposed in the second tank, and a power source for applying a voltage between the first electrode and the second electrode An outflow passage is connected above the second tank, and a cylindrical part capable of rising the aqueous liquid is connected above the first tank, and the second tank The flow path on the downstream side is provided with a flow rate regulator for controlling the flow in the flow path.

  According to the present invention, a novel apparatus for adjusting the quality of an aqueous liquid can be obtained.

FIG. 1 is a diagram schematically showing an example of the first apparatus of the present invention. FIG. 2 is a diagram schematically showing the function of the first device of the present invention. FIG. 3 is a diagram schematically showing another example of the first apparatus of the present invention. FIG. 4 is a diagram schematically showing an example of the second apparatus of the present invention. FIG. 5 is a diagram schematically showing an example of the third device of the present invention. FIG. 6 is a cross-sectional view schematically showing an example of the first activated carbon filter. FIG. 7 is a diagram schematically showing the potential of activated carbon. FIG. 8 is a cross-sectional view schematically showing an example of the second activated carbon filter. FIG. 9 is a diagram schematically showing another example of the first apparatus of the present invention.

  Embodiments of the present invention will be described below. In the following description, embodiments of the present invention will be described by way of examples, but the present invention is not limited to the examples described below. In the following description, specific numerical values and specific materials may be exemplified, but the present invention is not limited to these examples.

  The devices (first to third devices) of the present invention described below are devices for adjusting the quality of the aqueous liquid. Liquid quality includes dissolved hydrogen concentration, free chlorine concentration, and redox potential (ORP). In another aspect, the apparatus of the present invention is an apparatus for preparing an aqueous liquid containing dissolved hydrogen, an apparatus for preparing an aqueous liquid containing free chlorine, or an apparatus for adjusting a redox potential. Hereinafter, an aqueous liquid containing dissolved hydrogen may be referred to as “hydrogen water”. In another aspect, the apparatus of the present invention is an apparatus for increasing the dissolved hydrogen concentration of an aqueous liquid.

[First device]
The first apparatus includes a container in which an aqueous liquid is disposed, a separator that partitions the container into a first tank and a second tank, a first electrode disposed in the first tank, and a second tank. And a power source for applying a voltage between the first electrode and the second electrode. A first outflow path is connected above the first tank. A second outflow path is connected above the second tank. The first outflow path and the second outflow path are connected. The second tank and the second outflow path constitute a part of the flow path through which the aqueous liquid flows. Hereinafter, the flow path through which the aqueous liquid flows may be referred to as “flow path (P)”. The gas generated in the first electrode mainly flows from the first outflow path to the flow path (P).

In this specification, “aqueous liquid” means a liquid containing water. Examples of the aqueous liquid include water such as tap water and an aqueous solution. The aqueous liquid may be an aqueous solution in which a salt is dissolved. Further, the aqueous liquid may contain an organic solvent (for example, alcohol) other than water. Usually, the proportion of water in the solvent of the aqueous liquid is 50% by weight or more (for example, 80% by weight or more, 90% by weight or more, or 95% by weight or more), and 100% by weight or less. Typically, the aqueous liquid solvent is water. If the ion concentration in the aqueous liquid is too low, it becomes difficult for current to flow. On the other hand, if the ion concentration is too high, the efficiency is lowered or the pH change is increased. The conductivity of the aqueous liquid may be in the range of 100 μS / cm to 50 mS / cm (eg, 140 μS / cm to 2 mS / cm). When the concentration of ions is low, ions may be added to the aqueous liquid as necessary. For example, a salt may be dissolved in an aqueous liquid. The salt to be dissolved is not particularly limited, and may be a salt containing Na ⁺ , K ⁺ , Cl ⁻ , SO ₄ ²⁻ , PO ₄ ³⁻ , CO ₃ ^{2− and the} like. Examples of salts include sodium chloride, sodium sulfate, sodium hydrogen sulfate, sodium phosphate, sodium hydrogen phosphate, sodium nitrate, sodium carbonate, sodium hydrogen carbonate, and salts in which these sodium are replaced with potassium.

  There is no limitation in particular in the 1st and 2nd tank (container), What is necessary is just to be able to hold | maintain an aqueous liquid stably. Examples of the first tank and the second tank include a resin tank and a tank whose inner surface is made of resin. In a typical example, one container is partitioned by a separator (or a separator and a partition) to form first and second tanks. There is no particular limitation on the internal volume of the first tank. In a preferred example, the internal volume of the second tank is equal to or greater than the internal volume of the first tank.

  As the separator, a separator that can suppress a short circuit between the electrodes and suppress passage of gas generated on the surface of the electrode is used. The separator allows liquids and ions (both positive and negative ions) to pass through. On the other hand, the separator suppresses and preferably prevents the passage of gas (bubbles) in the aqueous liquid. The separator has an insulating property. In another aspect, the separator is a diaphragm that allows both cations and anions to pass therethrough (that is, a diaphragm that does not have ion exchange capacity), and is a porous and insulating diaphragm. The apparatus of the present invention usually does not include an ion exchange membrane (ion exchange material).

  In a preferred example, the separator is arranged in parallel with the flow of the aqueous liquid in the second tank. By disposing the separator as such, mixing of the aqueous liquid in the first tank and the aqueous liquid in the second tank can be suppressed.

  The separator preferably has hydrophilicity. By using a separator having hydrophilicity, gas permeation can be more effectively suppressed. Examples of the separator include a separator made of a resin (for example, resin fiber). Resins include natural resins and synthetic resins. Examples of the form of the separator include a cloth (woven fabric or non-woven fabric) and a membrane (porous membrane). Examples of the separator having hydrophilicity include a separator containing or made of a resin containing a hydrophilic group. Examples of the separator having hydrophilicity include a separator made of or made of a hydrophilic resin. The separator may be a cloth or a film formed of cotton, hemp, rayon, hair, silk, or the like.

  As a measure of whether or not it is hydrophilic, one of the measures can be whether or not a phenomenon such as a capillary phenomenon occurs. Specifically, a part of the separator is immersed in water, and the remaining part is taken out of the water. At that time, if the water rises against the gravity against the remaining portion, it can be estimated that the separator is hydrophilic.

  An aqueous liquid inflow path and an aqueous liquid outflow path (second outflow path) are connected to the second tank. The second outflow path is provided above the second tank. In a preferred example, the inflow path is provided below the second tank. In this example, the aqueous liquid that has flowed in from below the second tank flows out from above the second tank. In this case, the gas generated at the second electrode flows out from the second outflow path together with the aqueous liquid. Note that a filter for removing foreign substances may be provided in the inflow channel (the same applies to the second and third devices).

  The first tank is connected to a flow path (P) through which the aqueous liquid flows via a separator. That is, the aqueous liquid flowing through the flow path (P) moves into the first tank via the separator. In principle, the aqueous liquid in the first tank is mixed with the aqueous liquid outside the first tank (ie, the aqueous liquid in the second tank) only by passing the aqueous liquid through the separator, Or replaced by it. This example includes a case where the aqueous liquid in the first tank is discharged from the drainage channel, and the aqueous liquid in the second tank moves into the first tank accordingly. On the other hand, the aqueous liquid in the second tank is mixed with or replaced by the aqueous liquid outside the second tank as the aqueous liquid flows through the flow path (P).

  A first outflow path is provided above the first tank. The first outflow path and the second outflow path are connected by a connecting portion. At least a part of the gas generated in the first electrode flows through the flow path (P) through the first outflow path and the connection portion.

  As the first and second electrodes, electrodes capable of causing an electrolysis reaction of water are used. It is preferable that a metal that easily causes an electrolysis reaction of water exists on the surfaces of the first and second electrodes. Examples of metals that are susceptible to electrolysis of water include platinum. Examples of the first and second electrodes include metal electrodes, and metal electrodes that can exist stably in the electrolysis process are preferably used. A preferred example of the first and second electrodes is a metal electrode having platinum on the surface. Specifically, a platinum electrode or a metal electrode whose surface in contact with a liquid is coated with platinum is preferably used. Examples of metals coated with platinum include niobium, titanium, tantalum, and other metals. The surface of the electrode (anode) where oxygen gas is generated is preferably coated with platinum. An electrode made of a conductive material other than metal (for example, a conductive carbon material) may be used. Alternatively, an electrode obtained by coating the surface of these conductive materials with a metal (platinum or other metal) may be used.

  The distance between the first electrode and the second electrode may be in a range of 0.1 mm to 10 mm (for example, a range of 0.1 mm to 5 mm). The shorter the distance between the first electrode and the second electrode, the lower the voltage required for water electrolysis. Also, the shorter the distance between the first electrode and the second electrode, the easier it is for hydrogen ions and hydroxide ions to move from one tank to the other, so the aqueous liquid in the first tank The difference between the pH of the aqueous liquid and the pH of the aqueous liquid in the second tank can be reduced. Unless the first electrode and the second electrode are short-circuited, the first electrode and the second electrode may be in contact with the separator. The distance between the first electrode and the separator and the distance between the second electrode and the separator may be in the range of 0 mm to 5 mm (for example, in the range of 0 mm to 1 mm), respectively.

  Each of the first and second electrodes may have a shape that extends two-dimensionally. For example, the first and second electrodes may be flat electrodes. A through hole may be formed in the flat electrode. Further, each of the first and second electrodes may be composed of a plurality of linear electrodes arranged on a virtual plane. When the first and second electrodes have a shape that expands two-dimensionally, it is preferable that the first electrode and the second electrode face each other in parallel with the separator interposed therebetween. Further, the plurality of first electrodes and the plurality of second electrodes may be opposed to each other with the separator interposed therebetween.

  Each of the first electrode and the second electrode may include a plurality of linear electrodes arranged in a stripe shape along the vertical direction. By using such an electrode, the gas generated on the surface of the electrode is likely to rise in the vertical direction and is less likely to stay on the surface of the electrode.

  A direct current power source can be used as the power source. The power source may be an AC-DC converter that converts an AC voltage obtained from an outlet into a DC voltage. The power source may be a power generation device such as a solar cell or a fuel cell, or a battery (for example, a secondary battery). By using a power generation device or a battery as a power source, the device of the present invention can be used in regions and situations where power is not supplied.

  In an example of the first device, at least a part of the first outflow path may be present at a position higher than the connection portion between the first outflow path and the second outflow path. The part functions as a space capable of holding gas. In other words, this example has a space capable of holding gas at a position higher than the connection portion between the first outflow path and the second outflow path. According to this structure, it can suppress that the aqueous liquid of a 1st tank flows in into a 2nd outflow channel.

  The device (first to third devices) of the present invention may further include a water storage tank to which a flow path (P) (for example, a flow path on the downstream side of the second tank) is connected. And the circulation path (annular path) containing a water storage tank and a 2nd tank may be formed. This water storage tank may be a tank for using hydrogen water. Examples of such tanks include a tank for immersing a body or pet in hydrogen water. Examples of such tanks include a bathtub, a footbath tank, a face washing tank, and a pet tank. Moreover, the apparatus in which hydrogenous water is used may be connected to the water storage tank.

  In the apparatus (first to third apparatuses) of the present invention, the outflow path (flow path on the downstream side of the second tank) connected to the second tank is connected to a device in which hydrogen water is used. May be. For example, the outflow path may be connected to a shower device.

  The device of the present invention (first to third devices) can be controlled manually. However, the device of the present invention (first to third devices) may include a controller. The controller includes an arithmetic processing unit and storage means. Note that the storage means may be integrated with the arithmetic processing unit. Examples of the storage means include an internal memory, an external memory, and a magnetic disk (for example, a hard disk drive) of the arithmetic processing unit. A program for executing a necessary process (for example, an electrolysis process) is recorded in the storage means. An example of the controller includes a large scale integrated circuit (LSI). The apparatus of the present invention may include various devices (power supply, pump, valve, filter, etc.) and various measuring instruments (ammeter, pH meter, ion concentration meter, conductivity meter, dissolved oxygen meter, dissolved hydrogen meter, etc.). Good. The controller may be connected to these devices and measuring instruments. The controller may perform the electrolysis process by controlling the device based on the output of the measuring instrument.

  The device of the present invention (first to third devices) includes a conductivity meter for measuring the conductivity of an aqueous liquid and a device for confirming gas generation from the electrode in order to determine a voltage to be applied to the electrode. (For example, a combination of a light emitting element such as an LED or a laser diode and a light receiving element such as a photodiode) may be provided. Moreover, the apparatus of this invention may be equipped with the voltmeter for measuring the voltage applied between electrodes, and the ammeter for measuring the electric current which flows between electrodes.

  The controller may control the voltage application condition and / or the flow rate of the aqueous liquid based on the data obtained from various measuring instruments and the target value of the dissolved hydrogen concentration.

[How to adjust liquid quality]
An example of a method for adjusting the quality of the aqueous liquid using the first device will be described below. In addition, since the matter demonstrated about the 1st apparatus is applicable to the following method, the overlapping description may be abbreviate | omitted. Further, the items described for the following method can be applied to the first apparatus.

  In this method, first, an aqueous liquid is caused to flow through the flow path (P). As a result, the aqueous liquid is disposed in the first and second tanks. Next, water in the aqueous liquid is electrolyzed by applying a DC voltage between the first electrode and the second electrode (electrolysis step).

  The electrolysis process is performed in a state where the aqueous liquid flows through the flow path (P) (including the second tank). In another aspect, the electrolysis step is performed in a state where the aqueous liquid in the first tank is not substantially in a liquid-permeable state and the aqueous liquid in the second tank is in a liquid-permeable state. According to this configuration, it is possible to reduce the change in pH of the aqueous liquid treated in the second tank. The “liquid passing state” refers to a state in which the liquid is continuously changed by flowing the liquid continuously (typically in a continuous and constant direction).

  The voltage (DC voltage) applied between the electrodes in the electrolysis process is set so that electrolysis occurs at both the anode and the cathode. The applied voltage may be in the range of 3 volts to 50 volts (eg, in the range of 6 volts to 20 volts).

  In the apparatus (first to third apparatuses) of the present invention, the following step (a) and / or step (b) may be performed as the electrolysis step. When the apparatus of the present invention includes a controller, the following step (a) and / or step (b) may be performed by the controller. In that case, a program for executing the following step (a) and / or step (b) is stored in the storage means of the controller.

  In step (a), by applying a DC voltage between the first electrode and the second electrode so that the first electrode becomes an anode while the aqueous liquid is flowing through the second tank, An aqueous liquid containing dissolved hydrogen is prepared in the second tank. In step (a), a DC voltage is applied so that water electrolysis occurs in each of the first and second electrodes.

In the step (a), hydroxide ions (OH ⁻ ) and hydrogen gas are generated at the second electrode (cathode). As a result, the dissolved hydrogen concentration of the aqueous liquid flowing out from the second tank is higher than that of the aqueous liquid before flowing into the second tank. On the other hand, hydrogen ions (H ⁺ ) and oxygen gas are generated at the first electrode (anode). As a result, oxygen gas flows out from the outflow passage of the first tank.

  According to the step (a), an aqueous liquid containing dissolved hydrogen can be prepared, and hydrogen water having a high dissolved hydrogen concentration can be obtained. The dissolved hydrogen concentration of the hydrogen water varies depending on the ion concentration of the aqueous liquid, the flow rate of the aqueous liquid, the applied voltage, and the like. In one example, it is possible to obtain hydrogen water having a dissolved hydrogen concentration in the range of 0.4 to 1.6 ppm (for example, in the range of 0.8 to 1.3 ppm).

  The dissolved hydrogen concentration affects the redox potential (ORP) of the aqueous liquid, and the higher the dissolved hydrogen concentration, the lower the ORP. Therefore, from another viewpoint, the device of the present invention is a device for reducing the ORP of an aqueous liquid. In another aspect, an apparatus according to an example of the present invention is an apparatus capable of preparing an aqueous liquid having a low ORP (for example, an aqueous liquid having an ORP in the range of −600 mV to −100 mV near neutrality). .

  When the aqueous liquid contains chlorine ions (for example, when the aqueous liquid is tap water), chlorine gas is generated at the first electrode when step (a) is performed. Therefore, free chlorine (dissolved chlorine, hypochlorous acid, and hypochlorite ions) is generated in the first tank. Part of the generated free chlorine is taken into the aqueous liquid flowing through the flow path through the separator. In the first device, the chlorine gas generated in the first tank is dissolved in the aqueous liquid at the connection portion, and the free chlorine concentration of the aqueous liquid flowing through the flow path is increased. Therefore, when the aqueous liquid contains chlorine ions, the first device can prepare hydrogen water having sterilizing power by the step (a). Therefore, the first device is particularly preferably used for an application that requires sterilization.

  When preparing an aqueous liquid having a high free chlorine concentration, step (b) is carried out. In step (b), a DC voltage is applied between the first electrode and the second electrode so that the first electrode becomes a cathode while an aqueous liquid containing chlorine ions flows through the second tank. By doing so, an aqueous liquid containing free chlorine is prepared in the second tank. In the step (b), water is electrolyzed in the first electrode, and a DC voltage is applied between the electrodes so that chlorine ions become chlorine molecules in the second electrode. In a typical step (b), a DC voltage is applied between the electrodes so that water is electrolyzed at each of the first and second electrodes. Chlorine gas is generated at the second electrode by the step (b). As a result, an aqueous liquid containing free chlorine is prepared in the second tank. Moreover, since oxygen gas is generated in the second electrode by the step (b), the ORP of the aqueous liquid prepared in the second tank rises. Therefore, according to the step (b), an aqueous liquid having a high ORP and free chlorine concentration can be prepared.

  According to the step (b), an aqueous liquid containing free chlorine can be prepared, and an aqueous liquid having a high free chlorine concentration can be obtained. This aqueous liquid can be used for sterilization and the like. According to the apparatus of the present invention, it is possible to prepare an aqueous liquid having a high dissolved hydrogen concentration by step (a) and to prepare an aqueous liquid having a high free chlorine concentration by step (b). In the case of using hydrogen water flowing through the circulation path like a circulation bath, sterilization of the circulation path may be important. In such a case, the step (a) is usually executed, and the step (b) may be executed as necessary. The circulation path can be sterilized by the step (b). Further, it is possible to regenerate the electrode (removal of the accumulated scale) by the step (b). According to the apparatus of the present invention, hydrogen water and water for sterilization can be prepared from tap water.

  In the apparatus of the present invention, only step (a) may be executed, or only step (b) may be executed. When the process (a) and the process (b) are performed, any process may be performed first. Moreover, a process (a) and a process (b) may be performed repeatedly. For example, the step (a) and the step (b) may be repeatedly executed in the order of the step (a) and the step (b), or may be repeatedly executed in the order of the step (b) and the step (a). Also good.

When the flow path (P) is a circulation path, the amount of aqueous liquid (volume V1 (cm ³ )) disposed in the first tank and the aqueous liquid present in the flow path (P) in the electrolysis step. The pH of the aqueous liquid treated in the second tank may be adjusted by the ratio with the amount (volume V2 (cm ³ )). Here, when a water storage tank is included in the middle of the circulation path, the water path is included in the flow path (P). The larger the value of (V2 / V1), the smaller the pH change of the aqueous liquid treated in the second tank. The value of (V2 / V1) may be in the range of 10-2 × 10 ⁶ (for example, the range of 10-50000 or the range of 200-15000).

When the second tank does not constitute a part of the circulation path (for example, when the aqueous liquid treated in the second tank is used as it is), the amount of the aqueous liquid flowing in the second tank per minute ( The volume is in the range of 1 to 10 ⁶ times the amount of the aqueous liquid (or the internal volume of the first tank) placed in the first tank (for example, the range of 10 to 10 ⁵ times or 100 to 10 times ⁵ times the range). The higher this magnification, the smaller the variation in pH of the aqueous liquid treated in the second tank.

  In addition, the change of pH of the aqueous liquid processed by a 2nd tank can be suppressed especially by shortening the distance of an electrode (1st and 2nd electrode) and a separator (for example, it is set as the distance mentioned above).

  In the state immediately after the electrolysis step is performed, the pH of the aqueous liquid in the first tank and the pH of the aqueous liquid in the second tank often differ greatly. Therefore, in order to keep the pH of the aqueous liquid in the second tank at a value immediately after the electrolysis process is performed so as not to approach neutrality, the electrolysis process of the first tank is performed after the electrolysis process. The aqueous liquid and ions therein may be prevented from moving and diffusing into the second tank. For example, the water in the first tank may be discharged after the electrolysis process. Alternatively, after the electrolysis step, the first tank and the second tank may be partitioned by a shielding plate to prevent the movement and diffusion of the aqueous liquid and ions. If it is desired to return the aqueous liquid in the second tank to neutral after the electrolysis step, the aqueous liquid in the tank may be allowed to stand until the pH becomes a substantially constant value after voltage application. By passing hydrogen ions and hydroxide ions through the separator, the pH approaches neutrality. At this time, it is possible to promote the return of the pH to neutrality by circulating the aqueous liquid in the second tank without applying a voltage.

  In the method of the present invention, the pH of the aqueous liquid flowing through the second tank may be controlled by discharging a part of the aqueous liquid disposed in the first tank. Further, the pH of the aqueous liquid may be adjusted by disposing a drainage path in one or both of the first tank and the second tank and discharging the aqueous liquid from one tank. For example, when neutral water is electrolyzed, the aqueous liquid on the anode side becomes acidic and the aqueous liquid on the cathode side becomes alkaline. Therefore, it is possible to change the pH of the entire aqueous liquid by discharging the aqueous liquid in one of the first tank and the second tank during voltage application or after voltage application.

  In the device (first to third devices) of the present invention, an activated carbon filter may be disposed in the flow path (P). For example, in the first device, an activated carbon filter may be disposed in a flow path downstream of the connection portion between the first outflow path and the second outflow path. The activated carbon filter can remove unnecessary substances in the aqueous liquid. For example, the concentration of hypochlorite ions or dissolved oxygen can be reduced by an activated carbon filter. There is no limitation in particular in an activated carbon filter, You may use a well-known activated carbon filter. Other examples of the activated carbon filter will be described later.

  Examples of embodiments of the present invention will be described below with reference to the drawings. In the following description with reference to the drawings, the same parts may be denoted by the same reference numerals, and redundant description may be omitted.

[Embodiment 1]
In Embodiment 1, an example of the first apparatus of the present invention will be described. The configuration of the apparatus 100 of the first embodiment is schematically shown in FIG. The apparatus 100 includes a container 10, a separator 13, a first electrode 21, a second electrode 22, and a power source 23. The apparatus 100 may include a controller, a water tank, an activated carbon filter, a pump and a valve for controlling the movement of the aqueous liquid, and the like.

  The container 10 is partitioned into a first tank 11 and a second tank 12 by a separator 13. A first electrode 21 is disposed in the first tank 11, and a second electrode 22 is disposed in the second tank 12. A power source 23 is connected to the first electrode 21 and the second electrode 22.

  An outflow path (first outflow path) 11 b is connected above the first tank 11. An inflow path 12 a is connected to the lower side of the second tank 12, and an outflow path (second outflow path) 12 b is connected to the upper side of the second tank 12. In the second tank 12, the aqueous liquid flows from the lower inflow path 12a toward the upper outflow path 12b. The separator 13 is disposed in parallel with the flow of the aqueous liquid.

  Usually, a pump for moving the aqueous liquid is arranged in the inflow path 12a. The outflow path 11 b and the outflow path 12 b are connected at the connection portion 15 and further connected to the flow path 24. The inflow path 12a, the second tank 12, the outflow path 12b, and the flow path 24 function as a flow path (P) through which the aqueous liquid flows. At least a part of the outflow passage 11b exists at a position higher than the connection portion 15. The outflow passage 11b may be provided with an openable / closable valve for releasing the gas to the atmosphere. This valve is preferably provided at a position higher than the connecting portion 15.

  The outflow channel 11b and the outflow channel 12b may be pipelines cut off from the atmosphere. A pipe that is cut off from the atmosphere may be provided with a valve that is opened when the inside of the pipe exceeds a predetermined pressure. When the gas generated in the electrode accumulates in the pipe line, the aqueous liquid in the first tank is suppressed from flowing out to the flow path 24.

  Step (a) in the apparatus 100 will be described. In addition, since a process (b) can be performed by applying a voltage in the reverse direction to a process (a), description about a process (b) is abbreviate | omitted. Step (a) is performed in a state where an aqueous liquid is caused to flow through the flow paths (inflow path 12a, second tank 12, outflow path 12b, and flow path 24). When the aqueous liquid is caused to flow through the flow path, the aqueous liquid is disposed in the first tank 11 and the second tank 12. In that state, water in the aqueous liquid 101 is electrolyzed by applying a DC voltage so that the first electrode 21 becomes an anode (so that the second electrode 22 becomes a cathode). As a result, as shown in FIG. 2, oxygen gas is generated on the surface of the first electrode 21, and hydrogen gas is generated on the surface of the second electrode 22. Note that, when the aqueous liquid 101 contains chlorine ions, chlorine gas is also generated on the surface of the first electrode 21.

  The gas generated in the first electrode 21 accumulates in the outflow path 11 b connected to the upper side of the first tank 11. When the pressure in the first tank 11 increases, the water level of the aqueous liquid 101 in the first tank 11 rises, and the aqueous liquid 101 rises in the outflow path 11b. However, a portion of the outflow passage 11b that is higher than the connection portion 15 is filled with gas. Therefore, even if the aqueous liquid 101 rises in the outflow passage 11b, the water level is suppressed from becoming higher than the connection portion 15. As a result, it is possible to prevent the aqueous liquid 101 in the first tank 11 from flowing in a large amount into the flow path. Further, in the apparatus 100, even when the water level of the aqueous liquid 101 in the first tank 11 rises excessively, the aqueous liquid 101 only flows into the flow path, and the aqueous liquid 101 leaks out of the apparatus. Can be prevented. As described above, in the apparatus 100 of the first embodiment, it is basically unnecessary to control the water level of the aqueous liquid 101 in the first tank 11.

  As shown in FIG. 3, the flow path 24 may be connected to a water storage tank 40. Further, an activated carbon filter 50 may be disposed in the flow path 24 (downstream of the connection portion 15). The 2nd tank 12 is connected to the water storage tank 40 by the inflow path 12a. A pump 25 for moving the aqueous liquid is provided in the inflow passage 12a. The inflow path 12a, the second tank 12, the outflow path 12b, the flow path 24, and the water storage tank 40 function as a flow path (P) through which the aqueous liquid flows. These form a circulation path through which the aqueous liquid flows. The first tank 11 and / or the circulation path (P) may be provided with various measuring instruments, valves, drainage paths for discharging the aqueous liquid 101, and the like.

  In the configuration of FIG. 3, step (a) is performed in a state where the aqueous liquid 101 is circulating in the circulation path, thereby increasing the dissolved hydrogen concentration of the aqueous liquid 101. Therefore, even if the water storage tank 40 is in an open state, it is possible to maintain the dissolved hydrogen concentration at a high state.

  When the aqueous liquid 101 contains chlorine ions, chlorine ions are oxidized on the surface of the first electrode 21 to generate chlorine gas. Part of the chlorine gas and oxygen gas generated at the first electrode 21 is mixed into the aqueous liquid 101 at the connection portion 15 and dissolved in the aqueous liquid 101. Therefore, on the downstream side of the connection portion 15, the hypochlorite ion concentration and the dissolved oxygen concentration in the aqueous liquid 101 may increase. However, since the contact area between the aqueous liquid 101 and the chlorine gas or oxygen gas is small at the connection portion 15, the amount of the dissolved liquid in the aqueous liquid 101 is small. On the other hand, the amount of minute gas generated on the surface of the electrode dissolves in the aqueous liquid 101 is large. Therefore, the hypochlorite ion concentration and the dissolved oxygen concentration in the aqueous liquid 101 in the first tank 11 are high, and the dissolved hydrogen concentration in the aqueous liquid 101 in the second tank 12 is high. When it is desired to reduce the free chlorine concentration and dissolved oxygen concentration of the aqueous liquid 101 flowing through the flow path, reducing the amount of the aqueous liquid 101 in the first tank 11 mixed into the aqueous liquid 101 flowing through the flow path; and It is important to suppress the minute gas generated in the first tank 11 from moving to the second tank 12. In order to achieve these, the first tank 11 and the second tank 12 are partitioned by the separator 13, and the second tank 12 is set in a liquid state and the first tank 11 is not in a liquid state. is important.

  According to the apparatus of Embodiment 1, an aqueous liquid having a high dissolved hydrogen concentration, an aqueous liquid having a high free chlorine concentration, and an aqueous liquid having a high dissolved oxygen concentration are obtained.

  The activated carbon filter 50 can reduce the hypochlorite ion concentration and the dissolved oxygen concentration that have risen on the downstream side of the connecting portion 15. The activated carbon filter 50 may be a general activated carbon filter, for example, an activated carbon filter used in a domestic water purifier. The activated carbon filter 50 may be a first activated carbon filter or a second activated carbon filter described later, and may be, for example, an activated carbon filter 200 or 200a described later.

  When step (a) is performed, an aqueous liquid having a high dissolved hydrogen concentration (an aqueous liquid having a low ORP) flows through the activated carbon filter 50. In this case, even if the activated carbon filter 50 is a general activated carbon filter, the activated carbon in the activated carbon filter 50 is reduced and the potential of the activated carbon is lowered by flowing an aqueous liquid having a low ORP. The ability of the activated carbon is restored when the potential of the activated carbon decreases. That is, the ability of activated carbon to decompose and remove dissolved oxygen and hypochlorous acid is restored. Therefore, when performing a process (a), it becomes possible to maintain the capability of a general activated carbon filter for a long period of time.

  A valve may be provided in the outflow path 11b. The first tank 11 may be provided with a drain path. An example of a device provided with them is shown in FIG. The apparatus 100 of FIG. 9 is different from the apparatus 100 of FIG. 1 only in that it includes a valve 11bv and a drainage path 11p. The valve 11 bv is provided in the middle of the discharge path 11 b connecting the first tank 11 and the connection portion 15 and at a position higher than the connection portion 15. The valve 11bv may be a valve that is opened when a predetermined pressure higher than atmospheric pressure is reached. The drainage path 11 p is provided below the first tank 11. The aqueous liquid in the first tank 11 can be discharged from the first tank 11 by opening the valve 11pv provided in the drainage path 11p.

[Second device]
Below, the 2nd apparatus of this invention for adjusting the liquid quality of aqueous liquid is demonstrated. The second device includes a container in which the aqueous liquid is disposed, a separator that partitions the container into a first tank and a second tank, a first electrode disposed in the first tank, and a second tank. And a power source for applying a voltage between the first electrode and the second electrode. An outflow path is connected above the second tank. The second tank and the outflow path constitute a part of the flow path through which the aqueous liquid flows. On the other hand, the 1st tank is connected with the 2nd tank via the separator, and it will not be in a liquid flow state substantially. About the above point, since it is the same as that of a 1st apparatus, the overlapping description is abbreviate | omitted.

  In the second device, instead of the first outflow path, a cylindrical portion capable of rising the aqueous liquid is connected above the first tank. The flow path on the downstream side of the second tank has an open portion that is open to the atmosphere. The opening portion is provided at a position where the siphon effect by the flow path on the downstream side of the second tank is reduced. In order to reduce the siphon effect, it is preferable that the height difference between the highest position of the outflow path and the open portion is small. Moreover, it is preferable that an open part is located above the upper end of the 2nd electrode 22, and it is more preferable to be located above the upper end of a 2nd tank.

  In one example, the (height difference) is in the range of 0 cm to 50 cm (for example, the range of 0 cm to 20 cm or 0 cm to 10 cm). In this example, the height difference between the upper end of the second electrode 22 and the highest position of the outflow path may be in a range of 0 cm to 20 cm (for example, a range of 1 cm to 5 cm).

  In the second device, the liquid quality of the aqueous liquid can be adjusted in the same manner as in the first device by applying a voltage in the same manner as in the first device. Specifically, the quality of the aqueous liquid can be adjusted by performing the step (a) and / or the step (b).

[Embodiment 2]
In Embodiment 2, an example of the second device of the present invention will be described. An example of the second device is shown in FIG. 4 includes a container 10, a separator 13, a first electrode 21, a second electrode 22, and a power source 23. Since the apparatus 100a is the same as the apparatus 100 of the first embodiment except for the matters described as the features of the apparatus 100a, the overlapping description is omitted. For example, the device 100a may include a controller, an activated carbon filter, a water tank, a pump, a valve, and the like. Moreover, in the apparatus 100a, as shown in FIG. 3, the circulation path containing a water storage tank may be formed.

  A cylindrical portion 11 c is connected above the first tank 11. The cylindrical part 11c is open to the atmosphere. The cylindrical portion 11c is provided to prevent the aqueous liquid from leaking outside the apparatus when the water level of the aqueous liquid in the first tank 11 rises. A gas-liquid separation membrane or the like may be disposed on the cylindrical portion 11c.

  An inflow path 12 a is connected to the lower side of the second tank 12, and an outflow path 12 b is connected to the upper side of the second tank 12. The outflow path 12 b is connected to the flow path 24. The inflow path 12a, the second tank 12, the outflow path 12b, and the flow path 24 function as an aqueous liquid flow path. When the apparatus 100a includes a water tank, the inflow path 12a and the flow path 24 are connected to the water tank as in the apparatus of FIG. In that case, the inflow path 12a, the second tank 12, the outflow path 12b, the flow path 24, and the water storage tank function as a flow path through which the aqueous liquid flows, and form a circulation path.

  In the apparatus 100a, an electrolysis process is performed in the same manner as the apparatus 100. As a result, an aqueous liquid having a high dissolved hydrogen concentration, an aqueous liquid having a high free chlorine concentration, and an aqueous liquid having a high dissolved oxygen concentration are obtained. In the device 100a, the gas generated on the surface of the first electrode 21 is released to the atmosphere through the cylindrical portion 11c.

  At the connection portion between the outflow passage 12b and the flow passage 24, there is an open portion 12c that is open to the atmosphere. When there is no open portion 12c, a pulling force is applied to the aqueous liquid 101 in the second tank 12 by the amount of the drop in the flow path 24 (siphon effect). Therefore, if the head of the flow path 24 is large, the force applied to the aqueous liquid 101 in the second tank 12 increases, and as a result, the water level of the aqueous liquid 101 in the first tank 11 decreases and the first level is reduced. The electrode 21 may be exposed. The exposure of the first electrode 21 is not preferable because it lowers the efficiency of electrolysis and deteriorates the electrode. On the other hand, when the opening part 12c is provided, the siphon effect is brought about only in the portion of the head (level difference) from the highest position of the outflow path 12b to the opening part 12c. Therefore, the influence of the siphon effect can be reduced by reducing the drop from the highest position of the outflow path 12b to the open portion 12c. FIG. 4 shows a case where the head from the highest position of the outflow passage 12b to the open portion 12c is zero, but even if there is a head from the highest position of the outflow passage 12b to the open portion 12c, If is small, the influence of the siphon effect can be suppressed. Thus, in the apparatus 100a, the siphon effect can be suppressed by providing the open portion 12c in the flow path on the downstream side of the second tank 12. As a result, it is possible to prevent the aqueous liquid 101 in the first tank 11 from being excessively lowered due to the siphon effect.

[Third device]
Below, the 3rd apparatus of this invention for adjusting the liquid quality of aqueous liquid is demonstrated. The third device includes a container in which the aqueous liquid is disposed, a separator that partitions the container into a first tank and a second tank, a first electrode disposed in the first tank, and a second tank. And a power source for applying a voltage between the first electrode and the second electrode. An outflow path is connected above the second tank. The second tank and the outflow path constitute a part of the flow path through which the aqueous liquid flows. On the other hand, the 1st tank is connected with the 2nd tank via the separator, and it will not be in a liquid flow state substantially. About the above point, since it is the same as that of a 1st apparatus, the overlapping description is abbreviate | omitted.

  In the third device, instead of the first outflow passage, a cylindrical portion capable of rising the aqueous liquid is connected above the first tank. A flow rate controller for controlling the flow in the flow channel is provided in the flow channel on the downstream side of the second tank. The flow regulator can also be considered as a pressure regulator that regulates the pressure of the aqueous liquid in the second tank. A known flow rate adjusting valve or the like may be used for the flow rate regulator.

  In the third device, the liquid quality of the aqueous liquid can be adjusted similarly to the first device by applying a voltage in the same manner as in the first device. Specifically, the quality of the aqueous liquid can be adjusted by performing the step (a) and / or the step (b).

[Embodiment 3]
In Embodiment 3, an example of the third device of the present invention will be described. An example of the third device is shown in FIG. 5 includes a container 10, a separator 13, a first electrode 21, a second electrode 22, a power source 23, and a valve (flow rate regulator) 26. Since the device 100b is the same as the device 100 of the first embodiment except for the matters described as the features of the device 100b, the duplicate description is omitted. For example, the apparatus 100b may include a controller, an activated carbon filter, a water tank, and the like. Moreover, in the apparatus 100b, as shown in FIG. 3, the circulation path containing a water storage tank may be formed.

  A cylindrical portion 11 c is connected above the first tank 11. The cylindrical part 11c is open to the atmosphere. An inflow path 12 a is connected to the lower side of the second tank 12, and an outflow path 12 b is connected to the upper side of the second tank 12. The outflow path 12 b is connected to the flow path 24. The inflow path 12a, the second tank 12, the outflow path 12b, and the flow path 24 function as an aqueous liquid flow path. When the apparatus 100b includes a water tank, the inflow path 12a and the flow path 24 are connected to the water tank as in the apparatus of FIG. In that case, the inflow path 12a, the second tank 12, the outflow path 12b, the flow path 24, and the water storage tank function as a flow path through which the aqueous liquid flows, and form a circulation path.

  In the apparatus 100b, an electrolysis process is performed in the same manner as the apparatus 100. As a result, an aqueous liquid having a high dissolved hydrogen concentration, an aqueous liquid having a high free chlorine concentration, and an aqueous liquid having a high dissolved oxygen concentration are obtained. In the device 100b, the gas generated on the surface of the first electrode 21 is released to the atmosphere through the cylindrical portion 11c.

  A valve 26 for adjusting the flow rate of the aqueous liquid is disposed in the outflow path 12b (downstream side of the second tank 12). As shown in FIG. 5, when the flow path on the downstream side of the second tank 12 is descending, a siphon effect is generated due to the height difference. Therefore, the pulling force is applied to the aqueous liquid in the second tank 12 toward the outflow path 12b. When the aqueous liquid in the second tank 12 is pulled by this force, the water level of the aqueous liquid in the first tank 11 may be lowered and the first electrode 21 may be exposed. The exposure of the first electrode 21 is not preferable because it lowers the efficiency of electrolysis and deteriorates the electrode. In order to avoid such a problem, when the water level of the aqueous liquid in the first tank 11 decreases, the valve 26 may be throttled to increase the pressure of the aqueous liquid in the second tank 12. Thereby, the water level of the aqueous liquid in the first tank 11 can be raised. On the other hand, if the water level of the aqueous liquid in the 1st tank 11 rises too much, an aqueous liquid will overflow from the cylindrical part 11c. In such a case, the water level of the aqueous liquid in the cylindrical portion 11c can be lowered by opening the valve 26. Thus, by controlling the opening degree of the valve 26, it is possible to adjust the water level of the aqueous liquid in the tank.

  Adjustment of the valve 26 may be automated. In that case, the water level measuring device which measures the water level of the aqueous liquid in the 1st tank 11 and the cylindrical part 11c, and a controller are used. A known water level measuring device can be used as the water level measuring device. The controller controls the opening degree of the valve 26 based on the output of the water level measuring instrument. Specifically, the valve 26 is throttled when the water level of the aqueous liquid in the first tank 11 and the cylindrical portion 11c becomes low, and the valve 26 is opened when the water level becomes high.

  As described above, in the first to third apparatuses of the present invention, it is unnecessary or easy to control the water level of the aqueous liquid in the tank.

  In any of the above-described apparatuses, when the activated carbon filter is provided in the flow path, the first flow path including the activated carbon filter and the second flow path that bypasses the activated carbon filter may be provided in parallel. And you may enable it to switch a 1st flow path and a 2nd flow path. According to this configuration, it is possible to select and use either an aqueous liquid treated with an activated carbon filter or an aqueous liquid not treated with an activated carbon filter. Although the dissolved oxygen concentration and hypochlorite ion concentration are reduced by the activated carbon filter, an aqueous liquid whose concentration is not reduced can be used by using the second flow path that bypasses the activated carbon filter. For example, an aqueous liquid having a high hypochlorite ion concentration can be used for sterilization purposes. Further, a flow path that passes through the activated carbon filter may be used when the step (a) is being executed, and a flow path that bypasses the activated carbon filter may be used when the step (b) is being executed.

  The activated carbon filter may be any of the first and second activated carbon filters described below. Alternatively, the activated carbon filter may be a generally used activated carbon filter (an activated carbon filter that does not include an electrode or a hydrogen storage unit).

[First activated carbon filter]
The first activated carbon filter will be described below. The first activated carbon filter includes an adsorption part including activated carbon and an electrode that is not short-circuited with the adsorption part. In the first activated carbon filter, a DC voltage is applied between the adsorption part (activated carbon of the adsorption part) and the electrode so that the adsorption part (activated carbon of the adsorption part) becomes a cathode (so that the electrode becomes an anode). The

  The first activated carbon filter may include a plurality of adsorption units and a plurality of electrodes. In another aspect, the first activated carbon filter may include a plurality of pairs of adsorption portions and electrodes. Those pairs may be connected in parallel or in series.

  The adsorption part includes activated carbon and has a certain degree of conductivity as a whole. For example, the adsorbing portion may be formed of only granular activated carbon, or may be formed of a material including granular activated carbon, carbon black, and a binder. Since activated carbon and carbon black have conductivity, an adsorption part having conductivity can be obtained by using these materials. Further, fibrous activated carbon may be used. Moreover, you may form an adsorption | suction part using the cloth formed using activated carbon fiber. The adsorbing part may be formed of a known adsorbing material using activated carbon. For example, you may form an adsorption | suction part with the adsorption material currently used for the well-known activated carbon filter. The adsorption unit may include a conductor (such as a metal wiring or a metal foil) for applying a voltage to the activated carbon as evenly as possible. This conductor is arranged in direct contact with the activated carbon or connected to the activated carbon through a conductive material.

  The electrode is not particularly limited, and may be a metal electrode, an electrode made of a conductive carbon-based material (graphite or the like), or an electrode made of a combination thereof. In any case, an electrode that has little corrosion and easily generates oxygen due to electrolysis of water is preferable. In the electrode serving as the anode, oxygen is generated by electrolysis of water. An example of the electrode includes an electrode made of a metal coated with platinum (for example, stainless steel or titanium). The electrode preferably has a shape that allows liquid to pass through. For example, the electrode may be composed of a wire-like electrode wire or may be in a mesh shape.

  The first activated carbon filter may include a separator for preventing a short circuit between the adsorption portion and the electrode. A separator is arrange | positioned between an adsorption | suction part and an electrode. The separator is insulative and may be formed of an insulative resin. The separator preferably has a shape that allows liquid to pass through. For example, the separator may have a mesh shape, or may be a woven fabric or a non-woven fabric.

  The first activated carbon filter usually includes a power source for applying a DC voltage. The power source may be an AC-DC converter that converts an AC voltage obtained from an outlet into a DC voltage. The power source may be a power generation device such as a solar battery or a battery (for example, a primary battery or a secondary battery).

  Japanese Patent Laid-Open No. 6-238264 discloses a method of heating activated carbon with Joule heat by applying a DC voltage between two electrodes in contact with the activated carbon, thereby regenerating the activated carbon. The first activated carbon filter also applies a DC voltage to the activated carbon, but the voltage application is not intended to heat the activated carbon. In the first activated carbon filter, the electrode and the adsorption part are not in contact with each other, and water to be treated exists between the electrode and the adsorption part. For this reason, even when a voltage is applied between the electrode and the adsorption portion, unlike the case of JP-A-6-238264 where the electrode is in contact with the activated carbon, the flowing current is small. In the first activated carbon filter, a voltage is applied so that the activated carbon (adsorption part) becomes a cathode. At this time, a voltage is applied so that a current that allows the activated carbon to adsorb ions to form an electric double layer flows, but a current that greatly changes the liquid temperature does not flow, so the temperature of the activated carbon hardly increases. Specifically, the temperature rise of activated carbon due to voltage application is usually 10 ° C. or lower (typically 5 ° C. or lower). Moreover, when a voltage is applied in a state where water is flowing through the activated carbon filter, there is usually almost no temperature increase of the activated carbon (temperature increase is less than 1 ° C.). Thus, in the first activated carbon filter, the temperature rise of the activated carbon in the adsorption portion due to the application of a DC voltage is usually 10 ° C. or lower, for example, 5 ° C. or lower or 1 ° C. or lower. In the first activated carbon filter, the amount of current that flows per gram of activated carbon when a voltage is applied is usually 1 A or less, typically 0.1 A or less.

  In the first activated carbon filter, by applying a DC voltage, the potential of the activated carbon of the adsorption part is −0.8 V or higher, −0.6 V or higher, −0.4 V or higher, −0.2 V or higher with respect to the standard hydrogen electrode. It is good also as 0.8V or less, 0.6V or less, 0.4V or less, 0.3V or less, or 0.2V or less. For example, a range of -0.8V to 0.8V, a range of -0.8V to 0.6V, a range of -0.6V to 0.6V, a range of -0.4V to 0.5V, It is good also as the range of -0.4V-0.4V, the range of -0.4V-0.2V, the range of -0.3V-0.5V, and the range of -0.2V-0.4V. Hereinafter, these lower limit, upper limit, and range may be referred to as “example of potential of activated carbon of adsorption portion (1)”. In a preferable example, the potential of the activated carbon of the adsorption part is in the range of -0.8 V to 0.6 V, in the range of -0.6 V to 0.4 V, or in the range of -0.4 V to 0.4 V, based on the standard hydrogen electrode. It is in the range.

[First example of first activated carbon filter]
The first activated carbon filter includes two examples. First, the first example will be described. In the first example of the first activated carbon filter, in use, a DC voltage of 7 V or less is applied between the adsorption unit and the electrode so that the adsorption unit becomes a cathode. The voltage may be 2.5 V or less, or may be in a range of 0.5 V to 2 V (for example, a range of 1.2 V to 2 V). In this specification, “in use” means that the water to be treated is flowing through the activated carbon filter. In the first example of the first activated carbon filter, a DC voltage may be applied even when the water to be treated is not flowing through the activated carbon filter. That is, in the first activated carbon filter, a DC voltage may be constantly applied.

  In order to maintain the ability of the activated carbon in a high state, the applied voltage is preferably set to 0.5 V or higher (for example, 1.2 V or higher). In the absence of overvoltage, voltage drop due to water, activated carbon resistance, etc., water is electrolyzed by applying a voltage of about 1.2V. However, considering overvoltage and the like, if the applied voltage is 2.5 V or less, there is not much power consumption due to electrolysis of water. Therefore, in order to reduce power consumption, it is preferable to set the applied voltage to 2.5 V or less (for example, 2 V or less). However, even if the applied voltage is increased, the power consumption due to the electrolysis of water on the adsorption part side (cathode side) only increases and does not cause a big problem. Therefore, the applied voltage can be increased.

  When processing water having low electrical conductivity (for example, water having an electrical conductivity of 250 μS / cm or less) such as soft water tap water, or when the distance between the adsorbing portion and the electrode is relatively large (for example, 3 mm to In the case of 30 mm), the voltage drop becomes large. When the voltage drop is large or when the ability of the activated carbon is regenerated in a short time, it is preferable to increase the applied voltage, and in a range of 10 V or less (for example, a range of 1 V to 7 V or a range of 1.2 V to 6 V). The applied voltage may be increased.

  When the applied voltage is 2 V or less (for example, in the range of 1.2 V to 2 V), water is hardly electrolyzed, so that almost no power is consumed even when the voltage is constantly applied. A switch that is turned on only when the water to be treated is flowing may be provided so that the voltage is applied only when the water to be treated is flowing. For example, a switch that is mechanically turned on by the flow of water may be provided.

  In an example activated carbon filter, an electrode is arrange | positioned downstream from an adsorption | suction part. Consider a case where a voltage is applied so that the electrode becomes an anode when water is flowing through the activated carbon filter. Hypochlorous acid is generated when the potential of the electrode reaches the generation potential of hypochlorous acid by applying a voltage when water containing chlorine ions is flowing. However, when the applied voltage is 2 V or less, the potential of the electrode is not greatly shifted to the plus side with respect to the oxygen generation potential, so that generation of hypochlorous acid is suppressed.

  In another aspect, this specification discloses a first method of using an activated carbon filter including an adsorption part including activated carbon and an electrode that is not short-circuited with the adsorption part. In the first method of use, when the activated carbon filter is used, the direct current voltage (the first activated carbon filter's first voltage) is applied between the adsorption portion and the electrode so that the adsorption portion becomes a cathode (the electrode becomes an anode). The voltage illustrated in the example 1 is applied, for example, a DC voltage of 2.5 V or less.

[Second Example of First Activated Carbon Filter]
In the second example of the first activated carbon filter, a DC voltage is intermittently applied between the adsorption part and the electrode so that the adsorption part becomes a cathode. The activated carbon filter of the second example may include a switch for turning on / off application of a DC voltage. The voltage may be applied when the activated carbon capacity is reduced. Alternatively, the voltage may be applied periodically or irregularly, regardless of whether the activated carbon capacity has decreased. For example, the voltage may be applied by a user turning on a switch periodically or irregularly. Alternatively, the voltage may be applied by periodically turning on the switch using a timer. Alternatively, the power source may be a solar cell, and a voltage generated by the solar cell may be applied when the solar cell is irradiated with light. When a battery (primary battery, secondary battery, solar battery, etc.) is used as a power source, a predetermined voltage is applied by selecting the number and type of batteries connected in series and further using electrical resistance as necessary. be able to.

  When voltage is applied, water may or may not flow through the activated carbon filter, but water is preferably flowing.

  The voltage may be applied at a time when the activated carbon capacity is expected to decrease. Further, it may be determined whether or not the ability of the activated carbon has decreased, and a voltage may be applied when the ability of the activated carbon has decreased.

  There is no particular limitation on the voltage applied in the second example, and the voltage exemplified in the first example may be applied. However, if the applied voltage is small, it takes time to move the potential of the activated carbon of the adsorption part to the minus side. Further, the electrolysis of water in the activated carbon of the adsorption unit is suppressed until the potential of the activated carbon of the adsorption unit reaches the hydrogen generation potential. Therefore, in the second example, it is preferable to apply a relatively high voltage. For example, the applied voltage in the second example may be 1.2 V or more, or may be in the range of 3 to 50 V (for example, in the range of 4 to 20 V). As described above, even if the electrolysis of water on the surface of the activated carbon of the adsorption portion occurs, the power consumption due to the electrolysis of water on the adsorption portion side only increases, and it does not become a big problem.

  There is no particular limitation on the time for applying the voltage in the second example. The voltage application may be performed only for a time during which it is considered that the potential of the activated carbon in the adsorption portion can be moved to the minus side to some extent. The voltage application time can be shortened by increasing the applied voltage. The voltage application time may be in the range of 2 minutes to 300 minutes (for example, in the range of 5 minutes to 100 minutes).

  In another aspect, this specification discloses a second method of using an activated carbon filter including an adsorbing portion including activated carbon and an electrode that is not short-circuited with the adsorbing portion. In the second method of use, a DC voltage (second example of the first activated carbon filter) is intermittently provided between the adsorption part and the electrode so that the adsorption part becomes a cathode (so that the electrode becomes an anode). Is applied).

[Second activated carbon filter]
The second activated carbon filter includes an adsorption unit including activated carbon and a hydrogen storage unit including a metal that reversibly stores hydrogen (a metal that stores and releases hydrogen). The adsorption part (activated carbon of the adsorption part) and the hydrogen storage part are electrically connected, and electricity flows between them. Typically, the adsorption part (activated carbon of the adsorption part) and the hydrogen storage part are short-circuited.

  The adsorption part described in the first activated carbon filter can be used for the adsorption part. The hydrogen storage part may include at least one selected from the group consisting of a hydrogen storage alloy and palladium. Both the hydrogen storage alloy and palladium store hydrogen reversibly. There is no limitation in particular in a hydrogen storage alloy, The hydrogen storage alloy currently used for the nickel-hydrogen secondary battery may be used, and a palladium alloy may be used.

  Note that the second activated carbon filter may include a plurality of adsorption units and a plurality of hydrogen storage units. In another aspect, the second activated carbon filter may include a plurality of pairs of adsorption units and hydrogen storage units.

  Specific examples of the activated carbon filter used in the present invention will be described below with reference to the drawings. In the following description, the same parts may be denoted by the same reference numerals and redundant description may be omitted.

[Specific example 1 of activated carbon filter]
In Specific Example 1 of the activated carbon filter, an example of the first example of the first activated carbon filter will be described. A sectional view of the activated carbon filter 200 of Example 1 is shown in FIG. The activated carbon filter 200 includes a container 211, an adsorption unit 212, two separators 213, and two electrodes 214. When the switch 216 is on, a DC voltage is applied between the adsorption unit 212 and the electrode 214 by the DC power source 215. Note that the switch 216 can be omitted when a voltage is constantly applied or when a solar cell is used as a power source.

  The container 211 includes an inlet 211a into which treated water flows and an outlet 211b from which treated water flows out. The adsorption part 212 includes activated carbon. The separator 213 is made of an insulating resin. The separator 213 has a shape (mesh shape, woven fabric, non-woven fabric, etc.) that allows water to pass through. The separator 213 is arrange | positioned between the adsorption | suction part 212 and the electrode 214, and prevents those short circuits. The electrode 214 is a mesh electrode formed of a platinum-coated titanium wire.

When the activated carbon filter 200 is used, a DC voltage of 2.5 V or less is applied between the adsorption unit 212 and the electrode 214 so that the adsorption unit 212 becomes a cathode. FIG. 7 schematically shows the potential of the activated carbon. In FIG. 7, the potential E _C is the potential of the activated carbon when no charge is accumulated in the activated carbon. The potential E _H is a potential at which hydrogen ions begin to be reduced, and at a potential on the minus side of the potential E _H , the hydrogen ions are reduced to generate hydrogen molecules. The potential E _OX is a potential at which oxygen begins to be reduced and decomposed. On the negative side of the potential E _OX , oxygen is reduced and decomposed. The potential E _J is a potential at which free chlorine begins to be reduced and decomposed, and on the minus side of the potential E _J , free chlorine is reduced and decomposed.

When the potential of the adsorption unit 212 is on the minus side of the potential E _J , free chlorine that has contacted the adsorption unit 212 is reduced and decomposed. When the potential of the adsorption unit 212 is on the negative side of the potential E _OX , dissolved oxygen that has contacted the adsorption unit 212 is reduced and decomposed. Note that the potential E _J to present to the positive side than the potential E _OX, the potential of the suction unit 212 may be present on the negative side than the potential E _OX, free chlorine is also reduced and decomposed in contact with the suction portions 212.

Conventionally, activated carbon filters have attracted attention for their ability to adsorb substances by physical adsorption. However, as shown in FIG. 7, activated carbon at a predetermined potential has a function of electrically reducing and decomposing free chlorine and dissolved oxygen. Although it is not clear at present, it is thought that the reduction function of activated carbon is involved in the reduction of the free chlorine concentration by the activated carbon filter. For example, when tap water (including chlorine ions) with an increased dissolved oxygen concentration is circulated so as to be in contact with the activated carbon electrode containing activated carbon, the potential of the activated carbon electrode increases and the tap water becomes alkaline. From this, it is considered that the following reaction occurs on the surface of the activated carbon. In the following formula, “C” represents activated carbon.
C (surface charge: n negative charges) / n (adsorbed Na ⁺ ) -2e ⁻ → C (surface charge: (n−2) negative charges) / (n−2) (adsorbed Na ⁺ ) + 2Na ⁺
1 / 2O ₂ + 2e ⁻ + H ₂ O → 2OH ⁻

When sodium ions are released by utilizing the negative charge on the activated carbon surface for the reductive decomposition of dissolved oxygen, the negative charge on the activated carbon surface is reduced by the amount released. The dissolved oxygen is reduced and decomposed to produce hydroxide ions. Therefore, tap water is considered to be alkaline. Similarly, it is considered that free chlorine receives electrons from activated carbon and undergoes reductive decomposition as in the next reaction.
ClO ⁻ + 2e ⁻ + H ₂ O → Cl ⁻ + 2OH ⁻

The inventors of the present application paid attention to the reducing function of activated carbon, which has not been noticed conventionally. The principle of the activated carbon filter used in the present invention will be described below. First, the conventional activated carbon filter which does not control the electric potential of the activated carbon of the adsorption | suction part 212 is demonstrated. The potential of the activated carbon of the adsorption unit 212 is at the position of the potential E _C in FIG. 7 in the initial stage where no ions are adsorbed. However, when an activated carbon filter is used, reductive decomposition of free chlorine and reductive decomposition of dissolved oxygen occur on the surface of the adsorption part 212. Electrons are provided from the activated carbon of the adsorption unit 212 for their reductive decomposition. As a result, positive charges are accumulated in the activated carbon, and the potential of the activated carbon moves to the positive side (right side in FIG. 7). When the potential of the activated carbon moves to the plus side, the difference between the potential of the activated carbon and the potential E _OX and the difference between the potential of the activated carbon and the potential E _J become smaller. When these potential differences become small, the reductive decomposition reaction of free chlorine and dissolved oxygen becomes difficult to occur. This is considered to be a phenomenon in which the ability of activated carbon to reduce free chlorine concentration and dissolved oxygen concentration is reduced by use. Conventionally, attention has been focused on the physical adsorption of activated carbon. Therefore, in the conventional method for regenerating activated carbon, the adsorbed substance is desorbed from the activated carbon by heating. However, the ability of activated carbon to reduce free chlorine concentration and dissolved oxygen concentration can be maintained by controlling the potential of the activated carbon.

In order to prevent a decrease in the ability of the activated carbon (the ability to reduce and decompose free chlorine, dissolved oxygen, etc.) due to use, the first activated carbon filter applies a voltage so that the adsorbing portion 212 becomes a cathode during use. . This shifts the potential of the activated carbon to the negative side and restores the ability of the activated carbon to reduce free chlorine concentration and dissolved oxygen concentration. However, when the potential of the adsorption unit 212 is on the minus side of the potential E _H , power is consumed to generate hydrogen gas. Therefore, the potential of the adsorption unit 212 is preferably on the plus side of the potential E _H. In a preferred example, the potential of the suction unit 212 is in the vicinity of and potential E _H at the positive side than the potential E _H. Considering the above points, the voltage described above is applied to the first activated carbon filter. By setting the applied voltage to 2.5 V or less, power consumption due to water electrolysis can be suppressed, and power consumption can be extremely reduced.

In order to efficiently reduce the free chlorine concentration and the dissolved oxygen concentration, the potential of the adsorption unit 12 is required to be on the negative side of the potential E _OX, and is between the potential E _H and the potential E _C. Is preferred. When the hydrogen overvoltage is not considered, the potential E _H is about −0.4 V with respect to the standard hydrogen electrode. On the other hand, when the hydrogen overvoltage is considered, the potential E _{H at} which hydrogen gas is substantially generated is lower than −0.6V. Considering the hydrogen overvoltage, a large amount of hydrogen gas is not generated even when the potential of the activated carbon is about −0.8V. Further, the potential E _C of the activated carbon in the absence of surface charge is about 0.4 V, and the potential E _OX is about 0.8 V. Therefore, in the first activated carbon filter, the potential of the adsorption unit 12 at the time of use may be −0.8 V or more and 0.8 V or less based on the standard hydrogen electrode. It may be at the potential shown in “Example (1)”.

[Specific example 2 of activated carbon filter]
In specific example 2 of the activated carbon filter, an example of the second example of the first activated carbon filter will be described. Since the structure of the activated carbon filter of the specific example 2 is substantially the same as the activated carbon filter 200 shown in FIG. 6, the overlapping description is abbreviate | omitted. However, in the specific example 2, the voltage application method is different.

  In the activated carbon filter of the specific example 2, as in the specific example 1, a DC voltage is applied between the adsorption unit 212 and the electrode 214 so that the adsorption unit 212 becomes a cathode. However, in the activated carbon filter of the specific example 2, the activated carbon of the adsorption unit 212 is regenerated by intermittently applying a voltage. There is no particular limitation on the applied voltage, and the voltage described above may be applied.

  As described above, when the active carbon filter is used to reduce and decompose free chlorine and dissolved oxygen on the surface of the activated carbon, the potential of the activated carbon moves to the positive side, resulting in the reductive decomposition of free chlorine and dissolved oxygen. It becomes difficult. In the activated carbon filter of the specific example 2, the potential of the adsorption unit 212 is moved to the negative side by applying a voltage intermittently so that the adsorption unit 212 becomes a cathode. This restores the reduced ability of the activated carbon (the ability to reduce and decompose free chlorine, dissolved oxygen, etc.). Therefore, the activated carbon filter of Example 2 can be used for a long time without replacing the activated carbon. In the second activated carbon filter, the potential of the adsorption unit 212 after voltage application may be the potential shown in the above-mentioned “Example of potential of activated carbon of adsorption unit (1)” with reference to the standard hydrogen electrode. .

In the activated carbon filter of the specific example 2, a voltage may be applied periodically or a voltage may be applied irregularly. For example, the activated carbon may be regenerated by applying a voltage when the capability of the activated carbon decreases. In order to determine whether or not the ability of the activated carbon has decreased, a reference activated carbon electrode for measuring a change in the potential of the activated carbon in the adsorption section may be used. The activated carbon electrode for reference is arranged in an open state (floating state) upstream of the activated carbon filter. The potential difference between the activated carbon electrode for reference and the activated carbon in the adsorption part is maximized because the positive charge is sufficiently accumulated on the activated carbon surface of the activated carbon electrode for reference, and the potential of the activated carbon reaches the potential E _OX , This is when the potential of the activated carbon in the adsorption portion reaches the potential E _H by voltage application. The potential difference at that time is about 1.4V or more. The potential of the activated carbon electrode for reference becomes a potential in the vicinity of the potential E _OX with the passage of water. The potential of the activated carbon in the adsorption section also moves to the plus side depending on use. When the potential difference between the potential of the activated carbon in the adsorption section and the potential of the reference activated carbon electrode (near the potential E _OX ) becomes small, it is determined that the potential of the activated carbon in the adsorption section has approached the potential E _OX and voltage application (regeneration treatment) )It can be performed. For example, the voltage may be applied when the potential difference between the two reaches a predetermined potential difference in the range of 0.2V to 0.4V.

  Further, the voltage application may be stopped based on the potential difference between the potential of the reference activated carbon electrode and the potential of the adsorption portion. For example, when the potential difference becomes 0.6 V or more, it may be considered that the ability of activated carbon has been regenerated and the voltage application may be stopped. When the potential difference before the voltage application is 0.4 V and the potential difference becomes 0.6 V by the voltage application, the potential of the activated carbon has moved to the minus side by 0.2 V from before the voltage application. As a result, free chlorine and dissolved oxygen are easily reduced and decomposed by activated carbon.

[Specific example 3 of activated carbon filter]
In specific example 3 of the activated carbon filter, an example of the second activated carbon filter will be described. A cross-sectional view of the activated carbon filter 200a of Example 3 is shown in FIG. The activated carbon filter 200 a includes a container 211, two adsorption units 212, and two hydrogen storage units 231. The activated carbon filter 200a is an example of an activated carbon filter including a plurality of adsorption units 212 and a plurality of hydrogen storage units 231. The activated carbon of the adsorption unit 212 and the hydrogen storage unit 231 are in contact with each other. In other words, the activated carbon of the adsorption unit 212 and the hydrogen storage unit 231 are short-circuited. The container 211 and the suction unit 212 are the same as those described in the first specific example. The hydrogen storage unit 231 includes a hydrogen storage alloy or palladium. An example of the hydrogen storage unit 231 is mesh-like stainless steel whose surface is coated with palladium.

  The operation of the activated carbon filter 200a will be described below. When the water flowing through the activated carbon filter 200 a contains dissolved hydrogen, the dissolved hydrogen is occluded in the hydrogen occlusion unit 231. When the hydrogen storage unit 231 is in a floating state and the storage / release of dissolved hydrogen is in an equilibrium state, the potential of the hydrogen storage unit 231 is about −0.6V. Since the hydrogen storage unit 231 and the adsorption unit 212 are short-circuited, the potential of the adsorption unit 212 is affected by the potential of the hydrogen storage unit 231. As the water containing dissolved hydrogen flows through the activated carbon filter 200a, the dissolved hydrogen is stored in the hydrogen storage unit 231. As a result, the potential of the activated carbon in the adsorption unit 212 moves to the negative side. Therefore, as long as water containing dissolved hydrogen flows through the activated carbon filter 200a, the capability of activated carbon in the adsorption unit 212 (ability to reduce and decompose free chlorine and dissolved oxygen) is maintained. That is, according to the activated carbon filter 200a of the specific example 3, it is possible to reduce the concentration of a predetermined substance over a long period of time without replacing the activated carbon.

  The activated carbon filter of Example 3 has an advantage that a power source is unnecessary. The activated carbon filter of Example 3 can be preferably used as a filter for reducing the dissolved oxygen concentration or free chlorine concentration in water having a high dissolved hydrogen concentration (sometimes referred to as “hydrogen water”).

  The present invention will be described in more detail with reference to examples.

Example 1
In Example 1, the step (a) was performed using an apparatus having the same configuration as the apparatus 100 shown in FIG. In the water tank, 10 L of tap water having a temperature of about 37 ° C. was arranged. For the first and second electrodes, titanium electrodes coated with platinum were used. The flow rate of water flowing through the flow path was 1.0 L / min. With water circulating, a DC voltage of 24 V was applied between the first electrode and the second electrode so that the first electrode became the anode. And the change of the physical property of water by voltage application was measured. The physical properties of water were measured by collecting water at the outlet of the flow path 24. The measurement results are shown in Table 1.

  The dissolved hydrogen concentration in Table 1 was calculated by titration using a redox reagent (methylene blue). As shown in Table 1, the dissolved hydrogen concentration increased and the ORP decreased due to voltage application. There was little change in pH, but there was a tendency to increase slightly.

(Example 2)
In Example 2, step (b) was performed using an apparatus having the same configuration as the apparatus 100 shown in FIG. 10 L of tap water (temperature: about 29 ° C.) was placed in the water tank. A nickel electrode was used as the first electrode (cathode). A titanium electrode coated with platinum was used as the second electrode (anode). The flow rate of water flowing through the flow path was 1.5 L / min. In a state where water is circulating, a DC voltage of 36 V was applied between the first electrode and the second electrode so that the first electrode becomes a cathode. And the change of the physical property of water by voltage application was measured. The physical properties of water were measured by collecting water in the water tank. The measurement results are shown in Table 2.

  As shown in Table 2, the voltage application increased the ORP of water present in the circulation path and increased the free chlorine concentration. Moreover, pH fell a little. The increase in ORP is thought to be due to the increase in free chlorine concentration and dissolved oxygen concentration in water.

  The present invention can be used for an apparatus for adjusting the quality of an aqueous liquid.

DESCRIPTION OF SYMBOLS 10 Container 11 1st tank 12 2nd tank 15 Connection part 21 1st electrode 22 2nd electrode 23 Power supply 11b 1st outflow path 12a Inflow path 12b 2nd outflow path 12c Opening part 24 Flow path 25 Pump 26 Valve (Flow controller)
40 water tank 50, 200, 200a activated carbon filter 100, 100a, 100b apparatus

Claims (11)

An apparatus for adjusting the quality of an aqueous liquid,
A container in which the aqueous liquid is disposed;
A separator that partitions the container into a first tank and a second tank;
A first electrode disposed in the first tank;
A second electrode disposed in the second tank;
A power source for applying a voltage between the first electrode and the second electrode;
A first outflow path is connected above the first tank,
A second outflow path is connected above the second tank,
The second tank and the second outflow path constitute a part of a flow path through which the aqueous liquid flows,
The apparatus in which the first outflow path and the second outflow path are connected.   The apparatus according to claim 1, wherein at least a part of the first outflow path exists at a position higher than a connection portion between the first outflow path and the second outflow path.   The apparatus of Claim 1 or 2 with which the activated carbon filter is arrange | positioned in the said flow path downstream from the connection part of a said 1st outflow path and a said 2nd outflow path. The activated carbon filter includes an adsorption portion containing activated carbon, and an electrode that is not short-circuited with the adsorption portion,
The apparatus according to claim 3, wherein a direct current voltage is applied between the adsorption unit and the electrode so that the adsorption unit becomes a cathode. The activated carbon filter includes an adsorption part containing activated carbon and a hydrogen storage part containing a metal that reversibly absorbs hydrogen,
The apparatus according to claim 3, wherein the adsorption unit and the hydrogen storage unit are electrically connected. An apparatus for adjusting the quality of an aqueous liquid,
A container in which an aqueous liquid is placed;
A separator that partitions the container into a first tank and a second tank;
A first electrode disposed in the first tank;
A second electrode disposed in the second tank;
A power source for applying a voltage between the first electrode and the second electrode;
An outflow path is connected above the second tank,
A cylindrical part capable of rising the aqueous liquid is connected to the upper side of the first tank,
The apparatus in which the flow path on the downstream side of the second tank has an open portion that is open to the atmosphere. An apparatus for adjusting the quality of an aqueous liquid,
A container in which the aqueous liquid is disposed;
A separator that partitions the container into a first tank and a second tank;
A first electrode disposed in the first tank;
A second electrode disposed in the second tank;
A power source for applying a voltage between the first electrode and the second electrode;
An outflow path is connected above the second tank,
A cylindrical part capable of rising the aqueous liquid is connected to the upper side of the first tank,
An apparatus, wherein a flow rate controller for controlling a flow in the flow path is provided in a flow path on the downstream side of the second tank.   (A) by applying a DC voltage between the first electrode and the second electrode so that the first electrode becomes an anode while the aqueous liquid is flowing through the second tank; The apparatus according to claim 1, wherein the step of preparing an aqueous liquid containing dissolved hydrogen in the second tank is performed.   (B) A DC voltage is applied between the first electrode and the second electrode so that the first electrode becomes a cathode while an aqueous liquid containing chlorine ions is flowing through the second tank. The apparatus of any one of Claims 1-7 by which the process of preparing the aqueous liquid containing a free chlorine in a said 2nd tank is performed by applying. (A) by applying a DC voltage between the first electrode and the second electrode so that the first electrode becomes an anode while the aqueous liquid is flowing through the second tank; Preparing an aqueous liquid containing dissolved hydrogen in the second tank;
(B) A DC voltage is applied between the first electrode and the second electrode so that the first electrode becomes a cathode while an aqueous liquid containing chlorine ions is flowing through the second tank. The apparatus of any one of Claims 1-7 with which the process of preparing the aqueous liquid containing a free chlorine in a said 2nd tank is performed by applying. A water tank connected to the flow path;
The device according to claim 1, wherein a circulation path including the water storage tank and the second tank is formed.

Images