JP2000005756A - Production of residual chlorine-containing water and device therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably and inexpensively provide residual chlorine-containing water of stabilized quality enabling to sterilize even spore bearing bacteria to a user. SOLUTION: In a method for obtaining electrolyzed water stably including a high concentration of residual chlorine by using an aqueous soln. of a chloride as an electrolytic soln. and electrolyzing it by using a membrane, an alkali compound is incorporated in the electrolytic soln. introduced into anode rooms 3a, 3b of an electrolytic device, and also the device is operated in such a state that the anode rooms 3a, 3b are fulfilled with the liquid and also U.V. rays are cut off, and the anode liquid being electrolyzed water discharged from the anode rooms 3a, 3b is filled into a receiving container enabling to prevent both a flow of air and transmission of U.V. rays in a state of non gas-phase and in a state that U.V. rays are cut off.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a method for obtaining electrolyzed water containing a high concentration of residual chlorine, which is obtained by conducting a diaphragm electrolysis using a chloride aqueous solution as a raw material, and then applying the electrolyzed water to a point of use. The present invention relates to a method for producing residual chlorine-containing water having an effective sterilizing ability even for spores by transferring it and diluting it to a predetermined concentration at the point of use, and an apparatus therefor.

[0002]

2. Description of the Related Art In prevention of hospital-acquired infections in hospitals, control of environmental bacteria in food distribution, hygiene control of cooked foods, and control of bacteria in food production plants, etc., a high-concentration aqueous solution of sodium chloride as a chlorine-based disinfectant is used as a diaphragm. Strongly acidic anode water obtained by subjecting sodium hypochlorite or an aqueous solution of sodium chloride obtained by electrolysis to diaphragm electrolysis is used. In addition, for applications such as sanitizers for clean water, a high concentration of hypochlorite obtained by absorbing a chlorine solution obtained on the anode side with caustic soda obtained on the cathode side by subjecting a saturated aqueous solution of sodium chloride to diaphragm electrolysis. Acid soda is widely used.

[0003] However, in order for the above-mentioned sodium hypochlorite to exhibit a more powerful bactericidal effect with an aqueous solution thereof and also to kill spores, it is necessary to add HCl or the like at the site of use and control the pH. Needed. For this reason, it is inconvenient in terms of handling safety and the Food Sanitation Law when used for sterilization of foods and the like in general households and kitchens of restaurants, etc.It is also used in large-scale facilities such as food factories. However, in addition to the problem in the Food Sanitation Law, there is a problem that the cost required for sterilization is high because a large amount is required.

[0004] Strongly acidic anodic water obtained by electrolysis of a sodium chloride aqueous solution with a diaphragm has appeared to solve these problems, but when the residual chlorine concentration exceeds 15 ppm when the pH is 3 or less. Chlorine gas is emitted from the anode water into the atmosphere, so that a change over time inevitably occurs. Since the residual chlorine concentration in the anode water decreases, the sterilizing effect cannot be specified. Therefore, the anode water must be produced at the point of use and used as soon as possible. In addition, if the manufacturing location is different, the properties of the anode water change due to changes in water quality and water pressure for preparing an aqueous sodium chloride solution. At present, there is a strong demand for the stabilization of properties. Furthermore, the emission of chlorine gas requires safety in the working environment.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a user with safe and inexpensive residual chlorine-containing water capable of sterilizing spores of stable quality.

[0006]

That is, the present invention provides a method for obtaining electrolyzed water stably containing a high concentration of residual chlorine by subjecting a chloride aqueous solution as a liquid to be electrolyzed to electrolysis with a diaphragm. (Hereinafter referred to as "method A") wherein an alkaline compound is contained in a liquid to be electrolyzed introduced into an anode chamber of an electrolysis apparatus, and the anode chamber is filled in a liquid-filled state and protected from ultraviolet rays. Operating, filling the anolyte, which is the electrolyzed water discharged from the anode chamber, into a receiving container capable of preventing the flow of air and the transmission of ultraviolet rays in a state without a gas phase and in a state in which ultraviolet rays are blocked. Features. In addition, in this specification, "residual chlorine" means that measured by the ortho-tolidine arsenite method, unless otherwise specified.

In the method A, the alkaline compound may be contained in the electrolytic solution by adding an aqueous solution of the alkaline compound from outside the system to the electrolytic solution directly into the anode chamber or into the electrolytic solution introduced into the anode chamber. Or by mixing, the adjustment of the input amount or the mixing amount is performed based on the deviation between the set value of the pH of the anolyte and the detected value, and the adjustment of the residual chlorine concentration in the anolyte is performed. By controlling the current and / or voltage supplied to the electrolytic device based on the deviation between the set value of the residual chlorine concentration in the anolyte and the detected value (hereinafter referred to as “method A-
1a ").

[0008] An alkaline compound can be contained in the electrolyte to be treated by adding a cathode, which is electrolytic water discharged from a cathode chamber of an electrolysis apparatus, to the electrolyte to be introduced directly into or into the anode chamber. At least a part of the solution is charged or mixed, and the adjustment of the amount of the catholyte to be charged or mixed is performed based on the deviation between the set value and the detected value of the pH of the anolyte, and Adjustment of the residual chlorine concentration in the anolyte is performed by controlling the current and / or voltage supplied to the electrolysis apparatus based on the deviation between the set value and the detected value of the residual chlorine concentration in the anolyte (hereinafter, referred to as the “control”). , “Method A-1b”).

In the method A-1b, it is preferable that a predetermined amount of an aqueous solution of an alkaline compound is previously charged or mixed in a predetermined amount from outside the system directly into the anode chamber or into the electrolyte to be introduced into the anode chamber. . For the purpose of stabilizing the above control, the amount may be determined as appropriate in view of the balance between the amount of acid generated in the anode compartment and the amount of alkali in the catholyte introduced into the anode compartment. still,
As the aqueous solution of the alkaline compound, an aqueous sodium hydroxide solution is preferable from the viewpoint of easy handling and availability.

[0010] In addition, the incorporation of an alkaline compound into the electrolysis solution is achieved by supplying an aqueous chloride solution as an electrolysis solution to be supplied to the electrolyzer only to the cathode chamber of the electrolyzer and discharging the same from the cathode chamber. The electrolysis is performed by using at least a part of the catholyte, which is electrolyzed water, as an electrolyte to be introduced into the anode compartment, and the amount of the catholyte introduced into the anode compartment is adjusted by adjusting the amount of the anolyte.
Adjustment of the residual chlorine concentration in the anolyte is performed based on the deviation between the set value of the pH and the detected value, and adjustment of the residual chlorine concentration in the anolyte is performed by the electrolytic device based on the deviation between the set value and the detected value of the residual chlorine concentration in the anolyte. It is performed by controlling the supplied current and / or voltage (hereinafter, referred to as “method A-1c”),
It may be something.

In the method A-1c, it is preferable that a predetermined amount of an acidic compound is quantitatively charged or mixed in advance into an aqueous chloride solution as an electrolyte to be supplied directly to the cathode chamber or supplied to the cathode chamber. For the purpose of stabilizing the control, the amount may be appropriately determined by considering the balance between the amount of alkali in the catholyte circulated in the anode chamber and the amount of acid generated in the anode chamber. Good. As the aqueous solution of the acidic compound, an aqueous hydrochloric acid solution is preferable from the viewpoint of easy handling and availability.

In the method A (including the methods A-1a, -1b and -1c), the set value of the pH of the anolyte is determined by the bactericidal effect required for the residual chlorine-containing water finally produced in the present invention and the bactericidal effect. Considering the stability of high-concentration residual chlorine-containing water up to the point of final use, one standard is 6 ± 1.5.

Further, in addition to the above-mentioned features, the manufacturing method (method A) of the present invention uses the above-mentioned receiving container having a variable capacity as the receiving container and forming the above-mentioned anode without forming a gas phase therein. Filling the receiving container with the liquid comprises increasing the volume corresponding to the receiving amount while receiving the anolyte in a watertight manner into the receiving container having its internal volume near zero. Further, the method is characterized in that the volume of the anolyte is reduced in accordance with the transfer amount of the anolyte from the receiving container to the place of use under watertightness (hereinafter, referred to as "method A-2").

Further, the present invention relates to a method for transferring electrolyzed water stably containing a high concentration of residual chlorine obtained by electrolyzing a chloride aqueous solution to a diaphragm without impairing its stability. A method for producing residual chlorine-containing water having an effective sterilizing ability against spores by diluting it to a predetermined concentration at a location (hereinafter referred to as "method B"),
Filling an anolyte, which is electrolyzed water discharged from the anode chamber of the electrolytic cell, into a container for receiving the anolyte capable of preventing the flow of air and the transmission of ultraviolet rays without forming a gas phase therein; Filling the anolyte from a container into a transfer container capable of blocking the flow of air and the transmission of ultraviolet rays without forming a gas phase therein; and transferring the anolyte from the transfer container at the point of use. It is also characterized in that it is easily and accurately diluted and extracted with water to a required residual chlorine concentration without contact with the outside air.

Here, it is preferable that the receiving container is a bag-shaped container used in a state of being immersed in water. The advantage of the bag-shaped container is that the air present in the container is evacuated at the time of the initial filling of the anolyte into the receiving container, and the discharging of the anolyte from the container is performed under atmospheric pressure. Can be performed smoothly in a state where the contact with the device is cut off. On the other hand, the advantage of using the container in a submerged manner is that the stress applied to the container due to the change in the internal volume of the container can be reduced, and further, into and out of the container. The receiving and dispensing of the anolyte can be performed more smoothly in a state where the contact with the atmosphere is shut off, because the water pressure is applied.

It is more preferable that the water is a saturated solution of slaked lime. The advantage is that, in the unlikely event that the receiving container is damaged, the emission of chlorine gas from the anolyte can be suppressed.

Further, it is preferable that the transfer container is a bag-like container accommodated in a box capable of receiving the container at the maximum capacity. The advantage of being a bag-shaped container is the same as that of the above-mentioned receiving container, while the advantage of housing the container in a box body is that the container itself can be restrained from swaying during transfer, and the box body itself is made of ultraviolet light. This is because if the container has a blocking effect, it is not necessary to take such consideration into the container, and furthermore, it is possible to prevent a destructive factor from entering the container from the outside. When the box is required to have a function of preventing the destruction factor of the container from entering the box, a material that can prevent the destruction factor from entering, such as a plastic or a metal material, may be used. On the other hand, a corrugated cardboard may be used only for the purpose of suppressing the movement of the container during transfer and blocking ultraviolet rays.

Further, it is preferable that the box body holds slaked lime powder in an inner space thereof and an outer space of the transfer container at the maximum capacity. The advantage is that if the transfer container breaks,
The point is that emission of chlorine gas from the anolyte can be suppressed.

As a method of extracting the anolyte solution from the transfer container at the place of use without contact with the outside air while diluting the anolyte solution to a required residual chlorine concentration simply and accurately with water, fluctuations in the water pressure of the dilution water can be absorbed. What is necessary is just to be able to dilute the anolyte to a predetermined concentration accurately, without being affected by the fluctuation of the water pressure.
As such, there are two cylinders arranged in a state where their axes are the same and their spaces are vertically separated from each other, and pistons are provided so as to be able to slide on the inner walls of these cylinders, respectively. Lower space of the cylinder formed by the cylinder and the piston which is intermittently discharged from the cylinder to the outlet of the upper cylinder for dilution water (space between the top dead center and the bottom dead center of the piston) A restricted flow path is provided so that the accurately measured dilution water can be passed at high speed, while the lower space of the cylinder formed by the cylinder and the piston is provided at the outlet of the lower cylinder ( A watertight line connected to the piston so as to feed accurately metered anode water into the restricted passage at the space between the top dead center and the bottom dead center of the piston) The upper cylinder inlet, the lower cylinder inlet, and the lower piston are each provided with a check valve (the flow restricting direction is opposite to the inlet of the upper cylinder: the flow of the dilution water into the cylinder). Direction, the inlet of the lower cylinder: the direction opposite to the flow of anode water into the cylinder, the lower piston: the direction from the upper space of the lower cylinder to the lower space, that is, the lower piston has the upper space of the lower cylinder. A hole communicating with the lower space is formed, and the check valve controls the opening and closing of the hole. Valves are provided to open holes drilled in the piston so that the space and the lower space can communicate with each other, and to close when the upper piston reaches the bottom dead center. It is preferable to use are apparatus.

The upper cylinder of the apparatus has a means for communicating with a water supply source at the inlet of the upper cylinder, for example, a pipe, and a means for communicating with a container for transferring anode water at the inlet of the lower cylinder.
For example, a pipe is connected to the outlet of the restriction portion of the flow path with a communication means with a point of use, for example, a pipe. Here, it is preferable that a detachable attachment having a shutoff valve is provided in advance at an end of the communication means for communicating with the anode water container on the container side.

[0021] Still further, the present invention uses an aqueous chloride solution as a liquid to be electrolyzed, and obtains electrolyzed water stably containing a high concentration of residual chlorine by subjecting the electrolyzed membrane to electrolysis with a diaphragm. A method for producing residual chlorine-containing water having an effective sterilizing ability even for spores by transferring to a site without deteriorating its stability and diluting it to a predetermined concentration at the site of use (hereinafter, "method A + B") )
Including an alkaline compound in the electrolyte to be introduced into the anode chamber of the electrolysis apparatus, and operating the anode chamber in a liquid-filled state and in a state where ultraviolet rays are blocked,
Filling the anolyte, which is electrolyzed water discharged from the anode chamber, in a receiving container capable of preventing the flow of air and the transmission of ultraviolet light in a state without a gas phase and in a state where ultraviolet light is blocked; Filling the anolyte into a transfer container capable of preventing the flow of air and the transmission of ultraviolet rays without forming a gas phase therein, and contacting the anolyte with the outside air from the transfer container at the point of use. It may be characterized in that it is extracted while diluting with water to a required residual chlorine concentration without causing the residual chlorine concentration.

On the other hand, the present invention relates to an apparatus (hereinafter, referred to as an "apparatus") for using a chloride aqueous solution as a liquid to be electrolyzed and electrolyzing it with a diaphragm to obtain electrolytic water stably containing a high concentration of residual chlorine. A ”); at least,
An electrolytic cell separated by a diaphragm into an anode compartment having an anode therein and a cathode compartment having a cathode therein;
A supply unit for supplying an aqueous solution of chloride as an electrolytic solution; a unit for receiving an anolyte which is electrolytic water produced in the anode compartment; and a unit for supplying an alkaline compound to the anode compartment; The anode chamber and the means for receiving the anolyte have a structure in which a gas phase is not formed therein and a structure and / or property capable of blocking ultraviolet rays (hereinafter, referred to as "apparatus A1"). ,
It is characterized by.

Here, means for supplying the aqueous chloride solution (hereinafter referred to as “chloride aqueous solution”)
As “apparatus A1-a”), a water supply source; and a concentrated chloride aqueous solution storage tank (before supplying to the electrolysis apparatus, a separately concentrated aqueous solution of chloride and water are separately mixed to supply an electrolytic solution having a predetermined concentration. Communication means (hereinafter referred to as "communication means A1") between the water supply source and the anode chamber and the cathode chamber.
(Usually, a pipe and a pump-unnecessary if there is sufficient water pressure-and required valves. This pipe shares the anode chamber and the cathode chamber partway, and And a communication means (hereinafter referred to as "communication means A2") between the concentrated chloride aqueous solution storage tank and the communication means (A1) (generally, a pipe, a pump, and a required valve). In addition, this pipe is an arbitrary point of the pipe of the communication means (A1), and the communication means (A1)
One end thereof may be connected at any point between the delivery of the pump and the anode compartment / cathode compartment branch);
(Hereinafter referred to as “apparatus A1-a1”), or instead of the concentrated chloride aqueous solution storage tank, a chloride aqueous solution storage tank (chloride is previously dissolved in water to prepare an electrolytic solution of a predetermined concentration. In this case, a stirrer is also required when dissolving in this storage tank) (hereinafter referred to as “apparatus A1-a2”). In this case, the communication means (A1) and the communication means (A2) ) In place of the water supply source and the chloride aqueous solution storage tank (hereinafter referred to as "communication means A0") (necessary when dissolving in the chloride aqueous solution storage tank.
If there is sufficient water pressure, it is unnecessary-and it is constituted by the required valve) and means for communicating the aqueous chloride solution storage tank with the anode chamber and the cathode chamber (hereinafter referred to as "communication means A3")
(Normally, it consists of piping, pumps and required valves.
This pipe may be branched at any point after delivery of the pump).

The anolyte receiving means (hereinafter, referred to as anolyte)
“Apparatus A1-b”) includes a container for receiving the anolyte solution; and a communication means (hereinafter, referred to as “communication means A4”) between the anode chamber and the reception container (generally, a pipe and a required valve). In addition, this pipe is usually provided with a branch pipe for discharging an anolyte of an unspecified quality out of the system at the time of start-up of the electrolyzer and a switching valve therefor at an optional point). Mainly composed.
In the present invention, the anolyte is the main object, but the catholyte may also be used in the electrolysis system as described below. Therefore, the cathode having one end connected to the cathode chamber in the sense of completing the actual apparatus. It is preferable to provide a catholyte discharge means (hereinafter, referred to as "communication means A5") comprising a liquid pipe (and a valve if necessary).

On the other hand, as means for supplying an alkaline compound to the anode chamber (hereinafter referred to as "apparatus A1-c"), the following means can be mentioned. A storage tank for the aqueous solution of the alkaline compound; and a communication means (hereinafter referred to as "communication means A6") between the storage tank for the aqueous solution of the alkaline compound and the anode chamber (generally, a pipe, a pump, and a required valve. The piping may directly connect the storage tank for the aqueous solution of the alkaline compound and the anode chamber, or may be provided at any point of the piping of the communication means A1 or A3, except for the downstream of the delivery of the pump of the communication means. May be connected to an arbitrary point) (hereinafter, referred to as “apparatus A1-c1”). The device A1-c1 further includes communication means (hereinafter, referred to as "communication means A7") for circulating at least a part of the catholyte solution to the anode chamber (generally, a pipe, a pump, and a required valve. May directly connect any point of the piping of the communication means A5 to the anode chamber, or any point of the piping of the communication means A1 or A3, except for the downstream of the delivery of the pump of the communication means. (Hereinafter, may be connected to an arbitrary point) (hereinafter referred to as “apparatus A1-c2”). The device A1-
When the device A1-c2 is adopted as c, in addition to the anode chamber and the anolyte receiving container, the cathode chamber and the communication means A7 also have a structure in which a gas phase is not formed therein. It is important to keep

On the other hand, in the apparatus A of the present invention, the contact means of the communication means A1 or A3 of the apparatus A1 is limited to the cathode chamber only, and further, instead of the apparatus A1-c, a storage tank of an acidic compound aqueous solution;
Communication means between the storage tank for the aqueous solution of the acidic compound and the cathode chamber (hereinafter referred to as "communication means A8") (usually constituted by a pipe, a pump and a required valve. The storage tank and the cathode chamber may be directly connected to each other, or the contact point may be any point in the piping of the communication means A1 or A3 in which only the cathode chamber is used, except for the downstream of the delivery of the pump of the communication means. Means for supplying an acidic compound to the cathode chamber (hereinafter referred to as “apparatus A2-c”).
And a communication means A7 (provided that the pipe directly connects an arbitrary point of the pipe of the communication means A5 to the anode chamber, that is, the anode electrolyte contains a catholyte solution. (Hereinafter, referred to as “apparatus A2”). In the device A2, it is important to give the same consideration to the cathode chamber and the communication means A7 as in the case of using the device A1-c2 as the device A1-c in the device A1.

Next, the structure of the apparatus A in which a gas phase is not formed therein is the same as that of the anode chamber (the apparatus A1).
When the device A1-c2 is adopted as the device -c and the device A2
In the case of (1), the cathode chamber is also made of a container capable of maintaining a watertight state (objective: to cut off contact with the outside air and to minimize the possibility of formation of a gas phase); One end of A1 or A3 is placed under the anode chamber (when the apparatus A1-c2 is used as the apparatus A1-c and also the cathode chamber in the case of the apparatus A2), and one end of the pipe of the communication means A4 is connected to the anode chamber. (Apparatus A1 as apparatus A1-c
-When the c2 is adopted and in the case of the device A2, the cathode chamber is also connected to the lower portion (purpose: to minimize gas generation); and the other end is opened to the atmosphere via a check valve. A pipe is further provided, and one end of the pipe is connected to an arbitrary point of the pipe of the communication means A4 (an arbitrary point upstream of the switching valve installation point) (purpose: generated gas-mainly oxygen gas-and anolyte). The other end is located at a position higher than the arbitrary point.
Communication means A7 when the device A2 is adopted and when the device A2 is used.
A similar pipe is also provided. Its purpose is mainly gas-liquid separation of the generated gas-mainly hydrogen gas-and the catholyte solution); and the anolyte receiving container has the flexibility to make its internal volume close to zero and the anolyte solution. By increasing its volume by receiving the anolyte underwater tightly therein, and then decreasing its volume by dispensing the anolyte underwater tightly to the outside; .

Also, the device A having a property capable of blocking ultraviolet rays must be one that is not affected by anode water before having a function of blocking ultraviolet rays.
Plastics selected from the group consisting of polypropylene and ABS polymers; plastics reinforced with fillers and fibers; and steel materials coated with these materials may be used.

Further, the present invention relates to a method for transferring electrolyzed water stably containing a high concentration of residual chlorine obtained by electrolyzing a chloride aqueous solution to a diaphragm without impairing its stability. A device for producing residual chlorine-containing water having a sterilizing ability that is also effective against spores by diluting it to a predetermined concentration at a location (hereinafter, referred to as “device B”); and at least devices A1-b; Transfer means for receiving the anolyte from the device A1-b, transferring the anolyte to the point of use, and discharging the anolyte at the point of use (hereinafter referred to as "device B1");
And a diluting means (hereinafter, referred to as “device B
2)), and these means have a structure that does not generate a gas phase therein, and have a structure and / or property capable of blocking ultraviolet rays. It also does.

Here, the device B1 has a flexibility to make its internal volume close to zero, and its volume is increased by receiving the anolyte from the outside into the interior thereof in a watertight manner. Discharging the liquid to the outside under watertightness reduces its volume,
A container for transfer whose volume can be varied; and means for communicating the container and the apparatus A1-b in a watertight manner (hereinafter referred to as "communication means B1") (usually constituted by a pipe, a pump and required valves) Note that, depending on the positional relationship between the device A1-b and the transfer container, it may not be necessary to use a pump.).

The receiving container of the device A1-b is preferably a bag-like container disposed in a submerged state in an open-topped container capable of being submerged. More preferably, the water is a saturated solution of slaked lime.
The advantages of such a configuration are as described above in the section of the manufacturing method.

The container for transfer of the apparatus B1 is preferably housed in a box body capable of receiving the container in its maximum capacity. Further, the box may be a cardboard. Further, it is preferable that the box body is formed by holding slaked lime powder in the inner space thereof and the outer space of the transfer container at the maximum capacity. The advantages and reasons for selecting such a configuration are as described above in the section of the manufacturing method.

Further, the apparatus B2 is an apparatus which has already been described as a method for extracting the anolyte solution from the transfer container at the point of use without easily contacting with the outside air while diluting the anolyte solution to a required residual chlorine concentration simply and accurately with water; A pipe for connecting the apparatus to a water supply source; and a pipe for connecting the apparatus to a transfer container of the apparatus B1, wherein the container and the pipe are detachably attached to a connection portion with the container. And a pipe having an attachment to be obtained.

Further, the present invention comprises the apparatus A and the apparatus B.

[0035]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below based on an embodiment which is one embodiment thereof.

1 to 3 show a method for obtaining electrolyzed water stably containing a high concentration of residual chlorine, that is, a method A.
(However, the illustration of a part where the anode water as the electrolyzed water is filled in the receiving container in a state where no gas phase is present and the ultraviolet rays are shielded is omitted because the figure is complicated. Refer to the following description.) This is illustrated together with the main components of A (the receiving container is omitted) and a basic control system.

First, the electrolytic cell will be described (FIGS. 1 to 3).
reference). The electrolytic cell 1 includes casings 2a and 2b, an anode (anode) 4a, a cathode (cathode) 4b, a spacer 6a,
6 b and the diaphragm 5. Here, the space defined by the diaphragm 5 and the casing 2a and having the anode 4a therein is the anode chamber 3a, and the space defined by the diaphragm 5 and the casing 2b and the cathode therein. The space having 4b is the cathode chamber 3b.
In the figure, a single tank flat plate type is shown for simplicity, but a double tank flat plate type or a cylindrical type with an increased number of electrode sets may be used. In short, as the electrolytic cell itself, a known cell may be used as necessary.

The spacers 6 (6a, 6b) have a role of maintaining a constant distance between the electrodes and securing a flow path of the electrolyzed water. If the thickness of the spacer is reduced and the distance between the electrodes is reduced, electrolysis can be performed at a low voltage. However, the flow rate of the electrolyzed water increases, and as a result, the pressure loss increases. Is determined (set to 3 mm in the test examples described later).

It is preferable to use a neutral membrane capable of passing both cations and anions for the diaphragm 5, and the material thereof is preferably a fluorine-based material which is not affected by chlorine gas generated in the anode chamber ( Hydrocarbon-based membranes are not practical because they are easily attacked by chlorine gas). In addition, it is preferable to select a material having high water permeability as small as possible because it reduces the effect of the diaphragm.

Since the material of the anode 4a has a large effect on the electrolytic efficiency, it is preferable that the chlorine overvoltage is small and the oxygen overvoltage is large. The oxidation reaction of chlorine ions was made to proceed easily). On the other hand, the material of the cathode 4b was titanium in consideration of corrosion resistance in a test example described later.
Stainless steel may be used. A direct current is applied to both electrodes at a predetermined voltage from the power supply device 65.

Next, the method A-1, that is, the process of incorporating an alkali compound into the electrolyte to be introduced into the anode chamber (see FIGS. 1 and 2) will be described.

First, in the method A-1a (see FIG. 1), the water to be electrolyzed is supplied at a predetermined flow rate through the line 11 and the flow rate control valves 51 and 52 provided in the middle of the line 11 and the cathode chamber 3b. The lines are respectively supplied to the anode chamber 3a (in the figure, the line is branched into a sub-line 13 for the cathode chamber and a sub-line 12 for the anode chamber, and the flow control valve is installed at an arbitrary point in these sub-lines). The line 11 is provided with a line 21 connected to a chloride aqueous solution storage tank 31 for supplying a chloride aqueous solution (for example, a saline solution) as the water to be electrolyzed through the line (reference numeral 41 denotes a chloride aqueous solution). Supply pump). Where line 11
Is connected to a water supply source (not shown), from which fresh water such as city water is supplied to the line with a predetermined pressure, and supplied from a chloride aqueous solution storage tank 31 via a line 21. The mixture is mixed with a chloride aqueous solution at a predetermined ratio to form a predetermined concentration of water to be electrolyzed, and then supplied to the cathode chamber 3b and the anode chamber 3a, respectively. In this flow, the aqueous chloride solution is represented as a concentrated solution (maximum allowable concentration: saturated concentration), but of course, electrolyzed water of a predetermined concentration may be directly prepared in the aqueous chloride solution storage tank 31. In that case, the left end of the line 11 may be blind.

An alkaline compound (for example, caustic soda) for adjusting the pH of the anode chamber 3a is provided at an arbitrary point on the sub-line 12 (downstream of the flow control valve 51). In this case, it is a matter of course that ammonium chloride may be used as a chloride as an electrolytic substance. (Alkaline compound storage tank 32 and line 22 and a pump for alkaline compound disposed at an arbitrary point thereof) 42)
Is connected.

On the other hand, lines 15 and 14 are respectively connected to the cathode chamber 3b and the anode chamber 3a for discharging the alkaline catholyte and the acidic anolyte generated in the respective chambers from the respective chambers to the outside of the system. I have. A receiving container described later is arranged downstream of the anolyte discharge line 14.

The control of this process may be performed as follows. Residual chlorine concentration control A signal corresponding to the residual chlorine concentration in the anolyte emitted from the residual chlorine concentration measuring device 61 provided at an arbitrary point in the anolyte discharge line 14 is sent to the controller 63 and the controller 63 determines the residual chlorine concentration according to the determined relationship. The voltage or current of the power supply device 65 is controlled. Control of pH of Anolyte A signal corresponding to the pH of the anolyte emitted from a pH measuring device 62 provided at an arbitrary point of the anolyte discharge line 14 is sent to a controller 64, and a signal for an alkaline compound is determined by the controller according to a predetermined relationship. Controlling the discharge flow rate of the pump 42 (when the pump is a fixed-rate pump; a method using both a pump and a flow control valve, that is, a flow control valve on the discharge side of the pump, and the flow control valve on the line 22) The sub-lines returning to the alkaline compound storage tank from an arbitrary point upstream of the sub-line may be provided, and the opening degree of the flow control valve may be controlled by the controller.)

The result of verifying the effect of this process is shown below. The conditions of the apparatus are as follows (unless otherwise specified, test conditions other than Test Examples 1 to 3 also apply). 1. Electrolyzer type: Concentric cylindrical anode: Platinum or iridium coating on titanium plate Cathode:・ Titanium plate diaphragm ・ ・ ・ ・ ・ ・ Neutral membrane (transmittance: 0.3cc / cm ²
· Min.) Distance between electrodes ······ 4 mm (2: 2) Effective electrode area ··· 1,000 cm ² Process conditions Properties of raw water ······ Electric conductivity (163 μs / cm)
pH (7.1), residual chlorine concentration (<0.5 ppm) Salt solution concentration: Saturated saline solution (about 350 g-NaCl /
l) 3. Measurement method of measurement value ORP, pH ... Water test (manufactured by Hanna Instruments Japan Co., Ltd. It is also possible to measure water temperature and electric conductivity in addition to ORP and pH with the same equipment) Residual chlorine concentration .... Orthotrizine arsenite method

Test Example 1 Raw water alone (meaning that no salt solution was contained) was introduced into the anode chamber and the cathode chamber of the above apparatus at 1 l / min., Respectively, and electrolyzed (current: 20 A, voltage: 4.2 V). The obtained anolyte had pH = 2.5, ORP = 1,140 mV, and residual chlorine concentration = 5 ppm. As shown in FIG. 4, it can be seen that such a low concentration of residual chlorine is stable even at a low pH (see FIG. 4).

Test Example 2 Electrolyzed water (3.5 g-NaCl) obtained by diluting a saline solution with raw water
/ l) were introduced into the anode chamber and the cathode chamber of the above-described apparatus at 1 l / min., respectively, and electrolyzed (current: 20 A, voltage: 4.
2V). The resulting anolyte was pH = 2.5, ORP =
The result was 1,140 mV and the residual chlorine concentration was 225 ppm. As shown in FIG. 4, it can be seen that even at this level of residual chlorine concentration, it is extremely unstable at low pH (see FIG. 4).

Test Example 3 Electrolyte water obtained by adding 0.5N caustic soda solution to the water to be electrolyzed in Test Example 2 at 15, 30, 40, and 80 ml / min. /
Min. was introduced and electrolyzed (current: constant current electrolysis of 20 A). The properties of the obtained anolyte were as shown in the table below.
As shown in FIG. 4, the residual chlorine in the anolyte obtained by the alkali-added electrolysis is extremely stable even though the residual chlorine concentration is higher than that in Test Example 2, and the higher the pH, the better the stability. Figure-Amount of alkali added: 3
0 ml / min.-And-Alkali addition amount: 80 ml / min.-
reference).

[0050]

[Table 1]

On the other hand, as is well known, when performing DC electrolysis with a diaphragm, according to the following formula (for the sake of simplicity, the water to be electrolyzed is a saline solution), the chlorine ions are converted from hydrochloric acid to hydrochloric acid in the anode chamber 3a. Chlorous acid is generated, and caustic soda and hydrogen are generated from sodium ions in the cathode chamber 3b. The anode _{^{compartment: 2Cl - → Cl 2 + 2e}} , Cl 2 +
H ₂ O → H ⁺ + Cl ⁻ + HClO Cathode chamber : 2Na ⁺ + 2H ₂ O + 2e → 2Na
The anode water exhibits acidity due to the dissociation of OH + H _{2 and} hydrochloric acid, and exhibits oxidizing properties due to the presence of hypochlorous acid (actually, in addition to the above-mentioned substances, naturally includes unelectrolyzed saline).

On the other hand, the cathodic water becomes alkaline due to the dissociation of the caustic soda and shows a reducing property due to the presence of hydrogen (actually, in addition to the above-mentioned substances, naturally contains unelectrolyzed saline). Thus, the method A-1b (see FIG. 2) uses this cathode water as a substitute or supplement for the above-mentioned alkaline compound.

This process and the previous process (Method A-1)
The difference from a) is that a line 23 for circulating at least a part of the cathode water to the anode chamber 3a in addition to the means for introducing the alkaline compound, which is connected to an arbitrary point of the sub-line 12, is provided.
(In addition, a pump 43 is provided at an arbitrary point on the line. In the drawing, one end of the line is connected to the line 22 for supplying the alkaline compound from the alkaline compound storage tank 32. However, of course, it may be connected directly to the anode chamber, or may be connected to the chloride aqueous solution supply sub-line 12);
That is; Along with this change, the alkaline compound supplied from the alkaline compound storage tank 32 is metered as a base neutralizer. When this process is adopted, the reaction between an acid (hydrochloric acid as a strong acid and hypochlorous acid as a weak acid) and an alkali (caustic soda as a strong alkali) in the anode chamber is performed in a region near neutral. Therefore, the presence of hypochlorous acid works effectively, and the titration curve becomes gentle, so that the control of pH adjustment is stabilized, and further, there is an advantage that the utilization rate of chloride as an electrolyte is improved.

The result of verifying the effect of this process is shown below. Test Example 4 A part of the catholyte obtained in Test Example 2, 0.5 ml / min.
Was electrolyzed in the same manner as in Test Example 2 except that a line for circulating was passed through the anode chamber and electrolysis was performed. The obtained anolyte had pH = 7.7, ORP = 1,170 mV, and residual chlorine concentration = 400 ppm. As shown in FIG. 4, it can be seen that despite the higher residual chlorine concentration than in Test Example 2, the residual chlorine of the anolyte in the electrolysis by circulating the catholyte is extremely stable (see FIG. 4). The properties of the catholyte circulated in the anode compartment were pH = 12.0,
ORP = −924 mV, residual chlorine concentration = 5 ppm.

The advantage of this process (method A-1b), that is, the utilization of the catholyte, was taken one step further.
-1c (see FIG. 3).

This process and the previous process (Method A-1)
The difference from b) is that the aqueous chloride solution is supplied only to the cathode chamber 3b; and that the electrolyte for the anode chamber is only the catholyte (at least a part of the catholyte); and the alkaline compound (The means for introducing the acidic compound is usually the acidic compound storage tank 3).
4. A line 24 for supplying the acidic compound and a pump 44 arranged at an arbitrary point in the line). In this process, chloride as an object to be electrolyzed is subjected to electrolysis twice in the cathode chamber 3b and the anode chamber 3a, so that a higher chloride utilization rate can be obtained than in the method A-1b. When a large amount of is circulated, the pH of the anolyte becomes too high and a desired sterilization ability cannot be obtained at the final use of the anolyte. In order to save the line, supply line 11 of chloride aqueous solution
Is supplied via).

The result of verifying the effect of this process is shown below. Test Example 5 Electrolyzed water obtained by diluting saline with raw water (3.5)
g-NaCl / l) 1 l / min. with 0.5N hydrochloric acid solution at 20 ml / mi
n. was introduced only into the cathode compartment of the above-described apparatus, and electrolysis was performed while circulating the catholyte, which is an electrolysis product in the cathode compartment, to the anode compartment (current: 20 A).
, Voltage: 6.5 V). The resulting anolyte was pH = 7.
1. The residual chlorine concentration was 420 ppm. As shown in FIG. 4, the stability of the residual chlorine in the anolyte was completely satisfactory (see FIG. 4). The pH of the anolyte when the hydrochloric acid solution was added was 9.2 (provided that the electrolysis conditions were a current of 20 A and a voltage of 6.8 V).

Next, a test was conducted to further increase the concentration of residual chlorine in the anolyte (purpose: to improve the transfer efficiency to the point of use). The outline and results are shown below. Test Example 6 Electrolyzed water (5.3 g-NaCl) obtained by diluting saline with raw water
/ l) 40 ml / mi of 0.5N caustic soda solution to 1 l / min.
n. The added substances were introduced into the anode chamber and the cathode chamber of the above-described apparatus, respectively, and electrolyzed (process was carried out by method A-1a).
It is. The electrolysis conditions are constant current electrolysis with a current of 50 A). The obtained anolyte had a residual chlorine concentration of 1,0.
At 50 ppm the pH was 6.8. As shown in FIG. 4, there was no problem in the stability of the residual chlorine (see FIG. 4). In order to further increase the residual chlorine concentration, the amount of the above-mentioned alkali-added electrolyzed water charged into the electrolysis apparatus was reduced by half, and the residual chlorine concentration was 2,000 ppm and the pH was 6.9.
An anolyte was obtained. As shown in FIG. 4, there was no problem in the stability of the residual chlorine even at such a high concentration (see FIG. 4).

The purpose of the method (method A) of the present invention is to obtain electrolytic water containing a stable and high concentration of residual chlorine. The following tests were performed to confirm the methodology.

Test Example 7 First, the effect of ultraviolet rays was examined. PH = 6.5 and residual chlorine concentration = 1,100 produced by the method described so far.
The ppm anolyte was placed in a beaker, and irradiated with ultraviolet light from a mercury lamp of 400 W from a position 30 cm above the water surface under sealing. The results are shown in FIG. It can be seen that ultraviolet rays have a very large effect on the stability of residual chlorine.

Test Example 8 Next, the influence of the presence of the gas phase was examined. This is because the stability of the residual chlorine is of course important from the viewpoint of ensuring the safety of the user of the electrolyzed water produced in the present invention.
Concentration of chlorine gas in the gas phase on the surface of electrolyzed water obtained in step 5pp
m, which is dangerous if humans inhale.
According to safety standards, the gas concentration is 1 ppm or less-). The anolyte obtained in Test Example 6 was collected in a brown bottle, and the gas phase volume ratio on the water surface (the ratio of the gas phase volume to the total volume) was changed to determine the change over time of the residual chlorine in the anode solution. Observed. FIG. 6 shows the result. It can be seen that the decrease in the residual chlorine concentration is remarkable with the increase in the gas phase volume ratio.

From these results, in the present invention (both methods A and B), at least the anode chamber (and the cathode chamber as necessary) is operated in a liquid-filled state and in a state where ultraviolet rays are cut off. Filling the anolyte discharged from the anode chamber into a receiving container capable of preventing the flow of air and the transmission of ultraviolet rays in a state without a gas phase and in a state where ultraviolet rays are blocked (discharged from the cathode chamber as required) The same consideration must be given to the circulation of the catholyte to the anode chamber), and also to the filling of the anolyte into the transfer container from the receiving container and the discharge at the point of use from the transfer container. The same considerations must be given to filling the receiving container. In view of these facts, Test Examples 1 to 6 described above were all carried out in a state without a gas phase and in a state in which ultraviolet rays were blocked.

A specific example of these considerations is shown in FIG. 7 (the method A-1c application case is the most widely used and the system is configured on the premise of this case. Regarding the consideration regarding the ultraviolet shielding of the electrolytic cell, a usual material such as a plastic such as vinyl chloride or a metal material using a plastic that has corrosion resistance to chlorine and is capable of lining from the plastic material as a lining material is used as the material of the device. In the figure, the supply of the aqueous chloride solution and the acidic compound to the electrolytic cell 1, the circulation of the catholyte to the anode chamber 2b, and the anolyte from the electrolytic cell will be described. It should be noted that the direction related to the discharge of is drawn with priority given to the convenience of display, and does not indicate the actual direction.) In the following, each correspondence will be described.

(1) Prevention of gas components from being brought into the anode chamber from outside the system As described above, hydrogen is generated together with caustic soda in the cathode chamber 3b. On the other hand, Method A-1b and Method A-1c
Is adopted, (at least a part of) the catholyte as an electrolytic product in the cathode chamber is circulated and supplied to the anode chamber 3a as a substitute for an alkaline compound or an electrolytic solution containing an alkaline compound. Here, when the (at least part of) the catholyte is circulated as it is to the anode compartment, hydrogen generated in the cathode compartment flows into the anode compartment along with (at least part of) the catholyte. Become. Therefore, (at least a part of) the catholyte
The stand pipe 16
(One end: connected to the line, the other end: open to the atmosphere via the check valve 53, the position of the other end: a position higher than the one end), and hydrogen gas to the atmosphere from the other end. Release.

(2) Prevention of gas components from being brought into the anolyte filled container In the anode chamber 3a, oxygen is partially generated together with hydrochloric acid and hypochlorous acid. In some cases, chlorine gas may be generated. On the other hand, the anolyte discharged from the anode chamber to the outside of the system is configured to be filled in a receiving container 35 capable of preventing the flow of air and the transmission of ultraviolet rays without forming a gas phase therein. Here, when the anolyte is directly filled in the container, oxygen gas (and chlorine gas in some cases) is also entrained and filled in the receiving container, and consideration for the receiving container itself (described later) is neglected. Would. Therefore, the same treatment as (1) is performed on the anolyte discharge line 14. That is, a stand pipe 17 (one end thereof: connected to the line,
The other end is opened to the atmosphere via the check valve 54, the position of the other end is set to a position higher than the one end), and oxygen gas (and chlorine gas in some cases) is released to the atmosphere from the other end. Let it. This stand pipe is also one of measures for preventing the anolyte solution from being overfilled into the receiving container (by providing a level sensor 55 at the other end and on the other end side of the check valve). "Overfill" can be detected.
If this "overfill" is detected, any point on line 14-
The three-way valve 56 provided downstream of the connection point with the stand pipe 17 is operated via the controller 57 to discharge the anolyte discharged from the anode chamber 3a to the outside of the system.
Note that the same flow path switching using the three-way valve is also performed at the start-up of the electrolytic apparatus 1 in order to maintain the quality of the anolyte filled in the receiving container).

(3) Filling and discharging the anolyte into the receiving container without forming a gaseous phase 1) Consideration of the structure of the receiving container "The anolyte is flexible enough to make its internal volume near zero. , The volume of which is increased by receiving the anolyte in a watertight manner, and the volume of the anolyte is reduced by discharging the anolyte to the outside in a watertight manner. A bag-like container 35 made of plastic, for example, polyethylene and nylon is used. Here, the container has a port for receiving the anolyte therein, which can be connected to the line 14, and an anolyte from the outside (in the present invention, a transfer port). A port for dispensing to the container 36), which can be connected to the line 18 for dispensing; and a vent valve 58; Of course, the bag is provided with an ultraviolet transmission preventing treatment, for example, a coating of a paint having an ultraviolet transmission preventing ability. When the receiving container is placed under an ultraviolet ray blocking means, for example, a roof having a function of preventing ultraviolet ray transmission, no special treatment for the bag is required.

2) How to Use the Receiving Container The procedure may be as follows. Before using the container, the container is first put into a "squash" state (most of the air present inside is discharged to the outside by this operation). Next, the anolyte is received in the container (the volume of which naturally increases). In the course of the volume increase, the air remaining in the container is further discharged to the outside via the valve 58. ). When the container has received the anolyte to its maximum volume, the air initially present therein has been completely eliminated. Next, a part of the content liquid (anode liquid) is dispensed,
A state having a margin in the inner volume is formed. The anolyte is received and dispensed while maintaining a sufficient state of the inner volume (as long as this state is maintained, the content liquid does not come into contact with the atmosphere).

3) Other considerations related to receiving containers Required number: It is preferable that at least two are provided from the standpoint of spare. Installation mode: It is preferable to put in a container with an open top to prevent damage due to uncertain elements. A liquid, for example, an alkali compound such as slaked lime is mixed therein.
It is more preferable that the container is immersed in a container 35v in which the dissolved liquid can be filled. This is because the tension of the receiving container caused by the movement similar to breathing accompanying the increase and decrease of the content liquid is relieved by the hydrostatic pressure, and a measure against a breakage accident, that is, neutralization of the acid liquid by alkali is inevitably performed.

(4) Filling the transfer container with the anolyte solution without forming a gas phase 1) Consideration of the structure of the transfer container The volume of the anolyte is increased by receiving the anolyte therein in a watertight manner, and then the volume is reduced by discharging the anolyte to the outside in a watertight manner. A bag-like container 36 made of plastic, for example, polyethylene, polypropylene, or the like is used as the filling material. Specifically, a commercially available product called “Cubitiner” (trade name) may be used (the bag-shaped container is a box, more precisely, a cardboard 37).
It is housed inside. Of course, the cardboard may be replaced with a plastic box in order to prevent damage to the bag-shaped container during transfer.) However, even if the container is dispensed at the place of use, "without contact with the outside air"
Therefore, a special accessory, that is, a sealing member connected by a vinyl pipe 36b connecting the cap 36a and a male screw insert 36c with a shut-off valve, is provided solely in the container. A "mouth" for receiving and dispensing the liquid contents. In addition, since a normal corrugated cardboard does not transmit ultraviolet light, it is not necessary to perform a special treatment for preventing ultraviolet light transmission to the bag itself (see FIG. 8).

2) How to use the transfer container (at the time of filling the anolyte) The following procedure may be used. As with the receiving container, the container is first placed in a "squash" state before use (air present inside is almost completely discharged by this operation). Next, the anolyte is received in this container (a pump 45 is used for transfer from the receiving container 35.
At the end of line 18 (the number of which corresponds to the number of containers to be transported), a shut-off valve which engages in a watertight manner with a male threaded insert 36c with a shut-off valve constituting the "mouth" of the transport container. Provide a female screw insert. Thus, the anolyte flows into the vessel without contacting the atmosphere). This is done gently so that the container gradually inflates, and when it receives a little more than a predetermined amount, the valve of the male screw insert with shut-off valve is "closed" and the shut-off valve at the end of line 18 is closed. Female screw insert (of course, this valve is also "closed")
) Is released. The container is then somewhat compressed (manually possible) (while the valve on the male screw insert with the shut-off valve is "open", i.e. with the contents liquid slightly out). Completely forms a state in which no gas phase is present). Finally, the valve of the male screw insert with the shut-off valve is "closed" to complete the receiving operation (as long as this state is maintained, the content liquid does not come into contact with the atmosphere).

3) Other considerations related to transfer containers Required number: It is preferable to provide at least two (in order to facilitate the filling operation at the filling point and to fill the time lag between the next transfer at the point of use). Aspect: In order to ensure safety in the event of breakage due to an uncertain element, the container is housed in a box such as a cardboard box and the space between the box and the bag-like container filled with the anolyte therein. Slaked lime powder 36 as an anolyte neutralizer in a suitable place
e is preferably inserted (see FIG. 8).

(4) Discharge of Anode Solution from Container for Transfer without Forming Gas Phase 1) Consideration of Discharge System Arrangement of transfer container at the point of use: a plurality of transfer containers 36 Are housed vertically in a frame 38 having a storage portion 38a such as a locker, and a plurality of containers for transfer are connected in parallel to a suction line 39b of a mixing / diluting device 40 for the contents thereof. (The connection is made with a male screw insert 36 with a shut-off valve on the container.
c and a female screw insert 3 with a shut-off valve arranged at an arbitrary point on the suction line 39b of the mixing / diluting device.
9bV engagement. When the two are engaged with each other, a state in which the contents can be discharged from the bag-shaped container in a state where the contact with the atmosphere is cut off is inevitably formed. See FIG. 8).

2) Structural Considerations for Mixing / Dilution Apparatus An apparatus 40 ("DSA dispenser" (trade name)) as shown in FIG. Hereinafter, the structure and operation of this device will be described.
Appropriate water pressure, eg, 1-3 kg / cm, from a line 39a connected to the dilution water inlet 40a of the apparatus (where a check valve 40aV that allows the flow of dilution water in the receiving direction is arranged) ^When dilution water having ² · G, for example, city water, is introduced into the upper cylinder 40b, the upper piston 40c slidably disposed on the inner wall of the upper cylinder is moved upward. A lower cylinder 4 is attached to the other end of the shaft 40d having this upper piston engaged with one end thereof.
0e (both cylinders are water-tightly isolated) is engaged with the lower piston 40f slidably disposed on the inner wall, so that the lower piston moves with the upward movement of the upper piston. The upper piston and the lower piston are engaged with the shaft such that the axial distance between the shafts can be changed as appropriate by an adjustment mechanism 40g. Due to this movement, dilution water corresponding to the volume flows into a space formed by the inner wall of the upper cylinder and the lower surface of the upper piston (hereinafter, referred to as “dilution water inflow space”), and A space formed between the inner wall and the lower surface of the lower piston (hereinafter, referred to as an “anolyte inflow space”) is provided with an anolyte inlet 40h (here, a non-return valve that allows an upward flow of the shaft of the shaft). Valve 40hV is arranged)
The anolyte corresponding to the volume flows through (accurately, is sucked in). When the upper piston moves further upward (the driving force is the dilution water flowing into the dilution water inflow space) and reaches the top dead center, a hole passing through the upper piston in the axial direction of the shaft via a spring 40i. (Hereinafter referred to as “hole A”), the valve 40 cV
Operate in the direction of opening the hole A. As a result, the dilution water that has flowed into the dilution water inflow space moves into the space inside the upper cylinder head 40j, and the upper piston starts to descend rapidly due to the reaction. As the upper piston descends, the lower piston also starts to descend rapidly. The lower piston has a hole (hereinafter, referred to as "hole B") that penetrates the shaft in the axial direction of the shaft (hereinafter referred to as "hole B"). Not shown)
The anolyte inflow space is compressed, so that the anolyte that has been sucked into the anolyte inflow space by the compression action flows into the lower cylinder head 4.
It is moved to the space within 0k. On the other hand, an outlet of a passage 40l connected to the upper cylinder head is provided with a passage area limiting means 40 for accelerating the flow of the moved dilution water.
m is provided, and a hose 40o communicating with the lower cylinder head is connected to a space (mixing section 40n) immediately downstream of the passage area limiting means. Therefore, when the upper piston reaches its bottom dead center and the next dilution water starts to be received in the dilution water inflow space, the dilution water which has been moved to the space in the upper cylinder head first is transferred to the passage area limiting means. Anode water that has been extruded through the hose into the mixing section by the upward movement of the shaft through the mixing section (which had previously been moved into the space in the lower cylinder head) ) Will be mixed. As is clear from the structure of the mixing / diluting device, the mixing ratio of the dilution water and the anode water is determined uniquely by the volume ratio between the dilution water inflow space and the anolyte inflow space, and is independent of the dilution water inflow pressure. Therefore, even if the inflow pressure of the dilution water fluctuates, it is always kept constant. Therefore, the anolyte is always diluted to a predetermined concentration. Note that the predetermined concentration can be obtained by changing the axial distance between the upper piston and the lower piston in the shaft through the adjustment mechanism. Also,
The inflow of the dilution water into the mixing / diluting apparatus is performed by diluting the anodic water at the terminal (actual) point of use connected to the mixing section via the line 39c, for example, at the curan 39cV (s). Caused by use.

3) Operation of the Dispensing System The male screw insert 36c with the shut-off valve and the mixing / diluting device 40 of the transfer container 36 transferred to the point of use and stored in the storage portion 38a of the frame 38 together with the box 37. Arbitrary point of suction line 39b (position facing male screw insert 36c with each shut-off valve)
And a female screw insert 39bV with a shut-off valve arranged in the above. Male screw insert 3 with shut-off valve
6c and the 39cV female screw insert with shutoff valve are each "open". In this state, when the curan 39cV connected to the line 39c of the mixing / diluting device 40 is “open”, that is, when the anolyte water previously diluted to a predetermined concentration by the mixing / diluting device is actually used, the Dilution water flows through the water supply line 39a and anode water as the content in the transfer container 36 flows through the suction line 39b, respectively, to produce anode water diluted to the next predetermined concentration. The air present in each line of the dispensing system including the mixing / diluting device may be expelled by discharging the diluted anode water from the curran during the first operation of the system. With the discharge of the anode water diluted to a predetermined concentration from the curran, that is, with the use of the anode water, the internal volume of the transfer container gradually decreases (of course, there is no inflow of air from the outside), Eventually, payout becomes impossible (of course, payout may be intentionally stopped at a predetermined level determined at that level). The transfer container 36 in such a state is then "closed" with its male screw insert 36c with shut-off valve and the corresponding female screw insert 39cV with shut-off valve on line 39b, respectively. Disconnect the insert. The used transfer container may be used again as the transfer container 36 or may be discarded.

The results of verification of the safety and effect of the anode water diluted to a predetermined concentration at the place of use are shown below. Test Example 9 The anode water obtained in the same manner as in Test Example 6 except that the amount of caustic soda added in Test Example 6 was changed, was diluted 40 times with the above city water. The diluted sample 200
After placing each in a 300 ml Erlenmeyer flask for 10 minutes, a gas detector (manufactured by Gastech, detector tube: 8H)
H, 8H), the chlorine gas concentration in the gas phase space above the flask was measured. As shown in the table below, the chlorine gas concentration in the gas phase space in contact with the anode water after dilution is well below the safety standard of 1 ppm, indicating that it is extremely safe. The chlorine gas concentration of the gaseous space in contact with the anode water of 2.9 itself is> 10
It was 0 ppm and actually emitted a strong chlorine odor. On the other hand, the pH of the sample before dilution was 6.9 and the pH after dilution was 7.0, which was almost unchanged.)

[0076]

[Table 2]

Test Example 10 High-concentration residual chlorine-containing water was produced in a test plant in which the above-described test apparatus was scaled up. After 6 weeks from the production), each sample was diluted with the above tap water to a predetermined chlorine concentration, and the sterilization effect was verified. 1. Production of high residual chlorine-containing water Production process ... Method A-1b Production conditions ... As shown in the table below

[0078]

[Table 3]

2. Verification of stability Each sample manufactured in the manner described above was cut off from gas-liquid contact and allowed to stand under light shielding for a predetermined period. As shown in the table below, the results show that the pH decreased but the residual chlorine concentration did not change,
It was confirmed that the residual chlorine-containing water produced by the method of the present invention was extremely stable.

[0080]

[Table 4]

3. Verification of bactericidal effect After 6 weeks of each sample manufactured according to the above procedure, the sample was diluted with tap water to a predetermined concentration, and the bactericidal effect was verified according to the following procedure. Sterilization target: Aerobic spore-producing bacterium (spore bacterium) Preparation of bacteria: Commercially available granular black pepper is ground using a tabletop pepper grinder, and 100 g of sterile physiological saline is added to 20 g of the black pepper and shaken with a stomacher. After extraction of the seed-containing adherent bacteria, this solution was diluted and adjusted so that the viable cell count was in the order of 10 ⁶ cells / ml, and used as a sample solution. After mixing 0.1 ml of the sample solution and 10 ml of each sample described above and keeping the mixture at 25 ° C. for 10 minutes, the number of bacteria in the mixed solution was counted by a plate-pour culture method. The results indicated that, as shown in the table below, if at least 40 ppm of residual chlorine was contained, the number of residual bacteria could be reduced to "zero".

[0082]

[Table 5]

[0083]

As described above in detail, according to the present invention, electrolyzed water capable of sterilizing spores can be provided over a wide range safely and inexpensively.

[Brief description of the drawings]

FIG. 1 is a flowchart showing an example of a method for obtaining electrolyzed water stably containing a high concentration of residual chlorine according to the present invention.

FIG. 2 is a flowchart showing another example of a method for obtaining electrolyzed water stably containing a high concentration of residual chlorine according to the present invention.

FIG. 3 is a flow chart showing still another example of the method for obtaining electrolyzed water stably containing a high concentration of residual chlorine according to the present invention.

FIG. 4 is a diagram showing the results of verifying the stability of electrolyzed water containing various concentrations of residual chlorine.

FIG. 5 is a diagram showing the results of verifying the effect of ultraviolet light on the stability of residual chlorine in electrolytic water.

FIG. 6 is a diagram showing the results of verifying the effect of the presence of a gas phase on the stability of residual chlorine in electrolytic water.

FIG. 7 is a flow chart showing a method of filling an anode water receiving container and a transfer container according to the present invention.

FIG. 8 is a diagram showing a transfer container of the anode water of the present invention together with a procedure for dispensing the anode water at a place where the anode water is used.

FIG. 9 is a flow chart showing a method of mixing and diluting the anode water at a point of use according to the present invention.

FIG. 10 is a diagram showing a structure of an apparatus for mixing and diluting at a place where anode water is used according to the present invention.

[Explanation of symbols]

 1 ・ ・ ・ ・ ・ ・ ・ Electrolyzer 2a, 2b ・ ・ ・ ・ ・ ・ Casing 3a ・ ・ ・ ・ Anode chamber 3b ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ Cathode room 4a ・ ・ ・ ・ Anode (anode) 4b ・ ・ ・ ・ Cathode (cathode) 5 ・ ・ ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ Septum 6a, 6b ・ ・ ・ ・ ・ ・ ・ ・ ・ Spacer 11,14,15 ・ ・ ・ ・ ・ ・ Line 12,13 ・ ・ ・ ・ ・ ・ ・ ・ ・ Sub line 16,17 ・ ・ ・ ・・ ・ ・ ・ ・ ・ ・ ・ Stand pipe 18 ・ ・ ・ ・ Line 21,22,23,24 ・ ・ ・ Line 31,32,34 ・ ・ ・ ・ ・ ・ Storage tank 35 ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Reception container, bag-shaped container 35v ・ ・ ・ Receiving container storage container 36 ・ ・ ・ ・ Transfer Containers, bags 36a Cap 36b Vinyl pipe 36c Male screw insert 36e Neutralizing agent 37 Box, cardboard 38・ ・ ・ Frame 38a ・ ・ ・ Accommodation parts 39a, 39b, 39c ・ ・ ・ Line 39bV ・ ・ ・ ・ ・ ・ ・ ・ ・ Female screw insert 39cV ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Caran 40 ・ ・ ・ ・ Mixing / diluting device 40a ・ ・ ・ Dilution water inlet 40b ・ ・ ・ ・・ ・ ・ ・ ・ ・ Top cylinder 40c ・ ・ ・ Top piston 40d ・ ・ ・ Shaft 40e ・ ・ ・ Bottom cylinder 40f・ ・ ・ Lower piston 40g ・ ・ ・ Adjustment mechanism 40h ・ ・ ・ Anolyte inlet 40i ・ ・ ・ ・ ・ ・・ ・ ・ ・ ・ ・ Spring 40j ・ ・ ・ ・ ・ ・ ・ ・ ・ ・Upper cylinder head 40k Lower cylinder head 40l Passage 40m Passage area limiting means 40n・ ・ ・ ・ ・ ・ ・ ・ ・ Mixing section 40o ・ ・ ・ Hose 40aV, 40hV ・ ・ ・ ・ ・ ・ Check valve 40cV ・ ・ ・ ・ ・ ・ ・ ・ ・ Valves 41, 42 , 43,44 ・ ・ ・ Pump 45 ・ ・ ・ ・ Pump 51,52 ・ ・ ・ ・ ・ ・ Flow control valve 53,54 ・ ・ ・ Reverse Stop valve 55: Level sensor 56: Three-way valve 57: Controller 58:・ ・ ・ ・ ・ ・ ・ ・ ・ Air vent valve 61 ・ ・ ・ ・ Residual chlorine concentration measuring device 62 ・ ・ ・ ・ pH measuring device 63,64 ・・ ・ ・ ・ ・ ・ ・ ・ Controller 65 ・ ・ ・ ・ Power supply unit

 ──────────────────────────────────────────────────続 き Continuation of the front page (71) Applicant 591009071 Nippon Steel Technical Information Center 1-6-6 Kojimachi, Chiyoda-ku, Tokyo (71) Applicant 594008006 Nittetsu Fine Products Co., Ltd. 23 Suzukocho, Kamaishi-shi, Iwate No. 15 (72) Inventor Jinichi Ito 1-2-1 Nishi-Waseda, Shinjuku-ku, Tokyo Zipcom Co., Ltd. (72) Inventor Yasuaki Nishio 6-19 Mitsuya Motomachi, Nagahama-shi, Shiga Pref. ) Inventor Masao Sakashita 3-35-1, Ida, Nakahara-ku, Kawasaki-shi, Kanagawa Prefecture Nippon Steel Corporation (72) Inventor Hiroo Matsuda 1-6 Kojimachi, Chiyoda-ku, Tokyo Nippon Steel Technical Information Center (72) Inventor Naoko Tago 1-6 Kojimachi, Chiyoda-ku, Tokyo Nippon Steel Technical Information Center (72) Inventor Masakazu Nakamura Tokyo Kojimachi, Chiyoda-ku, 1-6, Ltd. Nippon Steel Technical Information Center in the F-term (reference) 4D061 AA03 AB07 AB10 BA02 BB01 BB04 BB12 BB28 BB30 BB31 BB37 BB39 BD12 CA11

Claims (34)

[Claims] 1. A method for obtaining an electrolyzed water containing a high concentration of residual chlorine stably by using an aqueous chloride solution as a liquid to be electrolyzed and subjecting it to a membrane separation, comprising an anode chamber of an electrolysis apparatus. To contain an alkaline compound in the electrolyte to be introduced into the electrolyte chamber, and to operate the anode chamber in a full state and in a state where ultraviolet rays are blocked, and to carry out the anolyte which is electrolytic water discharged from the anode chamber. A method of filling a receiving container capable of preventing the flow of air and the transmission of ultraviolet rays without a gas phase and with the ultraviolet rays blocked. 2. The method of incorporating an alkaline compound into the electrolyte to be carried out comprises adding or mixing an aqueous solution of an alkaline compound from outside the system directly into the anode chamber or into the electrolyte to be introduced into the anode chamber. The adjustment of the input amount or the mixing amount is performed based on the deviation between the set value of the pH of the anolyte and the detected value, and the adjustment of the residual chlorine concentration in the anolyte is performed by the The method according to claim 1, wherein the method is performed by controlling a current and / or a voltage supplied to the electrolytic device based on a deviation between a set value and a detected value of the residual chlorine concentration in the anolyte. 3. The method of incorporating an alkaline compound into the electrolyte to be carried out, wherein the electrolytic water discharged from the cathode chamber of the electrolysis apparatus is directly added to the anode chamber or added to the electrolyte to be introduced into the anode chamber. Is performed by charging or mixing at least a part of the catholyte solution, and the adjustment of the charging amount or the mixing amount of the catholyte solution is performed by the anolyte solution.
Adjustment of the residual chlorine concentration in the anolyte is performed based on the deviation between the set value of the pH and the detected value, and adjustment of the residual chlorine concentration in the anolyte is performed by the electrolytic device based on the deviation between the set value and the detected value of the residual chlorine concentration in the anolyte. The method according to claim 1, wherein the method is performed by controlling a supplied current and / or voltage. 4. The method according to claim 3, wherein a predetermined amount of an aqueous solution of an alkaline compound is quantitatively charged or mixed in advance from outside the system into the electrolyte to be introduced directly into the anode chamber or into the electrolyte to be introduced into the anode chamber. . 5. The method according to claim 4, wherein the aqueous alkaline compound solution is an aqueous sodium hydroxide solution. 6. Inclusion of an alkaline compound in the electrolytic solution is achieved by supplying an aqueous chloride solution as the electrolytic solution to be supplied to the electrolytic device only to the cathode chamber of the electrolytic device and discharging the aqueous solution from the cathode chamber. The electrolysis is performed by using at least a part of the catholyte, which is electrolyzed water, as an electrolyte to be introduced into the anode chamber, and the amount of the catholyte introduced into the anode chamber is adjusted by the anolyte. PH
The adjustment of the residual chlorine concentration in the anolyte is performed on the basis of the deviation between the set value and the detected value, and the adjustment of the residual chlorine concentration in the anolyte is performed based on the deviation between the set value and the detected value of the residual chlorine concentration in the anolyte. The method according to claim 1, wherein the method is performed by controlling the applied current and / or voltage. 7. The method according to claim 6, wherein a predetermined amount of an acidic compound is previously charged or mixed in a predetermined amount into an aqueous chloride solution as an electrolyte to be supplied directly to the cathode chamber or supplied to the cathode chamber. 8. The method according to claim 7, wherein the aqueous acidic compound solution is an aqueous hydrochloric acid solution. 9. The method according to claim 6, wherein the set value of the pH of the anolyte is 6 ±
A method according to any one of the preceding claims, wherein the method is 1.5. 10. The method according to claim 10, wherein said receiving vessel is of a variable volume and said anolyte is filled into said receiving vessel without forming a gas phase therein. The volume of the anolyte is increased corresponding to the amount of the anolyte received in the receiving container in a water-tight manner near zero, and the anolyte is further sealed from the receiving container in a water-tight manner to the point of use. The method according to claim 1, wherein the method is performed by reducing the volume corresponding to the transfer amount. 11. An electrolyzed water containing a high concentration of residual chlorine, which is obtained by electrolyzing a chloride aqueous solution with a diaphragm, is transferred to a point of use thereof without deteriorating its stability.
A method for producing residual chlorine-containing water having an effective sterilizing ability even for spores by diluting it to a predetermined concentration at the point of use, comprising: an anolyte that is electrolytic water discharged from an anode chamber of an electrolytic cell. Filling the anolyte receiving container capable of preventing the flow of air and the transmission of ultraviolet rays without forming a gas phase therein, and forming the anolyte solution therein from the receiving container. Into a transfer container that can block the flow of air and the transmission of ultraviolet light, and dilute the anolyte from the transfer container to the required residual chlorine concentration without contact with the outside air at the point of use. A method characterized by extracting while doing. 12. The receiving container and the transfer container, each having a variable capacity, are used, and the anolyte is filled into the receiving container without forming a gas phase therein. That is, the volume of the anolyte is increased in accordance with the volume of the anolyte while the volume of the anolyte is received in a watertight manner into the receiving container having its internal volume near zero, and the volume of the anolyte is further reduced from the receiving container. The volume of the anolyte is reduced corresponding to the amount of transfer of the anolyte under water tightness into the container,
On the other hand, filling the anolyte into the transfer container without forming a gaseous phase therein may first be carried out into the transfer container in which the internal volume of the transfer container has been reduced to near zero. The anolyte is received in a watertight manner while the volume of the anolyte is increased in accordance with the amount of the anolyte. Withdrawing while diluting to a concentration is achieved by utilizing the negative pressure generated by introducing the water for dilution into the anolyte, and discharging the introduced water for dilution from the anolyte. The sucked anolyte is discharged, and at the outlet therefrom, the discharged diluting water and the discharged anolyte are mixed accurately and uniformly and diluted to a predetermined concentration. A suction and mixing system, in response to the amount of suction in watertight under the said device and the volume of the containers for the transport is carried out by being reduced, claim 10
The method described in. 13. The method according to claim 11, wherein the receiving container is a bag-like container used in a state of being immersed in water. 14. The method of claim 12, wherein said water is a saturated solution of slaked lime. 15. The method according to claim 11, wherein the transfer container is a bag-like container that is housed in a box capable of receiving the container at its maximum capacity. 16. The method according to claim 14, wherein the box body holds slaked lime powder in an inner space thereof and an outer space of the transfer container at the maximum capacity. 17. The suction / mixing device can be rubbed with two cylinders arranged in the same axis and vertically separated from each other and with inner walls of these cylinders. A piston is provided at the outlet of the upper cylinder for dilution water, and the dilution water accurately measured in the lower space of the cylinder formed by the cylinder and the piston intermittently discharged from the cylinder at a high speed is provided. A restricted flow path is provided so that the anode water can be accurately metered in the lower space of the cylinder formed by the cylinder and the piston at the outlet of the lower cylinder. A watertight line is formed that connects to the restricted flow path so that it can be fed into the restricted flow path, and further includes an inlet for the upper cylinder, an inlet for the lower cylinder, and the lower pin. Each of the stons has a check valve, and the upper piston opens a hole formed in the piston so that the upper space and the lower space of the upper cylinder can communicate with each other when the upper piston reaches a top dead center. 13. The method of claim 12, wherein each of the valves is provided to close when the upper piston reaches bottom dead center. 18. An aqueous chloride solution is used as a liquid to be electrolyzed.
It is electrolyzed with a diaphragm to obtain electrolyzed water stably containing a high concentration of residual chlorine, and then the electrolyzed water is transferred to the place of use without deteriorating its stability. A method for producing residual chlorine-containing water having an effective bactericidal ability even for spores by diluting it into an alkaline solution in an electrolyte to be introduced into an anode chamber of an electrolysis apparatus, and Operating the anode chamber in a liquid-filled state and in a state where ultraviolet rays are blocked, the flow of air in a state where the anode liquid, which is electrolytic water discharged from the anode chamber, is in a gas-phase-free state and ultraviolet rays are blocked, and Filling a receiving container capable of preventing transmission of ultraviolet light, and preventing the flow of air and transmission of ultraviolet light without forming a gas phase in the anolyte from the receiving container. Be filled into containers for delivery, and how in the use position and wherein the extracting with diluted with water from the container for the transport to the required residual chlorine concentration without being exposed to the external air to the anolyte. 19. An electrolytic solution using a chloride aqueous solution,
A device for obtaining electrolyzed water stably containing a high concentration of residual chlorine by subjecting it to diaphragm electrolysis;
An electrolytic cell separated at least through a diaphragm into an anode chamber having an anode therein and a cathode chamber having a cathode therein; and a means for supplying an aqueous solution of chloride as an electrolyte;
Means for receiving an anolyte, which is electrolyzed water produced in the anode compartment; and means for supplying an alkaline compound to the anode compartment, wherein the anode compartment and the anolyte receipt means are provided therein. A device having a structure that does not form a gaseous phase and a structure and / or property that can block ultraviolet light. 20. A means for supplying an alkaline compound to the anode chamber, wherein the means for supplying the alkaline compound is a storage tank of an aqueous alkaline compound solution;
20. The apparatus according to claim 19, comprising: a storage tank for storing the aqueous solution of the alkaline compound and the anode chamber. 21. The means for supplying an alkaline compound to the anode chamber, wherein the means for supplying an alkaline compound is a storage tank of an aqueous solution of an alkaline compound;
20. The apparatus according to claim 19, comprising: a communication means for connecting the aqueous solution of the alkaline compound to the anode chamber; and a communication means for circulating at least a part of the catholyte solution to the anode chamber. 22. An aqueous solution of chloride as an electrolytic solution,
A device for obtaining electrolyzed water stably containing a high concentration of residual chlorine by subjecting it to diaphragm electrolysis;
An electrolytic cell separated by a diaphragm into an anode compartment having an anode therein and a cathode compartment having a cathode therein;
A means for supplying an aqueous solution of chloride as an electrolyte to the cathode chamber only; a means for receiving an anolyte which is electrolytic water produced in the anode chamber; and an aqueous solution of an acidic compound to the cathode chamber Means: and communication means for circulating at least a portion of the catholyte solution to the anode compartment;
An apparatus having a structure in which a gas phase is not formed therein and a structure and / or property capable of blocking ultraviolet rays. 23. An anode chamber, wherein the structure in which a gas phase is not formed therein is a container capable of maintaining a watertight state;
One end of which is connected to an upper part of the anode chamber as a supply means of a chloride aqueous solution; and one end thereof is connected to a lower part of the anode chamber, and a pipe as an anolyte receiving means; One end of the pipe as an anolyte receiving means is connected to an arbitrary point, and the other end is provided at a position higher than the arbitrary point and is opened to the atmosphere via a check valve arranged near the other end. Pipes having the flexibility to bring its internal volume close to zero and increasing its volume by receiving the anolyte therein in a watertight manner, and then discharging the anolyte to the outside in a watertight manner 21. A device as claimed in claim 19 or 20, comprising: a receiving vessel as a means for receiving the anolyte, the volume of which can be reduced thereby. 24. An anode chamber and a cathode chamber, each of which comprises a container capable of maintaining a watertight state, and one end of which is connected to an upper part of the anode chamber and the cathode chamber. A pipe serving as a means for supplying an aqueous solution of chloride; a pipe connected at one end thereof to a lower part of the anode chamber as a means for receiving an anolyte; and at least one of a pipe serving as a means for receiving the anolyte and a catholyte Pipes as communication means for circulating the part to the anode chamber, one end of each of which is connected to an arbitrary point, and the other end thereof is provided at a position higher than the arbitrary point, and the other end is provided near the other end. Each pipe opened to the atmosphere through a stop valve; and having a flexibility capable of reducing its internal volume to near zero and receiving the anolyte therein in a watertight manner. 22. A receiving container as a means for receiving the anolyte, the volume of which is variable, wherein the volume is increased and then the volume is reduced by discharging the anolyte to the outside in a watertight manner.
Or the apparatus of 22. 25. A plastic selected from the group consisting of vinyl chloride, polyethylene, polypropylene and ABS polymer, said plastic having a property capable of blocking ultraviolet rays; a plastic reinforced with a filler or fibers; The apparatus according to any one of claims 19 to 24, wherein the apparatus is formed using a material selected from the group consisting of steel materials coated with these. 26. Electrolyte water stably containing a high concentration of residual chlorine obtained by electrolyzing a chloride aqueous solution with a diaphragm, is transferred to a point of use thereof without impairing its stability,
An apparatus for producing residual chlorine-containing water having an effective sterilizing ability against spores by diluting it to a predetermined concentration at the point of use; and electrolyzed water produced at least in the anode chamber of the electrolyzer. A receiving container as an anolyte receiving means, which has a flexibility to make its internal volume close to zero, and whose volume is reduced by receiving the anolyte from the anolyte compartment into the interior thereof in a watertight manner. A variable-volume receiving container that increases and then reduces its volume by discharging the anolyte to the outside in a watertight manner; and a container for the transfer of the anolyte, the internal volume of which is reduced. It has a flexibility that can be close to zero, and its volume is increased by receiving the anolyte from the outside into the interior in a watertight manner, and the A variable-volume transfer container, whose volume is reduced by discharging the liquid to the outside in a watertight manner; and utilizing a negative pressure generated by introducing water for dilution into it. The anolyte is drawn off and the introduced diluting water is drained therefrom to discharge the sucked anolyte, and at the outlet therefrom the discharged diluting water and the discharged And a suction / mixing device for mixing the anolyte solution accurately and uniformly and diluting to a predetermined concentration, wherein the receiving container, the transfer container and the suction / mixing device are capable of blocking ultraviolet rays. And / or having properties. 27. The apparatus according to claim 23, wherein the receiving container is a bag-shaped container arranged in a submerged state in a top-openable container capable of being flooded. 28. The apparatus according to claim 27, wherein the water impregnated in said open top container is a saturated solution of slaked lime. 29. The apparatus according to claim 26, wherein the transfer container is a bag-shaped container. 30. The apparatus according to claim 29, wherein the transfer container is housed in a box capable of receiving the container at its maximum capacity. 31. The apparatus according to claim 30, wherein the box body holds slaked lime powder in an inner space thereof and an outer space of the transfer container at the maximum capacity. 32. The container according to claim 3, wherein the box is a cardboard.
An apparatus according to claim 1. 33. The mixing / suctioning device can be rubbed with two cylinders arranged in the same axis and vertically separated from each other and with the inner wall of these cylinders. A piston is provided at the outlet of the upper cylinder for dilution water, and the dilution water accurately measured in the lower space of the cylinder formed by the cylinder and the piston intermittently discharged from the cylinder at a high speed is provided. A restricted flow path is provided so that the anode water can be accurately metered in the lower space of the cylinder formed by the cylinder and the piston at the outlet of the lower cylinder. A watertight line is formed that connects to the restricted flow path so that it can be fed into the restricted flow path, and further includes an inlet for the upper cylinder, an inlet for the lower cylinder, and the lower pin. Each of the stons has a check valve, and the upper piston opens a hole formed in the piston so that the upper space and the lower space of the upper cylinder can communicate with each other when the upper piston reaches a top dead center. 27. The apparatus of claim 26, wherein a valve is provided for closing when the upper piston reaches bottom dead center. 34. An aqueous solution of chloride as an electrolytic solution,
It is electrolyzed with a diaphragm to obtain electrolyzed water stably containing a high concentration of residual chlorine, and then the electrolyzed water is transferred to its use site without deteriorating its stability. For producing residual chlorine-containing water having an effective bactericidal ability against spores by diluting it into an anode chamber having an anode therein at least through a diaphragm and a cathode therein. An electrolytic cell separated into a cathode chamber having: a supply means for supplying an aqueous solution of chloride as a liquid to be electrolyzed; a means for supplying an alkaline compound to the anode chamber; and electrolyzed water produced in the anode chamber. A receiving container as a means for receiving a certain anolyte, which has flexibility so that its internal volume can be reduced to near zero, and receives the anolyte from the anode chamber into the inside thereof in a watertight manner. A variable-volume receiving container, the volume of which is increased by discharging the anolyte to the outside in a watertight manner, and a variable-volume receiving container; and ,
Having the flexibility to bring its internal volume close to zero, and increasing its volume by receiving the anolyte from the outside into the interior in a watertight manner, and then discharging the anolyte to the exterior in a watertight manner A variable-volume transfer container, the volume of which is reduced by;
The anolyte is sucked using the negative pressure generated by introducing water for dilution into it, and the sucked anolyte is discharged by discharging the introduced water for dilution therefrom. A suction / mixing device in which the discharged water for dilution and the discharged anolyte are mixed accurately and uniformly at an outlet therefrom and diluted to a predetermined concentration; The anolyte receiving means comprises a structure that does not form a gas phase therein and has a structure and / or property capable of blocking ultraviolet rays, and the transfer container and the suction / mixing device are: An apparatus having a structure and / or property capable of blocking ultraviolet rays.