JP2002339089A - Method for producing electrolytic ozone water and apparatus therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for regenerating a solid high polymer electrolytic membrane deteriorated by a Si or heavy metal ions. SOLUTION: The method for producing electrolytic ozone water uses an electrolytic ozone water generator (2) in which the anode electrode (4) and the cathode electrode (6) are arranged with the solid high polymer electrolytic membrane interposed, both electrodes (4, 6) are connected to a d.c. power source. Water is passed through a channel (2a) on the anode side and a channel (2b) on the cathode side to electrolyze the water, respectively and ozone water is generated on the side of the anode. In this method, soft water is fed to the channels (2a, 2b) on both electrode sides, respectively and ozone water is produced. Further, when the solid high polymer electrolytic membrane (5) is deteriorated by one or more kinds selected from dissolved silica or heavy metal ions contained in the soft water, a solution selected from hard water, an aqueous solution of acetone or alcohol and hot water of >=70 deg.C is fed to the electrolytic ozone water generator (2), and the regeneration of the solid high polymer electrolytic membrane (5) is performed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ozone water production method for producing ozone water from tap water or well water using an electrolytic ozone water production apparatus. An object of the present invention is to provide a simple technique for regenerating a polymer electrolyte membrane (hereinafter sometimes simply referred to as “electrolyte membrane” or “membrane”).

[0002]

2. Description of the Related Art Conventionally, methods for sterilizing and cleaning foods, equipment and the environment using ozone water are well known.
Electrolytic ozone water production apparatuses for producing ozone water from tap water or well water have appeared, and the use of ozone water has been rapidly spreading in various fields.

As shown in the flow chart of FIG. 7, a conventional electrolytic ozone water producing apparatus generally uses tap water or well water as raw water and feeds the raw water. The water is first supplied from the water supply pipe L1 to the water softening device 1 via the valve V1, where calcium ions (Ca ⁺⁺ ) and magnesium ions (Mg ⁺⁺ ), which are hard water components, are ion-exchanged with sodium ions (Na ⁺ ). To soften the raw water. This softened water is divided into two via a water softener outlet pipe L2, and one is connected from the anode-side softened water pipe L21 of the electrolytic ozone water generator 2 to the anode-side water passage 2 of the electrolytic ozone water generator 2.
a and the other is supplied from the cathode side soft water pipe L22 of the electrolytic ozone water generator 2 to the cathode side water passage 2b.

The electrolytic ozone water generator 2 is disclosed in
As shown in, for example, JP-A-134677, it is a generally known device, and the main structure thereof is shown in FIG. That is, as shown in FIG. 8 and FIG. 7, the solid polymer electrolyte membrane 5 such as an ozone-resistant fluorine-based ion exchange membrane is used.
On one surface, an anode electrode 4 made of a noble metal wire mesh having an ozone generation catalytic function is disposed so as to overlap with the electrolyte membrane 5, and on the other surface, a cathode electrode 6 is similarly provided with the electrolyte membrane. 5, lath nets 15 and 16 made of corrosion-resistant metal such as stainless steel are arranged on the outer surfaces of both electrodes over the entire length. Each electrode is connected to a DC power supply 3 so that a DC voltage can be applied between the electrodes 5. An anode-side jacket 11 and a cathode-side jacket 12 are arranged on the outside so as to include the electrodes 4 and 6 and the lath nets 15 and 16, respectively. An inlet 14, an ozone water outlet 17, and an alkaline water outlet 18 are respectively formed.

In such an apparatus, when the electrodes 4 and 6 are connected to the DC power supply 3 and electrolysis is performed while supplying soft water from the respective soft water inlets 13 and 14, the OH generated by the electrolysis of water appears on the anode 4 side. The ions (OH ⁻ ) are collected, and the OH ions are converted into ozone (O ₃ ) by the action of the ozone generating catalyst of the anode, and are immediately dissolved in water to generate ozone water. The ozone water is supplied from the ozone water outlet 17 to the ozone water tank or the consumption area via the ozone water pipe L3. Here, in the vicinity of the outer surface of the anode electrode 4, a complicated and complicated flow path is formed by a lath net 15 having a shape in which a wire mesh is staggered, so that many small eddies are generated on the outer surface of the anode electrode 4. . As a result, the ozone generated on the electrode surface is entrained in the vortex and quickly dissolves in water,
The amount of ozone flowing out together with the water stream as ozone gas decreases. That is, it has been confirmed that the amount of dissolved ozone is increased to generate high-concentration ozone water of about 30 ppm.

[0006] The concentration of the generated ozone water is constantly monitored by an ozone water concentration meter 7 provided in the ozone water pipe L3, and the result is input to the control device 8.
The controller 8 compares the input ozone water concentration with the set concentration, and issues an instruction to the DC power supply 3 to increase the current value if the ozone water concentration is lower than the set concentration. DC power supply 3 to lower the current value if higher
Thus, the concentration of the ozone water supplied from the ozone water pipe L3 is kept substantially constant at a preset concentration.

On the other hand, hydrogen ions (H ⁺ ) generated by the electrolysis of water are collected on the electrode surface on the side of the cathode electrode 6 and are released as hydrogen gas from the water. The metal ions mainly containing sodium ions (Na ⁺ ) are also collected and concentrated, the water on the cathode side is converted into alkaline water, and the alkaline water outlet 18 together with the hydrogen gas described above.
Through the alkaline water pipe L4 to the alkaline water tank or the place of use. As described above, the metal ions (mainly Na ⁺ ) contained in a trace amount in the water together with the hydrogen gas are concentrated on the cathode side, and the water on the cathode side generates alkaline water having a pH of 9 to 11 or more. Has been confirmed. It should be noted that this pH value depends on the ratio of the amount of water supplied to both electrodes, and the pH value is relatively high if the amount of water supplied to the cathode side is smaller than the amount of water supplied to the anode side. Conversely, the higher the value, the lower the pH value.

[0008] If the operation of the electrolytic ozone water generator is continued, the solid polymer electrolyte membrane 5 is gradually deteriorated.
As described in detail in CT / JP01 / 779, an anode electrode 4 and a cathode electrode 6 for the solid polymer electrolyte membrane 5 are provided.
The method of regenerating the solid polymer electrolyte membrane 5 by changing the pressing force under predetermined conditions or releasing the pressing force for a predetermined time has been proposed and put into practical use. By the practical use of such a regeneration method, it becomes possible to continuously operate the electrolytic ozone water generator, which can only withstand continuous operation for several hours in the past, almost semi-permanently. Spread was expected.

[0009]

However, in the case where tap water is used as raw water and the softened water is supplied to the electrolytic ozone water generator 2 through the water softener 1, the continuous operation is carried out for a long time without any problem. Although it was possible, in large electrolytic ozone water production equipment that uses a large amount of raw water,
If you change raw water to cheap well water, depending on the area,
As soon as the solid polymer electrolyte membrane deteriorates, even if the solid polymer electrolyte membrane regeneration method such as the operation of changing the pressing force on the solid polymer electrolyte membrane or the operation of releasing the pressing force is applied, the membrane is not affected. It has been found that it is difficult to recover the performance. In addition, most of the used well water satisfies all water quality standards as drinking water, and in this respect, there is almost no difference from tap water.

Therefore, the solid polymer electrolyte membrane in the above apparatus was replaced with a new membrane, and the continuous operation was performed again to collect operation data. The result is shown in FIG. As is clear from the figure, the set ozone water concentration is 10 ppm, and until 12 days after the start of the operation, the current value is 105 amperes (A), and the ozone water concentration is 10 ppm, and almost constant stable operation continues. However, on the twelfth day, the deterioration of the solid polymer electrolyte membrane started, and the increase in the electric resistance of the membrane started. As a result, the current value started to increase due to the operation of the control device. And on the 18th day after the start of operation, the current value becomes
The current reaches the allowable maximum value of the used DC power supply of about 190 A, and thereafter, the maximum current value is constant. As a result, the deterioration of the solid polymer electrolyte membrane became apparent, the concentration of the generated ozone water began to decrease, and reached a level of less than 5 ppm on the 21st day, and a further decrease was observed on the 23rd day. At this point, operation of the device was discontinued.

Next, the deteriorated solid polymer electrolyte membrane was taken out and subjected to various investigations. In this study, for comparison, used solid polymer electrolyte membranes that did not cause any problems even after long-term continuous operation using Kobe city tap water and unused solid polymer electrolyte membranes A similar survey was conducted for. FIGS. 10 to 12 show the results of EDS analysis using an energy dispersive X-ray microanalyzer. FIG. 10 is an EDS analysis result of the deteriorated film,
FIG. 2A shows the EDS analysis result of the surface layer on the anode side of the deteriorated film, and FIG. 2B shows the EDS analysis result near the cathode side of the cross section of the deteriorated film, and FIG. Shows EDS analysis results of the cathode side surface layer of the deteriorated film. Similarly, FIG. 11 shows the results of EDS analysis of the used membrane after the long-term continuous operation using the tap water of Kobe City, and FIG.
FIG. 12B shows the EDS analysis result of the anode-side surface layer of the used membrane, FIG. 12B shows the EDS analysis result of the cathode-side surface layer of the used membrane, and FIG. FIG. 3A shows the EDS analysis result of the solid polymer electrolyte membrane, and FIG. 3A shows the EDS analysis result of the surface layer on the front side of the unused membrane, and FIG. 4 shows the EDS analysis result of the layer.

First, the elements C (carbon), O (oxygen), and F (fluorine) appearing in the chart (a) showing the EDS analysis results of the surface layer on the unused solid polymer electrolyte membrane shown in FIG. , Na (sodium) and S (sulfur) are all the constituent elements contained in the solid polymer electrolyte membrane used as the analysis object, and show the EDS analysis results of the other back surface layer (b). The elements that appear in the chart are exactly the same. On the other hand, the elements, C, O, F, and C appeared in the chart (a) showing the EDS analysis result of the anode-side surface layer in FIG.
All of Na and S are constituent elements contained in the used solid polymer electrolyte membrane.
Chart (b) showing the analysis result and EDS on the cathode side surface
The chart (c) showing the analysis results shows that Si (silicon), Fe (iron), and Pt not found in the chart (a) are used.
(Platinum) is detected. On the other hand, in the case of the used membrane which has been operated for a long time using the tap water of Kobe city in FIG. 11, the EDS analysis result of the anode side surface layer is shown in the chart of FIG. Then, K (potassium) is slightly detected, and the chart (b) showing the analysis result on the cathode side is the same.

From the results of this EDS analysis, the three elements of Si, Fe and Pt, which are not found in the results of EDS analysis of other solid polymer electrolyte membranes, are found in the vicinity of the cross section of the deteriorated film and on the cathode side surface layer. You can see that it has been detected. Pt in this is assumed to be derived from the platinum electrode, but other Si and Fe
Was considered to be derived from the raw material water, and the well water used was analyzed. As a result, about 50 [mg / liter] of ionic silica (dissolved silica) was detected in the well water, and Fe was reduced to about 0 mg / l. 0.5 [mg / liter] was detected. Incidentally, on the basis of tap water quality, dissolved silica is not subject to analysis, and Fe is less than 0.3 [mg / liter]. Therefore, it can be said that this well water does not satisfy the water quality standard only in the content of Fe. On the other hand, Ca and Mg
Is contained in an amount of 80 to 90 [mg / liter] in terms of calcium carbonate.
[Mg / L], but the film is deteriorated when used in an electrolytic ozone water generator. Therefore, the film is used through a water softening device. Ca and Mg have been removed to less than [mg / liter]. However, since the above-mentioned Si and Fe cannot be removed by the water softener, the Si and Fe contained in the raw water are not included.
Since Fe and Fe are directly supplied to the electrolytic ozone water generator, this is considered to be a cause of film deterioration.

[0014] In addition, water containing heavy metals such as manganese (Mn) other than iron does not contain a large amount of highly harmful heavy metals such as nickel (Ni) and chromium (Cr) even if they do not conform to the water quality standards of tap water. Aside from this, in wells containing a trace amount of these, ozonated water is used as ozonated water and used for floor cleaning. Use is also conceivable.

Therefore, the present invention provides an electrolytic ozone which can use water containing a relatively large amount of dissolved silica which cannot be removed by the above water softener or water containing heavy metals such as Fe and Mn as raw water. An object of the present invention is to provide a water production method and an electrolytic ozone water production apparatus used for the method.

[0016]

SUMMARY OF THE INVENTION The present invention has been made on the basis of this point of view, and a feature of the present invention is a method for producing electrolytic ozone water using the above-mentioned electrolytic ozone water generator. In, when the solid polymer electrolyte membrane is deteriorated by one or more of dissolved silica or heavy metal ions contained in soft water used for electrolysis, as a means for regenerating the deteriorated film, instead of soft water, hard water, or The regeneration of the deteriorated film is performed by supplying a regenerating solution composed of either acetone or a mixed solution of alcohol and water or hot water of 70 ° C. or higher to the electrolytic ozone water generator. In particular, when hard water is used as the regenerating liquid,
Since it is sufficient to supply the water to at least the anode-side water channel of the electrolytic ozone water generator, there is a method in which the soft water is continuously passed through the cathode-side water channel of the electrolytic ozone water generator. Incidentally, when the raw water is hard water, the soft water obtained through the water softener is supplied to the electrolytic ozone water generator, and at the time of membrane regeneration, it is preferable to use the raw water before passing through the water softener. It is a method.

When a mixed solution of acetone or alcohol and water or hot water of 70 ° C. or higher is used as the regenerating solution, the regenerating solution is supplied at least to the cathode side channel of the electrolytic ozone water generator. In particular, if the regenerating solution is supplied only to the cathode side water channel and the soft water is continuously supplied to the anode side water channel, ozone water production can be continued while performing membrane regeneration. Becomes possible.

The alcohol contains at least one of methanol, ethanol, propanol, and butanol. The supply of the alcohol aqueous solution or the acetone aqueous solution to the electrolytic ozone water generator is performed by using the electrolytic ozone water. There is also a method of injecting acetone or alcohol itself into the soft water supply pipe to the generator, especially if it is performed only on the cathode side soft water supply pipe, soft water is continuously passed through the anode side water channel. Therefore, it is possible to perform film regeneration while continuing production of ozone water.

The supply of the regenerating solution is performed by detecting the deterioration of the electrolyte membrane. The following methods are available for determining the deterioration of the electrolyte membrane. (1) A method of supplying the regenerating liquid by detecting that the concentration of ozone water generated in the electrolytic ozone water generator has dropped to a predetermined lower limit value. (2) Ozone generated in the electrolytic ozone water generator. While performing the production of ozone water while controlling the current value of the DC power supply so that the water concentration is maintained at a predetermined value set in advance, detecting that the current value has reached a predetermined power supply upper limit value, Method of supplying regenerating liquid (3) Ozone water is produced while controlling the current value of the DC power supply so that the concentration of ozone water generated in the electrolytic ozone water generator is maintained at a predetermined value. A method of supplying the regenerating liquid by detecting that the current value reaches a preset regeneration start current value equal to or less than a predetermined power supply upper limit value. (4) Ozone water generated in the electrolytic ozone water generator Predetermined concentration is preset The ozone water is produced while controlling the current value of the DC power supply so as to maintain the ozone water concentration, and after the current value has reached a predetermined power supply upper limit value, the ozone water concentration is equal to the predetermined value. A method of supplying the regenerating liquid by detecting that the regenerating liquid has decreased to a preset regeneration start concentration between the lower limit and the regenerating liquid at predetermined preset time intervals without detecting deterioration of the electrolyte membrane. There is also a method of supplying the water.

As an electrolytic ozone water producing apparatus, an anode electrode and a cathode electrode are arranged with a solid polymer electrolyte membrane interposed therebetween, and both electrodes are connected to a DC power supply, and are connected to an anode side water channel and a cathode side water channel. In an ozone water producing apparatus using an electrolytic ozone water generator that electrolyzes water by passing water and generates ozone water on the anode side, a water softening apparatus for softening raw water is provided with a raw water pipe and the water softening apparatus. A pipe is disposed between the electrolytic ozone water generator and a pipe for supplying the regenerating liquid to the electrolytic ozone water generator. In particular, when hard water is used as the regenerating solution, piping is provided so that it can be supplied to at least the anode side water channel of the electrolytic ozone water generator, and a mixed solution of acetone or alcohol as the regenerating solution, or 70 ° C. When the above hot water is used, the hot water is provided so as to be supplied to at least the cathode side water channel of the electrolytic ozone water generator.

As the supply control method of the regenerating solution, a method of stopping the supply of the soft water for electrolysis and supplying the regenerating solution or a method of supplying the soft water only to the anode-side water channel while continuing to supply the soft water to the cathode-side water channel. In the case of using a mixed solution of acetone or alcohol or hot water of 70 ° C or higher as regenerated water, supply the regenerated water only to the cathode side water channel and continue soft water to the anode side water channel. There is a method in which the membrane can be regenerated while the production of ozone water is continued by passing the water.

[0022]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the structure of the solid polymer electrolyte membrane used in the present invention is, as schematically shown in FIG. 13, a fluorocarbon-based repellent made of carbon (C), fluorine (F), oxygen (O), or the like. An aqueous backbone 20 and a sulfonic acid group (-S
O ₃ H), and the sulfonic acid groups are aggregated in a spherical shape to form clusters (bunches) 21. The cluster 21 has a structure in which water is stored, and protons (H ⁺ ) move as indicated by arrows in the figure to exhibit conductivity. Such proton transfer is described in the "Grotts mechanism",
Since the positive charges move by hopping, they can move at a much faster speed than other ions, though not as much as electrons, and this movement is thought to involve several water molecules. I have.

The sulfonic acid group cluster 21
As shown in the “cluster model” in FIG. 14, the sulfonic acid group forms a spherical cluster 21 having a diameter (D) of about 2 to 4 nm as shown in the “cluster model” in FIG. Reference numeral 21 is an image in which sulfonic acid groups are similarly connected by a columnar “path” 23 having a diameter of about 1 nm that closely covers the inside.

The above sulfonic acid groups and paths are factors that affect the electric resistance of the solid polymer electrolyte membrane. When water enters, the diameter D of the cluster 21 and the diameter d of the path 23 expand, and there is no water. As a result, the diameter d of the path 23, which is a bottleneck, becomes thin, making it difficult for water to pass through, and increasing the ion conduction resistance. In general, the higher the sulfonic acid group per unit weight of the solid polymer electrolyte membrane, the lower the ionic conduction resistance. However, during operation, the path 23 which is the bottleneck during the operation is also used. , The ion conduction resistance of the membrane tends to decrease.

Next, film deterioration (increase in electrical resistance) when water containing heavy metals such as Si, Fe, and Mn is used as raw material water will be examined. Since the reduction in the path diameter d is considered to cause an increase in the electrical resistance of the film, it is considered that the presence of the Si and the heavy metal caused the reduction in the sulfonic acid group and the substantial reduction in the path diameter d. According to the EDS analysis chart of the deteriorated film shown in FIG. 10, Si and Fe were confirmed on the back surface (cathode side) of the deteriorated film and near the back surface of the cross section. Silicate ion (Si
O ₄ ^4- ) is replaced by a sulfonic acid group, hydrogen of the sulfonic acid group is replaced by Fe ion, or silicate ion or iron ion or iron silicate ion containing both of them is moved in the film in the ion diameter. These large ions block the passage on the cathode side of the path 23, and
It is presumed that a substantial diameter reduction was caused.

Therefore, the present inventors first speculated that silicate ions and iron ions or iron silicate ions present on the cross-section back surface and the back surface of the deteriorated film might block the path 23, It is thought that it is possible to pass metal ions having a relatively large molecular weight through the path to drive them out, and Mg ions, which are hard water components contained in ordinary water but not contained in the raw material water for electrolysis, are considered. When water was passed through a hard water electrolytic ozone water generator paying attention to Ca and Ca ions, it was confirmed that the deteriorated film was regenerated.

FIG. 6 shows the voltage (V) and current (A) at this time.
And operation data showing the change over time of the ozone water concentration (C), and the state in which the ozone water concentration at the outlet of the electrolytic ozone water generator operating at the set concentration of 10 ppm has dropped to about 5 ppm (film deterioration has progressed). Operating data). In the figure, after the ozone water concentration has been reduced to about 5 to 7 ppm, the supply water to the electrolytic ozone water generator is supplied to the water softening device at about 10 hours in the elapsed time in the figure. When the supply of the hard water was performed for about one and a half hours while the production of the ozone water was continued while the production of the ozone water was continued, the ozone water concentration started to increase with the start of the supply of the hard water, and the water concentration was increased by about 1 hour. One-and-a-half hour at 10pp
m. At this point, the water was again switched to softened water through the water softening device, and the ozone water concentration gradually began to decrease.

From this fact, it was confirmed that the membrane deteriorated by the presence of silicate ions or iron ions can be regenerated by supplying hard water for a short time. That is, when performing electrolysis with hard water, Mg ions and Ca ions contained in the hard water move from the anode side to the cathode side together with water through the path 23 of the solid polymer electrolyte membrane, During this movement, silicate ions or iron ions that remain near the exit side (cathode side) of the path 23 and substantially reduce the diameter of the path, or iron silicate ions formed by these,
It is considered that these ions are discharged by ions or Ca ions. The mechanism of this discharge is not clear at present, but in any case, it has been found that the membrane is regenerated by passing hard water. When Mg ions or Ca ions are bonded to sulfonic acid groups, the Mg ions or Ca ions are replaced with hydrogen ions by passing weakly acidified soft water following the hard water. As a result, the film returns to the original sulfonic acid group (—SO ₃ H), and the regeneration of the film is completed.

The present invention has been made based on the above findings. First, a system for periodically supplying hard water to an electrolytic ozone water generator will be described. FIG. 1 is a flow sheet showing a flow of a first embodiment of an electrolytic ozone water producing apparatus according to the present invention, in which tap water (well water or the like) made of hard water is supplied from a pipe L1 by a water softening apparatus 1. Water is softened and divided into two parts, a part of which is supplied to the anode side water channel 2a of the electrolytic ozone water generator 2, and the remainder is the cathode side water channel 2 of the electrolytic ozone water generator.
b, the ozone water is generated on the anode side, and the ozone water is supplied from the ozone water pipe L3 to the use place of the ozone water or the ozone water tank, and the ozone water concentration is constantly measured by the ozone water concentration meter 7. It is the same as the previous device in that it monitors and transmits the value to the control device 8 and controls the charge value and voltage value of the DC power supply 3 according to the change in the ozone water concentration. In the apparatus of the present invention, a bypass pipe L12 that directly connects the raw water pipe L1 and the outlet pipe L2 of the water softening apparatus 1 and a valve V4 are provided in the pipe, and the raw water, which is hard water, is supplied to the water softening apparatus 1.
This is characterized in that it can be supplied directly to the electrolytic ozone water generator 2 without going through.

Next, an example (first method) of an operation method of this device will be described with reference to FIG. In the figure, the vertical axis represents the ozone water concentration (C) and the current supplied to the electrolytic ozone water generator (A).
5 is a time chart schematically showing the change over time of the present embodiment, and employs a method of controlling the current A so that the ozone water concentration C is maintained at a predetermined set concentration Cs. In the figure,
After the start of operation, the deterioration of the electrolyte membrane starts at time t1,
The current value A gradually starts increasing so as to maintain the ozone water concentration C at a predetermined concentration Cs. When the current value A reaches a predetermined maximum value Ae of the power supply, the current cannot be increased any more, so that the ozone water concentration C starts to gradually decrease and the time t3
Reaches the predetermined allowable lower limit Ce. If this state is continued, the ozone water concentration only continues to decrease. Therefore, in the present embodiment, when the time t3 is reached (when the ozone water concentration reaches the predetermined allowable lower limit Ce), as shown in FIG. V1 of the hard water supply pipe L11 of the water softener 1
Is set to "closed" and the valve V4 of the bypass pipe L12 is set to "open", the supply of hard water to the electrolytic ozone water generator 2 is started instead of the soft water, and the regeneration of the deteriorated film starts. . In this state, since the production of ozone water by electrolysis of water is continued, the membrane can be regenerated without stopping the production of ozone water.

If this hard water supply is continued for a long time,
Since new film deterioration due to hard water occurs, supply is performed only for a predetermined time (Δt1) until time t4, and after the predetermined time (Δt1) elapses, the valve V1 is opened. Then, the valve V4 is closed, and the operation shifts to the operation of the electrolytic ozone water generator 2 based on soft water. still,
As is clear from FIG. 4, it is also possible to detect that the ozone water concentration after the start of hard water supply has reached the predetermined set value Cs, and to switch the supply of hard water to soft water by this detection signal. Also, instead of completely switching between soft water and hard water,
The amount of raw water supplied to the water softening device 1 is reduced by narrowing the opening of the valve V1, and an amount of hard water corresponding to the reduced amount is supplied from the valve V4, the pipe L12 to the outlet pipe L2 of the water softening device. Is also possible. In this case, since the concentration of the hard water component supplied to the electrolytic ozone water generator 2 decreases,
It is easy to guess that the film regeneration time is long.

In the example shown in FIG. 1, hard water is supplied to both the anode-side water passage 2a and the cathode-side water passage 2b of the electrolytic ozone water generator 2. However, hard water components such as Mg ⁺⁺ and Ca ^{++ are used.} Moves from the anode side to the cathode side, so that hard water needs to be supplied only to at least the anode side. FIG. 2 is a flow chart showing an example of this case. The difference from FIG. 1 is that a bypass pipe L13 branched from a water supply pipe L1 is connected to an anode-side soft water pipe L21 of the electrolytic ozone water generator 2. They differ in their connection. In the case of this device, at time t3 (at the start of hard water supply) in FIG.
From the valve V2 of the anode-side soft water pipe L21
Is closed, the valve V5 of the bypass pipe L13 is opened, and the supply of hard water to the anode-side water passage 2a is started, and the predetermined time (Δt1) elapses as described above, or The supply of hard water is continued until the water concentration returns to the predetermined set value Cs. Also in this case, instead of switching the flow of water through the anode-side water passage 2a to 100% hard water, the amount of soft water supplied from the pipe L21 is reduced, and hard water corresponding to the reduced amount is supplied from the pipe L13 to the pipe L21. It goes without saying that you can do it.

Next, another example of the hard water supply control will be described. FIG. 5 is an operation time chart of each of the second system to the fifth system of the hard water supply control. First, the second system performs a short-time hard water supply every predetermined time before film deterioration occurs. This is a method in which the electrolyte membrane is used under certain conditions.
, The supply of soft water is stopped and the supply of hard water is started,
When the hard water supply time elapses a predetermined short time (Δt3) and reaches time t6, the supply of the soft water is restarted and the supply of the hard water is stopped. When the supply of the soft water is performed for a predetermined time (Δt2) and time t7 is reached, the hard water is supplied for a predetermined time (Δt3) until time t8. In this way, the supply of hard water and soft water is switched at regular intervals by the timer. Again,
Not only the method of changing the soft water supply amount from the predetermined amount (Q1s) to 0 (zero) and switching the hard water supply amount from 0 (zero) to the predetermined amount (Q2s), but also reducing the soft water amount Q1, It is also possible to set the hard water supply amount Q2 to an amount corresponding to the amount.
It is also possible to make only 21.

Next, the third method is a method in which hard water is supplied when the film deterioration has progressed to some extent, and is a method in which film deterioration due to hard water is suppressed as much as possible. In this case, the film deterioration starts at time t9, and the current value A starts increasing from the initial value As so as to compensate for the film deterioration. At this time, the current value A is preset to a value lower than the upper limit value Ae of the power supply. When the control start current value Ac reaches (time t10), the supply of soft water is stopped and the supply of hard water is performed for a predetermined time (Δt4) until time t11. The hard water supply time (Δt4) is a time required for the deteriorated film to be regenerated, is a time set in advance by a test, and is the hard water supply time (Δt
It takes longer than 3). In this case as well, the current value A that decreases with the regeneration of the film is detected, and when the current value A decreases to the initial value As, the supply of hard water is stopped, and the supply of soft water is started. It is also possible to do so. Further, also in this case, as described above, not only the method in which the soft water supply amount is changed from the predetermined amount (Q1s) to 0 (zero) but the hard water supply amount is switched from 0 (zero) to the predetermined amount (Q2s).
It is also possible to reduce the soft water amount Q1 and set the hard water supply amount Q2 to an amount corresponding to the reduced amount, and it is also possible to supply the hard water only to the anode side soft water pipe L21.

Next, the fourth method is a method in which hard water is supplied when the film deterioration further progresses, as compared with the third method, and the film deterioration due to hard water is further suppressed. In this case, the film deterioration starts at time t12, and the current value A starts increasing from the initial value As so as to compensate for the film deterioration. At time t13, the current value A finally reaches the upper limit value Ae of the power supply. From this point, the ozone water concentration C becomes a predetermined set value C
s, and when the control start concentration Cc is set to a value higher than the allowable lower limit Ce, the control start concentration Cc (time t1)
4) The supply of soft water is stopped, and the supply of hard water is performed for a predetermined time (Δt5) until time t15. This hard water supply time (Δt
5) is the time required for the deteriorated film to be regenerated,
A time set in advance by a test, wherein
The time is longer than the hard water supply time (Δt2, Δt3) of the third method. In this case as well, the current value A that decreases with the regeneration of the film is detected, and when the current value A decreases to the initial value As, the supply of hard water is stopped, and the supply of soft water is started. It is also possible to do so. Similarly, not only the method of changing the soft water supply amount from the predetermined amount (Q1s) to 0 (zero) and switching the hard water supply amount from 0 (zero) to the predetermined amount (Q2s), but also reducing the soft water amount Q1 as described above. It is also possible to set the hard water supply amount Q2 to an amount corresponding to the decrease amount, and it is also possible to supply the hard water only to the anode side soft water pipe L21.

Next, the fifth system is a system in which the supply of hard water is switched to immediately before the ozone water concentration lowers as compared with the fourth system. In this case, the film degradation starts at time t16, and the current value A starts increasing from the initial value As so as to compensate for the film degradation, and reaches the upper limit value Ae of the power supply at time t17. At this time, the ozone water concentration C has not decreased. Therefore, this power supply upper limit value Ae
At the time point (time t17), the supply of the soft water is stopped to start the supply of the hard water, and the hard water supply is performed for a predetermined time (Δt6) until a time t18. The hard water supply time (Δt6) is a time required for the deteriorated film to be regenerated, is a time set in advance by a test, and is a hard water supply time (Δt3, Δt4) of the second and third methods. ), But shorter than the hard water supply time (Δt5) of the fourth method. In this case as well, the current value A that decreases with the regeneration of the film is detected, and when the current value A decreases to the initial value As, the supply of hard water is stopped, and the supply of soft water is started. In addition to the method of changing the soft water supply amount from a predetermined amount (Q1s) to 0 (zero) and switching the hard water supply amount from 0 (zero) to a predetermined amount (Q2s), the soft water amount Q1 Can be reduced and the hard water supply amount Q2 can be set to an amount corresponding to the reduced amount, and the hard water can be supplied only to the anode side soft water pipe L21.

The above description is about the regeneration of a deteriorated film by silicate ions or iron ions with hard water. However, in the case where well water contains a relatively large amount of heavy metal ions such as Mn ions other than Fe ions. It is well known that this case also causes deterioration of the solid polymer electrolyte membrane.
The second method of the present invention is a method that can cope with film deterioration due to raw water containing these heavy metals. These heavy metals are not removed even through the water softening device, and are supplied to the electrolytic ozone water generator while being contained in the soft water. However, they are trapped in the electrolyte membrane and result in a significant increase in electric resistance. Then, the present inventors found that the performance of the deteriorated film was improved when the deteriorated film was immersed in an aqueous ethanol solution, left for a while, taken out and reused. That is, by immersing the electrolyte membrane in an aqueous ethanol solution, the electrolyte membrane is swollen, the path 23 between the clusters of the sulfonic acid groups is widened, and silicate ions and heavy metal ions trapped in the electrolyte membrane are removed. At the same time, it is considered that the electrical resistance was reduced by increasing the diameter of the path and the conductivity was improved.

Therefore, the second method of the present invention is a method of swelling and regenerating a membrane degraded by heavy metal ions or the like. As means for swelling the electrolyte membrane, the electrolyte membrane is mixed with a mixed solution of acetone or alcohol. Is immersed in hot water of 70 ° C. or higher.

First, a swelling method using a mixed solution with acetone or alcohol will be described. In the case of Nafion (registered trademark) manufactured by DuPont, in the case of a mixed solution of methanol, it swells about 1.35 times with water 20% by weight (the same applies hereinafter) / methanol 80%, and methanol 0% to 80% Up to this point, the swelling ratio increases substantially linearly. In the case of a mixed solution of water and ethanol, water 25% / ethanol 7
It swells about 1.45 times at 5%, and from 0% ethanol to 75%.
%, The swelling ratio increases substantially linearly. In the case of a mixed solution of water and isopropanol, swelling is about 1.65 times with 25% water / 60% isopropanol ethanol, and the swelling rate increases almost linearly from 0% to 60% isopropanol. In the case of a mixed solution of water and t-butanol, water 7
Swell about 1.6 times with 0% / t-butanol 30%, t
-The swelling ratio increases almost linearly from 0% to 30% butanol. In the case of a mixed solution of water and acetone, water 2
The swelling ratio is about 1.6 times at 5% / acetone 75%, and the swelling ratio increases almost linearly from 0% to 75% of acetone. As described above, by immersing the electrolyte membrane in alcoholic water or acetone water, the electrolyte membrane is swelled and the path diameter can be similarly increased.

Next, it is known that the electrolyte membrane swells even with water. In particular, the swelling effect of hot water at 70 ° C. or higher is remarkable. In this sense, when the electrolyte membrane is used for a fuel cell, the temperature is 70 ° C. or higher. Therefore, in the electrolytic ozone water generator of the present invention as well, although the normal use state is normal temperature, hot water can be used as a means for intentionally swelling it.

Next, a method for regenerating a deteriorated film by using acetone, alcohol or hot water will be described. FIG. 3 shows a flow in this case. Since the system for producing ozone water is the same as that in the above-described case, a duplicate description will be omitted here and only the film regeneration line will be described.
In the figure, reference numeral 9 denotes a regenerating liquid tank, which is the above-mentioned acetone or alcohol, or a mixed solution thereof with water;
Alternatively, hot water of 70 ° C. or higher is stored. When the membrane deterioration of the electrolytic ozone water generator 2 is detected in the above-described manner, in a state in which the power supply from the power supply 3 is stopped (that is, in a state in which the generation of the ozone water is stopped), the water supply pipe L1 is stopped. The valve V1 is closed, and the regenerating solution pipe L connected to the regenerating solution tank 9
5, the regenerating liquid in the washing water tank 9 is supplied from the pipe L5 to the pipe L51, the pipe L2, and the pipe L.
The regenerating liquid is supplied to the anode-side water passage 2a and the cathode-side water passage 2b of the electrolytic ozone water generator 2 via the pipe 21 and the pipe L22. Then, the electrolyte membrane 5 swells and the path diameter increases, and the silicate ions staying inside are discharged from the path. Here, in the structure of the electrolytic ozone water generator used in the present invention, as described with reference to FIG. 8, since the periphery of the electrolyte membrane 5 is fixed, swelling occurs such that the area of the electrolyte membrane 5 is widened. However, since the diameter of the path is expanded by swelling only in the thickness direction, there is no problem of swelling of the film on the apparatus side.

In the above method, the regenerating solution is supplied to the anode side waterway 2
Although the regeneration of the membrane is performed by stopping the generation of the ozone water because of the supply to both the a and the cathode-side water channel 2b, the regeneration of the membrane can be performed without stopping the generation of the ozone water. In this case, the valve V3 of the cathode side soft water supply pipe L22 is "closed" and the valve V2 of the anode side soft water supply pipe L21 is "open", that is, soft water is supplied to the anode side water passage 2a. Meanwhile, the regenerating liquid is supplied from the pipe L5 to the cathode-side soft water supply pipe L22 via the pipe L52, and the regenerating liquid is supplied into the cathode-side water passage 2b. Since the electrolyte membrane 5 used in the electrolytic ozone water generator is an extremely thin membrane, only by supplying the regenerating solution only to the cathode side water channel 2b, the expansion of the path diameter due to the swelling of the target membrane can be prevented. There is no problem because it occurs easily. This makes it possible to perform film regeneration while continuing generation of ozone water.

When washing water is supplied only to the cathode side, the regenerating solution tank is not made of acetone or a mixed solution of alcohol and water, but is made of pure acetone or pure alcohol only. The valve V3 of the supply pipe L22 is in a state where the flow rate is slightly reduced.
Pipe the pure acetone or pure alcohol into the soft water inside
It is also possible to form a mixed solution of acetone or alcohol and water in the pipe L22 by injecting from the pipe 52. In this case, it is possible to use the storage solution for a long time with the same storage amount, rather than storing the mixed solution in a tank.

Since acetone and methanol cannot be used for cleaning foods, it is preferable to use ethanol as a regenerating liquid in an electrolytic ozone water producing apparatus for producing ozone water used for cleaning and sterilizing foods. When producing ozone water used for floor cleaning, acetone or methanol can also be used as a regenerating solution.

[0045]

As described above, when well water is used in place of tap water as raw water for ozone water production,
Although the situation where the electrolyte membrane deteriorated with time occurred and the reason was not clear, according to the present invention, the cause was caused by the presence of heavy metal ions represented by Si ions and iron ions contained in the raw material water. Since the present invention proposes a countermeasure, the range of application of the raw water for the production of ozone water is greatly expanded, so that ozone water can be produced at low cost. It is expected to greatly contribute to the expansion and spread of use of ozone water.

In particular, when the raw water is hard water (ordinary tap water almost contains hard water components), when the electrolyte membrane is deteriorated, the raw water supplied to the ozone water generator is replaced with a water softener. By simply supplying the ozone water generator directly without passing through it, it is possible to easily regenerate the deteriorated film, and the hard water supply operation can be performed by various film deterioration detection means or by supplying hard water at a predetermined cycle. Since the operation can be performed by automatic operation, continuous operation of the apparatus becomes possible, and ozone water production cost can be reduced.

In the case of passing hard water, instead of passing water on both electrode sides of the electrolyte membrane, it is also possible to pass water only to the anode side. Since it can be performed without stopping the operation, it can be said that this is a film regeneration method suitable for automatic control of the apparatus.

It is also possible to supply an aqueous solution of alcohol or acetone or hot water instead of hard water, and it is also possible to appropriately select a regenerating solution according to the installation site of the ozone water generator. . Furthermore, it is also possible to supply these regenerating solutions only to the cathode side while continuously passing the softened water softened by the water softener to the anode side. It is possible to regenerate a deteriorated film without stopping production of the film.

As a result, it is possible to adopt a membrane regeneration method adapted to the quality of the raw water, to make continuous production of ozone water even easier, and to increase the sanitation control of the people through the dissemination of ozone water sterilization and washing methods. Improvement is expected.

[Brief description of the drawings]

FIG. 1 is a flowchart showing a first embodiment of an electrolytic ozone water producing apparatus according to the present invention.

FIG. 2 is a flowchart showing a modification of the first embodiment of the electrolytic ozone water producing apparatus according to the present invention.

FIG. 3 is a flowchart showing a second embodiment of the electrolytic ozone water producing apparatus according to the present invention.

FIG. 4 is an operation time chart showing a first embodiment of the electrolytic ozone water producing method according to the present invention.

FIG. 5 is an operation time chart showing second to fifth embodiments of the electrolytic ozone water producing method according to the present invention.

FIG. 6 is a graph of operation data showing an example of a change over time in operation conditions during continuous operation by the electrolytic ozone water production method according to the present invention.

FIG. 7 is a flowchart showing a conventional electrolytic ozone water producing apparatus.

FIG. 8 is a conceptual sectional view of a main part of an electrolytic ozone water generator used in the present invention.

FIG. 9 is a graph of operation data showing an example of a change over time in operation conditions during continuous operation according to a conventional electrolytic ozone water production method.

10A and 10B are charts showing EDS analysis results of a solid polymer electrolyte membrane deteriorated by well water, wherein FIG. 10A shows EDS analysis results of an anode-side surface layer, and FIG. 10B shows EDS analysis results near a cross-sectional cathode. (C) shows the ED of the cathode side surface layer.
It is a chart which shows an S analysis result.

FIG. 11 is a chart showing the results of EDS analysis of a used solid polymer electrolyte membrane using tap water in Kobe City, (a).
3 is a chart showing an EDS analysis result of the anode side surface layer, and (b) is a chart showing an EDS analysis result of the cathode side surface layer.

FIG. 12 is a chart showing the EDS analysis results of an unused solid polymer electrolyte membrane, where (a) shows the ED of the anode-side surface layer.
FIG. 3B is a chart showing S analysis results, and FIG. 4B is a chart showing EDS analysis results of the cathode side surface layer.

FIG. 13 is a schematic structural view of a solid polymer electrolyte membrane used in an electrolytic ozone water generator.

FIG. 14 is a schematic structural view of a cluster of sulfonic acid groups of a solid polymer electrolyte membrane used in an electrolytic ozone water generator.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Water softening apparatus 2 Electrolysis-type ozone water generator 2a Anode side waterway 2b Cathode side waterway 3 DC power supply 4 Anode electrode 5 Solid polymer electrolyte membrane 6 Cathode electrode 7 Ozone water concentration meter 8 Control device 9 Regeneration liquid tank L1 Raw material water ( Hard water) supply pipe L12 raw water bypass pipe L2 water softener outlet pipe L21 anode side soft water pipe L22 cathode side soft water pipe L51 regenerated liquid supply pipe L52 regenerated liquid supply pipe 20 water repellent main chain of solid polymer electrolyte membrane 21 sulfonate group Cluster 22 Side chain 23 Sulfonic acid cluster cluster path

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4D006 GA16 KC15 KC16 KD28 KD29 MA11 MC28 MC74 PB05 PC80 4D061 DA03 DB09 EA02 EB01 EB04 EB13 4K021 AA01 BA02 BB01 DB31 DB53

Claims (26)

[Claims] An anode (4) and a cathode (6) are arranged with a solid polymer electrolyte membrane (5) interposed therebetween, and both electrodes (4, 4) are disposed.
6) is connected to a DC power supply (3), and water is electrolyzed by flowing water through the anode-side water passage (2a) and the cathode-side water passage (2b), respectively. In the method for producing electrolytic ozone water using a water generator (2), a water channel (2a, 2) on both electrodes of the electrolytic ozone water generator is provided.
b) to supply soft water respectively to produce ozone water, and when the solid polymer electrolyte membrane (5) is deteriorated by one or more of dissolved silica or heavy metal ions contained in the soft water, hard water or And a regenerating solution selected from a mixed solution of acetone or alcohol and water, or hot water having a temperature of 70 ° C. or more, is supplied to the electrolytic ozone water generator (2) to remove the solid polymer electrolyte membrane (5). Method for producing electrolytic ozone water characterized by regenerating 2. The electrolytic ozone water production method according to claim 1, wherein the hard water is supplied to at least the anode side water channel (2a). 3. The method according to claim 1, wherein the hard water is supplied only to the anode side channel (2a), and the soft water is continuously passed through the cathode side channel (2b). Electrolytic ozone water production method 4. The soft water according to claim 2, wherein the soft water is soft water obtained by passing hard water through a water softening device (1), and the hard water is raw water before passing through the water softening device (1). Electrolytic ozone water production method 5. The electrolytic ozone water producing method according to claim 1, wherein the mixed solution of acetone or alcohol and water or hot water of 70 ° C. or higher is supplied to at least the cathode side water channel (2b). 6. The mixed solution of acetone or alcohol and water, or hot water of 70 ° C. or higher is supplied only to the cathode side channel (2b), and the soft water is supplied to the anode side channel (2a). 2. The electrolytic ozone water producing method according to claim 1, wherein the supply is continued. 7. The supply of the mixed solution of acetone or alcohol and water to the electrolytic ozone water generator (2) is performed by supplying the acetone or a mixed solution of water to the electrolytic ozone water generator (2) in a soft water supply pipe. The method according to claim 5 or 6, wherein the method is performed by injecting alcohol. 8. The supply of the mixed solution of acetone or alcohol and water to the electrolytic ozone water generator (2) is performed to a cathode side soft water supply pipe (L22). Or the electrolytic ozone water production method according to 6. 9. The method for producing electrolytic ozone water according to claim 5, wherein the alcohol is at least one of methanol, ethanol, propanol and butanol. 10. The generated ozone water concentration (C) in the electrolytic ozone water generator (2) is adjusted to a predetermined allowable lower limit (C).
The electrolytic ozone water production method according to any one of claims 1 to 9, wherein the supply of the regenerating liquid is performed by detecting that the temperature has dropped to e). 11. The current value (A) of the DC power supply (3) such that the generated ozone water concentration (C) in the electrolytic ozone water generator (2) is maintained at a predetermined value (Cs) set in advance. ), The production of ozone water is performed, and the supply of the regenerating liquid is performed by detecting that the current value (A) has reached a predetermined power supply upper limit value (Ae). The method for producing electrolytic ozone water according to any one of 1 to 9 12. The current value (A) of the DC power supply (3) such that the generated ozone water concentration (C) in the electrolytic ozone water generator (2) is maintained at a predetermined value (Cs) set in advance. ), While detecting that the current value (A) has reached a preset regeneration start current value (Ac) equal to or less than a predetermined power supply upper limit value (Ae), The electrolytic ozone water production method according to claim 1, wherein the supply of the regenerating liquid is performed. 13. The current value (A) of the DC power supply (3) such that the generated ozone water concentration (C) in the electrolytic ozone water generator (2) is maintained at a predetermined value (Cs) set in advance. ) Is performed while the current value (A) reaches a predetermined power supply upper limit (Ae), and the ozone water concentration (C) is changed to the predetermined value (Cs). The regenerating liquid is supplied by detecting that the regenerating liquid has decreased to a preset regenerating start concentration (Cc) between the regenerative liquid and the allowable lower limit value (Ce). Electrolytic ozone water production method 14. The electrolytic ozone water producing method according to claim 1, wherein the supply of the regenerating liquid is performed for a predetermined time (Δt1) set in advance. 15. The regenerated liquid is hard water, and after the start of the supply of the hard water, the generation of ozone water by the electrolytic ozone water generator (2) is continued, and the electrolytic ozone water generator (2) is used. 5. The method according to claim 1, wherein the supply of the hard water is continued until the concentration (C) of the ozone water generated by the method returns to a predetermined concentration (Cs). 6.
The method for producing electrolytic ozone water according to any one of 0 to 13 16. The supply of the regenerating liquid is performed at a predetermined time interval (Δt2) every predetermined time interval (Δt2).
3) The method for producing electrolytic ozone water according to any one of claims 1 to 9, wherein the method is performed. 17. An anode (4) and a cathode (6) are arranged with a solid polymer electrolyte membrane (5) interposed therebetween, and both electrodes (4, 6) are connected to a DC power supply (3); Electrolytic ozone water generation using an electrolytic ozone water generator (2) that electrolyzes water by passing water through the anode side water channel (2a) and the cathode side water channel (2b) to generate ozone water on the anode side. In the apparatus for producing ozone water using a water generator, a water softening device (1) for softening raw water is disposed between a raw water pipe (L1) and the electrolytic ozone water generator (2), and Outlet piping (L
2) a pipe (L12, L5) for supplying a regenerating liquid selected from hard water, a mixed solution of acetone or alcohol and water, or hot water of 70 ° C. or higher; Electrolytic ozone water production equipment 18. An inlet-side raw water pipe (L1) of the water softener (1) and an outlet pipe (L2) of the water softener (1).
18. An electrolytic ozone water producing apparatus according to claim 17, wherein a hard water can be supplied to the electrolytic ozone water generator (2) by providing a bypass pipe (L12) connected to the electrolytic ozone water generator (2). 19. A valve (V1, V4) is arranged on each of a pipe (L11) from the raw water pipe (L1) to the water softening device (1) and the bypass pipe (L12),
19. The electrolysis system according to claim 18, wherein during the production of ozone water, the control device (8) is controlled such that when one of these two valves is "open", the other is "closed". Ozone water production equipment 20. A regenerating solution tank (9) for storing a regenerating solution composed of either the mixed solution of acetone or alcohol and water or hot water of 70 ° C. or higher, and an outlet pipe of the water softening device (1). (L2) and a regenerating liquid supply pipe (L5) provided with a valve (V6).
(V6) and raw water pipe (L1)
The valve (V1) provided in the ozone water production,
The electrolytic ozone water producing apparatus according to claim 17, wherein the control device (8) controls the one of these two valves to be "open" and the other to be "closed". 21. An outlet pipe (L) of the water softener (1).
The electrolytic ozone water producing apparatus according to claim 17, wherein a regeneration liquid injection pipe (L51) for injecting acetone or alcohol is connected to 2) via a valve (V6). 22. An anode electrode (4) and a cathode electrode (6) are arranged with a solid polymer electrolyte membrane (5) interposed therebetween, and both electrodes (4, 6) are connected to a DC power supply (3); Electrolytic ozone using an electrolytic ozone water generator (2) that electrolyzes water by passing soft water through the anode side water channel (2a) and the cathode side water channel (2b) to generate ozone water on the anode side An ozone water producing apparatus using a water generator, comprising: a pipe (L1) for supplying raw water to a water softening apparatus (1); and an outlet pipe (L2) of the water softening apparatus (1). The pipe (L2) is divided into two, and one is formed as an anode-side soft water pipe (L21) for supplying one to the anode-side waterway (2a);
A cathode-side soft water pipe (L22) for supplying the other to the cathode-side water channel (2b) is provided. The raw water pipe (L) is connected to the anode-side soft water pipe (L21).
An electrolytic method characterized in that a hard water supply pipe (L13) branching from 1) for supplying raw water composed of hard water into the anode side soft water pipe (L21) is connected via a valve (V5). Ozone water production equipment 23. Hard water is injected from the hard water supply pipe (L13) into the anode soft water pipe (L21) while the soft water is passed through the anode soft water pipe (L21). The electrolytic ozone water producing apparatus according to Item 22 24. An anode electrode (4) and a cathode electrode (6) are arranged with a solid polymer electrolyte membrane (5) interposed therebetween, and both electrodes (4, 6) are connected to a DC power supply (3). Electrolytic ozone using an electrolytic ozone water generator (2) that electrolyzes water by passing soft water through the anode side water channel (2a) and the cathode side water channel (2b) to generate ozone water on the anode side An ozone water producing apparatus using a water generator, comprising: a pipe (L1) for supplying raw water to a water softening apparatus (1); and an outlet pipe (L2) of the water softening apparatus (1). The pipe (L2) is divided into two, and one is formed as an anode-side soft water pipe (L21) for supplying one to the anode-side waterway (2a);
A cathode-side soft water pipe (L22) for supplying the other to the cathode-side water channel (2b) is provided. Acetone or alcohol, or a mixed solution of acetone or alcohol and water, or 70 A regenerating liquid supply pipe (L52) for supplying hot water at a temperature of at least 100 ° C. connected via a valve (V6); 25. While passing the soft water through the anode-side soft water pipe (L21) and the cathode-side soft water pipe (L22), the acetone or alcohol, or a mixed solution of acetone or alcohol and water, is added to the cathode soft water pipe (L22). 25. The electrolytic ozone water producing apparatus according to claim 24, wherein the electrolytic ozone water producing apparatus is injected into the side soft water pipe (L22). 26. While passing the soft water through the anode-side soft water pipe (L21), stopping the flow of the soft water through the cathode-side soft water pipe (L22), the acetone or alcohol, or 25. The electrolytic ozone water producing apparatus according to claim 24, wherein water is passed through a mixed solution of acetone or alcohol and water, or hot water of 70 ° C. or higher.