JP2008000666A - Method and apparatus for producing ozone water and detergent to be used therein - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method and an apparatus for producing ozone water, in each of which work of handling a cleaning liquid or the used cleaning liquid is facilitated, the maintenance cost and the initial cost can be reduced and ozone water is produced by an underwater electrolysis method using an immobilized electrolyte membrane and to provide a detergent to be used in the method and the apparatus for producing ozone water. <P>SOLUTION: The cleaning liquid is produced by gradually eluting the detergent which contains an organic acid and is molded into a solid shape. A cathode arranged in a cathode chamber of an electrolytic cell, which is divided into an anode chamber and the cathode chamber by the immobilized electrolyte membrane, is cleaned by the produced cleaning liquid to prevent the deposition of hardly soluble salt, so that ozone water is produced by the underwater electrolysis method. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ozone water production method by an underwater electrolysis method using a fixed electrolyte membrane, an ozone water production apparatus, and a cleaning agent used in these.

Ozone is expected to be used and effective in various fields such as food-related, sewerage, human waste treatment, bathrooms, hospitals, elderly facilities, livestock, and fisheries due to effects such as sterilization, deodorization, and decolorization. Conventionally, as one method of producing ozone water, which is water in which ozone is dissolved, a production apparatus that directly generates ozone water by electrolyzing water in water using a solid electrolyte membrane and electrodes has been used. Yes. In this apparatus, ozone is generated together with oxygen from the anode chamber side in an electrolytic cell partitioned into an anode chamber and a cathode chamber with a solid electrolyte membrane, and the liquid becomes alkaline as hydrogen gas is generated on the cathode chamber side. On the cathode chamber side, cations such as Na ⁺ ions, Ca ²⁺ ions, and Mg ²⁺ ions pass through the solid electrolyte membrane. Among these, Ca ²⁺ ions and Mg ²⁺ ions are alkaline and combine with OH ^- ions and carbonate ions dissolved in carbon dioxide to form poorly soluble hydroxides and carbonates, which are deposited on the electrodes. Thus, it is known that the electrolytic performance is remarkably lowered.

In response to such problems, the acidic cleaning solution is circulated to the cathode chamber side by utilizing the property that Ca ²⁺ ions and Mg ²⁺ ions dissolve well in an acidic solution, thereby preventing the deposition of sparingly soluble salts on the cathode electrode. The method is known (for example, refer nonpatent literature 1). In addition, a water softener filled with Na-type ion exchange resin is installed on the upstream side of the ozone water production device, and the method of ion exchange of Ca ²⁺ ions and M ² g ⁺ ions, which are hardness components in tap water, to Na ⁺ ions Some have been adopted (see, for example, Patent Document 1).

"Instruction Manual Ozone Water Cleaning Machine FX2000" Silver Seiko Co., Ltd. Japanese Patent No. 3269784

However, the method of circulating the cleaning liquid to the cathode chamber side described in Non-Patent Document 1 is an excellent method that does not require pretreatment of raw material water as described in Patent Document 1, but the cleaning liquid is A highly soluble citric acid dissolved in a high concentration of 42% is employed. When producing ozone water, raw water containing Ca ²⁺ ions and Mg ²⁺ ions permeates the solid electrolyte membrane and moves to the cathode chamber side, and the cleaning solution on the cathode chamber side is diluted. It needs to be replaced at some point. However, it is not clear about the lower limit concentration of the cleaning liquid in which the hardly soluble salt precipitates. For example, the used cleaning liquid of the ozone water production apparatus of Non-Patent Document 1 is a waste liquid with a high concentration that is troublesome to handle with 40% or more organic acid. . Moreover, the standard of the cleaning liquid replacement of this ozone water production apparatus is the point of operation for about 50 hours, and there is a problem that replacement of the cleaning liquid is necessary frequently and requires labor and cost.

  In addition, hydrochloric acid, nitric acid, sulfuric acid, etc. can be used as the acid used in the cleaning solution, but organic acids such as citric acid are preferred because these strong acids are dangerous. However, in an apparatus where the concentration gradually decreases due to the mixing of raw material water, such as an ozone water production apparatus using an electrolysis method using a fixed electrolyte membrane, if a constant cleaning solution concentration is maintained for a long period of time, citric acid, etc. When using a cleaning liquid composed of a substance having high solubility, it is necessary to devise a device such as using a high-concentration solution that may be diluted or separately providing a periodic cleaning liquid supply device. However, if a solution with a high concentration is used unnecessarily, there is a problem of corrosion of pipes and tanks, and the used cleaning liquid becomes a waste liquid that is troublesome to handle, including a high concentration of acid. On the other hand, in a device that separately provides a periodic cleaning liquid supply device, it can be realized by an auxiliary device that periodically injects an acid solution with a timer or the like, but the device becomes complicated, and unless the minimum required concentration of the cleaning liquid is clear, There is no substitute for frequent replacement of the cleaning liquid.

  On the other hand, the ozone water production apparatus that performs the pretreatment of raw material water described in Patent Document 1 has a problem that an auxiliary apparatus such as a water softener filled with Na-type ion exchange resin is required, and the apparatus becomes complicated. When such pretreatment of raw material water is not performed, there is also a method of supplying the cleaning liquid directly to the raw water supplied to the cathode chamber side of the electrolytic cell, but the treatment is troublesome when the concentration of the cleaning waste liquid is high, Further, it is necessary to separately provide a regular cleaning liquid supply device, which complicates the device.

  The present invention provides an ozone water production method and an ozone water production apparatus by an underwater electrolysis method using a fixed electrolyte membrane, which is easy to handle and can reduce maintenance costs and initial costs in view of the above circumstances. And a cleaning agent used in these.

Means and effects for solving the problems

The ozone water production method according to the present invention uses ozone containing at least one of Ca ²⁺ ions and Mg ²⁺ ions as raw water, and produces ozone water by electrolyzing the raw water. The present invention relates to a water production method. And the ozone water manufacturing method which concerns on this invention has the following some features, in order to achieve the said objective. That is, the ozone water production method of the present invention comprises the following features alone or in combination.

  The first feature of the method for producing ozone water according to the present invention for achieving the above object is that the raw material water is supplied to the anode chamber in an electrolytic cell partitioned into an anode chamber and a cathode chamber by a fixed electrolyte membrane. A water supply step, a cleaning step of supplying a cleaning liquid to the cathode chamber to clean the cathode electrode disposed in the cathode chamber, and gradually eluting the cleaning agent that contains an organic acid and is molded into a solid state And an elution step for producing the cleaning liquid.

According to this configuration, ozone is generated by electrolysis of H ₂ O from the anode electrode disposed in the anode chamber in the raw water supply step. In the elution step, the cleaning agent molded into a solid form is gradually eluted by the amount of its solubility to produce a cleaning solution having a substantially constant concentration. Even if the raw material water permeates through the solid electrolyte membrane and moves to the cathode chamber side, the cleaning solution on the cathode chamber side becomes thin, so that the cleaning agent is gradually eluted by its solubility. It becomes a cleaning solution. In the cleaning process, since the cleaning liquid is supplied to the cathode chamber and the cathode chamber is kept in an acidic state, Ca ²⁺ ions and Mg ²⁺ ions contained in the raw water do not precipitate as poorly soluble salts on the cathode electrode. The state dissolved in the cleaning liquid can be maintained. As a result of the inventor's diligent research, the acid concentration of the cleaning liquid does not need to be high, and the cleaning performance can be ensured even at a low concentration. The process can be performed easily and safely.

  The second feature of the ozone water production method according to the present invention is that, in the cleaning step, the cleaning liquid that is circulated between the cleaning liquid tank storing the cleaning liquid and the cathode chamber is supplied to the cathode chamber. It is to be done.

  According to this configuration, the cleaning liquid can be circulated between the cleaning liquid tank for storing the cleaning liquid and the cathode chamber in the cleaning process. Therefore, the cleaning liquid can be used repeatedly.

  The third feature of the method for producing ozone water according to the present invention is that, in the elution step, the cleaning agent is gradually eluted into the cleaning solution in the cleaning solution tank in which the cleaning agent is disposed. Here, the method of arranging the cleaning agent is a method of sinking the cleaning agent as it is in the bottom of the cleaning liquid tank, a method of wrapping it in a net or the like and sinking it to the bottom of the cleaning liquid tank, a cleaning tank attached with a hanging device. A method of suspending the inside is conceivable.

  According to this configuration, since the cleaning liquid tank has an opening for introducing the cleaning liquid and has a certain volume for storing the cleaning liquid, it is possible to easily dispose the cleaning agent in the cleaning liquid tank.

  The fourth feature of the ozone water production method according to the present invention is that the raw material water is branched into an anode chamber side path for supplying the anode chamber and a cathode chamber side path for supplying to the cathode chamber. In the elution step, the cleaning agent is gradually eluted into the raw material water in the cathode chamber side passage where the cleaning agent is disposed. Here, as for the method of arranging the cleaning agent, the cleaning agent is sunk as it is in the buffer tank installed in the cathode chamber side path, the method of wrapping it in a net or the like, and a hanging device is attached. A method of suspending is conceivable.

According to this configuration, a water softener filled with Na-type ion exchange resin is installed on the upstream side of the ozone water production system, and Ca ²⁺ ions and M ² g ⁺ ions, which are hardness components in tap water, are ion-exchanged to Na ⁺ ions. Pretreatment of the raw material water, such as, is unnecessary. In addition, since the solid cleaning agent gradually elutes into the raw material water, a step of periodically injecting a liquid cleaning liquid is unnecessary, and the cleaning step is simple and easy to maintain.

Moreover, the 5th characteristic in the ozone water manufacturing method which concerns on this invention is that the strong electrolyte for raising the electrical conductivity of water is mixed with the said cleaning agent. Here, the phrase “a strong electrolyte is mixed” means that an electrolyte containing at least one of NaCl, Na ₂ SO ₄ , KCl, and K ₂ SO ₄ is mixed.

  According to this configuration, the electrical conductivity of the cleaning liquid is increased, and the power efficiency can be improved.

  The sixth feature of the method for producing ozone water according to the present invention is that the cleaning agent contains at least one of succinic acid and fumaric acid.

  According to this configuration, since succinic acid and fumaric acid are both acids having a moderate solubility or lower, it becomes possible to gradually dissolve the organic acid without mixing the dissolution rate adjusting agent with the cleaning agent. . As a result, the life of the electrode cleaning liquid can be maintained for a long time.

Further, the ozone water production apparatus according to the present invention uses water containing at least one of Ca ²⁺ ions and Mg ²⁺ ions as raw water, and produces ozone water by electrolyzing the raw water. The present invention relates to an ozone water production apparatus.
And the ozone water manufacturing apparatus based on this invention has the following some features, in order to achieve the said objective. That is, the ozone water production apparatus of the present invention comprises the following features alone or in combination as appropriate.

  The first feature of the ozone water production apparatus according to the present invention is that an anode chamber and a cathode chamber partitioned by a fixed electrolyte membrane, an electrolytic cell in which the raw water is supplied to the anode chamber, and the cathode chamber A cleaning liquid supplying means for supplying a cleaning liquid to the cathode chamber and cleaning the cathode electrode disposed in the cathode chamber, and by gradually eluting the cleaning agent containing the organic acid and molded into a solid state, And an elution part to be generated.

According to this configuration, ozone is generated by electrolysis of H ₂ O from the anode electrode arranged in the anode chamber of the electrolytic cell. In the elution part, the cleaning agent molded in a solid state is gradually eluted by the amount of its solubility to produce a cleaning solution having a substantially constant concentration. Even if the raw material water permeates through the solid electrolyte membrane and moves to the cathode chamber side, the cleaning solution on the cathode chamber side becomes thin, so that the cleaning agent is gradually eluted by its solubility. It becomes a cleaning solution. In the cleaning process, since the cleaning liquid is supplied to the cathode chamber and the cathode chamber is kept in an acidic state, Ca ²⁺ ions and Mg ²⁺ ions contained in the raw water do not precipitate as poorly soluble salts on the cathode electrode. The state dissolved in the cleaning liquid can be maintained. As a result of the inventor's diligent research, the acid concentration of the cleaning liquid does not need to be high, and the cleaning performance can be ensured even at a low concentration. The process can be performed easily and safely.

  Further, a second feature of the ozone water producing apparatus according to the present invention includes a cleaning liquid tank that stores the cleaning liquid, and the cleaning liquid supply means circulates the cleaning liquid between the cleaning liquid tank and the cathode chamber. The cleaning liquid is supplied to the cathode chamber.

  According to this configuration, the cleaning liquid can be circulated between the cleaning liquid tank for storing the cleaning liquid and the cathode chamber in the cleaning process. Therefore, the cleaning liquid can be used repeatedly.

  Moreover, the 3rd characteristic in the ozone water manufacturing apparatus which concerns on this invention is that the said elution part is formed as the inside of the said washing | cleaning liquid tank which arrange | positions the said washing | cleaning agent. Here, the means for disposing the cleaning agent includes means for sinking the cleaning agent as it is in the bottom of the cleaning liquid tank, means for wrapping it in a net or the like and sinking it to the bottom of the cleaning liquid tank, and attaching a hanging device to the cleaning liquid tank. A means for suspending it on the surface can be considered.

  According to this configuration, since the cleaning liquid tank has an opening for introducing the cleaning liquid and has a certain volume for storing the cleaning liquid, it is possible to easily dispose the cleaning agent in the cleaning liquid tank.

  The fourth feature of the ozone water production apparatus according to the present invention is that the raw water supply path branches into an anode chamber side path for supplying the raw water to the anode chamber and a cathode chamber side path for supplying the cathode chamber. And a buffer tank provided in the middle of the cathode chamber side path, in which the cleaning agent is disposed, and the elution part is formed as an interior of the buffer tank. Here, the means for disposing the cleaning agent is a means for sunk the cleaning agent as it is in a buffer tank installed in the cathode chamber side passage, a means for wrapping and sunk with a net, etc. Means to keep it are considered.

According to this configuration, a water softener filled with Na-type ion exchange resin is installed on the upstream side of the ozone water production system, and Ca ²⁺ ions and M ² g ⁺ ions, which are hardness components in tap water, are ion-exchanged to Na ⁺ ions. Pretreatment of the raw material water, such as, is unnecessary. In addition, since the solid cleaning agent gradually elutes into the raw water, there is no need for an elution part that regularly injects a liquid cleaning solution, and a welded part can be formed concisely and maintenance is easy. It becomes.

Moreover, the 5th characteristic in the ozone water manufacturing apparatus based on this invention is that the strong electrolyte for raising the electrical conductivity of water is mixed with the said cleaning agent. Here, the phrase “a strong electrolyte is mixed” means that an electrolyte containing at least one of NaCl, Na ₂ SO ₄ , KCl, and K ₂ SO ₄ is mixed.

  According to this configuration, the electrical conductivity of the cleaning liquid is increased, and the power efficiency can be improved.

  The sixth feature of the ozone water production apparatus according to the present invention is that the cleaning agent contains at least one of succinic acid and fumaric acid.

  According to this configuration, since succinic acid and fumaric acid are both acids having a moderate solubility or lower, it becomes possible to gradually dissolve the organic acid without mixing the dissolution rate adjusting agent with the cleaning agent. . As a result, the life of the electrode cleaning liquid can be maintained for a long time.

Further, the cleaning agent according to the present invention uses water containing at least one of Ca ²⁺ ions and Mg ²⁺ ions as raw water, and electrolysis partitioned into an anode chamber and a cathode chamber by a fixed electrolyte membrane. The present invention relates to a cleaning agent used in an ozone water production apparatus for producing ozone water by electrolyzing the raw material water in a tank. And the cleaning agent which concerns on this invention has the following characteristics, in order to achieve the said objective.

  The cleaning agent according to the present invention is characterized in that the cathode chamber contains at least one of succinic acid and fumaric acid, and is molded into a solid state and cleans the cathode electrode disposed in the cathode chamber. In order to produce a cleaning solution to be supplied to the product, it is used by being gradually eluted.

  According to this configuration, since succinic acid and fumaric acid are both acids with moderate solubility, a detergent that gradually dissolves the organic acid is formed without mixing the dissolution rate modifier with the detergent. be able to. As a result, the life of the electrode cleaning liquid can be maintained for a long time.

  Hereinafter, the best mode for carrying out the present invention will be described with reference to the drawings. In addition, since the ozone water manufacturing method which concerns on this invention is enforced by operating the ozone water manufacturing apparatus which concerns on this invention, the ozone which concerns on this invention is demonstrated with description of embodiment of the ozone water manufacturing apparatus which concerns on this invention. An embodiment of the water production method will be described. Moreover, the cleaning agent used in these ozone water manufacturing apparatus and ozone water manufacturing method is also demonstrated suitably with description of embodiment of an ozone water manufacturing apparatus.

(First embodiment)
FIG. 1 is a diagram showing an ozone water production apparatus 1 according to a first embodiment of the present invention. The ozone water production apparatus 1 of the first embodiment is an apparatus that includes an electrolytic cell 3 partitioned into an anode chamber 5 and a cathode chamber 6 by a fixed electrolyte membrane 4, a cleaning liquid tank 7 that stores cleaning liquid, and a circulation pump 8. is there. The arrows in FIG. 1 indicate the flow directions of raw water containing at least one of Ca ²⁺ ions and Mg ²⁺ ions (hereinafter referred to as raw water), ozone water, and cleaning liquid. The ozone water production apparatus 1 is an apparatus for producing ozone water by electrolyzing raw material water supplied from the outside to the anode chamber 5 in the electrolytic cell 3, and the produced ozone water was connected to the anode chamber 5. Discharge from the path 11.

The path 10 through which the raw water from the outside flows is a path connected to the anode chamber 5 of the electrolytic cell 3, and the raw water supplied to the anode chamber 5 via the path 10 (raw water supply process) 3 is electrolyzed by a DC voltage applied to the anode chamber 5 and the cathode chamber 6, and ozone water is produced on the anode chamber 5 side. At this time, cations such as Ca ²⁺ ions and Mg ²⁺ ions contained in the raw water and a part of the raw water pass through the fixed electrolyte membrane 4 and move to the cathode chamber 6 side. In the cleaning step of cleaning the cathode electrode disposed in the cathode chamber 6, the acidic cleaning liquid put in the cleaning liquid tank 7 is passed between the cleaning liquid tank 7 and the cathode chamber 6 of the electrolytic cell 3 by the circulation pump 8. Circulate through the connecting path 12. Here, on the cathode chamber 6 side, OH ⁻ ions are generated by electrolysis of water, and it is difficult for these OH ⁻ ions and cations such as Ca ²⁺ ions and Mg ²⁺ ions that have moved from the anode chamber 5 side. There is a possibility that a soluble salt is formed and deposited around the cathode electrode disposed in the cathode chamber 6. However, since these compounds do not precipitate when the liquid is in an acidic condition, hardly soluble salts are not precipitated by the washing step.

  The acid concentration of the cleaning liquid does not need to be high, and hydrochloric acid, nitric acid, sulfuric acid and the like can be used as the acid. However, since these strong acids are dangerous, organic acids such as succinic acid are preferable. However, not only succinic acid but also organic acids such as citric acid, gluconic acid, lactic acid, fumaric acid and DL malic acid can be used. On the other hand, the concentration of the cleaning liquid gradually decreases as a part of the raw material water passes through the fixed electrolyte membrane 4 and moves to the cathode chamber 6 side in the manufacturing process of ozone water. Here, in the elution step for generating the cleaning solution, the cleaning agent 9 is gradually eluted in the cleaning solution by the solubility of the succinic acid in the cleaning solution tank 7 in which the cleaning agent 9 in which the succinic acid is molded in a solid state is arranged ( Elution step), maintaining the acid concentration of the cleaning solution.

The cleaning agent 9 is not limited to one molded from succinic acid alone, and organic acids such as citric acid, gluconic acid, lactic acid, fumaric acid, and DL malic acid can also be used. The organic acid can be formed into a solid state by various methods. For example, in the case of an organic acid that melts when heated in a solid state at room temperature, it is heated to a temperature higher than the melting point, melted, poured into a mold, and cooled. For organic acids whose solubility decreases when cooled to a high temperature, a method of precipitating from a supersaturated solution, for organic acids that are solid at room temperature, a dry molding method using pressure, a powder using a compression processing machine such as a tablet molding machine. There is a way to compress the body. For organic acids that are liquid at room temperature, there are methods such as molding by adding and kneading solids such as silica, alumina or zeolite. Further, when the organic acid is molded into a solid state, the cleaning agent 9 mixed with a strong electrolyte such as NaCl is eluted into the cleaning liquid, which is suitable for increasing the electrical conductivity of the cleaning liquid and improving the power efficiency. is there. Here, strong electrolyte is not limited to NaCl, for _{example, Na 2 SO 4, KCl,} K 2 SO 4 , and the like.

  When an organic acid having a high solubility is used in the cleaning agent 9, the dissolution rate of the cleaning agent is decreased by using a mixture of a dissolution rate adjusting agent in a solid form, and the organic acid is gradually removed from the cleaning solution. It can be dissolved in Thereby, the lifetime of the cleaning liquid can be maintained. Here, examples of the dissolution rate adjusting agent include poorly water-soluble substances such as fatty acids having a low solubility and higher alcohols. As the shape of the cleaning agent 9, a disc shape, a ball shape, a columnar shape, a cubic shape, a rectangular parallelepiped shape, and the like are conceivable. As a method of disposing the cleaning agent 9 in the cleaning liquid tank 7, a method of sinking the cleaning agent 9 as it is in the bottom of the cleaning liquid tank 7, a method of wrapping it in a net or the like and sinking it in the bottom of the cleaning liquid tank 7, hanging A method of attaching a lowering device and suspending it in the cleaning liquid tank 7 is conceivable. On the other hand, not only a method of disposing the cleaning agent 9 in the cleaning liquid tank 7 but also a method of disposing the cleaning agent 9 in the path 12 circulating between the cleaning liquid tank 7 and the cathode chamber 6 may be used.

  As an example of the first embodiment, 100 g of succinic acid was heated to 200 ° C., melted, put into a mold, cooled, and then the cleaning agent 9 molded into a disk-like solid was used. In advance, 4 liters of 4% succinic acid cleaning liquid was put into the cleaning liquid tank 7, and the cleaning agent 9 was placed at the bottom of the cleaning liquid tank 7. As the ozone water production conditions, an operation was performed for 50 hours at an ozone concentration of 5 ppm and a water volume of 3 L / min. As a result, the succinic acid concentration in the cleaning liquid after the operation was about 5%, and precipitation of hardly soluble salt around the cathode electrode arranged in the cathode chamber 6 was not observed.

  Further, a cleaning agent 9 was used, which was prepared by adding 10 g of polyacrylic acid to 20 g of water to 100 g of succinic acid and 100 g of sodium chloride and then forming the solid by press working. Ozone water production apparatus 1, cleaning liquid, and ozone water production conditions were the same as described above, and operation was performed using 4 liters of 4% succinic acid cleaning liquid. As a result, compared with the case where the cleaning agent 9 to which sodium chloride was not added was used, the current value was lowered and the power consumption could be reduced. Moreover, precipitation of the hardly soluble salt around the cathode electrode arranged in the cathode chamber 6 was not recognized. Further, as a comparative example, the cleaning agent 9 was not used and 4 liters of a cleaning solution of 40% citric acid and 5% sodium chloride was used, and the operation was performed in the same manner as described above for the ozone water production measure 1 and the ozone water production conditions. As a result, when the citric acid concentration in the washing solution was analyzed by ion chromatography, the citric acid concentration was reduced to about 20%.

(Second Embodiment)
An ozone water production apparatus, an ozone water production method, and a cleaning agent used in the second embodiment of the present invention will be described. In FIG. 2, the ozone water manufacturing apparatus 2 which concerns on 2nd Embodiment of this invention is shown. The ozone water production apparatus 2 according to the second embodiment of the present invention includes a cleaning liquid tank 7, a circulation pump 8, and a path 12 that circulates between the cleaning liquid tank 7 and the cathode chamber 6 in the ozone water production apparatus 1 according to the first embodiment. It differs in that it does not have. Further, the ozone water production apparatus 1 of the first embodiment supplies raw water only to the anode chamber 5, but the ozone water production apparatus 2 of the second embodiment does not supply raw water on the upstream side of the electrolytic cell 3. The raw material water supply path 14 for supplying water is branched into two, one of the branched paths 15 (anode chamber side path) is connected to the anode chamber 5, and the other path 17 (cathode chamber side path 1) is the cleaning agent. 9 is connected to a buffer tank 13 connected via a path 18 (cathode chamber side path 2) to the cathode chamber 6 side for arranging 9 and raw water is supplied to the anode chamber 5 and the buffer tank 13. Different. In addition, the same code | symbol is attached | subjected to the member same as 1st Embodiment, and the description is abbreviate | omitted.

  On the downstream side of the raw material water supply path 14 into which the raw water from the outside flows, the path is a path 15 connected to the anode chamber 5 and a path 17 connected to the buffer tank 13 connected to the cathode chamber 6 side via the path 18. Branch into two. The raw material water supplied to the anode chamber 5 via the path 15 (raw water supply step) is electrolyzed by a DC voltage applied to the anode chamber 5 and the cathode chamber 6 of the electrolytic cell 3 and on the anode chamber 5 side. Ozone water is produced, and the produced ozone water is discharged from the path 16 connected to the anode chamber 5. The raw material water supplied to the buffer tank 13 via the path 17 comes into contact with the same cleaning agent 9 used in the first embodiment arranged in the buffer tank 13, and the cleaning agent 9 becomes the raw water. A washing solution is generated by an elution step that gradually elutes.

The cleaning liquid is supplied from the buffer tank 13 to the cathode chamber 6 via the path 18 and flows between the cathode electrodes arranged in the cathode chamber 6 (cleaning step), and a part thereof is electrolyzed by the cathode electrode, It is discharged to the outside as cleaning waste liquid via a path 19 connected to the cathode chamber 6. At this time, as in the first embodiment, cations such as Ca ²⁺ ions and Mg ²⁺ ions contained in the raw water and a part of the raw water pass through the fixed electrolyte membrane 4 and move to the cathode chamber 6 side. However, since the inside of the cathode chamber 6 is subjected to an acidic condition by the cleaning liquid, hardly soluble salts such as Ca (OH) ₂ and Mg (OH) ₂ do not precipitate. The acid concentration of the cleaning liquid supplied to the cathode chamber 6 is low and can prevent precipitation of sparingly soluble salts. Therefore, the acid concentration of the cleaning waste liquid discharged from the cathode chamber 6 via the path 19 can be kept low. Even if a neutralization treatment or the like is necessary, a simple and easy treatment can be achieved. Further, since the solid cleaning agent 9 disposed in the buffer tank 13 is gradually eluted into the raw material water (elution step), it is not necessary to separately provide a regular cleaning liquid supply device, and the apparatus becomes simple.

  As a method of disposing the cleaning agent 9 in the buffer tank 13, a method of sinking the cleaning agent 9 as it is in the bottom of the buffer tank 13, a method of wrapping it in a net or the like and sinking it in the bottom of the buffer tank 13, hanging A method of attaching a lowering device and suspending it in the buffer tank 13 is conceivable. As in the first embodiment, the cleaning agent 9 may be an organic acid such as succinic acid, citric acid, gluconic acid, lactic acid, fumaric acid, DL malic acid, and the like. In addition, it is possible to mold the organic acid into a solid state by various methods. For example, in the case of an organic acid that melts when heated in a solid state at room temperature, it is heated to a melting point or higher, melted, poured into a mold, and cooled. For organic acids that sometimes have high solubility and decrease in solubility when cooled, a method of precipitating from a supersaturated solution, for organic acids that are solid at room temperature, other methods such as molding by applying dry pressure, compression processing machines such as tablet molding machines are used. There is a method of pressing the powder. For organic acids that are liquid at room temperature, there are methods such as molding by adding and kneading solids such as silica, alumina or zeolite.

Further, when the organic acid is molded into a solid state, the cleaning agent 9 mixed with a strong electrolyte such as NaCl is eluted into the cleaning liquid, which is suitable for increasing the electrical conductivity of the cleaning liquid and improving the power efficiency. is there. Here, strong electrolyte is not limited to NaCl, for _{example, Na 2 SO 4, KCl,} K 2 SO 4 , and the like. When an organic acid having a high solubility is used in the cleaning agent 9, the dissolution rate of the cleaning agent is decreased by using a mixture of a dissolution rate adjusting agent in a solid form, and the organic acid is gradually removed from the cleaning solution. It can be dissolved in Thereby, the lifetime of the cleaning liquid can be maintained. Here, examples of the dissolution rate adjusting agent include poorly water-soluble substances such as fatty acids having a low solubility and higher alcohols. As the shape of the cleaning agent 9, a disc shape, a ball shape, a columnar shape, a cubic shape, a rectangular parallelepiped shape, and the like are conceivable.

  As an example of the second embodiment, a plurality of cleaning agents 9 in which fumaric acid is molded into a ball shape are arranged in the buffer tank 13 and the cathode-side inflowing water via the path 17 comes into contact with the cleaning agent 9. It was made to supply to the cathode chamber 6. Precipitation of hardly soluble salt was not observed on the cathode electrode after the ozone water production apparatus 2 was operated under these conditions to produce ozone water.

  Although the embodiments of the present invention have been described above, the present invention is not limited to the above-described embodiments, and various modifications can be made as long as they are described in the claims.

It is a figure which shows the ozone water manufacturing apparatus which concerns on 1st Embodiment of this invention. It is a figure which shows the ozone water manufacturing apparatus which concerns on 2nd Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ozone water production apparatus 3 Electrolysis tank 4 Fixed electrolyte membrane 5 Anode chamber 6 Cathode chamber 7 Cleaning liquid tank 8 Circulation pump 9 Cleaning agent 13 Buffer tank

Claims (13)

An ozone water production method for producing ozone water by using water containing at least one of Ca ²⁺ ions and Mg ²⁺ ions as raw water and electrolyzing the raw water,
A raw water supply step for supplying the raw water to the anode chamber in an electrolytic cell partitioned into an anode chamber and a cathode chamber by a fixed electrolyte membrane;
A cleaning step of supplying a cleaning liquid to the cathode chamber to clean the cathode electrode disposed in the cathode chamber;
An elution step for producing the cleaning liquid by gradually eluting a cleaning agent that contains an organic acid and is molded into a solid state;
A method for producing ozone water, comprising:   2. The method for producing ozone water according to claim 1, wherein in the cleaning step, the cleaning liquid that is circulated between the cleaning liquid tank that stores the cleaning liquid and the cathode chamber is supplied to the cathode chamber. .   The method for producing ozone water according to claim 2, wherein in the elution step, the cleaning agent is gradually eluted into the cleaning solution in the cleaning solution tank in which the cleaning agent is disposed. The raw water is supplied via a raw water supply path that branches into an anode chamber side path that supplies the anode chamber and a cathode chamber side path that supplies the cathode chamber,
2. The method for producing ozone water according to claim 1, wherein in the elution step, the cleaning agent is gradually eluted into the raw material water in the cathode chamber side path in which the cleaning agent is disposed.   The ozone water production method according to any one of claims 1 to 4, wherein a strong electrolyte for increasing the electrical conductivity of water is mixed in the cleaning agent.   The method for producing ozone water according to any one of claims 1 to 5, wherein the cleaning agent contains at least one of succinic acid and fumaric acid. An ozone water production apparatus for producing ozone water by using water containing at least one of Ca ²⁺ ions and Mg ²⁺ ions as raw material water and electrolyzing the raw material water,
An electrolytic cell having an anode chamber and a cathode chamber partitioned by a fixed electrolyte membrane, the raw material water being supplied to the anode chamber;
Cleaning liquid supply means for supplying a cleaning liquid into the cathode chamber and cleaning the cathode electrode disposed in the cathode chamber;
An elution part that generates the cleaning liquid by gradually eluting a cleaning agent that contains an organic acid and is molded into a solid state;
An ozone water production apparatus comprising: A cleaning liquid tank for storing the cleaning liquid;
The apparatus for producing ozone water according to claim 7, wherein the cleaning liquid supply means circulates the cleaning liquid between the cleaning liquid tank and the cathode chamber and supplies the cleaning liquid to the cathode chamber.   The ozone water production apparatus according to claim 8, wherein the elution part is formed as an inside of the cleaning liquid tank in which the cleaning agent is disposed. A raw water supply path that branches into an anode chamber side path for supplying the raw water to the anode chamber and a cathode chamber side path for supplying to the cathode chamber;
A buffer tank provided in the middle of the cathode chamber side path and in which the cleaning agent is disposed;
The ozone water production apparatus according to claim 7, wherein the elution part is formed as an inside of the buffer tank.   The ozone water production apparatus according to any one of claims 7 to 10, wherein a strong electrolyte for increasing the electrical conductivity of water is mixed in the cleaning agent.   The ozone water production apparatus according to any one of claims 7 to 11, wherein the cleaning agent includes at least one of succinic acid and fumaric acid. Water containing at least one of Ca ²⁺ ions and Mg ²⁺ ions is used as raw water, and the raw water is electrolyzed in an electrolytic cell partitioned into an anode chamber and a cathode chamber by a fixed electrolyte membrane. A cleaning agent used in an ozone water production apparatus for producing ozone water by
It contains at least one of succinic acid and fumaric acid and is molded into a solid form,
A cleaning agent characterized by being gradually eluted and used to produce a cleaning solution supplied into the cathode chamber so as to clean the cathode electrode disposed in the cathode chamber.

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