JP2010209370A - Production apparatus of ozone water and production method of ozone water - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a production apparatus of ozone water and a production method of ozone water, in which precipitation-deposition of a compound on an electrode can be prevented and reduction in the generation ability for ozone water can be prevented. <P>SOLUTION: The production apparatus 100 of ozone water includes water softening devices 1, 2 that remove cations in source water, an anion removing device 3 that removes anions in the source water, and an ozone water producing device 4 that electrolyzes the source water from which cations and anions are removed by the water softening devices 1, 2 and the anion removing device 2, to produce ozone water. Precipitation-deposition of a compound on a cathode electrode 33 is prevented, which prevents reduction in the electrolyzing performance of the ozone producing device 4 and prevents reduction in the generation ability for ozone water. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ozone water production facility and an ozone water production method capable of preventing the precipitation and adhesion of a compound to an electrode to prevent a decrease in the ability to produce ozone water.

  In general, since ozone has a strong oxidizing power, it is used in various fields such as sterilization, disinfection, decolorization, deodorization, oxidative decomposition and oxidation treatment. The demand for ozone water dissolving ozone is increasing because it is safer and easier to use than ozone gas. In order to produce the ozone water, methods for electrolyzing water have been well known (for example, JP-A-3-267390, JP-A-8-134679, JP-A-8-134678, etc.).

  In JP-A-8-134777 and JP-A-8-134678, as raw material water used for electrolysis, tap water or natural water, or water obtained by removing chlorine through an activated carbon layer is used. An ozone water production apparatus for producing concentrated ozone water is introduced.

However, in these apparatuses, since raw material water contains hardness components such as Ca ²⁺ and Mg ²⁺ and SO ₄ ²⁻ , PO ₄ ³⁻ , and NO ₃ ⁻ , these raw waters are used. In the electrolytic cell in which electrolysis is performed, the cation such as Ca ²⁺ and Mg ²⁺ in the raw water moves through the solid electrolyte membrane from the anode side to the cathode side, and SO ₄ ²⁻ , PO ₄ on the cathode side moves. ^3-, NO ₃ ^- combined with anions such, insoluble CaSO _4, MgSO ₄ compounds such as are likely to precipitate or adhere to the cathode electrode and the solid electrolyte membrane. This tendency is particularly remarkable when the anode side is alkaline. When these compounds are deposited and adhered to the cathode electrode or the solid electrolyte membrane, the electrical conductivity is lowered and the ability to generate ozone water is significantly lowered. The solid electrolyte membrane uses a cation exchange membrane that has the property of transmitting cations but not anions, so that it passes through the solid electrolyte membrane from the cathode side in the electrolytic cell where electrolysis is performed. Thus, the anion in the raw material water does not move to the anode side, and since the pH value of the raw material water on the anode side is neutral, no compound is deposited on the anode side. In this way, the compound deposited and adhered to the cathode electrode or the solid electrolyte membrane can be removed by dissolving with hydrochloric acid or the like, but not only the operation has to be interrupted, but also the removal and cleaning work takes a long time. .

In order to solve this problem, Japanese Patent No. 3269784 discloses that raw water is passed through a cation exchange part filled with a Na-type strongly acidic cation exchange resin to remove cations such as Ca ²⁺ and Mg ^{2+ in the} raw water. An apparatus for producing ozone water by electrolyzing the raw water is described. In the case of such an apparatus, the cations such as Ca ²⁺ and Mg ²⁺ contained in the raw water are removed by the Na-type strong acid cation exchange resin, so that CaSO is applied to the cathode electrode and the solid electrolyte membrane. ₄ , MgSO _{4 and the} like have an advantage that it is difficult to deposit and adhere.

JP-A-3-267390 JP-A-8-134777 JP-A-8-134678 Japanese Patent No. 3269784

However, even if raw material water is passed through a cation exchange resin using such an apparatus, trace amounts of cations such as Ca ²⁺ and Mg ²⁺ may remain in the raw material water. As the apparatus is operated for a long time, the remaining cations such as Ca ²⁺ and Mg ²⁺ are combined with negative ions such as SO ₄ ²⁻ , PO ₄ ³⁻ , NO ₃ ⁻ on the cathode side, and the cathode electrode In some cases, a compound such as CaSO ₄ or MgSO ₄ is deposited and adhered to the solid electrolyte membrane.

Therefore, the present invention has been made paying attention to the situation as described above, and its purpose is to use positive ions of hardness components such as Ca ²⁺ and Mg ²⁺ in raw water from raw water using a cation exchange resin. Even if trace amounts of cations of hardness components such as Ca ²⁺ and Mg ²⁺ remain in the raw material water while utilizing the advantage of removing ions, SO ₄ ²⁻ , PO ₄ ³ to be bonded with such cations. ^-, NO ₃ ^- by removing anions such, is possible to prevent a reduction in the CaSO _4, MgSO ₄ generation capability of preventing ozone water precipitation-deposition of a compound such as to the cathode electrode and a solid electrolyte membrane An ozone water production facility and a method for producing ozone water are provided.

  The ozone water production facility according to the first invention for achieving the above object includes a cation removing device for removing cations in raw water, an anion removing device for removing anions in raw water, and the cations. And an ozone water production apparatus for producing ozone water by electrolyzing the raw water from which cations and anions have been removed by the removal apparatus and the anion removal apparatus.

  According to this configuration, ozone water can be produced by electrolyzing the raw water from which the cations and anions have been removed by the anion removing device and the cation removing device. For this reason, even if a small amount of cation remains in the raw water from which the cation has been removed, by removing the anion that is a binding target of the cation, Precipitation / adhesion of anionic compounds can be prevented. Further, by preventing the precipitation and adhesion of the compound, it is possible to prevent a decrease in electrolysis performance and a decrease in the ability to generate ozone water.

  Further, the ozone water production facility according to the second invention is the ozone water production apparatus according to the first invention, wherein the ozone water production apparatus comprises a solid electrolyte membrane and an anode-side flow path provided on one of the solid electrolyte membrane and the solid electrolyte membrane. A cathode side channel provided on the other side, an anode electrode provided in the anode side channel, and a cathode electrode provided in the cathode side channel, and the raw material in the cathode side channel In the cathode side feeding path for feeding water, the cation removing device and the anion removing device are provided, and in the anode side feeding path for feeding the raw water into the anode side flow path, The cation removing device is provided.

  In general, the solid electrolyte membrane is a cation exchange membrane that has the property of allowing cations to permeate but not anions. Therefore, the solid electrolyte membrane is permeated from the cathode side of the cathode side channel where electrolysis is performed. Thus, the anion in the raw material water does not move to the anode electrode in the anode side channel, and the pH value of the raw material water in the anode side channel does not show alkalinity, so no compound is deposited on the anode side. Further, anions in the raw material water do not move through the solid electrolyte membrane from the anode side of the anode-side flow path where electrolysis is performed and move to the cathode electrode in the cathode-side flow path. On the other hand, since the solid electrolyte membrane allows cation to permeate, the cation in the raw material water passes through the solid electrolyte membrane from the anode side of the anode-side channel where the electrolysis is performed, and reaches the cathode electrode in the cathode-side channel. It moves and deposits and adheres to the cathode side. Then, with respect to the anion, if only the anion in the raw material water fed into the cathode-side flow path is removed, it is possible to prevent the compound from being deposited and adhered to the cathode side.

  Therefore, according to the configuration of the present invention, in the ozone water production facility, the cation removing device and the anion removing device are provided in the cathode side feeding path for feeding the raw material water into the cathode side flow path, and the anode Since the cation removing device is provided in the anode side feed path for feeding the raw material water into the side flow path, the anion removal is performed only for the raw water supplied into the cathode side flow path. . For this reason, since the anion removal is not performed on the raw water supplied to the anode side flow path, the anion removal device can be made compact. In addition, since the amount of raw water passing through the anion removing device can be limited to an amount necessary for electrolysis in the cathode side flow path, the life of the anion removing device can be extended.

  The ozone water production facility according to a third aspect of the present invention is the first or second aspect, wherein the cation removing device has a cation exchange resin that ion-exchanges cations in the raw water, and the anions The removing device has an anion exchange resin that ion-exchanges anions in the raw material water.

When the ionized substance in the raw material water is decreased, the electric conductivity of the raw material water may be lowered and the electrolysis performance may be deteriorated. Therefore, according to this configuration, the cation (anion) previously adsorbed on the cation exchange resin (anion exchange resin) and the Ca ²⁺ , Mg ^2+, etc. adsorbed and removed by the cation exchange resin (anion exchange resin) Cation (an anion such as SO ₄ ²⁻ , PO ₄ ³⁻ , NO ₃ ^−, etc., to which the cation is to be bound) is exchanged. For this reason, even if the cation (anion) in the raw material water is adsorbed and removed, the cation (anion) previously adsorbed on the cation exchange resin (anion exchange resin) is contained in the raw material water instead. It is possible to prevent a decrease in ionized substances in the raw material water and prevent a decrease in electrical conductivity.

  The ozone water production facility according to the fourth invention is the ozone water production facility according to the third invention, wherein the cation exchange resin is a Na-type cation exchange resin, and the anion exchange resin is a Cl-type anion exchange resin. It is characterized by being.

According to this structure, Na ⁺ cation exchange resin cations such as Ca ²⁺ and Mg ^{2+ in the} raw material water and Na ⁺ are ion-exchanged, and Cl type anion exchange resin makes SO ₄ ²⁻ , PO 4 ^_3-, NO ₃ ^- anions and Cl such as ^- and by ion-exchange, while maintaining the ionic substance of the material in water it is possible to prevent a decrease in electric conductivity. In addition, since the ions exchanged and discharged are hardly compounded and are water-soluble Na ⁺ and Cl ⁻ , the compound can be made difficult to deposit and adhere to the cathode electrode or the electrolyte membrane.

  The ozone water production facility according to a fifth aspect of the present invention is the fourth aspect of the invention, wherein the sodium chloride aqueous solution tank storing a sodium chloride (NaCl) aqueous solution and the sodium chloride aqueous solution stored in the sodium chloride aqueous solution tank are A sodium chloride aqueous solution supply device for supplying one of the cation removing device and the anion removing device and supplying the drainage to the other to regenerate the Na-type cation exchange resin and the Cl-type anion exchange resin; , Provided.

According to this configuration, the Na-type cation exchange resin is regenerated by Na ⁺ ions in an aqueous sodium chloride (NaCl) solution, and the Cl-type anion exchange resin is regenerated by Cl ⁻ ions in an aqueous sodium chloride (NaCl) solution. For this reason, the sodium chloride aqueous solution required for the regeneration of the Na-type cation exchange resin and the Cl-type anion exchange resin can be supplied in series to the cation removal device and the anion removal device, thereby improving efficiency. be able to. In addition, the amount of drainage discharged from the ozone water production facility can be reduced.

  Moreover, the ozone water manufacturing method which concerns on 6th invention is the ozone water manufacturing method which electrolyzes raw material water with an ozone water manufacturing apparatus, and manufactures ozone water, Before electrolyzing the said raw material water, the said raw material water A cation removing process for removing the cation and an anion removing process for removing the anion in the raw material water.

  According to this method, ozone water can be produced by electrolyzing the raw water from which cations and anions have been removed by the anion removal process and the cation removal process. For this reason, even if a small amount of cation remains in the raw water from which the cation has been removed, by removing the anion that is a binding target of the cation, Precipitation / adhesion of anionic compounds can be prevented. Further, by preventing the precipitation and adhesion of the compound, it is possible to prevent a decrease in electrolysis performance and a decrease in the ability to generate ozone water.

  The ozone water production method according to a seventh invention is the ozone water production apparatus according to the sixth invention, wherein the ozone water production apparatus comprises a solid electrolyte membrane, an anode-side channel provided on one of the solid electrolyte membranes, and the solid A cathode-side channel provided on the other side of the electrolyte membrane, an anode electrode provided in the anode-side channel, and a cathode electrode provided in the cathode-side channel, the cathode-side channel The electrolyzed raw water from which cations and anions have been removed in the cation removal process and the anion removal process is electrolyzed, and the cations are removed in the anode side flow path in the cation removal process. The raw water is electrolyzed to produce ozone water.

  According to this method, the raw water from which cations and anions have been removed in the cation removal process and the anion removal process is electrolyzed in the cathode side channel, and the cation is removed in the anode side channel in the cation removal process. The raw water from which ions have been removed can be electrolyzed to produce ozone water. That is, anion removal is performed only on the raw water supplied to the cathode channel side. For this reason, since the anion removal is not performed on the raw water supplied to the anode flow path side, the ion removal process can be made efficient.

  The ozone water production method according to an eighth aspect of the present invention is the cation removal process according to the sixth or seventh aspect, wherein the cation in the raw material water is ion-exchanged and removed by a cation exchange resin. In the ion removal process, the anion in the raw material water is ion-exchanged and removed by an anion exchange resin.

According to this method, the cation (anion) previously adsorbed on the cation exchange resin (anion exchange resin) and the hardness of Ca ²⁺ , Mg ²⁺ etc. adsorbed and removed on the cation exchange resin (anion exchange resin) Component cations (anions such as SO ₄ ²⁻ , PO ₄ ³⁻ , NO ₃ ^−, etc., to which the cations are bound) are exchanged. For this reason, even if the cation (anion) in the raw material water is adsorbed and removed, the cation (anion) previously adsorbed on the cation exchange resin (anion exchange resin) is contained in the raw material water instead. It is possible to prevent a decrease in ionized substances in the raw material water and prevent a decrease in electrical conductivity. In addition, Na ^<+> (salt type) etc. are used for the cation previously adsorb | sucked to cation exchange resin. In addition, Cl ⁻ (salt type) or the like is used as the anion that is previously adsorbed on the anion exchange resin.

  The method for producing ozone water according to the ninth invention is the method according to the eighth invention, wherein the cation exchange resin is a Na-type cation exchange resin, and the anion exchange resin is a Cl-type anion exchange resin. It is characterized by being.

According to this method, cation such as Ca ²⁺ and Mg ^{2+ in the} raw material water is ion-exchanged with Na ⁺ with the Na-type cation exchange resin, and SO ₄ ^{2− in the} raw material water is exchanged with the Cl-type anion exchange resin. PO 4 ^_3-, NO ₃ ^- anions and Cl such as ^- and by ion-exchange, while maintaining the ionic substance of the material in water it is possible to prevent a decrease in electric conductivity. In addition, since the ions exchanged and discharged are hardly compounded and are water-soluble Na ⁺ and Cl ⁻ , the compound can be made difficult to deposit and adhere to the cathode electrode or the electrolyte membrane.

  Further, the ozone water production method according to the tenth invention is the ninth invention, wherein the sodium chloride aqueous solution is supplied to one of the Na-type cation exchange resin and the Cl-type anion exchange resin, and the drainage is supplied to the other. And a regeneration step of regenerating the Na-type cation exchange resin and the Cl-type anion exchange resin.

According to this method, the Na-type cation exchange resin is regenerated by Na ⁺ ions in an aqueous sodium chloride (NaCl) solution, and the Cl-type anion exchange resin is regenerated by Cl ⁻ ions in an aqueous sodium chloride (NaCl) solution. For this reason, it is possible to regenerate the Na-type cation exchange resin and the Cl-type anion exchange resin by efficiently using a sodium chloride aqueous solution.

  Ozone water can be produced by electrolyzing the raw water from which cations and anions have been removed by the anion removal device and the cation removal device. For this reason, even if a small amount of cation remains in the raw water from which the cation has been removed, by removing the anion that is a binding target of the cation, Precipitation / adhesion of anionic compounds can be prevented. Further, by preventing the precipitation and adhesion of the compound, it is possible to prevent a decrease in electrolysis performance and a decrease in the ability to generate ozone water.

It is a block diagram showing ozone water production equipment concerning a 1st embodiment of the present invention. It is explanatory drawing which shows the result of having investigated the amount of various ions contained in raw material water. It is a graph which shows the value of the electrolysis current with progress of time. It is a block diagram which shows the ozone water manufacturing equipment which concerns on 2nd Embodiment of this invention. It is a block diagram which shows the ozone water manufacturing equipment which concerns on a modification.

  Hereinafter, embodiments for carrying out the present invention will be described with reference to the drawings.

(First embodiment)
FIG. 1 is a block diagram showing an ozone water production facility 100 according to the first embodiment of the present invention. As shown in FIG. 1, an ozone water production facility 100 includes a water softener 1 (cation removal device), a water softener 2 (cation removal device), an anion removal device 3, and ozone water (electrolytic ozone water). The ozone water production apparatus 4, the micro filter 6, the activated carbon filter 7, the anode side feeding path 8, the cathode side feeding path 9, and the flow rate adjusting electromagnetic valves 10 and 11 are configured.

The water softener 1 and the water softener 2 are cation removal devices filled with a Na-type cation exchange resin, and cations such as Ca ²⁺ ions and Mg ²⁺ ions in the raw water and Na ⁺ ions by the Na-type cation exchange resin. Are ion-exchanged to remove cations of hardness components such as Ca ²⁺ ions and Mg ²⁺ ions in the raw water. The anion removing device 3 is an anion removing device filled with a Cl-type anion exchange resin, and the Cl-type anion exchange resin allows SO ₄ ²⁻ ions, PO ₄ ³⁻ ions, NO ₃ ^{− in the} raw water. anions and Cl ions such as ^- an ion ion exchange. Then, anions such as SO ₄ ²⁻ ions, PO ₄ ³⁻ ions, and NO ₃ ⁻ ions in the raw material water, which are binding targets of cations of hardness components such as Ca 2 ⁺ ions and Mg 2 ⁺ ions in the raw material water, Remove. Further, the micro filter 6 and the activated carbon filter 7 remove iron, silica, chlorine and the like contained in the raw material water.

  Next, as shown in FIG. 1, the ozone water production apparatus 4 includes a solid electrolyte membrane 31, an anode side channel 34 provided on one side thereof, a cathode side channel 35 provided on the other side, and an anode side stream. The anode electrode 32 provided in the path 34 and the cathode electrode 33 provided in the cathode side channel 35 are configured. Then, the ozone water production apparatus 4 electrolyzes the raw material water supplied to the anode side channel 34 to generate electrolytic ozone water in the anode side channel 34. The solid electrolyte membrane 31 is made of a cation exchange membrane or the like that has the property of transmitting cations but not anions.

  The anode-side feed path 8 plays a role of feeding the raw material water that has passed through the activated carbon filter 7 into the anode-side flow path 34 via the water softener 1. The cathode-side feed path 9 plays a role of feeding the raw material water that has passed through the activated carbon filter 7 into the cathode-side flow path 35 via the water softener 2 and the anion removing device 3. The flow rate adjustment valve 10 plays a role of adjusting the feed amount of the raw material water to the anode side feed path 8, and the flow rate control valve 11 controls the feed amount of the raw material water to the cathode side feed path 9. Play a role to coordinate.

  Next, the operation of the ozone water production facility 100 of the present embodiment (the ozone water production method using this facility) will be described with reference to FIG.

First, from the water supply port 5, iron, silica, chlorine, ^{Ca 2+} and ^{Mg 2+,} etc. _{^{cations, SO 4 2-, PO 4 3-}} , NO 3 - raw water containing anions such as, producing ozone water It is supplied to the facility 100, and iron, silica, chlorine and the like are removed through the micro filter 6 and the activated carbon filter 7.

Next, the flow regulating valves 10 and 11 are opened. Then, the raw water is supplied to the water softener 1 filled with the Na-type cation exchange resin via the anode side supply path 8. Then, the Na-type cation exchange resin in the water softener 1, after the cations Ca ²⁺ and Mg ²⁺ and the like of the raw water was Na ⁺ ion and the ion exchange, the ozone water production apparatus through the anode-side feeding path 8 4 is fed into the anode-side flow path 34. Then, the raw material water fed into the anode-side channel 34 is electrolyzed, whereby ozone water and Na ⁺ ions are discharged from the anode-side channel 34.

Further, at the same time when the raw material water is supplied to the anode side supply path 8, the raw material water is supplied to the water softener 2 filled with Na-type cation exchange resin via the cathode side supply path 9. . Then, similarly to the water softener 1, after the cation such as Ca ²⁺ and Mg ^{2+ in the} raw water is ion-exchanged with Na ⁺ ions by the Na-type cation exchange resin in the water softener 2, the cathode-side feed path 9 The raw material water is fed to the anion removing device 3 via. Then, anion such as SO ₄ ²⁻ , PO ₄ ³⁻ , NO ₃ ^−, etc. in the raw water is ion-exchanged with Cl ⁻ ions by the Cl-type anion exchange resin in the anion removing device 3, and then sent to the cathode side It feeds into the cathode side flow path 35 of the ozone water production apparatus 4 through the supply path 9. Then, the raw material water fed into the cathode-side channel 35 is electrolyzed, whereby an aqueous solution containing H 2 or NaCl or an aqueous solution containing NaOH is discharged from the cathode-side channel 35.

Here, in the water softener 1 and the water softener 2, Ca ²⁺ ions and Mg ²⁺ ions are exchanged with Na ⁺ ions and removed from the raw water by the following reaction.
2R—SO ₃ Na + Ca ²⁺ → (R—SO ₃ ) ₂ Ca + 2Na ⁺
2R—SO ₃ Na + Mg ²⁺ → (R—SO ₃ ) ₂ Mg + 2Na ⁺
(R-SO ₃ Na represents Na-type cation exchange resin)

In the above formula, a resin having a sulfonic acid group as an exchange group (R—SO ₃ Na) was mentioned as an example of the Na type ion exchange resin, but the Na type cation exchange resin that can be used in the present invention is the same. As long as it has the above functions, it is not particularly limited.

Since the replaced new Na ⁺ ions from the ion exchange Ca ²⁺ ions, and Mg ²⁺ ions and the like, electric conductivity of the raw water it remains maintained.

Further, in the anion removal device 3, by such reactions below, _SO ^{4 2-ions,} _PO ^{4 3-} ions, NO ₃ ^- removed from being exchanged with ions raw water ^- anions Cl and ion Is done.
2R—N (CH ₃ ) Cl + SO ₄ ²⁻
→ (RN (CH ₃ )) ₂ SO ₄ + 2Cl ⁻
RN (CH ₃ ) Cl + NO ₃ ⁻
→ RN (CH ₃ ) NO ₃ + Cl ⁻
(R—N (CH ₃ ) Cl represents Cl type anion exchange resin)

In the above formula, RN (CH ₃ ) Cl was mentioned as an example of the Cl-type ion exchange resin, but the Cl-type anion exchange resin that can be used in the present invention has the same function. Well, not particularly limited.

In addition, since Cl ⁻ ions are newly replaced with SO ₄ ²⁻ ions, PO ₄ ³⁻ ions, NO ₃ ⁻ ions and the like by the ion exchange, the electrical conductivity of the raw material water remains maintained.

Here, using the ozone water production facility 100 shown in FIG. 1, the raw water on the entry side of the water softener 1 or the water softener 2 and the raw water on the outlet side of the water softener 1 or the water softener 2 and the anion removing device FIG. 2 shows the results of examining the amount of Mg ²⁺ ions, Ca ²⁺ ions, Cl ⁻ ions, NO ₃ ⁻ ions, PO ₄ ³⁻ ions, and SO ₄ ²⁻ ions contained in the raw material water on the outlet side of No. ³ . In addition, the water flow rate to the anode side feed path 8 is 3 L / min, and the water flow rate to the cathode side feed path 9 is 0.7 L / min. Moreover, the density | concentration of the ozone water produced | generated with the ozone water manufacturing apparatus 4 is 10 mg / L.

As shown in FIG. 2, the raw water supplied from the water supply port 5 passes through the water softener 1 or the water softener 2, so that the Mg ²⁺ ions decrease from 9.18 mg / L to <0.01 mg / L. Ca ²⁺ ions are decreased from 13 mg / L to 0.9 mg / L. However, Ca ²⁺ ions remain at 0.9 mg / L. Here, “<0.01 mg / L” indicates a value smaller than 0.01 mg / L.

In addition, the raw water supplied from the water supply port 5 is passed through the water softener 2 and the anion removing device 3, so that NO ₃ ⁻ ions are reduced from 0.4 mg / L to <0.1 mg / L. PO ₄ ³⁻ ions have decreased from 0.5 mg / L to <0.1 mg / L, and SO ₄ ²⁻ ions have decreased from 110 mg / L to <0.1 mg / L. Note that the Cl ⁻ ion increases from 56 mg / L to 150 mg / L because the ion exchange is performed by the Cl type anion exchange resin of the anion removing device 3 and the Cl ⁻ ion is released into the raw water. This is because.

  Furthermore, the result of having compared the value of the electrolysis current in the ozone water manufacturing apparatus 4 with progress of time with the apparatus (refer patent 3269784) of the conventional ozone water is shown in FIG. A solid line A in FIG. 3 indicates a change in electrolysis current (current value) in the ozone water production apparatus 4 in the ozone water production facility 100 according to the present embodiment. Moreover, the continuous line B of FIG. 3 has shown the change of the electrolysis current (electric current value) in the apparatus (refer patent 3269784) of the conventional ozone water manufacturing. In addition, the horizontal axis of FIG. 3 has shown the elapsed time after starting operation of the ozone water manufacturing apparatus 4 and the apparatus which manufactures the conventional ozone water. Moreover, the vertical axis | shaft has shown the value (electric current value (A)) of the electrolysis current in the ozone water manufacturing apparatus 4 and the apparatus which manufactures the conventional ozone water. Here, the value of the electrolysis current (current value (A)) is a value necessary for generating ozone water at an ozone water concentration of 10 mg / L.

As indicated by the solid line B in FIG. 3, the current value of the conventional one increases with time. That is, with the passage of time, the electrolysis current value required to generate ozone water at an ozone water concentration of 10 mg / L increases, indicating that the ozone water generating ability is reduced. This is because even if the raw water is passed through a water softener equipped with a cation exchange resin, trace amounts of cations such as Ca ²⁺ and Mg ²⁺ remain in the raw water. Residual cations such as Ca ²⁺ and Mg ²⁺ are combined with negative ions such as SO ₄ ²⁻ , PO ₄ ³⁻ and NO ₃ ⁻ on the cathode side, and CaSO ₄ , MgSO _4, etc. By depositing and adhering compounds.

On the other hand, as indicated by the solid line A in FIG. 3, according to the ozone water production facility 100 of the present embodiment, the current value does not increase even when time elapses and shows a substantially stable value. That is, with the passage of time, the electrolysis current value required to generate ozone water at an ozone water concentration of 10 mg / L does not increase, indicating that the ozone water generating ability is stable. This is because when the raw water is passed through the water softener 2, even if a small amount of cations such as Ca ²⁺ and Mg ²⁺ remain in the raw water, By removing anions such as SO ₄ ²⁻ , PO ₄ ³⁻ , NO ₃ ^{− and the} like, precipitation and adhesion of compounds such as CaSO ₄ and MgSO ₄ to the cathode electrode 33 and the solid electrolyte membrane 31 can be prevented. Because it is.

  As described above, according to the ozone water production facility 100, ozone water can be produced by electrolyzing the raw water from which cations and anions have been removed by the anion removing device 3 and the water softeners 1 and 2. . For this reason, even if a small amount of cations remain in the raw water from which the cations have been removed, the negative electrode 33 in the ozone water production apparatus 4 is removed by removing the anions that are to be combined with such cations. Precipitation / adhesion of a compound in which a cation and an anion are bound to each other can be prevented. And by preventing precipitation and adhesion of compounds, it is possible to prevent a decrease in the electrolysis performance of the ozone water production apparatus 4 and to prevent a decrease in the ability to generate ozone water.

In general, when the ionized substance in the raw material water decreases, the electric conductivity of the raw material water may decrease and the electrolysis performance may decrease. Therefore, according to the ozone water production facility 100, the cation (anion) previously adsorbed on the cation exchange resin (anion exchange resin) and the Ca ²⁺ adsorbed and removed by the cation exchange resin (anion exchange resin). And cations such as Mg ²⁺ (anions such as SO ₄ ²⁻ , PO ₄ ³⁻ , NO ₃ ⁻ ) are exchanged. For this reason, even if the cation (anion) in the raw material water is adsorbed and removed, the cation (anion) previously adsorbed on the cation exchange resin (anion exchange resin) is contained in the raw material water instead. It is possible to prevent a decrease in ionized substances in the raw material water and prevent a decrease in electrical conductivity. Note that Na ⁺ (salt type) or the like may be used as the cation previously adsorbed on the cation exchange resin. Further, Cl ⁻ (salt type) or the like may be used as the anion previously adsorbed on the anion exchange resin.

In the ozone water production facility 100, the cation exchange resin is a Na-type cation exchange resin, and the anion exchange resin is a Cl-type anion exchange resin. According to this structure, Na ⁺ cation exchange resin cations such as Ca ²⁺ and Mg ^{2+ in the} raw material water and Na ⁺ are ion-exchanged, and Cl type anion exchange resin makes SO ₄ ²⁻ , PO 4 ^_3-, NO ₃ ^- anions and Cl such as ^- and by ion-exchange, while maintaining the ionic substance of the material in water it is possible to prevent a decrease in electric conductivity. In addition, since the ions discharged after the ion exchange are hardly compounded and are water-soluble Na ⁺ and Cl ⁻ , the compound can be made difficult to deposit and adhere to the cathode electrode 33 or the solid electrolyte membrane 31.

(Second Embodiment)
FIG. 4 is a block diagram showing an ozone water production facility 200 according to the second embodiment of the present invention. In the following description, the same components as those in the ozone water production facility 100 according to the first embodiment described above are denoted by the same reference numerals, and the description thereof is omitted as appropriate.

  The Na-type cation exchange resin filled in the water softener 1 and the Cl-type anion exchange resin filled in the anion removing device 3 will break through if they are used for a long time. Regeneration is performed by passing an aqueous sodium chloride solution through the exchange resin and the Cl-type anion exchange resin. Therefore, if the Na-type cation exchange resin is regenerated using an NaCl aqueous solution, and the drainage is also used for the regeneration of the Cl-type anion exchange resin, the sodium chloride (NaCl) aqueous solution can be effectively used. .

  Specifically, as shown in FIG. 4, as in the first embodiment, the ozone water production facility 200 includes a water softener 1, an anion removal device 3, a micro filter 6, an activated carbon filter 7, an ozone water production device 4, an anode. The anode side feed path 8 for feeding the raw material water into the side channel 34 via the water softener 1, and the raw material water in the cathode side channel 35 via the water softener 1 and the anion removing device 3 Is provided with a cathode-side feeding path 9 for feeding the.

  Furthermore, as shown in FIG. 4, the ozone water production facility 200 in the second embodiment regenerates the Na-type cation exchange resin using an aqueous NaCl solution, and then regenerates the drainage of the Cl-type anion exchange resin. As a configuration used for the above, mainly a sodium chloride aqueous solution tank 201 for storing a sodium chloride (NaCl) aqueous solution, a regeneration drainage tank for storing a drainage liquid after regenerating the Na-type cation exchange resin using the NaCl aqueous solution. 202 (sodium chloride aqueous solution supply device) is added.

  Further, the ozone water production facility 200 connects a path 217 for feeding the sodium chloride aqueous solution from the sodium chloride aqueous solution tank 201 to the water softener 1, a pump 203 for pumping the sodium chloride aqueous solution, and the water softener 1 and the regeneration drainage tank 202. A route 214, a drainage route 204, a route 205 connecting the water supply port 5 and the anion removing device 3, a drainage route 206, a route 216 connecting the regeneration drainage tank 202 and the anion removal device 3, and the regeneration drainage tank 202. Pump 210 for pumping up the stored wastewater, solenoid valve 207, solenoid valve 209, flow rate regulating valve 211, three-way solenoid valve 208, three-way solenoid valve 215 for controlling the opening and closing of each route, the back flow of raw water or wastewater in each route Check valves 212 and 213 are provided to prevent this. In addition, these function as a sodium chloride aqueous solution supply apparatus.

  Next, the operation of the ozone water production facility 200 of the present embodiment (the ozone water production method using this facility) will be described with reference to FIG. The following description will focus on the regeneration process of the Na-type cation exchange resin filled in the water softener 1 and the Cl-type anion exchange resin filled in the anion removing device 3.

  First, the electromagnetic valve 207 and the electromagnetic valve 209 are closed so that the three-way electromagnetic valve 208 is in communication with the drainage path 204. In this state, the interior of the water softener 1 is washed with the raw material water fed from the water supply port 5 (first washing process). The raw water used for cleaning is drained from the drainage path 204. Thereby, impurities unnecessary for the regeneration process of the Na-type cation exchange resin filled in the water softener 1 are removed.

  Next, the three-way solenoid valve 208 is brought into a state leading to the path 214. In this state, the sodium chloride aqueous solution stored in the sodium chloride aqueous solution tank 201 is supplied to the water softener 1 by the pump 203 (regeneration process of the Na-type cation exchange resin). At this time, the sodium chloride aqueous solution passes through the Na-type cation exchange resin.

As a result, the following reaction occurs and the Na-type cation exchange resin is regenerated.
_{(R-SO 3) 2 Ca} + 2NaCl
→ 2R-SO ₃ Na + Ca ²⁺ + 2Cl ⁻
_{(R-SO 3) 2 Mg} + 2NaCl
→ 2R—SO ₃ Na + Mg ²⁺ + 2Cl ⁻

Then, after playing Na-type cation-exchange resin using aqueous sodium chloride solution as described above, the drainage ^- storing chlorine (Cl waste solution containing ions) to the reproduction drainage tank 202. When a predetermined amount of drainage is stored in the regeneration drainage tank 202, the supply of the sodium chloride aqueous solution from the sodium chloride aqueous solution tank 201 to the water softener 1 is stopped.

  Next, the three-way solenoid valve 208 is again connected to the drainage path 204. In this state, the interior of the water softener 1 is washed again by the raw material water fed from the water supply port 5 (second washing process). The raw water used for cleaning is drained from the drainage path 204. Thereby, the sodium chloride which remained in the water softener 1 is removed.

  Next, the electromagnetic valve 207 is opened, the three-way electromagnetic valve 208 is closed, and the three-way electromagnetic valve 215 is connected to the drainage path 206. In this state, the inside of the anion removing device 3 is cleaned by the raw water supplied from the water supply port 5 via the path 205 (third cleaning process). The raw water used for cleaning is drained from the drainage path 206. Thereby, impurities unnecessary for the regeneration process of the Cl-type anion exchange resin filled in the anion removing device 3 are removed.

Next, the electromagnetic valve 207 is closed. In this state, the pump 210 is used to feed the drainage stored in the regeneration drainage tank 202 to the anion removing device 3 via the path 216 (Cl type anion exchange resin regeneration process). At this time, the drainage liquid containing Cl ⁻ ions passes through the Cl-type anion exchange resin.

As a result, the following reaction occurs to regenerate the Cl-type anion exchange resin.
(RN (CH ₃ )) ₂ SO ₄ + 2Cl ⁻
→ 2R-N (CH ₃ ) Cl + SO ₄ ²⁻
RN (CH ₃ ) NO ₃ + Cl ⁻
→ RN (CH ₃ ) Cl + NO ₃ ⁻

Then, after the Cl-type anion exchange resin is regenerated using the drainage containing Cl ⁻ ions as described above, the drainage used for the regeneration of the Cl-type anion exchange resin is drained from the drainage path 206. Is done. When the drainage in the regeneration drainage tank 202 is reduced to a predetermined amount, the supply of drainage from the regeneration drainage tank 202 to the anion removing device 3 is stopped.

Next, the electromagnetic valve 207 is opened again. In this state, the inside of the anion removing device 3 is cleaned again by the raw water supplied from the water supply port 5 (fourth cleaning process). The raw water used for cleaning is drained from the drainage path 206. Thereby, the drainage liquid containing Cl ⁻ ions remaining in the anion removing device 3 is removed. Thus, the regeneration process for the Na-type cation exchange resin filled in the water softener 1 and the Cl-type anion exchange resin filled in the anion removing device 3 is completed.

  Thereafter, the paths of the solenoid valve 207, the three-way solenoid valve 208, and the three-way solenoid valve 215 to the drainage path 206 are closed, and the solenoid valve 209 is opened. Further, the flow rate adjusting valve 211 is adjusted to a predetermined opening and then opened. In this state, raw material water that has passed through the microfilter 6, the activated carbon filter 7, and the water softener 1 is fed into the anode-side flow path 34, and the microfilter 6, the activated carbon filter 7, the water softener 1, and the anion removing device 3 are supplied. The raw water passing through is fed into the cathode-side channel 35 and electrolyzed, whereby ozone water is discharged from the anode-side channel 34.

According to the ozone water production facility 200 of the second embodiment, the Na-type cation exchange resin is regenerated by Na ⁺ ions of a sodium chloride (NaCl) aqueous solution, and the Cl-type anion exchange resin is a sodium chloride (NaCl) aqueous solution. Regenerated by Cl ⁻ ions. For this reason, the sodium chloride aqueous solution necessary for the regeneration of the Na-type cation exchange resin and the Cl-type anion exchange resin can be supplied in series to the water softener 1 and the anion removal device 3. It is possible to reduce consumption and increase efficiency. Further, the amount of drainage discharged from the ozone water production facility 200 can be reduced. In addition, by using a sodium chloride aqueous solution for the regeneration of the cation exchange resin and the anion exchange resin, it is not necessary to use different types of solutions, and the management can be simplified.

(Modification)
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.

  For example, in the first embodiment, the two water softeners 1 and 2 are used. However, as shown in FIG. 5, the ozone water production facility 101 may be configured by one water softener 102. In this case, the raw water from which the cations have been removed by the water softener 102 is fed to both the cathode side channel 35 via the anode side channel 34 and the anion removing device 3.

  In this case, in the ozone water production facility 101, the water softener 102 (cation removing device) and the anion removing device 3 are provided in the cathode side feeding path 106 for feeding the raw material water into the cathode side channel 35. In addition, since the water softener 102 is provided in the anode-side feed path 105 that feeds the raw material water into the anode-side flow path 34, the removal of anions is the raw material supplied into the cathode-side flow path 35. Only for water. For this reason, since the anion removal is not performed on the raw material water supplied to the anode side flow path 34, the anion removing device 3 can be made compact. Further, since the amount of raw water passing through the anion removing device 3 can be limited to an amount necessary for electrolysis in the cathode side flow path 35, the life of the anion exchange resin filled in the anion removing device 3 is extended. be able to.

  Moreover, in the said embodiment, although the cation exchange resin is used for the water softeners 1 and 2 (cation removal apparatus) and the anion exchange resin is used for the anion removal apparatus 3, the ozone water production apparatus 4 is used. What is necessary is just to remove the cation and the anion which produce the compound which deposits on the cathode electrode 33. For example, a cation exchange membrane and an anion exchange membrane, a metal that adsorbs a cation or anion, an ion removal filter having a network corresponding to the size of the cation or anion to be removed, and the like can be mentioned.

DESCRIPTION OF SYMBOLS 1, 2 Water softener 3 Anion removal apparatus 4 Ozone water production apparatus 8 Anode side feed path 9 Cathode side feed path 31 Solid electrolyte membrane 32 Anode electrode 33 Cathode electrode 34 Anode side flow path 35 Cathode side flow path 100, 200 Ozone water production equipment 201 Sodium chloride aqueous solution tank 202 Recycled drainage tank

Claims (10)

A cation removing device for removing cations in the raw water,
An anion removing device for removing anions in the raw material water;
An ozone water production device for producing ozone water by electrolyzing the raw water from which cations and anions have been removed by the cation removal device and the anion removal device;
An ozone water production facility characterized by comprising: The ozone water production apparatus
A solid electrolyte membrane; an anode-side channel provided on one of the solid electrolyte membranes; a cathode-side channel provided on the other of the solid electrolyte membrane; an anode electrode provided in the anode-side channel; and the cathode side A cathode electrode provided in the flow path,
The cation removing device and the anion removing device are provided in the cathode side feeding path for feeding the raw water into the cathode side channel,
2. The ozone water production facility according to claim 1, wherein the cation removing device is provided in an anode side feeding path for feeding the raw water into the anode side flow path. The cation removing device has a cation exchange resin that ion-exchanges cations in raw water,
The said anion removal apparatus has an anion exchange resin which ion-exchanges the anion in raw material water, The ozone water manufacturing equipment of Claim 1 or 2 characterized by the above-mentioned. The cation exchange resin is a Na-type cation exchange resin,
The ozone water production facility according to claim 3, wherein the anion exchange resin is a Cl-type anion exchange resin. A sodium chloride aqueous solution tank for storing the sodium chloride aqueous solution;
The sodium chloride aqueous solution stored in the sodium chloride aqueous solution tank is supplied to one of the cation removing device and the anion removing device, the drainage is supplied to the other, the Na-type cation exchange resin and the A sodium chloride aqueous solution supply device for regenerating a Cl-type anion exchange resin;
The ozone water production facility according to claim 4, comprising: In the ozone water production method for producing ozone water by electrolyzing raw water with an ozone water production device,
A method for producing ozone water, comprising: a cation removal process for removing cations in the raw material water and an anion removal process for removing anions in the raw material water before electrolyzing the raw material water . The ozone water production apparatus includes a solid electrolyte membrane, an anode-side channel provided on one side of the solid electrolyte membrane, a cathode-side channel provided on the other side of the solid electrolyte membrane, and an inside of the anode-side channel A cathode electrode provided in the cathode-side flow path, and
In the cathode side flow path, the raw water from which cations and anions have been removed in the cation removal process and the anion removal process is electrolyzed, and in the anode side flow path, in the cation removal process. The ozone water production method according to claim 6, wherein the raw water from which the cations have been removed is electrolyzed to produce ozone water. In the cation removal process, the cation in the raw material water is ion-exchanged and removed by a cation exchange resin,
The method for producing ozone water according to claim 6 or 7, wherein in the anion removal process, anions in the raw material water are ion-exchanged with an anion exchange resin. The cation exchange resin is a Na-type cation exchange resin,
The method for producing ozone water according to claim 8, wherein the anion exchange resin is a Cl-type anion exchange resin. A sodium chloride aqueous solution is supplied to one of the Na-type cation exchange resin and the Cl-type anion exchange resin, and the effluent is supplied to the other to provide the Na-type cation exchange resin and the Cl-type anion exchange resin. The method for producing ozone water according to claim 9, comprising a regeneration process for regenerating the water.

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