JP2014079722A - Ozone water manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ozone water manufacturing method for efficiently manufacturing ozone water of a high concentration.SOLUTION: The provided ozone water manufacturing method is an ozone water manufacturing method for manufacturing ozone water 20a scheduled to be used at a use point following the dissolution of ozone into ultrapure water obtained by further treating water obtained from a primary pure water system 2 where an ultraviolet oxidation treatment of oxidizing the water obtained from the primary pure water system 2 with ultraviolet rays at an intensity yielding a hydrogen peroxide concentration of 15.0 μg/L or above, a hydrogen peroxide removal treatment of removing hydrogen peroxide from the water having undergone the ultraviolet oxidation treatment so as to realize a hydrogen peroxide concentration of 10.0 μg/L or below, and an ozone dissolving treatment of dissolving ozone into the water having undergone the hydrogen peroxide removal treatment so as to realize an eventual ozone concentration of 30 mg/L or above are performed and where carbon dioxide is dissolved into the water before the execution of the hydrogen peroxide removal treatment or after the execution of the hydrogen peroxide removal treatment and before the execution of the ozone dissolving treatment or during the ozone dissolving treatment.

Description

  The present invention relates to a method for producing ozone water in which ozone is dissolved at a high concentration in ultrapure water.

  In the manufacturing process of a semiconductor device (including a liquid crystal display device), a cleaning process is repeated on the substrate in order to remove organic substances, particles, and the like attached to the surface of the substrate. As the cleaning liquid used here, an organic solvent, an acid liquid, and the like are frequently used. Recently, ozone water having less environmental problems has begun to be used.

  The ozone water used in the semiconductor device manufacturing process is required to have a high ozone concentration from the viewpoint of reactivity and a high cleanness and no impurities due to the nature of the semiconductor device. In order to meet these requirements, the ozone water is usually manufactured by the following method.

  The ultrapure water production equipment includes a pretreatment system comprising a coagulation sedimentation device, a filter and a filtrate water tank, and a primary pure water system comprising an ion exchanger, a microfiltration membrane device, a reverse osmosis membrane device and a primary pure water tank. And a subsystem comprising a deaerator, an ultraviolet oxidizer, an ion exchanger, an ultrafiltration membrane device, and the like. Conventionally, ozone water is a sub-system of the ultrapure water production apparatus, and a part of the treated water extracted by the ultraviolet oxidizer is extracted and supplied to the ozone dissolving part, and this treated water is electrolyzed or generated by silent discharge. It was manufactured by dissolving ozone gas. When ozone gas is generated by electrolysis, ultrapure water is used as a raw material, and when ozone gas is generated by silent discharge, high-purity oxygen gas is mainly used as a raw material.

  Since ozone is an unstable substance and is prone to self-decomposition in water, a method for suppressing the self-decomposition of ozone in ozone water by adding TOC components and carbon dioxide in advance to ultrapure water that dissolves ozone gas, etc. (Patent Document 1: Japanese Patent No. 4827286).

  In addition, the ultraviolet sterilizer and the ultraviolet oxidizer used in the conventional ultrapure water production system generate about 20-100μg / L of hydrogen peroxide in ultrapure water, and this hydrogen peroxide significantly promotes ozonolysis. Therefore, there is also a method for suppressing self-decomposition at the time of water supply to a use point of ozone water having an ozone water concentration of 10 mg / L or less by controlling the hydrogen peroxide contained in the ultrapure water to a specific concentration or less. (Patent Document 2: Japanese Patent No. 3734207).

Japanese Patent No. 4827286 (Claims) Japanese Patent No. 3734207 (Claims)

  Ozone water is used only for cleaning, and recently it is considered to be applied to resist stripping. The ozone concentration of ozone water used for simple cleaning is about 5 mg / L, whereas the ozone concentration of ozone water used for resist stripping is usually 30 mg / L or more, 50 mg / L or more, or It may reach 100 mg / L.

  However, the conventional ozone water production method as described above does not produce high-concentration ozone water. For example, Patent Document 2 only describes that ozone water having a concentration of 10.0 mg / L or less is produced by controlling hydrogen peroxide contained in ultrapure water to a specific concentration or less. There is no specific disclosure about producing high-concentration ozone water exceeding / L.

  Therefore, an object of this invention is to provide the manufacturing method of ozone water for manufacturing high concentration ozone water efficiently.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, ozone water decomposes under the influence of dissolved hydrogen peroxide. (1) When the ozone concentration reaches 30 mg / L or more, it is peroxidized. (2) Therefore, when the concentration of hydrogen peroxide in the water in which ozone is dissolved is high, high concentration ozone of 30 mg / L or more is dissolved in ultrapure water. Ozone sometimes decomposes at the time of dissolution, and the ozone generator output cannot be obtained unless the output of the ozone generator is higher than the expected output. (3) Hydrogen peroxide concentration It was found that the output of the ozone generator can be kept low when producing high-concentration ozone water by making the specific range within the range, and the present invention has been completed.

That is, the present invention relates to an ozone water production method for producing ozone water to be used at a use point by dissolving ozone in ultra pure water obtained by further processing water obtained by a primary pure water system.
An ultraviolet oxidation treatment in which the water obtained by the primary pure water system is subjected to ultraviolet oxidation at an intensity such that the concentration of hydrogen peroxide is 15.0 μg / L or more;
Removing hydrogen peroxide in the water subjected to the ultraviolet oxidation treatment to reduce the hydrogen peroxide concentration to 10.0 μg / L or less;
Ozone-dissolving treatment for dissolving ozone in the water subjected to the hydrogen peroxide removal treatment until the ozone concentration becomes 30 mg / L or more;
And
Dissolving the carbon dioxide before the hydrogen peroxide removal treatment, or after the hydrogen peroxide removal treatment and before the ozone dissolution treatment, or at the time of the ozone dissolution treatment;
An ozone water production method is provided.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of ozone water for manufacturing high concentration ozone water efficiently can be provided.

It is a schematic diagram which shows the example of the form of the ultrapure water manufacturing system with which the ozone water manufacturing method of this invention is implemented. It is a schematic diagram which shows the example of the form of the ultrapure water manufacturing system with which the ozone water manufacturing method of this invention is implemented. It is a schematic diagram which shows the example of the form of the ultrapure water manufacturing system with which the ozone water manufacturing method of this invention is implemented. 1 is a schematic diagram showing an ozone water production system used in Example 1. FIG. It is a schematic diagram which shows the ozone water manufacturing system used in the comparative example 1. It is a graph which shows the result of the piping transfer test of an Example and a comparative example.

The ozone water production method of the present invention is an ozone water production method for producing ozone water to be used at a use point by dissolving ozone in ultrapure water obtained by further processing water obtained by a primary pure water system.
An ultraviolet oxidation treatment in which the water obtained by the primary pure water system is subjected to ultraviolet oxidation at an intensity such that the concentration of hydrogen peroxide is 15.0 μg / L or more;
Removing hydrogen peroxide in the water subjected to the ultraviolet oxidation treatment to reduce the hydrogen peroxide concentration to 10.0 μg / L or less;
Ozone-dissolving treatment for dissolving ozone in the water subjected to the hydrogen peroxide removal treatment until the ozone concentration becomes 30 mg / L or more;
And
Dissolving the carbon dioxide before the hydrogen peroxide removal treatment, or after the hydrogen peroxide removal treatment and before the ozone dissolution treatment, or at the time of the ozone dissolution treatment;
Is a method for producing ozone water.
In the present specification, high-purity water that is generally not clearly defined and described in terms of pure water, ultra-pure water, and the like is collectively referred to as “ultra-pure water”.

  The ozone water production method of the present invention will be described with reference to FIGS. 1 to 3 are schematic views showing an example of an ultrapure water production system in which the ozone water production method of the present invention is implemented.

  In FIG. 1, the ultrapure water production system 22a is processed by a pretreatment system 1 in which raw water 5 is treated, a primary pure water system 2 in which treated water of the pretreatment system is treated, and a primary pure water system. And a subsystem 30a in which the resulting water 3 is treated. The sub-system 30a treats the water 3 obtained in the primary pure water system 2, and ultrapure water 21 (superpure water that does not dissolve ozone) and ozone that is ultrapure water in which high-concentration ozone is dissolved. A system for obtaining water 20a, an ultrapure water production line comprising a deaerator 31, an ultraviolet oxidizer 10, an ion exchanger 32a, and an ultrafiltration membrane device 13a; Branched from the ultrapure water production line in the latter stage, hydrogen peroxide removing means 11, ion exchanger 32b, carbon dioxide dissolving means 12, ultrafiltration membrane device 13b, ozone dissolving section 14, and ozone generator 15 And an ozone water production line. In the sub system 30a, the ultrapure water production line is connected in the order of deaerator 31 → ultraviolet oxidizer 10 → ion exchanger 32a → ultrafiltration membrane device 13a. In the ozone water production line, the ultra violet oxidizer 10 is branched from the subsequent stage, and is connected in the order of hydrogen peroxide removing means 11 → ion exchanger 32b → carbon dioxide dissolving means 12 → ultrafiltration membrane device 13b → ozone dissolving part 14. The generator 15 is connected.

  In the ultrapure water production system 22a shown in FIG. 1, the pretreatment system 1 includes a coagulation sedimentation device, a filter and a filtrate water tank, and the primary pure water system 2 includes an ion exchanger and a microfiltration membrane device. , Comprising a reverse osmosis membrane device and a primary pure water tank (the same applies to the ultrapure water production system 22b shown in FIG. 2 and the ultrapure water production system 22c shown in FIG. 3).

  In order to produce ultrapure water and ozone water using the ultrapure water production system 22a, first, the raw water 5 is treated by the pretreatment system 1, and the suspended substances and colloidal substances in the raw water 5 are removed and heat exchange is performed. After performing a process etc., the obtained treated water is processed with a primary pure water system, and the treated water 3 of a primary pure water system is obtained. Next, the water 3 obtained by the primary pure water system is treated by the deaerator 31 to degas oxygen gas, nitrogen gas, carbon dioxide gas, etc. in the pure water, and then the degassed pure water is removed. Then, an ultraviolet oxidation process for performing ultraviolet oxidation using the ultraviolet oxidizer 10 is performed. In this ultraviolet oxidation treatment, the ultraviolet oxidation is performed at such an intensity that the concentration of hydrogen peroxide in the water after the ultraviolet oxidation becomes 15.0 μg / L or more. Next, the water subjected to the ultraviolet oxidation treatment is treated with the ion exchanger 32a to deionize, and then the deionized water is treated with the ultrafiltration membrane device 13a to filter the fine particles. To obtain ultrapure water 21 (ultrapure water in which ozone is not dissolved). Then, for use at the use point (UP), the obtained ultrapure water 21 is fed to the use point (UP). Further, a part of the water subjected to the ultraviolet oxidation treatment is extracted from the liquid feed pipe connecting the ultraviolet oxidizer 10 and the ion exchanger 32 a and fed to the hydrogen peroxide removing means 11. Then, the extracted water, that is, the water subjected to the ultraviolet oxidation treatment is treated by the hydrogen peroxide removing means 11 to remove the hydrogen peroxide in the water, so that the hydrogen peroxide concentration is 10.0 μg / L or less. To remove hydrogen peroxide. Next, the water that has undergone the hydrogen peroxide removal treatment is treated by the ion exchanger 32b and deionized. Next, carbon dioxide is dissolved in the deionized water using the carbon dioxide dissolving means 12. At this time, the amount of carbon dioxide dissolved is adjusted so that the pH in water after dissolving carbon dioxide is about 2 to 6. Next, the water in which carbon dioxide is dissolved is treated using the ultrafiltration membrane device 13b, and fine particle removal treatment is performed to remove the fine particles by filtration. Next, an ozone dissolution process is performed in the ozone dissolution unit 14 to dissolve the ozone 17 generated by the ozone generator 15 in the water subjected to the fine particle removal process. In this ozone dissolution treatment, the output of the ozone generator 15, the ozone gas flow rate, and the like are adjusted so that the ozone concentration in the ozone water after ozone dissolution becomes 30 mg / L or more. In this way, ozone water 20a which is ultrapure water in which high-concentration ozone is dissolved is obtained. Then, for use at the use point (UP), the obtained ozone water 20a is fed to the use point (UP).

  In FIG. 2, the ultrapure water production system 22b is processed by the pretreatment system 1 in which the raw water 5 is treated, the primary pure water system 2 in which the treated water of the pretreatment system is treated, and the primary pure water system. And a subsystem 30b in which the obtained water 3 is treated. The subsystem 30b treats the water 3 obtained by the primary pure water system 2, and ultrapure water 21 (superpure water that does not dissolve ozone) and ozone that is ultrapure water in which high-concentration ozone is dissolved. A system for obtaining water 20b, an ultrapure water production line comprising a deaerator 31, an ultraviolet oxidizer 10, an ion exchanger 32a, and an ultrafiltration membrane device 13a; It branches from an ultrapure water production line in the latter stage, ion exchanger 32b, carbon dioxide dissolution means 12, hydrogen peroxide removal means 11, ultrafiltration membrane device 13b, ozone dissolution part 14, and ozone generator 15 And an ozone water production line. In the sub-system 30b, the ultrapure water production line is connected in the order of deaerator 31 → ultraviolet oxidizer 10 → ion exchanger 32a → ultrafiltration membrane device 13a. 10 is branched from an ion exchanger 32b → carbon dioxide dissolving means 12 → hydrogen peroxide removing means 11 → ultrafiltration membrane device 13b → ozone dissolving part 14, and ozone dissolving part 14 includes ozone. The generator 15 is connected.

  In order to produce ultrapure water and ozone water using the ultrapure water production system 22b, first, the raw water 5 is treated by the pretreatment system 1, and the suspended substances and colloidal substances in the raw water 5 are removed and heat exchange is performed. After performing a process etc., the obtained treated water is processed with a primary pure water system, and the treated water 3 of a primary pure water system is obtained. Next, the water 3 obtained in the primary pure water system is treated with the deaerator 31 to degas oxygen gas, nitrogen gas, carbon dioxide gas, etc. in the pure water, An ultraviolet oxidation process for performing ultraviolet oxidation using the ultraviolet oxidizer 10 is performed. In this ultraviolet oxidation treatment, the ultraviolet oxidation is performed at such an intensity that the concentration of hydrogen peroxide in the water after the ultraviolet oxidation becomes 15.0 μg / L or more. Next, the water subjected to the ultraviolet oxidation treatment is treated with the ion exchanger 32a to deionize, and then the deionized water is treated with the ultrafiltration membrane device 13a to filter the fine particles. To obtain ultrapure water 21 (ultrapure water in which ozone is not dissolved). Then, for use at the use point (UP), the obtained ultrapure water 21 is fed to the use point (UP). In addition, a part of the water subjected to the ultraviolet oxidation treatment is extracted from the liquid feed pipe connecting the ultraviolet oxidizer 10 and the ion exchanger 32a, and is sent to the ion exchanger 32b. Then, the extracted water, that is, the water subjected to the ultraviolet oxidation treatment is processed by the ion exchanger 32b and deionized. Next, carbon dioxide is dissolved in the deionized water using the carbon dioxide dissolving means 12. At this time, the amount of carbon dioxide dissolved is adjusted so that the pH in water after dissolving carbon dioxide is about 2 to 6. Next, water in which carbon dioxide is dissolved is treated by the hydrogen peroxide removing means 11 to remove hydrogen peroxide in the water, so that the hydrogen peroxide concentration is reduced to 10.0 μg / L or less. I do. Next, the water that has undergone the hydrogen peroxide removal treatment is treated using the ultrafiltration membrane device 13b, and the fine particle removal treatment is performed to remove the fine particles by filtration. Next, an ozone dissolution process is performed in the ozone dissolution unit 14 to dissolve the ozone 17 generated by the ozone generator 15 in the water subjected to the fine particle removal process. In this ozone dissolution treatment, the output of the ozone generator 15, the ozone gas flow rate, and the like are adjusted so that the ozone concentration in the ozone water after ozone dissolution becomes 30 mg / L or more. In this way, ozone water 20b, which is ultrapure water in which high-concentration ozone is dissolved, is obtained. Then, for use at the use point (UP), the obtained ozone water 20b is fed to the use point (UP).

  In FIG. 3, the ultrapure water production system 22c is processed by the pretreatment system 1 in which the raw water 5 is treated, the primary pure water system 2 in which the treated water of the pretreatment system is treated, and the primary pure water system. And a subsystem 30c in which the obtained water 3 is treated. The subsystem 30c treats the water 3 obtained by the primary pure water system 2, and ultrapure water 21 (superpure water that does not dissolve ozone) and ozone that is ultrapure water in which high-concentration ozone is dissolved. A system for obtaining water 20c, an ultrapure water production line comprising a deaerator 31, an ultraviolet oxidizer 10, an ion exchanger 32a, and an ultrafiltration membrane device 13a; Branched from the ultrapure water production line in the latter stage, the hydrogen peroxide removing means 11, the ion exchanger 32b, the ultrafiltration membrane device 13b, the ozone dissolving part 14, the ozone generator 15, and the carbon dioxide supply pipe 18 And an ozone water production line. In the sub-system 30c, the ultrapure water production line is connected in the order of deaerator 31 → ultraviolet oxidizer 10 → ion exchanger 32a → ultrafiltration membrane device 13a. In the ozone water production line, the ultra violet oxidizer 10 is branched from the subsequent stage and is connected in the order of hydrogen peroxide removing means 11 → ion exchanger 32b → ultrafiltration membrane device 13b → ozone dissolving unit 14, and ozone generator 15 is connected to ozone dissolving unit 14. A carbon dioxide supply pipe 18 is connected to a supply pipe for supplying the ozone 17 generated by the ozone generator 15 to the ozone dissolving section 14.

  In order to produce ozone water using the ultrapure water production system 22c, first, the raw water 5 is treated by the pretreatment system 1, and the suspended substances and colloidal substances in the raw water 5 are removed and heat exchange treatment is performed. Then, the treated water obtained is treated with a primary pure water system to obtain treated water 3 of the primary pure water system. Next, the water 3 obtained by the primary pure water system is treated by the deaerator 31 to degas oxygen gas, nitrogen gas, carbon dioxide gas, etc. in the water, and then the degassed water is subjected to ultraviolet oxidation. Using the vessel 10, an ultraviolet oxidation process for performing ultraviolet oxidation is performed. In this ultraviolet oxidation treatment, the ultraviolet oxidation is performed at such an intensity that the concentration of hydrogen peroxide in the water after the ultraviolet oxidation becomes 15.0 μg / L or more. Next, the water subjected to the ultraviolet oxidation treatment is treated with the ion exchanger 32a to deionize, and then the deionized water is treated with the ultrafiltration membrane device 13a to filter the fine particles. To obtain ultrapure water 21 (ultrapure water in which ozone is not dissolved). Then, for use at the use point (UP), the obtained ultrapure water 21 is fed to the use point (UP). Further, a part of the water subjected to the ultraviolet oxidation treatment is extracted from the liquid feed pipe connecting the ultraviolet oxidizer 10 and the ion exchanger 32 a and fed to the hydrogen peroxide removing means 11. And the extracted water, ie. Hydrogen peroxide removal treatment is performed by treating the water subjected to the ultraviolet oxidation treatment with the hydrogen peroxide removal means 11 to remove the hydrogen peroxide in the water so that the hydrogen peroxide concentration is 10.0 μg / L or less. Do. Next, the water that has undergone the hydrogen peroxide removal treatment is treated by the ion exchanger 32b and deionized. Next, the deionized water is treated using the ultrafiltration membrane device 13b, and a fine particle removal process is performed to remove the fine particles by filtration. Next, an ozone dissolution process for dissolving ozone and carbon dioxide is performed in the ozone dissolution unit 14 in the water subjected to the fine particle removal process. At this time, a mixture gas of ozone 17 generated by the ozone generator 15 and carbon dioxide supplied from the carbon dioxide supply pipe 18 is supplied to the ozone dissolving part 14. In this ozone dissolution treatment, the output of the ozone generator 15, the ozone gas flow rate, and the like are adjusted so that the ozone concentration in the ozone water after ozone dissolution becomes 30 mg / L or more. Further, during the ozone dissolution treatment, carbon dioxide is dissolved, but the amount of carbon dioxide dissolved is adjusted so that the pH in water after dissolving the carbon dioxide is about 2-6. In this way, ozone water 20c in which ozone is dissolved at a high concentration in ultrapure water is obtained. Then, in order to use at the use point (UP), the obtained ozone water 20c is fed to the use point (UP).

  As described above, the ozone water production method of the present invention is a production method of ozone water for producing high-concentration ozone water for use at a point of use such as a process for stripping a resist. This is an ozone water production method for obtaining ozone water which is ultrapure water in which ozone is dissolved at a high concentration by dissolving ozone in ultrapure water obtained by further processing water obtained by the system.

  1 to 3 show an ultrapure water production system for implementing an embodiment of the ozone water production method of the present invention, the ozone water production method of the present invention is not limited to this. It is not something.

  The ultraviolet oxidation treatment according to the ozone water production method of the present invention is a treatment for ultraviolet oxidation of water obtained by a primary pure water system, and the concentration of hydrogen peroxide in the water after ultraviolet oxidation treatment (ultraviolet oxidation treatment water). Is a treatment for performing ultraviolet oxidation at such an intensity that the concentration becomes 15.0 μg / L or more.

  The treated water to be treated by the ultraviolet oxidation treatment is pure water obtained by the primary pure water system. In the embodiment of the ultrapure water production apparatus shown in FIGS. 1 to 3, the water to be treated by the ultraviolet oxidation treatment is treated with raw water by a pretreatment system comprising a coagulating sedimentation apparatus, a filter and a filtrate water tank. The water obtained by treating the treated water with a primary pure water system comprising an ion exchanger, a microfiltration membrane device, a reverse osmosis membrane device and a primary pure water tank is water deaerated with a deaerator. However, the water to be treated by the ultraviolet oxidation treatment is not limited to this, and any water can be used as long as the ionic components, organic components, fine particles, etc. are removed in the primary pure water system. It is not limited whether it is obtained using treated water, and it is not limited what primary pure water system is used. In addition, the water that is subjected to ultraviolet oxidation treatment in the ultraviolet oxidation treatment is water obtained by the primary pure water system, but the water obtained by this primary pure water system is immediately after being treated by the primary pure water system. This means that the water has been treated in the primary pure water system before the ultraviolet oxidation treatment. In other words, the water obtained by the primary pure water system may be pure water immediately after being treated by the primary pure water system, or after being treated by the primary pure water system, if necessary. For example, water that has been subjected to treatment such as deaeration, deionization, and heat exchange may be used. In other words, in the ozone water production method of the present invention, the water obtained by the primary pure water system may be subjected to ultraviolet oxidation treatment as it is, or after being treated by the primary pure water system, for example, deaeration, An ultraviolet oxidation treatment may be performed after a treatment such as deionization or heat exchange.

  The treated water of the primary pure water system is treated water obtained by pretreating, for example, industrial water, city water, well water, or the like as raw water with a pretreatment system. Examples of the pretreatment system include those that perform, for example, agglomeration pressure flotation treatment, activated carbon adsorption treatment, iron removal manganese removal treatment, heat exchange treatment, and the like in addition to those described above. Moreover, as a primary pure water system, what performs a vacuum deaeration process, a decarbonation process, an ultraviolet sterilization process etc. other than what was mentioned above is mentioned, for example.

  The water obtained by the primary pure water system which is the water to be treated by the ultraviolet oxidation treatment is water having a resistivity of preferably 1 MΩ · cm or more, particularly preferably 10 to 18 MΩ · cm, and TOC is preferably Is 1 to 100 μg / L, particularly preferably 1 to 10 μg / L of water.

  In the ultraviolet oxidation treatment, the organic matter in the water is oxidized and decomposed by irradiating the water obtained by the primary pure water system as the water to be treated with ultraviolet rays. At this time, the ultraviolet rays are irradiated with such an intensity that the concentration of hydrogen peroxide in the water after ultraviolet oxidation treatment (ultraviolet oxidation water) is 15.0 μg / L or more, preferably 20.0 to 50.0 μg / L. To do. The reason why the concentration of hydrogen peroxide in the water after ultraviolet oxidation treatment is in the above range is that when the hydrogen peroxide concentration in the water after ultraviolet oxidation treatment is less than 15.0 μg / L, the ultraviolet intensity oxidizes and decomposes organic substances in water. This is because it is insufficient. Moreover, even if it exceeds 50.0 μg / L, the effect of oxidizing and decomposing organic substances in water can be obtained, but the invalid consumption of ultraviolet rays increases and the processing cost increases, so from the viewpoint of cost, 50.0 μg / L The following is preferred.

  The ultraviolet oxidation apparatus for performing the ultraviolet oxidation treatment is not particularly limited as long as it can decompose organic substances in the water to be treated, but is equipped with an ultraviolet lamp capable of irradiating the water to be treated with a wavelength of at least about 185 nm. Is preferred. The ultraviolet oxidation apparatus is more preferably an apparatus that can irradiate ultraviolet rays having a wavelength near 254 nm, which has a lower ability to decompose organic substances, in addition to ultraviolet rays having a wavelength around 185 nm. There is an ultraviolet irradiation apparatus that irradiates a wavelength near 254 nm but hardly irradiates a wavelength near 185 nm. This ultraviolet irradiation apparatus is mainly used for sterilization purposes and is generally called an ultraviolet sterilization apparatus. It is used in distinction. In the present invention, it is preferable to use an ultraviolet oxidizer that can strongly irradiate ultraviolet rays having a wavelength of around 185 nm and a wavelength of around 254 nm because organic substances can be decomposed satisfactorily. The ultraviolet lamp used in the ultraviolet oxidation apparatus is not particularly limited, but a low-pressure mercury lamp is preferable. In addition, examples of the ultraviolet oxidation apparatus include a distribution type and an immersion type, and among these, the distribution type is preferable in terms of high processing efficiency.

  The hydrogen peroxide removal treatment according to the ozone water production method of the present invention is performed by treating the water subjected to the ultraviolet oxidation treatment with the hydrogen peroxide removal means to remove the hydrogen peroxide in the water, and the hydrogen peroxide removal treatment This is a treatment for reducing the hydrogen peroxide concentration in the subsequent water (hydrogen peroxide removal treated water) to 10.0 μg / L or less.

  In the hydrogen peroxide removal process, the water that is subjected to the hydrogen peroxide removal process is the water that has been subjected to the ultraviolet oxidation process. The water that has been subjected to the ultraviolet oxidation process is immediately after the ultraviolet oxidation process is performed. This means that the water has been subjected to ultraviolet oxidation treatment before the hydrogen peroxide removal treatment. In other words, the water subjected to the ultraviolet oxidation treatment may be water immediately after the ultraviolet oxidation treatment is performed, or after the ultraviolet oxidation treatment is performed, for example, deionization or dissolution of carbon dioxide. Water that has been subjected to treatment such as membrane filtration may also be used. In other words, in the ozone water production method of the present invention, the hydrogen peroxide removal treatment may be performed immediately after the ultraviolet oxidation treatment, or after the ultraviolet oxidation treatment, for example, deionization, dissolution of carbon dioxide, membrane filtration The hydrogen peroxide removal treatment may be performed after performing such treatment.

  In the hydrogen peroxide removal treatment, the method for removing hydrogen peroxide from water includes (i) a method in which hydrogen peroxide in water subjected to ultraviolet oxidation treatment is adsorbed on an adsorbent, and (ii) ultraviolet oxidation treatment is performed. There is a method of decomposing hydrogen peroxide in water.

  Examples of the adsorbent used in the method (i) include activated carbon and synthetic adsorbent.

  Examples of the method (ii) include a method of bringing the water to be treated into contact with the hydrogen peroxide decomposition catalyst, a method of bringing the water to be treated into contact with activated carbon, and a method of heating the water to be treated.

  Examples of the hydrogen peroxide decomposition catalyst in the method (ii) include a granular ion exchange resin carrying a platinum group metal, a metal ion type granular cation exchange resin, and a non-granular organic material carrying a platinum group metal. Examples thereof include a non-granular organic porous ion exchanger on which a porous body or a platinum group metal is supported. These hydrogen peroxide decomposition catalysts will be described later. Hereinafter, the non-particulate organic porous body on which the platinum group metal is supported is also referred to as a platinum group metal-supported non-particulate organic porous body, and the non-particulate organic porous ion exchanger on which the platinum group metal is supported, Also described as a platinum group metal-supported non-particulate organic porous ion exchanger.

  In the hydrogen peroxide removal treatment, the hydrogen-oxidized water is treated by the hydrogen peroxide removal means to remove the hydrogen peroxide in the water, and the hydrogen peroxide concentration in the water after the hydrogen peroxide removal treatment is reduced. 10.0 μg / L or less, preferably 2.0 μg / L or less, particularly preferably 1.0 μg / L or less. When the hydrogen peroxide concentration in the water after the hydrogen peroxide removal treatment is in the above range, the production efficiency of ozone water is increased.

As a method for quantifying low-concentration hydrogen peroxide in pure water, a known phenol phthaline method, for example, the method described in JP-B-56-54582 can be mentioned. Specifically, 30 ml of a test solution containing hydrogen peroxide was accurately collected in a beaker, 0.3 ml of a 4 × 10 ⁻³ M phenolphthalin alkaline solution was added, and a 4 × 10 ⁻⁴ M copper sulfate solution was added. Add 3 ml, stir gently and let stand for a few minutes. The solution exhibiting a pinkish red color is transferred to a colorimetric cell having an optical path length of 50 mm, and the absorbance is measured by spectroscopic analysis at a wavelength of 540 nm. From the absorbance-hydrogen peroxide concentration calibration curve prepared in advance based on the measured absorbance. What is necessary is just to determine the density | concentration of hydrogen peroxide. The lower limit of detection of hydrogen peroxide in this method is 1 mg / L.

  The ozone dissolution treatment according to the ozone water production method of the present invention is a treatment for dissolving ozone in the water subjected to the hydrogen peroxide removal treatment until the ozone concentration becomes 30 mg / L or more.

  In the ozone dissolution treatment, water in which ozone is dissolved is water that has been subjected to hydrogen peroxide removal treatment, but water that has undergone this hydrogen peroxide removal treatment has been subjected to hydrogen peroxide removal treatment. It does not mean water immediately after, but means water that has been subjected to hydrogen peroxide removal treatment before the ozone dissolution treatment. In other words, the water that has undergone the hydrogen peroxide removal treatment may be water immediately after the hydrogen peroxide removal treatment, or after the hydrogen peroxide removal treatment, Water that has been subjected to treatments such as ion dissolution, carbon dioxide dissolution, and membrane filtration may also be used. In other words, in the ozone water production method of the present invention, ozone dissolution treatment may be performed immediately after the hydrogen peroxide removal treatment, or after the hydrogen peroxide removal treatment, for example, deionization, carbon dioxide dissolution, Ozone dissolution treatment may be performed after treatment such as membrane filtration.

  In the ozone dissolution treatment, ozone generated by the ozone generator is supplied to the ozone dissolution portion, and ozone is dissolved in the water subjected to the hydrogen peroxide removal treatment in the ozone dissolution portion.

  The ozone generator is not particularly limited, and examples thereof include an ozone generator by a silent discharge method, an electrolysis method, or the like. In the silent discharge method ozone generator, if only high-purity oxygen gas is used as the raw material gas, the expected performance of the ozone generator is not exhibited, and the ozone concentration in the generated ozone gas is significantly reduced. is there. In order to reduce the ozone gas concentration in the ozone generator, a small amount of nitrogen gas is added to high-purity oxygen gas as a conventional raw material gas.

  The method of dissolving ozone generated by the ozone generator in water that has been subjected to hydrogen peroxide removal treatment in the ozone dissolving section is not particularly limited, and for example, the water to be treated is passed through a gas permeable membrane. A method of dissolving a film by injecting ozone gas, a method of bubbling ozone gas into the water to be treated, a method of dissolving ozone gas through the ejector in the water to be treated, and a pump for supplying the water to be treated to the gas dissolution tank For example, ozone gas is supplied to the upstream side and dissolved by stirring in the pump. As the gas permeable membrane used for the membrane dissolution method, a fluororesin-based hydrophobic porous membrane that can withstand the strong oxidizing power of ozone is suitable, but is not limited thereto.

  In the ozone dissolution treatment, ozone is dissolved in the water subjected to the hydrogen peroxide removal treatment until the ozone concentration becomes 30 mg / L or more, preferably 50 mg / L or more, particularly preferably 100 mg / L or more. In addition, although the upper limit of ozone concentration is suitably selected according to a use purpose, ozone water manufacturing cost, etc., it is usually 300 mg / L or less.

  In the ozone water production method of the present invention, carbon dioxide is dissolved before the hydrogen peroxide removal treatment, or carbon dioxide is dissolved after the hydrogen peroxide removal treatment and before the ozone dissolution treatment. Alternatively, carbon dioxide is dissolved together with ozone during ozone dissolution treatment.

By making carbon dioxide coexist in ozone water, decomposition of ozone is suppressed.
Such an effect of suppressing the decomposition of ozone is an effect of carbonate ions or an effect of making pH acidic. When carbon dioxide is dissolved in water to be treated (water in which carbon dioxide is dissolved), the pH of the water after dissolution is less than 7, preferably about 2 to 6, particularly preferably about 4 to 6. Dissolve carbon dioxide in treated water. Examples of the method for dissolving carbon dioxide in the water to be treated include bubbling carbon dioxide in the water to be treated, mixing with a line mixer, and dissolving a membrane with a gas permeable membrane. Gas-permeable membranes used for membrane dissolution are non-porous membranes such as polydimethylsiloxane, polyolefin, and polysulfone; hydrophobic porous membranes such as fluororesin, polyethylene, and polypropylene are modularized into hollow fibers and spirals. And the like.

  The dissolution of carbon dioxide in the water to be treated can be performed simultaneously with the ozone dissolution treatment. As a method of dissolving carbon dioxide simultaneously with ozone in the water to be treated (hydrogen peroxide-removed treated water), a method of supplying a mixed gas of ozone and carbon dioxide to the ozone dissolving part can be mentioned.

  In the ozone water production method of the present invention, after the hydrogen peroxide removal treatment and before the ozone dissolution treatment, the fine particle removal treatment for removing the fine particles in the water by filtration is performed. This is preferable in that fine particles that may be mixed in from the hydrogen peroxide removing means can be removed. Examples of the fine particle removing means for removing fine particles by filtration include membrane treatment devices such as a microfiltration membrane device and an ultrafiltration membrane device. As the microfiltration membrane, an organic membrane having pores having a pore diameter of about 0.1 to 1 μm is used. For the ultrafiltration membrane, a polysulfone membrane having a fractional molecular weight of about 3,000 to 10,000, a cellulose acetate membrane or the like is used. As the module shape in the microfiltration membrane device or the ultrafiltration membrane device, a hollow fiber shape, a spiral shape, a tubular shape, a flat membrane shape, or the like is used.

  In the ozone water production method of the present invention, further, if necessary, the suspended matter removal treatment, the ionic substance removal treatment, the sterilization treatment, the organic matter removal treatment, the fine particle removal treatment, the deaeration treatment, etc. Can be combined.

  The ozone water obtained by the ozone water production method of the present invention is ultrapure water in which high-concentration ozone is dissolved. The ozone concentration of ozone water obtained by the ozone water production method of the present invention is 30 mg / L or more, preferably 50 mg / L or more, particularly preferably 100 mg / L or more. In addition, although the upper limit of ozone concentration is suitably selected according to a use purpose, ozone water manufacturing cost, etc., it is usually 300 mg / L or less.

  If the ozone concentration in the ozone water is as high as 30 mg / L or higher, the decomposition of ozone due to the influence of hydrogen peroxide present in the ozone water will be significantly increased. When water is dissolved, if there is a lot of hydrogen peroxide in the water, ozone will be decomposed in large quantities. If the output of the ozone generator is not set higher than the expected output, ozone water of the desired concentration can be obtained. Absent. Note that the expected output refers to the output of the ozone generator necessary for generating the amount of ozone necessary for obtaining ozone water having a target concentration when there is no decomposition of ozone.

  Therefore, in the ozone water production method of the present invention, water whose hydrogen peroxide concentration has become 15.0 μg / L or more by the ultraviolet oxidation treatment is reduced to 10. The ozone concentration in the water to be treated is 30 mg / L or more, preferably 50 mg in the ozone dissolution treatment by adjusting it to 0 μg / L or less, preferably 2.0 μg / L or less, particularly preferably 1.0 μg / L or less. / L or higher, particularly preferably, when dissolving until it is 100 mg / L or higher, the output of the ozone generator can be lowered, that is, the production efficiency of ozone water can be increased.

  On the other hand, when the ozone concentration in the ozone water is a low concentration of about 10 mg / L or less, the decomposition of ozone due to the influence of hydrogen peroxide present in the ozone water is not so large. When dissolving ozone having a low concentration of about or less, if the output of the ozone generator is set to the same level or slightly higher than the expected output, ozone water of the target concentration can be obtained.

  In addition, when the ozone concentration in the ozone water is as high as 30 mg / L or more, the decomposition of ozone due to the influence of hydrogen peroxide present in the ozone water becomes remarkably large. Therefore, in ozone water having an ozone concentration of 30 mg / L or more When a large amount of hydrogen peroxide is present in the ozone water, the decomposition rate of ozone after production is remarkably increased.

  Therefore, in the ozone water production method of the present invention, water whose hydrogen peroxide concentration has become 15.0 μg / L or more by the ultraviolet oxidation treatment is reduced to 10. 0 μg / L or less, preferably 2.0 μg / L or less, particularly preferably 1.0 μg / L or less, and ozone has an ozone concentration of 30 mg / L or more, preferably 50 mg / L or more, particularly preferably 100 mg / L. By dissolving until it becomes above, ozone water having a low decomposition rate of ozone after production can be obtained.

<Hydrogen peroxide decomposition catalyst>
The hydrogen peroxide decomposition catalyst used for the hydrogen peroxide removal treatment includes a granular ion exchange resin carrying a platinum group metal, a granular ion exchange resin of a metal ion type, and a non-granular form carrying a platinum group metal. Examples thereof include an organic porous body or a non-particulate organic porous ion exchanger on which a platinum group metal is supported.

<Platinum group metal-supported non-particulate organic porous body, platinum group metal-supported non-particulate organic porous ion exchanger>
As the platinum group metal-supported non-particulate organic porous body, platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm are supported on the non-particulate organic porous body, and the non-particulate organic porous body is continuous. Consisting of a skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is 1 to 60 μm, the average diameter of the continuous pores is 10 to 200 μm, the total pore volume is 0.5 to 10 ml / g, and the platinum group metal is supported. Examples include a platinum group metal-supported non-particulate organic porous material having an amount of 0.004 to 20% by weight in a dry state.

  The platinum group metal-supported non-particulate organic porous ion exchanger is a non-particulate organic porous ion exchanger in which platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm are supported. The porous ion exchanger comprises a continuous skeleton phase and a continuous pore phase, the thickness of the continuous skeleton is 1 to 60 μm, the average diameter of the continuous pores is 10 to 200 μm, and the total pore volume is 0.5 to 10 ml / g. The ion exchange capacity per weight in the dry state is 1 to 6 mg equivalent / g, the ion exchange groups are uniformly distributed in the organic porous ion exchanger, and the supported amount of the platinum group metal is Examples include a platinum group metal-supported non-particulate organic porous ion exchanger of 0.004 to 20% by weight in a dry state.

  In addition, the average diameter of the opening of a non-particulate organic porous body or a non-particulate organic porous ion exchanger is measured by the mercury intrusion method, and indicates the maximum value of the pore distribution curve obtained by the mercury intrusion method. Further, the structure of the non-particulate organic porous body or the non-particulate organic porous ion exchanger and the thickness of the continuous skeleton are determined by SEM observation. The particle diameter of the platinum group metal nanoparticles supported on the non-particulate organic porous body or the non-particulate organic porous ion exchanger is determined by TEM observation.

The platinum group metal-supported non-particulate organic porous body or the platinum group metal-supported non-particulate organic porous ion exchanger has an average particle diameter of 1 to 1 to the non-particulate organic porous body or the non-particulate organic porous ion exchanger. since 100nm platinum group metal is supported, show a high hydrogen peroxide decomposition catalytic activity, and, thereby passed through the treated water at a space velocity of 200～20000H ^-1 preferably 2000~20000h ^-1 (SV) be able to.

  In the platinum group metal-supported non-particulate organic porous body, the carrier on which the platinum group metal is supported is a non-particulate organic porous body. This non-particulate organic porous exchanger is a monolithic organic porous exchange. Is the body. In the platinum group metal-supported non-particulate organic porous ion exchanger, the carrier on which the platinum group metal is supported is a non-particulate organic porous ion exchanger. A monolithic organic porous ion exchanger, in which an ion exchange group is introduced into the monolithic organic porous body.

  The monolithic organic porous body is a porous body having a skeleton formed of an organic polymer and a large number of communication holes serving as a flow path for a reaction solution between the skeletons. The monolithic organic porous ion exchanger is a porous body introduced so that ion exchange groups are uniformly distributed in the skeleton of the monolithic organic porous body. In the present specification, “monolithic organic porous material” is also simply referred to as “monolith”, and “monolithic organic porous ion exchanger” is also simply referred to as “monolith ion exchanger”, and is also an intermediate in the production of monoliths. The “monolithic organic porous intermediate” that is the body (precursor) is also simply referred to as “monolith intermediate”.

  Examples of the structure of such a monolith or monolith ion exchanger are disclosed in Japanese Patent Application Laid-Open No. 2002-306976 and Japanese Patent Application Laid-Open No. 2009-62512, and Japanese Patent Application Laid-Open No. 2009-67982. A co-continuous structure, a particle aggregation type structure disclosed in JP 2009-7550 A, a particle composite type structure disclosed in JP 2009-108294 A, and the like.

Examples of monoliths serving as carriers for the above monolith, that is, platinum group metal particles (hereinafter also referred to as monolith (1)) and monolith ion exchangers, that is, monolith ion exchangers serving as the carrier for platinum group metal particles Examples of the form (hereinafter also referred to as monolith ion exchanger (1)) include monoliths and monolith ion exchangers having a co-continuous structure disclosed in JP-A No. 2009-67982.
That is, the monolith (1) is a monolith before the ion exchange group is introduced, and has an average thickness composed of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of a crosslinked structural unit among all the structural units. Is a co-continuous structure comprising a three-dimensionally continuous skeleton of 1 to 60 μm in a dry state and three-dimensionally continuous pores having an average diameter of 10 to 200 μm between the skeletons, An organic porous body having a total pore volume of 0.5 to 10 ml / g in a dry state.
In addition, the monolith ion exchanger (1) has a three-dimensional average thickness of 1 to 60 μm in a dry state composed of an aromatic vinyl polymer containing 0.1 to 5.0 mol% of a crosslinked structural unit among all the structural units. A continuous structure and three-dimensionally continuous pores having an average diameter of 10 to 200 μm in the dry state between the skeletons, and the total pore volume in the dry state is 0 5 to 10 ml / g, having an ion exchange group, an ion exchange capacity per weight in a dry state of 1 to 6 mg equivalent / g, and the ion exchange group in the organic porous ion exchanger It is a monolithic ion exchanger that is uniformly distributed.

  The monolith (1) or the monolith ion exchanger (1) has a three-dimensional continuous skeleton having an average thickness of 1 to 60 μm, preferably 3 to 58 μm in a dry state, and an average diameter between the skeletons in a dry state. It is a co-continuous structure composed of three-dimensionally continuous pores of 10 to 200 μm, preferably 15 to 180 μm, particularly preferably 20 to 150 μm. The co-continuous structure is a structure in which a continuous skeleton phase and a continuous vacancy phase are intertwined, and both are three-dimensionally continuous. The continuous pores have higher continuity of the pores than the conventional open-cell type monolith and the particle aggregation type monolith, and the size thereof is not biased. Moreover, since the skeleton is thick, the mechanical strength is high.

  If the average diameter of the three-dimensionally continuous pores is less than 10 μm in the dry state, the pressure loss at the time of passing the liquid increases, which is not preferable. If it exceeds 200 μm, the reaction solution and the monolith or monolith ion exchanger As a result, the contact with the catalyst becomes insufficient, resulting in insufficient catalytic activity. Moreover, when the average thickness of the skeleton is less than 1 μm in a dry state, the monolith or the monolith ion exchanger is greatly deformed when the liquid is passed at a high flow rate. Furthermore, the contact efficiency between the reaction liquid and the monolith or monolith ion exchanger is lowered, and the catalytic effect is lowered, which is not preferable. On the other hand, if the thickness of the skeleton exceeds 60 μm, the skeleton becomes too thick, and the pressure loss during liquid passage increases, which is not preferable.

  The average diameter of the opening of the monolith (1) in the dry state, the average diameter of the opening of the monolith ion exchanger (1) and the opening of the monolith intermediate (1) in the dry state obtained by the I treatment in the production of the monolith described below The average diameter is measured by the mercury intrusion method and refers to the maximum value of the pore distribution curve obtained by the mercury intrusion method. The average thickness of the skeleton of the monolith (1) or the monolith ion exchanger (1) in the dry state is determined by SEM observation of the dry monolith (1) or the monolith ion exchanger (1). Specifically, the SEM observation of the dried monolith (1) or monolith ion exchanger (1) is performed at least three times, the thickness of the skeleton in the obtained image is measured, and the average value thereof is calculated as the average thickness. Say it. The skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

  The total pore volume per weight in the dry state of the monolith (1) or monolith ion exchanger (1) is 0.5 to 10 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of liquid passing is increased, which is not preferable. Further, the permeation amount per unit cross-sectional area is decreased, and the processing amount is decreased. Therefore, it is not preferable. On the other hand, when the total pore volume exceeds 10 ml / g, the mechanical strength is lowered, and the monolith or the monolith ion exchanger is greatly deformed particularly when the liquid is passed at a high flow rate. Furthermore, since the contact efficiency between the reaction liquid and the monolith (1) or the monolith ion exchanger (1) is lowered, the catalyst efficiency is also lowered, which is not preferable. If the three-dimensionally continuous pore size and total pore volume are within the above ranges, the contact with the reaction solution is extremely uniform, the contact area is large, and the solution can be passed under a low pressure loss. .

  In the monolith (1) or the monolith ion exchanger (1), the material constituting the skeleton is 0.1 to 5 mol%, preferably 0.5 to 3.0 mol% of a crosslinked structural unit in all the structural units. It is an aromatic vinyl polymer containing and is hydrophobic. If the cross-linking structural unit is less than 0.1 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the porous body tends to deviate from the bicontinuous structure. There is no restriction | limiting in particular in the kind of aromatic vinyl polymer, For example, a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, a styrene-divinylbenzene copolymer is used because of its ease of forming a co-continuous structure, ease of introduction of ion-exchange groups, high mechanical strength, and high stability against acids or alkalis. And vinylbenzyl chloride-divinylbenzene copolymer is preferred.

  In the monolith ion exchanger (1), the introduced ion exchange groups are uniformly distributed not only on the surface of the monolith but also inside the skeleton of the monolith. Here, “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution status of the ion exchange groups can be easily confirmed by using EPMA. In addition, if the ion exchange groups are uniformly distributed not only on the surface of the monolith but also within the skeleton of the monolith, the physical and chemical properties of the surface and the interior can be made uniform, so that they are resistant to swelling and shrinkage. Improves.

  The ion exchange group introduced into the monolith ion exchanger (1) is a cation exchange group or an anion exchange group. Examples of the cation exchange group include a carboxylic acid group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphoric ester group. Examples of anion exchange groups include quaternary ammonium groups such as trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group, methyldihydroxyethylammonium group, tertiary sulfonium group, and phosphonium group. Etc.

  The monolith ion exchanger (1) has an ion exchange capacity of 1 to 6 mg equivalent / g of ion exchange capacity per weight in a dry state. Since the monolith ion exchanger (1) has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, it is possible to dramatically increase the ion exchange capacity per volume while keeping the pressure loss low. When the ion exchange capacity per weight is in the above range, the environment around the catalyst active point such as the pH inside the catalyst can be changed, and thereby the catalyst activity is increased. When the monolith ion exchanger (1) is a monolith anion exchanger, an anion exchange group is introduced into the monolith anion exchanger (1), and the anion exchange capacity per weight in the dry state is 1 to 6 mg. Equivalent / g. When the monolith ion exchanger (1) is a monolith cation exchanger, a cation exchange group is introduced into the monolith cation exchanger (1), and the cation exchange capacity per weight in a dry state is 1 ~ 6 mg equivalent / g.

  Monolith (1) is a method for producing a monolithic organic porous material disclosed in JP-A-2009-66792, that is, a mixture of an oil-soluble monomer not containing an ion exchange group, a surfactant and water. The water-in-oil emulsion is then polymerized, and then the water-in-oil emulsion is polymerized to form a monolithic organic porous intermediate having a continuous macropore structure having a total pore volume of more than 16 ml / g and not more than 30 ml / g ( Hereinafter, it is also referred to as monolith intermediate (1).) I treatment, aromatic vinyl monomer, 0.3 to 5 mol% in total oil-soluble monomer having at least two vinyl groups in one molecule A mixture of an organic solvent and a polymerization initiator that dissolves the crosslinking agent, aromatic vinyl monomer and crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer. It is an organic porous body which is a co-continuous structure by performing polymerization in the presence of the monolith intermediate (1) obtained by standing the mixture obtained by the II treatment and II treatment, and in the presence of the monolith intermediate (1) obtained by the I treatment. It is obtained by performing the III treatment to obtain the monolith (1).

  A platinum group metal is supported on the platinum group metal-supported non-particulate organic porous body or the platinum group metal-supported non-particulate organic porous ion exchanger. The platinum group metal is ruthenium, rhodium, palladium, osmium, iridium, or platinum. These platinum group metals may be used alone or in combination of two or more metals, and more than one metal may be used as an alloy. Among these, platinum, palladium, and platinum / palladium alloys have high catalytic activity and are preferably used.

  The average particle size of the platinum group metal particles supported on the platinum group metal-supported non-particulate organic porous material or platinum group metal-supported non-particulate organic porous ion exchanger is 1 to 100 nm, preferably 1 to 50 nm. More preferably, it is 1-20 nm. If the average particle size is less than 1 nm, the possibility that the platinum group metal particles will be detached from the carrier increases, which is not preferable. This is not preferable because the catalytic effect cannot be obtained efficiently. In addition, the average particle diameter of a platinum group metal particle is calculated | required by image-analyzing the TEM image obtained by a transmission electron microscope (TEM) analysis.

  Platinum group metal-supported non-particulate organic porous material or platinum group metal-supported non-particulate organic porous ion exchanger supported amount of platinum group metal particles ((platinum group metal particles / platinum group metal-supported catalyst in dry state) × 100 ) Is 0.004 to 20% by weight, preferably 0.005 to 15% by weight. If the supported amount of platinum group metal particles is less than 0.004% by weight, the catalytic activity becomes insufficient, such being undesirable. On the other hand, when the amount of platinum group metal particles is more than 20% by weight, metal elution into water is observed, which is not preferable.

  There are no particular restrictions on the method for producing the platinum group metal-supported non-particulate organic porous material or the platinum group metal-supported non-particulate organic porous ion exchanger. By supporting the nanoparticles, a platinum group metal supported catalyst can be obtained. Examples of the method for supporting the platinum group metal on the non-particulate organic porous body or the non-particulate organic porous ion exchanger include the method disclosed in JP 2010-240641 A. For example, a monolith ion exchanger in a dry state is immersed in a methanol solution of a platinum group metal compound such as palladium acetate, and palladium ions are adsorbed on the monolith ion exchanger by ion exchange, and then contacted with a reducing agent to form palladium metal nano-particles. A method of supporting particles on a monolith ion exchanger, a monolith ion exchanger is immersed in an aqueous solution of a platinum group metal compound such as a tetraammine palladium complex, and palladium ions are adsorbed on the monolith ion exchanger by ion exchange, and then a reducing agent In which the palladium metal nanoparticles are supported on the monolith ion exchanger.

  The granular ion exchange resin carrying a platinum group metal is one in which a platinum group metal is carried on a granular ion exchange resin. The particulate ion exchange resin that serves as the platinum group metal carrier is not particularly limited, and examples thereof include strongly basic anion exchange resins. Then, the granular ion exchange resin is loaded with a platinum group metal by a known method to obtain a granular ion exchange resin loaded with the platinum group metal.

  The metal ion type granular cation exchange resin on which a metal is supported is obtained by supporting a metal such as iron ion, copper ion, nickel ion, chromium ion or cobalt ion on a granular cation exchange resin. The granular cation exchange resin to be a carrier is not particularly limited, and examples thereof include strongly acidic cation exchange resins. And metal, such as an iron ion, copper ion, nickel ion, chromium ion, and cobalt ion, is carry | supported by a granular cation exchange resin by a well-known method, and a metal ion type granular cation exchange resin is obtained.

(Example)
Next, the present invention will be specifically described by way of examples, but this is merely an example and does not limit the present invention.

<Production of platinum group metal-supported non-particulate organic porous ion exchanger>
(Production of monolith intermediate (I treatment))
9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.25 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture was added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Co.) as a planetary stirring device. Was stirred under reduced pressure to obtain a water-in-oil emulsion. This emulsion was quickly transferred to a reaction vessel and allowed to polymerize at 60 ° C. for 24 hours in a static state after sealing. After completion of the polymerization, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The internal structure of the monolith intermediate (dry body) thus obtained was observed by SEM. From the SEM image, although the wall section that divides two adjacent macropores is very thin and rod-shaped, it has an open cell structure, and the average of the openings (mesopores) where the macropores and macropores overlap measured by the mercury intrusion method The diameter was 40 μm and the total pore volume was 18.2 ml / g.

(Manufacture of monoliths)
Subsequently, 216.6 g of styrene, 4.4 g of divinylbenzene, 220 g of 1-decanol, and 0.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (II treatment). Next, the above monolith intermediate is placed in a reaction vessel, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and degassed in a vacuum chamber. The reaction vessel was sealed and allowed to polymerize at 50 ° C. for 24 hours. After completion of the polymerization, the content was taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure (III treatment).
The internal structure of the monolith (dry body) containing 1.2 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained was observed by SEM. From the SEM observation, the monolith has a co-continuous structure in which the skeleton and the vacancies are three-dimensionally continuous, and both phases are intertwined. Moreover, the average thickness of the skeleton measured from the SEM image was 20 μm. Further, the average diameter of the three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 70 μm, and the total pore volume was 4.4 ml / g. The average diameter of the pores was determined from the maximum value of the pore distribution curve obtained by the mercury intrusion method.

(Production of monolith anion exchanger)
Next, the monolith was put into a column reactor, and a solution consisting of 1600 g of chlorosulfonic acid, 400 g of tin tetrachloride and 2500 ml of dimethoxymethane was circulated and passed through, and reacted at 30 ° C. for 5 hours to introduce a chloromethyl group. . After completion of the reaction, the chloromethylated monolith was washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1600 ml of THF and 1400 ml of 30% aqueous solution of trimethylamine were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with methanol and then with pure water to obtain a monolith anion exchanger.
The obtained monolith anion exchanger had an anion exchange capacity of 4.2 mg equivalent / g in a dry state, and it was confirmed that quaternary ammonium groups were quantitatively introduced. Further, the thickness of the skeleton in the dry state measured from the SEM image is 20 μm, and the average diameter in the dry state of the three-dimensional continuous pores of the monolith anion exchanger determined from the measurement by the mercury intrusion method. Was 70 μm and the total pore volume in the dry state was 4.4 ml / g.
Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger, the monolith anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chloride ions was observed by EPMA. . As a result, it was confirmed that the chloride ions were uniformly distributed not only on the skeleton surface of the monolith anion exchanger but also inside the skeleton, and the quaternary ammonium groups were uniformly introduced into the monolith anion exchanger. It was.

(Supporting platinum group metals)
The monolith anion exchanger was ion-exchanged into Cl form, cut into a cylindrical shape in a dry state, and dried under reduced pressure. The weight of the monolith anion exchanger after drying was 1.2 g. This dried monolith anion exchanger was immersed in dilute hydrochloric acid in which 100 mg of palladium chloride was dissolved for 24 hours, and ion-exchanged to the palladium chloride acid form. After completion of the immersion, the monolith anion exchanger was washed several times with pure water, and immersed in an aqueous hydrazine solution for 24 hours for reduction treatment. The chloropalladium acid form monolith anion exchanger was brown, whereas the monolith anion exchanger after the reduction treatment was colored black, suggesting the formation of palladium nanoparticles. The sample after the reduction was washed several times with pure water and then dried by pressure detection drying.
When the amount of palladium supported was determined by ICP emission spectroscopy, the amount of palladium supported was 3.9% by weight. In order to confirm the distribution state of palladium supported on the monolith cation exchanger, the distribution state of palladium was observed by EPMA. It was confirmed that palladium was distributed not only on the surface of the skeleton of the monolith anion exchanger but also inside the skeleton, and it was relatively uniformly distributed inside, although the concentration was slightly higher. In order to measure the average particle diameter of the supported palladium particles, observation with a transmission electron microscope (TEM) was performed. The average particle diameter of the palladium nanoparticles was 8 nm.

Example 1
(Ozone water production test)
An ozone water production test was conducted using the ozone water production system 35 shown in FIG. In FIG. 4, the ozone water production system 35 includes an ultraviolet oxidizer 10, a hydrogen peroxide decomposer 36, an ultrafiltration membrane device 13 b, an ozone dissolver 14, and an ozone generator 15. . As the hydrogen peroxide decomposer 36, the palladium-supported monolith anion exchanger obtained above was packed in a column having an inner diameter of 57 mm and a layer height of 40 mm. For the ozone dissolving part 14, an ozone dissolving film was used. As the ozone generator 15, a silent discharge type ozone generator (Sumitomo Seimitsu Industry Co., Ltd. GRC-RG29) was used.

In the ozone water production test, primary pure water having a resistivity of 16 MΩ · cm or more and a TOC of 2.0 ppb or less is passed through the ultraviolet oxidizer 10 as raw water supplied to the ozone water production system 35 shown in FIG. The output of the ultraviolet oxidizer of the ultraviolet oxidizer 10 was obtained so that the hydrogen peroxide concentration in the treated ultrapure water was 15.0 μg / L. The hydrogen peroxide concentration was 15.0 μg / L, Using ultrapure water having a resistivity of 18 MΩ · cm or more and a TOC of 1.0 ppb or less, the supply amount of the water to be treated to the hydrogen peroxide decomposer 36, the ultrafiltration membrane device 13 b and the ozone dissolution unit 14 is 5 L. / Min., And the ozone generator 15 is supplied with a mixed gas of oxygen gas and nitrogen gas. The supply amounts thereof are 10 SLM for oxygen gas (L / min at 0 ° C., 1 atm) and 100 SCCM for nitrogen gas (mL / min). at 0 1 atm), carbon dioxide gas is supplied from the carbon dioxide supply pipe 18, the supply amount is 40 SCCM (mL / min at 0 ° C., 1 atm), and the ozone water concentration is 100.0 mg / L. The discharge power of the generator 15 was adjusted to produce ozone.
As a result, the hydrogen peroxide concentration in the ultrapure water (that is, the water to be treated in which ozone dissolution treatment is performed) after being treated by the hydrogen peroxide decomposer 36 is 1.0 μg / L or less, and the ozone generator 15 The discharge output was 80%, and the ozone concentration in the ozone-containing gas supplied from the ozone generator 15 to the ozone dissolving part 14 was 256 gO ₃ / Nm ³ .

(Pipe transfer test)
The ozone water produced as described above was sent to each use point, and the ozone concentration at each use point was measured. The result is shown in FIG. The phenol phthaline method was used for the determination of hydrogen peroxide. In addition, piping transfer time means the arrival time to each use point, and is calculated | required from the ozone water flow rate and the pipe length to each use point.

(Comparative Example 1)
(Ozone water production test)
An ozone water production test was performed using the ozone water production system 40 shown in FIG. In FIG. 5, the ozone water production system 40 includes an ultraviolet oxidizer 10, an ultrafiltration membrane device 13 b, an ozone dissolution unit 14, and an ozone generator 15. For the ozone dissolving part 14, an ozone dissolving film was used. As the ozone generator 15, a silent discharge type ozone generator (Sumitomo Seimitsu Industry Co., Ltd. GRC-RG29) was used. That is, no hydrogen peroxide removing means is installed in the ozone water production system 40 shown in FIG.

In the ozone water production test, primary pure water having a resistivity of 16 MΩ · cm or more and a TOC of 2.0 ppb or less is passed through the ultraviolet oxidizer 10 as raw water supplied to the ozone water production system 40 shown in FIG. The output of the ultraviolet oxidizer of the ultraviolet oxidizer 10 was obtained so that the hydrogen peroxide concentration in the treated ultrapure water was 15.0 μg / L. The hydrogen peroxide concentration was 15.0 μg / L, Using ultrapure water having a resistivity of 18 MΩ · cm or more and a TOC of 1.0 ppb or less, the supply amount of the water to be treated to the ultrafiltration membrane device 13b and the ozone dissolving part 14 is 5 L / min, and an ozone generator 15 is supplied with a mixed gas of oxygen gas and nitrogen gas, and the supply amounts thereof are oxygen gas 10 SLM (L / min at 0 ° C., 1 atm) and nitrogen gas 100 SCCM (mL / min at 0 ° C., 1 atm). ,two The carbon dioxide gas is supplied from the carbonized carbon supply pipe 18, the supply amount is 40 SCCM (mL / min at 0 ° C., 1 atm), and the ozone generator 15 is discharged so that the ozone water concentration becomes 90.0 mg / L. The output was adjusted to produce ozone water.
As a result, the discharge output of the ozone generator 15 was 80%, and the ozone concentration in the ozone-containing gas supplied from the ozone generator 15 to the ozone dissolving part 14 was 256 gO ₃ / Nm ³ . In addition, since the hydrogen peroxide removal means is not provided, the hydrogen peroxide concentration in the water to be treated in which the ozone dissolution treatment is performed is 15.0 μg / L.

(Pipe transfer test)
It carried out like Example 1 except using the ozone water manufactured as mentioned above. The result is shown in FIG.

(Comparative Example 2)
(Ozone water production test)
An ozone water production test was performed using the ozone water production system 40 shown in FIG. In the ozone water production test, primary pure water having a resistivity of 16 MΩ · cm or more and a TOC of 2.0 ppb or less is passed through the ultraviolet oxidizer 10 as raw water supplied to the ozone water production system 40 shown in FIG. The output of the ultraviolet oxidizer of the ultraviolet oxidizer 10 was obtained so that the hydrogen peroxide concentration in the treated ultrapure water was 15.0 μg / L. The hydrogen peroxide concentration was 15.0 μg / L, Using ultrapure water having a resistivity of 18 MΩ · cm or more and a TOC of 1.0 ppb or less, the supply amount of the water to be treated to the ultrafiltration membrane device 13b and the ozone dissolving part 14 is 5 L / min, and an ozone generator 15 is supplied with a mixed gas of oxygen gas and nitrogen gas, and the supply amounts thereof are oxygen gas 10 SLM (L / min at 0 ° C., 1 atm) and nitrogen gas 100 SCCM (mL / min at 0 ° C., 1 atm). ,two The carbon dioxide gas is supplied from the carbonized carbon supply pipe 18, the supply amount is 40 SCCM (mL / min at 0 ° C., 1 atm), and the discharge of the ozone generator 15 is performed so that the ozone water concentration becomes 100.0 mg / L. The output was adjusted to produce ozone water.
As a result, the discharge output of the ozone generator 15 was 100%, and the ozone concentration in the ozone-containing gas supplied from the ozone generator 15 to the ozone dissolving part 14 was 287 gO ₃ / Nm ³ . In addition, since the hydrogen peroxide removal means is not provided, the hydrogen peroxide concentration in the water to be treated in which the ozone dissolution treatment is performed is 15.0 μg / L.

(Pipe transfer test)
It carried out like Example 1 except using the ozone water manufactured as mentioned above. The result is shown in FIG.

When Example 1 is compared with Comparative Examples 1 and 2, in Example 1 in which the hydrogen peroxide concentration in the ultrapure water in which ozone is dissolved is 1.0 μg / L or less, the ozone water concentration is 100.0 mg / L. Comparative Example 1 in which the discharge output of the ozone generator was sufficient to produce ozone water was 80%, whereas hydrogen peroxide in ultrapure water for dissolving ozone was 15.0 μg / L. 2, in order to set the ozone concentration to 100.0 mg / L, the discharge output of the ozone generator needs to be 100%. If the discharge output is 80%, which is the same as that of Example 1, the ozone concentration is 90%. Only reached 0.0 mg / L. This means that the ozone water production method of the present invention can produce ozone water at a higher concentration than the conventional ozone water production method. Further, in the ozone water production method of the present invention, the ozone gas concentration required to be generated can be kept low when the ozone water concentration is constant, compared with the conventional ozone water production method. In addition, the initial investment can be reduced and the power consumption for ozone production can be reduced, so that highly efficient and highly concentrated ozone water can be produced.
Further, as apparent from the ozone water concentration attenuation tendency in FIG. 6, in Example 1, the decrease in ozone was small even when the pipe transfer time was long, whereas in Comparative Examples 1 and 2, ozone was reduced. The amount of ozone decrease increased with the remarkable decomposition of the gas and the longer the pipe transfer time. That is, the ozone water production method of the present invention means that ozone water can be used at a high concentration and stably compared to the conventional ozone water production method.

(Reference Example 1)
(Ozone water production test)
An ozone water production test was performed using the ozone water production system 40 shown in FIG. In the ozone water production test, primary pure water having a resistivity of 16 MΩ · cm or more and a TOC of 2.0 ppb or less is passed through the ultraviolet oxidizer 10 as raw water supplied to the ozone water production system 40 shown in FIG. The output of the ultraviolet oxidizer of the ultraviolet oxidizer 10 was obtained so that the hydrogen peroxide concentration in the treated ultrapure water was 15.0 μg / L. The hydrogen peroxide concentration was 15.0 μg / L, Using ultrapure water having a resistivity of 18 MΩ · cm or more and a TOC of 1.0 ppb or less, the supply amount of the water to be treated to the ultrafiltration membrane device 13b and the ozone dissolving part 14 is 5 L / min, and an ozone generator 15 is supplied with a mixed gas of oxygen gas and nitrogen gas, and the supply amounts thereof are oxygen gas 10 SLM (L / min at 0 ° C., 1 atm) and nitrogen gas 100 SCCM (mL / min at 0 ° C., 1 atm). ,two The carbon dioxide gas is supplied from the carbon supply pipe 18, and the supply quantity 40SCCM (mL / min at 0 ℃, 1atm) and, as a 7% discharge output of the ozone generator 15, to produce ozone water.
As a result, the ozone concentration in the ozone-containing gas supplied from the ozone generator 15 to the ozone dissolving part 14 was 31 gO ₃ / Nm ³ . The ozone concentration in the obtained ozone water was 9.9 mg / L. In addition, since the hydrogen peroxide removal means is not provided, the hydrogen peroxide concentration in the water to be treated in which the ozone dissolution treatment is performed is 15.0 μg / L.

(Pipe transfer test)
It carried out like Example 1 except using the ozone water manufactured as mentioned above. The result is shown in FIG.

(Example 2 and Comparative Example 3)
As raw water to be supplied to the ozone water production system 35 shown in FIG. 4, primary pure water having a resistivity of 16 MΩ · cm or more and a TOC of 2.0 ppb or less is passed through the ultraviolet oxidizer 10, The output of the oxidizer was obtained so that the hydrogen peroxide concentration in the treated ultrapure water was 15.0 μg / L. The hydrogen peroxide concentration was 15.0 μg / L and the electrical resistivity was 18 MΩ · cm. As described above, using ultrapure water with a TOC of 1.0 ppb or less, the supply amount of water to be treated to the hydrogen peroxide decomposer 36, the ultrafiltration membrane device 13b, and the ozone dissolution unit 14 is 5 L / min, and ozone is generated. A gas mixture of oxygen gas and nitrogen gas is supplied to the vessel 15, and the supply amounts thereof are 10 SLM for oxygen gas (L / min at 0 ° C., 1 atm) and 100 SCCM for nitrogen gas (mL / min at 0 ° C., 1 atm). And two Carbon dioxide gas is supplied from the carbonized carbon supply pipe 18, the supply amount is 40 SCCM (mL / min at 0 ° C., 1 atm), and the discharge output of the ozone generator 15 is 7%, 12%, 18%, Ozone water was produced as 32% and 80%. In addition, the hydrogen peroxide density | concentration in the to-be-processed water in which the ozone melt | dissolution process is performed at this time is 1.0 microgram / L or less.
Further, as the raw water supplied to the ozone water production system 40 shown in FIG. 5, primary pure water having a resistivity of 16 MΩ · cm or more and a TOC of 2.0 ppb or less is passed through the ultraviolet oxidizer 10. The output of the UV oxidizer was such that the hydrogen peroxide concentration in the treated ultrapure water was 15.0 μg / L, the hydrogen peroxide concentration was 15.0 μg / L, and the electrical resistivity was 18 MΩ. -Using ultrapure water with a centimeter of at least cm and a TOC of at most 1.0 ppb, the amount of treated water supplied to the ultrafiltration membrane device 13b and the ozone dissolving section 14 is 5 L / min, and oxygen is supplied to the ozone generator 15 Supplying a mixed gas of gas and nitrogen gas, and supplying each gas with oxygen gas 10 SLM (L / min at 0 ° C., 1 atm) and nitrogen gas 100 SCCM (mL / min at 0 ° C., 1 atm), carbon dioxide supply Tube 1 The carbon dioxide gas is further supplied, the supply amount is 40 SCCM (mL / min at 0 ° C., 1 atm), and the discharge output of the ozone generator 15 is 7%, 12%, 18%, 32%, 80%, respectively. As a result, ozone water was produced. In addition, the hydrogen peroxide density | concentration in the to-be-processed water in which the ozone melt | dissolution process is performed at this time is 15.0 microgram / L.
Table 1 shows the results of measuring the concentration of ozone water obtained by each ozone water production test.

＊表中の過酸化水素濃度は、オゾン溶解部でオゾン溶解処理が行われる被処理水（超純水）中の過酸化水素濃度である。

* The hydrogen peroxide concentration in the table is the hydrogen peroxide concentration in the water to be treated (ultra-pure water) that is subjected to ozone dissolution treatment in the ozone dissolution zone.

  From the results shown in Table 1, when the concentration of ozone water required at the time of ozone water production is 30 mg / L or more, the same discharge output is obtained when the hydrogen peroxide removal treatment is performed compared to when the hydrogen peroxide removal treatment is not carried out. It was found that the effect of increasing the ozone concentration in the ozone water that can be produced by the method is remarkably exhibited.

DESCRIPTION OF SYMBOLS 1 Pretreatment system 2 Primary pure water system 3 Water obtained by primary pure water system 5 Raw water 10 Ultraviolet oxidizer 11 Hydrogen peroxide removing means 12 Carbon dioxide dissolving means 13a, 13b Ultrafiltration membrane device 14 Ozone dissolving part 15 Ozone Generator 17 Ozone 20a, 20b, 20c Ozone water 21 Ultrapure water 22a, 22b, 22c Ultrapure water production system 30a, 30b, 30c Subsystem 31 Deaerator 32a, 32b Ion exchanger 36 Hydrogen peroxide decomposer 35, 40 Ozone water production system

Claims (4)

In an ozone water production method for producing ozone water to be used at a point of use by dissolving ozone in ultrapure water obtained by further processing water obtained by a primary pure water system,
An ultraviolet oxidation treatment in which the water obtained by the primary pure water system is subjected to ultraviolet oxidation at an intensity such that the concentration of hydrogen peroxide is 15.0 μg / L or more;
Removing hydrogen peroxide in the water subjected to the ultraviolet oxidation treatment to reduce the hydrogen peroxide concentration to 10.0 μg / L or less;
Ozone-dissolving treatment for dissolving ozone in the water subjected to the hydrogen peroxide removal treatment until the ozone concentration becomes 30 mg / L or more;
And
Dissolving the carbon dioxide before the hydrogen peroxide removal treatment, or after the hydrogen peroxide removal treatment and before the ozone dissolution treatment, or at the time of the ozone dissolution treatment;
A method for producing ozone water.   Performing the hydrogen peroxide removal treatment by adsorbing the hydrogen peroxide in the water subjected to the ultraviolet oxidation treatment to an adsorbent or decomposing the hydrogen peroxide in the water subjected to the ultraviolet oxidation treatment. The method for producing ozone water according to claim 1.   Contacting the platinum group metal-supported ion exchange resin, metal ion-type cation exchange resin, platinum group metal-supported organic porous material or platinum group metal-supported organic porous ion exchanger with water subjected to the above-mentioned ultraviolet oxidation treatment The ozone water production method according to claim 2, wherein the hydrogen peroxide removal treatment is performed.   The fine particle removal process of removing fine particles by filtration is performed after the decomposition of hydrogen peroxide in the water subjected to the ultraviolet oxidation treatment and before the ozone dissolution treatment. Ozone water production method.

Images