JP6047699B2 - Production method, production apparatus and ozone-containing aqueous solution of ozone-containing aqueous solution - Google Patents

Description

  The present invention relates to a method for producing an ozone-containing aqueous solution, a production apparatus, and an ozone-containing aqueous solution.

Ozone and ozone water in which ozone is dissolved in water have effects such as sterilization, deodorization, washing, purification and bleaching because of its strong oxidizing power, and are widely used in various fields. Ozone oxidizes organic compounds to break down the ozone itself into oxygen, or the ozone disappears in 10 minutes or at most 30 minutes by diffusion from the surface of the ozone water. Even if it is used for sterilization of tap water in a treatment facility, it does not remain in the treated water. In addition, it is also used for sterilizing foods, maintaining freshness, and removing bacteria and viruses in medical facilities. On the other hand, an aqueous sodium hypochlorite solution in which sodium hypochlorite, which is one of sodium salts of oxoacids of chlorine, is widely used. A hypochlorous acid aqueous solution prepared from a weakly acidic to neutral solution has an oxidizing power and has sterilizing, disinfecting, deodorizing, and bleaching effects. However, since hypochlorous acid resistant bacteria may occur, there is a possibility that the resistant bacteria cannot be sterilized only with an aqueous hypochlorous acid solution.
Therefore, there is an ozone-containing hypochlorous acid aqueous solution in which ozone water and sodium hypochlorite aqueous solution are mixed so that resistant bacteria can be sterilized.

  Electrolysis sterilization of conventional aqueous solution containing ozone and hypochlorous acid or sodium hypochlorite with enhanced sterilizing power by adding ozone to hypochlorous acid obtained by electrolyzing water containing chloride ions Water and its production method and apparatus are disclosed in Patent Document 1. Patent Document 2 discloses an apparatus for producing ozone-containing sterilized water and an ozone-containing sterilized water, which is prepared by acidifying a solution, dissolving sodium hypochlorite as a sterilizing agent, and using ozone together to enhance the sterilizing effect. ing.

JP-A-9-38655 JP-A-11-285524

  As a conventional method for obtaining sodium hypochlorite, there is a method of using sodium hydroxide aqueous solution and chlorine as raw materials, but since both are deleterious substances, handling is not easy. In addition, there is a method of electrolyzing water containing chloride ions such as saline, but it requires a lot of electric power, and an electrolyzer is required, which makes the manufacturing apparatus complicated. In addition, the ozone-containing hypochlorous acid aqueous solution has a problem that ozone remaining in water has low persistence and the effect as ozone water cannot be maintained for a long time.

  Therefore, the present invention has been made to solve the above-mentioned problems, and the object of the present invention is to be used for oxidative decomposition and sterilization of organic substances, and the sodium salt of chlorine oxoacid, ozone and hydroxy radicals coexist. Another object of the present invention is to provide an ozone-containing aqueous solution manufacturing method, a manufacturing apparatus, and an ozone-containing aqueous solution that can keep ozone in an aqueous solution and store ozone for a long period of time.

In order to achieve the above object, the method for producing an ozone-containing aqueous solution of the present invention comprises the following constitution. That is, the present invention relates to a production method for producing an ozone-containing aqueous solution in which ozone is supplied and reacted in a sodium chloride aqueous solution or a sodium hypochlorite aqueous solution , and ozone, a sodium salt of oxo acid of chlorine and a hydroxy radical coexist. The ozone generated by the ozone generator is supplied to the sodium chloride aqueous solution or the sodium hypochlorite aqueous solution in the reaction tank, and the liquid in the reaction tank is circulated between the fine bubble generator. In addition, the ozone generated by the ozone generator is supplied to the fine bubble generator to form fine ozone bubbles having nanometer-order bubbles in the liquid, and the liquid containing the bubbles is And a step of supplying to the reaction vessel . According to this configuration, ozone can be dissolved in an aqueous sodium hypochlorite solution to generate a sodium salt of oxo acid of chlorine and a hydroxy radical. In addition, the fine bubbles of ozone can be continuously supplied to the liquid containing the sodium chloride aqueous solution, the sodium chloride aqueous solution and ozone are reacted, and the aqueous solution in which the sodium salt of oxo acid of ozone and chlorine and the hydroxy radical coexist is obtained. Can be produced.

Moreover, in this invention, it is preferable to produce | generate the said sodium hypochlorite aqueous solution by supplying ozone to the said sodium chloride aqueous solution, and making the said sodium chloride aqueous solution and ozone react. According to this, since sodium hydroxide and chlorine are not used, and sodium salt of oxo acid of chlorine is prepared using sodium chloride and ozone, the raw material is easy to handle.

  Moreover, in this invention, it is preferable that the sodium salt of the said oxo acid of chlorine contains sodium hypochlorite. According to this, the ozone containing sodium hypochlorite aqueous solution which has the effect of disinfection, disinfection, deodorization, and bleaching can be manufactured.

  Moreover, in this invention, it is preferable to use salt water or / and seawater for the said sodium chloride aqueous solution. According to this, it is not necessary to purify sodium chloride from an aqueous solution containing sodium chloride as a main component, and an ozone-containing sodium hypochlorite aqueous solution can be produced even from an aqueous solution containing substances other than sodium chloride. In addition, a large amount of oxygen, seawater, etc. can be used, so there is no problem with raw material procurement.

  Moreover, in this invention, it is preferable that the said hydroxyl radical is produced | generated by including at least 1 or more types of process chosen from ozone addition, hydrogen peroxide addition, ultrasonic irradiation, a heating, and ultraviolet irradiation. According to this, it is possible to produce an aqueous solution in which the sodium salt of ozone and chlorine oxo acid and hydroxy radicals that can be used for water purification, air purification, and washing coexist.

In order to achieve the above object, an apparatus for producing an ozone-containing aqueous solution of the present invention has the following configuration. That is, the present invention is an apparatus for producing an ozone-containing aqueous solution for producing an aqueous solution in which a sodium salt of ozone and oxo acid of chlorine and a hydroxyl radical coexist, comprising: a reaction tank; and a sodium chloride aqueous solution or hypochlorous acid in the reaction tank. A raw material aqueous solution supply unit for supplying a sodium acid aqueous solution , an ozone supply unit for generating ozone by an ozone generator , supplying the generated ozone to the reaction tank, and reacting with the sodium chloride aqueous solution or the sodium hypochlorite aqueous solution The ozone supply unit further circulates the liquid in the reaction tank, and the ozone generated by the ozone generator is supplied into the liquid, and bubbles in the nanometer order are contained in the liquid. It has the fine bubble generator which generates the fine bubble of ozone which has this. According to this structure, the manufacturing apparatus of the ozone containing aqueous solution which can manufacture the sodium salt of the oxo acid of chlorine using sodium hypochlorite aqueous solution or sodium chloride aqueous solution, and ozone can be provided. In addition, ozone and sodium chloride react with each other, so that sodium hypochlorite is easily generated. Further, the reaction can be promoted by continuously supplying ozone into the liquid.

  Further, in the present invention, it includes at least one device selected from a device for adding hydrogen peroxide to the liquid in the reaction vessel, a device for irradiating ultrasonic waves, a device for applying heat, and a device for irradiating ultraviolet rays. Is preferred. According to this, it is possible to easily generate a hydroxy radical.

  In order to achieve the above object, the ozone-containing aqueous solution of the present invention has the following constitution. That is, the present invention is characterized in that the sodium salt of ozone, chlorine oxo acid, and a hydroxyl radical coexist in an aqueous solution. According to this structure, the ozone containing aqueous solution which can preserve | save ozone for a long period can be provided, and it can utilize for the oxidative decomposition | disassembly and disinfection of organic substance.

  Moreover, in this invention, it is preferable that the sodium salt of the said oxo acid of chlorine contains sodium hypochlorite. According to this, it is an aqueous solution in which ozone can be stored for a long time and hypochlorous acid and ozone coexist.

Process for producing ozone-containing aqueous solution according to the present invention, according to the manufacturing device and the ozone-containing aqueous solution, the fine bubbles of ozone with air bubbles on the order of nanometers, available to oxidative decomposition and sterilization of organic matter, sodium oxo acid chloride An ozone-containing aqueous solution in which salt, ozone, and hydroxy radicals coexist is easily produced, and an ozone-containing aqueous solution that can store ozone for a long period of time by keeping ozone in the aqueous solution can be produced.

It is a schematic block diagram of the ozone containing aqueous solution manufacturing apparatus which concerns on embodiment of this invention.

  DESCRIPTION OF EMBODIMENTS Hereinafter, embodiments of an ozone-containing aqueous solution manufacturing method, a manufacturing apparatus, and an ozone-containing aqueous solution according to the present invention will be described in detail with reference to the accompanying drawings.

[Overview]
FIG. 1 shows a schematic configuration diagram of an example of an apparatus 10 for producing an ozone-containing aqueous solution.
The apparatus 10 for producing an ozone-containing aqueous solution includes a reaction tank 12, a raw material aqueous solution supply unit 14 for supplying a sodium hypochlorite aqueous solution or a sodium chloride aqueous solution to the reaction tank 12, and generating ozone. And an ozone supply unit 16 that reacts the sodium hypochlorite aqueous solution or the sodium chloride aqueous solution with ozone. In this reaction tank 12, when sodium hypochlorite aqueous solution and ozone are reacted, or sodium chloride aqueous solution and ozone are reacted, sodium salt of ozone and chlorine oxo acid and hydroxy radical (.OH) are produced. A coexisting aqueous solution is produced.

In the reaction vessel 12, excited oxygen atoms (O ^* ) generated from ozone react with sodium chloride to produce sodium hypochlorite (NaClO) which is a sodium salt of chlorine oxoacid. At this time, hydroxy radicals (.OH) are also generated from ozone. In the reaction vessel 12, the excited oxygen atom and the hydroxy radical do not exist independently and coexist.
(Chemical formula 1)
NaCl + O ^* → NaClO

[Method for producing ozone-containing aqueous solution]
When ozone is injected into the sodium hypochlorite aqueous solution in the reaction tank 12 to react sodium hypochlorite with ozone, unreacted ozone remains in the reaction tank 12 and further the sodium salt of chlorine oxo acid. Is generated. Thereby, an aqueous solution in which ozone and a sodium salt of oxo acid of chlorine coexist is produced. The sodium salt of chlorine oxo acid prepared at this time includes sodium hypochlorite, and also includes sodium chlorite and sodium chlorate.
Further, an aqueous sodium chloride solution may be placed in the reaction tank 12. In this case, when ozone is injected into a sodium chloride aqueous solution and sodium chloride reacts with ozone, a sodium salt of chlorine oxo acid is generated, and unreacted ozone remains in the reaction vessel 12, and ozone and chlorine oxo An aqueous solution in which the sodium salt of the acid coexists is prepared.

The process by which sodium salt of oxo acid of chlorine is produced by the reaction of sodium chloride and ozone. When ozone (O ₃ ) in the reaction vessel 12 is decomposed, oxygen (O ₂ ) is generated. When ozone is decomposed by applying energy, excited oxygen atoms (O ^* ) having high energy are generated.
(Chemical formula 2)
O ₃ → O ₂ + O ^*

  Factors that generate excited oxygen atoms are chemical energy, thermal energy, mechanical energy, and light energy, such as hydrogen peroxide addition, ultrasonic irradiation (cavitation), heating, and ultraviolet irradiation. . Giving high energy is the starting point for the reaction between the aqueous sodium chloride solution and ozone to produce the sodium salt of chlorine oxoacid. Furthermore, the reaction proceeds further by dissolving the fine bubbles of ozone generated by bubbling using the fine bubble generator 26 in the liquid.

In the reaction vessel 12, the generated oxygen atom in the excited state reacts with sodium chloride to produce sodium hypochlorite which is a sodium salt of chlorine oxo acid. However, sodium chloride is almost ionized by ionizing into sodium ion and (Na ⁺ ) chloride ion (Cl ⁻ ) in an aqueous solution, so in the aqueous solution, excited oxygen atoms react with chloride ions. Hypochlorite ion (ClO ⁻ ) is generated.
(Chemical formula 3)
Cl ⁻ + O ^* → ClO ⁻
Moreover, since the acid dissociation constant of hypochlorous acid is pKa = 7.53, adjusting the pH of an alkaline solution containing hypochlorite ions to a range from acidic to neutral (pH = 5 to 7), An aqueous solution rich in hypochlorous acid (HClO) is produced.

Furthermore, some hypochlorite ions cause the following reaction. When hypochlorite ion reacts with excited oxygen atom, chlorite ion (ClO ₂ ⁻ ) is generated. When chlorite ion reacts with excited oxygen atom, chlorate ion (ClO ₃ ⁻ ) is generated. To do. However, hypochlorite ions and hypochlorous acid are the most in aqueous solutions. In this way, an aqueous solution containing a sodium salt of chlorine oxo acid is produced by reacting an aqueous sodium chloride solution with ozone. In addition, a solution containing hypochlorite ions, that is, an aqueous solution containing a sodium salt of oxo acid of chlorine is produced even when sodium hypochlorite aqueous solution is reacted with ozone.
(Chemical formula 4)
ClO ⁻ + O ^* → ClO ₂ ⁻
ClO ₂ ⁻ + O ^* → ClO ₃ ⁻

When ozone is injected into the sodium hypochlorite aqueous solution in the reaction tank 12 and sodium hypochlorite (hypochlorite ion and sodium ion in the aqueous solution) reacts with ozone, hydroxy radicals (.OH) are also generated. To do. Further, when ozone is injected into the sodium chloride aqueous solution in the reaction vessel 12 to react sodium chloride (chloride ions and sodium ions in the aqueous solution) with ozone, hydroxy radicals (.OH) are also generated.
The hydroxy radical is generated by including at least one process selected from ozone addition, hydrogen peroxide addition, ultrasonic irradiation, heating, and ultraviolet irradiation. Further, it is generated from fine bubbles obtained by bubbling ozone into the liquid. That is, the hydroxy radical is also generated in the process of generating an oxygen atom in an excited state, and an aqueous solution in which the sodium salt of ozone and chlorine oxo acid and the hydroxy radical coexist can be produced.
Moreover, sodium hypochlorite is produced even if the hydroxy radical reacts with the aqueous sodium chloride solution.
Hydroxyl radicals are generated by the above process, specifically, the self-decomposition of ozone dissolved in water, the reaction between ozone and hydrogen peroxide, the decomposition of water molecules in bubbles generated by ultrasonic irradiation, the decomposition by heating, the ozone-containing water Caused by UV decomposition of hydrogen peroxide.

  The addition of hydrogen peroxide promotes the reaction between the aqueous sodium chloride solution and ozone. As a result, the sodium salt of oxo acid of chlorine and the hydroxy radical are more easily generated. For this reason, it is preferable to add hydrogen peroxide. Since the concentration of the hydrogen peroxide solution to be added is not particularly limited, it can be used for medical purposes and reagents, can be diluted, and can be used at a concentration of 30% or more. Further, gaseous hydrogen peroxide may be dissolved in the solution in the reaction tank 12.

  In the reaction between the sodium chloride aqueous solution and ozone by ultrasonic irradiation, the frequency of ultrasonic waves to be irradiated is not particularly limited, and a general ultrasonic irradiation apparatus may be used. The apparatus for irradiating the ultrasonic wave is not particularly limited as long as the liquid in the reaction tank 12 is irradiated with the ultrasonic wave. The indirect irradiation method and ultrasonic horn for irradiating the ultrasonic wave from the bottom through the reaction tank 12 are not limited. A direct irradiation method of irradiating the liquid in a liquid may be used.

In addition, the hydroxy radical may be generated by a reaction between the generated hypochlorite ion and water.
(Chemical formula 5)
ClO ⁻ + H ₂ O → Cl ⁻ + 2HO.

  To stop the reaction between the aqueous sodium chloride solution and ozone, the supply of ozone to the reaction tank 12 is stopped. At this time, the supply of liquid from the reaction vessel 12 to the fine bubble generator 26 may be stopped to stop the circulation, or the supply of ozone from the ozone generator 22 directly to the reaction vessel 12 may be stopped. Moreover, even if all the chloride ions in the solution in the reaction tank 12 react to produce hypochlorite ions, the reaction stops.

Here, it is considered that one reason that ozone can be stored for a long period of time is that ozone decomposes into oxygen and reacts with hypochlorite ions to generate ozone.
(Chemical formula 6)
ClO ⁻ + O ₂ → Cl ⁻ + O ₃

  The produced ozone-containing aqueous solution has a pH of 5 to 7, and is an aqueous solution containing a large amount of hypochlorous acid. Moreover, in order to contain much hypochlorous acid, it is good also as pH = 5-7 by adjusting pH. Ozone contained in the produced ozone-containing aqueous solution can be stored for a long period of time, and can be stored in a sealed container for about two months.

  As the sodium chloride aqueous solution, not only purified sodium chloride but also salt water prepared using sodium chloride can be used, seawater may be used, and an aqueous solution containing sodium chloride mixed with these may be used as a raw material. Although the density | concentration of sodium chloride aqueous solution is not specifically limited, If the density | concentration of sodium chloride aqueous solution to be used is high, the production amount of the ozone containing aqueous solution of this embodiment will increase.

[Production equipment for ozone-containing aqueous solution]
The raw material aqueous solution supply unit 14 of the ozone-containing aqueous solution manufacturing apparatus 10 has an aqueous solution containing a chlorine-containing compound and supplies the aqueous solution to the reaction tank 12. The raw material aqueous solution supply unit 14 has a sodium chloride aqueous solution storage tank 18 for storing a sodium chloride aqueous solution, and can open the valve 50 to supply the sodium chloride aqueous solution into the reaction tank 12 through the pipe 20. Further, the raw material aqueous solution supply unit 14 has a sodium hypochlorite aqueous solution storage tank 19 for storing a sodium hypochlorite aqueous solution, and opens the valve 51 so that the sodium chloride aqueous solution is introduced into the reaction tank 12 through the pipe 20. Can supply. These aqueous solutions may be supplied to the reaction tank 12 by their own weight or using a pump.

  The ozone supply unit 16 of the ozone-containing aqueous solution manufacturing apparatus 10 supplies ozone to the sodium hypochlorite aqueous solution or the sodium chloride aqueous solution in the reaction tank 12. The ozone supply unit 16 includes an ozone generator 22. Ozone generated in the reaction tank 12 can be supplied from the ozone generator 22 through the pipe 24. Thereby, ozone and sodium hypochlorite aqueous solution or sodium chloride aqueous solution are made to react in the reaction tank 12, and the aqueous solution in which the sodium salt of ozone, the oxo acid of chlorine, and a hydroxyl radical coexist can be produced.

  The ozone generator 22 may be any device that generates ozone. The method of generating ozone gas in the ozone generator 22 may be any method such as a silent discharge method, an ultraviolet irradiation method, an electrolysis method, etc., and commercially available ozonizers can be used. Further, the electrolysis apparatus used here is used for generating ozone, and is not used for electrolyzing the sodium chloride aqueous solution in the reaction tank 12.

  The ozone supply unit 16 preferably has a fine bubble generating device 26 that generates fine bubbles of ozone in the liquid, and supplies ozone to the reaction tank 12 through the fine bubble generating device 26 and the pipe 28. More preferably, it has a circulation mechanism that circulates the liquid in the reaction tank 12 between the fine bubble generator 26 and the liquid in the reaction tank 12 is generated from the reaction tank 12 through the piping 40 and the circulation pump 42. The device 26 is supplied. When ozone fine bubbles are supplied to the sodium chloride aqueous solution, the hydroxy radicals generated from the ozone fine bubble generator 26 react with the sodium chloride aqueous solution, so that sodium hypochlorite is easily generated. Further, by circulating the solution, ozone continues to be supplied to the aqueous sodium chloride solution, and a sodium salt of oxo acid of chlorine is generated. Further, when ozone is continuously supplied to the sodium hypochlorite aqueous solution, ozone can be continuously dissolved in the sodium hypochlorite aqueous solution.

  Preferably, at least one selected from an apparatus for adding hydrogen peroxide to the liquid in the reaction vessel 12, an apparatus for irradiating ultrasonic waves, an apparatus for applying heat, and an apparatus for irradiating ultraviolet rays (all not shown). The above apparatus is included. These devices facilitate the production of hydroxy radicals in the reaction tank, and the reaction between the hydroxy radicals and aqueous sodium chloride solution facilitates the production of sodium hypochlorite.

  Hydrogen peroxide solution added from a device (not shown) for adding hydrogen peroxide solution is added to the liquid in the reaction tank 12 through a pipe (not shown). In addition, the ultrasonic irradiation apparatus is not particularly limited as long as the liquid in the reaction tank 12 is irradiated with ultrasonic waves. The indirect irradiation method in which ultrasonic waves are irradiated from the bottom surface through the reaction tank 12 or super A direct irradiation method in which a sonic horn is placed in a liquid for irradiation may be used. In addition, the apparatus for applying heat to the liquid in the reaction vessel 12 and the apparatus for irradiating ultraviolet rays are not particularly limited as long as they can be heated or irradiated with ultraviolet rays.

  Oxygen is supplied to the ozone generator 22 from the ozone raw material section 30 through a pipe 32. The ozone raw material section 30 includes a PSA type or oxygen enriched film type oxygen concentrator, an oxygen gas cylinder, and the like. In addition, air may be directly taken into the ozone generator 22. A gas containing ozone is generated from the ozone generator 22, and the ozone concentration in the gas containing ozone varies depending on the performance of the ozone generator 22, but is not particularly limited. When the generated ozone concentration is high, the generation amount of the ozone-containing aqueous solution of the present embodiment increases. Moreover, the ozone concentration dissolved in the ozone-containing aqueous solution also increases.

  The pipe 24 supplies ozone directly from the ozone generator 22 to the reaction tank 12 via a switching valve (not shown). Further, ozone may be supplied from the ozone generator 22 to the fine bubble generator 26 through a switching valve (not shown). The piping 28 supplies fine bubbles of ozone from the fine bubble generator 26 to the reaction tank 12. In the fine bubble generator 26, ozone fine bubbles are generated and dissolved in the liquid supplied from the reaction vessel 12. A liquid containing fine ozone bubbles is sent to the reaction tank 12 through the pipe 28 and circulated by the circulation mechanism. By circulating the liquid in the reaction tank 12, the liquid and ozone can be suitably brought into contact, and the reaction can be promoted. Thus, ozone may be supplied to the reaction tank 12 from either the ozone generator 22 or the fine bubble generator 26, or may be used in combination.

  The fine bubble generating device 26 may be any fine bubble generating method and is not particularly limited. For example, an apparatus such as a pressure dissolution method, a gas-liquid shear method, an ultrasonic method, or a method using shirasu porous glass (SPG film) can be used. Here, ozone generated from the fine bubble generating device 26 is made into fine bubbles, so that much ozone can be dissolved in water. Although the size of the ozone microbubbles is not particularly limited, it is preferable that the microbubbles have a size of nano-order.

  In the reaction tank 12, the supplied sodium hypochlorite aqueous solution or sodium chloride aqueous solution reacts with ozone to produce an aqueous solution in which ozone, a sodium salt of oxo acid of chlorine and a hydroxy radical coexist. The ozone-containing aqueous solution in the reaction tank 12 can be sent out by its own weight or by using a pump from the discharge port 34 through the pipe 36 by opening the release valve 52. Furthermore, the reaction vessel 12 is provided with a stirring device 38 for stirring the liquid. The stirrer 38 may be rotated by putting a stirring bar into the reaction vessel 12 like a magnetic stirrer, and the disc or propeller-shaped rotating body is separated from the tip of the rod or the tip like the mixer shown in FIG. You may attach to a position, rotate the stick | rod with a motor etc., and rotate a rotary body.

  The manufacturing apparatus 10 includes a pipe 44 that supplies purified water or tap water introduced from the outside to the reaction tank 12, and can adjust the concentration and pH of the solution in the reaction tank 12. In addition to water purified through ion-exchange resin, ultrapure water, pure water, pure water, distilled water and other purified water, tap water, etc. can be used, even if there is residual chlorine such as tap water it can. In addition, a purified water production apparatus 46 for purifying water introduced from the outside may be installed to produce purified water in the production apparatus 10. In this case, a pipe 44 for supplying water introduced from the outside to the purified water production apparatus 46 and a pipe 48 for supplying purified water from the purified water production apparatus 46 to the reaction tank 12 are provided. As the purified water production apparatus 46, for example, an ion exchange water production apparatus, an ultrapure water production apparatus, a pure water production apparatus, or a distilled water production apparatus may be used for purification.

  Production of an aqueous solution in which a sodium salt of ozone, chlorine oxo acid and a hydroxyl radical coexist by reaction of a sodium hypochlorite aqueous solution or a sodium chloride aqueous solution with ozone can be carried out by either batch treatment or continuous treatment. The amount of sodium hypochlorite aqueous solution or sodium chloride aqueous solution supplied to the reaction vessel 12 and the amount of ozone-containing aqueous solution flowing out of the reaction vessel 12 are adjusted so that the liquid stays in the reaction vessel 12 for a predetermined time. To do.

The aqueous solution in which the sodium salt of the generated ozone and chlorine oxo acid and hydroxy radicals coexist can be stored in a container, and the aqueous solution can be used to disinfect, disinfect, medical instruments in medical fields, medical equipment, It can be applied to various fields such as cleaning.
Furthermore, it can be used for purification treatment of contaminated water containing organic substances such as harmful substances and hardly decomposed substances. By supplying contaminated water to the reaction tank 12 and supplying and reacting with a series of sodium hypochlorite aqueous solution or sodium chloride aqueous solution and ozone, harmful substances and hardly decomposed substances are decomposed in the reaction tank 12. Is done. At this time, the generation of hydroxy radicals is promoted by including at least one process selected from hydrogen peroxide addition, ultrasonic irradiation, heating, and ultraviolet irradiation, and the ozone-containing aqueous solution of the present embodiment in which the hydroxy radicals coexist is obtained. , Hazardous substances and difficult-to-decompose substances are easily decomposed.

[Example 1]
Seawater having a sodium hypochlorite concentration of 0 ppm and a dissolved ozone concentration of 0 ppm was stored in a sodium chloride aqueous solution storage tank 18 and supplied into the reaction tank 12 through a pipe 20. Ozone was produced with the ozone generator 22. The ozone gas concentration is 30 g / m ³ . The produced ozone was supplied to the fine bubble generator 26, and further, seawater was supplied to the fine bubble generator 26 through a circulation mechanism to generate ozone fine bubbles. Seawater in which ozone was dissolved was supplied to the reaction tank 12 through the pipe 28.
Ozone fine bubbles were generated in sea water for 10 minutes, and sodium hypochlorite concentration and dissolved ozone concentration were measured. As a result, the produced ozone-containing aqueous solution had a sodium hypochlorite concentration of 23 ppm and a dissolved ozone concentration of 0.6 ppm. At this time, hydroxy radicals are also generated from ozone.
After 30 minutes, 100 L of an aqueous solution in which a sodium salt of ozone, chlorine oxo acid and a hydroxy radical coexisted could be produced.

[Example 2]
Salt water having a sodium hypochlorite concentration of 0 ppm, a dissolved ozone concentration of 0 ppm, and a salinity concentration of 0.8 wt% was stored in a sodium chloride aqueous solution storage tank 18 and supplied into the reaction tank 12 through a pipe 20. Ozone was produced with the ozone generator 22. The ozone gas concentration is 30 g / m ³ . The produced ozone was supplied to the fine bubble generating device 26, and further, salt water was supplied to the fine bubble generating device 26 through a circulation mechanism to generate ozone fine bubbles. Salt water in which ozone was dissolved was supplied to the reaction tank 12 through the pipe 28.
Ozone fine bubbles were generated in the salt water for 10 minutes, and the sodium hypochlorite concentration and the dissolved ozone concentration were measured. As a result, the produced ozone-containing aqueous solution had a sodium hypochlorite concentration of 12 ppm and a dissolved ozone concentration of 0.6 ppm. At this time, hydroxy radicals are also generated from ozone.
After 30 minutes, 100 L of an aqueous solution in which a sodium salt of ozone, chlorine oxo acid and a hydroxy radical coexisted could be produced.

The bactericidal effect of the ozone-containing aqueous solution was investigated. A test bacterial solution having a S. aureus concentration of 1.6 × 10 ⁷ cells / mL and a test bacterial solution having an E. coli concentration of 9.3 × 10 ⁶ cells / mL were used. Add 1 mL of Staphylococcus aureus test bacterial solution to 100 mL solution containing 50 mL of ozone-containing aqueous solution and 50 mL of sterilized physiological saline, and put the container containing this liquid in a constant temperature water bath at 37 ° C. for 1 minute. The number was investigated. Similarly, 1 mL of E. coli test bacterial solution was added, and the number of bacteria after the minute was investigated. As a result, in all cases, the number of test bacteria after 1 minute was 0, and the bacteria were completely sterilized.

DESCRIPTION OF SYMBOLS 10 Manufacturing apparatus 12 Reaction tank 14 Raw material aqueous solution supply part 16 Ozone supply part 18 Sodium chloride aqueous solution storage tank 19 Sodium hypochlorite aqueous solution storage tank 20 Pipe 22 Ozone generator 24 Pipe 26 Fine bubble generator 28 Pipe 30 Ozone raw material part 32 Piping 34 Discharge port 36 Piping 38 Stirring device 40 Piping 42 Circulating pump 44 Piping 46 Purified water production device 48 Piping 50 Valve 51 Valve 52 Opening valve

Claims (7)

A method for producing an ozone-containing aqueous solution in which ozone is supplied and reacted in a sodium chloride aqueous solution or a sodium hypochlorite aqueous solution , and ozone, a sodium salt of oxo acid of chlorine and a hydroxy radical coexist ,
Supplying ozone generated by an ozone generator to a sodium chloride aqueous solution or a sodium hypochlorite aqueous solution in a reaction tank;
The liquid in the reaction tank is circulated between the fine bubble generator and the ozone generated by the ozone generator is supplied to the fine bubble generator to have nanometer-order bubbles in the liquid. Forming a fine ozone bubble, and supplying the liquid containing the bubble to the reaction vessel . The method for producing an ozone-containing aqueous solution according to claim 1, wherein the sodium hypochlorite aqueous solution is generated by supplying ozone to the sodium chloride aqueous solution and causing the sodium chloride aqueous solution and ozone to react with each other. The method for producing an ozone-containing aqueous solution according to claim 1 or 2 , wherein the sodium salt of oxo acid of chlorine contains sodium hypochlorite. Method for producing an aqueous solution containing ozone as claimed in any one of claims 3, characterized by using brine and / or sea water to the sodium chloride aqueous solution. The hydroxyl radical is added ozone, hydrogen peroxide addition, ultrasonic irradiation, heating, any of claims 1 to 4, characterized in that it is produced by at least one or more steps selected from ultraviolet radiation A method for producing the ozone-containing aqueous solution according to claim 1. An apparatus for producing an ozone-containing aqueous solution for producing an aqueous solution in which a sodium salt of ozone and oxo acid of chlorine and a hydroxy radical coexist,
A reaction vessel;
A raw material aqueous solution supply section for supplying a sodium chloride aqueous solution or a sodium hypochlorite aqueous solution to the reaction vessel;
Ozone is generated by an ozone generator, and the generated ozone is supplied to the reaction vessel, and includes an ozone supply unit that reacts with the sodium chloride aqueous solution or the sodium hypochlorite aqueous solution ,
The ozone supply unit further circulates a liquid in the reaction tank, and supplies ozone generated by the ozone generator into the liquid, so that fine ozone of nanometer-order bubbles is contained in the liquid. An apparatus for producing an ozone-containing aqueous solution, comprising a fine bubble generator for generating bubbles . The apparatus includes at least one device selected from a device for adding hydrogen peroxide to the liquid in the reaction vessel, a device for applying ultrasonic waves, a device for applying heat, and a device for applying ultraviolet rays. 6. The apparatus for producing an ozone-containing aqueous solution according to 6 .

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