JP2007326101A - Ozone water treating method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a safe ozone water treating method without using any additive. <P>SOLUTION: This ozone water treating method comprises an ozone water producing process producing ozone water with particle sizes R (0<R≤1,000 nm) of contained ozone bubbles by a gas-liquid mixing method containing no additive; and an ozone water treating process treating a treating object using the ozone water produced in the ozone water producing process. With the diameter of the ozone bubbles within such a range, the bubbles hardly float up to the water level, causing very little degassing. Thus, the solubility/concentration of ozone can be kept high. The ozone water used contains no additive, making it safe. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an ozone water treatment method for treating an object to be treated such as water or a semiconductor wafer using ozone water.

As what shows an ozone water processing method, there exist some which were described in patent document 1 and patent document 2, for example. The ozone water treatment method (hereinafter referred to as “first ozone treatment method”) disclosed in Patent Document 1 is a method related to water purification, and the ozone water treatment method (hereinafter referred to as “second ozone water” described in Patent Document 2). The “processing method” is a method related to cleaning of a semiconductor wafer. It is well known that treatment with ozone water is effective for purification, disinfection, sterilization, washing, decolorization, deodorization and the like without being limited to the above examples. However, Patent Document 1 and Patent Document 2 do not include any specific description about the properties of ozone water used in the first ozone water treatment method and the second ozone water treatment method. The ozone water used in the first ozone water treatment method is such that the ozone (ozone gas) generated by the ozone generator is mixed into the water to be treated through the ejector. According to experiments, ozone solubility cannot be increased with ozone water generated by an ozone water generation method using an ejector. For this reason, a large amount of ozone is degassed from the ozone water, and the desired ozone treatment effect cannot be obtained. The reason why the ozone solubility cannot be increased is that the dissolved ozone bubbles have a particle size of approximately 1 μm (micrometer) or more, so that the ozone bubbles receive buoyancy from the water to be treated and rise to the water surface. . In order to make it difficult for the ozone bubbles to rise to the surface of the water, the particle size of the dissolved ozone bubbles should be approximately 1000 nm (nanometers) or less, preferably 500 nm or less. In Patent Document 3, an electrolyte such as iron, manganese, calcium, sodium, magnesium ions, and other mineral ions is mixed in an aqueous solution containing ozone bubbles having a diameter of 10 to 50 μm, and the mixed aqueous solution is discharged in water. It is described that nanobubbles of 50 to 500 nm can be obtained. The aqueous solution containing the nanobubbles is hereinafter referred to as “conventional ozone water”.
JP 2001-314870 A (see paragraph 0028, FIG. 1) JP 2006-49453 A (see paragraph 0034) JP 2005-246293 A (see paragraphs 0016 to 0025, FIG. 1)

  However, since the conventional ozone water described above contains an additive such as an electrolyte, the object to be processed must be unaffected by the electrolyte. For example, consider ozone water treatment of drinking water. If the conventional ozone water described above is mixed in the case where the drinking water is subjected to the ozone water treatment, the disinfecting and sterilizing effect will be obtained, but the provided drinking water contains the electrolyte. Electrolytes such as iron and manganese may not necessarily have a negative effect on the human body, but drinking water mixed with such impurities or additives will not require explanation that it is not suitable for drinking water. . Furthermore, since conventional ozone water first needs to generate an aqueous solution containing ozone bubbles having a diameter of 10 to 50 μm, and after adding an electrolyte, it is necessary to discharge in water. There is also a drawback that it must be complicated and large. In other words, even if ozone water treatment is performed using conventional ozone water due to the point that it contains electrolyte, the point that it takes time to produce, and the complicated size of the equipment cannot be avoided, the target object to be treated Must be very limited. This is not an easy-to-use ozone treatment method. The problem to be solved by the present invention is to provide an ozone water treatment method that overcomes the inconvenience that is a drawback of conventional ozone water.

  The inventor who has earnestly studied to solve the above problems has been able to obtain ozone water containing ozone bubbles having a diameter of 500 nm or less when ozone water is mixed with water to generate ozone water. The present invention intends to perform ozone water treatment using the ozone water. The detailed configuration of the invention will be described again. It should be noted that the definitions of terms used to describe the invention described in any claim are applicable to the invention described in other claims as long as possible in nature. In the present application, “raw water” is a concept including both raw water before ozone dissolution (ground water, tap water, river water, rain water, etc.) and ozone water generated by dissolving ozone in raw water. The raw water and the ozone water are properly used according to the ozone water generation process.

(Characteristics of the invention of claim 1)
The ozone water treatment method according to the invention of claim 1 (hereinafter referred to as “the treatment method of claim 1” as appropriate) is performed by adding ozone water in which the particle size R of the contained ozone bubbles is 0 <R ≦ 1000 nm, It includes an ozone water generation process that is generated by a gas-liquid mixing method that is not included, and an ozone water treatment process that processes an object to be processed using the ozone water generated in the ozone water generation process.

  According to the processing method of claim 1, it is possible to efficiently treat the object to be treated with ozone water. The contents of the ozone water treatment vary depending on the type and nature of the object to be treated. For example, the processing method which inject | pours into a to-be-processed object, spreads, bathes, and makes it immerse is mentioned. By performing the ozone water treatment, for example, a disinfection effect is brought about if the object to be treated is water, and a cleaning effect is brought about if it is a semiconductor wafer. In addition to the above effects, for example, effects such as disinfection, sterilization, cleaning, decolorization, and deodorization may be obtained by ozone water treatment. Here, the ozone water generated in the ozone water generating step has a very high ozone solubility because the particle size R of the ozone bubbles it contains is 1000 nm or less. As a result, there is no ozone to be degassed. But very few. That is, ozone bubbles having a particle size of 1000 nm or less have extremely small buoyancy from the water in which they are contained. For this reason, all or most of the ozone bubbles stay in the water without rising to the water surface. In other words, since the ozone bubbles having a particle diameter exceeding 1000 nm are considered to be easily degassed by the effect of the received buoyancy, the inventor excluded the ozone bubbles from the present invention. Since ozone (ozone gas) does not degas (it is difficult to degas), the ozone solubility is high and the ozone concentration can be maintained high. Being able to maintain a high ozone concentration means that the amount of ozone water to be generated in order to perform the same treatment can be reduced compared to ozone water having a low concentration. That is, it is possible to reduce the scale of an apparatus or a plant for generating ozone water by an amount corresponding to the increased concentration. In addition, it is known that ozone is harmful to the human body, etc. The fact that ozone is not degassed or is extremely difficult to degas is safe because it does not come out of ozone water. In terms of use, it is extremely convenient. It is also possible to directly treat livestock with ozone water. Furthermore, it greatly contributes to ensuring the safety of workers engaged in ozone water treatment. Furthermore, since no additive such as an electrolyte is used in generating ozone water from ozone water, the generated ozone water does not contain more than the raw water contains except dissolved ozone. For this reason, it is not necessary to consider the bad influence by an additive, and it can apply to all to-be-processed objects.

(Characteristics of the invention described in claim 2)
The ozone water treatment method according to the invention described in claim 2 (hereinafter referred to as “treatment method of claim 2” as appropriate) includes ozone water in which the particle size R of the contained ozone bubbles is 0 <R ≦ 500 nm, It includes an ozone water generation process that is generated by a gas-liquid mixing method that is not included, and an ozone water treatment process that processes an object to be processed using the ozone water generated in the ozone water generation process.

  According to the processing method of claim 2, it is possible to efficiently treat the object to be treated with ozone water. The contents of the ozone water treatment vary depending on the type and nature of the object to be treated. For example, the processing method which inject | pours into a to-be-processed object, spreads, bathes, and makes it immerse is mentioned. By performing the ozone water treatment, for example, a disinfection effect is brought about if the object to be treated is water, and a cleaning effect is brought about if it is a semiconductor wafer. In addition to the above effects, for example, effects such as disinfection, sterilization, cleaning, decolorization, and deodorization may be obtained by ozone water treatment. Here, the ozone water generated in the ozone water generation step has a very high ozone solubility because the particle size R of the ozone bubbles it contains is 500 nm or less. As a result, there is no ozone to be degassed. But very few. That is, ozone bubbles having a particle size of 500 nm or less have extremely low buoyancy from the water in which they are contained. For this reason, all or most of the ozone bubbles stay in the water without rising to the water surface. Ozone bubbles having a particle size of 500 nm or less tend to stay more easily than ozone bubbles having a particle size of more than 500 nm and 1000 nm or less, that is, more difficult to degas. On the other hand, in order to make the particle size smaller, it generally takes time and effort (for example, the number of times of dissolution and time for dissolution), so it is preferable to use them properly depending on the application. Since ozone (ozone gas) does not degas (it is difficult to degas), the ozone solubility is high and the ozone concentration can be maintained high. Being able to maintain a high ozone concentration means that the amount of ozone water to be generated in order to perform the same treatment can be reduced compared to ozone water having a low concentration. That is, it is possible to reduce the scale of an apparatus or a plant for generating ozone water by an amount corresponding to the increased concentration. In addition, it is known that ozone is harmful to the human body, etc. The fact that ozone is not degassed or is extremely difficult to degas is safe because it does not come out of ozone water. In terms of use, it is extremely convenient. It is also possible to directly treat livestock with ozone water. Furthermore, it greatly contributes to ensuring the safety of workers engaged in ozone water treatment. Furthermore, since no additive such as an electrolyte is used in generating ozone water from ozone water, the generated ozone water does not contain more than the raw water contains except dissolved ozone. For this reason, it is not necessary to consider the bad influence by an additive, and it can apply to all to-be-processed objects.

(Characteristics of Claim 3)
The ozone water treatment method according to the invention of claim 3 (hereinafter, referred to as “treatment method of claim 3” as appropriate) includes ozone water in which the particle size R of the contained ozone bubbles is 0 <R ≦ 50 nm, It includes an ozone water generation process that is generated by a gas-liquid mixing method that is not included, and an ozone water treatment process that processes an object to be processed using the ozone water generated in the ozone water generation process.

  According to the processing method of claim 3, it is possible to efficiently treat the object to be treated with ozone water. The contents of the ozone water treatment vary depending on the type and nature of the object to be treated. For example, the processing method which inject | pours into a to-be-processed object, spreads, bathes, and makes it immerse is mentioned. By performing the ozone water treatment, for example, a disinfection effect is brought about if the object to be treated is water, and a cleaning effect is brought about if it is a semiconductor wafer. In addition to the above effects, for example, effects such as disinfection, sterilization, cleaning, decolorization, and deodorization may be obtained by ozone water treatment. Here, the ozone water generated in the ozone water generation step has a very high ozone solubility because the particle size R of the ozone bubbles it contains is less than 50 nm. As a result, there is no ozone to be degassed. But very few. That is, ozone bubbles having a particle size of 50 nm or less have extremely small buoyancy from the water in which they are contained. For this reason, all or most of the ozone bubbles stay in the water without rising to the water surface. Ozone bubbles with a particle size of 50 nm or less tend to stay more easily than ozone bubbles with a particle size of more than 50 nm and 1000 nm or less, that is, they are more difficult to degas. On the other hand, in order to make the particle size smaller, it generally takes time and effort (for example, the number of times of dissolution and time for dissolution), so it is preferable to use them properly depending on the application. Since ozone (ozone gas) does not deaerate, the ozone solubility is high and the ozone concentration can be kept high. Being able to maintain a high ozone concentration means that the amount of ozone water to be generated in order to perform the same treatment can be reduced compared to ozone water having a low concentration. That is, it is possible to reduce the scale of an apparatus or a plant for generating ozone water by an amount corresponding to the increased concentration. In addition, it is known that ozone is harmful to the human body, etc. The fact that ozone is not degassed or is extremely difficult to degas is safe because it does not come out of ozone water. In terms of use, it is extremely convenient. It is also possible to directly treat livestock with ozone water. Furthermore, it greatly contributes to ensuring the safety of workers engaged in ozone water treatment. Furthermore, since no additive such as an electrolyte is used in generating ozone water from ozone water, the generated ozone water does not contain more than the raw water contains except dissolved ozone. For this reason, it is not necessary to consider the bad influence by an additive, and it can apply to all to-be-processed objects.

(Feature of the invention of claim 4)
In the ozone water treatment method according to the invention of claim 4 (hereinafter referred to as “treatment method of claim 4” as appropriate), as a preferred embodiment in the ozone water generation step of the treatment method of any one of claims 1 to 3, a small path is used. The raw water is passed through a Venturi tube having ozone, ozone is supplied to the Venturi tube, and a magnetic force is applied to at least the small path of the Venturi tube. The Venturi tube is sometimes called an ejector.

According to the processing method of claim 4, on the premise of the operational effect of any of the processing methods of claims 1 to 3, it is possible to cause a magnetic force to act on at least a small path of a venturi tube that supplies ozone. Generation of ozone water having a diameter R of 0 <R ≦ 1000 nm (500 nm, 50 nm) is extremely facilitated. The pressure of the raw material water passing through the venturi pipe increases at a stroke as it approaches the small path, and decreases at a stroke after passing through the small path. When the pressure is reduced, the inside of the Venturi tube is in a vacuum or a negative pressure state close to vacuum, and ozone supplied by this negative pressure state is sucked into the raw material water. The suctioned ozone is agitated and mixed all at once, with the pressure change and the change in the flow of water to be treated accompanying the passage of the small path intertwined in a complex manner. This series of actions is considered to be one of the factors that facilitate the generation of ozone water in combination with the action of magnetic force. The inventor is currently elucidating the causal relationship regarding the ability to reduce the particle size of ozone bubbles to 1000 nm (500 nm, 50 nm) or less by applying a magnetic force to a small path, but this point is the result of an experiment described later. Will become apparent. The structure necessary for generating ozone water is very simple and can be easily downsized.

(Feature of the invention of claim 5)
In the ozone water treatment method according to the invention of claim 5 (hereinafter, referred to as “treatment method of claim 5” as appropriate), as a preferred embodiment of the treatment method of claim 4, raw water (ozone water) that has passed through the venturi pipe ) And circulating the venturi at least once while supplying ozone.

  According to the processing method of claim 5, on the premise of the operational effect of the processing method of claim 4, ozone injection into the raw material water (ozone water) can be repeatedly performed by the circulation of the raw material water. If ozone injection is performed repeatedly, the ozone solubility and the ozone concentration can be increased in the latter than in the former by re-injecting ozone into the raw water (ozone water) once ozone injection has been completed. The number of times of circulation may be determined by the user of the apparatus according to the desired ozone solubility and ozone concentration.

(Characteristics of the invention described in claim 6)
In the ozone water treatment method according to the invention of claim 6 (hereinafter, referred to as “treatment method of claim 6” as appropriate), as a preferred embodiment of the treatment method of claim 4, the circulated raw water is once stored in a storage tank. Do storage.

  According to the processing method of Claim 6, on the premise of the effect of the processing method of Claim 4, raw water (ozone water) can be temporarily stored in a storage tank, and by this storage, raw water (ozone water) Can be put in a stable state, whereby ozone dissolution in the raw water (ozone water) can be promoted by an action similar to aging.

(Feature of the invention of claim 7)
In the ozone water treatment method according to the invention of claim 7 (hereinafter, referred to as “treatment method of claim 7” as appropriate), as a preferred embodiment of the treatment method of claim 6, the raw water stored in the storage tank is temporarily used. It takes out and hold | maintains in the range of 5-15 degreeC.

  According to the treatment method of the seventh aspect, the temperature of the raw water (ozone water) can be maintained in the above range by holding the temperature on the premise of the operational effect of the treatment method of the sixth aspect. In many cases, raw water used for generating ozone water is transported in a long pipe, and the raw water transported in such a case is easily affected by the weather. In particular, the water temperature rises significantly in the summer. Moreover, in order to circulate raw material water (ozone water), the energy for circulation is required, and there exists a pump as such an energy source, for example. The energy source described above generally generates heat, and the heat may increase the temperature of the raw water (ozone water). Ozone dissolution is affected by the water temperature, and the solubility decreases as the water temperature increases. Therefore, ozone dissolution is promoted by keeping the temperature of the raw water (ozone water) within a predetermined range. On the other hand, for example, when the raw water (ozone water) may freeze in a cold region, a heater device may be provided to heat the raw water (ozone water) treated water. If cooling or heating of raw water (ozone water) is not required, the temperature holding structure itself may be omitted, or the operation of the provided temperature holding structure may be stopped.

(Characteristics of the invention described in claim 8)
In the ozone water treatment method according to the invention of claim 8 (hereinafter referred to as “treatment method of claim 8” as appropriate), as a preferred embodiment of the treatment method of any one of claims 4 to 7, the raw material after supplying ozone Water is temporarily stored in a dissolution accelerating tank to promote ozone dissolution.

  According to the production apparatus of the eighth aspect, on the premise of the operational effect of the processing method of any one of the fourth to seventh aspects, the dissolution of ozone in the raw water (ozone water) is promoted by the action of the dissolution accelerating tank. The raw water (ozone water) stored in the dissolution accelerating tank is placed in a stable state by the storage. In the raw material water (ozone water) placed in a stable state, ozone dissolution is promoted by an action similar to aging.

(Feature of the invention of claim 9)
In the ozone water treatment method according to the invention of claim 9 (hereinafter, referred to as “treatment method of claim 9” as appropriate), as a preferred embodiment of the treatment method of claim 8, the top part of the dissolution accelerating tank is stored. The ozone degassed from the raw water (ozone water) treated water is discharged.

  According to the treatment method of claim 9, on the premise of the effect of the treatment method of claim 8, ozone that has not dissolved in the raw water (ozone water) in the process of circulating the raw water (ozone water) is discharged to the outside. can do. By discharging undissolved ozone, the ozone contained in the raw water (ozone water) becomes highly soluble. Therefore, ozone water with truly high ozone solubility is generated.

(Features of the invention of claim 10)
The ozone water treatment method according to the invention of claim 10 (hereinafter referred to as “treatment method of claim 10” as appropriate) is a magnetic field as a preferred embodiment of the ozone water generation step in the treatment method of any one of claims 1 to 3. The method includes a step of increasing the water pressure of the raw material water to the pressure peak, reducing the pressure immediately after reaching the pressure peak, and supplying ozone to the raw water reaching the pressure peak.

  According to the treatment method of the tenth aspect, on the premise of the operational effect of the treatment method of any one of the first to third aspects, the magnetic force of the magnet is caused to act in the process of mixing the raw material water and ozone. That is, not only the raw water but also the magnetic action acts on ozone dissolved in the raw water and ozone not dissolved in the raw water. The raw water used for ozone mixing contains ozone bubbles of various sizes, and the flow is very irregular turbulent flow. Therefore, the direction of the magnetic force acting on the raw water and ozone is extremely irregular and unstable. It is clear from the experimental results described later that the irregular and unstable magnetic action is effective for producing high-concentration ozone water having high solubility. However, the causal relationship between high-solubility and high-concentration ozone water and magnetic force is currently being elucidated.

(Characteristic of the invention of claim 11)
The ozone water treatment method according to the invention of claim 11 (hereinafter referred to as “the treatment method of claim 11” as appropriate) is a preferred embodiment in the ozone water treatment step of the treatment method of any one of claims 1 to 10. The method includes an ozone water injection step of injecting the ozone water into water or warm water which is a product.

  According to the treatment method of claim 11, purification or sterilization of water or hot water can be efficiently performed on the premise of the operational effect of the treatment method of any of claims 1 to 10. Since the treated water does not contain additives such as electrolytes, safe drinking water can be obtained by combining with treatment such as filtration. The ozone treatment at the current water treatment plant is, for example, a method of releasing ozone into the water stored in a treatment tower of about 30 meters, but this method requires huge equipment and the ozone treatment efficiency is also very high. However, according to the treatment method of claim 9, since the treatment uses ozone water with high solubility and high concentration, the ozone water treatment can be performed very efficiently.

(Feature of the invention of claim 12)
In the ozone water treatment method according to the invention of claim 12 (hereinafter, appropriately referred to as “treatment method of claim 12”), as a preferred embodiment of the treatment method of claim 11, in the ozone water injection step, ozone water injection is performed. Stir with water or warm water.

  According to the treatment method of claim 12, on the premise of the operational effect of the treatment method of claim 11, the raw water and the ozone water are efficiently brought into contact by stirring, so that the ozone water treatment is efficiently performed. Since the ozone water treatment is performed efficiently, the amount of treatment can be increased by that amount, or the equipment for treating the same amount of treatment can be reduced in size.

(Feature of the invention of claim 13)
According to a thirteenth aspect of the present invention, there is provided an ozone water treatment method (hereinafter referred to as “treatment method of claim 13” as appropriate). This is performed by injecting the ozone water into the water that has been passed through.

  According to the processing method of claim 13, on the premise of the operational effect of the processing method of claim 12, injection and stirring of ozone water is performed by an ejector or a static mixer, so that the injection and stirring can be efficiently performed with a small and simple structure. Can be done well.

  According to the present invention, an object to be treated can be treated with ozone water with ozone water generated without including an electrolyte and without taking time and effort to generate the electrolyte. There is no need to increase the size of processing equipment. From these things, the to-be-processed object used as the object of ozone treatment is not limited, and the ozone water treatment method which is very easy to use can be provided.

  The best mode for carrying out the present invention will be described with reference to the drawings. FIG. 1 is a schematic configuration diagram of a water purification apparatus including an ozone water treatment apparatus. FIG. 2 is a schematic configuration diagram of an ozone water treatment apparatus including an ozone water generation apparatus. FIG. 3 is a correlation diagram of members and structures constituting the ozone water treatment apparatus shown in FIG. 4 is a longitudinal sectional view of the raw water subdivision structure shown in FIG. FIG. 5 is a longitudinal sectional view of the first vortex pump. FIG. 6 is a longitudinal sectional view of the second eddy current pump. FIG. 7 is a longitudinal sectional view of the ejector. FIG. 8 is a longitudinal sectional view of the static mixer. FIG. 9 is a longitudinal sectional view of the cyclone. FIG. 10 is a schematic configuration diagram illustrating a first modification of the ozone water generating device. FIG. 11 is a longitudinal sectional view showing a modification of the vortex pump. FIG. 12 is a longitudinal sectional view showing a modification of the ejector. FIG. 13 is a schematic configuration diagram illustrating a second modification of the ozone water generation device. FIG. 14 is a front view of the gas-liquid mixing structure. FIG. 15 is a left side view of the gas-liquid mixing structure shown in FIG. 16 is a cross-sectional view taken along the line XX of the gas-liquid mixing structure shown in FIG. FIG. 17 is a plan view of the gas-liquid mixing structure with a part omitted. FIG. 18 is a longitudinal sectional view of the dissolution accelerating tank. FIG. 19 is a schematic configuration diagram of an ozone water generator for performing a comparative experiment. FIG. 20 is a schematic configuration diagram of an ozone water generator applied to the water purification apparatus shown in FIG.

(Schematic structure of ozone water treatment equipment)
An ozone water treatment apparatus for carrying out the ozone water treatment method in the present embodiment will be described with reference to FIG. The ozone water treatment device 303 is generally composed of an ozone water generation device 305 and an ozone water treatment structure 307. A reference numeral 309 indicates a water treatment tank disposed in the subsequent stage of the ozone water generation apparatus 305. The ozone water generation device 305 is a device for generating ozone water for performing ozone water treatment. The ozone water treatment structure 307 is a device for treating water that is an object to be treated with ozone water supplied from the ozone water generation device 305. The water treatment tank 309 is for, for example, filtering the water after the ozone water treatment. The ozone water treatment device 303 and the water treatment tank 309 constitute a water purification device 301 for purifying drinking water. Here, the terms will be amended to describe the configuration of each of the above members. First, an ozone water generator applicable to the ozone water generator 305 will be described.

(Usage example of ozone water generator)
Based on FIG. 1 and 2, the usage example of an ozone water production | generation apparatus is demonstrated. The code | symbol 1 has shown the ozone water processing apparatus (disinfection apparatus) provided with the ozone water production | generation apparatus. That is, the ozone water treatment apparatus 1 includes the water intake valve 3, the ozone water generation apparatus 5 for generating ozone water from the raw water (treated water) taken from the water intake valve, and the ozone water generated by the ozone water generation apparatus. A pressurizing pump 7 and a nozzle 9 for taking out and spraying are schematically configured. The intake valve 3 is an electromagnetic valve and is connected to a supply source of tap water or well water serving as raw water. The ozone water generating device 5 is for dissolving ozone in the water to be treated to generate ozone water having a predetermined concentration. In this embodiment, the ozone water generating device 5 is composed of a raw water subdividing structure 11 and an ozone dissolving structure 13 which will be described later. is there. The pressurizing pump 7 is a pump that pressurizes the generated ozone water to a predetermined pressure. The ozone water pressurized by the pressure pump 7 is sprayed through the nozzle 9 (nozzle group 9). Although the nozzle 9 is handled as a single unit for convenience of explanation, a plurality of nozzles 9 may be used. The ozone water treatment apparatus 1 is generally installed and used in a place or facility (for example, a livestock house such as a pig house or a poultry house) where ozone water spraying is to be performed. It can also be configured to be movable.

(Raw water subdivision structure)
This will be described with reference to FIGS. The raw water subdivision structure 11 is for subdividing the raw water cluster taken from the intake valve 3 to generate subdivided raw water. The raw water subdivision structure 11 comprises a metal casing 11a fixed concentrically with the pipe 4 on the outer periphery of the pipe 4 through which the raw water G flows, a packing 11b, and magnets 11c and 11c sealed in the casing 11a. is there. The magnets 11c and 11c are for causing a magnetic force to act on the raw water. The magnets 11c and 11c preferably have a magnetic force of about 1 to 1.5 T (10,000 to 15,000 gauss), for example. It is known that water such as raw water G forms a cluster Gc, but the raw water subdivision structure 11 has a function of subdividing the raw water cluster Gc into clusters Gs by applying energy. . The clusters Gc and Gs shown in FIG. 3 are conceptual diagrams shown for explanation only, and are not necessarily subdivided as shown in the figure, and the measurement method is not established, but the raw water subdivision As shown in Tables 1 and 2, it is apparent from the phenomenon that the concentration arrival time can be shortened and the ozone half-life can be extended as shown in Tables 1 and 2. It can be seen that the rate at which ozone is degassed and decomposed from the ozone water is effectively suppressed. Instead of the magnet 11c, a carbon chip group capable of acting a far-infrared effect, an ultrasonic generator capable of giving fine vibration, or the like can be used. The position where the raw water subdivision structure 11 is provided may be upstream or downstream of the intake valve 3. Furthermore, it goes without saying that the pipe 4 should be made of a material that does not interfere with transmission of far-infrared rays or magnetic force, such as vinyl chloride. In addition, the raw | natural water subdivision structure 11, ie, a magnet, can also be suitably provided in the upstream and / or downstream of a vortex pump, an ejector, and a static mixer so that it may mention later.

(Ozone dissolution structure)
Reference is made to FIGS. The ozone dissolution structure 13 includes a storage tank 15, an ozone supply structure (ozone supply device) 19, and a circulation structure 21. The storage tank 15 is a tank for storing raw water and / or ozone water injected through the intake valve 3, and has a storage amount of about 3 tons, for example. The ozone supply structure 19 is a device for generating and supplying ozone, but there is no limitation on the principle of ozone generation or the like as long as it can supply a necessary amount of ozone. The circulation structure 21 is for returning the water to be treated taken out from the storage tank 15, that is, the subdivided raw water and / or ozone water, to the storage tank 15 after ozone dissolution, and is constituted by a plurality of members and structures described later. It is.

(Circulation structure)
This will be described with reference to FIGS. The circulation structure 21 includes a first eddy current pump 31, an ejector 35, a first static mixer 41, a second eddy current pump 31 ', a second static mixer 51, a cyclone 55, an ozone water return pipe 61, an ozone return pipe 65, and each of the above. It is comprised by the piping group which connects a member. Among the configurations described above, the one excluding the ozone return pipe 65 is a circulation path for dissolving ozone in the subdivided raw water and / or ozone water taken out from the storage tank 15 and returning it to the storage tank 15 again. Is a circulation path for returning surplus ozone extracted from the cyclone 55 to the second vortex pump 31 '. Hereinafter, each component will be described. As described above, it is preferable to subdivide the cluster of raw water from the viewpoint of ozone dissolution. On the other hand, this cluster subdivision is an effective ozone dissolution means not only for raw water but also for ozone water. For this reason, it is good to make a magnetic force act on the circulating ozone water by providing the same or similar magnet as the magnet 11c mentioned above in the appropriate part of each member and apparatus which comprise the circulation structure 21. FIG.

(Vortex pump)
The first vortex pump will be described with reference to FIGS. The first vortex pump 31 is roughly composed of a thick disc-shaped pump body 32, a suction part 32a and a discharge part 32b protruding from the pump body 32 as a part of the pump body 32, and an impeller 33 rotating in the pump body 32. It is configured. The suction part 32a is connected to the storage tank 15 via the pipe 16, and the discharge part 32b is connected to the ejector 35 via the check valve 71 and the pipe 70, respectively. An annular boost passage 32d is formed in the pump body 32, and a suction passage 32e in the suction portion 32a and a discharge passage 32f in the discharge portion 32b are communicated with the boost passage 32d. The impeller 33 includes an impeller body 33a, a plurality of blade pieces 33b extending in the radial direction from the outer periphery of the impeller body 33a, and blade grooves 33c opened between the blade pieces 33b and 33b. ing. The impeller 33 is rotated in the pump body 32 by a motor (not shown) connected to a rotation shaft 33d provided at the center of the impeller body 33a. The impeller 33 rotates by rotating each blade piece 33b and each blade groove 33c in the pressure increase passage 32d, and at this time, pressure feeds the raw water (ozone water) sucked into the pressure increase passage 32d through the suction passage 32e while stirring. And it discharges from the discharge path 32f. Each blade piece 33b agitates raw water (ozone water) in each blade groove 33c by rotation and pumps it while promoting ozone dissolution. That is, the first vortex pump 31 has both a function as a mixing promotion structure for promoting ozone dissolution and a function as a pressure feeding structure.

  5 has basically the same structure as the first vortex pump 31. The difference is that the ozone feedback section 34 that the first vortex pump 31 does not have is used. It is only the point that has. That is, the ozone return part 34 is provided in the suction part 32a of the second vortex pump 31 ', and the return path 34a in the ozone feedback part 34 is communicated with the suction path 32e. Since the members other than the ozone feedback unit 34 are not different as described above, the same reference numerals as those shown in FIG. 4 are used for these members in FIG. 5, and description thereof is omitted. The suction part 32a of the second vortex pump 31 'is connected to the first static mixer 41 via a pipe 42, and the discharge part 32b is connected to the second static mixer 51 via a pipe 46, respectively. One end of an ozone return pipe 65 is connected to the ozone return section 34.

(Ejector)
Reference is made to FIGS. The ejector 35 has a gas-liquid mixing structure for dissolving ozone in subdivided raw water (ozone water), and includes a venturi pipe 36 having a small path 38 and an ozone supply pipe 37 for supplying ozone in the vicinity of the small path 38. It is generally composed of The subdivided raw water (ozone water) fed into the inlet path 36 a of the venturi pipe 36 is supplied from the supply path 37 a in the ozone supply pipe 37 by the negative pressure generated when passing through the narrow path 36 c in the small diameter path 38. Inhaled ozone is mixed and ozone dissolution is performed. The ozone water that has passed through the narrow path 36c in the small path 38 is pumped to the outside from the exit path 36b. Note that ozone is supplied from an ozone supply structure 19 (see FIG. 1) connected to the ozone supply pipe 37 via a pipe 20 and a valve 23 and a check valve 22 provided on the pipe 20.

(Static mixer)
This will be described with reference to FIGS. Since the 1st static mixer 41 and the 2nd static mixer 51 are comprised in the same structure, the structure of the 1st static mixer 41 is demonstrated here. The first static mixer 41 includes a cylindrical flow tube 41a and a baffle plate group 41b installed in the flow tube 41a. It is a mixing promotion structure for promoting the dissolution of ozone that has been mechanically sheared and fed together by subdivided raw water (ozone water) that has been pumped. Ozone water pumping to the first static mixer 41 is performed by the first vortex pump 31, and ozone water pumping to the second static mixer 51 is performed by the second vortex pump 31 ′. The discharge side of the second static mixer 51 is connected to a cyclone 55 via a pipe 52.

(Cyclone)
Reference is made to FIGS. The cyclone 55 includes a cyclone body 56 that is cylindrical and sealed, and a gas-liquid separator 57 that is connected to the top of the cyclone body 56. The cyclone main body 56 is configured to generate a cyclone effect and to promote dissolution with ozone by rotating and flowing ozone water pumped from the second static mixer 51 through the pipe 52 inside. That is, the gas-liquid separator 57 functions as a degassing structure for discharging ozone degassed from the ozone water, and the cyclone 55 functions as a dissolution accelerating tank for promoting ozone dissolution. The ozone in the ozone water rises while rotating, and surplus ozone degassed from the ozone water is discharged into the upper space 56a of the cyclone main body 56 and sent to the ozone return pipe 65 via the gas-liquid separator 57. The ozone in the ozone return pipe 65 is sucked by the negative pressure of the second vortex pump 31 'and mixed again into the ozone water.

(Pressure pump and nozzle)
The average particle diameter of the ozone water when spraying the pressurizing pump 7 and the nozzle 9 (nozzle group 9) is suitably set in the range of 40 to less than 200 μm or 200 to 1000 μm according to the purpose of use. Since the pressure of the ozone water to be sprayed needs to be set in the range of 0.2 to 0.8 MPa as described above, there is a certain limit to the average particle size in order to atomize within such a pressure range. This is because the ozone water sprayed from the nozzle can be efficiently distributed to livestock or barns, and there is little risk of catching a cold on piglets and the like. The ozone water taken out from the storage tank 15 through the pipe 17 is sucked into the pressurizing pump 7 from the suction port, pressurized there, and pumped to the water supply line 103 from the discharge port, and further through the electromagnetic valve 104. It is sent to the spray line 105 by pressure. As described above, a portion of the ozone water thus pumped from one side of the spray line 105 is sprayed from the nozzle 9, and the surplus ozone water remaining after spraying communicates with the other side of the spray line 105. It can be returned to the storage tank 15 via the return line 107. The solenoid valve 104 is a valve for blocking the supply of ozone water to the spray line 105, but the supply and shutoff of water can be controlled only by the operation and stop of the pressurizing pump 7, and can be omitted. is there.

(Operation of ozone water generator)
Please refer to FIG. Tap water (raw water, treated water) taken in via the intake valve 3 is injected into the storage tank 15 via the raw water subdivision structure 11. At this time, the injected tap water cluster is subdivided by the far-infrared action of the raw water subdivision structure 11, and the tap water is subdivided raw water. The subdivided raw water taken out from the storage tank 15 by the first vortex pump 31 is pumped to the ejector 35 that functions as a gas-liquid mixing structure by the first vortex pump. Ozone is supplied into the ejector 35 by the ozone supply structure 19, and ozone is dissolved in the subdivided raw water (treated water). The ozone water that has passed through the ejector 35 is accelerated in ozone dissolution by the first static mixer 41 and is pumped to the second static mixer 51 by the second vortex pump 31 ′. The ozone water whose ozone dissolution has been further promoted by the second static mixer 51 is injected into the cyclone 55. The ozone water in the cyclone 55 rotates and flows, and ozone dissolution is further promoted by the cyclone effect. The ozone water taken out from the cyclone 55 is returned to the storage tank 15 via the ozone water return pipe 61. At this time, the subdivided raw water injected into the storage tank 15 becomes ozone water. The above process is repeated until the ozone concentration of the ozone water (treated water) stored in the storage tank 15 reaches a desired concentration. The ozone water that has reached the desired concentration is taken out from the storage tank 15, is pumped by the pressurizing pump 7, and is sprayed from the nozzle group 9. The ozone water remaining after the spraying is returned to the storage tank 15 through the filter 109 and reused as described above.

  Here, the first vortex pump 31 and the second vortex pump 31 ′ are mixed while assisting in pressurizing each other. That is, the first eddy current pump 31 and the second eddy current pump 31 ′ have basically the same structure and ability, but the second eddy current pump is more than the discharge side of the first eddy current pump 31 by assisting in pressurization. The discharge side of 31 'has a slightly higher pressure (the ozone return pipe 65 returning to the second vortex pump 31' via the cyclone 55 and the gas-liquid separator 57 has the same pressure), but the second vortex pump 31 ' Excess ozone is returned to the second vortex pump 31 'by the negative pressure. That is, the generation of surplus ozone is extremely small, and this can reduce the burden on the ozone supply structure 19.

(First modification of ozone water generator)
With reference to FIGS. 9 to 11, an ozone water treatment apparatus 1A including the first modification of the ozone water generation apparatus described above will be described. The ozone water treatment apparatus 1A has a configuration that is basically common to the ozone water treatment apparatus 1. The difference between the two is mainly the ozone water generation apparatus 5 (ozone dissolving structure 13) according to the ozone water treatment apparatus 1. The ozone water generating device 5A (ozone dissolving structure 13A) of the ozone water treatment device 1A has a temperature holding device (temperature holding structure) 63 that the ozone water treatment device 1A does not have, a cyclone 55 that both have, and a dissolution promoting tank 206 is different in shape, the second eddy current pump 31'A has a magnet 32m that the second eddy current pump 31 'does not have, and the ejector 35A has a magnet 36m that the ejector 35 does not have. It is. In addition, although illustration is abbreviate | omitted, what provided the magnet in the static mixer 51 is also employable. The reason for providing a magnet in the static mixer is to increase the ozone solubility as will be described later. The dissolution accelerating tank 206 has the same structure as the dissolution accelerating tank 206 described in the description of the second modification described later. Therefore, the structure of the dissolution promoting tank 206 will be described in the description of the second modification.

  Based on FIG. 10, the difference between the second vortex pump 31′A according to the present modification and the second vortex pump 31 ′ according to the present embodiment will be described. About the point which is common in both, only the code | symbol same as the code | symbol used for 2nd eddy current pump 31 'is used in FIG. 10, The description about these points is abbreviate | omitted. That is, a plurality of magnets 32m,... Are attached to the outside of the pump main body 32 of the second vortex pump 31′A through a predetermined interval along the rotation direction of the impeller 33 as described above. Each of the magnets 32m is intended to increase the ozone solubility by dividing the clusters by applying a magnetic force to the ozone water in the pump main body 32. Therefore, the pump body 32 is made of a material that can transmit the magnetic force of each magnet 32m (for example, a metal such as stainless steel or a synthetic resin that can transmit the magnetic force). As will be described later, it is preferable to provide the first eddy current pump 31 with a magnet in the same manner as the second eddy current pump 31 ′ A in order to generate high-concentration ozone water having high solubility.

  Based on FIG. 11, the difference between the ejector 35 </ b> A according to the present modification and the ejector 35 according to the present embodiment according to the present embodiment will be described. About the point which is common in both, only the code | symbol same as the code | symbol used for the ejector 35 is used in FIG. 11, and description about these points is abbreviate | omitted. That is, as described above, a plurality of magnets 36m,... Are attached to the outside of the venturi tube 36 of the ejector 35A via a predetermined interval along the length direction. Each of the magnets 36m is intended to increase the ozone solubility by dividing the cluster by applying a magnetic force to the ozone water in the venturi tube 36. Therefore, the venturi tube 36 is made of a material that can transmit the magnetic force of each magnet 36m (for example, a metal such as stainless steel or a synthetic resin that can transmit the magnetic force). In addition, as a device that performs gas-liquid mixing, a dissolved membrane system that bundles a permeable membrane that is permeable to hollow fiber-like ozone gas in a membrane module instead of an ejector, and allows water to pass inside the permeable membrane and mix with ozone Can be used (not shown). It is also possible to subdivide the water cluster by providing a magnet in this dissolved film type apparatus.

(Second modification of ozone water generator)
A second modification of the ozone water generating device will be described with reference to FIG. The ozone water generating apparatus 201 according to the second modification includes a storage tank 202, an ozone supply structure 203 for generating and supplying ozone, and water to be treated extracted from the storage tank 202 for returning to the storage tank 202. The structure generally includes a circulation structure 204, a gas-liquid mixing structure 205 and a dissolution promoting tank 206 provided in the middle of the circulation structure 204, and a temperature holding structure 207 attached to the storage tank 202. For convenience of explanation, the following description will be made on the circulation structure 204 after the storage tank 202, the temperature holding structure 207, the ozone supply structure 203, the gas-liquid mixing structure 205, and the dissolution promoting tank 206 are performed.

(Structure around the storage tank)
As shown in FIG. 12, the storage tank 202 is configured to be able to inject raw water as treated water through a water intake valve 202v. The storage tank 202 is for storing raw water taken and water to be treated (ozone water) circulated through a circulation structure 204 described later. For example, the water to be treated stored in the storage tank 202 is held in the range of 5 to 15 ° C. by the temperature holding structure 207. The reason why the temperature is set in the above range is that it is suitable for efficiently dissolving ozone and not easily degassing the dissolved ozone. The temperature holding structure 207 is generally composed of a pump 211 for taking out the water to be treated from the storage tank 202 and a cooler 212 for cooling the taken out water to be treated. The storage tank 202 and the pump 211, The pump 211 and the cooler 212, and the cooler 212 and the storage tank 202 are connected by a pipe 213 through which the water to be treated passes. With the above configuration, the water to be treated (raw water and / or ozone water) stored in the storage tank 202 is taken out of the storage tank 202 by the action of the pump 211 and sent to the cooler 212. The cooler 212 cools the treated water sent to a temperature within a predetermined range and returns it to the storage tank 202. The pump 211 is operated only when the temperature of the water to be treated in the storage tank 202 measured by a thermometer outside the figure exceeds a predetermined range and needs to be cooled. The reason for providing the storage tank 202 is that the water to be treated is temporarily stored by allowing the cooling to be performed, and the water to be treated is put in a stable state, thereby dissolving ozone in the water to be treated by an aging-like action. This is to promote it. In addition, for example, when there is a possibility that the water to be treated may freeze in a cold district, the water to be treated is heated using a heater device in place of the cooler or together with the cooler. You can also.

(Ozone supply structure)
The ozone supply structure 203 is a device for generating and supplying ozone. As long as the necessary ozone amount can be supplied, there is no limitation on the ozone generation principle or the like on which the ozone supply structure 203 acts. Ozone generated by the ozone supply structure 203 is supplied to the gas-liquid mixing structure 205 through an electromagnetic valve 218 and a check valve 219 provided in the middle of the ozone supply pipe 217.

(Gas-liquid mixing structure)
Details of the gas-liquid mixing structure 205 will be described with reference to FIGS. The gas-liquid mixing structure 205 is generally constituted by a venturi tube 231, an ozone supply pipe 239, and a magnetic circuit 243. The venturi pipe 231 has a pipe-like appearance for allowing the treated water sent from the upstream side (right side as viewed in FIG. 15) to pass downstream (left side as viewed in FIG. 15) (FIG. 13). reference). The hollow portion penetrating the venturi pipe 231 in the longitudinal direction is communicated in the order of the upstream large path 232, the throttle inclined path 233, the small diameter path 234, the open inclined path 235, and the downstream large path 236 from the upstream side to the downstream side. Yes. The upstream large path 232 is connected to the small-diameter path 234 via a throttle ramp 233 that is inclined in the throttle direction with a steep angle of about 50 degrees with respect to the axial direction. It is opened with a gentle angle of around 30 degrees. The open inclined path 235 is connected to the downstream large path 236 having the same outer diameter as the upstream large path 232. On the other hand, the open end of the ozone supply pipe 239 faces the small path 234. An ozone supply pipe 217 communicating with the ozone supply structure 203 is connected to the supply end of the ozone supply pipe 239. Since the inside of the small path 234 or the vicinity thereof becomes a vacuum or a state close to a vacuum due to a change in the pressure of the water to be treated, ozone that has reached the open end is aspirated and diffused into the water to be turbulent Is done. Reference numeral 240 denotes a rib for reinforcing the space between the venturi pipe 231 and the ozone supply pipe 239.

  A magnetic circuit 243 is fixed to the venturi tube 231 with screws (not shown). The magnetic circuit 243 connects one magnet piece 245 and the other magnet piece 246 facing each other with the venturi tube 231 interposed therebetween, and connects the one magnet piece 245 and the other magnet piece 246 to each other, and the magnet piece to the venturi tube 231. And a connecting member 248 having a U-shaped cross section (see FIG. 14) having a mounting function. The magnet piece 245 and the magnet piece 246 are configured so that the magnetic lines of force (magnetic field) pass through the small path 234 (shown by a broken line in FIG. 14; see also FIG. 16) and / or the vicinity (especially the downstream side). It is good to distribute it. However, in practice, it is technically difficult to concentrate the magnetic lines of force only on the small path 234, and therefore, the magnetic lines of force will pass through both the small path 234 and the vicinity of the small path 234. This is because it is considered that ozone can be dissolved most efficiently in the water to be treated by applying a magnetic force to both the water to be treated and ozone. The magnet piece 245 and the magnet piece 246 are composed of neodymium magnets having a magnetic force of around 7,000 gauss. It seems that the stronger the magnetic force is, the higher the ozone dissolution effect is, but at least 3,000 gauss or more is desired. Here, the reason why the 7,000 gauss magnet is adopted is its easy procurement and economical efficiency. This is not to prevent the adoption of magnets (natural magnets, electromagnets, etc.) having a magnetic force of 7,000 gauss or more. The connecting member 248 is configured by a member (for example, iron) having a large magnetic permeability (μ) so as to suppress magnetic flux leakage and concentrate the magnetic action on the water to be treated as much as possible.

(Function and effect of gas-liquid mixing structure)
With the above configuration, the water to be treated that has passed through the upstream large path 232 is compressed when passing through the throttle ramp 233, and the water pressure is rapidly increased, and at the same time, the passage speed is rapidly increased. The peak of high pressure and high speed is when the small path 234 is reached. The treated water that has passed through the small-diameter path 234 is rapidly depressurized and decelerated in the open inclined path 235, and is turbulently received by the impact of collision with the subsequent treated water. Thereafter, the water to be treated passes through the large downstream path 236 and goes out of the gas-liquid mixing structure 205. The diffused ozone is entrained in the turbulent flow of the water to be treated, becomes bubbles of various sizes, and receives a stirring action. The small-diameter path 234 and at least the water to be treated (ozone) flowing downstream thereof are subjected to the magnetic action by the action of the magnetic circuit 243 along with the stirring action. That is, the pressure of the water to be treated is increased to the pressure peak (peak), the pressure is reduced immediately after reaching the pressure peak, and ozone is supplied to the water to be treated that has reached the pressure peak. Will be done. The stirring action and the magnetic action of the magnetic field produce a synergistic effect. As a result, ozone is dissolved in the water to be treated, and high-concentration ozone water having high solubility is generated.

(Dissolution promotion tank)
The dissolution promoting tank 206 will be described with reference to FIGS. The outer appearance of the dissolution accelerating tank 206 is constituted by a cylindrical outer wall 255 whose upper and lower ends are sealed by a top plate 253 and a bottom plate 254. A cylindrical inner wall 256 is provided on the lower surface of the top plate 253 so as to hang from the lower surface. A space surrounded by the inner wall 256 serves as a storage chamber 258 for storing treated water. The outer diameter of the inner wall 256 is set to be smaller than the outer diameter of the outer wall 255, so that an inter-wall passage 259 having a predetermined width is formed between the inner wall 256 and the outer wall 255. On the other hand, the lower end of the inner wall 256 does not reach the bottom plate 254 and forms a gap having a predetermined width with the bottom plate 254. This gap functions as a lower end communication path 257. That is, the storage chamber 258 surrounded by the inner wall 256 communicates with the inter-wall passage 259 via the lower end communication passage 257. On the other hand, a plurality of communication holes 256h, 256h,... Are passed in the vicinity of the top plate 253 of the inner wall 256, and the storage chamber 258 and the inter-wall passage 259 communicate with each other through the communication holes 256h. . An elongated pumping pipe 261 is erected at the approximate center of the upper surface of the bottom plate 254. The lower end of the hollow portion of the pumping pipe 261 communicates with a water inlet hole 254h that penetrates the bottom plate 254, and the upper end of the hollow portion communicates with the storage chamber 258 via a number of small holes 261h,. ing. The upper end of the pumping pipe 261 is located slightly below the position of the communication hole 256h of the inner wall 256. A drainage hole 255h is penetrated in the vicinity of about a quarter from the height direction of the outer wall 255. That is, the inter-wall passage 259 communicates with the outside through the drain hole 255h.

  A pumping hole 253h is passed through substantially the center of the top plate 253. The pumping hole 253h communicates with the inside of the gas-liquid separator 265 disposed outside the top plate 253. The gas-liquid separator 265 functions as a deaeration structure for separating and discharging the water to be treated pushed up from the storage chamber 258 via the pumping hole 253h and the ozone deaerated from the water to be treated. The ozone separated by the gas-liquid separation device 265 is decomposed and detoxified by the ozone decomposition device 267 and then released to the outside of the device. The ozone solubility in the water to be treated is very high. Therefore, the amount of ozone to be deaerated is very small, but an ozone decomposing device 267 and the like are provided in order to improve safety. The treated water sent into the storage chamber 258 by the pumping pipe 261 is pushed by the subsequent treated water and descends. The water to be treated that has reached the lower end is folded back at the lower end communication passage 257, rises in the inter-wall passage 259, and is drained to the outside through the drain hole 255h. A part of the water to be treated is pushed up into the gas-liquid separator 265. During this time, ozone is dissolved in the water to be treated by an action similar to aging, and ozone water with high solubility is generated. On the other hand, when there is ozone that has not been completely dissolved or has been once dissolved but degassed, the ozone rises into the gas-liquid separator 265 and is separated there. Therefore, most of the ozone that cannot be completely dissolved from the water to be treated can be eliminated. As a result, the ozone solubility of the water to be treated that has passed through the dissolution accelerating tank 206 is dramatically increased.

(Circulation structure)
The circulation structure will be described with reference to FIG. The circulation structure 204 has a function of circulating the water to be treated (which has already been changed from raw water to ozone water) that has passed through the gas-liquid mixing structure 205 and passing it again through the gas-liquid mixing structure 205. The reason why the gas-liquid mixing structure 205 is passed again is to further increase the solubility and concentration of ozone by injecting ozone again into the water to be treated in which ozone has already been dissolved. The circulation structure 204 has a pump 271 as a drive source, and a storage tank 202 and a dissolution promoting tank 206 as main components. That is, the pump 271 pumps the water to be treated taken out from the storage tank 202 through the pipe 270 to the gas-liquid mixing structure 205 through the check valve 272 and the pipe 273. The water to be treated that has passed through the gas-liquid mixing structure 205 by pressure feeding passes through the pipe 274 and the dissolution promoting tank 206 and is returned to the storage tank 202 through the pipe 275. The circulation structure 204 is configured such that the above-described steps can be repeated as necessary. The number of times of circulation can be freely set in order to obtain ozone solubility, ozone concentration, etc. of ozone water to be generated. Reference numeral 276 indicates a valve provided in the middle of the pipe 275. The valve 276 is provided mainly for controlling the water pressure of the water to be treated that passes through the small path 234 (see FIG. 15) of the gas-liquid mixing structure 205 by opening and closing thereof.

(Experimental example)
An experimental example will be described with reference to FIGS. The experimental examples shown here are mainly intended to show that there are significant differences in the solubility and concentration of ozone due to the difference between the method of using the magnet described in the Background Art section and the method of using the magnet according to the present invention. is there. In the present experimental example, the ozone generating apparatus shown in FIG. 12 (hereinafter referred to as “the present apparatus”) is used as the apparatus according to the present invention, and the ozone generating apparatus (hereinafter referred to as the “comparing apparatus” shown in FIG. 18 as the apparatus to be compared. ”). The comparison device is basically provided with the same structure as that of the present device, but only the mounting position of the magnetic circuit 243 is different. Therefore, in FIG. 18, the same reference numerals as those used in FIG. 12 are used except for the magnetic circuit. In the magnetic circuit shown in FIG. 18, the reference numeral 243a is provided on the upstream side of the gas-liquid mixing structure 205, and the downstream side is indicated. Reference numerals 243b are respectively attached to some of them. To summarize, the apparatus shown in FIG. 12 includes a gas-liquid mixing structure 205 integrated with the magnetic circuit 243, and the comparison apparatus shown in FIG. 18 includes a magnetic circuit 243a in the upstream pipe of the gas-liquid mixing structure 205. Similarly, the magnetic circuit 243b is configured to be attached to and detached from the downstream pipes simultaneously or selectively. As the gas-liquid mixing structure 205, a model 384 manufactured by MAZEI INJECTOR CORPORATION was used, and a magnetic circuit of 7000 Gauss was used.

(Concentration comparison experiment)
The concentration comparison experiment will be described with reference to Tables 3 and 4. Table 3 shows the relationship between the ozone concentration of ozone water and the concentration rise time. Table 4 shows the time required for the ozone concentration of the ozone water shown in Table 3 to become zero after the operation of the generator is stopped. The longer it takes to reach zero, the higher the ozone solubility. In Tables 3 and 4, the symbol “□” indicates ozone water generated using the present device (hereinafter referred to as “the present ozone water”), and the symbol “×” indicates a gas-liquid mixing structure in which only the magnetic circuit is removed from the comparison device. The ozone water (hereinafter referred to as “magnetism-free ozone water”) generated by using the reference numeral “Δ” is the ozone water generated by the gas-liquid mixing structure 205 and the magnetic circuit 243a in the comparison device (hereinafter referred to as “upstream magnetic field”). “Ozone water”), symbol “◯” indicates ozone water generated by the gas-liquid mixing structure 205 and the magnetic circuit 243b in the comparison device (hereinafter referred to as “downstream magnetic ozone water”), and symbol “◇”. 1 shows ozone water (hereinafter referred to as “both-side magnetic ozone water”) generated by the gas-liquid mixing structure 205 and both the magnetic circuit 243a and the magnetic circuit 243b in the comparison device. The temperature of the water to be treated was 5 ° C., the ambient humidity was 36 to 43%, and the ambient temperature was 17 ° C.

  As Table 3 shows, the ozone water reached an ozone concentration of 20 ppm after a generation time of 35 minutes after the start of the generator operation. Under the same conditions, the ozone water without magnetism was around 8 ppm in ozone, and the downstream ozone water The ozone concentration was around 11 ppm, the upstream magnetic ozone water was only raised to an ozone concentration of around 12 ppm, and the double-sided magnetic ozone water was only raised to an ozone concentration of around 13 ppm. From this, first, the ozone concentration can be increased by providing a magnetic circuit as compared with the case where it is not provided, and then, even if the same magnetic circuit is provided, it is integrated with the gas-liquid mixing structure and the gas-liquid mixing structure It was found that the former can generate ozone water that is at least 7 ppm higher than the latter when it is provided at a location other than. That is, the ozone concentration of the present ozone water was approximately 54% ((20-13) / 13 × 100) higher than the double-sided magnetic ozone water.

  As Table 4 shows, it took 32 hours or more for the ozone concentration of the ozone water that reached an ozone concentration of 20 ppm to reach zero, whereas the double-sided magnetic ozone water that took the longest among the ozone waters to be compared It took only about 3.5 hours for the ozone concentration to reach zero from 13 ppm. Therefore, this ozone water contained ozone for a time nearly 10 times that of the double-sided magnetic ozone water. In other words, the present ozone water retained ozone which was injected and dissolved in the same amount of ozone over the same time for nearly 10 times as compared with the double-sided magnetic ozone water. This shows the high ozone solubility of the ozone water.

(Ozone bubble particle size measurement experiment)
With reference to Tables 5 and 6, the experiment for measuring the particle size of ozone bubbles contained in the present ozone water will be described. Tables 5 and 6 show the particle size distribution of ozone bubbles contained in the present ozone water (see the left vertical axis). In this measurement experiment, four types of ozone water were measured from the relationship between ozone concentration and ozone concentration retention time. First, the ozone concentration is made into two types of 3 ppm and 14 ppm, then, ozone water immediately after reaching each concentration (hereinafter referred to as “3 ppm ozone water” and “14 ppm ozone water” respectively) and the concentration Then, it was divided into ozone water whose concentration was maintained for 15 minutes (hereinafter referred to as “3 ppm maintenance ozone water” and “14 ppm maintenance ozone water”, respectively). That is, four types of measurement objects according to this measurement experiment are “3 ppm immediately after ozone water”, “3 ppm maintenance ozone water”, “14 ppm immediately after ozone water”, and “14 ppm maintenance ozone water”. Here, pure water obtained by filtering tap water with a reverse osmosis membrane of 0.05 μm (50 nm) fine particle absolute filtration was used as the raw water of the present ozone water used in this measurement experiment. An apparatus used for obtaining pure water in this experiment is an ultrapure water apparatus (model name: Model UHP) manufactured by Sener Corporation. Since tap water contains impurities of 50 nm or more (for example, iron and magnesium), even if ozone water generated from unfiltered raw water is measured, the impurities contained in it are measured, resulting in measurement errors. This is because it is possible to correctly measure the bubble diameter of ozone by removing impurities in advance by filtration. The same applies to raw water other than tap water, for example, well water and river water. The measuring instrument used for the particle size measurement of ozone bubbles is a dynamic light scattering particle size distribution measuring device (Horiba, Ltd .: model LB500). Needless to say, if there is a means capable of correctly measuring the particle size of ozone bubbles without filtering impurities from the raw water, the means can be used for the measurement.

  First, based on Table 5, the ozone water immediately after 3 ppm and the 3 ppm maintenance ozone water will be considered. The graph on the right side of Table 5 shows ozone water immediately after 3 ppm, and the graph on the left side similarly shows 3 ppm maintained ozone water. It was found that the ozone water immediately after 3 ppm contained ozone bubbles having a particle size of 1.3 μm (1300 nm) to 6.0 μm (6000 nm). On the other hand, it was found that the 3 ppm maintained ozone water contained ozone bubbles having a particle size of 0.0034 nm (3.40 nm) to 0.0050 μm (5.00 nm).

  Next, 14 ppm ozone water and 14 ppm maintenance ozone water will be considered based on Table 6. The graph on the right side of Table 6 shows ozone water immediately after 14 ppm, and the graph on the left side similarly shows 14 ppm maintenance ozone water. It was found that the ozone water immediately after 14 ppm contained ozone bubbles having a particle size of 2.3 μm (2300 nm) to 6.0 μm (6000 nm). On the other hand, it was found that the 14 ppm maintained ozone water contained ozone bubbles having a particle size of 0.0034 nm (3.40 nm) to 0.0058 μm (5.80 nm).

  The first point clarified from the above experiment is that even if ozone water has the same concentration, ozone water immediately after reaching the concentration (immediately ozone water) and ozone water that maintains the concentration for a predetermined time ( This means that the particle size of ozone bubbles contained (hereinafter referred to as “bubble particle size”) is different from that of (maintained ozone water). In the case of 3 ppm ozone water, the minimum value of the bubble diameter of ozone water immediately after is 260 times (1300 / 5.0) the maximum value of the bubble diameter of maintenance ozone water. Similarly, in the case of 14 ppm ozone water, it has a size of about 400 times (2300 / 5.8). That is, it is possible to reduce the bubble particle size by maintaining the concentration for a predetermined time, that is, by circulating ozone water as the water to be treated. If the bubble diameter is 1000 nm or less, preferably 500 nm or less, and more preferably ozone bubbles having a bubble diameter of less than 50 nm, they can be more stably suspended in the aqueous solution. According to the ozone water treatment method of the present invention, ozone water containing ozone bubbles having a particle diameter R of less than 50 nm (0 <R <50 nm), that is, ozone water having high solubility is obtained. I found out that Ozone water containing ozone bubbles of 50 nm to 1000 nm can be obtained in the process of generating ozone water having a particle diameter of less than 50 nm. In other words, ozone water generated without circulation or ozone water with a short circulation time has a larger particle size than ozone water produced by circulation or ozone water with a long circulation time. In addition, the presence or absence of circulation and the circulation time may be adjusted. In addition to these, it may be fluctuated depending on the water pressure in the circulation system, the strength of the magnet acting on the venturi tube, the concentration and supply amount of the supplied ozone, and the atmosphere at the time of generation. This is the second point that has become apparent from the experiment. In addition, according to this experiment, the measured minimum value of the particle size R of the ozone bubbles is 3.4 nm, and a value less than that is not measured. It is thought that the reason why the measurement is not performed is due to the limit of the measurement capability of the measurement device. On the other hand, since the particle size R of the ozone bubbles is smaller after the concentration is maintained than immediately after the concentration is achieved, the ozone bubbles having a particle size R that is almost zero on the extension line of the particle size reduction. Can be easily imagined.

(PH measurement experiment)
A pH measurement experiment was performed on the above four types of ozone water, that is, “3 ppm ozone water”, “3 ppm maintenance ozone water”, “14 ppm ozone water” and “14 ppm maintenance ozone water”. The results are shown as line graphs in Tables 5 and 6 (see the right vertical axis). Any ozone water showed a pH of around 7.3 before and after ozone dissolution. That is, it was found that ozone dissolution hardly changes the pH of raw water. Well water and tap water are generally neutral (pH 6.5-7.5), so the ozone water produced by the gas-liquid mixing method is neutral even without the addition of additives for adjusting the pH. It was found that However, when the raw water is alkaline, it may be possible to generate alkaline ozone water because ozone dissolution does not change the pH of the ozone water.

  The above experimental results are summarized. The present ozone water that was the subject of the experiment was generated by gas-liquid mixing in which ozone was mixed with raw water without adding any additives. Furthermore, ozone is not easily degassed even under normal pressure because of high ozone solubility. Therefore, it is safe even if it is sprayed on livestock or the human body, for example, in terms of no addition and no ozone degassing. In addition, since the ozone concentration can be made extremely high, an efficient cleaning / sterilizing effect and the like can be obtained by using the present ozone water.

  This will be described with reference to FIG. The ozone water generator 305 includes an ozone generator 305a, a venturi tube with magnet 305b, a temperature holding device 305c, and a storage tank 305d. It is configured to be able to supply water. The ozone water treatment structure 307 is configured to stir and mix (ozone water treatment) the water supplied through the pipe 307a with the ozone water in the static mixer 307b. The treated water that has passed through the static mixer 307b is sent to a subsequent water treatment tank 309. A venturi tube (ejector) can be used instead of the static mixer, and there is ozone water treatment in which ozone water is mixed into water stored in the tank.

It is a schematic block diagram of a water purification apparatus provided with an ozone water treatment apparatus. It is a schematic block diagram of an ozone water treatment apparatus provided with an ozone water production | generation apparatus. It is a correlation diagram of the member and structure which comprise the ozone water treatment apparatus shown in FIG. It is a longitudinal cross-sectional view of the raw water subdivision structure shown in FIG. It is a longitudinal cross-sectional view of a 1st vortex pump. It is a longitudinal cross-sectional view of a 2nd eddy current pump. It is a longitudinal cross-sectional view of an ejector. It is a longitudinal cross-sectional view of a static mixer. It is a longitudinal cross-sectional view of a cyclone. It is a schematic block diagram which shows the 1st modification of an ozone water production | generation apparatus. It is a longitudinal cross-sectional view which shows the modification of an eddy current pump. It is a longitudinal section showing a modification of an ejector. It is a schematic block diagram which shows the 2nd modification of an ozone water production | generation apparatus. It is a front view of a gas-liquid mixing structure. It is a left view of the gas-liquid mixing structure shown in FIG. It is XX sectional drawing of the gas-liquid mixing structure shown in FIG. It is a top view of the gas-liquid mixing structure which abbreviate | omitted one part. It is a longitudinal cross-sectional view of a dissolution promotion tank. It is a schematic block diagram of the ozone water production | generation apparatus for performing a comparative experiment. It is a schematic block diagram of the ozone water production | generation apparatus applied to the water purification apparatus shown in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ozone water treatment apparatus 1A Ozone water treatment apparatus 3 Water intake valve 4 Piping 5 Ozone water production | generation apparatus 7 Pressure pump 9 Nozzle (nozzle group)
11 Raw water subdivision structure 11a Casing 11b Packing 11c Magnet (carbon chip group, ultrasonic generator)
13 Ozone dissolution structure 15 Storage tank 16 Piping 17 Piping 19 Ozone supply structure (ozone supply device)
20 piping 21 circulation structure 22 check valve 23 valve 31 first vortex pump 31 'second vortex pump 31'A vortex pump 32 pump body 32a suction section 32b discharge section 32d boost passage 32e suction path 32f discharge path 32m magnet 33 impeller 33a Impeller body 33b Blade piece 33c Blade groove 33d Rotating shaft 34 Ozone return part 34a Return path 35 Ejector 35A Ejector 36 Venturi pipe 36a Inlet path 36b Outlet path 36c Narrow path 36m Magnet 37 Ozone supply pipe 37a Supply path 38 Small path 41 Static mixer 41 Pipe 41b Baffle plate group 42 Piping 46 Piping 51 Static mixer 52 Piping 55 Cyclone 56 Cyclone main body 56a Upper space 57 Gas-liquid separator 61 Ozone water return pipe 63 Temperature holding device 65 Return pipe 70 Pipe 71 Check valve 103 Water supply line 104 Solenoid line 105 Spray line 107 Return line 109 Filter 201 Ozone water generator 202 Storage tank 203 Ozone supply structure 204 Circulation structure 205 Gas-liquid mixing structure 206 Dissolution promotion tank 207 Temperature maintenance Structure 231 Venturi pipe 232 upstream large diameter path 233 throttle ramp 234 small diameter path 235 open slope 236 downstream large diameter path 239 ozone supply pipe 243 magnetic circuit 245 one magnet piece 246 other magnet piece 265 gas-liquid separator 267 ozone decomposition apparatus

Claims (13)

An ozone water generating step for generating ozone water in which the particle size R of the contained ozone bubbles is 0 <R ≦ 1000 nm by a gas-liquid mixing method not including an additive;
An ozone water treatment process for treating an object to be treated using the ozone water produced in the ozone water production process. An ozone water generating step of generating ozone water having a particle size R of contained ozone bubbles of 0 <R ≦ 500 nm by a gas-liquid mixing method not including an additive;
An ozone water treatment process for treating an object to be treated using the ozone water produced in the ozone water production process. An ozone water generating step of generating ozone water having a particle size R of contained ozone bubbles of 0 <R ≦ 50 nm by a gas-liquid mixing method not including an additive;
An ozone water treatment process for treating an object to be treated using the ozone water produced in the ozone water production process. In the ozone water generation step, raw water is passed through a venturi pipe having a small path, ozone is supplied to the venturi pipe, and a magnetic force is applied to at least the small path of the venturi pipe. The ozone water treatment method according to any one of 1 to 3. The ozone water treatment method according to claim 4, wherein the raw water that has passed through the venturi pipe is circulated, and the venturi pipe is re-passed at least once while supplying ozone. The ozone water treatment method according to claim 4, wherein the circulated raw material water is temporarily stored in a storage tank. 7. The ozone water treatment method according to claim 6, wherein the raw water stored in the storage tank is once taken out and held in a range of 5 to 15 ° C. The ozone water treatment method according to any one of claims 4 to 7, wherein the raw water after ozone is supplied is temporarily stored in a dissolution accelerating tank to promote ozone dissolution. The ozone water treatment method according to claim 8, wherein ozone deaerated from the raw water stored in the dissolution accelerating tank is discharged to the outside of the dissolution accelerating tank. In the ozone water generating step, in the magnetic field, the step of increasing the water pressure of the raw material water until reaching the top of the pressure, reducing the pressure immediately after reaching the top of the pressure, and supplying ozone to the raw water reaching the top of the pressure. The ozone water treatment method according to any one of claims 1 to 3, wherein the ozone water treatment method is included. The ozone water treatment method according to any one of claims 1 to 10, wherein the ozone water treatment step includes an ozone water injection step of injecting the ozone water into water to be processed or hot water. The ozone water treatment method according to claim 11, wherein in the ozone water injection step, the ozone water injection is performed while stirring with water or warm water. The ozone water treatment method according to claim 12, wherein the ozone water injection step is performed by injecting the ozone water into water that has passed through an ejector or a static mixer.

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