Ozone water generator

Abstract

To provide a technique capable of contributing to facilitating production of ozone water with a desired concentration (ozone water with high concentration).SOLUTION: An ozone water generation device comprises: an ozone gas supply line L1a capable of supplying an ozone gas; a circulation line L2a for circulating a solvent in which the ozone gas supplied through a gas-liquid mixing device 21 can be dissolved; and a control part 6 for controlling the ozone gas supply line L1a and the circulation line L2a. The ozone gas supply line L1a has: an opening / closing valve 13 for switching propriety of distribution of an ozone gas in the ozone gas supply line L1a; and a pressure meter 14 capable of measuring a gas pressure on a downstream side of the opening / closing valve 13 on the ozone gas supply line L1a. The control part 6 compares a measurement value of the pressure meter 14 with any pressure threshold set so as to become equal to or lower than a saturation vapor pressure of the solvent, for switching control of the opening / closing valve 13. When the measurement value of the pressure meter 14 becomes equal to or higher than a pressure threshold, the opening / closing valve 13 is closed.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a technology that can contribute to an ozone water generation device.

Background Art

[0002] Ozone water obtained by dissolving ozone in a solvent (for example, raw water such as pure water) has a strong oxidizing power, and thus has been used for, for example, sterilization of tap water and food. The use of such ozone water is evaluated as an environmentally friendly means because ozone is easily decomposed into oxygen in the end and does not leave residual chemicals or the like.

[0003] In recent years, attempts have been made to use ozone water in the cleaning process carried out when manufacturing various industrial parts such as precision electronic parts (for example, display parts such as semiconductor elements and FPDs). Increasing the concentration of the ozone water and stably supplying it industrially have been studied.

[0004] In Patent Document 1, first, ozone water obtained by cooling (concentrating) ozone gas is vaporized again, and the ozone gas (concentrated ozone gas) obtained by the vaporization is collected by a cooling type collector. Further, the collected matter (liquid ozone or solid ozone) is dissolved in water to obtain ozone water, and a configuration for increasing the concentration of ozone water is disclosed.

[0005] In Patent Document 2, a cleaning liquid obtained by simultaneously dissolving ozone gas and carbon dioxide gas in raw water (for example, raw water at 25°C or lower (preferably 5°C to 20°C)) is brought into contact with a resist film (organic film) on a substrate in a state where it is heated to 45°C or higher. A configuration is disclosed in which the ozone concentration of the cleaning liquid is maintained at a high concentration, making it easier to remove the resist film.

[0006] Patent Document 3 discloses a system in which ozonated water is produced by mixing ozone gas from an ozone gas generator (in Patent Document 3, a device that uses oxygen gas as a raw material) with raw water using a gas-liquid mixer. This system includes an orifice between the ozone gas generator and the gas-liquid mixer, which prevents the ozone gas generator from becoming negatively pressurized (i.e., below normal pressure (approximately 101.33 kPa)) and improves the ozone gas dissolution efficiency.

[0007] Patent Document 4 discloses a configuration that includes an ozone water circulation line for circulating ozonated water and an ozone gas contact mechanism (a permeable membrane made of fluororesin) for bringing the waste ozone gas discharged from the ozone water circulation line into contact with raw water, thereby effectively utilizing the waste ozone gas to increase the concentration of ozonated water.

[0008] Patent Document 5 discloses a method for producing ozonated water by mixing ozone gas from an ozone gas generator (in Patent Document 5, a device that uses oxygen gas as a raw material) with raw water using a gas-liquid mixer, and by passing the ozonated water (ozone water in the tank indicated by reference numeral 34 in Patent Document 5), which has been reduced to a low concentration by the raw water, through the gas-liquid mixer, the concentration of the ozonated water is increased.

[0009] Non-patent document 1 discloses that when ozone may undergo a rapid autodecomposition reaction due to external factors (e.g., triggers such as electrical sparks or contaminants that induce decomposition), CF4 gas may be applied as an inhibitor to suppress the autodecomposition reaction.

[0010] While the configurations shown in Patent Documents 1 to 5 may allow for the generation of ozonated water with a certain ozone concentration (for example, around 100 ppm), cleaning processes requiring relatively high oxidizing power will likely require ozonated water with an even higher concentration (for example, 200 ppm or more in semiconductor device cleaning processes). [Prior art documents] [Patent Documents]

[0011] [Patent Document 1] Japanese Patent Application Publication No. 11-262782 [Patent Document 2] Patent No. 4296393 [Patent Document 3] Patent No. 4746515 [Patent Document 4] Patent No. 5213601 [Patent Document 5] Patent No. 7041466 [Non-patent literature]

[0012] [Non-Patent Document 1] Taiyo Nippon Sanso Technical Report No. 28 (2009) "Explosion Range Measurement Device" [Overview of the Initiative] [Problems that the invention aims to solve]

[0013] For example, a gas-liquid mixer used in an ozone water generating device as shown in Patent Documents 3 and 5 may have a configuration that includes a solvent flow passage through which a solvent (such as raw water) flows, and an ozone gas introduction passage connected to the solvent flow passage for introducing ozone gas supplied to the gas-liquid mixer into the solvent flow passage.

[0014] In such a gas-liquid mixer, a suction pressure is generated in the ozone gas introduction passage depending on the flow rate (flow velocity) of the solvent circulating in the solvent flow passage. Then, the ozone gas introduced from the ozone gas introduction passage into the solvent flow passage is mixed with and dissolved in the solvent according to the suction pressure generated in the ozone gas introduction passage (hereinafter simply referred to as suction pressure as appropriate).

[0015] However, if the suction pressure becomes too low, for example depending on the operating conditions of the ozone water generator, ozone gas will become less soluble in the solvent. This may make it difficult to produce ozone water of the desired concentration (such as high-concentration ozone water).

[0016] Incidentally, if the suction pressure becomes too low as described above, a phenomenon (hereinafter, simply referred to as the solvent backflow phenomenon as appropriate) in which the solvent in the solvent flow path flows backward with respect to the ozone gas supply source side (such as the ozone gas supply line described later) which is the upstream side of the ozone gas introduction path is likely to occur. In this case, moisture (for example, the solvent itself, water vapor evaporated from the solvent, etc.; hereinafter, simply referred to as moisture as appropriate) flows into and remains in the ozone gas supply source side, and ozone gas cannot be supplied to the gas-liquid mixer as desired. As a result, it may become more difficult to generate ozone water of a desired concentration.

[0017] The present invention has been made in view of the above circumstances, and an object thereof is to provide a technology that can contribute to facilitating the generation of ozone water of a desired concentration.

Means for Solving the Problems

[0018] The ozone water generation apparatus according to this invention can contribute to solving the above problems. In one aspect of the generation apparatus, it includes an ozone gas supply line capable of supplying ozone gas, a circulation line for circulating a solvent into which the ozone gas is supplied via a gas-liquid mixer and which can dissolve the ozone gas, and a control unit for controlling the ozone gas supply line.

[0019] The gas-liquid mixer has a solvent flow path through which the solvent flows in a circulating state in which the solvent circulates, and an ozone gas introduction path that is connected to the solvent flow path and introduces the ozone gas supplied from the ozone gas supply line into the solvent flow path.

[0020] The ozone gas supply line has a first on-off valve capable of switching the passage of the ozone gas in the ozone gas supply line, and a pressure gauge capable of measuring the gas pressure on the downstream side of the first on-off valve in the ozone gas supply line.

[0021] The control unit compares the measured value of the pressure gauge with an arbitrary pressure threshold set to be not higher than the saturated vapor pressure of the solvent, and controls the switching of the first on-off valve.

[0022] Further, when the vapor pressure of the solvent measured and derived by measuring the temperature of the solvent in the circulation state is set as the pressure threshold, and the measured value of the pressure gauge becomes not less than the pressure threshold, the control unit may close the first on-off valve.

[0023] Further, a discharge line capable of discharging moisture flowing into the downstream side is provided on the downstream side of the first on-off valve in the ozone gas supply line, and the discharge line may have a second on-off valve capable of switching whether or not the moisture can flow through the discharge line.

[0024] Further, when the vapor pressure of the solvent measured and derived by measuring the temperature of the solvent in the circulation state is set as the pressure threshold, and the measured value of the pressure gauge becomes not less than the pressure threshold, the control unit may open the second on-off valve.

[0025] Further, a sensor capable of detecting the moisture is provided on the downstream side of the first on-off valve in the ozone gas supply line, and when the sensor detects the moisture, the control unit may open the second on-off valve.

[0026] Further, when the measured value of the pressure gauge becomes larger than the supply pressure of the ozone gas, the control unit may close the first on-off valve.

Advantages of the Invention

[0027] As described above, according to the present invention, it is possible to contribute to making it easier to generate ozone water with a desired concentration (such as high-concentration ozone water).

Brief Description of the Drawings

[0028] [Figure 1] A schematic diagram illustrating the configuration of ozone water generator A according to an example. [Figure 2] (a) is the saturated vapor pressure curve for water, and (b) is a water vapor pressure table. [Figure 3] A schematic diagram illustrating the configuration of ozone water generator B according to the example. [Figure 4] A schematic diagram illustrating the configuration of generating apparatus B1, which is a modified version of generating apparatus B. [Figure 5] A schematic diagram illustrating the configuration of generating apparatus B2, which is a modified version of generating apparatus B. [Figure 6] A schematic diagram illustrating the configuration of generating apparatus B3, which is a modified version of generating apparatus B. [Figure 7] A schematic diagram illustrating the configuration of generating apparatus B4, which is a modified version of generating apparatus B. [Modes for carrying out the invention]

[0029] The ozonated water generating apparatus of the embodiment of the present invention is completely different from a configuration that simply uses a gas-liquid mixer, as shown in, for example, Patent Documents 3 and 5 (hereinafter referred to as the conventional configuration).

[0030] In other words, this embodiment includes an ozone gas supply line capable of supplying ozone gas, a circulation line that circulates a solvent capable of dissolving the ozone gas supplied via a gas-liquid mixer, and a control unit that controls the ozone gas supply line.

[0031] The ozone gas supply line includes an on / off valve (a first on / off valve in claim 1) that can switch the flow of ozone gas in the ozone gas supply line on or off, and a pressure gauge that can measure the gas pressure downstream of the on / off valve in the ozone gas supply line.

[0032] The control unit compares the pressure gauge reading with an arbitrary pressure threshold set to be below the saturated vapor pressure of the solvent, and controls the switching of the on / off valve accordingly. The control unit closes the on / off valve when the pressure gauge reading exceeds the pressure threshold.

[0033] According to this embodiment, when the pressure gauge reading exceeds the pressure threshold, as described above, the control unit closes the on / off valve in the event that, for example, the suction pressure drops and a solvent backflow phenomenon may occur. This makes it possible to suppress (block off) the inflow of moisture into the ozone gas supply line.

[0034] If the inflow of moisture into the ozone gas supply line can be suppressed in this way, then when the suction pressure rises and the solvent backflow phenomenon is resolved (for example, when the pressure gauge reading falls below the pressure threshold and it can be determined that the solvent backflow phenomenon has been resolved), it becomes easier to quickly restore the state in which ozonated water of the desired concentration can be produced. In other words, by opening the on / off valve with the control unit and supplying ozone gas from the ozone gas supply line to the gas-liquid mixer, the ozone gas can be introduced into the solvent flow path via the ozone gas introduction path, and the ozone gas can be dissolved in the solvent.

[0035] As described above, the generating apparatus of this embodiment only needs to be configured to switch on and off valves in the ozone gas supply line by comparing the measured value of a pressure gauge in the ozone gas supply line with a pressure threshold. In other words, it is possible to appropriately apply common technical knowledge in various fields (for example, the fields of ozone gas and ozonated water generation) and modify the design as needed by referring to prior art documents as appropriate, and the embodiments described later can be given as an example of this. In the embodiments described later, detailed explanations are appropriately omitted, for example, by referring to the same reference numerals for similar content.

[0036] ≪Reference≫ For example, in a conventional configuration, if the supply pressure of ozone gas to the gas-liquid mixer is simply increased (beyond atmospheric pressure), the ozone gas will dissolve more easily in the solvent, and it may be possible to obtain high-concentration ozonated water. However, as described above, simply increasing the supply pressure of ozone gas can easily lead to a rapid self-decomposition reaction of ozone, making it difficult to maintain practical safety and potentially preventing the realization of a stable industrial supply.

[0037] Furthermore, in the case of conventional ozone gas generators (ozonizers) used in conventional configurations, the ozone gas that can be produced is of low concentration (for example, ozone concentration of 20% by volume or less), and contains a large amount of gas from components other than ozone (for example, oxygen, etc.) (hereinafter referred to as non-ozone components as appropriate). Even when using such low-concentration ozone gas, it is difficult to produce high-concentration ozonated water, and the resulting water contains a large amount of dissolved non-ozone components.

[0038] Furthermore, when ozonated water is produced by dissolving low-concentration ozone gas in a solvent under high pressure, it contains not only ozone but also non-ozone components in a supersaturated state. When such ozonated water is released into the atmosphere, bubbles are easily formed from the non-ozone components, which then disperse into the atmosphere, and the ozone components also disperse easily, making it impossible to maintain the high-concentration state of the ozonated water.

[0039] In recent years, it has become possible to produce high-concentration ozone gas (for example, ozone concentration of 50% by volume or more) by concentrating ozone gas generated by ozonizers, etc., using methods such as adsorption concentration (a method utilizing surface adsorption of silica gel, etc.) or cooling concentration.

[0040] For example, Meidensha's cooling and concentration-type ozone gas generator (product name: Pure Ozone Generator) can produce extremely high concentrations of ozone gas (over 90% by volume) with an ozone concentration close to approximately 100% by volume, and has also achieved practical safety by obtaining international safety standard SEMI-S2 certification.

[0041] The supply pressure of the concentrated ozone gas is not particularly limited; for example, it can be set to a reduced pressure to prevent the rapid self-decomposition reaction mentioned above, but it is not limited to this.

[0042] As an example of setting a reduced pressure state as described above, in the case of ozone gas with an ozone concentration of 90% by volume or more and an oxygen concentration of less than 10% by volume, the total pressure of the ozone gas can be reduced to 30 kPa (abs) or less (i.e., the ozone partial pressure can be reduced to 30 kPa (abs) or less), thereby allowing the ozone gas to be safely stored.

[0043] Furthermore, in the case of ozone gas with an ozone concentration of 50% by volume or more and an oxygen concentration of less than 50% by volume, it is recommended to reduce the total pressure of the ozone gas to a reduced pressure of 60 kPa (abs) or less (i.e., a partial ozone pressure of 30 kPa (abs) or less), thereby enabling the safe storage of the ozone gas.

[0044] When the ozone gas supply pressure is low (for example, in a reduced pressure state as described above), solvent backflow may be more likely to occur. In such cases, it is advisable to actively suppress this solvent backflow phenomenon. For example, in the case of the control unit 6 described later, this could involve actively controlling the system by appropriately acquiring the state information described later (for example, by detecting and predicting events that are likely to cause solvent backflow).

[0045] Examples <Example configuration of generating apparatus A according to the embodiment> Figure 1 is a schematic diagram illustrating the configuration of an ozone water generating apparatus A according to an embodiment. Apparatus A mainly consists of an ozone gas supply unit 1 capable of supplying ozone gas with an ozone concentration of 50% by volume or more (for example, supplying it under reduced pressure), a circulation unit 2 that introduces and circulates a solvent capable of dissolving the ozone gas supplied by the ozone gas supply unit 1 (circulating in a clockwise direction in Figure 1), a solvent supply unit 3 that supplies the solvent and gas to the circulation unit 2, and a control unit 6 that appropriately acquires information indicating the status of the ozone gas supply unit 1, circulation unit 2, solvent supply unit 3, etc. (for example, the measured value of the pressure gauge 14 in the ozone gas supply line L1a described later, the measured value of the circulation flow meter 22 in the circulation line L2a (circulation flow rate), the measured value of the resistance thermometer 24 (solvent temperature), etc.; hereinafter, these will be collectively referred to as status information as needed) and controls the ozone gas supply unit 1, circulation unit 2, solvent supply unit 3, etc.

[0046] Furthermore, in the case of apparatus A shown in Figure 1, it includes a discharge unit 4 that releases the solvent from the circulation unit 2 to the outer periphery of the circulation unit 2 (releasing the solvent in which ozone gas is dissolved, i.e., ozonated water), and an exhaust unit 5 that can exhaust the gas phase gas separated from the solvent from the circulation unit 2, and each of these is controlled by a control unit 6 which acquires and controls their respective state information as appropriate.

[0047] <Example of Ozone Gas Supply Unit 1 Configuration> The ozone gas supply unit 1 shown in Figure 1 mainly comprises an ozone gas generator 10, an ozone gas supply line L1a that supplies the ozone gas generated by the ozone gas generator 10 to the circulation unit 2 (supplied via a gas-liquid mixer 21 described later), and a gas component discharge line L1b connected to the ozone gas supply line L1a that discharges gas components such as ozone gas from the ozone gas supply line L1a (for example, exhausting to adjust the gas pressure of the ozone gas supply line L1a).

[0048] In this ozone gas supply unit 1, the ozone gas generator 10 only needs to be capable of generating ozone gas with an ozone concentration of 50% by volume or more and supplying it under reduced pressure, and various configurations can be applied. As an example, one configuration is one in which ozone gas generated by an ozonizer or the like is concentrated by an adsorption concentration method or a cooling concentration method.

[0049] The adsorption concentration method utilizes surface adsorption phenomena, such as silica gel, to concentrate the ozone gas. If impurities such as NOx or heavy metals are present in the ozone gas to be concentrated, these impurities may also be concentrated during the concentration process. Therefore, it is preferable to remove such impurities beforehand if they are present.

[0050] On the other hand, the cooling concentration method involves cooling the ozone gas to be concentrated to obtain liquid ozone, which is then vaporized. Furthermore, because ozone gas and impurities have different vapor pressures (for example, by several orders of magnitude), the ozone gas concentrated by the cooling concentration method (the vaporized ozone gas) will, in principle, contain almost no impurities. Therefore, if there is a possibility that impurities are mixed into the ozone gas to be concentrated, it is preferable to apply the cooling concentration method.

[0051] Next, the ozone gas supply line L1a is equipped with a gas flow controller 11, which is configured to control the flow rate of ozone gas circulating through the ozone gas supply line L1a. Furthermore, upstream of the gas flow controller 11 (on the ozone gas generator 10 side), there is a pressure gauge 12 that measures the gas pressure of the ozone gas circulating upstream (i.e., the supply pressure of the ozone gas supplied to the gas-liquid mixer 21 described later).

[0052] Furthermore, downstream of the gas flow controller 11, there is an on / off valve (two on / off valves in Figure 1) 13 that can freely switch the flow of ozone gas (supply or backflow of ozone gas) in the ozone gas supply line L1a.

[0053] The on / off valve 13 (and the various on / off valves described later) may be, for example, a check valve, but is not limited to this, and can be switched as described above. As a specific example, in the case of the on / off valve 13, it may be a valve that switches according to the differential pressure between the supply pressure of ozone gas and the measured value of the pressure gauge 14 described later (the differential pressure when the supply pressure > measured value), and closes when the differential pressure reaches a certain value (for example, 1 kPa or less).

[0054] Furthermore, a pressure gauge 14 is provided downstream of the on / off valve 13 to measure the gas pressure downstream. This pressure gauge 14 can measure the gas pressure corresponding to the suction pressure when ozone gas is drawn in by the gas-liquid mixer 21 described later, and it is possible to evaluate this suction pressure.

[0055] Next, the gas component discharge line L1b is connected in communication with the gas flow controller 11 and the on / off valve 13 in the ozone gas supply line L1a, and is equipped with an on / off valve 15 that can switch on or off whether or not gas components such as ozone gas flow (exhaust) from the ozone gas supply line L1a. Furthermore, downstream of the on / off valve 15, there is an ozone decomposer (ozone killer) 16 that safely decomposes the gas components (especially ozone gas) flowing through the gas component discharge line L1b, and a vacuum pump 17 that sucks up and discharges the decomposed ozone gas.

[0056] <Example of the configuration of the circulation unit 2> The circulation unit 2 shown in Figure 1 mainly comprises a circulation line L2a into which the solvent from the solvent supply unit 3 can be introduced and circulated, a circulation tank 20 connected to the circulation line L2a and capable of introducing and storing a certain amount of solvent, a reflux line L2b that returns the solvent released from the circulation tank 20 to the circulation line L2a, and a gas-liquid mixer 21 that mixes the solvent and ozone gas.

[0057] In this circulation unit 2, the circulation line L2a is configured to allow ozone gas supplied from the ozone gas supply unit 1 to the gas-liquid mixer 21 to be introduced into the circulation line L2a via the gas-liquid mixer 21 and dissolved in the solvent. In the circulation unit 2 shown in Figure 1, the circulation line L2a and the gas-liquid mixer 21 are depicted as connected and integrated, but this is not the only configuration; the two may be separate components.

[0058] The gas-liquid mixer 21 can be, for example, an ejector, aspirator, or jet pump, but is not limited to these, and various configurations can be applied. In other words, the gas-liquid mixer 21 can have a solvent flow passage (not shown) through which the solvent flows, and an ozone gas introduction passage (not shown) connected to the solvent flow passage and provided to introduce the ozone gas supplied to the gas-liquid mixer 21 into the solvent flow passage.

[0059] In a gas-liquid mixer 21 configured as described above, which has a solvent flow path and an ozone gas introduction path, a suction pressure is generated in the ozone gas introduction path according to Bernoulli's theorem, depending on the flow rate (flow velocity) of the solvent flowing through the solvent flow path. In addition, vapor is generated in the ozone gas introduction path according to the saturated vapor pressure characteristics of the solvent. For example, if the solvent is raw water, the characteristics will be as shown in the saturated vapor pressure curve and water vapor pressure table of Figure 2.

[0060] Based on the saturated vapor pressure characteristics of the solvent shown in Figure 2, the range of suction pressures below the saturated vapor pressure of the solvent can be derived as the range in which ozone gas can be introduced into the solvent flow path via the ozone gas introduction path and dissolved in the solvent (hereinafter referred to as the suctionable pressure range). This allows the control unit 6 to make various settings that take the suctionable pressure range into consideration (for example, setting the pressure threshold described later to be below the saturated vapor pressure).

[0061] In the control unit 6, when the solvent temperature is measured (for example, by the resistance thermometer 24 described later) while the solvent is circulating in the circulation line L2a (hereinafter simply referred to as the circulation state), the vapor pressure at that solvent temperature can be derived by comparing the measured value with the saturated vapor pressure characteristics of the solvent. Then, various settings can be made taking the derived vapor pressure into consideration.

[0062] For example, the derived vapor pressure can be set as the pressure threshold described later, or the supply pressure of ozone gas to the gas-liquid mixer 21 can be set to be greater than the derived vapor pressure.

[0063] Furthermore, based on the saturated vapor pressure characteristics of the solvent as described above and the supply pressure of ozone gas to the gas-liquid mixer 21, it is possible to derive a range of solvent temperatures (hereinafter appropriately referred to as the aspirable temperature range) in which the vapor pressure in the ozone gas introduction path of the gas-liquid mixer 21 is lower than the supply pressure. It is preferable to set this aspirable temperature range to be a relatively low temperature range that does not cause the solvent to freeze (for example, a temperature higher than the freezing point of the solvent or a temperature that can maintain a supercooled state), taking into consideration the general solubility characteristics of the gas in the solvent (solubility tends to increase as the solvent temperature decreases).

[0064] Then, the control unit 6 appropriately controls the solvent temperature so that it is within the aspirable temperature range (as in the temperature control process described later), thereby setting the vapor pressure in the ozone gas introduction path of the gas-liquid mixer 21 to be lower than the supply pressure of the ozone gas supplied to the gas-liquid mixer 21. Specifically, this involves appropriately setting the pressure gauge 14 to be lower than the pressure gauge 12. This makes it easier for the ozone gas from the ozone gas supply line L1a to be introduced into the ozone gas introduction path of the gas-liquid mixer 21, and enables the ozone gas to be mixed with the solvent and dissolved.

[0065] Upstream of the gas-liquid mixer 21 is a circulation flow meter 22 for measuring the circulation flow rate of the solvent circulating in the circulation line L2a. Downstream of the gas-liquid mixer 21 is a circulation pump (two circulation pumps in Figure 1) 23 for circulating the solvent. As shown in Figure 1, by providing two circulation pumps 23a and 23b, it is possible, for example, to operate one of the circulation pumps 23a and 23b normally and have the other function as an auxiliary pump if the primary pressure of the one drops too low. However, the other pump may be omitted as appropriate depending on the conditions of the circulation unit 2 (circulation conditions, etc.).

[0066] Furthermore, downstream of the circulation pump 23, there is a resistance thermometer (two resistance thermometers in Figure 1) 24 for measuring the solvent temperature, and a temperature controller (e.g., a cooler) 25 for adjusting the solvent temperature. By appropriately controlling these resistance thermometers 24 and temperature controller 25 by the control unit 6, the solvent temperature can be set to be within the aspirable temperature range.

[0067] Next, the circulation tank 20 is equipped with a bottomed cylindrical peripheral wall 20a capable of introducing and storing a certain amount of solvent. On the upper side of the peripheral wall 20a, there is an inlet 26 that communicates with the downstream side of the temperature sensor 24b in the circulation line L2a (i.e., the downstream side of the gas-liquid mixer 21), an inlet 26a that communicates with the pressure adjustment line L3c described later, and an exhaust port 26b that communicates with the gas exhaust line L5 described later.

[0068] On the lower side of the peripheral wall 20a, there is an outlet 27 that communicates with the upstream side of the circulation flow meter 22 in the circulation line L2a (i.e., the upstream side of the gas-liquid mixer 21), and an outlet 28 that communicates with the solvent discharge line L4, which will be described later.

[0069] Next, the reflux line L2b is provided connected to the upstream side of the solvent discharge line L4 (described later) and the upstream side of the circulation flow meter 22 in the circulation line L2a, and is configured to allow the solvent on the upstream side of the solvent discharge line L4 (i.e., the solvent discharged from the outlet 28) to be refluxed into the circulation line L2a. Furthermore, the reflux line L2b is equipped with an ozone concentration meter 29 capable of measuring the ozone concentration of the solvent refluxed by the reflux line L2b. With the ozone concentration meter 29 provided in the reflux line L2b, it is possible to measure not only the ozone concentration of the solvent in the circulation line L2a, but also the same ozone concentration as the solvent actually discharged from the circulation tank 20 (i.e., the target ozonated water).

[0070] <Example of the configuration of the solvent supply unit 3> The solvent supply unit 3 shown in Figure 1 includes a solvent supply line L3a capable of supplying a solvent such as raw water to the circulation line L2a, a concentration adjustment line L3b capable of supplying a concentration adjustment gas (such as carbon dioxide gas) to stabilize the ozone concentration of the solvent in the circulation line L2a, and a pressure adjustment line L3c capable of supplying a pressure adjustment gas (such as inert gases like N2, Ar, and He) to adjust the pressure inside the circulation tank 20.

[0071] In this solvent supply unit 3, the solvent supply line L3a is connected in communication with both the circulation pumps 23a and 23b in the circulation line L2a and is equipped with a solvent flow rate controller 31 capable of controlling the flow rate of the solvent flowing through the solvent supply line L3a. Furthermore, downstream of the solvent flow rate controller 31, there is a water purification unit (e.g., a pure water production device) 32 capable of increasing the purity of the solvent flowing through the solvent supply line L3a, and an on / off valve 33 that can switch the flow of the solvent through the solvent supply line L3a on or off.

[0072] Next, the concentration adjustment line L3b is connected in communication with both the circulation pumps 23a and 23b in the circulation line L2a and is equipped with a gas flow controller 34 capable of controlling the flow rate of the concentration adjustment gas circulating in the concentration adjustment line L3b. Furthermore, downstream of the gas flow controller 34 is an on / off valve 35 that can switch the flow of the concentration adjustment gas in the concentration adjustment line L3b on or off.

[0073] Next, the pressure adjustment line L3c is connected to the inlet 26a of the circulation tank 20 and is equipped with a gas flow controller 36 that can control the flow rate of the pressure adjustment gas flowing through the pressure adjustment line L3c.

[0074] <Example of the configuration of the discharge section 4> The discharge unit 4 shown in Figure 1 is equipped with a solvent discharge line L4 that discharges the solvent in the circulation tank 20 to the outer periphery of the circulation tank 20. This solvent discharge line L4 is connected to the discharge port 28 in the circulation tank 20 and is equipped with a discharge flow rate controller 41 that can control the discharge flow rate of the solvent discharged through the solvent discharge line L4.

[0075] <Example of exhaust section 5 configuration> The exhaust unit 5 shown in Figure 1 is equipped with a gas exhaust line L5 that exhausts the gas (for example, the gas phase separated from the solvent) inside the circulation tank 20 to the outer periphery of the circulation tank 20. This gas exhaust line L5 is connected to the exhaust port 26b of the circulation tank 20 and is equipped with an on / off valve (back pressure regulating valve, etc.) 51 that can switch on or off whether the gas inside the circulation tank 20 is flowing (exhausted) while maintaining a constant pressure inside the circulation tank 20. Furthermore, downstream of the on / off valve 51, there is an ozone concentration meter 52 capable of measuring the ozone concentration of the ozone gas flowing through the gas exhaust line L5, and an ozone decomposer 53 that safely decomposes the ozone gas flowing through the gas exhaust line L5.

[0076] <Example of configuration of control unit 6> The control unit 6 shown in Figure 1 can be configured to appropriately acquire and control the state information of the ozone gas supply unit 1, circulation unit 2, solvent supply unit 3, discharge unit 4, and exhaust unit 5 in order to obtain the desired ozonated water, and various configurations can be applied.

[0077] For example, one configuration involves appropriately connecting the control unit 6 with the equipment (e.g., measuring instruments, regulators, controllers, on / off valves, circulation pumps, resistance thermometers, etc.) configured in each line (ozone gas supply line L1a, gas component discharge line L1b, circulation line L2a, reflux line L2b, solvent supply line L3a, concentration adjustment line L3b, pressure adjustment line L3c, solvent discharge line L4, gas exhaust line L5) via signal lines or the like (not shown in the figure).

[0078] With this configuration, it is possible to operate each line as needed to acquire status information of the equipment, and to output control commands to the equipment based on the acquired status information to control it.

[0079] <An example of a method for generating ozonated water using device A> In the apparatus A described above, it is possible to generate desired ozonated water by appropriately performing the following processes: circulation, temperature control, gas-liquid mixing, discharge, and exhaust.

[0080] First, in the circulation process, solvent is supplied to the circulation line L2a by opening the on / off valve 33 of the solvent supply line L3a, thereby filling the circulation line L2a with solvent. The amount of circulation that fills the circulation line L2a can be appropriately set, for example, so that the liquid level of the solvent in the circulation tank 20 is located between the inlet 26 and the outlet 27.

[0081] Then, by operating the circulation pump 23 of the circulation line L2a, the circulation line L2a is brought into a state of circulation at a predetermined circulation flow rate. In this circulation state, the concentration adjustment line L3b and pressure adjustment line L3c are also operated as needed to stabilize the ozone concentration of the circulating solvent in the circulation line L2a and adjust the pressure in the circulation tank 20.

[0082] Next, in the temperature control process, the aspirable temperature range is determined in advance based on the supply pressure of ozone gas from the subsequent ozone gas supply process and the characteristics shown in the saturated vapor pressure curve and vapor pressure table in Figure 2. Then, in the circulation state, the solvent temperature of the circulation line L2a is measured by the resistance thermometer 24 and adjusted by the temperature controller 25 so that the solvent temperature is within the aspirable temperature range. For example, when the goal is ozonated water with an ozone concentration of 300 ppm or higher, the aspirable temperature range is greater than the freezing point of the solvent and is in the range of 30°C or less, preferably in the range of 15°C or less.

[0083] Next, in the gas-liquid mixing process, ozone gas is supplied to the gas-liquid mixer 21 by opening the on / off valve 13 of the ozone gas supply line L1a while the mixture is circulating. Here, because the temperature of the circulating solvent is within the aspirable temperature range due to the temperature control process in the preceding step, the supply pressure of ozone gas to the gas-liquid mixer 21 is greater than the vapor pressure of the ozone gas introduction path of the gas-liquid mixer 21.

[0084] As a result, the ozone gas supplied to the gas-liquid mixer 21 is introduced into the solvent flow path via the ozone gas introduction path within the gas-liquid mixer 21, and is mixed with the solvent in the solvent flow path to become soluble. Then, as the ozone gas dissolves in the solvent, the solvent reaches the desired ozone concentration.

[0085] Furthermore, when ozone gas is being supplied through the gas-liquid mixing process, if the reading from pressure gauge 14 becomes greater than the reading from pressure gauge 12, the on / off valve 13 is switched to the open position. This prevents solvent backflow into the ozone gas supply line L1a.

[0086] Next, in the discharge process, the solvent in the circulation tank 20 is discharged (i.e., the target ozonated water is obtained) by appropriately controlling the discharge flow rate controller 41 of the solvent discharge line L4 while the system is circulating. In addition, the solvent is appropriately supplied from the solvent supply line L3a to the circulation line L2a so that the discharge flow rate of the solvent does not exceed the circulation flow rate of the solvent in the circulation line L2a.

[0087] This allows the solvent to be released while maintaining a constant amount of solvent stored in the circulation tank 20. In other words, it becomes possible to continuously extract ozonated water with a desired ozone concentration during the release process.

[0088] Next, in the exhaust process, the gas present in the circulation tank 20 (for example, the gas phase separated from the circulating solvent) is exhausted to the outer periphery of the circulation tank 20 by opening the on / off valve 51 of the gas exhaust line L5.

[0089] <Example configuration of generating apparatus B according to the embodiment> In apparatus A, the configuration is not limited to that shown in Figure 1, and the design may be modified as appropriate. For example, as in apparatus B shown in Figure 3, the solvent supply line L3a and the concentration adjustment line L3b of the solvent supply unit 3 may be located at points separated from each other in the circulation line L2a. Note that in Figure 3 (and in Figures 4 to 7 described later), the same elements as those shown in Figure 1 are depicted with appropriate omissions.

[0090] In the case of apparatus B shown in Figure 3, an ozone concentration meter 29a capable of measuring the ozone concentration of the solvent in the circulation state in the reflux line L2b is provided between the gas-liquid mixer 21 and the circulation flow meter 22 in the circulation line L2a. Furthermore, a gas-liquid mixer (for example, with the same configuration as the gas-liquid mixer 21) 38 for mixing the solvent and the concentration adjustment gas is provided downstream of the pump 23 in the circulation line L2a.

[0091] Furthermore, the solvent supply line L3a is provided to communicate and connect between the gas-liquid mixer 21 and the ozone concentration meter 29a in the circulation line L2a. In the case of the solvent supply line L3a shown in Figure 3, a temperature regulator (e.g., a heat exchanger) 37 for adjusting the solvent temperature upstream of the solvent flow rate controller 31 in the solvent supply line L3a is provided. This makes it possible to set the solvent temperature of the solvent flowing to the gas-liquid mixer 21 as desired, compared to the case of apparatus A in Figure 1.

[0092] In the concentration adjustment line L3b, the gas-liquid mixer 38 is provided to connect to the downstream side of the pump 23 in the circulation line L2a. This may make it easier to supply the concentration adjustment gas to the solvent in the circulation line L2a compared to the case of apparatus A in Figure 1.

[0093] In apparatus B described above, as with apparatus A, it is possible to generate the desired ozonated water by appropriately executing the aforementioned circulation process, temperature control process, gas-liquid mixing process, discharge process, and exhaust process.

[0094] <Example configuration for suppressing or easily eliminating solvent backflow phenomena> In devices A and B, even if the suction pressure decreases depending on the operating status of devices A and B (e.g., solvent temperature, circulation status), and a solvent backflow phenomenon may occur in the ozone gas supply line L1a, the solvent backflow phenomenon can be suppressed or eliminated by setting the above-mentioned suction pressure range and suction temperature range in the control unit 6 in advance and appropriately switching the on / off valve 13.

[0095] An example of a configuration that suppresses or eliminates the solvent backflow phenomenon will be described below based on apparatuses B1 and B2 shown in Figures 4 and 5, which are modified versions of apparatus B. In the control unit 6 of apparatuses B1 and B2, the pressure threshold for comparison with the measured value of the pressure gauge 14 is set within the range of suctionable pressure.

[0096] In the apparatus B1 shown in Figure 4, for example, when ozone gas is supplied by the gas-liquid mixing process, the control unit 6 reads the measured value of the pressure gauge 14 at predetermined intervals and makes a determination by comparing the measured value with the pressure threshold. In this case, for example, if the suction pressure of the gas-liquid mixer 21 decreases depending on the operating status of apparatus B1, the measured value of the pressure gauge 14 will increase.

[0097] Then, if the control unit 6 determines that the measured value of the pressure gauge 14 is above the pressure threshold, it closes the on / off valve 13 and temporarily interrupts or stops the gas-liquid mixing process.

[0098] As a result, even if the suction pressure decreases and solvent backflow occurs, potentially allowing moisture to flow into the ozone gas supply line L1a, the on / off valve 13 can suppress or block the flow of such moisture.

[0099] Subsequently, the control unit 6 reads the measured value from the pressure gauge 14 and compares it with the pressure threshold. If it determines that the measured value from the pressure gauge 14 is less than the pressure threshold (i.e., if it determines that the solvent backflow phenomenon has been resolved), it opens the on / off valve 13 and restarts the gas-liquid mixing process.

[0100] The apparatus B2 shown in Figure 5 is equipped with a sensor (e.g., a water level sensor, infrared sensor, electromagnetic wave sensor, etc.) 13c capable of detecting moisture flowing downstream of the on-off valve 13 in the ozone gas supply line L1a (between the on-off valve 13 and the gas-liquid mixer 21). A moisture discharge line L1c capable of discharging the moisture flowing downstream of the on-off valve 13 is connected in communication with the downstream side of the on-off valve 13. This moisture discharge line L1c is equipped with an on-off valve 13d that can switch the flow of moisture from the downstream side of the on-off valve 13 on or off. This on-off valve 13d is usually kept closed, for example, while the gas-liquid mixing process is being performed.

[0101] In the control unit 6 of such device B2, for example, while monitoring the condition downstream of the on / off valve 13 (presence or absence of moisture, etc.) with a sensor 13c, the control unit 6 reads the measured value of the pressure gauge 14 at predetermined intervals, similar to device B1, and compares the measured value with a pressure threshold to make a determination.

[0102] Furthermore, when the control unit 6 detects moisture downstream of the on / off valve 13 via the sensor 13c, and / or determines that the measured value of the pressure gauge 14 is above a pressure threshold, it closes the on / off valve 13 to temporarily interrupt or stop the gas-liquid mixing process.

[0103] As a result, even if the suction pressure decreases and solvent backflow occurs, potentially allowing moisture to flow into the ozone gas supply line L1a, the on / off valve 13 can suppress or block the flow of moisture. In this case, the on / off valve 13d may be left open. This allows, for example, moisture to flow downstream of the on / off valve 13 to be discharged via the moisture discharge line L1c.

[0104] Subsequently, the control unit 6 reads the measured value from the pressure gauge 14 and compares it with the pressure threshold. If it determines that the measured value from the pressure gauge 14 is less than the pressure threshold, and / or if moisture is not detected by the sensor 13c, the on / off valve 13 is opened (and the on / off valve 13d is closed), and the gas-liquid mixing process can be restarted.

[0105] In the ozone gas supply line L1a of the devices B1 and B2 described above, if it is acceptable to allow a certain amount of moisture to flow in due to solvent backflow, for example, as shown in Figures 4 and 5, the gas-liquid mixer 21 and the on / off valve 13 in the ozone gas supply line L1a are arranged to be separated from each other (isolated by a predetermined distance), and an allowable space 13e is provided between them.

[0106] For example, if the vertical orientation of devices B1 and B2 is the same as the vertical orientation shown in Figures 4 and 5 (hereinafter simply referred to as the vertical orientation shown), then the moisture that flows into the allowable space 13e will be stored sequentially from the bottom side of the allowable space 13e (the side of the gas-liquid mixer 21).

[0107] As a result, even if the suction pressure decreases and solvent backflow occurs, potentially allowing moisture to flow into the ozone gas supply line L1a, it is possible to suppress the inflow of moisture to the upstream side of the on-off valve 13 without switching control of the on-off valve 13, etc. (i.e., even if the on-off valve 13 is in the open state), until the allowable space 13e is filled with moisture.

[0108] Furthermore, the capacity of the allowable space 13e can be set as appropriate, and the larger the capacity, the easier it may be to suppress the inflow of moisture to the upstream side of the on / off valve 13.

[0109] <An example of a configuration for removing residual moisture from the ozone gas supply line L1a> In conventional configurations, if moisture is present in easily oxidized areas on the ozone gas supply side (for example, pipes, joints (welded parts), and various equipment made of metal or organic materials), exposing these areas to ozone gas will cause the moisture and ozone gas to interact, accelerating corrosion of those areas. Furthermore, the ozone gas will decompose more easily in these corroded areas, potentially making it even more difficult to produce ozonated water at the desired concentration.

[0110] On the other hand, in devices A and B, even if moisture (such as water vapor) flows into the ozone gas supply line L1a due to, for example, solvent backflow and remains there (for example, moisture adhering to the inner surface of the ozone gas supply line L1a), the control unit 6 can appropriately control the ozone gas supply line L1a and the gas component discharge line L1b (for example, by appropriately switching on / off valves 13, 15, etc.), thereby allowing the moisture to be discharged through the gas component discharge line L1b.

[0111] An example of a configuration for draining moisture in this way will be explained below based on apparatus B3 shown in Figure 6, which is a modified version of apparatus B. Note that when the on / off valve 18a described later is closed, the supply of ozone gas from the ozone gas generator 10 is stopped.

[0112] The device B3 shown in Figure 6 is equipped with an on / off valve 18a located upstream of the gas flow controller 11 in the ozone gas supply line L1a (on the ozone gas generator 10 side), which can switch on or off whether ozone gas (or gas components including residual moisture and the purge gas described later) can flow upstream.

[0113] Furthermore, a purge gas supply line L1d capable of supplying purge gas between the on-off valves 13 and 18a in the ozone gas supply line L1a (hereinafter simply referred to as "between the on-off valves 13 and 18a") is connected in communication with the two (in Figure 6, it is connected between the gas flow controller 11 and the on-off valve 18a). This purge gas supply line L1d is equipped with an on-off valve 18b that can freely switch the flow of the purge gas (or gas components containing moisture, etc., remaining in the ozone gas supply line) on or off.

[0114] In the case of the purge gas supply line L1d shown in Figure 6, an analyzer 18c capable of detecting and analyzing gas components remaining upstream of the on-off valve 18a in the ozone gas supply line is provided upstream of the on-off valve 18b in the purge gas supply line L1d.

[0115] In such a device B3, the control unit 6 may, for example, appropriately perform the following gas component discharge process, purging process, and analysis process.

[0116] First, in the gas component discharge process, the control unit 6 closes the on / off valves 13, 18a, and 18b and opens the on / off valve 15, and operates the pump 17, thereby drawing in and discharging the gas components remaining between the on / off valves 13 and 18a via the gas component discharge line L1b.

[0117] Such a gas component discharge process may be carried out, for example, until the pressure between the on / off valves 13 and 18a (measured by the pressure gauge 12) does not rise when the on / off valve 15 is closed after the gas component has been drawn in and discharged through the gas component discharge line L1b as described above (for example, for about 1 hour).

[0118] In the purging process, the control unit 6 closes the on / off valves 13 and 18a and opens the on / off valves 15 and 18b, and operates the pump 17 as appropriate. This allows the purge gas from the purge gas supply line L1d to be supplied between the on / off valves 13 and 18a, while the remaining gas components between the on / off valves 13 and 18a are drawn in and discharged (drawn in and discharged together with the purge gas) via the gas component discharge line L1b.

[0119] Such a purging process can be carried out using various inert gases (e.g., N2, Ar, He, etc.) or dry oxygen (e.g., those with a dew point of -60°C or higher) as the purging gas, and is not particularly limited; it can be performed as appropriate (for example, for about one hour).

[0120] In the analysis process, after performing, for example, the gas component discharge process and purging process described above, the control unit 6 closes the on / off valves 13, 15, and 18a and opens the on / off valve 18b, and operates the analyzer 18c as appropriate, thereby enabling the analysis of gas components remaining between the on / off valves 13 and 18a.

[0121] If the analysis process confirms the presence of water in the gas component, the gas component discharge process and purging process described above may be repeated as appropriate.

[0122] The analyzer 18c can be any device capable of analyzing the gas components remaining between the on / off valves 13 and 18a, as described above. Examples of such devices include a dew point meter, an infrared spectrophotometer (IR), and a mass spectrometer (MS).

[0123] When applying a dew point meter, one method is to introduce the gas component between the on-off valves 13 and 18a into the dew point meter (for example, by slightly opening the on-off valve 18a) and check whether or not there is an increase in the dew point.

[0124] When using an infrared spectrophotometer, the gas component between the on / off valves 13 and 18a is introduced into the infrared spectrophotometer (infrared spectroscopy gas cell) to detect the presence of water at wavenumbers of 3000-4000 cm⁻¹. -1 One way to check for an increase in the peak is to confirm whether or not there is an increase in the peak.

[0125] When using a mass spectrometer, one method is to introduce the gas component between the on / off valves 13 and 18a into the mass spectrometer and check for any increase in the peak intensity at m / z=18, which indicates the presence of water.

[0126] <An example of a configuration that suppresses temperature rise in a circulating solvent> In devices A and B, the solvent temperature may easily rise depending on the operating conditions and installation environment of devices A and B. For example, if the ambient temperature on the outer periphery of the circulation line L2a is high (for example, higher than the desired solvent temperature), or if there are heat-generating devices (for example, the circulation pump 23) in the circulation line L2a, heat from the ambient temperature or heat-generating devices may be transferred into the circulation line L2a, making it impossible to maintain the desired solvent temperature and causing the temperature to rise. If the solvent temperature cannot be maintained and rises (for example, above the temperature at the time of dissolution in the gas-liquid mixer 21), the ozone gas dissolved in the solvent may be degassed over time, potentially causing a decrease in the ozone concentration.

[0127] In such cases, it is conceivable to cover at least a portion of the outer periphery of the circulation line L2a with insulating material or to cool it appropriately with a cooling means. For example, in the case of apparatus B4 shown in Figure 7, which is a modified example of apparatus B, at least a portion of the outer periphery of the circulation line L2a, region R (the region enclosed by the dashed line in Figure 7), can be covered with insulating material or a cooling jacket not shown. In the case of region R shown in Figure 7, this region excludes the circulation flow meter 22, circulation pump 23, and ozone concentration meter 29a.

[0128] When such a region R is covered with insulating material, heat from the ambient temperature around the circulation line L2a and heat-generating equipment can be suppressed from being transferred into the circulation line L2a, making it easier to maintain the desired solvent temperature.

[0129] When region R is covered with a cooling jacket, it is possible to suppress the transfer of heat from the ambient temperature around the circulation line L2a and heat-generating equipment into the circulation line L2a, and it is also possible to cool the circulation line L2a, making it easier to maintain the desired solvent temperature.

[0130] Cooling jackets can be configured in various ways and are not particularly limited. For example, when a double-pipe structure is used, the inner piping of the double-pipe structure can be used as a circulation line L2a, and the refrigerant can be appropriately circulated through the outer piping of the double-pipe structure.

[0131] In a cooling jacket, when cooling the circulating solvent in the circulation line L2a, it is preferable to appropriately control the refrigerant temperature of the cooling jacket with the control unit 6 so that it is at least lower than the ambient temperature of the circulation line L2a.

[0132] More preferably, the circulating solvent is cooled to the lowest possible temperature without freezing. For example, an antifreeze (such as ethylene glycol) can be used as a refrigerant, and its temperature can be appropriately controlled to be within a range that is higher than the temperature at which the circulating solvent freezes, but below zero degrees Celsius.

[0133] By cooling the solvent in this way, it is possible to maintain a supercooled state in the solvent. Even if the solvent is cooled to or below its freezing point, freezing will not begin, and the solvent will remain in an unfrozen state.

[0134] In addition to applying insulating materials and cooling jackets as described above, another method is to fill a container capable of housing the circulation line L2a with refrigerant and immerse the circulation line L2a in the refrigerant to cool it.

[0135] Although the present invention has been described in detail only with respect to the specific examples described above, it will be obvious to those skilled in the art that a wide variety of modifications are possible within the scope of the technical concept of the present invention, and it is natural that such modifications fall within the scope of the claims.

[0136] For example, devices A, B, and B1-B4 may be applied separately, or their components may be combined with each other as appropriate. Furthermore, technical ideas other than those stated in the claims, which can be understood from the above embodiments, are described below.

[0137] [1-1] An ozone gas supply line capable of supplying ozone gas, The ozone gas is supplied via a gas-liquid mixer, and a circulation line circulates a solvent capable of dissolving the ozone gas, Equipped with, The aforementioned gas-liquid mixer is In a circulating state in which the solvent is circulating, a solvent flow path through which the solvent flows, An ozone gas introduction path is provided connected to the solvent flow path and introduces ozone gas supplied from the ozone gas supply line into the solvent flow path, It has, The ozonated water generating apparatus is characterized in that at least a portion of the outer periphery of the circulation line is covered with an insulating material.

[0138] [1-2] An ozone gas supply line capable of supplying ozone gas, The ozone gas is supplied via a gas-liquid mixer, and a circulation line circulates a solvent capable of dissolving the ozone gas, Equipped with, The aforementioned gas-liquid mixer is In a circulating state in which the solvent is circulating, a solvent flow path through which the solvent flows, An ozone gas introduction path is provided connected to the solvent flow path and introduces ozone gas supplied from the ozone gas supply line into the solvent flow path, It has, The ozonated water generating apparatus is characterized in that at least a portion of the outer circumference of the circulation line is covered by a cooling jacket through which a refrigerant can circulate.

[0139] [1-3] The system further includes a control unit capable of controlling the temperature of the refrigerant circulated through the cooling jacket, The ozone water generating apparatus according to [1-2], characterized in that the control unit controls the temperature of the refrigerant to be higher than the temperature at which the solvent in the circulation state freezes, and below zero degrees Celsius.

[0140] [1-4] The ozone water generating apparatus according to [1-2], characterized in that the control unit controls the temperature of the solvent in the circulation state to be higher than the temperature at which the solvent in the circulation state becomes frozen, and lower than or equal to the temperature on the outer circumference of the cooling jacket.

[0141] [2-1] An ozone gas supply line capable of supplying ozone gas, The ozone gas is supplied via a gas-liquid mixer, and a circulation line circulates a solvent capable of dissolving the ozone gas, A control unit for controlling the ozone gas supply line, Equipped with, The aforementioned gas-liquid mixer is In a circulating state in which the solvent is circulating, a solvent flow path through which the solvent flows, An ozone gas introduction path is provided connected to the solvent flow path and introduces ozone gas supplied from the ozone gas supply line into the solvent flow path, It has, The aforementioned ozone gas supply line is A first on / off valve capable of switching the flow of ozone gas in the ozone gas supply line, A pressure gauge capable of measuring the gas pressure downstream of the first on / off valve in the ozone gas supply line, A discharge line connected to the ozone gas supply line and capable of discharging gas components within the ozone gas supply line, It has, The discharge line is connected to the upstream side of the first on-off valve in the ozone gas supply line via a second on-off valve that can switch whether or not the gas components in the discharge line are allowed to flow. The ozonated water generating apparatus is characterized in that the control unit opens the second on-off valve in the discharge line when the supply of ozone gas in the ozone gas supply line is stopped and the first on-off valve is closed.

[0142] [2-2] The ozone gas supply line further comprises a purge gas supply line capable of supplying purge gas into the ozone gas supply line. The aforementioned purge gas supply line is Connected to the upstream side of the first on / off valve in the ozone gas supply line, The ozone water generating apparatus according to [2-1] is characterized by having a third on / off valve that can switch whether or not the purge gas flows in the purge gas supply line.

[0143] [2-3] The ozone water generating apparatus according to [2-2], characterized in that the control unit opens the third on-off valve when the supply of ozone gas in the ozone gas supply line is stopped and the first on-off valve and the second on-off valve are in a closed state.

[0144] [2-4] The ozone water generating apparatus according to [2-1], characterized in that an analyzer capable of detecting and analyzing the gas components is connected upstream of the first on / off valve in the ozone gas supply line.

[0145] [2-5] The ozone water generating apparatus according to [2-4], characterized in that the control unit detects and analyzes the gas components using the analyzer when the supply of ozone gas in the ozone gas supply line is stopped and the first on / off valve and the second on / off valve are closed. [Explanation of Symbols]

[0146] A,B,B1~B4…Generation device 1…Ozone gas supply unit 2…Circulation section 3…Solvent supply unit 4…Emission part 5… Exhaust section 6…Control Unit L1a... Ozone gas supply line L2a... Circulation line 21…Gas-liquid mixer

Claims

1. An ozone gas supply line capable of supplying ozone gas, The ozone gas is supplied via a gas-liquid mixer, and a circulation line circulates a solvent capable of dissolving the ozone gas, A control unit for controlling the ozone gas supply line, Equipped with, The aforementioned gas-liquid mixer is In a circulating state in which the solvent is circulating, a solvent flow path through which the solvent flows, An ozone gas introduction path is provided connected to the solvent flow path and introduces ozone gas supplied from the ozone gas supply line into the solvent flow path in the circulation state, It has, The aforementioned ozone gas supply line is A first on / off valve is provided in the ozone gas supply line and is capable of switching whether or not the ozone gas can flow in the ozone gas supply line, A pressure gauge is provided downstream of the first on / off valve in the ozone gas supply line, and is capable of measuring the gas pressure on the downstream side. It has, The control unit, The first on / off valve controls the flow by comparing the measured value of the pressure gauge in the circulation state with an arbitrary pressure threshold set to be less than or equal to the saturated vapor pressure of the solvent, which is used for comparison with the measured value. When the measurement value of the pressure gauge exceeds the pressure threshold, the first on / off valve is closed. When the measurement value of the pressure gauge falls below the pressure threshold, the first on / off valve is opened. An ozone water generating device characterized by the following features.

2. The ozone water generating apparatus according to claim 1, characterized in that the control unit measures the temperature of the solvent in the circulation state and derives the vapor pressure of the solvent, which is set as the pressure threshold.

3. The ozone gas supply line is provided with a discharge line downstream of the first on / off valve in the ozone gas supply line, which is capable of discharging moisture that has flowed downstream. The ozone water generating apparatus according to claim 1, characterized in that the discharge line has a second on-off valve capable of switching whether or not water flows from the downstream side of the first on-off valve in the ozone gas supply line.

4. The control unit, The vapor pressure of the solvent, derived by measuring its temperature in the aforementioned circulation state, is set as the pressure threshold. The ozone water generating apparatus according to claim 3, characterized in that the second on / off valve is opened when the measured value of the pressure gauge becomes equal to or greater than the pressure threshold.

5. A sensor capable of detecting moisture flowing into the downstream side is provided downstream of the first on / off valve in the ozone gas supply line. The ozone water generating apparatus according to claim 3, characterized in that the control unit opens the second on-off valve when the sensor detects moisture flowing downstream of the first on-off valve.

6. The ozone water generating apparatus according to claim 1, characterized in that the control unit closes the first on / off valve when the measured value of the pressure gauge becomes greater than the supply pressure of the ozone gas.

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