Ozone-containing gas-liquid two-phase flow generation device, ozone-containing solution production device, ozone-containing gas production device, ozone-containing gas-liquid two-phase flow generation method, ozone-containing solution production method, and ozone-containing gas production method

Abstract

This ozone-containing gas-liquid two-phase flow generation device generates ozone by using gaseous oxygen as a raw material, and comprises: an ozone-containing oxygen generation unit that generates an ozone-containing oxygen from the gaseous oxygen; an ozone condensing unit having an interior space to which the ozone-containing oxygen is guided; a cooling unit that cools the ozone condensing unit and sets the interior space thereof to a temperature zone in which oxygen becomes a gas state and ozone becomes a liquid state; and a gas-liquid two-phase flow outward-guiding path for guiding, outward in a gas-liquid two-phase flow state, liquid ozone which is obtained through liquefaction of ozone included in the ozone-containing oxygen by going through the ozone condensing unit and an ozone-containing oxygen (hereinafter, referred to as ozone-reduced oxygen) which has a reduced ozone content as a result of formation of the liquid ozone. This makes it possible to provide an ozone-containing gas-liquid two-phase flow generation device or the like that can continuously produce ozone.

Description

Ozone-containing gas-liquid two-phase flow generating device, ozone-containing solution manufacturing device, ozone-containing gas manufacturing device, ozone-containing gas-liquid two-phase flow generating method, ozone-containing solution manufacturing method, ozone-containing gas manufacturing method

[0001] The present invention relates to an apparatus for generating an ozone-containing gas-liquid two-phase flow for generating ozone using an oxygen source.

[0002] Traditionally, semiconductor cleaning and resist stripping processes have involved the use of large amounts of chemicals. However, as semiconductor production scales up, the release of these chemicals has the potential to violate environmental regulations. As a result, the use of ozone (ozone gas and ozonated water), which has a low environmental impact and does not violate environmental regulations, is increasingly being used instead of these chemicals. For example, ozone solutions, which are made by dissolving ozone gas in pure water, carbon dioxide, hydrofluoric acid, etc., are used to remove harmful particles, organic matter, metals, etc., adhering to the surface of semiconductor wafers. Semiconductor cleaning using this ozone solution is called ozone solution cleaning. Ozone water is also effective for resist stripping. After use, the ozone in ozonated water naturally dissipates during the wastewater treatment process.

[0003] The concept of ozone solution (ozone water) includes not only ozone completely dissolved in liquid (water), but also liquid (water) in which fine bubbles of gas containing ozone (ozone-containing gas) are mixed in. In this specification, both a liquid in which ozone is dissolved in solution (water) and a liquid (water) containing bubbles containing ozone will be collectively referred to as ozone-containing solution (ozone-containing water).

[0004] In cleaning with an ozone solution or resist stripping using ozone water, the higher the ozone concentration, the faster and more effective the cleaning results tend to be, and therefore, there is a demand for an improvement in the ozone concentration in order to speed up semiconductor manufacturing and increase mass production. To produce ozone-containing water with a high ozone concentration, possible measures include: Measure 1: increasing the ozone concentration in the ozone-containing gas used as a raw material; Measure 2: increasing the internal pressure of the tank in which the ozone gas and water are mixed; Measure 3: lowering the pH of the solution; Measure 4: lowering the temperature of the solution; and Measure 5: increasing the efficiency of dissolving ozone in the solution.

[0005] Measures 1 to 4 are all related to the value of Henry's constant, which indicates the ratio of the ozone partial pressure in the gas phase to the ozone concentration in the solution when the ozone-containing gas and solution (water) are mixed and in equilibrium. Henry's constant is expressed by the following formula according to Henry's law:

[0006] H=P / X (Equation 1) H (atm / molar fraction): Henry's constant P (atm): ozone partial pressure in the gas phase X (molar fraction): ozone molar fraction in the aqueous phase

[0007] This can be expressed in terms of X (molar fraction) as follows: X = P / H ... (Equation 2) From (Equation 2), the molar fraction of ozone in the aqueous phase is proportional to the partial pressure of ozone in the gas phase and inversely proportional to the Henry's constant. Therefore, in order to increase the ozone concentration in the aqueous phase at equilibrium, it is effective to increase the partial pressure of ozone in the gas phase and achieve a state with a low Henry's constant. Incidentally, the Henry's constant can be expressed as follows:

[0008] H = 3.842 x 10 ７ × [OH] ０．０３５ ×exp(-2428 / T) (Equation 3) [OH] (mol / L): OH- ion molar concentration in the solution T (K): temperature

[0009] [OH] can be expressed by the following formula based on the pH of the solution: [OH] = 10 （ｐｈ－１４） ... (Equation 4) As a result, the lower the pH, the smaller the [OH], and the lower the water temperature, the smaller the Henry's constant, and the larger the molar fraction of ozone in the aqueous phase. However, with regard to Measure 4, a decrease in the temperature of the ozone-containing water leads to a decrease in the semiconductor cleaning speed, making it difficult to put it into practical use.

[0010] Regarding Measure 5, the present applicant has developed a technology for increasing the efficiency of ozone dissolution by forming a swirling flow of ozone gas bubbles mixed with raw water (see Patent Document 1). This swirling flow ozone water production method has made it possible to obtain ozone-containing water with an ozone concentration of 105 ppm (105 mg / L) at a production rate of 10 L / min and 80 ppm (80 mg / L) at a production rate of 20 L / min.

[0011] In measures 2 and 3, the ozone concentration was increased to 200 g / m by adding either hydrochloric acid, acetic acid, or citric acid to lower the pH of the solution. ３ There is a technology for producing ozone-containing water at a relatively high ozone concentration at a high temperature of 60 to 90 degrees by setting the temperature at or above (standard temperature) and increasing the pressure during dissolution in the solution (see Patent Document 2).

[0012] Regarding Countermeasure 1, there is a technology for producing ozone-containing water containing high concentrations of ozone by first adsorbing the ozone in an ozone-containing gas onto an adsorbent such as silica gel at low temperature, then desorbing it by raising the temperature, and then pressurizing it to generate a high-concentration, high-pressure ozone-containing gas (see Patent Document 3).

[0013] Ozone generation sources that generate ozone gas are broadly divided into electrolysis and discharge types depending on the ozone generation method. Electrolysis types generate ozone by electrolysis using special electrodes in water. Discharge types generate ozone-containing gas (ozone gas) by generating discharges such as silent discharge and surface discharge in oxygen-containing gas. Electrolysis types can generate highly concentrated ozone water using relatively simple equipment, so they have been used early on in semiconductor cleaning processes.

[0014] When using a discharge-type ozone generator, methods for dissolving ozone gas into water include bubbling, microbubble generators, ozone dissolution membranes, ejectors, gas-liquid mixing pumps, and packed towers. Bubbling involves placing a porous bubble generator at the bottom of an ozone dissolution tank, generating ozone gas bubbles that rise through the water. Microbubble generators generate ozone gas bubbles with diameters small enough (e.g., microns) that are inconsequential during use and dissolve them in water. Ozone dissolution membranes involve flowing water through a thin hollow fiber formed by a fluororesin membrane that is impermeable to water but permeable to ozone gas. Ozone gas is introduced around the hollow fiber, dissolving the ozone gas in the water. This method is most commonly used in the semiconductor industry. In a packed tower, water is allowed to descend from the top of a column filled with packing materials such as Raschig rings, and ozone gas is allowed to rise from the bottom. The ozone gas and water are brought into contact in a gas-liquid countercurrent manner in the packed section, dissolving the ozone gas into the water. This high dissolution efficiency allows for the production of highly concentrated ozone water. Ejectors and gas-liquid mixing pumps are so-called ozone mixers that forcibly mix ozone gas bubbles with water (solution) to generate a gas-liquid two-phase flow, thereby producing ozone water. An ejector creates a narrow passage in the water flow path, and, according to Bernoulli's theorem, draws in ozone gas using the force generated in the narrow passage to generate a gas-liquid two-phase flow of ozone gas bubbles mixed with water, producing ozone water.

[0015] An ejector has the advantage that it can be configured compactly even when the flow rate is increased. For example, if the flow velocity at the narrow passage is set to about 15 (m / s) and the flow velocity before and after that is set to about 3 (m / s), the ejector will produce a gas-liquid mixing effect. For example, in the semiconductor cleaning field, when generating 90 (L / min) of ozone-containing water, which is considered a large volume, the cross-sectional area of ​​the narrow passage should be 1 (cm ２ ) (equivalent to a circular pipe diameter of about 12 (mm)), and the cross-sectional area before and after that is 5 (cm ２ ) (equivalent to a circular pipe diameter of about 25 mm) is sufficient. In this case, it is preferable to use a gas-liquid separation tank on the downstream side to separate excess ozone gas bubbles from the ozone mixture liquid that becomes a gas-liquid two-phase flow, thereby producing ozone water that is almost free of ozone bubbles.

[0016] Gas-liquid separation tanks are generally cylindrical, with a gas-liquid two-phase flow inlet located at the top and an ozonated water discharge pipe located at the bottom. In this gas-liquid separation tank, the gas-liquid two-phase flow supplied from the top descends, and by the time it reaches the ozonated water drain pipe, excess ozone bubbles rise due to buoyancy and are separated from the gas-liquid two-phase flow. As a result, ozonated water from which the excess ozone bubbles have been separated is discharged from the ozonated water drain pipe. Note that in the gas-liquid separation tank, the dissolution of ozone also progresses as the gas-liquid two-phase flow remains for the time being. As a result, the concentration of ozonated water increases the further down the tank is.

[0017] Japanese Patent No. 6954645 Japanese Patent No. 6635459 International Publication WO2011 / 139587

[0018] In recent years, there has been a demand for further yield improvements in semiconductor cleaning processes and resist stripping processes, and thus ozone-containing gases and ozone-containing water with higher concentrations than ever before are required. However, if an attempt is made to produce ozone-containing water with a higher concentration using the ozone-containing water production apparatus of Patent Document 1, it is necessary to reduce the amount of ozone-containing water produced per unit time, which poses a problem that the apparatus cannot be used in semiconductor manufacturing sites where mass productivity is required.

[0019] The silica gel adsorption method of Patent Document 3 is a batch process, and at the same time, the amount of ozone adsorbed per unit volume of adsorbent is small, so there is a problem that the scale of the equipment becomes large in order to produce a large amount of highly concentrated ozone-containing oxygen.

[0020] The present invention has been made in consideration of solving any of the above problems individually or simultaneously, and aims to provide an ozone-containing gas-liquid two-phase flow generating device, etc., that can continuously produce high-concentration ozone.

[0021] To achieve the above object, the present invention provides an ozone-containing gas-liquid two-phase flow generator for generating ozone using gaseous oxygen as a raw material, the apparatus comprising: an ozone-containing oxygen generator for generating ozone-containing oxygen from the gaseous oxygen; an ozone condenser into which the ozone-containing oxygen is introduced; a cooling unit for cooling the ozone condenser to set the internal space of the ozone condenser to a temperature range in which oxygen is in a gaseous state and ozone is in a liquid state; and a gas-liquid two-phase flow outlet path for discharging liquid ozone, which is formed by liquefying ozone contained in the ozone-containing oxygen after passing through the ozone condenser, and the ozone-containing oxygen whose ozone content has been reduced by the liquid ozone (hereinafter referred to as ozone-depleted oxygen), in a gas-liquid two-phase flow state, to the outside.

[0022] In the above-described ozone-containing gas-liquid two-phase flow generating device, the gas-liquid two-phase flow outlet passage may be characterized in that it outputs a portion of the ozone-depleted oxygen in the gas-liquid two-phase flow state.

[0023] The ozone-containing gas-liquid two-phase flow generating device may further include a gas outlet path for discharging the remaining ozone-depleted oxygen from the gas-liquid two-phase flow outlet path to the outside of the ozone condenser.

[0024] The above-mentioned ozone-containing gas-liquid two-phase flow generating apparatus may be characterized in that an oxygen discharge amount regulator capable of regulating the amount of ozone-depleted oxygen discharged is provided in the gas discharge path.

[0025] In relation to the above-mentioned ozone-containing gas-liquid two-phase flow generating device, the ozone condenser may have a liquid ozone receiving part that receives the liquid ozone, and one end of the gas-liquid two-phase flow outlet path may be arranged in the vicinity of the liquid ozone receiving part so as to be able to come into contact with the liquid ozone received in the liquid ozone receiving part.

[0026] In relation to the above-mentioned ozone-containing gas-liquid two-phase flow generating device, at least a portion of the gas-liquid two-phase flow outlet path may extend vertically within the ozone condenser, and a lower end of the gas-liquid two-phase flow outlet path may be disposed in the vicinity of the liquid ozone receiving part.

[0027] The above-mentioned ozone-containing gas-liquid two-phase flow generating apparatus may be characterized by having an oxygen circulation path that guides at least a portion of the ozone-depleted oxygen derived from the ozone condenser to the ozone-containing oxygen generating section.

[0028] The ozone-containing gas-liquid two-phase flow generating device may be characterized by having an oxygen supply amount adjusting unit that adjusts the amount of gaseous oxygen supplied.

[0029] In relation to the above-mentioned ozone-containing gas-liquid two-phase flow generation device, the cooling section may have a refrigerant storage section for storing a refrigerant, and the refrigerant in the refrigerant storage section may be brought into contact with the ozone condenser section to cool the internal space of the ozone condenser section.

[0030] The ozone-containing gas-liquid two-phase flow generating device may be characterized in that the refrigerant is liquid oxygen, liquid nitrogen, liquid argon, or helium gas.

[0031] In the above-described ozone-containing gas-liquid two-phase flow generating apparatus, the refrigerant may be liquid oxygen, and the gaseous oxygen obtained by vaporizing the liquid oxygen may be guided to the ozone-containing oxygen generating section.

[0032] In relation to the above-mentioned ozone-containing gas-liquid two-phase flow generating device, the cooling section may be characterized in that it has a sealed structure that seals the refrigerant storage section, and the internal pressure of the sealed structure is maintained at a pressure exceeding atmospheric pressure.

[0033] In the above-mentioned ozone-containing gas-liquid two-phase flow generating device, the refrigerant may have a temperature in the range of 80K to 120K.

[0034] In relation to the above-mentioned ozone-containing gas-liquid two-phase flow generation device, the cooling unit may have a heat exchange unit through which a refrigerant cooled by a refrigeration cycle circulates, and the internal space of the ozone condensing unit may be cooled by bringing the ozone condensing unit into contact with the refrigerant.

[0035] In the above-described ozone-containing gas-liquid two-phase flow generating apparatus, the cooling unit may cool the ozone-containing oxygen generating unit.

[0036] The apparatus for generating an ozone-containing gas-liquid two-phase flow may be characterized in that the amount of the liquid ozone stored before being discharged from the gas-liquid two-phase flow outlet path is 5 g or less.

[0037] In the above-described ozone-containing gas-liquid two-phase flow generating apparatus, the ozone condensing section may have a spiral pipe into which the ozone-containing oxygen is guided.

[0038] In relation to the above-mentioned ozone-containing gas-liquid two-phase flow generating device, the vicinity downstream of the ozone condenser and / or the gas-liquid two-phase flow outlet path may have a gas-liquid two-phase downward flow formation region that guides the liquid ozone and the ozone-depleted oxygen in a gas-liquid two-phase flow state in a direction having a vertical downward component, and the gas outlet path that discharges the remainder of the ozone-depleted oxygen may be connected above the gas-liquid two-phase downward flow formation region or midway in the vertical direction.

[0039] The ozone-containing gas-liquid two-phase flow generating device may be characterized by comprising an inner pipe that forms the gas-liquid two-phase downward flow formation region, and an outer pipe that is arranged outside the inner pipe so as to enclose the inner pipe and that forms part of the gas outlet path.

[0040] To achieve the above object, the present invention provides an ozone-containing solution manufacturing apparatus comprising the above-mentioned ozone-containing gas-liquid two-phase flow generating apparatus, and an ozone mixing section that mixes the liquid ozone and / or gaseous ozone formed by vaporizing the liquid ozone discharged from the gas-liquid two-phase flow outlet path with a solution to produce an ozone-containing solution.

[0041] In the above-described ozone-containing solution manufacturing apparatus, the ozone mixing unit may directly mix the liquid ozone with the solution.

[0042] In the above-described ozone-containing solution manufacturing apparatus, the ozone mixing section may mix the ozone-depleted oxygen, which is discharged from the gas-liquid two-phase flow discharge path, with the solution.

[0043] In relation to the above-mentioned ozone-containing solution manufacturing apparatus, the ozone mixing section may be characterized by comprising a solution guide path that guides the solution, and a confluence section that is provided midway along the solution guide path and that confluences the liquid ozone and / or gaseous ozone formed by evaporation of the liquid ozone with the solution.

[0044] The ozone-containing solution manufacturing apparatus may be characterized by comprising: a storage tank for storing the ozone-containing solution that has passed through the confluence; an ozone-containing solution circulation path for discharging the ozone-containing solution stored in the storage tank to the outside and returning the ozone-containing solution to the storage tank; and a second confluence provided midway along the ozone-containing solution circulation path for confluence of the liquid ozone and / or gaseous ozone formed by vaporization of the liquid ozone with the ozone-containing solution.

[0045] To achieve the above object, the present invention provides an ozone-containing gas manufacturing apparatus comprising the above-mentioned ozone-containing gas-liquid two-phase flow generating device and a vaporization section that vaporizes the liquid ozone discharged from the gas-liquid two-phase flow outlet path to form gaseous ozone.

[0046] The ozone-containing gas production apparatus may be characterized in that the ozone-depleted oxygen discharged from the gas-liquid two-phase flow outlet path and the gaseous ozone are mixed in the vaporization section.

[0047] To achieve the above object, the present invention provides a method for generating an ozone-containing gas-liquid two-phase flow for producing ozone using gaseous oxygen as a raw material, the method comprising: generating ozone-containing oxygen from the gaseous oxygen; guiding the ozone-containing oxygen into an internal space of an ozone condenser that is cooled to a temperature range where the oxygen is in a gaseous state and the ozone is in a liquid state; and discharging liquid ozone, which is obtained by liquefying ozone contained in the ozone-containing oxygen in the internal space, and the ozone-containing oxygen whose ozone content has been reduced by the liquid ozone (hereinafter referred to as ozone-depleted oxygen), in a gas-liquid two-phase flow state to the outside of the ozone condenser through a gas-liquid two-phase flow outlet.

[0048] The method for producing an ozone-containing gas-liquid two-phase flow may be characterized in that a portion of the ozone-depleted oxygen is discharged in the gas-liquid two-phase flow state.

[0049] To achieve the above object, the present invention provides a method for producing an ozone-containing solution, characterized in that the liquid ozone and / or gaseous ozone obtained by vaporizing the liquid ozone, which is discharged from the gas-liquid two-phase flow outlet path by the above-mentioned method for generating an ozone-containing gas-liquid two-phase flow, is mixed with a solution to produce an ozone-containing solution.

[0050] To achieve the above object, the present invention provides a method for producing an ozone-containing gas, characterized in that the liquid ozone discharged from the gas-liquid two-phase flow outlet path by the above-mentioned ozone-containing gas-liquid two-phase flow generation method is vaporized to form gaseous ozone.

[0051] According to the present invention, it is possible to obtain the excellent effect of continuously producing high-concentration ozone.

[0052]

[0023] Figure 1 shows the overall configuration of an ozone-containing solution manufacturing apparatus according to a first embodiment of the present invention. (A) is a side view showing a gas-liquid separation tank of the ozone-containing solution manufacturing apparatus, (B) is a cross-sectional view taken along the arrows B-B of (A), (C) is a cross-sectional view taken along the arrows C-C of (A), (D) is a cross-sectional view taken along the arrows D-D of (A), and (E) and (F) are cross-sectional views showing the internal structure of an ejector.

[0024] Figure 1 shows a detailed configuration of an ozone-containing gas-liquid two-phase flow generation device in the ozone-containing solution manufacturing apparatus.

[0025] Figure 1 shows graphs illustrating gas-liquid equilibrium vapor pressure curves of oxygen and ozone, with the horizontal axis representing temperature and the vertical axis representing pressure. (A) is a graph showing the gas-liquid equilibrium vapor pressure curve of liquid nitrogen, with the horizontal axis representing temperature and the vertical axis representing pressure, and (B) is a graph showing the gas-liquid equilibrium vapor pressure curve of liquid oxygen, with the horizontal axis representing temperature and the vertical axis representing pressure. 1A is a diagram showing the internal configuration of a control device of the ozone-containing solution producing apparatus, FIG. 1B is a block diagram showing the control configuration of the control device, and FIG. 1C is a block diagram showing the detailed control configuration of an ozone-containing gas-liquid two-phase flow control unit. 1A is a schematic diagram explaining the flow of ozone-containing water in a gas-liquid separation tank of the ozone-containing solution producing apparatus, and FIG. 1B is a plan view showing the swirling state of the ozone-containing water. 1B is a perspective view explaining the flow of ozone-containing water in a gas-liquid separation tank of the ozone-containing solution producing apparatus. 1C is a diagram showing the overall configuration of the ozone-containing solution producing apparatus when the gas-liquid separation tank is omitted. 1D is a diagram showing the detailed configuration of an ozone-containing gas-liquid two-phase flow generating device according to a first modified example of the ozone-containing solution producing apparatus. 1E is a diagram showing the detailed configuration of an ozone-containing gas-liquid two-phase flow generating device according to a second modified example of the ozone-containing solution producing apparatus. 1F is a diagram showing the overall configuration of a third modified example of the ozone-containing solution producing apparatus. 1G is a diagram showing the overall configuration of a fourth modified example of the ozone-containing solution producing apparatus. 1G is a diagram showing the overall configuration of an ozone-containing gas producing apparatus according to a second embodiment of the present invention. 1G is a diagram showing a first modified example of an ozone condenser of the ozone-containing gas-liquid two-phase flow generating apparatus according to the present embodiment. 1A is a diagram showing a second modified example of the ozone condenser of the ozone-containing gas-liquid two-phase flow generator of the first embodiment, and FIG. 1B is a diagram showing a third modified example of the ozone condenser of the ozone-containing gas-liquid two-phase flow generator of the first embodiment.

[0023] Figure 1 is a diagram showing the overall configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to a third embodiment of the present invention. (A) and (B) are graphs showing the results of an ozone condensation simulation calculation of the ozone-containing gas-liquid two-phase flow generation apparatus according to the third embodiment.

[0024] Figure 2 is a diagram showing the overall configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to a fourth embodiment of the present invention.

[0025] Figure 3 is a diagram showing the overall configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to a fifth embodiment of the present invention.

[0026] Figure 4 is a diagram showing the overall configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to a sixth embodiment of the present invention.

[0027] Figure 5 is a diagram showing the overall configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to a seventh embodiment of the present invention.

[0028] Figure 6 is a diagram showing the overall configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to an eighth embodiment of the present invention. (A) is a diagram showing the configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to a first concept of the present invention, and (B) is a diagram showing the configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to a second concept of the present invention. (A) is a diagram showing the configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to a third concept of the present invention, and (B) is a diagram showing the configuration of an ozone-containing gas-liquid two-phase flow generation apparatus according to a fourth concept of the present invention. Regarding the ozone-containing gas-liquid two-phase flow generating device in the ozone-containing solution manufacturing apparatus of the first embodiment, (A) is a diagram evaluating the liquefaction rate by the ozone condensation section, and (B) and (C) are diagrams evaluating the ozone concentration in the gas-liquid two-phase ozone-containing oxygen discharged from the gas-liquid two-phase flow discharge path.

[0053] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[0054] 1 shows an ozone-containing solution manufacturing apparatus 1 according to a first embodiment of the present invention. Note that, here, an example is shown in which water (or pure water) is used as a solvent for dissolving ozone, and ozone water is produced as an ozone solution, but the type of solvent for dissolving ozone is not limited to water.

[0055] <Overall system configuration> The ozone-containing solution manufacturing apparatus 1 includes an ozone-containing gas-liquid two-phase flow generation device 10 that generates ozone, a gas-liquid separation tank 30 that stores ozone-containing water, a solvent guide path 70 that supplies at least water as a solvent to the gas-liquid separation tank 30, an ozone solution discharge section 80 that guides (discharges) the ozone water from the gas-liquid separation tank 30 to the outside, a swirling flow generation section 50 that generates a swirling flow in the ozone-containing water in the gas-liquid separation tank 30, an ozone-containing solution circulation path 60 that draws out the ozone-containing water from the gas-liquid separation tank 30 and temporarily turns it into a circulating liquid and guides this circulating liquid back to the gas-liquid separation tank 30, and an ozone mixing section 20 that mixes liquid ozone, etc. supplied from the ozone-containing gas-liquid two-phase flow generation device 10 with water (solvent) or the circulating liquid.

[0056] In order to increase the amount of liquid ozone supplied by the ozone-containing gas-liquid two-phase flow generation device 10, it is preferable to connect multiple ozone-containing gas-liquid two-phase flow generation devices 10 in parallel to generate liquid ozone simultaneously.

[0057] The gas-liquid separation tank 30 is, for example, a container having a regular cylindrical shape with a bottom. The central axis of the cylindrical shape is set to be vertical, but the present invention is not limited to this, and the gas-liquid separation tank may be installed with the central axis inclined relative to the vertical.

[0058] The solvent guide path 70 is a flow path that connects a water supply unit 72, which supplies water as a raw material for the solvent, to the gas-liquid separation tank 30. A flow rate control valve 74 is disposed midway along the solvent guide path 70. This flow rate control valve 74 is a pneumatic valve, for example, an air pressure type flow rate control valve.

[0059] A solvent inlet 76 is formed at the downstream end of the solvent guide path 70, through which ozone-containing water is introduced (discharged) into the gas-liquid separation tank 30. As shown in Fig. 2(B) , the solvent inlet 76 introduces the ozone-containing water in a direction that includes a tangential component of the swirling flow SE to be generated in the ozone-containing water. Therefore, the solvent inlet 76 also serves as a tangential introduction section that generates a swirling flow by the flow of fluid introduced in the swirling flow generating section 50, which will be described later.

[0060] More specifically, the solvent inlet 76 opens directly into the cylindrical inner peripheral wall of the gas-liquid separation tank 30. The guide direction of the raw water in the solvent guide path 70 immediately before the solvent inlet 76 includes a circumferential component (tangential component) of the inner peripheral wall, and in this embodiment in particular, is approximately aligned with the tangential direction of the inner peripheral wall. The guide direction of the solvent guide path 70 immediately before the solvent inlet 76 is approximately horizontal (perpendicular to the vertical central axis of the gas-liquid separation tank 30). As a result of the above, the flow of ozone-containing water introduced from the solvent inlet 76 via the solvent guide path 70 becomes a swirling flow along the inner peripheral wall of the gas-liquid separation tank 30, as shown by arrow FB.

[0061] As shown in FIG. 2A, the solvent inlet 76 is disposed near the center of the gas-liquid separation tank 30 in the vertical direction or above it.

[0062] 2(D), a circulating liquid outlet 62 is formed at the upstream end of the ozone-containing solution circulation path 60. This circulating liquid outlet 62 is an opening for discharging (sucking in) the ozone-containing water in the gas-liquid separation tank 30. The circulating liquid outlet 62 discharges the ozone-containing water in a direction that includes a tangential component of the swirling flow SE generated in the ozone-containing water. Therefore, the circulating liquid outlet 62 also serves as a tangential outlet portion that generates a swirling flow by the flow of the fluid discharging in the swirling flow generating portion 50, which will be described later.

[0063] Furthermore, the circulating fluid outlet 62 opens directly into the cylindrical inner peripheral wall of the gas-liquid separation tank 30. The guide direction of the circulating fluid through the ozone-containing solution circulation path 60 immediately after the circulating fluid outlet 62 includes a circumferential component (tangential component) of the inner peripheral wall, and in this embodiment, the guide direction is substantially aligned with the tangential direction of the inner peripheral wall. The guide direction of the circulating fluid through the ozone-containing solution circulation path 60 immediately after the circulating fluid outlet 62 is substantially horizontal (perpendicular to the vertical central axis of the gas-liquid separation tank 30). As a result, the flow of ozone-containing water immediately before being discharged into the ozone-containing solution circulation path 60 via the circulating fluid outlet 62 becomes a swirling flow along the inner peripheral wall of the gas-liquid separation tank 30, as indicated by arrow FD. The swirling direction is the same as the swirling direction generated by the solvent inlet 76, and in this case, is counterclockwise when viewed from above.

[0064] 2A, the circulating liquid outlet 62 is disposed vertically below the solvent inlet 76 and the circulating liquid inlet 64. More specifically, it is disposed below the center of the gas-liquid separation tank 30 in the up-down direction and near the bottom surface thereof.

[0065] 2(C), a circulating liquid inlet 64 is formed at the downstream end of the ozone-containing solution circulation path 60. This circulating liquid inlet 64 is an opening for introducing the circulating liquid (ozone-containing water) guided by the ozone-containing solution circulation path 60. The circulating liquid inlet 64 introduces the circulating liquid in a direction that includes a tangential component of the swirling flow SE to be generated in the ozone-containing water. Therefore, the circulating liquid inlet 64 also serves as a tangential introduction section that generates a swirling flow by the flow of the fluid introduced in the swirling flow generating section 50, which will be described later.

[0066] Furthermore, the circulating liquid inlet 64 opens into the cylindrical inner peripheral wall of the gas-liquid separation tank 30. The guide direction of the ozone-containing solution circulation path 60 immediately before the circulating liquid inlet 64 includes a circumferential component (tangential component) of the inner peripheral wall, and in this embodiment, the guide direction is approximately aligned with the tangential direction of the inner peripheral wall. The guide direction of the ozone-containing solution circulation path 60 immediately before the circulating liquid inlet 64 is approximately horizontal (perpendicular to the vertical central axis of the gas-liquid separation tank 30). As a result, the flow of the circulating liquid introduced from the circulating liquid inlet 64 becomes a swirling flow along the inner peripheral wall of the gas-liquid separation tank 30, as shown by arrow FC. The swirling direction is the same as the swirling direction generated by the solvent inlet 76, and in this case, is counterclockwise when viewed from above.

[0067] 2A , the circulating liquid inlet 64 is disposed vertically between the solvent inlet 76 and the circulating liquid outlet 62. More specifically, it is disposed below the center of the gas-liquid separation tank 30 in the up-down direction and above the circulating liquid outlet 62.

[0068] Returning to Figure 1, a circulation pump 66 is disposed midway along the ozone-containing solution circulation path 60. This circulation pump 66 serves to drive the flow of the circulating liquid. A flow rate control valve 68 that adjusts the flow rate of the circulating liquid is disposed downstream of the circulation pump 66 in the ozone-containing solution circulation path 60. This flow rate control valve 68 is, for example, a pneumatic valve such as an air pressure flow rate control valve.

[0069] The ozone solution discharge unit 80 includes a discharge path 82 that discharges the ozone water generated in the gas-liquid separation tank 30 to the point of use U, and a flow control valve 84 that is provided midway along the discharge path 82 and that adjusts the amount of ozone water discharged. The upstream side of the discharge path 82 also serves as the ozone-containing solution circulation path 60, and an ozone solution discharge outlet 86 formed at the upstream end of the discharge path 82 also coincides with the circulating liquid discharge outlet 62. Therefore, as shown in FIG. 2(D), the ozone solution discharge outlet 86 discharges the ozone-containing water in a direction that includes a tangential component of the swirling flow SE generated in the ozone-containing water. The ozone solution discharge outlet 86 also serves as a tangential discharge unit that generates a swirling flow by the flow of fluid discharge in the swirling flow generating unit 50, which will be described later.

[0070] More specifically, the ozone solution outlet 86 is disposed at a location radially away from the central axis C of the swirling flow of the ozone mixed liquid in the gas-liquid separation tank 30. Excess ozone bubbles move toward the central axis C as a reaction to the centrifugal force of the swirling flow, making it difficult for excess ozone bubbles to enter the ozone solution outlet 86, making it possible to discharge ozone water with fewer bubbles.

[0071] 1 , the swirling flow generating unit 50 has a tangential inlet 50A that generates a swirling flow by introducing water or ozone-containing water in a direction that includes a tangential component of the swirling flow of the ozone-containing water stored in the gas-liquid separation tank 30. In this embodiment, as already described, the solvent inlet 76 and the circulating liquid inlet 64 also serve as this tangential inlet 50A. The swirling flow generating unit 50 has a tangential outlet 50B that generates a swirling flow by discharging the ozone-containing water stored in the gas-liquid separation tank 30 in a direction that includes a tangential component of the swirling flow. In this embodiment, as already described, the circulating liquid outlet 62 (or the ozone solution outlet 86) also serves as this tangential outlet 50B.

[0072] The ozone-containing solution manufacturing apparatus 1 has an ozone mixing section 20 including a solvent-side ozone mixer 22 disposed in the solvent guide path 70 and a circulation-side ozone mixer 24 disposed in the ozone-containing solution circulation path 60. The solvent-side ozone mixer 22 is disposed downstream of the flow control valve 74 (on the gas-liquid separation tank 30 side) and mixes liquid ozone and ozone-depleted oxygen supplied from the ozone-containing gas-liquid two-phase flow generating apparatus 10 with raw water while maintaining the gas-liquid two-phase flow. The gas-liquid two-phase fluid consisting of liquid ozone and ozone-depleted oxygen is referred to herein as "gas-liquid two-phase ozone-containing oxygen." The "gas-liquid two-phase ozone-containing oxygen" may include ozone gas obtained by vaporizing a portion of the liquid ozone.

[0073] An ozone gas circulation path 26 is connected above the gas-liquid separation tank 30 to guide excess ozone gas remaining above the ozone-containing water to the ozone-containing gas-liquid two-phase flow generation device 10 .

[0074] The circulation-side ozone mixer 24 is located downstream of the flow control valve 68 (on the gas-liquid separation tank 30 side) in the ozone-containing solution circulation path 60, and mixes the gas-liquid two-phase ozone-containing oxygen supplied from the ozone-containing gas-liquid two-phase flow generation device 10 into the circulating liquid as is.

[0075] As shown in Figure 2(E), the ozone mixing section 20 (solvent-side ozone mixer 22, circulation-side ozone mixer 24) is a so-called ejector (aspirator) 28. A liquid (mixed fluid) such as water or a solvent (ozone-containing water) is introduced at high speed through a nozzle 28A. Liquid ozone, ozone gas (vaporized ozone), and ozone-depleted oxygen are drawn into the negative-pressure space 28B formed around the nozzle 28A. A diffuser 28C with a narrowed section is provided downstream of the nozzle 28A. The mixed fluid, liquid ozone, ozone gas (vaporized ozone), and ozone-depleted oxygen are entrained and mixed to form ozone-containing water before passing through the narrowed section. The flow rate further decreases as the mixed fluid passes through the narrowed section, returning to its original flow rate. At the same time, the pressure of the ozone-containing water is restored in accordance with Bernoulli's principle. 2(F), liquid ozone, ozone gas obtained by vaporizing liquid ozone, and ozone-depleted oxygen may be drawn directly into the narrow portion of the diffuser 28C. Here, an ejector is used as an example of a mixer, but the present invention is not limited to this, and a mixing pump, a microchannel, or the like may also be used.

[0076] 1 , the gas-liquid separation tank 30 is provided with a liquid level sensor 36 for detecting the liquid level of the ozone-containing water, an ozone concentration sensor 38 for detecting the concentration of ozone dissolved in the ozone-containing water, and a pH meter 39 for measuring the pH of the ozone-containing water. The ozone concentration sensor 38 may be provided in the outlet path 82 or the ozone-containing solution circulation path 60, but it is preferable that the ozone concentration sensor 38 be able to detect a value as close as possible to the ozone concentration output from the ozone solution output portion 80. Therefore, in the case of the gas-liquid separation tank 30, it is preferable to place the ozone concentration sensor 38 near the bottom.

[0077] An open passage 40 is formed above the gas-liquid separation tank 30, and in the middle of this open passage 40, there are provided a back pressure regulating valve 42 that keeps the pressure inside the gas-liquid separation tank 30 constant, and an exhaust ozone decomposer 44 that decomposes excess ozone gas passing through the open passage 40.

[0078] 3 shows the detailed structure of the ozone-containing gas-liquid two-phase flow generating apparatus 10. The ozone-containing gas-liquid two-phase flow generating apparatus 10 includes an oxygen gas source 106, an ozone-containing oxygen generating unit 120, a condenser 128, a cooling unit 160, and a sealing structure 170.

[0079] (Ozone-Containing Oxygen Generator) The ozone-containing oxygen generator 120 generates ozone gas (ozone-containing oxygen) using oxygen gas supplied from an oxygen gas source 106, such as an oxygen cylinder or oxygen generator, via an oxygen supply path 120R1. The ozone-containing oxygen generator 120 converts a portion of the oxygen gas into ozone by passing the gas through the discharge gap of, for example, a silent discharge tube (ozonizer). The generated ozone-containing oxygen is supplied to an ozone condenser 130 of a condenser 128 disposed within the sealed structure 170 via an ozone-containing oxygen introduction path 120R2, which passes through a sealed structure 170 (described later). The oxygen supply path 120R1 between the oxygen gas source 106 and the ozone-containing oxygen generator 120 includes a supply amount controller 108, an adsorption section 110, which serves as an adsorption tube filled with an adsorbent such as silica gel to remove organic matter and moisture contained in the oxygen gas, and a supply amount meter 112. The supply amount measuring device 112 is, for example, a mass flow meter, and is capable of measuring the mass flow rate of oxygen gas (which may contain ozone-containing oxygen). The supply amount controller 108 is a flow control valve that adjusts the supply amount of oxygen gas based on the measurement results of the supply amount measuring device 112. Furthermore, an ozone concentration meter 121 is disposed downstream of the ozone-containing oxygen generator 120 in the oxygen supply path 120R1, and measures the ozone concentration of the ozone-containing oxygen generated in the ozone-containing oxygen generator 120.

[0080] (Carbon Dioxide Gas Source) In this embodiment, carbon dioxide from the carbon dioxide gas source 104 is supplied to the oxygen supply path 120R1 via the carbon dioxide supply path 120RC. A pH adjuster 105 is provided along the carbon dioxide supply path 120RC. The pH adjuster 105 is, for example, a flow control valve that adjusts the amount of carbon dioxide gas supplied based on the pH measurement results of the pH meter 39 in the gas-liquid separation tank 30. In this case, it is preferable that the supply amount meter 112 measures both the mass flow rate of oxygen gas and the mass flow rate of carbon dioxide gas.

[0081] (Ozone-containing gas-liquid two-phase flow generating apparatus) The ozone-containing gas-liquid two-phase flow generating apparatus 10 has a condenser 128 to which ozone-containing oxygen generated in the ozone-containing oxygen generating section 120 is guided, a cooling section 160 that cools the ozone condensing section 130 of the condenser 128, and a sealed structure 170 that houses the ozone condensing section 130 and the cooling section 160. The cooling section 160 adjusts the internal space (inner wall) of the ozone condensing section 130 to a temperature range where oxygen is in a gaseous state and ozone is in a liquid state.

[0082] (Cooling Temperature) As shown in FIG. 4 , the gas-liquid equilibrium vapor pressures Oa (kPa) of oxygen and Ob (kPa) of ozone, shown on the vertical axis, vary depending on the temperature (K) shown on the horizontal axis. For example, at a predetermined temperature T1, the gas-liquid equilibrium vapor pressure Oa1 of oxygen is greater than the gas-liquid equilibrium vapor pressure Ob1 of ozone. To convert oxygen into a gaseous state at the predetermined temperature T1, the internal pressure of the ozone condenser 130 must be adjusted to be equal to or lower than the gas-liquid equilibrium vapor pressure Oa1 of oxygen at the predetermined temperature T1. To condense ozone at the predetermined temperature T1, the internal pressure of the ozone condenser 130 must be adjusted to exceed the gas-liquid equilibrium vapor pressure Ob1 of ozone at the predetermined temperature T1. Furthermore, to prevent ozone from solidifying in the internal space (inner wall) of the ozone condenser 130, the temperature of the internal space (inner wall) must be set to a temperature equal to or higher than the melting point of ozone (80.7 K).

[0083] For example, when the inside of the ozone condensing section 130 is set to standard atmospheric pressure (101.325 kPa) Ps, in order to create an environment in which ozone that comes into contact with the inner wall of the ozone condensing section 130 quickly liquefies (condenses) and oxygen that comes into contact with the inner wall of the ozone condensing section 130 remains in a gaseous state, it is preferable to set the inner wall temperature of the ozone condensing section 130 to 90 K or higher.

[0084] For example, the gas-liquid equilibrium vapor pressure Ob of ozone is 1.4 kPa at 110 K. Assuming that the temperature is 110 K and the total pressure of ozone-containing oxygen is 100 kPa (approximately atmospheric pressure), the partial pressure of ozone is 10 kPa (10%), and of this, 1.4 kPa of gas-liquid equilibrium vapor pressure Ob of ozone (i.e., 14% of the total ozone) of gaseous ozone remains in the gas phase.

[0085] Therefore, from the viewpoint of ozone liquefaction efficiency, it is preferable to set the residual rate of gaseous ozone low, and for this purpose, it is preferable to set the inner wall temperature of the ozone condenser 130 to 120 K or higher, and more preferably to 110 K or lower. If the inner wall temperature of the ozone condenser 130 becomes higher than 120 K, the gas-liquid equilibrium vapor pressure Ob of ozone increases, and the condensation efficiency of ozone decreases.

[0086] Furthermore, for example, when the inside of the ozone condensing section 130 is set to a pressure Pu higher than the standard atmospheric pressure Ps, in order to create an environment in which oxygen remains gaseous in the ozone condensing section 130, the temperature of the ozone condensing section 130 may be adjusted to a temperature range in which the gas-liquid equilibrium vapor pressure Oa of oxygen exceeds the pressure Pu, that is, within a range of Tu (K) or higher, which is higher than 90 K. In other words, it can be seen that pressurizing the inside of the ozone condensing section 130 allows the cooling section 160 to have a smaller cooling capacity.

[0087] (Cooling section) The cooling section 160 has a refrigerant reservoir 162 that serves as a container for storing a cooling liquid (refrigerant), and a sealed structure 170 that seals the refrigerant reservoir 162. By disposing (immersing) all or a part of the ozone condenser 130 in the cooling liquid in the refrigerant reservoir 162, the cooling liquid comes into contact with the outer peripheral surface of the ozone condenser 130. The refrigerant reservoir 162 is preferably an insulated container that suppresses external heat absorption by the cooling liquid, and for example, a thermos bottle made of glass or the like can be used. In this embodiment, liquid nitrogen N is used as the refrigerant. ｌｉｑHowever, various other cooling liquids such as liquid oxygen, liquid argon, and alcohol can also be used. The refrigerant stored (circulated) in the refrigerant reservoir 162 is not limited to a liquid; for example, helium gas can also be used. Furthermore, in addition to using a cooling liquid (refrigerant), the ozone condenser 130 can be cooled using electronic components such as a Peltier element. Furthermore, the cooling unit 160 can employ a load-side heat exchanger that exchanges heat between the circulating refrigerant and the ozone condenser 130, and a refrigeration mechanism that circulates this circulating refrigerant within the refrigeration cycle. This circulating refrigerant may be circulated directly within the refrigeration cycle, or an indirect cooling structure in which the circulating refrigerant is cooled by an external refrigeration cycle (refrigerator) can be used.

[0088] The sealed structure 170 is an airtight container (pressure vessel) that houses the refrigerant reservoir 162 therein, and maintains the internal space at a desired pressure. Specifically, the sealed structure 170 has a cylindrical container portion 172 with a bottom and a lid portion 174 that covers the top surface of the container portion 172. The temperature of the cooling liquid is controlled by the pressure within the sealed structure 170. As shown in FIG. 5A, the gas-liquid equilibrium vapor pressure (kPa) of liquid nitrogen changes depending on the temperature (K). Therefore, liquid nitrogen N ｌｉｑ In this embodiment, when liquid nitrogen N is used, the pressure in the internal space of the sealed structure 170 must be maintained at 300 kPa or higher. ｌｉｑ The internal pressure of sealed structure 170 is set to 550 kPa in order to set the temperature of 95 K. Note that, although the example shown here is a case where container portion 172 and the container of refrigerant storage portion 162 have a double structure, the present invention is not limited to this, and the coolant may be stored directly in container portion 172.

[0089] The internal pressure of the sealed structure 170 is controlled by a pressure regulation valve 177 connected to a pressure regulation path 170R1 of the sealed structure 170. The pressure regulation valve 177 may be, for example, a back pressure regulation valve. ｌｉｑSince the liquid nitrogen vaporizes inside the sealed structure 170 and becomes nitrogen gas, the internal pressure can be controlled to a constant value by a back pressure regulating valve. It is preferable that the internal pressure of the sealed structure 170 be maintained constant at atmospheric pressure or a pressure higher than atmospheric pressure. The sealed structure 170 has a refrigerant introduction passage 170R2 for introducing a refrigerant (liquid nitrogen) into the internal space, and a refrigerant from an external refrigerant source 175 is supplied via the refrigerant introduction passage 170R2. An on-off valve 176 is connected midway through the refrigerant introduction passage 170R2. The on-off valve 176 is an electromagnetic valve that opens and closes the refrigerant introduction passage 170R2. A refrigerant detector 164 capable of detecting the liquid level of the coolant in the refrigerant reservoir 162 opens the on-off valve 176 when the liquid level L of the coolant reaches a lower limit value L2, thereby allowing the liquid nitrogen N from the refrigerant source 175 to flow through the refrigerant introduction passage 170R2. ｌｉｑ is transported to the refrigerant reservoir 162 within the sealed structure 170. ｌｉｑ The transport of the coolant is carried out by a pressure-feeding structure that utilizes the pressure of nitrogen gas vaporized in a coolant source 175. Meanwhile, when the coolant level reaches an upper limit L1, a coolant detector 164 closes an on-off valve 176 to stop the supply of the coolant. The internal pressure of the sealed structure 170 can also be electrically controlled by a pressure regulator 178 (a compressor or a vacuum pump).

[0090] The sealing structure 170 also serves as an ultraviolet ray shielding means for the ozone condensing section 130. Since ultraviolet rays can induce ozone explosion, by shielding the ultraviolet rays, the explosion of liquid ozone in the ozone condensing section 130 can be prevented.

[0091] (Refrigerant temperature control) The temperature of the refrigerant is controlled by maintaining the pressure in the refrigerant reservoir 162 at the gas-liquid equilibrium vapor pressure of the target temperature value using the pressure regulating valve 177 of the sealing structure 170 that seals the refrigerant reservoir 162. Figure 5(A) shows the gas-liquid equilibrium vapor pressure of nitrogen, and Figure 5(B) shows the gas-liquid equilibrium vapor pressure of oxygen. These equilibrium vapor pressures can also be calculated using the following approximate formula, although there may be some error. Approximate formula for nitrogen gas-liquid equilibrium vapor pressure: P Ｎ２ =101.325×10^(3.720822-293.94358 / T+0.001031993*T) (kPa) ・Oxygen vapor liquid equilibrium vapor pressure approximation formula P Ｏ２ =0.2866×T^2 - 41.52×T + 1516.3 (kPa) T: Liquid temperature (K)

[0092] For example, to obtain a temperature of 92 K, the pressure should be 423 kPa for liquid nitrogen and 122 kPa for liquid oxygen using these formulas. These values ​​are approximate and not necessarily accurate, but in practice, the target pressure obtained from the calculations of the control device using this approximate formula can be set.

[0093] (Condenser) The condenser 128 includes an ozone condenser 130, an ozone-containing oxygen introduction passage 120R2, a gas-liquid two-phase flow outlet passage 130R1, a gas outlet passage 130R2, and an oxygen circulation passage 130R3.

[0094] The ozone condenser 130 is a cylindrical container made of quartz glass that extends vertically and has a peripheral wall 130A, a ceiling surface 130B, and a bottom surface 130C. The bottom surface 130C of the ozone condenser 130 and the peripheral wall 130A around the bottom surface 130C function as a liquid ozone receiver where liquid ozone accumulates.

[0095] Here, the direction in which the peripheral wall 130A of the cylindrical container in the ozone condenser 130 extends (e.g., the axial direction of the cylinder) is defined as the air supply direction S. In this embodiment, since the air supply direction S is vertical, one end of the ozone condenser 130 in the air supply direction S is the upper end, where a ceiling surface 130B is located. The other end of the ozone condenser 130 in the air supply direction S is the lower end, where a bottom surface 130C is located. At one end (upper end) of the ozone condenser 130, an end (gas outlet) of an ozone-containing oxygen introduction channel 120R2 for introducing ozone-containing oxygen into the internal space 130D is located. The ozone-containing oxygen flows along the inner surface of the peripheral wall 130A from one end to the other end in the air supply direction S. The outer surface of the peripheral wall 130A is in contact with the coolant, and as a result, the inner surface is also cooled to a temperature close to that of the coolant.

[0096] The gas-liquid two-phase flow outlet path 130R1 is a flow path formed by a gas-liquid two-phase flow outlet pipe that penetrates the interior and exterior of the ozone condenser 130 near one end (here, the ceiling surface 130A) in the gas supply direction S. Here, it vertically penetrates the interior and exterior of the ozone condenser. This gas-liquid two-phase flow outlet pipe is a quartz glass tube and is held by a branch joint 140. The gas-liquid two-phase flow outlet path 130R1 inside the ozone condenser 130 extends in the gas supply direction S while being spaced away from the peripheral wall 130A, with one end (here, the lower end, which serves as an inlet for the gas-liquid two-phase ozone-containing oxygen) approaching the bottom surface 130C (liquid ozone receiver). When liquid ozone accumulates on the bottom surface 130C (liquid ozone receiver), the liquid ozone comes into contact with one end of the gas-liquid two-phase flow outlet path 130R1. The liquid ozone that comes into contact with the liquid ozone is sucked into the gas-liquid two-phase flow outlet 130R1 by the ozone-depleted oxygen gas flow, and becomes gas-liquid two-phase ozone-containing oxygen, which is then discharged to the outside. By adjusting the proximity between the gas-liquid two-phase flow outlet 130R1 and the bottom surface 130C, the maximum amount of liquid ozone that can be stored in the liquid ozone receiving section is set to preferably 5 g or less, more preferably 3 g or less, and even more preferably 1 g or less.

[0097] The diameter of the gas-liquid two-phase flow outlet passage 130R1 (the inner diameter of the gas-liquid two-phase flow outlet pipe) is preferably set to 1.0 cm or less, more preferably 0.5 cm or less, and in this embodiment is set to 0.3 cm. This increases the flow rate of ozone-depleted oxygen flowing through the gas-liquid two-phase flow outlet passage 130R1, thereby increasing the extraction capacity (suction force) of liquid ozone 900. Furthermore, the amount of liquid ozone present in the gas-liquid two-phase flow outlet passage 130R1 can be reduced, thereby improving safety.

[0098] The gas-liquid two-phase flow outlet path 130R1 located outside the ozone condenser 130 penetrates the lid 174 of the sealing structure 170. The other end of the gas-liquid two-phase flow outlet path 130R1 (here, the upper end, which serves as the outlet for the gas-liquid two-phase ozone-containing oxygen) is connected to the ozone mixing section 20 (the solvent-side ozone mixer 22 and the circulation-side ozone mixer 24). An outlet valve mechanism 109 is disposed midway along the gas-liquid two-phase flow outlet path 130R1 located outside the ozone condenser 130. The outlet valve mechanism 109 has, from upstream to downstream, a pressure adjustment valve 150, an on-off valve 152, and a check valve 154, in this order. The pressure adjustment valve 150 may be, for example, a back pressure adjustment valve, which is capable of adjusting the internal pressure of the ozone condenser 130. The ozone mixing section 20 fluctuates, for example, from atmospheric pressure to 10 kPa due to the action of the so-called ejector 28. However, the internal pressure of the ozone condensing section 130 is set to a pressure higher than that of the ejector 28 by the pressure regulating valve 150. The internal pressure of the ozone condensing section 130 is preferably set to, for example, 0.08 MPa or higher, more preferably 0.1 MPa or higher, and even more preferably atmospheric pressure or higher. The on-off valve 152 controls the ON / OFF of the supply of ozone-containing oxygen and / or liquid ozone to the ozone mixing section 20. The check valve 154 prevents backflow of the solution, ozone-containing oxygen, and liquid ozone from the ozone mixing section 20 side. In this embodiment, the ozone mixing section 20 has a solvent-side ozone mixer 22 and a circulation-side ozone mixer 24, and therefore an on-off valve 152 and a check valve 154 are provided for each.

[0099] In the gas-liquid two-phase flow outlet passage 130R1, a portion of the ozone-containing oxygen (hereinafter referred to as ozone-depleted oxygen) whose ozone content has been reduced due to liquefaction of the ozone contained in the ozone-containing oxygen introduced into the ozone condenser section 130 always flows vertically upward from one end (lower end) to the other end (upper end).

[0100] As the ozone-containing oxygen flows in the gas supply direction S along the peripheral wall 130A of the ozone condenser 130, the ozone contained in the ozone-containing oxygen condenses, and the resulting droplets (liquid ozone 900) fall under their own weight and accumulate on the bottom surface 130C. When the liquid ozone 900 contacts the lower end of the gas-liquid two-phase flow outlet path 130R1 (gas-liquid two-phase flow outlet pipe), the ozone-depleted oxygen gas flow S1 draws the liquid ozone 900 into the gas-liquid two-phase flow outlet pipe and causes it to rise. In other words, the ozone-depleted oxygen, liquid ozone, and, in some cases, ozone gas resulting from the evaporation of some of the liquid ozone flow together in a gas-liquid two-phase state in the gas-liquid two-phase flow outlet path 130R1. A temperature gradient exists in the gas-liquid two-phase flow outlet path 130R1 from one end (lower end) located in the ozone condenser 130 to the other end (upper end) located outside the ozone condenser 130. Therefore, there is a possibility that a portion of the liquid ozone moving in the gas-liquid two-phase flow outlet pipe will be vaporized during the movement. Therefore, in this embodiment, the liquid ozone moving in the gas-liquid two-phase flow outlet path 130R1 and the gaseous ozone that is formed by vaporizing this liquid ozone will be collectively referred to as "liquid-derived ozone."

[0101] The gas outlet path 130R2 is a flow path formed by a gas outlet pipe that leads a portion of the ozone-depleted oxygen (the remaining portion of the ozone-depleted oxygen flowing through the gas-liquid two-phase flow outlet path 130R1) to the outside of the ozone condenser 130. The gas outlet path 130R2 in this embodiment is a flow path that penetrates the inside and outside of the ozone condenser 130 near one end side of the ozone condenser 130 in the gas supply direction S (here, the ceiling surface 130A). Here, the gas outlet path 130R2 penetrates the inside and outside of the ozone condenser in the vertical direction. The gas outlet pipe is a quartz glass tube and is welded and held in a through-hole in the ceiling surface 130B.

[0102] The gas outlet passage 130R2 inside the ozone condenser 130 extends in the gas supply direction S away from the peripheral wall 130A, with one end (here, the lower end of the gas outlet pipe, which serves as the gas suction port) close to the bottom surface 130C (liquid ozone receiving portion). However, the one end (lower end) of the gas outlet passage 130R2 is located higher than the one end (lower end) of the gas-liquid two-phase flow outlet passage 130R1. As a result, the one end (lower end) of the gas outlet passage 130R2 does not come into contact with the liquid ozone accumulated on the bottom surface 130C (liquid ozone receiving portion). As shown by the airflow S2, excess ozone-depleted oxygen not discharged from the gas-liquid two-phase flow outlet passage 130R1 flows upward through the gas outlet passage 130R2.

[0103] The gas outlet passage 130R2 located outside the ozone condenser 130 penetrates the lid 174 of the sealed structure 170. An annular (cylindrical) through-joint 174x is attached to the gap between the through-hole of the lid 174 and the gas outlet passage 130R2, thereby ensuring the airtightness of the sealed structure 170.

[0104] The other end (gas outlet) of the gas outlet path 130R2 is connected to the oxygen circulation path 130R3. An oxygen outlet amount regulator 146, a cooler 147, and an ozone concentration meter 148 are arranged along the gas outlet path 130R2 outside the ozone condenser 130. The oxygen outlet amount regulator 146 is, for example, a gas transport pump, and regulates the flow rate (exhaust amount) of ozone-depleted oxygen flowing through the gas outlet path 130R2.

[0105] (Function of the Gas Outlet Path) When the flow rate (discharge rate) of ozone-depleted oxygen is increased by the oxygen output regulator (gas transport pump) 146, the flow rate of ozone-depleted oxygen flowing through the gas-liquid two-phase flow outlet path 130R1 decreases. As a result, the proportion of liquid ozone in the gas-liquid two-phase flow flowing inside the gas-liquid two-phase flow outlet path 130R1 increases, and the ozone concentration increases. Conversely, when the flow rate (discharge rate) of ozone-depleted oxygen is reduced by the oxygen output regulator 146, the flow rate of ozone-depleted oxygen flowing through the gas-liquid two-phase flow outlet path 130R1 increases. This ozone-depleted oxygen also serves as a dilution gas, and the proportion of ozone-depleted oxygen in the gas-liquid two-phase ozone-containing oxygen flowing inside the gas-liquid two-phase flow outlet path 130R1 increases, resulting in a decrease in the ozone concentration.

[0106] (Oxygen Circulation Path) When ozone-depleted oxygen is reused via the oxygen circulation path 130R3, the oxygen output regulator 146 also serves to adjust the circulation flow rate. The cooler 147 cools the ozone-depleted oxygen that has been heated through the condenser 128, thereby increasing the ozone generation rate in the ozone-containing oxygen generation unit 120. The ozone concentration meter 148 measures the ozone concentration of the ozone-depleted oxygen and calculates the amount of ozone liquefaction from the difference between the ozone concentration of the ozone-containing oxygen before depletion. Note that a flow control valve or the like may also be used as the oxygen output regulator 146. It is also preferable to provide a check valve in the oxygen circulation path 130R3.

[0107] One end of the oxygen circulation path 130R3 is connected to the gas outlet path 130R2, and the other end is connected to the oxygen supply path 120R1 downstream of the adsorption section 110. This oxygen circulation path 130R3 reuses ozone-depleted oxygen discharged from the gas outlet path 130R2 as part of the raw oxygen. In this case, if the gas pressure on the oxygen supply path 120R1 side is higher than the gas pressure in the oxygen circulation path 130R3, it is preferable to install an additional pressure pump midway along the oxygen circulation path 130R3. When ozone-depleted oxygen is released into the atmosphere from the gas outlet path 130R2 without using the oxygen circulation path 130R3, it is preferable to install an exhaust ozone decomposer upstream of the ozone concentration meter 148 to decompose the ozone to a lower concentration before discharging it. In this case, it is preferable to install an adsorbent, such as a silica gel tube, upstream of the exhaust ozone decomposer to prevent organic matter (catalyst) from the exhaust ozone decomposer from flowing back into the ozone condenser 130.

[0108] (Double-Tube Structure) In this embodiment, the gas outlet tube of the gas outlet path 130R2 surrounds the gas-liquid two-phase flow outlet tube of the gas-liquid two-phase flow outlet path 130R1. As a result, a double-tube structure is formed in which the gas outlet tube serves as the outer tube and the gas-liquid two-phase flow outlet tube serves as the inner tube. The gas outlet path 130R2 is formed by a gap between the outer periphery of the gas-liquid two-phase flow outlet tube and the inner periphery of the gas outlet tube. Including the ozone condenser 130, which is the outermost tube, this can also be described as a triple-tube quartz glass tube. The space surrounding the lower end of the gas outlet tube and the lower end of the gas-liquid two-phase flow outlet tube functions as a "gas branching section 190" that branches ozone-depleted oxygen into the gas outlet path 130R2 and the gas-liquid two-phase flow outlet path 130R.

[0109] (Regarding the Bottleneck) The gap between the peripheral wall 130A of the ozone condenser 130 and the outer circumferential surface of the gas discharge pipe that constitutes the gas discharge path 130R2 forms a bottleneck structure. The gap of this bottleneck structure is preferably set narrow to enhance the internal heat transfer coefficient of the ozone-containing oxygen passing through it, preferably 10 mm or less, more preferably 5 mm or less, and even more preferably 1 mm or less. For example, in this embodiment, it is 0.25 mm. The temperature of the ozone-containing oxygen decreases as it descends through the bottleneck, approaching the temperature of the coolant. The ozone in the ozone-containing oxygen condenses on the inner surface of the peripheral wall 130A when its partial pressure becomes equal to the gas-liquid equilibrium vapor pressure of ozone at that temperature. The condensation progresses as the temperature decreases.

[0110] The gas-liquid equilibrium vapor pressure Ob (kPa) of ozone shown in FIG. 4 is approximated using the following approximation formula: Ob=1.26E －２７ ×T １３．２２８T (K): Temperature As an example, let us consider a case where the total pressure of ozone-containing oxygen is 100 kPa and the ozone concentration is 10 mol%. At this time, the partial pressure of ozone is 10 kPa. Ignoring pressure loss in the flow path, the partial pressure of ozone is maintained at 10 kPa along the flow path. Therefore, when ozone-containing oxygen flows along a narrow passage, condensation begins when it reaches a temperature where the gas-liquid equilibrium vapor pressure is 10 kPa. Back-calculating from the above approximation formula, the temperature T where the gas-liquid equilibrium vapor pressure Ob of ozone is 10 kPa is 128.6 K. As a result, condensation and liquefaction of ozone begin at the point where 128.6 K is reached.

[0111] (Regarding the Branch Joint) A branch joint 140 is interposed in the gas outlet path 130R2 located outside the sealing structure 170. Here, the branch joint 140 is a three-way joint. A first port 140A on the lower side of the branch joint 140 holds (passes through) both the gas outlet pipe (gas outlet path 130R2) and the gas-liquid two-phase flow outlet pipe (gas-liquid two-phase flow outlet path 130R1), which have a double-pipe structure. The gas-liquid two-phase flow outlet pipe that passes through the first port 140A passes through the inside of the branch joint 140 and is held (passes through) by a second port 140B on the upper side. A third port 140C located between the first port 140A and the second port 140B holds (passes through) only the gas-liquid two-phase flow outlet pipe (gas-liquid two-phase flow outlet path 130R1). In other words, the branch joint 140 serves to separate (branch) the gas outlet channel 130R2 and the gas-liquid two-phase flow outlet channel 130R1, which have a double-pipe structure, into two directions.

[0112] In the ozone condenser 130, the end (gas outlet) of the ozone-containing oxygen introduction channel 120R2 is disposed upstream in the gas supply direction S, and the ends (suction ports) of the gas-liquid two-phase flow outlet channel 130R1 and the gas outlet channel 130R2 are disposed downstream in the gas supply direction S. As a result, the ozone-containing oxygen introduced from the ozone-containing oxygen introduction channel 120R2 flows along the gas supply direction S, and is cooled by the peripheral wall 130A of the ozone condenser 130.

[0113] (Simulation of Ozone Condenser) Figure 17 shows an example of the results of a simulation calculation that combines heat transfer and mass transfer calculations to calculate the temperature change of ozone-containing oxygen in the ozone condenser 130 and the ozone condensation and liquefaction processes. The operating conditions assumed in this simulation calculation are as follows: Ozone-containing oxygen pressure: 1 atm Ozone-containing oxygen flow rate: 1 to 10 L (std) / min (std: standard condition equivalent) Inlet temperature of ozone-containing oxygen to the ozone condenser: 293 K (20°C) Coolant temperature: 100 K

[0114] Next, the main dimensions of the ozone condenser 130 are as follows: Peripheral wall 130A: outer diameter 26.5 mm, inner diameter 24.5 mm Gas outlet pipe (gas outlet passage 130R2): outer diameter 24.0 mm, inner diameter 22.6 mm Gas-liquid two-phase flow outlet pipe (gas-liquid two-phase flow outlet passage 130R1): outer diameter 4 mm, inner diameter 2 mm Axial length of peripheral wall 130A (cooling distance): 200 mm

[0115] The horizontal axis of Fig. 17 is the flow rate of ozone-containing oxygen (standard condition conversion). Line G in Fig. 17 represents the amount of ozone contained in the ozone-containing oxygen generated per unit time (g / hour). Line L out represents the amount of liquid ozone produced (g / hour) calculated by simulation. Line EF represents the production ratio (%) of liquefied ozone L out to the amount of ozone present in the ozone-containing oxygen G in .

[0116] Here, we will discuss a method for setting the operating conditions of the ozone-containing gas-liquid two-phase flow generation system 10. The main operating condition setting parameters are the pressure, flow rate, and ozone concentration of the ozone-containing oxygen, the temperature of the coolant, and the supply amount of oxygen used as the raw material.

[0117] The pressure of the ozone-containing oxygen is set higher than the inlet pressure of the process (here, the ozone mixing section 20) that uses the ozone-containing gas-liquid two-phase flow. For example, if the inlet of the process is vacuum or reduced pressure, the pressure of the ozone-containing oxygen can also be set to a low pressure below atmospheric pressure. However, when operating at a low pressure, the pressure loss in the ozone condensing section 30 increases, and it becomes difficult to return the excess ozone-depleted oxygen to the ozone-containing oxygen generating section 120, which is usually operated at atmospheric pressure or higher. Therefore, it is preferable to operate the ozone-containing oxygen at atmospheric pressure or higher.

[0118] The lower the temperature of the coolant, the more compact the ozone condenser 30 becomes and the higher the ozone liquefaction rate becomes, so it is desirable. However, the temperature must be equal to or higher than the melting point of ozone, 80.5K.

[0119] Furthermore, it is desirable that the temperature of the coolant be above the temperature at which oxygen condenses. While this is acceptable if the amount of oxygen liquefied is smaller than the amount of ozone liquefied, controlling the temperature of the coolant at such a temperature is expected to be difficult. As a result, a temperature that avoids oxygen condensation is selected. The temperature at which oxygen condenses depends on the total pressure of the ozone-containing oxygen and the ozone concentration. For example, if the total pressure is 100 kPa and the ozone concentration is 10 mol%, the oxygen partial pressure is 90 kPa. The temperature at which the oxygen vapor-liquid equilibrium pressure becomes 90 kPa is approximately 89 K in Figure 4. As long as this temperature is maintained, oxygen does not condense, and the ozone liquefaction rate can be expected to reach 99% or more. However, this requires high-level temperature control of the coolant. A practical coolant temperature is set at a temperature above the temperature at which the operating pressure becomes the vapor-liquid equilibrium vapor pressure. For example, if operation is performed at 100 kPa, the coolant temperature should be 90 K or higher from the Oa line in Figure 4.

[0120] The ozone concentration in the ozone-containing oxygen is determined by the performance of the ozone-containing oxygen generating unit 120 used, and generally the higher the better. However, when using currently available ozone generators, the ozone concentration is in the range of 5 to 20 mol%.

[0121] As shown by the EF line in Figure 17, the ozone liquefaction rate decreases as the flow rate of ozone-containing oxygen increases. However, as shown by the LOUT line, increasing the flow rate of ozone-containing oxygen increases the amount of liquid ozone produced. In this sense, it is desirable to increase the flow rate of ozone-containing oxygen, but the greater the flow rate, the greater the pressure loss in the ozone condenser 30, and the greater the ozone concentration in the excess ozone-depleted oxygen. This causes the oxygen output regulator (gas transport pump) 146 used to deliver this oxygen to be affected by ozone degradation, resulting in a shortened lifespan of the equipment. Therefore, it is preferable to select an appropriate flow rate taking these points into consideration.

[0122] In principle, the mass flow rate of oxygen supplied from the oxygen gas source 106 is set to be equal to or greater than the mass flow rate of the liquid ozone produced. By utilizing ozone-depleted oxygen in a gaseous state and quickly discharging liquefied ozone in a gas-liquid two-phase flow state, the amount of liquefied ozone remaining in the ozone condenser 130 is reduced, thereby preventing the risk of an explosion.

[0123] 1, the ozone-containing solution manufacturing apparatus 1 includes a control device 46. As shown in Fig. 6(A), for example, this control device 46 includes a central processing unit CPU that processes programs deployed in memory M, a storage medium H that stores various information and control programs, an interface I that outputs control signals to external devices and receives detection signals from external devices, and the like, all of which are connected to one another by a bus or the like.

[0124] As shown in FIG. 6B, the control device 46 has, as control blocks (functional configurations realized by a program), a solvent supply control unit 46A, a circulation flow rate control unit 46B, an ozone-containing gas-liquid two-phase flow control unit 46C, a solution discharge amount control unit 46D, a liquid level detection unit 46E, and an ozone concentration detection unit 46F.

[0125] The liquid level detection unit 46E detects the liquid level of the ozone-containing water using the liquid level sensor 36. The ozone concentration detection unit 46F detects the ozone concentration of the ozone-containing water using the ozone concentration sensor 38. The solvent supply control unit 46A controls the flow rate of the newly supplied raw water based on the liquid level of the ozone-containing water by controlling the flow rate of the flow control valve 74. This flow rate may be controlled so that the liquid level remains constant, or may be controlled in a pulse waveform so that the supply begins when the liquid level reaches a preset lower limit and stops when the liquid level reaches a preset upper limit. The flow rate control valve 74 may be controlled by switching between fully open and fully closed positions to control the water volume, or by finely controlling the throttle amount of the flow control valve 74. Meanwhile, to effectively achieve the gas-liquid mixing effect of the solvent-side ozone mixer 22, it is desirable to fully open the valve when supplying raw water to increase the flow rate. Therefore, it is also desirable to control the valve by switching between fully open and fully closed positions.

[0126] The circulation flow rate control unit 46B controls the flow rate of the circulating liquid by controlling the circulation pump 66 and / or the flow rate adjustment valve 68. The flow rate of the circulating liquid may be constant, or may be controlled based on the ozone concentration of the ozone-containing water, for example. The circulation flow rate may be increased when the ozone concentration is lower than a target value, and decreased when the ozone concentration is higher than the target value. To stabilize the concentration of the ozone water, the flow rate of the circulating liquid is preferably always set to be greater than the water flow rate controlled by the solvent supply control unit 46A. For example, if the supply rate from the solvent supply control unit 46 is 20 L / min, the flow rate of the circulating liquid is set to a value greater than 20 L / min, for example, 40 L / min.

[0127] The ozone-containing gas-liquid two-phase flow control unit 46C controls the ozone concentration and the like of the gas-liquid two-phase ozone-containing oxygen generated by the ozone-containing gas-liquid two-phase flow generation device 10. The solution discharge amount control unit 46D controls the flow rate adjustment valve 84 to control the flow rate of the ozonated water discharged to the point of use U.

[0128] (Detailed configuration of ozone-containing gas-liquid two-phase flow control unit) As shown in FIG. 6(C), the ozone-containing gas-liquid two-phase flow control unit 46C includes an oxygen supply amount control unit 46C1, an ozone-containing oxygen generation control unit 46C2, an ozone liquid discharge valve control unit 46C3, an oxygen discharge amount control unit 46C4, a refrigerant supply control unit 46C5, and a pH control unit 46C6.

[0129] The oxygen supply amount control unit 46C1 controls the supply amount controller 108, which serves as a flow control valve, so that the measurement value (mass flow rate value of oxygen gas) of the supply amount measuring device 112, which serves as a mass flow meter, reaches a predetermined target value (oxygen supply amount target value), thereby adjusting the supply amount of new oxygen gas supplied from the oxygen gas source 106. When ozone-depleted oxygen is reused via the oxygen circulation path 130R3, the total mass flow rate of the supply amount from the oxygen gas source 106 and the reused amount of ozone-depleted oxygen becomes the target value.

[0130] The oxygen supply amount target value set by the oxygen supply amount control unit 46C1 is preferably calculated based on, for example, an ozone concentration control value of the gas-liquid two-phase ozone-containing oxygen.Furthermore, the ozone concentration control value of the gas-liquid two-phase ozone-containing oxygen is preferably calculated from a target value of the ozone concentration of the ozone-containing water measured by the ozone concentration sensor 38.

[0131] The pH control unit 46C6 controls the pH adjuster 105 to adjust the amount of carbon dioxide gas supplied from the carbon dioxide gas source 104 so that the pH measurement value of the pH measuring device 39 becomes a predetermined target value (e.g., pH 6).

[0132] The coolant supply control unit 46C5 controls the on-off valve 176 based on information on the coolant level L from the coolant detector 164 to replenish the coolant (liquid nitrogen) from the coolant source 175 to the coolant reservoir 162 in the sealed structure 170. Specifically, when the coolant level L reaches a lower limit L2, the on-off valve 176 is opened to supply the coolant. When the coolant level reaches an upper limit L1 as a result of the supply operation, the on-off valve 176 is closed to stop the supply of the coolant.

[0133] The ozone-containing oxygen generation control unit 46C2 controls the output of the ozone-containing oxygen generation unit 120 (applied voltage, frequency, or, in the case of pulse control, ON / OFF of the output itself). For example, the output (ON time) may be controlled so that the ozone concentration of the ozone-containing water measured by the ozone concentration sensor 38 reaches a predetermined target value. Furthermore, for example, during startup of the ozone-containing gas-liquid two-phase flow generation device 10, it is preferable to keep the ozone-containing oxygen generation unit 120 OFF (and the on-off valve 152 closed) to circulate oxygen gas through the oxygen supply path 120R1 → ozone condenser 130 → gas outlet path 130R2 → oxygen circulation path 130R3. After that, it is preferable to open the on-off valve 152 and gradually increase the O output (ON time) of the ozone-containing oxygen generation unit 120 to gradually increase the amount of liquid ozone discharged from the gas-liquid two-phase flow outlet path 130R1 until it reaches the predetermined target value.

[0134] The ozone liquid discharge valve control unit 46C3 controls the discharge valve mechanism 109. Specifically, it controls the opening and closing timing of the on-off valve 152 in the discharge valve mechanism 109. For example, at the start of operation, the on-off valve 152 is preferably opened before or simultaneously with turning on the ozone-containing oxygen generator 120. At the end of operation, the on-off valve 152 is preferably closed a short time after the ozone-containing oxygen generator 120 is turned off. Since liquid ozone may remain in the ozone condenser 130 for a short time even after the ozone-containing oxygen generator 120 is turned off, it is preferable to safely discharge the liquid ozone from the gas-liquid two-phase flow discharge path 130R1 using oxygen gas from the oxygen gas source 106 (or carbon dioxide gas from the carbon dioxide gas source 104) before closing the on-off valve 152. The ozone liquid discharge valve control unit 46C3 can also control the pressure regulation valve 150 to control the internal pressure of the ozone condenser 130.

[0135] The oxygen output control unit 46C4 controls the oxygen output regulator 146 to adjust the flow rate (exhaust rate) of ozone-depleted oxygen in the ozone condenser 130.

[0136] (Control of the Amount of New Oxygen Supply) Next, the control of the amount of new oxygen supplied from the oxygen gas source 106, which is controlled by the oxygen supply amount control unit 46C1, will be described in detail.

[0137] The mass balance in the ozone-containing gas-liquid two-phase flow generating device 10 is expressed by the following equation: Mass balance of total flow rate: Y2 + Yh = Y1 (Equation 5) Y1 (mol / min): supply flow rate of ozone-containing oxygen from the ozone-containing oxygen generating unit 120 Y2 (mol / min): flow rate of ozone-depleted oxygen exhausted from the gas outlet line 130R2 Yh (mol / min): flow rate of gas-liquid two-phase ozone-containing oxygen from the gas-liquid two-phase flow outlet line 130R1

[0138] Furthermore, the mass balance of ozone only is expressed by the following equation: C2×Y2+Ch×Yh=C1×Y1 (Equation 6), where Ch (mol fraction): ozone concentration control value of the gas-liquid two-phase ozone-containing oxygen in the gas-liquid two-phase flow outlet 130R1, C1 (mol fraction): ozone concentration of the ozone-containing oxygen supplied from the ozone-containing oxygen generator 120, and C2 (mol fraction): ozone concentration of the ozone-depleted oxygen exhausted from the gas outlet 130R2.

[0139] The following relationship can be derived from the above formulas 5 and 6: Ch×Yh=(C1×Y1−C2×(Y1−Yh))=(C1−C2)×Y1+C2×Yh (Formula 7)

[0140] The following relationship can be derived from Equation 7: Yh = (C1 - C2) x Y1 / (Ch - C2) (Equation 8)

[0141] Incidentally, the amount of oxygen contained in the gas-liquid two-phase ozone-containing oxygen (i.e., oxygen consumption) can be expressed as "(1-Ch) x Yh", and the amount of liquid ozone contained in the gas-liquid two-phase ozone-containing oxygen (i.e., ozone consumption) can be expressed as "Ch x Yh". To cover the total consumption of oxygen and ozone, it is necessary to replenish fresh raw oxygen from the oxygen gas source 106. However, here, it is assumed that the ozone consumption "Ch x Yh" is multiplied by a margin coefficient of 1.5 times to determine the amount of freshly replenished raw oxygen. As a result, the following relational expression is derived. Y ｎｅｗ =Ch×Yh×1.5+(1-Ch)×Yh=(1+0.5×Ch)×Yh...(Formula 9) Y ｎｅｗ (mol / min): Amount of new oxygen supplied by the oxygen gas source 106

[0142] From the above (Equation 8) and (Equation 9), the following relationship can be derived: Y ｎｅｗ=(1+0.5×Ch)×(C1-C2)×Y1 / (Ch-C2)...(Formula 10)

[0143] Here, Ch on the right side of Equation 10 is the ozone concentration control value of the gas-liquid two-phase ozone-containing oxygen, and C1, C2, and Y1 are measured values. ｎｅｗ The calculated new supply Y ｎｅｗ When the oxygen supply amount control unit 46C1 controls the flow rate of the raw material oxygen by the supply amount controller 108 based on the above, the ozone concentration control value of the gas-liquid two-phase ozone-containing oxygen discharged from the gas-liquid two-phase flow discharge path 130R1 is controlled to Ch (mol fraction).

[0144] (Safety-Based Discharge Amount Control) In the ozone-containing gas-liquid two-phase flow generating device 10, from the viewpoint of safety, the ozone concentration control value Ch (mol fraction) of the gas-liquid two-phase ozone-containing oxygen is set to a predetermined upper limit C ｍａｘ As a result, the following relationship holds: Cmax≧Ch (Equation 11)

[0145] The upper limit Cmax of the ozone concentration control value Ch is preferably determined based on the internal pressure of the ozone condenser 130. For example, when the internal pressure of the ozone condenser 130 is atmospheric pressure, the ozone concentration of the gas-liquid two-phase ozone-containing oxygen is set to 50 (mol fraction). That is, the ozone concentration control value Ch of the gas-liquid two-phase ozone-containing oxygen is preferably controlled to 50 (mol fraction) or less in an atmospheric pressure environment.

[0146] Furthermore, the following relationships can be derived from Equation 5 and Equation 7: Ch×(Y1−Y2)=(C1×Y1+C2×Y2) Ch=(C1×Y1+C2×Y2) / (Y1−Y2) (Equation 12)

[0147] From Equation 11 and Equation 12, the following relationship can be derived: C ｍａｘ ≧(C1×Y1+C2×Y2) / (Y1-Y2) Y2≦(C ｍａｘ -C1)×Y1 / (C2+C ｍａｘ )...(Formula 13)

[0148] In the right side of Equation 13, assuming that the supply flow rate Y1 of ozone-containing oxygen in the ozone-containing oxygen generating unit 120 is constant, the oxygen discharge amount control unit 46C4 calculates the exhaust amount Y2 of ozone-depleted oxygen from the gas discharge path 130R2 as follows: (C ｍａｘ -C1)×Y1 / (C2+C ｍａｘ ) or less, the ozone concentration control value Ch can be maintained at or below the upper limit Cmax, thereby reliably preventing ozone explosion.

[0149] On the other hand, if the exhaust amount Y2 of the ozone-depleted oxygen from the gas outlet passage 130R2 is too small, the ratio of ozone-depleted oxygen contained in the gas-liquid two-phase ozone-containing oxygen increases, and the ozone concentration control value Ch (mol fraction) decreases. This also means that the amount of ozone-depleted oxygen recycled decreases. This increases the cost of producing the gas-liquid two-phase ozone-containing oxygen. Therefore, a predetermined lower limit C is set for the ozone concentration control value Ch (mol fraction) in the gas-liquid two-phase ozone-containing oxygen from the viewpoint of production cost. ｍｉｎ (<C ｍａｘ ) and control it to a value not less than this. As a result, the following relational expression is established: Y2 ≥ (C ｍｉｎ -C1)×Y1 / (C2+C ｍｉｎ )...(Formula 14)

[0150] The oxygen discharge amount control unit 46C4 determines whether the exhaust amount Y2 of ozone-depleted oxygen is (C ｍｉｎ -C1)×Y1 / (C2+C ｍｉｎ ) or higher to reduce production costs.

[0151] Although the oxygen supply amount target value set by the oxygen supply amount control unit 46C1 is calculated based on the ozone concentration control value of the gas-liquid two-phase ozone-containing oxygen, the present invention is not limited to this. For example, the oxygen supply amount target value can also be calculated based on the target ozone concentration measured by the ozone concentration meter 121 downstream of the ozone-containing oxygen generation unit 120. The ozone concentration of the ozone-containing oxygen generated by the ozone-containing oxygen generation unit 120 can be controlled by the ratio (W / Q) of the output (discharge power W) of the ozone-containing oxygen generation unit 120 to the oxygen supply amount Q.

[0152] Alternatively, for example, the oxygen output control unit 46C4 may control the amount of ozone-containing oxygen exhausted so that the ozone concentration of the ozone-containing water measured by the ozone concentration sensor 38 reaches a target value. Assuming that the mass flow rate of oxygen gas measured by the supply rate measuring device 112 is constant (i.e., the amount of liquid ozone generated by the ozone condenser 130 is also constant), increasing the flow rate (exhaust rate) of ozone-depleted oxygen reduces the flow rate of ozone-depleted oxygen flowing through the gas-liquid two-phase flow outlet 130R1. As a result, the proportion of liquid ozone in the gas-liquid two-phase ozone-containing oxygen increases, resulting in an increase in the ozone concentration. Conversely, decreasing the flow rate (exhaust rate) of ozone-depleted oxygen increases the flow rate of ozone-depleted oxygen flowing through the gas-liquid two-phase flow outlet 130R1. As a result, the proportion of liquid ozone in the gas-liquid two-phase ozone-containing oxygen decreases, resulting in a decrease in the ozone concentration.

[0153] (Simulation of ozone concentration in gas-liquid two-phase ozone-containing oxygen) In the ozone-containing gas-liquid two-phase flow generating device 10 of this embodiment, the ozone concentration (g / m ) in the gas-liquid two-phase ozone-containing oxygen led out from the gas-liquid two-phase flow lead-in path 130R1 can be simulated by changing the oxygen supply amount and the ratio of the ozone-depleted oxygen led into the gas-liquid two-phase flow lead-in path 130R1 to the flow rate of the total ozone-depleted oxygen that has passed through the ozone condenser 130 and reached just before the gas branching portion 190 (hereinafter referred to as the "lead-out ratio of ozone-depleted oxygen to the gas-liquid two-phase flow"). ３ (std)) was evaluated, and the results are shown in Figures 27(A) to (C).

[0154] FIG. 27(A) shows the results of an evaluation to clarify the liquefaction efficiency of the ozone condenser 130, which is a prerequisite, and shows the flow rate of oxygen introduced to the ozone-containing oxygen generator 120 (L(std) / min), the inlet ozone concentration (g / m) of the ozone-containing oxygen generated through the ozone-containing oxygen generator 120 and introduced to the inlet of the ozone condenser 130. ３The graph shows the ozone flow rate (g / hour) of the ozone-containing oxygen at the inlet, the amount of ozone (g / hour) liquefied from the ozone-containing oxygen in the ozone condenser 130, and the ozone liquefaction rate (%), which is the ratio of the amount of liquefied ozone to the inlet ozone flow rate. The final cooling temperature of the ozone condenser 130 was set to 95 K. As the oxygen flow rate increases, the ozone concentration of the ozone-containing oxygen generated through the ozone-containing oxygen generator 120 decreases, but the absolute amount of the generated (gaseous) ozone flow rate and liquefied ozone increase. As the oxygen flow rate increases, the liquefaction rate decreases slightly.

[0155] FIG. 27(B) shows the ozone concentration (g / m) in the gas-liquid two-phase ozone-containing oxygen discharged from the gas-liquid two-phase flow discharge path 130R1 under the liquefaction conditions shown in FIG. 27(A). ３ (std)), and the oxygen flow rate (L(std) / min) introduced to the ozone-containing oxygen generating unit 120, the inlet ozone concentration (g / m ３ (std)), and the ozone concentration (g / m) in the gas-liquid two-phase ozone-containing oxygen when the ratio of ozone-depleted oxygen led out to the gas-liquid two-phase flow was changed to 0.1%, 1.0%, 20%, and 70%. ３ 27(C) shows the ozone concentration in the gas-liquid two-phase ozone-containing oxygen expressed in mol %.

[0156] For example, when the oxygen flow rate is 1.00 L(std) / min, the larger the ratio of ozone-depleted oxygen delivered to the gas-liquid two-phase flow, the lower the proportion of liquid ozone contained in the gas-liquid two-phase ozone-containing oxygen, resulting in a lower ozone concentration in the gas-liquid two-phase ozone-containing oxygen. This downward trend is similar for oxygen flow rates of 3.00 L(std) / min, 5.00 L(std) / min, and 10.00 L(std) / min, but becomes stronger as the oxygen flow rate increases.

[0157] For example, when the ratio of ozone-depleted oxygen delivered to the gas-liquid two-phase flow is 20%, if the oxygen flow rate is increased from 1.00 L(standard) / min to 10.00 L(standard) / min, the amount of liquefied ozone increases from 13.8 g / hour to 45.5 g / hour, as shown in Figure 27(A). However, the amount of ozone-depleted oxygen delivered to the gas-liquid two-phase flow increases even more with the increase in oxygen flow rate, resulting in a relative decrease in the ozone concentration in the gas-liquid two-phase ozone-containing oxygen. This decreasing trend remains the same whether the ratio of ozone-depleted oxygen delivered to the gas-liquid two-phase flow is changed to 0.1%, 1.0%, 20%, or 70%, but becomes stronger as the delivery ratio increases.

[0158] In general, within the dotted-line frames in Figures 27(B) and (C), the ozone concentration is higher in the upper left and lower in the lower right. As a result, when attempting to control the ozone concentration of gas-liquid two-phase ozone-containing oxygen so as not to exceed an upper limit, it is desirable to set the ratio of ozone-depleted oxygen delivered to the gas-liquid two-phase flow high when the oxygen flow rate is low, and to set the ratio of ozone-depleted oxygen delivered to the gas-liquid two-phase flow low when the oxygen flow rate is high. A practical range for the ratio of ozone-depleted oxygen delivered to the gas-liquid two-phase flow is preferably 0.1% to 70%, and this delivery ratio can be controlled based on the oxygen flow rate. Note that the ozone concentration in this gas-liquid two-phase ozone-containing oxygen refers to the concentration including both gaseous ozone and liquefied ozone.

[0159] <Basic Operation> Next, the operation of the ozone-containing solution producing apparatus 1 will be described.

[0160] (Internal Cleaning Process) First, in the ozone-containing gas-liquid two-phase flow generating device 10, liquid nitrogen N ｌｉｑ By supplying oxygen gas from the oxygen gas source 106 without replenishing the oxygen gas, and turning on the output of the ozone-containing oxygen generator 120, the ozone-containing oxygen (gas) is circulated through the oxygen supply path 120R1 → ozone condenser 130 → gas outlet path 130R2 → oxygen circulation path 130R3. In this way, organic matter adhering to the inner wall surfaces of the system is removed by using ozone.

[0161] (Standby Step of Ozone-Containing Gas-Liquid Two-Phase Flow Generator) First, in the ozone-containing gas-liquid two-phase flow generator 10, liquid nitrogen N is stored in the refrigerant reservoir 162. ｌｉｑ to cool the ozone condenser 130. Furthermore, by turning on the oxygen output regulator 146 while supplying oxygen gas from the oxygen gas source 106, the oxygen gas is circulated through the oxygen supply path 120R1 → ozone condenser 130 → gas output path 130R2 → oxygen circulation path 130R3. Furthermore, it is preferable to temporarily open the two on-off valves 152 to pass oxygen gas through the gas-liquid two-phase flow output path 130R1, thereby performing flushing.

[0162] (Step for starting liquid ozone generation by the ozone-containing gas-liquid two-phase flow generator) Next, in the ozone-containing gas-liquid two-phase flow generator 10, the output of the ozone-containing oxygen generator 120 is turned on, and at the same time, the on-off valve 152 on the solvent-side ozone mixer 22 side is opened to generate gas-liquid two-phase ozone-containing oxygen, which is then supplied to the solvent-side ozone mixer 22.

[0163] (Ozone-containing water production process) Simultaneously with the start of production of gas-liquid two-phase ozone-containing oxygen, raw water from the water supply unit 72 is guided to and stored in the gas-liquid separation tank 30 via the solvent guide path 70. The gas-liquid two-phase ozone-containing oxygen supplied from the ozone-containing gas-liquid two-phase flow generation device 10 mixes with the raw water via the solvent-side ozone mixer 22, and the ozone-containing water accumulates in the gas-liquid separation tank 30. When the amount of gas-liquid two-phase ozone-containing oxygen supplied from the ozone-containing gas-liquid two-phase flow generation device 10 is constant, if the supply flow rate of the raw water is high, the ozone concentration of the generated ozone-containing water decreases. On the other hand, if the supply flow rate of the raw water is low, the ozone concentration of the generated ozone-containing water increases.

[0164] In the gas-liquid separation tank 30, excess bubbles (ozone-depleted oxygen and ozone gas) contained in the ozone-containing water are separated and collected in the upper space. This ozone-depleted oxygen may be supplied to the oxygen supply line 120R1 via the gas circulation line 26 and reused as an oxygen source.

[0165] (Ozone-Containing Water Circulation Step) After the liquid level of the water or ozone-containing water in the gas-liquid separation tank 30 has risen sufficiently, the circulation pump 66 is started to circulate the ozone-containing water through the ozone-containing solution circulation path 60. At the same time, in the ozone-containing gas-liquid two-phase flow generation device 10, the on-off valve 152 on the circulation-side ozone mixer 24 side is opened. In the circulation-side ozone mixer 24, the gas-liquid two-phase ozone-containing oxygen supplied from the ozone-containing gas-liquid two-phase flow generation device 10 is mixed with the circulating liquid.

[0166] When the ozone concentration in the ozone-containing water reaches the target value, the flow rate regulating valve 84 is opened, and the ozone-containing water is delivered to the use point U. The supply of raw water by the water supply unit 72 is adjusted to match the consumption of the ozone-containing water delivered from the use point U. On the other hand, it is preferable that the circulation flow rate in the ozone-containing solution circulation path 60 is always controlled to a constant flow rate, regardless of these factors.

[0167] (Ozone Concentration Control Process) To control the ozone concentration of the ozone-containing water to a target value, the following operations can be considered, for example: (1) Control the flow rate of newly replenished ozone-containing water by controlling the flow rate adjustment valve 74; (2) Control the circulation pump 66 to control the circulation flow rate; (3) Control the on-off valve 152 to control the mixing amount of the gas-liquid two-phase ozone-containing oxygen; (4) Adjust the supply amount of new oxygen from the oxygen gas source 106 to control the ozone concentration of the gas-liquid two-phase ozone-containing oxygen; (6) Adjust the exhaust amount of ozone-depleted oxygen exhausted from the gas outlet path 130R2 to control the ozone concentration of the gas-liquid two-phase ozone-containing oxygen; (7) Control the output of the ozone-containing oxygen generator 120 to control the amount of liquid ozone produced in the ozone-containing gas-liquid two-phase flow generation device 10.

[0168] To maximize the ozone concentration of the ozone-containing water in the gas-liquid separation tank 30, the flow control valve 74 is controlled to reduce or stop the supply of newly replenished ozone-containing water, and the circulation pump 66 is controlled to maximize the circulation flow rate. In the circulation-side ozone mixer 24, the gas-liquid two-phase ozone-containing oxygen is continuously mixed with the ozone-containing water, thereby increasing the ozone concentration of the ozone-containing water.

[0169] 7A is a schematic diagram showing the state of the gas-liquid separation tank 30 while the ozone-containing solution manufacturing apparatus 1 is operating. Here, the liquid level of the ozone-containing water is shown to be approximately the same as the solvent inlet 76, but the present invention is not limited to this. For ease of explanation, in the gas-liquid separation tank 30, the space from the solvent inlet 76 to the circulating liquid inlet 64 is defined as a primary space 30A, and the space from the circulating liquid inlet 64 to the circulating liquid outlet 62 is defined as a secondary space 30B. The heights of the primary space 30A and the secondary space 30B are defined as L. １ , L ２ (m) is defined as

[0170] The flow rate of the ozone-containing water (or raw water) introduced from the solvent inlet 76 is Q １ (L / min), and the flow rate discharged from the outlet path 82 of the ozone solution outlet part 80 is defined as Q ３ (L / min), the flow rates of the ozone mixed liquid flowing down the primary space 30A are also Q １ =Q ３ (L / min). The flow rate of the circulating liquid passing through the flow rate adjusting valve 68 of the ozone-containing solution circulation path 60 is Q ４ (L / min), the flow rate Q of the ozone mixed liquid descending in the secondary space 30B is ２ (L / min) is Q １ +Q ４ As already mentioned, the flow rate of the circulating fluid Q ４ (L / min) is the flow rate of the solvent introduced through the solvent inlet 76, Q １ Therefore, the flow rate Q of the ozone mixed liquid flowing down the secondary space 30B is set to be larger than the flow rate Q of the ozone mixed liquid flowing down the secondary space 30B. ２ is the flow rate Q １ It is preferable that the flow rate is at least twice the flow rate (L / min).

[0171] 7(B), when a swirling flow is generated by the circulating liquid in the ozone-containing solution circulation path 60, bubbles K consisting of ozone-depleted oxygen move in the direction of the central axis C of the gas-liquid separation tank 30 as a reaction to the centrifugal force caused by the swirling flow S. Therefore, in the secondary space 30B, bubbles K located on the inner circumferential wall can move at least as far as the central axis C while swirling and descending from the circulating liquid inlet 64 to the circulating liquid outlet 62. In this embodiment, the circulating liquid outlet 62 (ozone solution outlet 86) is formed at a position radially outward from the central axis C, specifically, on the inner circumferential wall of the gas-liquid separation tank 30, so that bubbles K are not discharged together with the ozone water.

[0172] Figure 8 shows a visual representation of the state of bubbles K rising in the secondary space 30B. The bubbles K attempt to move toward the radial center due to the swirling flow, both descending due to the downward flow and rising due to buoyancy. As the bubbles attempt to move toward the center, they coalesce, increasing their particle size and buoyancy. At this time, they rise along a spiral upward path N formed in the swirling flow. The bubbles K are always located at a distance radially inward from the inner circumferential wall of the gas-liquid separation tank 30, achieving efficient gas-liquid separation.

[0173] Liquid ozone has the advantage of quickly dissolving in water. In this embodiment, the gas-liquid two-phase ozone-containing oxygen is mixed into water, allowing the liquid ozone to dissolve quickly and reach the target ozone concentration in a short time. Meanwhile, the dissolution of ozone gas contained in the ozone-depleted oxygen in water occurs through two processes: the diffusion of ozone molecules in the bubbles, and the diffusion of ozone molecules moving from the bubbles to the water at the gas-liquid boundary into the water. Because the diffusion rate of ozone molecules in the bubbles is significantly faster than the diffusion rate of ozone molecules in water, the actual rate at which ozone-depleted oxygen dissolves in water is determined by the diffusion rate of ozone molecules in water. The diffusion rate of ozone molecules in water depends on the concentration gradient (change in concentration per unit distance) of ozone molecules moving from the bubbles to the water at the gas-liquid boundary. However, if the concentration of ozone molecules in the surface water near the boundary is high, ozone tends to reach equilibrium at the boundary, slowing the rate at which ozone molecules move from the bubbles to the water.

[0174] In order to increase the rate at which ozone gas contained in ozone-depleted oxygen dissolves in water, it is preferable to increase the relative movement speed between the bubbles and the water, so that bubbles with a high ozone concentration come into contact with surface water with a low ozone concentration. In the case of this ozone-containing solution manufacturing apparatus 1, the centrifugal force of the swirling flow also increases the speed at which the bubbles move in the direction of the central axis C, so the relative speed between the bubbles and the water increases, and the ozone concentration of the ozone water can be increased.

[0175] In this embodiment, the ozone mixing section 20 includes the solvent-side ozone mixer 22 and the circulation-side ozone mixer 24, but the present invention is not limited to this, and the solvent-side ozone mixer 22 may be omitted, and the circulation-side ozone mixer 24 may also be omitted. Furthermore, a solvent-side ozone-containing solution production device that supplies liquid ozone to the solvent-side ozone mixer 22 and a circulation-side ozone-containing solution production device that supplies liquid ozone to the circulation-side ozone mixer 24 may be provided separately.

[0176] In addition, in the present embodiment, the gas-liquid separation tank 30 is used to remove air bubbles from the ozone-containing water, but the present invention is not limited to this. For example, as shown in Figure 9, the gas-liquid separation tank 30 may be omitted, and the ozone-containing water containing air bubbles may be directly guided from the solvent inlet 76 to the ozone solution outlet 86.

[0177] At this time, in order to disperse the ozone contained in the ozone-containing water introduced from the solvent inlet 76, it is preferable to pressurize and stir the ozone-containing water via a pressure pump 91, a stirrer 92 (e.g., a static mixer), and a back pressure control valve 93.

[0178] The ozone-containing solution manufacturing apparatus 1 of this embodiment makes it possible to continuously produce ozone-containing water at a high concentration and at a large flow rate.

[0179] The ozone-containing gas-liquid two-phase flow generating device 10 can continuously generate a gas-liquid two-phase flow of liquid ozone and ozone-depleted oxygen at a flow rate sufficient for practical use. Moreover, the ozone concentration of the gas-liquid two-phase ozone-containing oxygen can be made much higher than that obtained by conventional ozone generators, so the ozone concentration of the ozone-containing water to be generated can also be set very high while maintaining a production rate sufficient for practical use.

[0180] For example, in semiconductor cleaning processes and resist stripping processes, single-wafer processing apparatuses that process wafers one by one are the mainstream. In single-wafer processing apparatuses, the flow rate of the processing solution used to process one wafer is typically about 0.5 to 1.0 L / min. In mass-production of wafers, several dozen single-wafer processing apparatuses may be operated simultaneously. To achieve this with a single ozone-containing solution production apparatus, it is practically necessary to generate ozone-containing water with an ozone concentration of 392 ppm to 500 ppm at a rate of 10 L / min to 20 L / min.

[0181] According to the inventors' verification, in order to continuously produce ozone-containing water meeting the above conditions, the ozone concentration in the gas-liquid two-phase ozone-containing oxygen supplied from the ozone-containing gas-liquid two-phase flow generation device 10 needs to be 50 mol%, i.e., the amount of ozone generated by the ozone-containing gas-liquid two-phase flow generation device 10 needs to be 964 g / hour (15 x 60 / 22.4 x 40 x 50 / 100), and the ozone-containing gas-liquid two-phase flow generation device 10 of this embodiment can fully meet this requirement.

[0182] For example, assume that 1000 g / hour of ozone, which exceeds 964 g / hour, is liquefied in the ozone-containing gas-liquid two-phase flow generation apparatus 10. The temperature of the ozone condenser 130 of the ozone-containing gas-liquid two-phase flow generation apparatus 10 is 95 K, and the internal pressure of the gas-liquid separation tank 30 is 0.1 MPaG. If the flow rate of ozone-depleted oxygen, which forms the gas-liquid two-phase flow together with liquid ozone in the ozone-containing gas-liquid two-phase flow generation apparatus 10, is 20.83 mol / hour, the volumetric flow rate is 45.08 cc / sec (20.83 x 22.4 x 1000 x 95 / 273.15 / 3600). Since the specific gravity of liquid ozone at 95K is 1.56 g / cc, the volumetric flow rate of the generated liquid ozone is 0.18 cc / sec (1000 / 1.56 / 3600), and the volumetric flow rate of the entire gas-liquid two-phase flow is 45.26 cc / sec.

[0183] For example, when the inner diameter of the gas-liquid two-phase flow outlet passage 130R1 is 0.3 cm, the speed at which a gas-liquid two-phase flow of 45.26 cc / sec passes through the pipe is 6.42 m / sec (5.26 / ((π / 4)×0.3×0.3) / 100), which shows that liquid ozone can be transported without significant pressure loss.

[0184] Although the ozone-containing solution manufacturing apparatus 1 of this embodiment uses a swirl-type circulation gas-liquid separation tank 30, the present invention is not limited to this. However, if ozone-containing water is produced using a packed tower type or packed tower circulation type tank, ozone-containing water with a higher ozone concentration can be obtained by the dissolution action of the gas-liquid countercurrent flow of the packed tower type (details will be described later).

[0185] Although high-concentration ozone gas and liquid ozone are known to be explosive, the ozone-containing solution manufacturing apparatus 1 of this embodiment can reliably prevent ozone explosion during operation. Conventionally, explosions have been avoided by handling high-concentration ozone gas or liquid ozone in a low-pressure environment (vacuum chamber), but continuous generation of ozone gas becomes difficult in a low-pressure environment.

[0186] On the other hand, the ozone-containing gas-liquid two-phase flow generating device 10 of this embodiment avoids liquid ozone explosion by the following configuration: (1) Liquid ozone is discharged from the gas-liquid two-phase flow outlet path 130R1 in a gas-liquid two-phase flow state consisting of liquid ozone and ozone-depleted oxygen. In the case of a gas-liquid two-phase flow, liquid ozone 900 and gas-phase ozone-depleted oxygen alternately pass through the gas-liquid two-phase flow outlet path 130R1. Even if a local explosion of the liquid ozone 900 occurs, the propagation of the explosion is suppressed by the adjacent gas-phase ozone-depleted oxygen, preventing a continuous explosion of the liquid ozone 900 accumulated in the liquid ozone receiving section (the bottom surface 130C of the ozone condensing section 130). For example, the density of liquid ozone is 1.57 g / cc at 90.5 K (-183°C), while the density of oxygen at the same temperature is 0.0043 g / cc at atmospheric pressure (assuming ideal gas), resulting in a density difference of 365 times. Therefore, if 10% oxygen is mixed into the liquid ozone in terms of mass flow rate, the ratio of the volumetric flow rate of liquefied ozone to the volumetric flow rate of gaseous oxygen will be 1:35, and the flow of liquid ozone in the fine droplets flowing in the gas-liquid two-phase flow outlet 130R1 will be largely isolated by the flow of ozone-depleted oxygen. (2) If the ozone concentration in the gas-liquid two-phase ozone-containing oxygen exceeds a predetermined upper limit C from the viewpoint of safety, ｍａｘThis can reliably avoid the risk of ozone explosion. (3) When liquid ozone is generated in the ozone condenser 130, it is immediately discharged to the outside as a gas-liquid two-phase flow from the gas-liquid two-phase flow outlet path 130R1. By minimizing the amount of liquid ozone stored in the ozone condenser 130, the risk of liquid ozone explosion is avoided (even if an explosion occurs, it is limited to a small explosion). (4) The inner diameter of the gas-liquid two-phase flow outlet path 130R1 is set small. This can reduce the amount of liquid ozone moving inside the gas-liquid two-phase flow outlet path 130R1. Furthermore, since the flow velocity within the pipe is increased, the liquid ozone discharge speed is also increased. This reliably avoids the risk of liquid ozone explosion. For example, if the gas-liquid two-phase flow outlet pipe constituting the gas-liquid two-phase flow outlet path 130R1 has an outer diameter of 4 mm, an inner diameter of 2 mm, and a length of 1 m, its internal volume will be 3.14 cc, resulting in a very small amount of liquid ozone passing through. Furthermore, as described in (1) and (2) above, the proportion of liquid ozone in the gas-liquid two-phase flow outlet path 130R1 is small, so the maximum amount of liquid ozone that can simultaneously exist in the gas-liquid two-phase flow outlet path 130R1 is 0.3 cc. The total amount of liquefied ozone accumulated in the liquid receiver (described in (3) above) and the amount of liquefied ozone present in the gas-liquid two-phase flow outlet path 130R1 is estimated to be less than 1 cc. (5) The sealing structure 170 prevents ultraviolet rays from reaching the gas-liquid two-phase flow outlet path 130R1. Ultraviolet rays can impart energy to ozone, potentially becoming an ignition source. This reliably prevents the explosion of liquid ozone due to ultraviolet rays. (6) Organic matter contained in newly supplied oxygen is constantly removed by the adsorption unit 110. Organic matter can react with ozone and become an ignition source. This reliably prevents the explosion of liquid ozone due to organic matter.

[0187] The above measures (1) to (6) work in combination, so explosion of liquid ozone can be reliably avoided even if liquid ozone is not handled in a low-pressure environment (below atmospheric pressure). As a result, continuous supply of gas-liquid two-phase ozone-containing oxygen can be realized.

[0188] (Reduction of Oxygen Consumption) In the apparatus 10 for generating an ozone-containing gas-liquid two-phase flow according to the present embodiment, the ozone-depleted oxygen is reused by utilizing the oxygen circulation path 130R3, so that the amount of raw oxygen used can be significantly reduced.

[0189] For example, suppose 1000 g / hour of ozone is liquefied to generate a gas-liquid two-phase flow with an ozone concentration of 200 mg / L (standard). In this case, the amount of oxygen used is 5 m ３ (std) / hour. 1000 g / hour of ozone has a molar flow rate of 20.83 mol (1000 / 48) and a volumetric flow rate of 0.466 m ３ (std) / hour (= 20.83 × 22.4 / 1000). Assuming that the ozone concentration is 50 mol% and all the liquid ozone has evaporated, the oxygen and ozone have the same volumetric flow rate of 0.466 m ３ (std) / hour, and the maximum flow rate of gas-liquid two-phase ozone-containing oxygen is 0.932 m ３ (std) / hour.

[0190] As a result, the volumetric flow rate of the ozone-depleted oxygen led to the outside from the gas lead-out passage 130R2 is at least 4.098 m ３ (std) / hour (=5-0.932). When this ozone-depleted oxygen is reused through the oxygen circulation line 130R3, the oxygen recovery rate is approximately 80% compared to when all of the oxygen in the oxygen gas source 106 is exhausted.

[0191] Introduction of First Modification Figure 10 illustrates an ozone-containing gas-liquid two-phase flow generator 210 of an ozone-containing solution manufacturing apparatus 201 according to a first modification of the first embodiment of the present invention. The ozone-containing gas-liquid two-phase flow generator 210 uses liquid oxygen as a refrigerant. Note that parts and members with the same reference numerals between the ozone-containing gas-liquid two-phase flow generator 210 in Figure 10 and the ozone-containing gas-liquid two-phase flow generator 10 shown in Figure 3 are identical or similar. Therefore, descriptions of identical or similar parts will be omitted, and the following will focus on the different parts and members.

[0192] In the ozone-containing gas-liquid two-phase flow generating device 210, liquid oxygen O is stored in the refrigerant storage section 162. ｌｉｑ In addition, in the pressure regulation passage 170R1 that controls the internal pressure of the sealing structure 170, there is a pressure regulation valve 177 on the upstream side of the pressure regulation valve 177. ｌｉｑThe ozone-containing gas-liquid two-phase flow generating device 110 includes a raw material supply line 170R3 for guiding the oxygen gas generated by vaporization of the liquid oxygen O 2 used as a refrigerant to the oxygen gas source 106. ｌｉｑ However, the coolant (liquid oxygen) in the coolant source 175 may be replenished by a pump 175B.

[0193] As shown in FIG. 5B, the vapor-liquid equilibrium vapor pressure (kPa) of liquid oxygen varies depending on the temperature (K). ｌｉｑ When maintaining the liquid oxygen (LOX) at a desired temperature in the temperature range of 90 K or higher, it is preferable to maintain the internal space of the sealed structure 170 at 100 kPa or higher by the pressure adjusting valve 177. In other words, it is sufficient to maintain the internal space of the sealed structure 170 at atmospheric pressure or higher. In this embodiment, the liquid oxygen (LOX) ｌｉｑ In order to set the temperature to around 95K, it is preferable to set the internal pressure of the sealed structure 170 to 130 kPa or more, for example, 150 kPa.

[0194] Introduction of Second Modification Figure 11 illustrates an ozone-containing gas-liquid two-phase flow generation device 310 of an ozone-containing solution manufacturing apparatus 301 according to a second modification of the first embodiment of the present invention. The ozone-containing gas-liquid two-phase flow generation device 310 employs a refrigerator 180 as its cooling unit. Note that parts and members with the same reference numerals between the ozone-containing gas-liquid two-phase flow generation device 310 in Figure 11 and the ozone-containing gas-liquid two-phase flow generation device 10 shown in Figure 3 are identical or similar. Therefore, descriptions of identical or similar parts will be omitted, and the following will focus on the different parts and members.

[0195] The refrigerator 180 of the ozone-containing gas-liquid two-phase flow generation system 310 is, for example, a helium refrigerator using a helium refrigerant. The refrigerator 180 includes, along a refrigerant circulation path 180R1, a reservoir 187 for storing liquid helium (refrigerant), a load-side heat exchanger (evaporator) 182 to which the liquid helium from the reservoir 187 is guided and which cools the ozone condenser 130, a compressor 183 to which the cooled helium is guided and which compresses the helium, a condenser 184 to remove heat from the compressed helium and liquefy it, and a temperature regulator 186 to regulate the temperature of the liquefied helium. The liquid helium, heated and temperature-regulated to, for example, 95 K by the temperature regulator 186, is stored in the reservoir 187. Here, helium guided from the load-side heat exchanger (evaporator) 182 passes through a condenser 184 before reaching the compressor 183, thereby exchanging heat with the compressed high-temperature helium. The ozone condenser 130 can be cooled to 95 K by the refrigerator 180. Although a helium refrigerator is exemplified as the refrigerator 180 here, other types of refrigerators may also be used. Furthermore, although a structure in which the helium refrigerant circulates directly within the load-side heat exchanger 182 is exemplified here, a structure in which the refrigerant circulating through the load-side heat exchanger 182 is indirectly cooled by an external refrigerator may also be used.

[0196] <Introduction of Third Modification> Figure 12 illustrates an ozone-containing solution manufacturing apparatus 401 according to a third modification of the first embodiment of the present invention. The ozone-containing solution manufacturing apparatus 401 employs a packed-column type mixture as the ozone mixing section 20 that mixes liquid ozone in a gas-liquid two-phase flow state and ozone-depleted oxygen with water. Note that parts and members with the same reference numerals in the ozone-containing solution manufacturing apparatus 401 in Figure 12 and the ozone-containing solution manufacturing apparatus 1 shown in Figure 1 are identical or similar. Therefore, descriptions of identical or similar parts will be omitted, and the following will focus on the different parts and members.

[0197] The ozone mixing section 20 includes a vertically-oriented cylindrical packed tower 21A and a packing material 21B disposed inside the packed tower 21A. A solvent inlet 76 is disposed above the packing material 21B in the packed tower 21A, and water serving as a solvent is dripped onto the packing material 21B inside the packed tower 21A. A discharge port 130R1out at the downstream end of the gas-liquid two-phase flow outlet 130R1 is disposed directly below the packing material 21B in the packed tower 21A. A solution reservoir 21C is formed below the packing material 21B in the packed tower 21A, where ozone-containing water obtained by passing through the packing material 21B accumulates. A liquid level sensor 36, an ozone concentration sensor 38, a pH meter 39, and an ozone solution outlet 86 are provided in the solution reservoir 21C. An ozone gas circulation path 26 and an open path 40 are disposed at the top of the packed tower 21A.

[0198] The packing material 21B is, for example, a Raschig ring, and water supplied from the solvent inlet 76 falls through the packing material 21B. Meanwhile, when a gas-liquid two-phase flow of liquid ozone and ozone-depleted oxygen is supplied from the discharge port 130R1out, the liquid ozone vaporizes due to the temperature inside the packed tower 21A, becoming ozone gas. This ozone-containing oxygen then changes state to a gaseous, highly concentrated ozone-containing oxygen. This ozone-containing oxygen becomes a gaseous flow rising inside the packing material 21B, and the ozone in the gas dissolves in the raw water descending inside the packing material 21B. The ozone concentration in the raw water increases as the flow descends, and the ozone-containing water with the highest concentration accumulates in the solution reservoir 21C. This ozone-containing water is extracted from the ozone solution outlet 86 and guided to the point of use U via the outlet path 82.

[0199] On the other hand, the ozone-containing oxygen ascending through the packing material 21B has its ozone concentration reduced as it ascends, and becomes ozone-depleted oxygen, which is discharged from the ozone gas circulation path 26 at the top and / or the open path 40. The ozone-depleted oxygen that has flowed into the ozone gas circulation path 26 is reused as raw material oxygen.

[0200] Introduction of Fourth Modification Figure 13 illustrates an ozone-containing solution manufacturing apparatus 501 according to a fourth modification of the first embodiment of the present invention. The ozone-containing solution manufacturing apparatus 501 employs a circulating packed-column type mixture as the ozone mixing section 20 that mixes liquid ozone in a gas-liquid two-phase flow state and ozone-depleted oxygen with water. Note that parts and members with the same reference numerals in the ozone-containing solution manufacturing apparatus 501 in Figure 13 and the ozone-containing solution manufacturing apparatus 1 shown in Figure 1 are identical or similar. Therefore, descriptions of identical or similar parts will be omitted, and the following will focus on the different parts and members.

[0201] The ozone mixing section 20 includes a vertically placed cylindrical packed tower 21A and a packing material 21B disposed inside the packed tower 21A. A solvent inlet 76 is disposed above the packing material 21B in the packed tower 21A, and water serving as a solvent is dripped onto the packing material 21B inside the packed tower 21A. A solution reservoir 21C is formed below the packing material 21B in the packed tower 21A, where ozone-containing water obtained by passing through the packing material 21B is stored. A liquid level sensor 36, an ozone concentration sensor 38, a pH meter 39, and an ozone solution outlet 86 are provided in the solution reservoir 21C. An ozone gas circulation path 26 and an open path 40 are disposed at the top of the packed tower 21A.

[0202] The ozone mixing section 20 further includes an ozone-containing solution circulation path 60 for drawing out ozone-containing water from the solution storage section 21C and temporarily turning it into a circulating liquid, and for returning this circulating liquid to the packing 21B in the packed tower 21A, and a circulation-side ozone mixer 24 disposed midway along the ozone-containing solution circulation path 60 for mixing liquid ozone and ozone-depleted oxygen in a gas-liquid two-phase flow state supplied from the ozone-containing gas-liquid two-phase flow generation device 10 into the circulating liquid. The circulation-side ozone mixer 24 functions as an ejector. As a result, the circulating liquid becomes ozone-containing water and returns to the vicinity of the lower part of the packing 21B.

[0203] The filler 21B is, for example, a Raschig ring, and water supplied from the solvent inlet 76 falls through the filler 21B. The excess ozone-containing gas that is not dissolved in the ozone-containing water that is returned to the filler 21B as the circulating liquid becomes an air current that rises inside the filler 21B, and the ozone contained therein dissolves in the raw water that flows down inside the filler 21B, increasing the ozone concentration in the raw water as it flows down. This ozone-containing water mixes with the circulating liquid and falls into the solution reservoir 21C. The ozone-containing water in the solution reservoir 21C is extracted from the ozone solution outlet 86 (which also serves as the circulating liquid outlet 62 of the ozone-containing solution circulation path 60) and guided to the point of use U via the outlet path 82.

[0204] On the other hand, the ozone-containing oxygen ascending through the packing material 21B has its ozone concentration reduced as it ascends, and becomes ozone-depleted oxygen, which is discharged from the ozone gas circulation path 26 at the top and / or the open path 40. The ozone-depleted oxygen that has flowed into the ozone gas circulation path 26 is reused as raw material oxygen.

[0205] Second Embodiment An ozone-containing gas production apparatus 601 according to a second embodiment of the present invention is described in Fig. 14. Note that, in the ozone-containing gas production apparatus 601 in Fig. 14 and the ozone-containing solution production apparatus 1 shown in Fig. 1, parts and members with the same reference numerals are the same or similar members. Therefore, a description of the same or similar members will be omitted, and the following description will focus on the different parts and members.

[0206] The ozone-containing gas producing apparatus 601 has an ozone vaporizing section 90 instead of the ozone mixing section 20 and the gas-liquid separation tank 30 of the ozone-containing solution producing apparatus 1 .

[0207] The ozone vaporizer 90 vaporizes the entire amount of liquid ozone contained in the gas-liquid two-phase flow discharged from the gas-liquid two-phase flow outlet 130R1 to generate high-concentration ozone-containing oxygen in a gas phase. Specifically, the ozone vaporizer 90 includes a vaporization flow path 90R1 through which the gas-liquid two-phase flow is guided, and a constant-temperature chamber 92 that houses the vaporization flow path 90R1 and maintains it at a predetermined temperature. To ensure sufficient travel distance, the vaporization flow path 90R1 is preferably a spiral or labyrinth-shaped flow path. For example, the vaporization flow path 90R1 can be made of an ozone-resistant resin tube such as PFE or PTFE. Specifically, the constant-temperature chamber 92 includes a heater 92A, a fan 92B, and a thermometer 92C, allowing temperature control of the interior space of the constant-temperature chamber 92. Temperature control of the constant-temperature chamber 92 is performed by a gas temperature control unit 46G of the control device 46.

[0208] An ozone gas outlet 80G is connected to the lower end of the vaporization flow path 90R1. The ozone gas outlet 80G includes an ozone gas outlet path 82G that delivers the ozone-containing oxygen converted into a gas phase in the vaporization flow path 90R1 to the use point U, and a flow rate adjustment valve 84G that is provided midway along the ozone gas outlet path 82G and adjusts the amount of ozone-containing oxygen delivered. The flow rate adjustment valve 84G is controlled by the control device 46.

[0209] The vaporization flow path 90R1 is provided with an ozone concentration sensor 38 that measures the ozone concentration of the ozone-containing gas and a pH meter 39 that measures the pH of the ozone-containing gas. Furthermore, the vaporization flow path 90R1 may be provided with a pressure sensor that detects the pressure of the ozone-containing gas. An open path 40 is formed in the vaporization flow path 90R1, and along the open path 40, a back pressure regulating valve 42 that keeps the pressure in the vaporization flow path 90R1 constant and an exhaust ozone decomposer 44 that decomposes excess ozone gas passing through the open path 40 are provided. The back pressure regulating valve 42 allows the operating pressure of the vaporization flow path 90R1 to be set.

[0210] According to the ozone-containing gas production device 601 of this embodiment, it is possible to continuously generate a large flow rate of high-concentration ozone-containing oxygen. For example, the ozone-containing oxygen generation unit 120 using a silent discharge tube (ozonizer) can produce an ozone concentration of 350 g / m ３(standard) is the upper limit, but according to this embodiment, it is 1000 g / m ３ Ozone concentrations of 1000 psi or higher can be achieved.

[0211] The control device 46 utilizes the ozone concentration sensor 38 to control the ozone concentration of the ozone-containing gas flowing through the vaporization flow path 90R1 so that it is always below the explosion limit of ozone gas at the operating pressure of the vaporization flow path 90R1. For example, the control device 46 controls the amount of ozone generated in the ozone-containing oxygen generator 120 or the amount of new oxygen gas supplied from the oxygen gas source 106. When the operating pressure of the vaporization flow path 90R1 is set to atmospheric pressure, ozone explosion does not occur within the vaporization flow path 90R1 by controlling the gaseous ozone concentration to 50 mol% or less (preferably 44 mol% or less). The ozone concentration can be controlled by feedback control of the ozone-containing gas-liquid two-phase flow generator 10, the amount of oxygen supplied from the oxygen gas source 106, etc. For example, if the ozone concentration is higher than the set value, the oxygen supply rate is increased to increase the flow rate of ozone-depleted oxygen in the gas-liquid two-phase flow flowing through the vaporization flow path 90R1, thereby reducing the liquid ozone content and thereby decreasing the ozone concentration. On the other hand, if the ozone concentration is lower than the set value, the oxygen supply rate is decreased to reduce the flow rate of ozone-depleted oxygen in the gas-liquid two-phase flow flowing through the vaporization flow path 90R1, thereby increasing the liquid ozone content and thereby increasing the ozone concentration. Furthermore, if the ozone concentration is higher than the set value, the output of the ozone-containing oxygen generator 120 is reduced to reduce the amount of ozone generated. If the ozone concentration is lower than the set value, the output of the ozone-containing oxygen generator 120 is increased to increase the amount of ozone generated.

[0212] Furthermore, for example, by using a vacuum pump or the like to control the operating pressure of the vaporization flow path 90R1 to 10 kPa or less, the explosion of gaseous ozone is further suppressed, and the ozone concentration is 95 mol%, i.e., 2036 g / m ３ It is also possible to achieve an ozone concentration of (standard).

[0213] Although the gaseous ozone concentration at atmospheric pressure is set to 50 mol% or less (preferably 44 mol% or less), it is difficult to reach the so-called explosion limit, and in practical terms, it is preferable to control the upper limit to 70% in consideration of safety. As a result, it is desirable to control the gaseous ozone concentration within a range of 35 mol% or less (preferably 30.8 mol% or less) as a practical target value of the ozone concentration.

[0214] Although not specifically shown here, it is also possible to produce ozone-containing water by supplying the high-concentration ozone-containing oxygen vaporized by the ozone-containing gas production apparatus 601 of this embodiment to the ozone mixing section 20 and the gas-liquid separation tank 30 in Figure 1.

[0215] <First Modification of the Ozone Condenser of the Ozone-Containing Gas-Liquid Two-Phase Flow Generator> Figure 15 shows a first modification of the condenser 128 employed in the ozone-containing gas-liquid two-phase flow generator of this embodiment. In this condenser 128, a recess 131 for storing liquid ozone 900 is formed in the bottom surface 130C of the ozone condenser 130. This recess 131 serves as a liquid ozone receiver. When the lower end of the gas-liquid two-phase flow outlet path 130R1 enters the recess 131, the liquid ozone 900 stored in the recess 131 is immediately released. In this manner, the amount of liquid ozone 900 stored in the ozone condenser 130 can be reduced.

[0216] For example, if the recess 131 of the ozone condenser 130 is a cone with a diameter of 1 cm and a depth of 1 cm, the volume of the cone is 0.26 cc (π / 4×1 ２ Assuming that some liquefied ozone overflows from recess 131 and accumulates to a depth of 1 mm on bottom surface 130C of ozone condenser 130 having an inner diameter of 22.6 mm, the volume of the overflowing liquefied ozone is 0.4 cc, and the total amount of liquefied ozone stored can be less than 0.7 cc.

[0217] 16(A) shows a second modified example of the ozone condenser 128 employed in the ozone-containing gas-liquid two-phase flow generator of the present embodiment. In this condenser 128, the ozone condenser 130 has a flat structure that extends horizontally, with the end (gas outlet) of the ozone-containing oxygen inlet channel 120R2 disposed on one side in the horizontal direction (here, the left-right direction on the page), and the gas-liquid two-phase flow outlet channel 130R1 and the gas outlet channel 130R2 disposed on the other side in the horizontal direction.

[0218] The horizontal direction along the ceiling surface 130B and / or the bottom surface 130C is the direction S of supply of ozone-containing oxygen. In this case, the ceiling surface 130B and / or the bottom surface 130C serve as cooling surfaces, cooling the gaseous ozone and causing it to condense. A recess 131 for storing liquid ozone 900 is formed on the other side of the bottom surface 130C. This recess 131 serves as a liquid ozone receiver. When the lower end of the gas-liquid two-phase flow outlet channel 130R1 enters the recess 131, the liquid ozone 900 stored in the recess 131 is immediately released. The gas-liquid two-phase flow outlet channel 130R1 and the gas outlet channel 130R2 are independent of each other, rather than having a double-pipe structure. The ceiling surface 130B and / or the bottom surface 130C may be inclined to allow the condensed ozone to collect in the recess 131.

[0219] 16(B) shows a third modification of the ozone condenser 128 employed in the ozone-containing gas-liquid two-phase flow generator of the present embodiment. In this condenser 128, one end of a gas-liquid two-phase flow outlet channel 130R1 is directly connected to a recess 131 (liquid ozone receiving portion) formed in a bottom surface 130C, and this gas-liquid two-phase flow outlet channel 130R1 extends vertically downward.

[0220] When droplets of liquid ozone 900 enter the recess 131, the gas-liquid two-phase flow outlet channel 130R1 can simultaneously release the liquid ozone 900 as a gas-liquid two-phase flow. Note that although the gas-liquid two-phase flow outlet channel 130R1 extends vertically downward in this example, it may also extend horizontally.

[0221] Third Embodiment An ozone-containing gas-liquid two-phase flow generation apparatus 1010 according to a third embodiment of the present invention is shown in Figure 18. Note that parts and members with the same reference numerals in the ozone-containing gas-liquid two-phase flow generation apparatus 1010 in Figure 18 and the ozone-containing gas-liquid two-phase flow generation apparatus 10 shown in Figures 1 and 3 are identical or similar. Therefore, a description of identical or similar parts will be omitted, and the following description will focus on different parts and members.

[0222] In the ozone-containing gas-liquid two-phase flow generation system 1010, the ozone condenser 130 in the condenser 128 includes a condensation pipe 1132, a branch joint 1134, and a storage pipe 1136. The condensation pipe 1132 is preferably a flexible tube made of an ozone-resistant resin (e.g., a fluororesin such as PFA), and is arranged in a spiral or serpentine shape within the cooling liquid. One end of the condensation pipe 1132 is connected to the ozone-containing oxygen introduction path 120R2.

[0223] Here, the branch joint 1134 is a three-way joint. The branch joint 1134 is made of an ozone-resistant resin (e.g., a fluororesin such as PTFE). The first port 1134A on the upper side of the branch joint 1134 holds (passes through) the vicinity of the lower ends of both the gas outlet path 130R2 and the gas-liquid two-phase flow outlet path 130R1, which have a double-pipe structure. The second port 1134B on the lower side holds (passes through) the storage tube 1136, which is a bottomed quartz glass tube. The third port 1134C, located midway between the first port 1134A and the second port 1134B, holds (passes through) the other end of the condensation pipe 1132.

[0224] The lower end of the gas-liquid two-phase flow outlet path 130R1 passing through the first port 1134A passes through the inside of the branch joint 1134, enters the inside of the storage tube 1136 held in the second port 1134B, and approaches the bottom surface 1136C of the storage tube 1136. The storage tube 1136 functions as a liquid ozone receiving section in which liquid ozone accumulates.

[0225] Therefore, the branch joint 1134 functions as a "gas branching section 190" that branches the ozone-containing oxygen, which has been condensed and has a reduced ozone content due to liquid ozone, into the gas-liquid two-phase flow outlet path 130R1 and the gas outlet path 130R2.

[0226] The ozone contained in the ozone-containing oxygen introduced from the ozone-containing oxygen introduction passage 120R2 passes through the internal space 130D of the spiral condensation pipe 1132 immersed in the coolant along the gas supply direction S, and is condensed and liquefied on the peripheral wall 130A of the condensation pipe 1132 to become liquid ozone. This liquid ozone and the ozone oxygen with a reduced amount of ozone reach the branch joint 1134, where the liquid ozone flows down into the storage pipe 1136 and, together with some of the ozone-depleted oxygen, rises inside the gas-liquid two-phase flow outlet passage 130R1 and is discharged as an ozone-containing gas-liquid two-phase flow. The ozone-depleted oxygen other than the ozone-depleted oxygen discharged together with the liquid ozone rises up the gas outlet passage 130R2 and is discharged.

[0227] 19A shows the results of a first simulation calculation performed on the ozone liquefaction performance of the ozone condenser 130 in the ozone-containing gas-liquid two-phase flow generator 1010 of the third embodiment. The operating conditions assumed in this simulation calculation are as follows: Ozone-containing oxygen pressure: 1 atm Ozone-containing oxygen flow rate: 1 to 10 L (std) / min (std: standard condition equivalent) Inlet temperature of ozone-containing oxygen to the ozone condenser: 293 K (20° C.) Coolant temperature: 95 K

[0228] Next, the main dimensions of the ozone condenser 130 are as follows: Condenser pipe 1132: Material: PFA, outer diameter 6 mm, inner diameter 4 mm, pipe length 5 m Gas outlet pipe (gas outlet passage 130R2): Material: Quartz glass, outer diameter 8.0 mm, inner diameter 6.0 mm Gas-liquid two-phase flow outlet pipe (gas-liquid two-phase flow outlet passage 130R1): Outer diameter 4 mm, inner diameter 2 mm

[0229] The horizontal axis of Fig. 19(A) is the flow rate of ozone-containing oxygen (standard condition conversion). The line G in Fig. 19(A) is the amount of ozone contained in the ozone-containing oxygen generated per unit time (g / hour). The line L out is the amount of liquid ozone produced (g / hour) calculated by simulation. The line EF is the production ratio (%) of liquid ozone L out to the amount of ozone G in the ozone-containing oxygen.

[0230] 19B shows the results of a second simulation calculation performed on the ozone liquefaction performance of the ozone condenser 130 in the ozone-containing gas-liquid two-phase flow generator 1010 of the third embodiment. The operating conditions assumed in this simulation calculation are as follows: Ozone-containing oxygen pressure: 1 atm Ozone-containing oxygen flow rate: 3 to 15 L (std) / min (std: standard condition equivalent) Inlet temperature of ozone-containing oxygen to the ozone condenser: 293 K (20° C.) Coolant temperature: 95 K

[0231] Next, the main dimensions of the ozone condenser 130 are as follows: Condenser pipe 1132: Material: PFA, outer diameter 8 mm, inner diameter 6 mm, pipe length 10 m Gas outlet pipe (gas outlet passage 130R2): Material: Quartz glass, outer diameter 8.0 mm, inner diameter 6.0 mm Gas-liquid two-phase flow outlet pipe (gas-liquid two-phase flow outlet passage 130R1): Outer diameter 4 mm, inner diameter 2 mm

[0232] The horizontal axis of Figure 19(B) is the flow rate of ozone-containing oxygen (standard condition conversion). Line GIN in Figure 19(B) represents the amount of ozone contained in the ozone-containing oxygen generated per unit time (g / hour). Line LOUT represents the amount of liquid ozone produced (g / hour) calculated by simulation. Line EF represents the production ratio (%) of liquefied ozone LOUT to the amount of ozone present in the ozone-containing oxygen GIN. Thus, even if the flow rate of ozone-containing oxygen is increased, the ozone liquefaction efficiency can be maintained at an extremely high level by increasing the length of the condensation pipe 1132.

[0233] In this embodiment, if the outer diameter of storage tube 1136 is 8 mm and the inner diameter is 6 mm, even if liquefied ozone is stored to a depth of 1 cm, the volume will be just under 0.3 cc. As a result, the amount of liquid ozone stored in storage tube 1136 can be minimized, thereby avoiding the risk of liquid ozone explosion.

[0234] <Fourth embodiment> Fig. 20 illustrates an ozone-containing gas-liquid two-phase flow generation apparatus 2010 according to a fourth embodiment of the present invention. Note that, in the ozone-containing gas-liquid two-phase flow generation apparatus 2010 in Fig. 20 and the ozone-containing gas-liquid two-phase flow generation apparatus 1010 shown in Fig. 18, parts and members with the same reference numerals are the same or similar members. Therefore, a description of the same or similar members will be omitted, and the following description will focus on the different parts and members.

[0235] This ozone-containing gas-liquid two-phase flow generating device 2010 is characterized in that a "gas branching section 190" is located outside the cooling section 160 and branches the ozone-containing oxygen, whose ozone content has been reduced by condensation of ozone and liquid ozone, into a gas-liquid two-phase flow outlet path 130R1 and a gas outlet path 130R2.

[0236] The condensation pipe 1132 is arranged in a spiral or serpentine shape within the cooling liquid, and its downstream side passes through a through-joint 174x of the cooling section 160 and extends to the outside. The downstream end of the condensation pipe 1132 is connected to the gas branch section 190.

[0237] (Gas Branching Section) The gas branching section 190 includes a branching pipe 192 and a heat insulating layer 194 that insulates the branching pipe 192 from the outside air by covering the outside of the branching pipe 192. Note that it is preferable that the heat insulating layer 194 also covers the downstream side of the condensation pipe 1132 at the same time.

[0238] Branch pipe 192 is made of quartz glass or a fluororesin such as PFA or PTFE. Branch pipe 192 is arranged at an angle (vertical arrangement is also possible), and liquid ozone guided from condensation pipe 1132 flows and collects at a low point (recess 131 in this case) in branch pipe 192. One end of gas-liquid two-phase flow outlet channel 130R1 is arranged at the low point in condensation pipe 1132, and the liquid ozone that has flowed into the low point is discharged from gas-liquid two-phase flow outlet channel 130R1 in a gas-liquid two-phase state together with ozone-depleted oxygen.

[0239] Furthermore, a gas outlet path 130R2 is disposed in the branch pipe 192 at a higher position than one end of the gas-liquid two-phase flow outlet path 130R1. Ozone-depleted oxygen other than the ozone-depleted oxygen discharged from the gas-liquid two-phase flow outlet path 130R1 is discharged from this gas outlet path 130R2.

[0240] The ozone contained in the ozone-containing oxygen introduced from the ozone-containing oxygen introduction passage 120R2 passes through the internal space 130D of the spiral condensation pipe 1132, which is immersed in the cooling liquid, along the gas supply direction S, and condenses and liquefies on the peripheral wall 130A of the condensation pipe 1132 to form liquid ozone. This liquid ozone and the ozone-depleted ozone oxygen are then guided out of the cooling section 160 by the condensation pipe 1132 and reach the branch pipe 192. The liquid ozone flows down the branch pipe 192, forming an ozone-containing gas-liquid two-phase flow together with some ozone-depleted oxygen, and is then guided out of the gas-liquid two-phase flow outlet passage 130R1. The ozone-depleted oxygen other than the ozone-depleted oxygen guided along with the liquid ozone is guided out of the gas outlet passage 130R2. The condensation pipe 1132 and the branch pipe 192 are insulated by the insulating layer 192, maintaining their interiors at low temperatures, thereby suppressing evaporation of the liquid ozone during guidance.

[0241] The ozone-containing gas-liquid two-phase flow generating apparatus 1010 of the third embodiment and the ozone-containing gas-liquid two-phase flow generating apparatus 2010 of the fourth embodiment can be incorporated into the ozone-containing solution manufacturing apparatus 1 of the first embodiment and the ozone-containing gas manufacturing apparatus 601 of the second embodiment, respectively.

[0242] Fifth Embodiment An ozone-containing gas-liquid two-phase flow generation apparatus 3010 according to a fifth embodiment of the present invention is illustrated in Figure 21. Note that, in the ozone-containing gas-liquid two-phase flow generation apparatus 3010 in Figure 21 and the ozone-containing gas-liquid two-phase flow generation apparatus 1010 shown in Figure 18, parts and members with the same reference numerals are the same or similar members. Therefore, a description of the same or similar members will be omitted, and the following description will focus on the different parts and members.

[0243] The branch joint 1134, which is disposed within the refrigerant and functions as the gas branch section 190, is a three-way joint. The upper first port 1134A of the branch joint 1134 holds the vicinity of the lower end (upstream end) of the gas outlet path 130R2, which has a single-pipe structure. The lower second port 1134B holds the vicinity of the upper end (upstream end) of the gas-liquid two-phase flow outlet path 130R1, which also has a single-pipe structure. The third port 1134C, located midway between the first port 1134A and the second port 1134B, holds the other end of the condensation pipe 1132. The upper end (downstream side) of the gas outlet path 130R2 is led to the outside via an annular (cylindrical) through-joint 174x on the lid 174 side. The downstream side of the gas-liquid two-phase flow outlet path 130R1 connected to the second port 1134B extends vertically downward, then bends back in a U-shape, extends upward, and is discharged to the outside via an annular (cylindrical) through-joint 174y on the lid 174. If the portion of the gas-liquid two-phase flow outlet path 130R1 that extends vertically downward is defined as the "gas-liquid two-phase downward flow formation region," then the upstream end of the gas outlet path 130R2 is located above or midway through the "gas-liquid two-phase downward flow formation region."

[0244] The ozone contained in the ozone-containing oxygen introduced from the ozone-containing oxygen introduction passage 120R2 passes through the spiral-shaped internal space 130D immersed in the coolant along the gas supply direction S, and condenses and liquefies on the peripheral wall 130A. This liquid ozone and the ozone-depleted ozone oxygen reach the branch joint 1134, where the liquid ozone flows downward by its own weight into the gas-liquid two-phase flow outlet passage 130R1, where it merges with some of the ozone-depleted oxygen to form an ozone-containing gas-liquid two-phase flow that flows through the gas-liquid two-phase flow outlet passage 130R1. The ozone-depleted oxygen that is not introduced to the gas-liquid two-phase flow outlet passage 130R1 (the remaining ozone-depleted oxygen) rises up the gas outlet passage 130R2 and is discharged. As described above, the apparatus 3010 for generating an ozone-containing gas-liquid two-phase flow according to the fifth embodiment is configured such that only ozone-depleted oxygen is guided to the vertically upper side, and liquid ozone and ozone-depleted oxygen are guided to the vertically lower side by the gas branching section 190. Furthermore, the apparatus 3010 for generating an ozone-containing gas-liquid two-phase flow does not have a liquid ozone receiving section for temporarily storing liquid ozone.

[0245] Sixth Embodiment An ozone-containing gas-liquid two-phase flow generation apparatus 4010 according to a sixth embodiment of the present invention is illustrated in Figure 22. Note that, for the ozone-containing gas-liquid two-phase flow generation apparatus 4010 in Figure 22 and the ozone-containing gas-liquid two-phase flow generation apparatus 3010 shown in Figure 21, parts and members with the same reference numerals are the same or similar members. Therefore, a description of the same or similar members will be omitted, and the following description will focus on the different parts and members.

[0246] Gas-liquid two-phase flow outlet path 130R1, which is connected to lower second port 1134B of branch joint 1134 disposed within the refrigerant and functions as gas branch section 190, extends vertically downward and is discharged to the outside via annular (cylindrical) through-joints 174y provided on the bottom surfaces of refrigerant reservoir 162 and container 172. Therefore, the downstream side of gas-liquid two-phase flow outlet path 130R1 is not bent vertically upward in a U-shape, which prevents liquid ozone from accumulating midway through gas-liquid two-phase flow outlet path 130R1.

[0247] Seventh Embodiment An ozone-containing gas-liquid two-phase flow generation apparatus 5010 according to a seventh embodiment of the present invention is illustrated in Figure 23. Note that, in the ozone-containing gas-liquid two-phase flow generation apparatus 5010 in Figure 23 and the ozone-containing gas-liquid two-phase flow generation apparatus 1010 shown in Figure 18, parts and members with the same reference numerals are the same or similar members. Therefore, a description of the same or similar members will be omitted, and the following description will focus on the different parts and members.

[0248] A branch pipe 1135 disposed within the refrigerant and functioning as a gas branching section 190 branches in three directions. The branch pipe 1135 has a first port 1135A on the upper side, a second port 1135B on the lower side, and a third port 1135C located midway between the first port 1135A and the second port 1135B. The first port 1135A on the upper side of the branch pipe 1135 holds a condensation pipe 1132. The condensation pipe 1132 extends vertically within the branch pipe 1135, passing through the third port 1135C, with its downstream end 1132E approaching the second port 1135B at a distance. Therefore, the condensation pipe 1132 extending vertically within the branch pipe 1135 can be defined as a "gas-liquid two-phase downward flow formation region" where a gas-liquid two-phase flow descends. Furthermore, if the condensation pipe 1132 is defined as an inner pipe, the branch pipe 1135 can be defined as an outer pipe that contains this inner pipe.

[0249] The third port 1135C holds the vicinity of the upstream end of the gas outlet path 130R2, which has a single-pipe structure. The upper end (downstream side) of this gas outlet path 130R2 is led out to the outside via an annular (cylindrical) through-joint 174x on the lid 174 side.

[0250] The upper end (upstream end) of the gas-liquid two-phase flow outlet passage 130R1, which has a single-pipe structure, is continuous with the lower second port 1134B. The vicinity of the second port 1134B has a tapered shape, in which the pipe diameter gradually decreases from top to bottom. The downstream side of the gas-liquid two-phase flow outlet passage 130R1 is discharged to the outside via an annular (cylindrical) through-joint 174y provided on the bottom side of the refrigerant storage section 162 and the container section 172.

[0251] The ozone contained in the ozone-containing oxygen introduced from the ozone-containing oxygen introduction passage 120R2 passes through the internal space 130D of the spiral condensation pipe 1132 immersed in the coolant along the gas supply direction S, and condenses and liquefies on the peripheral wall 130A of the condensation pipe 1132 to form liquid ozone. This liquid ozone and the ozone-depleted oxygen resulting from the reduction in ozone content are discharged downward from the downstream end 1132E of the condensation pipe 1132 in the branch pipe 1135. All of the liquid ozone and a portion of the ozone-depleted oxygen flow directly into the gas-liquid two-phase flow outlet passage 130R1, forming an ozone-containing gas-liquid two-phase flow. The remaining ozone-depleted oxygen rises inside the branch pipe 1135, turning back and forth through the cylindrical space outside the condensation pipe 1132, and flows into the gas outlet passage 130R2, where it is discharged to the outside. That is, the branch pipe 1135 serving as the outer pipe also becomes a part of the gas discharge path 130R2.

[0252] In this embodiment, the branch pipe 1135 has a tapered shape near the second port 1134B, which allows the liquid ozone to be smoothly guided into the gas-liquid two-phase flow outlet path 130R1. Furthermore, the downstream end 1132E of the condensation pipe 1132, into which the liquid ozone is dripped, is close to the second port 1134B, which prevents the liquid ozone from flowing into the gas outlet path 130R2.

[0253] Eighth Embodiment An ozone-containing gas-liquid two-phase flow generation apparatus 6010 according to an eighth embodiment of the present invention is illustrated in Figure 24. Note that, for the ozone-containing gas-liquid two-phase flow generation apparatus 6010 in Figure 24 and the ozone-containing gas-liquid two-phase flow generation apparatus 4010 shown in Figure 22, parts and members with the same reference numerals are the same or similar members. Therefore, a description of the same or similar members will be omitted, and the following description will focus on the different parts and members.

[0254] In this embodiment, a portion of the ozone-containing oxygen generator 120 is disposed within the refrigerant. Specifically, the high-frequency, high-voltage power supply 120A of the ozone-containing oxygen generator 120 is disposed outside the container 172, and the metal ozone generating electrode 120B is disposed around the condensation pipe 1132 within the refrigerant. When a voltage is applied to the ozone generating electrode 120B by the high-frequency, high-voltage power supply 120A, a discharge phenomenon occurs within the condensation pipe 1132, and a portion of the oxygen gas flowing therethrough is converted into ozone. This ozone is instantly cooled within the condensation pipe 1132 without being heated during the process, thereby improving the efficiency of ozone liquefaction. The portion of the condensation pipe 1132 where the ozone generating electrode 120B is disposed is preferably made of a dielectric material such as glass.

[0255] In the ozone-containing solution manufacturing apparatus 1 of the first embodiment, the liquid ozone generated in the ozone-containing gas-liquid two-phase flow generator 10 is mixed with water in the ozone mixer 20 while remaining in the gas-liquid two-phase flow state, but the present invention is not limited to this. Liquid ozone quickly vaporizes due to the temperature increase as it travels through the gas-liquid two-phase flow outlet path 130R1. Therefore, all or part of the liquid ozone may be vaporized before being mixed with water.

[0256] Furthermore, while the first embodiment exemplifies the use of pure water or the like as a solvent, the present invention is not limited thereto. For example, this ozone-containing solution manufacturing apparatus can be used as a water treatment device that utilizes ozone to decompose organic matter or the sterilizing properties of ozone. In this case, the solvent can be a liquid (water) containing organic matter that undergoes a chemical reaction with ozone, or a liquid (water) containing at least one substance selected from viruses, bacteria, fungi, and microorganisms. This is not limited to cases where organic matter or viruses are treated in a gas-liquid separation tank, but also includes cases where the ozone contained in the ozone solution discharged from the gas-liquid separation tank treats organic matter or viruses over time.

[0257] Furthermore, in the above embodiment, a structure in which various pipes pass inside and outside the cooling section using a through joint is exemplified, but the present invention is not limited to this, and pipes may be passed inside and outside the cooling section using joints of other structures, tubular rubber stoppers made of silicone rubber or the like, PTFE sealing tape, etc.

[0258] Experimental Example An experiment was conducted using the ozone-containing gas-liquid two-phase flow generating device 3010 of the fifth embodiment shown in Fig. 21. The refrigerant temperature in the refrigerant reservoir 162 was set to -180°C, and ozone-containing oxygen was supplied to the condensation pipe 1132 at 1 L (standard) / min. In order to set the refrigerant temperature to -180°C, the liquid nitrogen N ｌｉｑ The refrigerant temperature was increased by about 16°C by pressurizing the refrigerant to about 0.3 MPaG.

[0259] After ozone liquefaction in condensation pipe 1132, ozone-depleted oxygen with a reduced ozone content was discharged from gas outlet line 130R2 at a rate of 0.75 L (standard) / min. Meanwhile, the remaining ozone-depleted oxygen and liquid ozone in a gas-liquid two-phase state were discharged from gas-liquid two-phase flow outlet line 130R1 and allowed to return to room temperature outside vessel 172, thereby vaporizing the liquid ozone. As a result, 0.25 L (standard) / min of ozone-containing gas was finally produced via gas-liquid two-phase flow outlet line 130R1.

[0260] The ozone concentration of the ozone-containing oxygen supplied to the condensation pipe 1132 was measured and found to be 120 g / m ３ (std), and the ozone concentration of the ozone-depleted oxygen discharged from the gas discharge path 130R2 was measured to be 18 g / m ３ (standard), and the ozone concentration of the ozone-containing gas generated through the gas-liquid two-phase flow outlet 130R1 was measured to be 118 to 302 g / m ３ As a result, it was revealed that when a gas-liquid two-phase flow is generated using the ozone-containing gas-liquid two-phase flow generation device 3010, a high-concentration ozone-containing gas can be generated.

[0261] <Explanation of the first concept of the present invention>

[0262] Next, the concept of the present invention will be described. Figure 25(A) shows an ozone-containing gas-liquid two-phase flow generating apparatus 9010 according to a first concept. The ozone-containing gas-liquid two-phase flow generating apparatus 5010 generates ozone using gaseous oxygen supplied via an oxygen supply path 120R1 as a raw material. The apparatus includes an ozone-containing oxygen generating unit 120 that generates ozone-containing oxygen from the gaseous oxygen, an ozone condensing unit 130 to which the ozone-containing oxygen is introduced via an ozone-containing oxygen introducing path 120R2, a cooling unit 160 that cools the ozone condensing unit 130 to adjust the internal space of the ozone condensing unit 130 to a temperature range in which oxygen is in a gaseous state and ozone is in a liquid state, and a gas-liquid two-phase flow outlet path 130R1 provided in the ozone condensing unit 130 that outputs, in a gas-liquid two-phase state, liquid ozone, which is condensed ozone from the ozone-containing oxygen, and ozone-depleted oxygen, the ozone content of which has been reduced by the condensation of the ozone, to the outside of the ozone condensing unit 130. Furthermore, in the ozone-containing gas-liquid two-phase flow generating device 9010, the ozone-depleted oxygen discharged from the gas-liquid two-phase flow outlet path 130R1 is only a portion of the total, and the remaining ozone-depleted oxygen is discharged to the outside from the gas outlet path 130R2. In this respect, the ozone-containing gas-liquid two-phase flow generating device 9010 has a gas branching unit 190 that branches the ozone-depleted oxygen obtained through the ozone condensing unit 130 into the gas-liquid two-phase flow outlet path 130R1 and the gas outlet path 130R2. In the first concept, because the gas branching unit 190 is provided within the cooling unit 160, liquid ozone can be discharged from the gas-liquid two-phase flow outlet path 130R1 without being vaporized.

[0263] Furthermore, the gas-liquid two-phase ozone-containing oxygen discharged from the gas-liquid two-phase flow outlet 130R1 of the ozone-containing gas-liquid two-phase flow generator 9010 is guided to the ozone mixer 20 for mixing with a solvent, or to the ozone vaporizer 90 for vaporizing the liquid ozone. When guided to the ozone mixer 20, the entire system constitutes an ozone-containing solution manufacturing apparatus, and when guided to the ozone vaporizer 90, the entire system constitutes an ozone-containing gas manufacturing apparatus.

[0264] 25(B) shows an ozone-containing gas-liquid two-phase flow generator 9010 according to the second concept. In this ozone-containing gas-liquid two-phase flow generator 9010, a gas branching unit 190 that branches ozone-depleted oxygen into a gas-liquid two-phase flow outlet path 130R1 and a gas outlet path 130R2 is disposed outside the cooling unit 160. The other configurations are the same as those of the first concept.

[0265] In the second concept, the gas branching section 190 is provided outside the cooling section 160, which allows for a simple structure inside the cooling section 160. On the other hand, if the temperature of the gas branching section 190 rises, liquid ozone becomes more likely to gasify as it passes through, so it is preferable to cover the gas branching section 190 with a heat insulating material or the like.

[0266] <Explanation of the Third Concept of the Present Invention> Figure 26(A) shows an ozone-containing gas-liquid two-phase flow generation apparatus 9010 according to the third concept. The cooling section 160 of this ozone-containing gas-liquid two-phase flow generation apparatus 10 cools the ozone condenser section 130 using a refrigerant such as liquid nitrogen or liquid oxygen. The cooling temperature can be adjusted by controlling the pressure of the refrigerant using a pressure adjustment valve 177. When liquid oxygen is used as the refrigerant, it is preferable to provide a raw material supply line 170R3 that guides oxygen generated when the cooling liquid evaporates to the oxygen supply line 120R1. The other configurations are the same as those of the first concept.

[0267] <Explanation of the Fourth Concept of the Present Invention> Fig. 26(B) shows an ozone-containing gas-liquid two-phase flow generator 9010 according to the fourth concept. This ozone-containing gas-liquid two-phase flow generator 10 includes a load-side heat exchanger 182 as the cooling section 160. A refrigerant circulates in the load-side heat exchanger 182 along a refrigerant circulation path 180R1. A refrigerator 180 for cooling the refrigerant and a temperature regulator 186 for adjusting the temperature of the refrigerant are disposed along the refrigerant circulation path 180R1. The refrigerator 180 is preferably a helium refrigerator, for example. The other configurations are the same as those of the first concept.

[0268] The present invention is not limited to the above-described embodiment, and it goes without saying that various modifications can be made without departing from the spirit of the present invention.

[0269] 1, 201, 301, 401, 501 Ozone-containing solution manufacturing apparatus 10, 210, 310, 1010, 2010, 3010, 4010, 5010, 6010 Ozone-containing gas-liquid two-phase flow generator 20 Ozone mixing section 21A Packed tower 21B Packing material 21C Solution storage section 22 Solvent-side ozone mixer 24 Circulation-side ozone mixer 26 Ozone gas circulation path 28 Ejector 28A Nozzle 28B Negative pressure space 28C Diffuser 30 Gas-liquid separation tank 30A Primary space 30B Secondary space 36 Liquid level sensor 38 Ozone concentration sensor 39 pH measuring device 40 Open path 42 Back pressure adjustment valve 44 Waste ozone decomposer 46 Control device 46 Solvent supply control unit 46A Solvent supply control unit 46B Circulation flow rate control section 46C Ozone-containing gas-liquid two-phase flow control section 46C1 Oxygen supply amount control section 46C2 Ozone-containing oxygen generation control section 46C3 Ozone liquid discharge valve control section 46C4 Oxygen discharge amount control section 46C5 Refrigerant supply control section 46C6 pH control section 46D Solution discharge amount control section 46E Liquid level detection section 46F Ozone concentration detection section 46G Gas temperature control section 50 Swirl flow generation section 50A Tangential direction introduction section 50B Tangential direction discharge section 60 Ozone-containing solution circulation path 62 Circulating liquid discharge port 64 Circulating liquid inlet 66 Circulation pump 68 Flow rate adjustment valve 70 Solvent guide path 72 Water supply section 74 Flow rate adjustment valve 76 Solvent inlet 80 Ozone solution discharge section 80G Ozone gas discharge section 82 Discharge path 82G Ozone gas outlet path 84 Flow rate adjustment valve 84G Flow rate adjustment valve 86 Ozone solution outlet 90 Ozone vaporization section 90R1 Vaporization flow path 91 Pressure pump 92 Stirrer 92 Constant temperature chamber 92A Heater 92B Fan 92C Thermometer 93 Back pressure adjustment valve 104 Carbon dioxide gas source 105 pH adjuster 106 Oxygen gas source 108 Supply amount controller 109 Outlet valve mechanism 110 Adsorption section 110 Ozone-containing gas-liquid two-phase flow generation device 112 Supply amount measuring device 120 Ozone-containing oxygen generation section 120 Ozone-containing oxygen generation section 120R1 Oxygen supply path120R2 Ozone-containing oxygen introduction channel 120R2 Carbon dioxide supply channel 121 Ozone concentration meter 128 Condenser 130 Ozone condenser 130A Peripheral wall 130B Ceiling surface 130C Bottom surface 130D Internal space 130R1 Gas-liquid two-phase flow outlet channel 130R2 Gas outlet channel 130R3 Oxygen circulation channel 131 Recess 140 Branch joint 140A First port 140B Second port 140C Third port 146 Oxygen output regulator 147 Cooler 148 Ozone concentration meter 150 Pressure adjustment valve 152 Opening / closing valve 154 Check valve 160 Cooling section 162 Refrigerant storage section 164 Refrigerant detector 170 Sealed structure 170R1 Pressure adjustment channel 170R2 Refrigerant introduction path 170R3 Raw material supply path 172 Container portion 174 Lid portion 176 On-off valve 177 Pressure adjustment valve 178 Pressure regulator 180 Refrigerator 180R1 Refrigerant circulation path 182 Load side heat exchanger (vaporizer) 183 Compressor 184 Condenser 186 Temperature regulator 187 Reservoir 190 Gas branching portion 601 Ozone-containing gas production device

Claims

1. An ozone-containing gas-liquid two-phase flow generation apparatus for generating ozone using gaseous oxygen as a raw material, comprising: an ozone-containing oxygen generation section for generating ozone-containing oxygen from the gaseous oxygen; an ozone condensation section into which the ozone-containing oxygen is guided to an internal space; a cooling section for cooling the ozone condensation section to set the internal space of the ozone condensation section to a temperature range in which oxygen is in a gaseous state and ozone is in a liquid state; and a gas-liquid two-phase flow discharge path for discharging liquid ozone formed by condensing ozone contained in the ozone-containing oxygen and the ozone-containing oxygen whose ozone content has been reduced by the condensation of the ozone (hereinafter referred to as ozone-depleted oxygen) in a gas-liquid two-phase flow state to the outside after passing through the ozone condensation section.

2. An ozone-containing gas-liquid two-phase flow generating device according to claim 1, characterized in that the gas-liquid two-phase flow outlet path outputs a portion of the ozone-depleted oxygen in the gas-liquid two-phase flow state.

3. An ozone-containing gas-liquid two-phase flow generating device as described in claim 2, characterized in having a gas outlet path for outletting the remaining ozone-depleted oxygen from the gas-liquid two-phase flow outlet path to the outside of the ozone condenser.

4. An apparatus for generating an ozone-containing gas-liquid two-phase flow as set forth in claim 3, characterized in that an oxygen discharge amount regulator capable of adjusting the amount of the ozone-depleted oxygen discharged is provided in the gas discharge path.

5. The ozone-containing gas-liquid two-phase flow generating device according to claim 1, characterized in that the ozone condensation section has a liquid ozone receiving section that receives the liquid ozone, and one end of the gas-liquid two-phase flow outlet path is arranged in the vicinity of the liquid ozone receiving section so as to be able to come into contact with the liquid ozone received in the liquid ozone receiving section.

6. The ozone-containing gas-liquid two-phase flow generating device according to claim 5, characterized in that at least a portion of the gas-liquid two-phase flow outlet passage extends vertically within the ozone condenser, and a lower end of the gas-liquid two-phase flow outlet passage is disposed in the vicinity of the liquid ozone receiving section.

7. An apparatus for generating an ozone-containing gas-liquid two-phase flow as claimed in claim 1, characterized in that it has an oxygen circulation path for guiding at least a part of the ozone-depleted oxygen derived from the ozone condensation section to the ozone-containing oxygen generation section.

8. The ozone-containing gas-liquid two-phase flow generating device according to claim 1, further comprising an oxygen supply amount adjusting section for adjusting the amount of the gaseous oxygen supplied.

9. The ozone-containing gas-liquid two-phase flow generating device according to claim 1, characterized in that the cooling section has a refrigerant storage section for storing a refrigerant, and the internal space of the ozone condensing section is cooled by bringing the ozone condensing section into contact with the refrigerant in the refrigerant storage section.

10. An ozone-containing gas-liquid two-phase flow generating device according to claim 9, characterized in that the refrigerant is liquid oxygen, liquid nitrogen, liquid argon or helium gas.

11. The ozone-containing gas-liquid two-phase flow generating device according to claim 10, characterized in that the refrigerant is liquid oxygen, and the gaseous oxygen generated by vaporizing the liquid oxygen is guided to the ozone-containing oxygen generating section.

12. The ozone-containing gas-liquid two-phase flow generating device according to claim 9, characterized in that the cooling section has a sealed structure that seals the refrigerant storage section, and the internal pressure of the sealed structure is maintained at a pressure exceeding atmospheric pressure.

13. An ozone-containing gas-liquid two-phase flow generating device according to claim 9, characterized in that the refrigerant has a temperature range of 80K to 120K.

14. The ozone-containing gas-liquid two-phase flow generating device according to claim 1, characterized in that the cooling section has a heat exchange section through which a refrigerant cooled by a refrigeration cycle circulates, and the internal space of the ozone condensing section is cooled by bringing the ozone condensing section into contact with the refrigerant.

15. The ozone-containing gas-liquid two-phase flow generating device according to claim 1, wherein the cooling section cools the ozone-containing oxygen generating section.

16. An apparatus for generating an ozone-containing gas-liquid two-phase flow as set forth in claim 1, characterized in that the amount of the liquid ozone stored before being discharged from the gas-liquid two-phase flow outlet path is 5 g or less.

17. The ozone-containing gas-liquid two-phase flow generating device according to claim 1, characterized in that the ozone condensing section has a spiral pipe into which the ozone-containing oxygen is guided.

18. An ozone-containing gas-liquid two-phase flow generating device as described in claim 3, characterized in that the vicinity downstream of the ozone condensation section and / or the gas-liquid two-phase flow outlet passage has a gas-liquid two-phase downward flow formation region that guides the liquid ozone and the ozone-depleted oxygen in a gas-liquid two-phase flow state in a direction having a vertical downward component, and the gas outlet passage that outlets the remainder of the ozone-depleted oxygen is connected above the gas-liquid two-phase downward flow formation region or midway in the vertical direction.

19. An apparatus for generating an ozone-containing gas-liquid two-phase flow as described in claim 18, characterized in comprising: an inner pipe that forms the gas-liquid two-phase downward flow formation region; and an outer pipe that is disposed outside so as to enclose the inner pipe and that constitutes a part of the gas discharge path.

20. An ozone-containing solution manufacturing apparatus comprising: the ozone-containing gas-liquid two-phase flow generating device according to any one of claims 1 to 19; and an ozone mixing section that mixes the liquid ozone and / or gaseous ozone formed by vaporizing the liquid ozone discharged from the gas-liquid two-phase flow outlet path with a solution to produce an ozone-containing solution.

21. The ozone-containing solution manufacturing apparatus according to claim 20, wherein the ozone mixing section directly mixes the liquid ozone into the solution.

22. The ozone-containing solution manufacturing apparatus according to claim 20, wherein the ozone mixing section mixes the ozone-depleted oxygen discharged from the gas-liquid two-phase flow outlet path into the solution.

23. The ozone-containing solution manufacturing apparatus according to claim 20, characterized in that the ozone mixing section comprises: a solution guide path that guides the solution; and a confluence section provided midway along the solution guide path that confluences the liquid ozone and / or gaseous ozone formed by vaporizing the liquid ozone with the solution.

24. The ozone-containing solution manufacturing apparatus according to claim 23, comprising: a storage tank for storing the ozone-containing solution that has passed through the confluence section; an ozone-containing solution circulation path for discharging the ozone-containing solution stored in the storage tank to the outside and returning the ozone-containing solution to the storage tank; and a second confluence section provided midway along the ozone-containing solution circulation path for confluence of the liquid ozone and / or gaseous ozone formed by vaporizing the liquid ozone with the ozone-containing solution.

25. An ozone-containing gas manufacturing apparatus comprising: the ozone-containing gas-liquid two-phase flow generating device according to any one of claims 1 to 19; and a vaporization section that vaporizes the liquid ozone discharged from the gas-liquid two-phase flow outlet path to produce gaseous ozone.

26. A method for generating an ozone-containing gas-liquid two-phase flow for generating ozone using gaseous oxygen as a raw material, comprising the steps of: generating ozone-containing oxygen from the gaseous oxygen; guiding the ozone-containing oxygen to an internal space of an ozone condenser which is cooled to a temperature range in which the oxygen is in a gaseous state and the ozone is in a liquid state; and discharging liquid ozone obtained by liquefying ozone contained in the ozone-containing oxygen in the internal space, and the ozone-containing oxygen whose ozone content has been reduced due to the condensation of the ozone (hereinafter referred to as ozone-depleted oxygen) to the outside in a gas-liquid two-phase flow state via a gas-liquid two-phase flow outlet path.

27. A method for producing an ozone-containing gas-liquid two-phase flow as set forth in claim 26, characterized in that a portion of the ozone-depleted oxygen is discharged in the gas-liquid two-phase flow state.

28. A method for producing an ozone-containing solution, comprising mixing the liquid ozone and / or gaseous ozone obtained by vaporizing the liquid ozone, which are discharged from the gas-liquid two-phase flow outlet path by the method for producing an ozone-containing gas-liquid two-phase flow as set forth in claim 26 or 27, with a solution to produce an ozone-containing solution.

29. A method for producing an ozone-containing gas, comprising vaporizing the liquid ozone discharged from the gas-liquid two-phase flow outlet path by the method for producing an ozone-containing gas-liquid two-phase flow as set forth in claim 26 or 27 to produce gaseous ozone.