WO2019163105A1 - Ozone solution generation apparatus and ozone solution generation method - Google Patents

Abstract

An ozone solution generation apparatus generates an ozone solution by dissolving ozone gas generated by an ozone gas generation device in a solvent. The ozone solution generation apparatus is provided with: a gas-liquid separation tank for storing an ozone gas-mixed liquid in which ozone gas and a solvent have been mixed by a gas-liquid mixer; a swirling flow generation unit for generating a swirling flow in the ozone gas-mixed liquid in the gas-liquid separation tank; and an ozone solution outlet for guiding the ozone solution generated by the ozone gas mixed liquid that has been subjected to the swirling flow to the outside of the gas-liquid separation tank. Provided thereby is an ozone solution generation apparatus that is compact and has a high ozone dissolution efficiency.

Description

Ozone solution generating apparatus and ozone solution generating method

The present invention relates to an ozone solution generator for dissolving ozone gas in water or the like as a solvent to generate an ozone solution.

Conventionally, in the field of semiconductor cleaning process and resist stripping process, it has been manufactured using a large amount of chemicals, but due to the large scale of semiconductor production etc., there is a possibility that the emission of chemicals may conflict with environmental regulations. In place of these chemicals, the use of ozone water that has a low impact on the environment and does not conflict with environmental regulations is progressing.

Ozone water production equipment is roughly divided into electrolytic and discharge types depending on the ozone generation method. In the electrolytic method, ozone is generated by electrolysis using a special electrode in water and dissolved in water. The discharge type generates ozone water by generating discharges such as silent discharge and creeping discharge in an oxygen-containing gas to generate ozone-containing gas (ozone gas) and dissolving it in water. Since the electrolytic method can generate high-concentration ozone water with a relatively simple apparatus, it has been used early in the semiconductor cleaning process.

In the case of using a discharge type ozone water generator, there are bubbling, a fine bubble generator, an ozone dissolving film, an ejector, a gas-liquid mixing pump, a packed tower, etc. as a method for dissolving ozone gas in water. In bubbling, a porous bubble generator is disposed at the bottom of the ozone dissolution tank, and bubbles of ozone gas are generated from the bubble generator to raise the water. Although the apparatus is simple, the ozone dissolution efficiency, that is, the ratio of the amount of ozone dissolved to the amount of ozone generated is low, and it is not often used for the production of high-concentration ozone water.

The fine bubble generator generates ozone gas bubbles having a diameter that is small enough (for example, in units of microns) so as not to cause a problem during use, and dissolves them in water. Although the ozone dissolution efficiency is high, the process of turning a large amount of ozone gas into fine bubbles is complicated and is not suitable for increasing the capacity.

The ozone-dissolving membrane allows water to flow into a small-diameter hollow fiber formed by a fluororesin membrane that does not transmit water but transmits ozone gas, introduces ozone gas around the hollow fiber, and dissolves ozone gas in water. And is most commonly used in the semiconductor industry. However, when the capacity is increased, a large amount of ozone permeable membrane (hollow fiber) proportional to the capacity is required, and it is difficult to make the apparatus compact.

The packed tower lowers water from the upper part of a column packed with a packing such as Raschig ring, raises ozone gas from the lower part, and makes ozone gas and water contact with each other in a gas-liquid countercurrent manner in the packed part. Dissolve in. Dissolution efficiency is high, and it is possible to generate high-concentration ozone water. Since this method cannot increase the flow rate of the descending water to a certain level or more, it requires a flow passage area proportional to the amount of ozone water produced, and it is difficult to make it compact when the capacity is large.

An ejector or a gas-liquid mixing pump is a so-called gas-liquid mixer, and is a method of generating ozone water by forcibly mixing ozone gas bubbles and water to generate a gas-liquid two-phase flow.

The ejector is provided with a bottleneck in a part of the water flow path, and by drawing the ozone gas using Bernoulli's theorem and using the induced power generated in the bottleneck, it generates a gas-liquid two-phase flow that mixes ozone gas bubbles and water. Use ozone water. The ejector has the advantage that it does not become too large as the flow rate increases. For example, if the flow velocity in the part of the bottleneck is about 15 (m / s) and the flow velocity before and after that is about 3 (m / s), the gas-liquid mixing effect is produced by the ejector. For example, when producing 90 (L / min) ozone water, which can be said to have a large capacity in the field of semiconductor cleaning, the cross-sectional area of the bottleneck is 1 (cm2) (about 12 (mm) when converted into a circular tube diameter) There is an advantage that a cross-sectional area of 5 (cm2) (about 25 (mm) when converted into a circular tube diameter) is sufficient. On the other hand, on the downstream side, it is necessary to separate the excess ozone gas bubbles from the ozone liquid mixture that becomes a gas-liquid two-phase flow using a gas-liquid separation tank to generate ozone water that hardly contains ozone bubbles. (See Patent Document 1).

The gas-liquid separation tank is generally cylindrical, with a gas-liquid two-phase flow inlet at the top and an ozone water discharge pipe at the bottom. In this gas-liquid separation tank, the surplus ozone bubbles rise by buoyancy and are separated from the gas-liquid two-phase flow until the gas-liquid two-phase flow supplied from the upper part falls and reaches the ozone water drain pipe. As a result, what is discharged from the ozone water drain pipe is ozone water from which excess ozone bubbles are separated. In the gas-liquid separation tank, the dissolution of ozone progresses with the passage of time during which the gas-liquid two-phase flow stays. As a result, in the gas-liquid separation tank, the concentration of ozone water becomes higher as it moves downward.

Japanese Patent No. 4977376

The conventional gas-liquid separation tank has the following problems.

(Problem 1) Since it is necessary to separate the ozone bubbles by the downward flow in the gas-liquid separation tank, when trying to increase the amount of ozone water used (discharged), the flow velocity of the downward flow increases and the ozone bubbles Insufficient separation is likely to occur. In particular, relatively large ozone bubbles (diameter 1 (mm) or more) are easily separated because of their large buoyancy, but it is difficult to remove small bubbles (approximately 0.1 mm in diameter). In order to solve this problem, it is necessary to increase the inner diameter of the gas-liquid separation tank to reduce the flow velocity of the downward flow, and the gas-liquid separation tank becomes larger.

(Problem 2) In the gas-liquid separation tank, ozone dissolves in water as the time changes simultaneously with the gas-liquid separation process. The stored gas-liquid two-phase flow has a higher ozone concentration as it moves downward from above. Therefore, when trying to increase the ozone concentration of ozone water, it is necessary to increase the height of the gas-liquid separation tank and ensure an extra large residence time for the gas-liquid two-phase flow. End up.

The present invention has been made in view of solving any of the above (Problem 1) to (Problem 2) individually or simultaneously.

The present invention that achieves the above object is an ozone solution generating apparatus that generates an ozone solution by dissolving ozone gas generated by an ozone gas generating apparatus in a solvent, wherein the ozone gas and the solvent are mixed to produce an ozone gas mixed solution. A gas-liquid mixer to be generated, a gas-liquid separation tank for storing the ozone gas mixture generated by the gas-liquid mixer, and a swirl flow generation for generating a swirl flow in the ozone gas mixture in the gas-liquid separation tank And an ozone solution derivation unit that guides the ozone solution generated by the ozone gas mixture that has passed through the swirling flow to the outside of the gas-liquid separation tank. .

In relation to the ozone solution generation device, the ozone solution outlet has an ozone solution outlet for leading the ozone solution to the outside of the gas-liquid separation tank, and the ozone solution outlet is It is located in the place which remove | deviated to the radial direction outer side from the central axis of the said swirl | vortex flow in the said ozone liquid mixture.

In relation to the ozone solution generating device, the swirl flow generation unit sets the range of the direction in which the solvent or the ozone gas mixture is introduced into the gas-liquid separation tank as a range including the tangential direction of the swirl flow. It has the tangential direction introduction part which produces a swirl flow by this.

In relation to the ozone solution generation device, the swirl flow generation unit includes a range of a direction in which the solvent, the ozone gas mixed solution or the ozone solution is derived from the gas-liquid separation tank, and includes a tangential direction of the swirl flow. It is characterized by having a tangential direction deriving section that creates a swirl flow by setting the range.

In relation to the ozone solution generating device, the swirling flow generating section includes a rotating body that generates the swirling flow by rotating in the ozone gas mixture.

In connection with the ozone solution generating device, the ozone gas mixed liquid in the gas-liquid separation tank is led out to be used as a circulating liquid, and the circulating liquid is returned to the gas-liquid separation tank. Is characterized in that the circulation side gas-liquid mixer for mixing the ozone gas supplied from the ozone gas generator and the circulating liquid is arranged.

In connection with the ozone solution generating apparatus, the ozone solution mixed liquid in the gas-liquid separation tank is led out to be used as a circulating liquid, and a circulating path for returning the circulating liquid to the gas-liquid separating tank is provided downstream of the circulating path. The circulating fluid introduction port located at the end has a tangential direction introduction section that creates a swirl flow by setting a range of the introduction direction of the ozone gas mixture into the gas-liquid separation tank as a range including a tangential direction of the swirl flow It is also characterized by serving.

In connection with the ozone solution generation device, the ozone solution mixture in the gas-liquid separation tank is led out to be a circulation liquid, and a circulation path for returning the circulation liquid to the gas-liquid separation tank is provided, upstream of the circulation path. The circulating fluid outlet located at the end includes a tangential direction deriving unit that creates a swirling flow by setting a range of a direction in which the ozone gas mixture is derived from the gas-liquid separation tank to a range including a tangential direction of the swirling flow. It is also characterized by serving.

In connection with the ozone solution generating apparatus, a circulating liquid inlet that is located at the downstream end of the circulation path and introduces the circulation into the gas-liquid separation tank is configured to supply the ozone mixed solution in the ozone solution outlet unit. Compared with the ozone solution outlet leading out to the outside of the gas-liquid separation tank, it is arranged above.

In relation to the ozone solution generation device, at least in the middle of the solvent guide path for guiding the solvent to the gas-liquid separation tank, the gas-liquid mixer for mixing the solvent and the ozone gas is disposed, The gas-liquid mixer is supplied with the ozone gas separated and recovered from the ozone gas mixture in the gas-liquid separation tank.

In relation to the ozone solution generation apparatus, at least a solvent introduction port located at a downstream end of a solvent guide path for guiding the solvent to the gas-liquid separation tank is provided in a direction in which the solvent is introduced into the gas-liquid separation tank. By making the range a range that includes the tangential direction of the swirl flow, it also serves as a tangential direction introduction section that creates a swirl flow.

In connection with the ozone solution generator, water containing an organic substance that causes a chemical reaction with ozone is used as the solvent, and the solvent is used for treating the organic substance in the water.

In relation to the ozone solution generating apparatus, water containing at least one of a virus, bacteria, fungi, and microorganism is used as the solvent, and the solvent is used for treating the substance in the water. To do.

In relation to the ozone solution generator, the ozone solution generator has a standby space for temporarily retaining the ozone solution derived from the ozone solution deriving unit.

The present invention that achieves the above object is an ozone solution generation method for generating an ozone solution by dissolving ozone gas generated by an ozone gas generation device in a solvent, wherein the ozone gas and the solvent are mixed to form an ozone gas mixture. The generated gas-liquid mixing step, and the ozone gas mixture generated by the gas-liquid mixing step is stored in a gas-liquid separation tank, and a swirl flow is generated in the gas-liquid separation tank to generate a swirl flow in the ozone gas mixture An ozone solution generation method comprising: a step; and an ozone solution deriving step of guiding the ozone solution generated by the ozone gas mixed solution having passed through the swirl flow to the outside of the gas-liquid separation tank. .

According to the present invention, it is possible to achieve an excellent effect of providing an ozone solution generating apparatus that is compact and has high dissolution efficiency.

It is a figure showing the whole ozone solution generating device composition concerning a first embodiment of the present invention. (A) is a side view showing a gas-liquid separation tank of the ozone solution generating apparatus, (B) is a cross-sectional view taken along the line BB of (A), and (C) is a CC line of (A). It is arrow sectional drawing, (D) is DD sectional view taken on the line of (A), (E) And (F) is sectional drawing which shows the internal structure of an ejector. (A) is a figure which shows the internal structure of the control apparatus of the same ozone solution production | generation apparatus, (B) is a block diagram which shows the control structure of the same control apparatus. (A) is a schematic diagram explaining the flow of the ozone gas liquid mixture in the gas-liquid separation tank of the same ozone solution production | generation apparatus, (B) is a top view which shows the turning state of an ozone gas liquid mixture. It is a perspective view explaining the flow of the ozone gas liquid mixture in the gas-liquid separation tank of the same ozone solution production | generation apparatus. (A) is a graph which shows the time change state of the derived | led-out amount of ozone water in the same ozone solution production | generation apparatus, (B) is a graph which shows the time change state of ozone concentration of ozone water on the same conditions as (A). It is. (A) is a figure which shows the whole structure about the ozone solution production | generation apparatus which concerns on 2nd embodiment of this invention, (B) and (C) are sectional drawings of a gas-liquid separation tank. (A) is a figure which shows the whole structure about the ozone solution production | generation apparatus which concerns on 3rd embodiment of this invention, (B) and (C) are sectional drawings of a gas-liquid separation tank. (A) is a figure which shows the whole structure about the ozone solution production | generation apparatus which concerns on 4th embodiment of this invention, (B) thru | or (D) are sectional drawings of a gas-liquid separation tank. (A) is a figure which shows the whole structure about the ozone solution production | generation apparatus which concerns on 5th embodiment of this invention, (B) thru | or (D) are sectional drawings of a gas-liquid separation tank. About the ozone solution production | generation apparatus which concerns on 6th embodiment of this invention, (A) is a figure which shows the whole structure, (B) thru | or (E) are sectional drawings of a gas-liquid separation tank. (A) is a figure which shows the whole structure about the ozone solution production | generation apparatus which concerns on 7th embodiment of this invention, (B) thru | or (D) are sectional drawings of a gas-liquid separation tank. About the ozone solution production | generation apparatus which concerns on 8th embodiment of this invention, (A) is a figure which shows the whole structure, (B) thru | or (D) are sectional drawings of a gas-liquid separation tank.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the drawings.

FIG. 1 shows an ozone solution generating apparatus 1 according to the first embodiment of the present invention. In addition, although the case where water (or pure water) is employ | adopted as a solvent which melt | dissolves ozone and ozone water is produced | generated as an ozone solution is illustrated here, the kind of solvent which melt | dissolves ozone is not limited to water.

<Device configuration>
The ozone solution generation apparatus 1 includes an ozone gas generation unit 10 that generates ozone gas, a gas-liquid separation tank 30 that stores an ozone gas mixed liquid that is mixed with ozone gas and water to form a gas-liquid two-phase flow, and a gas-liquid separation tank 30. In addition, a solvent guide path 70 for supplying at least water as a solvent, an ozone solution outlet 80 for guiding (discharging) ozone water from the gas-liquid separation tank 30 to the outside, and an ozone gas mixture in the gas-liquid separation tank 30 A swirling flow generating unit 50 for generating a swirling flow, and a circulation path for deriving the ozone gas mixed liquid in the gas-liquid separation tank 30 to be temporarily used as a circulating liquid and guiding the circulating liquid to the gas-liquid separating tank 30 again. 60 and an ozone gas mixing unit 20 for mixing ozone gas and water (solvent) or ozone gas and circulating liquid.

The ozone gas generation unit 10 generates ozone gas by, for example, passing an oxygen gas 6 as a raw material between discharge gaps of a silent discharge tube (ozonizer). In addition, the density | concentration of the produced | generated ozone gas is adjusted with the adjustment gas 8, such as a carbon dioxide gas. You may adjust with nitrogen gas etc. with low reactivity besides carbon dioxide. The ozone gas discharged from the ozone gas generation unit 10 is supplied to the ozone gas mixing unit 20 via a valve mechanism 9 that serves as a check valve or a flow rate adjustment valve that prevents a back flow of liquid. In order to increase the supply amount of ozone gas in the ozone gas generation unit 10, it is preferable to connect a plurality of ozonizers in parallel and generate ozone gas in parallel.

The gas-liquid separation tank 30 is, for example, a bottomed cylindrical container with a bottom. Although the axial direction of the central axis of the cylindrical shape is set to be vertical, the present invention is not limited to this, and the gas-liquid separation tank may be installed with the central axis inclined with respect to the vertical.

The solvent guide path 70 is a flow path that connects the water / liquid separation tank 30 to the water supply unit 72 to which water as a raw material of the solvent is supplied. A flow rate adjustment valve 74 is disposed in the middle of the solvent guide path 70. The flow rate adjustment valve 74 is a pneumatic valve such as a pneumatic flow rate adjustment valve.

At the downstream end of the solvent guide path 70, a solvent introduction port 76 for introducing (discharging) at least water (actually an ozone gas mixed solution) is formed in the gas-liquid separation tank 30. As shown in FIG. 2B, the solvent introduction port 76 introduces water in a direction including a tangential component of the swirl flow S generated in the ozone gas mixture. Therefore, the solvent introduction port 76 also serves as a tangential direction introduction unit that generates a swirl flow by the flow of introducing the fluid in the swirl flow generation unit 50 described later.

More specifically, the solvent inlet 76 opens directly to the cylindrical inner peripheral wall of the gas-liquid separation tank 30. The direction in which the raw material water is guided in the solvent guide path 70 immediately before the solvent introduction port 76 includes a circumferential component (tangential component) of the inner peripheral wall, and in this embodiment, in particular, substantially matches the tangential direction of the inner peripheral wall. The guide direction of the solvent guide path 70 immediately before the solvent introduction port 76 is substantially horizontal (perpendicular to the vertical central axis of the gas-liquid separation tank 30). As a result, the flow of the raw water (ozone gas mixture) introduced from the solvent introduction port 76 via the solvent guide path 70 is a swirl flow along the inner peripheral wall of the gas-liquid separation tank 30 as indicated by an arrow FB. Become.

As shown in FIG. 2 (A), the solvent introduction port 76 is disposed near the center of the gas-liquid separation tank 30 in the vertical direction or above it.

As shown in FIG. 2D, a circulating fluid outlet 62 is formed at the upstream end of the circulation path 60. This circulating fluid outlet 62 serves as an opening for leading out (sucking) the ozone gas mixture in the gas-liquid separation tank 30. The circulating fluid outlet 62 guides the ozone gas mixture in a direction including the tangential component of the swirl flow S generated in the ozone gas mixture. Therefore, the circulating fluid outlet 62 also serves as a tangential direction deriving unit that generates a swirling flow by a flow of deriving a fluid in the swirling flow generating unit 50 described later.

Further, the circulating fluid outlet 62 is directly open to the cylindrical inner peripheral wall of the gas-liquid separation tank 30. The guiding direction of the circulating fluid by the 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, in particular, substantially matches the tangential direction of the inner peripheral wall. . The direction in which the circulating fluid is guided by the circulation path 60 immediately after the circulating fluid outlet 62 is substantially horizontal (perpendicular to the central axis in the vertical direction of the gas-liquid separation tank 30). As a result, the flow immediately before the ozone gas mixed liquid led out to the circulation path 60 via the circulating liquid lead-out port 62 becomes a swirl flow along the inner peripheral wall of the gas-liquid separation tank 30 as indicated by an arrow FD. The turning direction coincides with the turning direction generated by the solvent introduction port 76, and here, the turning direction is counterclockwise as viewed from above.

As shown in FIG. 2 (A), the circulating fluid outlet 62 is disposed below the solvent inlet 76 and the circulating fluid inlet 64 in the vertical direction. More specifically, the gas-liquid separation tank 30 is disposed below the center in the vertical direction and in the vicinity of the bottom surface thereof.

As shown in FIG. 2 (C), a circulating fluid inlet 64 is formed at the downstream end of the circulation path 60. The circulating fluid inlet 64 serves as an opening for introducing the circulating fluid (ozone gas mixture) guided by the circulation path 60. The circulating fluid inlet 64 introduces the circulating fluid in a direction including a tangential component of the swirl flow S generated in the ozone gas mixture. Therefore, the circulating fluid introduction port 64 also serves as a tangential direction introduction unit that generates a swirl flow by a flow of introducing a fluid in a swirl flow generation unit 50 described later.

Further, the annular liquid inlet 64 is opened in the cylindrical inner peripheral wall of the gas-liquid separation tank 30. The guide direction of the circulation path 60 immediately before the circulating fluid inlet 64 includes a circumferential component (tangential component) of the inner peripheral wall, and in this embodiment, in particular, substantially matches the tangential direction of the inner peripheral wall. The guide direction of the circulation path 60 immediately before the circulating fluid inlet 64 is substantially horizontal (perpendicular to the vertical central axis of the gas-liquid separation tank 30). As a result, the flow of the circulating fluid introduced from the circulating fluid inlet 64 becomes a swirl flow along the inner peripheral wall of the gas-liquid separation tank 30 as indicated by the arrow FC. The swirl direction coincides with the swirl direction generated by the solvent introduction port 76, and here is counterclockwise as viewed from above.

As shown in FIG. 2 (A), the circulating fluid inlet 64 is disposed between the solvent inlet 76 and the circulating fluid outlet 62 in the vertical direction. More specifically, the gas-liquid separation tank 30 is disposed below the center in the vertical direction and above the circulating fluid outlet 62.

Referring back to FIG. 1, a circulation pump 66 is disposed in the middle of the circulation path 60. The circulation pump 66 plays a role of promoting the flow of the circulating fluid. A flow rate adjustment valve 68 for adjusting the flow rate of the circulating fluid is disposed on the downstream side of the circulation pump 66 in the circulation path 60. The flow rate adjusting valve 68 is a pneumatic valve such as a pneumatic flow rate adjusting valve.

The ozone solution deriving unit 80 is configured to derive the ozone water generated by the gas-liquid separation tank 30 to the use point U, and a flow rate that is provided in the middle of the deriving path 82 and adjusts the amount of ozone water derived. An adjustment valve 84 is provided. The upstream side of the outlet path 82 also serves as the circulation path 60, and the ozone solution outlet 86 formed at the upstream end of the outlet path 82 also coincides with the circulating liquid outlet 62. Therefore, as shown in FIG. 2 (D), the ozone solution outlet 86 guides the ozone gas mixture in the direction including the tangential component of the swirl flow S generated in the ozone gas mixture. The ozone solution outlet 86 also serves as a tangential direction derivation unit that generates a swirl flow by a flow for deriving a fluid in the swirl flow generation unit 50 described later.

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 mixture in the gas-liquid separation tank 30. Since the surplus ozone bubbles move to the central axis C side as a reaction of the centrifugal force of the swirling flow, the surplus ozone bubbles are difficult to enter the ozone solution outlet 86, and ozone water with few bubbles can be discharged.

Next, the swirl flow generator 50 will be described. As shown in FIG. 1, the swirl flow generation unit 50 introduces water or an ozone gas mixture in a direction including a tangential component of the swirl flow of the ozone gas mixture stored in the gas-liquid separation tank 30 to generate a swirl flow. It has a tangential direction introduction part 50A to be produced. In the present embodiment, as already described, the solvent introduction port 76 and the circulating fluid introduction port 64 also serve as the tangential direction introduction unit 50A. The swirl flow generation unit 50 has a tangential direction deriving unit 50B that generates a swirl flow by deriving the ozone gas mixture stored in the gas-liquid separation tank 30 in a direction including the tangential component of the swirl flow. In the present embodiment, as already described, the circulating fluid outlet 62 (or the ozone solution outlet 86) also serves as the tangential direction outlet 50B.

Next, the ozone gas mixing unit 20 will be described. The ozone solution generation apparatus 1 according to the present embodiment includes, as the ozone gas mixing unit 20, a solvent side gas / liquid mixer 22 disposed in the middle of the solvent guide path 70 and a circulation side gas / liquid mixture disposed in the middle of the circulation path 60. A container 24. The solvent-side gas-liquid mixer 22 is disposed on the downstream side (gas-liquid separation tank 30 side) with respect to the flow rate adjustment valve 74, and mixes raw water and excess ozone gas generated in the gas-liquid separation tank 30. Accordingly, an ozone gas circulation path 26 that guides the surplus ozone gas remaining above the ozone gas mixture to the solvent-side gas-liquid mixer 22 is connected above the gas-liquid separation tank 30.

The circulation side gas-liquid mixer 24 is disposed downstream of the flow rate adjustment valve 68 (gas-liquid separation tank 30 side) in the circulation path 60, and mixes the circulation liquid and the ozone gas supplied from the ozone generator 10. To do.

The ozone gas mixing unit 20 (solvent side gas-liquid mixer 22, circulation side gas-liquid mixer 24) is a so-called ejector 28 as shown in FIG. Ozone gas is drawn from the negative pressure space 28 </ b> B formed around it by introducing it at a high speed from 28 </ b> A. On the downstream side of the nozzle 28A, a diffuser 28C having a narrow portion is provided in the middle, and the ozone gas mixed solution is mixed together until reaching the narrow portion, and further passes through the narrow portion, the flow velocity further decreases, At the same time as returning to the original flow velocity, the pressure of the ozone gas mixture also returns according to Bernoulli's theorem. Like the ejector 28 shown in FIG. 2 (F), ozone gas may be directly drawn into the narrow portion of the diffuser 28C. Here, an ejector is exemplified as a method of mixing a solvent such as water and ozone gas. However, the present invention is not limited to this, and a mixing pump, a microchannel, or the like may be used.

Returning to FIG. 1, the gas-liquid separation tank 30 is provided with a liquid level sensor 36 for detecting the liquid level of the ozone gas mixed liquid and an ozone concentration sensor 38 for detecting the concentration of ozone dissolved in the ozone gas mixed liquid. It is done. The ozone concentration sensor 38 may be provided in the derivation path 82 or the circulation path 60, but it is preferable that a value close to the ozone concentration derived from the ozone solution derivation unit 80 can be detected as much as possible. Therefore, in the case of the gas-liquid separation tank 30, it is preferable to arrange it near the bottom surface.

An open path 40 is formed above the gas-liquid separation tank 30, and in the middle of the release path 40, a back pressure adjustment valve 42 that keeps the pressure in the gas-liquid separation tank 30 constant, and a release path 40. The exhaust ozone decomposer 44 which decomposes | disassembles the surplus ozone gas which passes through is provided.

The ozone solution generator 1 includes a controller 46. For example, as shown in FIG. 3A, the control device 46 is controlled by a central processing unit CPU that processes a program developed in the memory M, a storage medium H that stores various information and control programs, and an external device. An interface I for outputting a signal and receiving a detection signal from an external device is provided, and these are connected to each other by a bus or the like.

As shown in FIG. 3B, the control device 46 includes a solvent supply control unit 46A, a circulation flow rate control unit 46B, an ozone gas control unit 46C, and a derived amount control unit 46D as control blocks (functional configuration realized by a program). , A liquid level detection unit 46E, and an ozone concentration detection unit 46F.

The liquid level detection unit 46E detects the liquid level of the ozone gas mixture using the liquid level sensor 36. The ozone concentration detector 46F uses the ozone concentration sensor 38 to detect the ozone concentration of the ozone gas mixture. The solvent supply control unit 46A controls the flow rate adjustment valve 74 based on the liquid level of the ozone gas mixed solution, and controls the flow rate of the newly supplied raw material water. The flow rate may be controlled so that the liquid level is always constant, and the supply is started when the preset lower limit liquid level is reached, and the supply is stopped when the preset upper limit liquid level is reached. You may control to such a pulse wave shape. Further, as a control method of the flow rate adjustment valve 74, the water amount may be controlled by switching between full open and full close, and the throttle amount of the flow rate adjustment valve 74 may be finely controlled. On the other hand, in order to effectively obtain the gas-liquid mixing action of the solvent-side gas-liquid mixer 22, it is desirable that the raw water is fully opened to increase the flow rate when the raw water is supplied. It is also desirable to control.

The circulation flow rate control unit 46B controls the flow rate of the circulating fluid by controlling the circulation pump 66 and / or the flow rate adjustment valve 68. The flow rate of the circulating fluid may be constant, but may be controlled based on, for example, the ozone concentration of the ozone gas mixture. If the ozone concentration is lower than the target value, the circulating flow rate is increased and When the concentration is high, the circulation flow rate may be decreased. On the other hand, in order to stabilize the concentration of ozone water, it is preferable that the flow rate of the circulating liquid is always set larger than the amount of water controlled by the solvent supply control unit 46A, for example, supply by the solvent supply control unit 46 When the amount is 20 (L / min), the flow rate of the circulating fluid is set to a value larger than 20 (L / min), for example, 40 (L / min).

The ozone gas control unit 46C controls the concentration of ozone gas generated by the ozone gas generation unit 10 based on the ozone concentration of the ozone gas mixture and / or the circulation flow rate controlled by the circulation flow rate control unit 46B. The derived amount control unit 46D controls the flow rate adjustment valve 84 to control the flow rate of the ozone water discharged to the use point U.

<Basic operation>
Next, the operation of the ozone solution generator 1 will be described with reference to FIG. The raw water of the water supply unit 72 is guided and stored in the gas-liquid separation tank 30 via the solvent guide path 70. Ozone gas is generated by the ozone gas generation unit 10, and ozone gas is supplied to the gas-liquid separation tank 30 via the circulation side gas-liquid mixer 24. Extra ozone gas stored in the gas-liquid separation tank 30 is supplied to the solvent-side gas-liquid mixer 22 via the ozone gas circulation path 26. As a result, the raw water supplied from the solvent guide path 70 becomes an ozone gas mixture. When the liquid level of water or the ozone gas mixture becomes high in the gas-liquid separation tank 30, the circulation pump 66 is activated to circulate the ozone gas mixture in the circulation path 60. The circulating liquid is mixed with high-concentration ozone gas from the ozone gas generator 10 in the circulation-side gas-liquid mixer 24. After the ozone concentration of the ozone gas mixture reaches the target value, the flow rate adjustment valve 84 is opened and the generated ozone water is led out to the use point U. The supply of the raw material water by the water supply unit 72 is adjusted to the flow rate of ozone water guided to the use point U by the ozone solution deriving unit 80. On the other hand, the circulation flow rate of the circulation path 60 can always be controlled at a constant flow rate without depending on these.

In FIG. 4, the state of the gas-liquid separation tank 30 in the middle of the ozone solution production | generation apparatus 1 is operating is shown typically. Here, a case where the liquid level of the ozone gas mixed solution is substantially coincident with the solvent introduction port 76 is shown, but the present invention is not limited to this. For convenience of explanation, in the gas-liquid separation tank 30, a space from the solvent introduction port 76 to the circulating fluid introduction port 64 is defined as a primary space 30A, and a space from the circulating fluid introduction port 64 to the circulating fluid outlet 62 is defined as a secondary space 30B. The respective heights of the primary space 30A and the secondary space 30B are defined as L ₁ and L ₂ (m).

The flow rate of the ozone gas mixture (or raw material water) introduced from the solvent introduction port 76 is defined as Q ₁ (L / min), and the flow rate discharged from the lead-out path 82 of the ozone solution lead-out unit 80 is defined as Q ₃ (L / min)), the flow rates of each other will coincide if they are equalized. The flow rate of the ozone liquid mixture descending the primary space 30A is also Q ₁ = Q ₃ (L / min). Further, when the flow rate of the circulating fluid passing through the flow rate adjusting valve 68 of the circulation path 60 is Q ₄ (L / min), the flow rate Q ₂ (L / min) of the ozone mixed solution descending the secondary space 30B is Q _1. + the _{Q 4.} As already described, the circulating fluid flow rate Q ₄ (L / min) is set so that the introduction flow rate of the solvent introduction port 76 is larger than Q ₁ (L / min). Accordingly, the flow rate Q ₂ of the ozone mixture to lower the secondary space 30B, it is preferable that the flow rate Q _{1 (L} / min) twice or more.

When the diameter of the gas-liquid separation tank 30 is defined as d (m), in the primary space 30A of the gas-liquid separation tank 30, the ideal piston flow downward flow, that is, the flow velocity depending on the location in the circular cross section perpendicular to the axis. Assuming a uniform downward downward flow, the flow velocity V ₁ (m / s) of the downward flow is defined by the following equation 1.

Equation _{1: V 1 = Q 1/} 6000 × (4 / πd 2) = 2.12 × 10 5 × Q 1 / πd 2

Next, the diameter of the surplus ozone gas bubbles (hereinafter referred to as bubbles) to be separated is D _p (m), the gravitational acceleration is g (m / s ² ) (= 9.8 (m / s ² )), and the ozone gas mixture The density is ρ (kg / m ³ ) (here, the density of water is approximated by 1000 (kg / m ³ )), and the viscosity coefficient of the ozone gas mixture is η (Pa · s) (here 0.001 (Pa · s)) The bubble rising speed Z ₁ (m / s) in the still liquid is approximately obtained by the Stokes equation (2).

Formula ^{_{2: Z 1 = D p 2}} × ρ × g / (18η)

The diameter D _p (m) of the bubbles to be separated is preferably set to 0.0001 (m), that is, 100 μm or more, which may cause problems in practical use. Therefore, if this value is substituted, the ascending speed Z ₁ is 5.44 × 10 ⁻³ (m / s).

In order to prevent bubbles from being mixed into the ozone water discharged from the outlet path 82, it is required that the bubbles are not drawn to the bottom surface due to the downward flow. As a result, Equation 3 is established.

Formula 3: V ₁ ≦ Z ₁

As already described, the diameter D _p (m) of the bubbles to be separated is 0.0001 (m), and the amount of ozone water generated from the lead-out path 82 is 90 (L / min), the diameter d (m) of the gas-liquid separation tank 30 is calculated to be 0.59 (m) or more from the above equations 1 to 3. Therefore, as in the conventional case, when only a simple piston flow downward flow is used, it means that 100 μm bubbles cannot be separated unless the inner diameter of the gas-liquid separation tank 30 is increased to about 0.6 (m) or more.

Next, with reference to FIG. 4, the effect | action by the swirling flow production | generation part 50 in the ozone solution production | generation apparatus 1 of this embodiment is demonstrated. Here, it is assumed that the swirling flow is mainly generated by the circulating fluid in the circulation path 60.

As shown in FIG. 4B, as a reaction of the centrifugal force due to the swirl flow S, the bubbles K move in the direction of the central axis C of the gas-liquid separation tank 30. In the secondary space 30B, the acceleration (centrifugal force acceleration) when the bubble K moves in the central axis direction is defined as A ₂ (m / s ² ), and the circumferential flow velocity of the swirling flow S is U ₂ (m / s). s) When the rotational radius of the swirling flow is defined as r ₂ (m), this centrifugal force acceleration A ₂ is expressed by Equation 4.

Formula 4: A ₂ = U ₂ ² / r ₂

Temporarily, the gas-liquid separation tank 30 reduced in size by this embodiment is assumed. The inner diameter of the gas-liquid separation tank 30 (diameter) d (m) and 0.15 (m), the vertical distance of H ₂ secondary space 30B assuming 0.5 (m), swirling flow introduced from the circulating fluid inlet 64 defining the flow velocity _{U 2} 3 and (m / s). The turning radius r ₂ of the swirling flow is 0.075 (m) of d / 2, and A ₂ is calculated as 120 (m / s ² ) from Equation 4. In other words, the centrifugal force acceleration A ₂ is a vertical gravitational acceleration g (= 9.8) of 12 times or more.

As the bubble K by centrifugal force acceleration A ₂ of the swirling flow S to define the speed of moving in the direction of the central axis C J ₂ and _(m / s), the gravitational acceleration g of the Stokes formula of the formula 2, the centrifugal force acceleration A2 And is derived by Equation 5 substituting

Formula 5: J ₂ = D _p ² × ρ × A ₂ / (18η)

Further, when the flow rate Q ₂ (L / min) descending the secondary space 30B is 40 (L / min), the following items (1) to (6) are calculated.

(1) lowering speed _{V 2} of the ozone gas mixture in the secondary space 30B is in reference to the above equation _{1, V 2 = Q 2/} 6000 × (4 / πd 2) = 0.1224 a (m / s).

Speed Z ₂ bubbles K rises vertically upward (2) secondary space 30B is the same result as in the above formula 2, and ^{_{Z 2 = 5.44 × 10 -3 (}} m / s).

(3) In the case of the above virtual condition, in the secondary space 30B, V ₂ > Z ₂ and the bubble K can be lowered. The descending speed V _2d (m / s) of the substantial bubble K is V ₂ −Z ₂ = 0.1171 (m / s).

(4) The time T _2d (s) required for the bubble K to descend at the descending speed V _2d and the secondary space 30B having the height H ₂ is H ₂ / V _2d = 4.27 (s).

(5) The velocity J _{2 at which} the bubble K located on the peripheral wall moves to the central axis C by the swirling flow S in the secondary space 30B is obtained by substituting A ₂ = 120 (m / s ² ) into Equation 5. 0.067 (m / s).

(6) In the secondary space 30B, the distance r _2d (m) that the bubble K moves toward the center within the time T _2d (s) when the bubble K descends is J ₂ × T _2d , which is 0.28 (m). . This moving distance exceeds the radius d / 2 (m) of the gas-liquid separation tank 30.

From the above, in the secondary space 30B, the 100 μm bubble K located on the inner peripheral wall can move to at least the central axis C while descending while turning from the circulating fluid inlet 64 to the circulating fluid outlet 62. Become. In the present embodiment, the circulating fluid outlet 62 (ozone solution outlet 86) is formed at a position away from the central axis C in the radial direction, specifically, on the inner peripheral wall of the gas-liquid separation tank 30. Therefore, the bubbles K do not have to be discharged together with the ozone water.

The above verification, the circulating liquid flow rate U ₂ that are introduced from the circulating fluid inlet 64, it is assumed that not attenuated until the end. However, as verified above, the distance r _2d (m) that the bubble K moves toward the central axis C is 0.28 (m), which is 0.075 (m), which is the radius (d / 2) of the gas-liquid separation tank 30. Is also significantly larger. Therefore, even if the flow velocity U ₂ is somewhat attenuated no problem. Specifically, in the secondary space 30B, the minimum moving speed for the bubble K to reach the central axis C having a radius (d / 2) by the dwelling time T _2d (s) during descent. J _{2min is, J 2min = (d / 2} ) / T 2d (m / s) , and the from the _{T 2d = 4.27 (s),} d / 2 = 0.075 (m), the minimum movement speed _{J 2min} is 0.0175 (M / s). When calculating the minimum flow rate U _2min of the circulating fluid using this minimum moving speed J _2min , the following formula 6 derived from formula 4 and formula 5 can be used.

Equation _{6: U 2min = √ {J} 2min × 18η × (d / 2) / (D p 2 × ρ)}

The result of Equation 6 is 1.53 (m / s). That is, if the flow rate U ₂ of the circulating fluid to be introduced from the circulating fluid inlet 64 was 3 (m / s), Even if decayed to about half 1.53 (m / s), is no problem I understand that there is no. Further, even if the bubble K does not reach the central axis C, it is sufficient if it is separated from the inner peripheral wall to some extent inside, so that further attenuation is allowed.

FIG. 5 shows a visual state when the bubble K rises in the secondary space 30B. The bubble K tends to move to the center in the radial direction by the swirling flow, accompanied by both the descending by the descending flow and the rising by the buoyancy. When these bubbles try to move to the center, the bubbles merge to increase the particle size and buoyancy. At this time, it rises along the spiral ascending path N formed in the swirling flow. The bubbles K are always present at a position radially inward from the inner peripheral wall of the gas-liquid separation tank 30, so that efficient gas-liquid separation is realized.

Incidentally, based on (6) of the verification items, the distance r _2d (m) moved in the direction of the central axis C by the swirl flow S is not less than the radius (d / 2) (m) of the gas-liquid separation tank 30. The following equation 7 can be derived.

Formula 7: r _2d ≧ d / 2

R _{2d in} Equation 7 can be expanded into the following Equation 8.

Expression 8: r _2d = J ₂ × T _2d = {D _p ² × ρ × A ₂ / (18η)} × {H ₂ / V _2d } = {D _p ² × ρ × A ₂ / (18η)} × _{{H 2 / (V 2 -Z} 2)} = {D p 2 × ρ × U 2 2 × 2 / (d × 18η)} × {H 2 / (Q 2/6000 × (4 / πd 2) - D _p ² × ρ × g / (18η))} = D _p ² × ρ × U ₂ ² × 2 × H ₂ × 6000 × πd / {Q ₂ × 4 × 18η−D _p ² × ρ × g × 6000 × πd ² }

Substituting the expansion result of r _2d in Expression 8 into Expression 7 and further expanding to the reference of d as follows, Expression 9 is obtained. It is preferable that the ozone solution generating apparatus 1 of the present embodiment satisfies the inner diameter d of Equation 9.

D _p ² × ρ × U ₂ ² × 2 × H ₂ × 6000 × πd / {Q ₂ × 4 × 18 η−D _p ² × ρ × g × 6000 × πd ² } ≧ d / 2

D _p ² × ρ × U ₂ ² × 4 × H ₂ × 6000 × π ≧ {Q ₂ × 4 × 18 η−D _p ² × ρ × g × 6000 × πd ² }

Formula 9: d ≧ √ {(Q ₂ × 4 × 18 η−D _p ² × ρ × U ₂ ² × 4 × H ₂ × 6000 × π) / (D _p ² × ρ × g × 6000 × π)}

Therefore, when increasing the flow rate Q ₂ to which descends the secondary space 30B, at the same time, gas-liquid two-phase flow of the swirling flow of the flow velocity U _{2 (m} / s) from also increased that, by the circulating flow, the gas-liquid It can be seen that the inner diameter d of the separation tank 30 can be reduced.

Specifically, in the case of the ozone solution generation apparatus 1 of the present embodiment, for example, the inner diameter (diameter) d (m) of the gas-liquid separation tank 30 is less than 0.6 (m), desirably 0.5 (m) or less, and more desirably. Can be set to 0.3 (m) or less.

Similarly, the above equation, by expanding the flow rate Q ₂ based is as follows 10. Ozone solution generating apparatus 1 of the present embodiment is preferably controlled to satisfy the flow rate Q _2.

Formula ^{_{10: (D p 2 × ρ}} × g × 6000 × πd 2 + D p 2 × ρ × U 2 2 × 4 × H 2 × 6000 × π) / (4 × 18η) ≧ Q 2

Similarly, the above equation, the following equation 11 by expanding the flow velocity U ₂ as a reference. Ozone solution generating apparatus 1 of the present embodiment is preferably controlled to satisfy the velocity U _2.

Formula 11: U ₂ ≧ √ {(Q ₂ × 4 × 18η−D _p ² × ρ × g × 6000 × πd ² ) / (D _p ² × ρ × 4 × H ₂ × 6000 × π)}

By the way, the dissolution of ozone gas in water involves a process in which ozone molecules diffuse in bubbles (mixed gas) and a process in which ozone molecules that have moved from the bubbles to the water side at the gas-liquid boundary diffuse into water. It is done in two processes. Since the diffusion rate of ozone molecules in the bubbles is extremely higher than the diffusion rate of ozone molecules in water, the rate limiting of the actual dissolution rate of ozone gas in water is the diffusion rate of ozone molecules in water. The diffusion rate of ozone molecules in water depends on the concentration gradient of ozone molecules from the bubble to the water side at the gas-liquid boundary (change in concentration per unit distance), but the concentration of ozone molecules in the surface water near the boundary is high Then, ozone tends to be in an equilibrium state at the boundary, and the moving speed of ozone molecules from the bubbles toward the water side decreases.

Therefore, in order to increase the dissolution rate of ozone gas in water, it is preferable to increase the relative movement speed of the bubbles and water so that the bubbles having a high ozone concentration are brought into contact with the surface water having a low ozone concentration. In the case of a downward piston flow that is uniform in the vertical direction as in the prior art, the relative speed between the bubbles and the water coincides with the rising speed of the bubbles. On the other hand, in the case of the present ozone solution generating apparatus 1, the speed at which the bubbles move in the direction of the central axis C is also added due to the centrifugal force of the swirling flow, so the relative speed between the bubbles and water is larger than the conventional one, The ozone concentration of the ozone water can be increased, and the control response can be increased.

As described above, according to the ozone solution generating apparatus 1 of the present embodiment, a gas-liquid two-phase flow (swirl flow S) that rotates about the cylindrical axis of the tank is generated inside the gas-liquid separation tank 30. . As a result, bubbles of excess ozone gas move to the central axis side due to the reaction of centrifugal force during turning. By disposing the ozone solution outlet 86 (circulating fluid outlet 62) at a position offset radially outward from the central axis C, bubbles are less likely to be mixed into the discharged ozone water. Therefore, even if the discharge flow rate is increased, the gas-liquid separation tank 30 can be constructed in a compact manner. Further, the swirl flow increases the relative movement speed of the water serving as the solvent and the ozone gas bubbles, so that it is possible to generate ozone water with high dissolution efficiency.

As means for creating a swirl flow, tangential direction introduction that introduces a swirl flow by introducing water or an ozone gas mixture in a direction including a tangential component of the swirl flow in the horizontal plane, such as the solvent introduction port 76 and the circulating fluid introduction port 64. Since it has the part 50A, a swirl flow can be created efficiently. In particular, it becomes possible to create a stable and powerful swirl flow by using a circulating liquid that does not depend on the consumption of ozone water, and the secondary space 30B allows the separation of excess ozone gas using centrifugal force and the ozone gas. Can be dissolved in water. Further, the flow velocity of the swirling flow can be arbitrarily controlled by the circulating fluid.

Further, as a means for generating a swirl flow, a tangential direction deriving unit 50B that generates a swirl flow by deriving the ozone gas mixture stored in the gas-liquid separation tank 30 in a direction including a tangential component of the swirl flow in the horizontal plane. Therefore, it is possible to create a swirl flow more efficiently. In particular, it is difficult for excessive ozone gas bubbles to enter the tangential direction deriving portion 50B. By using this as the ozone solution outlet 86, it is possible to derive only ozone water with few bubbles. At the time of derivation, the flow of the swirling flow is hardly disturbed, and the swirling flow can be stably maintained. Incidentally, if ozone water is derived in a direction that does not coincide with the swirling flow, an individual small swirling flow is generated in the vicinity of the outlet, and bubbles of excess ozone gas may be sucked up.

Moreover, in this ozone solution production | generation apparatus 1, the ozone gas of the ozone gas production | generation part 10 is mixed in the circulation side gas-liquid mixer 24 arrange | positioned at the circulation path 60 of the circulation liquid in which ozone is already high concentration. In the ozone gas generation unit 10, since the concentration of ozone gas is controlled with high accuracy, the concentration of the ozone water mixed here can be controlled with high accuracy and high response. Specifically, the time constant of the concentration control of the ozone water is the ratio between the amount of the ozone gas mixture stored in the gas-liquid separation tank 30 and the amount of circulating fluid circulated by the circulation pump 66. By setting this ratio small, the response speed of the ozone concentration control can be increased. For example, the circulation flow rate Q ₄ by the circulating pump 66 and 40 (L / min), inner diameter 0.15 of the gas-liquid separation tank 30 (m), if the water level of the reservoir is ozone gas mixture from the bottom with 0.5 (m), The storage amount is about 8.8 (L). Therefore, the control time constant is about 8.8 / 40 = 0.2 (minutes), that is, about 13 (seconds). To further reduce the time constant, it increases the circulation flow rate Q _4, so that may be reduced to the reservoir volume.

Further, since the surplus ozone gas separated from the ozone gas mixture is reused and mixed to the pure water side by the solvent-side gas-liquid mixer 22, it is possible to greatly increase the use efficiency of the ozone gas. . In other words, because the surplus ozone gas separation efficiency by the swirling flow using the circulating liquid is high, the utilization efficiency of the ozone gas can be further increased by reusing it.

<Verification example>
Using this ozone solution generating apparatus 1, in the case of changing the flow rate Q ₃ of the ozone water discharged from the ozone solution deriving unit 80, shown in FIG. 6 the results of actual measurement of the variation of ozone concentration. Here, the flow rate of the ozone gas generated by the ozone gas generation unit 10 is set to 15 (L / min), and the ozone gas generation unit 10 is duty-controlled so that the control concentration of the ozone water is 80 (ppm), which is a relatively high concentration. And adjust the concentration of ozone gas. Further, the pressure of the gas-liquid separation tank 30 is set to 0.17 (MPa), the height of the solvent inlet 76 from the bottom of the gas-liquid separation tank 30 is 0.6 (m), and the height of the circulating liquid inlet 64 is 0.3 (m). The water level was made to coincide with the height of the solvent inlet 76.

5 flow Q ₃ As can be seen from FIG. 6 (L / min), 10 (L / min), 15 (L / min), even varied to 20 (L / min), the concentration of ozone water 80 It can be seen that (ppm) is maintained. Specifically, with respect to the change of the flow rate Q _3, momentary fluctuations in ozone concentration in the ozone water becomes 3 (ppm) or less. Further, in the midst of the flow rate Q ₃ is stable (after 2 minutes from the flow changes), fluctuation of the ozone concentration of ozone water is 1 (ppm) or less (measured value by 0.43 (ppm)), and the coefficient of variation ( = Standard deviation / average value) is 1% or less (measured value is 0.54%). It can also be seen that even at a relatively high flow rate of 20 (L / min), 80 (ppm) of ozone water with a high concentration can be generated.

Furthermore, according to the verification experiment of the present inventors, the concentration of ozone gas generated by the ozone gas generation unit 10 is 160 (g / m ³ ) or more, preferably 170 (g / m ³ ), using the present ozone solution generation apparatus 1. and above, further, the ozone gas flow rate 10 (L / min) or more, preferably a 15 (L / min) or more and further, the circulation flow rate Q ₄ by the circulating pump 66 20 (L / min) or more, preferably Even if it is 40 (L / min) or higher, more preferably 60 (L / min) or higher, the ozone water discharge is 15 (L / min) or higher, preferably 20 (L / min) or higher. Ozone water of 90 (ppm) or more is obtained.

Next, an example that is a modification of the ozone solution generation apparatus 1 according to the first embodiment of the present invention will be described. In order to avoid duplication, parts and members to be described below are the same as or similar to those in the ozone solution generating device 1 of the first embodiment, and the reference numerals in the description are made to coincide with each other. A description will be given centering on differences in one embodiment and the like.

FIG. 7 shows an ozone solution generation apparatus 101 according to the second embodiment. In this ozone solution generating apparatus 101, the downstream side of the circulation path 60 is merged with the solvent guide path 70, so that the solvent introduction port 76 and the circulation liquid introduction port 64 serve as both, and the solvent side gas-liquid mixer 22 and the circulation are provided. It also serves as the side gas-liquid mixer 24. The solvent introduction port 76 and the circulating fluid introduction port 64 also serve as the tangential direction introduction unit 50A. On the other hand, as shown in FIG. 7C, the ozone solution outlet 86 or the circulating fluid outlet 62 disposed in the gas-liquid separation tank 30 supplies ozone water radially outward with respect to the gas-liquid separation tank 30. It is designed to derive and does not have a function to generate a swirling flow. Even in this case, a swirl flow can be sufficiently created by the upper tangential direction introduction portion 50A. In the solvent guide path 70, when stable raw material water is always supplied from the water supply unit 72, the circulation path 60 can be omitted as shown by the dotted line.

Moreover, although the case where it supplied directly to an ozone gas mixing part was illustrated in 1st embodiment as a recycle method of the surplus ozone gas stored above the gas-liquid separation tank 30, ozone gas circulation path 26 like 2nd embodiment was illustrated. May be supplied to the ozone gas generator 10 via the dehumidifier 27. In the ozone gas production | generation part 10, the utilization efficiency of ozone gas can be improved by producing | generating ozone gas newly, mixing the surplus ozone gas and raw material oxygen which are circulated.

In the ozone solution generating apparatus 101 of the second embodiment, the solvent introduction port 76 and the circulating fluid introduction port 64 are also used as the tangential direction introduction unit 50A, but the present invention is not limited to this. Like the ozone water generator 201 of the third embodiment shown in FIG. 8, the solvent introduction port 76 and the circulating fluid introduction port are made so that the ozone solution outlet 86 and the circulating fluid outlet 62 also serve as the tangential direction outlet 50B. 64 may be introduced so as not to include the tangential component of the swirl flow S.

As in the ozone water generator 301 of the fourth embodiment shown in FIG. 9, only the circulating fluid inlet 64 serves as the tangential direction inlet 50A, and the solvent inlet 76 and the ozone solution outlet 86 (circulating fluid outlet 86). 62) may have a structure that does not create a swirling flow. Further, the ozone gas mixing unit 20 may omit the solvent side gas-liquid mixer as the circulation side gas-liquid mixer 24 only.

As in the ozone water generator 401 of the fifth embodiment shown in FIG. 10, the ozone gas mixing unit 20 may be the solvent side gas / liquid mixer 22 only, and the circulation side gas / liquid mixer may be omitted. In this case, the solvent-side gas-liquid mixer 22 may mix ozone gas supplied from the ozone generator 10.

In the first embodiment, the case where the outlet path 82 and the ozone solution outlet 86 serve as the circulation path 60 and the circulating fluid outlet 62 is illustrated, but the present invention is not limited to this. For example, as in the ozone water generator 501 of the sixth embodiment shown in FIG. 11, the outlet path 82 and the ozone solution outlet 86 are arranged independently of the circulation path 60 and the circulating liquid outlet 62. Also good. At this time, it is preferable to arrange the ozone solution outlet 86 below the circulating fluid outlet 62, whereby a tertiary space 30 </ b> C can be formed between the circulating fluid outlet 62 and the ozone solution outlet 86. The flow rate Q ₃ (L / min) of the downward flow in the tertiary space 30C is smaller than the flow rate Q ₂ (L / min) of the secondary space 30B, and is matched with Q ₁ (L / min) of the primary space 30A. since it is, compared to the secondary space 30B, it can be reduced down velocity _{V 3} of the tertiary space 30C. Result, even increased the circulation flow rate of the secondary space 30B, so lowering the flow velocity V ₃ of the tertiary space 30C is kept small, more air bubbles in the ozone solution outlet 86 is in a state not easily enter. As shown in FIG. 11 (F), the flow immediately before the ozone gas mixture led to the lead-out path 82 via the ozone solution lead-out port 86 is the flow of the gas-liquid separation tank 30 as indicated by the arrow FE. It becomes a swirl flow along the inner peripheral wall.

In the first embodiment, the case where the swirl flow is generated in the ozone gas mixture stored in the gas-liquid separation tank 30 by the introduction force of the raw water or the circulating liquid is exemplified, but the present invention is not limited to this. For example, like the ozone water generating device 601 of the seventh embodiment shown in FIG. 12, the swirling flow generating unit 50 may have a rotating body 56 that generates a swirling flow by rotating in the ozone gas mixture. The rotating body 56 has rotating blades 56A as shown in FIGS. 12B to 12D, and the rotating shaft extending in the vertical direction rotates on the upper surface and / or the bottom surface of the gas-liquid separation tank 30. It is held freely and is forcibly rotated by a motor MT or the like. By rotating the rotary blade 56A, the swirl flow S is generated in the ozone gas mixture, and at the same time, the effect of causing the rotary blade 56A to crush and disperse bubbles having a relatively large diameter gathered on the rotary shaft. Ozone dissolution efficiency is improved.

Further, the structure of the rotating body 56 is not limited to the wing type. For example, like the ozone water generating device 701 of the eighth embodiment shown in FIG. A swirling flow S may be generated. It is also preferable to arrange a plurality of rotating bodies 56 in the vertical direction.

In the above embodiment, the case where the liquid level in the gas-liquid separation tank 30 is made to coincide with the solvent introduction port 76 is exemplified, but the present invention is not limited to this. For example, it is also preferable to set the liquid level above the solvent introduction port 76, and a swirling flow can be effectively generated by the raw material water introduced from the solvent introduction port 76 that is submerged. On the other hand, it is also preferable to set the liquid level below the solvent introduction port 76.

Moreover, although the case where pure water etc. are used as a solvent is illustrated in the said embodiment, this invention is not limited to this. For example, the ozone water generating device can be used as a water treatment device that utilizes the decomposition of organic matter using ozone and the sterilization characteristics of ozone. In this case, a liquid (water) containing an organic substance that chemically reacts with ozone, or a liquid (water) containing at least one of a virus, a bacterium, a fungus, and a microorganism can be used as the solvent. The present invention is not limited to the case where organic substances and viruses are treated in the gas-liquid separation tank, but includes the case where ozone contained in the ozone solution derived from the gas-liquid separation tank treats organic substances and viruses over time.

The organic matter, virus, bacteria, fungi, microorganisms, and the like to be treated vary greatly in the product of ozone concentration and time required for treatment in the ozone solution depending on the type. Therefore, the ozone concentration may be controlled according to the type, and the residence time (circulation time) in the gas-liquid separation tank may be controlled. In addition, a standby space such as a storage tank or piping is prepared on the downstream side of the ozone solution outlet, and the ozone solution derived from the gas-liquid separation tank is temporarily retained in the standby space, so that the ozone treatment is performed. Time may be secured. Note that this standby space can also be used as a place to additionally deaerate bubbles such as ozone that have remained in the ozone solution.

It should be noted that the present invention is not limited to the above-described embodiment, and it is needless to say that various modifications can be made without departing from the gist of the present invention.

Claims (15)

1. An ozone solution generator that generates an ozone solution by dissolving ozone gas generated by an ozone gas generator in a solvent,
   A gas-liquid mixer that mixes the ozone gas and the solvent to produce an ozone gas mixture;
   A gas-liquid separation tank for storing the ozone gas mixture produced by the gas-liquid mixer;
   A swirl flow generating section for generating a swirl flow in the ozone gas mixture in the gas-liquid separation tank;
   An ozone solution derivation unit that guides the ozone solution generated by the ozone gas mixture that has passed through the swirling flow to the outside of the gas-liquid separation tank;
   An ozone solution generation device comprising:
2. The ozone solution outlet has an ozone solution outlet for leading the ozone solution out of the gas-liquid separation tank;
   The ozone solution outlet is located at a location that is radially outward from the central axis of the swirling flow in the ozone mixture,
   The ozone solution generation device according to claim 1.
3. The swirl flow generator is
   It has a tangential direction introduction part that creates a swirl flow by setting the range of the introduction direction of the solvent or the ozone gas mixture into the gas-liquid separation tank to include the tangential direction of the swirl flow. ,
   The ozone solution generation apparatus according to claim 1 or 2.
4. The swirl flow generator is
   A tangential direction deriving unit that creates a swirling flow by setting a range of a deriving direction of the solvent, the ozone gas mixed solution or the ozone solution from the gas-liquid separation tank to a range including a tangential direction of the swirling flow; Features
   The ozone solution production | generation apparatus in any one of Claims 1 thru | or 3.
5. The swirl flow generator is
   It has a rotating body that generates the swirling flow by rotating in the ozone gas mixture,
   The ozone solution production | generation apparatus in any one of Claims 1 thru | or 4.
6. A circulation path for deriving the ozone gas mixture in the gas-liquid separation tank to be a circulation liquid and returning the circulation liquid to the gas-liquid separation tank;
   In the middle of the circulation path, the circulation-side gas-liquid mixer for mixing the ozone gas supplied from the ozone gas generation device and the circulation liquid is disposed,
   The ozone solution generation device according to any one of claims 1 to 5.
7. A circulation path for deriving the ozone gas mixture in the gas-liquid separation tank to be a circulation liquid and returning the circulation liquid to the gas-liquid separation tank;
   The circulating fluid introduction port located at the downstream end of the circulation path generates a swirl flow by setting the range of the introduction direction of the ozone gas mixture into the gas-liquid separation tank as a range including the tangential direction of the swirl flow. It also serves as a tangential direction introduction part to create,
   The ozone solution production | generation apparatus in any one of Claims 1 thru | or 6.
8. A circulation path for deriving the ozone gas mixture in the gas-liquid separation tank to be a circulation liquid and returning the circulation liquid to the gas-liquid separation tank;
   The circulating fluid outlet located at the upstream end of the circulation path creates a swirling flow by setting a range of a direction in which the ozone gas mixture is led out from the gas-liquid separation tank to a range including a tangential direction of the swirling flow. It also serves as a tangential direction deriving part,
   The ozone solution production | generation apparatus in any one of Claims 1 thru | or 7.
9. The circulating fluid inlet that introduces the circulation into the gas-liquid separation tank located at the downstream end of the circulation path is ozone that guides the ozone mixture to the outside of the gas-liquid separation tank in the ozone solution outlet. Compared with the solution outlet, it is arranged above,
   The ozone solution generation device according to any one of claims 6 to 8.
10. At least in the middle of the solvent guide path that guides the solvent to the gas-liquid separation tank, the gas-liquid mixer for mixing the solvent and the ozone gas is disposed,
    The gas-liquid mixer is supplied with the ozone gas separated and recovered from the ozone gas mixed liquid in the gas-liquid separation tank,
    The ozone solution production | generation apparatus in any one of Claims 1 thru | or 9.
11. At least a solvent introduction port located at a downstream end of a solvent guide path that guides the solvent to the gas-liquid separation tank has a range of a direction in which the solvent is introduced into the gas-liquid separation tank in a tangential direction of the swirl flow. It also serves as a tangential direction introduction part that creates a swirling flow by including the range,
    The ozone solution generation device according to any one of claims 1 to 10.
12. As the solvent, a liquid containing an organic substance that causes a chemical reaction with ozone is used as a treatment application of the organic substance in the liquid.
    The ozone solution generation device according to any one of claims 1 to 11.
13. As the solvent, a liquid containing at least one of a virus, a bacterium, a fungus, and a microorganism is used, and the solvent is used for processing the substance in the liquid,
    The ozone solution generation device according to any one of claims 1 to 12.
14. It has a waiting space for temporarily retaining the ozone solution derived from the ozone solution deriving unit,
    The ozone solution generation device according to any one of claims 1 to 13.
15. An ozone solution generation method for generating an ozone solution by dissolving ozone gas generated by an ozone gas generation device in a solvent,
    A gas-liquid mixing step of mixing the ozone gas and the solvent to produce an ozone gas mixture;
    A swirling flow generating step of storing the ozone gas mixed solution generated in the gas-liquid mixing step in a gas-liquid separation tank, and generating a swirling flow in the ozone gas mixed solution in the gas-liquid separation tank;
    An ozone solution derivation step for guiding the ozone solution generated by the ozone gas mixture that has passed through the swirling flow to the outside of the gas-liquid separation tank;
    An ozone solution generation method comprising:

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